Full text of "Journal"
JOURNAL
OP
THE CHEMICAL SOCIETY
€ommitkt of '^nhlkution :
H. E. AEMSTEONa, Ph.D., RR.S.
A. Bvvnt, Ph.D., F.R.S..
C. Graham, D.Sc.
F. R. Japp, M.A., Ph.Di
Heebeet McLeod, F.R.S>.
Hugo Mullee, Ph.D., F.R.Si
W. H. Peekin, Ph.D., F.R.S..
W. J. Russell, Ph.D., F.R.S.
E. SoHUNCK, Ph.D., F.R.S..
J. MiLLAE Thomson.
P. P. Bedson, D.Sc-
H. Bae:ee.
D. Bendix.
C. H. Bothamlet.
B. Beaunee, Ph.Di
B. H. Beou&h.
T. Caenellet, D.Sc,
C. F. Ceoss.
J. K. Ceow, D.Sc.
Joseph Fletcheb.
A. J. Geeenaway.
Otto Hehnee.
(^Viiox :
Hbnby Watts, B.A., F.R.S..
^nh-€Vttox:
G. E. Groves, F.R.S..
^h^txnttoxB :
D. A. Louis.
A. K. MiLLEE, Ph.D:
J. M. H. MuNEO, D.Sc.
D. Page, M.D.
E. W. Peevost, Ph.D.
E. H. Rennie, M.A., DjSo.-
R.ROUTLEDGE, B.Sc.
L. T. Thoene, Ph.D.
V; H. Velet^ M.A..
John I. Watts.
W. C. Williams.
Vol. XLIV.
1883. ABSTKACTS.
LONDON:
J. VAN VOORST, 1, PATERNOSTER ROW.
1883.
LONDON :
HifiEISON AND SONS, PRINTERS IN ORDINARY TO HER MAJESTY, ST. MARTIN*S LAKE.
CONTENTS.
PAPERS READ BEFORE THE CHEMICAL SOCIETY:—
General and Physical Chemistry.
PAGE
LiYEiNG (Or. D.) and J. Dewae. Spectrum of Carbon .... 1
LiVBiNG (G-. D.) and J. Dewae. Disappearance of some Spectral Lines, and
the Variation of Metallic Spectra due to Mixed Yapours ... 2
ToMMASi (D.). Action of Light on Silver Bromide 3
HoLZEE (A.) . Sources of Error in Polarising 3
JouBEET (J.). Method of Determining. the Ohm 4
BiCHAT (E.) and R. Blondlot. Oscillations of the Plane of Polarisation by
Electric Discharges 4
ToMMASi (D.). Zinc-carbon Couples in Electrolysis . . . . . 4
Jamin and Gr. Manbtjveiee. The Reaction Current of the Electric Arc . 4
Spottiswoode (W.) and J. F. Moulton. Movement of Gras in " Yacuum
Discharges" 5
YiOLLE (J.). Apparatus for the Determination of Specific Heats by
Cooling 6
Thoulet and Lagaede. Specific Heats of Small Quantities of Sub-
stances 6
Beethelot and Ogibe. Specific Heat of Gkseous Acetic Acid ... 6
Hill (S. A.). The Constituent of the Atmosphere which absorbs Radiant
Heat 7
Raoult (F. M.). Law of Freezing of Aqueous Solutions of Carbon Com-
pounds 7
ToMMASi (D.). Nascent Hydrogen 7
Beethelot. Reciprocal Displacement of the Halogens .... 8
Beethelot. Perchloric Acid 8
Beethelot. Berthollet's Laws, and the Combinations of Mercuric Oxide
with Acids 10
Beethelot and Ilosvat. Double Salts formed by Fusion . . . . 11
Ditte (A.). Decompositions of Salts by Fused Substances .... 11
Alexejeff (W.) . Mutual Solution of Liquids 11
Dixon (H. B.). Yelocity of Explosion of a Mixture of Carbonic Oxide and
Oxygen with Yarying Quantities of Aqueous Yapour .... 12
Dixon (H. B.). Influence of Aqueous Yapour on the Explosion of Carbonic
Oxide and Oxygen 12
LossEN (W.) . Specific Yolumes of Liquids 13
Zandee (A.). Specific Yolumes of Allyl and Propyl Compounds . . . 13
Langley. Observations on the Solar Spectrum 137
Egoeoff. Absorption Spectrum of the Earth's Atmosphere . . . 137
DE Chaedonnet. Reflection of Actinic Rays : Influence of the Reflecting
Surface 138
Monckhoven (D. v.). Widening of the Lines in the Hydrogen Spectrum . 139
LiVEiNG (G. D.) and J. Dewae. Spectrum of Water 140
MoNCKHOVEN (D. V.). Influence of Temperature on the Spectra of Non-
Metals 140
SoEET (J. L.) and E. Saeasin. Circular Polarisation of Quartz . . . 140
GoossENS (B. J.). The Metallic Galvanic Circuit of Ayrton and Perry . 141
Elstee (J.) and H. Geetel. Electricity of Flame 141
a 2
iv CONTENTS.
7A01
ToMMASi (D.). Electrolysis of Hydrochloric Acid 142
Desains (P.). Distribution of Heat in the Ultra-red Region of the Solar
Spectrum 143
ToMMASi (D.). Laws of Thermal Constants of Substitution . . . . 143
RiviEBE (C.). Law of Cooling 144
Ceafts (J. M.) . Comparison of Mercurial Thermometers with the Hydrogen
Thermometer 144
Hannat (J. B.). Limit of the Liquid State 145
Spring (W.). Expansion of Isomorphous Salts 146
Klein (D.). Modification of the Usual Statement of the Law of Iso-
morphism 147
BEtJaELMANN (G".). Observations on Crystallisation 147
Beugelmann (G-.). Experiments on Crystallisation exemplifying Berthollet's
Law of Affinity . • * ... 148
Mallaed and Le Chateliee. Nature of the Vibratory Movements which
accompany the Propagation of Flame in Mixtures of Combustible Gases 148
Beethelot. The Light emitted by Comets 261
Janssen (J.). Telluric Rays and the Spectrum of Water Yapour . . 261
LiVEiNG (G-. D.) and J. Dkwae. Spectra of Carbon and its Compounds . 261
LiVEiNQ (G-. D.) and J. Dewae. The Ultra-violet Spectra of Elements . 262
LiTEiNG (G-. D.) and J. Dewae. An Arrangement of the Electric Arc for
the Study of Radiation of Vapours 262
Haetlet (W. N.). Reversal of MetaUic Lines in Over-exposed Photographs
of Spectra _ 263
Haetlet (W. N.) . Researches on Spectrum Photography .... 263
Nasini (R.). Atomic Refraction of Sulphur 264
Goldstein (E.). Electric Discharge in Rarefied Gases .... 266
D1VEE8 (E.). The Leclanche Cell and the Reactions of Manganese Oxides
with Ammonium Chloride 272
BeAED. Currents Produced by Fused Nitrates in Contact with Incandescent
Carbon 273
Determination of High Temperatures 274
Bellati (H.) and R. Romanese. Specific Heat and Heat of Transforma-
tion of Silver Iodide and its Alloys with Cuprous and Lead Iodides . 274
Raabe (F. W.) . Direct Determination of the Heat of Combination of cer-
tain Gases . . . • . 274
Beethelot. Lead Iodides 275'
Beethelot. Ethylene Oxide " . . . . 275
Pawlewski (B,). Critical Temperatures of Alkyl Salts .... 276
Ansdell (G.). Critical Point of Mixed Gases . . . ' . . . 277
Raoult (F. M.). Law of Freezing of Solvents 278
Blaseena (P.) and S. Cannizzaeo. Report on a Memoir by R. Schifif "On
the Molecular Volumes of Liquids " 279
Gal (H.). Passage of Alcoholic Liquids through Porous Vessels . . . 279
HoFMANN (A. W.). Lecture Experiments 279
Kittlee (E.). Electromotive Force of a Daniell's Element . . . . 409
Steeintz (F.). Galvanic Polarisation 410
Haga (H.). Amalgamation Currents 412
Elstee (J.) and H. Geitel. Electricity of Flame 412
Hankel (W. G.). Actino-electric and Piezo-electric Properties of Quartz,
and their Relation to the Pyro-electric 412
Beaun (F.) . Electrical Energy and Chemical Action 413
KoHLEAUSCH (W.). Specific Conductivity of Sulphuric and Pyrosulphuric
Acids, and the Specific Gravity of Concentrated Sulphuric Acid . . 413
Wachtee (F.). Particles of Matter in the Electric Spark .... 415
RiESS (P.). Electric Shadows 416
Steeckee (K.). Specific Heat of Gaseous Compounds of Chlorine, Bro-
mine, and Iodine with one another and with Hydrogen .... 417
Jaeolimek (A.). Relation between Pressure and Temperature in the Satu-
rated Vapours of Water and Carbonic Anhydride 417
COXTENTS. V
PAGE
Weoblewski (S. v.). Absorption of Gases by Liquids under High
Pressure 418
Enklaab (J. E.). Osmosis of Salts 420
ScHEODER (H.). Constitution of Liquid Compounds ..... 422
Tayloe (I.). Eupert's Drops 422
Pfaijndlee (L.). Explosion of a Tube containing Liquid Carbonic Anhy-
dride 422
Lagaede (H.). Photometric Intensity of the Lines of the Hydrogen Spec-
trum 537
Hagenbach (E.). Stokes's Law of Fluorescence 537
ScHEODEE (H.)- Dependence of Molecular Kefraction of Liquid Carbon
Compounds on their Chemical Constitution 538
Siemens (W.)- Luminosity of Elame 539
Baetoli (A.) . Constitution of Electrolytes 540
Baetolt (A.) and G-. Papasogli. Electrolysis of Water and of Solutions
of Boric Acid 540
Semmola (E.). New Experiment in Electrolysis 540
Hankel (W. G.). Therinoelectric Properties of Minerals .... 540
Neesen (F.). Specific Heat of Water 541
"Vieille. Measurement of Pressures developed in Closed Vessels by the
Explosion of Gaseous Mixtures 542
Mallaed and Le Chateliee. Momentary Pressures produced during the
Combustion of Gaseous Mixtures 542
Thomsen (J.). Thermochemical Investigation of the Chlorides of Iodine . 543
Thomsen (J.). Thermochemical Investigation on the Chlorides of Sulphur,
Selenium, and Tellurium . . , 543
Thomsen (J.).. Method of Estimating the Heat of Formation of Difficultly
Combustible Volatile Carbon Compounds 543
Thomsen (J.). Heat of Formation of the Chlorides of Phosphorus and
Arsenic 544
Thomsen (J.). Heat of Formation of the Chlorides and Oxides of Anti-
mony and Bismuth 541
Thomsen (J,). Heat of Formation of Carbon Tetrachloride and Etbylene
Perchloride 544
NiES (F.) and A. Winkelmann. Volume- change of Metals on Fusion . 545
ScHTJLLEE (A.). Distillation in a Vacuum 545
Geenez (D.). Velocity of Solidification of Bodies in a State of Super-
fusion 546
Langee (C.) and V. Meyee. Dissociation of Chlorine and Bromine . . 54(3
Wiedemann (E.). Dissociation-heat of the Water-molecule and the Elec-
tric Luminosity of Gases 547
ISAMBEET. Ammonium and Hydrogen Sulphide 548
ScHiFF (R.)- Constant of Capillarity of Liquids at their Boiling Points . 549
Gal (H.). Passage of Alcoholic Liquids through Membranes . . . 540
Menschutkin. Mutual Displacements of Bases of Neutral Salts in Homo-
geneous Systems ........... 550
Goodwin (W, L.). Nature of Solution 550
LiVEiNG (G. D.) and J. Dewae. Origin of the Hydrocarbon Flame
Spectrum 641
Ogiee (J.). Sulphiiric Monochloride 642
Beethelot. Heat of Formation of Chromic Acid 642
FoECEAND (de) . Heat of Formation of Solid Gly collates . . . . 64 1
IsAMBEET (F.). Vapour of Carbamide. ..*.... 645
PiCKEEiNG (S. U.). Supersaturation 645
TiMiEiAZEFF (C). Chlorophyll and the Distribution of Energy in the Solar
Spectrum . 617
HiTTOEP (W.). Luminosity of Flame 697
Feomme (C). Electric Researches 697
TeouviS. Modification of the Bichromate Battery ...... 700
Reyniee (E.). Observations on Trouve's Paper on the Bichromate Battery 700
VI CONTENTS.
PAOB
Heez (H.). Electric Discharges 700
FoussEEEAU (&.). Influence of Temper on the Electrical KeBistance of Glass 701
Metee (H.). Electric Eesistance of Psilomelane 701
Baue (C). Kadiation of Kock-salt at Various Temperatures . . . 702
Chappuis (P.) . Evolution of Heat in the Absorption of Gases by Solids and
Liquids 702
Wiedemann (E.). Thermochemical Eesearches 704
Beethelot. Alkaline Sulphites 704
Beethelot. Pyrosulphites 705
Beethelot. Alkaline Thiosulphatcs 7t>7
Beethelot and Vieille. Nitrogen Selenide 707
Beethelot. Chromates 707
ToMMASi (D.). Heat of Formation of GlycoUates 708
De Foeceand. Heat of Formation of Glycollates 708
Menschutkin (N.). Mutual Displacement of Bases of Neutral Salts in
Homogeneous Systems 708
Teafbe (M.) . A Correction 709
Wesendonck (K.), Spectra of Carbon Compounds 761
Becqueeel (H.) . Observations of Infra-red Spectra by Means of Phospho-
rescence 761
Vogel (H. W.). Lockyer' 8 Dissociation Theory 762
Wiedemann (E.). Molecular Refraction 762
Dufet (H.). Variation of the Indices of Refraction of Water and Quartz
with the Temperature 762
Lommel (E.). Fluorescence of Iodine Vapour 763
Radziszewski (B.). Theory of Phosphorescence 763
DvoEAK (V.). Researches in Statical Electricity 763
Clausius (R.). The Units of Electricity and Magnetism . . . . 764
Beatjn (F.). Electromotive Force of certain Galvanic Combinations . . 764
Teguve. Reply to the Observations of Reynier on Bichromate Batteries . 765
KoNiG (A.). Substitution of Hydrogen Peroxide for Nitric Acid in Galvanic
Batteries 765
Baekee (G. F.). Secondary Batteries 765
Feomme (C). Electric Researches 766
Edlund (E.). Researches on the Heat-changes at the Poles of a Volta-
meter 767
Peobeet (I.) and A. W. Sowaed. Effect of Absorbed Qtises on the Elec-
trical Conductivity of Carbon 769
Beaun (J.). Unipolar Conductivity of Solid Bodies 769
Kohleausch (W.). Electrical Conductivity of Silver Halol'd Salt 8 . . 769
Stephan (C). Fluidity and Galvanic Conductivity 769
Hoadley (J. C). Platinum-water Pyrometer 769
Violle (J.). Radiation from Silver at the Solidifying Point . . . 771
Vieille. Specific Heats of Gases at High Temperatures .... 771
Beethelot. Some Relations between Temperatures of Combustion, Specific
Heats, Dissociation, and Pressure of Explosive Mixtures . . . 771
Meyee (L.). Basis of Thermo-chemistry 773
DE Foeceand. Neutralisation of Glycollic Acid by Bases .... 774
DE Foeceand. Salts of Glycollic Acid 775
Tommasi (D.). Heat of Combination of Glycollates 775
ISAMBEET. Ammonium Hydrosulphide and Cyanide 775
Beethelot and Vieille. ' Wave of Explosion 777
Geuthee (A.). Affinity-values of Carbon 779
Mijllee-Eezbach (W.). Specific Gravity and Chemical AflSnities of Ele-
ments in Various AUotropic Modifications 779
Wiedemann (E.). Constitution of Hydrated Salts 780
Abney (W. W.) and R. Festing. Atmospheric Absorption of the Infra-red
of the Solar Spectrum 837
Liveing (G. D.) and J. Dewae. Note on the Absorption of Ultra-violet
Rays by various Substances 837
CONTENTS. Vll
PAGH
LiVEiNG (Q-. D.) and J. Dewae. Reversal of Hydrogen Lines . . . 83S
LiYEiNG (Gj-. D.) and J. Dewae. Order of Keversibility of Lithium
Lines 839
Feankland (E.). Chemistry of Storage Batteries 839
Scrivanow's Chloride of Silver Element 840
Peeece (W. H.). EfPects of Temperature on the Electromotive Force and
Resistance of Batteries 840
BiDWELL (S.). Electric Resistance of Carbon Contacts .... 84^
Ceafts (J. M.). Thermometric Measurements 842
Mallaed and Le Chateliee. Combustion of Glaseous Mixtures. . . 844
BuTLEEOW (A.) . Notice on the Atomic Weights 846
St. Maetin (L. Q-. de). Special Form of G-asometer 847
Obeebeck (A.). Electro-dynamic Interference of Alternating Currents . 897
GoFT. Distortion of Polarised Electrodes 897
Feiedel (C.) and J. Cueie. Pyroelectricity of Quartz .... 897
ViEiLLE. Specific Heats of G-ases at High Temperatures .... 898
Jamin (J.). Critical Point of Gases 898
Schwaez (H.). Modification of V. Meyer's Vapour-density Apparatus . 899
Meyee (L.). Air-baths 900
Quincke (G.) . Electric Researches 945
WiTKOWSKi (A.). Theory of Galvanic Circuits 948
Hellmann (H,). Difference of Positive and Negative Discharge . . . 949
Heez (H.). Researches on the Glow Discharge 949
Hankel (W.). Observations on Thermo- and Actino-electricity of Quartz . 950
Pawlewski (P.). Determination of Vapour-density 951
Jaeolimek (A.). Relation between the Tension and Temperature of Satu-
rated Vapours 951
Raoult (F. M.) . Congelation of Aqueous Solutions of Organic Bodies . 952
Kanonnikoff (J.). Refractive Power of Organic Compounds in Solution . 1041
Beauns (R.). Cause of the Anomalous Double Refraction of certain Salts
Crystallising in the Regular System 1041
Keijss (G.) and S. CEgonomides. Relation between the Composition of
Organic Compounds and their Absorption Spectra 1041
Jahn (H.) . Electrolytic Researches 1042
Mullee-Eezbach. Relation of the Heat of Combustion of Isomeric Or-
ganic Compounds to their Densities 1044
SCHIFF (R.). Molecular Volume of Liquid Substances .... 1044
Keouchkoll. Variation of the Constant of Capillarity of the Surfaces,
Water-Ether, and Water-Carbon-bisulphide under the Action of Electro-
motive Force 1047
ScHEFFEE (J. D. R.). Experiments on the Diffusion of some Organic and
Inorganic Compounds 1047
DoNATH (E.) and J. Mayehofee, Affinity and its Relation to Atomic
Volume, Atomic Weight, and Specific Gravity 1048
Inorganic Ghemistry.
Combes. On the Supposed Compound NHj 14
ScHiJTZENBEEGEE (P.) and A. CoLsoN. Silicon 15
Sabatiee (P.) . Compounds of Silicon with Sulphur 15
CoLSON (A.). Combination of Tetratomic Elements 15
KiENLEN (P.). Extraction of Selenium from a Waste Product ... 16
Teoost (L.). Boiling Point of Selenium 17
NicoL (W. W. J.). Coefficient of Expansion of Sodium Sulphate Solu-
tions 17
Keaut (K.). "Chloride of Lime" and " Chloride of Lithia" ... 17
Lunge (G.) and R. Schoch. Calcium Hypoiodite 17
Cleye (P. T.). Didymium .18
BuAUNEE (B.). Didymium . 18
VIU CONTENTS.
PAOI
Detillb (H. Sainte-Claibe) and H. Debeay. Explosive Alloys of Zinc
with certain Platinum Metale 19
ToMMASi (D.). Action of Aluminium on Cupric Chloride .... 19
ToMMASi (D.). Stability of Cupric Hydroxide 19
Staed (A.). Transformations of Cuproso-cupric Sulpliites .... 20
BoiSBAUDEAN (L. de). Separation of GFallium 21
Batjbignt (H,). Action of Ammonium Sulphide on Stannous Sulphide . 22
Peud'homme (M.) and F. Bindee. Chromic Acid and Chromates . . 22
MoissAN (H.). Chromous Sulphate 22
Klein (D.). New Class of Borotungstates 23
ToMMASi (D.) and G. Pellizzaei. Change which Ferric Hydrate undergoes
after a Time 24
ToMMASi (D.). Ferric Hydrates 24
Baubigny (H.). Action of Hydrogen Sulphide on Solutions of Normal
Nickel Sulphate .-24
Baubigny (H.). Action 'of Hydrogen Sulphide on Nickel Sulphate in
Acetic Acid Solution 25
Baubigny (H^). Action of Heat on an Acid Solution of Nickel Sulphate
in Presence of Hydrogen Sulphide ........ 25
VoETMANN (Gr:). Cobalt Sulphate 25
VoETMANN (G^.). Cobaltamine Compounds 25
G-eedes (B.). Electrolysis of Ammonium Carbamate and Carbonate . . 27
Deechsel (E.). Ammonioplatinum-diammonium Compounds ... 28
LiDOFF (A ) and W. Tichomieoff. Action of the GralTanic Current on
Chlorates 149
Teaube (M.). ^Oxidation of Carbonic Oxide by Palladium Hydride and
Oxygen 150
Amagat (E. H.). Compressibility of Nitrogen 150
Thenaed (P.). Black Phosphorus . . 150
FiLHOL (E.) and Sendeeens. Neutral Phosphates of the Alkalis ., . 151
Webee (A.). Calcium Chloride 151
Mallet (J. W.). Properties otf Pure Aluminium . . . . . 151
Geandeau (H.). Decomposition of Phosphates by Potassium Sulphate at
High Temperatures 151
NiLSON (L. F.). Determination of the Equivalent of Thorium . . . 152
NiLSON (L. F.). Metallic Thorium .152
Keaut (K.). Magnesia alba . . . . 153
BoiSBAUDEAN (L. de). Separation of Ghllium . . . . ^ . 153
BoiSBAUDEAN {L. de). Separation of Gallium 156
DiTTE (A.). Compounds of Tin Disulphide and Diselenide .... 156
Fehemann (A.). Preparation of Lead Dioxide , 157
Meschtcheesky (I.). Barium Compounds of Bismuth Peroxide . . 158
Paementiee (F^. a Hydrate of Molybdic Acid 158
Wagnee (A.). Oxygen prepared from Potassium Chlorate . . .. . 281
Kappel (S.). Formation of Ozone and Hydrogen Peroxide . . . 282
Teaube (M.). Activity of Oxygen . * 282
Muldee (E.) and H. G. L. van dee Meulen. Ozone in Presence of Plati-
num-black 284
VoGLEE (C. A.). Yariation of the Amount of Oxygen in the Atmosphere . 284
Cook (E. H.). Carbonic Anhydride in the Atmosphere .... 284
Kappel (S.). Nitrification in Presence of Copper and other Metals . . 286
B.IBAN (J.). Conversion of Tricalcium Phosplmte into Chlorine Compounds
of Phosphorus 287
ScHEETEL (A1). Volume- weight of Sulphuric Acid 288
PiLLiTZ <W.). Argentous Oxide 288
Beckman (E.). Barium Aluminates 289
V. Bemmelen (J. M.). Beryllium Hydroxides 291
Cleve (P. T.). Atomic Weight of Yttrium . . . . . . 292
ScHWAEZ (H.). Lecture Experiment illustrating the Combination of Zinc
with Sulphur .... ... 292
CONTENTS. IX
PAGB
BoiSBAUDEAN (L. de). Separation of Gallium 293
DiTTE (A.) Stannous Oxide and some of its Compounds .... 294
Wellee (A.). A Higher Oxide of Titanium 295
ScHULZE (H.). Arsenious Sulphide in Aqueous Solution .... 295
DiTTE (A.). Formation of Crystallised tJranates in the Dr J Way . . 296
Pavel (O.). Nitroso-sulphides and Nitroso-cyanides 297
Debrat (H.). Artificial Production of Iridosmin 298
Teaube (M.). Action of Platinum and Palladium on Carbonic Oxide and
Hydrogen 422
Beethelot and J. Ogiee. Researches on the Hyponitrites . . . 422
Yeeneuil. Nitrogen Selenide . 423
Ogiee (J.). Pyrosulphuric Chloride . . . . . . ' . . 423
Baelow (W. H.). Mechanical Properties of Aluminium .... 424
Pemberton (H.) . Potash Alum from Felspar 424
Rammelsbeeg (C). Double Chloride of Potassium and Thallium . . 424
Rammelsbeeg (C). Thallium and Lithium Phosphates .... 424
Eeis (K.) and B. Ratman. Compounds of Tin with Bromine . . . 424
Austin (P. T.). Preparation of Stannic Oxide from Sodium Stannate . . 425
WiESNEE. Uranyl-potassium Chromate 425
Beethelot. Natural Formation of Manganese Dioxide, and some Reactions
of Peroxides 425
DiTTE (A.). Crystallisation of Chlorine Hydrate 550
Voglee (C. A.). Variation in the Amount of Oxygen in the Air . . . 551
Basaeoff (A.). Oxidation of Sulphur in the Air 551
Beethelot. Reactions between Sulphur, Sulphur Oxides, Carbon, and
Carbon Oxides 551
KoNOVALOFF (D.). Pyrosulphuryl Chloride 553
NiLSON (L. F.). Crystalline Form, Specific Heat, and Atomicity of
Thorium 553
Cleye (P. T.). Atomic Weight of Lanthanum 553
Engel (R.). Alio tropic Arsenic 554
Pfoedten (O. v.). Reduction of Tungsten Compounds . . .^ . 554
Joegensen (S. M.). Chemistry of the Chromammonium Compounds .' . 554
Maquenne. Ammonio -cobalt Compounds 557
GoEGEU (A.). Manganese Sulphite 558
Blomsteand (C. W.). Oxy-acids of KDhlorine 645
Metee (V.). Hydroxylamine Hydrochloride 646
IsAMBEET (F.), Dissociation of Phosphine Hydrobromide .... 646
Ogiee (J.). Pyrosulphuric Chloride 646
Rammelsbeeg (C). Potassium Sesquicarbonate 646
DuNSTAN (W. R.) and F. Ransom. Constitution of Liquor soda chloratce 647
DuNSTAN (W. R.) and F. Ransom. Action of Chlorine on Solution of
Sodium Carbonate 647
DiTTE (A.), Production of Brom -apatites and Bromo-wagnerites . . 648
Beckmann (E.). Basic Halogen-salts of Barium 649
Beckmann (E.). Barium Aluminates 649
NiLSON (L. F.). Specific Heat and Valency of Thorium .... 649
Speing (W.). Formation of Arsenides by Pressure 650
Knoeee (Q-. v.) . Tungsten Compounds 650
Jannetaz (E.). A Phosphide of Nickel 651
Ceafts (J. M.). Density of Chlorine at High Temperatures . . . 710
Jacobsen (O.). Phosphorescence of Sulphur 710
FiLHOL (E.) and Sendeeens. Action of Sulphur on Oxides . . . 710
BiLLiTZ (G-.) and K. Heijmann. New Modes of Formation of Pyrosulphuric
Chloride and of Chlorosulphonic Acid 710
Hetimann (K.) and P. Kochlin. Pyrosulphuric Chloride .... 710
Hautefeuille and Maegottet. Crystallised Phosphates .... 711
SCHULTEN (A. de). Barium Potassium Phosphate and Barium Sodium
Phosphate 711
Landein (E.). Action of Different Varieties of Silica on Lime-water . . 712
X CONTENTS.
PAGE
Le Chatelieb (H.). The Setting of Plaster of Paris 712
Debeat (H.). Preparation of Cerium Oxide 713
ANDR:fi (G-.). Ammoniobromides and Oxy bromides of Zinc . . . .713
Delachaelonny (P. M.). Aluminium Sulphate 714
G-UCKELBEEGEE (Gt.). Ultramarine 714
BoiSBAUDEAN (L. de). Separation of Gallium 715
DiTTE (A.). Crystallised Stannates 716
Andee (G.). Double Chlorides of Lead and Ammonium and Oxychlorides
of Lead 717
Taqtjet (C). Chromic Selenite 717
G-oEGEU (A.). Double Sulphites of Manganese and the Alkalis . . . 718
MAirMEN]^ (E.). Chlorine Hydrates 780
Weoblewski (S.) and K. Olszewski. Liquefaction of Oxygen and Nitro-
gen J Solidification of Carbon Bisulphide and of Alcohol . . . 781
Heumann (K.) and P. Kochlin. Action of Heat on Sulphuric Monochlo-
ride and Dichloride 781
KoNOWALOFF (D.). Pyrosulphuric Chloride ...... 782
Hautefeuille (P.) and J. Maegottet. Combination of Phosphoric Acid
with Silica 782
Hatjtefeuille (P.) and J. Maegottet. Phosphates 782
FiLHOL (E.) and Sendeeens. Action of Sulphur on Alkaline Phosphates . 783
Ditte (A.). Bromapatites and Bromowagnerites 783
Ditte (A.). lodo-apatites 784
ScHTJLZE (H.). Antimonious Sulphide in Aqueous Solution . . . 784
Ditte (A.). Production of Crystallised Vanadates in the Dry Way . . 784
Feeih (O.). Reduction of Tungsten Compounds 785
Klein (D.). Borotungstates 786
Hoppe-Seylee (F.). Activity of Oxygen in Presence of Nascent Hydrogen 848
Specific Gravities of Solutions of Ammonia and Ammonium Carbonate . . 849
Scheueee-Kestnee (A.). Formation of Nitrous Acid in the Evaporation of
Water 850
Walleoth (K. a.). Action of Microcosmic Salt on various Oxides . . 850
Specific Gravity of Sulphuric Acid 851
Boenteagee (H.). Preparation of Selenium on a Large Scale . . . 852
Cleve (P. T.). Atomic Weight of Didymium 852
PiCKEEiNG (S. TJ.). Basic Sulphates of Copper ....,-. 853
Ceoss (C. F.). Rehydration of Ferric Oxide . . . . . . 853
Schottlandee (P.). Gold Compounds 853
Dewae (J.) and A. Scott. Atomic Weight of Manganese .... 856
Teaube (M.). Action of Nascent Hydrogen on Oxygen Gas . . . 900
Ceoss (C.) and A. Higgin. Decomposition of Water by Metalloids . . 900
KoNOWALOW (D.). Pyrosulphuric Chloride 900
IsAMBEET. Phosphorus Sesquisulphide 901
Engel (R.). Analogy between the AUotropic Modifications of Phosphorus
and Arsenic 901
Fluckigee (F. a.). Potassium Carbonate 902
Reychlee (A.). Silver Nitrate and Ammonia ...... 902
Ande^ (G-.). Double Salts of Lead 903
Klingee (H.). Basic Double Salts 904
Speing (W.). Formation of Sulphides by Pressure 904
Speing (W.). Colloidal Copper Sulphide 904
BoiSBAUDEAN (L. de). Iridium and Potassium Sulphate .... 905
BoiSBAUDEAN (L. de). Reactions of Iridium 905
Weoblewski (S.) and K. Olszewski. Liquefaction of Nitrogen and of
Carbonic Oxide 952
Lunge (G-.) and P. Naef. Bleaching-powder and Analogous Compounds . 953
Thal^n (T.). Spectral Researches on Scandium, Ytterbium, Erljium, and
Thulium 954
ScHEAMM (J.) . Position of Thallium in the Chemical System and its Pre-
sence in Sylvin 954
CONTENTS. XI
PAGE
WiLM (F.). Preliminary Notice 954
Hoppe-Setleb, (F.). Activity of Oxygen 1048
Ladenbueg (A.) . Lecture Experiments 1048
Ttndall (J.). Unobserved Resemblance between Carbonic Anhydride and
Carbon Bisulphide , . 1049
IsAMBEET. Phosphorus Sulphides 1049
ScHULZE (H.). Phosphorus Subsulphide 1049
Wenzell (W. T.). Preparation of Phosphoric Acid by the Oxidation of
Phosphorus v^^ith Air in Presence of Moisture 1050
Hexjmann (K.) and P. Koechlin. Thionyl Chloride and Pyrosulphuryl
Chloride 1051
WiTTJEN (B.) and H. Peecht. Blue Eock Salt 1051
Philip (J.). Silver Hypophosphate 1052
LoNQi (A.). Iodide of Argentammonium 1052
Lescceue (H,). Hydrates of Baryta 1052
Maumen:^ (E. J.). Hydrates of Baryta 1052
Ballo (M.) . Platinised Magnesium as a Reducing Agent .... 1053
Bailey (E.). Dried Alum 1053
DEMAE9AY (E.). Thorium Sulphate 1053
Debeay. Solubility of Cupric Sulphide in Alkaline Thiomolybdates . . 1054
Weight (L. T.). Colloidal Copper Sulphide 1054
Thomsen (J.). Hydrogen G-old Chloride 1054
BoiSBAUDEAN (L. de). Separation of Qallium 1054
PicciNi (A.) . Oxidation of Titanic Acid 1055
BoNGAEiL (J.). Atomic Weight of Antimony ■ . 1056
WiLM (T.). Chemistry of the Platinum Metals 1057
BoiSBAUDEAN (L. de). Yiolet Iridium Sulphate . ..... 1057
JoEGENSEN (S. M.). Contributions to the Chemistry of Rhodammonium
Compounds 1058
Mineralogical Chemistry.
Page (W. T.). Metallic Iron accompanying Native Gold in Montgomery
Co., Virginia 29
Beandl (J.) . Chemical Composition of Minerals of the Cryolite Group . 29
NoELLNEE (A.), Some Artificial Products from Cryolite .... 30
NoEDSTEoM (T.). The Pyrolusite Mines of Bolet 31
BouEGEOis (L.). Artificial Production of Witherite, Strontianite, and
Calcite 31
Beun (A.). Mineralogical Notes 31
Des Cloizeaux and Damoue. Chalcomenite, a New Mineral Species (Sele-
nite of Copper) 31
Seamon (W. H.). Fergusonite from Brindletown, Burke Co., N. Carolina . 32
Seamon (W. H.). Analysis of a Niobate which has been improperly called
Euxenite, from Mitchell Co., N. Carolina 32
Mann (P.). Rutile as a Pi'oduct of the Decomposition of Titanite . . 33
Schulten (A. de). Artificial Production of a Crystallised Hydrated
Silicate 33
Schulten (A. de). Artificial Analcime 34
Sandbeegee (F.). Rutile in Phlogopite 34
Musgeave (R. N.). Analysis of Beautifully Crystallised Albite from
Amelia Co 34
Becze (F.). Euclase from the Alps 34
ScHUBEET (B.). Occurrence of Minerals at Jordansmuhl, in Silesia . . 35
Beeteand (C). Waltherite from Joachim sthal 36
GoNNAED (F.). The Granites on the Banks of the Sa6ne .... 36
RicciAEDi (L.). Composition of Yarious Layers of a Lava-current from
Etna 36
XU CONTENTS.
PAGE
Meuniee (S.). Lithological Determination of the Meteorite of Esther-
villa, Emmet Co., Iowa 37
Seamon (W. H.) . Supposed Meteorite found in Augusta Co., Yirginia . 37
Pebal (L.). Mechanical Separation of Minerals 158
GoLDSCHMiDT (V.). Application of a Solution of Potassium and Mercury
Iodides to Mineralogical and Petroaraphical Researches . . . 159
Seamon (W. H.). Native Palladium Gold from Taguaril, Brazil . . 160
Seamon (W. H.). Alloys of G-old, Silver, &c., found in Grains along with
the Native Platinum of Columbia 160
PiNAED (G.) . On a Bed of Coal Discovered in Algiers, and on the Layers of
White Sand accompanying the same 160
Demel (W.). Dopplerite from Aussee 160
Page (W. T.). New Sulphide received as Tetrahedrite from Great Eastern
Mine, Colorado . ' 161
Silliman (B.). Martite of the Cerro de Mercado, or Iron Mountain of
Durango, Mexico, and Iron Ores of Sinaloa 162
Daeton (N. H.). New Locality for Hayesine 162
Penfield (S. L.). Occurrence and Composition of some American Varieties
of Monazite 162
Massie (F. A.). Colourless Mimetite from the Richmond Mine . . . 163
Hidden (W. E.). Notes on some N. CaroHna Minerals .... 163
Allen (C. L.) . Composition of Two Specimens of Jade .... 163
Seamon (W. H.). Analysis of a Mineral Allied to Orthite . . . 164
Ceoss (W.) and W. F. Hillebeand. Minerals, mainly Zeolites, occurring
in the Basalt of Table Mountain, near Golden, Colorado . . . 164
SzABO (J.). Garnet and Cordierite in the Trachytes of Hungary . . . 166
Haeada (T.). The Lugano Eruptive District 167
Geoddeck (A. v.). Sericite Rocks occurring in Ore Deposits . . . 168
Sommeelad (H.) . Basalt Rocks containing Hornblende .... 169
Flight (W.). Examination of certain Meteorites 169
BoussiNGAULT. Deposits of Manganese on the Surfaces of Rocks . . 170
Theesh (J. C). The Orchard Alum Spring 171
POTiLiTziN (A.). Analysis of Waters accompanying Petroleum and of
those Ejected by Mud-Yolcanoes 171
GuTOT (P.). Analysis of the Coal of the Muaraze 299
NiLSON (L. F.). The Thorite of Arendal -.299
Jannettaz (E.). Study of " Longrain," and Measure of the Foliation in
Schistose Rocks by means of their Thermic Properties .... 300
DiEULAFAiT. Lithium, Strontium, and Boric Acid in the Mineral Waters
of Contrexeville and Schinznach (Switzerland) 301
SCHLAGDENHAUFFEN (M.). Presence of Arsenic in the Waters of Bareges . 302
ScHLAGDENHAUFFEN (M.). Origin of Arsenic and Lithium in Waters con-
taining Calcium Sulphate 302
JoLY (N.) . Glairin or Baregin 302
NoEDSTEOM (T.). Silver Amalgam from the Sala Mines .... 426
CoLLiEE (P.). A Remarkable Platinum Nugget 426
Lewis (H. C). Substance Resembling Dopplerite from a Peat Bog near
Scranton, Pa 427
SCHAEIZEE (R.). Idrialite 427
Feiedel (C.) and M. Balsohn. Artificial Production of Mellite . . . 427
Klein (C). Cryolite, Pachnolite, and Thomsenolite 427
d'Aechiaedi (A.). Minerals found near Massa, in the Apuanian Alps . 428
Beun (A.). Galena with Octohedral Cleavage 428
RuMPF (J.). Analysis of Miargyrite from Pribram 428
KoNiG (G. A.). Alaskaite, a new Bismuth Mineral 429
Zecchini (M.). Compact Magnetic Iron Ore from Cogne, Valley of
Aosta 429
ToENEBOHM (A. E.). Occurrence of Iron Ores at Taberg, in Smaaland . 429
de Geee (G.). a Manganese Mineral from Upsala 429
HiNTZE (C.) . Pseudomorphic Senarmontite Crystals 430
CONTENTS. xiii
PAGE
Aezhttni (A.). Artificial and Natural Q-aylussite 430
Friedel (C.) and others. Composition of Dawsonite 430
Venator (E.). Strontianite in Westphalia 431
SiLLiMAN (B.). Turquoise from New Mexico 431
Friedel (C.) and E. Sarasin. Artificial Production of Phosgenite . . 431
G-EOTH (P.). Natural Barium Nitrate 431
SCHOBER (J. B.). Examination of the Ores from Amberg, and of the
accompanying Phosphates 432
G-ONNARD (F.). Existence of Apatite in the Pegmatite of Lyons . . 432
Weisbach (A.). Mineralogical Notes 432
Jannrttaz (E.) and L. Michel. Kelation between the Chemical Composi-
tion and Optical Characters in the G-roup of Pyromorphites and Mimet-
esites 433
Aezruni (A.). Dietrichite 433
Baerwald (C.). Thenardite from Aguas Blancas 434
LiNDGREN (W.). Arsenates from Laangban . . . . . . 434
Hallock (E. D.). Analysis of Columbite 434
Mallet (J. W.). Crystalline Form of Sipy lite 435
Koch (S.). Wulfenite 435
Hidden (W. E.). Anatase and Xenotime from Burke Co., N. Carolina . 435
Schmidt (A.). Pseudobrookite 435
Fischer (H.). Tin Ores, Ayenturine Glass, and Green Aventurine Quartz
from Asia, and Krokydolite Quartz from Greenland .... 435
Sjogren (H.). Composition of Minerals of the Chondrodite Group . . 436
V. Rath (G.). Iron Glance and Augite from Ascension .... 436
Jannettaz (E.) and L. Michel. Nephrite or Jade af Siberia . . . 436
Arzruni (A.). Jadeite Axe from E-abber, Hanoyer 437
LuDwiG (E.). Danburite from the Scopi, in Graubiindten .... 437
Haines (R.) . Helvite from Virginia 437
Lacroix (A.). Melanite from Lantgne (Rh6ne) 438
Erdmann (E.). Change of Colour in Felspar under the Influence of
Light 438
Bamberger (E.). Bechi's so-called Picranalcime from Monte Catini Mine,
Monte Caporciano 438
Brush (G. J.) and E. S. Dana. Spodumene and the Products of its Altera-
tion 438
Smith (J. L.) and others. Hiddenite, an Emerald-green Variety of
Spodumene 440
SoND^N (K.). Analysis of Petalite from Uto 440
Sipocz (L.) . Analyses of Scapolite 440
Heddle (M. F.) . New Face on Stil bite (Desmin) 441
Doelter (G.). Crystalline Form of lodocrase (Vesuyian) .... 441
Sadtler (B.). Minerals from Fritz Island, Pennsylyania .... 441
CoRSi (A.) and E. Bechi. Prehnite from Tuscany, &c 441
Bechi (E.). Prehnite and Laumontite from Monte Catini] .... 442
Trechmann (C. O.). Epistilbite 442
Jannasch (P.). Epistilbite and Heulandite 442
Bertrand (E.) and Damour. Zinc Aluminite, a New Mineral Species . 443
Baret. Chlorophyllite from Loquidy, near Nantes 443
LuDWiG (E.). Chemical Composition of Epidote 443
Becke. Hornblende and Anthrophyllite after Oliyine 444
GoNNARD (F.). Gedrite in the Gneiss of Beaunan, near Lyons . . . 444
Starkl (G.). Bole from Steinkirchen, near Budweis, in Bohemia . . 444
Starkl (G.). Polyhydrite from St. Cristoph Mine, Breitenbrunn, in
Saxony 444
CossA (A.) and A. Arzruni. Chromic Tourmalin, and the Deposits of
Chrome-iron Ore in the Urals 444
Bauer (M.). Dioptase from the Corderillas of Chili 446
CossA (A.). Chemical and Microscopical Eesearches on Italian Ilocks and
Minerals 446
XIV CONTEXTS.
PAOB
WOETSCHACH (Or.). The Granite Hills of Konigshain, in Oberlausitz, with
especial regard to the Minerals found therein 446
V. IJNaEEN-STEKNBEBG (T.) . The Rapakiwi Granite, from Finland . . 447
Genitz (E.). Phyllite from Rimogens, in the Ardennes .... 447
MiCHKL-L:6vT (A.) . Micaceous Porphyrite of Morvan 447
Stein (G. E.). The Melaphyres of the Little Carpathians .... 447
GiJMBEL (C. W.). The so-called Andesites of South and Central America . 448
KiJHN (J.). Examination of Ophites from the Pyrenees .... 448
Tecklenburq. The Clay Ironstone of Rheinhesse 448
Ceonquist (A. W.). The Lake Deposits of Kolsnaren, Viren, and Hogsjon,
Sodermanland, Sweden 448
FoiJQu^ (F.) and Michel-L:6vt. Artificial Formation of Various Rocks . 448
DArBE^E (A,). Meteorite of Louans (Indre-et- Loire) 449
Ceonquist (A. W.) . Analysis of a Spring Water from Rindo, near Stock-
holm 449
Iles (M. W.) . Occurrence of Smaltite in Colorado 559
Deeby (O. A.). Brazilian Specimens of Martite 559
Classen (E.). Analysis of a Variety of Siderite 559
Hautefeuille (P.) and J. Maegottet. Silica and Lithium Sihcates . . 559
Wiiz (F. J.). Relation between the Optical Properties and Chemical Com-
position of Pyroxene and Amphibole 560
BouEGEOis (L.). Artificial Production of Wollastonite and Meionite . . 560
WiiK (F. J.). The so-called Ersbyite from Pargas 561
WiiK (F. J.). Emerald from Paavo, in Finland 561
Haeeington (B. J.). Diorites of Montreal 561
Renaed (A.) . Monazite and Zircon from the Quarries of Nil-St. Vincent . 561
Iles (M. W.). Vanadium in the Leadville Ores 562
Macpheeson (J.) . Occurrence of Aerinite 563
HussAK (E.). Serpentine from the Alps 562
Dana (J. D.) . Metamorphism of Massive Crystalline Rocks . . . 562
Coleman (A. P.). The Melaphyres of Lower Silesia 563
Poleck (T.). Analysis of a Mineral Spring at Salzbrunn .... 563
Damoue (A.) . Aluminium Borate from Siberia 719
Stelznee (A.). Melilite and Melilite Basalts 719
Doltee (C). The Volcanic Rocks of the Cape Verde Islands . . . 720
Beoggee (W. C). The Silurian Rocks of Christiania .... 723
Williams (G. H.). The Eruptive Rocks near Try berg in the Black Forest . 723
DiEULAFAiT. Manganese in Sea-water and in Certain Marine Deposits . 725
Bolton (H. C). Application of Organic Acids to the Examination of
Minerals 857
BiJTTGENBACH. Separation of Minerals according to the Degree of Cohesion 858
Geiffiths (A. B.). Analysis of some Minerals 858
WiLM (T.). Magnetic Property of Platinum Ore 859
Geiffiths (A. B.). An Ammonio-phosphatic Deposit in the Vicinity of
Cape Town 859
GoEGEU (A.). Artificial Hausmannite 859
KosMANN. Minerals from Upper Silesia 955
CossA (A.) . Hieratite, a New Mineral Species 955
SCHEAUF (A.). The So-called Liebigite from Joachimsthal . . . . 955
Damofe (A.). Rhodizite 956
SCHEAUF (A.) and others. Danburite from Switzerland .... 956
Ceoss (C. W.) and W. F. Hillebeand. Minerals, mainly Zeolites, from
Table Mountain, Colorado 956
Spezia (G.). Beryl from Craveggia, Piedmont 958
Renaed (A.). Qtimet and Amphibole Rocks of the Bastogne Region . . 958
Will (W.) and K. Albeecht. Diabase from Weilburg .... 959
Fontaine (W. F.). Notes on the Occurrence of certain Minerals in Ameha
Co., Virginia 959
Spezia (G.). The Gneiss of Beura 960
Loeenzen (J,). Minerals in the SodaUte Syenite of South Greenland . . 960
CONTENTS. XV
PAGE
EoHEBACH (C.)- Application of a Solution of Barium and Mercury Iodide
to Petrographical Purposes 1060
Beeteand (E.). Optical Properties of Nocerine 1060
BoDEWiG (C.). Analyses of Magnetic Pyrites 1061
Ltjedecke (O.). Tinder Ore from the Harz 1061
Feiedel (C). Brucite from Cogne 1061
Weisbach (A.). Brucite 1061
Peinz (W.) . The Inclusions in Sapphire, Ruby, and Spinel . . . 1062
GoEGEU (A.). Artificial Production of Barytes, Celestine, and Anhy-
drite 1062
Beeteand (E.). Optical Properties of Cobalt Carbonate .... 1062
Haeton (N. H.) . New Locality for Hayesine, and its Novel Occurrence . 1062
Shepaed (C. it.) . Two New Minerals, Monetite and Monite, with a Notice
of Pyroclasite 1063
Baeewald (C). Analysis of a Pyromorphite from Zahringen, in Baden . 1063
Baeewald (C.) . Analysis of Crocoisite 1063
Hidden (W. E.). Notes on some North Carolina Minerals .... 1063
ScACCHi (A.) . New Sublimates from the Crater of Vesuvius . . . 1064
Kenngott (A.). Calculation of Analyses of Augites and Amphiboles from
Finland 1065
Meuniee (S.). Formation of Bauxite and of Pisolitic Iron Ore . . . 1065
Ceoss (W.) and W. F. Hillebeand. Note on some Interesting Minerals
occurring near Pike's Peak, Colorado 1065
Claassen (E.). Mineraloffical Notes 1066
Damoue (A.) . Chemical Composition of a Green Mica from Syssert . . 1066
Catheein (A.). Saussurite 1066
Keennee. Jadeite 1066
Des Cloizeaux and Jannettaz. Nepheline in the Oligoclase of Denise . 1067
KoEN (O.). Idocrase from Kedab6k in the Caucasus 1067
Jannasch (P.) . Discovery of Fluorine in the Idocrase from Vesuvius . . 1067
Jannettaz. Analysis of a Q-reen Pyroxene from the Diamond Mines of the
Cape 1067
Nicolajew (D. P.). Chemical Composition of Walujewite . . . . 1068
Beck (W. v.) and J. W. v. Muschketow. Nephrite 1068
Catheein (A.) . Chemical Composition of Diallage 1068
Kenngott (A.) . Analyses of Humite 1068
Q-EiNiTZ (F. E.). Pseudomorph of Nacrite after Fluorspar . . . . 1069
ScHEEEEE. Analysis of the Mansfeld Copper Slate 1069
Tbllee (F.) and C. v, John. Dioritic Rocks of Klausen in the Tyrol . . 1069
Le Conte (J.) and W. B. Rising. Metalliferous Vein Formation at Sulphur
Bank 1070
Hauee (F. v.) and others. The Klausenburg Meteorite .... 1070
Gallia (J.) and A. Beezina. The Meteorites of Alfianello .... 1071
Teeeeil (A.). Mineral Water at Montrond (Loire) 1071
Organic Chemistry.
Maqitenne (L.). Action of Ozone on Hydrocarbons ....
NoELTiNG (E.). Dissociation of Trichloro methyl Sulphochloride .
Habeemann (J.) and M. Honig. Action of Cupric Hydroxide on Sugars
Phillipps (S. J.). Conversion of Maltose into Glucose
SoxHLET (P.) and A. Behe. Manufacture of Starch-sugar .
Waage (A.) . Action of Ammonia on Propaldehyde ....
Emmeet (A.) and R. Feiedeich. y-Diethylbutyrolactone .
Zatzek (E.). Bees' Wax
Chanlaeoff (M.). Action of Thiacetic Acid on Ethyl Thiocyanate .
Metee (V.) and E. J. Constam. Azaurolic Acids ....
Ceeesole (M.). Acetoacetic Acids
CuisiNiEE (L.) and H. Kiliani. Saccharin and Lactic Acid from Sugars
37
38
38
38
39
39
39
39
39
40
41
42
XVI CONTENTS.
PAOB
Fkuhling (J.). y-Hydroxybutyric Acid 42
Obach (E.). Purification of Carbon Bisulphide 43
Ilosvay. Physical Properties of Carbon Oxysulphide 43
Claus (A.) . Dibromosuccinic Acid and Diamidosuccinic Acid ... 43
Le Bel (J. A.). Geonaetrical Formulae of Maleic Acid and Fumaric Acids. 44
Conrad (M.) and M. G-uthzeit. Ethylic Methenyltricarboxylate and
Ethylic Acetomalonate 44
BiscHOFF (C. A.). Ethylic Ethenyltricarboxylate 45
BisCHOFF (C. A.). Ethylic Monochlorethenyltricarbaxylate. ... 45
BiscHOFF (C. A.). Ethereal Salts of Propenyltricarboxylic Acid ... 45
Waltz (Gr.) . Ethylic Propyl- and Isopropyl-ethenyltricarboxylates . . 46
BiscHOFF (C. A.). Ethylic Isallylenetetracarboxylate 46
Conrad (M.) and C. A. Bischoff. Tetrethylic Acetylenetetracarboxylate . 46
GuTHZEiT (M.) . Diethylic Acetylenetetracarboxylate . . ... 46
Conrad (M.) and M. G-uthzeit. Tetrethylic Dicarbontetracarboxylate . 46
Hill (H. B.) and C. E. Sanger. Action of Potassium Nitrite on Muco-
bromic Acid ............ 47
Spring (W.) and E. Legros. Alkylthiosulphuric Acids .... 47
Wallach (O.). Action of Phosphorus Peutachloride on Acid Amides. . 48
SciCHiLONB (S.) and A. Denaro. Mannitine, a new Alkaloid from Man-
nitol 50
Ladenbttrg (A.) . Benzene Formulae 51
Meyer (R.). Benzene Formulae 51
Jacobsen (O.). Isodurene, Isodurylic Acids, and the Third Trimethyl-
benzene 52
DuMREiCHER (O. V.) . Action of Aluminium Chloride on the Monohalogen
Derivatives of Benzene 53
Ehrlich (A.). Metatoluidine 54
NoELTiNG (E.). Rosaniline Derivatives 54
LiPPMANN (E.) and F. Fleissner, Azyliues 55
MiCHAELis (A.) and L. Czimatis. Trimethylphosphorbenzobetaine . . 55
Meter (L.), Formation and Decomposition of Acetanilide .... 56
Griess (P.). Constitution of the Azimido-compounds 56
Czimatis (L.). Mixed Aromatic Tertiary Phosphines 57
Meunier (J.) . Action of Potassium Carbonate on Benzyl and Benzylene
Chloride 58
LiEBMANN (A.). Isobutyl- and Amyl-phenols 59
NoLTiNG (E.) and E. v. Salis. Nitro-derivatives of the Cresols ... 59
Barth (L.) and J. Schreder. Fusion of Orcinol and Gallic Acid with
Soda 59
ScHiFF (H.). Methylarbutin 60
Schubert (S.). Di-isobutylquinol 60
Heberand (A.). Compounds of Benzo- and Tolu-quinol with Amines, and
of Q.uinone with Nitranilines 61
Etti (C). Compounds of Vanillin with Pyrogallol and with Phloroglucol . 61
Paal (C). Action of Acetic Chloride on Benzaldehyde in presence of Zinc-
dust 62
Gabriel (S). Orthamidobenzaldehyde 62
RoMBURGH (P. v.). Action of Benzoic Anhydride on Epichlorhydrin . . 62
Komburgh (P. v.). Action of Benzoic Anhydride on Monochloracetone
and on Pyruvyl Benzoate 63
Meyer (R.) and E. Muller. Synthesis of Cumic Acid .... 63
Gabriel (S.). Phenylacetic Acid 64
Noelting (E.) and R. Bourchart. Action of Sulphuric Acid on Proto-
catechuic Acid 65
Millot (A.). Oxidation-products obtained from Carbon by Electrolysis . 65
KoRNER (G.) . CafFeic Acid from Cuprea Bark 66
Canzoneri (F.). Dibromonaphthalene from /3-Naphthol .... 67
HoNiG (M.) and F. Berger. Action of Chloroform on Naphthalene in
presence of Aluminium Chloride 68
CONTENTS. xvli
Worms (R.). Constitution of Nitronaphthols 69
Pabst (M. a.). Indophenol 69
Elsbach (L.). a-Naphthaquinone-ethylanilide . . . . . . 70
Bernthsen (A.) and F. Bender. Derivatives of Styrolene . ... 70
BoRNSTEiN (E.). Metliylanthraquinone and some of its Derivatives . . 70
RoEMER (H.). New Nitro- and Amido-anthraquinones .... 71
LiEBERMANN (C.) and A. Hagen. Action of Concentrated Sulphuric Acid
on Dinitroanthraquinone. . . . , 72
LiEBERMANN (C.) and A. Hagen. Derivatives of Anthrol Salts ... 73
ScHULER (Gr.). Dihydroxyanthracene from a-Anthraquinone - sulphonic
Acid (Flavol) 74
Brunck (H.) and C. Graebe. Soluble Alizarin-blue 74
TiLDEN (W. A.). Hydrocarbons of tlie Formula (CaHs)^ .... 75
Chapoteaut (P.). Essence of Sandal Wood ...... 76
Michael (A.). Synthesis of Salicin, and of Anhydrosalicylic Glucoside . 76
Cannizzaro (C.) and G-. Carnelutti. Santonous and Isosantonous Acids . 77
Spica (G-.). Psoromic Acid, a new Acid extracted from Psoroma crassmn . 80
OuDEMANS (A. C). Laws of the Variation of the Specific Rotatory Power
of Alkaloids under the Influence of Acids 81
CiAMiciAN (Gr. L.) and M. Dennstedt. Action of Nascent Hydrogen on
Pyrroline .82
Hantzsch (A.). Synthesis of Pyridine-derivatives from Etliyl Acetoacetate
and Aldehydammonia 82
Skraup (Z. H.) and Or. Vortmann. Dipyridyl-derivatives .... 85
CoNiNCK (O. de). Quinoline from Cinchonine 88
HooGEWERFE (S.) and W. A. v. Dorp. The Quinoline of Coal-tar, avid
of the Cinchona Alkaloids, and its Oxidation by Potassium Perman-
ganate 89
La CosTE (W.). Nitro- and Amido-bromoquinoline 90
Fischer (O.). Hydroxyquinolines . 91
Skraup (Z. H.). Synthetic Researches in the Quinoline Series ... 92
Rhoussopoulos (A.). Quinoline-derivatives 96
La Coste (W.). Bromoquinolinesulplionic Acids. ..... 96
Tanret. Caffeine 97
Hesse (O.). Hydrocinchonidine 97
RosER (W.). Xeronic and Pyrocinchonic Acids 98
GoLDSCHMiDT (H.). Strychnine 99
ScicniLONE (S.) and y. Magnanimi. Distillation of Strychnine with Zinc-
dust 99
Baumert (G.). Action of Dehydrating Agents on Lupinine . . . 100
Phipson (T. L.). Colouring Matter (Ruberine) and Alkaloid (Agarythrine)
in Agaricus ruler 100
Gautier (A.) and A. ]6tard. Bases Formed by Putrefaction . . . 100
Gautier (A.). Formation of iLlkaloids from Normal Human Fluids . . 101
Nencki (M.) and N. Sieber. Urorosein 101
HuppE (F.). Behaviour of Unorganised Ferments at High Temperatures . 101
Mayer (A.) and others. The Temperature most favourable to the action
of Invertin 101
Bauer (E.). Influence of Invertin on the Fermentation of Cane-sugar . ]i)l
KuTSCHEROFF (M. G.) . Action of Hydrocarbons of the Acetylene Series on
Mercuric Salts 172
Aronstein ( L.) . Transformation of Propyl Bromide into Isopropyl Bromide,
under the Influence of Heat 172
Henry (L.). a-Monochlorallylic Alcohol and its Derivatives . . . 173
Berthelot. Ethylene Oxide 174
Urech (F.). Strobometric Determination of the Rate of Inversion of Cane-
sugar, and Transition of the Birotation of Milk-sugar to its Normal
Rotation 174
Hesse (O.). Anhydrous Grape-sugar from Aqueous Solution . . . 175
Baubigny. Transformation of Amides into Amines 175
VOL. XLIY. b
xvill CONTENTS.
PAOI
Louise (E.). Action of Anhydrous Aluminium Chloride on Acetone . . 176
Bkedt (J.). Action of Nitric Acid on Fatty Acids containing the Isopropyl-
group 176
CouBTONNE (H.). Solidification of different Mixtures of Naphthalene and
Stearic Acid 176
WiLLGEEODT (C). ConTcrsion of Acetone-chloroform into Hydroijiso-
butyric Acid 177
WiLLGEEODT (C). Byc-products in the Preparation of Acetone-chloro-
form 177
Cone AD (M.). Halogen Substitution-compounds of Etliyl Acetoacetate . 177
LiPPMANN (E.). Addition of Bromine to Ethyl Acetoacetate . . . 177
Menschutkin (N.). Decomposition of Tertiary Amyl Acetate by Heat . 178
Ljubavin (N.). Action of Ammonium Cyanate on Glyoxal . . . 178
Sell(W. T.). Series of Salts contrtining Chromium and Urea . . . 178
HoEBACZEWSKi (J.). Synthesis of Uric Acid 179
Baenee (F.). Crystallographic Examination of a- and^-Dinitroparaxylene
and of Dinitroparaxylene (m. p. 93°) 179
Etaed (A), Benzyleneorthotolylamine and Methylphenanthridine . . 179
Samohoef (N.), Azoxylene . . . 180
MoLTCHANOEFSKY (N.). Klinger' 8 Method of; preparing Azoxy benzene . 180
Q-EiESS (P.). Diazo-compounds 180
LiPPMANN (E.) and E. Fleisnee. Azylines 184
Lellmann (E.). Phenylenethiocarbamides . 185
Bambeegee (E.). Formation of Phenylxanthamide ..... 185
MiCHAELis (A.) and L. Gleichmann. Aromatic Isophosphines . . .• 185
ScHULTE (C). Phenylarsine Sulphides . 186
MiCHAELis (A.) and C. Schulte. Arsenobenzene, Arsenonaphthalene, and
Phenylcacodyl 187
Feiedlandee (P.) and B. Heneiques. E«duction of Orthonitrobenz-
aldeliyde 187
TiEMANN (F.) and R. Ludwig. Metahydroxybeiizaldehyde and some of its
Derivatives 188
VoswiNCKEL (H.). New Derivatives of Salicylaldehyde .... 189
Wegscheidee (E.). Isovanillin 190
GIevekoht (H.). Preparation of the Three Isomeric N itracetophenones . 191
Teaube (J.). Action of Cyanogen Chloride on Amido-aeids . . ■ . 192
Teaube (J.). Contributions to tlie Knowledge of Meta-uramidobenzoic Acid
and Carbamidodibenzoic Acid 194
LiPPMANN (E.). Diamidocumic Acid 194
Plochl (J.). Constitution of the Halogen Cinnamio Acids .... 194
Gabeiel (S.). Hydrocinriamic and Cinnamic Acids ..... 195
Eelenmeyee (E.). Derivatives of Cinnamic Acids 196
Baeyee (A.) and F. Bloem. Orthamidophenylpropiolic Acid and its
Derivatives ... 196
Tiemann (F.) and R. Keaaz. Derivatives of HomoferuHc Acid . . . 198
Tiemann (F.) and K. Piest. Phi nylplienamidoacetic Acid and its Amide
and Nitrile . . 198
Tiemann (F.). a-Pheuamidoisobuty ric Acid and its Amide and Nitrile . 199
Tiemann (F.) and R. Stephan. Nitriles of a-Phenamido-, a-Paratolu-
amido-, and a-Orthotoluamidopropionic Acids and their Amides and
Nitriles 199
Tiemann (F.) and W. Will. Constitution of ^tculetin .... 199
Tiemann (F.) and R. Keaaz. Constitution of Eugenol .... 200
Baeyee (A.) and S. (Economides. Isatm 201
Beckee (P.)- Metanitrodiphenylmethane 202
Claus (A.). Amarine 203
Feiedlandee (P.) and A. Weinbeeg. Constitution of Carbostyril and
Hydrocarbostyril 204
SCHWAEZ (H.). a; P; and y-Pyrocrcsolcs 204
>WiDMAN (O.). a- and j-Dichloronaphthalenes 208
CONTENTS. XIX
I PAOK
Walder (H.). ^-Dinaphthol 208
ZiNCKE (T.) and F. Brauns. Action of Amines on Quinone . . . 209
Paterno (E.). Lapachic Acid 210
Cazeneuve (P.). A New Monochlorocamphor ...... 214
S WARTS (T.). Contributions to the History of the Isomerism of tlie Dibro-
mocamphors 214
Kachler (T.) and F. Y. Spitzer. Action of Nitric Acid on Oxycamphor
from j3-Dibromocamphor 215
Maumen^ (E. J.). CEnocjanin 215
Eykman (J. F.). The Tohonous Constituent of Andromeda Japonica . . 215
GriNTL (W.) and F. Reinitzer. Constituents of the Leaves of Fraxinus
excelsior ............. 216
Spiegel (A.). Euxanthic Acid . -. . . ... . . . 219
CoNiNCK (W. O. de). Hydrates of Pyridic Bases derived from Cincho-
nine ............... 220
ScHOTTEN (C). Conine . . . 220
HoFMANN (A. W.). Conhydrine 220
DuviLLTER (E.). Compounds of the Creatinine Group . . . .220
Gerichten (E. v.) and H. Schrotter. Morphine ..... 221
Weidel (H.) and K. Hazara. .Cinchonine 222
Lextreit. Strychnine Sulphate 223
Baumert (G.). Preparation of Lupinine Hydrochloride from Lupinine
Eesidues . . . ^ . . . 221
Gautier (A.) and A. Etard. Putiiid Fermentation, and the Alkaloids
Produced by it 224
Kjedahl (M. J.). Invertin 225
Staedel (W.). Relation between Boilinw Points and Specific Volumes . 302
RoMBURGH (P. V.) . Conversion of Organic Chlorides into Iodides by means
of Calcium Iodide ' . . 303
Berthelot. Decomposition of Cyanogen . . . . . . . 303
Mulder (E.). Properties of Normal Cyanic Acid 304
Mulder (E.). A Reaction of the Compounds of Normal Cyanuric Acid and
Cyanetholhie 305
Berthelot. Ethyl Peroxide 305
Faucoknier (A.). Second Anhydride of Mannitol ..... 305
Urech (F.). Influence of Mass and Time on the Inversion of Su^j^r . . 306
Pfeiffer (T.) and others. Formula of Starch ....... 307
Reboul (E.). Action of Triethylamine on Symmetrical Trichlorhydrin and
on the two Dichloropropylenes 307
Radziszewski (B.). Glyoxaline and its Homologues 308
Menschutkin (N.). Decomposition of Tertiary Amyl Acetate by Heat . 309
Hill (H. B.) and C. F. Mabert. Tetra-substituted Propionic Acids . . 3( 9
Hill (H. B.). Constitution of the Substituted Acrylic and Propionic Acids 310
Melville (W. H.). Crystalline Form of Tribroraacrylic Acid . . . 310
Melikoff (P.). Addition of Hypochlorous Acid to /S-Crotonic Acid . .311
Matthews (A. E.) and W. R. lioDGKiNSON. Ethyl Acetoacetate . . 311
Klepl (A.). Preparation of Methyl Chlorocarbonate 311
Conrad (M.) and M. Guthzeit. Action of Chloroform on Sodium Ethyl-
malonate ............ 311
Mulder (E.) andG. Hamburger. Action of Sodium Ethy late on the Sodium
Salt of Symmetric Dibromosuccinic Acid 312
Ciamician (G. L.), and M. Dennstedt. Derivatives of Citraconic Acid . 312
Baudrowski (E.). Acetylenedicarboxylic Acid 313
Baudrowski (E.). Propargylic Acid 314
Conrad (M.) and M. Guthzeit. Derivatives of Barbituric Acid . . 314
ScHULZE (E.). Extraction of Asparagine from Liquids .... 315
Meyer (V.). Benzene from various Sources 315
Hepp (P.). Trinitro-derivatives of Benzene and Toluene . . . . 315
Hepp (P.). Addition-products of Nitro-derivatives with Hydrocarbons . 317
Aschenbrandt (H.). Paradiethylbenzene . 318
h 2
XX CONTENTS.
PAOS
Spica (P.). Camphor-cymene and the so-called Second Sulphonic Acid of
Paracymene 320
KoENEE (H.). Paradipropylbenzene 321
Louise (E.). A New Hydrocarbon 323
Staedel (W.) . The History of the Metanitrils 323
HiNSBEBO (O.). Oxalic Acid Derivatives of Metanitroparatoluidine and
3—4 Diamidotoluene 323
HoPMANN (A. W.). Crystalline Cumidine 324
Lellmann (E.). The Three Isomeric Phenylenediamines .... 324
Janovsky (H.). Substitution-products of Azobenzene .... 324
Tobias (Q-.). Formation of Anilides 325
Tobias (G^.)- Formanilide and its Homologues • 325
Menschutkin (N.). Decomposition of Acetonilide by Water . . . 326
MiCHAELis (A.) and A. Eeese. Aromatic Arsenic and Antimony Com-
pounds 327
Heneiqu^s (R.). New Nitro-derivatives of Phenol 327
Wallach (O.). Conversion of Tolylenediamine into an Amidocresol and
•y-Orcinol ... 329
WiDMAN (O.). Synthesis of Indole from Cuminol 329
Canzonebi (F.) and P. Spica. Brominated Derivatives of Toluquinone . 330
Fbiedlandee (P.). Orthamidobenzaldehyde 331
MoHLAU (R.). Bromacetopbenone 332
MoHLAU (R.). Action of Bromacetopbenone on Phenol .... 332
MoHLAU (R.). Acetophenoneanilide 332
GiSSMANN (R.)- Oxidation of Durene by Chromic Acid. Dinitrodurylic
Acid 333
ScHiEF (H.) . Protocatechutannic Acid and Anhydrides of Aromatic Hydr-
oxycarboxylic Acids 335
SciCHiLONE (S.), Allyloxybenzoic Acids 335
Baeyee (A.). Benzoylacetic Acid 336
CuETius (T.) . Synthesis of some Acids analogous in constitution to Hip-
puric Acid 337
Tiemann(F.). Triphenyl Orthoformate 340
"Weddige (A.). Tribasic Nitrophenyl Orthoformate 340
Calm (A.). Paradichlorazobenzene-monosulphonic Acid .... 341
Baeyee (A.) and V. Deewsen. Preparation of Indigo-blue fix)m Orthoni-
trobenzaldehyde 341
MoHLAU (R.). Diphenyldiisoindole 342
MoHLAU (R.). Azo-colouring Substances from Diphenyldiisoindole . . 342
Lellmann (E.). Derivatives of Diphenyl . . . . . . . 343
Lellmann (E.). A Case of Physical Isomerism 343
Meez (V.) and W. Weith. Nitro-derivatives of Naphthalene . . . 343
Maechetti (C). Picrates of «- and /3-Naphtliol 344
Ageestini (A.) . Derivatives of Naphthalene Hexhydride . . . . 345
Beilstein (F.) and E. Wiegand. Some Ethereal Oils .... 346
Hjelt (E.) and U. Collan. Ledum Camphor 346
ScHiFF (H.). Glucosides 347
EiJKMAN (J. F.). Foisonons 'Principle of Andromeda japonica . . . 348
Eedmann (E.) and Gt. Schultz. Heematoxjlin and Hajraatem . . . 349
CiAMiciAN {Gt. L.) and M. Dennstedt. Compounds of the Pyrroline Series 350
Fbiedlandee (P.)- Substitution-derivatives of Quinoiine .... 351
Meyee (E. v.). Cyanethine and Bases derived from it .... 352
SCHWEBEL (P.). Specific Rotatory Power of Salts of Nicotine . . . 354
Fischer (E.). Cafleine, Theobromine, Xanthine, and Guanine , . . 354
Gbimaux (E.). Some Derivatives of Morphine 358
OuDKMANS (A. C). Specific Rotatory Power of Apocinchonine and Hydro-
chlorapocinchonine under the Influence of Acids 359
RiTTHAUSEN (H.). BchaviouT of Conglutin from Lupines towards Saline
Solutions 360
RiTTHAUSEN (H.). Albuminoids in Peach-kernels and Sesame-cake . . 360
CONTENTS. Xxi
PAGK
KoMBUEGH (P. V.) . Isomeric Monoclilorallyl Iodides 449
NiEDEBiST (G-.). Trimethylene Glycol and Trimethylene Bases . . . 450
Fbanchimont (A. P. N.). Action of Anhydrides on Aldehydes, Ketones,
and Oxides 452
Franchimont (A. P. N.). Paraldehyde ....... 453
FiTTiG (R.). Non-saturated Acids (Part VI) 454
GoTTSTEiN (L,). Two New Caprolactones 454
Wolff (L.). ^-Lactone of Normal Caproic Acid 455
YoTJNG (S.). Hepto- and Octo-lactones 455
Hjblt (E.). Lactones from Allylmalonic, Diallylmalonic, and Diallylacetic
Acids 456
Young (S.). Peculiar Decomposition of the Ethereal Salts of Substituted
Acetoacetic Acids 456
Maquenne. Decomposition of Formic Acid by the Silent Discharge . . 457
MuLDEB (E.). Synthesis of Optically Active Carbon Compounds. . . 457
Beeb (A.). Itamalic, Paraconic, and Aconic Acids 457
RoTHEB (R.). Ferrous Citrate and its Double and Secondary Salts . . 458
Spica (P.), A Metacymene and a New Isomeride of Thymol . . . 459
PiEPBE (R.)- Four Metameric Benzanisethyl-hydroxylamines . . . 460
Mazzaba (G-.) . Isopropyl-, Di-isopropyl-, and Dipropyl-metacresols . . 463
Hebzig (J.). Action of Nitrous Acid on Guaiacol 464
Nietze:i (R.). Quinones and Q.uinols . 465
Babth (L.) and J. Scheedeb. Action of Melting Potassium Hydroxide on
Benzoic Acid ............ 468
Sussenguth (H.). Monobromopseudocumic Acid and Dibromomesilylenic
Acid 469
Hebzig (J.). Q-uaiaconic and Q-uaiaretic Acids 470
FiTTiG (R.) and H. W, Jayne. Phenylhydroxypivalic Acid . . . 471
Begun (P. H.). Ethoxymetatoluic Acid 471
Ebeet (G.). Coumarin 471
Jayne (H. W.). Phenylbutyrolactone and Phenylparaconic Acid . , 472
Penfielu (S. L.). Pht nylhomoparaconic Acid 473
FiTTiG (R.) and G-. Ebeet. Coumarilic Acid . 474
Eedmann (E.) . ActioTi of Sulphuric Acid on Cinnamic Acid . . . 474
Landsbeeg (M.). Imides of Bibasic Acids 475
RoDATZ (P.)>. Constitution of some Azobenzenedisulphonic Acids . . 477
RoDATZ (P.). Brominated Azobenzenedisulphonic Acids .... 478
Shenstone <(W. A.). JafPerabad Aloes 480
Jackson (C. L.) and A. E. Menke. Certain Substances obtained from
Turmeric 480
Jackson (C. L.) and A. E. Menke. Turmeric Oil : Turmerol . . . 482
Feank (A. B.). Hypochlorin and its Formation 4S3
Meyee (A.). Nature of Pringsheim's Hypochlorin Crystals . . . 483
Weidel (H.) and M. Russo. Researches on Pyridine ..... 483
Baumhauee (H.). The Trapezohedral Hemihedry of Strychnine Sulphate . 485
BuBi (E.). Hydropiperic and Piperhydronic Acids 485
Mayee (A.). Action of Invertin • . 486
Maekownikoff (W.) and W. Ogloblin. Chlorination of Hydrocarbons
from Caucasian Petroleum 564
LosANiTSCH (S M.). Formation of Dibromodinitromethane and of Villiers'
Tetranitroethylene Bromide 564
G-usTAVSON (G.). Conversion of the Propyl- into the Isopropyl-group . 565
Beethelot. Direct Combination of Hydrogen with Ethylene . . . 565
Pawleski (B.). Stability of Trimethyl Carbinol 565
WoEM-MiJLLEE and J. Otto. Schwarz's Process for preparing Pure Grape-
sugar 565
KiLiANi (H.). Saccharin and Saccharic Acid 565
Kltekoff (a.). Some Oxides of the Ethylene Series and their Action on
Water 566
Meyee (G.). Aldehyde-ammonium Bases 568
XXll CONTENTS.
PAOB
TcHEENiAC (J.) and T. H. Noeton. Tliiocjanopropimine .... 568
Meyek (V.). Isonitroso -compounds 569
Peteaczek (J.). Aldoximes 669
LiEBEN (A.) and S. Zeisel. Condensation-products of Aldehydes and their
Derivatives 570
Meyek (V.) and M. Ceeesolb. Constitution of Nitroso- compounds . . 572
Teeadwell (F. p.) and B. Westenbeegee. Nitroso-ketones . . . 572
ScHEAMM (C). Isonitroso -ketones 573
Peoppee (M.). Action of Nitric Acid on Ethyl Acetoacetate and Chlor-
acetoacetate ............ 573
KoLUE (C.) . Brom-addition-derivatives of the Crotonic Acids and of Meth-
acrylic Acid 673
NoACK (E.). New Method for Preparing Carbonic Oxide .... 574
Ballo (M.). Carbonic Hydroxide 574
OsTWALD (W.). Action of Acids on Acetamide 675
Q-USTAVSON (Gt.). Action of Aluminium Chloride and Bromide on Hydro-
carbons 577
Noyes (W. a.). Oxidation of the Nitrotoluenes by Potassium Ferri-
cyanide . . . .' 577
RoBiNET (C.) . Derivatives of Mesitylene 577
Louise (E.). Benzoylmesitylene 577
Wallach (O.). Metanitrils 577
Keinhaedt (H.) and W. Staedel. Methylation and Ethylation of Aniline
and Toluidine 578
Staedel (W.). Hydrobromides and Hydriodides of Aromatic Bases . . 578
Beenthsen (A.). Nitrotoluidines from Liquid Dinitrotoluene . . . 579
Wellee (A.). Ethylnitraniline 579
Baue (H. v.) and W. Staedel. Dimethylxylidines, Dimethylmetachlor-
aniline, and Dimethylmetamidophenetoil 579
Beenthsen (A.). Preparation of the Base C19H13N from Benzoyldiplienyl-
amine 580
Janny (a.). Acetoximes . 580
Janny (A.). Acetoximes 581
G-ABEiel (S.). So-called Nitrosomethylbenzene Compounds . . . . 581
Wellee (A.). Phenacy ethvlanilide \ . . . . . . . 582
LosANiTSCH (S. M.). Action of Iodine on Mono- and Di-nitrodiphenyl-
thiocarbamide 582
GiEAED (C.) and A. Pabst. Azo-derivatives 583
Wallach (O.) and E. Schulzb. Azo- and Diazo-derivatives of Phenylene-
diamine 583
BoHN (R.) and K. Heumann. Parazophenol 583
Wallach (0.). New Azo- and Diazo-compounds 584
Klepl (A.). Compound of Phenol- with Carbonic Anhydride . . . 584
HoLZEE (A.). Compound of Phenol with Sulphurous Anhydride . . . 585
Staedel (W.) and others. New Ethereal-derivatives of Phenols . . . 585
ScHULZE (E.). Appendix to the Paper on Cholesterin .... 586
TiEMANN (F.) and R. Ludwig. Isomeric Nitrobenzaldehydes . . . 586
Staedel (W.). Bromacetophenone and Acetophenone-derivatives . . 586
FisCHEE (E.) and H. Ruzel. Ethylic Ortlionitrocinnamylacetoacetate . 587
FisCHEE (E.) andH'. Kuzel. Ethylic Orthonitrocinnamylacetoacetate (Pt. II) 588
Hentschel (W.). Conversion of Phenyl Ethers of Carbonic Acid into
Salicyhc Acid 588
Jacobsen (O.) and H. Meyee. Sulphamic and Hydroxy -acids from
Pseudocumene 589
Scheamm (C). Acetoximic Acids 590
Baetoli (A.) and Gt. Papasoqli. Electrolysis of Hydrofluoric Acid and of
Potassium Antimonate, with Carbon Electrodes 590
Baetoli (A.) and G-. Papasogli. Electrolysis, with Carbon Electrodes, of
Solutions of Binary Compounds and of various Acids and Salts . . 592
Jacobsen (O.) and H. Leddeeboge. Amidometaxyloncsulphonic Acid . 593
CONTENTS. XXin
PAGB
Ehelich (A.). Glycocines, Grlycocine Ethers, and Oxethylenecarbamides
of the Toluyl and Xylyl Series 593
Benz (Q-.). Primary and Secondary Naphthylamines 594
FiTTiG (R.) and H. Eedmann. Synthesis of a-Naphthol .... 595
BoESSNECK (P.). a- Naphthoic Cyanide and its Derivatives , . . . 595
Aenell (K. E.). «-Chloronaphthylsulphonic Acid 595
Alen (J. E.). Nitronaplithalenedisulphonic Acids 596
Japp (F. E.). Addition of Acetone under the Influence of Caustic Alkalis . 5.)6
Liebeemakn (C). Action of Concentrated Sulphuric Acid op Dinitro-
anthraquinone. ............ 597
WiJETZ (A.). Madder Colours 59S
Cazenetjve (P.). Physical Isomerism of Monocliloro-camphor . . . 598
Renaed (A.). Products of the Distillation of Colophony .... 599
CiAMiciAN (G-. L.) and M. Dennstedt. Action of Cyanogen Chloride on
Potassium-pyrroline . . 599
Rhoussopoulos (O.). Action of Chloroform and Iodoform on Quinoline . 600
Besthoen (E.) and O. Fischer. A New Class of Colouring-matters . . 600
Salomon (G-.) . Paraxanthine, a New Constituent of Human Urine . . 601
Hesse (O.). Cuprea Bark . 601
Hesse (O.). Hydroconquinine and. Conquinine- 602
Doebnee (O.) and W. v. Millee. Quinaldine 602
PoEHL (A.). Formation of Peptone and its Conversion into Albuminoid
Substances 603
ScHOELEMMEE (C.) and T. E. Thoepe. Normal Paraffins .... 651
DiJEiN (E.). Hydrocarbons from Peat 652
Heezfeld (A.). Maltose and Isomeric Gluconic Acids .... 652
Gal (H.). Action of Zinc-ethyl on Amines and Phosphines . . . 653
Meyee (E. v.). Cyanmethine 653
TcHEENiAC (J.) and R. Hellon. Thiocyanacetone ..... 654
Landolf (F.). Decomposition of a-Fluoboracetone by Water . . . 655
Jahn (H.). New Metliod lor Preparing Carbonic Oxide .... 655
Leeds (A. R.). Insoluble Residue from the Distillation of Castor-oil . . 655
DuisBEEG (C). Addition of Bromine to El hyl Acetoacetate . . . 656
Hjelt (E.). Allylsuccinic and Carbocaprolactonic Acids .... 656
Mennel (E.). Meconic Acid and some of its Derivatives .... 656
Feeydl (J.). Dry Distillation of Tartaric and Citric Acids with Excess of
Lime 658
Resinski (F.). Biuret D icy anamide 658
ScHTJLZE (E.) and E. Bosshaed. Glutamine 658
Spring (W.) and C. Winssingee. Action of Chlorine on Sulpho-derivatives
of Organic Oxysulphides 659
Dafeet (F. W.). Amylbenzene . 659
Leeds (A. R.). GEnanthal-aniline, CEnanthal-xylidine,.and (Enanthal-naph-
thylamine 650
SiLBEESTEiN (H.). Diazo-derivatlves of Symmetrical Tribromaniline . . 660
Staedel (W.). Substitution-products of Ethereal Derivatives of Phenols . 6(i2
Staedel (W.). Nitrocresols 662
Staedel (W.). Bromonitro- and Bromamido-anisoils and -phenetoils . . 662
Klepl (A.). Hydroxybenzoic Acid 664
GoLDSCHMiEDT (G.) . Products of the Distillation of Calcium Parahydroxy-
benzoate .... 66 ^
GoLDSCHMiEDT (G.) . Products of the Distillation of Salicylic Anhydrides . 664
Leeds (A, R.). Acrole'inureide and Condensed Ureides .... 66 1
Andeeasch (R.). Oxidation of the Bases obtained by the Action of Halogen
Compounds on Thiocarbamide 66i
Treadwell (F. p.) and V. Meter. Molecular Weight of Isoindole . . 665
Waldee (H.). a-jS-Hydroxynaphthobenzoic Acid 66(}
Lachowicz (B.). Action of the Chlorides of Phosphorus on Phenanthm-
quinone 666
Cazeneuve (P.)- Cliloronitro-camphor . 667
XXIV CONTENTS.
PAGE
Traub (M. C). Action of Phthalic Anhydride on Quinoline . , . 667
Grimaux (E.). Phenolquinoline 668
Leeds (A. K.). Cryptidine 689
Griess (P.). Creatine-compounds of the Aiwnatic Group . . . . 669
Hanriot. Strychnine-derivatives 669
Ladenburg (A.). Constitution of Atropine 670
Zeisel (S.). Colchicine and Colohiceine 672
Maly (R.) and F. Emich. Behaviour of the Bile Acids with Albumin and
Peptones : Antiseptic Action of the Bile Acids 673
Kretschy (M.). Oxidation of Kynurine and Kynurenic Acid . . . f-74
Johnson (G. S.). Action of Potash on Albumin 674
RiTTHAUSEN (H.). Legumin 675
Bachmann (A.). Aldehydethyl Chloride and Behaviour of Acetals with
Alcohols at a High Temperature . . , . . . . . 726
Isambert. Vapour-tensions of Ethylamine and Diethykmine Hydrosul-
phides 727
Nageli (E.). The Hydroxylamine Reaction 728
Radziszewski (B.). Synthesis of Oxaline Bases 728
Clermont (A.). Preparation of Ethers of Trichloracetic Acid . . . 729
PoETSCH (W.). Action of Carbonic Oxide on a Mixture of Sodium Acetate
and Sodium Isopentylate . 729
FiTTiG (R.) and F. Roeder. A Non-saturated Acid Isomeric with Itaconic
Acid ... . .730
Pawlow (W.). TetricAcid 730
Fittig(R). Action of Water on Lactones 730
FiTTJG (R.). Conversion of Unsaturated Acids into the Isomeric Lactones . 730
Pinner (A.). Conversion of Nitrils into Imides. Action of Hydrocyanic
Acid and Ethylene Cyanide on Hydrochloric Acid and Alcohol . . 731
NiETZKi (R.). Colouring Matters of the Safranine Series .... 731
FiiVRE (A.). Mononitroresorcinol 733
CoLSON (A.). An Aromatic Tribromhydrin 734
Kalckhoff (F.). Amidophenols 734
NoACK (E.). Phenyl Salts of Phosphorous Acid 735
Lewinstein (I.). i8-Naphthoitri8ulphonic Acid 737
RoEMEB (H.). Dinitroanthraquinone and Diorthamidoanthraquinone : a
New Method of preparing Anthrarufin • . 737
Kelbe (W.) and J. Lwoff. Occurrence of Methyl Alcohol in the Products
of the Dry Distillation of Colophony 738
CoNiNCK (O. de). Bases of the Pyridine and Quinoline Series . . . 738
CoNiNCK (O. de). Isomerism in the Pyridine Series 740
Arnold (C.). Poisonous Principles contained in certain Lupines . . 740
Kohnlein (B.). Preparation of Paraffins 787
Henry (L.). " Reaction Aptit udes " of the Halogens in Mixed Haloid Ethers 787
Bloxam (C. L.). Reconversion of Nitroglycerol into Glycerol . . . 788
Laatsch (H.). Ethylidene Oxyehloride 788
HoFMANN (A. W.). Action of Bromine on Amines in Alkaline Solutions . 789
Fischer (E.). Triacetonainine 790
Grodzki (M.). Test for Acetal 700
Meyer (V.) and A. MOller. Constitution of Nitrosomalonic Acid . . 790
OsT (H.). Derivatives of Meconic Acid containing Nitrogen, and their Con-
version into Pyridine .......... 791
Kelbe (W.). Oxidising Action of Dilute Nitric Acid on Metaisobutyl-
tolueno * . 796
Gattermann (L.). Symmetrical Tribromaniline 796
KoCHLiN. Gallo-cyanins . . 796
ZiMMERMANN (J.) and M. Kntrim. Action of Ethyl Chloraeetate on
Primary Diamines 797
Lkllmann (E.). Cyanic Acid Derivatives of Three Isomeric Phenylene-
iiamines . . . . . . 798
Reisenkgger (H.). Compounds of the Hydrazines with the Ketone!^. . 798
CONTENTS. XXV
PAGB
Bahemann (E.). Amarine and Furfurine 799
BoTTCHEB (W.). Anhydro-conipounds 800
Lellmann (E,). Nitro- and Amido-derivatives of Benzeneaulplionanilide
and Benzenesulphonparatoluide ........ 800
Steudemann (H.). Metanitroplienylthiocarbimide 801
Meez (V.). Conversion of Phenols into Nitrils and Carboxylic Acids . . 802
Pfaff (P.). Eeduction of Substituted Phenols 802
Heney (L.). Phenol-derivatives 802
Benedikt (R.). Nitro-derivatives of Resoreinol 803
WiTTENBERa (M.) and V. Metee. Benzil 803
Jouedan (F.). Decomposition of Benzil by Potassium Cyanide . . . 805
Paal (C). Action of Acetic Chloride on Benzaldehyde in presence of Zinc-
dust 805
Fischee (E.) and H. Koch. Ethylic Phthalylacetoacetate .... 806
Kelbe (W.). Displacement of the Sulphonic G-roup by Chlorine . . . 806
Kelbe (W.). Barium Paratoluenesulphonate 807
Anschijtz (R.). Action of Aluminium Bromide on Symmetrical Dibrom-
ethylene and Benzene 807
Meldola (R.)- Kosaniline Colouring-matters 807
Boessneck (P.). Derivatives of a-Naphthoic Acid 807
Pechmann (H. v.). Synthesis of Dihydronaphthoic Acid .... 808
ANSCHiJTZ (R.) and F. Eltzbachee. New Synthesis of Anthracene . . 809
Baebiee (P.). Liquid Terebenthene Hydrochloride .."... 809
Naudin (L.). Essence of Angelica Root 809
Reutee (A.). Action of Zinc Chloride on Camphor 810
Meyee (A.). G^entianose 810
La Coste (W.). Nitroquinolines 811
Jacobsen (E.) and C. L. Reimee. Action of Phthalic Anhydride on Quino-
line 812
Fischee (E.) and H. Kuzel. Quinazole-compounds . . . , . . 812
HoFMANN (A. W.). Piperidine and Pyridine . ; . .... 813
ScHOTTEN (C). Oxidation of Piperidine ....... 813
Ploscz (P.). New Crystalline Colouring Matter ip Urine .... 814
Hoppe-Seylee (F.). Metahsemogiobin 814
Klinkenbeeg (W.) and A. Stutzee. Nucle'in 814
Leglee (E.). a New Product of the Slow Combustion of Ether . . . 860
Maquenne (L.). Action of Carbonic Oxide on Steam 860
Doebnee (A.) . Compounds of Benzotrichloride with Phenols and Phenyl-
amines 861
Staedel (W.). Action of N itric Acid on Phenols 861
Staedel (W.). Nitrophenols and Nitrocresols 864
Staedel (W.) . Ethyl Amido-cresols 866
Janovsky (J. v.). Nitro- and Amido-derivatives of Azobenzene . . 867
LiPPMANN (E.) and F. Fleissnee. Azylines 868
GoLDSCHMiEDT (Gr.). Pyreupquinone 869
Lieben (A.) and L. Haitingee. Chelidonic Acid 870
Preparation of Methyl- and Ethyl-derivatives of Hydroxyquinolinetetra-
hydride . . ' 871
i^CHMiDT (E.). Action of Hydrochloric Acid on Xanthine .... 871
Schmidt (E.) and H. Peesslee. Theobromine 872
Schmidt (E,). Occurrence of CafPeine in Cacao 873
Schmidt (E.). Action of Hydrochloric Acid on Caffe'ine .... 873
Hammaesten (O.). Metalbumin and Paralbumin 874
Hell (C.) and F. Ueech. Carbon Thiobromides 907
Hell (C.) and F. Ueech. Formation of a New Colouring Matter by the
Action of Heat on Carbotrithiohexbromide 907
Bambeegee (E.). Dicyandiamide, 1 907
Le Bel (J. A.). Formation of Amyl Alcohol in Alcoholic Fermentation . 908
Liebeemann (C.) and C. Paal. Allylamine-derivatives .... 908
Ladenbueg (A.). Imines 910
XXVI CONTEXTS.
PACK
Wallach (O.). Oxaline and Glyoxalines 910
BiscHOFF (C. A.). Synthesis of KetoTiic Acids (II) 912
Andreasch (R.). Potassium Ethylene-disulphonate 912
Hill (H. B.). Substituted P^romucic Acids 912
LiPPMANN (E. O.). Occurrence of a New Acid in Beet-juice . . . 913
Q-AL (H.), Metallic Derivatives of Amides : Method of Distinguishing
between Monamides and Diamides 913
Ceeesole (M.). Violuric Acid 913
Tezcinski (W.). Action of Dibromobarbituric Acid on Thiocarbamide and
Thiocyanates 913
Chancel (G.). Alkyl-nitrous Acids 914
PiERSON (A.) and K. Heumann. Action of Ethyldichloraraine on Aromatic
Amines and on Hydrazobenzene 915
Kelbe (W.). Action of Acid Amines on Aromatic Amines .... 915
Gabriel (S.). Nitrobenzaldoxime 916
Bernthsen (A.). Methylene -blue 916
Typke (P. G. W.). Nitro-derivatives of Resorcinol 917
Pfaff (P.). A New Homologue of Resorcinol 918
Claus (A.). Sulphonic Acids of Paracyraene 918
Friedlander (P.) and J. Mahly. Isoindole 918
BisCHOFF (C. A.). Action of the Alkyl-derivatives of the Halogen -substi-
tuted Fatty Acids on Aniline 919
Gabriel (S.). Aromatic Nitroso-compounds 919
Klinger (H.). Isobenzil 920
Claus (A.) and H. Lippe. Oxidation of Pentachloronaphthalene . . 921
Holm (J.). Fluorene Derivatives 921
Jacobsen (E.) and C. L. Reimer. Coal-tar Quinoline 922
WuRTZ (A.). Quarternary Base derived from Hydroxy quinoline . . . 923
Fischer (O.) and C. Riemerschmid. Pyridenemonosulphonic Acid . . 923
KossEL (A.). Xanthine and Hypoxanthine 924
Hanriot and Blarez. Solubility of Strychnine in Acids .... 924
Brieger (L.). Putrefaction Alkaloids . 924
Salkowski (E. and H.). Basic Products of Putrefaction .... 925
B^CHAMP (A.). Zymase of Human Milk . 926
Poehl (A.). Peptone 926
De Forcrand. Compounds of Hydrogen' Sulphidfe with Ethers . . ' . 961
Kachler (J.) and F. V. Spitzer. Bromodinitromethane .... 961
KiLiANi (H.). Saccharone and Saccharin 962
Lieben (A.) and S. Zeisel. Condensation-products of Aldehydes and
their Derivatives * . . 963
Natterer (K.). ay-Dichlorocrotonaldehyde, a Condensation-product of
Monochloraldehyde .......... 964
WiSLiCENUS (J.). Methyl jS-Butyl Ketone and its Derivatives . . .966
Elsasser (E.). Specific Volumes of the Alkyl Salts of Fatly Acids . . 967
Friedrich (R.). Monohalogen-derivatives of Crotonic Acids . . . 968
Melikoff (P.). Derivatives of the Isomeric Crotonic Acids . . . 969
Bauer (A.). New Acids of the Series C„H2„_406 970
Hjelt (E.). Dicarbocaprolactonic Acid ....... 970
Beilstein (P.) and E. Wiegand. Alkvlsulphamic Acids . . . .971
Engelcke (J.). Dialkyldisulplioisetliionic Acids 972
NiSHACK. Methylsulphonic Acid 972
Geuther (A.). Constitution of the Compounds of the Sulphcmat«s with
Alkyl Sulphates. Constitution and Dimorphism of Sulphates . . 973
Emich (P.). Biguanide 973
Reibenschuh (A. P.). Methylgu inide and its Compounds . . . 974
Emich (P.). Ethylbiguanide and its Compounds 974
Spindler (P.). Nitration of Benzene-derivatives 975
WisPEK (P.) and R. Zubee. Action of AUyl Chloride on Benzene in the
Presence of Aluminium Chloride 977
Schramm (J.). Action of Bromine on Aromatic Hydrocarbons . . . 977
OOXTENTS. XXVn
PAGE
Dafert (F. W.). Kesearches on Periodides 978
Renouf (E.). Derivatives of Triphenylmethane ...... 981
Meyer (R.) and H. Kreis. Hydroxyazo-compounds 982
Glaus (A.) and K. Elbs. Amarine 982
Martini (A.) and A. Weber. Silicates of the Phenols .... 983
Plochl (J.) and F. Blumlein. Constitution of Benzoyl-carbinol . . 983
Meyer (R). Hydroxy lation by Direct Oxidation 983
Benedikt (R.). Chloroxy- and Bromoxy-derivatives of Benzene . . 984
Barth (L.) and J. Schreder. Hydroxyquinol, the Third Isomeric Tri-
hydroxybenzene 987
Haitinger (L.). Action of Sulphur on Sodium Phenate .... 988
Schroder (H.). Similarity of the Boiling Points of the Corresponding
Ketones, Ethereal Salts, and Chloranhydrides 990
Staedel (W.). Aromatic Ketones ........ 990
Erlenmeyer (E.) and A. Lipp. Cinnamic Acid Derivatives . . . 992
Erlenmeyer (E.) and A. Lipp. Synthesis of Tyrosine .... 994
Lipp (A.). Phenylglyceric Acid 994
Etti (C). Tannins of Oab-bark • . . .994
Wegscheider (R.). Deri'vatives of Opianic A-cid 996
Bauer (A.) . Pimelic Acid 998
Thompson (C. M.). Metazophenyl-glyoxylic A-eid 998
PiUTTi (A.). Phthalamidobenzoic Acid . 999
Paterno (C.). Cymene-sulphonic Acids 999
Stengel (F.). Dialkyldisulphobenzoates . .- 999
Elbs (K.). Syntheses with Chloropicrin 1000
DuTT (U. K.). o-Naphthonitrilsulphonic Acid 1001
GoLDSCHMiEDT (Q-.) and R. Wegschneider. Pyrene-derivatives . . IdOl
Pastrovich (P.). Reichenbach's Picamar 1004
Pastrovich (P.). Coerulignol : Reichenbach's Oxidising Principle . . 1005
Kachler (J.) and F. V. Spitzer. Action of Sodium on Camphor . . 1006
Kachler (J.) and F. Y. Spitzer. Mode of Formation of the Isomeric
Dibromocaraphors 1007
Kachler (J.) and F. V. Spitzer. Reaction of the two Isomeric Dibromo-
camphors with Nitric Acid 1008
Kachler (J.) and F. V. Spitzer. Hydroxycamphor from j8-Dibromo-
camphor 1008
Claus (A.) and F. TossE. Addition-products of Quinoline .... 1008
Claus (A.) and F. Q-lyckher-Rv Oxidation of (Quinoline Benzyl Chlo-
ride 1009
Skeaup (Z. a.) and A. Cobenzl. a- and /3-Naphthaquinoline . . . 1010
Maly (R.) and R. Andreasch. CafTeine and Theobromine .... 1016
Wood (C. H.) and E. L. Barret. Notes on Cinchona Alkaloids . . . 1018
Brucker (E.). Alkophyr, and the True and So-called Biuret Reaction . 1019
Meyer (R.). Hydroxylation by Direct Oxidation 1072
Beilstein (F.) and E. Wiegand. Caucasian Ozokerite .... 1073
Reformatsky (S.). Hydrocarbon, CjoHig, prepared from Ally! Dipropyl
Carbinol . . . . 1073
NiKOLSKY (W.) and A. Saytzeff. Hydrocarbon, Ci^Hj-o, prepared from
Allyl Dimethyl Carbinol . . .• 1074
Steiner (A.). Conversion of Fulminates into Hydroxylamine . . . 1074
Schulze (J.). Preparation of Ammonium Thiocyanate .... 1074
Frentzel (J.). Normal Primary Hexyl Alcohol 1075
Keafft (F.) . Preparation of Normal Primary Decyl, Dodecyl, Tetradecyl,
Hexadecyl, and Octodecyl Alcohols 1075
DiEFF (W.). Bye-product of the Preparation of Allyl Dimethyl Car-
binol 1076
Meyer (V.) and E. Nageli. Oxoctenol 1076
Ladenburg (A.). Preparation of Chlorhydrins 1077
Urech (P.). Effect of Temperature and Concentration of Acid on the
Rate of Inversion of Saccliarose 1077
XXVlll CONTENTS.
PAGE
Tappkineb (H.). Fermentation of Cellulose 1077
LiEBEKMANN (C.) and C. ScHEiULEB. Reduction of Saccharin . . . 1078
Meter (Q-.). Some Anomalous Reactions 1078
Combes (A,). Base derived from Crotonaldehyde 1079
WiLLGERODT (C), Acetone-cliloroform 1079
PiNNEB (A.). Condensation of Acetone 1079
Schramm (J.). Action of Sodium on Methyl Ethyl Ketone . . . . 1079
Schramm (J.). Diethyl Ketone 1080
Clark (W. I.). Ethyl Acetate 1080
Hantzsch (A.). Action of Aldehyde Ammonia on Methyl Acetoacetate . 1082
Conrad (M.) and M. Guthzeit. Halogen -substituted Ethyl Aceto-
acetates 1082
Hantzsch (A.) . Condensation-products of Ethyl Acetoacetate . . . 1083
Perkin, Junr. (W. H.). Action of Trimethylene Bromide on Ethyl Aceto-
acetate, Benzoylacetate and Ethyl Malonate 1083
Herrmann (F.) . Constitution of Ethyl Succino-succinate .... 1084
FiTTiG (R.). So-called Tetric, Pentic, and Hexic Acids .... 1085
De FoBCRAND. Formation of Disodium Gly collate 1085
Philipp (J.). Basic Potassium Beryllium Oxalate 1085
Thompson (C). Lithium Citrate 1086
Bambebgeb (E.). Melanuric Acid 1086
Liebebmann (C.) and A. Hagen. Action of Sulphuric Acid on Di- and
Tri-Allylamine 1086
Radziszewski (B.). New Glyoxalines 1086
CuRTius (T.). GUycocine 1087
ScHULZE (J.) . Preparation of Acetamide and other Amides of the Acetic
Series 1088
Pinner (A.). Derivatives of Ethyloximide and Ethyl-succinimide . . 1088
Pinner (A.). Conversion of Nitrils into Imides 1089
Meter (Q-.). Aldehydammonium Bases 1C90
Bambebgeb (E.). Dicyanodiamide 1090
Meteb (V.) . Thiophene, a Substance contained in Coal-tar Benzene . . 1091
Q-alle (K.). Tetrethylbenzene and Hexethylbenzene 1091
Meteb (V.). Coal-tar Toluene 1092
Abelli (M.). Chlorides of Ortho- and Meta-nitrobenzyl .... 1092
Claus (a.) and H. Beckeb. Trinitrotoluene and Liquid Dinitrotoluene . 1093
Dafebt (W.). Derivatives of Diethyl-toluene 1093
Robinet and Colson. Mesitylene 1095
WisPEK (P.). Derivatives of Mesitylene 1095
Wallach (O.) and M. Wusten. Reaction of Aromatic Amines with Lactic
Acid . . . 1096
Liebebmann (C). Decomposition of Rosaniline by Water .... 1097
Fischeb O. and L. GtEBMAN. The Violet- derivatives of Triphenylmethane . 1097
Wichelhaus (H.). Dye-stuff from Dimethylaniline and Chloranil . . 1098
Bernthsen (A.). Formation of Nitril Bases from Organic Acids and
Amines 1099
Pinner (A.). Action of Acetic Anhydride on the Amidines . . . 1099
LiPPMANN (E.) and F. Fleissneb. Azylines 1100
Janovskt (J. v.). Substitution-products of Azobenzeneparasulphonic Acid 1101
Javonskt (J. v.). Amidazobenzeneparasulphonic Acid .... 1101
Gbiess (P.)- Diazo-derivatives 1102
Eblenmeteb (E.). Constitution of the Nitrosamines 1103
Lach (B.). Aldoximes 1104
Gabbiel (S.) and M. Hebzbebg. Paranitrobenzaldoxime and Amidobenz-
aldehyde 1104
Q-abbiel (S.). Metamidobenzaldoxime 1105
Richter (V.) V. Cinnoline-derivatives 1105
Ehrlich (A.). Orthotoluyihydantoin 1106
Mainzeb (K.). Products of the Decomposition of Mixed Aromatic Thio-
carbamides by Acids 1106
CONTENTS. XXIX
PAGB
AscHAN (O.). Action of Phenylthiocarbamide on Amido-acids . . . 1107
Hentschel (W.). Diphenyl carbamide and Triphenylguanidine . . . 1107
Heim (R.). Phenolic Phosphates 1108
Chandelon (T.). Chlorophenols obtained by the Action of Alkahne Hypo-
chlorites on Phenol 1108
ScHALL (C). Action of Iodine on Sodium Phenate 1109
SCHALL (C). Diiodophenol 1109
ScHOFF (F.). Reduction of Monobromorthonitrophenol .... 1109
Kalckhoff (F. a.). Amidophenols 1109
Hantzsch (A.). Reaction of Ethyl Acetoacetate with Orthamidophenol . 1111
Heim (R.). Conversion of Phenols into Nitrils and Acids .... 1111
Claus (A.) and P. Riemann, Dichloroparacresol and Dichlororthocresol . 1111
RiCHTEE (A. K.). Thymol-derivatives . . 1112
Kolbe (H.). Preparation of Phenetoil . . . . . . . 1113
BoTTCHEB (W.). Molecular Transformations ...... 1113
Hazuea (K.). Nitroresocinolsulphonic Acid 1114
Setda (A.). Sulphonic Acids of Quinol ....... 1115
Levy (S.^i. Chlorine and Bromine-derivatives of Q.uinone . . . . 1117
ZiNCKE (T.). Action of Amines on Quinones 1117
Bbnedikt (R.) and M. v. Schmidt. Halogen Derivatives .... 1118
Baeyee (A.) and P. Beckee. Paranitrobenzaldehyde and Acetone . . 1120
GoLDSCHMiDT (H.) and V. Meyee. Benzil 1120
Jacobsen (O.) and F. Wieess. Derivatives of Orthotoluic Acid . . 1121
Gabeiel (S.) and O. Boegmann. Benzyl Derivatives 1121
Schulze (E.) and J. Baebieei. Formation of Phenylamidopropionic Acid
by the Action of Stannous Chloride on Albuminoids . . . .1122
Schulze (E.) and J. Baebieei. Phenylamido-propionic and Phenylamido-
valeric Acid from Lupine-shoots 1122
FiTTiG (R.). Perkin's Reaction 1122
Gabeiel (S.) and M. Heezbeeg. Derivatives of Cinnaraic and Hydro-
cinnamic Acids 1123
Jacobsen (O.). Hydroxytoluic and Hydroxyphthalic Acids . . . 1124
Lewkowitsch (J.) Lsevorotatory Mandelic Acid 1124
Lewkowitsch (J.). Separation of Inactive Mandelic Acid into Two
Optically Active Isomerides 1124
Balbiano (L.). Dry Distillation of Sodium Dibromanisate .... 1125
Napolitano (M.). Derivatives of ParacresolglycoUic Acid .... 1126
Deechsel (E.^). Action of Phthalic Anhydride on Amido-acids . . . 1126
Claus (A.) and G. Hemmann. Azophthalic Acid 1126
Gabeiel (S.). Constitution of Phthalylacetic Acid 1127
BOTTINGEE (C). Anilpyruvic Acid 1128
Hinsbeeg (O.), Derivatives of Anhydroamidotolyloxamic Acid . . . 1129
Claus (A.). Cymenesulphonic Acids 1129
MiJLLEE (A.). Isonitroso-acids 1129
Kolbe (H.). Isatin 1130
Baeyee (A.) and W. Comstock. Oxindole and Isatoxirae .... 1130
Baeyee (A.), Nitrosoxindole and Nitrosindoxyl ^ 1131
FiscHEE (O.) and L. Geeman. New Synthesis of Skatole .... 1132
ANSCHiJTZ (R.) and F. Eltzbachee. Synthesis of Unsymmetrical Tetra-
phenylethane 1132
FiscHEE (E.) and H. Kuzel. Ethylhydrocarbazostyril .... 1132
Beenthsen (A.) and F. Bendee. Synthesis of Acridines .... 1133
Fischee (O.). Acridine 1134
Beenthsen (A.) and F. Bendee. Acridine 1134
BoESSNECK (P.). Methylnaphthalene 1135
ZiNCKE (T.). Phenylliydrazine-derivatives of the Quinones . . . . 1135
Landshoff (L.). j3-Napthylaminesulphonic Acid 1135
Limpach (L.). Naphtholtrisulphonic Acid 1136
Kauffmann (G.). j3-Naphthacoumarin 1136
Henzold (0.). New Method qf Forming Anthracene 1137
XXX CONTEXTS.
PAOB
RoEMER (H.). Reduction in the Anthracene Series 1137
RoRMEE (H.) and W. Link. Amidomethylanthranol 1137
RoEMER (H.) and W. Link. Nitro-, Amido-, and Hydroxy-methylanthra-
quinone 1138
BoLLERT (A.). Derivatives of Anthramine 1139
Meissen (P.). Addition-products of some Terpenes 1140
ScHiFP (II.). Aldehydic Nature of Oxidation-products of Terebene . . 1141
Naylor (W. A. H,). Bitter Princiiple oi JIt/menodicti/on excelsum . . IIH
Gantter (F.). Colouring-matter of Wine 1141
ScHMiEDEBERG (O.). Active Principle of the Root of Ajpocynum canna-
bimim 1141
CiAMiciAN (Q-. L.) and M. Dennstedt. Action of Nascent Hydrogen on
Pyrroline 1142
Hoffmann (L.) and W. Konigs. Tetrahydroquinoline .... 1143
Fischer (O.). Derivatives of Hydroxyquinoline 1146
RiEMERSCHMiED (C). ^-Hydroxyquinoline 1147
Friedlander (P.) and C, F. Gohring. Preparation of Substituted Quino-
lines 1148
Drewsen (V. B.). a-Methylquinoline 1149
DoEBNER (O.) and W. v. Miller. Phenylquinoline 1149
Rhoussopout.os (A.). Methylenediquinoil Hydrochloride .... 1150
Spalteholz (VV.). Colouring-matters from Coal-tar Quinoline . . . 1150
Ladenburg (A.), Syntheses in the Pyridine Series 1151
ScuiFF (R.) and J. Puliti. Introduction of Hydrocarbon Radicles into the
Pyridine-group 1151
Ladenburg (A). Syn thesis, of Ethylpyridine 1151
Riedel (C.)- Qixinoline- and Pyridine-carboxy lie Acids .... 1152
Fischer (E.). Triacetonalkamine . 1153
Dtivillier (F].). Compounds of the Creatinine-group 1153
Ladenburg (A.). Action of Methyl Alcohol on Piperidine Hydrochloride . 1154
Ladenburg (A.). Hydrotropidine 1155
Hay (M.). New Alkaloid in Cawwaii* iwc^ica or Indian Hemp . . . 1155
Luxardo (0.). Existence of a Basic Substance in Maize . . . .1156
GuARESCHi (J.) and A. Mosso. Ptomaines 1156
Poehl (A.). Putrefaction Alkalotds 1157
Brieger (L.). Putrefaction Alkaloids .1159
Salkowski (E. and H.). Putrefaction Alkaloids 1159
McMuNN (C. A.). Colouring-matter of Bile of Invertebrates and Verte-
brates, and unusual Urine Pigments 1159
Fhysiological Chemistry,
KoNiG (J.). Nutritive Value of Skim Milk 102
Ritthausen. Skim Milk as Food 102
Findeisen. Feeding Horses with Flesh Meal 102
Kellner (O.). Researches on the Digestibility of Purified Lupine Seeds by
the Horse, and Observations on the Working Power of the Horse when
Fed with Lupines and Oats 102
CuAPOTEAUT (J.). The Gastric Juice 103
B^champ (A.). Decomposition of Hydrogen Peroxide by certain Organised
Bodies . . . 103
BtcHAMP (A.). Microzymas, the Cause of the Decomposition of Hydrogen
Peroxide by Animal Tissues 103
B^CHAMP (A.). Action of Hydrogen Peroxide on the Red Colouring Matter
of the Blood and on Hsematosin 103
Croft (H. H.). Rattlesnake Poison lo4
Marcus and O. de Coninck. Physiological Action of ^-Collidine . . 104
B^CHAMP (A.). Spontaneous Fermentation of Animal Matters . . . 226
Wbiskb (H.) and others. EfEect of Food on Sheep of DifEerent Breeds . 226
I
CONTENTS. XXXI
PAGK
Pfeiffee (T.). Artificial and Natural Digestion of Nitrogenous Matter . 227
Power (J. B.). Excretion of Nitrogen from the Skin 227
Erlenmeyek. Milking of Cows Twice or Thrice Daily .... 227
MusGEAVE (R. N.). Nitrites in Human Saliva 227
B^CHAMP (A.). Evolution of Oxygen from Hydrogen Peroxide by Fibrin . 227
Haemuth and others. Lupine Sickness in Sheep 228
ScHMiEDEBERG (O.). Oxidations and Syntheses in the Animal Organism . 361
ScHMiEDEBEEG (O.^. Decomposition and Synthesis in the Animal Organism 361
Brockhaus. Expei-iments on the Poisonous Action of Potato Brandy . 362
BiNZ (C.) . Behaviour of Ozone with Blood 486
Hoffmann (M.). Digestibility of Casein from Warmed Milk . , . 487
Ellenberger and Hofmeister. The Digestive Fluids and Digestion of
the Horse 487
Chatin (M.). Hygienic Action of Maize as Fodder 488
Chittenden (E,. H.) and J. S. Ely. Alkalinity and Diastatic Action of
Human Saliva 488
KucKEiN (F.). Tissue- waste in the Fowl during Starvation. . . . 603
OhlmIjllee (W.). Decrease in Weight of Individual Organs in Children
Dying from Atrophy 606
Hasebrock (K.). Coagulation of the Blood ...... 608
Weiske (H.). Occurrence of Crystals of Ammonium Magnesium Phosphate
in Urine 609
Reiset (J.). Exhalation of Nitrogen Gas during the Respiration of
Animals . 675
Paul (G-. A.) Feeding Calves with Skim-milk 675
Hofmeister (F.). Distribution of Peptone in the Animal Body . . . 675
Hofmeister (F.). The Proportion of Peptone in the Gastric Mucous
Membrane . 677
HiJFNEE (G.) . On the Oxygen Pressure at which, at a Temperature of 35°,
the Oxyhsemoglobin of the Dog begins to give up its Oxygen . . 678
Lebedeff (A.). Nutrition by Fat . . 740
Reiset (J.). Blue Milk 742
Wassilieff (N. p.). Influence of Calomel on Fermentation and the Life of
Micro-organisms ........... 743
Fort (J. A.). Physiological Action of Coffee 745
Blake (J.). Relative Toxic Power of Metallic Salts 745
Kietz (A.). Researches on Digestion in the Stomach ..... 815
Edingee (L.). Reaction of the Living Mucus Lining of the Stomach . , 815
KoNiGSBERG (P.). Digestibility of Meat 815
Hoffmann (M.). Digestibility of Casein from Heated Milk . . . 815
Langley (J. N.). Decomposition of Digestive Ferments .... 815
Langsdorff (K. v.). Fattening of Calves 815
Feeding of Cattle with Dry Fodder 816
KiJHN (G.) and others. Digestibility of Meadow Hay and Wheat Bran
treated with Hot and Cold Water 816
Ellenberger. Results of the Suppression of Perspiration of Animals. . 817
Seegen (J.). Peptone the Source of Sngar in the Liver .... 818
Stumpf. Alteration in the Secretion of Milk under the Influence of
Drugs 818
Zweifel. Behaviour of Blood when Deprived of Oxygen .... 818
Rohrmann (F.). Observations on a Dog with Biliary Fistnla . . . 818
Blendeemann (C). Formation and Decomposition of Tyrosine . . . 818
Eeman. Adipocere 818
Anackee. Poisoning of Cattle by Earth-nut Cake 818
Wallace (W.). Insensibility arising from a Deficiency of Oxygen in the
Air 819
Beunton (T. L.) and T. Cash. Action of Calcium, Barium, and Potassium
Salts on Muscle 875
Abeles (M,). Secretion cf the Kidney fed with Defibrinated Blood . . 875
Gareod (A. B.). Formation of Uric Acid in the Animal Economy . . 876
XXXll COXTENJS.
PAOB
Blend ERMANN (H.). Formation and Decomposition of Tyrosine in the
Body
876
HoBBACZEWSKi (J.). Behaviour of Elastin in Peptic Digestion . . . 927
Cbameb (T.). Vegetarianism from a Physiological Standpoint . . . 928
Tappeineb (H.). Comparative Investigations of Intestinal Gases. . . 928
PouCHET (A. G.). Sugar from the Lungs of Phthisical Patients . . . 929
Lawes (J. B.) and J. H. Gilbert. Composition of the Ash of the Entire
Animals, and of Certain Separate Parts of some of the Animals, used as
Human Food 1019
BiscHOFF (C). Distribution of Poisons in the Human Organism in Cases
of Poisoning 1020
Bell (J.). Chemistry of Food 1160
Pavy (F. W.). Physiology of Carbohydrates in the Animal System . . 1160
E.UNEBEEG (J. W.). Filtration of Albumin Solutions through Animal
Membranes . 1160
Jaksch (R. v). Acetonuria IIGI
Teb-Gbigobiantz. Hemialbumosuria 1162
Lehmann (V.). Further Contributions to the Distribution and Elimination
of Lead 1163
Chemistry of Vegetable Physiology and Agriculture.
Hayduck (M.) . Influence of Alcohol on the Development of Yeast . . 104
Bauer (E.). Nature and Formation of Dextran 105
Engelmann (T. W.). Elimination of Oxygen from Plant-cells . . . 105
Wilson (W. P.). Elimination of Carbonic Anhydride by Plants in Absence
of Oxygen . . . . .105
Detmeb (W.), Action of various Gases, especially Nitrous Oxide, on Plant-
Cells 105
Deh]6ratn (P. P.). Influence of the Electric Light on the Development of
Plants 105
Nachbatjr (K.). Embryos of Ungerminated Rye 107
Criper (W. R.). Analyses of Indian Wood 107
Dixon (W. A.). Inorganic Constituents of some Epiphytic Ferns . . 108
Knop (W.). Percentage of Ash in the Sugar-cane . . . . . 110
Danger (L.) and others. Parasitic Diseases of Plants, and their Prevention 110
Thumen (F. v.) and others. Vine Diseases, and Remedies .... 110
KuHN (J.) and H. Joulie. Diseases of Sugar-beet Ill
Petermann (A.). Composition of Fodders Ill
Dbechsleb. Specific Gi*avity of Cereal Grains Ill
Composition of Malt from 1877 Barley \ . HI
Renouabd (A.). Cotton Cake Ill
KoNiG (J.). Cultivation of Lupines . . 114
Leydheckeb (A.) and others. Potato Culture 114
RiMPAU (W.) and others. Sugar-beet Culture 114
Ladubeau (A.). Cultivation of the Sugar-beet 114
Wabington (R.). Nitrification in Soils 115
Mabi^-Davy. Nitrification in the Soil 116
Salfeld (A.). Comparative Manuring Experiments 116
Wagneb (P.). Influence of the State of Division of Manures on their
Action 117
Edleb. Manuring Potatoes with Potassium Nitrate 117
Lecouteux (E.). Composition of Pig Dung 117
Analysis of Mud from the Mouth of the Eider 117
Guillaume (L.). Mineral Phosphates on Arable Soil 118
Kebn (E.). A New Milk Ferment . . . . . . . .229
i^TABD (A.) and L. Olivier. Reduction of Sulphates by Living Orga-
nisms 229
D:6hebain and Maquenne. Reduction of Nitrates in the Soil . . . 229
CONTENTS. XXXUi
PAGP
DiE^BAiN and Maquenne. Reduction of Nitrates in Arable Soil . . 229
G-AYON and Dupktit. Fermentation of Nitrates 230
Phillips (F, C). Absorption of Metallic Oxides by Plants . . . . 231
RicciARDi (L.). Composition of the Banana at Different Stages of
Maturity 231
SiEWEBT (M.). Oxalic Acid in Potatoes and in Malt 232
Feemster (J. H.), Average Amount of Caffeine in the G^uarana of Com-
merce compared with that in the Seeds ....... 232
KtTTZLEB (V.). Researches on the Causes of Clover Sickness . . . 233
Lafittb (P. de) and others. On Phylloxera 233
Jensen (J. L.). Cure for Potato Disease 233
MuNTZ (A.) and E. Aubin. Atmospheric Nitrification .... 233
RiNiCKER and Dossekel. Hailstorms and their Origin .... 234
FiTTBOGEN (J.) and others. Cultivation of Various Crops .... 235
KiNCH (E.). Soja-bean 235
Leplay(H). White Sugar-beet of Silesia 235
ToBiscH. Influence Exerted by the Weight of Potato '* Sets" . . . 236
Stumpf. Amoimt of Gluten in Wheat 236
BoHMEB (C). Albuminoid and Non-albuminoid Nitrogen-compounds of
certain Yegetables 236
Hensen (N.). Fertility of a Soil as Dependent on the Action of Worms . 237
WoLLNY (E.). Effect on the Fertility of the Soil Produced by Covering it
with Farmyard Manure 237
Beseleb. Manuring Sugar-beet with Dung 238
Marcker (M.). Manuring Alpine Meadows 238
Lenn^ (A.). Employment of Peat as Litter 238
Delacharlonny (P. M.). Transformation of Blood into a Solid Inodorous
Manure 239
Marpmann (G-.), Schizomycetic Fermentation 363
Marpmann (G-.). Progress in the Knowledge of Bacteria .... 364
Marcano (V.). Direct Fermentation of Starch 365
Mori (A.). The First Product of Plant- Assimilation .^ .... 365
Vbies (H. db). Function of Resins in Plants ...... 365
Leplay (H.), Chemistry of the Maize Plant ...... 866
Leplay (fl.). Chemistry of White Silesian Beetroot 368
G-RiJNiNG (W), Chemistry of the NymphaeacesB . , , . , 369
RoMANis (R.). Analysis oif Tobacco Ash 372
Dtjgast (M.). Composition of Different Varieties of Fodder-cabbage , . 373
D^HERAiN (P.P.). Loss and Gain of Nitrogen in Arable Land under the
Influence of different Systems of Cultivation 373
G-RiFFiTHS (A. B.). Analysis of a new Guano from Austraha . . . 375
Utilisation in Agriculture of the Slag from the Basic Dephosphorising
Process 375
Kretzschmar (L.). The Test for Life 489
Hoppe-Seyler (F.). Influence of Oxygen on Fermentation . , . 489
Detmer (W.). Contributions to the Dissociation Hypothesis . . . 489
Will (H.). Effect of Steeping and Drying on the Germination of Seeds . 490
Liebenberg (A. v.). Part played by Lime in the G-ermination of Seeds . 490
HoBNBERGER (R.) and E. V. Raumeb. Researches on the G-rowth of the
Maize Plant 491
D^HERAiN (P. P.) and Meyer. Development of Wheat .... 493
Reynolds (J. E.). Comparative Effect of Two Metameric Bodies on the
Growth of Nicotiana longijlora ........ 495
G-RiFFiTHS (A. B.). growth of Plants under Special Conditions . . . 496
Farsky. Chlorine as a Plant-food 497
MiJLLEB (H,). Contributions to the Knowledge of the Interchange of
Material in Amylaceous Plant Organs 497
GoDLEWSKi (E.). Respiration of Plants 498
Jandous (A.). Composition of Ivy Berries ....... 499
Mangon (H.). The Ice Plant {Mesembrianthemum vr^stallmum) . 499
VOL. XLIV. C
XXXIV CONTENTS.
PAGE
BiLLWiLLEE (R.). Influence of Fallen Snow on the Temperature of the
Air 500
WOLLNY (E.). Influence of the State of Aggregation on the Temperature of
and Moisture in a Soil * . . 500
Tbucheet. Irrigation of Meadows by Waste Water from Beet-sugar
Factories 500
Peteemann (A.). Manurial Value of " Dissolved Wool " . . . , 500
GuiLLAUME (L.) . Chemical Manures and Farmyard Manure . . . 501
Di^H^EAiN (P. P.) and Maquenne. Reduction of Nitrates in the Soil . . 503
Peteemann (A.). Analysis of Materials used in the Preparation of Com-
posts ... 504
RiEFAED (Q-.) . Artificial Manuring of Sugar-canes ..... 506
Mayee (A.) and F. Clausnitzee. Analysis of Gas-lime .... 506
Gayon (U.) and G-. Dupetit. Reduction of Nitrates and Nitrites . . 609
P^fliEAiN (P. P.) and L. Maquenne. Butyric Ferments in Arable Soils . 610
PiiATJcnuD. Reduction of Sulphates by " Sulfuraires," and Formation of
Natural Mineral Sulphides 610
Weyl (T.) . Infl.uence of Chemical Agents on the Assimilative Capacity of
Green Plants .611
Engelmann (T. W.). Assimilation by Hsematococcus .... 611
BoEGMANN (E.). Presence of Formic and Acetic Acid in Plants . . . 611
LiPPMANN (E. O. v.). Occurrence of Coniferin in the Woody Structure of
the Beetroot 611
Dupetit (G.). Poisonous Principle of Edible Mushrooms .... 611
Niessing (C.) and others. Diseases of Plants and their Prevention . . 612
Keauch (C.). Poisoning of Plants 612
Steebel and others. Cultivation of Cereals 612
DoHN (W.) and F. Nobbe. Cultivation and Feeding Value of some Varieties
of Vetches 612
Weiske (H.) and others. Comparative Feeding Value of Symphytum
asperrimum 613
Ge:6goiee (T.). Cultivation of Gombo 613
Geibel (P.) and others. Removal of the Leaves of Roots .... 613
CoEENWiNDEE (B.). Biological Researches on the Beetroot. . , . 613
KoHNE and others. Employment of Dried Potatoes 614
Fankhausee. Comparative Meteorological Observations in Forests . " . 614
Wollny (E.). Influence of Chmate and Weather on the Amount of Car-
bonic Anhydride in Air . 614
Stellwaag (A.) . Rise of Temperature induced in Soils by the Condensation
of Liquid and Gaseous Water and of Gases 615
Stutzee (A.) and W. Klingenbeeg. Decomposition of Nitrogenous
Animal Manures 615
Masuee (F.). Evaporation of Water from the Soil ..... 615
Reindees (G.) . Manuring Experiments in Holland ..... 617
MUEL (M. E.). Manuring of Forest Trees ....... 617
Gayon and others. A Denitrifying Ferment in Soils 679
;^TAED (A.) and others. Reduction of Sulphates by Algse .... 680
Heckel (E.). The Ice-plant {Mesemhrianthemum crystallinum) . . . 680
Caeeieees (E. a.) and others. Phylloxera and Means for its Destruction . 680
SCHULZE (F.) and others. Cultivation of Potatoes 680
MoEGEN (A.) . Feeding Value of Fresh and Dried Diffusion-residue . . 680
Heineich (R.). Influence of the Percentage of Moisture in Peaty Soils on
Vegetation 681
Dfmas (L.) . Retentive Capacity for Plant-food possessed by Soils . . 681
Maeckee (M.). Manuring with Sulphuric Acid ...... 681
JoEDAN (W. H.). Action of Manures on the Quantity and Quality of a
Wheat Crop 681
KoNiG (A.) and others. Researches on the Behaviour of Insoluble Phos-
phates in Peaty Soils and in Dilute Solvents 681
Cochin (D.). Action of Air on Yeast 746
CONTENTS. XXXV
PAGE
Leplay (H.). Chemistry of the Maize-plant 747
Babth^lemt (A.). Eespiration of Aquatic and Submerged Aero-aquatic
Plants .747
Klinkenbeeg (W.). Proportion of Nitrogen in the Form of Amides, Albu-
min, and Nuclein in different Feeding-stuffs * . ^ . . . 74S
D:^herain (P. P.). Loss and Grain of Nitrogen in Arable Land . . . 749
Loew (O.). Chemical Character of Living Protoplasm .... 819
Eeinke (J.) . Autoxidation of Plant-cells 819
Engelmann (T. W.). Colour and Assimilation 819
BoHM (J.). Formation of Starch from Sugar ...... 820
Walther (F.). Experiments on the Value of Various Fodders for Cows . 820
WoLDE (W;). Rice and Earth-nut Meal as Food for Milch Cows . . 820
Ullik (P.). Nitrogenous Constituents of Malt, Wort, Beer, and Bread . 821
Hoppe-Seyler (F.). Fermentation of Cellulose 821
Wagner (F.). Influence of Organic Manures on the Temperature of the
Soil 821
Fleischer (M.) and R. Kissling. Application of Insoluble Phosphates to
Soils 822
Warden (C. J. H.). Ash- ot Fistia Stratiotes or ''T^niiSaiV' . . .822
TscHuscHKE (A.). Manuring of Sugar-beet ....... 823
Reinkb (J.). Easily Oxidisable Constituents of Plants .... 880
Amthon (C). Studies on Ripe Grapes ; . 881
ViBRANS. Influence of Manuring on the Composition of Potatoes . . 882
Wortmann (J.) . Diastatic Ferment of Bacteria ...... 930
BoussiNGATJLT. Cultivation of the Cacao Tree 933
Meissl (E.) and F. Bocker, Constituents of the Beans of Soja Mspida . 1024
Heckel and ScHLAGDENHArPEEN. Chemistry of Globularia . . . 1025
KiJHN (J.) . Phoma Gentiance : a newly-observed Parasitic Fungus . . 1025
Kern. Artificial Digestion of Meadow-hay 1025
Marcker (M.). Decomposition of Diffusion-residues from Beetroot . . 1025
KoETH (D. v.). Culture of Various Descriptions of Sugar-beet . . . 1026
Sutton (F.). Hay and EnsUage from a Poor Quality of G-rass . . . 1026
Krauch (C.) . Eif ect of Water containing Zinc Sulphate and Common Salt
on Soils and Plants ........... 1027
Gasparin (P. de). Submersion of Vineyards 1164
Attfield (J.). Sap 1164
Howard (J. E.). Effect of Altitude on the Alkaloids of the Balrk of Cin-
chona sueciruhra 1165
Paul (B. H.). Cinchona Bark grown ini Jamaica 1165
McCallum (H.) . Seeds of Camellia oleifera 1166
Stutzer (A.) . Occurrence of Nuclein in Moulds and in Yeast . . . 1166
Analytical Chemistry,
Crova (A.). A New Condensation Hygrometer . . . . . .118
VoRTMANN (G.). Direct Estimation of Chlorine in Presence 6f Bromine
and Iodine 119
MiJNTZ (A.) and E. Aubin. Estimation of Carbonic Anhydride in the
Atmosphere 121
Ppordten (O. V. D.). Estimation of Phosphoric Acid. . . . . 121
Craig (G. E.). Estimation of Sulphur in Iron and Steel .... 121
Ledebur (A.). Estimation of Oxygen and Carbon in Iron .... 121
Millot (A.). Electrolytic Estimation of Zinc 122
Ppordten (O. V. D.). Reduction of Molybdenum Compounds . . . 122
Krauch (C). Otto's Method for the Estimation of Fusel Oil in Brandy . 123
David (J.). Estimation of Glycerol in Fatty Matters 123
Wiley (H. W.). Estimation of Dextrose, Maltose, and Dextrin, in Starch-
sugar ............. 123
Mareck (G.). Diffusion of Sugar in Befet ....... 124
XXXVl CONTENTS.
PAOB
Salomon (F.). Estimation of Rice Starch 124
Chandblon (T.). Volumetrical Estimation of Phenol .... 124
TOLLENS (B.). Ammoniacal Silver Solution as a Test for Formaldehyde 125
ScHEPPEB (H. Y. de) and A. Geibel, Examination of Fat . . . . 125
Haitingee (L.). Oecnrrence of Organic Bases in Commercial Amyl
Alcohol 127
Laar (C.)- Use of Diphenylamine and Aniline in Qualitative Analysis . 239
Mixteb (W. G-.). Sauer's Method of Estimating Sulphur .... 239
Pickering (S.). Testing for Barium or Sulphuric Acid .... 240
ScHFLZE (B.). Estimation of Sulphuric Acid in Presence of Alkaline
Chlorides 240
G-iiADDiNG (T. S.). Estimation of Phosphoric Acid as Magnesium Pyro-
phosphate ... 240
Mayer (L.) and E. v. Schmid. Estimation of Phosphoric Acid . . . 241
Guyot-Dannecy. Analysis of Potassium Thiocarbonate .... 241
Britton (B.). Normal Solutions for the Yolimietric Estimation of Iron . 241
FoHR (K. F.). Sources of Error in Estimating Iron in Ores by the Stannous
Chloride Method 242
DiEHL (W.). Volumetric Estimation of Peroxides . • . . . . 242
Ledebuhr (A.). A Colour Method for the Estimation of Manganese . . 242
JiJPTNER (H. v.). Haswell's Method for the Yolumetric Estimation of
Mercury 242
Solthien. Separation of Silver from Alloys 243
Pateouillard (C). Use of Oxalic Acid as a Test f or Arsenites in Alka-
line Salts 243
LtrSTGARTEN (S.). Detection of Iodoform, Naphthol, and Chloroform . 243
Allihn (F.). Reducing Power of Grape-sugar for Alkaline Copper Solu-
tions 244
Mach (E.) and C. Portele. Amount of Extract in Tyrolese Wines . . 245
Remont (A.). Rapid Method of Estimating Salicylic Acid in Wines . . 245
DiRCKS (Y.). Occurrence of Myronic Acid, and Estimation of Mustard Oil
in the Seeds of Cruciferae and in Oil-cakes ...... 245
Emmerich (R.). Estimation of Milk Fat 246
B ASTELAER (A. V.) . Analysis of Butter 246
MuNiER (J.). Butter Testing 247
Gabel (D.). Margarimeter of Leune and Harbulet . . . . •. 247
Garnier (L.). Albumin from Urine coagulated by Nitric Acid and soluble
in Alcohol 247
LoGES (G.). Estimation of Humus in Soils 247
TscHiRCH (A.). Microchemical Reaction Methods 376
Harcoubt (A. Y.). An Instrument for Correcting Gaseous Yolume . . 378
Geppert (J.). Improvements in Gas Analysis Apparatus .... 378
Arnold (C.). Estimation of Organic Nitrogen 378
Mulder (E.) and H. J. Hamburger. Estimation of the Halogens in Carbon
Compounds 379
Knop (W.). Analysis of Silicates 379
Broockmann (K.). Estimation of Phosphoric Acid and of Manganese . 380
Kratschmer and Sztankovanszky. Yolumetric Estimation of Phosphoric
Acid 380
Tobias (G.) . Behaviour of Alkaline Phosphates to various Indicators . . 380
Testing Silver Nitrate 381
WiEGAND (E.). Estimation of Titanic Acid in Presence of Iron . . . 381
Weller (A.). Detection and Estimation of Titanium 381
Hager (H.). Detection of Arsenic Microscopically 381
Lenz (W.). Examination of Bismuth Subnitrate. ..... 382
TiCHBORNE (C. R.) . New Form of Apparatus for Estimating Ammonia in
Potable Waters 382
Knublauch (O.). Determination of Sulphur in Coal-gas .... 382
Drown (T.M.). Sulphur in Coal . 383
Stoddard (J. T.) . Flashing Point of Petroleum ...... 383
CONTENTS. xxxvil
PAGE
LiEBEEMANN (L.). Detection of Sulpliurous Acid in Wine .... 384
ScHMiTT (C.) and C. Hiepe. Estimation of Fixed Organic Acids in Wine . 384
Wolff (C. H.). Detection of Eosaniline Hydrochloride in Wine by Means
of Stearin * . .384
Amthor (C). Glycerol in Beer 385
Bachmeyeb (W.). Test for Organic Acids in Phenol 385
Ubech (F.) . Kapidity of Separation of Cuprous Oxide by the Action of
Invert-sugar on Fehling's Solution . 385
Meissl (E.). Detection of Benzoic and Boric Acids in Milk . . . 385
Bachmeyer (W.). Test for Sodium Carbonate in Milk .... 885
G-ELis (A. and T.). Sulphocarbometer . ....... 386
Arnold (B.). New Colour Eeactious of the Alkaloids 386
Meyer (H.). Quantitative Estimation of Cinchona Alkaloids . . . 388
Gawalovski (A.). Estimation of Tannin 391
Simand (F.). Estimation of Tannin 391
WiTTMACK. Detectiooi of Adulterations of Flour with Eye-meal . . . 392
Geatzel (A.). Creasote from Beechwood Tar 393
Berthelot. Properties of Chlorinated Organic Gases and Yapours . . 394
Beanley (E.). Estimation of Haemoglobin in Blood by Optical Means . 394
Casamajor (P.). Asbestos Filters 506
Macaluso (D.) and G. Grimaldi. Influence of Hygroscopic Condensation
in Glass Vessels on the Determination of the Density of Aqueous
Vapour 507
Haevey (J. W, C). A Modified Process for the Estimation of Chlorine in
Bleaching Powder ........... 507
TopsoB (H.). Estimation of Chlorides, Bromides, and Iodides, in Presence
of Sulphuretted Hydrogen . . 508
SoNDi^N (K.). Modification of Scheibler's Azotometer 508
Boehmee (C.). Estimation of Nitric Oxide and Nitric Acid . . . 508
Ollech (H. v.). Estimation of " Half Soluble " Phosphoric Acid . . 508
SiDERSKY (D.). Separation of Strontium and Calcium .... 509
Eansom (F,). Detection of Strontium 50H
Weil's Method for the Determination of Copper, Iron, and Antimony . . 509
Werner (H.). The Thiocyanate Eeaction for Iron 610
Tamm (A.). Analysis of Iron 510
Austin (P. T.) and G. B. Hurff. Eeduction of Ferric Salts . . . 512
Craig (G.). Estimation of Sulphur in Iron and Steel 512
Eocholl (H.). Estimation of Sulphur in Pig-iron 512
Harvey (J. W. C). Volumetric Estimation of Manganese Dioxide . . 513
Halberstadt (W.). Separation of Vanadic Acid from Metals . . .513
Naylor (W. a. H.) and J. O. Braithw^aitb. Test for Arsenic . . . 513
Hitchcock (E.). Examination of Water and Air for Sanitary Purposes . 514
Marsh (C. W.). Ammonia Process fpr Water Analysis . . . . 514
Davy (E. W.). Determination of Nitrites 515
Stapleton (J.). Preparation of Alkaline Potassium Permanganate Solution
for Water Analysis . . , . . . . . . . . , . . . 516
Tichborne (C. E. C). Preparation of a Volumetric Solution for Determin-
ing the Hardness of Water 516
VoGEL (A.). Estimation of the Fertility of a Soil 517
Stoddard (J. T.). Determination of the Flashing-point of Petroleum . 517
Galloway (E.), Estimation of Coke and Volatile Products in Coal . . 517
Nessler (J.) and M. Barth. Estimation of Alcoholic Liquors . . . 618
Boegmann (E.). Eelation between the Glycerol and Alcohol in Wine . 518
Feesenius (E.) and E. Boegmann. Analyses of Pure Wines . . . 618
pEGENER (P.) and F. Allihn, Estimation of Sugar by Alkaline Copper
Solutions . . 519
Aebos (J.). Pyrolein . . . .. . . . . ... . 519
Pfeiffee (E.). Milk Analysis . . 521
Schmitt (E.). Adulteration of Butter . . .... . . 521
!|R.^m;ont (A.). Estimation of Salicylic Acid in Milk and Butter . .. . 522
c 2
XXXVm CONTENTS.
PAGE
Coppola (F.). Genesis of Ptomaines 522
JoFFRE (J.). Niew Method of Detecting Dyes in Yams or Tissues . . 523
Meyee (V.). Vapour-density Determination 618
OsTWALD (W.). Manufacture and Correction of Burettes .... 619
LoBWB (J.). Storage of Oxygen in Zinc Gasholders 619
Gaspaein (P. de). Estimation of Phosphoric Acid in Arable Soils . . 619
Estimation of Phosphoric Acid in Manures 620
Waetha (v.). Estimation of Sulphurous Acid in Wine .... 621
Oeth (A.). Mechanical and Chemical Analysis of Soils .... 621
Voetmann (G.). Separation of Nickel from Cobalt 621
Geigoeeff (P.). Analysis of some Moscow Waters 622
Wolff (C. H.). Examination of Molasses for Dextrin Syrup . . . 624
Feancke (G.). Estimation of Starch in Grain 624
Coppola (F.). Genesis of Ptomaines . 624
Thomas (C). Examination of Wine Coloured by Aromatic Sulphonie
Derivatives 625
Fleming (H.). Glycerylphosphoric Acid 682
Thomson (R. T.). Litmus, Methyl-orange, Phenacetolin, and Phenol-
phthalein as Indicators ... 682
Shepheed (H. H. B.). Determination of Nitrogen in Mixtures containing
Nitrogenous Organic Matter, Ammoniacal Salts, and Nitrates . . 685
Haevet (J. W. C.) . Yolumetric Estimation of Chromic Acid in Chromates
and Dichromates 686
Lehmann (v.). Methods of Detecting Lead, Silver, and Mercury in the
Body in Cases of Poisoning ... 687
Dbspeax (P.). Ready Method of Estimating the Alkalinity of Limed Baet-
syrup 689
Dttnstan (W. R.) and F. W. Shoet. Assay of Nux Vomica . . .689
Benedikt (R,). Tests for Resorcinol Dyes 689
Taubee (E.). Estimation of Phosphorus by the Molybdate Method . . 750
Examination of Butter ........... 750
Meyee (L.). Recognition of Suint in Suet and other Fats .... 750
Examination of Oil-cakes ^ . . 751
Meyee (R.). Microscopic Investigation of Dyed Cotton Fabrics . . . 751
Etaed and C. Richex. Estimation of the Reducing Power of Urine and of
the Extractive Matter which it contains 751
Tayloe (J.) . Preparation of Hydrogen Sulphide from Coal-gas . . . 824
Thomson (R. T.). Litmus, Methyl-orange, Phenacetolin, and Phenol-
phthalein as Indicators 824
Thomson (R. T.). Use of Rosolic Acid as Indicator; Additional Notes on
Phenol-phthalein and Methyl-orange 827
Lunge (G.). Determination of Caustic Alkalis in presence of the Carbo-
nates 828
Macaethue (R.). Determination of Zinc as Sulphide 828
Jackson (E.). A New Test for Titanium and the Formation of a New
Oxideof the Metal. .......... 828
McCay(L. W.). Water Analysis . ........ 829
BoEGMANN (E.). Sulphuric Acid in Sherry . ....... 829
WoEM-MiJLLEE, Estimation of Sugar in Urine 829
LoEW (O.) and T. Bockoeny. Employment of Magenta with Sulphurous
Anhydride as a Microcheraical Test for Aldehyde 829
Penzoldt (F.) and E. Fischer. New Reaction for Aldehydes . . . 829
Loges (G.). Estimation of Humus in Soils 830
Estimation of Iron and Steel . . ' 882
Determination and Investigation of Drinking Water 883
Casamajoe (P.). Detection of Anhydrous Glucose mixed with Refined
Cane-sugar 884
Baitmann (E.). Detection and Estimation of Phenols and Hydroxy-acids in
the Urine . .885
HiSLAM (A. B.). Detection of Albumin in Urine . 885
CONTENTS. ^ XXXlX
PAGE
Detection of Rice-meal in Buckwheat Flour 885
Classen (A.) and O. Bauer. Use of Hydrogen Peroxide in Analytical
Chemistry 934
KiTicsAN (S.). Distillation of Wine 934
MiJNTZ (A.). Estimation of Carbon Bisulphide in Thiocarbonates . . 935
Claus (A.). Occurrence and Estimation of Free Tartaric Acid in Wine . 935
ZuLKOWSKY (K.). Examination of Fats 936
G-KOUVEN (H.). Nitrogen Estimation, a Method of G-eneral Application . 1028
KoNiG (J.). Comparative Estimation of Nitrogen in Guano . . . 1030
Geete (E. A.). Nitrogen-estimation in Saltpetre by Potassium Xanthate , 1031
Gbete (E. A.). Phosphoric Acid Determination 1031
Gisevitjs (P.). Specific Gravity of Minerals and their Mechanical Separa-
tion 1031
Stead (J. E.). New Method of Estimating Carbon in Iron and Steel. A
New Form of Chromometer 1032
Thomas (N. W.) and E. F. Smith. Electrolysis of Bismuth Solutions . 1034
McCay (L. W.). New Volumetric Method 'for the Estimation of Arsenic . 1034
Legler (L.) . Estimation of Methaldehyde 1035
ZuLKOWSKY (K.). Analysis of Fats 1036
Scheibe (E,). Separation of Morphine in Chemico-legal Investigations . 1036
Bloxam (C. L.). Detection of Urea in an Aqueous Solution . . . 1036
Drechsel (E.). Experiments on the Small Scale in Sealed Tubes . . 1167
WiELAND (J.). Alkalimetric Indicators 1167
Barnes (J. B.). Separation of Chlorine, Bromine, and Iodine . . . 1167
Miller (O.). Detection of Free Sulphuric Acid in Presence of Aluminium
Sulphate 1168
Krutwig (J.) and A. Cocheteux. Estimation of Iron by means of Per-
manganate Solution 1168
Storch (L.) . Precipitation of Iron by Hydrogen Sulphide .... 1169
Storch (L.). Solubility of Metallic Sulphides in Thio-acids . . . 11^9
Paschkis (H.). Detection of Mercury in Animal Tissues .... 1169
Mallet (J. W.). Determination of Organic Matter in Potable Water . . 1171
LoNGi (A,). Testing for Hydrocyanic, Hydrochloric, Hydrobromic, Hydr-
iodic, Chloric, Bromic, Iodic, Hydroferrocyanic, and Hydroferricyanic
Acids 1172
BoRCHERS (W.). Method of Determining Hydrochloric, Hydrocyanic, and
Thiocyanic Acids simultaneously present 1173
Cripps (R. A.). Estimation of Hydrocyanic Acid 1174
Struve (H.). Milk 1174
CowNLEY (A. J.). Ether-test for Quinine 1174
Bloxam (C. L.). Use of Bromine in testing for Alkaloids .... 1175
Jackson (H.). Bromine as a Test for Strychnine 1175
DuNSTAN (W. R.) and F. W. Short. Analysis of Nux Vomica . . . 1175
Johnson (G.) . Picric Acid as a Test for Albumin and Sugar in Urine . 1176
Struve (H.). Dialysis of Putrescible Substances 1177
Drechsel (E.). Use of Phosphoric Acid in Pettenkofer's Reaction for Bile
Acids 1177
Technical Chemistry,
Galloway (W,). Influence of Coal-dust in Colliery Explosions .
RoMANiS (R.). Water of Rangoon
Allen (A. H.). Action of Water on Lead
RoBiNET (E.) and H. Pellet. Antiseptic Action of Salicylic Acid
Brame (C). Certain Properties of Hydrogen Cyanide
Boiler Explosions
Schaeppi (H.). Recovery of Sulphur by Mond's Process .
Abraham (K.). The Currents of the Gases in Sulphuric Acid Chambers
127
128
128
128
129
129
129
129
XI CONTEXTS.
PAGE
Wachtkl (Or.). Utilisation of the Nitrogen Compounds from the Manufac-
ture of Sulphuric Acid 130
Pahlberg (C). Preparation from Bauxite of Aluminium Sulphate free
from Iron 130
KoRSCHELT (O.). Japanese Soils : a Natural Cement 131
On Cement and its Application 131
Iron Industry 132
Utilisation for Agricultural Purposes of the Basic Slag obtained in the
Dephosphorising Process 133
Hampe. Desilvering of Lead 134
Huntington (A. K.). Reactions of the Mexican Amalgamation Process . 134
Blas and Miest. Extraction of the Precious Metals from all kinds of
Ores by Electrolysis . 134
MoRiTz (J.). Freezing of Wine 135
Bauer (A. H.). Preserration of Beer 136
Boer-grains 136
Griessmater (V.). Loss of Sugar by Long Steaming of the "Mash". . 136
V, Mering. Does Potato-sugar contain any Deleterious Matter? . . . 136
ScHOTT and others. Purification of Sugar-beet Juice 136
Absorption and Utilisation of the Sulphurous Anhydride contained in
Furnace Oases . 248
Mater (A.). Antiseptics 240
Koch (R.). Disinfectants 249
Treve. Prevention of Explosions in Boilers by Means of Sheet Zinc . . 250
GuYOT (P.). Industrial Value of Crude Alunite 250
Outzkoff's Process for the Separation of Gold in California .... 251
Blarez. Deplastering of Wines 252
KoTTMAN (G.). ^Application of Strontium Chloride in Purifying Syrups . 252
Scheibler (C). Recovery of Sugar from Molasses by means of Strontium
Hydroxide 252
Preparation of Brown and White Cellulose 253
Preparation of the Homologues of Phenol, Naphthol, and Resorcinol . . 253
Fleischmann (W.) and R. Sachtleben. Becker's Creaming Process . . 253
Fleischmann (W.) and R. Sachtleben. Jacobsen's Testing Chum . . 253
Gabel (D.) . On Creaming . . . . 253
Barff and others. Preservation of Milk, &c 253
Dietzell (B.). Preservation of Milk 254
BussE. Preservation of Milk 254
Fleischmann (W.). Preserved, Milk, &c . . . . 254
SCHRODT (M.) and others. On Milk 254
Hagemann (W.). Preservation of Butter 254
ViETH (P.) and others. Cheese, Oleomargarin-cheese, &c 256
ScHAAL (E.). Injurious Action of a Cupriferous Oil used in Turkey-red
Dyeing . 256
KoECHLiN (M. H.) . Fixation of Artificial Colouring Matters by Means of
Metallic Mordants . , 256
Preparation of Aluminium Thiocyanate . • . • . . 256
SOHMID (H.). Application of Baeyer's Artificial Indigo .... 257
Debus (H.). Chemical Theory of Gunpowder 258
Haerling. Cause of the Acid Reaction of some Kinds of Paper . . . 2f 0
MiJLLER (A.). Cleaning of Glass Laboratory Vessels 395
Obernetter (J. B.) . Silver Bromide Gelatin-emulsion .... 395
KoLBE (H.). Antiseptic Properties of Carbonic Anhydride .... 895
Sinidor, a Disinfectant . . . • 396
Harnack (E.). Carlsbad Salts .396
Ivan (A.). Bauxite 397
GuTOT (P.). Calcination of Alunite 397
Wagener (G.). Glass Enamels, Porcelain, Stoneware, and- Refractory Clay. 397
PusCHER (C). Weather-proof Cement Work . . . . . .398
Fischer (F.). Application of Electricity in Metallurgy .... 398
CONTENTS. xli
PAGE
LiJBiscH (T.). Toughened Glass 399
Arnold (H.). Bromine Amalgamation Process 399
KosMANN. Boasting of Zinc-blende 399
Roessler's Method for the Separation of G-old, Silver, Lead, and Copper
from Sulphides by Air-blast 400
Separation of Copper from Lead by Refining in Freiberg .... 400
Modification of the Hunt-Douglas Process for the Extraction of Copper. . 400
Improvements in the Manufacture of Iron ....... 402
Iron Industry 402
Influence of Charcoal on the Amount of Phosphorus in Pig-iron . . . 403
Delafond. Steel from Pig-iron containing Phosphorus .... 403
Wasum. Influence of Sulphur and Copper on the working of Steel . . 404<
G-alvanising and Nickeling of Iron in Cleveland, Ohio 404
Pascheb (C). Argentine 405
LiEBEE, (K.). Application of Aluminium Palmitate ..... 405
Sestini (F.). Preparation of Thiocarbonates for the Destruction of
Phylloxera 405
New Dyes 406
NiBDERSTADT. Meat Extract from South America 406
Fluckigee (F. a.) and W. v. MiLlee. American Storax .... 407
Malenfant. Alteration of Syrup of Tolu . 407
Lowe (J.) . Adulteration of Cochineal 408
Baudet. Prevention of Boiler Incrustation 408
Raydt (W.). Liquid Carbonic Anhydride as a Fire Extinguisher . . 408
LiDOFF (A.). Analysis of Petroleum Coke . 408
Fletchee (T.) . Flameless Combustion 523
Removal of Fixed Grlass Stoppers 524
Pfaundlee (L.). Explosion of a Zinc Gasometer containing Oxygen . 524
Lunge (G.). Recent Progress in the Soda Industry 524
Improvements in the Preparation of Alkalis 528
Geigoejeff (p.) . New Mineral Manure Deposits 529
Demaechi (L.) and O. Fodeea. Production of Pozzolana .... 529
English Cement 530
MiCHAELTS (W.). Portland Cement and its Adulteration .... 530
PusCHEE (E.). Process for Rendering Cement and Lime less subject to
Atmospheric Influences 530
Egleston (T.). Tellurium in Copper 531
Novelties in the Iron Industry 531
Tungsten Steel 533
RiNMAN (L.) . Composition of Firwood Charcoal 533
Naweatil (A.). Examination of Galician Petroleum 533
New Source of Benzene, Naphthalene, and Anthracene 534
Feiedbueg (L. H.). Carbon Bisulphide 535
Dentjc^ (D,). Preservation of Wine by Salicylic Acid .... 635
Langee (T.) . Amount of Carbonic Acid in Beer 535
Geiessmatee. The Ferment of Chica Beer 535
ScHEiBLEE (C). The Strontia Process for the Separation of Sugar from
Molasses 536
Meldola (R.) . Action of Dibromonaphthol on Amines .... 536
Cement for Conduct-pipes 536
Boegmann. Photo-electric Battery . 625
Fischee (F.). Practical Application of Thermo-electricity . . . . 625
Beaed. Fuel to Produce Electricity . 626
Fischee (F.). Flameless Combustion 626
Weldon (W.). Manufacture of Sodium Sulphide 627
Segee (H.). Analysis of Clay from Lothain 627
Landein (E.). Analysis of Puzzuolanas and Estimation of their Compara-
tive Values 628
Stoltlee (L.). Crystals in Cementation Steel 629
Presence of Gold in German Standard Silver Coins 629
xlii CONTENTS.
PAGE
Than (C. v.). Examination of Illuminating Gas 629
Manufacture of Spirit from Wheat 630
Simultaneous Employment of Potatoes and Grain in Spirit Factories . . 630
Salzer (L.). Purification of Alcohol prepared from Molasses or Beetroot . 630
Waohter (H.). Analysis of Markgrafler of different Districts and
Vintages 631
Henningeb. a New Alcohol in Wine. 631
Detmeii (W.). Influence of Foreign Matter in the Conversion of Starch by
Diastase . . . 631
On Malt 631
BooKMANN (F.). Manufacture of Sorgho- and Imphy-sngar in the Unit<?d
States 633
LoEW (O.) and others. Changes occurring in Preserved Milk . . . 634
ScHATz (F.). Oiling and the Operations connected therewith in Turkey-red
Dyeing 635
Process for Preparing Crocin -scarlet and Crocin-yellow ..... 635
Alizarin-blue 635
New Coal-tar Colours 636
TcHEENiAC (J.) and others. Manufacture of Thioeyanates . i . , 639
Dressing for Driving^bands * i . 640
Hallbeeg (C. S.). Ergot 640
KoNiG (J.). Purification of Contaminated Waters ..... 691
BoussiNGAULT. Bronze Implements used by the Miners of Peru * . 691
KusTEL. Eoasting of Gold Telluride ........ 691
Wehmer (J.) . Preparation of Pressed Yeast 692
Degener (P.). Influence of Chlorides of the Alkalis and Alkaline Earths
on the Precipitation of Lime Saccharate from Warm Solutions . . 692
New Process for the Extraction of Fish-oil ....... 692
Gibbons (W.). Uranium Oleate 692
WeidMakn (M.). Composition and Ripening of Emmenthal Cheese . . 692
Paul (B. H.). Liquid Extract of Cinchona 693
Cross (C.F.). Technical Aspects of Lignification . . ; . . 694
Koechlin (H.). Indophenol 695
BiJROW (F.). New Process for Preparing Press-cake from Maize, &c. . . 695
Preservation of Diffusion Residues from the Beet-sugar Manufacture . . 695
Fleiohtinger. Cause of the Acid Reaction exhibited by some kinds of
Paper 696
Ceos (0.) and A. VeeQeraud. A New Photographic Paper . . . 752
Jacquelain. Preparation and Purification of Carbon for Electric Lighting 752
HouzEAU (A.). Variation of the Amount of Ammonia in Rain-water . . 753
Preparation and Testing of Cement 753
Landrin (E.), Hydraulic Silica and its Functions in Hydraulic Cements . 754
Le Ch Atelier (H*). Hydraulic Silica . . ^ . * . . . 755
Gruner. Relative Oxidisability of Cast and Malleable Iron and Steel . 755
PiCHAED (P.). Plastering of Wines ; Rapid Estimation of Cream of Tartar 755
Influence of Barley on the Fermentation Process ....;. 756
Defecation of Beet- juice with Strontium Saccharate . . . . 756
Litache (A.). Action of Certain Metals on Oils 756
Investigations on Milk 757
Fleischmasn (W.) and A. Morgen. Scherff's Preserved Milk . . . 757
Preservation of Milk 758
Preparation of Blue and Violet Dye-stuffs ....... 759
Archbold (G.). a New Method of Manufacturing Paper-pulp . . . 759
Haerling. Cause of the Acid Reaction exhibited by some Kinds of Paper 759
Waterproof Paint for Stones, &c 760
Landrin (E.). Action of Water on the Lime of Theil. Existence of a New
Compound, " Pouzzo-Portland " 830
Le Chalelier (H.) . Hardening of Cements 831
Stead (J. E.). Chemistry of the Bessemer Converter . . . . . 832
Gfndeemann. Purification of Molasses 835
CONTENTS.
xliii
Pellet (H.) aud A. Dubaele. Manufacture of Sugar without Bone
charcoal, Sand, or Sulphurous Anhydride
Te:6ves. Prevention of Boiler Explosions
ToBiN (T. W.). Explosive and Dangerous Dusts .
FiscHEB (F.). Contribution to a Knowledge of Sewer Gases
Pembeeton (H.). Working of Sulphuric Acid Chambers
Scheukee-Kestnee (A.). Notes on the Soda Industry
Mayee (L.) and O. Wagnee. Analysis of Bauxite
Clay and Earthenware Groods
Process for Preparing Dichromates ....
Scale of Hardness of Metals . . ' .
Extraction of Lead from Ores occurring in the Upper Hartz
Process for Preparing Litharge and Red Lead
Spontaneous Combustion of Coal , . , . ,
Italian Red Wines
Pampe (P.) . Contribution to the Problem of Frothy Fermentation
Winthee (A.), Process for Preparing Orcinol .
A dulterated Soaps , .
Laubee and A. Steinheil. Use of Soap in Dyeing
Mordants used for Fixing Artificial Colouring-matters
Novelties in Dyeing and Calico-printing
UtiUsation of Battery Residues ....
Preparation of Terra-cotta Lumber ,
Polychrome Varnish for White Metal .
Process for Preparing Printing Ink
VoGEL (H. W.). Modification of Silver Bromide and Chloride
Zweifel (P.). Scientific Basis of Antisepsis, and Origin of Septic Poison
Kesslee (L.). Hardening of Soft Calcareous Rocks by m pans of FluosiU
cates of Insoluble Bases
Delattee. Treatment of the Washings from Wool
BoussiNGAiTLT. Mineral Combustibles .
FiscHEE (F.). Investigation on Boiler Fires
Process for Preparing Weatherproof Wall Paintings
Stanfoed (!]. C. C). New Substance obtained from some of the
Species of Marine Algae ......
Keen (S.). Russian Basic Steel
Wallace (W.). Decay of Building Stones .
MiJLLEE (A.). Utilisation of Butter-milk in Bread-making
Hall (F. P.). Action of Certain Vegetable Acids on Lead and Tin
Tappeinee (H.). Marsh-gas Fermentation in the Mud of Ditches, Swamps
and Sewers
RoHAET. New Properties of Ferric Sulphate
FoESTEE (J.) . Employment of Boric Acid for Preserving Food
Feiedbueg (L. H.) . Manufacture of Tartaric Acid
Atwatee (W. O.). Chemistry of Fish
MoussETTE. Fermentation of Bread .
Chicandaed (G-.). Fermentation of B|read .
Poeeo (B.)r Italian Petroleums , , , ,
commoner
PAGE
835
835
836
886
887
887
888
888
890
890
891
89L
892
892
892
893
893
894
894
895
896
896
896
896
936
937
940
940
941
942
942
943
1036
1036
1037
1038
1177
1178
1178
1178
1179
1179
1179
1180
JOURNAL
OF
THE CHEMICAL SOCIETY.
ABSTRACTS OF CHEMICAL PAPERS PUBLISHED IN
BRITISH AND FOREIGN JOURNALS,
General and Physical Chemistry.
Spectrum of Carbon. By Gr. D. Liveing and J. Dewar (Proc.
Boy. Soc.j 33, 403 — 410). — The results obtained by the authors in
their spectroscopic investigations on the reversals of the lines of metallic
vapours (Abstr., 1882, 254 — 256) have shown the importance of an
accurate knowledge of the ultra-violet spectra, for the lines of short
wave-length are, as a rule, the more readily reversed.
Angstrom and Thalen have mapped the line-spectrum of carbon in
the visible part, and shown it to consist of 11 lines, of which the
single line in the yellow, followed by a triplet in the green and a
strong line in the blue, recall the spectrum of magnesium. Photo-
graphs were taken of the spark of a large induction coil between poles
of purified graphite in air, car})onic anhydride, hydrogen, and coal-gas ;
the wave-lengths were determined by a Rutherford diffraction grating,
having 17,296 lines to the inch, and found to be for the principal lines
2296-5, 2478-3, 2509, 2511*9, 2836-3, and 2837*2. When the spark
was taken in air, the photographs showed, besides the carbon lines
above, the six cyanogen flutings in the blue, and those between K and
L and near N, but this practically disappeared when carbonic anhy-
dride was substituted for air.
The spectrum of Swan's incandescent lamps was examined and
found to be continuous until the thread gave way, when the character-
istic green flutings of carbonic oxide appeared ; in some cases a sort
of flame appeared at the positive electrode when the current was not
quite intense enough to rupture the thread. The spectrum of the
rarefied atmosphere within the envelope of the lamp revealed the pre-
sence of carbonic oxide. By interposing different flames between the
incandescent lamp and the slit of the spectroscope, a comparison could
be made of the probable temperature of the flames and filament, and
VOL. XLIY. b
2 ABSTRACTS OP CHEMICAL PAPERS.
from tlie experiments it is inferred that the emissive power of the
carbon thread for ligfht of the refrangibility of the D lines is approxi-
mately balanced by that of sodium at the temperature of the flame of
cyanogen burning in air, but is sensibly less than that of sodium at
the temperature of a jet of coal-gas or hydrogen, in oxygen. It is
thus probable that the temperature of the incandescent thread is not »
far different from that conveyed to sodium by the cyanogen flame
burning in air. V. H. V.
Disappearance of some Spectral Lines, and the Variations
of Metallic Spectra due to Mixed Vapours. By G. D. Liveing
and J. Dewar (Proc. Boy. Soc.^ 33, 428 — 434). — The most commonly
received theory of spectral lines is that the motions of the luminiferous
ether producing them are not due to any translated motion of the
molecules, but rather to vibrations within the molecules themselves ;
whilst the mutual action of the molecules, although it may give nse to
irregular vibrations producing the lines, affects the regular vibrations
only by converting a part of the motions of translation into internal
vibrations. According to this theory, the spectral lines will be limited
to a certain number, of fundamental lines, and others harmonically
related to them. .Variations of temperature, by altering the rapidity
and violence of the mutual action of the molecules, will alter the in-
tensity of the vibrations, bnt not their periods, unless the molecule is
disintegrated, which would give rise to new molecules with new funda-
mental periods of vibration.
With a view of subjecting this theory to an adequate test, the
authors have made a minute examination of the spectrum of magnesium
under various conditions, and have failed to detect the formation of
such new molecules (vide Abstr., 1882, 254 — 256). The authors
have extended these experiments by the observation of the spectrum
emitted by a block of magnesia rendered incandescent by an oxy-
hydrogen jet. In the visible part of the spectrum, no discontinuity was
observable, and the photographs of the ultra-violet region showed a
continuous spectrum, on which only one line, X 2852, comes out,
sometimes bright, sometimes reversed ; this line is the strongest line
of burning magnesium and of the arc spectrum. This observation
offers corroborative evidence of the theoretical view that alterations in
temperature cannot stop any fundamental vibrations of the molecule.
But the question arises how far the presence of a mixture of mole-
cules of different elements affects their respective vibrations ; this
condition was obtained in the authors' observation of the spectrum of
the arc in crucibles, as well as in the solar atmosphere. Thus the
authors have observed the effect of hydrogen in producing the reversal
of chromium and iron lines, and the effects of a mixture of metallic
vapours in developing bright lines. These effects are the more frequent
in the case of metals which produce a large number of lines, such
as nickel and titanium. A large quantity of nickel may be introduced
into a crucible of magnesia through which the arc of a Siemens
dynamo-machine is passing without the lines of nickel being
developed, but on the introduction of iron and chromium into the
crucible, the nickel lines come out with great brilliance. A similar
GENERAL AND PHYSICAL CHEMISTRY. 3
result was obtained in the case of titanium. In some cases, when a
fragment of a metal is dropped into the crucible, brilliant lines,
hitherto unrecorded, reveal themselves, and it is difficult to establish
without further examination whether these lines belong to the newly
introduced metal or to those previously put in..
Figures are given in the paper to illustrate' these phenomena.
A line X 4923, which occurs so often in the chromosphere, and is
generally attributed to iron, is so near to lines which come out in the
crncibles that the authors doubt whether- it can be absolutely
identified with the iron line. Similarly a line, % 4!921*3, which comes
out on the addition of chromium and titanum, is probably identical
with a line observed by Young in the chromosphere,, but which up to
the present has been attributed to sulphur. The au-thors in conclusion
draw attention to the large amount of work necessary before any of
the solar lines can be considered not to be due to terrestrial elements,
and they deprecate any hasty geueralisaiion based upon the present
state of knowledge. Y. H. V.
Action of Light on Silver Bromide. By D. Tommasi (Bull.
Soc. Ghim. [2], 37, 291 — 293). — Thirty grams freshly prepared silver
bromide were exposed in water to the action of sunlight for three
months. At the end of this time, it had become brown, and had lost
2*3 per cent, of bromine. The author concludes that the change is
a case of dissociation rather than decomposition.* Under the influence
of the sun's rays, the bromide undergoes partial decomposition to an
extent which depends on the surface exposed, the time of insolation,
and the intensity of the light. A small quantity is transformed into
AgaBr, which, on prolonged exposure, decomposes into silver and
bromine. The brown silver bromide consequently contains variable
proportions of argentic bromide, AgBr, argentous bromide, Ag2Br, and
metallic silver. C,. H. B.
Sources of Error in Polarising. (Preliminary Communication.)
By A. HoLZER (Ber., 15, 1932— 1938).— The author has undertaken
the investigation of the causes of discrepancy so frequently found in
different observations of the specific rotatory power of the same body
by different experimenters. Starting with colourless sugar solutions
of definite strength, he added small quantities of known colouring
matters, such as picric acid, and noted the effect of the latter on the
specific rotatory power of the solution, as determined by Mitscherlich's
apparatus with day and lamp light, and by Laurent's apparatus with
sodium light. His experiments show that when compound light is
employed, the specific rotatory power is increased or diminished
according to the colouring matter added, the error in some cases
amounting to as much as 4°, or to 20 — 24 per cent, of the rotation.
On the contrary, with Laurent's apparatus and monochromatic
sodium light, only small and inconsiderable differences were found to
result from the introduction of colouring substances. From these
results, the author also explains the discrepancies in the relation of
* According to the author, decomposition differs from dissociation, in that the
former takes place in a very short time. -
b 2
4 ABSTRACTS OP CHEMICAL PAPERS.
[a]^: [a];. According'to Mongolfier, [aji, : [a]j = 1 : 1-129. Accord-
ing to Weiss, [ai|D : [a]j = 1 : 1'034. According to author [ajo :
[a]^- = 1 : 1-03239 when a lamp is used, and 1 : I'lGOlO when day-
light is employed. Differences were also observed with clear and
clouded skies. A. K. M.
Method of Determining the Ohm. By J. Joubeet (Compt.
rend., 94, 1519 — 1521). — The paper contains a mathematical investi-
gation of a method of measuring electrical resistances, which is capable
of easy practical application under conditions whereby the measures
and calculations may be made with great exactness. R. R.
Oscillations of the Plane of Polarisation by Electric Dis-
charges. By E. BiCHAT and E,. Blondlot (Compt. rend., 94, 1590 —
1592). — The experiments described in this paper show that electric
discharges from u Leyden jar are capable of making the plane of
polarisation oscillate about its normal position. The electric and the
optical phenomena are simultaneous, or at all events the interval
between them is less than the ^-o^oo P^^^ ^^ ^ second. R. R-
Zinc-carbon CauplBS in Electrolysis. By D. Tommasi (Compt,
rend., 94, 1709). — Two zino-platinum couples with dilute sulphuric
acid fail to decompose a solution of potassium sulphate, but when
carbon is substituted for the platinum, the decomposition is effected.
This result cannot be due to metallic substances contained in the
carbon, as these would diminish rather than increase the difference of
potential at the electrodes. On the other hand, E. Becquerel observed
in 1856 that the substitution of pure carbon for platinum in the couple
with dilute sulphuric acid diminished the electromotive force. But it
has since been found that in cells with two couples the substitution
of carbon for platinum may either leave the electromotive force
unchanged or, in some <jases, may much increase it. The author has
found that in order to obtain good results with carbon, that substance
must contain in its pores some gas, like carbonic anhydride, which may
retard or prevent the polarisation of the cells. It is possible that the
absorption of certain gases by the carbon may cause the increased
energy of the couple, but there is no experimental proof of this.
R. R.
The Reaction Current of the Electric Arc. By Jamix and
G. Maneuvrier (Compt. rend., 94, 1615 — 1619). — The Currents from
the Gramme dynamo-electric machine are absolutely equal, so that they
neither decompose water nor affect a tangent galvanometer interposed
in the circuit. When one or more electric lamps are in the circuit
this equality is still unaltered, provided the two carbons are alike,
similarly arranged, and equally heated. If the carbons are unequal
in size, then that current of the machine prevails which passes from
the larger to the smaller carbon, i.e., from the less heated to the more
heated. Between a large mass of carbon or a mass of metal, on the
one hand, and a carbon point on the other, the phenomenon attains a
maximunv : the intensity of the differential current under such condi-
GENERAL AND PHYSICAL CHEMISTRY. 0
tions was found to be equal to the following' numbers of Bunsen cells :
with iron, 3'2 ; with retort-coke, 5*0 ; with copper, 50'6 ; with mer-
cury, 103* 7. As the resistance of the are was found to be independent
of the direction of the current, the latter cannot be fche cause of the
differential current. The carbon-mercury burner in fact changes the
action of the machine, for one set of currents is abolished, or at least
greatly weakened, and the other set is formed by snccessive currents
of greater intensity and duration. An electric arc lamp introduced
into such a circuit acts in the same way as if it were worked with a
battery current, that is, there is greater heat at the positive pole and
transference of matter to the negative pole. The machine, moreover,
before incapable of decomposing water, now acts as energetically as a
pile of 100 Bunsen elements; similarly other chemical actions, the
magnetisation of soft iron, the reduction of metals, &c., can be effected
by it as by a machine with constant currents. Those magneto-electric
machines which give alternating currents can be used only for the
production of light, and the attempt to make them available for
chemical work by rectifying their currents by means of a commutator,
has failed. It is now seen that this commutator may be replaced by
one or more arcs formed between mercury and a charcoal point, if the
economic conditions of that transformation should be favourable.
B,. R.
Movement of Gas in " Vacuum Discharges." By W. Spottis-
WOODE and J. F. Moulton {Froc. Boy. Soc, 33, 453 — 455). — In the
course of preparation of vacuum tubes, the authors observed that after
the exhaustion had been carried to a certain degree, the passage of a
strong current increased the pressure, probably from an expulsion of
gas from the terminals themselves. On the other hand, after the tube
had been taken off the pump and sealed, the passage of a current
seemed to decrease the pressure. Again some completed tubes showed
a decreased pressure after prolonged passage of a strong current, others
an increased pressure, but among both classes tubes were found which
recovered their original pressure after the cessation of the discharge.
The authors examined more carefully a tube, the exhaustion of which
was near the phosphorescent state, and whose terminals were metallic
cones. In its normal condition, it showed three or four large striae with
a dark space around the negative terminal ; but on passing the discharge
the dark space increased, the striae became feebler, while the green
phosphorescence began to show itself, and the discharge manifested
the signs of reduced pressure. On reversing the current, the phe-
nomena were reversed, and the feature of the discharge corresponded
to an increase of pressure.
The authors explain these phenomena by supposing that the effect
of the discharge is to drive occluded gas out of one terminal into the
other ; and on reversing the discharge, the operation is reversed and
the occluded contents of one terminal are thrown along the tube to be
occluded at the other. These phenomena appear to have an important
bearing on the mechanism of the discharge, and the authors are
examining at which terminal the gas is occluded or ejected.
V. H. V.
6 ABSTRACTS OF CHEMICAL PAPERS.
Apparatus for the Determination of Specific Heats by Cool-
ing. By J. ViOLLE (Comjot. rend., 94, 1510 — 1512). — A thin glass
bottle is employed having a narrow neck and double envelope, the
spaces between the outer and inner shell being exhausted. The surface
of the interior shell therefore being contained in a vacuum, the condi-
tions of cooling are always the same. An agitator and a thermometer
pass through the neck of the bottle, the former supplying the means
of equalising the temperature throughout the mass of the contained
liquid. With this apparatus the method by cooling may be used for
the determination of the specific heats. The outer surface of the inner
envelope may be silvered to render the radiation slower. R. R.
Specific Heats of Small Quantities of Substances. By
Thoulet and Lagaede (Compt. rend., 94, 1512 — 1514). — The authors
make use of thermo-electric indications of the rise in temperature of a
small quantity of liquid into which is dropped O'l to 0'5 gram of the
heated substance, the specific heat of which is to be found. The test
determinations quoted show remarkable accuracy. E.. R.
Specific Heat of Gaseous Acetic Acid. By Berthelot and
Ogier (Bull. Soc. Ghim. [2], 38, 60— 64).— It is well known that the
vapour-density of acetic acid varies with the temperature, and the
change is generally supposed to be due to a greater complexity of the
molecule at the lower temperature, although a variation in the inter-
molecular action is possible, in which case an increase of kinetic
energy would not necessarily correspond with an increase of volume.
The authors have made a series of determinations of the specific
molecular heat of gaseous acetic acid with the following results : —
Specific molecular
Temperature,
Total heat.
heat.
110—140^
1000°
90-1°
140—180
3050
76-2
180—220
2280
57-0
220—260
1530
38-2
260—300
1140
28-5
The specific, molecular heat decreases rapidly with the temperature,
and at about 300'' reaches a minimum which is approximately equal to
the number 27*21 required by theory. From the results of these
numbers a general rule for the molecular heat of gaseous acetic acid
—^ = 150"3 — '467^. The authors remark that the sums of the heats
H
absorbed by the change of state of vaporisation of acetic acid, 9'905, is
approximately equal to those of vapour of water (9 '65), and alcohol
(9'8), substances which acquire at once their theoretical vapour-den-
sity. This seems to show that the work done is equal in the three
cases, and that the abnormal vapour-density of acetic acid is a purely
physical phenomenon, and not due to a change of molecular com-
plexity. V. H. Y.
GENERAL AND PHYSICAL CHEMISTRY. 7
The Constituent of the Atmosphere which Absorbs Radiant
Heat. By S. A. Hill (Proc. Roy. Soc, 33, 435— 436).— By a com-
parison of actinometric observations made at Dehra and Mussooree,
the author has shown in a former communication (Abstr., 1882, 566),
that water-vapour in the atmosphere is the principal absorbent of
radiant heat ; in the present paper the relative absorbtive powers are
calculated from the data of the obsei-vations.
Starting with Pouillet's formula r = Rp^ in which e represents the
atmospheric thickness, and p the fraction of total radiation which
would penetrate through an atmosphere of unit thickness ; jp may be
separated iuto two factors, a and y3, representing the diathermacy of
dry air and water- vapour respectively.
The masses of dry air and vapour will be approximately propor-
tional to the barometric pressure j? and the vapour-tension/; and the
length of an oblique ray through any atmospheric stratum is
proportional to sec z. So the above formula may be written log r =
log R -f & sec z log a + / sec z log /3.
The data of these observations give, by the use of this formula, the
following results : —
a. jS. 1— a. 1—^.
1st set 0-99856 0-;6030 0-00144 0-2397
2nd „ ...... 0-99853 0-69536 0'00145 0-30464
The absorption due to dry air of one-inch pressure is invariable and
equals 01445 per cent, of the total radiation, while that due to water-
vapour of the same pressure varies from 24 — 30 per cent., and possibly
between wider limits ; in the two cases above = 27-217 per cent.
'Since the quantities of air (Q) and water- vapour (Qi) in a vertical
column of sectional area are in the ratio -5^ = - x — X — - , where C
Qx / a, Ci'
and Ci are constants of logarithmic formulae for vertical distribution,
the absorptive powers for equal masses of the two gases will be in the
ratio 5ii^ X 5 X ?54^ = _i_. Water- vapour at the dates of
27-217 8 66,218 764-4 ^
observation, 12th and 14th November, 1879, had 764*4 times the
absorptive power of air for the sun's radiant heat. V. H. V.
Law of Freezing of Aqueous Solutions of Carbon Com-
pounds. By F. M. Raoult {Compt. rend., 94, 1517—1519).—
Operating with 1 gram of substance in 1 litre of water, the author has
found that the lowering of the freezing point is subject to the follow-
ing law : the product of the molecular weight of the substance into
the lowering of the freezing point, produced by 1 gram of the sub-
stance, is nearly constant. It may therefore be affirmed that the
molecules of different organic substances dissolved in the same
quantity of water lower the freezing point to the same extent.
R. R.
Nascent Hydrogen. By D. Tommasi {Bull. Soc Chim. [2], 38,
148 — 152).— The author has examined the question whether the ipecu-
3 ABSTRACTS OP CHEMICAL PAPERS.
liar redncing properties of hydrogen at the moment of liberation from
its compounds are due to an allotropic modification of hydrogen, or to
a difference of thermic conditions. Among the cases investigated were
the reduction of the halogen salts of silver, chlorates and perchlorates,
ferric chloride, nitrates, and chloral. It was found that silver chloride
is not reduced by sodium amalgam and acidulated water, although it
is immediately reduced when an electric current is passed through
acidulated water in which the salt is suspended.
Again, a saturated solution of potassium chloi*ate is not reduced by
zinc and sulphuric acid, but is reduced by sodium amalgam and sul-
phuric acid ; or again, potassium perchlorate is unaltered by most
reducing agents which give off hydrogen, but is immediately reduced
by sodium hyposulphite.
Examples such as these show that the properties of so-called nascent
hydrogen are not due to any allotropic modification, for if this were
the case, the same result would be obtained, whatever the reagents used
for the production of the hydrogen : these differences, therefore, can
be attributed only to differences of thermic conditions, i.e., the heat
developed, which obtain in the several reactions. This view is con-
firmed by the combination of sulphur with hydrogen; for it is well
known that hydrogen at the moment of its liberation readily combines
with sulphur at ordinary temperatures, but to make hydrogen combine
directly with sulphur it is necessary to pass the gas over melted sul-
phur. In these reactions, sulphur and hydrogen require a certain
amount of heat to effect their combination ; in the first case this heat
is furnished by a chemical reaction, but in the second case from an
external source. V. H. V.
Reciprocal Displacement of the Halogens. By Beethelot
(Compt. rend., 94, 1619 — 1625). — The well-known displacement of
bromine by chlorine in haloid salts, has by recent experiments been
shown to be to a certain extent capable of inversion in presence of a
large excess of bromine, and to a small extent the inverse action
occurs even with equal equivalents. These results have induced the
author of this paper to repeat the experiment under definite thermo-
chemical conditions, and he has thus been led to the discovery of
certain hitherto unknown intermediate compounds which intervene in
these inverse actions. Such are the metallic perbromides and chloro-
bromides, and the chloride of bromine. The heats of formation and
the dissociation of these secondary compounds explain all the pheno-
mena. The inverse substitution is least with potassium chloride,
greater with barium chloride, and most marked wiih silver chloride.
The whole of the facts are shown to be in accordance with the provi-
sions of thermo-chemistry, the data of which are adduced in the
paper. R. R.
Perchloric Acid. By Berthelot (Bull. 8oc. GUm. [2], 37, 381
— 385). — The author in continuation of his researches on the oxyacids
of chlorine has made a thermo-chemical investigation of perchloric
acid. The acid, HCIO4, may be obtained in the crystalline form by
subjecting the liquid acid containing a trace of water to a freezing
GENERAL AND PHYSICAL CHEMISTRY. i)
mixture, and decanting off tlie motlier-liquor ; the crystals when puri-
fied melt at 15°. This acid dissolved in 100 times its weight of water
at 19°, disengages + 20'3 cal., a number which exceeds the heat of
solution of other monohjdroxyl acids. This phenomenon explains
the great difference in chemical properties between the anhydrous and
the dilate acid, for the latter is unaffected by every known reducing
agent, whilst the former ignites hydriodic acid and sodium iodide,
and attacks arsenious acid with great energy.
The following determinations of the heat of neutralisation of the
acid are recorded : —
1 eq. in 1 eq. in
6 litres. 6 litres. cal.
HCIO4 + iNa,0 disengages + 14-25
+ NaaO „ + 0-07
+ iBaO
+ BaO
+ NH3
+ 2NH3
>j
+ 14-47
+ 0-08
+ 12-90
nil.
For the heats of solution of the perchlorates, the following values
were obtained: —
KCIO4 absorbs -12*1 BaCClOOa absorbs -I'B
NaClOi „ - 3-5 NH4CIO4 „ -0-6
For the heat of formation of the acid, the author in conjunction
with Vieille has foand —
CI + O4 + K = KCIO4 (solid) disengages + 112-5 cal.
From this number and the preceding data, the values below are
deduced —
CI + O4 + H = HCIO4 (liquid) disengages + 19-1 cal.
CI3 + O7 + H2O = 2HCIO4 (dilute) „ + 78-70 „
CI + O4 + K = KCIO4 (dissolved) „ -f 100*4 „
CI -h O4 + Na = NaClO* (solid) „ + 1002 „
(dissolved) 96-7
CI + O4 + Hi + N = NH4CIO4 (solid) „ + 79-7 cal.
Hence for the heats of decomposition of the acid and its salts — •
HCIO4 (liquid) = HCl (gas) + O4 disengages + 2-9 cal.
2HCIO4 (liquid) = CI2 + O7 + H,0 (gas) „ + I9-8H0O
HCI4O4 (dilute) = HCl (dilute) + O4
2HCIO4 (dilute) = CI2 (gas) + O7 + H2O
KCIO4 (solid) = KCl (solid) + O4
NaClOi (solid) = NaCl (solid) + O4
Ba(C104)2 (solid) = BaCl2 (solid) + 2O4
These numbers explain the difference in stability between the con-
centrated and dilute acid, and the readiness with which the concen-
(liq.) = 29-8 cal
nil.
- 9-8 cal.
- 7-5 „
- 3-0 „
- 2-2 „
k
10 ABSTRACTS OF CHEMICAL PAPERS.
trated acid decomposes. The change of the perchlorate into the
chloride absorbs heat, whilst the reverse is the case with the chlorates ;
the conversion of potassium chlorate into the perchlorate is conse-
quently an exothermic reaction, for 4KCIO3 = SKCIO* -j- KCl, would
disengage + 63 cal. at ordinary temperature. According to calcu-
lation, the decomposition of ammonium perchlorate should be explo-
sive, for NH4CIO4 (solid) = CI + O2 + N + 2H2O (liquid) disengages
+ 58".3 cal. ; and this is verified by experiment, for ammonium per-
chlorate wheu heated at first melts, and then the liquid mass becomes
incandescent, assuming the spheroidal form, and finally decomposes
with production of yellowish flame. V. H. V.
Berthollet's Laws and the Combinations of Mercuric Oxide
with Acids. By Berthelot (Compt. rend., 94, 1672—1678). — An
equivalent of mercuric oxide disengages heat in combining with the
under-named acids as follows : —
Acetic acid -h 46 cal.
Oxalic acid + 7'1 ,,
Hydrochloric acid + 11'7 „
Hydrocyanic acid + 17'0 „
Hence the principles of thermo-chemistry indicate that oxalic acid
should decompose mercuric acetate ; hydrochloric acid should decom-
pose both mercuric acetate and oxalate ; and hydrocyanic acid should
decompose mercuric acetate, oxalate, or chloride. On the other
hand, Berthollet's laws indicate that acetic acid and hydrochloric acid
severally combined with mercuric oxide should be displaced by oxalic
acid, because mercuric oxalate is insoluble. In the former case, the
thermo-chemical laws and those of Berthollet agree in their previsions
and are in accordance with experiment. In the latter case, the facts
are that mercuric chloride is not precipitated by oxalic acid, and the
absence of any disengagement of heat shows that this is not due to
the formation of any preponderating double salt ; and again, mercuric
oxalate is entirely dissolved by hydrochloric acid, the disengaged heat
corresponding with the difference of the heats of neutralisation. That
is, the facts entirely conform to thermo-chemical laws, and are in
direct opposition to those of Berthollet.
The contrast between the precipitation of mercuric oxalate from the
acetate, conformably to Berthollet's laws, and the re-solution of the
precipitate by hydrochloric acid, contrary to the same laws, may be
shown in a single experiment by first adding oxalic acid to a solution,
of the acetate, when 4*4 cal. of heat is developed, and then adding
hydrochloric acid, when there is a further development of heat amount-
ing to 3*0 cal.
Similarly, oxalic acid fails to precipitate mercuric cyanide, whilst
hydrocyanic acid dissolves the oxalate, with development of the
amount of heat indicated by thermo-chemical theory.
Reactions analogous to the above are obtained by acting on mercuric
salts with potassium salts instead of with the acids. The general
interpretation of the phenomena is the same, but double salts intervene
in the reactions. R. R.
GENERAL AND PHYSICAL CHEMISTRY. 11
Double Salts Formed by Fusion. By Berthelot and Ilosvat
(Compt. rend., 94, 1487—1493, and 1551— 1557).— These papers have
reference to the thermic phenomena attending the formation and de-
composition of double salts. The anhydrous double salts are divisible
into two classes, viz., salts of the one class are permanent at ordinary
temperatures, and are formed even in the cold with disengagement of
heat ; whilst those of the other class prepared by fusion subsist only
temporarily at ordinary temperatures, and gradually revert in a longer
or shorter period to the state of simple salts, the transformation being
attended with development of heat. The heat of formation of double
salts (Ft) can scarcely ever be directly measured, but is inferred from
the thermic effects obtained by dissolving, under identical circum-
stances, the double salt, and each of its components, and again by
mixing the two latter solutions. T being the temperature at which,
the salt is formed by fusion, and t that at which it is dissolved, C, Ci,
and C2 the several molecular specific heats, and 0, 0i, and 02 the heats
of fusion, we have —
Fx = F^ + (Ci + a -C) (T-0 + 01 + 02 -0.
Tables of the numerical values of the quantities concerned in numerous
determinations are given in the papers, and they furnish also a number
of important deductions which throw a new light on the properties of
many double salts. R. B/.
Decompositions of Salts by Fused Substances. By A. Ditte
(Compt. rend., 94, 1592 — 1595). — The results obtained by treating
calcium phosphates with sodium chloride or with potassium chloride
in fusion, show that the decomposition of the phosphates takes
place in the same way as the decomposition of salts by water or other
liquids at ordinary temperatures, and that it is governed by similar
laws of equilibrium.
These properties are also observed in analogous compounds con-
taining arsenic and vanadium, and in salts other than those of lime.
B. R.
Mutual Solution of Liquids. By W. Alexejeff (Bull. 80c. Chim.
[2], 38, 145 — 148). — The author remarks at the outset that the pheno-
menon of mutual solution is not so simple as the hypothesis of Dossios
supposes, for the mutual solubility does not in every case increase
with the temperature, but sometimes decreases until a certain limit is
reached, which the author denominates the minimum of solubility.
Phenol and water in contact form two layers, of which the upper is
a solution of water in phenol, the lower a solution of phenol in water,
but the mutual solubility increases at a temperature of 68°, until a
homogeneous liquid is formed; a similar phenomenon occurs with
mixtures of aniline and water.
From numerous experiments, the author concludes that liquids which
dissolve one another appreciably at ordinary temperatures mix en-
tirely at temperatures considerably below their absolute boiling points ;
so that there is no essential difference between the laws of mutual solu-
bility of liquids and solids, a conclusion which is confirmed by the
following experiments : — Sealed tubes containing water aud salicylic
12 ABSTRACTS OF CHEMICAL PAPERS.
acid in various proportions were heated to 100°, and allowed to cool
slowly ; no trace of turbidity appeared until a temperature of 91° was
reached, when the contents separated into two layers ; this shows that
within certain limits of temperature there is a reciprocal solution of
water and liquid salicylic acid, for at 100° water dissolves only 8 per
cent, of salicylic acid. These experiments seem to point to a physical
isomerism existing between solutions of solid and liquid salicylic
acid, the calorific capacities of which the author proposes to examine.
V. H. V.
Velocity of Explosion of a Mixture of Carbonic Oxide and
Oxygen with Varying Quantities of Aqueous Vapour. By
H. B. Dixon (Ghem. News, 46, 151— 152).— The velocities of explo-
sion were measured by observing the pressure registered in a mercurial
gauge attached to the eudiometer in which the gases were fired. The
gauge (1 mm. bore) was U-s-haped, and contained air in the closed
limb. Near the bend, two bulbs were blown to act as reservoirs, so
that the mercury could be lowered in the eudiometer without the air
escaping from the closed limb. The index employed was carried up
and left at the highest point reached by the mercury.
In the experiments the same mass of carbonic oxide and oxygen
was exploded each time at nearly constant temperature and volume ;
therefore the heat evolved in each explosion and the cooling surface
being the same, a quicker explosion would bring the gases to a higher
average temperature than a slower one, and would consequently cause
a sharper push on the mercury column. From a series of experiments
in which the tension of aqueous vapour varied from a mere trace to
40 mm. of mercury, it would appear that the larger the quantity of
water the quicker the combustion. D. A. L.
Influence of Aqueous Vapour on the Explosion of Car-
bonic Oxide and Oxygen. By H. B. Dixon {Ghem. Neivs, 46,
151). — It is a known fact that the addition of a minute quantity of
aqueous vapour to a non-explosive mixture of dry carbonic oxide and
oxygen causes explosive combination when the spark is passed. This
phenomenon has been thus explained : — The carbonic oxide does not
combine directly with oxygen at a high temperature, but it decom-
poses the water, combining with its oxygen to form carbonic anhy-
dride ; the liberated hydrogen immediately unites with more oxygen
to re-form water, which undergoes the same changes until all the
oxygen is transferred to the carbonic oxide ; therefore a comparatively
small quantity of water would suffice to convert a large quantity of
carbonic oxide, inasmuch as that quantity would remain unaltered.
This hypothesis is now confirmed by the author's experiments, and
may be illustrated at the lecture table in the following manner : —
A glass tube 2 feet long, closed at one end, and provided with
platinum wires, is bent so that the shorter arm makes an angle of 60°
with the longer arm. The tube is heated and filled with mercury
heated to 130° C. The mixture of gases is then passed up into the
longer arm and some dry phosphoric anhydride introduced, care being
taken that none of it comes in contact with the platinum. After a
GENERAL AND PHYSICAL CHEMISTRY.
13
few hours, strong sparks from a Ley den jar or Holtz machine or coil
may be passed through the gaseous mixture without causing ignition.
Sometimes, however, when a coil is used and the platinum wires
become red hot, explosion ensues. This, the author suggests, is pro-
bably due to the presence of occluded hydrogen in the platinum,
which is given off on heating, and forms steam with the oxygen
present.
In another experiment, a tube open at both ends and bent thus,
\/\/, is employed^ the open ends are short, and the platinum wires are
in the highest bend ; the tube is filled with hot mercury, a dry mix-
ture of 5 volumes of air and 2 volumes of carbonic oxide is introduced,
and some phosphoric anhydride passed up one arm. After a short
time, the spark may be passed through the gases without causing an
explosion. Some water is now introduced into the other arm and the
spark passed immediately ; the gases ignite in the wet arm only.
D. A. L.
Specific Volumes of Liquids. By W. Lossen (Annalen, 214,
81 — 137). — After referring to the researches of Buff (Ann., Suppl., 4,
129), Thorpe (this Journal, Trans., 1880, 141 and 327), Ramsay, ibid.,
1879,463; 1881, 49, 63 and 66), Schroder (Ber., 13,1561), and Kopp
on specific volumes, the author points out that the specific volumes of
acids of the acetic series follow Kopp's law. The specific volumes of
the alcohols (with the exception of methyl alcohol) are lower than the
calculated values, and this difference increases with the molecular
weight. The specific volumes of the aldehydes are generally lower
than the calculated values. The difference between the specific
volume of an aldehyde and the corresponding alcohol is nearly constant,
viz., 5-2 — 5'9 ; but the difference between the specific volume of an
aldehyde and the corresponding acid increases with the molecular
weight.
Univalent elements appear to have the same value in different com-
pounds. This is not the case with regard to multivalent atoms.
w. c. w.
Specific Volumes of Allyl and Propyl Compounds. By A.
Zander (Annalen, 214, 138 — 193). — The author has determined the
specific volumes of the following substances at 0*^ and at their re-
spective boiling points : —
B.p.
Sp. gr.
atO°.
Sp. gr. at
boiling
point.
Vol. at b. p.
compared with
vol. at 0^ as
unity.
Sp. TOI.
Allyl alcohol
Allyl chloride
Allyl bromide
Ally] iodide
96 •5*'
46-0
70-5
102-7
94-3
59-5
244-0
155-5
97-4
0 -8724
0 -9610
1 -4593
1 -8696
0 -8223
0 -7074
0 -9680
0-8206
0-8177
0 7830
0 -9002
1 -3333
1 -6601
0 -7217
0 -6508
0 -7667
0 -6826
0 -7369
1 -11453
1 -06747
1 -09417
1 -12602
1 -14097
1 -08681
1 -26045
1 -20229
1 -10956
73-9
84-7
90-5
100-9
Allyl ether
135-5
Diallyl
125-7
Diallylaniline
Triallylamine
Propyl alcohol
225-2
200-3
81 -«
14
ABSTRACTS OF CHEMICAL PAPERS.
Isopropyl alcohol
Propyl chloride
Isopropyl chloride . . . .
Propyl bromide
Isopropyl bromide . . . .
Propyl iodide
Isopropyl iodide
Propyl ether
Isopropyl ether
Dipropyl
Di-isopropyl
Di-propylaniline
Di-isopropylaniline . , .
Tripropylaniline
Acetone
Propionic acid
Propylene bromide . . .
Trimethylene bromide
Propylene glycol
Trimethylene glycol . .
B.p.
82
46
36
71
60
102
89
90
68
69
58
245
221
156
56
140
141
165
188
214
Sp. gr.
atO".
0 -7996
0 -9123
0 -8825
1 -3835
1 -3397
0 -7633
0-7435
0 -6753
0 -6829
0-9240
0 -9338
0 -7699
0 -8125
1-0199
1 -9617
2 -0060
1 -0527
1-0625
Sp. gr. at
boiling
point.
0-7231
0 -8536
0 -8326
•2639
-2368
•5867
■5650
6743
0-6715
0-6129
0 -6286
0-7267
0-7504
0-6426
0-7489
0 '8657
1 -6944
1-7101
0 -8899
0 -9028
Vol. at b. p.
compared with
Tol. at 0° as
unity.
10565
06876
1-05699
09465
08312
-13220
-10733
•10171
•08636
•27156
-24^66
1 -19830
1 -08505
1 -17811
1 -15783
1-17300
1 -18289
1 -17701
Sp. vol.
82
91
94
97
99
106
108
150
151
140
136
243
235
222
77
85
118
117
85
84
The above table shows that — (1) Normal propyl and isopropyl com-
poupds do not possess identical specific volumes. (2) The specific
volumes of allyl compounds are higher than the values calculated
from the observed specific volumes oi the corresponding normal
propyl compounds. W. C. W.
Inorganic Chemistry.
On the Supposed Compound NHo. By Combes (Compt. rend.,
94, 1717). — Reference is made to a communication from Maumene
{Compt. rend., 1882), in which he claims to have produced a new sub-
stance, NBL2, by the reaction of potassium permanganate on am-
monium oxalate. As the existence of NH2 or rather of N2H4, is theo-
retically probable, the author has repeated the experiments, with the
following results : — The carbonate mentioned by Maumene, treated
w4th hydrochloric acid and platinum chloride, gives a crystalline
precipitate identical in form with ammonium platinochloride, and
containing 1*9 per cent, of hydrogen (NH4Cl,PtCl4 = 1^8 per cent. H),
whilst Maumene obtained only 1*35. The aqueous solution of the
supposed new body, saturated with hydrochloric acid, yields crystals
identical in form with ammonium chloride, and this is confirmed by
the analytical results. The reaction, therefore, yields only ammonia
an(^ carbonic acid. . K. R.
INORGANIC CHEMISTRY. 15
Silicon. By P. Schutzenberger and A. Colson (Compt. rend., 94,
1710 — 1713). — Platinum foil, heated to a red dish- white heat amidst a
mass of lamp-black, is found to contain silicon, which must have been
carried through the lamp-black from the crucible. Other experiments
detailed in the paper show that the silicon reaches the platinum in the
vaporous form, and that nitrogen, and probably also oxygen, play a
part in the transference of the silicon, as well as in the formation of the
carbo-silicic compounds which the authors have previouslv described.
R. R.
Compounds of Silicon with Sulphur. By P. Sabatier (Bull
Soc. Ghim. [2], 38, 153 — 154). — When dry hydrogen sulphide is
passed over crystalline silicon at a red heat, a violent reaction occurs,
and at the cooled part of the tube a ring of a reddish substance is ob-
tained, in which fine white needles of silicon disulphide, SiSo, are found.
Beyond the ring, the tube is covered with an orange-yellow powder,
which is given off in fumes during the course of the reaction. The
yellow and brown substances seem to be identical with those obtained
by Colson {vide following Abstract). The latter has a variable composi-
tion, and is probably a mixture of the disulphide with amorphous silicon
or a subsulphide ; on treatment with water, it gives off hydrogen sul-
phide and leaves a brown residue. In the tube, there is always
present a deposit of crystalliae silicon, which the author explains
by supposing the formation at the high temperature of a volatile sub-
sulphide, which at the lower temperature is decomposed into disulphide
and silicon. The yellow substance seems to consist for the greater
part of the disulphide contaminated with a certain quantity of the
subsulphide, to which the author attributes a probable formula SisSi.
Y. H. Y.
Combination of Tetratomic Elements. By A. Colson {Bull.
Soc. Cliim. [2], 38, 56—60, and Compt. rend., 94, 1526— 1528). -If
a current of ethylene or hydrogen saturated with benzene is passed
over silicon contained in a porcelain tube surrounded by a clay jacket-
ing tube which is heated in a reverberatory furnace, a carbosilicide of
the formula SiC02 is obtained ; the necessary oxygen is derived from
the silica of the tube. This compound is a whitish powder, and is unat-
tacked by acids, chlorine, or oxygen at a red heat. It is decomposed
by fused potash, or a. mixture of litharge and lead chromate. On sub-
stituting carbonic anhydride for ethylene, a compound of the formula
SiaCaO is formed, with liberation of carbonic oxide. The author
explains the fact that an oxygen-containing compound like carbonic
anhydride yields a less oxygenated product than ethylene, by suppos-
ing a simultaneous loss of oxygen of the silica and carbonic anhydride,
analogous to the simultaneous loss of hydrogen when benzene and
methane are passed through a red-hot tube. On heating pulverised
silicon in a carbon crucible surrounded by a titaniferous (carbon and
rutile) jacket, and heated to a white heat, a compound of formula
SiaCsOg was obtained.
If vapour of carbon bisulphide is passed over silicon at a white
heat, two compounds are formed, the one a yellow volatile compound
of the formula SiS, the other a yellowish substsmce of probable compo-
16 ABSTRACTS OF CHEMICAL PAPERS.
sition SiSO. Both these substances are decomposed by water or dilute
alkalis, with evolution of hydrogen. If the contents of the tube are
further heated with a boiling solution of potash to remove the excess
of silicon and its sulphur compounds, and then digested for some time
with warm hydrofluoric acid, a greenish powder of the composition
SiiCiS is obtained: when heated in a current of oxygen this does
not alter in weight, but is converted into an oxygenated compound,
Si4C402.
The author draws attention to the fact that the analogy of sulphur
and oxygen does not hold good at high temperatures, for COo yields
SUCA, but CS2 yields SiS and Si^C^S. Y. H. V.
Extraction of Selenium from a Waste Product. By P.
KiENLEN (Bull 80c. Ghim. [2], 37, 440— 443).— The selenious anhy-
dride produced by the combustion of seleniferous pyrites is reduced
by sulphurous anhydride in the Grlover tower to the state of selenium,
which partly dissolves in the acid, partly remains in suspension. At a
works where pyrites from Sain Bel, near Lyons, are used, the amount
of selenium present in the acid is often sufficient to impart to it a
distinct blood-red tint.
The amount of selenium in the sulphuric acid may be estimated by
diluting a considerable quantity of the acid with three times its bulk
of water, and leaving it in a warm place for a long time. The clear
liquid is then decanted or siphoned oS", the selenium collected on a
weighed filter, washed, and dried at 100°. Glover tower acid of sp. gr.
1*606 was found to contain 28'3 mgrms. of selenium per litre, or 17*6
mgrms. per 1000 grams, whilst chamber acid of sp. gr. 1'532 con-
tained 34-2 mgrms. per litre, or 22*3 mgrms. per 1000 grams.
When the sulphuric acid containing selenium is used for the manu-
facture of salt-cake, the selenium volatilises along with the hydro-
chloric acid, and is deposited in the first condensers, sometimes in
such quantity that it imparts a red fluorescence to the acid. It is the
deposit in these condensers which constitutes the new source of sele-
nium. This deposit forms a brick- red mud, which becomes black on
drying. When dried at 100° it contains from 41 to 45 per cent, of
selenium. The selenium is estimated by suspending 20 grams of the
dried mud in water in a flask with a long neck, adding soda to
feeble alkaline reaction, and then adding bromine drop by drop with
continual agitation. After some time the liquid is filtered, the filtrate
mixed with the washings, boiled with a little hydrochloric acid, and
the selenium precipitated by sulphurous acid.
In order to extract selenium from the deposit, it is suspended in
water, and treated with a current of chlorine in large Woolf 's bottles.
The selenium is converted into tetrachloride, and this is decomposed
by the water, yielding selenious acid, which is partially oxidised to
selenic acid. As soon as the brick-red tint in the first vessel has dis-
appeared, the vessel is removed, and the second vessel put in its place,
another vessel containing fresh mud being put on at the end. The
dark-coloured liquid thus obtained contains selenious, selenic, and
hydrochloric acids. It is filtered through cloth, and boiled with
excess of hydi'ochloric acid, which reduces the selenic acid to sele-
INORGANIC CHEMISTRY. 17
nioTis acid, then diluted to its original volnme, and ttie seleninm pre-
cipitated by adding sodium hydrogen sulphite until the liquid smells
strongly of sulphurous anhydride. The selenium is deposited in large
red flakes, which agglomerate to a pitchy mass with a bronze lustre.
The liquid is boiled by passing in steam, when the precipitate rapidly
agglomerates and contracts, forming a spongy steel-grey mass, which
is then washed, dried, fused in a clay muffle, and cooled under water
or in glass moulds. By this method large quantities of selenium can
be easily and rapidly obtained in a state of considerable purity.
C. H. B.
Boiling Point of Selenium. By L. Troost (Compt. rend., 94,
1508 — 1510). — The author finds that the boiling point of selenium
under 760 mm. pressure is 665°, and he suggests the use of boiling
selenium as a means of maintaining a constant temperature for the
determination of vapour-densities, &c. R. R.
Coefficient of Expansion of Sodium Sulphate Solutions.
By W. W. J. NicoL (Ber., 15, 1931— 1932).— On the assumption that
in sodium sulphate solutions the salt is in the anhydrous condition
above 33 — 34°, and hydrated below this temperature, the author
thought it probable that a solution of this salt would show a suddenly
increased or diminished coefficient of expansion at about this tempera-
ture. He has examined solutions of different strengths between 20°
and 40°, and has found that the coefficient of expansion gradually in-
creases with rise of temperature up to 34 — 36°, when it suddenly
diminishes. It increases again with further rise of temperature.
A. K. M.
" Chloride of Lime " and " Chloride of Lithia." By K. Keaijt
(Annalen, 214, 254—360). — When chlorine is passed over moist
lithia, a mixture of lithium chloride and hypochlorite is produced, but
half of the lithia present takes no part in the reaction —
4LiOH + 2C1 = LiOCl + LiCl + H^O + 2LiOH.
"When exposed to the action of carbonic acid, the hypochlorite is de-
composed, and the hypochlorous acid which is set free acts on the
chloride, and chlorine is evolved. A similar reaction takes place
when a mixture of basic calcium chloride and calcium hypochlorite is
submitted to the action of carbonic acid.
As it would not be possible for a monad metal, such as lithium, to
form a compound having a composition analogous to ClCaOCl, the
author concludes that Odling's formula for bleaching powder is incor-
rect, w. c. w.
Calcium Hypoiodite. By G. Lunge and R. Schoch (Ber., 15,
1883—1888). — The hypoiodites are generally stated to be highly un-
stable compounds, of which, however, little is known, as they have not
been isolated.
By the action of iodine on lime suspended in water (several hours
being allowed to complete the reaction), the authors have obtained a
colourless solution, which has an odour of iodoform, and gives the
VOL. XLIV. C
18 ■ ABSTRACTS OF CHEMICAL PAPERS.
following reactions : — Addition of acid produces immediate separation
of iodine ; solution of starch gives no coloration ; hydrogen peroxide
in acid solution produces turbidity and abundant evolution of oxygen ;
cobaltous nitrate gives a green-coloured precipitate ; coal-tar colours
are not affected, whilst cochineal, logwood, litmus, &c., are bleached.
From these results, and more especially from the bleaching power of
the solution, the authors conclude that by the action of iodine on lime
at the ordinary temperature the compound CaOIz = Ca(0I)2 + Calj
is produced, besides calcium iodide and iodate. From quantitative
experiments on the bleaching power of this iodide of lime, they show
that it is much more stable than the alkaline hypoiodites are generally
supposed to be. It decomposes slowly in the dark, more rapidly when
exposed to sunlight, and by boiling for many hoars is decomposed only
to the extend of one-half. A. K. M.
Didymium. By P. T. ClIive (Compt. rend., 94, 1528—1530).—
The author has for several years suspected the presence of a new
element accompanying didymium, and he has recently by fractional
precipitation and decomposition separated a portion, the spectrum of
which, besides the known lines of didymium and lanthanum, gave new
lines, and amongst these a very strong one of wave-length = 4333'5.
This line was previously observed by Thalen in 1868, in a mixture of
lanthanum and didymium, but was absent from the spectra of samples
of lanthanum and of didymium prepared by the author in 1874.
The atomic weight of the first fraction precipitated by potassium
sulphate was 146 ; that of the last fraction, 142. Without naming
the new element, the author proposes to designate it by the symbol
Di3'.
. The author intends to continue his researches on didymium.
R. B.
Didjrmium. By B.Braits^u (Compt. rend,, 94,1718^1719).— In
this paper the author does not claim priority over Cleve (preceding
Abstract), but uierely asserts that his observations are independent,
and were announced in the Anzeiger der Acad. Wissenschaft in Wien of
6th October, 1881, and 9th June, 1882. He found that lanthanum
sulphate may by repeated crystallisations be divided into two frac-
tions, the more basic having an atomic weight = 138*3, and the less
basic = 140-2. By repeatedly treating didymium free from oxide of
lanthanum with ammonium nitrate, the author obtained an earth
having the atomic weight of 1406, the atomic weight of the remaining
didymium being 142-5; but by repeated precipitations a product was
obtained with an atomic weight of 146-6. In the spark spectra of the
different fractions, rays were found belonging to none of the known
cerite metals. These phenomena are doubtless due to the fourth
element designated Di/3 by Cleve. The author succeeded in sepa-
rating another earth of a higher atomic weight than 145"4. Ordinary
didymium appears to be a mixture of at least three elements. One
is true didymium (Di = 145-4) ; another (the Di/J of Cleve) is a more
basic metal, and has an atomic weight of about 141; the third, of a
higher atomic weight, is less basic than didymium. R. R.
IXORGAXIC CHEMISTRY. 19
Explosive Alloys of Zinc with Certain Platinum Metals.
By H. Sainte-Claire Deville and H. Debray (Gompt. rend., 94,
1557 — 1560). — Oxide of iridium is projected into fused zinc, the
mass is kept in fusion for six hours, and the cooled ingot treated with
hydrochloric acid to remove the excess of zinc, &c. When the
graphite-like residue, washed and dried at 100°, is heated to 300^ it
instantly takes fire, almost explosively, giving off fumes of zinc and of
osmic acid. This deflagration occurs also in a vacuum, but naturally,
without production of zinc oxide or of osmic acid. At 300°, there is
therefore a change of state attended by great development of heat,
which in the air occasions combustion. This phenomenon is so
marked that by its means 1 or 2 per cent, of iridium may be detected
in platinum. Ruthenium and rhodium produce similar effects.
R. R.^
Action of Aluminium on Cupric Chloride. By D. Tommasi
(Bull. Soc. Chim. [2], 37, 443 — 445). — Aluminium acts rapidly, even
at ordinary temperatures, on a solution of cupric chloride, with libera-
tion of hydrogen and copper, and formation of an aluminium oxychlo-
ride, the composition of which depends on the concentration of the
copper solution. With a 31*25 per cent, solution of cupric chloride,
the aluminium oxychloride had the composition 2Al2H606,3Al2Cl6,
and with a 7'81 per cent, solution, the composition Al2B[606,4Al2CIfi.
These oxychlorides are easily decomposed and will not crystallise :
They are not true compounds, but variable mixtures of aluminium
chloride and oxychloride. The action of metallic aluminium on these
oxychlorides yields as a final product the compound
Al2Cl6,6AloH606 + I2H2O.
To obtain this compound, a 31*25 per cent, solntion of cupric chloride
is treated with aluminium until all the copper is precipitated ; the
liquid is filtered, the filtrate heated, and aluminium added in succes-
sive small quantities until it ceases to dissolve, water being added from
time to time to make up for loss by evaporation. The clear liquid is
then evaporated to a syrup, and finally dried at 40 — 50°. In this way
the oxychloride is obtained in white flakes resembling those of potas-
sium boro-tartrate. A solution of this oxychloride, like that of ferric
oxychloride, is precipitated by sulphuric acid and by certain salts, such
as the sulphates of sodium, ammonium, potassium, magnesium, zinc,
copper, and iron ; but it is not precipitated, even on boiling, by the
chlorides of potassium, ammonium, sodium, copper, or barium, by
potassium iodide, potassium bromide, ammonium nitrate, or potassium
nitrate. The aluminium hydroxide thrown down is but slightly
soluble in sulphuric acid, and appears to be an isomeric modification,
probably the modification b, described by the author {Gompt. rend.j
1880). C. H. B.
Stability of Cupric Hydroxide. By D. Tommasi (Bull. Sac.
Ghim. [2], 37, 197 — 202). — Cupric hydroxide, perfectly free from
oxide, can be obtained only by using very dilute solutions of copper
sulphate and sodium hydroxide, the precipitation being effected at 0°.
The author has determined the influence of the presence of various
c 2
20 ABSTRACTS OP CHEMICAL PAPERS.
salts on the dehydration of tlie cupric hydroxide. In contact with
distilled water at 6 — 8", cuprir; hydroxide undergoes sensible dehydra-
tion after 120 hours. A sensible amount of dehydration takes place
in 24 hours in presence of sodium hydroxide, and is greater the more
dilute the soda solution. It is most marked with a 0*2 per cent, solu-
tion, but with a 10 per cent, solution the hydroxide remains blue, even
after 48 hours ; it becomes black, however, after 96 hours. In
presence of sodium acetate, carbonate, or sulphate, dehydration takes
place more slowly, and, in presence of calcium chloride, sugar, man-
ganese sulphate, or potassium chlorate, no dehydration is perceptible,
even after a long time. Haloid salts of the alkalis appear to form
small quantities of oxyhalo'id copper compounds. The presence of
small quantities of certain substances altogether prevents the dehydra-
tion of the copper hydroxide ; the presence of 0'3 per cent, man-
ganese sulphate, for example, prevents dehydration, even at 100°.
Cupric hydroxide added to a solution of nickel sulphate is converted
into an apple-green precipitate which contains both copper and nickel,
probably in the form of a double basic sulphate. No copper passes
into solution. When the hydroxide is added to a solution of lead
nitrate, the copper displaces a portion of the lead, which is precipitated
as hydroxide, whilst the copper passes into solution.
The influence of diiferent salts on the temperature of dehydration
is shown by the following table : —
Strength of Temperature of
Salt. * solution. dehydration.
KaaCOs 5 per cent. 50°
KCl 10 „ 71
NaHO 10 „ 74.
H2O — 11
NaC.HaOa .... 10 „ 78
Na,S04 10 „ 79
NaHO 1 „ 83
NaHO., 0-5 „ 84
KBr 10 „ 85
KCIO3 — 85
KI 10 „ 8t>
Mn^sb;.: ;::::: lo ;; l^o dehydration,
Sugar 10 ,; J evenatlOO.
C. H. B.
Transformations of Cuprosocupric Sulphites. By A. £tard
{GoTYvpt. rend., 94, 1475 — 1477). — The formula for the precipitate,
obtained by the addition of an insufficient quantity of sulphurous acid
or sodium hydrogen sulphite to a solution of cupric acetate, was given
by Pean as S03Cu2,S03Cu,5H20. The author's analyses of this salt
lead him to assign to it the composition S8027Cu"io(Cu2) + 26H2O,
with the foUovving rational formula: —
S8032CU'2,CU"2,CU"8(H8)H2 + 2IH2O,
after a type already adopted by him, and he proposes to call the sub-
stance acid cu;proso-cujpric octg^id^hite.
INOROANIG CHEMISTRY. 21
By the action of sulpbiiron.i acid, tlie above salt is transformed into
Chevreul's salt, SOaCuaSOa/iHoO, and by the action of sodium
hydrogen sulphite into a yellow salt already described by the author
as acid octosulphite of (•uprosum, ciipricumj and sodium {ibid. ,Q^y 1422).
The reaction is represented tbus : —
S803,Cu'2Cu"2Ca''8(H#)U2,21H20 + SsO^iTS^a^Hs = S^OsHs +
8H2O + S8032Cll'20u"2Cu"8(Na8).H2,S602iHo4,5H20.
R. R.
Separation of Gailium. By L. de Boisbaudean (Compt. rend.,
94, 1439—1442; l(j'lh—lQ2^).—Sepa,ation from Ghicinum.—Uhe
gallium is precipitated by potassium ferrocyanide from a solution
containing hydrochloric .acid in large- excess, or it may be thrown
down along with arsenious sulphide.
Separation from Cerium,, Lanthanum, Did^mium, Samarium, Yttrium,
Holmium, and Thulium. — These earths may be precipitated by potas-
sium hydroxide in considerable excess at the boiling temperature, and
the gallium separated from the alkaline solutiion by means of cupric
hydroxide or by addition of ammonia and long boiling after previous
neutralisation with hydrochloric acid. Gallium may also be separated
from the above-named metals by precipitating it with potassium ferro-
cyanide from solutions containing excess of hydrochloric acid. Gal-
lium is carried down when arsenious acid is precipitated by hydrogen
sulphide.
Separation from Iron. — This is effected by a boiling solution of potas-
sium hydroxide, but as the iron oxide carries down with it a little
gallium, it must be re-dissolved and re- precipitated four or five times.
When the quantity of iron present is relatively large, it is preferable
to reduce the ferric salt with metallic copper, add a small excess of
cuprous oxide, and, after repeating this operation three or four times,
to pass hydrogen sulphide through the last strongly acid hydrochloric
acid solution. The remainder of the iron is then eliminated by two
or three treatments with boiling potassium hydroxide.
Separation from. Thorium. — The methods with potassium hydroxide,
with potassium ferrocyanide, and with arsenious sulphide are all
applicable in this case.
Separation from Zirconium. — This may be effected either by boiling
with potassium hydroxide or by arsenious sulphide, but not by potas-
sium ferrocyanide, because the latter precipitates very acid and dilute
solutions of zirconium.
Separation from Manganese. — For this nine processes are given.
That by potassium hydroxide is applicable, but it must be several
times repeated, and has no advantages in the presence of much mam-
ganese. Barium carbonate or calcium carbonate separates gallium in
the cold after some hours, leaving manganous chloride in solution.
Very good separations may be obtained by arsenious sulphide^ also by
cupric hydroxide used hot. The reaction with potassium ferrocyanide
may be used, but with special modifications, of which a long and
detailed account is given in the paper.
Separation from Zinc. — The method with copper hydroxide com-
pletely separates gallium from 2inc- Barium or calcium carbonate
1
22 ABSTRACTS OP CHEMICAL PAPERS.
precipitates gallium, but considerable quantities of zinc are carried
down with it. R. R.
Action of Ammonium Sulphide on Stannous Sulphide. By
H. Baubigny (Cojnpt. rend., 94, 1473 — 1475). — Stannous sulphide is
quite insoluble in pure normal ammonium sulphide. If air has access,
however, the oxygen decomposes the ammonium sulphide with forma-
tion of sulphur ; this unites with a portion of the stannous sulphide
and transforms it into stannic sulphide which is soluble in the liquid.
Sulphide of ammoninm or of the alkaline metals is employed in
analysis to dissolve and separate stannous sulphide, but these reagents
act as solvents only when they contain sulphur in excess, and are
without action when reduced to the state of normal sulphides. This
source of uncertainty would be avoided if the ammonium sulphide
used in analysis were always fully sulphurised by previously dissolving
in it a sufficient quantity of sulphur. R. R.
Chromic Acid and Chromates. By M. Peudhomme and F.
Binder (Bull Soc. Ghim. [2], 37, 194— 196).— When barium chlonde
is added to a solution of potassium dichromate, normal barium
chromate is precipitated, and potassium chloride and chromic acid
remain in solution, thus : KaCrjOv -f- BaClj = BaCr04 + 2KC1 + CrO,.
This reaction furnishes additional evidence in favour of the view that
potassium dichromate is a molecular combination of the normal
chromate with an easily displaceable molecule of chromic anhydride,
a view also supported by the fact that many dichromates (NH4, K, Ca,
&c.), can be prepared by the direct action of chromic anhydride on a
molecule of the corresponding normal chromate. By treating di-
chromates with alkalis, alkaline earths, or the corresponding car-
bonates, double chromates are frequently formed. Zinc, aluminium,
cupric, and chromic hydroxides, when heated with potassium dichro-
mate, form normal potassium chromate and a chromate of the parti-
cular base. In this way, certain chromates, e.g., ZnCr04, can be pre-
pared, which were formerly obtained only by the action of chromic
acid on the carbonate or oxide. This method of preparation explains
the formation of chromium chromate when potassium dichromate is
treated with hydrogen sulphide or sodium thiosulphate. Chromic
hydroxide is first formed, and is then acted on by the excess of di-
chromate. When a strong solution of potassium dichromate is added
to a solution of sodium hydrogen sulphite of 30° B., a green solution is
obtained, which rapidly solidifies, owing to the formation of green
chromic oxide. If the dichromate is in excess, bi*own chromium
chromate is formed. C. H. B.
Chromous Sulphate. By H. Moissan (Bull Soc. Chim. [2], 37,
296 — 298). — The greater part of this paper has already appeared in
the Compt. rend. (Abstr., 1881, p. 684). Chromous sulphate does not
decompose w^ater at 100°. 12'35 grams of the salt dissolve in 100 c.c.
of water at 0°, but it is only slightly soluble in alcohol. With potas-
sium or sodium hydroxide, a solution of chromous sulphate gives a
black precipitate, insoluble in excess ; with ammonia, a black precipi-
INORGANIC CHEMISTRY. 23
tate, soluble in excess, forming a blue solution; with alkaline carbo-
nates, a reddish precipitate; with potassium chromate, a mgiroon
precipitate; cupric salts, a brick-red precipitate; ammonium nioljb-
date, a dark maroon precipitate ; ^old chloride, a deposit of metallic
gold ; hydrogen sulphide, no precipitate ; alkaline hjdrosulphides, a
black precipitate.
When moist chromous carbonate or acetate is treated with a large
excess of concentrated sulphuric acid, the hydrate CrS04 -j- SHgO is
obtained in white crystals, more stable when exposed to air than the
hydrate CrSOi -f 7H2O. In contact with a small quantity of water,
it passes into the normal hydrate CrS04 -f 7H3O. C. H. B.
New Class of Borotungstates. By D. Klein (Bull. 80c. GUm.
[2], 37, 202— 208).— The disodium salt previously described {Bull.
Soc. Chim., 35, 14) may be a boroduodecitungstate, or a boro-
quatuordecitungstate, or a boroquindecitungstate. The analytical
results agree equally well with all three formulae.
' The barium salt is obtained in white crystals by adding a boiling
saturated solution of barium chloride in excess to a warm saturated
solution of the sodium salt. If the mixed solutions are allowed to
boil, the small quantity of hydrochloric acid which is set free preci-
pitates tungstic acid. Too frequent crystallisation from water also
decomposes the salt, probably with separation of metatungstic acid
and formation of a basic salt. The addition of a few drops of hydro-
chloric acid appears to prevent this decomposition. The amount of
water of crystallisation in the salt appears to be very variable, and
the salt is in all probability efflorescent. When dried at 160°, the
composition of the salt agrees more closely with the formula
14W03,B203,3BaO,5H20 than with 15W03,B203,3BaO,5H20.
The potassium salt is obtained in slender needles, closely resem-
bling dipotassium tungstoborate, by decomposing the barium salt with
potassium sulphate. It has the composition 14\V03,B203,3K20,H20 +
2IH2O.
The silver salt is obtained by adding silver sulphate to a solution of
the barium salt. It is a white crystalline powder, almost insoluble in
cold, and very slightly soluble in hot water. It cannot be completely
dried without partial decomposition, but appears to have the compo-
sition 14W03,B203,3Ag20,H20 + 7H2O.
When a limited quantity of bar.ium chloride is added to the solution
which yields the sodium salt on acidification, and the precipitate fil-
tered off, the filtrate deposits small granular crystals, very slightly
soluble in cold, more soluble in hot water. They have the composition
14W03,B203,(3iBaO,llNa20),6H20 + 29H20. This complicated double
salt resembles the double paratungstates obtained by Marignac. The
corresponding strontiumcompound, 14W03,B203, (3^Sr0.1 JNa20),6H20
+ 29H2O, is obtained in a similar manner by mixing saturated solu-
tions of strontium chloride and the sodium salt. All these salts form
a new group of boroquatuordecitungstates. The barium-sodium and
strontium-sodium compounds are possibly not true double salts, but
molecular combinations of the two salts. The author was unable to
obtain the tetrapotassiam or pentapotassium salts. When potassium
24
ABSTRACTS OF CHEMICAL PAPERS.
carbonate is added to tripotassiura boroquatuordecitungstate, potas-
sium tungstoborate and a precipitate of potassium paratangstate are
formed. C. H. B.
Change which Ferric Hydrate undergoes after a Time. By
D. ToMMASi and G. Pellizzari (Bull. Soc. Chim. [2], 37, 196—197).
— Ferric hydrate kept under water for a year loses its gelatinous
structure, and changes in colour from brown to yellowish-red. About
30 per cent, passes into a modification insoluble in dilute acids, and
about 0"3 per cent, is converted into a soluble modification identical
with Graham's colloidal hydrate. The change is very slightly, if at
all, affected by light. C. H. B.
Ferric Hydrates. By D. Tommasi {Bull. Soc. Chim. [2], 38, 152
— 153). — The author separates the ferric hydrates into two isomeric
classes, the a or red series, and the ^ or yellow series, the main points
of difference between which are given in the table below : —
Bed or cc-serles.
Obtained by precipitating a
ferric salt with alkalis.
a-re203,2H20 begins to be de-
hydrated at 50°.
a-Fe203,H20 dehydrated at 92°.
a.-Ye^O'^ is brown.
Sp. gr. of Fe^Oa = 5*11.
The hydrates dissolve in dilute
acids.
The hydrates are dehydrated
on boiling with water.
Yellovj or 0-series.
Obtained by oxidation of ferrous
hydrate, f erroso-f erric hydrate,
or ferrous carbonate.
/3-Fe203,2H20 begins to be dehy-
drated at 105°.
^.Fe203,H,0 dehydrated at 150°.
yS-FcoOa is red or yellowish-red.
Sp. gr. of FeoOa = 3-95.
The hydrates are sparingly solu-
ble in concentrated acids.
The hydrates, even on long boil-
ing, retain a molecule of
water, which can easily be re-
moved by a concentrated solu-
tion of calcium chloride.
The hydrates of the a-series may not only be distinguished, but
separated from the hydrates of the jS-series ; for the former are soluble
in ferric chloride and are reprecipitated by the addition of sodium sul-
phate or sulphuric acid, whereas the latter are quite insoluble in the
same reagent. V. H. V.
Action of Hydrogen Sulphide on Solutions of Normal
Nickel Sulphate. By H. Baubigny (Cornet, reiui., 94, 1473 —
1475). — The experiments described in this paper show that the pre-
cipitation of nickel from a solution of the normal sulphate by hydro-
gen sulphide depends on the tension of the gas. The quantity of
sulphide thrown down in a given time is gi'eater as the liquid is richer
in hydrogen sulphide, and the effect of heating at 100° in closed
vessels is that the same limits of precipitation are obtained in a few
hours which at the ordinary temperature would require as many
weeks.
INORGANIC CHEMISTRY. 25
The precipitation of the nickel is complete when the solution does
not contain more than I gram of sulphate in the litre.
The limit of precipitation does not depend entirely on the degree of
acidity acquired by the liquid, but varies according to other circum-
stances.
The action of heat on a solution of neutral nickel sulphate in the
presence of hydrogen sulphate furnishes an exact method of separating
nickel from manganese, aluminium, &c., whose salts are not decom-
posed by hydrogen sulphide, but not from iron. R. R.
Action of Hydrogen Sulphide on Nickel Sulphate in Acetic
Acid Solution. By H. Baubignt {Compt. rend., 94, 1715—1717).—
The action of hydrogen sulphide on nickel sulphate in solution is re-
tarded or entirely prevented if a sufficient quantity of acetic acid is
added in proportion to the quantity of nickel salt present. At the
temperature of 100°, however, and in a closed vessel, acetic acid
has no power to retard the action of hydrogen sulphide on dissolved
nickel sulphate, the reaction taking place as with an aqueous solution
of the neutral sulphate. R. R.
Action of Heat on an Acid Solution of Nickel Sulphate in
Presence of Hydrogen Sulphide. By H. Baubigny (Compt. rend.,
94, 1595 — 1598). — The experiments detailed in this paper lead to the
conclusions that —
1. In acid solutions of nickel sulphate, as in neutral solutions,
when the ratio of the weights of the acid and the metal remains
constant, the precipitation of the nickel by hydrogen sulphide is more
complete as the solution is more dilute.
2. Whatever the ratio of the volumes of gas and of liquid, the
amount of nickel precipitated increases with the time. R. R.
Cobalt Sulphate. By G. Vortmann (Ber., 15, 1888—1889).—
On adding concentrated sulphuric acid to an aqneous solution of a
cobalt salt, and then evaporating, cobalt sulphate containing 1 mol. of
water of crystallisation is produced. The same compound is also
formed on treating purpureocobaltic chloride with a small quantity of
water and strong sulphuric acid until dissolved, and then heating to
220°. It forms a crystalline peach-coloured powder, sparingly soluble
in cold water, being less soluble than the anhydrous salt. A low red
heat is required to drive off the water. In contact with moist air, it
absorbs water very slowly. A. K. M.
Cobaltamine Compounds. (Part III.) By G. Yortmann (Ben,
15, 1890 — 1903). — Octamine Compounds. — Instead of preparing these
compounds from the carbonate, as dcwscribed in his first paper (Ber., 10,
154), the author heats the decamine-purpureo chloride for some time
on a water-bath with dilute ammonia and solid ammonium carbonate.
On evaporating the solution it assumes the dark cherry-red colour of
the octamine carbonate. If any luteo-chloride should be present, it
will separate out on cooling, and can be filtered off. Octamine-roseo-
cohaltic chloride, Co3(NH3)8(2H20)Cl6 + 4HaO, generally crystallises
2G ABSTRACTS OF CHEMICAL PAPERS.
(as previously shown by the author) with 2 mols. H2O, but by adding
concentrated hydrochloric acid to the cold solution above-mentioned,
it is obtained with 4H2O. With mercuric chloride, the compound
Co2(NH3)8(2H,0)Cl6,e)H^Cl2 + SHjO is precipitated of a pale-red
colour. Heated to 100° it loses 3H2O. Octamine-purpureocobaltic
chloride also forms a double salt with mercuric chloride ; this when
treated with concentrated hydrochloric acid and evaporated on a water-
bath yields greyish-violet crystals of Co2(NH3)8Clfi,3HgCl2 4- H2O, but
on further concentration, green crystals of the praseo double salt,
Co2(NH3)8Cl6,HgCl2, are obtained. This compound is sparingly
soluble in cold water ; hot water converts it into octamine-purpureo-
cobaltic chloride. On adding praseocobaltic chlornitrate to acidu-
lated mercuric chloride solution, a green precipitate of
C02(NH3)8Cl6,2HgCl2
is produced. Octaraine-cobaltic nitrate, prepared by adding nitric
acid to a solution of the corresponding carbonate, forms a crys-
talline precipitate of the formula Co2(NH3)8(N03)62H20. It has
also been obtained with 1 and with 6 mols. H2O, also anhydrous.
Octmnine-cobaltic chromate, Go2(NH3)8(2H20)(Cr04)3 + 2H2O, is pre-
pared by the action of potassium dichromate on the octamine-pur-
pureo chloride, sulphate, or nitrate, and may be purified by crystal-
lisation from a weak acetic acid solution : it- forms bronz3-coloured
plates. If normal potassium chromate is employed, the compound ob-
tained is olive-green, and contains 8 mols. H2O. Solutions of both
compounds in strong acetic acid when evaporated yield an orange-
red body of the formula Co2(NH3)8(2H20)(Cr04)2,Cr207 -f H2O. A
platinochloride has been prepared, but its formula is not established.
The acid carbonate, to which the author previously gave the formula
Co203(NH3)8,4C02 -f- 2H2O, contains 3H2O, 2 mols. of which ai-e
driven off at 100°. Praseocobaltic chlornitrate, C02(NH3)8(N03)2Cli +
2HoO, is precipitated on adding dilute nitric acid or potassium niti^te
solution to solution of praseocobaltic chloride. With potassium dichro-
mate the latter gives a yellowish-green precipitate of the chlorochro-
mate, Co2(NH3)8(Cr207)Cl4 + H2O.
Hexamine Compounds — To an ammoniacal solution of octamine-
cobaltic chloride, ammonium carbonate is added, and the solution
evaporated to dryness. On redissolving and repeating the same treat-
ment, the residue consists of cobalt hydroxide and hexaminecobaltic
carbonate, and from this other hexamine salts are obtained by the
action of acids. Hexamine-cobaltic chloride is a green compound, of
the formula Co2(NH3)6Cl6 -f 2H2O. It dissolves in cold water to a
bluish- violet solution, which changes to violet-red on warming; from
this solution concentrated hydrochloric acid precipitates octamine-
purpureocobaltic chloride. Hexamine-cobaltic sulphate was obtained
as an oil, which after frequent treatment with alcohol gradually be-
came crystalline. It forms a red powder, easily soluble in water. Its
formula is Coo(NH3)6(S04)3 + 6H2O. The nitrate, Coo(NH3)6(N03)6
-f 8H2O, is a dark cherry-red dehquescent body. The carbonate,
Co2(NH3)6(OH)2(C03)2 + 8H2O, is formed in preparing the octamine-
carbonate, and is precipitated by alcohol as an oil, which after
INORGANIC CHEMISTRY. 27
repeated solution, precipitation, and treatment witli alcohol, becomes
crystalline.
"^Heptamine Compounds. — The author has in a previous paper given a
method for the preparation of melanocobaltic chloride. In order to
confirm the formula which he gave for Rose's " black salt,"
Co2(NH3)6(NH2Cl)Cl4,
he has prepared other derivatives, which he finds to be of analogous
composition. Melanucobaltic chlorochromate,
C02(NH3)6(NH2Cl)Cl2,Cr207 + H2O,
by precipitating the melanochloride with potassium dichromate.
With platinum chloride, the melanochloride gives a brownish-black
precipitate of Co2(NH3)6(NH2Cl)Cl4,PtCl4. On heating melanocobaltic
chloride solution, it becomes red; with platinum chloride this red
solution gives a reddish-brown precipitate, which (air-dried) has the
formula Co2(NH3)6(NH2Cl)C]2(OH)2,PtCl4. With mercuric chloride,
pale-red needles of Co2(NH3)6(NH2Cl)C]2(OH)2,3HgCl2 + H^O, are
precipitated. With picric acid, melanocobaltic chloride gives a brown
precipitate, which explodes violently on heating. A. K. M.
Electrolysis of Ammonium Carbamate and Carbonate with
Alternating Currents and Platinum Electrodes. By B. Gerdes
(/. pr. Ghem. [2], 26, 257— 276). — Drechsel has observed (/. pr.
Ghem. [2], 22, 476) that on electrolysing solutions of ammonium
carbamate and carbonate with alternating currents, the platinum
electrodes become strongly corroded, with formation of soluble and
insoluble platinum bases, of urea, and of an oily substance soluble in
ammonia. The author has isolated and studied the platinum bases
referred to. He used platinum electrodes two inches by one inch, a
battery of 4 — 6 Grove's cells, and alternated the current about 10
times in each second, the duration of each experiment being 10 — 12
hours, and the solution being kept cool. After that time a thick
yellowish or white precipitate had formed, the solution being colour-
less, and the electrodes much attacked.
Besides ammonium nitrite and nitrate, urea, and a fatty substance,
the filtrate was found to contain a soluble platinum salt thrown down
as a blue or green precipitate by hydrochloric acid, and crystallising in
needles. It was not, however, obtained in quantity sufficient to allow
of detailed investigation.
The white precipitate contains most of the platinuiri dissolved off
the electrodes. It is a carbonate insoluble in cold water, but on heat-
ing dissolves sparingly, forming an alkaline solution. After having
been dried over sulphuric acid, it does not lose weight at 110°, but at
higher temperatures it first becomes yellow and then suddenly decom-
poses, with evolution of ammonia and water, leaving metallic platinum
in a very fine state of division. Its composition corresponds well
with the formula PtIsr6HioC206. The carbonate dissolves in dilute
soda, and is precipitated without alteration from its solution by car-
bonic anhydride. When dissolved in hydrochloric acid and precipi-
tated by sodium carbonate in sufiiciently dilute solutions small well
formed octohedrons separate.
28 ABSTRACTS OF CHEMICAL PAPERS.
The chloride, Pt(NH3)6Cli, is easily obtained in small rhombohedrons
or in needles ; it dissolves readily in hot water, and with gold or
platinum chloride gives precipitates resembling ammonium platino-
chloride. The nitrate, Pt(NH,)6(NO;i)4, is readily soluble in water,
and crystallises in needles. The sulphate is practically insoluble in
water, even calcium sulphate solution giving an immediate precipitate
with solutions of the soluble salts. It could only be obtained m the
amorphous condition. Other compounds have been prepared, but
have not been analysed. Chromates produce a yellow, hydroflaosilicic
acid a white precipitate. The free base has not yet been isolated in a
state of purity.
If during the action of the electric current the solution of carbonate
or carbamate is not artificially cooled, the temperature of the fluid
rises to 40 — 50°, and no precipitate of the carbonate just described
is obtained, but on cooling, long prismatic highly refractive crystals
separate from the solution. These likewise consist of a carbonate,
Pt2N7C40i4Ho7. Their solution gives with nitric acid a colourless pre-
cipitate, which gradually changes into bright blue octohedrons of
platodiammoniiim nitrate, Pt(NH3)4(N03)2.
The author believes the formation of the several platinum bases to
take place as follows : — Electrolysis at first takes place in the ordinary
manner, (^114)2003, splitting up into 2NH4 and CO3, the former com-
bining in the nascent state with the negative electrode, forming
PtH2(NH3)2. The current alternating, the negative pole becomes
positive, and CO3 is added to the compound formed, yielding H2 +
Pt< ]^fT^r)l!>"CO, that is to say, platosammonium carbonate, which salt
directly combines with NH3, yielding platodiammonium carbonate,
{NH NH O
NH^'nh'^O'^^^* ^^ *^® latter, on further alternation of current,
2NH4 are added, giving g^^^>Pt<^^^-^g'Q>CO, from which in
a similar manner the insoluble carbonate —
^^<NH3>^*<NH3.NH30>^^ ^' ^°"^^^- O. H.
Ammonioplatinum Diammonium Compounds. By E. Drech-
SEL {J. pr. Chem. [2], 26, 277 — 281). — In an appendix to the previous
paper, the author points out the striking similarity of the reactions of
the platinum base described by Gerdes with those of barium com-
pounds, the solutions being precipitated by sodinm carbonate, potas-
sium dichromate, sodium phosphate, sulphuric acid, calcium sulphate,
hydrofluosilicic acid, and alkaline oxalates, hyposulphates and ferro-
cyanides. By the reagents named in fact the platinum compound
cannot be distinguished from baryta. Hydric sulphide and ammonium
sulphide produce precipitates only after some time. The ammonio-
platinum diammonium compounds stand therefore in the same relation
to the alkaline earths as ammonium does to the alkalis. 0. H.
MINERALOGIOAL CHEMISTRY. 29
Mineralogical Chemistry.
Metallic Iron accompanying Native Gold in Montgomery
Co., Virginia, a.nd in Burke Co., N. Carolina. By W. T. Page
(Chem. News, 46, 206). — Tlie grains of iron removed by a magnet
from gold, obtained by alluvial washing in the bed of Brush Creek,
have a sp. gr. 7*20, and consist of —
Fe. Cu. S. Quartz.
97-12 0-04 1-47 0'82 = 99-45.
C, P, Ni, Co, Sn, and Mn absent. This iron is shown not to be derived
from tools employed by workers, but is a case of the occurrence of
native iron with gold. Similar specimens from Carolina had a sp. gr. =
7' 5 7, and consisted of —
Fe. Co. Sn. Quartz.
99-77 trace trace (?) 0-25 = 100-02.
E. W. P.
Chemical Composition of Minerals of the Cryolite-group.
By J. Brandl (Jah7b. f. Mm., 1882, 2, Ref., 201—203).
a. h. cl. c2. cS.
Al... 13-01 18-606 13-04 13-00 13-26
Ca — 18-83 17-22 17-21 17-22
Mg — — 0-39 0-20 —
Na 32-41 11-73 1002 1049 10-43
F 54-29 55-69 50-65 50-62 50-61
H2O — — 8-48 8-33 8-42
99-71 99-856 99-80 99-85 99-94
d. el. c2. /.
Al 22-14 17-66 1764 2337
Ca 1-53 — — 1619
Mg 3-56 — — 0-11
Na 5-50 24-97 25-00 0*33
F 57-12 57-30 57-30 35-01
H2O 1000 — — 12-41
99-85 99-93 99-94 87-42
Loss reckoned as oxygen 12- 58
10000
a. Cryolite, representing the formula AIF3 + 3NaF. b. Pachnolite,
AIF3 + CaFg + NaF. Pachnolite contains no water, and thus differs
from thomsenolite. c 1, 2, and 3, are analyses of thomsenolite, agree-
ing with the formula AIF3 + CaFa + NaF -|- HoO. d. Ralstonite,
4AIF3 -f 3Na (MgCa)F + 3H2O. e 1, 2, are analyses of chiolite from
30 ABSTRACTS OF CHEMICAL PAPERS.
Miask. They represent the formula 3AIP3 -f 6NaF. / is an analysis
of prosopite from Altenberg in Saxony. It proves that this mineral
is free from silicon. Supposing that the oxygen is combined with
aluminium, so that the aluminium is partly combined with fluorine and
partly with oxygen, the analysis gives the following results : —
Ca.
Mg.
Na.
Al.
AI2O3.
F.
H2O.
,619
0-11
0-33
9-22
26-55
3501
12-41
Taking for granted that fluorine and hydroxyl can replace each
other, the formula for prosopite should be Ca(Mg,Na)Al2(F,OH)2.
This mineral does not yield up its water at 260**. B. H. B.
Some Artificial Products from Cryolite. By Noellner (Jahrh.
f. Min., 1882, 2, Ref., 200— 201).— In order to determine, experi-
mentally, if the minerals crystallised out in the cavities of cryolite
have originated from the action of salt solutions, the author digested
for three months at 100° about 12 grams finely powdered cryolite with
a saturated solution of barium chloride. Saturated solutions of stron-
tium nitrate, calcium chloride, and magnesium chloride, were also
employed. Cryolite was also treated with the same solutions for
six days in closed tubes at a temperature of 180 — 190°. The products
thus obtained were then dried and analysed, giving the following
results : —
Products of the reaction.
Material.
a. At 180°
h. At 100° after
(Cryolite = AlsNagFio.
after 6 days.
3 months.
1.
Cryolite + BaCl,
Al4Ba4Na,4F2i
Al4Ba5Na2F24 + HoO
2.
Cryolite + SrNoOc . .
AUSr4Na4F24
Al4Sr5Na2Fo4 + 4H2O
3.
Cryolite + CaCU
Al4Ca4Na4F24
AliCa^NasFs^ + 4Ho.O
4.
Cryolite + MgCU . . .
Al4Mg4Na4F24
AUMgsN^tjFj* .+ 4H2O
The product Ko. 3ti was further treated with MgCl2 at 180° for
six days, and the product had the composition Al8Ca4Mg5N'a6F48 + 8H2O.
In the same way the product No. 4a- was heated at 180° for six days
with CaCl2, and yielded a body of the composition Al8Mg7Ca«Na6F48 +
8H,0.
From these experiments the author deduces: — (1), that cryolite is
decomposed by solutions of salts of the alkaline" earths; (2), that the
alkaline earths displace the sodium which goes into solution ; (3), that
the degree of change effected is dependent on the time, the tempera-
ture, and the proportion of the salt in the solution ; (4), that the perfect
displacement of the sodium did not occur, but that it would probably
be effected after the lapse of sufficient time. (5.) That the substituted
calcium or magnesium can be partially replaced by magnesium or
calcium. (6.) That in all these reactions water is taken up ; the
amount being dependent on the nature of the incoming elements.
(7.) That the products obtained artificially closely resemble the natural
minerals crystallised out in the cavities of cryolite, and that the
theory of their formation by the same chemical process is highly
probable. B. H. B.
mXERALOGICAL CHEMISTRY. 31
The Pyrolusite Mines of Bolet. By T. Nordsteom (Jahrb. f.
Min., 1882, 2, Kef., 195). — At Bolet, in Sweden, pyrolusite occurs in
sufficient quantity to be worked. The veins and pockets are found at
the contact of finely granular gneiss and mica-slates with granitic gneiss,
which is a variety of Orebro granite. The cavities were first filled
with mica and chlorite, which was then partially replaced by pyrolusite.
The latter is, in places, accompanied by heavy spar, calcspar, quartz,
felspar, vanadinite, fluorspar, and calcspar coloured black by tine needles
of pyrolusite. B. H. B.
Artificial Production of Witherite, Strontianite, and Cal-
cite. By L. Bourgeois (Bull. Soc. Chim. [2j, 37, 447— 448).— If
small quantities of precipitated barium, strontium, or calcium car-
bonate are thrown into a fused mixture of potassium and sodium
chlorides in equivalent proportions, no carbonic anhydride is given ofF,
but the carbonates dssu me a distinct crystalline form, identical in each
case with that of the corresponding mineral. Barium carbonate forms
hexagonal plates, sometimes elongated in a direction parallel with the
faces of the prism. Strontium carbonate forms elongated prisms, and
calcium carbonate usually forms agglomerations of crystals resembling
snow crystals. C. H. B.
Mineralogical Notes. By A. Brun (Jahrb. f. Min., 1882, 2,
Ref., 198). — (a.) Stypticite from Chili. — The empirical formula of this
salt, Feo03,2S03 + lOH^O, should be HiFeaS^On + 8Aq, as the water
is given up at 80 — 180"^, with the exception of the last 8 per cent.,
which is only driven off at a dull red heat together with the sulphuric
acid. On dissolving it in boiling water, brown basic iron sulphate is
precipitated.
(h.) Dolomite from Teruel in Spain. — This is shown by the micro-
scope to be composed of grey and brown zones ; the latter being
coloured by numerous opaque granules (magnetic iron ore). The
analysis gave 2*63 per cent. FeO, and traces of MnO.
(c.) Minerals of the Miage Glacier, M. Blanc. — In the moraine of
the " Glacier de Miage," crystals of quartz ha\^e_been found, on which
only 11(1011) is developed, without — R(Olll). The author also
found galena, albite (complicated crystals), orthoclase (simple com-
binations), various micas, chlorite, asbestos, and small crystals of
beryl. B. H. B.
Chalcomenite, a New Mineral Species (Selenite of Copper).
By Des Cloizeaux and Damour (Jahrb. f Min., 1882, 2, Ref., 204).
— For some time the existence has been known of selenium-lead,
selenium-silver-copper-lead, and selenium-copper-lead ores at the Cerro
de Cachenta, about 50 miles south- west of Mendoza in the Argen-
tine Republic. Accompanying these ores, Des Cloiseaux found some
very small crj'stals of a violet-blue colour, which he called chalcomenite.
The system of this new mineral is monoclinic ; the axes have the pro-
portion a:b:c = 0'722187 : 1 : 0-246037. 3 = 89° 9'. Chalcomenite
has the formula CuSeOa + 2H.>0 ; and is therefore a representative
of a group, the selenious acid salts, up to the present time unknown in
nature. When heated in a tube closed at one end, the mineral gives
32 ABSTRACTS OF CHEMICAL PAPERS.
up first water, which is acid, then selenious acid, and finally melts to a
brown mass. Heated on charcoal before the blowpipe, it melts to a
black slag, gives off selenium vapours, and colours the flame dark blue.
In a bead of microcosmic salt, it is quickly dissolved, and gives a
greenish-blue glass, which becomes red in the reducing flame, especi-
ally after the addition of tin. The mineral is soluble in the ordinary
acids. A drop of the solution in sulphuric acid, placed on a bright
plate of copper, gives a black stain which cannot be removed by wash-
ing, and the mineral can thus be distinguished from the phosphates
and arsenates of copper. Its sp. gr. is 3*76. The analysis gave the
following result : —
SeO. CuO. HgO. Total.
48-12 35-40 15-30 98-82
At the request of Des Cloizeaux, Friedel and Sarasin prepared chal-
comenite artificially. They employed for the purpose a neutral solution
of potassium selenide, and to this they added copper sulphate, when a
white amorphous precipitate was formed, which became converted into
a blue crystalline powder. Seen nnder the microscope this was found
to be a mass of small rectangular pyramids, which might be rhombic
or monoclinic. The analysis gave results corresponding with the
formula of chalcomenite. B. H. B.
Fergusonite from Brindletown, Burke Co., N. Carolina. By
W. H. Seamon (Chem. News, 46, 205). — The crystals are small, of
tetragonal habit, reddish-brown, and give a yellow-brown streak.
Lustre between vitreous and resinous, brittle, fracture conchoidal.
Hardness = 6. Sp. gr. 5-6.
NbA- TaPg. W03,Sn02. UrOa. Y2O3, &c. CeaOg. DiaOa^La-Ps-
43-78 4-08 0-76 581 37-21 0-66 3-49
TeO. CaO. H2O.
1-81 0-65 1-62
Counting the water as basic, the above figures lead to the orthonio-
bate formula M'^NbO^. E. W. P.
Analysis of a Niobate "which has been improperly called
Enxenite from Mitchell Co., N. Carolina. By W. H. Seamom
(Chem. News, 46, 205). — This mineral, formerly described by J. L.
Smith, in no way agrees with the mineral of that name from Norway ;
it is reddish-brown in colour, with lustre between resinous and
adamantine. Hardness = 5*5. Sp. gr. 433. Freed from mica and
crust the mineral contains :—
KbaOg.
WOgSnOa.
UrOs.
Ya03.
CeaOa.
DisOaLaaOs.
FeO.
CaO. HoO.
47-09
0-40
15-15
13-46
1-40
4-00
7-09
1-53 9-55
but very little of any oxide of the erbium or ytterbium class could be
detected by the spectroscope ; the orthoniobate formula is therefore
M"3Nb308, in which about one-eighth of the hydrogen of the water is
MINERALOGICAL CHEMISTRY. 33
basic, tlie actual distribution of the elements being (ffM' + f^M"
+ I^M'" 4- -i-gM'''')Nb208; euxenite, besides containing much titanic
oxide, is a metaniobate. E. W. P.
Rutile, as a Product of the Decomposition of Titanite. By
P. Mann {Jahrl. f. Min., 1882, 2, Briefw., 200— 201).— In some
fojaites from the vSerro de Monchique, the titanite (sphene) was com-
pletely decomposed, and the author found in the decomposed mass
numerous bright yellow crystals which, by the help of the microscope,
he proved to consist of rutile.
The lime had probably been extracted by the action of water and
converted into carbonate of lime, whilst the titanic acid, mixed
perhaps with some amorphous silica, formed the decomposed crust.
B. H. B.
Artificial Production of a Crystallised Hydrated Silicate.
By A. DE ScHULTEN {Bull. Soc. Chim. [2], 37, 449— 457).— When
lime-water is added to a concentrated solution of potassium silicate
until a slight precipitate is formed, and the mixture is then heated in
sealed tubes at 180 — 200° for 24 hours, the gelatinous mass which
forms on cooling encloses a small quantity of some substance crystal-
lised in prismatic needles. If the tube is heated for several days with
occasional agitation, the gelatinous matter gradually disappears, and
the quantity of the crystals increases. By repeated levigation, the
plates of silica can be removed, and the prismatic crystals are then
obtained, mixed only with a small quantity of hexagonal plates : the
quantity of hexagonal plates increases, and that of the needles dimi-
nishes if the lime-water is added in too small quantity ; if, however,
too much lime-water is added, no crystals are formed at all. The
prismatic crystals are white, have a nacreous lustre, melt before the
blowpipe, and are decomposed by hydrochloric acid with separation
of gelatinous silica which retains the form of the original crystals.
They have the composition :■ —
SiOs.
AI2O3.
CaO.
Na^O.
KsO.
H2O.
64-2
07
147
3-3
2-2
14-5 =
99-6,
which corresponds with the formula (K2,N"a2,Ca)0,3SiOa,2H20, the
ratios between K20,Na20 and CaO being 1 : 2 : 10. The soda is
derived from the glass tubes, and the presence of alumina is due to the
presence of the hexagonal plates, which probably consist of levyne,
formed by the action of potassium silicate on the aluminous glass.
When dried in a water-bath, the crystals lose 4 to 5 per cent, of water.
No natural zeolite has the composition of these artiScial crystal?.
Okenite consists of calcium silicate, and contains Si02, 56'60 ; CaO,
26-42; H2O, 16-98.
Examined by polarised light, between crossed nicols, the crystals
exhibit brilliant colours which are extinguished longitudinally. The
greatest axis of elasticity corresponds with the direction of elongation.
If sodium silicate is used instead of potassium silicate, a compound
is obtained which has a very similar composition. C. H. B.
VOL. xiiv. d
34 ABSTRACTS OF CHEMICAL PAPERS.
Artificial Analcime. By A. de Schulten (Bull. Soc. CUm. [2],
37, 448 — i49). — When solutions of sodium silicate and sodium alu-
minat/C are mixed in such proportions that the silica and the alumina
are in the same ratio as in analcime, a suitable quantity of lime-water
added, and the liquid heated in a closed copper tube at 180° for 18
hours, crystals are obtained which have a composition identical with
that of natural analcime. The lime-water simply facilitates crystallisa-
tion. If it is not added, isolated crystals are rarely obtained ; the
crystals separate out in spherical aggregations with rough surfaces.
The crystals are sometimes cubical trapezohedrons, sometimes hexa-
hedrons. Apparently the trapezohedrons are formed when the solu-
tions are concentrated and strongly alkaline, and the hexahedrons
under the reverse conditions. Unlike the artificial analcime obtained
in glass tubes (Abstr., 1881, p. 25), the crystals have no action on
polarised light, even when a quartz plate cut parallel with the axis is
interposed. The optical properties of natural analcime are similar to
those of crystals of the quadratic system ; the optical properties of the
artificial variety previously obtained {loo. cit.) are those of the hexa-
gonal system. The optical behaviour of the new crystals is identical
with that of crystals of the cubic system. It is evident therefore, that
the axes of elasticity of the crystals of analcime undergo slight
changes sufficient to modify their optical properties, but not sufficient
to alter the external forms of the crystals from those of the cubic
system. C. H. B!
Rutile in Phlogopite. By Sandbeegee (Jahrh. f. Min., 1882, 2,
Brief w., 192 — 193). — The author received a crystal of phlogopite,
about a pound in weight, from Ontario, in Canada. In it he dis-
covered, by means of a lens, numerous colourless crystalline needles,
which he proved by analysis to consist of pure titanic acid. This is,
without doubt, the best material to illustrate the separating out of
titanic acid from a decomposing mica. B. H. B.
Analysis of beantifally Crystallised Albite from Amelia Co.
By R. N. MusGRAVE (Chem. News, 46, 204). — This mineral occurs in
masses of clear colourless flattened crystals, having a hardness = 6 ;
sp. gr. = 2'605 J and a composition of —
SiOs. AI2O3. Na-P. X.2O.
68-44 19-35 11-07 0-43 = 9989.
E. W. P.
Euclase from the Alps. By F. Becke (Jahrh. f. Min., 1882, 2,
Ref., 209). — Small pale yellow crystals, which proved to be euclase,
have been found in the Alps, together with pericline. The crystals
were about 0-5 mm. long. The following combination is tolerably
general : cxj^co, oo^2, oo]^20, 2^co, ooP, 3^00, —P. The accompany-
ing minerals are pericline and ankerite as the oldest, also rock crystal
in long prisms. The euclase appears to have been formed at the same
time as the rock crystal, as do also little globules of helminth.
B. H. B.
MINERALOGICAL CHEMISTRY. 35
Occurrence of Minerals at Jordansmiihl, in Silesia. Bj B.
Schubert {JaTirh. f. Min., 1882, 2, Hef., 193— 195).— This paper
describes the following minerals and rocks found in the serpentine bed
at Jordansmiihl.
Prehnite occurs partly in crystals, partly in crystalline aggregates.
It is rose-red, orange-yellow, or greenish, rarely colourless. _ The fol-
lowing faces occur : coPoo, ooPco, OP, ooP, Poo, fPoo, fPco, ^Pco,
P, :JP. The analysis yielded : —
SiOg.
AI.O3.
reaOg.
CaO.
MgO.
H2O.
44-12
26-00
0-61
26-26
traces
4-90
rH4Si04
approximating to the prehnite formula HiCaiAUSieOai = < 2Ca2Si04.
LAI4S13O12
White garnet, for which the formula is calculated to be Ca3Al2Si30i2.
Chromium garnet forms an emerald-green coating over prehnite.
Garnet rocJc, of a white colour, has the following composition : —
Si02. AI2O3. FePg. CaO. HgO. Total.
38-91 24-29 0-70 37-07 0-45 101-42
From this the formula of the lime-alumina-garnet may be calculated.
A second piece of rock gave —
SiOs.
AI0O3.
CaO.
MgO.
H2O.
Total.
43-94
21-79
34-19
1-54
0-60
102-06
From this is calculated the formula Ca3Al2Si30i2 + Si02.
By the help of the microscope, the rock was proved to consist of
lime-alumina- garnet and quartz. A third rock of a dirty pink colour
gave —
SiOs.
AI2O3.
Fe203.
CaO.
MgO.
H2O.
Total.
36-84
31-53
2-78
25-53
1-92
2-51
101-11
It contained diaspore, and probably some quartz.
Vesuvian, characterised by its fine blood-red colour and the combi-
nation of the forms coP, ooPoo, P, Pco, OP. It occurs in drusy
cavities of the white garnet rock ; the analysis gave —
Si02. AI2O3. FesOg. CaO. MgO. H..0. Total.
37-51 21-24 0-69 35*45 2-11 277 99-77
Diaspore occurs in compact garnet ; analysis gave —
AI2O3. H2O.
82-66 17-44
Natrolite, in drusy cavities of the garnet rock in radiated aggre-
gates, in the combination cx^P, P.
d 2
36 ABSTRACTS OP CHEMICAL PAPERS.
Manganese-ore. — Pseudomorphs, apparently pyrolusifce after calcite,
consisting of
MnOg. MnO. SiOj. H2O. FejOg. MgO. Total
62-92 4-80 800 1879 277 4-41 101-69
Quartz Each. — This rock was rich in quartz, of a rose-red colour,
and occurred in great beds. It gave on analysis : —
SiOj. AI2O3. FeaOa. CaO. H2O. MgO. Total.
69-48 19-21 0-34 10*29 0-34 trace 99-66
It probably consists of a mixture of quartz and a lime felspar.
Opalj of a bright green colour, gave on analysis : —
SiOg. AI2O3. FegOa. FeO. CaO. MgO. HjO. Total.
81-43 4-11 1-04 0-83 8-06 4-65 0'80 100-92
Serpentine, containing magnetic iron ore, gave on analysis : —
SiOj. AI2O3. FegOs. MgO. HgO. Total.
42-21 9-59 1-40 34-88 13-28 101-36
B. H. B.
Waltherite from Joachimsthal. By C. Bertrand (Jahrb. f.
Min., 1882, 2, Ref., 195— 197).— Vogl described, under the name of
waltherite, a mineral from Joachimsthal, occurring in thin prisms of
a brown and green colour. This is now proved to consist of two
distinct minerals. The brown fibrous mineral cleaves easily. It is
rhombic ; coP = 116°. The cleavage is in the direction of OP, coP,
and coPdo.
The green mineral, on the other hand, is not so distinctly fibrous,
and does not cleave so easily as the brown. The system could not be
determined, on account of the smallness of the crystals.
B. H. B.
The Granites on the Banks of the Sadne. By F. Gonxard
{Jahrb. f. Min., 1882, 2, Bef., 199). — During the construction of a
water reservoir near Lyons, a bed of pegmatite was laid bare, in which
the following accessory minerals were found : —
(1.) Garnet. Almandine, combinations coO, 202 of 15 — 20 mm.
diameter. The smaller crystals were partly opaque and partly trans-
lucent, of a fine red colour, and simple (202).
(2.) Small columnar crystals of black tourmaline.
(3.) Pinite. Only one crystal was found, 10 mm. long and 4J mm.
diameter, enclosed in the quartz of the pegmatite.
(4.) A mineral belonging to ihe Cordierite group, very similar to
the chlorophyllite of Haddam.
(5.) A yellowish- grey mica, of silky lustre, and easily scratched
with the nail ; it appears to be related to sericite. B. H. B.
Chemical Composition of Various Layers of a Lava Current
from Etna. By L. Ricciardi {Compt. rend., 94, 1657— 1659).— The
results given in this paper go to prove that samples of lava taken from
one current at various depths on the same vertical plane differ only
J
ORGANIC CHEMISTRY. 37
in the greater or lesser quantity of protoxide and peroxide of iron they
contain, the quantity of the latter being greater where the parts have
been in contact with aqueous vapour or the atmosphere. The lavas
belonging to one and the same eruption, however, if collected at
different points, may differ in their chemical and mineralogical compo-
sition. R. R.
Lithological Determination of the Meteorite of Estherville,
Emmet Co., Iowa (10th May, 1879). By S. Meunier (GompL
rend., 94, 1659 — 1661). — The Emmet meteorite belongs to the type
designated logronite by the author in 1870. The chief piinerals it
contains are olivine, bronzite, peckhamlte (Lawrence Smith), pyrrhotine,
schreibersite, ferric oxide, and nicheliferous iron. R. R.
Supposed Meteorite found in Augusta Co., Virginia. By
W. H. Seamon (Ghem. News, 46, 204). — The mass of metallic iron,
which weighed 1'25 kilos., and was covered with a crast 13 mm. deep,
was at first supposed to be a meteorite, but the analyses show that it is
not so.
Fe. Mn. C. S. P. SiOa- Al^Og. CaO. O and loss.
90-45 0-10 0-19 0-15 0-37 4-18 0*49 2-16 1-91
Sp. gr. = 5*76 ; Ni and Co absent ; SiOg soluble in sodium carbonate.
Widmanstatt figures not produced by treatment with acids.
E. W. P.
Organic Chemist r|y.
Action of Ozone on Hydrocarbons. By L. Maquenne (Ball
8oc. Gliim. [2], 37, 298— 300).— Coal-gas, purified by being pass3d
through sulphuric acid and potash, is oxidised " by ozone, with formi-
tion of formic acid, together with small quantities of methaldehyde
and a substance which reduces cupropotassic tartrate, probably me-
thylenitan. A small quantity of an amber liquid, which sometimes
explodes violently, is also formed ; it is possibly either oxybenzene
or a nitrogen compound. Nitrogen tetroxide also combines readily
with hydrocarbons. A sensible quantity of nitrobenzene is quickly
formed when benzene mixed with sulphuric acid is exposed to the
action of ozonised air. Pure methane is not affected by ozone, but if
a mixture of methane and oxygen is subjected to the silent discharge,
formic acid and methaldehyde are formed. These results confirm
Berthelot's view of the experiments of MM. Thenard (Gompt. rend.,
1873), The products obtained by the action of the silent discharge on
a mixture of carbonic anhydride and methane are undoubtedly formed
by the oxidation of the latter, and the sugar produced is methylenitan,
C7H14O6. The same substance is formed by the action of hydrogen on
carbonia oxide.
38 ABSTRACTS OF CHEMICAL PAPERS.
These facts possibly explain the formation of carbohydrates in
plants. Methane may occupy an intermediate position between the
carbohydrates and the mixture CO + H2, produced in the chlorophyll
cells under the influence of light ; by simple oxidation, it yields
methylene oxides and sugars ; by polymerisation analogous to that
which takes place under the influence of the silent discharge, it yields
the complex hydrocarbons and various products so common in the
vegetable kingdom. * C. H. B.
Dissociation of Trichloromethyl Sulphochloride. By E.
NoELTiNG (Bull Soc. CUm. [2], 37, S92—S94>) .—Trichloromethyl suU
phochloride, CCI3.SO2CI, was heated in sealed tubes for eight or ten
hours at a temperature between 170° and 200°. At 170° some un-
altered compound remains, but at 200° it is completely decomposed
into sulphurous anhydride, carbon tetrachloride, carbon oxychloride,
and thionyl chloride, thus : CClg-SOaCl = CCU + SO2 and CCI3.SO2CI
= COCI2 + SOCI3. C. H. B.
Action of Cupric Hydroxide on Sugars. By J. Habermann
and M. Honig {Monatsh. Ghem., 3, 651 — 667). — By the action of
cupric hydroxide in neutral solution on cane-sugar, inverted sugar,
grape-sugar, and fruit-sugar, there were obtained in each case car-
bonic anhydride, formic acid, glycollic acid, and a mixture of acids
whose uncrystallisable calcium salts gave an amount of calcium inter-
mediate between that required for erythroglucic and glyceric acids.
In the experiments made in alkaline solution (with baryta-water) the
same products were observed, but were obtained in shorter time and
in increased amount : in one experiment, in which a solution of
grape-sugar was heated with soda and copper hydroxide, gluconic
acid was obtained. Although the products were the same with each
of these sugars, there were great differences in the course of the reac-
tions. In the case of cane-sugar, the reduction commenced only after
some hours' boiling, apparently not until the sugar had been inverted.
With inverted sugar, reduction of the copper oxide commenced shortly
after the boiling point was reached. With grape-sugar in neutral
solution the reduction was rather slow, whilst in alkaline solution it
started with the introduction of the copper oxide into the warm
liquid. With fruit-sugar the reduction was much quicker than with
grape-sugar.
In conclusion, the authors give reasons for doubting the accuracy
of the statements of Reichardt (Annalen, 127, 297), that gum and
gummic acid, and of Claus (ibid., 147, 114), that tartronic acid are
amongst the products of the oxidation of sugar with copper oxide.
A. J. G.
Conversion of Maltose into Glucose. By S. J. Phillipps
(Bied. Centr., 1882, 710). — Maltose yields glucose under the influence
of ferments ; artificial gastric juice produces no change. Maltose
appears in the intestinal canal after feeding with starchy matters.
Maltose appears in the urine if it has been previously injected into a
vein ; subcutaneous injection of maltose results in the conversion of a
ORGANIC CHEMISTRY. 3&
portion of ifc into glucose. After feeding with starch, the blood of
the mesenteries contains glucose only. E. W, P.
Manufacture of Starch-sugar. By F. Soxhlet and A. Behr
(Bied. Gentr., 1882, 698; compare Abstr., 1882, 1274).— From con-
centrated grape-syrup at 30 — 35°, Behr has obtained crystallised
anhydrous grape-sugar by the introduction of a crystal of the same.
The sweetness of grape- as compared with that of cane-sugar is
1 : If. E. W. P.
Action of Ammonia on Propaldehyde. By A. Waage (Monatsh.
Chem., 3, 693 — 695). — By the action of ammonia gas on propalde-
hyde, cooled by a mixture of ice and salt, a small quantity of a solid
product, CsHeOjNHa, and an oil were obtained. The oil appears to
be a mixture, and on exposure to an atmosphere containing carbonic
acid, long colourless tabular crystals separate, of the formula
C15H29N3 (m. p. 74"), soluble in ether and alcohol, but insoluble in
water. What part the carbonic acid plays in the formation of these
crystals could not be ascertained.
By heating the crude product of this reaction for some days at
200° in sealed tubes, a dark-brown liquid is obtained ; and when this
is distilled, and the fraction 170 — 210° dissolved in hydrochloric acid,
separated from resinous and oily matters, and distilled with potash,
a colourless base, C9H13N, is obtained, boiling at 193 — 195° (corr.),
probably parvoline. A. J, G.
7-Diethylbutyrolactone. By A. Emmert and R. Friedrich (Ber,,
15, 1851 — 1852). — From succinic chloride and zinc-ethyl, Wischin
(Annalen, 143, 262) obtained ethylene diethyl diketone, which decom-
posed on distillation. On repeating his experiments, a body of acid
reaction was obtained which boiled at 230 — 235° without decom-
position, and on analysis gave numbers corresponding with a mixture
of nearly equal parts of 7-diethylbutyrolactone and fy-diethyloxy-
butyric acid. The latter was converted into the lactone by standing
over solid potassium carbonate ; the liquid then boiled at 228 — 233"'.
The barium and calcium salts were prepared, both soluble in alcohol
and in water.
On attempting to convert the acid into lactone by means of phos-
phoric anhydride, a hydrocarbon (CsHu),, distilled over at 270°.
J. K. 0.
Bees' Wax. By E. Zatzek (Monatsh. Chem., 3, 677—679).—
Schalfeef has stated (this Journal, 1877, i, 454) that Brod.ie's cerotic
acid is in reality a mixture of acids, into which it may be resolved by
fractional precipitation with lead acetate. The author has repeated
these experiments, but entirely fails to confirm Schalfeef 's results.
The first fraction which, according to Schalfeef, should contain an
acid C34H68O2, gave numbers perfectly agreeing with those required for
Xerotic acid (C27H54O2). A. J. G.
Action of Thiacetic Acid on Ethyl Thiocyanate. By M.
Chanlaroff {Ber.j 15, 1987 — 1989). — On heating these substances
40 ABSTRACTS OF CHEMICAL PAPERS.
too^ether for 10 — 15 minutes, they combine, forming e^i/Zic ocetylditMo-
cirhamate, CS(SEt).NHXc ; it crystallises in brilliant yellow needles,
melting at 122 — 123°, and is readily soluble in alcohol, ether, and hot
water. On being heated, it decomposes into its original constituents.
When boiled with baryta-water, it yields mercaptan and barium thio-
cyanate and acetate ; with dilute hydrochloric acid, it gives ethylic
dithiocarbamate, mercaptan, carbon oxysulphide, acetic acid, and
ammonium chloride. A. J. G.
Azaurolic Acids. By Y. Meter and E. J. Constam (Annalen,
214, 328 — 353).— The ethylnitrolic acid used in the preparation of
ethyl azaurolic acid is best obtained by the following process : — 6 c.c.
nitroethane are brought into a vessel containing small pieces of ice,
15 c.c. of potash solution (=z 6'7 grams KOH) are added, and the mix-
ture is shaken until the nitroethane is dissolved. The liquid, having
been transferred to a beaker containing ice, is mixed with 15 c.c. of
sodium nitrite solution (15 c.c. = 8 grams NaN02). Dilute sulphuric
acid is now added until the red colour of the mixture changes to pale
yellow, when the solution is rendered alkaline by the addition of
potash. The liquid is three times alternately acidified and made alka-
line. It is finally acidified with sulphuric acid, and three times ex-
tracted with one-sixth of its volume of ether. The nitrolic acid is
deposited on evaporating the ether.
In order to prepare ethylazaurolic acid, 45 grams of 5 per cent,
sodium amalgam are added to 2 grams of ethylnitrolic acid, suspended
in 10 c.c. of water. The vessel in which the operation is conducted is
surrounded by ice and salt, so as to keep the temperature about zero.
The alkaline liquid is separated from the metallic mercury and acidified
wiih dilute snlphnric acid, whereupon ethylazaurolic acid is deposited
in needle-shaped crystals, which are purified by recrystallisation from
boiling alcohol. The pure acid forms orange-coloured prisms, sparingly
soluble in water and in ether. It melts at 142° with detonation, forming
leucazone, nitrous oxide, and water. On oxidation with chromic acid
mixture, it is converted into acetic and carbonic acids. An ammo-
niacal solution of ethylazaurolic acid gives a brown precipitate with
silver nitrate, and yellow precipitates with lead and zinc salts. Ethyl-
azaurolic acid is decomposed by warm dilute hydrochloric acid into
ethylleucazone and hydroxylamine : to separate these bodies, the
hydrochlorides are converted into sulphates by treatment with silver
sulphate, and on adding a large quantity of alcohol to a cold concen-
trated aqueous solution of the sulphates, hydroxylamine sulphate is
precipitated, and on evaporating the alcoholic filtrate, ethylleucazone
sulphate is deposited in colourless prisms, melting at ]61-5°. By
double decomposition with baryta-water, the sulphate is converted
into the free base C4B7N3O, which crystallises in white needles, melting
at 1 58°, and soluble in alcohol and in water. The aqueous solution
gives a reddish-brown coloration with ferric chloride. The barium
salt, (C4H6N30)2Ba, is a colourless hygroscopic powder. On the
addition of silver nitrate to a solution of leucazone, leucazone silver
nitrate, C4H7N30,AgN03, is deposited as a white crystalline preci-
pitate. Ethylleucazone is also produced by the action of strong
ORGANIC CHEMISTRY. 41
ammonia or of sodium amalgam on ethyl azaurolic acid. The
constitution of azaurolic acid may perhaps be represented by
CMe(NO):N.T^H.CMe(NOH), or more probably by the formula
CHMe(NO).N ! N.CHMe.NO.
PropylazauroUc acid, CsHbTnTsO, prepared from propylnitrolic acid,
forms pink crystals, soluble in ether and in alcohol. It melts at 127*5^
to a colourless liquid, which does not solidify on cooling.
Methylazaurolic acid has not yet been obtained in the pure state.
w. c. w.
Acetoacetic Acids. By M. Ceresole (Ber., 15, 1871—1878).—
These acids were isolated by saponification with potash, and treatment
with sulphuric acid. The ethyl salt of the acid required is shaken up
with a slight excess of a 2J per cent, aqueous solution of potash until
the ether is dissolved. The mixture is then left for 24 hours in the
cold, acidified with sulphuric acid, and shaken with ether. The
ethereal solution is carefully evaporated and the mixture of the new
acid and unchanged salt treated with barium carbonate and water, the
acid going into solution as barium salt, whilst the unaltered ethyl salt
is removed by ether. The free acid is obtained from the barium salt
by treatment with sulphuric acid, shaking with ether, evaporating
the ethereal solution, and drying over sulphuric acid.
Acetoacetic Acid. — The free acid is a hygroscopic and very acid
liquid, miscible with water in all proportions, and decomposing rapidly
below 100" into carbonic anhydride and acetone. The silver and
copper salts are less stable than the barium salt, which is very deli-
quescent, but stable in dilute solutions ; on evaporation, it undergoes
partial decomposition into acetone, barium carbonate, and carbonic
acid ; on boiling its aqueous solution, it was found that 1 molecule of
carbonic anhydride was given ofi" for each molecule of barium carbo-
nate thrown down. The dried barium salt was analysed volumetrically
with satisfactory results, the admixed barium carbonate being esti-
mated and allowed for. By dry distillation, it yields barium carbonate
and acetone.
Moyiomethylacetoacetic acid, prepared in the same way as acetoacetic
acid, is a viscid liquid of similar properties. On boiling, it decom-
poses into carbonic anhydride and ethyl methyl ketone. The barium
salt is very soluble, and gives no precipitate with silver nitrate ; by
dry distillation it yields ethyl methyl ketone. Nitrous acid converts
the acid into nitrosomethyl acetone, melting at 74°.
Dimethylacetoacetic add, dried over sulphuric acid, forms colourless
crystals of agreeably acid smell, which are however undergoing con-
tinual decomposition, and deliquesce at once in the air. The barium,
salt can also be obtained crystalline, and possesses similar properties
to those of the other two acids. On dry distillation, it yields the cor-
responding ketone.
Benzylacetoacetic acid is an acid and aromatic oil, sparingly soluble
in water, and easily decomposable. Its barium salt is soluble, but not
deliquescent, an d yields benzyl acetone on dry distillation. Concen-
trated solutions give a precipitate with silver nitrate. With nitrous
acid, nitrosobenzyl-acetone was obtained in white needles melting at
42 ABSTRACTS OP CHEMICAL PAPERS.
80 — 81°. The barium salts of all the acetoacetic acids give violet or
brown colorations with ferric chloride.
The above acids were obtained from the corresponding ethyl salts by
saponification, without any separation of ketone or acid. Their most
prominent characteristic is their instability, and in this they agree
with other ketone acids in which the carbonyl and carboxyl groups are
only separated by one methylene or substituted methylene. Wherp,
however, separation is effected by several methylene groups or by an
aromatic residue, the ketone acids appear to be stable, as in the case
of Isevnlic or benzoylbenzoic acids. J. K. C.
Formation of Saccharin and Lactic Acid from Sugars. By
L. CuisiNiER and H. Kiliani (^Bied. Centr., 1882, 703— 705).— If
maltose is treated with lime, a solution is obtained which after con-
centration yields coloured crystals of the composition CiaHooOioCaO +
H2O (14*07 per cent. CaO). This salt has been termed maltate of lime,
and is soluble in 100 parts hot water ; from it, oxalic acid separates
" maltic" acid, CeHioOs, which melts at 95° and resembles saccharin ;
a 10 per cent, solution of the crystals has a dextrorotatory power of
[a]D = + 63°, which is reduced by dilute acids, but raised to + 73*5°
by concentrated acetic acid. Maltic acid is readily soluble in water,
glycerol, methyl, and ethyl alcohol, reduces alkaline copper solutions,
and does not ferment. The salts are laevorotatory, and so is the free
acid when first separated, but after being kept, and more rapidly when
heated with an acid, it changes into a dextrorotatory modification ; it
is therefore analogous to saccharin, and the name maltosaccharin is
proposed for it, in contradistinction to glucosaccharin.
Maltate of lime has also been obtained from lactose. In another
communication, it is stated that glucose loses its rotatory power when
in contact with alkalis in the cold, but not its reducing action on
copper solutions ; in the presence of alkalis, oxygen is absorbed from
the air.
Kiliani prepares lactic acid from inverted sugar by the following
process: 500 grams of cane-sugar are heated for three hours at 50'
in a stoppered flask with 250 c.c. water and 10 of acid (3 parts
H2SO4 with 4 parts HoO) ; after cooling, 400 c.c. of soda solution
(1 NaHO in 1 H2O) are added in small portions, the whole being kept
cool, but afterwards the mixture is to be heated to 70° until it only
colours Fehling's solution green, then sulphuric acid is added in quan-
tity equivalent to the soda present, and the freed lactic acid is sepa-
rated by 93 per cent, alcohol, and converted into the zinc salt. Saccharin
is also formed at the same time ; it is converted by silver oxide and
water into glycollic acid, together with a small quantity of formic and
a,cetic acids. E. W. P.
7-HydroxybutyriG Acid. By J. Fruhling (Monatsh. Chem., 3,
696 — 704). — Trimethylene glycol (100 parts) was heated with hydro-
bromic acid (70 parts) at 100° for five hours. The resulting trimethylene
hromhydrin, CH2Br.CH2.CH2.OH, forms a colourless liquid distilling
between 98° and 112° under a pressure of 185° mm. Its sp. gr. at
20° is 1'5374. On treatment with potassium cyanide, it gives the
ORGANIC CHEMISTRY. 43
corresponding cyanhydrin, which by the action of moderately concen-
trated hydrochloric acid or of potash is converted into ^-hydroxybutyrio
acid, thus completely confirming Saytzeff's formula,
CH.(0H).CH2.C00H,
for this acid. A. J. Gr.
Purification of Carbon Bisulphide. By E. Ohach (/. pr. Chem.
[2], 26, 281 — 307). — The author finds that potassium permanganate
is without action on pure carbon bisulphide or on the odorous im-
purities present in the commercial article, hydric sulphide excepted.
Under the influence of daylight the pure bisulphide however yields
some sulphuretted hydrogen, which is oxidised by permanganate, free
sulphur passing into solution. In the case of impure bisulphide, treat-
ment with permanganate causes a rise in the amount of dissolved solid
matters, chiefly sulphur.
Effectual purification is obtained by first filtering the bisulphide
through a dry paper filter to separate water and dirt, distilling from,
calcined lime, treatment of the distillate with about 5 grams per litre
of dry powdered permanganate, then with metallic mercury until all
free sulphur has combined, and lastly with mercuric sulphate. The
bisulphide is then redistilled from calcium chloride, and must be kept
in the dark. 0. H.
Physical Properties of Carbon Oxysulphide. By Ilosvat
(BidL Soc. Chim. [2], 37, 294— 296).— Carbon oxysulphide can be
freed from carbon bisulphide by passing the gas over a column of
wood charcoal. The mean coefficient of expansion of the gas between
0° and 100° at constant volume is 0'0037817; at constant pressure,
0*0037908. The pressure necessary to liquefy the gas at different
temperatures is given in the following table. The critical point is
105°.
Temperature : 0° 3-8° 10'7° 120° 17-0° 39-8* 41-2° 63 0" 69-0° 74 6° 85-0°.
Press, in atmos. ; 12-5 150 17-5 196 215 440 450 590 65'0 740 80.
Liquid carbon oxysulphide is colourless, mobile, and highly refrac-
tive. It dissolves sulphur, and mixes with alcohol or ether, but not
with water or glycerol. If the pressure is suddenly released, solid
flakes are deposited, and persist for some time. These experiments
show that the physical and chemical properties of carbon oxysulphide
are intermediate between those of carbon bisulphide and carbon
dioxide, and also afford further evidence that the coefficient of
expansion of an easily liquefiable gas is greater than that of a gas
difficult to liquefy.
Carbon oxysulphide, mixed however with mercaptan, carbon
dioxide, hydrogen sulphide, &c., can be obtained by the action of
sulphuric acid on potassium ethyl-thiocarbonate, COgSKEt.
C. H. B.
Dibromosuccinic Acid and Diamidosuccinic Acid. By A.
Claus (Ber., 15, 1844 — 1851). — In the preparation of diethyl dibro-
mosuccinate by Kekule's method, after separation of the ethereal
44 ABSTRACTS OF CHEJVIICAL PAPERS.
salt by adding water and evaporating the solution, a crystalline sub-
stance is left, which is the monoethylic salt of dibromo-succinic acid
(m. p. 275°). Potassium and sodium ethyl-dibromosuccinates were
formed by mixing alcoholic solutions of the alkalis with the acid, as
crystalline groups, easily soluble in water : the silver salt is a white
crystalline precipitate. With ammonia, the ammonium salt of di-
bromosuccinamic acid is obtained, but an attempt to isolate the acid
failed. Methyldihromosuccinic acid is prepared in the same way as
the ethyl compound. Its sodium and ethyl salts (m. p. 62*5°) were
obtained in the usual way.
When ethyl dibromosuccinate is treated with sodium and ethyl
bromide, only diethyl and black products are obtained; if, however,
the sodium is replaced by zinc, the ethyl bromide is not attacked, and
distils over unchanged, while one or two atoms of zinc enter into com-
bination with the acid, without removing the bromine, and syrupy
liquids are formed containing varying percentages of zinc. Heated
with ethyl bromide in sealed tubes at above ISO"*, fumaric acid and
zinc bromide are the chief products.
According to Lehrfeld, the amide of ethyl imidosuccinate is formed
by the action of ammonia gas on an alcoholic solution of ethyl dibro-
mosuccinate. The author, however, on repeating the experiment
could obtain nothing beyond ethyl diamidosuccinate. Lindner, by
treating free dibromosuccinic acid with ammonia, claims to have pre-
pared the diamido-acid, which he states is insoluble in water, alcohol,
and ether. This body the author was also unable to prepare, and he
is of the opinion that Lindner worked with impure materials, and
that the body he describes was perhaps produced from the glass of
the sealed tube.
As regards bromamidosuccinic acid, traces of the diamido-acid are
always formed, whether excess of ammonia or of dibromosuccinic acid
be present. The pure acid can only be obtained by fractional precipi-
tation of the silver salt, the middle fractions consisting of pure silver
bromamidosuccinate. J. K. C.
Geometrical ForaiTJilge of Malelc and Fumaric Acids deduced
from their Products of Oxidation. By J. A. Le Bel {Bull, Soc.
Chim. [2], 37, 300 — 302). — By oxidation, fumaric acid yields racemic
acid, and maleic acid yields mesotartaric acid. The only supposition
which agrees with these and other known properties of the two acids
is that the four hydrogen-atoms are in the same plane as the carbon-
atoms and form a rectangle. In maleic acid, the rectangle is symme-
trical about a plane perpendicular to the rectangle and bisecting it.
The COOH-groups are at opposite ends of one side of the rectangle,
and the H-atoms at opposite ends of the other side. In fumaric acid,
the rectangle is symmetrical about its central point, the COOH-groups
being one at each end of one diagonal, and the H-atoms one at each
end of the other diagonal. It follows from these structures that
maleic acid can yield only mesotartaric acid, whilst fumaric acid can
yield only racemic acid. C. H. B.
Ethylic Methenyltricarboxylate and Ethylic Acetomalonate.
ORGANIC CHEMISTRY. 45
By M. Conrad and M. Guthzeit {Annalen, 214, 31 — 38). — EtJiylic
methenyltricarhoxylate, CH(C00Et)3, prepared by warming a mixture
of ethyl chlorocarbonate, benzene, and ethyl sodium malonate, crys-
tallises in needles or prisms which melt at 29°, and boil at 253^^. Its
sp. gr. at 19° is I'lO compared with water at 15°. The crystals are
soluble in ether and alcohol. On sapouificatiori, it yields malonic acid.
Methenyltricarboxylic acid could not be isolated.
Uthylic acetomalonate described by Ehrlich (Ber., 7, 892) decomposes
on saponification, forming alcohol, acetone, carbonic and acetic acids.
w. c. w.
Ethylic Ethenyltricarboxylate. By 0. A. Bischoff (Annalen,
214, 38 — -44). — The preparation of the ethylic salt of ethenyltricar-
boxylic acid has been described by Full (Ber., 14, 752). This com-
pound is a colourless liquid (b. p. 278°) soluble in alcohol and ether.
Its sp. gr. at 17° is 1*1089 compared with water at 15°. It is readily
saponified by a solution of soda, and oa decomposing the sodium salt,
ethenylt near boxy lie acid, COOH.CH2.CH(COOH)2 is obtained in pris-
matic crystals soluble in alcohol, ether, and water.
The acid melts at 159°, decomposing into carbonic and succinic
acids. Barium tri-ethenylcarboxylate crystallises in white prisms
sparingly soluble in hot water. The zinc salt contains 2 mols. H2O.
It is less soluble in hot than in cold water. W. C. W.
Ethylic Monochlorethenyltricarboxylate. By C. A. Btschoff
(Ajinalen, 214, 44— 53). — When a current of chlorine is passed through
warm ethylic ethenyltricarboxylate, the monochlorinated derivative,
CCl(C00Et).CH2.C00Et,
is produced. This substance is purified by distillation under reduced
pressure. It boils at 205 — 215° under 160 mm. pressure. Continued
boiling with dilute hydrochloric acid splits up the ethereal salt into
carbonic and fumaric acids. On saponification with an aqueous solu-
tion of potash, it yields malic acid (m. p. 130 — 135°), which appears to
be identical with the malic acid which Loydl (ibid., 192, 80) obtained
from fumaric acid. Treatment with alcoholic potash converts ethylic
monochlorethenyltricarboxylate into ethoxyethenyltricarboxylic acid.
w. c. w.
Ethereal Salts of Propenyltricarboxylic Acid. By C. A.
Bischoff (Annalen, 214, 53 — 58). — Mkylic projpenyltricarboxylate,
CHMe(C00Et).CH(C00Et)2, prepared by the action of ethyl a-bro-
mnpropionate on an alcoholic solution of the sodium compound of
ethyl malonate, is a colourless oil (b. p. 270°) miscible with alcohol
and ether. Its sp. gr. at 16° is 1*092. Diethylic monomethyl properiyU
tricarboxylate, COOEt.CH(COOEt).CHMe.COOMe, is obtained when
methylic a-chloropropionate is substituted for ethyl bromopropionate
in the above reaction. This liquid boils at 267°. It is soluble in alcohol
and ether. Its sp. gr. is 1*079 at 15° compared with water at 4°.
Fropenyltricarboxylic acid melts at 146°, splitting up into carbonic and
pyrotartaric acids and alcohol. The barium salt, Ba3(C6H506)2 is
sparingly soluble in water. W. C. W.
46 ABSTRACTS OF CHEMICAL PAPERS.
Ethylic Propyl- and Isopropyl-ethenyltricarboxylates. By
G. Waltz (Annalen, 214, 58—61). — Ethylic propylethenyltricarboxyl-
ate, CPr(COOEt)2.CH2.COOEt, prepared by the action of sodium
ethylate and propyl iodide on ethylic ethenyltricarboxylate, is a
colourless oil miscible with ether and alcohol. It boils at 280° with
partial decomposition. Its sp. gr. at 13° = 1'052. The free acid,
CPr(COOH)2.CH2.COOH,
forms lustrous needles (m. p. 148°) soluble in water, ether, and
alcohol. A solution of ammonium propylethenyltricarboxy late gives a
crystalline precipitate with barium, silver, and lead salts. Zinc, cal-
cium, iron, and copper are precipitated from hot solutions. The acid
begins to decompose at its melting point, yielding carbonic, propyl-
succinic, and traces of butyric acids.
Fropylsuccinic acid, CHPr(C00H).CH2.C00H, melts at 91°. The
neutral solution gives a white crystalline precipitate with silver and
lead salts.
Ethylic isopropylethenyltricarhoxylate was not obtained in a state of
purity. The impure compound decomposes at 180° forming isopropyl-
succinic acid (m. p. 114°). W. C. W.
Ethylic Isallylenetetracarboxylate. By C. A. Bischoff
(Annalen, 214, 61 — 67). — The preparation and properties of isallylene-
ietracarboxylic acid, (C00H.CH.>)2C(C00H)o, and of its ethyl salt
have already been described by the author (Abstr., 1881, 156). The
following salts were prepared : — C7H4Ag408, somewhat soluble in hot
water : C7H4Pb20e + H2O and CTHioZngOs are crystalline salts. The
tricarballyllic acid, obtained by heating isallylenetetracarboxylic acid,
is identical with the acid described by Miehle {Annalen, 190, 325).
w. c. w.
Tetrethylic Acetylenetetracarboxylate. By M. Conrad and C.
A. Bischoff {Annalen, 214, 68—72). — The ethereal salt,
(COOEt)2CH.CH(COOEt)2,
formed by the action of ethyl monochloromalonate on ethyl sodium
malonate, crystallises in needles (m. p. "1^°) soluble in alcohol, ether,
and benzene. It boils at 305° with partial decomposition. When
heated with hydrochloric acid or with alkalis, it splits up into alcohol,
carbonic and ethenyltricarboxylic acids. W. C. W.
Diethylic Acetylenetetracarboxylate. By M. Gothzeit {An-
nalen, 214, 72 — 75). — When an alcoholic solution of tetrethylic
acetylenetetracarboxylate is treated with potash at 0°, the diethyl salt,
COOEt.CH(COOH).CH(COOH).COOEt + iH^O,
is deposited. This substance forms deliquescent plates soluble in
alcohol and ether. It melts at 132° with decomposition, and at 180°
it splits up into carbonic and succinic anhydrides and ethyl succinate.
w. c. w.
Tetrethylic Dicarbontetracarboxylate. By M. Coxrad and M.
GuTHZEiT {Annalen, 214, 76—80). — Tetrethylic dicarbontetracar-
ORGANIC CHEMISTRY. 47
boxylate, (COOE^aC ! C(C00Et)2, prepared by warming an alcoholic
solution of sodium ethylate with ethyl chloromalonate, crystallises in
monoclinic plates soluble in ether and in boiling alcohol. It melts at
68° and boils at 325 — 328° with partial decomposition. On saponifying
it with potash solution, the potassium salt, C6H2O&K2, is obtained in
monoclinic prisms. The lead, zinc, and calcium (CeOsCao + 7H2O)
salts are crystalline ; the silver salt, AgiCeOs, explodes when heated.
.The free acid is an unstable compound. It decomposes below 100°.
w. c. w.
Action of Potassium Nitrite on Mucobromic Acid. By H.
B. Hill and C. R. Sanger (Ber.,15, 1906— 1910).— The reaction took
place in alcoholic solution ; on gently warming it, carbonic anhydride
was given off, and a reddish-yellow potassium salt, K2C3HN3O7, sepa-
rated out in small flat needles. This salt is easily soluble in cold water,
sparingly in dilute alcohol. When dry, it explodes on warming or
when struck, also on moistening it with concentrated mineral acids. It
is decomposed by water at 40°, but can be crystallised unchanged from
dilute potash. When heated with strong potash, a new and very un-
stable compound is obtained, the composition of which has not yet been
determined. By the action of bromine on K2C3HN3O7 suspended in
carbon bisulphide, the compound CsHBraNgOs was produced. It crys-
tallises like ammonium chloride, and is easily soluble in carbon bisul-
phide, sparingly in cold chloroform. On heating K2C3HN3O7 with
water or dilute alcohol to 40 — 60°, an evolution of carbonic anhydride,
hydrocyanic acid, and nitrous acid takes place, and, on evaporating
the solution, crystals of the composition KC3H2N04,H20 were ob-
tained which lost their water over sulphuric acid. This salt explodes
on heating. It is easily soluble in water, sparingly in alcohol.
From sodium nitrite and mucobromic acid, the corresponding sodium
salt, Na2C3HN307, could not be obtained, but, on heating the solution
to 40 — 60°, the compound Na03H2NO4,H2O was formed and crystal-
lised out on cooling. The calcium salt, Ca(C3H2N04)2,4H20, crystal-
lises in sparingly soluble prisms. Salts of barium, lead, copper, and
silver have also been prepared. Attempts to prepare the free acid
have as yet been unsuccessful.
The action of potassium nitrite on ethyl mucobromate was found to
differ from its action on the free acid, a compound of the formula
KCeHeNOe being formed. A. K. M.
Alkylthiosulphuric Acids. By W. Spring and E. Legeos (-Ber.„
15, 1938 — 1940). — The sodium salts of ethyl- and methyl-thiosul-
phuric acids, prepared by digesting equivalent quantities of the alco-
holic iodides with sodium thiosulphate, have already been described
(Ber., 7, 646 and 1162; also Ber., 15, 946). The authors have con-
tinued their experiments, and have succeeded in preparing sodium
salts of propyl-, primary isobutyl-, and amyl-thiosnlpburic acids. All
three crystallise well, and are soluble in water and in alcohol. When
decomposed, they yield disulphides of the radicles, sodium sulphate
and sulphurous anhydride. Attempts to make alkylthiosulphates con-
taining other radicles have been unsuccessful. With allyl and iso-
propyl iodides, the authors obtained allyl and isopropyl bisulphides,
48 ABSTRACTS OF CHEMICAL PAPERS.
togef^lier with sodium sulphate and sulphurous acid. Chloroform,
ethylidene dichloride, and some other similarly constituted bodies also
yielded negative results.
The conclusions drawn by the authors are that the only alkyl-
thiosulphates which can exist are those in which the alkyl-group is
primary and saturated, and that they are the more easily formed the
simpler the organic radicle. It also seems that compounds do not
exist in which more than one SgOaNa group is joined to one carbon-
atom.
Propyl bisulphide, (C3H7)2S2 (normal and iso-), butyl bisulphide,
(04119)282, and amyl bisulphide, (C5Hn)2S2, which were obtained in
course of the research, are liquids having the characteristic odour
and. other properties belonging to this class of compounds.
A. K. M.
Action of Phosphorus Pentachloride on Acid Amides.
Part II. By 0. Wallace (A^malen, 214, \9S—S27) .—Action of Phos-
phorus Pentachloride on the Amides of Monobasic Acids in which oie
Hydrogen-atom of the NH2 group has been replaced by a Hydrocarbon
Radicle. — The imidochloride, CMeCl ! NCeHiMe, obtained by the action
of phosphorus pentachloride on acetoparatoluidide, and the amines de-
rived from this compound, have already been described (this Journal,
1877, i, 91). Analogous products can be prepared from acetortho-
toluide. On carefully heating the imidochloride obtained in this way,
a base, O18H19OIN2 (m. p. 52°), is formed. Orthotolylacetamidine,
NHOvHv.OMe ! NO7H7, melts at 69° ; the corresponding para-com-
pound melts at 120°, and the mixed orthopara-amidine melts at 142°.
The imidochloride of benzoylbenzyl sulphamide, OPhCl 1 NS02Ph
(Abstr., 1878, 669) melts at 80°, and at a higher temperature decom-
poses into benzonitrile and benzenesulphonic chloride, instead of yield-
ing a new base. By the action of aniline on the chloride, phenylsulphO'
phenyl benzamidine, NHPh.OPh! NS02Ph, is produced. This amidine
crystallises in plates (m. p. 139°), soluble in alcohol and benzene. On
distillation it decomposes into diphenylamine, benzonitrile, and phenyl
sulphide.
TolylsulrphojphenyTbenzamidiney C6H4Me.NH.CPh !NS02Ph, forms
monoclinic crystals (m. p. 145°), soluble in alcohol and benzene. On
distillation, tolylphenylamine is produced.
Benzenesulphodiphenylamine, PhS02.NPh2, prepared by heating a
mixture of benzene sulphochloride and diphenylamine at 200°, crystal-
lises in silky needles (m. p. 124°), soluble in alcohol, ether, and ben-
zene. Benzene sulphanilide, PhS02.NHPh, forms octahedra, which
melt at 102°. It is completely decomposed by heating at 220° with
lead dioxide.
The products of the action of phosphorus pentachloride on mono-
and tri-chloracetanilide, and on mono-, di-, and tri-chloracetethyl-
amide, have been previously described by Kamenski (Abstr., 1880.
547).
The amidine, C4H30.C(NHEt) ! NEt, prepared by distilling ethyl-
amine pjromucamide, C4HsO.CONHEt, with phosphorus penta-
chloride (Abstr., 1881, 714), boils at 240°. It forms a crystalline
platinochloride. When phosphorus pentachloride and formanilide are
ORGANIC CHEMISTRY. 49
brought together, carbonic oxide and hydrochloric acid are evolved,
leaving a mixture of phosphorus oxyohloride and diphenvl-formami-
dine, NHPh.CH :NPh, melting at 137°.
II. Action of Phosphorus Pentachloride on those Amides of Mono-
basic Acids in which the Hydrogen of the 'NYii-group has heen com-
pletely replaced by Hydrocarbon lladlcles. — No new bases were obtained
by treating acetodipthylamide, MeCONEtj (b. p. 185°) or diphenyl
benzamide, PhCONPhg (m. p. 176°) with phosphorus pentachloride.
Dipheni/lacetaniide, MeCONPh,, (m. p. 101°), yields a base which was
not obtained in a state of purity. From acetomethijlanillde^
MeCONMePh,
a base is derived which probably has the composition CnHnClN'a.
Acetopiperidide when treated with phosphorus pentachloride yields
the chloride CMeClo.NCsHio. The following reaction takes place when
phosphorus pentachloride acts on diethylformamide : — ■
HCONEta + PCI5 = POCI3 + CHCla.NEta, and
2CHCl2.NEt2 = CioHigCN-^ + 3HC1.
III. Action of Phosphorus Pentachloride on the Amides of Dibasic
Acids. — Camphor ethyliniidethylimidiyie, Ci4Ho4N^20, prepared by heating
ethylamine camphorate with phosphorus pentachloride (Abstr., 1881,
284), is decomposed by hydrochloric acid at 200° into ethylamine
hydrochloride and camphoric ethylimide.
This decomposition may be represented by —
CgHu.O ! NEt p^
I I + H0.O = C8H:4<p);>NEt + NH^Et.
CO — NEt ^^
Camphor ethylimi'dethj^limidine can be prepared synthetically by
treating the product of the action of phosphoric chloride on cam-
phor ethylimide with ethylamine (Abstr., 1881, 285).
lY. Action of Phosphorus Pentachloride on the Amides of Oxalic
Acid. — An account of the substituted oxamides and formamides has
been previously published {Ber., 14, 735 — 751 ; this Journal, Abstr.,
1881, 717). Chloroxalethyline and many of its derivatives have also
been described (Abstr., 1880, 546—547). By the action of bromine
on a solution of chloroxalethyline in chloroform, cl dor oxalethy line
hydrobromide, CeHgClNsjHBr, and dibromide, CeHgClNajBrj, are pro-
duced. The crystals of the hydrobromide are colourless; those of
the dibromide have a deep red colour. A mixture of bromochlor-
oxalethyline hydrobromide, C6H8ClBrN2,HBr, and bromochloroxalethijline
dibromide, C6H8ClBrN2,Br2, is formed when bromine acts on a solution
of chloroxalethyline dibromide in chloroform. Bromochloroxalethyline
dibromide crystallises in red needles or prisms melting at 113". It is
soluble in alcohol and ether, and sparingly soluble in chloroform. The
hydrobromide forms bright red monocliuic prisms (m. p. 133°), which
dissolve freely in chloroform. Both the hydrobromide and the dibro-
mide are decomposed by hot water, yielding bromochloroxalethyline,
CeHgBrClNo. From this solution, the fiee base is obtained by adding
VOL. XLIV. e
50 ABSTRACTS OF CHEMICAL PAPERS.
an alkali to the solution, and extracting the mixture with chloroform.
On evaporating the extract, the base remains as an oily liquid, which
slowly solidifies to a crystalline mass. The hydrcchloride,
CeH3rClN2,HCl,
and the nitrate form prisms containing water of crystallisation. The
^latinochloride, (C6H8BrClN2,HCl)2,PtCl4, and the silver salt^
(C6H8BrClN02,AgNO3,
can be recrystallised from alcohol.
Chloroxalethyline is decomposed by dilute sulphuric acid at 240**,
with formation of ammonia and ethylamine. On oxidation with
chromic acid, ethyloxamide, oxalic and (probably) ethyloxamic acids
are produced. When a mixture of chloroxalethyline and lime is dis-
tilled, pyrroline, ammonium chloride, and para-oxalmethyline, CiHeNj,
are formed. This base crystallises in silky needles, melting at 136°.
JDioxaletUyline, Ci2Hi8lS'4, prepared by the action of sodium on chlor-
oxalethyline, is an oily liquid which boils above 300°. On distilla-
tion with lime, oxalethyline yields pyrroline, hydrocyanic acid, para-
oxalmethyline, and ammonium chloride. When oxalethyline is
heated with dilute sulphuric acid at 240°, it yields ethylamine, and
on oxidation with potassium permanganate it splits up into ammonia,
acetic and oxalic acids.
The derivatives of oxalmethyline and propyline have been pre-
viously described (Abstr., 1881, 572).
Ghloroxalamyline, Ci2H2iClN'2, prepared by the action of phosphoric
chloride on di-amyloxamide (m. p. 128°), is a liquid boiling at 267 —
270°. It is not miscible with water. The hydrochloride and platino-
chloride are crystalline.
Oxalmethyline has been shown to be identical with methyl-glyoxaline,
ISTH : C<^g'>N (Abstr., 1882, 821), but oxalethyline and oxalpropy-
line are not identical with propyl- and amyl-glyoxalines.
The constitutional formulae of these two oxalines is either —
/CH2.CH2, CHMe^
nh:c< \n or nh:c/ >n
.CH2.CH2^ ^CMe2^
nh:c< >ch2 or nh:c< ^.
W. C. W.
Mannitine, a New Alkaloid obtained from Mannitol. By S.
SciCHiLONE and A. Denaro (Gazzetta, 12, 416 — 424). — This base,
C6H8N2, is formed by distilling mannite with ammonium chloride, the
reaction, which takes place according to the equation, C6H6(OH)6 4-
2(NH3,HC1) =2HC1 + 6H2O + CeHsNa, being analogous to that of
sal-ammoniac on ethyl alcohol, by which Berthelot obtained ethyl-
amine (Ann. Chim. Fliys. [3], 38, 63), and to that of the same
salt on glycerol, by which Etard obtained glycoline, CioHioN'2
ORGANIC CHEMISTRY. 51'
(Abstr., 1881, 708). The distillate is a red- brown liquid, having a
strong but pleasant odour, and containing a few drops of oil, the
quantity of which is increased on adding strong potash-ley ; and on
agitating the liquid several times with ether, separating the ethereal
solution by a tap-f iinnel, and distilling it, the mannitine remains in
the form of a brown strong- smelling oil soluble in hydrochloric acid,
and precipitated therefrom by potash. It was purified by converting
it into hydrochloride, and decomposing that salt with potash, and then
gave by analysis 66*77 per cent. C, 6-32 H, and 25*84 N, agreeing
nearly with the formula CeHgNg, which requires 66-67 C, 7"40 H, and
25'93 N". Its vapour-density, determined by V. Meyer's method, is
3*82 (air = 1), the formula requiring 3' 74. Mannitine boils without
alteration at 170° (bar. 760 mm.). It dissolves in alcohol, in ether,
and to a perceptible amount in water ; it has a very bitter taste, and
exhibits the following reactions : with sodium phosphomolybdate, im-
mediate orange-yellow precipitate, soluble in ammonia ; with potassio-
mercuric iodide, reddish-yellow amorphous precipitate; with iodised
potassium iodide, reddish-yellow, insoluble in dilute hydrochloric acid ;
with mercuric iodide, flesh-coloured precipitate soluble in ammonium
chloride ; with Frohdes reagent, indistinct yellow coloration ; with
auric chloride, black precipitate. H. W.
Benzene Formulae. By A. Lade^burg {Ber., 15, 1782—1783).—
Ac3ording to Clans, the best expression of the atomic relationship in
benzene is shown by the appended figure.
1<
\
Claus meets the objection raised by the author, that when the
atomic linking only is taken into consideration, the combinations 1 : 2,
1 : 4, and 1 : 6, are equal, by quoting another of his statements, that
the geometrical relationships of a formula must represent correspond-
ing relative attractions of the atoms, and that therefore 1 : 4, as repre-
senting a diagonal, cannot be equal to 1 : 2, which expresses a side.
To this the author replies that such an assumption necessitates the
hypothesis that one of the combining affiaities of the carbon-atom
is different from the rest. As such a hypothesis is opposed to all
known facts, he considers the above graphic formula untenable.
J. K. C.
Benzene Formulae. By K. Meyer {Ber., 15, 1823— 1828). —The
so-called " diagonal " formula, defended by Claus, has been repre-
sented by the author as only allowing the possibility of two isomeric
bisubstitution products : this statement being denied by Claus, the
author proceeds to explain his reasons. In the prism formula, the
positions represented by the two kinds of sides, differ from one
another in other respects than in their functions as sides of triangles
or quadrilaterals. For example, the two carbon-atoms 1 and 3, besides
e 2
52 ABSTRACTS OF CHEMICAL PAPER?.
being in direct combination, are also bonnd indirectly tlironjrh 5,
whilst 1 and 4 are indirectly bound by two atoms, 3 and 6 or 5 and 2.
\7'
6
In other words, the difPerence of the positions (1, 3) and (1, 4) is
not a geometrical one only, but expresses also a difference in the
atomic linking. On the other hand, in the diagonal formula —
1<
k
the indirect communication between (1, 2) is exactly the same as
between (1, 4), for instance, (1, 6, 3, 2) and (1, 6, 3, 4), &c.
To this Glaus answers that the diagonal Unkings have a different
value from the ordinary or side bonds, but this assumption the author
regards as arbitrary and as introducing a new definition into the
science. The objection to the prism formula, that it does not express
the well-known tendency of ortho-compounds to form " inner anhy-
drides," becomes groundless, -when it is recollected that a similar
objection was raised against the formulae of quinones.
Glaus considers that it is more than probable that the formula of
naphthalene is unsymmetrical, as it would be if represented by the
diagonal formula. If such were the case, however, there would exist
four isomeric mono-derivatives, whilst as yet only two have been dis-
covered. Molecules like those of benzene and naphthalene, which
possess such an extraordinary degree of stability, must exhibit a very
stable equilibrium in the position of the various component atoms,
and this would be best attained by a symmetrical structure.
J. K. C.
Isodnrene, Isodurylic Acids, and the Third Trimethyl ben-
zene. By 0. Jacobsen (Ber., 15, 1853 — 1858). — Isodurene is obtained
by the action of methyl chloride and aluminium chloride on niesitylene
(b. p. 195°). Dibromisodurene (m. p. 209") is formed from this by
treating it with excess of bromine in presence of iodine : it crystal-
lises from hot alcohol in long needles. The dinitro-compound crystal-
lises from the same solvent in colourless prisms melting at 156*^. The
sulphonic acid was obtained in fine plates, and its barium and sodium
salts prepared : the corresponding amide (m. p. 118") may be obtained
in thin needles from its aqueous solution, by the usual method. By
fusing sodium isodurenesulph(mate with potash, isodurenol is obtained
as a crystalline mass melting at 108°.
Isodurylic Acids. — Isodurene is boiled for some time with dilute
nitric acid, and after removal of the nitro-compounds the liquid is
steam-distilled. From the mixture of the three acids, the a-acid may
be separated as crystalline barium salt, the other two acids being left
ORGANIC CHEMISTRY. 53
in the iincrystallisable mother-liquor : in its properties it agrees with
Bielefeldt's description. The remaining- acids are precipitated by
hydrochloric acid, and separated by crystallisation from petroleum.
The less soluble, termed )3-isodurylic acid, is obtained in hard
shining prisms, melting at 151°: its calcium salt, crystallises from
water in a mass consisting of fine needles. On evaporating the petro-
leum solution, 7-isodurylic acid (m. p. 84 — 85°) is left behind in
crystalline crusts, and may be purified from adhering ^-acid by taking
advantage of the greater solubility of its calcium salt. It is preci-
pitated from the latter in flakes, and crystallises from alcohol and
water in needles. The barium and potassium salts are uncrystalli sable.
By the oxidation of isodurenesulphonamide with potassium perman-
ganate, sulphaminisodurylic acids are formed, , corresponding to the
above jS- and 7-acids.
The three isodurylic acids were distilled with lime in order to ascer-
tain their constitution. a-Isodury lie acid yields the third trimethyl-
benzene called by the author hemellithene : it is therefore represented
as C6HoMe3COOH [COOH : Me : Me : Me = 1 : 3 : 4: 5]. From the
/3-acid [COOH : Me: Me: Me = 1 : 2 :4 :6] pure mesitylene was ob-
tained, and pseudocumene from the 7-acid, [COOH : Me : Me : Me =
1:3:5:6]. Hemellithene, CeHaMeg [Me : Me : Me = 1 : 2 : 3], was ob-
tained pure from its sulphamide by heating it with hydrochloric acid
at 200 . It boils at 168 — 170°. Tribromhemellithene crystallises
from alcohol in fine needles, melting at 245°. SemelUthenesul'phonic
acid crystallises well in six-sided plates, and its amide in short trans-
parent prisms, melting at 196°. Coal-tar cumene does not contain
hemellithene. J. K. C.
Action of Aluminium Chloride on the Monohalogen Deriva-
tives of Benzene. By 0. v. Dumreicher {Ber., 15, 1866 — 1870).—
Chlorobenzene is not acted on even when boiled for several days with
aluminium chloride ; with bromobenzene, however, a lively reaction
sets in above 100°, hydrochloric and hydrobromic acids are evolved in
large quantities, and after eight or ten hours a black mass is formed.
When this is steam- distilled, and the oil fractioned, pure benzene, and
two dibromobenzenes, para and liquid, together with unaltered bromo-
benzene, are obtained, the benzene and dibromobenzene being formed
in equal molecular weights.
lodobenzene reacts with aluminium chloride at 80°, the liquid be-
coming violet from separation of iodine. No hydriodic acid is given
oif, the products of the reaction being benzene and diiodobenzene,
with large quantities of iodine. The benzene formed is very large in
comparison with the diiodobenzene, and the latter consists chiefly of
the para-compound. It appears that the hydriodic acid formed
decomposes at once with iodobenzene into free iodine and benzene.
The author explains the action of aluminium chloride on bromo-
benzene by the following equations : —
(1.) Allele + CeHsBr = BrCl + Al^Cls-CeHj.
(2.) CeHjBr + BrCl = CeH.Br^ + HCl.
(3.) AUClsCCeHs) + HCl = AI2CI6 + CeHe. J. K. C.
'54 ABSTRACTS OF CHEMICAL PAPERS.
Metatoluidine. By A. Ehrltch (Ber., 15, 2009— 2012).— The
greater portion of this paper describes improvements in the details of
the methods for the preparation of metatoluidine proposed by Beil-
stein and Kuhlberg and by O. Widman.
Metatoluylglycocine is obtained as a non -crystalline mass by the
action of 2 mols. metatoluidine in ethereal solution on 1 mol. raono-
cliloracetic acid. The copper salt, (C9HiolS'02)2Cu,2H20, forms brilliant
grass-green plates. Ethylmetatoluylghjcordne, CH2(NH.C7H7).COOEt
(ethyl metatoluylamidoacetate), is obtained by the action of metato-
luidine on ethyl chloracetate ; it crystallises in flat plates melting at
68°, and is readily soluble in alcohol and ether, but only sparingly in
hot water. By the action of ammonia in alcoholic solution, it is
converted into the amide of toluylglycocine crystallising in long
spear-shaped needles. A. J. G.
Rosaniline-derivatives. By E. Noelting (Bull. Soc. Chim. [2],
37, 390— 392).— The introduction of the NOa-group into the halogen-
derivatives of the hydrocarbons of the benzene series renders the
halogen more easily displaceable. Ammonia, for example, has no
action on monochlorobenzene, but yields dinitraniline by its action on
monochlorodinitrobenzene. The chloro-derivatives of the benzene
series are without action on rosaniline, but the chloronitro-derivatives
form substitution-products which give various shades of brown and
maroon. The author has obtained such compounds by acting on
rosaniline with [1:2:4] chlorodinitrobenzene chlorotrinitrobenzene,
and a mixture of chloronitronaphthalenes obtained by treating mono-
chloronaphthalene with a mixture of nitric and sulphuric acids.
1 mol. rosaniline is heated with 1 mol. of the chloronitro-derivative,
e.g., chlorodinitrobenzene, and some glacial acetic acid in an oil- bath at
180—200° for five or six hours. When cold, the product is extracted
with very dilute acid to remove unaltered rosaniline, then dried and
treated with benzene to remove excess of the chloride and resinous
compounds. The residue consists of the hydrochloride of the new
base, mixed with carbonaceous products. The hydrochloride and the
sulphate are insoluble in water, but soluble in alcohol ; the acetate is
soluble both in water and in alcohol. The hydrochloride is extracted
from the residue by means of alcohol, and the solution mixed with
sodium hydroxide, which precipitates the base in the form of a paste.
The base is dissolved in dilute acetic acid, and can then be used for
dyeing. On silk, it yields a very fast violet garnet colour, approaching
maroon. The dried base forms an amorphous black powder ; the salts
are green, with metallic lustre, but are not crystalline.
The new colouring matter formed from chlorodinitrobenzene is in
all probability dinitrophenyl-rosaniline formed in accordance with the
equation C2oHi9N3,H20 + C6H3Cl(NOo), = C2oHi8N3.C6H3(N02)2,HCl +
H2O. Attempts to introduce two or three dinitrophenyl-groups were
unsuccessful. Any excess of chlorodinitrobenzene always remained
unaltered. No satisfactory results were obtained by heating neutral
or alkaline alcoholic solutions in sealed tubes. It is worthy of note
that the introduction of two nitroxyl-groups changes the colour of
monophenylrosaniHne from violet to maroon.
ORGANIC CHEMISTRY. 55
Phenylrosaniliae is converted into a sulphonic acid by the action of
strong sulphuric acid. Dinitrophenylrosaniline is carbonised without
formation of sulphonic acid. The sulphonic acid may, however, be
obtained by the action of chlorosulphonic acid SO3HCI. It forms
salts which yield colours very similar to those of the original base.
Nitronaphthylrosaniline has a much more violet colour than the
nitrophenyl- derivative. C. H. B.
Azylines. By E. Ltppmann and F. Fleissner (Monatsh. Chem.^ 3,
705 — 714). — The authors apply the term azylifies to a series of bases
obtained by the action of nitric oxide on tertiary amines, and in which
the tetravalent-group >N— N<^ is contained in union with benzene
nuclei. At present, tertiary azylines of the aromatic series alone haye
been obtained. These compounds are crystalline, and of red colour;
dissolve in hydrochloric acid to fine purple liquids, and in acetic acid to
green solutions, from which they are reprecipitated in the amorphous
form on adding water. They yield crystalline compounds with the
chlorides of platinum, iron, gold, &c. The picrates are crystalline
and sparingly soluble. When heated with alcoholic iodides at 100°,
the azylines form ammonium compounds. With nitrous acid, nitroso-
coinpounds are formed ; as these give Liebermann's colour-reaction
with phenol and sulphuric acid, the tertiary nature of the compounds
is rendered highly probable. If treated with stannous chloride or with
hydriodic acid and phosphorus, the azylines yield unstable hydro-com-
pounds, from which crystalline platinochlorides can be prepared.
Dimethylanilineazyline, NMea-CeHg I N.N ! CeHa-NMca (m. p. 266^),
has been already described , (Abstr., 1881, ] 61, the formula, CgHiaNv,
there ascribed to it being due to an error in analysis). Its formation
is represented by the equation 2C8HiiN + 2N0 = 2H2O + CieHisNi.
On oxidation, it yields oxalic acid and carbonic anhydride. The^^^'cra^e
js obtained as an alcoholate, Ci6Hi8N4,C6H3(N02)30 + CaHeO, in
brilliant leaf-green needles.
IJiethijlmiilineazyline^ GaoH26N4 (m. p.l70°), forms red needles soluble
in chloroform and hot alcohol, sparingly soluble in cold alcohol. The
picrate, C2oH26N4.2[C6H3(N02)30], crystallises in yellow needles.
JJipi'opylanilineazyUne, C24H34N4, crystallises in red tables of the
rhombic system, melting at 90°. The crystals were measured by
Scrauf, and gave axial relations a : b : c = 1 : 0*629 : 0*913. The
most important faces are 101 : 100 : 110 : 001.
DihiLtylobnilineazyline, C28II42N4, crystallises in needles melting at
158°.
Biamylanilineazyline, C32H54N4 (m. p. 115°), forms red spear-shaped
crystals, soluble in hot alcohol. It dissolves in concentrated hydros
chloric acid, but is decomposed on boiling. A. J. G.
Trimethylphosphobenzobetaine. By A. Michaelis and L.
CziMATis (-Ber., 15, 2018 — 2020). — Trimethylphosphobenzobetaine is
obtained as chloride by the oxidation of paratolyltrimethylphospho-
nium chloride with potassium permanganate at a temperature of 55*^.
The chloride forms short, thick, brilliant, colourless prisms of %he
56 ABSTRACTS OF CHEMICAL PAPERS.
formula C6H4(COOH),PMe3Cl ; it is insoluble in ether, soluble in hot
alcohol, and very soluble in water. It is decomposed by heat. The
platinochloride is obtained as a light yellow crystalline precipitate.
-CO-
The free betaine, CJii<^'p^ '^0,3H20, is obtained by neutralisation
of a solution of the chloride ; it crystallises in rhombohedrons, and
effloresces readily. It does not give salts with bases, but with acids it
gives well characterised compounds. The acetate crystallises in
slender needles of nacreous lustre, the nitrate in needles. With
excess of dilute sulphuric acid, it gives an acid salt also crystallising
in needles. On heating the chloride with potash, it is decomposed
according to the equation —
C6H4(COOH).PMe3Cl + KOH = CeHg.COOH + PMcaO + KCl.
By the action of potassium permanganate, on the addition-product
of ethylene bromide and dimethyltolylphosphine, a compound,
C6H4(CGOH).PMe20,
is obtained ; it crystallises in colourless prisms of faint acid taste,
melts at 243*^, and can be< sublimed with but little decomposition.
A. J. G.
Formation and Decomposition of Acetanilide. By L. Meyer
(Ber., 15, 1977 — 1978). — With regard to the formation of acetanilide,
the results obtained at 130° by Steudel in the author's laboratory
agree with those of Menschutkin ; at 155° a complete reaction never
takes place, but in the reverse reaction an impoiiant difference occurs.
According to Menschutkin, the incompleteness of the reaction is due
to the resulting water reacting on the acetanilide and partially decora-
posing it ; but on heating acetanilide with water at 130° for some
time, no trace of an acid reaction could be obtained, so that the
incompleteness of the reaction cannot be due to that cause.
A. J. G.
Constitution of the Azimido-compounds. By P. Griess (Ber.,
15, 1878 — 1882). — Under the above definition, the author includes
those bodies which have so far been obtained only by the action of
nitrous acid on aromatic orthodiamido-compounds, the first of which
was prepared by Hofmann from orthodiamidonitrobenzene. Amongst
others, two have been obtained by the author from (3- and 7-diamido-
benzoic acids. Two different views of the constitution of these
bodies have been proposed, the one by Keknle, and the other by
Ladenburg. According to the former, Hofmann's compound would be
represented by NOa.CgNa/ "^N, while Ladenburg assigns the for-
/^
mula NOa.OeHsCNHa)^ II .
The author's investigations, however, lead him to represent the
ORGANIC OHEMISTEY. 57
above compound thus : NOz-CeHgC | yNH, and he bases his view on
the following facts : —
[3- and ^-nitrouramido-benzoic acids,
COOH (1) (1)
NO2.C6H./NH.CO.NH3 (3) (4)
^NH^ (4) (3)
when heated to boiling with concentrated potash-solution, are both
converted into ^-azimidobenzoic acid with formation of ammonia and
carbonic anhydride.
According to Kekule's view, two isomeric acids would be formed ;
whilst, if Ladenburg's view were correct, the production of an azimido-
benzoic acid would in this case be impossible.
When the above fS- and ^-acids are treated with tin and dilute
hydrochloric acid, they are converted into the corresponding diami do-
acids, which by nitrous acid are converted into the same azimido-
uramidobenzoic acid, a fact which only admits of- explanation when
the formula proposed by the author is employed.
In the same manner, 7-nitrouramidobenzoic acid can be converted
into azimido-compounds; the a- and e-acids, however, react in a
totally different way. J. K. C.
Mixed Aromatic Tertiary Phosphines. By L. Czimatis (J5er.,
15, 2014 — 2018). — These compounds were prepared from the homo-
logues of phosphenyl chloride by the action of the zinc alkyls.
Faradimethyltoli/lphosphine, CeHiMe.PMea, is a colourless liquid of
disagreeable odour ; it boils at 210°, and does not solidify at — 10° ;
it has basic properties, and dissolves in acids ; the chloride yields a
yellow flocculent precipitate with platinum chloride. It does not
oxidise on exposure to air, but is converted by mercuric oxide into
dimethyltolylphosjphine oxide, C6H4Me.PMeO, forming a thick oily
liquid. With mercuric chloride, this yields the double salt,
C6H4Me.PMe20,HgCl2,H20,
crystallising in slender silky needles, melting at 156°. Methyl iodide
uuites violently with dimethyltolylphosphine, yielding the phos-
phonium iodide, C6H4Me.PMe3l ; it crystallises in colourless needles
melting at 255°, readily soluble in water and hot alcohol, sparingly in
cold alcohol, insoluble in ether. With mercuric chloride it gives an
unstable double salt crystallising in needles. The hydroxide is obtained
by the action of silver oxide and water as a strongly basic deliquescent
mass ; on treatment with hydrochloric acid and platinum chloride, the
platinochloride, (C6H4Me.PMe3Cl)2,PtCl4, is obtained in orange-yellow
plates melting at 230°. Trimethy Italy lj)hosphonium periodide,
C6H4Me.PMe3l3,
obtained by the action of iodine on the iodide, crystallises in steel-
blue rhombs, soluble in alcohol, and sparingly in benzene and ether.
Dimethyltolylphosphine combines with benzyl chloride to an uncrys-
B.p.
Diff.
. . 210°
20°
.. 240
20
Diff.
20°
20
58 .IBSTRACTS OP CHEMICAL PAPERS.
talline mass ; the platinochloride, (CflH4Me.PMe2.ClC7H7)2,PtCl4, melts
at 226°.
ParadiefhyltohjlphosjpJiine, C6H4Me.PEt2, boils at 240°, and resembles
the preceding compound. The methiodide crystallises in colourless
needles melting at 137° ; the platinochloride in clear yellow plates.
Dimethylxijlyljphosjphine, CeHaMca-PMea, is a colourless liquid boih'ng
at 230°.
Biethylxyhjljphosfhine, CeHsMea.PEta, is a thickish liquid of faint
colour, boiling at 260°. The methiodide (m. p. 90°), and ethiodide
(m. p. 136°), form white crystalline powders, readily soluble in water
and hot alcohol, insoluble in ether. Methyldiethylphosphonium
platinochloride crystallises in cadmium-yellow rhombic plates, melting
at 202°.
A comparison of the boiling points of the phosphines shows a rise
of 20° for the entry of a methyl-group into the aromatic nucleus, whilst
the difference of boiling points of the members of the series is 30°.
B.p.
CeHs.PMes 190° C6H4Me.PMe2
C6H5.PEt2 220 CeH^Me.PEts
B.p.
CeHsMes.PMej 230°
CeHsMes.PEta 260
Dimethylphenylphosphine and carbon bisulphide, when mixed in
ethereal solution, give a compound of the formula C6H5.PMe2,CS2,
crystallising in glistening red scales, soluble in carbon bisulphide, in-
soluble in ether. It melts in open tubes, with dissociation, at 97° ; in
closed tubes at 101°. It has basic properties, is dissolved by dilute
acids, and reprecipitated by soda. The platinochloride,
(C6H5.PMe2,HCl,CS2)2,PtCl4,
is obtained as an amorphous pale yellow precipitate; on exposure to
air, it loses carbon bisulphide, and is converted into dimethylphos-
phonium platinochloride. When the original compound is treated with
dry hydrochloric acid or methyl iodide, it is decomposed, carbon bisul-
phide being eliminated and phosphonium compounds formed. Water
decomposes the compound slowly at ordinary temperatures; rapidly
on heating.
Dimethyltolylphosphine unites with carbon bisulphide, forming
clear red plates of the formula CeHiMePMezjCSz, melting at 110° in
an open tube, at 116° in closed tubes. It closely resembles the pre-
ceding compound ; the platinochloride, however, is more stable when
exposed to the air.
Dimethyl xylylphosphine and carbon bisulphide form the compound
C6H3Me2.PMe2,CS2 ; it crystallises in clear red plates, and melts at
115° in open, and at 121° in closed tubes.
Diethylphenylphosphine unites slowly with carbon bisulphide,
forming a red crystalline product which could not be obtained in a
state of sufi&cient purity for analysis. A. J. Gr.
Action of Potassium Carbonate on the Chlorides of Benzyl
and Benzylene. Bj J. Meunier {Bull. Soc. Chim. [2], 38, 159—
ORGANIC CHEMISTRY. 59
160). — By heating ethylene bromide with an aqueous solution of
potassium carbonate, Zeller and Hiifner have obtained glycol directly
(this Journal, 1876, ii, 64) ; the author has studied an analogous
reaction with benzyl and benzylene chlorides. In the case of benzyl
chloride the corresponding or benzylic alcohol was obtained, but with
benzylene chloride benzaldehyde was formed, the yield being two-
thirds of that required by theory. Y. H. Y.
Isobutyl- and Amyl- phenols. By A. Liebmann (Ber., 15, 1990 —
1992). — Isobutylphenyl ethyl oxide boils at 241 — 242° uncorr. (not
234 — 236°, as given in the author's previous communications, Abstr.,
1882, 171, 727). By treatment with nitric acid, it yields the nitro^
ether as an oil volatile with water vapour, boiling with decomposi-
tion at about 300"", and yielding the amido-ether on reduction. Amyl-
phenyl ethyl oxide boils at 259 — 261°, and yields mononitro- and
amido-compounds like the above. A. J. G.
Nitro-derivatives of the Cresols. By E. Nolting and E. v.
Salis (Ber., 15, 1858 — 1865). — Dinitro-paracresol. — The ethylic ether
of this body is prepared by treating the silver salt suspended in alcohol
with ethyl bromide or iodide ; it melts at 73°. The corresponding
diamido-salt, of which only the hydrochloride was prepared, shows the
characteristic reactions of metadiamides.
Dinitro-orthocresol, C6H2Me(N02)2.0H [N'Oz : NO2 = 4:6], agrees
in all its properties with that obtained by Picard from saffron sub-
stitute. The ethylic ether melts at 46°. The barium salt crystallises
in shining yellow needles, easily soluble in hot water. The hydro-
chloride of the diamido-compound decomposes in the air, and must be
evaporated in a stream of sulphuretted hydrogen.
Trinitro-cresul, obtained from coal-tar cresol, is identical with that
prepared from meta-cresol : it separates from water in slender
yellowish-white needles melting at 106°. Like picric acid, it forms
molecular compounds with hydrocarbons. Its composition is repre-
sented by the formula —
[NO2 : OH :N02: Me : NO2 = 1 : 2 : 3 : 4 : 5].
The ethyl ether is easily converted into trinitro-toluidine by treat-
ment with ammonia ; no separation of a nitro-group occurs as would
be the case if two of these groups were in the ortho-position to each
other. The ethylic ether may be prepared by treating the silver salt
with ethyl bromide, and forms thick white needles, melting at 72°.
Trinitro-metatoluidine forms small crystals melting at 126°, very
soluble in alcohol and ether, and having weak acid characteristics.
Heated with alkaline solutions, it is convered into trinitro- cresol.
J. K. C.
Fusion of Orcinol and Gallic Acid with Soda. By L. Baeth
and J. ScHEEDER (Monatsh. Chem., 3, 645 — 650). — Orcinol, when
fused with sodium hydroxide, yields resorcinol (15 — 16 per cent.),
phloroglucol (about 1*5 per cent.), pyrocatechol (1 — 1'5 per cent.},
and a new body, C13H12O4 (about 5 per cent.). This latter is, in all
probability, tetrahi/droxydiphe'nlymethane, CH2[C6H3(OH)2]2, it forms
long, satiny, snow-white needles, readily soluble in alcohol and ether ;
60 ABSTRACTS OF CHEMICAL PAPERS.
it commences to decompose at 260°. It gives no coloration with
ferric chloride. In this reaction, it would appear that the methyl-group
is first oxidised, and then split oif, so that resorcinol is formed, which
by further oxidation yields phloroglucol: a very large proportion of
the orcinol however is completely oxidised. The substance, C13HJ2O4,
is an intermediate product, and the catechol is due to a secondary
reaction. In accordance with this view, when the heating is continued
further, little but phloroglucol is obtained.
By the action of fused soda on gallic acid, phloroglucol is formed
in small quantity (0*6 — 0*8 per cent.) in addition to pyrogallol and
hexhydroxydiphenyl (Abstr., 1879, 926).
Catechol is acted on by soda at a high temperature only, and is then
completely oxidised. Quinol also is but slowly attacked by soda ;
the products of the reaction have not yet been obtained in the pure
state. A. J. G.
Methylarbutin. By H. Schiff (Ber., 15, 1841— 1844).— This
body has already been prepared by Michael- from me thylquinol and
acetochlorhydrose ; it was thought advisable to prepare it by another
method, and to compare the substances obtained. Equal volumes of
methyl alcohol solutions of methyl iodide and potassium hydroxide,
were gradually added to a solution of arbutin in the same medium,
the mixture being boiled after each addition : after concentration and
cooling, the methylarbutin- which separated was purified by repeated
crystallisation from water ; it was found to differ in two points from
Michael's preparation : it melted at 175 — 176° (168 — 169 Michael),
and contained 1 mol. H2O instead of half a molecule. Mixed with
arbutin (m. p. 187°) it melted at a much lower temperature. From
concentrated solutions containing potassium iodide it can be recrys-
tallised free from water. It is soluble in water especially when hot,
and in alcohol, but only sparingly in ether. Commercial arbutin con-
tains about 30 per cent, methylarbutin, identical with that obtained
by the author. Whether the latter is the same as that prepared by
Michael is still open to question. J. K. C.
Di-isobutylquinol. By S. Schubert (Monatsh, Cliem., 3, 680 —
687). — Di-isobutylquinol (paradi-isobutoxijlenzene)^ C6H4(C4H90)2, is
prepared by heating together quinol, potassium isobutyl sulphate, and
potassium hydroxide, in sealed tubes, for 4 — 5 hours at 150°. It forms
a colourless leafy crystalline mass of fatty lustre, is insoluble in water,
more soluble in benzene and light petroleum, readily soluble in
alcohol and in hot glacial acetic acid. It boils at about 262°. By the
action of chlorine, it yields chloranil, dichlorodl-isobutylquinol, crystal-
lising in colourless rhombic plates, and tetrachlorodi-isohutylquinol,
forming long, colourless, interlaced needles, of silky lustre. The only
bromine-derivative obtained was dibrotnodi-isobutylquinol, crystallising
in colourless quadratic plates. Tetranitrodi-isobutylquinol crystallises
in long thin needles, sparingly soluble in water, readily soluble in
alcohol, ether, and hot glacial acetic acid. A. J. Gr.
Compounds of Benzo- and Tolu-quinol with Amines and of
Quinone with Nitranilines. By A. Heberand {Ber., 15, 1973 —
ORGANIC CHEMISTRY. 61
1976). — Occasionally, in tlie preparation of quinonedianilide, a com-
pound of quinol and aniline, C6H4(OH)2,(C6H5NH2)2, is found in the
mother-liquor. It forms large micaeous plates, melting at 89 — 90°,
and is readily soluble in hot water and in alcohol. In aqueous solution,
it is readily oxidised to quinonedianilide. It is decomposed when boiled
with benzene, and quinol crystallises ont, but the same substance can
be prepared by boiling quinol and aniline in aqueous solution. The
corresponding paratoluidine compound, C6lIt('OH)2,(C7H7.NHo)2 (m. p.
95 — 98°), prepared directly from quinol, resembles the aniline com-
pound. Orthotoluidine and naphthylamine compounds could not be
obtained in the pure state.
Attempts were made to prepare siniilar compounds with phenol,
resorcinol, and pyrogallol, but without success. With toluquinol, an
aniline compound, crystallising in white needles, melting at 82 — 85°,
and a paratoluidine compound, crystallising in nacreous plates, melt-
ing at 90°, were obtained.
Quinone and Paranitr aniline. — On mixing hot alcoholic solutions of
these bodies and cooling, large dark-red crystals (m. p. 115 — 120°)
separate, which by heating or by boiling with water are resolved into
their constituents. The composition of this substance varied in dif-
ferent preparations from —
C6H40,CeH4(N02)NH2, to 2C6H402,3(N-02.C6H4.NH2).
In acetic acid solution, or by long boiling with alcohol, the course of
the reaction is different, quinonedinitranilide being formed in small
brown needles, together with a substance of acid nature, crystallising
in red-violet plates, melting at 18B°.
Quinone and Orthonitraniline. — Solutions of these substances, when
mixed, yield large red crystals melting at 94 — 97° ; with excess of
nitraniline, a new body of the formula C6H402,2(NOo.C6H2.NH2), is
obtained. When boiled with glacial acetic acid, it yielded the corre-
sponding diniiranilide, crystallising in brownish-red needles. Meta-
nitraniline and quinone yield nothing but quinonedimetunitranilide,
forraing yellowish-brown needles.
With orthonitraniline toluquinone gives an addition- product (m. p.
37°) resembling those already described. A. J. Gr.
Compounds of Vanillin with Pyrogallol and with Phloro-
glucinol. By C. Etti (Monatsh. Chem., 3, 637— 644). —Singer has
recently shown ( Abstr., 1882, 1122) thsit the deep red coloration im-
parted to pine wood by phloroglucol in presence- of hydrochloric acid,
is due to a compound formed with the vanillin which is present in the
wood. The author has further investigated this compound, and also
the analogous one of pyrogallol with vanillin.
Pyrogallovanillem, C2oHi«08, is prepared by mixing vanillin and pyro-
gallol with alcohol and an excess of concentrated hydrochloric acid ;
it forms colourless crystals destitute of odour, insoluble in water,
sparingly soluble in ether, readily soluble in strong alcohol. By long
standing over sulphuric acid, or by drying at 110°, 2 mols. of the sub-
stance lose 1 mol. of water, yielding the body C40H30O15. When
crystallised from solutions containing free hydrochloric acid, pyro-
Qi ABSTRACTS OF CHEMICAL PAPERS.
gallovanillein is obtained in fine violet-blue crystals, which contain
however, a trace of hydrochloric acid.
Phloroglucinolvanillem, prepared in a manner similar to the above,
forms yellowish-white crystals, and behaves towards solvents like
pyrojrallovanillein. It loses water more readily with formation of the
brownish-red compound, C40H34O15. Crystallised from hydrochloric
acid solutions, the characteristic fiery-red compound is obtained, but
as in the previous case the amount of chlorine contained is too small
to estimate. The formation of these vanilleins is expressed by the
equation —
COH.C6H3(OH).OMe + 2C6H,(OH)3 =
CH[C6H2(OH)3]2.C6H3(OH).OMe + H^O,
and they must be regarded as derivatives of triphenylm ethane.
On rubbing together resorcinol with vanillin and hydrochloric acid,
a deep bluish-violet coloration is produced ; but the colour vanishes
after a time ; the addition of water causes the precipitation of a white
crystalline powder. A. J. G.
Action of Acetic Chloride on Benzaldehyde in presence of
Zinc-dust. By C. Paal (Ber., 15, 1818— 1820).— When acetic chlo-
ride is dropped into an ethereal solution of benzaldehyde in which
zinc-dust is suspended, a violent reaction takes place ; zinc chloride is
formed, and the ethereal solution, after being washed with water and
evaporated, deposits a yellow crystalline mass from which alcohol
extracts a substance crystallising in white needles of the formula
CgHgOg, melting at 125—128°. Heated with amorphous phosphorus
and hydriodic acid, it yields dibenzyl, and, when distilled with zinc-
dust, it gives rise to stilbene : these decompositions, however, throw
no light on its constitution. A reaction similar to the above occurs
when ethaldehyde is treated with acetic chloride. J. K. C.
Orthamidobenzaldehyde. By S. Gabriel (Ber., 15, 2004 —
2006). — The author has already shown, in conjunction with R. Meyer
(Abstr., 1882, 188), that nitrosomethylorthonitrobenzene yields ortho-
nitrobenzaldehyde on oxidation, and (Abstr., 1882, 1070) that the cor-
responding meta-compounds give similar results ; as this appears to be
a general reaction for nitrosomethyl compounds, he has applied it to
nitrosomethylorthamidobenzene. The oxidation was effected by a
slightly insufficient quantity of ferric chloride ; during the reaction,
some salicylic aldehyde distils. The contents of the retort are made
alkaline and distilled, when orthamidobenzaldehyde is obtained as an
oil, solidifying to a crystalline mass on cooling ; it melts at the tempe-
rature of the hand. In an exsiccator over sulphuric acid, it appears to
decompose, the walls being covered with a crystalline deposit, whilst
the other (greater) part of the substance is converted into a yellow
body not melting at 100°. A. J. G.
Action of Benzoic Anhydride on Epichlorhydrin. By P.
VAN RoMBURGH {Eec. Tvav. Chim.yl,4:{) — 52).* — When these two bodies
* Recueil des Travaux Chimiques des Pays-Bas : par W. A. ran Dorp, A. P. N.
Franchimont, S. Hoogewerlf, E. Mulder, et A. C. Oudemans, Jr. Leide. 1882.
ORGANIC CHEMISTRY. 63
in molecular proportion are heated together in sealed tubes at about
190° for seven to ten hours, and the product is left at rest for some
time, the whole concretes to a mass of small crystals soaked in a thick
liquid. By solution in ether and spontaneous evaporation, colourless
crystals (m. p. 70°) are obtained containing a small quantity of chlo-
rine, and by recrystallising these from alcohol crystals are formed free
from chlorine, and melting at 74°. These crystals have the composi-
tion C12H10O3, or rather C24H20O6, and are resolved by saponification
with alcoholic potash into benzoic acid and glycerol. The compound
is therefore tribenzoicin, formed according to the equation
CH2 : CHO.CH2CI + 2Bi30 = B^Cl + OBi.CH(CH2.0Bi)2';
Epichlorhydrin. Tribenzoicin..
and, as thus prepared, it is identical in its properties with that which
is obtained by heating glycerol with benzoic acid or benzoic anhydride.
Its formation in the manner above described is accompanied by that of
a liquid, which the author regards as probably consisting of a mixture
of mono- and di-benzoicin. H. W.
Action of Benzoic Anhydride on Monochloracetone and on
Pyruvyl Benzoate. By P. van Romburgh {Eec. Trav. Chim., 1, 53 —
54). — Monochloracetone and benzoic anhydride, heated together for
three hours in a sealed tube at 180°, formed a black solid substance
containing benzoic acid, and having a faint odour of benzoic chloride.
By heating monochloracetone with potassium benzoate in alcoholic
solution for 12 hours, then filtering and expelling the alcohol by eva-
poration, a liquid is obtained which, when distilled at 245° under a
pressure of 380 mm., yields a yellow distillate solidifying when sur-
rounded by ice ; and on pressing the solid mass between bibulous
paper to remove oily products, then dissolving it in ether and evapo-
rating, pyruvyl benzoate, C10H10O3 = COMe.CH2.OBz, is obtained
in splendid colourless crystals which melt at the heat of the hand (25°)
and have a density of 1*143 at 25°. Their alcoholic solution has no
action on polarised light. Pyruvyl benzoate, like monochloracetone,
reduces potassio-cupric sulphate, even at ordinary temperatures.
Heated with benzoic anhydride in a sealed tube at 180°, it gradually
blackens and yields a sublimate of benzoic acid. H. W.
Synthesis of Cumic Acid. By R. Meter and E. Mijller (Ber.^
15, 1903 — 1906). — The authors have repeated their synthesis of cumic
acid (Ber., 15, 496) on a laf-ger scale with the view of examining the
cause of discrepancy between the melting point (110°) of their syn-
thesised acid and that (116°) of ordinary cumic acid. The cumene
was prepared by the action of isopropyl bromide on benzene in the
presence of aluminium bromide, then converted into parabroraocumene,
and this, after careful purification, was submitted to the action of
sodium and moist carbonic anhydride. The acid obtained in this way
differed from that previously prepared in having the correct melting
point (116 — 117°), and it agreed in all respects with ordinary cumic
acid. Since both the para-propylbenzoic acids have now been made
synthetically by similar reactions, there can be no further doubt of
64 ABSTRACTS OF CHEMICAL PAPERS.
their coiistitution— cumic acid containing the isopropyl group, and its
isomeride, normal propyl.
An attempt to prepare pro pylben zoic acid by the action of sodium
amalgam on para-propylbenzene and chlorocarbonic ether did not yield
very definite results, for although a small quantity of propylbenzoic
acid appeared to be formed, the chief product of the reaction was a
new body of the formula Hg(C6H4. €3117)2 [Hg : C3H7 = 1 : 4] (m. p.
109°). A. K. M.
Phenylacetic Acid. By S. Gabeiel (Ber., 15, 1992— 2003).— By
the action of fuming nitric ai^^id on bromacetamidobenzyl cyanide
(m. p. 127 — 129°),. acetamidohromnnitrobenzyl cyanide^
C6H2(CH2.CN)(N02)(NH5^)Br =[1:3: 4 -'S],
is obtained in slender pale-yellow needles melting at 190 — 191°, and
sparingly soluble in cold water, more readily in alcohol and glacial
acetic a<3id. When boiled with hydrochloric acid, it yields amidobromo-
nitrophenylacetic acid, CeHoCNOa) (NH2)Br(CH2.COOH) = [3:4:5:1],
crystallising in long golden-yellow needles melting at 191 — ^192°, and
sparingly soluble in cold water, readily in hot alcohol, moderately
soluble in chloroform and benzene. By reduction with tin and hydro-
chloric a-cid, it is reduced to the diamido-acid,
C6Ho.Br(NH2)2.CH2.COOH.
This forms groups of long colourless needles, which darken at 190°
and melt with intumescence to a black mass at 195 — 200°. The
results of the reduction show that the nitro-group must have entered
the benzene nucleus at the 3-position, as in the case of th-e other
possibilities [2 or 6], an inner anhydride, bromandido-oxindole,
NH2C6HoBr<^^^>CO,
would be produced on reduction.
Metanitroparamidophenylacetic acid (m. p. 143"5 — •144'5°) gives
on reduction the diamido-acid, CeHaCXHOCNH^JCCHa.COOH) =
[3:4: 1], crystallising with 1 mol. H2O in short hard compact forms
showing numerous faces, sparingly soluble in hot Alcohol.
By the action of a my 1 nitrite and hydrochloric acid on the above
metanitro-acid (m. p. 191 — 192"), a large yield of a substance giving
diazo-reactions was obtained, but no formula could be deduced from
its analysis, the fact that it contains chlorine and bromine in no simple
ratio to one another pointing to a mixture of substances. On gently
heating it with alcohol, a crystalline mass is obtained which, on being
mixed with soda and distilled with steam, gives an oil solidifying after
a time to a mass of crystals insoluble in soda, whilst the residue in the
retort, after acidification and renewed distillation with steam, yields
colourless crystals (m. p. 108 — 109°) soluble in water. The results of
analysis showed these to be a mixture of dihalogen nitrosomethvl-
benzenes, CeHsXa.CHaNO (X2 = CI2 or Br2 or BrCl). The crystals
insoluble in soda first obtained (broad flat needles melting at 65 —
65*5°) gave results agreeing with a mixture of dihalogen benzaldehyde,
and on oxidation yielded a mixture of dihalogen cinnamic acids.
A. J. G.
ORGANIC CHEMISTRY. 65
Action of Sulphuric Acid on Protocatechuic Acid. By E.
NoELTiNG and R. Bourchakt {Bull. Soc. GJdm. [2], 37, 394—397).—
1 gram protocatechuic acid is heated with 2 grams of benzoic acid and
50 grams of sulphuric acid of Q^" B. at 140 — 145° for eight hours, and
the product is poured into water, which throws down a deep brown
flocculent precipitate ; this is collected, dissolved in dilute soda solu-
tion, and precipitated by hydrochloric acid, this treatment being
repeated several times. The clear brown flocculent substance thus
obtained produces with mordants almost the same shades as alizarin,
but is distinguished from the latter by the reddish-brown colour of its
alkaline solution and by its absorption- spectrum. The yield is very
small, whatever the proportion of sulphuric acid, the time of heating,
and the temperature. The benzoic acid appears to play no part in the
reaction, for, when protocatechuic acid is heated alone at 140 — 145°
with 20 — 25 times its weight of sulphuric acid, the same product is
obtained, although in this case also the yield is very small.
The substance thus formed yields an orange-yellow alcoholic solu-
tion, which becomes violet with a yellowish fluorescence on addition of
potash. After some time, the compound is precipitated in red flocks.
Alcoholic lead acetate throws down 'a flocculent brown precipitate:
calcium cJiloride and barium chloride produce a violet fluorescence in
the yellow solution, and after some time a precipitate is formed ; ferric
chloride gives a blackish-brown, ammonia a violet-brown, and alum a
reddish precipitate. Its solution in dilute ammonia is brownish-red,
approaching violet. In this - solution calcium and barium chlorides
produce a brown, lead acetate a reddish-brown, and absolute alcohol a
violet-brown precipitate. Its solution in dilute potash gives, with
absolute alcohol, a reddish precipitate, with alum a reddish-lake, and
with ferric chloride a blackish-green lake. The substance is dissolved
by strong sulphuric acid, with formation of a brownish- violet solution
which, when poured into water, yields a yellow solution and a slight
precipitate. It also dissolves in glacial acetic acid, forming an orange
solution. It cannot be sublimed without decomposition.
The properties of this substance agree with those of rujiopine,
CO
C6H2(OH)2<^p>'-.^C6H2(OH)2, obtained by Anderson (Annalen, 98,
51) by the action of concentrated sulphuric acid on opianic acid at
180°, and described by Liebermaun and Chonjnacki (Annalen, 162,
321). By analogy from the behaviour of other hydroxyl-derivatives
of benzoic acid, protocatechuic acid ought to form a colouring matter
according to the equation
2CeH3(OH)2COOH = C6H2(OH)2<^Q>C6H2(OH)2.
This reaction is more complicated in the case of opianic acid ; but
since in both compounds the hydroxyl-groups occupy the same posi-
tions with respect to the carboxyl-groups, it is highly probable that
they will yield identical condensation-products when acted on by
sulphuric acid. C. H. B.
Oxidation-products of Carbon obtained by Electrolysis.
By A. MiLLOT (Bull. Soc. Ghim. [2], 37, 337— 839).— The gas-
VOL. XL IV. /
66 ABSTRACTS OF CHE:^^CAL PAPERS.
carbon electrodes (Abstr., 1880, 482) are much more rapidly attacked
in alkaline solutions than in pure or acidulated water. The dark solu-
tion obtained by the electrolysis of a 5 per cent, solution of ammonia
with gas-carbon electrodes becomes acid on evaporation. It contains
ammonium nitrate and an acid which may be isolated by evaporating"
almost to dryness, heating the precipitated black matter with alcohol,
and evaporating the alcoholic solution, when crystals of the ammo-
nium salt of the acid, mixed with ammonium nitrate, separate out.
The crystals are dissolved in water and mixed with lead nitrate
which produces a crystalline precipitate. This precipitate is sus-
pended in water, treated with hydrogen sulphide, the solution filtered
from lead sulphide and evaporated, when the acid separates out in
needles. Its composition will be determined when a sufficient quantity
has been obtained.
The black matter precipitated by the addition of an acid to the solu-
tion obtained by the electrolysis of a 2 per cent, solution of potassium
hydroxide has the composition O 37-72; C, 58-65; H, 327 ; N, 0-56.
The whole of the nitrogen was evidently not removed from the carbon
electrodes, although the latter were treated with chlorine for 150 hours.
The black substance is soliible in boiling water even after being dried
at 100°, but is precipitated by ebullition in contact with air. It is
insoluble in alcohol, ether, benzene, and chloroform. When an
aqueous solution of the black substance is treated with a current of
air, it absorbs a considerable quantity of nitrogen, which however is
again partially removed by continued passage of the air, the substance
at the same time being oxidised and destroyed. C. H. B.
Caffeic Acid from Cuprea Bark. By G. Korner (Pharm. J.
Trans. [3], 13, 246). — The bark employed differs from ordinary
cinchona bark, in that its aqueous solution becomes reddish- violet on
the addition of potash, and, moreover, it yields caffeic acid when em-
ployed for the manufacture of sulphate of quinine ; the caffeic acid is
found in the mother-liquors as quinine caffeate. The author has
obtained the acid from the bark by the following process, the yield
being about 0*5 per cent. : — The powdered bark is first extracted with
ether and then thoroughly with boiling alcohol. The latter extract is
evaporated to dryness and the residue treated with 2^ times its weight
of boiling water and its own weight of potash ; the whole is then
boiled for three hours, supersaturated with dilute sulphuric acid, fil-
tered hot, and extracted with ether. This extract is concentrated
until crystals form. The crystals are well washed with small quantities
of ether, and are purified by boiling with animal charcoal and recrys-
tallising. They form brilliant hard yellowish tables, with 4-8 per cent,
water of crystallisation. From acetic acid they separate in crusts of
opaque nodules, which decompose without melting at 21 2*^, and have
the formula C9HSO4 + JH2O, and they give the characteristic reac-
tions of caffeic acid. Dimethylcaffeic acid and methylic dimethyl-
caffeate were prepared from the acid and identified.
The presence of this acid furnishes an additional proof of the re-
lationship existing between the coffee and cinchona plants.
D. A. L.
ORGANIC CHEMISTRY. 67
Dibromonaphthalene from ^-Naphthol. By F. Canzoneri
(Gazzetta, 12, 424 — 431). — When 10 g. of the monobromonaphthol
which A. J. Smith obtained by the action of bromine on naphthol
(this Journal, 1879, Trans., 789) is mixed in a retort with 15 g. phos-
phorus tribromide, no action takes place in the cold ; but on gradually
heating the mixture to a temperature above its melting point, an
action commences, attended with rapid evolution of hydrogen bromide.
This, however, ceases in a few minutes, and if the mixture be then
gradually heated, the action recommences less energetically, the con-
tents of the retort at the same time distilling over. This distillation,
if carried on to a red heat, yields : — (1) A quantity of unaltered phos-
phorous bromide ; (2) an oil having a faint yellow colour ; (3) a thick
yellow oil, solidifying in the neck of the receiver. In the retort there
remains a considerable quantity of charcoal.
The second fraction, which constitutes by far the larger fraction of
the product, solidifies either at once or after renewed distillation (at
about 300°) to a mass of hard transparent crystals melting at 67 — 68°.
The substance thus obtained is a dibromonaphthalene, CioH6Br2, and
when recrystallised from a small quantity of alcohol, forms large
monoclinic prisms, cleaving easily parallel to the base OP, less easily
parallel to ooP. It' is but slightly refractive, and exhibits only a faint
coloration in polarised light.
This dibromonaphthalene does not dissolve in nitric acid of sp. gr.
1*40, but fuming nitric acid dissolves it, especially if the mixture be
gently heated and immediately afterwards cooled. On subsequently
adding water, a yellow disagreeably-smelling oil separates, which soon
solidifies, and is best purified by dissolving it in a small quantity of
alcohol and precipitating with water, whereupon it separates in yel-
lowish-white flocks, apparently made up of slender needles. These
crystals, after drying, melted at 100 — 105°, and gave by analysis 47*50
per cent, bromine, the formula CioH6Br2(N02) requiring 48'34. The
substance is probably a new nitrodibromonaphthalene isomeric with
that (m. p. 116-5°) which Jolin obtained (Bull. Soc. Cliim. [2], 28,
515) by the action of nitric acid on the y3- dibromonaphthalene, which
melts at 81°.
The third portion of the above-mentioned distillate, the quantity of
which was relatively very small, consisted of opaque yellow scales
impregnated with a yellow oil difficult to separate ; but by crystallisa-
tion from dilute acetic acid and afterwards from alcohol, the substance
was obtained in white silvery scales, melting at 55 — 60°, and giving
by analysis numbers agreeing nearly with the formula of monobromo'
naphthalene, CioH7Br. As only two such compounds are possible, and
one of them (a) is liquid, the compound obtained. in the manner just
described must be the y3-modification which was obtained by Lieber-
mann and Palm (Annalen,, 183, 267) from |S-naphthylamine, and
described as crystallising in laminae, having the same appearance, but
melting at 68° ; the difference in the melting points perhaps arising
from the circumstance that the author's determinations were made
with a very small quantity of material. The formation of this mono-
bromonaphthalene may perhaps be ascribed either to the action of the
phosphorous bromide on small quantities of iS-naphthol contained in
/2
68 ABSTRACTS OF CHEMICAL PAPERS.
the broTnonaphtliol, or to decomposition of the dibromonaphtLalene at
the high temperature of the reaction.
From the perfect agreement in melting point between the dibromo-
naphthalene above described and that recently isolated by Guareschi
(Abstr., 1882, 734), from Glaser's impure product (melting at 76°),
the author infers the identity of the bodies obtained in these several
ways, and thence deduces the constitutional formula of the dibromo-
naphthalene in question. This body in fact, having been obtained by
Glaser from a-bromonaphthalene, must have one of its bromine-atoms
in the a-position, but since it is also producible from monobrom-/3-
naphthol, it must have the other in the /^-position, and consequently
must be an a-/?-dibromonaphthalene. Now of the ten possible dibromo-
naphthalenes, four only have the a-/3-structure, viz. : [1 : 2], [1 : 3],
[1, 2'], [1 : 3']. Moreover, A. J. Smith (loc. cit.), by oxidising mono-
brom-jS-naphthol with permanganate, obtained phthalic acid or anhy-
dride, and thence inferred that in this brom-)3-naphthol the hydroxyl-
and the bromine-atom must be found in the same benzene-ring. The
same conclusion may be extended to the dibromonaphthalene derived
therefrom : consequently, the two bromine-atoms of this latter cannot
be in the positions 1 : 2' or 1 : 3', and must therefore have the posi-
tion 1 : 2 or 1 : 3. Now, Meldola in a recent memoir (Ber., 12, 1962)
describes a dibromonaphthalene melting at 64^ — obtained by the
action of nitrons acid on dibromonaphthylamine — to which he assigns
the formula [1 : 3] ; and since there appears to be no reason for sup-
posing that this product is identical with the above-described dibromo-
naphthalene melting at 67 — 68°, the author infers that the latter must
be represented by t'.ie formula [1 : 2].
Appendix. — The author has likewise obtained an acetyl -derivative
and a nitroso- derivative of bromo-/S-naphthol. The former is a dense
faintly yellow liquid, decomposed by distillation under ordinary
pressures, but passing over undecomposed at about 215° under a
pressure of 20 mm. By bromine in acetic acid solution, it is con-
verted into a brominated derivative, which is resinified by boiling with
potash.
The nitroso-derivative separates from solution in ether in unstable
green crystals, melting at 61 — 65°. H. W.
Action of Chloroform on Naphthalene in presence of
Aluminium Chloride. By M. Honig and F. Berger (MoHatsh.
Chem., 3, 668 — 672). — This reaction has been already investigated by
Schwartz (Abstr., 1881, 912), who could not obtain any definite pro-
ducts from it. A pitch-like mass is obtained, from which solvents
fail to extract any well-characterised substance. The crude product is
dissolved in benzene, filtered, the benzene distilled off, and the residue
after being heated at 230° for some time to remove unaltered naphtha-
lene, is distilled in a vacuum. The distillation begins far above 360°,
and wfiS carried on to redness. By a long series of crystallisations, a
substance was obtained from the distillate, forming plates of a pale
yellow colour (m. p. 189 — 190°, uncorr.), whose formula would appear
to be a multiple of CuHio (C42H30?). It is possible that this hydro-
carbon may be identical with Zeidler's synanthrene {Annalen, 191,
ORGANIC CHEMISTRY. 69'
2P8). Two substances, melting respectively at 170 — 175° and at 215°,
were also obtained and are being investigated. A. J. G.
Constitution of Nitronaphthols. By E,. Worms (Ber., 15,
1813 — 1818). — Two nitronaphthols from a-naphthol are known: in
one the nitro-group occupies the para- or a-position ; in the other one
of the /S-positions, but it is not known which. An anhydro-base from
a-naphthol is also known, but the corresponding nitro-compound has
not been isolated, and it appeared interesting to compare it with the
other known nitro-a-naphthols. For this purpose benz-a-naphthalide
was converted in small quantities into the corresponding nitro-com-
pounds. On cooling, the para-compound crystallises out, and the fil-
tered hquid is thrown into water to precipitate the ortho-compound.
It crystallises from alcohol in yellow needles, melting at 174°. On
boiling it with potash and adding an acid, orthonitro-a-naphthol is
obtained in yellow crystals, melting at 128°. It is identical with the
yS-nitro-a-naphthol obtained by Liebermann and Dittler (Annalerij
183, 228). That the nitro-group occupies the ortho-position with
respect to the hydroxyl is shown by the fact that the corresponding
nitrosonaphthol is easily converted into an anhydro-base. To this end,
yS-nitroso-a-naphthol benzoate was first prepared by treating the cor-
responding sodium-nitrosonaphthol with benzoic chloride in the cold.
The benzoate (m. p. 162''), purified by crystallisation from chloroform,
is treated with tin and hydrochloric acid, when a violent reaction sets
in, and the anhydro-base, benzenyl-jS-amido'^a-naphthol, CioHti\ "^CPl,
is obtained in small needles (m. p. 122°), which mny be purified by
sublimation.
It appeared also of interest to ascertain whether an anhydro-base
could be produced from the a-nitroso-/^-naphthol of Stenhouse and
Groves {AimalpM, 189, 153), in which the nitroso-group and the
hydroxyl have been shown to stand relatively in the ortho-position.
The same process was used as above, the sodium salt and then the
benzoate (m. p. 114°) being first prepared, and the latter reduced with
tin and hydrochloric acid. Benzenyl-a-amido-(3-raphthol was thus
obtained in colourless prisms melting at 120°, and soluble in water
and alcohol ; it may be purified by sublimation.
The formation of anhydro-bases in the naphthalene series seems
thus to be a property of the ortho-position. It is also noteworthy that
orthonitro-a-naphthol can be separated by steam from the solid para-
compound, just in the same way as in the case of the two nitrophenols.
J. K. C.
Indophenol. By M. A. Pabst (Bull Svc. GUm. [2], 38, 160—
162). — Meldola, and Koechlin and Witt have obtained colouring
matters by the action of nitrosodimethyl- or nitrosodiethyl-aniline on
phenols or naphthols. One of these substances, indophenol, is manu-
factured by the oxidation of sodium a-naphthol and amidomethyl-
aniline with potassium dichromate or sodium hypochlorite. It gives
a blue dye on reduction, like indigo, and can be fixed on fabrics by
70 ABSTRACTS OF CHEMICAL PAPERS.
stannous oxide. It is more stable than indigo to light and soap, and
is less costly, but is destroyed by concentrated mineral acids. The
colour varies from a violet to a greenish- blue, according to the par-
ticular phenol employed.
Koechlin, by the action of nitrosodimethylaniline on tannin, gallic
acid, and the catechins, obtained a violet dye, gallocyanine ; it forms
beautiful crystalline salts, and can be fixed on cotton by chromiam
sesquioxide.
These colouring matters are prepared in France by Durand and
Huguenin, and it seems probable that from their cheapness and
stability they will replace alizarin for violet, and indigo for blue
tints. Y. H. V.
a-Naphthaquinone-ethylanilide. By L. Elsbach (Ber., 15,
1810 — 1813). — Two parts of a-naphthaquinone are heated in a flask
with five parts of glacial acetic acid and three parts ethylaniline ; the
reaction proceeds by itself when the mixture has begun to boil. On
cooling, the mass is extracted with alcohol, and by repeated crystalli-
sations the pure a-naphthaquinone-ethylanilide,
(/3)NEtPh.CioH5:02(a),
is obtained in dark violet needles, melting at 155°. When boiled with
strong caustic soda, it is converted into a reduction product and a re-
sinous mass. It is a feeble base, and combines readily with acids to
form salts, which are easily decomposed.
During its formation by the above reaction, a yellowish-green bye-
product is formed, which amounts to one-fifth of the yield. After
iDoiling it with alcohol and ether, it was analysed, and found to con-
tain no nitrogen, numbers being obtained corresponding with the
formula C20H10O4. It is soluble only in fuming nitric acid. Zinc and
hydrochloric acid reduce it, forming a green fluorescent solution. In
all probability, therefore, it appears to be the a-product corresponding
with the /3-dinaphthadiquinone discovered by Stenhouse and Groves.
J. K. C.
Derivatives of Styrolene. By A. Bernthsen and F. Bender
{Ber., 15, 1982 — 1986). — In addition to the method already described
(Abstr., 1882, 201), paramidostyrolene, C6Hi(NH2)C2H3, can be pre-
pared by heating paranitrocinnamic acid in a paraffin-bath until the
mass is in quiet fusion. The melting point is difficult to determine ;
softening occurs at 7Q°, complete fusion at 81".
Far ally droxy styrolene appears to be obtained in small quantity by
distilling barium paracoumarate mixed with sand, and forms a nearly
colourless oil, of phenol-like odour, sparingly soluble in water. The
solution is precipitated by bromine.
Styrolene unites directly with hydrobromic acid, yielding a hrom-
ethylhenzene. This is a pale-yellow liquid, of odour resembling that
ot benzyl chloride, sp. gr. 1-3108 at 23 . When heated, it is decora-
posed into hydrobromic acid and styrolene. It is probable that it has
the constitution CHaPh.CHaBr. A. J. G.
Methylanthraquinone and some of its Derivatives. By E.
BoKNSTEiN {Ber.j 15, 1820 — 1823). — The substance bearing this name.
ORGANIC CHEMISTRY. 71
and sold commercially, was examined for the purpose of identification.
After repeated crystallisations from alcohol, it melted at 175 — 176",
and gave on analysis numbers corresponding with the formula of
methylanthraquiuone. Reduced with zinc and ammonia, and boiled
with xylene, greenish-yellow crystals of methylanthracene were ob-
tained and analysed. After repeated crystallisation, it melted at 203°.
By oxidation with chromic acid, anthraquinonecarboxylic acid was
formed, and a dibrominated product was also prepared, melting at
148°. Attempts to prepare a definite methylhydroanthranol have
hitherto been unsuccessful. J. K. C.
New Nitro- and Amido-anthraquinones, and New Method
of Preparing Erythroxyanthraquinone. By H. Roemer (Ber.,
15, 1786 — 1794). — Nitro- and amido-anthraq^inones have been ob-
tained by Bottger and Petersen (Ber., 6, 16), and an isomeric ainido-
compound by von Perger (Ber., 12, 1566). Other experimenters
have failed to obtain a nitro- compound by Bottger and Petersen's
method, and have recommended another, viz., to treat dibromanthra-
cene with fuming nitric acid. The author was also forced to have
recourse to this process, but on repeating his experiments could obtain
no product of settled composition. Another method was therefore
tried, and with success. Anthraquinone dissolved in sulphuric acid
was treated with the requisite quantity of nitric acid ; crystals were
formed, and after two days the whole was poured into a large quantity
of water. The white precipitate thus obtained could be separated into
three bodies by crystallisation from alcohol. The body of medium
solubility attracted attention at once by the beauty and size of its
crystals.
The following method was - found to give the largest yield : —
10 grams of anthraquinone dissolved in sulphuric acid were treated with
4"5 grams of nitric acid (sp. gr. 1*48), and left for two days. The crude
product after being washed with water was extracted with ether, the
extract distilled until crystals began to form, and after cooling, the
filtered liquid was found to contain the body most soluble in alcohol,
whilst the crystals contained the wished-for product, purifiable by
recrystallisation. For larger quantities, the crude product can be
simply extracted by repeated small quantities of hot alcohol : after the
second extraction the body is obtained almost pure. The pure pro-
duct on analysis gave numbers closely agreeing with the fonnula for
nitranthraquinone. That it is not a mixture of anthraquinone and
its dinitro-compound is proved by its behaviour with ammonium sul-
phide, the latter converting it into a body soluble in cold strong
hydrochloric acid, in which anthraquinone is insoluble, even after
treatment with ammonium sulphide.
Nitranthraquinone sublimes in yellow crystals (m. p. 220°), inso-
luble in water, sparingly soluble in alcohol, ether, and glacial acetic
acid, and crystallising therefrom in brilliant prismatic needles, but
more soluble (with yellow colour) in benzene, chloroform, and con-
centrated sulphuric acid. Its solution in the latter becomes red when
heated, and on being thrown into water gives a reddish-violet preci-
pitate, which yields a purple solution in alcohol, showing two dark
72 ABSTRACTS OF CHEMICAL PAPERS.
bands. It tlins exhibits decided differences from the body described
by Bottger and" Petersen, which become more striking when the amido-
compound is examined.
Orthamidoan'thraquinone is easily obtained in a pnre state by dis-
solving the above nitro-componrid in alcohol, precipitating with
water, and adding an alkaline solution of stannous oxide. A clear
green solution is at once obtained, which after twelve hours' standing
becomes reddifeh-yellow, and deposits the amido-com pound in beautiful
red needles, purified by washing with water. Analysis shows them to
consist of amidoanthraquinone (m. p. 241°). It sublimes without
charring in deep-red needles, insoluble in water, but giving reddish-
yellow solutions with alcohol, ether, benzene, chloroform, glacial
acetic, sulphuric, and hydrochloric acids. From its hot saturated
solution in the last, the hydrochloride separates out on cooling in white
needles. Its acetyl-compound is obtained by boiling it with acetic
anhydride and sodium acetate, and may be separated by adding water;
It crystallises from alcohol in orange-red neeJdles melting at 202°, or
39° lower than Perger's acetyl-compound, exactly the same difference
being observed between the two amidoanthraquinones. Perger's
description and results were also confirmed by the author, and as his
amidoanthraquinone is a meta-compound, it seemed probable that the
bodies obtained by the author belonged to the ortho-series, an assump-
tion which was confirmed by their conversion into erythro-oxyanthra-
quinone in the following way : — The amidoanthraquinone was dis-
solved in glacial acetic acid, a little concentrated sulphuric acid added,
and then potassium nitrite until the solution had become yellow.
After standing a short time water was added, the mixture boiled
until yellow flakes separated, increasing in quantity as the acetic
acid evaporated. Crystallisation from alcohol then yields at once
orange-yellow feathery crystals melting at 191°, and agreeing in
every other characteristic with erythroxyanthraquinone. The nitro-
and amido-anthraquinones obtained by the author belong therefore to
the ortho-series. J. K. C.
Action of Gontsentrated Sulphuric Acid on Dinitroanthraqui-
none. By C.'Liebermann and A. Hagen (Ber., 15, 1801 — 1806). — By
the action of hot concentrated sulphuric acid on dinitroanthraquinone,
a dye-stuff is formed (Ber.^3, 905), which has not received a thorough
investigation. 'To obtain it, the anthraquinone is heated with 15 times
its weight of sulphuric acid at 200°, and the cooled mixture poured
into water. A brown precipitate is thrown down, dissolving in alkalis
with violet colour ; after being thrown down again by hydrochloric
acid, it is purified by boiling with baryta-water, in which it partly
dissolves. The substance is again precipitated by acid from the solu-
tion, washed, and transferred in the pasty condition into cold baryta-
water. After standing, the filtered liquid is again treated with acid,
the precipitate washed, and crystallised repeatedly from alcohol. On
analysis, numbers were obtained corresponding with the formula
C^H,sN,07.
On heating it with hydrochloric acid, a colouring matter is obtained
free from nitrogen. With nitrous acid, however, it splits up into
ORGANIC CHEMISTRY. 73
eryfliroxyanthraquinone and purpuroxanthin. It appears therefore
probable that the dye-stuff in question consists of a mixture of the
amides of these two bodies. The action of sulphuric acid on dinitro-
anthraquinones is first an oxidati(m, sulphurous and phthalic acids
being formed : the sulphurous acid then reduces the nitro-groups,
forming amides, and this part of the process can be greatly accele-
rated by introducing sulphurous anhydride or zinc. The amido-
groups are then partially attacked by sulphuric acid and converted
into hydroxyls. A complicated mixture of substances is thus formed,
of which the substance investigated by the authors forms but a small
part. " J. K. 0.
Derivatives of Anthrol Salts. By C. Liebermann and A. Hagen
{Ber., 15, 1794— 1800).— In a former communication (jBer., 15, 1427),
the authors have given the name of ethyl dinitroanthrolate to the body
obtained by the action of nitric acid on ethyl anthrolate. Further
experiments have, however, shown that this view is not correct, both
its reduction and oxidation products pointing to another formula.
Boiled with glacial acetic acid, tin, and hydrochloric acid, ethyl mon-
amidoanthrolate is formed, and the other half of the nitrogen is found
in solution as ammonia. One only, therefore, of the nitro-groups
possesses the ordinary characteristics of aromatic nitro-groups, and
the other is in reality a nitroso-group. The body in question is there-
fore termed by the authors the nitroso-anthrone of ethyl mononitro-
anthrolate, CbH4<^£~>C6H2(N-02) .OEt.
By oxidation with boiling acetic and chromic acids, the correspond-
ing nitroxyanthraquinone ethylate is obtained in colourless needles
melting at 243° ; and this when boiled with glacial acetic acid and
granulated tin until the solution becomes red, yields ami doxy anthra-
quinone ethylate in red crystals melting at 182°. Contrary to the
author's expectation, the ethyl-group in the above compounds could not
be eliminated by boiling with alkalis or acids, or with alcoholic potash:
by fusion with potash, they are, however, decomposed in a more com-
plicated way. The reactions of the hydroxyanthraquinone salts were
therefore studied in order to throw light on this curious behaviour.
Ethyl anthrolate was oxidised in acetic acid with excess of chromic
acid, hydroxyanthraquinone ethylate being formed (m. p. 135°), very
soluble in alcohol. This is also proof against all alkaline solutions, and
is only gradually attacked by fused potash and converted into alizarin.
The ethyl ether of anthrafla vol was also found to exhibit this stability,
which appears to be characteristic of the hydroxyanthraquinones. A
decomposing agent was, however, found in hot concentrated sulphuric
acid. On heating a solution of the ether in this acid to 200°, it turns
brown, and on cooling and adding water, hydroxyanthraquinone is
thrown down (m. p. 301°). A similar reaction takes place with the
ethers of anthraflavol. Amidoanthraquinone ethylate was therefore
treated in the same way, and was found to be converted into alizarin-
amide, easily recognised by its rr actions.
The constitutional formula of the nitroso-anthrone of ethyl nitro-
anthrolate is therefore —
74' ABSTRACTS OF CHEMICAL PAPERS.
OeH,<-jJg->CeH,<g^^^ [NO.: OEt =1:2].
J. K. C.
Dihydroxyanthracene from a - Anthraquinonedisulphonic
Acid (Flavol). By a. Schuler (Ber., 15, 1807— 1810).— Commercial
sodium a-anthraquinonedisulphonate was redaced with zinc-dust and
ammonia to obtain the sodium salt of flavanthracenedisulphonic acid,
which forms j'ellowish-grey crystals, dissolving in water with intense
blue fluorescence. The thallium and barium salts are whit« and
crystalline, those of silver and lead are yellowish precipitates. Sodium
anthrosulphonate, Ci4Hf,(OH).S03Na, is obtained by fusing the cor-
responding disulphonate with potash until the mass has become
thin : when cold, it is treated with acid filtered and alcohol added ;
the precipitated salt is recrystallised from water, to which it communi-
cates a greenish fluorescence ; precipitates are formed with the heavy
and earth metals.
Flavol, Ci4H8(OH)2, is formed when the fusion with potash is con-
tinued until the mass becomes intensely black, and gives off' a tarry
odour. By decomposing the product with acid, and repeatedly re-
crystallising the insoluble portion from alcohol, flavol is obtained as a
bright yellow crystalline powder (m. p. 260 — 270°), soluble in alkalis
with yellow colour and very fine green fluorescence. Diacetylflavol,
prepared in the usual way, crystallises in white plates, melting at
254 — 255°. The diethylic ether, obtained by saturating an alcoholic
solution of flavol with hydrochloric acid, melts at 229° after being
purified by crystallisation from glacial acetic acid.
Flavol differs from the other known dihydroxyauthracenes in the
strong fluorescence of its alkaline solutions and in the higher melting
points of its salts. J. K. C,
Soluble Alizarin Blue. By H. Brunck and C. Graebe (Ber., 15,
1783 — 1786). — Alizarin blue being but sparingly soluble, and there-
fore difficult to fix on the fibre, has not been as extensively applied
as was to be expected from its otherwise valuable properties. In
order to convert it into a more soluble form, experiments were
made by Brunck, ending in the issue of a patent, from which the
method of obtaining the soluble blue may be briefly extracted as
follows : —Alizarin blue in a fine state of division, and in the form of
a paste containing 10 — 12 per cent, blue, is stirred up with 25 — 30 per
cent, of a solution of sodium hydrogen sulphite (sp. gr. 1'25), and the
mixture left for 8 — 10 days. It is then filtered, unchanged blue being
left behind, and the soluble blae separated from the filtrate in reddish-
brown crystals by addition of common salt, or evaporation at a low
temperature. The dry powder can be heated to 150° without under-
going change, but its aqueous solution begins to decompose at 60°, and
on boiling, the blue separates out. In the cold a solution of chromic
acetate produces no change, but at 60 — 70°, the blue chromium lake
is thrown down. This fact is made use of in printing ; the soluble
blue and chromic acetate mixed with starch are printed on the fabric,
and the latter steamed for 10 or 20 minutes and then washed.
After making due allowance for the sodium chloride present, an
ORGANIC CHEMSTRY. 75
analysis of tlie commercial article gave numbers corresponding with
the formula CnH<,N'04 + 2HNaS03.
Neither alizarin nor the purpurins possess the property of combin-
ing with alkaline bisulphites ; qninoline, however, forms very soluble
crystalline compounds, whose aqueous solutions decompose in the same
way as those of soluble alizarin blue. It appears therefore probable
that the capacity for combining with bisulphites rests in both cases with
the nitrogen-group. J. K. C.
Hydrocarbons of the Forimila (CsHg)^. By W. A. Tilden
{Chem. News, 46, 120 — 121). — The author has already suggested
(Trans., 1878, 85 — 88) that the liquid terpenes and citrenes (CioHie)
are not correctly represented as dihydrides of cymene. He now finds
that the hydrocarbons of the formula CsHs appear to supply important
evidence in connection with this question. The author has farther
examined isoprene, the most interesting of these hydrocarbons, and
observes that it boils at 35° (not 38°), has the vapour-density for CsHs,
that it forms a tetrabromide, C5H8Br4, an oily yellowish liquid which
cannot be distilled without decomposition, and remains liquid at —18°,
and moreover he confirms Bourchardat's statement that when heated
for some time at 280° it forms di-isoprene, CioHie (b. p. 174 — 176"),
apparently identical with terpilene from turpentine, yielding the same
hydrochloride, and being converted by the action of dilute acids into
terpin, C10H22O3, having the same crystalline form as the terpin from tur-
pentine. It likewise resembles turpentine in its behaviour with sulphuric
acid. Hence it seemed to the author that isoprene might be obtained
by depolymerising turpentine. When turpentine is passed through a
red-hot iron tube, among the other products a substance is found
(b. p. about 37", vap.-den. 35°, CoHe requires 34°), having the same
composition and some of the properties of isoprene. A litre of
turpentine yields about 20 c.c. of the fraction (37 — 40°). Reboul's
valerylene from amylene dibromide, and Hofmann's piperylene ( Abstr.,
1881, 571), are both isomerides of isoprene. Valerylene differs from
piperylene by not forming a tetrabromide and from isoprene by form-
ing a ketone when digested with mercuric bromide and water ; isoprene
is unaffected. Theoretically there are eight compounds of the formula
CsHg, all open chains ; of these, three are acetylenes, forming copper
and silver derivatives, thus differing from the above isomerides. As
valerylene is easily converted into a ketone, it would probably be cor-
rectly represented as a dimethylallene, either CHMe '. C 1 CHMe or
CMe2 .* C I CH2 ; and as isoprene does not undergo this change the
author is inclined to regard it as /S-methyl-crotonyiene, —
CH2 : CMe.CH : CH2.
It would be difficult to explain how such a substance could be poly-
merised into a methylpropylbenzene, therefore the author is of opinion
that terpene may be more correctly represented either by the formula
CH2 : CH.CMe : CH.CH : CHPr^ or thus :— "
CH2 : CPr^.CH : CH.CMe ! CH2.
He also feels disposed to look on isoprene as the first term of a series
somewhat analogous to the olefines, CsHs, CioHie, C15H24, &c. Colo-
76' ABSTRACTS OF CHEMICAL PAPERS.
phene from turpentine, seems to be a saturated hydrocarbon of this
form. The absorption spectrum of isoprene at the ultra-red end
has, according to Abnej, the characteristics of that of an aromatic
body. At the other end, according to Hartley, it resembles that of
australene, the main constitutent of common turpentine.
D. A. L.
Note. — Bourchardat has described two bromides of isoprene (Gompt.
rend,, 89, 1117—1120: this Journal, Abstr., 1880, 323).— D. A. L.
Essence of Sandal Wood. By P. Chapoteaut (Bull. Soc. Chim.
[2], 37, 303 — 305). — Essence of sandal wood, obtaining by distilling
the wood with water, is a somewhat thick liquid of sp. gr. 0*945 at
15°, and boiling between 300° and 340°. It consists almost entirely
of two oxygenated bodies, the more abundant of which is Ci5H2iO (b. p.
300°) ; and the other, CisHseO (b. p. 310°). When treated with phos-
phoric anhydride essence of sandal wood yields two hydrocarbons,
CxsHos (b. p. 248°), and O15H24 (b. p. 260°). Oil of cedar, when
puritied from oxygen compounds, has the composition C15H22, and boils
at the same temperature as the hydrocarbon from essence of sandal
wood. The two products are probably identical. The hydrocarbon,
C15H04, is either isomeric or identical with oil of copaiba.
When slowly distilled, essence of sandal wood yields products boiling
below 250° and above 350°, together with water and hydrogen, but the
decomposition is not complete. If the essence is heated in sealed
tubes at 310°, it splits up in accordance with the equations 4Ci5H240 =
C20H30O + CioHe^Og + 2R2, and G,,U,^0-, = C40H60O2 + H2O. The
compound, C90H30O, boils at 240°, and when treated with phosphoric
anhydride yields a cymene boiling at 175 — 180°. The product,
C40H62O3, is a thick liquid, boiling at about 340°, and the third body,
C4oHfio02 boils at 350°, and has the consistence of honey. The essence,
C15H26O, apparently splits up in a similar manner.
When heated at 150° under pressure for seven or eight hours with
half its weight of glacial acetic acid, essence of sandal wood yields two
products, CsoHi^O (b. p. 280—285°), formed from 2C,5H240 by loss of
H2O, and C17H08O2 (b. p. 298°), the acetate derived from the body
C15H26O. With hydrochloric acid at 125°, essence of sandal wood
yields a hydrochloride boiling at about 275°, but the reaction is more
complex than with acetic acid. The compound, C15H26O, has therefore
the properties of an alcohol ; the compound C17H24O has the properties
of an aldehyde, and is probably the aldehyde of CigHoeO.
C. H. B.
Synthesis of Salicin and of Anhydrosalicylic Glucoside.
By A. Michael (Z?er., 15, 1922 — 1925). — By the action of sodium
amalgam on helicin obtained from salicin, Lisenko succeeded in reform-
ing the latter body. The author has repeated this with artificial helicin
prepared by the action of acetochlorhydrose on potassium salicylate,
and has obtained salicin identical in properties with natural salicin.
In an attempt to make the glucoside of salicylic acid, the action of
acetochlorhydrose (2 mols.) on disodium salicylate (1 mol.) in
alcoholic solution was tried. The sodium chloride, which separated
out after several days, was filtered off, and by the spontaneous evapora-
ORGANIC CHEMISTRY. 77
tion of the filtrate, a body of the formula CajHaoOig was obtained,
crystallising in needles. A portion of the same substance also sepa-
rated with the sodium chloride. This new compound melted at 184 —
185° ; it is almost insoluble in water and cold alcohol, moderately
soluble in hot alcohol. It is insoluble in cold ammonia, but dissolves
gradually in cold soda. Boiling it with alkalis or acids decomposes it
into salicylic acid and dextrose. When heated with acetic anhydride
and sodium acetate, it forms an acetyl-derivative, C26H22O15XC8, melting
at 110—111°. A. K. M.
SantonoTis and Isosantonoiis Acids. By C. Cannizzaro and
G. Carnelutti {Gazzetta, 12, 393— 416). — I. Santonous Acid,
C15H20O3. — This acid, containing 2 atoms of hydrogen more than
syntonic acid, is prepared by heating santonin in a reflux apparatus
with hydriodic acid (b. p. 127°) and amorphous phosphorus. On
filtering the resulting liquid through asbestos, and digesting the solid
mass on the filter with cold aqueous sodium carbonate^ the santonous
acid dissolves, and on acidifying with hydrochloric acid and leaving
the liquid to cool, separates in needle-shaped crystals, which may be
purified by repeating this treatment several times, and finally crystal-
lising from ether. The acid thus purified crystallises in white needles,
melts at 178 — 179°, and resolidifies on cooling. Under a barometric
pressure of 5 mm., it distils unaltered at 200 — 260° ; under ordinary
pressure, it is partly decomposed by distillation. It is very soluble in
absolute alcohol and in ether, slightly in cold water, and crystallises
from a boiling aqueous solution on cooling. Its solutions are optically
dextrogyrate, a character by which it is most readily distinguished
from isosantonous acid, which is optically inactive. It dissolves at the
ordinary temperature in aqueous solutions of the alkaline carbonates,
and of the earthy-alkaline hydroxides. Its alkali salts are very
soluble in water and in alcohol, slightly also in a mixture of alcohol
and ether. — The sodium salt, CisHigNaOa, crystallises in very small
needles ; the silver salt, obtained by precipitation, blackens very
quickly even in the dark. — The barium salt, Ba(Ci6Hi903)2, is soluble
in water, and on evaporation in a vacuum separates in efflorescent
crystals ; on the other hand a cold saturated aqueous solution when
heated deposits a salt which is not efflorescent, although it contains
water of crystallisation ; it is also much more soluble than the salt
deposited at higher temperatures.
Ethyl santonite, CnH2403 = C15H19O3.C2H5, prepared in the usual
way, and purified by repeated crystallisation from ether, forms white
crystals, soluble in alcohol and ether, melting at 116 — 117°. Its solu-
tions are dextrogyrate. — Methyl santonite, prepared in like manner, is
white, very soluble in ether, and melts at 81 — 84°. -^E thy lie sodium-
santonite, CisHigNaOs-Et, obtained by boiling under pressure a solu-
tion of ethyl santonite in absolute ether with sodium, separates as a
white powder, and is instantly resolved by cold water into ethyl santo-
nite and sodium hydroxide. — Ethylic henzoT/l-aantonite, C24H08O3 =
CsHisBzOsEt, formed by heating ethyl santonite with benzoyl chlo-
ride in a reflux apparatus, is a white crystalline body, very soluble in
ether, melting at 78°. By boiling with alcoholic potash it is resolved
78 ABSTRACTS OF CHEMICAL PAPERS.
into benzoic and santonous acids. — Ethylic ethyhamtonite, CigHagOg =
CisHigEtO^.Et, obtained by heating ethylic sodinm-santonite with
ethyl iodide under pressure, crystallises in long needles, melts at 31 —
32°, dissolves in alcohol, and -very easily in ether. — Ethyhsaiitonous
acid, C17H24O3 = Ci6Hi9(C2H5)03, obtained by boiling ethylic ethyl-
santonite with alcoholic potash, crystallises in long slender needles,
melts between 115'5° and 116°, and exhibits strong acid properties.
It is reconverted into the ethylic ether by passing hydrogen chloride
through its alcoholic solution. The preceding facts show that san-
tonous acid contains, in addition to acid hydroxyl-groups, an alcoholic
or phenolic hydroxyl.
IsosANTONOUs AciD, C10H20O3. — When a mixture of santonous acid
(1 pt.) and barium hydroxide (3 pts.) is heated to a temperature above
the melting point of lead, a fused yellowish mass is obtained ; and on
exhausting this mass with hot water, and passing carbonic anhydride
into the filtered solution, barium carbonate is precipitated together with
a phenol ; and on again filtering and treating the filtrate with hydro-
chloric acid, isosantonous acid is precipitated in larger or smaller
quantity, according to the time for which the heating with baryta has
been prolonged. The acid is purified by dissolving it in alcohol, pre-
cipitating with hot water, pressing the precipitate between cloth, and
washing with water, till the liquid passes through clear. This treat-
ment is repeated several times, and the product finally crystallised
from ether. Isosantonous acid crystallises in laminae, different in
appearance from those of santonous acid, melts at 153 — 155°, and
resolidifies on cooling. It distils unaltered at 150 — 160° under a pres-
sure of 4 mm. ; under ordinary pressure, it partly distils, partly decom-
poses like santonous acid. It is soluble in alcohol and in ether, very
sparingly in cold water, and separates from a boiling aqueous solution
as it cools in shining plates. The solutions are optically inactive,
Isosantonous acid is a strong acid, and is easily etherified. The
ethylic ether, C17H24O3, prepared by passing hydrogen chloride through
the alcoholic solution of the acid, forms white crystals melting at 125°.
In this ether, as in ethyl santonite, an atom of hydrogen may be
replaced by benzoyl, sodium, or potassium, or by ethyl, whereby a series
of derivatives is obtained isomeric with the corresponding santonites,
but differing therefrom in melting point and other characters, especially
by the absence of rotatory power.
The following table exhibits a comparative view of the melting
points of the two isomeric acids and their ethereal derivatives : —
Santonous acid, C15H20O3 Isosantonous acid,
178°. 154°.
Ethylic santonite, CisHigOs.Et Ethylic isosantonite,
117°. _ 125°.
Ethylic benzoylsantonite, CisHisBzOa.Et Ethylic benzoylisosantonite,
78°. 91°.
Ethylic ethylsantonite, CisHisEtOa.Et Ethylic ethylisosantonite,
31°. 54°.
Ethylsantonous acid, CigHisEtOa.H Ethylisosantonous acid,
116°. 143°.
ORGANIC CHEMISTRY. 79
These two Isomeric acids further yield the same products of decom-
position, viz., dimethyl-naphthol and dimethyl-naphthalene.
DiMETHYL-NAPHTHOL, C12H12O = CioHvMez-OH. — This is the phenol
obtained, as already observed, together with isosantonous acid, by
heating santonous acid with barium hydroxide. It is also formed,
together with dimethyl-naphthalene, by distilling santonous acid with
zinc-powder, and may be separated by agitating the distillate with
potash-ley, and extracting with ether the portion not dissolved by the
alkali. The impure phenol, prepared in either way, may be purified
by dissolving it in alcohol, precipitating with hot water, washing the
precipitate on a cloth filter, and repeating this treatment till the pro-
duct presents a homogeneous appearance. Dimethyl-naphthol thus
purified crystallises in shining needles, melts without alteration at
135 — 136°, sublimes under ordinary pressure at 100°, and may be
boiled and distilled under reduced pressure. It is very soluble in
ether, soluble also in alcohol, very sparingly soluble in cold water, and
separates on cooling from its solution in boiling water in very small
needles. It dissolves in aqueous baryta, soda, and potash, and is pre-
cipitated by excess of the latter in a crystalline form.
Methylic dimethylna^phtholate, prepared by heating the phenol under
pressure with methyl alcohol and methyl iodide, crystallises in hard
white prisms, melts at 68°, is volatile, and dissolves in ethyl alcohol,
methyl alcohol, and more abundantly in ether. — The ethylic ether is a
viscid liquid, the solution of which in chloroform gives with bromine
a crystalline product which melts at 90°.
Acetyl-dimetkylnaphthol, CUH14O2 = Ci^Hn-XcO, prepared by boiling
the phenol with fused sodium acetate and excess of acetic anhydride,
crystallises after purification in white scales melting at 77 — 78°.
Dimethyl-naphthol, oxidised in acetic acid solution with chromic acid,
yields yellowish rhombic plates, and a very small quantity of white,
apparently rhomboidal prisms, both of which melt between 104° and
105°. The yellow crystals gave by analysis numbers agreeing nearly
with the formula C12H12O2. — This substance when treated with potash
blackens without dissolving. Heated with hydriodic acid and red
phosphorus, it is reconverted into dimethylnaphthol.
Dimethyl-naphthalene, C12H12 = doHeMea may be prepared by
heating dimethyl-naphthol with 10 parts of zinc-powder, and passing
the resulting vapour through a column of the same powder heated to
low redness, whereupon a yellow liquid distils over, from which potash
dissolves out unaltered dimethyl-naphthol. The whole is then dis-
tilled with steam, and the watery distillate, holding an oil in suspen-
sion, is mixed with potash and shaken with ether, which dissolves out
the dimethyl-naphthalene, together with a small quantity of naphtha-
lene. The ether having been evaporated off, the remaining oil is
boiled several times with sodium in a reflux apparatus till the globules
of the metal remain bright, and is then distilled in a Sprengel vacuum
at the heat of a salt-bath. By careful fractionation in this manner, it
is possible to separate small quantities of naphthalene, but the removal
of thQ last traces is very difficult.
Dimethyl-naphthalene purified in this manner as completely as
80 ABSTRACTS OF CHEMICAL PAPERS.
possible, boils at 262 — 264° under a pressure of 761 mm., has a density
of 1-0283 at 0°, and 1-10199 at 12°, and a vapour-density = 77-8°
(H. = 1), the calculated density being 78. It unites with picric acid,
forming a very characteristic compound, which may be obtained by
mixing the two bodies in hot concentrated alcoholic solution, and
crystallises on cooling in long orange-yellow needles melting at 139°.
Dimethyl-naphthalene also forms a characteristic tribromo-derivative,
CioHgBr'a, which crystallises in white needles melting at 228°.
The dimethyl-naphthalene obtained as above from diniethyl-naphthol,
may also be prepared by the action of methyl iodide on Gla.ser'8
dibromonaphthalene melting at 81° (Annalen, 135, 49) ; and finally,
together with the above-mentioned dimethyl-naphthol, and a small
quantity of xylene, by distilling santonous acid over zinc- powder in an
atmosphere of hydrogen.
Santonin, doHigOs (from wormseed), distilled with zinc-powder in
a stream of hydrogen, yields the same dimethyl-naphthalene, together
with propylene and a dimethyl-naphthol, apparently identical with that
which is obtained by the decomposition of santonous acid. The
authors have not been able to confirm the statement of Saint-Martin
(Gompt. rend., 75, 1120), according to which santonin distilled with
zinc-powder yields -a compound, which he calls santonal, partly liquid,
partly crystalline, and having the composition C30H18O2. H. W.
Psoromic Acid, a New Acid extracted from Psoroma
crassum. By G. Sptca (Gazzetta, 12, 431 — 433). — This lichen
grows in a few localities in Sicily, and the small quantity with which
the author's experiments were made was gathered near Dahlia, province
of Caltanisetta. By exhaustion with ether in a percolator, it yielded
a yellow substance (A) crystallisiiig in needles from the ether on cool-
ing, and a brown residue (B), which remained in considerable quantity
on distilling ofE the solvent.
The crystallised body is soluble in warm alcohol, ether, chloroform,
and acetic acid, and recrystallises from these solvents more or less on
cooling, but benzene, unless employed in large excess, dissolves only
a part of it, leaving a nearly white crystalline residue. The consti-
tuent soluble in benzene was purified by repeated crystallisation from
that liquid ; the insoluble portion by crystallisation from alcohol and
repeated washing with cold alcohol.
The yellow substance crystallised from benzene is usnic acid,
CisHigOs, melting at 195 — 197°, and yielding a sodium salt,
Ci8HnNa08,2H20,
which crystallises from warm water in stellate groups of needles.
The white substance only slightly soluble in benzene crystallises from
alcohol in silky needles, dissolves in the solvents above mentioned,'
and to a slight amount in water, to which it imparts a faint acid
reaction. It dissolves also in alkalis and alkaline carbonates, and in
sulphuric, nitric, and hydrochloric acids, melts with decomposition at
263 — 264°, and begins to sublime, but resolidifies at a high tempera-
ture, about 215°. Dried at 100° it gave by analysis 60-23 — 60-2y per
cent, carbon, and 3-71 — 3-97 hydrogen, leading to the formula C20H14O9,
ORGANIC CHEMISTRY. 81
which requires 60*30 carbon and 3*51 hydrogen. Its silver salt, obtained
by precipitation, forms white flocks, which alter on exposure to light.
The analysis of this salt leads to the formula C2oHi5AgOio, showing
that the corresponding acid (psorormc acid) has the composition
CzoHieOio, and that the compound C20HUO9 extracted from the lichen
as above described, is not the acid but the anhydride. The acid itself
has not been obtained in the free state.
Psoromic anhydride boiled with aniline is converted into a crystalline
yellow substance, which when further heated does not melt, but decom-
poses, yielding a carbonaceous residue, and a liquid having a charac-
teristic acetic odour, probably psoromic anilide. The anhydride heated
with water in sealed tubes at 240°, yields a yellow-brown liquid and a
brown residue, which, as well as the residue left on evaporating the
solution, exhibits the characters of an acid, and gives with ferric
chloride a dark green coloration, not produced by psoromic acid.
The brown residue B, left on evaporating the ether used for the
extraction, yields to benzene a small quantity of a resinous substance,
together with psoromic acid.
The lichen, after exhaustion with ether, yields to boiling alcohol a
substance having the characters of a wax. This the author reserves
for further examination. H. W.
Laws of Variation of the Specific Rotatory Power of Alka-
loids under the Influence of Acids. By A. 0. Oudemans, Jun.
(Bee. Trav. Ghim., 1, 18 — 40). — The author records and tabulates a
large number of observations relating to the influence of acids, organic
and inorganic, on the mon-acid bases quinamine and conquinaniine,
and on the biacid bases quinine, quinidine, cinchonine, and cinchoni-
dine, both in aqueous and in alcohohc solution, — and deduces from
these observations the following general conclusions : —
1. The specific rotatory power of the mon-acid bases, as mani-
fested in the aqueous solutions of their normal salts, is the same for
all the salts, and is independent of the chemical character of the acid
with which the base is united. Small differences occasionally ob-
served are due to partial and unequal decomposition of these salts
under the influence of water, and to the varying influence of the
degree of concentration on the different salts.
2. As long as the normal salt is not decomposed by water, this
speciflc rotatory power coincides with the maximum value, the small
differences sometimes observed arising from partial decomposition.
3. Biacid bases form two series of salts, in each of which series the
base exhibits a distinct specific rotatory power, the value of which is
usually much smaller in the basic than in the normal salts.
4. The real specific rotatory power of the biacid bases in the form
of normal salts and in aqueous solution is probably the same for all
the salts, and independent of the chemical nature of the acid with
which the base is combined ; but in consequence of partial decomposi-
tion and of the unequal influence of concentration on the various salts,
the specific rotatory power cannot show itself with its true value.
6. The real specific rotatory power of the biacid bases in the form of
VOL. XLiv. g
82' ABSTRACTS OF CHEMICAL PAPERS.
hasic salts is probably the same for all the salts, the difierences between
the observed values being due to partial decomposition, and for the
most part to the unequal influence of concentration on the different
salts. H. W.
Action of Nascent Hydrogen on Pyrroline. By G. L. Ciamicun
and M. Dennstedt (Ber., 15, 1831 — 1832). — An acetic acid solution
of pyrroline is heated with zinc-dust for some days, the excess of pyrrol
distilled off with steam, the zinc removed by sulphuretted hydrogen,
and the acetic replaced by hydrochloric acid. The solution is then
treated with potash and steam-distilled, the distillate treated with
hydrochloric acid and evaporated to dryness on a water-bath, redis-
solved, and steam-distilled with potash. The first portions of the dis-
tillate richest in the base are mixed with solid potash, whereby the
base is separated as an oil, and, after drying over fresh potash is
again distilled. It boils at 90 — 91°, and is a colourless liquid having
a strongly alkaline reaction and ammoniacal odour ; it is very soluble
in water, from which it is not easily separated. The platinochloride
alone was analysed, as the free base could not be obtained in a suffi-
ciently dry state. The former is a yellow precipitate almost insoluble
in cold water. Analysis of this compound leads to the formula C4H7N
for the free base. J. K. C.
Synthesis of Pyridine Derivatives from Ethyl Acetoacetate
and Aldehydammonia. By A. Hantzsch (Annalen, 215, 1—82). —
Diethyl hydrocollidinedicarhoxi/late, C5Me3(COOEt)2H2N', is prepared by
warming a mixture of 52 grams of ethyl acetoacetate and 13'5 grams
of aldehydammonia for five minutes, and then adding an equal bulk
of dilute hydrochloric acid to the mixture. After extracting the
crude product with dilute hydrochloric acid and with water, . it is
recrystallised from boiling alcohol. Diethyl hydrocollidinecarboxylate
crystallises in monoclinic or triclinic plates or needles (m. p. 131°)
freely soluble in chloroform and hot alcohol. It begins to boil at 315°,
but rapidly decomposes at this temperature. This ethereal salt resists
the action of aqueous solutions of potash, but is completely decom-
posed by .alcoholic potash. By the action of warm fuming hydro-
chloric acid, it is split up, yielding acetone, ethyl chloride, ammonium
chloride, and aldehyde, diHaiOiN + 3H2O + 3HC1 = 2C0a +
2C2H6CI + 2C8H60 4- C2H4O -h NH4CI.
Ethyl dihromhydrocolUdinedicarhoxylate dibromidej
C8H7Br2(COOEt)2H2N,Br2,
formed by the action of bromine diluted with carbon bisulphide on the
previously-mentioned ethylic salt, crystallises in thick prisms (m. p. 88°)
of a yellow colour. The substance dissolves freely in hot alcohol.
By the action of strong nitric acid, it is converted into ethyl dibromo-
colUdinedicnrhoxylate dibronude, C8H7Br2(COOEt)2NBr2, which crystal-
lises in white needles (m. p. 102°) soluble in ether and in alcohol.
When chlorine is passed into a solution of ethyl hydrocollidinecar-
boxylate in chloroform, the hepta- derivative, C8H4Cl5(COOEt)2Cl2N,
ORGANIC CHEMISTRY. 83
is produced. This siibstance crystallises in needles (m. p. 150°)
sparingly soluble in hot alcohol.
Ethyl coUidi7iedicarboxylate, C5NMe3(COOEt)2, is best prepared by
the action of nitrous acid on a mixture of equal weights of alcohol
and ethyl hydrocoUidinedicarboxylate. When the reaction is complete,
the excess of alcohol is removed by evaporation, and a dilute solution
of sodium carbonate is added to the residue, which causes the ethyl
collidinedicarboxylate to separate out in the form of a heavy oil boiling
at 310°. This ethylic salt has the sp. gr. 1-087 at 15°. It combines
readily with acids. The hydrochloride, Ci4H904]Sr,HCl, is deliquescent.
The platinochloride, (Ci4Hi90iN)2H2,PtCl6, forms pink-coloured tri-
clinic plates melting at 184°, insoluble in alcohol and ether, but soluble
in water. The nitrate crystallises in vitreous needles which melt at 92°
and decompose at 122°. The hydriodide crystallises in plates, soluble
in water and in hot alcohol. It melts at 170° with decomposition.
By the action of an alcoholic solution of iodine, this salt is converted
into the triodide, CuHi902N'HI,l3. The methiodide, CuHi904N,MeI,
crystallises in white needles soluble in alcohol and water. Although
it is precipitated from its aqueous solution by soda, it has a strongly
acid reaction. The crystals melt at 138'' and decompose at 160"".
Ethyl collidinedicarboxylate is not attacked by strong hydrochloric
acid or by ammonia at 150°, but it is easily saponified by alcoholic
potash. From the potassium salt, lead collidinedicarboxylate and the
free acid can be prepared. GolUdinedicarboxylic acid, C5N'Me3(COOH)2,
forms needle-shaped crystals, sparingly soluble in alcohol, ether, and
cold water. The salts which this acid forms with the alkalis and
alkaline earths are very soluble in water and do not crystallise well ;
C8H9N(COO)2Ba 4- 3H2O is more soluble in water than the calcium
salt C8ll9N(COO)2Ca + HjO^ which crystallises in needles. The
silver salt, C8H9N(COOAg)2, is an amorphous body insoluble in water.
The pale-green precipitate, obtained by the addition of potassium
collidinedicarboxylate to a solution of copper sulphate, has the com-
position 2C8H9N(CO)20 + 3CaO + IIH2O. On boiling the mixture
a pale-blue salt is produced which has the composition C8H9N(CO)aO
-f 3CuO.
The hydrochloride of collidinedicarboxylic acid, C10IIUO4NHCI -f
2H2O, and the platinochloride, (CioHu04N)2,H2PtCl6, are crystalline.
On heating potassium collidinedicarboxylate with lime, ^-collidine,
or |S-trimethylpyridine, C5NMe3H2, is obtained. The following table
shows the most marked points of difference between a- and jS-coUi-
dine : —
84
ABSTRACTS OF CHEMICAL PAPERS.
Solubility
Exposure to air
C8Hii]S,HAuCl4
The addition of CrOs giyes
Mn, Co, and Fe salts . . . .
AgNOs
a-Collidine.
B. p. 178°, sp. gr. 0-953.
Very sliglitly soluble
in water.
No change.
Does not melt under
water.
Red oil.
No precipitate.
No precipitate.
/3-Collidine.
B. p. 171°, sp. gr. 0-917 at 15'
More soluble in cold than hot
water.
Turns brown.
Melts under water; the dry
salt melts at 112°.
Red crystalline precipitate of
(C8HnN),H2Cr207.
Slow precipitation of hydr-
oxides.
White crystalline precipitate
soluble in hot water.
An ethereal solution of ethyl hydrocollidinedicarboxylate absorbs
hydrochloric acid gas, forming ethyl coUidinedicarboxylate and other
products. Dilute hydrochloric acid decomposes ethyl dihydrocoUi-
dinedicarboxylate at 100°, yielding ethyl chloride, carbonic anhydride,
and ethyl dihydrocollidinemonocarhoxylate, CsHnNH.COOEt, as a
colourless oil. On treating the alcoholic solution of this ethylic salt
with nitrous acid, it yelds ethyl collidinemonocarhoxylate^
C5NHMe3,COOEt.
The platinochloride, (CiiHi502N)2,H2PtCl6, crystallises in prisms
melting at 194°, soluble in water. By the action of dilute hydrochloric
acid on ethyl dihydrocollidinedicarboxylate at 125°, a mixture of di-
hydrocoUidine, tetrahydrodicoUidine, a ketone, CsHiaO, and another
body of the composition C8H14O2, is obtained. On distilling the crude
product in a current of steam, the two bases are found in the residue.
Dihydrocollidine, C&H13N, is a strongly alkaline liquid, boiling at
176 — 180°, and having a penetrating odour. It dissolves in cold
water, but is reprecipitated on heating the solution. The pluthw-
chloride, (C8Hi3N)2,H2PtCl6, and the hydriodide, CgHisN,!!!, are crys-
talline. DihydrocoUidine readily precipitates the hydroxides of mag-
nesium, iron, manganese, and nickel from solutions of their salts,
and forms a crystalline compound with methyl iodide. It is not
oxidised by nitrous acid. TetrahydrodicoUidine., C16H26N2, boils at 255 —
260°. The hydriodide, C16H26N2JHI, is very soluble in water and
alcohol. The jjlatinochloride^ Ci6H26N2,H2PtCl6, crystallises with
difficulty.
The ketone, C8H12O, is a mobile liquid having a pleasant odour and
boiling at 208°. It combines directly with bromine to form the tetra-
bromide C8Hi2Br40, an oily liquid. By the action of bromine on this
compound a crystalline substance is obtained of the composition
C8H8Br40 or C8H6Br40, melting at 138°.
Oxidation-products of CoUidinedicarhoxylic Acid. — Potassium coUi-
dinedicarboxylate is converted into the lutidinedicarboxylate by boil-
ing it with the theoretical amount of potassium permanganate solution
for two hours. From the potassium salt, the lead salt and the free
ORGANIC CHEMISTRY. 85
acid are prepared. Lutidinetricarloxylic acid, CioHgOeN + 2H2O,
resembles collidinedicarboxylic acid. It crystallises in rhombohedrons,
which lose their water of crystallisation at 120° and melt at 212° with
decomposition. The neutral potassium salt of this acid is deliquescent ;
the ammonia salt is very soluble in water : (CioH606N)2Ba3 + 8H2O
forms hygroscopic needles ; (CioH60&N)2Ca3 + 8H2O is gelatinous ;
(CioH606N)2Mg3 4- IOH2O is also amorphous and freeJy soluble.
CioHeOe^Aga and the lead and merourous salts are insoluble or
sparingly soluble. Lutidine, C6Me2H3N, obtained by heating a mix-
ture of potassium lutidinetricarboxylate and lime, boils at 154°.
By the prolonged action of potassium permanganate on potassium
collidinedicarboxylate, the potassium salts of picolinetetracarboxylic
acid and pyridinepentacarboxylic acid are produced. To obtain pico-
linetetracarboxylic acid, strong nitric acid is added to a solution of the
crude potassium salt, which precipitates an acid salt of the composition
C5lSrMe(COOH)3(COOK)2 + 4H2O. The concentrated solution of this
salt is decomposed by strong sulphuric acid, and the free acid extracted
with ether. Pyridinepentacarboxylic acid is obtained by a similar
process. Picolinetetracarboxylic acid, C5NMe(COOH)4 + 2H2O, crys-
tallises in prisms which lose their water of crystallisation at 120°, and
melt with decomposition at 199°. The acid dissolves freely in water.
Its salts do not crystallise well. The dipotassium salt forms large
rhombic plates ; the mono-potassium salt, C5NMe(COOH)3.COOK +
2H2O, crystallises in needles. C5NMe(C204Ca)2 + ^HgO is sparingly
soluble. Picoline, CgNMeHi, boils at 135°.
Pyridinepentacarboxylic acid, C5N(COOH)5 + 2H2O, dissolves freely
in water, forming a strongly acid solution. The crystals lose their
water of crystallisation at 120°, and decompose without melting at
220°. It is a powerful acid, resembling oxalic acid in its property of
forming acid and double salts. The following pyridinepentacarboxyl-
ates were prepared: — C10H4O10NK 4- 3 or 2H,.0, shining needles.
C10H3O10NK2 + 4 or S^HaO, cubes. C5N(COOK)5, crystalline powder,
freely soluble in water. (CioOioN)2Ba5 + IIH2O is deposited as a
crystalline powder when barium chloride is added to the free acid.
(CioOioN)2Ca5 + I2H2O, sparingly soluble non- crystalline powder.
CioOioNHaCa -1- -^1120, sparingly soluble crystalline powder.
Ci60ioNCa2.NH4 -f 5H2O is deposited as an amorphous precipitate
when pyridinepentacarboxylic acid is added to an ammoniacal solution
of calcium chloride. The ammonium in this salt can be replaced by
potassium or sodium. Acid potassium oxalate also forms a double salt
with potassium pyridinepentacarboxylate, viz., C10O10NH4K -|- C2O4HK
+ 5H2O. Pyridine, C5H5N, obtained by the action of lime on potas-
sium pyridinepentacarboxylate, boils at 120°. W. C. W.
Dipyridyl Derivatives. By Z. H. Skraup and G. Vortmann
(Mo7iatsh. Chem., 3, 570 — 602). — In this paper, the authors show that
the reaction which takes place in the synthesis of quinoline, hitherto
applied only to mono-substituted derivatives of benzene and phenol
(Abstr., 1881, 919 ; also this vol., p. 89), may be extended to the
diamidobenzenes, and in particular they describe the results ob-
tained by heating a mixture of m-diamido- and m-dinitro-benzene
86 ABSTRACTS OF CHEMICAL PAPERS.
with salphnric acid and glycerol. The diaraidobenzene — which waa
employed in the form of stannochloride — was prepared by the action
of tin and hydrochloric acid on m-nitraniline ; and the solution
obtained by treating this stannochloride with glycerol and sulphuric
acid — after being freed from separated resin and rendered alkaline —
was shaken up with alcoholic ether. The ethereal liquid was then
exhausted with hydrochloric acid ; the solution of the new base thus
obtained was evaporated ; and the hydrochloride which crystallised
out from it after addition of alcohol was converted by potassium
dichromate into a sparingly soluble chromate (foreign matters being
at the same time destroyed by oxidation) ; this chromate, heated
with ammonia, yielded the base in the form of a hydrate, which when
left over sulphuric acid, or more quickly when heated at 100°, gave off
its water, leaving the anhydrous base, which was purified by distil-
lation.
The base thus obtained is regarded by the authors, for reasons to be
explained further on, as formed by the attachment of two pyridine-
rings to a benzene-ring, in the manner represented by the right-hand
fio;ure below, and may be called phenanthroline, from the analogy
of its structure to that of phenanthrene.
N
N
Phenanthrene. Phenanthroline.
Pure phenanthroline forms a white crystalline mass made up of four-
sided plates. It has a faint odour when cold, becoming stronger on
heating, and resembling that of naphthaquinoline. It melts at 78 —
78*5°, remains liquid for some time after cooling, but then solidifies
instantaneously on being touched with a solid body. It is somewhat
hygroscopic, the clear crystals when exposed to the air becoming
covered with a white opaque coating, and ultimately falling to powder.
When the fused substance is covered with a very thin film of water
and rubbed with a glass rod, it is completely converted into the
hydrate, which is thus obtained as a perfectly dry mass. Phenanthro-
line is nearly insoluble in cold, more easily soluble in boiling water,
dissolves in all proportions in alcohol, but is nearly insoluble in ether,
benzene, and light petroleum ; dilute acids dissolve it readily. The
aqueous solution is nearly neutral when cold, but has a distinct alka-
line reaction at the boiling heat. The pure base may be distilled with-
out decomposition, and boils at a temperature much above 360°. It
volatilises to a slight extent with the vapour of water. The hydrated
compound, Ci2H8N2,2H20, crystallises in long soft needles, which do
not effloresce on exposure to the air, but give off their water over
sulphuric acid, and melt in a capillary tube at 65"5°.
Phenanthroline in most of its salts appears as a mon-acid base, and
it is only with a great excess of acid and very strong solutions that
normal salts can be obtained in which it is bi-acid. The basic hydro-
chloride, Ci2H8N2,HCl + H2O, separates from alcoholic solution, even
in presence of excess of acid, in long white prisms, easily soluble in
ORGANIC CHEMISTRY. 87
water, sparingly in aicohol. The normal salt, Ci3H8N2,2HCl + 2H,0,
separates in small prisms on cooling from a warm solution of the base
in a small quantity of strong hydrochloric acid. It is very unstable,
and is decomposed by water. The platinochloride, Ci2H8N2,H2PtCl4 +
H2O, forms small reddish-yellow prisms, sparingly soluble in alcohol.
The chromate, (Ci2H8N2)2Cr207, forms golden-yellow needles, slightly
soluble in cold water. The picrats, Ci2H8N2,C6H2(N02)3.0H, crystallises
in light-yellow prisms, very slightly soluble in alcohol, melting at
238 — 240°. The sulphate is sparingly soluble in alcohol ; the tartrate
both in alcohol and in water.
A methiodide, Ci2H8N2,MeI + H2O, obtained by heating phenan-
throline at lOO'' with methyl alcohol and excess of methyl iodide,
crystallises in broad prisms, dissolves easily in water, sparingly in
alcohol, and gives off its water of crystallisation with great facility.
Its aqueous solution turns red on addition of potash-lye, and deposits
a non-solidifying oil.
Bromides. — On adding bromine to a hot concentrated alcoholic
solution of phenan thro line, an octohromide, Ci2H8N2,Br8, separates in
red crystals melting at 176 — 178°. The dibroniide, Ci2H8N2,Br2, sepa-
rates on adding bromine-water to an aqueous solution of phenan-
throline hydrochloride, as a light yellow crystalline precipitate melting
at 149° ; heated for a short time with a small quantity of alcohol,
it is converted into dark-red crystals which have the composition
(Ci2H8N'2)2Br3, or C,2H8N2,Br2 -\- Ci2H8lSr2,HBr, melting at 178°, and
giving ofl' bromine when heated with water. By prolonged boiling with
alcohol, the dibromide is converted first into orange-red slender needles,
then into thick yellow prisms, and finally into nearly colourless needles,
consisting of phenan throline hydrobromide, Ci2H8N2,HBr + -^1120,
melting at 278 — 280°. When, on the other hand, phenanthroline is
heated at 120 — 130° with excess of bromine and water, it yields a
brownish-yellow bromine-compound, which dissolves in glacial acetic
acid, and separates therefrom in non-crystalline crusts, and appears to
be a mixture of Ci2H6Br2N2 and Ci2H5Br3N2.
Hydrides. — By reduction with tin and hydrochloric acid, phenan-
throline is converted into an amorphous compound purifiable by dis-
tillation, and probably consisting of a mixture of tetra- and octo-hydride
of phenanthroline, Ci2H8N2,H4 and Ci2H8N2,H8.
Dipyridyl-carboxylic Acids. — Phenanthroline is readily oxidised
by potassium permanganate in very dilute solution (5 : lUOO), yielding
as chief product — together with a small quantity of quinolinic or
pyridine-dicarboxylic acid — an acid, C12H8N2O4, or CioH6N3(COOH)2,
called phenanthrolinic or dipyridyl-di carboxylic acid, which
may be isolated by nearly neutralising the concentrated filtrate with
nitric acid, adding the calculated quantity of silver nitrate, and pre-
cipitating the resulting silver salt of phenanthrolinic acid by further
cautious addition of nitric acid. This silver salt decomposed by
hydrogen sulphide, yields the phenanthrolinic acid in large triclinic
tablets, having the axes a : h : c = 0*5909 : 1 : 0*9773, and exhibiting
the faces coPoo, OP, ooPj, oo;P, P', 'P, ,P, P,. They contain crystal-
water, have a slightly acid taste, dissolve sparingly in cold, more
freely in boiling water, easily in alcohol, very sparingly in ether and
B8 ABSTRACTS OF CHEMICAL PAPERS.
in benzene. They give off their water at 100°, melt with evohition of
carbonic anhydride at 217**, give a blood-red to yellow-red coloration
with ferrous sulphate, a yellowish gradually crystallising precipitate
with ferric chloride and sodium carbonate, no precipitate with bro-
mine-water.
Phenanthrolinic acid forms salts both with bases and with acids.
The normal potassium salt is extremely deliquescent, and remains on
evaporating its aqueous solution, as a vitreous mass, which becomes
crystalline when left in contact with alcohol. The acid potassium salt^
Ci2H7N'204K,llH20, may be crystallised in like manner. The calcium
salt, Ci2H6N204Ca,.3H20, forms transparent shimmering laminae ; the
barium salt, Ci2H6N204Ba,lJH20, very sparingly soluble granules ; the
copper salt, Ci2H6N204Cu,3H20, nearly insoluble greenish-blue granules ;
the normal silver salt forms microscopic laminae ; the acid silver salt,
C,2H7lSr204Ag,4!H20, is a precipitate composed of stellate groups of
needles. The hydrochloride, Ci2H8N204,2HCl, prepared with strong
hydrochloric acid, forms transparent prisms. The platinochloride,
(Ci2H8]Sr204,HCl)2,PtCl4 -f 6H2O, separates gradually in large thick
yellow prisms, and the mother-liquor when left to evaporate yields the
salt Ci2H8!N"204,H2PtCl6 in orange-red tablets.
Dipyridyl-monocarboxylic acid,
CuHsN^Oa = CioH^NaCCOOH),
is obtained by heating phenanthrolinic acid to its melting point, and
crystallises in delicate white needles containing 2H2O, which they give
off at 100°. The dehydrated acid cakes together at 179°, melts at
182"5^ — 184°, solidifying to a vitreous mass on cooling, and is but
slightly decomposed by distillation. It dissolves with difficulty in cold
water and alcohol, easily with the aid of heat ; gives no coloration
with ferrous sulphate, yellow-brown with ferric chloride ; a lightrblue
crystalline precipitate with cupric acetate, and with silver nitrate a
white precipitate soluble in excess of the acid and of the precipitant;
with bromine-water a cinnabar-red precipitate. The calcium salt,
(CuH7N202)2Ca,2H20, forms long shining easily soluble needles, which
give off their water at 220° ; the silver salt, CiiH7]N'202Ag,-|H20, is a
dense precipitate, which becomes crystalline on standing.
Adipyridyl, CioH8N'2, is obtained by distilling calcium dipyridyl-
monocarboxylate with quicklime, and passes over as a colourless oil,
boiling at 149'5°. Its picrate, CioH8N2,C6H..(N02)3-OH, forms small
dull-yellow needles, slightly soluble in cold water, melting at 1495° ;
and its platinochloride, CioH8N2,H2PtCl6 + iH20, is a light-yellow
precipitate, very slightly soluble in water and in hydrochloric acid.
This dipyridyl, which differs distinctly from Anderson's dipyridine,
and from the isodipyridine of Cahours and £ltard, is related to pyri-
dine in the same manner that diphenyl is related to benzene. The
formation of dipyridyl-dicarboxylic acid has led the authors to assign
to phenanthroline the constitutional formula above given (p. 86),
analogous to that of phenanthrene. H. W.
Quinoline from Cinchonine. By 0. de Coninck (Bull. Sac.
ORGANIC CHEMISTRY. 89
CUm. [2], 37, 208—209 ; see this vol., 414).— The hydrochloric acid
solution of the fraction of crade quinoline boiling between 226 — 231°
is repeatedly treated with ether, which removes a small quantity of a
neutral compound having a strong odour, and boiling at about 220°.
The purified base is then distilled. It is at first colourless, but darkens
somewhat rapidly, even when protected from air and light ; sp. gr. at 0°
= 1-1055 ; at 11-5, 1-0965 ; b. p. 236—237° at 775 mm. The quinoline
obtained by adding potash to crystalHsed quinoline tartrate, also boils
at 236 — 237° under the same pressure. Quinoline obtained by synthesis
boils at 228° (Skraup and Koenigs), or 232° (Baeyer and others).
Quinoline hydrochloride forms white deliquescent crystals, which emit
an odour of quinoline, and melt at 93 — 94° to a colourless liquid. The
hydrochloride is very soluble in warm, slightly less soluble in cold
water, soluble in all proportions in absolute alcohol and chloroform,
only slightly soluble in cold, but very soluble in hot ether or ben-
zene. C. H. B.
The Quinoline of Coal-tar and of the Cinchona Alkaloids,
and its Oxidation by Potassium Permanganate. By S. Hooge-
WERFF and W. A. V. Dorp {Uec. Trav. Chim., 1, 1 — 17 and 107—131).
— After a historical sketch of the discussion as to the identity or
isomerism of the bases C9H7N, obtained from the cinchona alkaloids
(quinoline), and from coal-tar (leucoline), the authors describe the
methods which they adopted for purifying the bases obtained from
these two sources, and give as the mean results of their analyses
of both bases C = 83-58 per cent., H = 5*8. The boiling points
found were for quinoline 238-25° to 239*25°, and for leucoline
239-25° to 240*25° (thermometer wholly in vapour). Moreover,
both yield the same hydrate, 2C9H7N,3H20, platinochloride,
(C9H7N)2,H2PtCl6 + 2H2O,
dichromate, (C9H7N)2H2Cr207, and argentonitrate. By oxidation with
potassium permanganate in alkaline solution, both bases yield, as
principal products, carbonic anhydride and quinoleic acid, C7H5NO4,
according to the equation C9H7N -|- O9 = C7H6NO4 + 2CO2 + H2O,
together with very small quantities of oxalic acid and ammonia. The
identity of the bases from the two sources may therefore be regarded
as established, and the name "leucoline" may be dropped.
The quinoleic acid may be separated from the products by neutra-
lising with nitric acid, removing the crystals of potassium nitrate
which separate on concentration, then precipitating with calcium
nitrate, treating the concentrated filtrate with lead nitrate, decom-
posing the resulting precipitate with hydrogen sulphide, and con-
centrating the solution filtered therefrom. Quinoleic acid is then
deposited in small honey-yellow monocliuic crystals, having the axes
a:b:c = 0-5418 : 1 : 0*6075 and fi = 64° 54'. Observed faces, coP,
Poo, ooP<>o, and a pyramidal face not determined. Cleavage, parallel
' to the clinopinacoid. *
Quinoleic acid is but slightly soluble in cold, rather more so in hot
water, very slightly soluble in alcohol, insoluble in benzene, and is
removed from its aqueous solution by ether. It is but very slightly
90
ABSTRACTS OF CHEMICAL PAPERS.
attacked by potassium permanganate in alkaline solution, easily in
acid solution. When heated to 100°, it gives off CO2 and leaves
nicotic acid, CeHsNOj. Heated in capillary tubes, it begins to turn
brown at 175°, and melts at 228 — 230°, but if rapidly heated it melts
at about 180°, giving off gas and resolidifying, after which it melts
at 228°. Heated with lime, it yields an oil smelling of pyridine.
A cold moderately dilute aqueous solution of this acid exhibits the
With—
Fe2Cl6 : yellow - brown, amor-
phous.
CuSOi : light - bine, apparently
amorphous, nearly insoluble in
water and acetic acid, even at
boiling heat.
Hg(N03)2 : white pp. ; micro-
scopic needles.
Pt(C2H302)2 ; like the last.
AgNOa : shining needles of acid
salt (infra).
following reactions.
CaCl2: gelatinous pp., gradually
becoming crystalline.
BaCU : gelatinous pp.
ZnSOi : pp. of microscopic needles
after a few hours.
MuSOi : like the last, but smaller
crystals.
00(^03)2 : like the last ; pp. rose-
coloured.
]S'iS04 and HgCla : no pp.
FeS04: orange colour; yellow-
brown crystalline pp. after some
time.
Quinoleic acid is a pyridine-dicarboxylic acid,
12 3
C5H3N(COOH)(COOH).
It is therefore bibasic. The acid potassium salt, C7H4N04K,2H20,
forms limpid triclinic crystals, which give off their water at 100°. The
normal barium salt, C7H3N04Ba, obtained by adding a soluble barium
salt to a cold solution of the acid neutralised with ammonia, crystal-
lises sometimes with 1^, sometimes with 2| mols. HoO, part of which
goes off at 100°, the last semi-molecule only at 260°. The normal
silver salt, C7H3N04Ag2, is obtained by adding silver nitrate to a cold
neutralised solution of the' acid, as a gelatinous precipitate which
becomes granular or crystalline on standing. The acid salt,
C,H4N04Ag + H2O,
is obtained by adding a hot aqueous solution of the acid to an acid
solution of silver nitrate diluted with boiling water, and separates on
cooling in concentric groups of shining needles. Sometimes, how-
ever, a hyper-acid salt, C7H4N04Ag,C7H5N04, is deposited under these
conditions, in concentric groups of small needles.
Quinoleic acid, when heated at 120 — 140° and upwards, gives off water
and carbonic anhydride, and is converted into nicotic acid, C6H6NO2
= C7H6NO4 — CO2. The same result is obtained by heating quinolei«
acid with acetic acid. The nicotic acid thus produced agrees in
chai*acter with that which is obtained by other methods. Its calcium
salt, (C6H4N02)2Ca, forms monoclinic crystals ; a : b : c= 1'5372 : 1 :
0-6293. (S = 62-50. Observed faces, 00 P, Pob. H. W.
Nitro- and Amido-bromoquinoline. By W. La Coste (Ber., 15,
1918 — 1922). — Bromoquinoline (prepared from parabromaniline) is
ORGANIC CHEMISTRY. 91
added gradually to a mixture of two parts sulphuric acid and one
part fuming nitric acid, the whole being cooled if necessary. On
pouring the product into water and neutralising with sodium carbo-
natCj nitrobromoquinoline is precipitated, and can be purijBed by
crystallisation from alcohol. It forms long yellowish-white needles,
which melt at 133°. It dissolves readily in ether and in boiling
alcohol, and is slightly soluble in boilinor water, from which it crys-
tallises in long thin colourless needles. With platinum chloride, nitro-
bromoquinoline gives a bright-yellow crystalline precipitate,
[C9H5NBr(N02),HCl]2,PtCl4.
Bromoquinoline, obtained by the bromination of quinoline, also yields
a nitro-compound which melts at 133°. It crystallises from hot
alcohol in short yellowish needles, grouped together in nodules. It
gives a yellow granular precipitate with platinum chloride.
For the reduction of nitro- to amido-bromoquinoline, it is best to
heat it in alcoholic solution with an acid (HCl) solution of stannous
chloride. The double salt which crystallises out on cooling is dissolved
in water, and treated with dilute soda-solution, when amidobromo-
quinoline separates in flocks, and may be crystallised from boiling
water. It forms long almost colourless needles, containing 1 mol.
H2O, which it loses over sulphuric acid. It melts (anhydrous) at
164°. 5 Amidobromoquinoline is a weak base, which forms salts with
acids. The nitrate, C9H5NBr(NH2),HN03, forms gold-coloured groups
of needles ; it explodes on heating. The hydrochloride crystallises in
very soluble red prisms, which contain water of crystallisation ; it forms
a platinochloride. Acetamidohromo quinoline, C9H5NBr.NII.COMe,
crystallises in colourless plates melting at 104 — 105°.
A. K. M.
Hydroxyqninoline. By 0. Fischer (J?er., 15, 1979—1981).—
Quinoline yields two isomeric monosulphonic acids, of which the
ortho-acid, as previously described (Abstr., 1882, 869), yields the
hydroxyqninoline of melting point 75 — *7Qi°. The meta-acid crystal-
lises in long thin colourless needles, and is more readily soluble in
water than the ortho-acid ; it is best separated by the difference of
solubility of the calcium salts, the meta-salt being the more soluble.
The best yield of the md^a-acid is obtained by conducting the reaction
at 140 — 150°, the yield being then 10 — 15 per cent.
Metahydroxy quinoline forms colourless silky needles, melting at about
230°, it is readily soluble in alcohol and benzene, sparingly in water,
ether, and light petroleum. With ferric chloride, it yields no colora-
tion in the cold, but on heating a faint red tint appears. The platino-
chloride forms brownish-yellow prisms.
Metamethoxy quinoline, prepared in a similar manner to the ortho-
compound .{loc. cit.), is a limpid oil, boiling with partial decomposition
at 275° under 720 mm. pressure. The platinochloride crystallises in
long brownish-yellow prisms ; the picrate crystallises in tufts of thin
needles, both salts are sparingly soluble in water. The oxalate forms
silky needles, readily soluble in water.
On distilling sodium quinolinorthosulphonate with potassium
cyanide, the distillate was found to contain a mixture of ortbo- and
92 ABSTRACTS OF CHEMICAL PAPERS.
meta-cyanoquinolines, the latter being in excess, intra-molecnlar
change having occurred. A. J. G.
Synthetic Researches in the Quinoline Series. By Z. H.
Skraup (Monatsh. Chem., 3, 531 — 569). — Htdroxtquinolines,
C9H7NO = CeHaN : CeHaOH.
These bases (ortho, meta, and para, according to the relative positions
of the ]N -atoms and the OH-group) are formed by heating a mixture
of an amidophenol (or better its hydrochloride) and the corresponding
nitrophenol, with sulphuric acid and glycerol, according to the equation
C6H4(NH2).OH + C3H8O3 = CgHeNOH + SH^O + H^. The amido-
phenols used for the purpose must be pure, as even small quantities of
foreign substances greatly diminish the yield of hydroxyqn incline.
Ortho-hydroxyquinoline is but very slightly soluble in water,
easily soluble in absolute alcohol, less soluble in aqueous alcohol.
From water and from dilute alcohol, it separates in anhydrous brittle
prisms, from absolute alcohol in more compact crystals. Ether dis-
solves it with difficulty, warm benzene in all proportions. The solu-
tions in nearly absolute alcohol and in benzene are colourless ; the
former becomes deep yellow on addition of a small quantity of water,
colourless again when mixed with a large quantity of alcohol. The
solutions in acids and alkalis are yellow.
o-Hydroxy quinoline quickly becomes reddish on exposure to sun-
shine; it has a peculiar phenolic odour and burning taste; sublimes
very easily both from its solutions and in the solid state, softens at 72°,
melts at 73 — 74", and usually solidifies at 53 — 55°. Under a pressure
of 752 mm. it boils at 258*2° (corr.). The impure substance decom-
poses on discillation, the pure substance scarcely at all. The dilute
alcoholic solution is coloured blackish-green by ferric chloride, the
colour becoming darker on addition of sodium carbonate, which
ultimately throws down a dingy brownish-green flocculent precipitate.
The coloration is prevented by the presence of free hydrochloric acid
but not by acetic acid. Ferrous sulphate forms a dark brown-red pre-
cipitate soluble in acetic acid with silver nitrate. The solution of
this hydroxy quinoline in potash gives a yellow flocculent precipitate
becoming crystalline on standing ; with mercuric chloride an orange-
yellow crystalline precipitate ; with lead nitrate a light yellow floccu-
lent precipitate, and with barium chloride a white pulverulent pre-
cipitate. The acid sulphate, C9H7NO,H,S04, crystallises in light yellow
prisms containing 2 mol. H2O, 1 mol. of which is given off over sul-
phuric acid. The hydrochloride^ C9H7N0,HC1 + H2O, forms yellow
prisms easily soluble in water and in alcohol; the platinochloride,
(C9H7NO,HCl)2PtCl4 + 2H2O, forms long golden-yellow sparingly
soluble needles ; the picrate, C9H7NO,C6H2(N02)3.0H, crystallises in
yellow prisms very slightly soluble in cold alcohol, caking together at
170° and melting at 203 — 204°. A characteristic copper-compound,
(C9H6NO)2Cu, is precipitated as a siskin-yellow powder on adding
cupric acetate to an alcoholic solution of the hydroxy quinoline.
The acetyl-com pound, CuHgNO = CsHfrSxNO, prepared by boil-
ORGANIC CHEMISTRY. 93
ing the hydroxy quinoline with acetic anhydride and sodium acetate, is
a nearly colourless oil which remains fluid at —20°, boils at about
280°, is gradually decomposed by exposure to the air, more quickly
by bases, with separation of o-hydroxyquinoline ; it dissolves readily in
hydrochloric acid, and the solution mixed with platinic chloride forms
the salt (CgHgJcNOjHCyzPtCU + 2H2O, which separates in tufts of
small yellow needles.
Nitro-com pounds. — Strong nitric acid converts o-hydroxyquino-
line into a mixture of the mono- and dinitro- derivatives, C9H6(N02)0
and C9H5(N02)20, the latter greatly predominating. The mixture
dissolves in hot dilute potash-ley, forming a deep yellow solution,
which on cooling deposits a potassium derivative in slender yellow
needles. The alcoholic solution is coloured deep garnet-red by ferric
chloride.
Bromine-compound, C9H5Br2]S'0. — This compound separates on
dropping bromine (1 mol.) into an alcoholic solution of o-hydroxy-
quinoline, as a mass of needles, and may be obtained by re crystallisa-
tion from alcohol or benzene in white brittle prisms. It appears to be
converted into a bromine addition-product by excess of bromine.
o-Methoxyquinoline or o-Quinanisoil, C10H9NO = C9H6NOMe,
is prepared, not from the hydroxy quinoline, but directly by treating a
mixture of o-amidanisoil and o-nitranisoil with glycerol and sulphuric
acid. It is a nearly colourless oil, which boils at 265 — 268°, turns
brown on exposure to the air and forms a platinochloride —
CioH9NO,H2PtCl6 + 2H2O,
which crystallises in short reddish-yellow prisms.
Hydro-o-hydroxyquinoline, CgHuNO, previously obtained by
Bedall u. Fischer (Ber., 11, 1368), is prepared by the action of tin and
hydrochloric acid on the hydroxy quinoline. The aqueous solution of
its hydrochloride gives a blood-red colour with ferric chloride, and is
distinguished from that of the para-derivative by not emitting the
odour of quinone when boiled.
Para-hydroxyquinoline. — This base, prepared like the o-compound,
is best purified by recrystallisation of its hydrochloride. The free base
crystallises from alcohol in small brittle prisms, melts at 193°, boils
above 360°, dissolves very sparingly in water and ether, still less in
benzene and in chloroform, more freely in alcohol, easily in acids and
alkalis. Ferric chloride colours the alcoholic solution faintly yellow ;
ferrous sulphate produces no coloration. The alkaline solution gives
with silver nitrate a yellowish gelatinous precipitate ; with mercuric
chloride a light yellow, with lead nitrate a nearly white precipitate,
with barium nitrate none; with cupric acetate, after neutralisation
with ammonia, a green precipitate.
The hydrochloride, C9H7N0,HC1 -f H2O, is colourless when pure, very
soluble in water, sparingly in absolute alcohol, insoluble in ether, very
slightly soluble in strong hydrochloric acid, and in a saturated solution
of sodium chloride ; it gives off its crystal-water easily at 100°. The
platinochloride, (C9H7NO,IICl)2,PtCl4 + 2H20, is a reddish-yellow crys-
talline precipitate. A cojpper-quinoline acetate, (C2H6N02)2Cu,2C2H402,
separates gradually from an alcoholic solution of p- hydroxy quinoline
94 ABSTRACTS OF CHEMICAL PAPERS.
mixed with a dilute solution of cupric acetate, in groups of acnte
wedge-shaped crystals nearly black by reflected, amethyst-blue by
transmitted light.
Nitro-^-hydroxyqu.inoline is obtained as a nitrate —
C9H6(N02)NO,HN03 + H^O,
on adding ^-hydroxyquinoline to 4 — 5 parts strong nitric acid, warm-
ing the liquid till the whole is dissolved, and diluting the red-brown
solution with water. The salt then separates in orange-red acnte
prisms which become whitish at 100°. It dissolves easily on heating
with a small quantity of water, less easily in a larger quantity, easily
in alcohol. By dissolving it in sodium carbonate and acidulating with
acetic acid, the free nitrohydroxyqninoline, C9H6(N02)NO, is obtained
in small yellow needles, insoluble in water, sparingly in cold, easily in
hot alcohol, easily also in acids and alkalis. It melts at 139 — 140^, and
sublimes when cautiously heated. Its alcoholic solution is coloured
reddish by ferric chloride, gives a yellow-brown precipitate with
cupric acetate, and orange-yellow with silver nitrate. Its potassium
salt forms yellowish-brown brittle needles ; the barium salt, orange-
yellow needles slightly soluble in cold water.
Bromo-p-hydroxyq uino line, CgHeBrNO, is obtained on slowly
adding bromine to an alcoholic solution of ^-hydroxyquinoline, as a
hydrobromide, C9H6BrNO,HBr, which separates in reddish-yellow heavy
granules. This salt dissolves sparingly in absolute, easily in hot
aqueous alcohol, and with partial decomposition in a large quantity of
hot water. Its dilute alcoholic solution, when treated with sodium
carbonate, deposits the free bromhydroxyqninoline, CgHeBrNO, in
nearly colourless needles, easily soluble in hot dilute alcohol, melting
at 184 — 185°. With silver nitrate, on addition of ammonia, it gives
a yellowish flocculent precipitate ; with cupric acetate, after neutrali-
sation, an olive-green precipitate.
The acetyl-compound, CgHe^xNO, prepared like the correspond-
ing ortho-compound, is a light yellow scentless oil, boiling at 298°,
easily soluble in alcohol and ether, soluble also in hot water. When
cooled to —20°, it remained liquid for nearly half an hour, but began
to crystallise soon after its removal from the freezing mixture. The
white crystals thus obtained melted between 36° and 38° to a colour-
less liquid which solidified only in contact with the solid substance.
The 'platinochloride, (CnHgNOojHCOajPtCU,^ a yellow crystalline pre-
cipitate. The benzoyl- compound, CgHeBzN'O, prepared by boiling
the hydroxyquinoline with benzoic chloride, crystallises from glacial
acetic acid in white slender needles, nearly insoluble in water, alcohol,
ether, and hydrochloric acid, slightly soluble in alkalis, and melting at
230—231°.
jp-Quinanisoil, CgHe^.OMe, prepared like the ortho- compound,
is a non-solidifying-oil. This hydrochloride crystallises in long white
prisms, deliquescing in water, moderately soluble in alcohol, sparingly
in ether alcohol. The platinochloride, (C9H6N.OMe,HCl)2,PtCl4 + H30,
crystallises in acute orange-red prisms, easily soluble in hot water.
Hydro-^-hydroxyquinoline, CgHnNO, has been obtained as a
hydrochloride, though not quite pure, by the action of tin and hydro-
ORGANIC CHEMISTRY. 95
chloric acid on ^^-hydroxyquinoline. The hydrochloride is easily
soluble in water and separates by evaporation over sulphuric acid, in
feathery groups of large white prisms, afterwards in small white
needles. The free base is coloured reddish-violet by ferric chloride,
becoming brownish on boiling, and emitting a strong odour of
quinone.
Meta-hydroxyquinoline. — This base is most readily purified by
fractional precipitation of the acid oxalate. It crystallises from
absolute alcohol in prisms, from dilute alcohol knd from ether in
needles, from chloroform, and by spontaneous evaporation of its
aqueous solution, mostly in graimlar aggregates. It melts, with
partial blackening, at 235 — 238°, sublimes undecomposed when quickly
heated, and boils with rapid decomposition at a higher temperature
than the para-compound. It is inodorous and nearly tasteless,
slightly soluble in water, much less soluble in alcohol than jp-hydroxy-
quinoline, more soluble in chloroform, moderately in other solvents.
Its solutions in alkalis and acids have a deep yellow colour, so long as
any of the undissolved substance is present, but they become colourless
when the whole is dissolved. It dissolves readily in caustic potash
and baryta, sparingly in ammonia. All the solutions, especially
the dilute alcoholic, have a distinct green fluorescence. Ferric chloride
added to the dilute alcoholic solution, produces a fine brown-red
colour, becoming lighter on addition of sodium carbonate; ferrous
sulphate produces no reaction. The meta- compound withstands the
action of potassium dichromate moi-e completely than its isomerides,
which are thereby oxidised.
The hydrochloride, C9H7N0,HC1 + IIH2O, crystallises in prisms,
colourless when quite pure, but mostly light yellow, freely soluble in
water, very sparingly in alcohol ; the platinochloride —
(C9H7NO,HCl)2,PtCl4 + 2H2O,
in orange-yellow needles ; the picrate, in light yellow needles melting
with decomposition at 244 — 245°. The copper-compound —
(C9H6N0)2CU,2C2H402,
is obtained in violet crystals when an alcoholic solution of hydroxy-
quinoline mixed with an equivalent quantity of cupric acetate and a
small quantity of acetic acid, is left to evaporate.
Nitro-m-hy droxyquinoline, C9H6(N02)NO, is obtained on adding
m-hydroxyquinoline to fuming nitric acid, precipitating with water,
and recrystallising the yellow granules thereby thrown down from hot
water, in yellow shining laminae which melt with evolution of gas at
255°, and unite with acids, forming salts which are decomposed by
water.
Bromine-compound. — On adding bromine-water to the hydro-
chloride of m-hydroxyquinoline, a bromide of bromhydroxyquinoline
is obtained, which when boiled with alcohol, is converted into a
hydrobromide, CgHeBrKOjBrH.
A benzoyl-derivative is obtained in the same manner as the
corresponding para-compound in the form of an oil which slowly
96 ABSTRACTS OF CHEMICAL PAPERS.
solidifies, melting at 88 — 89°, and yields a platinochloride having the
composition (C9H6B^NO,HCl)2,PtCl4.
Hydro-m-hydroxyquinoline. — The hydrochloride of this base is
obtained in colourless well-defined prisms by heating a solution of
m-hydroxyquinoline in hydrochloric acid with excess of metallic tin,
precipitating the excess of tin with hydrogen sulphide, and evaporating.
When heated with ferric chloride, it first turns light yellow, then
brown-red, and gives off an odour slightly resembling that of quinone.
H. W.
Quinoline-derivatives. By A. Rhoussopoulos (Ber., 15, 2006 —
2009). — By the union of quinoline with ethyl monochloracetate, a com-
pound, CisHuNOzCl = C9H7N(CH2.COOEt)Cl, is obtained, crystallising
in stellate groups of white needles. It is extraordinarily soluble in
water, readily soluble in alcohol, insoluble in ether. The platino-
chloride, CisHuNOoClajPtCU, crystallises in small thin needles. The
compound, C13H14NO2CI, treated with freshly precipitated silver oxide,
yields quinoUne-heta'ine, according to the equation —
C9H,N(C2H202Et)Cl + AgOH -f- H^O = AgCl +
Quinoline-betaine forms short thick crystals, readily soluble in water
and alcohol. It begins to decompose at 168°, and fuses at 171°.
Hydrochloric acid converts it into the hydrochloride, which unites
with platinum chloride, yielding stellate groups of orange-colonred
needles of the formula (CuHgNOzjHC^zjPtCU. A. J. G.
Bromoquinolinesulphonic Acids. By W. La Coste (Ber., 15,
1910 — 1918). — Bromoquinoline, prepared as previously described by
the author (Abstr., 1882, 978), was gradually added to five times its
weight of warmed fuming sulphuric acid, and the product when cold
was mixed with a considerable quantity of water and well stirred ; the
heavy crystalline precipitate consisted of two isomeric bromoquinoline-
sulphonic acids, which can be easily separated by means of their
potassium salts. The acid from the less soluble potassium salt is
called by the author a-, and that from the more readily soluble salt
jS-bromoqui iiolinesulphonic acid.
The a- acid crystallises from boiling water in short thin anhydrous
needles, sparingly soluble in cold water and in alcohol. The potas-
sium salt, CgHsNBr.SOsK, forms short prisms, which decrepitate on
heating. The hanum salt, (C9H5NBr.S03)2Ba, is a sparingly soluble
crystalline precipitate. The magnesium salt, (C9H5NBr.S03)2Mg -f-
IOII2O, forms colourless plates, which lose their water at 120°. The
zinc salt, (C9H6NBr.S03)2Zn + 4H2O, slender needles, which lose
their water at 120° F. The manganese salt, (C9H5NBr.S03)2Mn +
4H2O, forms short greenish -yellow needles ; and the silver salt,
CgHsNBr.SOsAg, anhydrous needles.
(S-Bromoquinolinesulphonic acid crystallises in short needles with
1 mol. H2O, which it loses at 150 — 160°. It is sparingly soluble in cold
water, although considerably more soluble than the a-acid. Tlhe potas-
sium salt, CgHsBr.SOsK -f 1^H20, crystallises in plates of moderate size,
which are easily soluble in water. The barium salt, (C9H5NBr.S03)2Ba
ORGANIC CHEMISTRY. 97
+ 2H2O, forms crystalline groups of needles ; the magnesium salt,
(09H5lSrBr.SO3)2Mg + 9HoO, small needles, and the zinc salt,
(C9H5NBr.S03)2Zn + 9H2O, large transparent six-sided plates, easily
soluble in hot water. The manganese salt, (C9H5NBr.S03)2Mn + 6H2O,
crystallises in colourless plates, easily soluble in hot water, and the
silver salt, CgHsNBr.SOsAg, forms colourless needles. The a- and /3-acids
both form crystallisable salts with aniline. A. K. M.
Caflfeine. By Tanret (/. Fharm. Chim. [5], 5, 591— 595).— The
salts of caffeine which it is generally supposed to form, are here shown
for the most part not to exist. Owing to its weak basic properties and
neutral reaction, it does not neutralise the smallest trace of acid, and
even relatively concentrated solutions of it do not give a precipitate
with potassium-mercuric iodide.
Caffeine does not form salts with the organic acids. Acetic, valeric,
lactic, and citric acids merely dissolve it, and on cooling the solution,
pure caffeine separates out. Caffeine crystallised from valeric acid
retains the odour of the acid, which, however, may be removed by
washing, so that the substance sold for caffeine valerate is only the
base, whilst caffeine citrate is a mixture of caffeine and the acid. To
dissolve one equivalent of caffeine, three equivalents of citric acid are
required, which is the inverse of the proportion which would be
required for the formation of the citrate.
With mineral acids, however, caffeine does form salts, the sul-
phate being crystallised with difficulty, whilst the hydrochloride and
hydrobromide crystallise well. They are, however, decomposed by
water into caffeine, which is precipitated, and the free acid ; the hydro-
chloride decomposes even on exposure to the air. Such compounds,
as well as its solutions in organic acids, are useless for hypodermic
injections.
It appeared, however, that the compound which exists in coffee,
chlorogenate of potassium and caffeine might be used for this purpose ;
but the difficulty of preparing it in large quantities, its instability,
and sparing solubility in water, prohibit its use. It was found, how-
ever, that caffeine forms with benzoate, cinnamate, and salicylate of
sodium, compounds similar to the natural compound, and very soluble
in water. They are prepared by treating caffeine with its equivalent
of the sodium salt, dissolved in a small quantity of water. One equi-
valent of sodium cinnamate dissolves one equivalent of caffeine,
yielding a compound containing 58'9 per cent, caffeine. The double
benzoate contains 48*5 per cent., and the salicylate 61 per cent.
These compounds are not stable, however, being readily decomposed
by chloroform. 100 parts of water dissolve 2 parts of the benzoate
and cinnamate, and 3 parts of the salicylate.
Similar compounds have been obtained with sodium acetate, lactate,
citrate, sulphate, and chloride.
By means of these compounds, caffeine may be used for hvpodermic
injections. L. T. O'S.
Hydrocinchonidine. By O. Hesse (Annalen, 114, 1 — 17). —
Hydrocinchonidine, C19H24N2O, is contained in considerable quantities
VOL. XLIV. h
y8 ABSTRACTS OF CHEMICAL PAPERS.
in the aqneons mother-liquor from the preparation of homocinchonidine
sulphate. The alkaloids are precipitated from this solution by ammo-
nia and reerystallised from alcohol. The crystalline mass is dissolved
in hydrochloric acid, and by fractional precipitation with sodium tar-
trate the homocinchonidine is separated from the hydrocinchonidine
tartrate ; the latter is contained in the last precipitate. The tartrate
is converted into the neutral chloride : this is purified by recrystallisa-
tion from water, and then decomposed by ammonia, when it yields pure
hydrocinchonidine. The pure alkaloid melts at 230" (uncorr.), and
does not decolorise potassium permanganate immediately. The sul-
phuric acid solution is not fluorescent. Hydrocinchonidine is deposited
from an alcoholic solution in six-sided plates or prisms, which are inso-
luble in boiling chloroform, and but sparingly soluble in ether or in
water. It is scarcely attacked by strong hydrochloric acid at 160".
The following salts were prepared : — Ci9H24N20,HCl -f 2H2O, short
six-sided prisms, soluble in water and in alcohol. (Ci9Ho4N20)2,H2PtCl6,
-f 3H2O, yellow amorphous precipitate. Ci9H24N20,H2PtCl6, orange-
coloured six-sided plates. The thiocyanate and the neutral oxalate
form anhydrous needles. The salicylate does not crystallise. The
quinate crystallises in anhydrous needles, soluble in water. The tar-
trate, (Ci9H24N20)2,C4H606 -|- 2H2O, is sparingly soluble in cold water.
The crystals of the thiosulphate containing 1 mol. HgO dissolve in
117 parts of water at 10°. Ci9H24N20,H2S04 + 4H2O, is deposited in
lustrous prisms, sparingly soluble in cold water. (Ci9H24N20)2,H2S04
-f 7H2O, dissolves freely in alcohol and hot water. At 10° one part
of the sulphate requires 57 parts of water for solution. The phenol
sulphate, (Ci9H2iNoO)2S03,C6H60 + 5H2O, forms white prisms, sparingly
soluble in cold water. The acetic derivative, C19H23ACN2O, is a hygro-
scopic amorphous powder, soluble in alcohol, ether, acetone, and
chloroform.
Amorphous hydrocinchonidine is formed when the acid sulphate of
this base is heated at 160° with hydrochloric acid, and is precipitated
in the form of a resin on the addition of soda to the aqueous solution
of the crude product. The pure base melts below 100°. It is easily
soluble in ether, alcohol, chloroform, and acids. Hydrocinchonidine
deviates the ray of polarised light to the left much more powerfully in
an acid than in a neutral solution. W. C. W.
Xeronic and Pyrocinchonic Acids. By W. Roser (Ber., 15,
2012 — 2014). — In a previous communication (Abstr., 1882, 1114) the
author has shown that pyrocinchonic acid is probably dimethylfumaric
acid, and stated his belief that xeronic acid is the homologous diethyl-
fumaric acid. In accordance with this view, he now finds that calcium
xeronate yields propionic acid when oxidised.
By heating pyrocinchonic acid with hydriodic acid, an acid, CeHioOi,
is obtained, which from its reactions is probably identical with the
unsymmetrical dimethylsuccinic acid of Pinner (Bar., 15, 682). As
acetic acid is obtained by the oxidation of pyrocinchonic acid (2 mols.),
pointing to a symmetrical constitution, intermolecular change must
have occurred in one or other of these reactions.
A. J. G.
ORGANIC CHEMISTRY.
99
Strychnine. By A. Goldschmidt (Ber., 15, 1977). — A preliminary
notice that the author has obtained indole by fusing strychnine with
caustic potash. A. J. G.
Distillation of Strychnine with Zinc. By S. Scichilone and
O. Magnanimi (Gazzetta, 12, 444 — 448). — By heating strychnine with
zinc-powder in small glass retorts to a temperature near the melting
point of the glass, a distillate is obtained, separable by treatment with
ether and fractional distillation, into two portions, boiling respectively
at 165—180° and 230—300°. In a second distillation the first of
these fractions yielded a light yellow fragrant oil boiling at 173°, and
the second yielded two yellow liquids, one boiling at 240 — 250°, the
other at about 292°, and crystallising in a mixture of snow and salt.
The liquid boiling at 173° gave by analysis numbers agreeing with
the formula C7H9N, which was confirmed by its vapour-density, deter-
mined by Meyer's method (exp. 3*89 ; calc. 3" 70) ; and from the odour
of this base and the pyridic nature of strychnine, the authors infer
that it is a lutidine, distinguishing it as 7-lutidine (a-lutidine boils
at 145°, )3-lutidine at 163 — 168°). This base is insoluble, or nearly so,
in water, soluble in alcohol and ether, and smells somewhat like
liquorice. The other two liquids, which were obtained in very small
quantity only, are also nitrogenous compounds, and the second, which
boils at about 292°, solidifies in a mixture of snow and salt, whereas
the first remains liquid.
The behaviour of the three bases with, the usual tests for alkaloids,
is shown in the following table : —
Sodium phospho-
molybdate.
Potassio - mercuric
iodide.
Iodised potassium
iodide.
Mercuric chloride.
Auric chloride . . . .
FrShde's reagent . .
Picric acid
Platinic chloride
y-Lutidine (b. p.
173°).
Dark-yellow preci-
pitate soluble in
NH3 with faint
blue colour.
Yellow amorphous
precipitate.
Crimson precipitate
insoluble in dilute
hydrochloric acid.
White curdy preci-
pitate soluble in
NH4CI.
Dirty white preci-
pitate.
Faint red colour.
Liquid,
b. p. 240-250°.
White precipitate
soluble in ammo-
nia without
coloration.
Dirty yellow preci-
pitate.
White precipitate
soluble in NH4 CI.
Brown precipitate.
Yellow amorphous
precipitate.
Reddish precipitate.
Liquid,
p. about 292°
Light yellow preci-
pitate soluble in
ammonia, without
coloration.
Red-brown precipi-
tate.
White precipitate
soluble in NH4CI.
Brown precipitate.
Yellow amorphous
precipitate.
Red-brown precipi-
tate.
H. W.
h 2
100 ABSTRACTS OP CHEMICAL PAPERS.
Action of Dehydrating Agents on Lupinine. By G. Baumebt
(Annalen, 214, 361 — 376). — Anhydrolwpinine^ C21H38N2O, and dian-
hydrolupinine, C21H36N2, are formed by the action of phosphoric anhy-
dride or of fuming hydrochloric acid at 200° on lupinine, C21H40N2O2.
Anhydrolupinine is an oily liquid insoluble in water. It turns brown
on exposure to the air, and begins to decompose at 150°. The platino-
chloride, C2iH38N20,H2PtCl6, forms quadratic plates, soluble in water
and in alcohol. Dianhydrolupinine is an oily liquid (b. p. 220°), which
rapidly absorbs oxygen from the air. It yields a platinochloride,
C2iH36N2,H2PtCl6 crystallising in dark red needles.
Oxijlujpinine, C21H40N2O5, prepared by the action of phosphoric anhy-
dride on lupinine hydrochloride at 176°, is an unstable oily liquid.
The platinochloride C2iH4oN205,H2PtCl6, forms orange-coloured plates,
insoluble in water and alcohol. This salt is decomposed by pro-
longed boiling with water. If the mixture of phosphoric anhydride
and lupinine hydrochloride is heated at 185 — 190° for five hours,
hydrochloric acid is evolved, and anhydrolupinine is produced.
w. c. w.
Colouring Matter (Rnberine) and Alkaloid (Agarythrine) in
Agaricns Ruber. By T. L. Phipson (Chem. News, 46, 199). —
Ruberine is insoluble in water and in alcohol ; it is rose-red by re-
flected, bright blue by transmitted light, and gives two wide and dark
absorption- bands in the green. As it is soluble in water, a heavy
fall of rain washes it out from the head of the fungus. Frequently
the upper surface of A. ruber is eaten through by slugs, which, how-
ever, do not penetrate deep. A yellowish-white alkaloid (agarythrine)
is extracted by ether from the fungus itself, after removal of the skin.
It has a bitter taste at first, which changes to a burning sensation,
resembling that produced by aconitine; the chloride is soluble in
water, but the sulphate, although insoluble in water, is soluble in
alcohol. Nitric acid solutions become red. Bleaching powder pro-
duces also a red coloration with agarythrine, but the colour is soon
bleached. When the solution is shaken up with ether, it is oxidised by
the air to a red colouring matter ; this is probably the cause of the
red colour of the surface of the fungus, the alkaloid being oxidised by
the air in presence of light. E. W. P.
Bases formed by Putrefaction. By A. Gautier and A. ^tard
(Bull Soc. Ghim. [2], 37, 305— 307).— The authors have extracted from
putrid animal matter two liquid alkaloids, which have a strongly alka-
line reaction, attack tissues in the same manner as potash, saturate
strong acids, and appear to absorb carbonic anhydride from the atmo-
sphere with formation of crystalline carbonates. One of these alka-
loids boils at about 210°, and is a colourless, syrupy, bitter, and very
caustic liquid; its sp. gr. at 0° is 10296. Its hydrochloride forms
slender needles, somevshat stable when pure, but rapidly reddened
by excess of acid. It is very soluble, and has a very bitter taste. The
platinochloride is also stable, and crystallises well. It is precipitated
immediately from moderately concentrated solutions, dissolves on
heating, but separates out again on cooling in slightly curved needles.
The aurochloride is very unstable, and rapidly deposits metallic gold.
ORGANIC CHEMISTRY. 101
The various salts of this base rapidly reduce ferric chloride to the
ferrous state.
The second alkaloid boils at a higher temperature, but decomposes
on boiling into ammonia and products which have a carbolic odour, and
are only slightly soluble in ether.
These alkaloids appear to be accompanied in the putrid matter by
other more complex and more unstable basic compounds. When the
crude ethereal solution of the alkaloids is evaporated to dryness, and
the residue treated with potash, a strong odour of carbylamine is given
oIF. The carbylamines are doubtless produced by the action of the
potash on the complex basic compounds. C. H. B.
Formation of Alkaloids from Normal Human Fluids. By
A. Gautier (Bied. Gentr., 1882, 710). — If saliva be evaporated and the
residue dried for some hours, it will act as a poison on birds ; this sub-
stance, like the ptomaines, turns potassium ferricyanide and ferrichlo-
ride blue. An easily oxidisable alkaloid, which combines and forms
crystalline compounds with gold and platinum chloride, has been pre-
pared from urine. E. W. P.
Urorosein. By M. Nencki and N". Sieber (J. pr. Chem. [2], 26,
333 — 336). — The urine of a diabetic patient was found to become
bright pink on the addition of pure hydrochloric acid. The colouring
matter is extremely unstable. It dissolves in amylic alcohol, and the
solution shows a characteristic absorption-band between the lines D
and E, the maximum of intensity corresponding to 557 millionth
millimetres wave-length. O. H.
Behaviour of Unorganised Ferments at High Temperatures.
By F. HuPPE (Bied. Centr., 1882, 718).— ^Pepsin, when dry and heated
to 100", is not injured, but at 170° its power is diminished, although
not entirely destroyed.
Malt diastase is not affected by a temperature of 100°. Pancreatin
still dissolves albumin, even after being heated to 160° ; the tempera-
ture at which all are killed is about 160—170°. E. W. P.
The Temperature most Favourable to the Action of Inver-
tin. By A. Mayer, W. Hagemann, and W. Heubach (Bied. Centr.,
1882, 706). — In a previous communication, it has been shown that pre-
cipitation by alcohol destroys the fermenting power of invertin, and
further experiments have not resulted in the discovery of any method
for the separation of this ferment in the pilre state. The temperature
at which action is most intense is about 30°, but if an acid be present,
then the temperature may be raised to boiling ; with various prepara-
tions the temperature may be different, ranging from 31 — + 48°.
E. W. P.
Influence of Invertin on the Fermentation of Cane-sugar.
By E. Bauer (Bied. Gentr., 1882, 707). — It is generally stated that the
fermentation of cane-sugar induced by invertin proceeds with equal
rapidity, whether it is previously inverted before the ferment is intro-
duced or not ; such a supposition is incorrect, as unless the sugar be
102 • ABSTRACTS OF CHEMICAL PAPERS.
previously inverted, the fermentation will proceed but slowly, although
the complete change does finally take place, and the time occupied is
longer. E. W. P.
Physiological Chemistry.
Nutritive Value of Skim Milk. By J. Konig (Bied. Centr.,
1882, 693— 696).— Comparing skim milk (N.R. 1 : 2) with whole milk
(N.R 1 : 3*5), the author shows that skim milk is by far the cheapest
and most nutritious food for adults ; also it is shown that the price
paid for the albuminoids in skim milk is lower than that paid for them
in any of the ordinary foods which appear in the markets, excepting
stockfish; as for example 1000 nutritive units in skim milk cost
41*7 pfennings, whilst in pork they cost 71 '4 ; in butter, 81"7 ; and in
eggs, 201'2. Stohmann has calculated that 1 litre skim milk corre-
sponds in nutritive value to 160 grams boneless meat, the latter costing
19*2 pfennings, whilst the former costs only 8*10. E. W. P.
Skim Milk as Pood. By Ritthausen {Bied. Centr., 1882, 641).
— Skim milk is a valuable food for man and beast, as 2*8 litres of it
contain as much nitrogenous inatter as a pound of meat, and it is
much cheaper. E. W. P.
Feeding Horses with Flesh Meal. By Findeisen {Bied. Centr.,
1882, 671). — Old horses fed with Huch's flesh meal increased in
weight, and this food was found to be very satisfactory in cases of
illness. E. W. P.
Researches on the Digestibility of Purified Lupine Seeds
by the Horse, and Observations on the Working Power of the
Horse when Fed with Lupines and Oats. By 0. Kellxer {Bied.
Centr. y 1882, 588 — 592). — The digestive coefficients of lupine seeds
when eaten by horses, in combination with hay, ai'e as follows : —
Dry inatter. Org. matter. Albuminoids. Fibre. Fat. Extractires.
70-63 72-29 . 94-16 50-82 27-32 50-79
Lupine seeds therefore approach in feeding power to peas, beans,
and maize, being more easily, and oats less easily digested. To deter-
mine the comparative value of oats and lupines as food during labour,
a horse was fed with 6 kilos, purified lupine seeds, corresponding to
2-77 dry untreated seeds, and 8-5 kilos, hay. After the performance of
certain labour in a wheel, the amount of labour being so regulated that
the live weight remained the same, the lupines were replaced by 4 kilos,
oats daily, and again labour was performed under the same conditions.
The labour performed during the "oat" period was in excess of that
PHYSIOLOGICAL CHEMISTRY. 103
done during the " lupine " period by 380,300 kilogram-meters, the
nutrient ratio in the oat period being 1 : 738 ; during the other,
1 : 304. From the calculations given it would appear that 1 kilo,
oats produces the same working power in a horse as 1 kilo, of air-
dried and purified lupines, but as the ratio in the lupines is so narrow,
it is not advisable to replace more than 2'5 kilos, oats by lupines,
otherwise a great decrease in fat is likely to take place.
E. W. P.
The Gastric Juice. By J. Chapoteaut (CompL rend., 94, 1722).
— On evaporating an aqueous solution of gastric juice, prepared from
the stomach of a sheep, a pepsin is obtained capable of dissolving
3000 times its weight of fibrin. Alcohol precipitates from the solu-
tion a white neutral pulverulent substance, while the liquid acquires
an acid reaction : the liquid freed from alcohol is without solvent
power, but the white substance when acidified possesses a considerable
power of dissolving fibrin, and indeed appears to retain the special pro-
perties of pepsin. It precipitates metallic salts and solutions of lime
and baryta, and froths with a solution of albumin. The acid liquid is,
however, certainly one of the active elements of pepsin, for the solvent
powers of the white substance are much inferior to those of the
original liquid. R. R.
Decomposition of Hydrogen Peroxide by certain Organised
Bodies. By A. B^champ (Goinpt. rend., 94, 1601— 1604).— The
paper discusses previously published observations by the author
{Compt. rend., 59, 713) in relation to investigations by Dumas,
Thenard, Bert, Begnard, and others. He will shortly show that the
granulations which decompose oxygenated water can be isolated from
blood without formation of fibrin, and that the more the serum of
blood is deprived of microzymas and globules, the less energetic is its
action in decomposing oxygenated water. B-. B.
Microzymas the Cause of the Decomposition of Hydrogen
Peroxide by Animal Tissues. By A. B^champ (Gompt. rend., 94,
1653 — 1656). — The paper discusses some observations of Thenard's
on the decomposition of hydrogen peroxide by various animal tissues,
and the results of the author's experiments are given in a tabular
form. The removal of the microzymas of the blood itself from the
several tissues presented some difficulties, but the author conceives
that he has proved by these experiments that the microzymas of the
different tissues are not only functionally different, but that they act on
hydrogen peroxide with different degrees of energy. R. R.
Action of Hydrogen Peroxide on the Red Colouring Matter
of the Blood, and on Hsematosin. By A. B^champ (Gompt. rend.,
94, 1720 — 1722). — The serum of ox blood freed from microzymas by
passing it through a filter covered with barium sulphate is without
action on hydrogen peroxide ; but the red solution obtained from the
blood globules, even after passing through a similar filter, disengages
oxygen. Haemoglobin is distinguished from fibrin and from tissues
that act like it, in that it is capable, after coagulation by alcohol or
104 ABSTRACTS OF CHEMICAL PAPERS.
by heat, of being dried at 120° without losing its power of decora-
posing hydrogen peroxide and becoming colourless. This phenomenon
corresponds with a profound chemical reaction, and the oxygen disen-
gaged is due to an action analogous to those observed by Thenard,
in which the action of hydrogen peroxide on sugar and starch gave
rise to both oxygen and carbonic anhydride at the same time. Blood
contains two causes for this decomposition, the microzymas and
haemoglobin, and if hydrogen peroxide is ever formed in the blood
it is immediately employed in effecting transformations similar to
those described. R. R.
Rattlesnake Poison. By H. H. Croft (Chem. News, 46, 165). —
A favourite antidote for rattlesnake poison, in Mexico, is a strong solu-
tion of iodine in potassium iodide. The author has tested some of the
poison itself with this solution, and finds that a light brown amor-
phous precipitate is formed, the insolubility of which explains the
beneficial action of the antidote. When iodine cannot be readily
obtained, a solution of potassium iodide, to which a few drops of ferric
chloride has been added, can perhaps be used as an antidote to snake
poison ; it is a very convenient test for alkaloids. D. A. L.
Physiological Action of y3-Collidine. By Marcus and 0. de
CoNiNCK (Bull. Soc. Chim. [2], 37, 457). — (3-collidine exerts a strong
poisonous action, and in this respect has no analogy with the cinchonine
from which it is derived. Subcutaneous injection of 0'05 — 0'15 gram
produce general and progressive weakness, with paralysis of the psycho-
motor centres. Reflex motions are not affected, with the exception of
that of the cornea, which is destroyed. The blood pressure diminishes,
the cardiac muscle becomes weaker and weaker, the temperature
decreases, and the heart stops from diastole.
Weak doses produce a temporary effect characterised by the same
symptoms. The alkaloid is eliminated by the organs of secretion,
which it excites, and the organisms reassume their normal functions.
The reflex action of the cornea, however, does not return.
C. H. B.
Chemistry of Vegeta^ble Physiology and Agriculture-
Influence of Alcohol on the Development of Yeast. By M.
Hayduck {Bied. Centr., 1882, 635 — 637). — From this continuation of
former experiments (Abstr., 1882, 761) we learn that the presence of
alcohol retards the development of yeast, and that fermentation
proceeds more slowly in proportion as the amount of alcohol originally
present is greater. * E. W. i*.
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 105
Nature and Formation of Dextran. By E. Bauer (Bied.
Centr., 1882, 630). — The microscopic appearance of the organisms
which induce the formation of dextran is described, and it is stated
that mucus fermentation can occur only in neutral or slightly alkaline
solutions ; it does not occur, therefore, in the fermentation of must,
as much acid is present; but it does occur in the fermentation of
molasses, owing to the presence of alkali in small quantity.
E. W. P.
Elimination of Oxygen from Plant Cells. By T. W. Engel-
MANN (Bled. Gentr., 1882, 673). — By means of his bacteria method
(Abstr., 1882, 335) and with a microspectroscope, the author finds
that the action of the light between the B and C lines is the most
intense, and not, as according to other authors, in the vellow.
E. w. p.
Elimination of Carbonic Anhydride by Plants in Absence
of Oxygen. By W. P. Wilson (Bied. Gentr., 1882, 674).— Diminu-
tion of the amount of oxygen admitted to plants is accompanied by a
reduction in the quantity of carbonic anhydride expired. For example,
in air, Lupinus luteus expired 5" 7 CO2 in the first half-hour, whereas
in hydrogen only 1*5 CO2. Plants, whether in air or in hydrogen, are
not influenced by the presence or absence of light. E. W. P.
Action of Various Gases, especially Nitrous Oxide, on Plant
Cells. By W. Detmer (Bied. Gentr., 1882, 675— 677).— Seeds of
Pisum sativum and Triticum vulgare cannot germinate in pure nitrous
oxide, but they do not lose the power of germinating afterwards in
air, if they be not kept too long in the former gas ; still to a certain
extent harm is inflicted on the embryo, reducing its energy and the
intensity of evolution, and this reduction in its activity is the greater
the longer it has been in contact with the gas, and the higher the
temperature. Seeds can germinate in a mixture of air and nitrous
oxide, but the growth ceases as soon as the free oxygen is absorbed, and
decomposition of nitrous oxide never occurs. Heliotropic motion does
not take place, neither do etiolated plants become green in nitrous oxide.
These observations were also made when the atmosphere consisted of
pure hydrogen or carbonic anhydride. Chloroform vapour kills ger-
minating plants, or at least stops their growth, breathing however,
still continues. Dead cells do not breathe, so that respiration is
dependent on the presence of living protoplasm; but it sometimes
occurs that carbonic anhydride is eliminated from dead plants : this
must be due to the action of lower but live organisms acting on the
dead cellulose matter. E. W. P.
Influence of the Electric Light on the Development of
Plants. By P. P. D:6h^eain (Annates Agronomiques, 7, 551 — 575). —
The author's experiments were made at the Palais d'Industrie during
the Electric Exhibition of August, 1881. A greenhouse was con-
structed and divided into two compartments, one of which was glazed
with blackened perfectly opaque glass, whilst the other was exposed
to the ordinary diffused daylight of the Exhibition building. The
darkened chamber was illuminated continuously, night and day, by a
106 ABSTRACTS OF CHEMICAL PAPERS.
2000-candle arc-light from a Gramme machine, driven by an Otfo gas-
engine. The transparent chamber was illuminated at night only by
the electric light. Five series of comparative observations were inade,
viz. : —
1. Plants exposed night and day to the electric light alone.
2. Plants exposed during the day to the diffuse daylight of the
Palais, and during the night to the electric light.
3. Plants living during the day in the open air, and receiving the
electric illumination at night.
4. Plants passing the day in the diffuse daylight of the Palais, and
the night in darkness.
6. Plants living normally in a garden.
The plants submitted to experiment were barley, flax, beans, and a
number of garden and greenhouse plants.
Action of the Unprotected Light. — At the end of seven days the naked
electric light was seen to have an injurious effect both on those plants
which were constantly subjected to it, and in a less degree on those
which were exposed to it during the night only. The leaves blackened,
withered, and dropped off; the injury was confined to the epidermal
layers, and was due to the direct impact of the luminous radiations
(and not to the formation of nitrogen oxides) ; for where one leaf was
partly shaded by another, a sharp line was photographically im-
pressed.
Experiments on Elodea canadensis, submerged in flasks of water,
showed that whilst the diffuse daylight of the building was unable to
cause decomposition of carbonic anhydride and evolution of oxygen,
the direct rays of the electric light were able to do so, about as much
oxygen being obtained during an exposure of foar or live days and
nights to the electric light as could be obtained in an hour or so in
bright sunlight. At the end of 15 days the arc lights were enclosed
in globes of transparent glass, Siemens' just published experiments
having shown that the injurious action of the direct radiations was
thereby modified.
Action of the Protected Light. — A number of fresh and uninjured
plants were placed in the greenhouse, and in addition sowings of
barley, oats, peas, maize, beans, which had just appeared above the
ground. All the seedlings exposed exclusively to the electric light
perished sooner or later, and the leaves of some of them were blackened
as with the naked light. The mature plants, on the other hand, con-
tinued to vegetate, but in no case, save a plant of barley, were flowers
and seeds produced, the vegetation being purely foliaceous. The
barley grains were normal, and germinated on being sown. The
electric light employed was clearly insufficient by itself to determine
the assimilation of any considei*able quantity of material ; direct expe-
riments also proved that it is not more powerful in exciting trans-
piration of water, a leaf exposed to it giving off in an hour only about
one-fiftieth of the quantity of water evaporated under similar circum-
stances in sunlight. As the evaporation of water by the leaves is one
of the chief agencies in causing the migration of material necessary
for the maturation of seed, the failure of the plants to produce flowers
and seeds receives its explanation. It is known that yellow and red
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 107
rays are most powerful in causing transpiration, whilst the electric
light is particularly rich in blue and violet rajs. The author considers
the electric light employed as too feeble to allow of any conclusion as to
the necessity of a nocturnal rest to plants. It was, however, evident
that the electric illumination during the night was advantageous to
those plants which passed the day in the rather feeble diffused day-
light of the palace. In a third series of experiments, the intensity of
the electric light was practically augmented by placing the plants
nearer the lamp. The experiment was again fatal to young seedlings
receiving the electric light exclusively, but many of the hardier and
more mature plants survived, although the leaves of some were
blackened by their too great proximity to the light ; and again the
nocturnal electric illumination was decidedly favourable to the plants
which passed the day in the light of the palace. The author sums up
his conclusions thus : —
1. The electric arc-light emits radiations which are injurious to
vegetation.
2. Most of these radiations are arrested by colourless glass.
3. The electric light emits radiations powerful enough to maintain
mature plants in vegetation for two months and a half.
4. The beneficial radiations are not sufficiently powerful to cause
the growth of germinating seeds, or to allow of the maturation of fruit
in older plants. J. M. H. M.
Embryos of Ungerminated Rye. By K. Nachbaur (Monatsh,
Chern., 3, 673 — 676). — Analyses of the sample of Russian rye
employed, and of the embryos carefully separated from it, gave the
following results : —
Rye. Embryos.
Water 11'92 9'58
Protein substances 14-12 42*12
Fat 1-16 1204
Ash 1-63 4-44
Gum, starch, dextrin, and "I 71.17
woody fibres J
Soluble matter — 45*11
Sp.gr 1-245 1-13
The especial object of the investigation was to ascertain if the
diastatic ferment observed in the grain was contained in the embryo,
which for this purpose was extracted by glycerol according to Gorup-
Besanez's method, but with negative results. A. J. G.
Analyses of Indian Wood. By W. R. Griper (Chem. News, 46,
187). — After exposure to the sun, the woods chiefly used for fuel have
the following composition : —
108 ABSTRACTS OF CHEMICAL PAPERS.
Mango.
Carbon 4272
Hydrogen 5'70
0-hN 36-23
Ash 2-88
Sand 2-97
Water 9-50
100-00
Sal.
Dhaka.
43-58
40-61
6-45
5-11
38-09
35-36
1-24
6-25
0-44
1-00
11-20
11-67
100-00
100-00
3458
3259
Heat -units calc.^
from analysis, I 3^3^
not incmdmg f
sand J
During the rainy season, the wood contains about 20 per cent, of
water ; the heat-units for Sal would be 3054 ; therefore for equal
weights coal has 2-32 times the heating power of ordinary wood.
E. W. P.
Inorganic Constituents of some Epiphs^tic Ferns. By W. A.
Dixon (J. Boy. 80c. New South Wales, 15, 175— 183).— The ferns
examined were Platicy cerium grande,P. alcicorne, and Asplenium nidus,
from the Clarence River, and a specimen of the second from New-
castle, ISr.S.W. The following table exhibits the results obtained by
analysis of the ash of these ferns, the live fronds and the humus mass,
consisting mainly of dead fronds mixed with rootlets, being analysed
in each case. Contrary to what might have been expected from their
mode of growth, the amount of ash in the growing fronds is quite as
high as in the leaves of most plants ; and those of Asplenium nidus
are rather rich in inorganic matter. Of Platy cerium alcicorne, two
specimens were examined, one growing on a rock, the other on a tree.
The humus mass of the rock specimen contains a considerable
quantity of sand, consisting almost wholly of white quartz. The
withered fronds and humus of the tree-plant contain copper oxide,
proceeding from the smoke of copper-works situated about three-
quarters of a mile from the locality in which the fern grew. In the
table, the sand and copper oxide have been deducted.
The high percentage of sand in the ashes of the humus masses, as
well as the copper oxide in the specimens from Newcastle, show that
the ferns must obtain much of their inorganic matter in the form of
dust, as with the exception of P. alcicorne, which grew upon a rock,
they could not obtain it directly. They are all plants requiring con-
siderable quantities of alkalis, and when these are deficient, the grow-
ing parts take up as much as possible from the withered fronds and
humus. The humus being partly composed of rootlets, must neces-
sarily retain some of the inorganic constituents. Thus P. alcicorne,
growing upon a rock, is very deficient in potash and soda, and, as will
be seen from the table, has extracted almost the whole of these con-
stituents from the humus and dead fronds, and has made up for its
deficiency of alkalis by assimilating a large quantity of magnesia,
lime, and alumina. The same species from Newcastle contains more
than double the quantity of alkalis, which it has removed chiefly from
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
109
m
X
OC
J> N
lO
iH <M
1
ii
9
-fi
00 CO
CO
O tH
o:
Tjt
CO -^
^
OS »o
"1
(N
cr.
^
(N
(M (N
■<s>
i
.
^
00 CD (M Oi
T?
OS O
S4i
C
cq t» N Oi
t-
cq t>
oT
O"
lo CO Oi cq
o
CO CO
^
■^
00 CO (M
00
^ r^
«M
o:
<N r-l Cq
to
-!f
i-H 05 CO C
) tS
(M ->?
cr.
-f th 00 «x> op
r? M
if
^
1 00 CO lO »0 00
00 CO
tH 1> rH (M
cq
b^ o
tS
e g
P w
Tf
(M t^ 00 00 r-l Oi
cc
> \o
^i3
S-^
u:
O t^ xfl ip CO <p
-f ^ 1
■ii
1 2
«
CD CO -^ M CO \0
I— 1 CO 05
cc
T— 1
la
^^
•
1> «c
U3 Tfl O O (M
r-l (M
ftn
OC
t* »H 00 CD W
(M 1 00 CO N -^
CO
oo t-
rH 00
a
(M iH
«H
r-
J
■*■
<))
s
3.-
-'fl
(M 00 CO CO
(y
Tfl
1
1
00
t^ CO t-l iH
i-l rH 1> M
CO OS
CD (M
•1 3
w ^
I— 1
O rH '^ tP
i-l CO
?. 2
c
cr.
CO ir:
^
OS 00 Irt
<M CO 1
2j '4-1
\r.
t^ 1 tJ( 05 i> 00 <p OC
^ CO 1
*i
(N
c
1 Tfl rH lO ^N. US i> '^J
r-l
«
0-
a
\0 CO CO tJ
I—
r-i
!>;>
«M
P^
-^^
s
CO
<M (T.
^ f
o-
1—
CD
^ 1
9 ?
«
cq
t> 1 J> v^
O 1-
\r.
1
Tj
O
^
(M
a
■^
<N
•£
1
05
cc
cc
IC
c
^
c-.
i>
cr.
t^
1
cc
1 «
^
CO C<1
O '-'
OC
CO
rH CD
OS (M
Q.
r^
1
1
c
•3
1
a
'I
1
1-^
e5
1
1
1
" 1
J
'S
i
o
"1
4
110 ABSTRACTS OF CHEMICAL PAPERS.
the withered fronds, but has still leffc considerable quantities in them
and in the humus, whilst, although lime and magnesia are present in
the humus in greater abundance than in the other plant, the living
plant has not taken up so much. P. grande seems to have had an
abundant supply of all its constituents, whilst A. nidus has been
deficient only in sodium salts, which it has removed completely from
the humus. H. W.
Percentage of Ash in the Sugar-cane. By W. Knop (Bingl.
])olyt. /., 245, 435). — The following is an analysis of a sample of
sugar-cane from Pernambuco, the cane having been overgrown with
fungi. It contained 80 per cent, of water. 100 parts of the dried
substance gave —
SiOs. P2O5. SO3. CI. 1:20. NaaO. CaO. MgO.
0-81 0-07 0-08 0-29 0'86 traces O'OG 0'16 parts
also traces of ferric and manganic oxides.
It is a remarkable coincidence that the ash, although small in
quantity, contains so large an amount of magnesia and chlorine.
Whether this peculiarity in the composition of the ash favours the
spreading of fungoid disease cannot be ascertained without making a
number of ash determinations of sound canes. D. B.
Parasitic Diseases of Plants, and their Prevention. By L.
Danger and others (Bied. Ge7itr., 1882, 615 — 619). — Cabbages and
cauliflowers suffer from a sudden fall in the temperature ; the damage
is due to rending of the epidermis cells, whereby the flow of sap
is impeded.
Sugar-beet is frequently destroyed by the larvae of Atomaria
linearis or of the centipede, which eat the rootlets, but so long as
the inner bundle of rootlets remains unattacked, the beets will
flourish. To provide other food for these larvae, J. Kiihn recom-
mends that the weeds should be allowed to grow up to the fifth
leaf, and that the beet seed should be pickled with a mixture of
5 parts of magnesium sulphate dissolved in 100 of water, to which
may be added 1 part of phenol. Hess describes the slightly known
larva of Silpha reticulata, which destroys the cotyledon leaves ; this
larva prefers, however, to feed on Atriplex hortensis and the Cheno-
podiacese, which should therefore be carefully weeded out.
Pi-illieux describes a fungoid growth belonging to the Discomycetes,
which attacks beans, hemp, clover, carrots, and chicory. The un-
usable portion of these plants should be burnt, and not placed in
compost heaps. G. Kreiss states that all plants of berberry, buck-
thorn, blackberry, and several belonging to Boraginaceae should be
removed from the neighbourhood of fields bearing grain, as these
plants harbour the germs of Accidium, which produces rust in the
grain. E. W. P.
Vine Diseases, and Remedies. By F. v. Thumen and others
(Bied. Centr., 1882, 688 — 690). — Thiimen recommends a mixture
containing one-twelfth road dust, one-twelfth ferrous sulphate, and
VEGETABLE PHYSIOLOGY AND AGRICULTURE. Ill
five-sixtlis gypsum as a remedy against Peronoapora viticola, the
winter spores of which Prillieux has found on leaves to the number
of 200 per square mm. of surface. Clissey burns all portions of the
vines affected with Sphaceloma ampelinum. Thiimen describes the
appearance of a new disease, called in France " Aubernage," which is
produced by Sphaerella pampini. J. Kiibler describes the effects of
disease produced in Switzerland by Cicada or Typhlociha vitis.
E. W. P.
Diseases of Sugar-beet. By J. Kuhn and H. Joulie {Bied. Gentr.,
1882, 607 — 612). — Various methods were tried for the destruction of
nematodes, which destroy sugar-beet. The most satisfactory plan is
to sow some fine-rooted variety of garden-cabbage, or the same mixed
with cress. The nematodes feed on this, and the larvge then remaining
may be burnt when this supplementary crop is removed, which should
be in about 30 days after brairding.
Experiments show that this method relieves a soil of beet-sickness.
Joulie has noticed that sugar-beet does not thrive on reclaimed forest
lands without the addition of manures containing potash, such as
farmyard dung, &c. ; the roots being feeble and wanting in sugar, and
the leaves weakly. The ash of these weak roots on analysis shows that
potash is decidedly in too small a quantity, and consequently the plant
is enfeebled. E. W. P.
Composition of Fodders. By A. Peteemann (Bied. Centr., 1882,
642). — Tables of analyses of a dozen kinds of fodder.
Specific Grayity of Cereal Grains. By Drechsler (Bied,
Centr., 1882, 715). — The sp. gr. of cereal grains has no connection
with their agricultural value, which is determined by their absolute
weight, the heavier corns producing the highest yield. To estimate
the actual weight, it is necessary to weigh at least 400 grains. It has
been found, from an extended series of experiments, that 100 grains of
winter rye, wheat, and oats weigh 4 grams, and 100 grains of barley
6 grams. E. W. P.
Composition of Malt from 1877 Barley. (Bied. Centr., 1882.
632 — 634.) — Tables showing the composition of the original and
malted barley from various districts, as also of the ash of the barley
and malt. Malt contains more lime than barley. E. W. P.
Cotton Cake. By A. Renouard (Annales Agronomiques, 7, 511 —
524). — Since 1872 the consumption of cotton cake in France has been
extending, and it is now largely used for feeding cattle. In 1880 the
amount of cotton cake imported was 446,467 kilos., and of cotton
seed 21,588,363 kilos. In the same year the quantity of cotton cake
exported (almost entirely to England) was 2,704,807 kilos. The chief
supply, both of cake and seed, is derived from Egypt, Turkey, and
Italy, very little coming into France from the United States.
England, on the other hand, imports cotton cake chiefly from the
United States, and cotton seed chiefly from Egypt. The cotton-seed
oil, expressed at Marseilles and Rouen, is used by painters and varnish
makers, and in soap making. The extraction of this oil on a com-
112 ABbTRACTS OF CHEMICAL PAPERS.
mercial scale dates from 1860, before which time vast heaps accumu-
lated and perished on the cotton plantations ; at the present day the
seed is often more profitable to the planter for its oil and oil-cake than
for its cotton, of which it contains only about 25 per cent, by weight.
In the United States, the cotton-seed harvest takes place in October
and November, and the seed, after having been carefully gathered by
women, is spread out to dry until hard to the teeth : the cotton wool
is then separated from the remainder of the seed by suitable machines.
The earlier seeds are of inferior quality to those gathered later in the
season ; they are more watery, the kernel is greener and softer, the
cotton less easily removed, and they are apt to be crushed by the
decorticators : the oil obtained from them contains more water, resin,
and mucilage, clarifies with dijQficulty and easily becomes rancid. In
order to extract the oil, the seeds are screened, crushed between fluted
rollers, ground into a paste which is heated in an oven to coagulate
the albumin ; then submitted to a pressure (in England) of 8500 lbs.
per square inch in a hydraulic press. The greater part of the oil is
extracted at the first pressure, which lasts five minutes; the cakes
are then crushed, with addition of 5 per cent, water, dried by steam-
heat, and re-pressed ; the pressing is sometimes repeated a third time,
after which the cake does not retain more than 9 — 10 per cent, of oil.
The cakes are finally trimmed and allowed to dry for about 20 days,
when they become hard enough for transport. French cotton cakes
are generally square, 35 x 35 X 0*5 centimetre, and weigh 2'4i kilos.
There are three qualities : —
1. Cottony, so called because they contain debris of cotton. The
Syrian cakes contain more cotton than the Catanian.
2. Brown. Levantine or Alexandrian cakes are made from Egyp-
tian seed, and are free from cotton.
3. Purified cake, made at Marseilles, and consisting of the brown
cake deprived of a portion of the husks by a summary method.
In England, the only qualities are rough or common cotton cake
(answering to the tourteaux bruts), and decorticated cotton cake, which
is unknown in France.
Cottony Cake has a deep-brown colour and granular fracture,
showing fibres of cotton.
Catanian. Syrian.
Water 8-4 7'4
Oil 5-2 6-92
Organic matter 79-81 80*33
Ash 6-59 5-28
100-00 100-00
Nitrogen 3-23 2-86
Phosphoric acid 202 1-12
Cottony cake is chiefly used in the south of France as manure. If
given to stock, the cotton-fibres are apt to collect into balls which
obstruct the intestines. Cottony cake is sometimes adulterated with
earthy matter.
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 113
Brown Cake. — The fresh cake has a greenish colour which becomes
brown with age. The fracture shows a large number of hard, black
fragments of the testaceous covering of the seed. It is used solely
for feeding stock, in admixture with pulped potatoes or mangel, and
with hay or chaff after maceration for 12 hours. It is never given to
pigs. In England and America, it has to a considerable extent taken
the place of linseed cake. Cotton cake should never be boiled, for it
then developes an essential oil which animals dislike.
Composition.
Water 10-98
Oil 6-09
Organic matter 77'OS
Ash 6-00
100-00
Nitrogen 4-03
Phosphoric acid 2-07
Purified Cake is yellow, sprinkled with numerous dark spots.
Cattle like it better than the preceding, and it is excellent for fatten-
ing, and, above all, for producing milk, being preferred even to rape
cake for this purpose.
Composition.
Water 1126
Oil 4-80
Organic matter 78'7G
Ash 5-28
100-00
Nitrogen 4-43
Phosphoric acid 1*96
Decorticated Cotton Cake has a pale-yellow colour, and is made
only in England and America. The seeds are crushed by decorticators
and the husks then winnowed from the kernels, which are ground to
meal and then made into cakes in the ordinary manner. The husks
are used to make paper. The cakes are hot pressed only when the oil
is to be used for industrial purposes ; virgin oil for use at table is
always obtained by pressing in the cold.
In the United States, a salad oil is obtained by cold pressing equal
parts of sesame meal and cotton-seed meal. The semi-solid fat, which
is a bye-product in this operation, is used for making artificial butter.
Ordinary
decorticated Cold-pressed Hot-pressed
cotton cake. (Voelcker). (Yoelcker).
Water 9-52 9-08 9*28
Oil 11-58 19-34 26-05
Organic matter 73-27 64-2 66-62
Ash 6-63 7-38 8-05
100-00 100-00 100-00
Nitrogen 7-64 6-93 6-58
VOL. XLIV. *
114 ABSTRACTS OP OHEMIOAL PAPERS.
The varieties of cotton cake in the market vary so mnch in com-
position, that buyers should always require a specification and
guarantee of quality. J. M. H. M.
Cultivation of Lupines. By J. Konig (Bi^d. Centr., 1882, 642).
— Continuous cropping with lupines cannot be carried on for more
than 5—10 years. E. W. P.
Potato Culture. By A. Letdhecker and others {Bied. Centr. ^
1882, 598 — 605). — Leydhecker finds that the best yield of potatoes is
obtained by removal of the side eyes rather than of the end eyes, whether
the sets be planted shallow or deep ; also that deep setting lowers the
yield of tubers and haulms. E. Wollny having planted potatoes, of
which the sets were half-potatoes cut either along the long diameter
or short diameter, found that the pointed half produced the highest,
the other half the lowest yield ; that the tubers from the pointed sets
were larger than those produced from medium- sized whole sets ; and
that large whole sets gave a larger yield than halved potatoes. The
rest of this article consists of tables merely showing the yields and
percentage of starch of varieties of potatoes grown by several experi-
menters. E. W. P.
Sugar-beet Culture. By W. Rimpau and others {Bied. Centr. ^
1882, 594 — 598). — Rimpau notices that the earlier the beet is sown,
the greater will be the number of young shoots, and that their growth is
aided by the cold frosty nights of March ; also that a greater number of
shoots will be thrown up if the seed be planted deep. From France it
is reported that it is best to plant deep, as the percentage of sugar is
then higher, and that the shallow-sown roots generally grow up forked.
Desprez reports that the beets with compact flesh and wrinkled skin
contain a higher percentage of sugar than other kinds. E. W. P.
Cultivation of the Sugar-beet. By A. Ladureau (Annales
Agronomiques, 7, 575 — 587). — In this paper are detailed the results of
experiments carried out in 1880. The manuring experiments are the
only ones of chemical interest.
The soil of the experimental plots has received no manure for many
years, and is remarkable as being quite destitute of phosphoric acid.
Sample taken to a depth of 40 cm. contained per cent. : — P2O5, none ;
N as NH3, 0012 ; organic N, 0-065 ; nitric N, 0-022 (total N, 0-099) ;
K2O, 0-035; CaO, 0-370; MgO, 0*151; AI3O3 and Fe^O^, 3-259; NazO,
0-084; CI, 0-091 ; SO3, traces.
Nitrogenous Manures. — These were employed in equivalent quanti-
ties, at the rate of 200 kilos, nitrogen per hectare, the size of each
experimental plot being one " are." The leather used in experiment
No. 9 had been torrefied by superheated steam. The " azotine " used
in No. 9 is prepared by the action of steam on torrefied wool-waste
{Annates Agronomiques, 7, 28), and contains organic nitrogen in a
soluble form ; it can be bought at 2 francs per kilo, of contained N.
The trimethylamine of No. 10 is produced by the destructive distilla-
tion of certain beet- distillery residues, and is sold as a brown, badly
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
115
smelling liquid, containing about 10 per cent, nitrogen, at a price
equivalent to I'SO francs per kilo, of N; the principal results are
embodied in the annexed table.
Manure.
N
per cent.
of
Manure.
Kilos.
Manure
per
hectare.
Kilos.
Beet
per
hectare.
Kilos.
Sugar
per
hectare.
1. Unmanured
2. Ammonium sulphate
3. Sodium nitrate
4. Potassium nitrate . . .
5. Arachida cake
6. "Wool refuse
7. Torrefied wool
8. Torrefied leather. . . .
9. Azotine
10. Trimethylamine ....
960
1265
1500
2750
4440
6660
3330
2170
2090
32,400
47,400
54,800
51,200
52,400
49,600
50,100
48,100
60,100
43,600
3292
4569
5310
4392
5622
4925
4954
5334
5775
4407
The seed was sown on April 7th, and the roots lifted November 13th.
These experiments show clearly the superiority of nitrate of soda to
sulphate of ammonia, and even to nitrate of potash (for this soil), and
the value of the organic nitrogen in such manures as arachida cake,
wool refuse, and azotine.
PJiosphatic Manures. — The quantity of each was so adjusted as to
represent 100 kilos, phosphoric anhydride per hectare. To the super-
phosphate in No. 5 was added the same quantity of ammonium sul-
phate as was used in No. 2 of the preceding experiments.
Manure.
1. Unmanured
2. Ardennes phosphates
3. Burgundy phosphate
4. Superphosphate
5 . S uperphosphate and ammonium
sulphate.
P205
Kilos.
per cent.
Manure
of
per
Manure.
hectare.
34-8
280
29-5
340
13-5
750
1 13-5
r 750
I 960
Kilos.
Beet
per
hectare.
32,400
33,800
33,400
44,700
55,400
Kilos.
Sugar
per
hectare.
3292
3596
3610
4559
5246
J. M. H. M.
Nitrification in Soils. By R. Waeington (Bied. Gentr., 1882,
660—663; from Jour. 80c. Arts, 1882, 532— 544).— The following
table represents the average quantity of nitrogen as nitrates in the
drainage-water which flowed from depths of 20 and 60 inches of un-
manured and uncultivated soil at Rothamsted during the years 1877 —
1882 :—
i 2
116
ABSTRA€TS OP CHEMICAL PAPERS.
Rainfall in incbes.
Drainage
in inches from
20 ins.
60 ins.
Nitrogen as nitrates
in 1,000,000.
20 ins.
60 ins.
Kilos, per acre.
20 ins. 60 ins.
January . .
February .
March . . .
April
May
June
July
August . . .
September
October . .
November
December .
Total ,
1-57
2-85
1-36
2-51
2-68
2-62
3 04
4-20
2-83
2-95
3-38
2-51
1-26
2-74
0-53
1-03
0-63
0-56
0-7g
1-86
1-23
1-68
2-55
2-01
•34
9-
•39
8^
•61
6-
•33
9^
•68
11 •
•62
9-
•68
16-
•64
15-
•14
17-
•50
15-
•40
11-
•01
8-
111
9^8
9-2
9 1
11^5
10 5
14^2
14 0
13 3
13^0
11-8
0 9
1-25
2-39
0-32
100
0 74
0-54
1^25
3 01
2 15
2-66
3 05
182
151
2 38
0 57
113
0-86
0-66
0^98
2-34
1-54
199
2-89
2 24
32-50
16-83
16-34
11-8
11-05
20-17
19-09
The greatest amount is eliminated during the summer and autumn
period, the summer being the season when nitrification proceeds most
rapidly. The analyses of drainage of fallows, at a depth of 27 inches,
show a loss of nitrate nitrogen amounting to about 26 kilos, per acre ;
but although the nitrates are formed in the upper portion of the soil,
rain has carried them down, and they appear in larger quantities in
the second 9 inches of soil below the surface. The conclusions drawn
from these and other analyses are, that so long as the winter is not
wet, no great loss of nitrates occurs,|but that nearly all are removed if
the winter be otherwise, consequently the crops will suflfer. To avoid
this loss, it is recommended that som« rapid growing crop, as mustard,
be sown during the summer ; this will retain the nitrates, and convert
them into an insoluble form which can then be utilised by the crop
sown during the winter months. K W. P.
Nitrification in the Soil. By Mari^-Davy {BiecL Gentr., 1882,
663). — Water containing 20 6 mgrm. N as ammonia, and O'Sas nitrates,
was brought in contact with a mixture of sand and flint ; 31 litres of
this water appeared after its passage through the soil (in 31 days) as
25^2 litres clear water, which contained only V7 mgrm. N as ammonia,
but 21*5 mgrm. per litre N as nitrates. In another experiment rye-
grass was allowed to grow in the soil, and was watered with the same
water, which, after its passage through, contained only 0*8 mgrm, N"
as ammonia, and 20*5 mgrm. N as nitrates per litre ; nearly all the
phosphoric acid present in the water was absorbed. E. W. P.
Comparative Manuring Experiments. By A. Salfeld {Bied.
Centr.f 1882, 585 — 587). — At three different stations on sandy soils,
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
117
the effects of various combinations of lime, kainite and bone-meal with
Chili saltpetre, &c., were tried on oats, grass, and rye. Kainite and
lime alone were nowhere found to be a financial success, but mixtures
of kainite and bone-meal with a little saltpetre, and of kainite with
Mejillones phosphate gave satisfactory returns. E. W. P,
Influence of the State of Division of Manures on their Action.
By P. Wagner (Bied. Centr., 1882, 665).— With the exception of
sodium nitrate, all manures should be in a fine state of division,
whereby they can be more readily absorbed by the soil. Even super-
phosphates, when finely ground, produce better crops than the same
in a coarse state of division, as experiments on peas show (Comp.
Abstr., 1882, 90, 550). E. W. P.
Manuring Potatoes with Potassium Nitrate. By Edler
(Bied. Centr., 1882, 577 — 580). — In previous communications from
the agricultural station at Gottingen, it was shown that the use of
potassium nitrate raised the yield above that produced by sodium
nitrate, that both manures produce larger tubers, and that with potash
manures the disease was less than with the sodium compound. More-
over it was shown that the percentage of starch was lowered by sodium
nitrate, but not by the potassium salts. The experiments have been
continued during the two succeeding seasons (1880 and 1881), but
owing to the bad season of 1880 the results obtained were incon-
clusive ; the season of 1881, however, was more favourable, and the
results obtained corroborate those obtained in 1879. Potash saltpetre
distinctly increased the total yield, as also the yield of large tubers,
and it did not lower the percentage of starch in the large tubers,
whereas sodium nitrate did ; the percentage of starch in the medium
and small-sized tubers grown on the unmanured plots, was, however,
higher than that contained in the corresponding sized tubers, but
which had been manured. The application of potassium nitrate was
also a financial success. E. W. P.
Composition of Pig Dung. B.y G. Lecouteux (Bied. Centr.,
1882-, 640). — According to Gassend, pig dung consists of water 80*57
per cent., N 0711, F^O, 0187, K2O 1*859. The pigs were fed with
barley and potatoes, and the production of the manure cost 7*11 M per
1000 kilos. The value of the manure, calculated from the market
prices of its components, was 24*66 M per 1000 kilos. (7'11 kilos. N
= 14-22 M, 1-87 P2O5 = 1-52 M, 18*59 K^O = 8*92 M), consequently
there was a gain of 17*5 M per 1000 kilos. E. W. P.
Analysis of Mud from the Mouth of the Eider. (Bied.
Centr., 1882, 639.)
Hydrochloric acid extract of the air-dried mud.
CaO.
CaO combined
with CO2.
K,0.
P2O5.
SO3.
4-89
4 09
4-42
3-63
0-15
0-07
0-15
0 08
0-18
0-06
118
ABSTRACTS OF CHEMICAL PAPERS.
H2O. N. CI. Loss on ignition.
1 2-91 0-26 0-56 S'SH
II 079 0-10 0-09 3-25
I. Within harbour of Tdning. II. Outside harbour.
E. W. P.
Mineral Phosphates on Arable Soil. By L. Guillaume
(Aniiales Agronomiques, 7,687 — 591). — Experiments were undertaken
by the author to test Deherain's statement that soils containing less
than 0*04 per cent, of phosphoric anhydride are benefited by the
addition of mineral phosphate. Deherain considers that most arable
soils which have been cultivated for a long time with the aid of farmyard
manure, are by that means sufficiently supplied with assimilable phos-
phoric acid, and that addition of mineral phosphate is useless. The
soil on which the author's experiments were conducted is a loam of
Jurassic origin, and has been for a long time under cultivation and in
receipt of a large dressing of farmyard manure. It contains 0"05 per
cent, phosphoric anhydride, 3'61 per cent, calcium carbonate, and a
considerable amount of ferric oxide. The experimental plots were
'fifteen in number, each of 1 acre, and a mineral phosphate from
Auxois was used, containing 24 per cent. P2O5.
The results, per hectare, are annexed: —
1. Wheat (Bordeaux) —
Stmw
Grrain
2. Oats (Yellow Flanders) -
Straw , . .
Grain
3. Maize
(cut green August 22nd)
4. Potatoes
5. Beet
Unmanured.
4,900 kilos.
708 „
4,900 „
2,544 „
15,200 „
160 hectolitres
26,400 kilos.
15,000
kilos, farm-
yard
manure.
5,600
1,596
5,900
3,256
17,360
265
27,600
15,000 kilos, farm-
yard manure
and 1,000 kilos,
phosphate.
5,700
1,760
5,950
3,397
17,800
240
27,900
Thus, in no case was the increase sufficient to cover the cost of the
mineral phosphate applied. The author intends to repeat the experi-
ments with superphosphates. J. M. H. M.
Analytical Chemistry.
A New Condensation Hygrometer. By A. Crova (Compt. rend.,
94, 1514. — 1516). — The hygrometers now in use are subject to several
causes of errors more or less considerable. To obviate these, the author
has contrived an instrument consisting of a tube of highly polished
nickel, closed at each end by discs of glass, one clear, the other ground.
I
ANALYTICAL CHEMISTRY. 119
Throngli this tube the air is slowly drawn, and the moment of depo-
sition of moisture can be very sharply observed by viewing the inte-
rior of the tube through a lens. The cooling is effected by passing a
current of air through bisulphide of carbon contained in a vessel
surrounding the tube. R. R.
Direct Estimation of Chlorine in Presence of Bromine and
Iodine. By Gr. Vortmann (Monatsh. Chem. , 3, 510—530) .—Two years
ago the author published a short notice on the detection of chlorine in
presence of bromine and iodine, depending on the reactions of chlo-
rides, bromides, and iodides with the peroxides of lead and manganese,,
in presence of acetic acid of various degrees of dilution (Abstr., 1880,
509) ; and more recently he has given a sketch of the application of
these reactions to quantitative analysis (ibid.j 1882, p. 1230). In the
present paper, the reactions concerned in these processes are more
fully discussed, and the methods of estimation are described in
detail, and illustrated by numerous examples.
Estimation of Chlorine in Presence of Bromine. — ^When the quantity
of bromine present is but small, it is sufficient to heat the mixture of
chloride and bromide with lead dioxide and acetic acid of 2 — 3 per
cent, two or three times on the water- bath. With la.rger quantities
of bromine, complete separation is somewhat difficult ; the method of
effecting it will be further considered in connection with the separation
of chlorine from bromine and iodine together.
Estimation of Chlorine in Presence of Iodine. — This is effected in the
same manner as in the last case, lead dioxide being used when the
quantity of iodide present is but small, manganese dioxide being pre-
ferable when it is large. In this case also, the evaporation with dilate
acetic acid must be repeated several times. The expulsion of the
iodine may be accelerated by first boiling the liquid for a few minutes
in a small flask ; this, however, can be done only when lead dioxide is
employed, as the use of manganese dioxide quickly gives rise to
violent percussive ebullition. In the latter case, the liquid must be
heated in a beaker on the water- bath, while a stream of air is passed
through it. The estimations come out sharp, even when large quan-
tities of iodine are present. In using lead dioxide when small quan-
tities of chlorine are to be estimated in presence of much iodine,
the results are apt to come out too high.
Estimation of Bromine in Presence of Iodine. — This estimation is vety
easily performed by evaporating down the mixture of bromide and
iodide with manganese dioxide and dilute acetic acid several times on
the water-bath, the evaporation being accelerated, if desired, by pass-
ing a stream of air through the liquid.
Estimation of Chlorine in Presence of Bromine and Iodine together. —
This may be effected either by boiling with lead dioxide and dilute
acetic acid, whereby the iodides and bromides are decomposed simul-
taneously ; or by first expelling the iodine by evaporating down with
manganese dioxide and acetic acid, and then the bromine by repeating
this operation after addition of lead dioxide. In operating by the
first method, the mutual action of iodine and bromine gives rise to
the formation of iodic acid, to prevent which, as far as possible, it is
120 ABSTRACTS OF CHEMICAL PAPERS.
advisable to add the lead oxide to the boiling solation by small portions
at a time. The liquid having been boiled for about half an hour, and
the water as it evaporates renewed from time to time, the dissolved lead
is precipitated by hydrogen sulphide, without previous filtration ; and
the liquid, after being once more treated with hydrogen sulphide, is
warmed for some time on the water-bath and filtered. The filtrate is
then evaporated to complete dryness on the water-bath, the residue
drenched with dilute acetic acid, and the liquid evaporated down after
addition of a small quantity of lead dioxide. The evaporation to dry-
ness is then once more repeated, the residue finally dissolved in water,
and the chlorine precipitated from the filtrate by nitrate of silver. In
working by the second of the methods above mentioned, the mixture
of the halogen-compounds is several times evaporated down on the
water-bath with lead dioxide and acetic acid, and the chlorine in the
residue is estimated in the usual way. This method is preferable to
the former, in so far as it affects the expulsion of all the iodine and
bromine without formation of oxy-acids, and may also afford the
means of estimating these two halogens at the same time. Moreover,
it gives more exact results than the first method ; but on the other
hand it has the disadvantage that in decomposing the iodides by
manganese dioxide, manganese passes into solution and is precipitated
in the subsequent treatment with lead dioxide, in the form of manga-
nese dioxide, or leather of a compound of this oxide with dioxide of
lead, Mn02,4Pb02: this precipitate is difficult to wash, and it is
only after prolonged treatment with boiling water that filtrates are
obtained which no longer become opalescent on addition of silver
nitrate.
The numerous analyses given in the paper show that the method
therein described is applicable in all cases to the separation of chlorine
from bromine and from iodine. Moreover it gives satisfactory results
in the estimation of relatively large quantities of chlorine in presence
of small quantities of bromine. When on the other hand much
bromine is present, the results, even with careful working, come out
too high by several units per cent.
Finally the author observes that it is not necessary to bring the
chlorine into combination with an alkali-metal by decomposing the
lead chloride obtained in the process with potassium sulphate, inas-
much as the entire process is performed with hot dilute solutions, and
the solubility of the lead chloride is very considerably increased by
the presence of the dilute acetic acid and solution of lead acetate, so
that an incomplete solution of the lead salt is not to be apprehended.
The manganese dioxide and lead dioxide added in excess are very easy
to wash, and the filtrates after a short time give not the slightest
turbidity with silver nitrate.
The bromine or iodine given off in these processes of separating
chlorides from bromides and iodides may be collected and estimated.
With regard to the estimation of iodine in presence of chlorine or
bromine, the author has already obtained satisfactory results. For
bromine, the numbers hitherto obtained are less satisfactory ; but he
hopes soon to arrive at more exact results, which may form the
subject of a further communication. H. W.
ANALYTICAL CHEMISTRY. 121
Estimation of Carbonic Anhydride in the Air at Cape Horn.
By A. MiJNTZ and E. Aubin (Compt. rend., 94, 1651).— The scientific
mission to Cape Horn has been provided with an apparatus for esti-
mating the carbonic anhydride in the air. There are two sheet-iron
aspirators, representing 300 Htres of air ; and drawn-out tubes con-
taining potassium hydroxide are fixed in metallic cases, to guard
them from accident, and are so arranged that they need not be re-
moved from the cases when the air is being drawn through them.
R. E.
Estimation of Phosphoric Acid. By O. v. d. Pfordten (Ber.,
15, 1929 — 1930). — This method depends upon the conversion of phos-
phoric acid into ammonium phosphomolybdate, and subsequent esti-
mation of the molybdenum (see p. 122). A. K. M.
Estimation of Sulphur in Iron and Steel. By G. E. Craig (Chem.
Neivs, 46, 199). — The method now recommended is more rapid and
quite as accurate as that in which potassium chlorate and hydrochloric
acid are employed ; 100 grains of the metal are placed in a 10 oz. flask,
with ^ oz. water, 1^ oz. hydrochloric acid is added by means of a
stoppered funnel ; the gas evolved is passed by means of tubes, &c.,
through an empty flask or test-tube (to condense vapours) into a nitro-
gen bulb containing | oz. hydrogen peroxide, and i oz. ammonia;
when the action becomes sluggish heat is to be applied. After blow-
ing air through, the contents of the nitrogen bulbs and the preceding
condensing flask are washed out into a beaker, and barium chloride
is added after acidifying the solution with hydrochloric acid and boil-
ing. A blank experiment should be made with each new sample of
hydrogen peroxide. The presence of copper has no influence on the
results. E. W. P.
Estimation of Oxygen and Carbon in Iron. By A. Ledebur
{Vingl.jpolyt. J., 245, 293). — The author found oxygen in many kinds
of malleable iron, wrought iron containing ferrosoferric oxide as a
mixture principally, whilst ingot iron contains ferrous oxide, either in
the dissolved state or as an alloy. The oxygen, especially in the latter
case, has a marked influence on the properties of the iron: hence its
determination in ingot iron is almost as important as that of the
sulphur and phosphorus. For analysis, clean dry iron filings free from
fatty constituents should be employed. For the removal of the last
traces of moisture and organic matter, the filings are heated in a
current of pure dry nitrogen gas, obtained by heating a mixture of
1 pt. sodium nitrite, 1 pt. ammonium nitrate, 1 pt. potassium dichro-
mate, and 10 pts. water, passing the gas through a solution of ferrous
sulphate, and over red hot copper turnings, and finally drying it by
means of phosphoric anhydride. The hydrogen gas is made from
zinc and sulphuric acid. It is passed through soda-lye and an
alkaline solution of lead, then through a heated tube filled with plati-
nised asbestos, and eventually dried over concentrated sulphuric acid
and phosphoric anhydride ; 15 grams of iron borings are placed in a
porcelain boat, and pushed into a glass tube of which one end is
connected by means of a T-piece with the nitrogen and hydrogen
122 ABSTRACTS OF CHEMICAL PAPERS.
tubes, whilst the other end is drawn out and communicates with the
absorption-tube containing phosphoric anhydride. In commencing
the analysis, the tube with the copper turnings is heated, and a slow
stream of nitrogen passed through the apparatus. After two hours the
tube with the iron borings is heated, nitrogen gas being passed over con-
tinuously, in order to expel all volatile constituents. The absorption-
tube is then attached to the apparatus, the current of nitrogen stopped,
and hydrogen passed through. After 30 — 45 minutes' heating, the
apparatus is cooled slowly, hydrogen still being passed over. The
absorption- tube is then removed, and after expelling the hydrogen
in the tube by means of air dried over phosphoric anhydride, it is
weighed. The porcelain boat and contents are also weighed, and the
weight of the oxygen of the water absorbed should agree with the
loss in the weight of the porcelain boat. Analyses of a variety of
samples of iron are given, the high percentage of oxygen in wrought
iron being explained by the admixture of slag. The determination of
oxygen is therefore said to afford a means of determining approxi-
mately the quantity of slag present. For determining the carbon, the
author recommends M'Greath and Ullgren's method. D. B.
Electrolytic Estimation of Zinc. By A. Millot (Bull. Sue. Chim.
[2], 37, 339 — 341). — 2*5 grams of the mineral are dissolved in 50 c.c. of
hydrochloric acid, and a small quantity of potassium chlorate is added
to the boiling solution in order to precipitate the iron. If the mineral
contains much silica, it is previously evaporated to dryness with hydro-
chloric acid. The liquid is cooled, diluted, and mixed with 100 c.c. of
ammonia and 50 c.c. of a saturated solution of ammonium carbonate
in order to precipitate the lead and calcium. The liquid is diluted to
600 c.c, filtered, and 100 c.c, corresponding to 0'5 gram of the mineral
and containing from 0*2 to 0'3 gram of zinc, are mixed with 1 gram of
pure potassium cyanide and placed in a beaker in which is suspended
a cylinder of platinum gauze which acts as the positive pole, and a
platinum cone like that in Riche's apparatus which acts as a negative
pole. Two Bunsen cells or a Clamond thermo-electric pile of 150 ele-
ments may be used to effect precipitation, which is complete in about
ten hours. The firmly adhering deposit is washed with water, then
with alcohol, and dried. If the mineral contains copper the latter is
deposited with the zinc. The deposit on the cone must in this case be
dissolved in nitric acid and the copper precipitated from the acid solu-
tion. If cadmium is present, it must be removed by treatment with
hydrogen sulphide. The potassium cyanide should be used in the
proportion given above ; if more is added, the metal is deposited very
slowly, whilst if less is added the deposit of zinc is not adherent. Any
action on the electrodes may be prevented by mixing the solution with
ammonium acetate or nitrate. The latter, however, retards the pre-
cipitation of the zinc. C. H. B.
Reduction of Molybdenum Compounds. By 0. v. d. Pfordten
{Ber.f 15, 1925 — 1929). — The author has examined Pisani's method
for estimating molybdenum. He finds that the end-product of the
reduction of molybdic acid with zinc and hydrochloric acid is not
)
ANALYTICAL CHEMISTRY. 123
M02O3, but Mo507(= 2M02O3 + MoO). This, however, becomes
oxidised, by exposure to air, to MoiOs. A method for the volumetric
estimation of molybdic acid is founded on this reduction, and subse-
quent oxidation with standard potassium permanganate.
A. K. M.
Otto's Method for the Estimation of Fusel Oil in Brandy.
By C. Krauch (Bied. Centr., 1882, 718). — Krauch does not find Otto's
method of any use. The oxidation-products, which according to Otto
contain valeric acid, the author finds to be acetic acid.
E. W. P.
Estimation of Glycerol in Fatty Matters. By J. David
(Compt. rend., 94, 1477 — 1479). — 100 grams of the fat are melted;
65 grams of barium hydrate, BaOjOHjO, are added with brisk
stirring ; when most of the water has been expelled, the heating is
discontinued ; 80 c.c. of alcohol of 95° are poured on the mass, and
the whole is well stirred ; 1 litre of water is then added, and the whole
boiled for an hour. The barium soap remains insoluble, whilst the
glycerol is dissolved by the water, which is freed from the excess of
barium, reduced in volume by boiling, and finally evaporated in a
vacuum at a low temperature ; or, preferably, the quantity of glycerol
is inferred from the density of the solution. The barium soap after
being boiled with water is decomposed by h3-drochloric acid and the
fatty acid separated and weighed. Its melting point will indicate
approximately the proportions of stearic and oleic acids it contains.
R. R.
Estimation of Dextrose, Maltose, and Dextrin in Starch-
sugar. By H. W. Wiley (^Chem. News, 46, 175— 177).— The method
employed was as follows : — (1) 10 grams undried sugar dissolved in
1000 c.c. water; (2) 10 grams dissolved in 100 c.c. and polarised in
200 mm. tube; (3) 10 c.c. of the solution (2) is treated with excess of
mercurous cyanide (120 grams HgCyo and 120 grams NaHO per litre)
boiled, and excess of strong hydrochloric acid added and made up to
60 c.c. ; this solution is polarised in 500 mm. tube and the angular rota-
tion multiplied by 2. Solution (1) reduced by Fehling gives the total
percentage of reducing matter, viz., dextrose with reducing value of
100, maltose 62. The first polarisation gives the apparent specific
rotation due to all optically active bodies present, viz., dextrose = 52,
maltose — 139; dextrin = 193. The second reduction (3) leaves only
dextrin unaffected, and the amount of this is determined by the second
polarisation. If solid starch-sugar is employed, it must be boiled for
some time to destroy birotation; after reduction by cyanide, it is
unnecessary to use charcoal, as the addition of the acid destroys the
red colour generally present.
Calculation of the results: from (1) we obtain the reducing per
cent, of dextrose d, + that of maltose m, which latter, compared with
the former, is only 0'62.
(1.) n = d + 0-62 m.
(2.) P = 52 cZ -f 139 m -f- 193 df.
(3.) P' = 193 d'. (Second polarisation).
124 ABSTRACTS OF CHEMICAL PAPERS.
To find d and m.
(4.) P-P' = 52(Z + lS9m.
Multiply (1) by 52 and substract from (4).
(5.) P -- P' - 52 R = 106-76 m.
(6.) Whence ^ = ^-j^^-f^>
(7.) d=n - 0-62 m.
This process agrees well with that proposed by Allen. Several
analyses are given. E. W. P.
Diflfusion of Sugar in Beet. By G. Mareck {Bingl. pohjt. /.,
245, 345 — 350). — In determining the differences in the sp. gr. of
whole roots and of roots cut into sections, the author found that the
weight of the former was generally below that of the separate parts
of the root, the differences being greater the smaller the sp. gr. of the
whole root. The valuation of beet according to the density of the
juice is said to give more accurate results than the determination of
the sp. gr. of the roots. A table is given showing the results of
experiments on the distribution of sugar in the beet. D. B.
Estimation of Rice-starch. By F. Salomon {J. pr. Chem. [2],
26, 324 — 333). — The results of a series of experiments are given
which show that while potato-starch, when heated with hydrochloric
acid, yields the full theoretical amount of glucose (lll'll per cent.),
rice-starch cannot be made to yield more than about 107 per cent.
The sp. gr. of the inverted solution is, however, identical with that
obtained from potato- starch, proving that about 4 per cent, of sub-
stances are formed which have no reducing action on Pehling's
solution. O. H.
Volumetrical Estimation of Phenol. By T. Chandelon (Bull.
8oc. Ghim. [2], 38, 69 — 7*1). — The introduction of phenol as an anti-
septic has necessitated a rapid and easy method for its estimation.
Koppershoor has proposed to act on phenol with a standard solution of
bromine in potassium bromide so as to convert the phenol into tribromo-
phenol. The excess of bromine used may be determined by sodium
thiosulphate ; or a mixture of potassium bromide and bromate acidified
by hydrochloric acid may be substituted for bromine-water. Giacosa
used a solution of bromine- water which has been standardised by a
phenol solution of known strength, but as the precipitate of tri-
iDromophenol invariably retains a certain quantity of bromine, the
results are far from being exact.
The author proposes potassium hypobromite which, like bromine,
converts the phenol into tribromophenol. The method of operation is as
follows : — The hypobromite solution is prepared by dissolving 14 — 15
grams pure potassium hydroxide in 1 litre of water and adding gra-
dually to it 10 grams bromine. The solution is then diluted until it
ANALYTICAL CHEmSTRY. 125
is of sncli a strength, that 50 c.c. corresponds to 10 c.c. of a normal solu-
tion of phenol of 10*5 per cent, or 0*05 gram of pure phenol. In order
to ascertain the strength of any phenol solution, 50 c.c. of the hypo-
bromite is placed in a flask and the phenol solution is added nntil a
drop of the solution gives no blue coloration with potassium iodide and
starch solution. The method is sufficiently exact for clinical purposes,
the error being about 1'2 per cent. If it is required to estimate
phenol in urine, the latter is distilled with dilute sulphuric acid : in the
case of lint or cotton, the vapours of water, slightly acidulated with
hydrochloric acid, are passed over them and subsequently condensed,
and the phenol in the distillate estimated after neutralisation with
potassium hydroxide. V. H. V.
Ammoniacal Alkaline Silver Solution as a Test for Form-
aldehyde. By B. ToLLENS (Ber., 15, 1828—1830), — Salkowski
having noticed the formation of fulminating silver in a solution of
silver which had been treated with caustic soda and ammonia, the
author states that this has not occurred with his solution when pre-
pared in the way described. If, however, it is allowed to evaporate in
a shallow dish, small quantities of a detonating compound are formed,
but not when it is kept in a stoppered bottle. The best way is to
keep the component parts separate, and mix them when required.
With regard to the quantitative determination of aldehydes by the
above solution, for each molecule of formaldehyde 2 atoms of silver in
general are thrown down ; but irregularities have occurred which
have not yet been avoided. The best proportions for the solution
as yet have been found to be equal weights of a solution of 1 part
silver nitrate in 10 parts water, and 1 part caustic soda in 10 parts of
water mixed together, and the ammonia added drop by drop until
complete solution of the silver oxide is effected. J. K. C.
Examination of Pat. By H. Y. de Schepper and A. Geibel
(Dingl. jpolyL /., 245, 295 — 302). — In order to ascertain the value of
a fat, it is necessary to determine the non-fatty constituents, i.e., the
amount of water, sand, fibrous matter, &c., the total quantity of fatty
acids and glycerol, and the amount of " candle material," i.e., the solid
fatty acids present in the latter. The water is determined by placing
50 — 60 grams of the substance in a tared beaker and drying it at
110° for one hour, stirring the mixture occasionally with a tared glass
rod. The temperature is then increased to 125°, and after two hours*
heating the beaker with contents is weighed, the loss in weight giving
the amount of water. The sand and other substances are determined
by filtering 50 — 60 grams of the fat through a tared filter at 60 — 70°,
washing with hot benzene, drying and weighing. If, owing to the
presence of glycerol, the dried product is deliquescent, it is washed
with alcohol before weighing. The process for determining the fatty
acids and glycerol is based on the following conclusions. From the
equation indicating the decomposition of fats in general :
C3H5(03C„H2„4-i)3 + 3H2O = C3H6(OH)3 + 3C„H2„ + i02H,
it follows that (calling a the molecular weight of the fatty acid)
126 ABSTRACTS OF CHEMICAL PAPERS.
an equivalent of fat, expressed by (3a -\- 92 — 3 x 18)^, g^ives
Sa grams fatty acids and 92 grams glycerol (g). Tf a represents the
mean molecular weight of the different fatty acids contained in fat,
we obtain the following formulae for the quantity of fatty acids and
glycerol calculated as per cent, on the fat : —
. 300a , 9200
3a + 38 ^ 3a-f38
To ascertain the factor a in a fat, 60 grams of the latter are saponified
with 40 c.c. potash-ley of sp. gr. 1*4 and 40 c.c. alcohol ; boiled in a
litre of water for about an hour, decomposed with sulphuric acid, and
the fatty acids, after washing and drying, titrated with standard
potash-ley, 10 c.c. neutralising exactly 1 gram margaric acid, or
100 c.c. = 1000 : 270 = 37-037 c.c. standard acid. By calling a the
tenths of c.c. necessary to neutralise 1 gram of fatty acid, we obtain
270 X 100
the following ratio between a and a : — a = To determine
a,
the amount of neutral fat N", 1 gram of dried and filtered fat is
titrated with the above solution. By taking n to indicate the tenths
of c.c, and assuming that the various triglycerides are all decomposed
in the same manner, the amount of free fatty acids is equal to the
following : —
F = M!L, also N = 100 - 1^ per cent, of the fat.
By making use of these formulae we obtain the following general
equations : —
100[l-(n:a)] _^00^ + ioO%nd
•^ 100 3a + 38 a
_100[1- (n:a)] 9200
300 3a -I- 38
It was found that the molecular weight of fatty acids from tallows
ranged between 280 and 274 — hard tallows being nearest to the higher
number. For palm oils, the molecular weight is 270 : without, there-
fore, causing too serious an error, this number may be taken to repre-
sent the molecular weight of tallows and palm oils, or mixtures of
both, which simplifies the above method. The percentage of neutral
fat in this case is N = 100 — n, whilst the above formulae may be
modified as follows : —
f = 95' 52 "" ^ + n per cent., and g = 10'85 — ~ ^^ per cent.
By taking into consideration the fact that all fats contain from 1 to
1*5 per cent, albumin or cellulose, and that the percentage of fatty
acids in tripalmitines is less than 95*5, and the glycerol more than
10'85, the above formulae require a further alteration, viz. : —
- f.A.t: 100 — n , J t^kIOO — n
^ - ®*^ ^00- +^•'^^3 = 10-5 ^Q^-,
TECHNICAL CHEMISTRY. 127
or, / = 94-5 and g = 10-5 if n = 0, ond/ = 100, and g = 0 ii n =
100, i.e., an increase in the percentage of neutral fat N from 0 to 100
raises the percentage of fattj acids 55, whilst the glycerol is reduced
by 10'5 per cent. ; so that the following formnlge are obtained which
may be used for determining the percentages of fatty acids and
glycerol : —
/ = 100 - 0-055 1^, and g = 0-105 N.
The value of the fatty acids is ascertained by determining the crys-
tallising points. It is, however, necessary to test the acids for neutral
fat by dissolving 1 gram in hot alcohol and adding strong ammonia
to the solution. In the presence of mere traces of neutral fat, the
solution is rendered turbid on the addition of ammonia. D. B,
Occurrence of Organic Bases in Commercial Amyl Alcohol.
By L. Haitinger (Monatsh. Ghem., 3, 688—692). — With reference to
the use of amyl alcohol in testing for alkaloids, the author calls atten-
tion to the fact that pyridine and other bases are frequently present,
even in the conimercially " pure " alcohols. A. J. Gr.
Technical Chemistry,
Influence of Coal-dust in Colliery Explosions, By W. Gal-
loway (Proc. Eoij. Soc, 33, 437 — 445, and 490 — 495). — A continua-
tion of the author's experiments. The apparatus finally adopted to
investigate the influence of coal-dust consists of (1) an explosion
chamber 6 feet by 2 feet, lined with strips of wood, with three open-
ings for admitting the fire-damp, letting out the air displaced, and
for igniting the mixture respectively. It is provided with a small
centrifugal fan for mixing the air and the fire-damp. (2.) A gallery
126 X 2 X 2 feet, consisting of seven pieces, each 18 feet long,
placed end to end and hooped by iron bands, one side of which, of
dimensions 18 feet by 2 feet 3 inches, can be opened like a door.
Before an experiment, these doors are opened and coal-dust strewed on
the floor to a thickness of one- eighth to a quarter of an inch, and
some laid on shelves in the several sections. The method of procedure
is as follows : — The explosion chamber is drawn back, and several
sheets of paper inserted between it and the gallery to act as a
diaphragm ; the chamber and gallery are then bolted together, the
fire-damp introduced from a measuring cylinder, and mixed with the
air by the aid of the fan, and the mixture exploded. When no coal-
dust was introduced, or the floor or shelves damped, the fire-damp
explosion travels along the gallery for about 12 feet ; if the coal-
dust was dry, and all the sections closed so as to make the gallery
continuous, the flame extended to 50 or 60 feet (experiments showed
that the greater or less moisture in the atmosphere exerted an appre-
128 ABSTRACTS OF CHEMICAL PAPERS.
ciable effect on the coal-dust), and finally if the doors and the fourth
and fifth sections were opened, the flame reached to 60 or 70 feet. In
all cases, a thick cloud of coal-dust and air was driven by the explo-
sion-wave through the gallery, and on emerging into the open air
assumed large proportions, and exhibited all the phenomena of
incipient explosive combustion. Crusts of coked coal-dust were
found on the shelves the farthest removed from the explosion
chamber, which corroborated the hypothesis proposed in connection
with explosions at collieries, that these crusts are deposited during a
retrograde movement of the air, travelling back towards the origin of
the explosion. From observations made by the author at the Peny-
graig Colliery after an explosion, similar crusts of coked coal-dust
were found deposited in a direction opposite to that of the explosion.
The results of the experiments given in the papers confirm the
view put forward by the author as to the manner in which the
flame of an explosion is originated and propagated, but they further
show that the presence of fire-damp is unnecessary, provided that the
scale of the experiments be large, and the coal-dust be suflBciently fine
and dry. Y. H. V.
Water of Rangoon. By R. Romanis (Chem. News, 46, 187).— In
the water stored in reservoirs at Rangoon, the vegetation increases
largely during the hot season, but the quantity of free ammonia is
highest during March. Albuminoid ammonia sometimes reaches as
high as 0'82 in July, the minimum quantity during two years
being 0-24. E. W. P.
Action of Water on Lead. By A. H. Allen (Chem. News, 46,
145 — 146). — In a recent trial (J. J. Milnes against the Huddersfield
Corporation), the question arose as to the influence which the presence
of sulphuric acid had on the intensity of the action of water on lead ;
and from the scientific evidence given it was inferred that a trace of
free sulphuric acid was rather beneficial than otherwise, as it would
tend to protect the pipes from the action of the water by depositing
insoluble lead sulphate. The author has proved this suggestion falla-
cious, for he has found by experiment that water containing free sul-
phuric acid dissolves more lead than water which is either altogether
tree from acid or which has been neutralised. The experiments were
made by adding definite quantities of decinormal sulphuric acid to
250 c.c. of water, and then immersing in the liquid equal sized pieces
of sheet lead, scraped clean immediately before use. The results
vary. Some water after standing in lead pipes all night contained
0'61 grain of lead per gallon. Water taken from the main, having
marked acid reaction to Poirier's orange, left in contact with clean lead,
dissolved 0*42 to 0*56 grain per gallon, but when previously rendered
faintly alkaline with lime-water, only 0*14 of lead was dissolved. The
author is of opinion that the free acid in drinking-water is more likely
to be hydrochloric than sulphuric acid. D. A. L.
Antiseptic Action of Salicylic Acid. By E. Robinet and
H. Pellet {Bied. Centr.y 1882, 637), — Salicylic acid added to must in
TECHNICAL CHEMISTRY. 129
quantities of 0*3 gram per litre preserves it perfectly from fermenta-
tion, and when yeast has been added to the must, 0'-5 gram per litre is
sufficient to destroy its action. E. W. P.
Certain Properties of Hydrogen Cyanide. By C. Brame
(Compt. rend., 94, 1656). — Aqueous solution of hydrocyanic acid
copiously precipitates albumin from its aqueous solutions. Bodies
of animals poisoned by hydrocyanic acid have been preserved for a
year. When the bodies of animals injected with hydrocyanic acid
have been preserved in closed receptacles for several months, they lose
all odour of the acid, and acquire that of ammonium formate, which
salt may be found in the serous liquids. In embalming by means of
hydrocyanic acid, it is necessary to introduce into the body, after the
acid, a small quantity of zinc chloride. R. R.
Boiler Explosions. (Dingl. polyt. J., 245, 617.) — It is mentioned
that a silent boiling of liquids is due to the formation of gases. If
instead of feeding a boiler with fresh water, boiled or condensed
water be used, which contains less absorbed air, explosive boiling may
occur after heating the boiler for some time, and as in this case a
large amount of steam is formed in a short time, the plates of the
boiler are endangered, owing to the sudden increase in the pressure
of steam. D. B.
Recovery of Sulphur by Mond's Process. By Schaeppi (Bingl.
polyt. /., 245, 341—345, and 387— 392).— The following is a sum-
mary of the author's results and conclusions : — The longer the time
the liquors and oxidised residue are allowed to remain in contact, the
more sulphide is dissolved. It is best to oxidise in as concentrated a
solution as possible, and to lixiviate for two or three hours. The
weaker the liquor, the more sulphides does it contain ; the stronger it is
the larger is the quantity of thiosulphates : hence the longer the liquor
is oxidised the greater is the importance of working with weaker solu-
tions. In the commencement, a solution was used of 16" T. ; subse-
quently this was reduced to 12°, so that it was possible to oxidise
with twice the quantity of air without over-oxidising the liquor,
whereby a considerable increase in the yield of sulphur was obtained.
A further modification was the use of hot water, which not only dis-
solves a larger proportion of sulphides in a shorter time, but prevents
the cooling of the residue. Formerly this residue required four to six
hours' heating to render it effective, whilst at the present time it can
be used at once for a further oxidation. By mixing the liquor and
acid in closed vessels before bringing them into the decomposer, the
loss of sulphuretted hydrogen due to defective decomposition is re-
duced, whilst, owing to the possibility of working with smaller vessels,
the operation is considerably facilitated. It is necessary, however, to
heat the liquor to 80 — 90°, otherwise the sulphur is deposited in a form
difficult to filter. D. B.
The Currents of the Gases in Sulphuric Acid Chambers.
By K. Abraham (Dingl. pohjt. /., 245, 416—421). — The success of
YOL. XLIY. k
130 ABSTRACTS OF CHEMICAL PAPERS.
the mantifactiire of sulphuric acid depends largely on the uniformity
of the admixture of the reacting gases, not only at the point of
entrance but throughout the chamber. Schwarzenberg's theory is
that these currents move in horizontal strata from the roof to the floor
of the chamber. His views are based on observations of the tem-
perature and sp. gr. of the gaseous mixture at successive points. The
author from his own investigations concludes that Schwarzenberg's
theory is untenable. He states that the gases on entering come into
contact with a gaseous mixture which differs only slightly from them
in sp. gr., and therefore undergo a uniform distribution over the first
portion of the chamber considered in vertical section, the production
of sulphuric acid showing a corresponding uniformity. The cooHng
action of the sides and roof of the chamber effects a decrease in
the temperature : hence the gases travel upwards from the centre and
downwards along the side walls of the chamber. The author for-
mulates these phenomena in the following manner : — The gases move
in vertical strata perpendicular to the exit, each gaseous molecule
describing a spiral line whose axis is parallel to the length of the
chamber. The practical conclusions arrived at are these : — The inlet
of the gases should be at the middle height o£ the chamber, and to
determine the point of origin of the screw motion as closely to the
fore side of the chamber as possible and. prevent the ingress of the
gases in too rapid a manner, the tube is enlarged with a conical
opening. The outlet tube is arranged in a similar manner. The
steam should not be introduced in jets along the chamber, but should
be admitted through several openings in the roof, each tube to supply
two perpendicular jets, the orifices of the tubes being sufficiently large
to prevent the entrance of the steam in powerful jets. D. B.
Utilisation of the Nitrogen-compounds from the Manufac-
ture of Sulphuric Acid. By G-. Wachtel (Dingl. polyt. J.\ 245,
517). — Although the loss of potassium nitrate in the manufacture of sul-
phuric acid has been greatly diminished, about 50 per cent, of the total
nitrogen in the potassium nitrate still escapes with the exit gases from
the Gay-Lussac tower. For recovering these nitrogen compounds,
the exit gases are drawn by means of a' Korting's injector through
cast iron or clay retorts filled with iron filings heated to redness. The
oxygen compounds of the nitrogen are thereby converted into ammo-
nia, which may be absorbed by means of sulphuric or hydrochloric
acid. This process is specially adapted for sulphuric acid works not
using the Gay-Lussac tower. D. B.
Preparation from Bauxite of Aluminium Sulphate free
from Iron. By C.Fahlbekq {Bull. Soc. Ghim, [2], 38, 154—156).—
Attempts to prepare aluminium sulphate free from iron from bauxite
have hitherto been unsuccessful, for the methods proposed have been
found to be too costly or too complex. The author, in conjunction
with Semper, has practically solved the problem by the use of lead per-
oxide, which is prepared by first triturating a mixture of 2 parts lead
monoxide and 1 part sodium chloride, until the mass assumes the
white tint of lead oxychloride ; the product is then boiled with bleach-
TECHNICAL CHEMISTRY. 131
ing powder until lead peroxide is formed, which is washed and pre-
served in the damp state. This paste is added to a neutral or slightly-
alkaline solution of bauxite in sulphuric acid ; for every part of iron
contained in the solution 20 parts of the dioxide are required. It is
necessary to work with concentrated solutions and to avoid a rise of
temperature ; the iron must also be as a ferric salt. In order to recover
the peroxide employed, the solid matter is separated by a filter-press,
suspended in water, and then dilute sulphuric or nitric acid added,
which leaves the peroxide undissolved, so that it can be employed a
number of times without losing any of its properties.
Y. H. V.
Japanese Soils: a Nsitural Cement. By 0. Korschelt (Chem.
News, 46, 187). — The soil below Tokio yields to hot hydrochloric acid
asmnch as 80 per cent., and this contains about 30 per cent. Si02 and
80 per cent. AI2O3 -f FejOs, and 1*5 to 3*0 per cent. K2O was found in
the lower layers ; it contains little or no quartz, but 60 to 60 per cent,
of zeolites. The tufa soils have a low sp. gr., varying from 2"097 —
2"291. Full analyses of many samples taken from di:tferent depths are
given. When mixed with lime paste, they form a satisfactory cement,
the temperature rising 7° during the mixing; the proportions used are
1 vol. lime to 6 vols, earth. The analyses show a decrease of nitrogen
from the surface downwards : in the top layer it amounts to 0'521 per
cent. E. W. P.
On Cement and its Application. (Bingl. polyt. J., 245, 381
—387, 456—464, and 499— 506) .— Delbriick mentions that in tender-
ing for large cement contracts it no longer suffices to give the price
only, but that the strength of extension forms an important item.
The value of cement is determined, therefore, according to the price
and the guaranteed weight which 1 part cement mixed with 3 parts
sand bears after 28 days' setting. In comparing cements differing in
the rate of setting (slow, medium, and rapid), it is necessary to con-
sider the time. According to G. Dyckerhoff, the packing of cement in
bags is 10 per cent, cheaper than in casks. It is also mentioned that
when rollers are used in the grinding of cement, the motive power
consumed is less than in the case of the ordinary cement mills. This
is confirmed by Heyn, Delbriick, Nagel,'and Kaemp, who add, that not
only is a more finely divided product obtained, but the wear and tear
of the machinery is considerably reduced. For sifting the ground
cement, Nagel and Kaemp recommend the use of shaking sieves, made
of perforated sheets of steel, the holes being 1 mm. in diameter.
These are said to be stronger than wire sieves, but, like the latter, do
not produce a cement fine enough to pass through a sieve with
5000 meshes per sq. cm., without leaving a residue of about 30 per
cent, on the sieve. The air sieve constructed by Michaelis is said to
overcome this difficulty. The cement is put into a centrifugal machine
and whirled, the fine dust produced being collected in a chamber in
communication with the machine. The process, however, is not
practicable, owing to the excessive consumption of motive power and
the enormous wear and tear of the machine. According to Heintzel,
132 ABSTRACTS OF CHEMICAL PAPERS.
cement made up with 33^ per cent, water hardens in 9^ hours ; with
30 per cent, in 7| hours ; with 26^ per cent, in 4 hours ; with 23^ per
cent, in 37 minutes ; and with 20 per cent, in 4 minutes. In com-
paring the time which cement requires for setting, it is usual to mix it
with water to the consistency of a thick paste. It is difficult, how-
ever, to fix the quantity of water necessary to effect this result, as
some kinds of cement absorb more water than others. It is best,
therefore, to use an excess of water in all cases. Herzog has found
that in preparing a large block of cement, the temperature increases
considerably, especially after the mass has been beaten down. In
buying cement, it is often stipulated that during the hardening the
temperature should not rise more than 3° to 5°, although the quantity
of cement to be used to determine this point is not mentioned, so that
by using larger quantities greater differences are obtained, the result
being the rejection of good samples of cement. In order to economise
heat, Tomei, in burning cement, uses a battery of shaft furnaces con-
nected with one another, and worked continuously. Dyckerhoff has
made a series of useful experiments as to the profitable application of
Portland cement to the preparation of mortar and concrete. He shows
that concrete, when beaten down in the air, requires twice as much
flint as sand, and that it is not economical to throw concrete direct
into water. For concreting under water, not more than equal parts of
sand and flint should be used, otherwise the firmness of the concrete
will not be the same as that of the mortar used in its preparation.
The firmness of mortar and concrete, when beaten down or brought
into water depends on the quantity of sand used and the quality of
the cement. Mortars were examined as to their impermeability to
water and resistance to atmospheric influences. The following
mixtures were found to give good results : — 1 part cement with 1 part
fine sand, or 2 parts ordinary sand and 0'5 part lime, or 3 parts sand
and 1 part lime, or 6 parts sand and 2 parts lime. D. B.
Iron Industry. (Dingl polyt. /., 245, 392— 394.)— In 1877 the
Prussian Chamber of Commerce made a series of tests with a view
of comparing Rhenish- Westphalian foundry pig with English and
Scotch brands. It was shown that the prevailing prejudices against
German cast iron were no longer tenable, so that since that time the
imports of foreign foundry pig into Germany have decreased by about
12 per cent., whilst the home production has been doubled.
Analysis of flne-dust from a Whitwell apparatus : —
KgO. NasO. CaO. MgO. FeaOg. ZnO. MuO.
17-05 9-53 25-95 2-31 0-91 1-30 037
• CO2, HoO, ON, and residue.
S. SiOg. AiA- V J ^ /
1-71 2405 10-09 6-73
The silica is partly free, partly combined ; the sulphur is present as
potassium and calcium sulphides, also as alkaline thiosulphate. The
potash and soda are in combination with silicic acid, thiosulphuric
acid, thiocyanates, cyanides, and ferrocyanides.
TECHNICAL CHEMISTRY.
133
The folio mng table gives the chemical analysis of the various irons
examined in the comparison mentioned above : —
Name of pig iron.
0
8
CD
o
t
o
1^
ll
u
i
1
a
g
g
3
&
6
6
^
2
Col
Lai
Cla
tness No. 1 . • . . s . . . . .
3-50
2-93
2-52
3-08
2-45
0-984
0-752
1-490
1-800
0-977
0-022
3-30
3-40
3-39
3-33
3-28
0-20
0-46
0-13
0-12
0-26
0-099
0-071
0-038
0-045
0-060
1-58
90-24
igloan No. 1 * . .
0
0
0
0
041
055
025
Oil
1
0
0
0
62
68
82
18
90
91
89
92
51
renee No. 3
40
rence No, 3
8^
d
fNo. 1. Foundry A . . .
40
y
No. 3. Foundry A . . .
1-87
0-935
0
008
2-93
0-50
0-055
0
16
93
45
^
No. 1. Foundry B . . .
2-45
0-988
0
035
3-40
0-19
0-039
1
48
91
10
5^
No. 3. Foundry B . . .
1-75
0-812
0
034
3-12
0-15
0-039
1
92
91
80
S -j No. 1. Foundrv C . . .
2-11
0-850
0
021
3 16
0-49
0-040
0
97
92
00
^
No. 3. Foundry C . . .
1-61
0-790
0
C44
2-97 0-61
0-055
0
86
92
78
a
No. 1. Foundry D . . .
1-30
0-930
0
005
3 -22 1 0 -23
0-055
0
72
93
32
<6
No. 1. Foundry D . . .
2-01
0-850
0
018
3 -33 1 0 -42
traces
0
99
91
50
P^ l^No. 3. Foundry D . . .
3-50
0-966
0
010
3-27 1 0-15
0-039
0
79
91
10
No. 3 from Lorraine
2-70
1-830
0
040
3-08!0 1I
0-060
0
63
91
20
No. 2 from Luxemburg . . .
1-86
2-210
0-058
2 -88 ; 0 -55
1
0-820
0-099
91-50
The following is an analysis of the slags from samples Nos. 1 to 3
compared with slag obtained from fibrous puddled iron : —
No.l.
No. 5.
Si02
A1203
CaO.
MgO
27-50 28-30
9-75 11-61
58-90 ' 54-94
1-37 0-98
31-37 33-30
1309 13-09
52-04 52-04
116 116
No. 3.
31-20
10-81
5317
1-08
Puddled
iron.
32-20
8-17
48-92
4-79
The ratio of the oxygen of the silicic acid to that of the bases in
slag No. 1, is as 2 : 3 ; in No. 2, 3 : 4 ; in No. 3, 4 : 5, and in puddled
9. '■■ D, B.
iron, 8
Utilisation for Agricultural Purposes of the Basic Slag
obtained in the Dephosphorising Process. (Dingl. polyt. J., 245,
513.) — At a large steel works in Westphalia some investigations were
made as to the possibility of using the slag from the dephosphorising
process for agricultural purposes, in the place of phosphate. The
cinder gave on analysis : —
AI2O3 and
sand, alkalis,
SiO.2.
CO2.
S.
P2O5.
Fe.
Mn.
CaO. magnesia, &c.
6-20
1-72
0-56
19-33
9-74
9-50
47-60 2-68
It was found that 10*94 per cent, phosphoric acid, corresponding to
56-6 per cent, of the total phosphoric acid, was soluble in ammonium
IBT ABSTRACTS OF CHEMICAL PAPERS.
citrate, and therefore present in a form which will allow it to be
assimilated readily by plants (compare Abstr., 1882, p. 1229).
D. B.
Desilvering of Lead. By Hampe (Dingl polyt. /., 245, 515).—
The author mentions that while the refining of copper by means of
electricity is being worked with success on a large scale, Keith's pro-
cess of desilverising lead by electrolysis has not made much progress.
This is mainly due to the fact that the refined lead does not answer
the requirements of commercially pure lead, and that lead precipitated
electrolytically from acid solutions does not give a compact substance,
but forms lamellar masses, diffused over the whole of the solution.
To obtain crystals of lead sufficiently large to fall to the bottom of the
solution, it is necessary to increase the distance between the elec-
trodes ; however by doing this the resistance, and with it the consump-
tion of electricity required to surmount it, are proportionately
increased. D. B.
Reactions of the Mexican Amalgamation Process. By A. K.
Huntington (Ghem. News, 46, 177). — Mercury worked up with silver
sulphide and sodium chloride extracted seven-eighths of the silver
chloride, which was three times as much as that extracted when
sodium chloride was absent: ferric oxide causes loss when sodium
chloride is present, as calomel and ferric chloride are formed ; very
little iron causes much loss. When cupric sulphate is present in the
mixture, loss of mercury is greater, and the yield of silver less. The
action of cuprous and cupric chlorides on silver sulphides occurs in
two stages : —
Ag2S + CuCl2 = 2AgCl + CuS
CuS + CuCl2 = CU2CI2 + S,
which results in the formation of silver chloride and free sulphur.
The amount of free sulphur and cuprous chloride formed depends on
the strength ^nd quantity of a solvent for cuprous chloride present,
such as sodium chloride or CuCl2, the temperature and the pressure.
The action of the air in facilitating the action is due to the conversion
of cuprous chloride into insoluble oxy chloride :
3CU2CI0 + 3H2O -f 30 = 3CuO,CuCl2,3H20 + 2GnCh.
Cuprous chloride and free sulphur are formed when cupric chloride
and silver sulphide are heated in a closed vessel to a high temperature,
and if heated long enough, the sulphur is oxidised to sulphuric acid ;
if, however, all air be excluded, no sulphur is formed, but cupric
sulphate and cuprous chloride instead. Cuproijs chloride and silver
sulphide yield silver chloride and cuprous sulphide. This is contrary
to the statements of Malaguti and Durocher, who obtained metallic
silver, but it was because they employed ammonium as a solvent, and
not sodium chloride. E. W. P.
Extraction of the Precious Metals from all Kinds of Ores by
Electrolysis. By Blas and Miest (Ghem. News, 46, 121 — 122). —
The authors have discovered that if, in electrolysis, compressed sulphur-
TECHNICAL CHEMISTRY. 135
ores are used as anode in a bath of an electrolyte containing the same
metal as the metal of the ore, on the passage of the current the ore is
decomposed, the sulphur, &c., being precipitated at the anode, whilst
the metal collects at the cathode. Thus with pure galena in a lead
nitrate bath, the separation is complete and easy. If the ore contains
silica as well, then the silica is deposited along with the sulphur, and
remains uncombined ; antimony and arsenic, if present, behave in a
similar manner, being precipitated as insoluble oxides ; they are very
easily separated by subsequent electrolysis. When large quantities of
arsenic are present, a part of it combines with the sulphur, and forms
realgar or orpiment. When ores containing several metals are
operated on, the precious metals, being most easily precipitated, are
thrown down first in the metallic state at the cathode under the action
of a moderate current. The final separation of these metals requires
very little battery power, for the mass of metal when dissolved under
the action of the current regenerates sufficient heat for the ulterior
separation of each metal separately. The products at the anode are
extracted and purified by treatment with carbon bisulphide, and after-
wards by separate electrolysis. The decanted carbon bisulphide
solution of sulphur is distilled, the latter- being left pure. If the ore
is a polysulphide, and is mixed with much iron, sulphur and iron
oxide are obtained in the first operation. These are best separated by
electrolysing in a dilute sulphuric acid-bath ; pure sulphur is obtained
at the anode and basic iron sulphate at the cathode. By this process,
I^ horse-power is required to produce I kilo, of copper from a sul-
phurous ore in one hour. As an example of the working with a com-
plex ore, they describe the treatment of an argentiferous lead ore
containing iron, copper, and zinc. The current being sufficiently
strong, the iron and zinc will dissolve as readily as the other metals,
but will not be precipitated so easily, therefore the solution will
gradually become saturated with iron and zinc ; the current is then
regulated so that only the lead, silver, gold, and copper are precipitated
on the cathode, while the zinc remains dissolved as nitrate. As the
bath becomes saturated, the iron yields to the zinc, and is precipitated
to the bottom as ferric oxide, and as soon as the solution is nearly
saturated with zinc nitrate, it is syphoned ofi"; the metals are then
removed from the cathode, the sulphur and silica from the anode, and the
iron oxide from the bottom, of course all separately. The sulphur, &c.,
and the metals are treated as above described. The zinc nitrate
solution is treated with a small quantity of zinc oxide, which throws
down the iron ; the lead, copper, and silver retained (if any) are pre-
cipitated by passing a current through the solution, using a zinc anode.
The pure zinc nitrate may be treated by a stronger electric current
if metallic zinc is required, or chemically if zinc oxide is wanted.
D. A. L.
Freezing of Wine. By J. Moritz (Bied. Centr., 1882, 716).—
Wine shows a tendency to remain liquid below its true solidifying
point; the percentage of alcohol present determines the freezing
point ; the higher the percentage the lower will be that point, ranging
from 3'3 — 6'9° for an alcoholic strength of 7'8 — 12*5 of alcohol by
volume. E. W. P.
136 ABSTRACTS OF CHEMICAL PAPERS.
Preservation of Beer. By A. H. Bauer {Bied.Cevtr., 1882, 719).
Unless salicylic acid is present in large quantities, it will not preserve
beer, but Pasteurising and a small addition of acid preserves beer for
3—6 months. Borax is useless as a preservative. E. W. P.
Beer-grains. (Bied. Centr., 1882, 717.) — To estimate the amount
of wort removed in the grains, 60 grams of the grains are shaken up
with 200 c.c. water for 10 minutes, the sp. gr. of the liquid after filter-
ing is then taken, and the percentage of extract deduced. To estimate
the starch left in the grains, a sample is weighed and dried and
powdered, and then submitted to the action of diastase at 60° ; an ex-
tract is then made, and the difference between the sp. gr. of the first
and second extract corresponds to the starch in the grains.
E. W. P.
Loss of Sugar by long Steaming of the " Mash." By V. Griess-
MATER (Bied. Cenlr., 1882, 717). — This loss has been attributed to
the formation of furfural, but the author believes it to be due to the
phosphoric acid in the nucle'in, which converts the starch into leevu-
linic acid. Maltose is converted by acids under pressure into dextrose,
and then furfural and formic acid may be produced. In sugar-beet,
however, the action of the acid is to produce dextrose and laevulose,
and from the latter Isevalinic acid is formed. E. W. P.
Does Potato-sugar contain any Deleterious Matter? By
V. Mering (Bied. Centr., 1882, 699). — It has been stated by Schmitz
and Nessler that in the unfermentable portion of potato-sugar there
is some substance which produces ill effects on animals. By experi-
ments the author proves that this unfermentable substance is not dele-
terious, but that it is a compound allied to the carbohydrates, and is
of some nutritive value. E. W. P.
Purification of Sugar-beet Juice. By Schott and others (Bied.
Centr., 1882, 697). — According to Schott's patent, the amount of
potassium present in the juice must first be estimated, and then if
there is not a sufficiency of lime present, gypsum is to be added, so as
to have 0*593 part CaO for every 1 part K2O, then a dilute solution
of ferrous sulphate is poured in, and the whole heated nearly to
boiling, finally allowing it to settle, filtering through " charred peat,"
and evaporating.
Siegert in his patent states that after boiling the juice with lime a
fresh supply of lime is to be added, and after passing it through a
filter-press, the lime is to be removed by carbonic anhydride. By
this process, treatment with charcoal may be avoided. Licht has
patented a "barium chloride" method, whereby the organic acids are
precipitated as salts of barium. A similar patent is that of Kottmann,
in which strontium chloride is employed. E. W. P.
137
General and Physical Chemistry.
Observations on the Solar Spectrum. By Langley (Gompf,
rend., 95, 482 — 487). — The observations were made on Mount
Whitney, which is almost as high as Mont Blanc, and overlooks the
dryest and most deserted district of South California. Observations
of the total solar radiation were made with the spectro-bolometer, and
also with Pouillet's heliometer, and Violle's actinometer. The calca-
lations are not yet completed, bat the author obtains a value of about
8 cal. ; in other words, if the terrestrial atmosphere were removed,
the sun's rays would raise the temperature of 1 gram of water through
3° C. for every square centimeter of earth's surface exposed under
normal conditions. This number is higher than that obtained by
Pouillet (1*7 cal.), or by S)ret, or Crova and Vi'olle (2*2 — 2*5 cal.).
The author has already shown that Pouillet's formula is only appli-
cable to homoofeneous rays, and gives results too low. »
On Mount Whitney, and also at the Alleghany Observatory, the
author has examined both with a prism and with a diffraction grating
the distribution of energy in the spectrum from X, 3,500 to \ 28,000.
The length of the ultra-red portion of the spectrum is much greater
than was supposed. If the terrestrial atmosphere were entirely
removed, this portion of the spectrum would doubtless extend much
farther, whilst the ultra-violet portion would not be affected to any-
thing like the same extent, there being but little terrestrial absorption
in this region. The actual results obtained with the prism and with
the grating are given in the form of two curves. One-fourth of the
total energy is situated in the visible and ultra-violet portion of the
spectrum, the remaining three-fourths being in the ultra-red region.
In the latter region, there are several broad absorption-bands or cold
spaces, probably made up of a number of lines which are not separated
by the bolometer. In the visible spectrum, the maximum energy is in
the orange.
Contrary to the usual opinion, the author finds that in a dry climate
the general terrestrial absorption diminishes up to the extreme infra-
red. In both the terrestrial and solar atmospheres absorption in-
creases as the wave-lengths diminish. Combining, by means of
Maxwell's discs, the colours which would be visible at the surface of
the photosphere if all intervening absorbing layers were removed, it is
found that the true colour of the photosphere is similar to that of the
spectrum near F, i.e., blue. C. H. B.
Absorption Spectrum of the Earth's Atmosphere. By
Egoroff {Gom.pt. rend., 95, 447 — 449). — The electric light at Mont
Valerien, 10 kilos, distant, was observed at the Paris Observatory by
means of a spectroscope with two Thollon's prisms attached to the
VOL. XLIY. I
138 ABSTRACTS OF CHEMICAL PAPERS.
Foucault telescope. The brilliant spectrum thus obtained was crossed
by a large number of absorption lines. Four could easily be distin-
guished between D and D2, and on either side of D, bat especially on
the less refrangible side, they are very numerous and distinct. The
group a is almost complete, and the region of C contains a large
number of lines. B is partially resolved into eleven pairs separated
by equal distances, and A can be easily distinguished by usiag a
cobalt glass. All the groups are characteristic and easily distin-
guished.
With a Drummond light, at a distance of 1600 meters, B, a, and A
could be clearly distinguished, between B and a there were two faint
nebulous lines, and traces of absorption lines could be seen between D
and C. With a Drummond light, at a distance of 240 meters, the only
lines visible were : A very distinct, and a very feeble, but apparently
intensified by a heavy shower of rain. When the light was 80 meters
from the end of the telescope, A could still be seen, although with
difficulty ; all the other lines had disappeared. C. H. B.
Reflection of Actinic Rays : Influence of the Reflecting
Surface. By de Chaedonnet (Gompt. rend., 95, 449 — 451). — The
author has photographed the spectrum of sunlight reflected from the
surfaces of a large number of substances, including white and black
enamel, uranium glass, crude haematite, polished haematite, diamond,
compressed carbon both rough and polished, vermilion, gold, lead,
nickel, Arcet's alloy, copper, polished steel and rough steel, Prussian
blue, green leaves, speculum metal, mercury, and mercury covered
with a plate of quartz. His results show that there is no selective
absorption, precisely the same spectrum being obtained in all cases.
Silver at first appears to be an exception, because it becomes trans-
parent to the second half of the ultra-violet; but with sufliciently
long exposure this part of the spectrum also becomes distinctly visible.
In this case it is better to push the exposure to the first degree of
inversion pointed out by Janssen. A positive impression is thus
obtained in the neighbourhood of H, and a negative in the neighbour-
hood of P.
Similar results were obtained with a number of liquids, including
water, solution of magenta, quinine acetosulphate, ammonio-copper
sulphate, potassium dichromate, milk, and ink. The author confirms
the statement of Cornu that platinum mirrors, speculum metal, and
mercury covered with quartz, do not absorb any of the more refrangi-
ble rays radiated from the sun.
With regard to the visible rays, the author arrives at the following
conclusions. Every surface reflects in varying proportion all the rays
of the spectrum ; pure colours can consequently never be obtained by
reflection. The reflecting power of a liquid is independent of the
substances which it holds in solution or in suspension. This law
apparently holds good for solid media, for a mirror of black enamel gave
the same spectrum as a mirror of white enamel. It is not necessary to
conclude that the incident rays do not penetrate into the reflecting
surface to a depth comparable with the wave-lengths. These lengths
would be too small to produce appreciable absorption. A layer of
GENERAL AND PHYSICAL CHEMISTRY. 139
quinine acetosulphate showing Newton's rings (yellow of the first and
bine of the second order) has no absorptive effect on the solar
spectrum. The same substance gives the same reflection whether
rough or polished : the polished surface increases the total quantity
of reflected rays, but the relative intensity of different regions of the
spectrum, i.e., the actinic colour of the substance, depends on the
nature of the substance employed. C. H. B.
Widening of the Lines in the Hydrogen Spectrum. By D.
V. MoNCKHOVEN {Gompt. rend.., 95, 378 — 381). — The author employed
a vacuum tube in the shape of a capital H, the horizontal part being
a capillary tube 0'5 mm. in diameter, whilst the vertical limbs were
wider and were provided at each end with an electrode, of which there
were consequently two pairs. Under varying degrees of pressure, and
with induction coils of different power, he found that the widening of
the hydrogen lines begins at different pressures, but always at the point
where the silent discharge passes into a spark discharge. Under con-
stant pressure, variations in temperature obtained by using different
coils, produced no effect on the width of the hydrogen lines. When
the current from a powerful coil is passed through a hydrogen tube
under low pressure for one minute, the temperature rises considerably
but the lines remain narrow. If, however, the coil is connected with
a Leyden jar, the gas is scarcely warmed, but the lines C and F are
broad. If the current from an induction coil connected with a Leyden
jar is passed through the tube previously described, the tube being
filled with hydrogen at a pressure of 1 — 2 mm., the hydrogen lines
are broad. If now a current from a powerful coil is passed through
the tube, by means of the other pair of electrodes, the lines do not
thicken, but a bright fine line is seen down the centre of each broad
line; in other words two spectra are superposed. Since the use of
vacuum tubes and disruptive discharges gave no satisfactory proof as
to whether the widening of the hydrogen lines is due to pressure or to
temperature, the author passed an electric arc, obtained from a con-
tinuous current, through pure hydrogen contained in a tube connected
with a Sprengel pump. At atmospheric pressure the hydrogen lines,
C and F, are seen on the continuous spectrum of the incandescent
carbon particles, F is considerably widened, C less so. The lines are
uniformly brilliant, and have an appearance identical with that of the
hydrogen lines in the sun and some stars; whereas in the vacuum
tubes the widened lines decrease in brilliancy from the centre to the
edges. At 0*25 m., the width of the lines G and F decrease, and at
0'09 m. they are almost narrow, H7 is invisible, but the arc and the
lines increase considerably in brilliancy. At 0-02 m., C and F are
quite narrow and very brilliant, and H7 becomes visible. At 0*008 m.,
I? H7 becomes still more brilliant. By varying the distance between the
electrodes, or by altering the power of the current, the temperature
was made to vary considerably, but the breadth of the lines always
remained the same. The author therefore concludes that the loidening
of the lines in the spectrum of h//drogen is due solely to pressure and is
alsolutely indeperidetit of temperature. C. H. B.
I 2
140 ABSTRACTS OF CHEMICAL PAPERS.
Spectrum of Water. By G. D. Liveing and J. Dewab (Proc,
Boy. Soc, 33, 274 — 276). — This paper is illustrative of a photograph
of the spectrum of an oxyh jdrogen flame ; in no cases were lines of a
wave-length less than \ 2200 observed. V. H. V.
Influence of Temperature on the Spectra of Non-metals.
By D. V. MoNCKHOVEN (Gompt. rend,, 95, 520—622). — PlUcker has
shown that most of the non-metals give two perfectly distinct spectra,
one of which he regards as being dne to a high, the other to a low-
temperature. If the H-shaped tube with four electrodes, previously
described (preceding page), is filled with oxygen or some other
non-metal, and the gas is subjected to the simultaneous action of two
currents, one from an induction-coil alone, the other from a coil con-
nected with a Leyden jar, the high temperature spectrum and the low
temperature spectrum are seen superposed. According to Pliicker's
hypothesis, the gas must therefore be at two different temperatures at
the same instant, a supposition which is inadmissible. The superposi-
tion of the two spectra is not due to the fact that the contact breakers
of the two coils do not vibrate in unison, thus producing alternations
of the two spectra which appear to be superposed, owing to the per-
sistence of the images, for in some tubes, especially if the tube be
filled with oxygen, the light is radiated for several tenths of a second
after the current is interrupted. The author attributes the changes in
the spectra of the non-metals to a particular state of vibration of their
molecules, depending directly on the nature of the electricity employed.
A hydrogen vacuum tube subjected to the action of ordinary sparks
presents an appearance very different from that produced by induction
sparks. The stratification in a vacuum tube changes entirely accord-
ing as it is produced by ordinary sparks, by induction sparks, or by a
battery of high tension. Further, each variation in the appearance of
an incandescent gas (i.e., change of stratification, alteration of the
colour of the light emitted, &c.) always corresponds with a partial,
often an entire, change in the character of the spectrum, the effect
being certainly independent of the temperature. C. H. B.
Nvte hy Abstractor. — The author's supposition that the change in
the spectra of the non-metals is due to a particular form of molecular
vibration, depending on the nature of the electricity employed, is sup-
ported by Schuster's observation of the peculiar spectrum of oxygen
in the neighbourhood of the negative pole. C. H. B.
Circular Polarisation of Quartz. By J. L. Soeet and
E. Sakasin {Gompt. rend., 95, 635 — 638). — In continuing their
researches, the authors have adopted the following improved method
of determining the original plane of polarisation. Between the
polariser and the analyser is placed a first quartz plate, say Isevogyrate,
of thickness E, a black band is brought into coincidence with a line in
the spectrum, and the position of the analyser noted. The first quartz
being left in position, a second quartz is added of inverse rotation,
and of a thickness equal to 2E. The general appearance of the
spectrum is not modified in the least, but there is a rotation to the
right equal to 2E0 degrees, where ^ denotes the angle of rotation for
i
f
GENERAL AND PHYSICAL CHEMISTRY. 141
a thickness of 1 mm. A black band is brought into coincidence witli
the same spectral line, and from the angle through which it is necessary
to turn the analyser, plus a certain multiple of 180°, the value of 0 is
deduced. The results obtained by this method agree with those
previously published. A table is given of the values of the angle of
rotation for different rays at 20°, deduced from observations on two
pieces of quartz, one 30 mm., the other 60 mm. thick. The observed
values agree closely with those calculated by Boltzmann's formula
reduced to its two first terms,
. ^ 7-1082930 0-1477086
\ being the length in millimeters of the wave in air, and this for-
mula may be used to calculate the angle of rotation of a • ray of any
wave-length between A and O. For rays more refrangible than O,
the formula no longer holds good, even though three or four terms of
the series are taken. By substituting Z, the wave-length in quartz,
for X,, the wave-length in air, a formula is obtained, which when
reduced to two terms, approximately represents the observed rotation
throughout the entire spectrum. The agreement between the observed
and calculated values is not, however, complete, and the differences
are greater than errors of observation would be. No better results are
obtained by nsing three terms. By addition of a third term, HZ^,
the divergence usually becomes greater.
The influence of temperature on the rotation is not constant for all
rays, as is generally supposed, but increases with the refrangibility.
For line 24 of cadmium, the formula for correction between 0^ and
20° is 0 = 00 (1 -h 0-0001790. This coefficient is greater than the
number 0"0U0149 obtained by several observers as the mean coefficient
between 0** and 100° for sodium light, and is, of course, still greater
than the coefficient for the same light between 0"" and 20°.
C. H. B.
The Metallic Galvanic Circuit of Ayrton and Perry. By
B. J. GrOOSSENS {Ann. Phijs. Ghem. [2], 16, 551 — 554). — According to
Perry and Ayrton {Proc. Boy. Soc, 27, 219) a galvanic circuit is
obtained by dipping strips of platinum and magnesium into mercury,
but they were unable to obtain a similar effect with other metals.
The author shows that the current obtained as above by Ayrton and
Perry is a true thermo-current, caused by the evolution of heat in the
formation of the magnesium amalgam (compare Obach, Pogrj. Ann.,
SuppL, 7, 300). T. C.
Electricity of Flame. By J. Elster and H. Gbrtel (Ann. Phys.
Chem. [2], 16, 193 — 222). — The longitudinal polarisation of flame is
only apparent, and is caused by the unequal immersion of the wires
serving as electrodes. In its cross section, however, the flame appears
to be strongly polarised, the electrode in the zone of air immediately
surrounding the flame being always positive towards the one in the
flame. The electromotive power is independent of the size of the
flame. The change in the polarity of the flame may be produced by
a suitable shiftingf of the electrodes. The electromotive force of the
142 ABSTRACTS OF CHEMICAL PAPERS.
flame is dependent on the nature of the metals used as electrodes, and
on the nature of the burning gas. It is especially great with elec-
trodes of alumininm or zinc, and very weak if the electrode situated
in the surrounding zone of air is covered with a salt, such as potassium
chloride. An undoubted electrical action is obtained by the use of
water electrodes and exclusion of metals, the electrode in the air being
positive towards that in the flame. Flames may be combined hke
j?alvanic elements, and a number of them may be united so as to
form a flame battery. The following theory is advanced in explanation
of the above facts. Free electricity is not produced within the flame
during combustion ; but the gases from the flame, and the zone of air
surrounding the flame, have the property in contact with metals or
liquids, of exciting the latter like an electrolyte ; and in addition io
this there is a thermoelectric excitement determined by the glow-
ing condition of the electrodes. This being so, the amount and
nature of the electric excitement is independent of the size of the
flame, but dependent on the nature and superficial condition of the
electrodes, on the nature of the burning gases, and on the glowing
condition of the electrodes. These conclusions have been confirmed
by numerous experiments.
The authors conclude therefore that Hankel's (Pogg. Ann.f 81, 212)
theory as to the electricity of flames is incorrect. T. C.
Electrolysis of Hydrochloric Acid. By D. Tommasi {Compt.
rend., 95, 689 — 691). — With platinum electrodes and concentrated
acid, the positive electrode is attacked by the chlorine, and conse-
quently behaves as a soluble electrode ; with dilute acid, on the other
hand, chlorine compounds are liberated at the positive pole, but the
platinum is not attacked.
Concentrated Acid. — The decomposition of 2 mols. of hydrochloric
acid in solution absorbs 78*6 cals., but since the positive electrode'
is attacked, the heat of formation of platinum chloride must l>e sub-
tracted from this number. The electromotive force necessary to
effect decomposition is consequently much less than 78 6 cals. A
single Daniell element is indeed sufficient to produce very slow de-
composition, but a Daniell element (49 cals.) and a zinc-cadmiuni
element (16 6 cals.) decompose the acid rapidly, with liberation of
hydrogen at the negative pole, but no liberation of gas at the positive
pole. After 20 hours, the evolution of gas continues at the negative
pole only. With two Daniell elements (98 cals.) decomposition
IS very rapid. At first there is no evolution of gas at the positive
electrode, but after about an hour bubbles of gas begin to form.
After 20 hours, decomposition continues with evolution of hydrogen
at the negative and oxides of chlorine at the positive pole. Similar
results are obtained with acid of different degrees of concentration,
but the limit is reached with acid of 10 per cent., when the amount of
platinum dissolved is very small.
Dilute Acid. — On closing the circuit, gas is evolved at the negative
pole, whilst the liquid round the positive pole becomes coloured faintly
yellow, and bleaches litmus- paper. Even after continuous passage of
the current for 100 hours, no trace of platinum is dissolved.
GENERAL AND PHYSICAL CHEMISTRY. 143
Similar results were obtained with acid of different strengths down to
1 per cent. The chlorine appears at the positive pole in the form of
oxides of chlorine, with probably hypochlorous acid, and perhaps
traces of free chlorine. Whether the oxides of chlorine are produced
by the decomposition of the hydrate HC1,6H20, or by the action of the
oxygen of the water on the hydrochloric acid, cannot be ascertained.
C. H. B.
Distribution of Heat in the Ultra-red Region of the Solar
Spectrum. By P. Desains (Compt. rend., 95, 433— 436).— The
author has continued his measurements of the distribution of heat
in that portion of the solar spectrum less refrangible than the red
(Abstr., 1879, 864), using respectively flint glass and crown glass
prisms with a refracting angle of 60**. In the following table d and d*
indicate in minutes the angular distance of the cold band from the line D,
i and i' the relative intensities of the bands. It must not be assumed,
however, that the intensity of the band at IS' from D with a crown
glass prism is equal to that of the band at 42' from D with a flint
glass prism.
Crown Glass (July llth, I2t\ ISth, 1881).
d. lo'O 18 0 24 31-0 34-5 44-5 50-5
t. 200 19-0 22 26-6 23-5 17-0 19-0
d. 60-5 805 92 117-4 127-4 147'0
», 15-0 5-5 10 — . 2-5 —
Flint Glass (July Vth, I9th, 1881),
d\ 42 45-0 65 58-0 68*0 73 77*2 82 88 92-5 96 ,
i\ 20 18-0 16 23-0 26-5 24 25-0 24 16 20'0 16
d'. 100 1030 108 122-0 1300 142 157-0 170 175 185-0
i'. 25 21-5 26 16-5 20-0 6 155 7 2 —
With prisms of flint and crown glass, the spectrum extends to a
much greater distance beyond the extreme red than with a prism of
rock salt. With rock salt, the limit is only 80' from the extreme red,
whilst with flint glass it extends as far as 1° 40'. C. H. B.
Law of Thermal Constants of Substitution. By D. Tommasi
(Compt. rend., 95, 453 — 456), — It has been stated that the author's
law (Abstr., 1882, 1257) does not hold good in the case of soluble
salts formed by weak acids. He therefore cites a number of examples
to show that wherever the calculated number differs from that actually
obtained, the difference is due to the dissociation which takes place oa
solution, the coefficient of dissociation of the particular substance not
being the same as that of the corresponding potassium salt. The
close agreement between the calculated and actual numbers in the
case of sodium, ammonium, lithium, strontium, and calcium sulphides
shows that the coefficient of dissociation of these compounds is the
same as that of potassium sulphide. The difference between the
numbers found and calculated is considerable in the case of ammonium
cr rbonate and ammonium plienate, where also the dissociation is con-
144 ABSTRACTS OP CHEMICAL PAPERS.'
fiiderably greater than that of the potassium compounds. For the
same reason there is a considerable difference between the two
numbers in the case of mercuric cyanide. C. H. B.
Law of Cooling. By C. RiyiJiee (Compt. rend., 95, 452 — 453). —
The radiating body was a platinum wire heated by means of an
electric current. The temperature was calculated from variations in
its conductivity, and the quantity of heat lost was calculated by
Jonle's law. Under the low pressures at which the experiments vrere
made, the cooling effect due to the gas present becomes of consider-
able importance. The quantity of heat carried off by the air under a
pressure of 0*12 mm. of mercury is given approximately in the follow-
ing table : —
Heat radiated ia
a yacuum,
A 200 10 times.
A 400 3 „
A 600 1 „
A 800 f „
A 1000 i „
With a platinum thread 0*1 mm. diameter placed horizontally in a
glass cylinder O'lZ mm. in diameter, and snrrounded by air under a
pressure of less than O'OOOl mm. of mercnry, the cylinder being cooled
by a current of cold water, the following numbers were obtained : —
Temperature of the cylinder 17*3°.
Excess. Heat lost. iwa«(a'-l). «T2(T-e).
50** 38-6 38-4 354
100 94-8 94-7 930
160 175-6 177-4 1776
200 284-0 2987 293-6
250 448-0 476-7 445-7
300 708-0 738-0 638'0
400 1610-0 1684-0 11640
600 3300-0 3721-0 19070
600 6035-0 8107-0 2904-0
700 10160-0 17552-0 4193-0
800 15980-0 37891-0 58(8-0
900 24110-0 81688-0 7788*0
1000 34800-0 176006-0 10168-0
The values in the third and fourth columns are calcnlated from
the formulae of Dulong and Petit, and of Rosetti respectively, the
constants being obtained from an experiment in which the excess of
the temperature of the wire was 136-3'' above that of the surrounding
space. These results afford further proof of the fact that the numbers
given by Dulong and Petit's formula increase far too rapidly.
C. H. B.
Comparison of Mercurial Thermometers with the Hydrogen
Thermometer. By J. M. Crafts {Compt. rend., 95, 836—839).—
GENERAL AND PHYSICAL CHEMISTRY. 145
The table of corrections for mercurial thermometers, which is to be
found in ordinary text-books, was compiled 30 years ago by Regnault,
but that experimenter himself pointed out that owing to the great
variation in the composition of glass, errors might arise from the
application of his tables to all mercurial thermometers. Regnault's
instruments have been destroyed, and the manufactory in which tliey
were made has ceased to exist ; moreover the composition of the glass
now used in France differs very considerably from that of the glass
used by Regnault. The author has therefore undertaken a revision of
the table. The boiling of water at different pressures gives the means
of determining accurately temperatures between 80° and 150°.
Between 140° and 350" the author uses naphthalene and benzophenone
at varying pressures. He has described elsewhere the methods used
for determining with the aid of a hydrogen thermometer the exact
pressures corresponding to any given boiling points of these liquids.
By tabulating these results, he obtains the pressure under which it is
necessary to boil either liquid to maintain for any required time a
constant temperature. By these means, he has compared 15 ther-
mometers with hydrogen thermometers. Two sets of seven of these
thermometers were of flint glass, by two different French makers, and
the other of soda glass, by a German maker. A table* showing the
amount of error of the mercurial thermometers for temperatures from
110 — 330° accompanies the paper. The same table gives the com-
parison of these errors with those given by Regnault. The results
have been confirmed by experiments with twelve other thermometers
of peculiar construction. E. H. R.
Limit of the Liquid State. By J. B. Hannat (Proc. Boy. Soc,
33, 294 — 321). — A continuation of the author's researches (Abstr.,
1882, 268). After some remarks on the uncertainty of our knowledge
of the exact condition of a fluid immediately above and below its
critical point, the author proceeds to divide fluids into three classes —
(1) liquids^ which exhibit surf ace tension, as capillarity or a permanent
limiting surface ; (2) gases, which cannot be reduced to liquids by
pressure alone ; and (3) vapours, which can be so reduced. A further
distinction of gases and vapours lies in the fact that the curve repre-
senting pressure and volume of a gas is a continuous straight line,
whereas a part of the curve representing pressure and volume of a
.vapour is asymptotic. The author proposes to show that the gaseous
state is entirely dependent on the mean velocity, and not on the free
path of the molecule. Numerous experiments were made to ascertain
the critical temperature and pressure of alcohol under its own vapour,
and under that of certain gases, as hydrogen and nitrogen, which do
not attack and are not dissolved by the alcohol. A modified form of
Andrews's apparatus was used. The manometers were filled with hydro-
gen, as the only gas which follows Boyle's law at high pressures, and
the alcohol was carefully purified by an elaborate method.
The mean of over 100 experiments gave a critical point for alcohol
* The author has informed the editor that there is a misprint in the table in the
original ; the letters B and C should be transposed. — C. Jt. Q.
146 ABSTRACTS OF CHEMICAL PAPERS.
tincier its own vapour of 235*47° nnder a pressure of 67*07 atnio-
spheres. In order to study the critical temperature of alcohol nnder
greater pressures, hydrogen was introduced over the alcohol, in order
to allow of the limiting surface of the liquid to be seen ; but it was
found that the critical temperature was practically unaltered, even
under a pressure of 178"8 atmospheres. Similar results were obtained
when nitrogen was substituted for hydrogen. The method of measur-
ing the capillary height of a liquid under various temperatures and
pressures was also tried, and it was shown that the capillary height of
a liquid is lowered by a gas under pressure impinging on its surface;
this phenomenon would follow naturally from a constant disturbance
of the surface of the liquid, owing to the high velocity of the hydro-
gen molecules striking it. Capillarity is not then a true measure of
the cohesion of a fluid, for were the pressure sufficiently high, the
surface of the liquid mig-ht be made to disappear while its interior
was in a truly liquid condition.
Similar experiments were made with carbon bisulphide and 4;etra-
chloride and with methyl alcohol, the same general results being ob-
tained. The critical point of carbon bisulphide under its own vapour was
found to be 277-68° at 78*14 atmospheres ; under hydrogen, 274*93° at
171*54 atmospheres; under nitrogen, 273*12° at 141*45 atmospheres;
this last result is probably affected by the solubility of the nitrogen in
the carbon bisulphide. The capillary action of this liquid is also
weakened by a gas impinging upon its surface.
Determinations of the critical point of methyl alcohol under its
own vapour gave the following results: — 232*76° at a pressure of
72*85 atmospheres; under hydrogen 230*14° at 128*60 atmospheres;
and under nitrogen, 277*92° at 191*40 atmospheres, or 2-25-82° at
262 atmospheres. With carbon tetrachloride, the results were 282*51° at
57*57 atmospheres under the pressure of its own vapour, and 277 56°
at 142*82 atmospheres under nitrogen. It was found impossible to
use hydrogen, for it attacked the tetrachloride, with formation of chlo-
roform, and other compounds. In conclusion, the author views the
four states of matter thus : — 1st, the gaseous, which exists from the
highest temperature down to an isothermal passing through the critical
point, and depending on temperature or molecular velocity ; 2nd, the
vaporous, bounded on the upper side by the gaseous, and on the lower
by absolute zero, and dependent upon the length of the mean free path
of the molecule ; 3rd, the liquid, bounded on the upper side by the
gaseous, and on the lower by the solid state ; 4th, the solid. The
gaseous state is thus the only one which is not affected by pressure
alone, or in which the molecular velocity is so high that the collisions
cause a rebound of sufficient energy to prevent grouping. Another
distinction between the gaseous and vaporous states lies in the fact thai;
the former is capable of acting as a solvent of solids (Abstr., 1882,
271). V. H. V.
Expansion of Isomorphous Salts. By W. Spring (Ber., 15,
1940—1945;. — Between 0° and 100° the expansions of ammonium and
rubidium sulphates are sensibly equal, potassium chromate only
expands at a slightly greater rate, but in the case of potassium sulphate
GENERAL AND PHYSICAL CHEMISTRY. 147
the expansion is about 10 per cent, greater. The discrepancy is
explained by the fact that a given volume of potassium sulphate con-
tains a larger number of molecules than the other salts, for on dividing
the sp. gr. by the molecular weight of each salt there is obtained :
K2SO4 : -015316; AmaSOi : -013664 ; Rb.SO*: -013657 ; K^CrOi : -01412.
Taking the ratio of the molecules of K2SO4 to Am2S04, there is
obtained 0-015316 -^ 0-013664 = 121, whilst the ratio of the expan-
sions of the same two salts is about the same figure, 0-012645 -^
0011191 = 1-29. From these results, it is probable that the expan-
sions of the alums are not absolutely the same, although the differences
fall within the limits of error (cf . Spring, Abstr., 1882, 1020 ; Petter-
son, Abstr., 1882, 1259). A. J. G.
Modification of the Usual Statement of the Law of Iso-
morphism. By D. Klein (Compt. rend., 95, 781— 784).— Mitscher-
lich stated the law of isomorphism as follows: — 1. Two bodies are
called ipomorphous when, having the same crystalline form, they can
crystallise together in the same crystal. 2. Isomorphous bodies have
an analogous chemical composition. The author gives in the order of
their discovery certain exceptions to the second part of this law. He
goes on to state that in previous communications he has described
a tangstoboric acid, 9W03,B203,2H20 + 22Aq, isomorphous with
Marignac's octohedral silicotungstic acid, 12W03,Si02,4H20 + 29Aq;
also a monosodium tungstoborate, 9W03,B203,Na20 + 23 Aq, iso-
morphous with the acids just mentioned ; and further a diammoniura
tungstoborate, 9W03,B203,2NH40 -h 19Aq, isomorphous with an
ammonium metatungstate described by Marignac, and a dibarium
tungstoborate, 9W03,B203,2BaO + 18Aq, isomorphous with the cor-
responding metatungstate. The author states that the tuugstoboric
acid employed by him contained only a trace of silica, and that his
analyses have in this respect been confirmed by Marignac. In con-
sequence of these facts, a modification of Mitscherlich's law has become
necessary, and the author therefore gives the following, already pro-
posed by Marignac, as a substitute for the second part of the law in
question : — Isomorphous bodies have either a similar chemical composition^
or possess only a slightly different percentage composition, and all contain
either a common group of elements or groups of elements of identical
chemica functions, which form by far the greater part of their weight.
E. H. R.
Observations on Crystallisation. By G. Brugelmann {Ber., 15,
1833 — 1839). — After giving a short account of the development of the
theories of isomorphism, dimorphism, &c., with special reference to
their bearing on chemical composition, the author proceeds to show at
some length that crystallisation of two substances in the same tbrm or
the same crystal does not always depend on any relation in their
chemical composition, a fact which has already been pointed out in
several instances, notably by G. Bose, in the case of sodium nitrate
and calcspar. The examples brought forward by the author are copper
sulphate and potassium dichromate, copper sulphate and cobalt chlo-
ride, borax and potassium chlorate ; in most cases the cold saturated
solutions were mixed in varying proportions, but in some crystals of the
148 ABSTRACTS OF CHEMICAL PAPERS.
one substance were introduced into saturated solutions of the other.
In all cases coloured solutions were used, and perfect co-crystallisation
was observed, the colours being different in various parts of the same
crystal. Compounds therefore of the most dissimilar atomic constitu-
tion can crystallise together, their power of so doing being a function
of the physical conditions in which they are found, and not of their
chemical composition. The occurrence therefore of a body in a definite
crystalline form is no criterion of its individuality, and the conception
of isomorphism possesses only a nominal significance, as it cannot be
used as a separate means of classification, but only in confirmation of
facts otherwise obtained. J. K. C.
Experiments in Crystallisation Exemplifying Berthollet's
Law of Affinity. By G. BiiiJGELMANN (Ber., 15, 1840— 1841).— The
following experiments are of interest as touching Berthollet's law, that
a liquid in which two salts have been dissolved contains the acids and
bases of each reciprocally combined. Equal volumes of cold saturated
solutions of cobalt chloride and nickel sulphate were mixed and allowed
to evaporate spontaneously; the crystals obtained consisted of both
metals in the form of sulphates, and the chlorides of the two metals
were left in solution. Similar results were obtained with copper sul-
phate and cobalt chloride, as well as with copper sulphate and potas-
sium dichromate ; in the former case, the first^crop of crystals contained
both metals as sulphates, together with small quantities of chlorides ;
in the latter, crystals of the mixed sulphates of copper and potassium
were first deposited, then various mixtures of the chromates and
sulphates, and finally a mixture of chromates of the two metals. In
every case the crystallisation seems to have proceeded in a liquid con-
taining four different salts. J. K. C.
Nature of the Vibratory Movements which accompany the
Propagation of Flame in Mixtures of Combustible Gases.
By Mallard and Le Chatelier {Gompt.retid., 95, 599 — 560; see also
Abstr., 1881, 971). — The authors employed a tube 3 meters long and
0"03 meter in diameter. The combustible gas was a mixture of nitric
oxide and vapour of carbon bisulphide. An image of the tube was
thrown on to a cylinder covered with sensitive paper and rotating
with a known velocity. The photographs show that the flame travels
at first with a uniform velocity, but afterwards performs a series of
very rapid oscillations, the regularity, duration, and amplitude of
which vary at different parts of the tube. Uniform motion continues
with a velocity of I'lO meter per second to a distance of 0*75 meter
from the mouth of the tube. Beyond this point the flame, and con-
sequently the mass of gas, is thrown into vibration, the vibrations
being both simple and compound. The points at which the vibration
is simple are generally spaces of one or two-fifteenths the length of
the tube. The duration of successive vibrations varies between 0*025
and 0*0034 of a second. The durations are in the simple ratios of
1, 2, 3, 4, 5, 6, but no relations could be traced between these times
and the position of the flame in the tube. As a matter of fact, the
vibrating mass of gas is composed of two distinct columns, one of
burnt gas, the other of cold gas, the lengths and densities of which
INORGANIC CHEMISTRY. 149
vary at every instant. The amplitude appears to be greatest for
vibrations of long period, and is particularly great in the last third of
the tube, at the point where one of the vibrating segments is situated
when the tube gives the first harmonic from its fundamental note.
The amplitude at this point is as high as 1*10 meter. Since the
oscillations of the flame are simply those of layers of burning gas,
these experiments gave the first precise idea of the amplitude of the
vibrations of a mass of gas emitting a sound. These vibratory move-
ments necessarily correspond with high pressures. From calculations
b'ased on the variation in volume, measured by the oscillation of the
flame, it is found that the mean pressure is at least five atmospheres,
and for mixtures in which the initial velocity is greater than 1 meter,
tlie pressures will be considerably higher. The mean velocity of pro-
pagation appears to increase with the amplitude and rapidity of the
vibrations. In one experiment, the limits were 1*10 meter and
5'40 meters, in another, 0"97 meter and 8*60 meters. In another
experiment, the explosive wave was formed at a distance of two-thirds
the length of the tube from the mouth, i.e., at the point where the
amplitude of vibration was greatest, and the last third of the tube was
completely shattered. The brilliancy of the flame varies at successive
phases of the same vibration, being greater when the flame moves
forward than when it moves backward ; these differences increase with
the amplitude of vibration, and are undoubtedly connected with
variations in pressure.
With a tube 0*01 meter in diameter, the flame is extinguished at a
distance of about 1*5 meter from the mouth. The vibratory move-
ment is produced at a distance of 0'18 meter from the mouth of the
tube, instead of at 0*75 meter, and the amplitude of vibration increases
more rapidly. The mean velocity of propagation is at first very small,
but attains a rate of 4*50 meters per second at a distance of 05 meter,
and becomes almost nothing just before the extinction of the flame.
The narrowing of the tube favours the development of the vibratory
motion with all its consequences. C. H. B.
Inorganic Chemistry.
Action of the Galvanic Current on Chlorides and Chlorates.
By A. LiDOFF and W. Tichomiroff {Jour. Buss. Ghem. Soc, 1882, 341 —
349). — In a former paper (Abstr., 1882, 925) the authors have found
that by the action of the electric (galvanic) current on a solution of
chlorides, hypochlorites are first formed, which, by an elevation of tem-
perature, are converted into chlorates. But later on they found that
even at the ordinary temperature, as soon as the solution becomes
more concentrated, hypochlorites are converted into a mixture of chlo-
rates and chlorides by the sole action of the current. They propose to
apply this process to the manufacture of chlorates, more especially of
the sodium salt, which is difficult to prepare in the ordinary way. On
150 ABSTRACTS OF CHEMICAL PAPERS.
acting with a current of a powerful Gramme machine for 25 hours, on
a solution of 400 grams of potassium chloride in 900 grams of water,
210 grams of crystals, containing 70 per cent, of chlorate, were
obtained. ' The crystals contain, together with potassium chlorate, a
considerable quantity of the chloride, and 5 — 12 per cent, of carbon
from the electrodes. As soon as about 30 per cent, of the original
salt is transformed into the chlorate, the positive electrode is most
strongly corroded, and no further separation of the crystals from the
liquid takes place.
If, instead of a high tension- current (2 electrodes) a divided
current (8 electrodes) is employed, far less chloride is converted into
chlorate in the same space of time. The corrosive action of the liquid
on the positive electrode is due to its oxidation by the oxygen of the
potassium chlorate, which is reduced to chloride (about 80 per cent,
in 10 hours). For this reason, potassium chloride cannot be com-
pletely converted into chlorate, but a limit is reached after some time,
when the energy of formation of potassium chlorate from the chloride
becomes equal to the energy of its decomposition. Electrodes of
another material than carbon cannot be used for the conversion of
chlorides into chlorates, for all metals, even platinum, are corroded by
the chlorine which is set free at the same time. If, however, a solu-
tion of potassium chlorate be electrolysed by means of platinum
electrodes, no chlorine, but ozone, is evolved on the positive pole. At
the same time crystals of potassium per chlorate separate from the
liquid, and only traces of potassium chloride are formed at the same
time. In this respect the action of electricity on potassium chlorate
is analogous to the action of heat on the same salt ; in both cases
oxygen is evolved, and potassium chlorate and chloride are formed,
although the proportion in the quantities of these two salts is widely
different. The corrosion of carbon in the above case is due to the
action of ozone, and the products of this action in presence of water
are mellitic and hydromellitic acids. B. B.
Oxidation of Carbonic Oxide by Palladium Hydride and
Oxygen. By M. Traube (Ber., 15, 2325— 2326).— The changes
which occur when carbonic oxide is converted into the anhydride by
the action of palladium hydride and oxygen are as follows: — In the
first place palladium hydride and moist oxygen form hydrogen per-
oxide, and this compound in presence of metallic palladium oxidises
carbonic oxide to carbonic anhydride. W. C. W.
Compressibility of Nitrogen. By E. H. Amagat (Gompt rend., 95,
638 — 641). — A summary of the experiments made by Cailletet and by
the author with a view to determine the compressibility of nitrogen.
Curves are given representing the results obtained by both observers.
The author considers Cailletet's method inferior in accuracy to his own.
The curve representing Cailletet's results is very irregular, whilst that
representing the author's results is perfectly regular. C. H. B.
Black Phosphorus. By P. Thenard (Compt. rend., 95, 409—410).
— A quantity of phosphorus was being cast in the usual way, and a
INORGANIC CHEMISTRY. 151
dozen sticks liad been obtained of the asnal colour, when the thirteenth
suddenly blackened at the moment of congelation. Subsequently a
second stick, about 20 cm. long, blackened for about 4 cm. of its
length, the remainder being unchanged. A portion of the black phos-
phorus was brought in contact with ordinary phosphorus, in a state of
super-fusion at 10° under ice. In the first experiment, the white phos-
phorus became black on solidifying, but the same effect was not again
obtained once in more than twenty experiments under precisely similar
conditions. The specimen of black phosphorus became white when
fused, and remained white if cooled suddenly, but if super-cooled it
again became black when brought in contact with either black or
white phosphorus. Black phosphorus dissolves almost entirely in
carbon bisulphide, leaving a slight yellow residue apparently consist-
ing of amorphous phosphorus. C. H. B.
Neutral Phosphates of the Alkalis. By E. Ftlhol and
Senderens (Bied. Gentr., 1882, 641). — Careful neutralisation of phos-
phoric acid with sodium hydroxide results in the formation of a
mixture which reacts on red or blue litmus ; crystals obtained from
the solution contain 1 mol. of the mono- and 1 mol. of the di -sodium
phosphate. Neutral potassium or ammonium phosphates have not
been obtained, whilst potassium sodium and sodium ammonium phos-
phates crystallise readily. E. W. P.
Calcium Chloride. By A. Weber (Ber., 15, 2316—2317).—
Calcium chloride dried at 180 — 200° is practically anhydrous. It
contains from 0*12 to 0"24 per cent, of water and 0'047 per cent. CaO.
w. c. w.
Properties of Pure Aluminium. By J. W. Mallet (Chem.
News, 46, 178).— Sp. gr. at 4° = 2-583; atomic vol., 10-45 ; sp. heat
= 0-2253 between 0 — 100°; atomic heat, 6-09°; less fusible than the
commercial metal, and less easily acted on by alkalis and acids. It is
nearly pure tin-white, with no bluish tinge, and has a lustre like that
of tin. It is more malleable and less easily hardened by ha.mmering
than ordinary aluminium. E. W. P.
Decomposition of Phosphate by Potassium Sulphate at
High Temperatures. By H. Grandeau {Gompt. rend., 95, 921 —
922j. — Debray {Bull. Soc. Ghim., 3, 251) has shown that on heating
to a high temperature aluminium phosphate with excess of an alka-
line sulphate, an alkaline phosphate and crystallised aluminium are
obtained. This reaction has been used by Derome {Gompt. rend., 89,
925, and this Journal, 38, 286) for the separation of phosphoric acid
from iron and aluminium. To determine the conditions of the re-
action, a mixture of aluminium phosphate and potassium sulphate
was heated for several hours in a platinum crucible. At a high
temperature, not only is alumina formed, but also a crystalline double
phosphate of aluminium and potassium. At a still higher tempe-
rature, the quantity of alumina increases, but even on very vigorous
heating it is impossible to completely decompose the double phos-
152 ABSTRACTS OF CHEMICAL PAPERS.
phate. Similar results were obtained by substituting phosphates of
glucinum, cerium, and didymium for aluminium phosphate. But
when phosphates of calcium, magnesium, &c., were used, the double
phosphate alone was formed under the conditions of the experiment;
whilst with nickel and cobalt phosphates results similar to those with
aluminium phosphates were obtained. With chromium and uranium
phosphates, the final products are potassium chromate and uranate.
The investigation is being continued. L. T. O'S.
Determination of the Equivalent of Thorium. By L. F.
NiLSON (Compt. rend., 95, 729 — 730). — As a mean of ten determina-
tions, the author finds .58*10 to be the equivalent of thorium, that of
oxygen being 8, and of snlphur 16. He makes the atomic weight,
therefore, to i)e 232-36. These results were obtained by calcining two
different specimens of the sulphate, a and b. Specimen h was obtained
from the mother-liquors of a. The first six determinations were made
on specimen a, which contained nine molecules of water. In these
six experiments the author used the hydrated salt, because the dehy-
drated substance was found to be extremely hygroscopic. In the
other four experiments this was impossible, because specimen b (the
crystals of which differed from those of specimen a) contained only
eight molecules of water, and absorbed water during the process of
weighing. In the latter four experiments, therefore, the anhydrous
sulphate was used. The two specimens gave practically identical
results.
Sulphate a.
Water. SO3. ThOs- Equiv. At. Wt.
Mean of six experiments 27-573 27*336 45*091 58*11 232*43
Sulphate b.
Mean of four experiments — 37*703 62*297 58*09 232*30
The author concludes by drawing attention to the wide discrepancies
in the values of the atomic weight as determined by other chemists.
E. H. R.
Metallic Thorium. By L. F. N"ilson {Compt rend., 95, 727 —
729). — The author obtains metallic thorium by heating with sodium
in an iron crucible a mixture of the anhydrous double chloride of
thorium and potassium with sodium chloride. After treatment of the
residue with water, metallic thorium remains as a heavy greyish
brilliant powder. Examined under the microscope, the powder is
seen to consist of minute crystals, more or less brilliant and united in
groups. The metal is brittle and almost infusible. The powder
assumes a metallic lustre under pressure, is unalterable in air up to
120°, takes fire in air or oxygen below a red heat, and burns with
dazzling brilliancy, leaving a perfectly white oxide. It takes fire
when heated with chlorine, iodine, bromine, and sulphur. It is not
attacked either by hot or by cold water. Dilute sulphuric acid causes
a feeble evolution of hydrogen in the cold, becoming more rapid on
the application of heat, but the metal is attacked slowly ; hot con-
centrated sulphuric acid also acts but slowly, disengaging sulphurous
INORGANIC CHEMISTRY. 153
anhydride. Nitric acid, whether hot or cold, strong or dilute, exerts
no sensible action. Dilute hydrochloric acid dissolves the metal slowly
even when heated, but concentrated acid attacks it very easily. Aqua
regia acts like hydrochloric acid. Alkalis have no action. The metal
obtained by the author behaves, therefore, exactly like that obtained
by Berzelius. The mean sp. gr. is nearly 11; this is much higher
than that found by Chydenius (7'657 to 7' 795) : hence the specimen
obtained by the latter chemist must have contained much impurity,
probably derived from the glass tube in which it was prepared. The
densities of two different specimens of the oxide were 102207 and
10-2198 respectively. These numbers are again much higher than
those obtained by Berzelius, Damour, and Chydenius (9*402, 9"366,
9*288). Admitting that the metal is quadrivalent, the atomic volume
is 21*1. This number coincides with the atomic volume of zirconium
(21*7), cerium (23 '1), lanthanum (22"6), and didymium (21*5); and
this fact serves to confirm the author's opinion that the rare earth-
metals form a series of quadrivalent elements. E. H. E,.
Magnesia Alba. By K. Kraut (Arch. Pharm. [3], 20, 180—187).
— In this criticism of Beckurts' paper on the composition of magnesia
alba (this vol., p. 13), the author shows that analytical errors have crept
in, as no direct estimation of the water lost by heating was made,
&c. ; the formula proposed by Beckurts therefore is incorrect, and
the original formula 5Mg04C03,H20, as proposed by Kraut, is the
right one ; also by boiling for some time, the composition may be
altered to 4MgO,3C02,6H20, but never to 7MgO,5C02.
E. W. P.
Separation of Gallium. By L. de Boisbaudran (Compt re7id.,
95, 410—413; 503—506. See also Abstr., 1882, 897, 1323).— ^rom
Indium. — Precipitation of the gallium by potassium ferrocyanide, in
presence of hydrochloric acid, is to be recommended only when it is
required to separate a little indium, together with other metals, such
as aluminium and chromium. The following is the only trustworthy
method : — The moderately concentrated solution is boiled for some
minutes with a slight excess of potassium hydroxide ; the precipitated
indium hydroxide retains small quantities of gallium, which may be
removed by a repetition of the process. The alkaline solutions contain
only very slight traces of indium ; to remove these, hydrochloric acid
is added in slight excess, and the gallium and indium are precipitated
together by boiling with an excess of ammonia, or better, by means of
cupric hydroxide. The gallium and indium chlorides are then converted
into sulphates ; the slightly acid solution mixed with a quantity of
ammonium sulphate rather more than sufficient to convert the gallium
into alum is evaporated to small bulk, and, after cooling, mixed M'ith
four or five times its volume of alcohol of 70 per cent. Gallium alum
is thus thrown down as a crystalline powder, which is washed once or
twice with alcohol, dissolved in warm water containing a minute quan-
tity of sulphuric acid, and reprecipitated. By several repetitions of
this process, the gallium is obtained in the form of alum, free from
indium. The alcoholic washings, which contain small quantities of
gallium and indium, are evaporated to small bulk, the metals jre-
VOL. XLIV. m
154 ABSTRACTS OP CHEMICAL PAPERS.
cipitated by boiling with ammonia or by means of cupric hydroxide,
the precipitate dissolved in hydrochloric acid, and the solution boiled
with a slight excess of potassinm hydroxide ; a small quantity of
indium hydroxide is thus obtained free from gallium. The gallium
remaining in solution may be separated as alum. Usually the indium
dissolved by the potash is removed by four crystallisations of the
ammonium-gallium alum ; but if the gallium hydroxide contains more
than 4} per cent, of indium hydroxide, seven or eight crystallisations
are necessary.
From Cadmium. — In presence of much free hydrochloric acid,
cadmium is not completely precipitated by hydrogen sulphide, whilst if
the solution is but feebly acid, the cadmium sulphide contains gallium.
The somewhat acid solution is treated with hydrogen sulphide, the
precipitate redissolved in hydrochloric acid, the solution diluted, and
again treated with hydrogen sulphide. By two or three repetitions
of the process, the greater part of the cadmium is obtained as sulphide
free from gallium. The filtrates which contain the gallium, mixed
with a little cadmium, are evaporated to expel excess of acid, diluted
with water, and saturated with hydrogen sulphide. The cadmium
sulphide thus thrown down is reprecipitated two or three times.
Excess of boiling potassium hydroxide precipitates cadmium oxide,
and dissolves gallium hydroxide ; the cadmium oxide is redissolved
and again precipitated, in order to separate the last traces of gallium.
If the amount of cadmium is large, this process must be repeated
four or five times. The alkaline solution which contains gallium and
a small quantity of cadmium is slightly acidified with hydrochloric
acid, and the gallium precipitated by means of cupric hydroxide, the
filtrate is mixed with ammonium acetate, and treated with hydrogen
sulphide, which throws down copper and cadmium : this precipitate
is dissolved in aqua regia, evaporated with hydrochloric acid, and
hydrogen sulphide is passed into the strongly acid solution ; copper
sulphide is thus precipitated, whilst cadmium remains in solution.
The following methods are more rapid: — (1.) The solution, which
must contain a sufficient quantity of ammonium chloride, is boiled with
excess of ammonia : cadmium then remains in solution, and gallium
hydroxide is precipitated ; this precipitate is redissolved and again
precipitated, in order to remove the last traces of cadmium. (2.) Gal-
lium is precipitated by means of potassium ferrocyanide in a solution
which contains at least one-third of its volume of strong hydrochloric
acid ; the cadmium ferrocyanide remains in solution. (3.) Cupric
hydroxide precipitates gallium on gently warming ; the pi*ecipitate
retains small quantities of cadmium, which may be removed by a
repetition of the process. (4.) When it is necessary to remove iron
as well as cadmium, the warm solution is reduced by metallic copper
and then mixed with a slight excess of cuprous oxide : the pre-
cipitated gallium hydroxide contains traces of cadmium, which may
be removed by reprecipitation.
The reactions with cupric hydroxide, and with metallic copper and
cuprous oxide, are the most satisfactory.
Fi'om Uranium. — (1.) The boiling slightly acid solution of the
chloride is treated with cupric hydroxide ; the precipitate is then dis-
INORGANIC CHEMISTRY. 153
solyed in hydrochloric acid, diluted, and again precipitated with cupric
hydroxide, the treatment being repeated four or five times. (2.) If
it is required to separate iron at the same time, the solution is reduced
with metallic copper, and then boiled with excess of cuprous oxide;
the precipitate is redissolved and the treatment repeated about four
times. Neither of these methods is affected by the presence of con-
siderable quantities of alkaline salts. (3.) The slightly acid solution
of the chloride is mixed with an excess of acid ammonium acetate,
zinc chloride free from gallium added, and the liquid is treated with
hydrogen sulphide : the zinc sulphide formed carries down the gallium,
whilst the uranium remains in solution. The precipitate is difficult to
wash and must be redissolved in hydrochloric acid, and again preci-
pitated in presence of an acetate. The zinc and gallium are separated
by the method previously described. (4.) The uranium is preci-
pitated in the form of alkaline uranate by adding a slight excess of
potassium hydroxide, the precipitate dissolved in hydrochloric acid,
and again precipitated. To remove traces of uranium from the fil-
trate, the latter is slightly acidified with hydrochloric acid, and boiled
with cupric hydroxide. When the potassium hydroxide contains car-
bonate, the quantity of uranium in the filtrate is increased.
From Lead. — (1.) The slightly acid solution of the chloride is boiled
with cupric hydroxide, the last trace of lead being^ removed by a second
precipitation. The reagents must be free from sulphuric acid. This
method is very accurate, and may be used to separate gallium sulphate
from the minute quantities of lead which remain in solution after
precipitation of lead as sulphate. (2.) The solution of chloride or
sulphate is boiled with metallic copper and then with cuprous oxide,
traces of lead being removed by a second precipitation. If a solution
of the chlorides is used, the presence of sulphuric acid in the reagents
must be avoided. (3.) The moderately acid solution is treated with
hydrogen sulphide, the filtrate evaporated almost to dryness to expel
free acid, diluted with water, and again treated with hydrogen sul-
phide. If sulphuric acid is present, it should be partially neutralised
with ammonia. To extract the gallium retained by the lead sulphide,
the latter is treated with strong hydrochloric acid, alcohol is added, the
liquid is filtered, and the filtrate, after evaporation to expel water and
alcohol, is diluted, and saturated with hydrogen sulphide. (4.) The
gallium is then precipitated as ferrocyanide by means of potassium
ferrocyanide in a solution containing one- third or one-fourth its volume
of strong hydrochloric acid. A second precipitation is sometimes
necessary in order to remove the last traces of lead. (5.) The solu-
tion is mixed with sulphuric acid, and two volumes of alcohol of 90°
added ; the precipitated lead sulphate, after being washed with alcohol
acidified with sulphuric acid, is suspended in dilute hydrochloric acid
and treated with hydrogen sulphide; and the filtrate, after being
boiled to expel excess of the gas, is treated with cupric hydroxide to
precipitate the last traces of gallium. The gallium in the alcoholic
solutions is precipitated by cupric hydroxide, after boiling off the
alcohol. (6.) The solution is mixed with twice its volume of 90 per
cent, alcohol ; a slight excess of hydrochloric acid is added, and the
precipitated lead chloride is washed with acidulated alcohol, whereby it
m 2
156 ABSTRACTS OF CHEMICAL PAPERS.
is obtained free from gallium. The filtrate is evaporated to small
balk, the nitric acid removed, and the liquid treated either with hydro-
gen sulphide, with cupric hydroxide, or with metallic copper and
cuprons oxide. C. H. B.
Separation of Gallium. By L. db Boisbaudran (Compt.
rend., 95, 703 — 706). — Separation from Tin. — Sulphide of tin pre-
cipitated from a hydrochloric acid solution containing tin and
gallium, retains none of the latter metal. On adding hydrochloric
acid in excess to a solution of the sulphides of tin and gallium in an
alkaline sulphide, sulphide of tin free from gallium is thrown down.
Salts of manganese added to a solution of the mixed sulphides in an
alkaline sulphide give a precipitate of manganese sulphide, which
contains gallium : this makes it possible to extract the latter metal
from large quantities of sulphide of tin. The author draws atten-
tion to one or two points, of which notice must be taken in analysing
mixtures containing gallium. A solution containing even a con-
siderable amount of gallium is not precipitated by potassium ferro-
cyanide if a large amount of stannic chloride is present ; so that tin
must be separated before attempting to estimate gallium by ferro-
cyanide. Tin and gallium, when alloyed, cannot be completely
separated by nitric acid, because the metastannic acid formed retains
sensible quantities of gallium, even after prolonged washing with
nitric acid. It is difficult to obtain a complete separation of gallium
and tin by precipitating the latter metal with zinc, because in a solu-
tion strongly acid the tin is not entirely thrown down, and in a nearly
neutral solution a certain quantity of gallium becomes insoluble.
Finally, tin dioxide, precipitated by boiling with sulphuric acid,
retains much gallium.
Separation from Antimony. — Gallium may be separated from anti-
mony by sulphuretted hydrogen, or by addition of an acid to a solution
of the sulphide in an alkaline solution, just as described in the case of
tin, except that in the case of the solution in the alkaline sulphide, it
is advisable to repeat the process. Potassium ferrocyanide precipitates
gallium from a solution containing antimony, but the precipitate
contains traces of the latter metal, which must be removed by dis-
solving it in potash and reprecipitating by addition of a large excess of
hydrochloric acid and a few drops of ferrocyanide. Salts of man-
ganese can be used to separate traces of gallium from antimony, just
as in the case of tin. Precipitation of the antimony by zinc does not
answer well. E. H. R.
Compounds of Tin Bisulphide and Diselenide. By A. Ditte
'){mipt. rend.y 95, 641 — 644). — Potassium ihiostannate,
SnSo,K2S,3H20,
foi-ms transparent colourless or very slightly yellow prisms, very solu-
ble in water, but decomposed by a large quantity of that liquid, with
precipitation of hydrated stannic sulphide. It is obtained by dissolv-
ing stannous sulphide in a solution of potassium polysulphide, or
more easily by boiling a concentrated solution of potassium mono-
INORGANIC CHEMISTRY. 157
sulphide witli the theoretical amount of sulphur and a slight excess of
tin, and evaporating the clear yellow solution by boiling or in a
vacuum. Potassium seleniothiostannate, SnSe2,K2S,3H20, is obtained
by substituting selenium for sulphur in the preceding operation. It
forms yellow octohedrons, very soluble in water, with formation of a
rose or red solution, according to the degree of concentration. Both
the solution and tbe crystals alter when exposed to air, black crystal-
line selenium being liberated. Potassium seleniosta7matej
SnSe2,K2Se,3H20,
is obtained by saturating a solution of potassium selenide with tin
diselenide and evaporating in a vacuum. It forms crystals which
alter rapidly when exposed to air. Sodium thiostannate and sodium
seleniostannate are obtained in the same way as the corresponding
potassium compounds, and have similar properties. Ammonium thio-
stannate, 3SnS2,(NH4)2S,6H20, is obtained by heating sheet tin with
a solution of ammonium polysnlphides, and evaporating the clear
yellow liquid in a vacuum over potassium hydroxide and sulphuric
acid. It forms yellow plates, which are decomposed by water with
separation of hydrated stannic sulphide. The crystals alter quickly
even in a vacuum, losing water and acquiring a superficial violet tint.
When gently heated, they lose water, ammonium sulphydrate, and
sulphur, a residue of tin sulphide being left. Am,monium seleniothio-
stannate, 3SnSe2,(NH4)2S,3H20, is obtained by treating an excess of
hydrated tin diselenide with a concentrated solution of ammonium
sulphydrate in the cold, filtering, and evaporating the red filtrate in a
vacuum over potassium hydroxide and sulphuric acid. It forms
yellowish-red plates, less stable than the preceding compound. The
crystals are decomposed by water, with separation of red flakes of tin
diselenide.
Tellurium dissolves in boiling concentrated solutions of the alkaline
sulphides, but yields no compounds with tin analogous to those
already described. Tellurium is deposited in crystals when the solu-
tion cools.
Barium thiostannate, SnS2,BaS,8H20, obtained by dissolving tin
in a boiling solution of barium polysnlphides and evaporating the solu-
tion in a vacuum, forms transparent citron-yellow crystals, soluble in
cold water without decomposition. From this solution dilute acids
immediately precipitate yellow stannic sulphide. Strontium thio-
stannate, SnS2,SrS,12H20, produced in a similar manner, forms bulky,
transparent, colourless prisms, soluble in cold water without decom-
position. Calcium thiostannate, SnS2,2CaS,14H20, also obtained in
a similar manner, forms transparent citron- yellow crystals, soluble in
cold water without decomposition. C. H. B.
Preparation of Lead Dioxide. By A. Fehrmann (Ber., 15, 1882).
— A concentrated solution (GO — 70° C.) of lead chloride is treated with
solution of chloride of lime until a filtered sample does not show
further separation of the dioxide ; the latter is then filtered off and
washed out of contact with air. Lead dioxide so prepared is quite
pure and nearly Llack,^ and keeps best in the moist state. When
158 ABSTRACTS OF CHEMICAL PAPERS.
prepared from sugar of lead it is not so cheap, and liable to nndergo
decomposition from the impurities of the lead acetate. J. K. C.
Barmm Compounds of Bismuth Peroxide. By I. Meschtchbr-
SKY (Journ. Buss. Chem. Soc, 1882, 280 — 281). — On fusing a mixture
of bismuth trioxide, baryta, and potassium chlorate, a black mass is
obtained, which, when washed with water, begins to decompose, with
evolution of oxygen. The black or reddish-brown residue remaining
after the extraction of soluble salts by water consists of compounds of
bismuth peroxide with barium, and decomposes hydrochloric acid with
evolution of chlorine. Analogous compounds with calcium or magne-
sium could not be obtained. If the above compound has been well
washed with water, it does not lose oxygen under pure water, but
decomposition takes place sudderdj in contact with barium peroxide or
solution of potassium chlorate. Fusion with potassium nitrate gives
rise to compounds containing more oxygen, e.g., one of the following
composition : 14BaO, SBigOs, BiOz, SHgO. B. B.
A Hydrate of Moiybdic Acid. By F. Parmentter (Gompt. rend.,
95, 839 — 841). — The author has examined the yellowish crystalline
substance which always separates after a time from solutions of alka-
line molybdates in nitric acid. He finds that it contains no nitrogen,
but is a hydrate of moiybdic acid, having the composition Mo03,2H20.
This substance is not formed in hydrochloric acid solutions of alkaline
molybdates. It is very sparingly soluble in water, a litre dissolving
only 0*5 gram at 15°. The crystals are efflorescent, and lose half their
water in a vacuum over sulphuric acid. Heated to 200°, they lose all
their water, and leave a white residue which sublimes completely on
further heating. E. H. li.
Mineralogical Chemistry.
Mechanical Separation of Minerals. By L. Pebal (Monatsh.
Chem., 3, 723 — 725). — In this paper, which is partly a reply to
Doelter's remarks on the same subject (Abstr., 1882, 656, 1173).
the author recommends the following modification of his method or
moving the electromagnet about in water holding the finely pul-
verised mineral in suspension. To avoid the formation of lumps,
arising from the enclosure of air- bubbles, the fine powder of the
mineral is made slowly to absorb water — or alcohol if water will not
wet it^ — from one side only, after which it is treated as follows : — A
number of moderate-sized beaker- glasses are filled with distilled water ;
the moistened rock-powder is introduced into the first; into this
powder is thrust the end of the iron rod surrounded with a coil of
wire ; and the circuit is closed, while the water is briskly agitated.
The electromagnet is then dipped into the second glass ; the circuit is
broken ; and this treatment is repeated till the magnet in the first
mXERALOGIOAL CHEMISTRY. 159
glass no longer attracts any particles. After all the magnetic particles
have thus been transferred to the second glass, the process is repeated
in exactly the same manner with the second and third glass, then with
the third and fourth, and so on till the magnetised bar no longer
leaves any residue in the last glass but one. The contents of the last
glass are then collected on one filter, and those of all the others on a
second filter. With a moderate amount of care in carrying out this
process, it is easy to avoid loss of substance. One point, however,
must not be overlooked, namely, the behaviour of solid diamagnetic
bodies in diamagnetic liquids, whereby, if the diamagnetism of the
liquid is stronger than that of the solid body, repulsion becomes
converted into attraction. H. W.
Application of a Solution of Potassium and Mercury Iodides
to Mineralogical and Petrographical Researches. By V. Qold-
SCHMIDT {Jahrh. f. Min., 1881, 1, Beil. Bd., 179— 238).-^lt is to be
regretted that the subject of the separation of the constituents of a
rock has been neglected of late, in consequence of the success which
has attended microscopic investigation, as there are cases in which the
latter method cannot be relied on. The separation may be effected
chemically or mechanically ; in the latter case advantage is taken of
the difference in the sp. gr. of the substances. In 1877 Church (" On'
a Test of Sp. Grr.," Min. Mag., 1877) proposed to separate the con-
stituents of a rock according to their sp. gr. by the help of an aqueous
solution of the iodides of potassium and mercury. The paper gives
at some length an account of J. Thoulet's researches on the same
subject (Bull. 8oc. Min., 1879, No. 1).
On investigating the subject further, the author decided to employ
a solution in which the weight of potassium iodide present is to the
mercury iodide as 1 is to 1"239 ; and this solution has a sp. gr. of
3'196, so that fluorspar floats in it; while the solutions of Thoulet
and Church gave as the maximum sp. gr. 2*77 and 3'01 respectively.
The maximum density is, however, not constant. It depends on the
moisture of the atmosphere and on the temperature. In summer the
maximum was 3'196, whilst in winter it was only 3"17.
The difficulties which attend this simple method of separation of
the rock constituents according to the sp. gr. are due to the variation
in the sp. gr. of the predominating mineral ; the close combination of
the constituents ; the smallness of the grains ; the great similarity, or,
in some cases, identity of sp. gr. of different minerals occurring
together, such as quartz and oligoclase; the tendency of the lighter
grains when they are in great excess to bring the heavier with them
to the top ; and the liability of the solution to change by evaporation
or by taking up water.
In considering this method, the question arises : Is the value of the
sp. gr. constant enough for the mineral to be determined by it, and
if a separation is effected between narrow limits of weight, can it
with certainty be asserted that the mineral sought for has been
separated ? Theoretically it is so. In order to answer the question
practically, the author submitted the felspar-group to the strictest
investigation, and came to the conclusion that, with fresh material
160 ABSTRACTS OF CHEMICAL PAPERS.
and perfect separation, the determination of the sp. gr. gives an exact
conclusion as to the nature of the felspar.
The apparatus used for the separation of the rock-constituents pro-
posed by Thoulet is described, but the author prefers to effect the
separation in small beakers of about 40 — 50 c.c. capacity, the
principal advantage of which is that the parts swimming above can
be better manipulated with the glass rod, and, consequently, the heavier
grains which are enclosed more easily separated. A number of
minerals whose sp. gr. has been exactly determined, are used as indi-
cators in the solution. The powdered rock and the indicators are
introduced into about 30 c.c. of the concentrated solution and stirred,
then allowed to subside, and the lighter parts removed. The success
of the separation depends on the skill of the experimenter, on the
choice of the indicators, but, above all, on the nature of the substance
to be separated.
It is evident, then, that Thoulet's opinion that the constituents of a
rock can be qualitatively and quantitatively separated, holds good only
very rarely, and it would be necessary also in most cases to make use
of auxiliary methods, such as treating the powder with various
reagents or with the magnet. B. H. B.
Native Palladium-Gold from Taguaril, Brazil. By W. H.
Seamon (Chem. News, 46, 216).— Sp. gr. = 1573. Analysis:—
Au. Pd. Ag. Fe.
91-36 8-21 trace trace E. W. P.
Alloys of Gold, Silver, &c., found in Grains along with the
Native Platinum of Columbia. By W. H. Seamon (Chem. Neivs,
46, 215). — Occurring with native platinum, alloys were found having
the following composition: — (Ag + Cu')Au3, (Cu' + Ag)4Au6, (Ag +
Hg')2Au8, Ag4Auio. Analyses are given, together with the densities ;
but the results are not of much value, owing to the smallness of the
quantity of material at hand. E. W. P.
On a Bed of Coal discovered in Algiers, and on the Layers
of White Sand accompanying the same. By G. Pinard (CompL
rend., 95, 708 — 709). — The author states that the results of experi-
ments made with the coal of Bou-Saada in Algiers show that, both in
respect of the amount of gas yielded and the illuminating power of
the latter, it is quite equal to the best English and French coals. The
yield of coke varies from 60 to 66 per cent, of the coal used.
The coal is always accompanied by beds of white sand arising from
the disintegration of bands of sandy loam. This sand can be used for
the manufacture of superior glass. E. H. B;.
Dopplerite from Aussee. By W. Demel (Monatsh. Chem., 3,
763 — 769). — A perfectly homogeneous specimen of this mineral freed
from adhering peat and dried at 100 — 120°, gave by analysis 56'42 and
o6'51 per cent, carbon and 5*34 — 5*20 hydrogen, leading to the formula
CizHuOe, which requires 56*69 C, 5*52 H, and 37-79 0. It yielded
also 5*1 per cent, ash having the following composition: —
MINERALOGICAL CHEMISTRY.
161
CaO 72-67
MgO 2-03
K.CNa^O 0-99
Al203,Fe203 12-02
SO3 4-36
CI 109
Insoluble 6-80
99-96
The higli percentage of lime seems to show that this base may be
present as carbonate, but the percentage of CO2 directly determined
was only 0'16 ; and this, together with the smallness of the amounts
of SO3 and CI, shows clearly that the greater part of the lime must be
combined with the organic matter, a conclusion which is confirmed by
the behaviour of the mineral with caustic potash. On suspending the
dopplerite in water and treating it with strong potash-lye, the mass
becomes thick, pasty, and very hot, and the alkali appears to be satu-
rated, as it no longer absorbs carbonic acid from the air. On boiling
the liquid the dopplerite dissolves, yielding a dark brown-red solution,
and from this, after filtration, acids throw down a brown flocculent
precipitate which, after thorough washing and drying, becomes shining
and brittle, and very much like the original dopplerite. This substance
dried at 110° gave 0-73 per cent, ash, and its combustion yielded
56-86—56-99 per cent. C and 4-90— 4 97 H, leading to the formula
C12H12O6, which contains 2 at. hydrogen less than that of the original
dopplerite.
The alkaline solution of dopplerite gives with calcium salts a brown
precipitate containing calcium, which when dried forms a blackish-
brown mass like dry dopplerite; it contains about 2-71 per cent.
CaC03, and, deducting this, the composition of the salt is found to
agree very nearly with the formula C26H22CaOi2, thereby affording
further evidence that the substance isolated from dopplerite in the
manner above described has the composition C12H12O6.
Dopplerite fused with potassium hydroxide is converted into proto-
catechuic acid (m. p. 199 — 201°), together with resinous and dark-
coloured products containing more than 70 per cent, carbon.
Ulmin (prepared from cane-sugar) also gave, on fusion with potash,
protocatechuic acid, together with black amorphous masses very rich
in carbon.
From the similarity of the compounds above described to humus-
substances in general, and from the mode of occurrence of dopplerite
in peat-beds, this mineral may be regarded as the calcium salt of one
or several acids belonging to the series of humus-substances.
H. W.
New Sulphide received as Tetrahedrite from Great Eastern
Mine, Colorado. By W. T. Page (Chem. News, 46, 215).— Steel-
grey metallic
lustre ; structure
crystalline but indefinite, britt
Hardness
= 4
: sp. gr. =
4-89.
Composition :—
-
Silicious
S.
Sb.
Cu.
Zn.
Fe.
Pb.
residue.
26-88
34-47 23-20
7-14
1-38
119
6-86 = 100-12
This corresponds to —
{fCu'aS + |(Cn",Zn,Fe,Pb)S}Sb2S3.
162 ABSTRACTS OP CHEMICAL PAPERS.
This mineral might be considered as a distinct species of stylotypite,
but it is better to class it as a variety of bournonite.
E. W. P.
Martite of the Cerro de Mercado, or Iron Mountain of
Durango, Mexico, and certain Iron Ores of Sinaloa. By B.
SiLLiMAN (Am. J. Sci. [3], 23, 375— 379).— This remarkable hill
exposes masses of the ore all over its surface ; they appear to be
derived from one or more immense beds of specular iron standing
nearly vertical ; the fragments form a talus on the slopes of the
mountain and conceal the underlying porphyry. There is nothing to
show that it is a pseudomorph of pyrites. An average sample con-
tained—
1^6304.
207
FegOg.
77-57
MnsOg. TeOa. CaO.
0-11 0-71 5-u5
MgO.
0-36
SO3.
0-21
P2O5. SiOg. H2O, &c. AI2O,
304 7-76 1-98 —
In the ores from Sinaloa there still remains in the martite about one-
third of the original magnetite. H. B.
New Locality for Hayesine. By N. H. Daeton (Am. J. Sci.
[3], 23, 458 — 459). — This very rare mineral occurs with datholite
and calcite in the trap rock of Bergen Hill. Slender acicular crystals
grouped on the calcite crystals ; they are probably a decomposition-
product of datholite ; the rock is soft, and permeable to water.
CaO.
Found 18-39
BA.
H2O.
46-10
35-46
= 99-95.
H. B,
Occurrence and Composition of some American Varieties
of Monazite. By S. L. Penfield (Am. J. Sci. [2], 24, 250—255).—
(1.) The specimen was apparently homogeneous. Sp. gr. = 5*20 —
5-25 ; locality, Pelton's Quarry, Portland, Conn. (2.) Picked grains
from the monazite sand from gold washing in the Brindletown dis-
trict, Burke Co., N. Carolina ; sp. gr. = 5-10. (3.) A specimen, also
apparently pure, from Yale College.
P205.
Ce203.
(La,Di)203.
ThOs.
SiOj.
Ignition.
(1.) 2818
33-54
28-33
8-25
1-67
0-37 = 100-34
(2.) 29-28
31-38
30-88
6-49
1-40
0-20 = 99-63
(3.) 2612
29-89
26-66
14-23
2-85
0-67 = 100-42
These numbers are in most cases the mean of two or three deter-
minations.
The ratios (Ce,La,Di),03 : P2O5 are 1 : 106, 1 : 1-08, and 1 : 1-07;
those of ThOa to SiOz 1 : 0-90, 1 : 0-92, and 1 : 088 respectively.
The varying amounts of ThOg and Si02, and their chemical differen';e
from the cerite metals, made it probable that the thorium silicate
exists as an impurity ; this was proved by microscopic examination,
MINERALOGIOAL CHEMISTRY. 163
the mechanically mixed thorite being distinguished by its darker
colour and easy decomposition by acids.
The thoria was separated by sodium thiosulphate ; the remaining
oxides were heated with dilute sulphuric and oxalic acid, and the
evolved carbonic anhydride collected in potash bulbs. The joint
atomic weight of the oxides obtained from the Portland specimen was
140'1, which number was also used to calculate the results of the
other analyses. H. B.
Colourless Mimetite from the Richmond Mine, Nevada.
By F. A. Massie (Ghem. NewSy 46, 215). — Slender acicular hexagonal
prisms, colourless, transparent, and with adamantine lustre. Hard-
ness = 3 ; sp. gr. 6'92, easily fusible. Composition : —
AsgOg. P2O5. PbO. PbClg.
23-41 trace 6821 869 = 100-31
agreeing with the known formula PbCl2,3Pb3As208. E. W. P.
Notes on some N. Carolina Minerals. By W. E. Hidden
(Am. J. Sci. [3], 24, 372— 377).— In Alexander Co., emerald and
beryl crystals, on which the rare forms 3Pf and ^P^ are largely
developed, are occasionally found.
The supposed ceschynite from Ray's Mine, Yancey Co., is columbite.
Uraniriite from Mitchell Co. has sp. gr. = 8'97 — 9-22, and hence is
not entirely free from alteration.
Euxenite from Wiseman's mica mine has been reanalysed by J. W.
Mallett ; titanic acid is absent ; it is therefore probably altered
samarskite, with which it is intimately associated.
Fergusonite from Burke Co. has also been analysed by Mallett.
NbgOg. TasOg. SnOs.WOg. T2O3, &c. C2O3. DiaOgXaA-
43-78 4-08 0-76 37-21 0-66 349
TJ2O3. FeO. CaO. HjO.
6-81 1-81 0-65 1-62 = 99-87.
Allanite has recently been found at two new localities, viz., Alex-
ander Co. with the a,bove-mentioned emerald crystals, and Wiseman's
mica mine, Mitchell Co. ; in both cases the crystals are well
developed.
SiOs.
AI2O3.
Y2O3. €6203. FeaOa.
FeO.
MgO.
CaO.
H2O.
39-03
14-33
8-20 1-53 7-10
5 22
4-29
17-47
2-78 = 99-95
H. B.
Composition of Two Specimens of Jade. By C. L. Allen
(Ghem. News, 46, 216). — The first specimen came from the Karakash
Valley, on the borders of Turkestan; it is of a pale green colour,
translucent ; hardness = 6*5 ; sp. gr. = 2'98, and contains —
SiOs. AI2O3. FeO. MgO. CaO. NasO. KjO- HjO.
57-35 1-03 1-22 2273 13-40 025 023 269 = 989
164 ABSTRACTS OF CHEMICAL PAPERS.
The other specimen came from Hokotika, New Zealand, and is sub-
translucent, with hardness = 6 ; sp. gr. 3'026. Composition : —
SiOg. ALA- FeO. MgO. CaO. NasO. K2O. H2O.
56-34 1-60 4-86 20-23 13-51 0 27 0-31 3-57 = 100-69
These specimens therefore represent the nephrite variety of amphi-
bole, and the first analysis corresponds to (i^Mg + y^oCa)SiO»,
whilst the second corresponds to (|Mg + iCa)Si03. E. W. P.
Analysis of a Mineral allied to Orthite. By W. H. Seamon
(Chem. News, 46, 215). — Crystals flat, well defined, imbedded in
soft kaolin, pitch-black, submetallic lustre ; brownish-grey streak ;
imperfect conchoidal fracture; hardness = 6 ; sp. gr. 3-15. Com-
position : —
SiOg. AI2O3. Y2O3. Ce^Og. ¥6203. FeO. MgO. CaO. H2O.
3903 14-33 8-20 1-53 710 5-22 429 17-47 2-78 = 99-95
Distribution of elements (y^M' -|- y\M" + -^'M."')SiOi.
E. W. P.
Communications from the U. S. Geological Survey, Rocky
Mountains Division. 1. Minerals, mainly Zeolites, occurring
in the Basalt of Table Mountain, near Golden, Colorado. By
W. Cross and W. T. Hillebeand (Am. J. Sci. [3], 23, 452—458,
and 24, 129 — 138). — Leucite does not occur. The formation of
the mountain is due to two protecting sheets of lava, an upper and a
lower one, of 115 feet in thickness. In the cavities of the upper
portion of the lower sheet (felspar basalt) are many beautifully
crystallised zeolites, associated with calcite and arragonite. The
zeolites are often found together ; the following have been determined,
viz., analcite, ap )phyllite, chabasite, mesolite, natrolite, stilbite, and
thomsonite. Chabasite is apparently the oldest zeolite, as it generally
lines the cavities, and the other zeolites are formed upon it.
Thomsonite — Crystals, thin rectangular blades, grouped together in
various ways ; where calcite crystals are not covered by chabasite,
thomsonite never fails to coat them. Toward the close of the zeolitic
formation, a second generation of thomsonite, and sometimes also of
chabasite, was deposited.
Si02.
AI2O3.
CaO.
NaaO.
H2O.
I.
40-68
30-12
1192
4-44
12 86 =
= 100-02
II.
42-66
29-52
10-90
4-92
12-28 =
= 100-01
III.
41-60
—
, —
—
IV.
40-88
—
—
—
—
I is of the older growth, and II of the newer. No. I was most
carefully freed from any chabasite. No. II contained a comparatively
few crystals of mesolite, and their complete removal was impossible.
Ill is of the ends of the thin blades, and the microscope showed the
presence of irregular rounded isotropic particles imbedded. in the
outer parts of the crystals. No. lY was from some very fine crystals,
containing but a very few of these rounded particles. The silica is
MINERALOGICAL CHEMISTRY. 165
higher than that allowed by the generally accepted formula; the
oxygen ratios being —
I. ..
KO
... 1
AI2O3 : SiOo
3-09 : 4-76
: 3-10 : 517
3-00 : 4-00
H2O.
: 2-51
11. ..
Accep
ted formula.
... 1
... 1
: 2-48
: 2-50
Analcite follows thomsonite in time of deposition. Form 202 and
also f 0, which is very characteristic for this locality. The double
refraction was very regular. A second generation of small and clear
crysLals upon apophyllite was observed. Analcite is often found alone
in the cavities ; natrolite is almost invariably deposited on aualcite.
Apophyllite, form ooP . P. Crystals large and rough, or small and
smooth ; the terminal edges of the pyramid are slightly furrowed.
Sections parallel to OP exhibit between crossed Nicols a square dark
centre, whose sides are parallel to the traces of the prism faces, and
from whose corners dark lines proceed to the margin ; the appearance
must be caused by internal tensions. The composition is quite normal.
SiOj. AI2O3. FeoOa. CaO. KgO. NagO. H2O. Fl. O for Fl.l
61-89 1-54 0-13 24-51 3*81 0-59 lG-52 170 -.0-72=99-97
Much of the apophyllite is altered to a white pearly substance con-
taining much silica, alumina, and water. Galcite has been deposited
in three stages — firstly, wine-yellow crystals, preceding chabasite and
deposited directly on the basalt ; secondly, colourless or only slightly
yellow; and lastly, aragonite as a snow-white incrustation, mostly on
chabasite, sometimes on apophyllite and thomsonite.
MesoUte is the last mineral deposited ; it occurs in groups of
exceedingly delicate needles, too small to recognise any crystalline
form.
SiOa. AI0O3. CaO. NasO. FgO.
10015.
SiOa.
AI0O3.
CaO.
NasO.
F2O.
46-14
26-88
8-77
619
12-17
46-02
26-87
—
—
12-17
46-33
—
—
—
12-13
This corresponds very nearly with 1 mol. of natrolite substance plus
2 mols. scolecite substance, i.e., Naumann's formula.
A second series of zeolites differing in time and manner and also in
composition, are found as semi-stratified deposits in the bottoms of
many cavities, forming a kind of floor. The sandstone-like substance is
crystalline, granular, and yellow, or white in colour, and in one large
cavity this consisted entirely of laumontite, as was shown by optical
and chemical examination — (a), white crystals ; (5), yellow crystals : —
SiOg. AI2O3. FeaOa. CaO. NajO. KoO. H2O.
(a.) . . 51-74 21-65 0-y5 11-95 0-19 0-35 1330 = 100-13.
(b.) . . 52-84 21-62 — 11-41 0-48 0-42 13 32 = 100-09.
The low amount of water is due to only some of the grains being
clear, others being turbid ; laumontite easily loses some of its water.
In other cases a mixture of laumontite and stilbite grains was
present, often accompanied by reddish spherules of thomsonite, as
shown by analysis ; this mineral is also similarly deposited alone on
166 ABSTRACTS OF CHEMICAL PAPERS.
tlie lower lava sheet. In many cases, fissnres filled with these three
minerals have been found leading into cavities also containing them ;
they were certainly deposited previously to the other zeolites, whose
crystals are attached to the walls of the cavities,, or to this older
deposit. H. B.
Garnet and Cordierite in the Trachytes of Hungary. By
J. SzABo {Jahrh. f. Min., 1881, 1, Beil. Bd., 302— 326).— Red garnet
has often been found in the trachytes of Hungary, and the researches
of Szabo prove that the garnet represents a type of trachyte which is
characterised by its associated minerals, as well as by its relative age
and the manner of its origin. He also found that the Hungarian tra-
chytes very frequently contain cordierite. The garnet is almost
always red. The grains are usually so large that they can be distin-
guished with the naked eye. The predominating form of the crystals
is an ikostetrahedron, with subordinate rhombic dodecahedron. It
fuses easily before the blowpipe, thus indicating the almandine variety.
The minerals accompanying it are felspar, amphibole, biotite, magne-
tite, and cordierite. The latter has previously been found in the
trachytes of Spain and Tuscany, but was first discovered in the Hun-
garian trachytes by Vogelsang, having formerly been mistaken either
for quartz or for felspar. The cordierite has a violet-blue colour, and
resembles amethyst-coloured quartz. It gave on analysis —
SiOg. FeA and AI2O3. MgO. CaO. Total.
56-85 2876 11-84 106 98-51 per cent.
The remainder is probably soda. It is dichroic, and scratches quartz.
It is associated with an orthoclase rich in soda, also with biotite,
amphibole, and almandine.
The author employs a new method of distinguishing cordierite for
petrographic purposes. The dichroism alone is not sufficient, as it is
not distinctly marked in light-coloured varieties, and although the
mineral is harder than quartz, the difference in this respect is too
small to afford any serviceable distinction : for these reasons chemical
tests are to be preferred. Before the blowpipe it shows the presence
of soda by faintly colouring the flame. The amount of soda is so
slight, that it would in a chemical analysis be regarded merely as a
trace ; but it is here of the greatest importance, since it serves, together
with the fact of its being slightly fusible, to distinguish the mineral
from quartz.
Garnet is not found in the trachytes of Servia, of Auvergne, or of
the Rhine district. It has, however, been found in the trachytes of
the Rocky Mountains {United States Geol. Exploration of the 4^th
Parallel. C. King, 1877, p. 561).
The trachyte family may be classed according to the felspar present,
as follows : — (a) orthoclase trachyte ; (6) oligoclase trachyte; (c) labra-
dorite trachyte ; (c?) anorthite trachyte. Most of the Hungarian tra-
chytes are biotite trachytes, in which the predominating felspar is
labradorite, but andesine (oligoclase) also occurs subordinately : hence
it can be seen that the garnet indicates the presence of a lime-soda
MINERALOGICAL CHEMISTRY. 167
felspar, and therefore, if garnet is found in a Hungarian trachyte
the latter may be considered a biotite-labradorite trachyte, or, in other
words, a garnet trachyte.
Cordierite occurs under quite different conditions ; it is not bound to
any particular felspar ; it may be found or be wanting, in any of the
types of trachyte mentioned above. The presence of cordierite is of
importance, as it indicates with certainty that the trachyte has under-
gone metamorphism. B. H. B.
The Lugano Eruptive District. By Totokitjsi Haeada (Jakrh.f.
Min., 1882, 2, Beil. Bd., 1 — 48). — The paper gives a topographical and
geological review, and a petrographical description of the Lugano
eruptive rocks.
1. The Black Porphyry. — This is an intermediate rock, with an
exclusively felspathic ground-mass. The minerals which compose it,
according to the relative age in which they separated out, are the fol-
lowing : — Zircon, titanite, apatite, magnetite, biotite, hornblende,
plagioclase, orthoclase, quartz, and lastly, the various products of
decomposition, especially kaolin, mica, chlorite, and epidote. The
plagioclase is proved to be oligoclase, with a sp. gr. of 2"65. An
exact determination of the sp. gr. of the black porphyry itself cannot
be expected, on account of its state of decomposition. The compara-
tively undecomposed rock had a sp. gr. of 2*672 — 2'675. The chemical
analysis of the rock gave the following result : —
SiOa. AI2O3. FegOg. OaO. MgO. IKgO. NagO. CO2. HgO.
69-44 17-26 7-35 347 3*60 3-28 323 062 2-22=100-87
The black porphyry may be regarded as a quartz porphyrite, the
structure of which varies between that of quartz diorite and quartz
felsophyrite.
2. The Bed Porphyry. — This is widely different from the black
porphyry ; it is very acid, and has a magma rich in recent quartz. The
four essential constituents are biotite, plagioclase, orthoclase, and quartz,
and besides these zircon, apatite, and magnetite occur. The latter are
always found enclosed in the other minerals, especially in the biotite.
Kaolin, potash mica, epidote, ferric hydrate, calcite, quartz, chalcedony,
pyrites, and chlorite appear as secondary constituents. The order in
which the minerals separated out from the magma is the following : —
1. Zircon and apatite. 2. Magnetite. 3. Biotite. 4. Oligoclase.
5. Orthoclase. 6. Quartz.
The chemical analyses of the red porphyry gave the following
results : —
SiO.2.
AI2O3.
FegOs.
FeO.
MnO. CaO.
MgO.
I. 72-32
13-37
0-57
2-34
-- 1-88
3-57
II. 73-71
12-20
2-42
1-55
trace 0-40
3-63
K2O.
KasO.
H2O.
I. 2-30
2-76
0-68
= 99-79
II. 2-28
1-83
1-69
= 99-71
The sp. gr.
is 2-59.
108 ABSTRACTS OK CHEMICAL PAPERS.
Tourmaline is to be regarded as a secondary constituent both of the
red and black porphyries.
3. The Tufas. — These originate from the comminution of the red
porphyry, as is shown by the fact that fragments of the latter are
found in its deepest beds, and that the red porphyry and the tufa
beds exhibit perfect conformability. B. H. B.
Sericite Rocks occurring in Ore Deposits. By A. v. Groddeck
(Jahrb.f. Min., 1882, Beil. Bd., [ii], 72— 138).— The "white rock" of
Holzappel, on the Lahn, Wellraich and Werlau, on the Rhine, the slate
bed of Mitterberg, in the Salzburg Alps, and the white slate of
Agordo, in the Venetian Alps, which up to the present time have
been described as talc slates, are sericite rocks.
The analyses of the sericite gave the following result : —
Phosphoric
SiOs.
AI2O3.
FeO. MgOg. CaO.
Kp.
N2O.
H2O. acid.
45-58
3676
1-13 0-85 003
9-29
]-36
516 trace = 10016
Sp. gr. 2'87 — 2*88. The analysis thus corresponds pretty exactly
with the formula of potash mica, H2(KNa)Al3(Si04)3, which confirms
Laspeyre's theory that sericite is not a distinct mineral, but a crypto-
crystalline potash mica.
A part of the " white rock " contains pseudomorphs after felspar,
augite, magnetite, and titanic iron ore, and is hence an altered erup-
tive rock, probably a diabase. In the white rock of Wellmich large
crystals of apatite are enclosed, which are without doubt of secondary
origin.
The sericite rocks of Mitterberg and Agordo are very probably
metamorphic rocks from normal clay slates, or Greywacke slates.
An exact knowledge of these rocks seems suita,ble for opening up
new points of view for several most important questions regarding ore
deposits, as it is highly probable that the sericite rocks described
always occur with ore-deposits where there is conformability between
the deposit and the strata of the surrounding rocks. The ore-deposits
of Holzappel, Wellmich, Werlau, and Mitterberg are doubtless veins
resembling interstratified beds. It had long been doubtful whether
the Salzburg and Tyrol copper ore deposits of Mitterberg, &c., were
true beds or lodes resembling beds, but the general opinion now is
that all the occurrences belong to the group of lodes resembling beds.
These seem to be always accompanied by sericite rocks. The Agordo
deposit resembles in a remarkable degree that of Mitterberg; it is
therefore very probable that it is also a bed-like lode. The white
slates of Agordo correspond, according to v. Cotta, with the rock at
Fahlun, in Sweden, so it is very possible that the latter also belongs
to the sericite rocks. Although sericite rocks occur with such typical
bed-like lodes as those of Holzappel and Mitterberg, they are entirely
absent in the case of typical stratified pyrites deposits, as the beds of
Goslar, Schmollnitz, and Meggen.
It has long been a moot question whether ore deposits, which are
conformably interstratified in sedimentary rocks, must be considered as
MINERALOGICAL CHEMISTRY. 169
beds, or lodes resembling beds. To settle this question, the character
of the surronnding rock has never yet been taken into account, but the
author is of the opinion that if the sericite rocks are truly the original
surrounding rock altered by the formation of a mineral vein, they can
only occur in the presence of mineral veins, and their absence must
confirm the opinion as to the bedded nature of the deposit.
B. H. B.
Basalt Rocks containing Hornblende. By H. Sommerlad (Jahrh,
f. Min.,18S2, Beil. Bd. [ii], 139— 185).— The hornblende basalts, charac-
terised macroscopically by their richness in porphyritic amphibole
crystals, contain microscopically as essential constituents, plagioclase,
augite, hornblende, magnetite, and olivine. In the Rhon rocks,
nepbeline occurs, although never in distinct crystals, and is of no
special importance for the composition of the rock, as the chemical
analysis also proves. A glassy basis is rarely met with.
The hornblende basalts form a subdivision of the felspar basalts.
When nepheline is present in greater quantity, they pass into basa-
nites ; in the absence of plagioclase, and with predominence of a glass
basis they approach the limburgites. The most interesting constituent,
the hornblende, frequently shows remarkable peculiarities of structure.
Rounded crystals are specially characteristic of it. It was without
doubt an original ingredient of the rock, which has separated very
early out of the magma. The hornblende basalts of the Rhon-moun-
tains, where they seem to be most widely distributed, never form high
peaks. They are of older origin than the basalts, which are free from
hornblende, as can at least be proved in the case of the Rhon and the
Vogelsberg.
The chemical composition indicates that the hornblende basalts are
tolerably basic, owing to their richness in magnetite, hornblende, and
augite. The percentage of silica scarcely rises above 44 ; that of soda
varies between 2*57 and 3*25 ; thus it may be seen that it is not
greater than in other felspar basalts, and this proves that the nephe-
line does not play a special part in the hornblende basalts. The per-
centage of potash varies between 1*36 and 1"54. Only a few varieties
from the Rhon gelatinise weakly with hydrochloric acid, with separa-
tion of little cubes of sodium chloride.
The rocks from Beuelberg, near Kircheip, and from Naurod, near
Wiesbaden, contain hornblende and augite, but no felspar can be found
microscopically in them as an essential constituent, and they contain
large amounts of olivine ; they belong to the group of the tertiary
picrite porphyries. B. H. B.
Examination of certain Meteorites. By W. Flight (Proc. Roy.
Soc, 33, 343 — 347). — I. The Bruce meteorite, found at Cranbourne,
near Melbourne, is shown by the author to consist entirely of metallic
minerals ; the iron contains no combined carbon, from 7 — 9 per cent,
nickel, some cobalt, silicon, and copper. On the surface were metallic
plates of a flexible mineral of composition FcoNiz, which the author
proposes to name Edmondsite. Among other minerals present were
rhabdite, Fe4Ni3P, a brittle coarse powder, probably identical with
a schreibersite of formula (FcgNi);?, brass-coloured oblique crystals of
VOL. XLIV. n
170 ABSTRACTS OF CHEMICAL PAPERS.
composition ^69^1262, and square, black metallic prisms of composition
re7Ni2P, together with triolite and graphite ; the occluded gases
amounted to 3*69 times the volume of the iron, and consisted of —
C02.
CO.
H.
CH4.
N.
012
31-88
4579
4-55
17-66
, II. The Rowton siderite fell on April 24th, 1876, at Rowton, near
Wellington, Salop. It is covered with a thin black crust of the mag-
netic oxide ; some fragments of the block were found on analysis to
contain —
Fe. NL Co. Cu.
91-145 8-582 0371 trace
thus closely resembling the iron of Nevagolla, in India. The occluded
gas was 6" 38 times the volume of the iron, and consisted of —
CO2. H. CO. N.
5-155 11-11^ 7-345 9722
III. The MiddlesboTOugh siderite fell at Middlesborough on March
14th, 1881 ; it is in the form of a low pyramid, slightly scolloped, the
summit and side being deeply grooved and polished. It contained
9*379 per cent, of nickel iron, containing iron, 76*99; nickel, 21*32;
cobalt, 1*69 per cent ; the remaining constituents consist of a soluble
silicate identical with olivine, and an insoluble silicate, bronzite.
V. H. Y.
Deposits of Manganese on the Surfaces of Rocks. By Bous-
SINGAULT (Compt. rend., 95, 368 — 373). — The author has found
manganese in the magnesia prepared from sea-water by Schloesing's
process. Dieulafait has detected manganese in considerable quantity
ill the ashes of marine plants, and the " Challenger " expedition dredged
up, from the bottom of the deep sea, nodules containing a large
proportion of manganese dioxide. There can, therefore, be no doubt
that manganese is present in sea-water. The manganese found in
such large quantity on the sea bottom by the "Challenger" is apparently
of volcanic origin, for it was always found where pumice stone was
present. The nodules have an oolitic appearance, and frequently
consist of concentric layers of manganese dioxide surrounding a
nucleus of red clay, but they show no trace of organic structure.
Buchanan regards the nodules as due to the intervention of animal
substances, which reduce the sulphates in the sea- water to sulphides.
Giin)bel supposes that the manganese is derived from submarine
springs which rise in volcanic districts, and contain manganese car-
bonate in solution. The manganese carbonate is deposited, and is
oxidised by the oxygen dissolved in the water. This explanation is
very similar to that which the author has advanced to account tor the
deposits of manganese dioxide on the surface of rocks on the banks
of the Orinoco and in other localities (Abstr., 1882, 1270).
C. H. B.
MINERALOGICAL CHEMISTRY. 171
The Orchard Alum Spring. By J. C. Thresh (Pharm. J. Trans.
[3], 13, 361). — This spring, which issnes from an old coal mine near the
summit of Axe Edge, in the Peak country, has long been valued as a
vermifuge, but it is not adapted as a tonic, owing to the amount of
aluminium sulphate present. The water has a decided red tint, which
varies according to the wetness of the season ; it is acid in reaction,
but contains no free acid. When heated to 66° it becomes opaque,
basic ferric sulphate separating, but the deposit redissolves as evapora-
tion proceeds ; the water is colourless if the deposit is allowed to
settle. The sp. gr. = 1*00351, and the composition per gallon is as
follows : —
re23S04 174-426 grains.
FeaOa 6-275 „
AI23SO4 72-908 „
MgS04 21-055 „
CaS04 14-381 „
FeS04 1-596 „
Na2S04 0-537 „
K2SO4 0-822 „
AIPO4 0-456 „
KCl 0-282 „
NH4CI 0125 „
KNO3 0-170 „
SiOg 5-776 „
298-809
The source of the spring is above the millstone grit, which is over-
laid by aluminous shale. The author proceeds to show theoretically
the formation of ferric sulphate from the ferric sulphide in the shale.
E. W. P.
Analysis of Waters accompanying Petroleum and of those
Ejected by Mud Volcanoes. By A. Potilitzin (Jour. Buss. Chem.
Soc.^ 1882, 300 — 310). — The author has analysed waters of the above
kind from the Caucasian and Caspian petroleum district. The waters
have an alkaline reaction, and contain large quantities of sodium
chloride, besides sodium bromide and iodide, the latter in such quan-
tities as have never been found before in any mineral water, viz.,
0-098 — 0-118 gram Nal in 1000 grams. The author found also con-
siderable quantities of a free organic acid belonging to the fatty series ,
most probably capric acid. He regards the above petroleum wells
as a new source of iodine. B. B.
n 2
172 ABSTRACTS OP CHEmCAL PAPERS.
Organic Chemistry.
Action of Hydrocarbons of the Acetylene Series on Mer-
curic Salts. By M. G. Kutcheroff (Jour. Buss. Chem. Soc, 1882,
326 — 327). — On shaking aqueous solutions of mercuric salts with
allylene, white, dense, and sometimes crystalline precipitates of the
general formula mRgX2,nHgO,p(C3HJlgO) separate out. The coeffi-
cients m, w, and p are different for different salts, e.g.^ for HgCl2 :
m = S, n = 1, p = 2 ; for Hg(C2H302)2 : m = n = 1, p = 2 ; for
HgS04 : m = 1, n = 2, p = S. The formation of the precipitates
from the acetate, sulphate, and chloride takes place as easily as the
reaction between allylene and an ammoniacal solution of cuprous or
silver salts, both reactions being equally delicate. A solution of mer-
curic bromide gives a slight precipitate, but mercuric iodide in water
or in potassium iodide gives no precipitate. The precipitates are
insoluble in water, easily soluble in acids, acetone being set free at the
same time. They do not explode when heated. The author regards
these compounds as combinations of basic salts of mercury with
acetone, the two hydrogen- atoms of which are replaced by one atom
of mercury. A solution of mercuric iodide in potassium iodide and
hydroxide, however, absorbs allylene with formation of a crystalline
precipitate ; this is soluble in acids with separation of allylene.
The author explains the hydration of hydrocarbons of the acetylene
series by means of mercuric salts, already announced by him in a
former paper, by the formation of the above intermediate compounds.
B. B.
Transformation of Propyl Bromide into Isopropyl Bromide
under the Influence of Heat. By L. Aronstein (Bee. Trav. CUm.,
1, 134— 142).— The author has already shown (Abstr., 1882, 567)
that normal propyl bromide, CHzMe.CHaBr or Pr^Br, heated in
sealed tubes at 280°, is converted into isopropyl bromide, CHMczBr
or Pr^Br.
Supposing then, in accordance with the received theory of dissocia-
tion, that the number of molecules dissociated remains constant at a
given temperature, the recomposition of dissociated molecules and the
dissociation of pre-existing molecules going on simultaneously at the
same rate, the author was led to expect that normal propyl bromide, if
exposed for a sufficient time to the temperature of dissociation, might be
completely converted into isopropyl bromide. Experiment, however, does
not confirm this expectation, but shows, on the other hand, that after
propyl bromide has been exposed to the temperature of dissociation
for 20 hours, further heating does not increase the quantity of iso-
propyl bromide formed, the transformation not being complete even if
the heating be continued for 100 hours.
This result, which appears at first sight to be at variance with the
fundamental principles of the theory of dissociation, may, according to
ORGANIC CHEMISTRY. 173
the author, be reconciled with that theoryin two ways, viz. : — (1.) By
supposing that the propylene and hydrobromic acid resulting from, the
decomposition of the propyl bromide recombine partly as Pr^'Br and
partly as Pr^Br. If this be the case, Pr^Br heated in sealed tubes
should be partly converted into Pr*Br. Such, however, is not the
case : for the author finds that Pr^Br may be heated in sealed tubes at
280° for a week with scarcely any alteration, nearly the whole after-
wards distilling over at 69 — 62° (b. p. of Pr^Br), and only a few
drops of dark-coloured high-boiliug liquid remaining in the retort,
probably consisting of hydrobromides of polymeric propylenes.
(2.) Another cause capable of preventing the complete transforma-
tion of Pr*Br into Pr^Br may, in the author's opinion, be found in the
pressure to which the liquid in the sealed tubes is subjected. It is
known indeed that dissociation is retarded by increased pressure, and
the author finds, by determination of the vapour- densities of the pro-
ducts obtained by the action of heat on the two propyl bromides, that
at any given temperature, Pr^Br decomposes more quickly than Pr*Br :
consequently, as the proportion of Pr^Br in the mixture becomes
greater, so also will there be an increase in the number of molecules
resolved in a given time into CsHe and HBr, the pressure exerted on
the yet undecomposed molecules, increasing in proportion thereto;
and this increase of pressure will retard the decomposition of the
normal propyl bromide, and consequently prevent its complete con-
version into the isopropyl compound.
Similar results have been obtained by Eltekoff (Ber., 8, 1144 ; G. /.,
1876, 541), with regard to the conversion of isobutyl bromide into
tertiary butyl bromide.
Attempts to convert other propyl compounds into isopropyl com-
pounds by heating in sealed tubes were unsuccessful. Propyl chloride,
propyl alcohol, and propyl acetate, heated for several days above 300°,
showed no sign of alteration; and the same was the case with the
dibromide of ethylene (? propylene). H. W.
a-Monochlorallylic Alcohol and its Derivatives. By L.
Henry {Gompt. rend., 95, 849 — 851). — On boiling the compound
CH2 ! CCI.CH2CI (b. p. 95°) with a dilute solution of potassium
carbonate for some hours in a wide flask with reflux condenser, the
chloride gradually disappears ; and on distilling the product the alcohol,
CH2iCCl.CH2.OH, comes over in the first portions of the distillate,
and may be completely separated from the water by means of potas-
sium carbonate. It forms a perfectly limpid colourless liquid, having
a faint smell. Its sp. gr. at 19° is 1*164, and it boils unaltered at 186
under a pressure of 763 mm. It dissolves easily in water, but less
easily than allylic alcohol. The ethereal acetate, CH2 ! CCl.CHz^^c,
produced by the action of acetic chloride, boils at 145°. The bromide,
CH2 '. CCl.CHgBr, formed by the action of phosphorus tribromide,
boils at 121°. The corresponding thiocyanate obtained by the action
of the chloride on potassium thiocyanate, boils at 180 — 181° without
decomposition. When freshly distilled, it is colourless, and recalls
exactly the odour of oil of mustard, but after a time it becomes brown.
B}-- the action of ammonia upon it, monochlorothiosinnamiue is
174 ABSTRACTS OF CHEMICAL PAPERS.
obtained, melting at 90 — 91°. A mixture of concentrated nitric and
sulphuric acids, well cooled, converts the alcohol into the compound
CH2 : CHCI.CH2.NO3.
a-Monochlorallylic alcohol dissolves easily in sulphuric acid with
development of heat, and hydrochloric acid is evolved. Distilled with
a large quantity of water, the liquid yields a product having all the
properties of pyruvic alcohol, CH3.CO.CH2.OH.
The author draws attention to the great difference in physiological
properties between the compound above described and y3-monochlor-
allylic alcohol, described by Van Romburgh {Bull. Soc. Chim., 36,
557), the latter being intensely caustic. E. H. R.
Ethylene Oxide. By Beethelot (Bull. Soc. Chim., 39, 488^
491). — The basic properties of ethylene oxide, as evidenced by its
ready combination with hydrochloric acid, have been pointed out by
Wurtz ; this reaction the author has made the subject of a ther mo-
chemical study.
The equation C2H4O + HCl = C2H5CIO develops heat = + 36-0
cal., a number comparable in value to C2H4 + HCl = C2H5CI =
+ 38 cal., although in the first case a compound analogous to the
hydrate and alcoholates of hydrochloric acid is at first formed, whilst
no such intermediate product is possible with ethylene. But the
values for the combination of ethylene oxide and ammonia with hydro-
chloric acid are approximately equal: for NH3 + HCl = NH4CI =
+ 42'5,if the heat of solidification of ethylene chlorhydrin be taken into
account ; and further, C2H4O2 (very dilute) + HCl (very dilute) =
C2H5CIO (dissolved) = + 12 4, a value equal to the heat of combus-
tion of ammonia or potash with hydrochloric acid under the same
conditions.
Attention is also drawn to the fact that ethylene oxide com-
bines with hydrochloric acid in the presence of a large quantity
of water with evolution of a considerable amount of heat ; this
phenomenon explains the reaction between ethylene oxide and the
metallic chlorides observed by Wurtz ; for in the presence of water
a certain quantity of hydrochloric acid is formed, and an equilibrium
is established dependent upon the heat of formation of the metallic
chloride and oxychloride, and the degree of dissociation of the hydrate
and the oxychloride in presence of water.
Ethylene oxide, doubtless, combines with the other haloid acids, but
this is not the case with the organic acids, for dilute acetic acid is
not appreciably neuti-alised by the oxide even after the lapse of many
hours. V. H. V.
Strobometric Determination of the Rate of Inversion of
Cane-sugar, and Transition of the Birotation of Milk-sugar
into its Normal Rotation. By F. Urech (Ber., 15, 2130—2133).
— In continuation of his former work on this subject (Abstr., 1881,
242), the author finds that although the ultimate result of the inver-
sion is unaffected by the concentration of the solution, strength of acid
used, or temperature, the rate of inversion varies very greatly under
ORGANIC CHEMISTRY. 175
variations of these conditions. The volume of the solution remaining
constant, increase in the percentage of acid present decreases the time
required for the inversion. The percentage of acid to water being
constant, increase of volume decreases the time, but percentage of acid
to sugar being constant, increase of volume (i.e., dilation with water)
increases the time. Increase of temperature shortens the time of re-
action. In the case of sugar of milk, the rate o-f transition of the
birotation to the normal seems independent of the proportion of water
to sugar. An addition of a small quantity of hydrochloric acid
quickens the action at first, but does not shorten the total time of
reaction. When 3 grams of sugar of milk were dissolved in 50 c.c.
of hydrochloric acid of sp. gr. 1*155, the rotation was at once reduced
from 10° 6' to 6°, but after two hours had returned to 10°. (See also
Schmoger, Ber., 13, 1927.) L. T. T.
Anhydrous Grape-sugar from Aqueous Solution. By 0.
HESiSE (Ber. J 15, 2349 — 2350).— A question of priority.
Transformation of Amides into Amines. By Baubigny
{Compt. rend., 95, 646 — 648). — When a primary or secondary amine
is heated with an ethereal salt, an amide is formed and the alcohol of
the ethereal salt is set free. Ethylamine and methyl acetate, for
example, yield ethylacetamide and methyl alcohol. Under certain
conditions, these amides combine with water, reproducing the original
salt. The author finds that when the amides are heated at a tempe-
rature higher than that necessary for their formation, they combine
with alcohol, forming the original salt, in which, however, the amine
is replaced by a substituted amine derived from the alcohol employed.
Acetamide, heated with ethyl alcohol, yields ethylamine acetate ; and
ethylacetamide, under the same conditions, yields diethylamine acetate.
The reaction has been observed with methyl, ethyl, and amyl alcohols,
with alcohols of the benzene series, and with acetic, valeric, and benzoic
acids. The amide and the compound amine can be formed in suc-
cessive stages of the same operation by heating first at a low, then at
a high temperature. When ammonium benzoate is heated with
ethyl alcohol, or when ammonia in alcoholic solution is heated with
ethyl benzoate, benzamide is first formed, with elimination of water,
and then after some hours' heating at a higher temperature, ethyl-
amine benzoate is formed by the action of the amide on the alcohol.
With a mixture of aniline, glacial acetic acid, and methyl alcohol,
phenylacetamide and water are first formed, then methylaniline and
acetic acid, the salt formed by their union being very unstable. This
change can be repeated so as to produce successively, for example,
ethylamine benzoate, diethylamine benzoate, and triethylamine ben-
zoate. The final product contains either the tertiary amine alone or a
mixture of different amines, according to the proportion of alcohol
employed. Ammoniums are not formed, and in this respect the reac-
tion differs from the action of the amines on alcoholic chlorides, &c.
It is worthy of note, that no aniline is formed by the action of
acetamide on phenol, even after heating at 300° for eight hours. It
is possible that the cyanides derived from the amides by loss of water
176 ABSTRACTS OF CHEMICAL PAPERS.
will combine with alcotol in a similar manner. A large series of new
compounds would thus be formed. C. H. B.
Action of Anhydrous Aluminium Chloride on Acetone. By
E. Louise (Compt. rend., 95, 602 — 603). — If acetone is gently heated
and aluminium chloride added in successive poriiions, the mixture,
after about 20 hours, is converted into a blackish solid and liquid.
This product, when distilled in steam, yields a yellow liquid, amounting
to about 35—40 per cent, of the acetone used. It consists of conden-
sation-products from acetone, mixed with unstable chlorine-derivatives
of the same products. When treated with potash and distilled, it
yields a more volatile portion, consisting mainly of mobile colourless
mesityl oxide CeHioO, (b. p. 128 — 130°, vapour- density found, 3*51,
calculated, 3*39), and a less volatile portion, which contains crystal-
lisable phorone, CgHuO (m. p. 28°, b. p. 195 — 196°, vapour-density
found, 4*51, calculated, 4i-77), mixed with higher condensation-pro-
ducts which will not crystallise.
The double chloride of aluminium and sodium acts on acetone in a
similar manner. C. H. B.
Action of Nitric Acid on Fatty Acids containing the
Isopropyl.group. By J. Bredt (Ber., 15, 2318—2325). — When
isovaleric acid is acted on by nitric acid, a mixture of methylmalic
acid [identical with the metlioxy succinic acid described by Demar^ay
{Compt. rend., 82, 1337) and Morris (this Journal, 1860, 6)], and
/5-nitrovaleric acid is produced. The two acids are easily separated by
recrystallisation, the nitro-acid being much less soluble than methyl-
malic acid. j8-nitroiso valeric acid crystallises in glistening plates
belonging to the monoclinic system, a: b : c= 1*8346 : 1 : 1'7442 y3 =
87° 28'. On reduction with tin and hydrochloric acid, /3-amido-
isovaleric acid is obtained. It is identical with the acid described by
Heintz (Annalen, 198, 42). Nitroiso valeric acid is decomposed by
strong nitric acid, yielding dinitroisopropane (m. p. 50°, b. p. 187°),
which has been described by Meyer and Locher {ibid., 180, 147).
This hydrocarbon is also obtained as a bye-product of the action of
nitric acid on isovaleric acid from valerian root. Under similar treat-
ment, isovaleric acid from fermentation amyl alcohol yields methyl-
malic acid, nitroisovaleric acid, and dinitroisopropane. W. C. W.
Solidification of Different Mixtures of Naphthalene and
Stearic Add. By H. Courtonne {Compt. rend., 95, 922 — 924). —
The results of Heintz and of Gottlieb on the melting points of mixtures
of fatty acids are borne out by mixtures of bodies widely differing in
their chemical properties, such as stearic acid and naphthalene.
Commercial stearic acid was used ; the results are, therefore, only
relative : but if it be admitted that a definite compound is formed
(m. p. 47°) by melting 100 parts stearic acid with 40 parts naphtha-
lene*, by a simple calculation the solidifying points of the three first
mixtures given in the following table may be found. These numbers
are given in the fourth column : —
* These numbers were taken as approaching most nearly the relation between
the molecular weights of the two bodies.
ORUANIC CHEMISTRY. Ill
Naphthalene.
Point of sc
)lidification.
Stearic acid.
Found.
Calculated.
100-0
0-00
56-00
—
))
7-50
53-50
53-80
))
15-00
51-50
51-90
))
22-50
50-00
50-20
>)
40-00
47-00
—
})
45-00
47-50
48-00
»>
50-00
47-60
—
)}
5»
55
—
ii
79-00
55-60
—
})
90-00
58-50
—
))
135-00
66-00
—
»
270-00
73-00
—
jj
»
5J
—
0-0
100-00
79-00
—
The solidifying point of the last four mixtures is not constant.
What reaction takes place between these two bodies ? Whether a
compound analogous to that of stearic acid with glucose or those of
naphthalene with di- and tri-nitrophenol is formed, will form the
subject of further research. L. T. O'S.
Conversion of Acetonechloroform into Hydroxyisobutyric
Acid. By C. Wtllgerodt (Ber., 15, 2305— 2308).— Acetonechloro-
form, OH.CMe2.CCl3, is decomposed by water at 180°, forming hydro-
chloric and hydroxyisobutyric acids, CMe2(0H).C00H.
w. c. w.
Bye-products in the Preparation of Acetonechloroform. By
C. WiLLGERODT (Ber., 15, 2308 — 2313). — On acidifying the residue
obtained in the preparation of acetonechloroform, an oily liquid is
liberated (b. p. 192 — 212"), which contains acetonaloxyisobutyric acid,
COOH.CMeg.O.CMea.O.CMes.COOH. This acid probably owes its
formation to the action of potash on a mixture of acetonechloroform
and diacetonechloroform, potassium acetonate and acetoneoxyisobuty-
rate being formed in the first instance. Two molecules of the latter
salt lose a molecule of water, and form potassium acetonaloxyiso-
butyrate. W. C. W.
Halogen Substitntion-compounds of Ethyl Acetoacetate.
By M. Conrad (Ber., 15, 2133— 2134).— In reference to the denial by
Duisberg (Abstr., 1882, 1192) of the existence of ethyl dibroma(ietate
dibromide described by the author (Annalen, 186, 232), he is inclined
to look upon this body as identical with the tetrabromacetoacetic
ether, CeHeBriOa, obtained by Duisberg, instead of CeHaBrzOa^Brg, as
originally proposed by himself. L. T. T.
The Addition of Bromine to Ethyl Acetoacetate. By E.
LippMANN (Ber., 15, 2142 — 2144). — The author upholds the correct-
ness of his ethyl acetoacetate dibromide, CeHioOaBrj (Wien. Ahad.
178 ABSTRACTS OF CHEMICAL PAPERS.
Ber.j 1868, 58 [2], 310), the existence of which is denied by Daisberg
(Abstr., 1882, 1192). This dibromide is very unstable, and he believes
JDaisberg's preparation, which was kept 14 days before analysis, to be
a decomposition-product formed according to the equation CeHioOaBrj
= CeHgBrOa + HBr. L. T. T.
Decomposition of Tertiary Amyl Acetate by Heat. By K
Menschutkin (Compt. rend., 95, 648—651). — The author has pre-
viously found (Abstr., 1881, 36) that the etherification of acetic acid
and tertiary amyl alcohol takes place very slowly and only to a very
limited extent. He has therefore investigated the dissociation of
tertiary amyl acetate at 155° by the method described in a former
paper. During the first 20 hours, the rate of decomposition is very
slow; it then rapidly increases and attains a maximum after 48
hours ; then again decreases until, after 92 hours, the decomposition
almost ceases. The decomposition, C5Hn.C2H302 = C5H10 + C2H4O2,
is limited by the inverse change, C5H10 + C2H4O2 = C5H11.C2H3O2 ;
but the effect of this inverse change is very slight, for the limit of
decomposition at +53° is as high as 97*42 per cent. The limit of
etherification of acetic acid and tertiary amyl alcohol at the same
temperature was previously found (loc. cit.) to be 2*53 per cent. The
rate of decomposition is materially affected by the temperature. At
100° there is no decomposition; at 125° it is only perceptible after
some days' continuous heating, and even at 140° it is extremely slow.
The higher the temperature, the more quickly does decomposition
commence, and the greater is its rapidity in all phases ; but under
the most favourable conditions decomposition is not perceptible until
after two hours' heating ; and whatever the temperature, the rate of
decomposition is at first very slow, then increases and attains a
maximum, then decreases until the limit of decomposition is rea^jhed.
The author was unable to ascertain definitely whether the limit
depends on the temperature ; at 145° it was found to be 96'59 per
cent., at 155° 97*42 per cent. C. H. B.
Action of Ammonium Cyanate on Glyoxal. By N. Ljubavin
(Jour. Buss. Chem. Soc, 1882, 281 — 291). — The author describes ex-
periments by which he proves that the compound obtained in the above
reaction, and formerly regarded by him as diamidosuccinic acid, is in
reality glycocine ; but up to the present time he has not been able to
ascertain the course of the reaction. B. B.
Series of Salts containing Chromium and Urea. By W. T.
Sell (Proc. Boy. Soc, 33, 267 — 274). — When urea is moistened with
chromium oxy chloride, there is considerable development of heat, and
on treating the product with water a green crystalline powder is
obtained ; this compound is insoluble in alcohol and ether and dissolves
in hot water with decomposition, another salt separating out in olive-
green needles ; this latter body is a dichromate of a base containing
urea and chromium, and has the composition
{ (CON2H4)i2Cr2} (Cr207)3,3H20 :
ORGANIC CHEMISTRY. 179^
it is sparingly soluble in cold, more freely in hot water ; its aqueous
solution gives crystalline precipitates with platinum chloride and
potassium ferrocyanide. The platinochloride,
{(CON,H4)i2Cr,}(PtCl6)3,2H20,
crystallises in green silky needles, sparingly soluble in cold water ;
the chloride, (CON"2H4)i2Cr2Cl6,6H20, obtained by decomposing the
dicbromate with lead chloride and water, crystallises in slender silky
needles, sparingly soluble in cold, readily soluble in hot water. Its
aqueous solution is precipitated by potassium dichromate and ferro-
cyanide and by platinum chloride. The sulphate,
(CON2H4)i2Cr2(SO4)3,10H3O,
obtained from the chloride by the action of silver sulphate, crystallises
in dark-green prisms ; the nitrate, (CON2H4)i2Cr2(N03)6, also presents
a similar form. The formation of a hydroxide was suspected, but it
was not obtained in a state sufficiently pure for analysis.
Y. H. V.
Synthesis of Uric Acid. By J. Horbaczewski (Monatsh. Chem.,
3, 796). — Pure glycocine (from hippuric acid) was finely pulverised
and mixed with ten times its weight of pure urea prepared from
ammonium cyanate, and the mixture was heated in a small flask placed
in a metal bath at 200 — 230° till, the liquid, at first colourless and
transparent, became brownish-yellow and tarbid. The melt when cold
was dissolved in potash, and the solution, after supersaturation with
sal-ammoniac, was precipitated with a mixture of ammoniacal silver
solution and magnesia-mixture. The resulting precipitate was well
washed with ammoniacal water and decomposed with potassium sul-
phide, the liquid filtered from silver sulphide, and the filtrate, after
acidulation with hydrochloric acid, was concentrated on the water-
bath, whereby uric acid was separated. The crude product thus
obtained was redissolved in potash- lye, and the above-described process
twice repeated, whereby ultimately a yellowish crystalline powder was
obtained exhibiting the composition, physical properties, and all the
reactions of uric acid. H. W.
Crystallographic Examination of a-/3-Dinitroparaxylene
and of the Dinitroparaxylene which melts at 93°. By F. Barner
{Ber., 15, 2302— 2305).— The crystals melting at 99-5°, which Jannasch
and Stiinkel (Abstr., 1880, 808) obtained on crystallising a mixture of
a- and /3-dinitroparaxylenes from glacial acetic acid, or preferably
from benzene, belong to the rhombic system and exhibit sphenoidal
hemihedry. The ratio of the axes a : 6 : c is 0-69649 : I : 1-06850.
Dinitroparax^^lene (m. p. 93°) is deposited from a solution in benzene
in lustrous prisms belonging to the monoclinic system, a : 6 : c =
0-869502 : 1 : 0-63818 ; i3 = 81" 14' 52". W. C. W.
Benzyleneorthotolylamine and Methylphenanthridine. By
A. Etard (Compt. rend., 95, 730 — 732). — When orthotoluidine and
benzaldehyde are mixed in molecular proportions, heat is evolved,
water is separated, and a substance is produced which boils at 314*
180 ^ ABSTRACTS OF CHEMICAL PAPERS.
(iincorr.). Analysis and determination of vapour- density lead to the
formula CsHiMe.N : CHPh. Water, especially at 100°, decomposes this
substance into orthotoluidine and benzaldehyde. Concentrated hydro-
chloric and nitric acids give rise to the products of the action of these
acids on orthotoluidine and benzaldehyde respectively. When bea-
zyleneorthotolylamine is allowed to fall drop by drop into an iron tube
at a bright red heat, two simultaneous decompositions result. One of
these is represented by the equation CeHiMe-N" ! CH.CgHs = CeHjMe
+ CeHg.CN ; the other consists in the removal of 2 atoms of hydro-
gen from the original substance and the formation of a new body
which the author terms methylphenanthridine.
CeRMe.l^ CeHaMe.N
II = H. + I II .
CeHs.CH. G6H4 — Cm
The new substance bears the same relation to methylphenanthrene
that pyridine does to benzene. To isolate the new base, the mixed
product is steam-distilled, by which means the toluene and benzonitrile
are removed, and the residue is distilled. The substance is easily
purified, by crystallisation from ether, when it melts at 170° and boils
above 360°. It is insoluble in water, sliorhtly soluble in alcohol, very
soluble in ether. Aqueous hydrochloric acid does not dissolve it, but iu
alcoholic solution a hydrochloride is obtained which gives a crystalline
double salt with platinic chloride. The author has obtained similar
results with ortho- and para-toluidine and other aldehydes.
E. H. K.
Azoxylene. By K Samonoff (Jour. Buss. Chem. Soc, 1882, 327 —
328). — On adding a mixture of potassium hydroxide and ferrocyanide
toxylidine sulphate (b. p. 198 — 210°), an orange precipitate separates
out at first, and later on resinous compounds are formed : the pre-
cipitate is separated from the liquid, dissolved in alcohol, and treated
with chlorine in order to destroy the resinous bodies. Dark-red crys-
tals separate from the solution, which after purification by repeated
crystallisation melt at 128°. This compound is identical with the
azoxylene which Werigo obtained in 1864 by reducing the unsym-
metrical nitroparaxylene with sodium- amalgam. The author proposes
to examine the azoxylenes. B. B.
Klinger's Method of Preparing Azoxybenzene. Note by K
MoLTCHANOFFSKY (Jour. Buss. Chem. Soc, 1882, 360). — On repeating
Klinger's method for obtaining azoxybenzene, the author could not
get more than 32 per cent, of the theoretical yield, though Klinger
would seem to have got a yield of 100 per cent. (48 grams from 60
grams of nitrobenzene) ; moreover the preparation obtained by the
above method was far from being pure. The author recommends
therefore the use of his own method (Abstr., 1882, 965), the yield of
which is over 87 per cent, of the theoretical. B. B.
Diazo-compounds. By P. Griess {Ber., 15, 2183— 2201).— This
is the first of two papers in which the author intends summarising
ORGANIC CHEMISTRY. 181
the results of several years' work on this subject. In the present
notice he details the results of the action of paradiazobenzenesulphonic
SO
acid (parabenzene-diazine sulphite), C6H4<[ -sr^^i on various primary
ainido-corapounds.
• When molecular proportions of paradiazobenzenesulphonic acid and
aniline hydrochloride are heated together in aqueous solution for about
24 hours, the product is found to consist of diazobenzene hydrochloride,
sulphanilic acid, and a new compound, which the author names
amid'oazohenzenesulphonic acid. The reactions probably take place
according to the two equations —
(i.) aH4S03l^2 + CeHs.Ts^HsCl = C6H4(S03H).N..C6H4.NH2 + HCl,
(ii.) CeH^SOaN-s + NHaPhCl = Ph.N^Cl + C6H4(S03H).NH2.
When free aniline was used instead of the hydrochloride, the diazo-
benzene hydrochloride formed in the above reaction was replaced by
diazoamidobenzene.
AzoamidobenzenesulpJionic acid,
C6H4(S03H).N-2.C6H4.NH2 [SO3H : N2 : NH2 = 4 : 1 : 4],
is precipitated from a solution of its ammonium salt in glittering
yellowish-white microscopic needles, which are almost insoluble in
water, alcohol, ether, and chloroform. When heated, it carbonises
and gives off SO2. Reduced with tin and hydrochloric acid, it splits
up into sulphanilic acid and paraphenylenediamine. The barium salt,
(Ci2HioN3.S03)2Ba + 6H2O, crystallises in reddish-yellow needles,
sparingly soluble in water.
Diazoazobenzenesulphonic acid (azobenzenediazine sulpJiite),
is obtained when azoamidobenzenesulphonic acid suspended in water
is treated for some time with nitrous acid. It forms pale yellow
microscopic needles, almost insoluble in the usual neutral solvents.
It is dissolved by potash, and reprecipitated unchanged by mineral
acids. It has scarcely any taste, and decomposes with explosive
violence at high temperatures. If boiled for some time with water, it
is converted into phenolazobenzene'parasulphonic acid,
C6H4(S03H).N2.NC6H4(OH) [N : SO3H = 1:4],
already described by the author (Abstr., 1879, 315). Heated with
dilute alcohol, an azobenzenesulphonic acid, C6H4(S03H).N"2.C8H5,
is produced identical with that previously obtained by the author
(Annalen, 154, 208) by the action of fuming sulphuric acid on
azobenzene.
Azoamidohenzenedisulphonic acid, C6H4(S03H).N2.C6H3(S03H).NH2,
is produced on heating azoamidobenzenesulphonic acid with four
times its weight of fuming sulphuric acid at 100° until water no
longer causes a precipitate. This acid crystallises in glistening
violet-coloured needles, easily soluble in boiling, sparingly so in cold
182 ABSTRACTS OF CHEMICAL PAPERS.
water, but easily soluble in alcohol, from which it is repreoipitated by
ether; on exposure to the air, it effloresces to a brown powder. It
dyes silk and wool a fine yellow. Reduced with tin and hydrochloric
acid, it splits up into sulphanilic acid and an acid crystallising in
white needles, which the author believes to be diamidobenzenesulphonic
acid. Barium azoamidobenzenedisulphonate, Ci2H7N2(NH2)(S03)2Ba +
r^HzO, is easily soluble in boiling water, and on cooling, crystallises
Out in reddish-yellow needles.
Biazoazobenzenedisuljplionic acid is obtained from the foregoing acid by
the action of nitrous acid, and is precipitated from its alcoholic
solution by ether in dirty yellow needles, which carbonise easily when
heated. An azohe7izenedisulpJionic acid, SO3H.C6H4.N2.C6H4.SO3H, is
formed on heating it with alcohol.
The author finds that the above-mentioned azoamido-mono- and
di-sulphonic acids are identical with those prepared according to
Grassler's patent by heating azoamidobenzene with 3 to 5 times its
bulk of fuming sulphuric acid. The author also states that the
process for preparing azoamidobenzenemonosulphonic acid patented
by Grassier was described by himself as early as 1876, and that, more-
over, this process is valueless from a technical point of view.
Action of Paradiazobejizenesulphonic Acid on the Isomeric Toluidines.
— The general reactions (taking the chlorides as examples) are —
(i.) C6H4S03N-2 + C,H,.NH3C1 = C6H4(SO.H).N2.C,H6.NH2 + HCl,
(ii.) C6H4S03lSr2 + C7H7.NH3CI = C7H7.N0.CI + C6H4(S03H).NH2.
With orthotoluidine, the reaction takes place principally according to
(ii), orthodiazotoluene chloride and sulphanilic acid being the chief
products. With metatoluidine, reaction (i) plays the principal part,
azo-o-amidotoluene-p-benzenesulphonic acid forming the greater part
of the product. With paratoluidine, reaction (ii) alone takes place,
no trace of azo-p-aniidotoluene-j9-benzenesulphonic acid having been
found. The author notes here the incorrectness of the generally
received idea that in hydrated and amidated benzenes the jpara-covcL-
pounds are incapable of reacting with diazo-compounds to form
azo-compounds, because the hydrogen-atom in the para-position to the
OH or NH2 group is always the one acted on : parahydroxy-
benzoic acid and paradiazobenzenesulphonic acid, for instance, com-
bine to form azo-^-sulphobenzene-p-hydroxybenzoic acid,
C6H4(S03H).N2.C6H3(OH).COOH,
in which [SO3H : N = 4 : 1] and [OH : COOH = 1 : 4]. This acid
crystallises in pale yellow needles, easily soluble in boiling, sparingly
in cold water, and very much resembling the corresponding azo-acid
obtained from salicylic acid.
Pari.'diazohenzenesulphonic acid combines very readily with x- and
^-naphthylamine to form azoamidonaphthalenehenzenesul^lionic acid, no
secondary reactions taking place, as in the case of the toluidines and
aniline.
Azo-oL-amidonaplitlialeneparahenzenesulpTionic acid (Ber., 12, 224)
forms a potassium salt crystallising with SHgO, and a barium salt
also with 3H2O.
ORGANIC CHEMISTRY. 183
Azo-^-amidonaphthaleneparahenzenesulpJionic acid,
C6H4(S03H).N2.CioH6.NH2 [SO3H : N = 4 : 1] and [N : NH2 = 1:2],
prepared by acting on |S-naphthylaraine hydrochloride witli para-
diazobenzenesnlphonic acid, is obtained in yellowish-red needles or
groups of needles, slightly soluble in boiling water. It is very soluble
in alcohol, thus differing from its isomeride. It carbonises easily,
giving off naphthylamine. The potassium salt crystallises in yellowish-
red flakes with 7^H20.
Both these acids split up under the action of tin and hydrochloric
acid into the corresponding diamidonaphthalenes and sulphanilic acid.
Diamidonapkthale7ie from the a-acid crystallises in white needles or
small prisms, which quickly turn green, especially if moist. It is
easily soluble in alcohol, ether, and chloroform, sparingly in boiling
water ; its aqueous solution decomposes quickly. It has an extremely
burning taste, producing on the tongue soreness lasting for days. It
melts at 120° to a brown oil having an odour similar to that of
quinone. Ferric chloride produces a-naphthaquinone in a hydro-
chloric acid solution of this body. The hydrochloride crystallises in
white glistening flakes, easily soluble in hot water, almost insoluble in
hydrochloric acid. This diamidonaphthalene is almost certainly
identical with that obtained by Perkin (this Journal, 18, 181) from
azo-a-amidonaphthalene, and that which Liebermann and Ditfeler
prepared (Annalen, 183, 239) from a-amidonitronaphthalene.
Biamidona'phthalene from the /5-acid is equally soluble with its
isomeride in alcohol, ether, and chloroform, more sparingly so in hot
water, from which it separates in white rhombic plates (m. p. 95*^)
having a silvery lustre, soon turning to grey. Ferric chloride pro-
duces change of colour in its solution, but no quinone or other crys-
talline body could be detected. The chloride is easily soluble in
water, and is reprecipitated by hydrochloric acid. The author
assigns to the first mentioned diamidonaphthalene (from the a-acid,
as also Perkin's, and Liebermann and Dittler's), the formula
Ci„H6(NH2)2 [NH2:ISrH2=l : 4], and that from the/3-acid [NH2 : NH2=
1 : 2], and to Aiguar's (Ber.j 7, 307) a-diamidonaphthalene (m. p.
189"), [NH2 : NH2 = 1 : 4'], and to the same investigators )3-diamide
(m. p. 66°) LNH2 : NH2 = 1:1'].
With the isomeric amidonaphthalenesulphomc acids, paradiazobenzene-
sulphonic acid forms compounds analogous to those with the isomeric
naphthylamines.
Azo-a,-amidosulp7ionaphthalene--p-'benzene8ulphon')c acid,
NH2.aCioH6(S03H).N2.C6H4(S03H),
(the only one of these compounds which the author has investigated in
detail), is easily soluble in alcohol and water, insoluble in ether, and
colours silk and wool yellow. With barium it forms an acid salt,
(CifiHi2l^3S206)2Ba -h 8H2O, very sparingly soluble in boiling water,
and a neutral salt, (CifiHiiN3S206)Ba + T-JHsO, easily soluble in boil-
ing water. Treated with tin and hydrochloric acid, diamidonapJitha-
lenesulphonic and sulphanilic acids are produced.
When paradiazobenzenesulphonic acid acts on either of the isomeric
184 ABSTRACTS OF CHEMICAL PAPERS.
diamidobenzenes, nitrogen is evolved, and a brown gummy mass
results. If orthodiamidubenzene chloride be used instead of the free base,
small quantities of sulphaniUc acid and azimidoibenzene, C6H4<' | yNH,
are produced identical with that which Ladenburg obtained by acting
on orthodiamidobenzene with nitric acid.
B-Diamidobenzoic add, [COOH : NH2 : NH2 = 1:3:5], combines
directly with the diazo-acid to form azo-Tp-sulphobenzene-S-diamidoben-
zoic acid, C6H4(S03H).N2.C6H2(NH3)2.COOH. This acid is sparingly
soluble in water, alcohol, and ether, and decomposes very easily, even
on boiling with water. Treated with tin and hydrochloric acid,
it gives Rulphanilic acid and a new triamidobenzoic acid,
C6H2(NH3)3COOH [COOH : NH2 : NH3 : NH2 =1:2:3:5].
This acid crystallises from hot water in colourless compact crystals,
very sparingly soluble in alcohol, insoluble in ether, and having a
bitter taste. On attempting to distil it, it almost entirely carbonises,
but a small quantity of a base distils over, which may be triamido-
benzene. Sulphuric acid gives a salt, C7H9l!ir302,H2S04. Taking into
account the origin of this acid, and that the only other known
triamidobenzoic acid (Salkowsky, Annalen, 163, 12) has the formula
[COOH : NH, : NH2 : NH2 =1:3:4:5], the formula given above
must be the correct one. From this it would appear that the azo-acid
must have the formula —
C6H5(S03H).N : KC6H2(NH2)oCOOH [COOH : N : NH2 : NH^ =
1:2:3:5]. L. T. T.
Azylines. By E. Lippmann and F. Fleisnee (Ber., 15, 2136—2142).
— The authors give the name of azylines to a series of bodies obtained
by the action of nitric oxide on tertiary bases of the aromatic series,
and containing the tetrad-group ZiN — NUI. They intend also to try
whether similar bodies can be obtained from secondary amines, and
from amines belonging to the fatty series.
These bodies are obtained by passing nitric oxide into a solution of a
tertiary amine in alcohol or benzene, whereupon carbonic acid is freely
given oflF, and red crystals are deposited. They are insoluble in water,
soluble in hydrochloric acid with reddish-purple, in acetic acid with
emerald-green coloration. They crystallise from alcohol and benzene in
well-formed red crystals. Their fusing point descends as the molecular
weight ascends (except the propyl compound, which melts lower than
the butyl and amyl bodies). With the chlorides of platinum, gold, zinc,
cobalt, &c., they form double salts. By the action of stannous chloride,
or of phosphorus and hydriodic acid, unstable hydrogenised bodies
are produced, which, however, yield crystallisable platinochlorides.
Mineral acids decompose the azylines, splitting off ammonia. Picric
acid gives sparingly soluble crystalline salts. Bromine and iodine
readily yield substitution- products. The haloid ethers combine with
them at 100°. Nitrous acid produces nitroso-compounds, giving
Liebermann's colour reaction with phenol and sulphuric acid. The
following equation expresses the reaction in the case of dimethyl-
ORGANIC CHEMISTRY. 185
aniline, 2C8HnlSr + N2O2 = 2H2O + Ci6Hi8:N'4. The authors believe
the general constitutional formula to be RaN'.CeHa ! !N".N '. CeHs.NRg.
DimethylaniUneazyline, C16H18N4, first obtained by Frankland
(Annalen, 99, 342) fuses at 266°. By careful oxidation with potassium
permanganate in the cold, it yields carbonic and oxalic acids. This,
according to Wallach and Claissen's I'esearches (Ber., 8, 1237), tends
to show the correctness of the above formula. The picrate,
0i6Hi8N'4,C6H2(NO2)3OH + EtOH, forms green needles, which contain
alcohol of crystallisation. It decomposes at 100°.
Diethylanilineazyline, C20H26N4, forms red needles melting at 170°,
deliquescent in chloroform, and sparingly soluble in cold alcohol. The
picrate, C2oH26l^4,[2C6H2(N03)2.0H], crystallises in yellow needles,
sparingly soluble in alcohol and ether.
DipropylanilineazTJUne, C24H34N4, fuses at 90°. The crystals belong
to the rhombic system (a : 6 : c = 1 : 0'629 : 0913), their principal
faces being coP, ooPcx), Fco.
Dipropylaniline boils at 240 — 242°, and forms a yellow crystalline
platinochloride, which is decomposed by water.
Dihutylanilineazyline, C28H42N"4, crystallises in needles, and fuses at
158°.
Diamylanilmeazyline, C32H50N4, fuses at 1 15°. L. T. T.
Phenylenethiocarbamides. By E. Lellmann (Ber., 15, 2146 —
2147). — Orthodiamidobenzene thiocyanate, formed by evaporating an
aqueous solution of orthodiamidobenzene hydrochloride with ammo-
nium thiocyanate, is further heated in an air-bath at 120 — 130°, and
the dry residue extracted with water; orthophenylenefMocarbamide,
C7H6N2S, remains undissolved. This body is easily soluble in alcohol,
sparingly so in water, and crystallises in violet plates. It melts at
about 280°, but becomes brown at 260°. Metadiamidobenzene gives
a similar body which, with the corresponding para- compound, is
now under investigation. The author proposes the constitutional
formula C6H4<JJ|[>CS for these bodies. L. T. T.
Formation of Phenylxanthogenamide. By E. Bamberger (Ber.,
15, 2164— 2166).— In a previous paper (Abstr., 1882, 394) the author
described some crystalline bodies obtained by heating phenylthio-
carbimide with various acid amides in alcoholic solution. He now
finds that in all cases the body formed is plienylxanthogenamide, and
that the character of the acid amide has no influence on the reaction.
L. T. T.
Aromatic Isophosphines. By A. Michaelis and L. Gleichmann
(Ber., 15, 1961 — 1964). — In the course of the investigation of the
mixed aromatic phosphines, the authors endeavoured to obtain the
corresponding phosphonium iodides without the use of the zinc alkyls,
by heating together alkyl iodides, phosphenyl chloride, and metallic
zinc, and obtained good results. ~ On substituting benzyl chloride for
the alkyl iodides, however, a new class of bodies, the isophosphines,
were obtained.
Isohenzylphenylphosphine is prepared by gently warming a mixture
VOL. XLIV. O
186 ABSTRACTS OF CHEMICAL PAPERS.
of 2 parts benzyl chloride and 1 part phosphenyl chloride, with granu-
lated zinc in a vessel provided with a reflux condenser; a violent
reaction takes place, and is completed without further heating. The
excess of benzyl chloride is then decanted, the residual zinc compound
decomposed by soda, and the isophosphine purified by solution in
alcohol, precipitation by water, and crystallisation from glacial acetic
acid, from which it separates in long, fine, interlaced needles (m. p.
70 — 71°), of the formula C13H13P or C25H24P2. Its properties render it
improbable that it is an ordinary secondary phosphine. It does not
unite with the alkyl iodides, nor is it changed by heating with them and
zinc oxide in sealed tubes. It unites with acetic anhydride, forming an
unstable compound, completely resolved into its components by long
exposure to air or by heating at 60 — 70°. It dissolves in benzyl chloride,
but is not further affected by it even on heating at 200° for 15 hours.
Strong oxidising agents convert it into benzoic and phosphoric acids ;
on heating it with soda-lime, phosphoric acid, benzene, and toluene,
are formed ; nascent hydrogen does not act on it. In an atmosphere
of chlorine, isobenzylphenylphosphine liquefies to a viscous yellow
mass, from which, after treatment with soda to remove the chlorine
taken up, an oxide, C13H13PO or C25H29P2O2 (m. p. 154 — 155°) is
obtained, crystallising from acetic acid or alcohol in long, colourless,
matted needles. It is insoluble in alkalis, and is similarly indifferent
to reagents. Isobenzylphenylphosphine would appear to be closely
related to the dibenzylphosphine, C14II15P, obtained by Hofmann
(Ber., 5, 100) by heating together benzyl chloride, phosphonium iodide,
and zinc oxide.
IsotolylbenzijlpJwspMne is prepared in a manner similar to isobenzyl-
phenylphosphine, and closely resembles it in properties ; it crystal-
lises in light, colourless, felted needles (m. p. 187°) of the formula
CuHiaP or C27H28P2. A. J. G.
Phenylarsine Sulphides. By C. Schulte (Ber., 15, 1955 —
1960). — Phenylarsine monosulpMde, AsPhS, is obtained by the action
of sulphuretted hydrogen on phenylarsine oxide or chloride ; it crys-
tallises in fine white needles, is sparingly soluble in benzene, alcohol,
and ether, readily soluble in hot benzene and in carbon bisulphide.
Nitric acid oxidises it to phenylarsenic acid. It is but slightly soluble
in ammonia, but dissolves in hot soda, and is reprecipitated by hydro-
chloric acid. It is sparingly soluble in ammonium monosulphide or
Bulphydrate, but dissolves readily in the yellow sulphide ; addition of
an acid to the solution precipitates phenylarsine sesquisulphide. The
monosulphide melts at 152° to a yellow liquid, and on dry distillation
in a stream of carbonic anhydride, yields arsenic sulphide and tri-
phenylarsine. By the action of mercury-ethyl, it is converted into
phenyldiethylarsine and mercury sulphide.
Phenylarsine sesquisulphide, AsPh2S3, is best prepared by the action
of hydrogen sulphide on an ammoniacal solution of phenylarsenic acid,
and subsequent precipitation with hydrochloric acid. When crystal-
lised from benzene, it forms pale yellow transparent prisms, readily
soluble in benzene and carbon bisulphide, moderately in boiling glacial
acetic acid, sparingly soluble in hot alcohol and ether. It melts at
ORGANIC CHEMISTRY. 187
130° to a clear liquid, and decomposes at higher temperatures. Nitric
acid .converts it into phenylarsenic acid. It is nearly insoluble in
ammonia, sparingly soluble in soda, but dissolves readily in yellow
ammonium sulphide.
Disodium phenylsulpli arsenate, AsPhS(SNa)2,6H20, is obtained by
dissolving phenylarsine mono- or sesqui-sulphide in sodium sulphide
containing excess of sulphur; on evaporation and addition of absolute
alcohol to the thick liquid, it separates in slender needles. It is readily
soluble in water, sparingly in alcohol. A. J. Gr.
Arsenobenzene, Arsenonaphthalene, and Phenylcacodyl.
By A. M1CHAELI& and C. Schulte (J9er., 15, 1952 — 1955). — In addi-
tion to the method previously given (Abstr., 1881, 722), arsenoben-
zene can be prepared by the reduction of monophenylarsenic acid. It
reacts readily with sulphur, yielding the phenylarsine sulphides (pre-
ceding Abstract). If fused with excess of sulphur, it gives arsenic
sulphide and phenyl sulphide.. When heated with mercury ethyl in
sealed tubes at 150°,. it gives mercury and diethylphenylarsine.
Attempts to reduce arsenobenzene to phenylarsine, AsPhHg, have so
far failed, as when heated with alcoholic ammonium sulphide it yields
benzene, arsenic sulphide, and metallic arsenic, whilst hydriodic acid
has no action in the cold^and on heating, gives benzene, arsenic iodide,
and metallic arsenic.
Arseno7ia,phthalene, (CioH7)2As2r is obtained by the reduction of
naphthylarsineoxide as a powder composed of slender yellow needles
(m. p. 221°) ; it is sparingly soluble in alcohol, benzene, carbon bisul-
phide and chloroform, insoluble in water and in ether. It unites with
chlorine, forming naphthylarsine chloride ; with sulphur, forming
naphthylarsine sulphide ; and is oxidised by nitric acid to naphthyl-
arsenic acid. On dry distillation, it decomposes, with formation of
naphthalene and arsenic, and separation of much carbonaceous matter.
Phenylcacodyl, As2Ph4, as obtained by the reduction of diphenyl-
arsine oxide with phosphorous acid, forms a white crystalline mass
melting at 135°, and soluble in alcohol, less readily in ether. It
quickly oxidises in the air, forming diphenylarsenic anhydride. With
chlorine it forms diphenylarsine trichlaride, AsPhaCla. It yields
arsenic and triphenylarsine on dry distillation. A. J. Gr.
Reduction of Orthonitrobenzaldehyde. By P. Friedlander
and R. Heneiques (J5er., 15, 2105— 2110).— Rudolph {Ber., 13," 310)
obtained a base, C^^<^ \\ , by the reduction of orthonitrobenzalde-
hyde (obtained by the nitration of benzaldehyde, and containing the
meta-compound). The authors have repeated and extended these
experiments, employing jture orthonitrobenzaldehyde, obtained from
ethyl nitrocinnamate (Abstr., 1882, 840). They are unable to confirm
Rudolph's results, having obtained a body C7H5NO.
If soda solution in excess be added to the product of the action of
tin and acetic acid on orthonitrobenzaldehyde, and the whole distilled
with steam, scarcely anything passes over, but anthranilic acid is
0 2
188 ABSTRACTS OF CHEMICAL PAPERS.
found in the residue. If, however, the acid mixture is neutralised
with sodium carbonate and distilled with steam, an oil is obtained of
the formula C7H5NO, which the authors propose to call anthranil.
Anthranil is a colourless mobile liquid, slightly soluble in hot water,
easily so in the usual solvents. It does not solidify at — 18° C, has
an odour resembling that of benzaldehyde, and of the vegetable bases,
and is easily volatile with steam. Exposed to air and light, it becomes
brown and resinous. It begins to boil at 210 — 215°, but decomposes
at the same time. Anthranil has feeble basic properties, dissolving
easily in concentrated mineral acids, but is reprecipitated on adding
water. Its salt« and double salts are very unstable, the only com-
pound obtained being C7H5NO,HgCl2 ; this compound fuses at 174**,
and is readily decomposable. Dilute soda dissolves anthranil slowly
in the cold, quickly on heating ; ammonia requires a temperature of
120°, and water has scarcely any action at 130°. In these reacticms
nnthraniUc acid is produced : C7H5NO + H2O = NHa.CeHi.COOH.
Boiled with acetic anhydride and mixed with H2O, it gives acetylan-
tJirmdlic acid, C7H6N025^. These reactions render it probable that
anthranil is an internal anhydride of anthranilic acid, having one of
CO C.OH
the two following formulae : C6H4<( | or C6H4^ || . No halogen-,
^NH ^N
methyl-, or nitroso-substitution-compounds could be obtained. Fur-
ther reducing action gave an amorphous compound, probably a con-
densed amidobenzaldehyde ; also, small quantities of amidobenzyl
alcohol.
With zinc and hydrochloric acid in alcoholic solution, an amorphous
substance was obtained, which dissolved in hydrochloric acid, but was
partly reprecipitated by water, entirely by sodium acetate. It bears
great resemblance to the amorphous meta- and para-amidobenzalde-
hyde, and is probably n corresponding condensed orthamidobenzalde-
iiyde. This body is undergoing further investigation. L. T. T.
Metahydroxybenzaldehyde and some of its Derivatives. By
F. TiEMANN and E. Ludwig (Ber., 15, 2043— 2059).— Metahydroxy-
benzaldehyde has been obtained by Sandemann {Ber., 14, 969) by
partial reduction of metahydroxybenzoic acid with sodium -amalgam.
It is hest obtained, however, from metamidobenzaldehyde by the
diazo-reaction. For this purpose metanitrobenzaldehyde, prepared by
the method of Friedlander and Henriques (Ber., 14, 2802), is mixed
with exactly the necessary quantity of zinc chloride and hydrochloric
acid, and after the reaction is finished a solution of potassium nitrite
is added, the mixture being kept cold. A double salt, having the
composition (COH.C6ll4.N2.Cl)2,SnCl4, then separates, and this on being
decomposed with water easily gives metahydroxybenzaldehyde. The
latter crystallises in white needles, melting at 104°. It yields metahy-
droxybenzoic acid on fusion with potash. The potassium compound
suspended in ether and heated with acetic anhydride, yields the
acetyl-derivative, an oil boiling at 263°. Metahydroxybenzaldehyde,
wheu boiled for some hours with excess of acetic anhydride, yields a
compound, CH(OAc)2.C6H4.0Ac, melting at 76°.
ORGANIC CHEMISTRY. 189
MethylmetaJiydroxyhenzaldeJiyde is a liquid boiling at 230°.
Acetumetacoumaric acid is prepared by heating a mixture of metahy-
droxybenzaldehj^de, anhydrous sodium acetate, and acetic anhydride.
It crystallises from water in white needles melting at 151°. On
heating it with solution of potash, it yields metacoumaric acid, which
crystallises from hot water in white prisms melting at 191". This
acid can also be obtained by the diazo-reaction from metamidocin-
namic acid. On treatment with sodium-amalgam, it is reduced to
hydrometacoumaric acid, which crystallises in long needles, melting at
111°. .
Methylmetacoumaric acid melts at 115°, and methylhydrometacou-
marie acid at 51°.
Nitration of Metahydroxyhenz aldehyde. — When this aldehyde is
warmed with 10 parts of nitric acid (sp. gr. 1*1), and the product
poured into water, a yellow crystalline mass separates out, which is
partly soluble in benzene and chloroform. After being recrystallised
from water, the portion insoluble in benzene melts at 166°, and is
termed by the author ^-nitrometahydroxybenzaldehyde. The portion
soluble in benzene is separated by a mixture of benzene and light
petroleum into two bodies, the less soluble melting at 138°, termed the
7-corapound, and the other, melting at 128°, the a-compound. These
are all mononitro-derivatives, and easily yield methyl ethers.
Nitration of Metliylmetahydroxyhenzaldehyde. — On nitrating this com-
pound under diiferent conditions, a mixture of two isomeric dinitro-
compounds is always obtained. These may be separated by boiling
water, in which the i8-compound (m. p. 155°) is almost insoluble, the
a-compound (m. p. 110°) being easily soluble.
Constitution of the Nitro-derivatives. — Four mononitro-derivatives of
metahydroxybenzaldehyde are theoretically possible, in which the NOo-
group occupies respectively the two ortho-, the para-, and the meta-
position with reference to the hydroxyl. According to the known
laws of substitution in phenol-like bodies, the authors think it probable
that the three nitro-derivatives prepared by them are those in which
the NOa-group occupies the three former positions. In this case the
methyl ethers should, by reduction and the diazo-reaction, yield
respectively /3-metamethoxysalicylaldehyde (i?er., 14, 2022), vanillin,
and a-metamethoxysalicylaldehyde. Now, the so-called 7-compound
yields by this treatment a body smelling like vanillin, and the authors
therefore ascribe to it the constitution C6H3(COII)(OMe)(N02)
[1:3:4]. The jS-compound yields, however, a body which does not
agree in its properties with either of the metamethoxysalicylaldehydes,
and therefore the authors think that it probably has the constitution
C6H3(COH)(OMe)(N02) [1:3: 5]. The a-compound does not yield
any vvell-detined produce. E. H. R.
New Derivatives of Salicylaldehyde. By H. Yoswinckel
(Ber., 15, 2021 — 2027). — Tiemann and Reimer have shown (Bar., 9,
1268; 10, 1562) that, by the chloroform reaction, salicylic acid yields
both para- and ortho-aldehydosalicylic acids, but parahydroxybenzoic
acid only one product, namely, orthoaldehydosalicylic acid. Applying
the same reaction to salicylic and parahydroxybenzaldehydes, the author
190 ABSTRACTS OF CHEMICAL PAPERS.
has obtained analogons results. In the former case two bodies are
formed, the one easily, the other sparingly, soluble in light petroleum.
The former, a-hydroxyisophthalaldehyde,
C6H5(OH)(COH)2 [OH : COH : COH = 1:2:6],
crystallises from water in tufts of needles raeUino^ at 88°, the latter,
^-hydroxyisopUhalaldehyde, CeH^COHXCOH), [OH : COH : COH =
1 : 2 : 4], in long needles melting at 108°. When parahydroxybenz-
aldehyde is used, only one body is formed, namely, the a-compound.
The constitution of these dialdehydes is determined by fusing them
with potash, whereby they are converted into hydroxy isophthalic acid.
Attempts to form bodies containing a third COH-group proved
fruitless.
Methylsalicylaldehyde. — The author finds that the reaction between
the sodium compound of salicylaldehyde and methyl iodide is com-
pleted by digestion on the water-bath. By removing every trace of
salicylaldehyde, the methyl- derivative is obtained in prisms melting
at 35°.
Salicylaldehyde c2/a*2%cZrm, C6H4(OMe)[CH(OH).CN] [1 : 2]. This
compound is easily obtained by the action of potassic cyanide and
hydrochloric acid on salicylaldehyde dissolved in ether. It separates
from benzene in colourless transparent crystals melting at 71°.
Attempts to obtain the corresponding amide were unsuccessful, and
orthomethoxymandelic acid was obtained only as a syrup in an impure
condition. By the action of the equivalent quantity of a 10 per cent,
solution of ammonia in closed vessels at 60 — 70", the compound
(OMe.C6H4.CH.CN)2N'2H, is produced. It melts when freshly pre-
pared at 123°, but soon alters on exposure to air.
Nitrile of orthomethoxypheii/ylphenamido acetic acid^
C6H4(OMe)[CH(NHPh).CN [1 : 2].
This body is easily obtained by the action of aniline on the cyanhydrin
of methylsalicylaldehyde. It forms colourless six-sided tables melting
at 61°.
Nitromethylsalicylaldehyde, CeHsfNOs) (OMe) .COH. — The author has
prepared this compound by dissolving the aldehyde in fuming nitric
acid, and precipitating by water. It forms fine white needles melting
at 88°. The author is engaged in investigating its constitution.
E. H. R.
Isovanillin. By R. Wegscheider (Monafsh. Ghem., 3, 789 — 795).
This compound is formed, together with others, by the action of dilute
hydrochloric acid on opianic acid. When these two substances are
heated together in a sealed tube at 160 — 170°, a mixture of dark and
nearly colourless crystals is obtained, together with a reddish-yellow
liquid ; and on filtering, boiling the crystals with water, and filtering
again, a black mass remains undissolved, and the light red filtrate, boiled
with animal charcoal and evaporated, yields crystals of isovanillin. On
further evaporation, a small quantity of unaltered opianic acid separates
out, and the last fraction gives with ferric chloride a green colour,
probably due to the formation of a trace of protocatechuic aldehyde.
Isovanillin recrystallised from water forms anhydrous prisms
ORGANIC CHEMISTHY. 191
having a vitreous lustre, softening at 115°, melting at 116 — 117°.
These crystals are monoclinic, having the axial ratio a : 6 : c =
0-6370 : 1 : 0-9228; /3 = 96-9. Observed faces coFSo, OP, 2Pc^,
coP, + p. Habit, tabular by predominance of the clinopinacoid.
Face of cleavage Poo.
Iso vanillin is not much more soluble in caustic soda than in water,
but dissolves easily in ammonia and still more in potash-lye, forming
yellow solutions. From concentrated alkaline solutions, it is precipi-
tated by acids. Strong sulphuric acid colours it yellow, then yel-
lowish-red, and slowly dissolves it, both at ordinary temperatures and
at 100° ; on raising the temperature to the boiling point of the acid, a
blood-red colour is produced. The aqueous solution is neutral, and
gives no reaction with ferric chloride or lead acetate. It reduces
ammoniacal silver nitrate very slightly in the cold, more abundantly
at boiling heat.
Isovanillin is inodorous in the cold, but when heated, and especially
when its aqueous solution is boiled, it emits a pleasant odour like that
of vanilla, or fennel, or anise-oil. When heated on platinum-foil, it
gives off a stronger odour like that of vanilla, and still more like that
of burning opianic acid.
It decomposes slightly when sublimed, and volatilises to a small
extent when its aqueous solution is distilled. Like vanillin, it forms
soluble compounds with alkaline bisulphites, and may be separated
from solution in ether by agitation with strong solution of sodium
hydrogen sulphite.
If the action of hydrochloric acid on opianic acid be carried beyond
the point at which isovanillin is formed, the product subsequently
obtained is protocatechuic aldehyde, a result which, when viewed in
connection with the fact that isovanillin must diifer in constitution
from vanillin, shows that the former must be represented by the
formula C6H3(COH)(OH)(OMe) [1:3: 4].
In the formation of isovanillin from opianic acid, as well as in that
of methylnoropianic acid from opianic acid, and of methylnorhemi-
pinic acid from hemipinic acid, it appears that whenever a single
methyl-group is detached from hemipinic or opianic acid, the meth-
oxyl-gfoup attacked is always that which stands in the ortho-position
relatively to the carboxyl. H. W.
Preparation of the Three Isomeric Nitracetophenones. By
H. Gevekoht (Ber., 15, 2084 — 2086). — By acting on ethylic sodace-
toacetate with the three isomeric nitrobenzoic chlorides {Ber., 12, 351),
the three corresponding ethylic nitrobenzacetoacetates are produced,
and these on saponification yield the three nitracetophenones. The
meta- and para-nitracetophenones thus produced agree exactly with
those obtained in other ways. The ortho- compound is now for the
first time obtained pure. It is a pale yellow oil, which can be distilled
in a vacuum, and does not solidity at — 20°. It is easily reduced by
tin and hydrochloric acid to the corresponding amido-compound,
which is a pale yellow oil possessing basic properties, and capable of
being distilled unchanged in a vacuum. Jl^. H. R.
192 ABSTRACTS OF CHEMICAL PAPERS.
Action of Cyanogen Chloride on Amido-Acids. By J. Traube
(Ber., 15, 2110 — 2122). — The author hoped in this way to obt-ain cyan-
amido -acids, none of which have hitherto been known in the free state.
Cyanogen chloride acts but very sh'ghtly on an aqueous solution of
alanine, producing small quantities of lacturamic acid. When a stream
of cyanogen chloride is passed through fusing sarcosine, water is
evolved, and methylhydantoin is produced, as also an anhydride,
formed by the abstraction of one molecule of water from two mole-
cules of sarcosine. Sarcoeine-anhydride, CeHjaNzOs, crystallises in
hexagonal colourless plates, melting at 143 — 146° : it is easily soluble
in water, alcohol, and ether : it has a bitter taste, and is reconverted
into sarcosine by dilute hydrochloric acid. This anhydride differs
from sarcosine in giving no crystalline compound with zinc chloride,
and by its double platinochloride, (C6Hi2N203)2,H2PtCl€, containing no
water of crystallisation.
Cyanogen chloride acts very readily on an alcoholic solution of
metamidobenzoic acid, and if the product of the reaction is at once
poured into a large quantity of water, metacyanamidobenzoic acid is
produced — a secondary reaction sets in very quickly if the alcoholic
solution is allowed to stand before dilution.
Metacyanamidohenzoic acid, CN.NH.C6H4.COOH, crystallises in flat
white rounded needles, containing J mol. H2O : it is almost insoluble
in cold, moderately soluble in boiling water : very soluble in boiling
alcohol, ether, and chloroform, sparingly so in benzene. Cyanamido-
benzoic acid begins to decompose at 140°, but does not fuse below 200°,
when gas is evolved. Its taste is decidedly acid, and it decomposes
carbonates. When heated at 140° with solution of barium hydroxide,
it is decomposed into amidobenzoic acid, ammonia, and carbonic anhy-
dride. Boiling it with water causes no decomposition, and even
strong soda solution is slow in its action. Acids decompose it. much
more readily. Most of its salts are easily soluble, but the lead salt
forms a white flocculent precipitate, soluble in excess of lead acetate
and in boiling water. Ferric chloride produces a pale yellow amor-
phous precipitate ; silver nitrate a white gelatinous one insoluble in
cold water, soluble in ammonia: it is a mixture of the salt,
CN.NH.CeHi.COOAg, with small and varying quantities of
NAg(C]Sr).C6H4.COOAg.
A brown amorphous copper salt was also obtained. This production
of a brown copper salt appears to be a common property of the cyan-
amides, and serves to distinguish cyanamido benzoic acid from all other
known derivatives of metamidobenzoic acid.
Heated alone, metacyanamidobenzoic acid decomposes slowly at
140°, quickly at 210 — 220°, evolving cyanic acid freely, and leaving a
white amorphous product insoluble in water, alcohol, ether, and hydro-
chloric acid, but easily soluble in concentrated sulphuric acid, from
which it is reprecipitated on dilution with water. Analyses show the
composition of this body to be a mixture of bodies of the general for-
mula mC8H6N202 — nCNOH. This decomposition appears to be
analogous to that observed by Bassler (/. pr. Chem., 16, 125) in the case
of ethyl cyanocarbamate. A similar mixed product is obtained by the
ORGANIC CHEMISTRY. 193
action of cyanogen chloride on fusing metamidol)enzoic acid, but here
CO(NH.C6H4.COOH)2 is also amongst the products of the reaction.
With dilute hydrochloric acid, a similar reaction takes place, as in
the case of cyanocarbamic acid compounds, metauramidohenzoic acid
(^ being formed.
^ Hydrogen sulphide is absorbed very slowly by raetacyanamidoben-
zoic acid, but with ammonium sulphide a rapid and quantitative
reaction takes place, , tJiiouramidohenzoic acid, identical with that
obtained by Arzruni (this Journal, 24, 570), being produced.
TJiiouramidohenzoic add crystallises in groups of needles melting at
187°, and at the same time evolving ammonia and hydrogen sulphide,
and leaving products free from sulphur.
Several of the salts of metacyanamidobenzoic acid decompose
slowly in contact with boiling water. A concentrated solution of
barium cyanamidobenzoate heated for several days on the water-bath,
gives off ammonia and leaves the barium salt of an acid corresponding
tolerably closely with the formula C24Hi7N507. It is easily soluble in
ether, alcohol, and water, and gives insoluble zinc, lead, copper, and
mercury salts.
No addition-product of ammonia could be obtained from cyanamido-
benzoic acid. By digesting it with aniline, phenylbenzocreatinCf
NHPh.CNH.NH.CeH^.COOH,
is produced. Phenylhenzocreatine is nearly insoluble in ether and
alcohol, easily soluble in boiling water, from which it crystallises in
compact groups. It fuses with decomposition at 165° ; it forms com-
pounds both with acids and with alkalis, and gives a yellowish-red
platinochloride.
When cyanamidobenzoic acid is heated with acetamide, it gives a
body, C30H29N5O6, only soluble in fuming nitric and concentrated sul-
phuric acids. The reaction is not analogous to that of acetamide and
phenylcyanamide, studied by Berger (Abstr., 1881, 810).
Paracyanamidophenylacetic acid is produced by the action of cya-
nogen chloride on an alcoholic solution of paramidophenylacetic acid.
It crystallises in colourless glittering plates, very easily soluble in
water, ether, and alcohol, and fusing with decomposition at 134°. It
is a strong acid, and gives a brown copper salt which, like that of
metacyanamidobenzoic acid, quickly blackens in contact with water.
The brown salt differs from that of the meta-acid in being very soluble
in alcohol.
Paracyanamidophenylacetic acid is very unstable, decomposing even
when recrystallised. Evaporated with a very small quantity of hydro-
chloric acid, it is converted into para-uramidophenylacetic acid.
Para-uramidophenylacetic acid crystallises in compact groups con-
taining IJ mol. H2O, which are given up at 110°. It is easily soluble
in alcohol and ether, tolerably so in water. It fuses with decomposi-
tion at 174°. With the alkalis and alkaline earths it forms soluble
salts ; with copper, lead, zinc, and mercury insoluble. Ferric chloride
gives a characteristic yellowish-red precipitate.
Cyanogen chloride has no action on tyrosine or hippuric acid in
alcoholic solution. L. T. T.
194 ABSTRACTS OF CHEMICAL PAPERS.
Contributions to the Knowledge of Meta-uramidobenzoic
Acid and Carbamido-dibenzoic Acid. By J. Tradbe (Ber., 15,
2122 — 2129). — This investigation was undertaken in order to clear up
the divergent statements of Griess (Ber., 2, 147) and Menschutkia
(Annalen, 153, 85) on this subject. The author substantially confirras
Menschutkin's remarks on uramidobenzoic acid, and believes Griess's
preparation not to have been perfectly pure. Crystallised uramido-
bezoic acid, NHa.CO.NH.CeHi.COOH, contains 1 mol. H^O ; the
anhydrous acid is soluble in 139 parts of 96 per cent, alcohol ; and in
786 parts of ether.
Uramidobenzoic acid decomposes at 200°, producing a body to which
CO NH
Menschutkin gave the formula C6H4<^-j^tt^ TO-^' *^^^ Griess,
CO(NH.C6H4.COOH)2.
The author finds that Griess's formula is the correct one. This de-
composition would be represented by the equation —
2(NH2.CO.NH.C6H4.COOH) = CO(NH.C6H4.COOH)2 + COCNHJa.
He has also obtained this body according to the two equations —
(i.) NH,.CO.NH.C6H4.COOH + NH^.CeHi.COOH =
CO(NH.C6H4.COOH)2 + NH3, and
(ii.)2(NH3.C6H4COOH) + CO(NH2)2=CO(NH.C6H4.COOH)2 + 2NH3.
The latter equation explains at once the bad yield of uramidobenzoic
acid by Griess's method of fusing together equal molecules of urea
and amidobenzoic acid. The author therefore recommends Mens-
chutkin's method of preparing this acid by the action of potassium
cyanate on aqueous amidobenzoic acid hydrochloride. The yield is
nearly quantitative, and the acid nearly pure. • L. T. T.
Diamidociimic Acid. By E. Lippmann (Ber., 15, 2144 — 2146).
— By the reduction of dinitrocuwic acid {Monatsh., 1, 822), the author
obtained diamidocumic acid, C6H2Pr^(NH2)2.COOH, crystallising from
ether in yellowish plates melting at 192". Crystallised from water it
contains 1 mol. H2O, which is given ofE at 100°. The silver salt,
CioHi3N202Ag + H2O, is slightly soluble in water, and decomposes
readily. Diamidocumic acid hydrochloride, CioHuN202,HCl + H2O,
crystallises in pale brown prisms, soluble in water, but reprecipitated
on the addition of hydrochloric acid. No hydroxy-acid could be ob-
tained by the action of nitric oxide. L. T. T.
Constitution of the Halogen Cinnamic Acids. By J. Plochl
(Ber., 15, 1945 — 1946). — The position of the bromine-atom in the
side-dhain of the two bromocinnamic acids has never been determined
with certainty. Glaser (Annalen, 143, 330) termed the acid melting
at 131° the a-acid, and that melting at 120° the /S-acid, but did not
determine their constitution. With the chlorocinnamic acids (Jutz,
ORGANIC CHEMISTRY. 195
Abstr., 1882, 1073) tlie acid of highest melting point (142°) was also
termed the a-acid.
The author has endeavoured to settle the question by sjnthesising
an acid of the formula Ph.CH ! CCl.COOH, and has effected this by
heating a mixture of sodium monochloracetate, acetic anhydride, and
benzaldehyde, when an acid melting at 142° and agreeing in all its
other properties with Jutz's a-chlorocinnamic acid, was obtained.
(y8-Chlorocinnamic acid, unlike yS-bromocinnamic acid, does not
change into the a-acid even by repeated distillation, so that molecular
interchange was not likely to have occurred at the low temperature
[100 — 110°] of the reaction.) The supposition of Barisch (Abstr.,
1880, 43) that the acid of (S-position had the highest melting point is
thus shown to be erroneous. A. J. G.
Hydrocinnamic and Cinnamic Acids. By S. Gabriel (5er.,
15, 2291 — 2301). — Metanitroparamidohydrocinnamic acid (m. p. 145")
is converted into diamidohydrocin7iamic acid by reduction with tin and
hydrochloric acid. The hydrochloride of the new acid, although
freely soluble in water, is sparingly soluble in strong hydrochloric
acid, Diamidohydrocinnamic acid is deposited from a hot aqueous
solution in transparent crystals containing 1 mol. H2O, which is
expelled at lOO''. The anhydrous acid (m. p. 143°) is freely soluble in
glacial acetic acid and in hot alcohol.
Bromacetoparaviidohydrocinnamic acid is deposited in colourless
needles (m. p. 160°), when bromihe- water is added to a warm solution
of paracetamidohydrocinnamic acid. The crystals are soluble in
ether, warm alcohol, benzene, and acetic acid. The acetic group is
expelled from this compound by strong boiling hydrochloric acid, the
hydrochloride of bromamidohydrocinnamic acid being formed. The
free acid, obtained by the cautious addition of ammonia to the hydro-
chloride, melts at 104-5°. On adding sodium nitrite to an alcoholic
solution of the hydrochloride, diazoamidohromhydrocinnamir, acid,
(C6H3r.C.>H4.C00H)2N3H, is deposited in brown-coloured needle-
shaped crystals. It is decomposed by hydrochloric acid, yielding
metahromhydrocinnamic acid, C6il4Br.C2H4.COOH. This acid is depo-
sited from an acetic acid solution in glistening prisms (m. p. 75°),
soluble in alcohol, ether, benzene, chloroform, carbon bisulphide, and
hot water.
The nitrocinnamic acids can be converted into bromocinnamic acids,
by acting on the nitro-acid with freshly precipitated ferrous oxide,
which reduces it to the amido-acid. From the amido-acid, the diaz(<-
compound is prepared, and this is converted into the bromocinnamic
acid by the action of hydrobromic acid.
OrtJbohromocinna'niic act'c? crystallises in needles or scales (m. p. 212°),
soluble in hot alcohol, acetic acid, and ether. When treated with
hydriodic acid and phosphorus, it yields orthobromhydrocinnamic
acid melting at 98°. This acid is soluble in ether, alcohol, benzene,
acetic acid, and chloroform. Metabromo cinnamic acid forms pale-
yellow needles, melting at 178°, and soluble in ether, alcohol, acetic
acid, and also in hot benzene, chloroform, or carbon bisulphide. Para-
hromocinnainic acid also crystallises in needles of a pale-yellow colour,
196 ABSTRACTS OF CHEMICAL PAPERS.
which melt about 252". An aqueous solution of paradiazocinnamic
acid decomposes at 100°, apparently yielding paracoumaric acid.
w. c. w.
Derivatives of Cinnamic Acid. By E. Erlenmeyer (Ber., 15,
2159 — 2160). — From the results of the further study of this subject,
the author draws the following conclusions: — (1.) Phenyldichloro-
propionic acid prepared by the action of hydrochloric acid on Glaser's
phenyl chlorolaciic acid, is identical with that formed by the addition
of chlorine to cinnamic acid. (2.) The phenylchlorobrovwpropionvi
acid, obtained by the action of hydrobromic acid on Glaser's phenyl-
chlorol actio acid, is isomeric but not identical with that obtained by
acting on phenylbromolactic acid with hydrochloric acid. When
boiled with water, the former gives chlorostyrol, the latter bromostyrol.
(3.) The phenylbromolactic acid, prepared by the addition of hypo-
bromous acid to cinnamic acid, is identical with that produced by
boiUng phenyldibromopropionic acid with water. (4) The halogen^
cinnamic {phenyl-halog en-acrylic) acids of higher fusing point contain
the halogen in the a- position, those of lower fusing point in the
j8-position. L. T. T.
Orthamidophenylpropiolic Acid and its Derivatives. By
A. Baeye£ and F. Bloem {Ber., 15, 2147 — 2155). — Orthamidophenyl-
propiolic acid, NH2.C6Ht.C : C.COOH, has been obtained by the authors
by reducing orthonitrophenylpropiolic acid with ammonia and ferrous
sulphate. It crystallises in pale-yellow microscopic needles, almost
insoluble in water, chloroform, and light petroleum ; sparingly soluble
in ether, rather more so in cold alcohol. Boiling alcohol dissolves it
freely, but it does not separate out on cooling, or on the addition of
water. Heated to 125 — 130°, it decomposes with stormy evolution of
carbonic anhydride, leaving a resinous residue, from which traces of
orthamidophenylacetylene are extracted by acids. If boiled with
water, it is decomposed, orthamidoacetophenone passing over with the
steam. When boiled with potash, the acid gives a characteristic red
colour on the addition of hydrochloric acid ; excess of hydrochloric
acid destroys this colour, but it is reproduced on adding alkali. The
potassium, sodium, and ammonium salts are very soluble, the barium
salt less so. The yellowish- white insoluble silver salt decomposes
when exposed to the light and air, and explodes on heating. The
ethyl salt crystallises in yellow needles, melting at 55°.
Boiled with dilute hydrochloric acid, amidophenylpropiolic acid
gives <^-chlorocarhostyril, CgileNOCl, crystallising in colourless needles,
melting at 24b°, and subliming at a higher temperature. In a similar
way, fi-hromocarhostyril, colourless needles melting at 266°, and
'^-iodocarhostyril, melting at 276°, can be obtained; both sublime
unchanged. It being probable from the investigations of Friediander
and Ostermaier (Ber., 15, 332) that carbostyril is a-hydroxyquinoline,
the authors acted on the chloro-derivative with phosphoric chloride,
and succeeded in obtaining a dichloroquinoline, Cg £15^012, insoluble in
water, easily soluble in alcohol, ether, benzene, and chloroform, and
ORGANIC CHEMISTRY. 197
melting at 67°. This is different from that obtained by Baeyer (Ber.,
12, 1320), m. p. 104°. This has probably the formula
y ^ ^
1. UH4<-^ _ ^^^>
a
The new body wonld therefore be represented by the formula
y ^
a
and would be an a-/3-dichloroquinoline. The 7-ehlorocarbostyril
described above would then necessarily have the formula
y ^ iS
n XT .^CCl ! CH- v^
a
Thus, on the addition of hydrochloric acid to amidophenylpropiolic
acid, the chlorine goes to the carbon-atom nearest the benzene-nucleus.
Heated at 145° with concentrated sulphuric acid and the resulting
product mixed with water, amidophenylpropiolic acid yields hydrowy-
carbostyril, C9H7NO2, crystallising in colourless needles, which sublime
above 320° without previous fusion. It differs from the isomeric
amidopropiolic acid in subliming without fusing, and in its silver salt
not exploding when heated. Treated with phosphoric chloride, it
yields the same dichloroquinoline as chlorcarbostyril. The OH-group
has, therefore, like the chlorine- atom, become attached to the carbon-
atom next the benzene-nucleus, and the formula must be
p„ .C(OH):CH.
^et±i<^ : c(OH)— >•
When it is heated with sulphuric acid at 200 — 220°, hydroxy carbostyril-
sulphonic acid, C9H7NO5S, is produced, easily soluble in boiling water,
sparingly so in cold. Its barium and silver salts are soluble.
Of the three related acids, orthamidohydrocinnamic acid, orthamido-
cinnamic acid, and orthamidophenylpropiolic acid, the first forms an
internal anhydride spontaneously, the second only with difficulty, and
the third, so far as at present known, not at all. When the side
nuclei close to a ring, this is always accompanied by the addition of
HCl, HBr, HI, or H(OH), to the unsaturated pair of carbon -atoms.
When distilled with water, orthamidophenylpropiolic acid gives
amidoacetophenmie accompanied by traces of amidophenylacetylene. In
this reaction, however, by far the greater part of the acid resinifies. A
better way of preparing this body is from amidophenylacetylene, by
Friedel and Balsohn's process (Ber., 14, 364).
Orthamidoacetophenone, NH2.C6H4.COMe, is a thick light-yellow oil
of basic properties. It distils almost without decomposition between
242° and 252°, and is very stable. The sulphate and hydrochloride are
soluble in alcohol and water, and crystallise from the latter in prisms.
198 ABSTRACTS OF CHEMICAL PAPERS.
It forms a platinochloride. AcetijlorthoamidoacetophHtione is produced
by the action of acetic anhydride on amidoacetophenone. It forms
colourless needles melting at 76°. L. T. T.
Derivatives of Homoferulic Acid. By F. Tiemaxn and R.
Kraaz {Ber., 15, 2070— 2072).— The authors describe the following
compounds, which are prepared by the usual methods, and present no
peculiarities : —
Hydrohomoferulic acid, M. p.
C6H3(CH2.CMeH.COOH)(OMe).OH 114—115"
Methylic methyl ho m of erulate,
CeHaCCH : CMe.COOMe) (0Me)2 65-66
Methylhomoferulic acid,
CeHsCCH : CMe.C00I[)(0Me)2 140—141
Methoxyhydrohomoferulic acid,
C6H3(CH2.CMeH.COOH)(OMe)2 58—59
E. H. R.
Phenylphenamidoacetic Acid and its Amide and Nitrile.
By F. TiEMANxN and K. Piest {Ber., 15, 2028— 2034).— By heating
together in a closed vessel for two hours at 100° a mixture of equal
molecular weights of benzaldehyde-cyanhydrin and aniline dissolved
in alcohol, and adding water to the product, a crystalline precipitate
is obtained, which has the composition NHPh.CHPh.CN, and is
formed according to the following equation: — CHPh(OH).CN +
NH,Ph = NHPh.CHPh.CN + H2O. It crystallises from dilute
alcohol in slender white needles, melting at SS**. This substance has
already been prepared by Cech by the action of hydrogen cyanide on
tlie compound NPh'.CHPh. The authors find that the latter body
melts at 48 — 49°, and not at 42° as stated by Cech, and they have pre-
pared the above-mentioned nitrile by Cech's method. Heated by
itself, it gives off hydrogen cyanide, and forms a polymeride of
NPh ! CHPh. When heated with concentrated or dilute hydrochloric
acid, it splits up into aniline and benzaldehyde, whilst with caustic
potash it yields aniline and mandelic acid ; when dissolved in concen-
trated sulphuric acid, however, and allowed to stand two days and
then gently heated, it yields the amide NHPh.CHPh.CONH,, which
is a crystalline substance, easily soluble in alcohol, ether, and concen-
trated acids. On further heating with dilute hydrochloric acid, it
yields the acid NHPh.CHPh.COOH, melting at 173—175°. This
substance combines with both acids and bases, and if heated quickly,
yields aniline, resinous products, and a small quantity of benzyl-
phenylamine. When the compound NHPh.CHPh.CN is treated with
bromine in alcoholic solution, a dibromo-derivative is obtained, having
the formula CeHsBrz.NH.CHPh.CN (m. p. 92°), which, on being
warmed with concentrated sulphuric acid, splits up into benzaldehyde
and dibromaniline, C6H3(NH2)Br.Br. [1:2: 4]. By heating the body
NHPh.CHPh.CN with sulphur, the authors obtain a compound
N
CPhx NCeHi, to which they give the name benzenylorthamido-
phenylmercaptan. E. H. R.
ORGANIC CHEMISTRY. 199
a-Phenamidoisobutyric Acid and its Amide and Nitrile. By
F. TiEMANN (Ber., 15, 2039— 2043).— The author has applied the
reaction described in the foregoing abstracts to acetonecyanhjdriu,
and has obtained the following compounds which are analogous in
every respect to those previously described : —
M. p.
NHPh.CMea.CN" 93—94°
NHPh.CMeaCON'Ha 137
NHPh.CMe2.COOH 184—185
E. H. U,
Nitriles of a-Phenamido-, a-Paratoluamido., and a-Ortho-
toluamidopropionic Acids and the corresponding Amides and
Nitriles. By F. Tiemann and R. Stephan (Ber., 15, 2034—2039).—
By methods precisely analogous to those described in the previous
abstract, but using acetaldehyde-cyanhydrin and para- and ortho-
toluidine, as well as aniline, the authors have obtained the following
compounds : —
M. p.
Acetaldehyde- f (XHPh).CHMe.CN 92°
cyanhydrin, { (NHPh).CHMe.C0NH2 140- 141°
and aniline. ( (NHPh).CHMe.COOH 162°
Acetaldehyde- ( (NHCvHO.CHMe.CN 81—82=
cyanhydrin, and (NHC7H7).CHMe.CONH2 .... 145°
• paratoluidine. ( (NHC,H0.CHMe.COOH . . . . 152"
Acetaldehyde- f (NHCvHO.CHMe.CN 72—73^
cyanhydrin, and { (NHCvHO-CHMcCONHa .... 125°
othotoluidine. { (NHC7H7).CHMe.COOH —
E. H. R.
Constitution of .ffisculetin. By F. Tiemann and W. Will (Ber.,
15, 2072 — 2084). — Coumarin, umbelliferone, and aesculetin are repre-
sented respectively by the following formulae : — C9H6O2, CgHgOs,
C9H6O4. Since umbelliferone has been shown by Tiemann and Reimer
(Ber., 12, 993) to be a hydroxy coumarin, it ^ obvious that aesculetin
may be represented as a dihydroxycoumarin. When the hydrogen of
the hydroxyl in umbelliferone is replaced by methyl, the ether thus
produced shows all the properties of coumarin; the authors have
therefore endeavoured to show that by replacing 2 atoms of hydrogen
in aesculetin by methyl, a body is produced behaving exactly as cou-
marin. By the usual process the authors obtain a mixture of mono-
and di-methylaesculetin, easily separable by ammonia, in which the
latter is insoluble. Monomethyloesculetin melts at 184°. Dimethyl-
cesculetin crystallises in shining white needles melting at 144°. Di-
methylaesculetin, methylumbelliferone, and coumarin behave in an
exactly similar manner towards reagents, solutions of potassium hy-
droxide for example. Further, all three exhibit fluorescence. These
resemblances point to a similarity in constitution.
The authors have endeavoured to obtain further evidence on this
point. Perkin has shown that by the action of methyl iodide on
sodium coumarin in presence of methyl alcohol isomeric ethers may
be obtained according to the conditions of experiment ; and he has
)0
>o
200 ABSTRACTS OP CHEMICAL PAPERS.
also obtained these two isomeric ethers and the corresponding acids
by other methods (this Journal, 39, 409). The authors have repeated
Perkin's work, and fully confirm it, and they have further shown that
by oxidation of both a- and /S-orthocoumaric acids (Perkin, loc. cit.)
one and the same methyl-salicylic acid is formed. They have applied
these reactions to methylumbelliferone and aesculetin.
Methylic dimethoxyumhellate, CM^{CYL '. CH.COOMe)(OMe)(OMe)
[1:2: 4], produced by the usual process from methylumbelliferone,
forms shining white needles melting at 87°. No isomeric ether could
be obtained, although the temperature used did not exceed 100° (that
used by Perkin) ; but the authors think it not impossible that an ether
analogous to that of a-methylorthocoumaric acid may be produced,
but, being much less stable than the latter, is transformed at once into
its isomer ide.
DimethoxyumhelUc acid, C6H3(CH ! CH.C00H)(0Me)2 [1:2: 4],
is prepared by saponification of the ether and melts at 184°. On
oxidation it yields the acid C6H3(COOH)(OMe)2 [1:2: 4].
Methifl trimetlwxymsculeafe, C6H2(CH ! CH.C00Me)(0Me)3, pre-
pared from dimethylaesculetin in the same manner as the correspond-
ing compound from methylumbelliferone, forms very pale -yellow
glistening prisms melting at 109°. On saponification, it yields the
corresponding acid, which melts at 168°. From want of material the
oxidation-products of the latter could not be determined.
These researches show that methylumbelliferone and dimethyl-
aesculetin give exactly analogous results, when their sodium-compounds
are treated with methyl iodide in methyl alcohol solution, and hence
there can be little doubt that aesculetin is a dihydroxycoumarin. The
authors hope to determine from which trihydroxy benzene aesculetin is
derived. E. H. R.
Constitution of Eugenol. By F. Tiemann and R. Kraaz (Ber.,
15, 2059 — 2070). — Some time since Tiemann and Nagai (Ber., 10,
201) showed that by oxidation of acetoeugenol under certain condi-
tions, acet - a - homoYanillic acid, C6H3(CHo.C00H)(0Me05c)
[1 : 3 : 4], is obtained ; and Erlenmeyer concluded (Ber., 10, 630)
from these experiments that the CsHg-group in eugenol has the con-
stitution — CHa-CH ! CHg. The authors have endeavoured to deter-
mine this point.
Pt'opiohomoferulic Acid. — By the action of sodium propionate and
propionic anhydride on vanillin an acid is obtained melting at 128 —
129°, to which the authors ascribe the formula
C6H3(CH : CMe.COOH)(OMe)(OC3H50) [1:3: 4].
They discuss the changes which take place in Perkin's reaction, and
come to the conclusion that in the formation of the homologues of
cinnamic acid condensation takes place between benzaldehyde and the
anhydrides of the higher fatty acids, which are either already present
or are formed by the action of acetic anhydride on the sodium salts of
those acids, and the following equations represent what takes place : —
CeHs.COH + CHoR.COO.CO.CHaR = CeH^.CH : CR.CO.O.CO.CH^R
and CeHs.CH ! CR.CO.O.CO.CH^R + H2O = CeHg-CH ! CR.COOH
ORGANIC CHEMISTRY. 201
+ CHaR.COOH. Since the homologues of cinnamic acid formed in
this way, and also the hydro-acids derived from them by addition of
2 atoms of hydrogen, behave exactly as cinnamic and hydrocinnamic
acids {e.g., in the formation of the so-called inner anhydrides from
their orthamido- and orthhydroxyl- derivatives), they must be repre-
sented as produced by sabstitution in the side-chain of cinnamic acid,
Homoferulic acid, CgHsCCH ! CMe.COOH)(OMe)(OH) [1:3: 4],
is formed by saponification of the last-described compound. It crys-
tallises in tables melting at 167 — 168°. By distilling it with lime a
body is obtained which is isomeric with eugenol, and termed isoeugenol.
It boils at 258—262°, the boiling point of eugenol being 247—249°.
The two substances are further distinguished by their benzoyl-deriva-
tives, which differ widely in melting point. From the formation of
isoeugenol it follows that its formula is
CsHaCCH : CHMe)(OMe)(OH) [1:3: 4],
and therefore the formula CeHgCCHz-CH ! CH2)(0Me)(0H) must
be assigned to eugenol. The authors are endeavouring to synthesise
it by the action of allyl chloride, &c., on guaiacol in presence of
aluminium chloride. E. H. R.
Isatin. By A. Baetee and S. CEconomides {Ber.^ 15, 2093—
2103). — The authors have prepared ethers of isatin and bromisatin,
and studied their properties.
Ethers of Isatin. — By acting on isatin-silver with methyl iodide,
using certain precautions (for an account of which reference must be
made to the original paper), methylisatin can be obtained in large
rhombic prisms of a blood-red colour. This body dissolves slowly in
dilute potash, and acids precipitate unaltered isatin from the solution.
It undergoes change spontaneously with the greatest readiness, and is
converted into a yellow body of much higher melting point, 219°
(methylisatin melts at 100 — 101°). If care be not used in the pre-
paration of the methyl ether, the yellow body, which the authors
term methylisato'id, is obtained instead : the latter gives numbers on
analysis agreeing with a formula intermediate between that of isatin
and methylisatin, CgHgNOa + C9H7NO2 = Ci7Hi2N'204. It dissolves
in boiling soda solution, and acids precipitate isatin therefrom.
Ethers of Bromisatin. — The ethers of bromisatin show less tendency
to form isato'id compounds. Methylbromisatin forms blood-red needlts
melting at 147°. It changes spontaneously into methylhromisato'id,
m. p. 280—231°.
Ethylhromisatin is similar to the methyl-compound, and melts at
107 — 109°. An alcoholic solution of the former, treated with a small
quantity of potash, becomes reddish- violet, and on addition of more
potash yellow, with formation of potassium bromisatate. Hence
potassium bromisatin is first formed and then converted into the
bromisatate. Ethylhromisatoid is best obtained by allowing a solu-
tion of the ether in acetic anhydride to stand for some days. It behaves
with boiling potash like the ether. Acetylbromi satin melts at 170 —
172°, and on treatment with dilute potash, forms a yellow solution,
from which acids precipitate acetylbromisatic acid, melting at 178 —
VOL. XLIV. p
202 ABSTRACTS OF CHEMICAL PAPERS.
180". Isohutylbromisatn'id melts at 210°. To account for the forma-
tion of these isatoid compounds, the authors suppose that moisture
causes a partial saponification, and condensation then takes place.
Ethers of Dihromi satin. — These differ from the ethers of isatin and
bromisatin in not forming isatoid compounds. The authors prepare
dibromi satin by heating on the water-bath a saturated solution of
bromisatin in glacial acetic acid, with twice the quantity of bromine
necessary to produce dibromisatin. Since the melting point of dibrom-
isatin (250°) is 5° lower than that of bromisatin, the second bromine-
atom probably takes the ortho-position with reference to the nitrogen,
the first bromine-atom having taken the para-position. Ethyldibrom'
isatin melts at 87 — 89**. Treated in the cold with a 5 per cent, solu-
tion of potassium hydroxide, it forms a blue- violet powder, which is
the potassium- derivative, but this soon becomes changed, without
going into solution, into potassium dihromisatate. From the latter acids
separate dibromisatic acid, which changes in a few days into dibrom-
isatin. Ethyl dihromisatate crystallises in yellow tables, melting at
105°.
The authors discuss the formula of isatin considered in the light of
these new facts. Acetylisatin, on treatment with potash, yields potas-
sium acetylisatate. Ethylisatin, under the same conditions, yields
first potassium isatin and then potassium isatate. It follows that the
acetyl does not take up the same position as the ethyl, and that the
latter must be attached to oxygen, whilst the former is directly
attached to nitrogen. Oiily one constitution can be assigned to
CO CO
acetylisatin, viz. : C6H4<^_-|^jr-_>'. The most probable formula for
y-C6H4-
isatin is 'N-/' j>CO. This method of representing it explains
^C(0H/
easily its formation and also the fact that isatin chloride is red and
enters extremely readily into reaction.
The relation between ethylisatin or its bromine substitution-pro-
ducts and isatin chloride is further shown by the fact that the former,
like the latter, yields indigo or substituted indigos. That isatin does
not behave in a similar manner, shows that the formation of indigo
depends on an alteration of the hydroxyl-group.
It follows from the above that the true acetylisatin, that namely in
which the hydroxylic hydrogen is replaced by isatin, has not yet been
prepared.
Finally, the authors call attention to the great similarity between
the formation of isatin, as represented by the new formula, and that
of carbostyril, which Friedlander and Weinberg (this vol., p. 204)
have shown to be hydroxy quinoline, and not an imido-compound as
hitherto supposed. The authors propose the name lactam for bodies
formed like acetylisatin, and lactim for those formed like isatin.
E. H. R.
Metanitrodiphenylmethane. By P. Becker (Ber., 15, 2090—
2093). — The author has obtained this body as a brownish liquid by
agitating a mixture of metanitrobenzyl alcohol (prepared according to
ORGANIC CHEMISTRY. 203
R. Meyer's method, -Ber., 14, 2394) and benzene,, with a large excess
of concentrated sulphuric acid, keeping the mixture well cooled.
Metadinitrodibenzylhenzene is produced at the same time, and is a white
crystalline substance melting at 165°. By nitration, metanitrodiphenyl-
raethane yields a dinitro-compound melting at 94°, and isomeric with
those described by Staedel. Metamidodipheni/lmethane, obtained by
reduction of the corresponding nitro-body with tin and hydrochloric
acid, is a crystalline base melting at 46°. On oxidation with chromic
mixture, metanitrodiphenylmethane yields metanitrobenzophenone, a
bright yellow crystalline body melting at 92°. E. H. R.
Amarine. By A. Glaus (Ber., 15, 2326— 2336).— It has been
previously pointed out by the author (Ber.y 13, 1418) that a mixture
of hydrodimethylamarine, methyl chloride, and hydro methylbenzyl-
amarine is produced by the action of benzyl chloride on a boiling alco-
holic solution of dimethylamarine, 2CoiHi6Me2N2 + C7H7CI + '2iH.oO
= C^iHisMcCCtHONsO + aiHisMeaNaO.MeCl.
Sydrometliylhenzylamarine, (C2iHi8Me)C7H7]Sr20, is deposited from an
alcoholic solution in colourless crystals (m. p. 208°), which dissolve
freely in chloroform, but are insoluble in water. The hydrockloride
forms colourless transparent crystals which melt, with loss of water,
at 102°. The dried salt, C29H28N20,HC1, melts at 205°. The platino-
chloride, (C29H28N20)2,H2PtCl6 + 2H2O, is deposited from a w^arm
alcoholic solution in orange- colon red. needles. The anhydrous salt
melts at 168°.
Hydrodimethylamarine methyl chloride is a crystalline salt (m. p. 168°),
freely soluble in water, alcohol, and chloroform, but insoluble in ether.
The aqueous solution is not acted on by ammonia, but on treatment
with potash or silver oxide, it yields hydrotrimethylamarine,
CoiHnMegNaO.
This base crystallises in transparent prisms (m. p. 158°), soluble in
ether, alcohol, and chloroform. The hydrochloride (m. p. 204^) is
insoluble in chloroform and sparingly soluble in water. On adding
ammonia to the aqueous solution, the free base is precipitated. The
jjlatinochloride, (02iHi7Me3N'20).2,H2PtCl6 + 2H2O, obtained as a
yellow precipitate, soluble in alcohol, melts at 195°. The platino-
chloride of hydrodimethylamarine methyl chloride only contains 1 mol.
H2O. It is a bright yellow powder, melting at 244°, and soluble in
alcohol, and in water containing a small quantity of acid.
Dibenzylamarine does not combine with alcoholic chlorides, bro-
mides, or iodides. When ethyl iodide acts on dibenzylamarine, a
mixture of hydriodide of dibenzylamarine and its di-iodide is pro-
duced. The hydriodide, C2iHi6(C7H7)2N2,HI, forms colourless plates,
insoluble in water. The dl-iodide, C21 Hie (C7H7) 2^2,111,12, is deposited
from an alcoholic solution in golden needles.
Dibenzylamarine is not oxidised by chromic acid, but on treatment
with dilute nitric acid (sp. gr. 1*13) it yields benzoic and paranitro-
benzoic acids, and also two intermediate products, viz., a body crystal-
lising in yellow needles melting at 142°, and a substance deposited
from alcohol in pale yellow prisms melting at 95°.
p 2
204 ABSTRACTS OF CHEMICAL PAPERS.
Dimetbylamarine may be represented by the formula
,NMe : CPb
PhC^ I
^-NMe.CHPh W. C. W.
Constitution of Carbostyril and Hydrocarbostyril. By P.
Friedlander and A. Weinberg {Ber.^ 15, 2103). — By the action of a
concentrated solution of zinc chloride on ethyl orthamidocinnamate,
an ethylcarbostyril is obtained identical with that produced directly
from carbostyril or chloroquinoline. It follows, therefore, that ethyl-
carbostyril contains an ethoxyl- group ; and carbostyril must be re-
garded as a hydroxyquinoline.
In a similar manner the authors obtain an ether of hydrocarbo-
styril which is easily saponified by dilute acids (J5er., 15, 1421). But
when hydrocarbostyril is heated with potassium hydroxide and ethyl
iodide in the usual way, an ethylhydrocarbostyril is obtained, which
remains unaltered even when heated with concentrated sulphuric acid
at 150°. The same body i« obtained by heating ethylorthamidocin-
namic acid with sodium-amalgam, ethylorthamidohydrocinnamic acid
being thereby produced, which, on acidifying its alkaline solution,
becomes converted into ethylhydrocarbostyril. The stable form of
ethylhydrocarbostyril is therefore represented by Figure I, while
Figure II indicates the constitution of its isomeride —
CH CH2 CH CH2
CH pjp^ CH, CH f^/^\ CH,
CH N.Et • CH If
I. II.
E. H. R.
New Compounds from Coal-tar: a- j8- 7-Pyrocresoles. By
H. ScHWARZ (Monatsh. Chem., 3, 726 — 744). — These compounds were
prepared from a buttery distillate occurring amongst the last products
of the rectification of carbolic acid in a tar-distillery at Angern near
Vienna. The buttery mass, on rectification, began to boil at 180°,
the boiling point often remaining stationary for a while at 207°, and
then slowly rising to 225°. A small quantity passed over between
225° and 265° ; more at 265—320°, the distillate then beginning to
solidify. Between 320° and 330°, a copious light yellow distillate was
obtained, which quickly solidified; at 330 — 350° the distillate was
dark yellow, and above 350°, brown-yellow and softer. Finally,
charcoal remained in the retort. On dissolving the crude distillate in
glacial acetic acid at the boiling heat, and then heating it with zinc-
dust, it becomes much lighter in colour, and if then distilled, yields a
colourless product, which only gradually becomes coloured.
On heating the oily non-solidifying portion of the product with
potash-ley, filtering from neutral oil, saturating the filtrate with hydro-
chloric acid, and distilling it with steam, collecting the oil which
sinks to the bottom of the distillate, drying it with calcium chloride
ORQANIO CHEMISTRY. 205
and rectifying, there passes over an acid oil, the chief part of which
has the composition (77'34 per cent, carbon and 7'45 hydrogen) and
boiling point (193 — 195°) of meta-cresol.
Preparation of Pure Pyrocresole (a, /3, and 7). — The solid products
of the distillation just described, as well as the press-cakes obtained
on the large scale, and the buttery mass expressed therefrom, were
found — after being subjected to a series of purifying processes by solu-
tion, especially at boiling heat, in benzene, light petroleum, carbon
sulphide, chloroform, ether, and alcohol — to crystallise on cooling in
silvery laminae, which, after one more crystallisation, appeared to be
pure enough for analysis. Nevertheless these apparently pure pro-
ducts exhibited very considerable differences of melting point and
solidifying point, the latter — which admitted of more exact determi-
nation than the former — varying from 85° to 195° ^ and by washing
with cold alcohol, boiling first with dilute and then with continually
stronger alcohol, extraction with light petroleum and with ether in a
percolator, &c., a number of isomeric bodies were obtained exhibiting
different degrees of solubility. No separation could be effected by
difference of boiling point.
The bodies of lowest melting point were also the most soluble, but
the differences of solubility were not great enough to effect the
definite separation of more than the products of highest and lowest
melting point. The former were most readily separated by repeated
crystallisation from boiling benzene, whereby, from the original press-
cake solidifying at 127°, products were obtained solidifying at 147°,
157°, 169°, 181^, and finally at 195°, this last product crystallising in
large laminae having a silvery and satiny lustre, and dissolving with-
out colour in benzene. The substance crystallised from this solution
exhibited the same solidifying point, as did also that which was ob-
tained from the mother-liquor by distilling off the benzene. It is,
moreover, eminently sublimable, so much so indeed that it can
scarcely be melted in an open vessel, the greater part subliming before
it fuses. When quickly heated in a test-tube, it fills the tube with
white coherent flocks, so that its boiling point cannot be determined.
Dissolved in glacial acetic acid and oxidised by chromic acid, it yields
a product crystallising in splendid needles. The other derivatives of
this substance (to be described further on) are distinguished by great
tendency to crystallise, relatively high melting point, and sparing
solubility.
At the other end of the series is a substance which crystallises con-
stantly at 104 — 105°. It may be separated by concentrating the
mother-liquors, and is likewise obtained from the greasy mass which
runs out on hot-pressing in the manufacturing process. It may be
freed from colouring matter by treating it in the melted state with hot
glacial acetic acid and zinc-dust. This substance is much more soluble
than that which solidifies at 195° ; it is not sublimable ; its derivatives
are less crystallisable ; and its oxidation-product melts under hot
water.
A third substance has also been separated, less well-defined than the
two above mentioned. From a press-cake solidifying at 127 — 128°,
the author, by repeated treatment with alcohol, ether, and benzene,
206 A.BSTRAOTS OP CHEMICAL PAPERS.
obtained the bodies solidifying at 195° and 104°, bat did not succeed
in resolving the mass completely into these two compounds ; and he
supposes that it contained also a third substance solidifying at 124*',
crystallising in smaller laminae, and intermediate in solubility between
the two former.
All these three substances were found by analysis to have the same
elementary constitution, viz. : —
C. H. O.
84-87 to 85-24 6-61 to 6*84 7*97 to 8-48
agreeing most nearly with the formula CuHigO, which reqaires
85-28 0, 6-64 H, and 8-08 O, An uneven number of hydrogen-atoms
being however inadmissible, the author assigns to these isomeric
bodies the double formula C28H26O2 (which is confirmed by some of
the substitution-derivatives), and designates them as pyrocresoles,
supposing them to be produced from cresol by elimination of water
and hydrogen as shown by the equation, 4C7H8O = C28H2602 + 2H2O
+ Hg. They are distinguished as a, melting at 195, ft at 124°, 7 at
104°. They may perhaps be regarded as ditolyl-ditolylene dioxides,
Pyroceesole oxides, C28H22O4, are obtained by treating the three
pyrocresoles either with nitric acid of sp. gr. 1-40, or with a mixture of
potassium dichroraate and sulphuric acid, or with chromic anhydride
in glacial acetic acid, the action being represented by the equation
CosHoeOj +04 = 2H2O + C28H22O4. The a- compound, which is espe-
cially fine, may be precipitated from its solution in glacial acetic acid
by water, in groups of needles, and when washed, dried, and recrys-
tallised from boiling alcohol, forms beautiful somewhat yellowish
needles, becoming somewhat darker on exposure to light. It solidifies
at 168°, i.e., 27° lower than a-pyrocresole, and is more soluble than the
latter in alcohol, &c. It distils unaltered, but shows little tendency to
sublime.
The |S- and 7-oxides solidify at much lower temperatures than the
a-compound ; they are also more soluble, and show less tendency to
crystallise.
Oxynitro-products, C28Hi5(N02)704, are produced, with evolution of
nitrous fumes, by treating the three oxides with a mixture of 1 vol.
NOgH and 2 vols. SO4H2, and separate as light yellow, more or less
crystalline bodies, the separation being completed by addition of water.
The washed and dried products melt when heated in test-tubes, and
detonate at higher temperatures, leaving a large quantity of pulveru-
lent charcoal. The a-nitro-compound crystallises from hot nitroben-
zene or from glacial acetic acid in light yellow laminae ; from strong
nitric acid on cooling and dilution, in nearly white laminae and needles.
The 7-moditication is much more soluble in boiling acetic acid, and
separates on cooling in yellow grains and nodules. The y3-compound
crystallises from a mixture of nitric and acetic acids in yellow laminae.
The analyses of these bodies show that they have not yet been ob-
tained quite pure.
Amido-compowids appear to be formed by the action of tin and
ORGANIC CHEMISTRY. 207
hydrochloric acid on the nitro-products, but they have not yet been
isolated.
Bromine-compounds. — When a solution of a-, /?-, or 7-pyrocresole in
glacial acetic acid is treated with excess of bromine, likewise dissolved
in glacial acetic acid, a reddish-yellow crystalline precipitate is formed,
which after draining, washing with glacial acetic acid, and drying on
earthenware plates over quicklime or potassium hydroxide, remains
nearly unaltered. Part of the bromine contained in it is, however,
very loosely combined, and may be removed by drying at 100°, or by
washing with alcohol, or best by boiling with water, a white substance
then remaining, which may be crystallised from boiling alcohol or
glacial acetic acid.
Of the bromine-compounds thus formed, the a-product is the least
soluble. On adding 6Br to 1 mol. a-pyrocresole, beautiful laminge are
thrown down, which contain only traces of free bromine, and may be
rendered nearly colourless by treatment with a small quantity of
alcohol. The 7-product obtained in like manner is best purified by
recrystallisation from boiling alcohol. When on the other hand a
larger quantity of bromine is added to 7-pyrocresole, torrents of
hydrogen bromide are evolved, yellowish granular crusts separate out,
and water throws down a yellowish compound, which melts even at
the heat of boiling water. The analysis of the reddish-yellow a-com-
pound thus obtained gave as a mean result, 32*62 per cent. C, 2*30 H,
60*32 Br, and 476 0, agreeing approximately with either of the three
formulae, CasHoiBrgOi, CasHziBrsOa, and C28H24Br802, the first agreeing
best with the quantity of bromine found by experiment, the third
better with the carbon. The equation C28H26O2 + lOBr = 2BrH -f
C28H94Br802, is in accordance with the experiment in which 1 mol.
pyrocresole was acted upon with 10 at. Br, of which only a small
quantity remained free.
By distilling the reddish -yellow a-compound with water, 61 — 62 per
cent, of white residue was obtained, together with 24*10 to 12*55 per cent .
hydrogen bromide, and 18*66 to 24*71 per cent, free bromine. The white
residue exhibited a constant composition agreeing with the formula of
tribromopyrocresole, C28H23Br302, its quantity agreeing closely
Avith the calculated amount, viz., 61 per cent. The reddish-yellow
body is its perbromide, and is converted into tribromopyrocresole
by loss of HBr + Br. A similar perbromide is obtained from 7-pyro-
cresole, but has not yet been examined. |3-pyrocresole does not
appear to yield a bromine-compound.
To obtain pure tribromopyrocrfisole, it is sufiicient to treat the solu-
tion of 1 mol. a- or 7-pyrocresole in glacial acetic acid with only 6 at.
bromine, according to the equation C28H26O2 + 6Br = 3BrH +
C28H23Br302; the solution on cooling deposits the tribromo-compound
in thin rhombic laminae, which may be washed with water and recrys-
tallised from alcohol.
7- Pyrocresole treated at the boiling heat with a slight excess of
bromine, yielded also another compound in yellow crusts, a further
quantity of which was separated on dilution with water. This com-
pound, not yet fully examined, melts under boiling water, whereas
a-tribromopyrocresole solidifies at 200°, and the 7-compound at 183°.
208 ABSTRACTS OF CHEMICAL PAPERS.
On attempting to brominate pyrocresole oxide by treating its solu-
tion in glacial acetic acid with bromine, fine reddish-yellow needles
were obtained, which turned white when exposed to light over solid
potash, and when boiled with water quickly turned white, with for-
mation of hydrobromic acid and evolution of bromine. The residual
substance dissolved readily in warm alcohol, and crystallised there-
from in slender white needles, having the composition ofpyrocresoie
dioxide, CssHszOe.
SuLPHONic Compounds. — a- and 7-Pyrocresole nnite somewhat ener-
getically with sulphuric acid, forming a red-brown syrup, which,
howev^er, on dilution with water, deposits nothing but the unaltered
pyrocresole. The same solution saturated with carbonate and hydr-
oxide of barium, then filtered and evaporated, yielded only in the case
of a-pyrocresole, a salt which crystallised from the hot liquid in
needles, giving by analysis 25'05 and 24'95 per cent. Ba, and 11'57 S,
the formula of barium pyrocresole-tetrasulphonate requiring 27"84
Ba and 13*08 S. The salt was perhaps mixed with di- or tri-sulpho-
nate. A sodium salt was likewise prepared containing 16*11 per
cent. S, 10-33 Na, and 4-84 H2O, the formula C28H23Na4S40u + 2H2O,
requiring 14'92 S, 1072 Na, and 419 H2O.
The solution obtained by treating a-pyrocresole oxide with sulphuric
acid, deposited on dilution with water nothing but the unaltered oxide,
and the filtered liquid treated with barium carbonate took up scarcely
any traces of baryta. No sulphonic acid had therefore been formed.
H. W.
a- and f-Dichloronaphthalenes. By O. Widman (Ber., 15, 2160 —
2163) . — In the hope of explaining the anomaly that the a- and ^-di-
chloronaphthale7ies both give the same dichloronaphthalene tetrachloride,
which, when oxidised with nitric acid, gives the same dichlorophthalic
acid as that obtained from iS-dichlornaphthalene (Bull. Soc. Chini., 28,
505), the author has submitted (x-dicldoronaphthalene (obtained by
acting on the pure tetrachloride with potash) to careful purification.
The author has succeeded in separating from this a-compound a small
quantity of t-dichloronaphthalene fusing at 120°, and identical with
that obtained by Leeds and Everhardt (Amer. Chem. Soc, 1880, 2,
205), by acting on naphthalene tetrachloride with moist silver oxide at
200°. No trace of /3- dichloronaphthalene could be obtained. a-Dichloro-
napJithalene fuses at 38° (formerly the fusing point was given as 35 —
36°), and gives, by V. Meyer's method, the vapour- density 7*02 (theory
6*69) , showing that it could contain no double-compound. Nevertheless,
on treating this perfectly pure a-dichloronaphthalene with chlorine,
/3-dichloronaphthalene tetrachloride is produced. This point, there-
fore, is still obscure.
The author declines to allow as valid the arguments put forward by
Claus in favour of his proposed new formula for naphthalene.
L. T. T.
yS-Dinaphthol. By H. Waldee {Ber., 15, 2166— 2178).— The
author has investigated many new derivatives of ^-dinaphthol. The
/3-dinaphthol used was prepared by oxidising |S-naphthol in ethereal
solution with anhydrous ferric chloride. On distillation, iS-dinaphthol
ORGANIC CHEMISTRY. 209
decomposes, /?-naplitliol and some ^-dinaphthol distilling over, and a
carbonaceous residue being left in the retort.
^.Dinaphthol picrate, C2oHi403,2[C6H2(N02)3.0H], melts at 174°, and
is solnble in alcobol and benzene. a-Dinaphthyl is produced when 18- di-
naphthol is heated with zinc-dust. a-Dinaphthyl, heated with picric
acid dissolved in benzene, yields a crystalline body melting at 145'';
it crystallises from benzene in reddish-brown needles. By heating
/3-dinaphthol with zinc chloride at 270°, the author obtained a yS-di-
naphthalene oxide, which appears to be isomeric and not identical
with that obtained by Dianin from |S-naphthol and phosphoric anhy-
dride. The oxide is soluble in the usual solvents, melts at 157°, and
gives a picric acid compound, C2oHi20,2[C6H2(N02)3-OH], melting at
135°. On heating y3-dinaphthol with zinc ammonium chloride at 320 —
330° for 60 hours, a substance was obtained melting at 159°, and having
the formula C20H13N. The author looks upon this body as difiajphthy-
^loHe. p -TT
lenamide, \ >NH, or NH<p'":S''>NH. It is soluble in the usual
solvents and yields rhombic crystals. It dissolves in concentrated
sulphuric acid with blood-red coloration. With picric acid it gives a
compound, C2oHi3N',C6H2(N02)3.0H, melting at 217°. Heated with
CioHe
excess of acetic anhydride, it forms an acetyl-compound, | \NZc,
CioHe
crystallising in greyish-white needles melting at 144°. Substituting
zinc aniline chloride for zinc ammonium chloride, a dinaplithylene-
CioHe. Q Tg
phenylamine, I ^NPh, or PhN< p^"tt^^ >NPh, is obtained, soluble
^lo-tle
in benzene, ether, acetone, alcohol, and acetic acid, but not in dilute
mineral acids. Sulphuric acid dissolves it with violet coloration. It
crystallises in white needles melting at 144°. This amine also yields
a picric acid compound, C26Hi7N,2[C6H2(N02)3.0H], melting at 169°.
Acetic chloride attacks dinaphthylenamine, but not the tertiary
dinaphthylenephenylamine. L. T. T.
Action of Amines on Qninone. Part VI. By T. Zincke and
F. Brauns (Ber., 15, 1969 — 1972). — A continuation of the authors'
researches on this subject (Abstr., 1880, 48; 1861, 595, 915; 1882,
735, 967). The ethers of /S-naphthoquinonetoluide can be prepared
from the silver salt by heating an alcoholic solution of the sodium salt
with alcoholic bromides or iodides.
The methyl ether, Ci7Hi2N02Me, crystallises from alcohol in fine
red crystals melting at 150°. The ethyl ether, CnHi2N02Et, forms
large red crystals melting at 135 — 137°. The isopropyl ether,
CivHizNOa/SPr,
melts at 137 — 189°. These ethers, when boiled with acetic acid,
yield ditoluide; they are saponified by hot concentrated sulphuric acid
with formation of /J-naphthoquiuonetoluide. By the long continued
action of hydrochloric acid, hydroxynaphthaquinones are formed.
210 ABSTRACTS OP CHEMICAL PAPERS.
Nitric acid dissolves the ethers ; and on adding water precipitates are
formed ; in the case of the ethyl ether, a yellow crystallisable sub-
stance (ra. p. 177 — 179°) being obtained.
Nitrous acid acts on /3-naphthoquinonetoluide, and in presence of
acetic acid and alcohol, gives a substance of the formula C34H22N4O6,
crystallising from glacial acetic acid in small red needles, and appear-
ing to be a nitroso-compound. It unites with alcohol, forming a white
crystalline compound, which is decomposed by heat, the alcohol being
driven off. On reduction, best by means of potassium bisulphite, a deep
blue compound, C34H26N"404, is formed ; this forms red salts with acids,
which are only stable in alcoholic solution ; with alkalis it yields fine
green salts, insoluble in alcohol ; with acetic anhydride it yields a
tetraceti/l-deriYSitive, C34H22N4(OXc)4, forming yellow crystals, melting
at 190 — 191°. On oxidation, the blue compound is converted into a
yellowish-red substance, C34H22N4O4 (m. p. 260 — 265°), crystallising
from acetic acid in needles ; reducing agents reconvert it into the
blue compound. By the action of soda on the nitroso-compound
O34H22N4O6,
a yellow crystalline body (m. p. 224°) is obtained ; it is not attacked
by the strongest oxidising agents ; potassium bisulphite gives an
unstable white reduction-product which readily reoxidises. Chromic
acid converts the nitroso-compound into a body crystallising from
alcohol in small yellow needles melting at 212 — 214°. A. J. G.
Lapachic Acid. By E. PATERNd (Gazzetta, 12, 337— 392).— This
acid is extracted from the ground lapacho wood by boiling it with a
dilute solution of sodium carbonate : the solution acquires a blood-red
colour, and when cold is filtered and neutralised with hydrochloric
acid ; an abundant yellow precipitate of lapachic acid is then formed,
amounting to about 8 per cent, of the original weight of the wood.
In order to purify the crude product, it is crystallised successively
from ether and from benzene, in which the resinous matters are
insoluble ; it then forms small well-defined monoclinic prisms of a fine
canary-yellow colour, and very soluble in boiling alcohol, from which
it separates in thin plates. It melts at 138°, and at a higher tempera-
ture decomposes, leaving an abundant carbonaceous residue. Lapachic
acid, C15HUO3, is easily soluble in solutions of the alkaline hydroxides
and carbonates, giving bright red solutions. Sodium laj)achate,
CisHnNaOa + 5H2O,
separates from concentrated solutions as a radiated crystalline mass of
deep red colour, which after a time loses its crystalline structure and
becomes almost black. It melts in its water of crystallisation at about
50°. Potassium lapachate, C15H13KO3, closely resembles the sodium-
compound in appearance. Ammonium lapachate, C15H13O3.NH4, crys-
tallises in large brick-red needles, which lose ammonia quickly on
exposure to the air, leaving a residue of pure lapachic acid. Silver
lapachate, CisHisAgOa, calcium lapachate^ (Ci5Hi303)2Ca 4- HoO, and
strontium lapachate, (Ci5Hi303)2Sr 4- l^HgO, are obtained from the
ammonium salt, by precipitation, as red amorphous powders. The
ORGANIC CHEMISTRY. 211
harium salt, (Ci5Hi303)2Ba + 7H2O, very sparingly soluble in cold,
but more so in hot water, crystallises in long slender blood-red
needles. The lead compound forms an orange-red precipitate. The
aniline and toluidine salts were also prepared ; they are orange-yellow
crystalline compounds melting at 121 — 122° and 129*5 — 130° respec-
tively.
Action of Bromine on Lapachic Acid. — On mixing bromine (35
grams), diluted, with acetic acid with a solution of lapachic acid
(50 grams), in the same solvent, a yellowish-brown solution is ob-
tained, which yields an abundant orange-yellow precipitate when
poured into a large quantity of water. The monobromolapachic acid^
CisHisBrOa, thus obtained is easily purified by washing it with ether
and crystallising from boiling alcohol ; it separates in large lustrous
plates of an orange-red colour, melting at 139 — 140°. It has none of
the characters of an acid, being quite insoluble in cold potash solution,
and although alcoholic potash dissolves it, it is precipitated unchanged
on diluting with water and adding hydrochloric acid. It dissolves in
nitric or sulphuric acid at the ordinary temperature, and is precipi-
tated unaltered on adding water to the solution. When boiled with
nitric acid, however, it is gradually decomposed, bromine is given off,
and the solution leaves phthalic acid on evaporation.
Acetyl-derivatives. — Lapachic acid is not altered by boiling with
acetic chloride or anhydride under the ordinary atmospheric pressure,
but on heating it with the anhydride at 150° for three hours, a mon-
ace^t'c-derivative, C15H13O3XC, is formed; this may, however, be prepared
more conveniently by heating a mixture of lapachic acid (2 parts),
sodium acetate (2 parts), and acetic anhydride (5 parts), the liquid
rapidly assumes a wine-red colour which passes into yellowish-brown,
and finally becomes green ; as soon, however, as the mixture begins
to assume a green tinge, the reaction is stopped by adding water ; this
throws down a yellowish-brown oil which soon solidifies to a crystal-
line mass, the yield being almost the theoretical. It is easily purified
by recrystallisation from alcohol, when it forms lustrous sulphur-
coloured prisms, insoluble in water, but very soluble in ether ; it melts
at 82 — 83°. When heated with acetic anhydride in closed tubes, it
yields a green resinous compound. It is not acted on by water at
] 20°, but is easily decomposed by alcoholic ammonia in the cold with
formation of ammonium acetate and lapachate. With bromine, it
yields monobromolapachic acid, and with nitric acid an acetomononitro-
lapachic acid, Ci5Hi2(N02)03.Ac ; this crystallises in orange-red plates
which melt at about 166 — 168°, but undergo decomposition at the
same time. If the mixture of acetic anhydride, sodium acetate, and
lapachic acid above mentioned, instead of being heated until it com-
mences to turn green, is boiled for about 15 minutes, it no longer
contains a trace of monacetolapachic acid, but another compound
which is precipitated as a brownish-green oil on adding water to the
product ; this becomes crystalline after some time, and is then
powdered, washed with ether to remove a greenish resin, and finally
purified by recrystallisation from alcohol or from dilute acetic acid.
It forms dirty-white needles or minute prisms melting at 131 — 132°,
and very sparingly soluble in ether or cold alcohol. Although the
212 ABSTRACTS OF CHEMICAL PAPERS.
analytical results correspond very closely with the formula of biaceto-
lapachic acid, yet, as it has not been found possible to reconvert it
into lapachic acid, it is highly improbable that it is the biaceto-deriva-
tive. It is not altered by heating it with water at 150°, neither does
it dissolve in solutions of the alkaline carbonates or of their hydrox-
ides ; it is decomposed, however, by alcoholic potash, which dissolves
it with brownish-yellow colour, and on diluting the solution with
water, and adding an acid, a new compound is obtained as a brownish-
yellow precipitate. This is very soluble in alcohol, ether, and ben-
zene, but may be crystallised from dilute alcohol, when it forms small,
silky, flat needles of orange colour, melting at 140 — 141°. The author
thinks it probable that these two compounds have the formulae I and
II respectively : —
J (OZc)2Ci5H30v^ _ p TT n TT (^2)" • C15H3O V. _p -pr i-v
The action of nitric acid on the acetic- derivative seems to give rise
to two nitro-substitution-compounds, one of which crystallises in red
needles melting at 147 — 148", whilst the other, less soluble in ether,
forms yellow needles melting at a somewhat higher temperature.
When lapachic acid is oxidised by potassium permanganate, it
yields oxalic acid in small quantity ; with ordinary nitric acid of
sp. gr. 1*38 it yields phthalic acid in abundance, exceeding 75 per
cent, of the lapachic acid taken.
On distillation with zinc-dust, lapachic acid yields naphthalene and
a hydrocarbon boiling at about 250°, and melting at a lower tempera-
ture than naphthalene, probably a homologue of the latter ; of the
gaseous products, the portion absorbed by bromine gave two bromides,
one isobutylene bromide, CMeaBr.CHjBr, the other derived apparently
from a hydrocarbon containing Ce.
Action of Beducing Agents. — As the general conduct of lapachic acid
and the fact that it yields naphthalene on distillation with zinc- dust,
indicate that it is a hydroxj^quinone derived from some homologue of
naphthalene, it was of importance to examine the effect of reducing
agents. The acid when dissolved with excess of an alkaline hydroxide
and treated with zinc-dust, is acted on immediately, the intense red
colour of the solution becoming pale yellow ; the hydrolapachic acid
formed, however, is oxidised so readily that it was found to be impos-
sible to obtain it in a state sufficiently pure for analysis. It is soluble
in boiling water, and crystallises in colourless needles melting at about
100°.
An energetic reaction takes place on heating lapachic acid with red
phosphorus and concentrated hydriodic acid, and when it is complete
the mixture separates into two layers, the lower of which is an oily
hydrocarbon boiling at 304 — 306°. It combines with trinitrophenol,
forming a compound which crystallises from boiling alcohol in large
orange- red needles melting at 140 — 141''. From analyses of the picric
acid compound, the hydrocarbon would seem to be an amylnaphthalene^
C10H7.C5HU.
Action of Concentrated Acids. — Lapachic acid (1 part) dissolved in
concentrated sulphuric acid (4 parts) in the cold gives a solution of
ORGANIC CHEMISTRY. 213
the colour of bromine, and this, when poured into a large quantity of
water, deposits an orange-yellow flocculent substance, which may be
purified by crystallisation from alcohol. This new compound is lapa-
cone, C15H14O3, isomeric or polymeric with lapachic acid. It forms
magnificent flattened needles melting at 155 — 156°, of orange-red
colour and silky lustre. It is insoluble in water, easily soluble in
benzene and alcohol, but less so in cold alcohol or ether. It dissolves
also in concentrated sulphuric, nitric, and hydrochloric acids, and is
precipitated unaltered on addition of water ; it also dissolves in potash
when heated. In like manner when lapachic acid is dissolved in well
cooled concentrated nitric acid of sp. gr. 1*49, it is converted into
lapacone, but a small quantity of another substance, more soluble in
ether and cold alcohol, is formed at the same time ; this crystallises
from alcohol in canary-yellow needles melting at 116 — 117°. It does
not contain nitrogen, and on analysis gave numbers nearly the same as
those obtained with lapachic acid.
Lapacone is energetically acted on by acetic anhydride and sodium
acetate ; on heating the mixture, it becomes green and brilliant plates
make their appearance in the liquid ; the addition of water now throws
down a dark green precipitate, which is washed with ether to remove
a green resin, leaving the new compound in magnificent plates of
metallic lustre with blue iridescence, bronze-red by reflected and
golden-yellow by transmitted light ; when pressed under a glass rod
on paper they give an indigo-blue spot with coppery lustre like indigo.
There is the greatest difficulty in purifying this substance, as it is
almost insoluble in the usual solvents ; it may, however, be recrystal-
lised from a large quantity of boiling acetic anhydride. It is also
slightly soluble in carbon bisulphide, yielding a beautiful blue solution,
but on evaporation it is deposited in the amorphous state. It is not
altered by boiling potash solution. Sulphuric acid dissolves it, but it
is not reprecipitated on adding water; nitric acid dissolves it with red
colour, but the product has not been examined. This substance is
also formed by the action of acetic anhydride and sodium acetate on
monobromolapachic acid.
These results incline the author to believe that it is an anhydride of
lapacone, admitting — what is highly probable — that lapacone is a
polymeride, CsoHagOe, of lapachic acid, analogous to the compound
obtained by Stenhouse and Groves from y3-naphthaquinone. In this
case it would have the formula CaoHoeOs.
The author then proceeds to discuss the identity of lapachic acid
with taiguic acid and groenhartin, pointing out that these three sub-
stances are obtained from varieties of the same species, although not
from the same plant; the properties of lapachic acid and also its
melting point agree closely with those given by Arnoudon for taiguic
acid ; there is, however, a great difference in the amount of carbon,
lapachic acid containing 74*5 per cent., whilst Arnoudon gives 70*9
for taiguic acid ; it should be noted, however, that he does not con-
sider the formula as absolutely settled. As regards groenhartin, the
analyses given by Stein agree very closely with those of lapachic acid ;
Stein, however, says that he obtained an unstable bromo-derivative
containing 37 per cent, bromine, whilst monobromolapachic acid con-
214 ABSTRACTS OF CHEMICAL PAPERS.
tains but 25, and no definite dibromo-derivative could be obtained. The
author suspects that the product analysed by Stein was not pure, bat
contained a resinous substance richer in bromine, the formation of
which he himself has observed. It seems highly probable that these
three substances are identical, and it is very desirable that Arnoudon
and Stein should study taiguic acid and groenhartin so as to definitely
settle this point. In an appendix, the author states that he has
examined the acid obtained from a fragment of the very same piece
of wood employed by Arnoudon, and finds it to be identical with
lapachic acid.
Constitution of Lapachic Acid. — The results of the analyses of
lapachic acid and its substitution-products, and especially of the
silver salt, closely agree with the formula C15H11O3, whilst its chemical
character and the action of reducing agents prove distinctly that it is
a hydroxyqu-inone derived from naphthalene of the formula
C5H9.C,oH,(00".OH.
The results obtained by the distillation of lapachic acid with zinc-dust,
and the nature of the bromide obtained from the gaseous hydrocarbon
evolved, indicate that the side chain C5H9 has the constitution
— CH : CH.CHMe2.
The author assigns valid reasons for believing that in monobromo-
lapachic acid the bromine takes the place of the hydrogen in the
OH-group, and that its formula is Ci5Hi3(02)".OBr, and that the
acetate is Ci5Hi3(02)".OZc. Finally, he discusses the formula of
lapacone, and considers it highly probable that it is
OH.C,oH4(C5H9)<g;^>(aHe)CioH4.0H.
c. e: g.
A New Monochlorocamphor. By P. Cazeneuve (Cmnpt.
rend., 94, 1530 — 1532). — When dry chlorine is passed into a mixture
of camphor (760 grams) and absolute alcohol (230 grams), there is
development of heat and the camphor dissolves. On cooling the
product to about 15°, it becomes a pasty mass of crystals, which, after
being collected, washed with water, and crystallised from alcohol,
forms long colourless needles of monoclilorocamijlior^ C10H15CIO. It
has an odour resembling that of camphor, is sparingly soluble in
water, but easily in ether and benzene. It softens at 75°, melts at
83 — 84°, and distils almost without decomposition at 244 — 247°. It is
also easily volatile in the vapour of water. Its specific rotatory
])ower [a]j = + 90°, is greater than that of camphor, or of the di-
chloro-derivative. It is not decomposed by an alcoholic solution of silver
nitrate or by alcoholic potash, differing greatly in this respect from
Wheeler's monochlorocamphor {Bull. Sac. Chim.y 10, 289), which
melts at 95°, and is readily decomposed when heated. C. E. G.
Contributions to the History of the Isomerism of the
Dibromocamphors. By T. Swarts (Ber., 15, 2135 — 2136). — By
heating a,-dihromocamphor for six hours at 120° in a sealed tube, in
ORGANIC CHEMISTRY. 215
•wliicli Hydrobromic acid was being evolved from a mixture of phos-
phorus bromide and syrupy phosphoric acid, the author has converted
it into ^-dihromocamphor. Hydrochloric acid does not produce the
change.
a-Dibromocamphor forms a liquid compound with chloral hydrate ;
j8-dibromocamphor has no action. The bromine-atoms in the a-body
appear very immobile ; one at least of those in the /3-body is easily
replaced, producing, with silver acetate, silver bromide and a crystalline
acetic compound.
The author believes trihromocamphor to partake of the constitution
of the two di-bromocamphors. Treated with nascent hydrogen in
alkaline solution, it gives an oil resembling turpentine, boiling at 258
— 260°. Heated with fuming nitric acid, it erives a nitro-body melting
at 175°. ^ L. T. T.
Action of Nitric Acid on Oxycamphor from /S-Dibromo-
camphor. By J. Kaohler and F. Y. Spitzer (Ber., 15, 2336 —
2337). — Oxycamphor (b. p. 259°), obtained by the action of sodium
amalgam on an alcoholic solution of /3-dibromocamphor, forms a crys-
talline barium salt, Ba(CioHi502)2. When treated with nitric acid,
oxycamphor yields a mixture of oxalic acid and nitroxycamphor,
CioHi5N04. This substance crystallises in colourless needles (m. p.
170°), which dissolve freely in hot alcohol. W. C. W.
OSnocyanin. By E. J. Maumen^ (Gompt. rend., 95, 924). —
(Enocyanin, the colouring-matter of black grapes and red wines, is of
colourless origin, and becomes blue through oxidation, and probably
hydration, which may be shown by placing a green grape picked from
a bunch which is just beginning to turn red, in a vacuum of 1 to 2 mm.
over boiled sulphuric acid for three or four days, or sufficient time
to allow of the grape becoming hard and dry. The colour becomes
yellow, but on admitting air, moisture and oxygen are rapidly
absorbed, the colour changing to blue-black at the same time.
L. T. O'S.
The Poisonous Constituent of Andromeda Japonica. By
J. F. Eykman (Pharm. J. Trans. [3], 13, 365— 367).— The aqueous
extract of the leaves of this plant, which has long been considered
as poisonous in Japan, contains a glucoside, "asebotoxin." It is a
transparent brittle colourless substance, melting at 120°, and contains
C = 60-48, H = 7-405, O = 32-115 percent. ; it is only slightly soluble
in cold water, but easily in ethyl and amyl alcohol, chloroform, &c.
The aqueous solutions are unaffected by ferric, mercuric, or gold
chloride, or by lead acetate ; but they reduce alkaline copper solutions.
The fatal dose for rabbits by hypodermic injection is 3 mgrms. for each
kilogram of the animal ; the symptoms are detailed.
Asebotoxin exhibits some fine colour-reactions, which are of im-
portance toxicologically. If an alcoholic solution of the substance
is poured into a watch-glass and strong hydrochloric acid added, a
magnificent blue colour is gradually developed, and, at the same time,
a peculiar odour resembling that of Spircea ulmaria. On evaporating
the blue solution on a water-bath, a tine violet-red tint develops itself
216 ABSTRACTS OF CHEMICAL PAPERS.
at tlie edge of the liquid. If the blue solution be left to itself, it tarns
after some time to reddish-grey, and the liquid becomes turbid from
the separation of a bluish-grey substance. Concentrated sulphuric
acid dissolves asebotoxin with a red colour, which after some time be-
comes fine rose-red, while the liquid is rendered turbid from the sepa-
ration of a bluish-grey substance. If asebotoxin is boiled with
diluted hydrochloric acid, the liquid assumes a fine rose-red colour,
and a brown resinous substance separates. The same effect is pro-
duced by diluted sulphuric acid. E. W. P.
Constituents of the Leaves of Fraxinus Excelsior. By W.
GiNTL and F. Reinitzer {Monatsh. Ghem., 3, 745 — 7G2). — The
aqueous decoction of the leaves of the ash-tree contains, as chief con-
stituents, calcium malate and a tannin, designated fraxitannic acid
by the authors, together with smaller quantities of mannitol and
inosol, and still smaller quantities of quercitrin, dextrose, ^ummy
matter, and free malic scid. To separate the fraxitannic acid, the
aqueous extract was precipitated by normal lead acetate, and the pre-
cipitate, after being quickly washed with cold water, was treated two
or three times at boiling heat with acetic acid of about 10 per cent.,
which dissolved nearly all the tannate of lead, leaving undissolved the
greater part of the malate, together with other bodies. The resulting
still impure acetic solution of the lead tannate was then precipitated
by ammonia in nine separate fractions, of which the third, fourth, and
fifth yielded the purest tannic acid, whereas the first and second con-
tained also oxidised products, which, however, being less soluble in
acetic acid than the pure lead tannate, could be separated by treating
the precipitates with quantities of acetic acid not sufficient to dissolve
the whole. The resulting solutions were then precipitated by ammo-
nia, and the precipitates, as well as those previously obtained, were
washed as quickly as possible by decantation with cold water, and de-
composed by hydrogen sulphide ; the solutions thus obtained were
filtered into a flask previously filled with carbonic anhydride ; the
filtrates were freed from hydrogen sulphide by a stream of the same
gas ; and the solutions thus purified were evaporated to dryness in a
vacuum over sulphuric acid. The first and second fractions thus
obtained were but very slightly hygroscopic, and easily pulverisable ;
the third, fourth, and fifth also only slightly hygroscopic ; whereas the
sixth, which contained considerable quantities of malic acid, and the
seventh, eighth, and ninth, were very hygroscopic, and formed syrupy
strongly acid masses, the first two containing — together with small
quantities of tannic acid — a moderate quantity of malic acid, a little
inosol, a gummy substance, and a somewhat considerable quantity of
amorphous silica, whilst the ninth fraction was destitute of tannic
acid, contained only small quantities of malic acid and mannitol, and
consisted mainly of the gummy substance just mentioned.
The first five fractions were next digested with absolute alcohol in
closed flasks, filled with carbonic anhydride and kept in the dark,
whereby the greater part of the tannic acid was dissolved to a yellow
liquid, leaving only a small quantity of a blackish-brown substance,
easily soluble in water. The united alcoholic filtrates were then freed
ORGANIC CHEMISTRY. 217
from the greater part of the alcohol by distillation in a stream of car-
bonic anhydride ; the residue was treated with water, which dissolved
it all with the exception of a very small quantity of substance, pro-
bably an anhydride, formed by the prolonged boiling with alcohol ;
and lastly, the filtrate was evaporated to dryness. The substances
thus obtained from the five fractions agreed so closely in composition,
solubility, and reactions, that they may, without hesitation, be regarded
as one and the same chemical compound.
This compound, fraxitannic acid, is an amorphous, yellow- brown,
shining, brittle mass, yielding a golden-yellow powder, which, on
exposure to moist air, gradually deliquesces to a yellow-brown shining
tenacious mass. It dissolves in water, yielding, according to the
degree of concentration, a golden-yellow to brown-red liquid, which
has a rough, bitter taste, and reddens litmus slightly; alcohol, acetic
acid, and ethyl acetate dissolve it readily, but it is quite insoluble in
benzene, chloroform, and anhydrous ether, slightly soluble in ether
containing water. The moderately concentrated aqueous solution is
precipitated by sulphuric and hydrochloric acids, yielding a light-
yellow precipitate, soluble in excess of the acids and on warming, and
reappearing as the liquid cools. From its aqueous solution, unless
very dilute, it is completely precipitated, like other tannins, on satu-
ration with common salt. The aqueous solution is not precipitated by
tartar emetic, but with normal lead acetate it gives a fine golden-yellow
precipitate, easily soluble in acetic acid, becoming brown-green on
exposure to the air, and at the same time less soluble in acetic acid.
Ferric chloride imparts a fine dark-green colour to the aqueous and
alcoholic solutions of the acid, forming a precipitate at the same time,
the colour changing to blood-red on addition of an alkaline hydroxide,
normal carbonate, or acid carbonate, these colours becoming dingy on
exposure to the air. A small quantity of the tannin solution added to
an alkaline cupric solution, throws down cuprous oxide on warming ;
with mercuric chloride, it forms a slight precipitate of calomel.
Heated with dilute acids or with baryta-water, it does not yield
glucose ; with the latter reagent, it appears to yield protocatechuic acid.
Fraxitannic acid dried in a vacuum at ordinary temperature has the
composition CuHieO?, and when heated at 100" in a stream of carbonic
anhydride, it gives off water and is converted into an anhydride,
C26H30O13 = 2C13H16O7 — H2O, which is nearly insoluble in cold, and
only slightly soluble in hot water.
The acid, if heated on the water-bath with acetic anhydride, is
converted into an acetyl-derivative, C17H20O9 = Ci3Hi4(OXc)205, form-
ing an amorphous yellowish mass, which gradually softens when
heated to 100°, and melts at a slightly higher temperature; the
liquid, after cooling, appears transparent with amber-yellow colour in
thin layers, dark brown in thicker layers. It becomes very strongly
electric on trituration. Its melting point is not determinable, as it
passes into the liquid state by very slow degrees.
The corresponding henzoyl-derivative, C27H24O9 = Ci3E[u(OBz)206,
is prepared by heating the tannic acid with fused benzoic anhydride
for several hours in a paraffin-bath at about 130° ; exhausting the mass
which solidifies on cooling with ether, which leaves the whole of the
VOL. Y.L1Y. q
218 ABSTRACTS OF CHEMICAL PAPERS.
benzoyl -derivative undissolved, tlien dissolving the residue in alcohol,
and either evaporating on the water-bath, whereby a dark-brown
residue is obtained yielding a light-brown powder, or precipitating the
alcoholic solution with water, adding calcium chloride, and heating the
liquid to cause the precipitate to settle down. The benzoyl-compound
is thus obtained as a light-brown powder insoluble in water and in
ether, but soluble in alcohol. It becomes electric by friction, though
not so strongly as the acetyl-compound. Its alcoholic solution gives
no coloration with ferric chloride.
On dropping bromine or fuming nitric acid into a well-cooled solu-
tion of acetylfraxitannic acid in glacial acetic acid, or, better, in acetic
anhydride, then precipitating with water, washing the precipitate with
cold water, and drying it in a vacuum over sulphuric acid, a light
orange-yellow powder is obtained, which dissolves very sparingly in
water or in ether, easily and with brown-red colour in alcohol. The
nitro- compound, heated on platinum-foil, suddenly takes fire with slight
detonation.
The bromacetyl-compound has the composition CaiHarBraOis + 2H2O
or a.6H25(5^0)4Br30,o + 2H2O.
The constitution of this body shows that fraxitannic acid contains
four hydroxyl-groups, and that its molecular formula is the double of
that above given, viz., CoeHsaOu = C26H28(OH)40io.
The acid, treated with manganese dioxide and sulphuric acid, gives
off a strong odour of quinone. When heated in a stream of carbonic
anhydride it liquefies at 120°, then becomes viscid and frothy, once more
fluid at 180°, and between 220° and 260° yields a small quantity of
yellowish-green oil, giving with ferric chloride a fine green colour,
probably due to admixed catechol.
The insoluble residue left in small quantity in the purification of
fraxitannic acid with absolute alcohol (p. 216), is a shining, brown-
black, easily friable, non-hygroscopic substance, which dissolves in
water to a yellowish-brown liquid, giving with lead acetate a brown-
green precipitate, similar in colour to lead f raxitannate which has been
exposed to the air. Dried in a vacuum, it has the composition
CisHieOs ; after drying at 100°, C26H30O15 = 2C13H16O8 - HzO.^ It
therefore bears to fraxitannic acid the relation of an ordinary acid to
its aldehyde.
Another body is formed when a neutral or very slightly alkaline
solution of fraxitannic acid is repeatedly evaporated on the water-
bath in an open vessel, and remains, on drenching the residue with
water, as a soft adhesive brown mass running together in a cake at the
bottom. This substance, after being dried in a vacuum, forms a brown
brittle resinous mass having the aspect of catechu. It is very slightly
soluble in cold, somewhat more in hot water, and separates on cooling
as a milky cloud, which gradually aggregates to a brown glutinous
mass. For purification, it was dissolved in alcohol of 96 per cent,
which left a residue, and separated by water into two portions, the
portion thereby precipitated being treated with absolute alcohol to
remove a small quantity of matter insoluble therein. When thus
purified, it formed a brown powder perfectly soluble in absolute, and in
not too much diluted alcohol, also in strong acetic acid and in ethyl
ORGANIC CHEMISTRY. 219
acetate, but insoluble in water, ether, and benzene. Boiling water
dissolves it in small quantity, and deposits it on cooling as a yellowish
precipitate. It dissolves readily in alkalis with deep-yellow colour
and a faint odour of tea. The alcoholic solution reacts with ferric
chloride and an alkaline cupric solution, just like fraxitannic acid.
This compound forms an acetyl- and a benzoyl-derivative, and is con-
verted by fusion with potash into a substance which gives the reaction
of protocatechuic acid with ferric chloride. Dried at 100° in a
stream of carbonic anhydride, it gives by analysis numbers agreeing
with the formula CvHgOa. It appears, however, to be formed by sepa-
ration of CO2 and H2O from several molecules of fraxitannic acid, as
shown by the equation —
5C13H16O7 - (2CO2 + 4H2O) = C,^SnOn = 9C7H8O3,
Its henzoyl-derivative, C105H96O33 = C63H66BZ6O27, is a light-brown powder
insoluble in water, alcohol, and ether, soluble in chloroform j it begins
to blacken, without fusing, at 120°.
Volatile Oil of Ash-leaves. — In preparing the aqueous decoction of
the leaves, a pleasant smell of tea is given off, due to a very small
quantity of a volatile oil, which may be separated by distilling the fresh
leaves with water, shaking the aqueous distillate with pure ether,
evaporating off the ether, dissolving the residue in alcohol, mixing
the alcoholic solution with solution of common salt, separating the oily
layer which rises to the surface, and rectifying it over calcium chloride.
The oil thus rectified forms a colourless liquid having a strong and
very pleasant odour like that of syringa flowers. It boils at 175°, and
gives by analysis numbers leading to the formula C10H20O2. It probably
belongs to the class of terpenes, but has the formula of anhydrous
terpin, although it is liquid. H. W.
Euxanthic Acid.. By A. Spiegel (Ber., 15, 1964—1969).— Eu-
xanthic acid has long been known as a conjugated compound, but the
nature of the substance into which, together with euxanthone, it is
resolved by the action of acids, has never yet been clearly ascertained.
The author employed the action of 2 per cent, sulphuric acid in sealed
tubes, and then found the product to be euxanthone and the anhy-
dride of glycuronic acid. The identity of this latter with the glycuronic
anhydride of Schmiedeberg and Meyer (Jahrb. Chem., 1879, 986)
was proved by a comparison of the crystallographic forms and chemical
reactions of the two preparations. The author considers that the
substance described by Erdmann as hamathionic acid was in reality a
sulphate of glycuronic acid, the analysis given by Erdmann of a basic
lead salt agreeing much better with the formula of the latter than
with that assigned by him to hamathionic acid. In conclusion the
author thinks that some light is thrown on the source of purree by
these results ; the view that it is a dried sediment from camels or ele-
phants' urine has lately met with disbelief, but as conjugated glycu-
ronic acids have lately been obtained several times from the urine of
animals subjected to feeding experiments, it seems reasonable to con-
clude that euxanthic acid may have a similar origin. A. J. G,
92
220 ABSTRACTS OF CHEMICAL PAPERS.
Hydrates of Pyridic Bases derived from Cinchonine. By W.
O. DE CoNiNOK (Bee. Trm. Chim., 1, 132).— The author finds that /3-col-
lidine (b. p. 195—196°) and ^-lutidine (b. p. 165—166°), left for two
months over a basin of water covered with a bell-jar, take np quanti-
ties of water, agreeing with the formulae C8HiiN,H20 and C7H9N',H20 ;
he does not, however, regard the products thus obtained as well-
defined hydrates. H. W.
Conine. By C. Schotten (Ber., 15, 1947— 1951).— The only
oxidation-product of conine at present known is normal butyric acid.
As substances of pronounced acid or basic properties are frequently
unsuitable for direct oxidation, the author first converted conine into
its urethane, a completely neutral body.
Conylurethane, CgHieN.COOEt, is best prepared by the action of ethyl
chlorocarbonate on conine in presence of aqueous potash. It is a
colourless liquid (b. p. 245°) of agreeable ethereal odour, and is lighter
than water. It is insoluble in water and in acids. It is not decom-
posed by boiling with concentrated potash or with hydrochloric acid,
nor is it decomposed when heated with aqueous ammonia in sealed
tubes at 200°. Hydrochloric acid in sealed tubes at 100° decomposes
it into conine, carbonic anhydride, and ethyl chloride. On distillation
with phosphoric acid, it yields, amongst other products, a hydrocarbon
which is probably conylene. By the action of well-cooled nitric acid
on conylurethane, a monobasic acid of the formula CvHuOo.COOEt is
obtained as a nearly colourless heavy oil of well-marked acid proper-
ties. On heating this acid with hydrochloric acid in sealed tubes at
100°, the COOEt-group is eliminated (as ethyl chloride and carbonic
anhydride), and on evaporating the solution, large crystals are
obtained of a body having the formula C7H,502N,HC1. This body is
readily soluble in water, has no poisonous properties, and gives a
platinochloride crystallising in needles or prisms. The author regards
it as the hydrochloride of an amido- or imido-acid, but he has not
succeeded in isolating the acid. A. J. G.
Conhydrine. By A. W. Hofmann (Ber., 15, 2313— 2316).— When
conhydrine, CeHnNO, is acted on by dehydrating agents, e.^., phosphoric
anhydride or concentrated hydrochloric acid, conine is not produced as
stated by Wertheim (Annalen, 127, 75), but an oily liquid is obtained
which consists of a mixture of different compounds. W. C. W.
Compounds of the Creatinine-group. By E. Duvilliee
(Com.pt. rend.^ 95, 456 — 459). — Methylarnido-ci-hutyrocyamidine or
oc-butyric-creatinine^ CeHuNaO, is obtained by the prolonged action of
cyanamide in concentrated and slightly ammoniacal aqueous solution
on methylamido-a-butyric acid. The substances are mixed in the
proportion of equal molecules, and after about one month lamellar
crystals begin to separate out, and continue to form for about four
months. At the end of this time, the crystals are removed and about
half the original quantity of cyanamide is added to the mother-liquor.
A further crop of crystals is thus obtained. The crystals dissolve in
boiling alcohol, and separate out on cooling in slender silky needles
ORGANIC CHEmSTRY. 221
composed of small rectangular plates. Tlie creatinine is not formed
by the dehydrating action of the alcohol on the original crystals, for
the latter contain no water of crystallisation and have sensibly the
same composition as the pnrified product. This is the first instance of
the formation of a creatinine without the intermediate formation of
the corresponding creatine.
Methylamido-isovalerocyamidine or Isovaleric Creatinine, CvHiaNsO, is
obtained in a similar manner by the action of cyanamide on methyl-
amido-isovaleric acid. It forms slender needles, readily soluble in
boiling alcohol.
The formulae of these compounds are —
Methylamido-a-butyrocyamidine. Methylamido-isovalerocyamidine.
^NMe.CHEt ^NMe.CH.CHMe^
nh:c< I nh:c< | ,or
^-JSTH.CO ^-NH.CO
NH : C : N.C0.Cn,ISrH(Me).CH2.Me NH :G:N.C0.CH(NHMe).CHMe2
according as the view of Strecker and Erlenmeyer, or that of Kolbe,
on the constitution of creatine and creatinine is accepted.
C. H. B.
Morphine. By E. v. Gerichten and H. Schrotter (Ber., 15,
2179 — 2183). — The object of this investigation was to examine the
nature of the two non-nitrogenous bodies C15H10O2 and Ci5H9Br02,
which the authors obtained from codeine and monobromocodeine
(Abstr., 1882, 1112). Their insolubility in dilute alkalis pointed to
their still containing the methoxyl-group present in codeine. An
attempt to split off methyl from the compound C15H10O2 by heating
with hydrochloric acid, was unsuccessful. Godethyline, C19H21NO3,
treated by Hofmann's reaction (Abstr., 1882, 921), yielded a non-
nitrogenous body, O16H12O2, homologous with the above-cited codeine
derivative. Both these bodies yield phenanthrene — leaving no doubt
of the presence of a methoxyl-group — when heated with zinc-dust,
and may therefore probably be considered as phenanthrene deriva-
tives. The following table shows the relationship of these compounds
to the morphine alkaloids : —
222
ABSTRACTS OF CHEMICAL PAPERS.
Alkaloid.
Formula.
Non-nitro-
genous deriva-
tive.
Hypothetical
intermediate
product
between non-
nitrogenous
derivative
and phenan-
tlu*ene.
Phenan-
threne.
Morphine
Codeine (mor- "
phine mono-
methylether) .
Bromocode'ine . . .
Codethy line (mor-
phine mono-
ethyl ether) , .
/OH
Oi;Hi7NO<(
\0H
/OH
C,;H,7N0<
\OMe
/OH
Ci7Hi6BrNO<
^OMe
/OH
Ci;Hi7N0<
\OEt
C14H7O.OH*
CnHyO.OMe
m. p. 65°.
Ci4H6BrO.OMe
m. p. 121— 122'
C^HyO.OEt
m. p. 59°.
► ChHsO*
CuH,
The authors consider this hypothetical intermediate product to have
,CeH
CsH*.
either the formula (i) 0<^ | yC2H2 or (ii) | y>C20, and taking
CeHs C6H4
into account the ease with which it is reduced by zinc-dust, they con-
sider (ii) as the more probable. The non- nitrogenous derivatives of
O IT
codeine and codethyline would then have the formula q^, n h*-^^*^
(where R = Me and Et respectively).
The non-nitrogenous derivative CuHvO.OEt, obtained from codethy-
line, is insoluble in water, but soluble in ether, alcohol, and acetic acid.
It crystallises well, melts at 59°, and distils almost without decom-
position. On heating it in sealed tubes with the calculated quantity
of hydriodic or hydrochloric acid, ethyl iodide or chloride is pro-
duced, together with a resinous mass, from which a very small quan-
tity of a body crystallising in white needles was extracted, insufficient
for investigation. C16H12O2 is soluble in strong sulphuric acid to a
yellow liquid having a green fluorescence, and is reprecipitated un-
changed on adding water. A nitro-derivative was obtained. Ci6Hi202
is oxidised by chromic acid, and is easily reduced to phenanthrene by
heating it with zinc-dust. L. T. T.
Cinchonine. By H. Weidel and K. Hazara (Monatsh. Chem., 3,
770 — 788). — Cinchonine oxidised with chromic acid yields, as chief
products, ciuchoninic acid and an acid brownish syrup, together with
small quantities of carbonic and formic acids.
The syrupy liquid freed from cinchoninic acid and other substances
by a series of processes for which the original paper must be con-
sulted, dried up in the exsiccator to a soft gummy mass, which showed
* C14H8O2 and CuHgO have not yet been obtained.
ORGANIC CHEMISTRY. 223
no tendency to crystallise, even after standing for a year. Its aqneous
solution decomposes carbonates at boiling heat, yielding deliquescent
uncrystallisable salts. When neutralised with an alkali, it does not
precipitate metallic salts. Heated with oxidising agents, it does not
yield either cinchoninic or pyridine-tricarboxylic acid, whence the
authors infer that the syrupy liquid obtained by the oxidation of cin-
chonine does not contain any portion of that half of the cinchonine
molecule which yields cinchoninic acid.
The syrupy liquid treated for a day with nitric acid yielded a small
quantity of nitrohydroxyquinoUne, C9H5(N'02)(OH)N, a compound
which unites both with bases and with acids, the salts which it forms
with the latter being however very unstable. Its platinochloride,
(C9H6N"203,HCl)2PtCl4, forms monoclinic crystals, in which a : b : c =
0-9705 : 1 : 0-8806 ; /i = 96° 20' 4". Optic axes nearly perpendicular
to the base. Observed faces ooPco, OP, coP, -hP, and —P.
When the residue left on evaporating the syrup over the water-
bath is distilled with zinc-dust, a light-yellow oil passes over, and
afterwards a brown viscid distillate, containing — together with ammo-
nium carbonate, pyrroHne, and bodies related thereto — the three fol-
lowing bases : —
Pyridine, CsHsI^. Ethyl-pyridine, C7H9N. Quinoline, CsHtIN'.
b. p. 120°. b. p. 161—164° b. p. 233—237°
These bases are formed from that half of the cinchonine-molecule
which is converted by oxidation into the syrupy product, and their
formation shows that cinchonine must contain two hydrogenised quino-
line-nuclei — a conclusion strengthened by the fact that tetrahydro-
cinchoninic acid, as shown by Weidel (G. J., Abstr., 1882, 531), yields
by oxidation, not cinchoninic acid, but a syrupy mass, which as the
authors find by preliminary experiments, also yields by distillation over
zinc-dust, bases of the pyridine series, respecting which they promise
a further communication. H. W.
Strychnine Sulphate. By Lextreit (/. Pharm. Chim. [5], 6,
259 — 266). — Regnault assigned to strychnine sulphate the formula
C2iH22N'202.H2S04 n" 7II2O, which was adopted by the Codex of 1866,
but subsequent researches by Schabus, Des Cloizeaux, and Rammels-
berg, who have described preparations containing from 5 to 6*5 mols. of
HoO, have failed to confirm this formula. Although a great number
of samples used in pharmacy were analysed, not one satisfied the above
formula.
To determine what hydrates exist, and the conditions under which
they form, the following research was undertaken : —
When a neutral and saturated aqueous solution of strychnine sul-
phate is allowed to crystallise between 109° and 95°, a salt of the com-
position C21H22N2O2 -f- H2SO4 + 5H2O separates out, but if the tem-
perature sinks below 95° some crystals containing 6 mols. H2O are
formed. When crystallised from alcohol it always crystallises with
5 mols. H2O. To prepare this compound, 10 parts of strychnine and
1*27 parts sulphuric acid are mixed in a flask, and 50 parts strong
224 ABSTRACTS OP CHEMICAL PAPERS.
alcohol added and gently warmed. When solution is complete, the
mixture is left to cool, and the salt crystallises ; a further crop of
crystals may be obtained from the mother-liquors. If dilute alcohol is
used, the crystals are very bulky, but its strength must not be
less than 50", otherwise square tables containing 6H2O will be formed.
The salt crystallises in slender needles from aqueous solutions, and
from alcoholic in clinorhombic prisms identical with those described
by Des Cloizeaux (Ann. Mineral, 1858, 14, 389), containing 6H2O, and
by Rammelsberg containing SHjO.
The hydrate, (C2iH22N202)2H2S04 + 6H3O, is obtained in long
slender needles when a hot concentrated solution of the neutral sul-
phate is cooled between 95 — 50° ; below 50° tabular crystals separate
out. 10 parts of strychnine are dissolved in a mixture of 1*27 parts
sulphuric acid and 35 parts water, the solution boiled, and allowed to
crystallise at 70° ; above 70° a mixture of this and the previous salt is
obtained. This salt crystallises in octohedrons, which confirms the re-
sults of Rammelsberg (Ber., 1882). Des Cloizeaux {Compt. rend., 44,
909) also obtained a salt crystallising in octohedrons, but found it to
contain 6*5 HgO. The crystals do not alter when exposed to the air,
but slowly lose their water of crystallisation over sulphuric acid, and
quickly at 100°. The anhydrous crystals reabsorb a portion only of
the water they have lost.
The salt containing 7H2O, described by Regnault, is shown by the
author from the analytical data of the former not to agree with the
formula ascribed to it.
The acid .sulphate, C21H22N2O2H2SO4 + 2H2O, is prepared by treat-
ing 1 mol. of strychnine with 1 mol. of sulphuric acid, and crystal-
lising either from alcohol or water. It forms short needles when
crystallised at a high temperature, but when slowly formed at low
temperatures they may be obtained several centimeters long. Their
form could not be determined. L. T. O'S.
Preparation of Lupinine Hydrochloride from Lupinine Resi-
dues. By G. Baumert (Ber., 15, 1951 — 1952). — In the preparation of
pure lupinine, a large amount of mother-liquors are obtained from the
frequent recrystallisations ; these contain considerable quantities of
lupinine, whose crystallisation is prevented by the impurities present.
The mother-liquors, after removal of ether, are shaken with an equal
volume of cold water, and the emulsion heated for a few minutes on
the water-bath, when it separates into two layers, the upper consisting
of water containing lupinine in suspension. On cooling, the turbidity
vanishes and the lupinine dissolves. The aqueous layer is poured off,
a.nd the residue treated several times with water in the same manner.
The aqueous extracts are then neutralised with hydrochloric acid,
evaporated, dissolved repeatedly in absolute alcohol, and evaporated to
remove water, freed from a black syrup by pressure betw^een filter-
paper, and finally crystallised from absolute alcohol, when pure lupi-
nine hydrochloride is obtained. A. J. G.
Putrid rermentation, and the Alkaloids produced by it.
By A. Gautier and A. £tard (Compt. rend., 94, 1598— 1601).— The
ORGANIC CHEMISTRY. 225
authors consider that the apparently complex phenomena of patrid
fermentation may be explained by regarding putrefaction as a breaking
up by hydration of the complex albuminoid molecule into the simple
nuclei which enter into its composition. As in the results Schiitzen-
berger obtained with barium hydroxide, so by the action of the
bacteria, the albuminoid molecule splits up first into two principal parts ;
one of these is relatively stable, giving rise to the glucoproteins and
leucines to which Schiitzenberger attributes the formula C„H2m_4N"202,
whilst the other is unstable, and decomposes rapidly, with formation of
ammonia, carbonic anhydride, and formic, acetic, and oxalic acids.
But whilst Schiitzenberger's method is incapable of hydrating the
amides formed, — the leucines and leuceines, — bacteria slowly change
them into aramoniacal salts, and also by the hydration of the crystalline
body, CiiH26N'206, produced abundantly in the putrefaction of fish.
Putrefaction being essentially a process of hydration, it follows
that the aromatic derivatives and the bases formed during the fer-
mentation pre-exist as nuclei in the albuminoid molecule. In order
to obtain the bases, the liquid products of putrefaction of the skate
are acidulated with sulphuric acid and evaporated in a vacuum,
whereby indole, phenol, and other volatile products are removed ; the
residue is then treated with baryta and chloroform, which dissolves the
bases. After purification, they are colourless oily liquids having all
the characters of the bases described by Selmi. They have an odour
like that of the carbylamines, recalling that of hawthorn and hydro-
collidine, resinify rapidly, and give the reactions of the ptomaines.
The hydrochlorides crystallise well, and yield sparingly soluble crys-
talline platinochlorides.
By fractionation, two bases were isolated, one having the formula
of parvoline, C9H13N, and yielding a platinochloride which becomes
rose-coloured on exposure to the air, the other an oil boiling at about
110°. The latter gives a hydrochloride crystallising in slender needles
of bitter taste. The platinochloride is pale-yellow, and sparingly
soluble ; the aurochloride is very unstable. Although the analytical
results agree better A\ith the formula CgHuN, the author assigns to
this base the formula CsHigN, as the boiling point, viscosity, and
general properties so very closely resemble those of Cahours and
Etard's hydrocoUidine, with which he believes it to be isomeric.
From these considerations, the occurrence of indole and of pyridic
and of hydropyridic bases amongst the products derived from albu-
minoids by putrefactive hydration, the authors feel compelled to
admit the existence of the homologous series CsHeN and C5H7N in
the radicles of the prote'id molecule. C. E. G.
Invertin. By M. J. Kjeldahl (Bied. Centr., 1882, 791).— Tem-
perature has different effects on the action of invertin from surface
and from bottom yeast. Bottom yeast acts best on saccharose at 52 —
53^, whilst surface yeast is most energetic at 56°. The action of the
invertin also increases with the concentration until a certain limit
(20 per cent.) is attained.
At the commencement, the action is proportional to the time of
action, and also the amount of invertin, so long as not more than
226 ABSTRACTS OF CHEMICAL PAPERS.
40 per cent, of the whole sugar originally present has been converted.
Alkalis and mercury salts cause the action to cease, whilst acids aid
it at starting. On leevulose, dextrose, maltose, dextrin, and inulin,
invertin has no effect. E. W. P.
Physiological Chemistry.
Spontaneous Fermentation of Animal Matters. By A.
B^CHAMP {Gomjpt. rend., 94, 1533 — 1536). — The results already pub-
lished by the author and others show that alcohol is produced in
the spontaneous fermentation of animal matters, such as eggs, liver,
horse-flesh, &c., thus raising the question as to whether alcohol is not
produced in the tissues of the human organism itself ; this has been
answered in the affirmative, alcohol having been found in the uriue of
a subject who had abstained from taking alcoholic drinks, in freshly
drawn milk, and in the muscles of animals recently killed.
The only histological elements in the organism which persist after
death being the microzymas, it is natural to regard them as the orga-
nised ferments, producing alcohol, acetic acid, &c. ; moreover, the pre-
sence of alcohol in the tissues indicates one of the causes of the dis-
appearance of sugar. The fermentable matter which is the first to
disappear after death is glucose or glycogen, and this change is caused
by the microzymas from which the bacteria are evolved, since they
never attack the albuminoid matters until after the sugars have been
completely destroyed, and it is then only under certain conditions,
with free access of oxygen, that the animal matter is finally resolved
into carbonic anhydride, water, and nitrogen, or nitrogenous com-
pounds.
The author concludes by affirming that the microzymas are the
active chemical and physiological agents, whereby the transforma-
tions in the organism are effected both when living and after death.
C. E. G.
Effect of Pood on Sheep of Different Breeds. By H. Weiske,
G. Kennepohl, and B. Schulze {Bied. Gentr., 1882, 743 — 745). — It
is a well-known fact that the same quantity and quality of food given
to sheep of different breeds does not produce like effects. To prove
this fact experimentally, a sheep of the Bambouillet breed and a
Southdown-merino were fed with like food. The digestive coefficients
for each constituent of the food was found to be almost identical.
Comparison of the amount of nitrogen retained by the two sheep
showed that the Rambouillet sheep, which is well known as a bad
" doer," retained the largest quantity, and this is probably due to the
great amount of wool which grew. So far these experiments show no
great difference between the races. A further set of experiments
will be made to determine whether the difference lies in the laying on
of fat, &c. E. W. P.
PHYSIOLOGICAL CHEMISTRY. 227
Artificial and Natural Digestion of Nitrogenous Matter.
By T. Pfeiffer {Bied. Centr., 1882, 739— 743).— Stutzer (Abstr.,
1239) divides proteid matter into albuminoids (digestible) and nnclein
(indigestible), and considers that by means of artificial digestion a
quantitative separation of the two can be accomplished. The author,
however, judging from experiments on sheep, considers that Stutzer's
conclusions are incorrect, as nuclein does not pass through the system
unaltered, and he finds that the nucle'iu nitrogen excreted is 25 — 30
* per cent, less than that given in the food. E. W. P.
Excretion of Nitrogen from the Skin. By J. B. Powee (Proc.
Boy. Soc, 33, 354 — 360). — The results obtained by various experi-
menters on the excretion of nitrogen in the sweat have proved contra-
dictory ; Berzelius, Favre, Punke and others, have found nitrogen,
whilst Voit, Ranke, and Parkes have denied its existence. The author
takes exception to Funke's method of procedure, which presupposes
an equality of secretive power, and identity of chemical composition
of the sweat from the arm with that excreted from the rest of the
body. The author by a suitable apparatus and a method whereby the
sweat from the whole of the body is collected, finds, as a mean of 25
experiments, that 0"038 gram of nitrogen existing in some soluble form
is excreted per hour. Healthy subjects were operated on, and also
patients suffering from Bright's disease, catarrh, gout, acute rheuma-
tism, and nephritis.
Several determinations were made of the quantities of nitrogen pre-
sent in some insoluble form, e.g., epithelium, and also of the sodium
chloride in the sweat ; the proportion of the latter to the nitrogen
is about 10 : 1. The author concludes that the cutaneous excretion of
nitrogen is so small, that it can never replace the renal excretion to
any appreciable extent. V. H. Y.
Milking of Cows Twice or Thrice Daily. By Erlenmeyer
(Bied. Centr., 1882, 785). — The amount of milk is dependent on the
activity of the milk glands, as well as on the fodder supplied. Mid-
day milk is the richest in fat, morning milk the poorest, because a
longer timehaving elapsed since the evening milking, a greater quantity
of milk is formed. Experimental data- are given in support of these
statements. E. W. P.
Nitrites in Human Saliva. By R. N. Musgrave (Ghem. News,
46, 217). — By means of sulphanilic acid followed by naphthylamine
hydrochloride, nitrites were detected in the saliva of numerous per-
sons, the quantity varying between 0'4 — 2*0 parts nitrogen per mil-
lion ; the amount varied for the same person at different times, for
example, the amount present before breakfast was O'O, after breakfast
(10 — 11 A.M.) 2*2, and between 1 and 2 p.m., 1*3 parts per million.
E. W. P.
Cause of the Evolution of Oxygen from Hydrogen Peroxide
by Fibrin ; Influence of Hydrocyanic Acid in Preventing the
Activity of Fibrin. By A. B^champ (Compt rend., 95, 925—926).
Thenard believes that fibrin decomposes hydrogen peroxide in a man-
228 ABSTRACTS OF CHEMICAL PAPERS.
ner similar to silver and platinum ; he ascertained that oxygen was
not absorbed, neither was carbonic anhydride evolved ; and from the
conditions of his experiments, he concludes that the fibrin does not
lose weight, and suffers no modification. The liberation of oxygen
from hydrogen dioxide by the red colouring matter of blood and by
haematosin has been shown by the author to be accompanied with
oxidation, and a change in the bodies themselves. The author is of
opinion that Thenard was misled in his conclusions by the amount of
oxygen absorbed, and the loss of weight being too small to be mea-
sured. The author shows that this property soon ceases, and with it
that of rendering starch soluble.
30 grams of fibrin were treated three times with 60 c.c. of hydrogen
peroxide (containing 10*5 c.c. oxygen per c.c.) free from acid. The
first time, oxygen was rapidly evolved, the second time more slowly,
and the third time after 24 hours no more gas was evolved. After
ascertaining that the solution contained excess of hydrogen peroxide,
the experiment was stopped. From 180 c.c. of hydrogen peroxide
1600 c.c. of oxygen were evolved by 30 grams fibrin in 48 hours. The
solutions were separated from the fibrin which was finally pressed, and
evaporated at about 90" ; the residue dried at 100° amounted to 0*2
gram, of which 0*16 gram was organic matter. The fibrin remain-
ing did not decompose hydrogen dioxide nor render starch soluble
even after remaining in contact with it eight days, whilst fibrin
from the same source previous to treatment with hydrogen peroxide
rendered starch-paste fluid in six hours. Moreover, it gave rise to no
bacteria.
The stoppage of the action of fibrin on hydrogen peroxide by
hydrocyanic acid is thought to be due to the oxidation of the acid,
since if sufficient hydrogen peroxide is present, the action is resumed
after a certain time. L. T. O'S.
Lupine Sickness in Sheep. By Haemuth and others (Bied,
Centr., 1882, 74i6 — 749). — Harmuth attributes an attack of lupine
sickness which occurred to one of his flocks to dirt, &c., which was
blown by a high wind and settled on the crop, whilst another crop
which was not thus afl'ected, produced no evil effects on sheep.
Cream of tartar and sulphur readily cured the flock. It is quite pos-
sible that the dirt and sand thus taken in did do some harm, but
Arnold refers the sickness to fungus. Arnold and Kuhn consider
that in lupines there is a substance, ictrogen, which becomes more in-
soluble as the plant ages, so that if the crop be exposed to rain,
ictrogen is more or less removed according to the age of the plant,
but this ictrogen under the action of a ferment produces the poisonous
compound. E. W. P.
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 229
Chemistry of Vegetable Physiology and Agriculture.
A New Milk Ferment. By E. Kern (Bted. Gentr., 1882, 789).—
In the Caucasus " kephir," a thick acid drink, which on keeping
changes into coumiss, is prepared from sweet milk by adding to it
masses of a ferment ; the ferment consists of yeast and schizomycetes
cells, and these last seem to be allied to Bacillus, and have been named
Dispora caucasica ; drying has no effect on the activity of this fer-
ment, and the dispora growing threadwise retains its life though
dried hard as a stone. E. W. P.
Reduction of Sulphates by Living Organisms. By A. JfixAiiD
and L. Olivier (Gompt. rend., 95, 846 — 849). — In the protoplasm of
the cells of certain algae, such as Beggiatoa, dark granules are found
soluble in ether, chloroform, and especially in carbon bisulphide.
These granules disappear when the algae are placed in water free from
sulphates, but on the contrary are formed when the organisms in
question are cultivated in liquids rich in calcium sulphate. Hence
the authors conclude that these granules consist of sulphur. These
algse flourish extremely well in liquids containing, in addition to sul-
phates, traces of selenium. At least three distinct kinds of algae
possess the power of reducing sulphates and disengaging sulphuretted
hydrogen. Most authors in treating of mineral waters state that the
organic matter exists in solution in the liquid, and becomes insoluble
in contact with the air. The authors' experiments have led them to
think that living organisms exercise an influence on the saline
matters present in water, which could not be suspected, except by
the light of the above experiments, and they think that sufficient
notice of these facts is not taken in works on medicine.
E. H. E.
Reduction of Nitrates in the Soil. ByD^n^RAiN and Maquennb
{Go7npt. rend., 95, 691 — 693). — The reduction of nitrates takes place
only in arable soils containing a considerable proportion of organic
matter, and only when the atmosphere surrounding the soil is entirely
free from oxygen. The proportion of gas evolved is influenced to a
greater extent by the amount of organic matter present than by the
amount of nitrate, but even when the proportion of organic matter is
large, its volume never corresponds with the volume of gas in the
nitrate. The gas given off consists of carbonic anhydride and
nitrogen, but under certain special conditions nitrous oxide is evolved.
In one experiment with 300 grams of garden earth containing 30 grams
of potassium nitrate, the nitrous oxide amounted to 11*75 per cent, of
the volume of gas evolved: and with 300 grams of earth and 10 grams
of nitrate, it amounted to 9*35 per cent. C. H. B.
Reduction of Nitrates in Arable Soil. By D^h^rain and
Maquenne {Gompt. rend.y 95, 732 — 734 and 854 — 856). — Schloesing
230 ABSTRACTS OF CHEMICAL PAPERS.
and Miintz have sliowii that soil capable of producing nitrates loses
that property if heated to 100", or if treated with chloroform, but that
soil rendered inactive by heat regains its activity if mixed with a
little fresh active soil. The authors, following exactly the methods
described by Pasteur, have shown that the same effects are produced
by similar treatment on soils capable of reducing nitrates. The fer-
ment capable of effecting the reduction of nitrates seems to be in-
capable of living iu oxygen, since in no case did the authors find any
action when oxygen was present. Since Schloesing has found that
nitrification takes place, although with less energy, in an atmosphere
poor in oxygen, whereas the converse action never takes place but in
the complete absence of that gas, it seems highly improbable that
reduction commonly happens in arable soils ; but it is very likely that
in many instances the loss of nitrogen observed is due to the forma-
tion of nitrates and their subsequent removal by drainage-water.
When soil capable of reducing nitrates in the absence of air is
added to a 1 per cent, solution of sugar mixed with a small quantity
of nitre, and the whole placed in a flask completely filled with the
liquid and kept at about 35°, fermentation commences and gas is
evolved, consisting of a mixture of carbonic anhydride, nitrous oxide,
and nitrogen, and in some cases hydrogen. The composition of the
gas varies with the energy of the fermentation. When hydrogen is
evolved, the water from the flask smells of butyric acid. This led the
authors to suspect the presence of the butyric ferment of Pasteur,
described by Van Tieghem under the name Bacillus amylohacter, and
large numbers of these organisms were detected by microscopic ex-
amination. Hence the authors attribute the reduction of nitrates to
the action of this organism. E. H. R.
Fermentation of Nitrates. By Gaton and Dupetit (Compt
rend., 95, 644 — 646). — If sewage-water is mixed with 0'02 gram
of potassium nitrate per litre and some decomposed urine is added, the
nitrate gradually disappears and the liquid becomes full of micro-
scopic organisms. By successive cultivations, O'l and even 0*2 gram
of potassium nitrate per litre can be reduced, "but the reaction ceases at
this limit. With fowl-broth neutralised with dilute potash, however,
5 per cent, potassium nitrate can be completely decomposed, and
10 per cent, partially. The denitrification is effected by the organisms
which are developed ; for if the liquid is sterilised by heat, or is mixed
with chloroform or copper sulphate, the liquid remains clear and the
nitrate is not altered. The temperature most favourable to the deve-
lopment of these organisms lies between 35° and 40°, and the presence
of organic matter is essential. Sugar, ordinary alcohol, and especially
propyl alcohol, give the best results. Phenol and salicyhc acid, added
in quantities even greater than those which are usually antiseptic, do
not prevent fermentation, but, like other forms of organic matter, are
decomposed together with the nitrate. In the process of fermentation,
a large proportion of nitrogen is given ofi" as gas, the remainder
forming ammonia, and perhaps nitrogen-compounds derived from the
organic matter; the oxygen is converted into carbonic anhydride,
which remains in solution in the form of neutml or acid carbonate.
VE(iETABLE PHYSIOLOGY AND AGRICULTURE. 231
The organic matters cause the products of the fermentation of the
nitrate to enter into new combinations. Sodium, ammonium, and
calcium nitrate ferment in the same manner as the potassium salt.
C. H. B.
Absorption of Metallic Oxides by Plants. By F. C. Phillips
(Ghem. News, 46, 224 — 226). — Freytag has always upheld that
plants absorb oxides which are unnecessary for their growth, and
poisonous ; and as others have combatted this statement, the author
grew several plants in soils to which had been added various oxides.
Ageratums placed in soil containing 0*5 per cent, white lead matured
and produced flowers ; their roots were abundant, but the leaves were
yellowish ; lead was absorbed into the plant. Geraniums in soil con-
taining 0"5 per cent, zinc carbonate grew normally, but contained
zinc. Achyranthes in soil containing 0*5 per cent, copper carbonate
grew at first normally, but the leaves soon darkened and the roots
died ; their ash contained copper in small quantities. Coleas in soil
containing 0"5 per cent, calcium arsenate soon languished and died in
two weeks. In another series, coleas growing in soil to which had been
added 0*25 per cent, calcium arsenate, never matured, and the roots
perished ; only traces of arsenic were discovered in the ash. Although
zinc was found in considerable quantities in the ashes of pansies
growing in soil containing 0*5 per cent, zinc carbonate, yet the plants
appeared healthy. The conclusions drawn from the experiments are —
that plants may absorb small quantities of lead, copper, zinc, and
arsenic ; zinc and lead may enter into the tissues without causing any
disturbance in the formation of the plant ; compounds of copper and
arsenic exert a distinctly poisonous effect. E. W. P.
Composition of the Banana at Different Stages of Maturity.
By L. RicciARDi (Gompt. rend., 95, 393 — 395). — The pulp has the
following composition : — •
Q-reen. Ripe.
Water (driven off at 110°) .... 70-92 6678
Cellulose 0-36 0-17
Starch 12*06 traces
Tannin 6*53 0-34
Fat 0-21 0-68
Inverted sugar O'OS 20*07
Cane-sugar 1*34 4*50
Prote'id substances 3*04 4*92
Ash. 1-04 0-95
Other substances 4*42 1*69
100-00 100-00
The ash freed from carbon and carbonic anhydride contains —
SiOa. SO3. P2O5. CI. FeaOg. CaO. MgO.
6-77 3-06 23-18 traces traces 6-13 9*79
NagO. KoO.
6-79 45-23 = 99 95
232 ABSTRACTS OF CHEMICAL PAPERS.
The green fruit contains aboat 12 per cent, of starch, which dis-
appears in the ripe fruit. The sugar in the fruit which ripens on the
plant is almost entirely cane-sugar, but that in fruit cut and ripened
by exposure to air consists of about 80 per cent, invert sugar and
20 per cent, cane-sugar; the organic acids and tannin in the green
fruit disap])ear in the ripe fruit. The pulp of the fruit allowed to stay
on the vine until the rind becomes almost black contains no ethyl
alcohol. It is evident, therefore, that the carbonic anhydride given off
by the banana in the third stage of its maturity is not produced by
alcoholic fermentation. Neither can it be derived from the destruction
of the tannin, since the latter has almost entirely disappeared in the
ripe fruit. The evolution of carbonic anhydride is possibly the result
of true eremacausis. C. H. B.
Oxalic Acid in Potatoes and in Malt. By M. Siewert
(Landw. Versuchs.-Stat.j 28, 263 — 270). — An incrustation found in
the worm of an apparatus used for cooling the sweet wort, on being
analysed, proved to be crystallised calcium oxalate ; the mash usually
employed consisting of potatoes and malt. In order to decide the
question of the origin of this incrustation, samples were taken of the
sweet uncooled, and the fermented wort, of the slime deposited from
the mash, and of fresh potatoes and nialt, and investigated with
regard to their percentage of oxalic acid.
It was found unnecessary to filter the wort hot, as no oxalate sepa-
rated on cooling. One litre of the cold filtered sweet wort contained
0077 gram oxalic acid; the total amount in one litre of unfiltered
wort being 0'134 gram, or 0"059 per cent, of the total acids. The
fermented mash contained 0'155 gram oxalic acid per litre, or 0'189
per cent, of total sohds ; whilst in the deposit was found O'l 96 gram
per litre, or 0*4 per cent, of dry substance.
The amount of oxalic acid in potatoes was determined by boiling
the pulp with sodium carbonate, precipitating the filtrate with calcium
chloride and excess of acetic acid ; the decomposition with soda and
reprecipitation with calcium chloride being repeated until a tolerably
pure product was obtained. The first sample of potatoes analysed
contained 0*017 per cent., and the second 0*057 per cent, of acid.
This was, however, not sufficient to account for the whole of the
oxalic acid in the mash, and the malt used was therefore investigated.
In this case, the starch was first made soluble by heating with tartaric
acid at 145° ; but this process was found to be attended by a con-
siderable decomposition of oxalic acid. The starch was therefore
converted into sugar by heating the malt for some time at 62*, and
the oxalic acid then determined in the usual manner. The malt was
found to contain only 00015 per cent., and germinated grain 0*064 per
cent, oxalic acid. J. K. C.
Average Amount of Caffeine in the Guarana of Commerce
as compared -with that in the Seeds, &c. By J. H. Feemster
{Pharm. J. Trans. [3], 13, 363). — From several samples of guarana
seeds, 5*08 per cent, caffeine was obtained. Using this as a basis
of comparison with five samples of guarana, it was found that
f
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 233
their average percentage amounted to 4-32. The best method of ex-
tracting the caffeine was found to be Greene's (Ghem. J., 1877, 2,
627). The best menstruum for the extraction was a solution con-
taining 8 parts of alcohol, 4 of glycerol, made up with water to 20
parts. Dilute alcoholic extracts have a tendency to form a deposit.
E. W. P.
Researches on the Causes of Clover Sickness. By V.
KuTZLEB (Bied. Gentr., 1882, 728— 735) .—As the result of the exami-
nation of a special district affected with clover sickness, the author
comes to the conclusion that this condition is due to want of potash
in the soil, especially the want of soluble salts of potassium in the
subsoil. The theory that clover sickness is due to decaying vegetable
matter is incorrect, as is also that put forward by Linde, who attributes
all to the presence of Pleosporco herharum ; the reduction in the yield of
clover may in part be due to the presence of parasites, such as Peziza
ciborioides, or Tylenchtis devastatrix, or T. havensteinii ; but in the cases
when these parasites were found, the general appearances did not
resemble those presented by clover sickness. A form of Phacidium
medicaginis has been found on clover; but as it is also to be found
on other allied plants which do not suffer, the disease cannot be
attributed to this parasite. E. W. P.
On Phylloxera. By P. de Lafitte and others (Bied. Gentr., 1882,
761). — Lafitte does not approve of V. Mayet's method of treating
infected vineyards (Abstr., 1881, 1069). According to Boiteau, the
winged insect was not produced in such great numbers as usual,
owing to the dryness of July, August, and September, 1881 ; con-
sequently, he concluded that winter eggs would be fewer in number,
as also the galls in 1882. These conclusions have now been found to
be correct. Pellicot and Jaubert recommend ferrous sulphate as
destructive to phylloxera. Vannuccini considers that the natural and
artificial moisture of sandy soils, together with the character of the
vines themselves, is the only cause of the power of resisting the
disease possessed by certain vines growing in such soils.
E. W. P.
Cure for Potato Disease. By J. L. Jensen (Bied. Gentr., 1882,
755 — 759). — It is recommended that, after the disease has attacked the
leaves, the soil should be well ridged up, forming a ridge steep
enough to induce the rain to run into the furrows ; it should also be
made so that the haulms should be bent over the furrow. All this
is proposed so that the disease spores which fall off the leaf may not
be washed down by rain into the soil and so attack the tubers. It is
best not to lift the potatoes until 2 — 3 weeks have elapsed after the
full ripening, as it appears that the germs retain vitality up to that
date. E. W. P.
Atmospheric Nitrification. Ry A. Muntz and E. Aubin (Gompt.
rend., 95, 919 — 921). — The authors have examined six samples of
rain, three of mist, and four of snow at the summit of the Pic du Midi
for the presence of nitrates, but, with two exceptions, they failed to
VOL. XLIY. r
234 ABSTRACTS OF CHEMICAL PAPERS.
detect any ; in these two cases the amount present was somewhat less
than O'l mgram. per 10 litres. In the examination, 10 litres were used,
and the rain gange was of sufficient size to allow of that amount of water
being collected in so short a time as to exclude the idea of the reduction
of nitrates.* The results are at variance with those of Barral, Bence
Jones, and Boussingault, who, with rare exceptions, always found
nitrates present in rain, the experiments of Boussingault giving a
mean of 0'5 mgram. per litre.
This absence of nitrates at an altitude of nearly 3000 meters would
lead to the conclusion that the formation of nitrates in the atmosphere
during thunderstorms takes place in regions below that height.
Observations have shown that 184 thunderstorms have been observed
from the Pic du Midi from August, 1873, to August, 1882, with an inter-
ruption from September, 187ii, to June, 1874. Of these, only 23 took
place at altitudes above 2300 meters. No observation is recorded
of a storm taking place at a greater height than the summit of the Pic.
It may therefore be concluded that in the Pyrenean region the violent
electric disturbances which give rise to storms do not take place at an
altitude of 3000 meters, and therefore the formation of nitrates under
their influence takes place in lower regions.
Although these results are isolated, yet their concordance may lead
to the following generalisation. Atmospheric nitrification is pro-
duced in the lower regions of the atmosphere in the zone between the
levels of the earth and sea and the mean height of the clouds. The
ammonium nitrate is in a state of powder, and does not rise to any
great height. The observations confirm the opinion of Boussingault
that the ammonium nitrate is not in a state of tension in the atmo-
sphere, otherwise it would diffuse itself uniformly throughout the
different atmospheric strata in a manner similar to the carbonic
anhydride and ammonia. This absence of powdered nitrates at
great altitudes accounts for the transparency of the atmosphere in
them, and shows that the mountain vegetation and mountain soils can
derive the nitrogenous matters which hthey contain only from the
atmospheric ammonia. L. T. O'S.
Hailstorms and their Origin. ByRiNiCKER and Dossekel (Bied.
Centr., 1882, 721). — The transformation of a thunderstorm into a
hailstorm is caused by local peculiarities ; the direction of these storms
is from S.W., W., and N.W., and the fall of hail occurs only when
after a succession of hot days thunder-clouds pass first over barren
and thinly- wooded high land, and then, meeting with contrary or side-
winds, are brought to rest over well- wooded and warm valleys. Hail-
storms are never produced from thunderstorms which have passed
over high-lying fir woods, for then the electricity has been sufficiently
abstracted to prevent the formation of hailstones. The size of the
stones is proportional to the height from which they fall, high locali-
ties receiving only small stones ; stones of the size of hazel-nuts fall
* During the evaporation of the water, access of air was prevented, thus avoid-
ing contamination by the nitrates contained in the products of combustion of
the source of heat, a source of error pointed out by Schonbein, and subsequently by
Warington.
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 235
from a height of 100 m., while those as large as walnuts have fallen
through a distance of 200 m. Storms descending into villages from
the ridges of high mountains are the most severe. From all the
observations made it is clear that by planting the higher mountainous
regions with trees, the greater number of hailstorms which would
otherwise occur may be prevented.
Dossekel in another district of Switzerland comes independently to
the same conclusion as those mentioned above. E. W. P.
Cultivation of various Crops. By J. Fittbogex and others
{Bied. Gentr., 1882, 745 — 762). — Fittbogen, comparing the crops
obtained by sowing Hallett's Pedigree, SheriflTs Square-head, and New
Zealand White Wheat, finds that Square-head produces the best yield
in all respects, and that the amount of nutrients in all three sorts is
the same. Oppenau grew three sorts of roots, and found that Chaoi-
pion Yellow Globe gave the highest yield and with the narrowest
nutrient ratio. Hoffmann obtained a yield of prickly comfrey of
1200 — 3000 cm. per morgen, cutting it twice in the first year, but
4 — 5 times during each of the succeeding 20 years; it should be
mixed with chaff, &c., as owing to its roughness it is at first some-
what distasteful to animals. E. W. P.
Soja Bean. By E. Kinch (Bied. Gentr., 1882, 753— 755).— A
number of analyses of the bean from various sources are given : 10
per cent, of the carbohydrates are analogous to mellitose, and of the
albuminoids 1 per cent, is as peptone, and 1 — 2 per cent, as amides ;
the high percentage of albuminoids (37*8 per cent, in the Japanese)
places this bean above all other leguminosaB — in fact the composition
in this respect approximates to that of meat ; moreover, the straw
surpasses in value that of wheat and lentils and also hay as regards
nitrogen. Tables of the composition of various Japanese foods made
from soja are also given, as well as of the ash-constituents of the bean
and straw. E. W. P.
Chemical Studies on the White Sugar-beet of Silesia, By
H. Leplat (Compt. rend., 95, 760—763; 851— 854).— These papers
contain the results obtained by the analyses of the roots, stalks, and
leaves of the beet in different stages of its growth, and the author gives
an account, first, of the amounts of organic salts of potassium and
calcium, taken as a whole, in different parts of the plant at different
stages of vegetation ; secondly, of the quantities of these salts in the
soluble state in the juice, and in the insoluble state in the tissues ;
and, finally, of the condition of that portion of these salts which is
found in the insoluble state in the tissues. The author discusses also
to some extent the effect of different soils on the amounts of potassium
and calcium to be found in the plant.
In continuation of his researches on this subject, the author has
analysed the roots, leaves, and stalks of the beet, with especial reference
to the richness of the roots in sugar. The quantity of sugar found
appears to be closely connected with the quantity of calcium in the
form of organic insoluble salts in all parts of the plant during growth.
r 2
236 ABSTRACTS OP CHEMICAL PAPERS.
Whenever the richness in sugar decreases, the quantity of organic in-
soluble calcium salts diminishes in all parts of the plant. These
calcium salts have also an important influence in diminishing the rate
of decrease of richness with increase of volume of the root.
The decrease of richness of the root under the influence of increase
of volume and weight corresponds to a decrease in the quantity of
calcium carbonate in the immediate neighbourhood of the root.
The means of diminishing the exhaustion of the soil and conse-
quently the influence of that exhaustion on the richness of the root,
consists in multiplying the points of contact of the rootlets with the
soil by increasing the number of roots to a given surface of soil — that
is, by growing the roots more closely together. This corresponds
with the well-known fact that the yield of sugar is very much in-
creased when the plants are grown close together. E. H. B.
Influence Exerted by the Weight of Potato "Sets." By
ToBisCH (Bied. Gentr.j 1882, 759). — To the advantage gained by using
heavy sets there is a limit beyond which the increase of yield is less
than the weight of the sets employed ; moreover, the number of
diseased tubers increases with increased size of the sets.
E. W. P.
Amount of Gluten in Wheat. By Stumpf (Bied. Cmtr., 1882,
786). — The best German and American summer wheats contain
24 per cent, of gluten ; South Russian, 45 per cent. ; Californian and
Australian 23 — 24 per cent. Russian wheat is mixed with starchy
English wheat, and sold under the name of " Mixed Danzig Wheat."
E. W. P.
Albuminoid and Non-albuminoid Nitrogen Compounds of
certain Vegetables. By C. Bohmer (Landw. Versuchs.-Stat, 28,
247 — 262). — The vegetables examined were those ordinarily used for
human food ; they were grown in the garden of the Experimental
Station at Miinster, and cut and dried when fit for use. The samples
were analysed with regard to total nitrogen, fibre, ash, &c. : the
amount of total nitrogen varied from 1*9 in carrots, to 5*57 per cent,
in broad beans, but ranged in all cases, except the former, between
4 and 5*5 per cent. : the percentage of water varied from 4*3 in the
trufile to 96 in asparagus.
In splitting up the nitrogenous bodies into their various groups, the
method of Stutzer was employed, together with precipitation by lead
hydroxide, and the method by difference. Concordant results were
obtained by all three methods. The ammonia was determined by
means of milk of lime, as recommended by Schloesing and modified by
Schulze and Emmerling, and estimated as platinochloride. To sepa-
rate and determine the quantities of amido-acids and acid amides, the
albuminoids were precipitated with cupric hydroxide, and the filtrate
was concentrated and divided into three equal parts, the first of which
was treated at once with hypobromite, and the second after two hours'
boiling with hydrochloric acid and neutralisation : the difference of
the two gave the nitrogen of the carboxyl-groups, i.e., of the amido-
acid amides. The third portion, after being boiled first with hydro-
chloric acid and then with potash to drive off ammonia, was used for
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
237
tbe determination of the pure amido-acids by means of nitrous acid,
the nitric oxide formed being absorbed by a strong solution of per-
manganate.
As the following table shows, the above determinations do not
exhaust the total quantity of nitrogen present ; the remainder was
found not to belong, in any considerable quantity, to the peptone-
group, but must be classed under the heading of peptoid bodies, sub-
stances which have a position intermediate between peptones and the
crystalline final decomposition-products of albumin.
The appended table gives the percentages in the dried substance : —
Total
nitrogen.
Spinach 4*56
Peas 4-69
Beans b'b7
Asparagus 4' 13
Lettuce 4'85
Carrot 1-91
Turnip -cabbage. ... 4*64
Cauliflower 6'11
French beans. 4*32
Mushrooms 4*68
Truffles 4-50
Nas
N as amido-
Nas
albumi-
Nas
acid
amido-
noids.
NH3.
amide.
acid.
3-51
0-021
0-123
0-068
3-56
0-020
0-052
0-361
4-39
0-013
0-027
0-059
3-33
?
—
—
2-97
0-024
0-155
0-154
1-57
0-006
0-013
0-142
2-05
0-018
0-151
0-231
2-60
0-017
0-104
0-566
2-67
0-010
0-061
0-442
3-34
0-011
0-092
0-416
3-63
0-008
0-072
0-202
J. K. 0.
Fertility of a Soil as Dependent on the Action of Worms.
By N. Hensen (Bied. Gentr., 1882, 723— 727).— A portion of this
paper is devoted to a short account of the work of others on the
action of worms in the soil ; the analyses of "worm earth" as com-
pared with that of ordinary soil are given, and from these analyses
it is evident that the composition of worm earth is not far removed
from that of ordinary leaf mould. That the ordinary earthworm
(Lumhricus terrestris) eats earth is undoubted, but it does so only for
the purposes of forming its burrow, whilst for the purposes of
nourishment it feeds on decayed vegetable matter. By its varied
actions the worm causes an even distribution of natural manurial
matter through the soil ; by removing leaves and other loose particles
from the wind the decay of matter is rendered more rapid, decayed
matter is distributed through the soil, and the subsoil is rendered
more open for the roots of plants. The worms as a rule live in the
upper soil, descending only during very cold weather. The passages
left by worms are of importance to rootlets, for there they always find
moisture and an atmosphere rich in carbonic anhydride, and even
during winter there is always moisture to be found in these passages,
for moisture rising from below and unable to pass away from the
surface owing to its frozen condition, is condensed like dew on the
rootlets. E. W. P.
Effect on the Fertility of the Soil produced by Covering
it with Farmyard Manure. By E. Wollnt {Bied, Centr., 1882,
238 ABSTRACTS OP CHEMICAL PAPERS.
735 — 738). — A not unimportant effect produced by spreading dung
on a field is that the soil is kept warmer in winter and cooler in
summer, and this action is intensified by a larger amount of enclosed
air, as in the case of straw, which shelters the ground more than well-
rotted dung. Again, this covering of manure lowers the evaporation
of water, which results in a higher percentage of moisture in the
soil, and a consequent increase in the amount of drain age- water.
These actions are not always of use, so much depending on the
character of the soil. Clover, sainfoin, and lucerne are all benefited
by shelter, and are enabled to start growing earlier in the spring.
But if a soil, such as clay, is highly retentive of moisture, then the
quantity of water retained is too great, and the crops suffer in con-
sequence. Further, close heavy soils which are benefited by frost,
whereby they are lightened, remain heavy, and if the field is on a
hill-side, and soaked with water, heavy rains will wash away
all nourishment. The covering of manure raises the percentage of
drainage-water running from light soils, and thus there is a loss of plant
food ; but on soils of medium texture this method of application
cannot be too strongly recommended, and no loss of ammonia will
occur, except perhaps during the very hottest weather.
E. W. P.
Manuring Sugar-beet with Dung. By Beseler (Bied. Centr.,
1882, 784). — Sheep-dung must not be applied alone, for the high per-
centage of nitrogen and potash is detrimental to the quality of the
sugar-beet. Cow- dung must be applied in the late summer or autumn,
and allowed to lie some time before ploughing in ; thus the roots ob-
tain the nitrates in the early stage of growth, for if nitrates are
applied in the later stage the yield of sugar is reduced.
E. W. P.
Manuring Alpine Meadows. By M. Marcker (Bied. tJerUr.,
1882, 783). — Meadows in the Alps are generally manured with liquid
manure, farmyard manure mixed with water, also with superphos-
phate. In East Switzerland, no potash is added to the superphos-
phate, but in Western Switzerland, where the soil is more chalky,
potash is added. The result of such manuring is that the hay crop is
at least three weeks earlier than on the unmanured meadows ; a second
crop may also be taken. Observations have shown that the presence
of chalk is necessary for the satisfactory action of potash, and that the
atmospheric ammonia absorbed by the salts of potash is converted into
nitrates by the agency of the lime, whilst nitrification does not occur
when lime is absent. These facts account for the unsatisfactory
results obtained when potash is added to unmarled sandy soils.
E. W. P.
Employment of Peat as Litter. By A. Lenn^ (Bied. Centr.,
1882, 785). — The following is the analysis of horse manure when
peat was used as litter instead of straw. The use of the latter is the
more expensive of the two.
ANALYTICAL CHEMISTRY. 239
In 1000 parts. Peat manure. Straw manure.
P2O5 2-23 1-18
K2O 4-37 4-50
N 6-06 3-90
H2O 705'8,1 750-00
E. W. P.
Transformation of Blood into a Solid and Inodorous
Manure by Means of a new Ferric Sulphate. By P. Dela-
CHARLONNT (Gompt. rend., 95, 841 — 843). — The author states that by
use of an acid ferric sulphate having the composition
Fe203,4S03,12H20,
instead of the neutral sulphate as usually employed, a coagulum is
obtained from the blood at the ordinary temperature, which loses half
its water by simple drainage, whilst the remaining water can be
expelled to a great extent by hydraulic pressure. Great expense is
thus saved, as far less evaporation is necessary. The sulphate in ques-
tion can easily be obtained by oxidising ferrous sulphate with nitric
acid, sufficient sulphuric acid having been added to make up the
quantity required for an acid sulphate of the above composition. On
concentrating the solution sufficiently, the salt crystallises out,
K H. R.
Analytical Chemistry,
Use of Diphenylamine and Aniline in Qualitative Analysis.
By C. Laar (Ber., 15, 2086— 2090).— The author recommends di-
phenylamine in preference to aniline as a qualitative reagent for
detecting (more especially) chloric acid. A solution of the base in
concentrated sulphuric acid gives with dilute chloric acid a beautiful
blue coloration. The author tmds, however, that other oxidising agents
give a similar colour. E. H. R.
Sauer's Method of Estimating Sulphur, and some Modifi-
cations of it. By W. G. MixTER (Che7n. Neivs, 46, 217). — Sauer's
method of burning the compound in oxygen and oxidising the sulphu-
rous anhydride by bromine is liable to error, by reason of the uncon-
densed fumes of sulphuric acid which are lost ; these may, however,
be retained, and the amount estimated, by passing the mixed gases into
a large empty flask, when the fumes remain at the bottom and slowly
condense. A hydrochloric acid solution of bromine is found to be no
better than bromine-water as an oxidiser, and as there is a consider-
able loss of bromine if the mixed gases pass through saturated bro-
mine-water, an ordinary two-bulb U-tube with a constriction at one
end of the horizontal part just below the bulb is used. By using
this apparatus a minimum of bromine is lost, and a constant supply
of it is preserved for the purposes of oxidation. E. W. P,
240 ABSTRACTS OP CHEMICAL PAPERS.
Testing for Barimn or Sulphuric Acid. By S. Pickering
{Ghem. News, 46, 223). — The smallest quantity of barium which can
be detected is 1 part Ba in 833,000 parts HgO ; the reaction is not
rendered more delicate by the use of alkaline ammonium sulphate.
The light should fall vertically, there being a black background,
allowing the light to fall on a portion only of the liquid.
E. W. P.
Estimation of Sulphuric Acid in Presence of Alkaline Chlo-
rides. By B. ScHULZE (Landw. Versuchs-Stat, 28, 161— 165).— The
influence of nitrates on the precipitation of barium sulphate has
already been studied by Fresenius, and he recommends warming the
ignited precipitate with hydrochloric acid and washing with hot
water. After filtration, the filtrate is evaporated to dryness to sepa-
rate dissolved barium sulphate, the latter added to the rest of the
precipitate, and the whole weighed. By this means, the nitrates are
removed, but he does not enter into the question as to whether chlo-
rides are also to be found in the precipitate. In the estimation of
sulphur in organic substances by fusion with potash and saltpetre,
excess of alkaline salts is always present : when they are in the form of
nitrates, the precipitated barium sulphate will have to be purified by the
above method ; the author, however, prefers to convert the nitrates into
chlorides by heating to dryness with hydrochloric acid. Upon re-dissolv-
ing and filtering, the sulphuric acid is precipitated by a little barium
chloride, and the precipitate after filtration ignited alone, and finally
with sulphuric acid, and weighed in the usual manner. A precipitate
obtained this way was treated with a few drops of hydrochloric acid,
and then with boiling water, and filtered. The filtrate showed quite a
strong sulphuric acid reaction with barium chloride, which could only
have arisen from the presence of alkaline sulphates in the precipitate,
and was of course due originally to the co-precipitation of alkaline
chlorides. In general, about 3 per cent, of the original precipitate
was removed in this manner. To ascertain whether barium sulphate
was also removed in any quantity by this process, so as to necessitate
the evaporation of the wash- water, as in Fresenius's method, further
portions were treated two or three times with hydrochloric acid, and
the change of weight in each case noted. The loss by the second and
third treatment was however found to be so small that it could be
neglected ; but one treatment with acid seems to be essential in all
cases where excess of alkaline chlorides is present. J. K. C.
Estimation of Phosphoric Acid as Magnesium Pyrophos-
phate. By T. S. Gladding (Chem. News, 46, 213).— The processes
at present in use for the estimation of phosphoric acid as magnesium
phosphate are not sufficiently accurate, as an error of even 0*1 per
cent, in the amount of phosphoric acid can affect the value of a cargo
of phosphate to the amount of several pounds. Various modifications
of the usual magnesium process have been tried, and it has been
found that the following is the best to employ : —
To the solution of phosphate 75 c.c. in volume and strongly ammo-
niacal, add magnesia mixture from a burette at the rate of one drop per
second, stirring meanwhile; after the addition of the magnesia, add
ANALYTICAL CHEMISTRY. 241
25 c.c. of strong ammonia, leave the whole at rest for three hours,
and wash the precipitate with strong ammonia water (1 : 3), the im-
portant point being the gradual addition of the magnesia mixture. The
errors then range from 0'05 per cent, without previous precipitation as
molybdate to O'l per cent, with previous precipitation as molybdate.
E. W. P.
Estimation of Phosphoric Acid. By L. Mayer and E. v.
ScHMiD (Bied. Centr., 1882, 784). — The solution of any superphos-
phate is made according to the usual method, and is then freed from
silica ; to 50 c.c. of this solution, 5 c.c. ammonia is added until a
permanent precipitate is formed, and then 50 c.c. of a solution of ammo-
nium citrate (1 : 1), 25 c.c. of the usual magnesia mixture, and 100 c.c.
concentrated ammonia solution are to be added. The mixture is to be
thoroughly stirred every ten minutes, and after three hours filtered,
the precipitate washed with ammonia water (1 : 3) and ignited. The
presence of much alumina and lime is detrimental to the results, but
the addition of 10 — 15 c.c. strong ammonium chloride solution counter-
acts the influence of the alumina ; to remove the lime, the imperfectly
washed precipitate is to be dissolved in a little dilute hydrochloric
acid, and reprecipitated by 30 c.c. citrate, a few drops of magnesia
mixture, and 60 c.c. ammonia solution. E. W. P.
Analysis of Potassium Thiocarbonate. By Gutot-Dannect
(/. Pharm. [5], 6, 336 — 337). — A flask of two litres capacity contain-
ing 100 grams zinc chloride dissolved in a litre of water is fitted
with a doubly perforated cork. In one perforation, a funnel tube is
inserted which passes to within 1 cm. of the bottom, whilst in the
other a tube bent at right angles is inserted, and by its means the
flask is connected with a condenser, to which is attached a receiver
immersed in ice. The flask is heated to 60° in a water-bath, and the
potassium thiocarbonate added in small quantities at a time ; a brisk
effervescence takes place with evolution of carbon bisalphide, all
effervescence is allowed to cease before a fresh quantity of the thio-
carbonate is added. When all the thiocarbonate is added, the distilla-
tion is continued until all the carbon bisalphide has passed over to the
receiver. From its weight the quantity of thiocarbonate present is
obtained : the weight of the zinc sulphide gives the proportion of
other substances.
Instead of using a water-bath for heating the flask, the author
prefers to suspend the flask by means of a cord over a flame, whereby
it is sheltered from the chance of breakage, and allows the flask to be
gently shaken without disturbing the apparatus, and thus to prevent
bumping. L. T. O'S.
Normal Solutions for the Volumetric Estimation of Iron.
By B. Britton (Ghem. Centr., 1882, 733). — The author has examined
a number of specimens of iron, such as are generally used for
standardising, and found them much more impure than is generally
supposed. The average percentage of iron found in a number of
pianoforte wires was 98' 76. The purest sample of bar iron from
242 ABSTRACTS OF CHEMICAL PAPERS.
Norway and Sweden contained, however, 99*6 per cent. iron. Iron
salts were found to be still less trustworthy than metallic iron.
A. K. M.
Sources of Error in Estimating Iron in Ores by the Stannous
Chloride Method. By K. F. Fohr (Dingl. polyt. J., 246, 236).—
According to the author very appreciable quantities of ferric chloride
are volatilised and lost whilst an iron ore is being heated with hydro-
chloric acid, especially when the operation is conducted in an open
vessel. In the case of some ores, this source of error is, however,
counterbalanced by another error, due to the presence of manganese
dioxide. In this case, the liberated chlorine remains to a slight extent
in solution, and may therefore make up for the loss of ferric chloride.
A. K. M.
Volumetric Estimation of Peroxides. By W. Diehl {Dingl,
polyt. J., 246, 196 — 200). — The author has made direct comparisons
between Bunsen's method of distilling the peroxide with hydrochloric
acid, passiDg the liberated chlorine into solution of potassium iodide,
&c., and Mohr's modification, according to which the peroxide is
digested with the hydrochloric acid and potassium iodide. He has
also tried the effect of substituting other acids for hydrochloric acid.
The substances experimented with are potassium dichromate, the two
oxides of manganese, MU3O4 and MnOa, and lead dioxide. His results
show that the more simple method of Mohr can be relied on, and
that in some cases other acids can be employed in place of hydro-
chloric acid. The same results are obtained with potassium dichro-
mate, whether hydrochloric or oxalic acid is used, but with the
oxides of manganese the latter acid cannot be employed. Acetic acid
can be used in the case of manganese dioxide, and with advantage
also in that of lead dioxide. The author also finds that the presence
of iron does not interfere in estimating the available oxygen in pyro-
lusite by this method. A. K. M.
A Colour-method for the Estimation of Manganese. By A.
Ledebuhr (Ghem. Centr., 1882, 733). — This method depends on the
conversion of manganese into permanganate, and is recommended by
Goetz for the estimation of that metal in iron and steel. He dissolves
0'2 gram of the iron to be tested in nitric acid, and dilutes with dis-
tilled water to 100 c.c. To 10 c.c. of this solution 2 c.c. of nitric acid
are added, the mixture heated to boiling, and then well shaken with
an excess of lead dioxide. After again warming, the liquid is allowed
to cool and is filtered through asbestos into a burette. Potassium
permanganate solution of known strength is poured into a similar
burette, and water added until the same tint is obtained as in the first
burette. The strength of the solution is calculated from the amount
of dilution necessary. A. K. M.
Haswell's Method for the Volumetric Estimation of Mercury,
By H. V. JiJPTNER (Chem. Centr., 1882, 727). — To a solution contain-
ing mercuric chloride, standard solution of ferrous sulphate, acidulated
with sulphuric acid, is added in excess. The solution is then made
strongly alkaline with potash, and afterwards acidulated with a con-
ANALYTICAL CHEmSTRY. 243
siderable excess of hydrochloric acid. On well shaking, the precipi-
tate of mercurous chloride becomes quite white. The excess of ferrous
salt in the solution is next oxidised by standard permanganate, and
on then adding a few drops of stannic chloride solution and a further
quantity of permanganate, the mercurous chloride becomes converted
into mercuric chloride, the disappearance of the precipitate indicating
the completion of the reaction. Each molecule of permanganate,
added after oxidation of the excess of ferrous sulphate, corresponds
with 1 atom of mercury. A. K. M.
Separation of Silver from Alloys. By Solthien (Arch. Pharm.
[3], 20, 201). — The author simplifies the process published by him in
this Journal, 1880. The alloy is dissolved in the minimum quantity
of crude nitric acid, and then decomposed by a strong excess of ammo-
nia; in this liquid placed in cylinders is suspended strips of copper,
upon which the silver will be deposited. E. W. P.
Use of Oxalic Acid as a Test for Arsenites in Alkaline Salts.
By C. Patrouillard (Pharm. J. Trans. [3], 13, 362). — An answer to
a paper in this Journal by Naylor and Braithwaite, who afiirmed
that, contrary to the statement of the author, oxalic acid does not
reduce arsenic acid. The author repeats his statement made in 1874,
that oxalic acid does reduce arsenic acid in combination, and the more
completely the more neutral the combination. In tlie original paper
the uncombined acid was not referred to. E. W. P.
Detection of Iodoform, Naphthol, and Chloroform in the
Fluids and Organs of the Animal Body. By S. Lustgarten
(Monatsh. Ghem., 3, 715 — 722). — Iodoform and naphthol being now
used, as well as chloroform, in medical practice, it becomes a matter
of importance to be able to detect them in animal fluids and organs.
1. Iodoform. — The recognition of this substance by its saffron-like
smell, and its peculiar crystallisation in six-rayed stellate groups,
being often greatly hindered by the presence of other compounds
occurring in animal liquids, the author directs attention to a new
reaction not open to this objection. When iodoform is added by small
quantities to a solution of phenol (20 grams) and sodium hydroxide
(40 grams) in 70 c.c. water, heated on the water-bath or to 120° in a
paraffin- bath, it quickly dissolves and colours the liquid red ; and if
the heating be continaed till about 60 g. iodoform have been dis-
solved— which takes several days at the heat of the water-bath, or a
shorter time in the paraffin-bath, and the solution be then acidulated
with hydrochloric acid and distilled with steam — the excess of phenol
will pass over, probably together with salicylic and parabenzoic
aldehydes, while in the flask there will remain a resin, soft and black -
brown while warm, brittle and red-brown after cooling. This resin
dissolves easily in alcohol, with yellowish, and in alkalis with a fine
crimson colour, which disappears on adding a slight excess of acid,
but reappears on neutralisation ; the alkaline solution is coloured
dark-red by potassium ferrocyanide. The product of the above reac-
tion, like that resulting from the action of an alkaline phenate on
chloroform, doubtless consists of rosolic acid and allied bodies. To
244 ABSTRACTS OF CHEMICAL PAPERS.
exhibit the reaction on a small scale, an alkali phenate is placed at the
bottom of a short test-tube, in very small quantity' only, because the
brown colour which these salts acquire when heated, would mask
any slight red coloration that might afterwards be developed. An
alcoholic solution (1 — 3 drops) of iodoform is then added, and the
mixture is cautiously heated over a small flame ; whereupon, after a
few seconds, there appears at the bottom of the tube a red deposit,
which dissolves with crimson colour in a few drops of dilute alcohol.
To detect iodoform in urine by this reaction, the liquid is distilled
with steam till about 50 c.c. has passed over, and the distillate, mixed
with a small quantity of potash-ley, is shaken with ether in a tap-
funnel ; the ethereal extract is evaporated to dryness ; the residue
treated with absolute alcohol ; and the alcoholic solution tested with
phenol as above.
For detection in blood, the liquid, diluted with 2 vols, water, is
made alkaline and distilled with steam, and the distillate is treated in
the manner just described, excepting that the ethereal extract sepa-
rated from the aqueous alkaline solution is mixed with a little sulphuric
acid to neutralise any amines that may have passed over in the dis-
tillation. The smallest quantity of iodoform that can thus be detected
in blood is 4 — 5 mgrms.
In the reaction above described, the phenol may be replaced by
resorcinol, but not by quinol or catechol.
2. NapJithol. — When chloroform is added to a solution of a- or
/3-naphthol in strong potash-ley, and the liquid is heated to about 50°,
a fine Prussian-blue colour is developed, changing, in contact with the
air, into blue-green, green, green-brown, and finally brown. The
same reaction is produced by crystals of chloral hydrate, which, in
presence of the alkali, is converted into formic acid and chloroform.
To detect naphthol in urine by this reaction, the liquid is acidulated
with hydrochloric acid and distilled with steam till about half has
passed over ; the distillate is shaken with ether ; the ether evaporated ;
and the residue, dissolved in potash, is tested for naphthol as above.
As, however, the alkaline solution is always brownish, the colour pro-
duced on adding the chloroform inclines more or less to green. The
residue in the retort may also be tested for naphthol in a similar
manner ; but as its ether solution is always strongly coloured, it is
necessary to evaporate this solution to dryness, dissolve the residue in
alcohol, decolorise with animal charcoal, warm, filter, evaporate the
filtrate to dryness, and test the residue as above.
3. Chloroform. — This compound may be detected in animal fluids
exactly in the manner just described, with addition of naphthol
instead of chloroform to the alkaline solution. H. W.
Reducing Power of Grape-sugar for Alkaline Copper Solu-
tions. By F. Allien {Chem. Centr., 1882, 731). — Soxhlet and others
have shown that the power of grape-sugar to reduce Fehling's
copper solution is not constant, but varies under different conditions.
The author has examined the method described by Degener (Abstr.,
1882, 104), but finds it open to the same objection as Fehling's
method. A. K. M.
ANALYTICAL CHEMISTRY. 245
Amount of Extract in Wines (Tyrolese). By E. Mach and
C. PoETELE {Bied. Centr., 1882, 773— 775).— In thin sour wines, O'l per
cent, sugar is perceptible by the taste, and in some cases as little as
0*05 per cent, can be detected. The factors influenqing the per-
centage of extractive matter are many : continued dryness lowers
extract and acidity ; old wines are poorer in extract than new ; as the
quality of a red wine rises so does the percentage of extract, reaching
even higher than 4 per cent. The lowest observed (but there may be
lower) percentage of extract in pure white wine was 1'42 per cent. ;
in red, 176 per cent. E. W. P.
Rapid Method of Estimating Salicylic Acid in Wines, &c.
By A. Remont (Gompt. rend., 95, 786 — 788). — The author prepares a
solution of salicylic acid to serve as a standard of comparison. 50 c.c.
of a liquid analogous to that to be tested are taken, and into it is
introduced the maximum amount of salicylic acid allowed by law. This
is then shaken several times with 50 c.c. of ether, and the whole left
at rest for a time. 25 c.c. of the ethereal solution are then taken and
evaporated at a temperature below its boiling point in the presence of
10 c.c. of water, so that the latter dissolves the salicylic acid from the
ether as it volatilises. The 10 c.c. of water are then made up to
25 c.c, and the liquid thus prepared is used as a standard of com-
parison.
In testing a wine, for example, 10 c.c. are treated with 10 c.c.
of ether. 5 c.c. of the ethereal solution are then evaporated, as
described above, with 1 c.c. of water, which is then made up to 5 c.c.
This is placed with the wash- water in a glass vessel of 30 c.c. capacity
and of 15 mm. internal diameter, the standard liquid being placed in
an exactly similar vessel. A solution of ferric chloride, containing
10 grams to the litre, is then added drop by drop to both vessels, until
the colour no longer deepens (three or four drops usually suffice).
The comparison of the depth of tint is sufficient to decide whether
the liquid tested contains more or less salicylic aqid than the standard.
It is always advisable to take as a standard of comparison a liquid
similar to that to be tested. The method is applicable, without modi-
fication, to fruits and syrups. E. H. R.
Occurrence of Myronic Acid and Estimation of the Cor-
responding Mustard Oil in the Seeds of Cruciferse and in
Oil-cakes. By Y. Dircks (Landw. Versuchs.-Stat., 28, 179—200).—
The amount of mustard oil is determined by oxidation with alkaline
solution of permanganate, and precipitation with barium chloride.
Test experiments were made with mustard oil, which was in some
cases directly oxidised, and in others distilled into the oxidising solu-
tion. In the former method, a weighed quantity of oil was introduced
into a thick flask with excess of alkaline permanganate solution, the
flask sealed up, thoroughly shaken, and heated for some time on a
water-bath, until the green colour had disappeared, and it was again
red. It was then opened, the contents evaporated to dryness, and
taken up with hydrochloric acid, again evaporated, dissolved, and pre-
cipitated hot with barium chloride. Comparative experiments with
246 ABSTRACTS OF CHEMICAL PAPERS.
nitric acid as oxidising agent were fairly satisfactory. In the dis-
tillation method the oil was weighed out into a tubulated retort con-
nected with a condensing apparatus and receiver with a doubly- bored
cork, into the other bore of which a Will-Varrentrapp nitrogen appa-
ratus bent at right angles was passed, connected at its other end with
another of the same, and the whole apparatus communicated with an
air-pump. The receiver and nitrogen bulbs were filled with perman-
ganate solution, and after the oil was distilled over, were treated as
before. Experiments showed that the sulphur determinations were
rather too low ; and this the author thinks is due to the excess of
alkaline chlorides present, in which, as some test experiments show,
barium sulphate is slightly soluble, 0-025 gramKCl and 0'175 gramNaCl
representing about 5'5 mgrms. BaSO*.
The mustard oil was determined by this method in cake and seeds
of black mustard and rape, and in the seeds of Sinapis arvensis. The
finely-powdered substance was mixed with ten times its weight of
water, and allowed to stand nine hours at 50°, this being necessary
to allow of the easy distillation of the oil. It was then steam-
distilled, a current of air being drawn through at the same time to
ensure thorough mixture, the sulphuric acid being estimated as
before. By observing these precautions, constant and trustworthy
results may be obtained. The thorough stirring of the contents of the
retort is absolutely essential to expel the whole of the oil, and this is
best done by a tube stopped up at the end and perforated with small
holes, so that the current of air is well divided in passing through the
liquid. The amount of fat present and the relative quantities of sub-
stance and water do not seem to have any effect. The following
percentage quantities of mustard oil were found : Black mustard seed-
cake, 1*39 ; rape seed from 0*018 to 0*037 ; rape seed cake, 0*020 to
0*109 ; yellow mustard seed cake, 0*018 ; turnip seed, 0*038 ; seeds of
Sinapis arvensis, 0*006. In the case of rape seed cake, the quantity of
oil decreases apparently with the age of the cake. Whether this is
due to a decomposition of the myrosin or of the ferment, the author is
still engaged in determining. As the seeds of the wild plant Sinapsis
arvensis are used for adulterating rape seed, and as the former contain
scarcely any mustard oil, the amount of the latter in rape seed may be
almost taken as a standard of purity, if it should be found that the
amount of oil does not greatly vary in samples from different localities.
J. K. C.
Estimation of Milk Fat. By R. Emmerich (Bied. Centr., 1882,
762). — Emmerich has compared the gravimetric estimation of milk fat
with the processes of Soxhlet, Hoppe-Seyler, and Feser. Soxhlet's
and Hoppe-Seyler's method gives a difference of 0 — 0*4 per cent.,
whilst the error of Feser's optical method is on the average 0*25 per
cent, too high. E. W. P.
Analysis of Butter. By A. v. Bastelaer (Ghem. Centr., 1882,
731). — A weighed quantity of butter is heated at 100 — 120°, the loss
in weight indicating the amount of water present. The fat is then
extracted by means of benzene, and its amount found on weighing the
dried residue. This is finally ignited, the loss indicating the casein, and
ANALYTICAL CHEMISTRY. 247
the asli the sodiam chloride. The presence of oleomargarine can be
detected by its odour when butter is heated to drive off the water, and
also by the high percentage of casein due to the admixture of milk.
A. K. M.
Butter Testing. By J. Munier (Ghem. Centr., 1882, 730).— The
author has examined a number of different sorts of butter in each
month from October, 1880, to February, 1882. He adopted Reichert's
modification of Hehner's method, and found that the proportion of
volatile acids differed from time to time. It was lowest between
October and January, increased from February to August, and after-
wards again diminished. The author concludes, therefore, that in
reporting upon a sample of butter it will be necessary to make allow-
ance for the time of year at which the butter was made.
A. K. M.
Margarimeter of Leune and Harbulet. Bj D. Gabel (Bied.
Centr., 1882, 766). — This instrument resembles a hydrometer, the
zero of the instrument being that point to which it sinks when floating
in butter heated by the vapour from boiling water ; the other degrees
are supposed to indicate the percentages of added fats ; the results
obtained by its use are very untrustworthy, for in one case it indi-
cated 20 per cent, of foreign fats present in perfectly pure butter,
moreover, a very slight variation in the temperature greatly affects the
readings. E. W. P.
Albumin from Urine, coagulated by Nitric Acid and soluble
in Alcohol. By L. Garnier (/. Pharm. [5], 6, 339— 340).— In ex-
amining for albumin the urine of persons to whom turpentine and
balsams have been administered, it has been shown that nitric acid
precipitates resins soluble in alcohol simultaneously with the albumin.
In two cases of nephritis, the urine treated by Heller's process gave
precipitates soluble in alcohol, although the patients had not taken
turpentine or balsams. The reactions of the urines are as follows :
The albumin is coagulated by boiling alcohol, nitric acid, trinitro-
phenol, and gives a red colour with Millon's reagent, but the precipi-
tate with nitric acid is soluble in alcohol. It is necessary, therefore,
to avoid confounding such precipitates with resinous matters.
L. T. O'S.
Estimation of Humus in Soils. By G. Loges (Landw. Versuchs-
Stat., 28, 229— 245).— Of the three methods usually employed for
the estimation of humus, namely, loss on ignition, oxidation with
chromic acid, and combustion with cupric oxide, the intermediate one
is usually preferred, as being both rapid and safe. Later investigations,
however, by Warington and Peake (this Journal, p. 617) have shown
that lower results are obtained by oxidation with chromic acid than
by ordinary combustion ; the author was able to put this to the test
in a long series of experiments. In employing the chromic acid
method, the proportions given by Wolff were strictly followed out,
and the carbonic anhydride was absorbed in a Pettenkofer's appa-
ratus. For combustion, the weighed quantity of soil was treated with
a dilute solution of phosphoric acid, and dried over a water-bath : it
was then powdered, mixed with cupric oxide, and transferred to a
248 ABSTRACTS OF CHEMICAL PAPERS.
combustion-tube open at both ends. The products of combustion
were first passed tbrough a Fresenius' drying tube, with moist wad-
ding at the top, which was found quite sufficient for absorbing any
oxides of nitrogen which might be formed : the carbonic anhydride
being absorbed by a Pettenkofer apparatus. Samples of 40 different
soils were analysed by both methods, as well as by loss on igni-
tion, and the conclusions of Warington and Peake were confirmed ;
oxidation by chromic acid giving on the average only 84 per cent, of
the carbonic anhydride yielded by combustion, the extreme limits
being 96 and 64 per cent.
In nearly all the experiments, the estimation of humus by loss on
ignition gave results very much too high, the only exceptions being in
the cases of moor and certain sandy soils.
The deficit in carbon exhibited by the chromic acid method is
attributable to two causes : either there are certain compounds in soil
not attacked by chromic acid, or else the whole of their carbon cannot
be converted into its ultimate oxidation-product. Experiments were
therefore made with certain substances, of which presumably the
humus is compounded, such as fibre, roots, &c. ; the fibre was found
to be fully oxidised, but not the roots ; humic acid yielded 91 per
cent, of its carbon by this method, but in this case the formation of
3 per cent, of acetic acid was observed, as well as the production of a
higher carbon acid. In the insoluble residue also, a small proportion
of unattacked carbon was found, which probably had existed in the
form of brown coal. J. K. C.
Technical Chemistry.
Absorption and Utilisation of the Sulphurous Anhydride
contained in Furnace Gases. {Dingl. polyt. /., 246, 228 — 236.)
— According to Hasenclever, sulphurous anhydride and the vapours of
sulphuric acid can be removed from a mixture of gases by sulphuric
acid. Precht recommends cooling the gases to about 100°, and then
passing them over moistened magnesium hydroxide previously mixed
with 1 to 2 per cent. coal. The product consisting principally of
magnesium sulphite is then heated, and the evolved sulphurous anhy-
dride is used for the manufacture of sulphuric acid. The addition of
the coal is to help the decomposition of a small quantity of sulphate
which is formed on igniting the sulphite. Aluminium hydroxide can be
substituted for magnesium hydroxide, but works more slowly. Schnabel
employs zinc oxide and basic zinc carbonate for absorbing sulphurous
anhydride. The zinc oxide must be kept continually moistened with
water to prevent its becoming coated with a layer of sulphite. As in
Precht's method, coal must be mixed with the zinc oxide, so that after
a time the latter becomes contaminated with a very appreciable
amount of ash. In order to remove this, the mixture is again exposed
TECHNICAL CHEMISTRY. 24^
to furnace gases and the resulting zinc sulphite separated from the
ash by solution in water. The solution is used instead of water for
moistening the zinc oxide in the next operation. Fleitmann passes
the furnace gases together with air through a furnace containing a
mixture of oxide of iron and coal ; ferrous sulphide being produced by
the reducing action of the latter.
According to Kosmann's method, the gases are submitted to the
action of steam and water, by which a part of the sulphurous
anhydride becomes oxidised and converted into sulphuric acid. The
remaining sulphurous anhydride is then decomposed by a solution of
hydrogen calcium sulphide, thus : —
5SO2 + 2H2CaS2 + 2H,0 = 7S + 2CaS04,2H20.
A. K. M.
Antiseptics. By A. Matee {Bied. Centr., 1882, 777). — Stuttgart
" preservative salt" consists of a mixture of 2 parts boric acid and 3 of
sodium chloride. " Septon," to preserve cheese from mould, &c., is
only a mixture of equal parts of acetic acid and water. " Glacialin salt
mixture" and "glacialin rose-extract" are both mixtures of boric acid
with borax, the second mixture being intended to preserve meat
without altering its colour. E. W. P.
Disinfectants. By R. Koch (Chem. Centr., 1882, 509—512).—
The mode of action of individual disinfectants has not been sufficiently
investigated, because of our incomplete knowledge of the infectious
matter. An efficient disinfectant ought, in the author's opinion, to kill
all living organisms and render all germs innoxious within twenty-four
hours. To test a disinfectant thoroughly, its action must be tried on
all disease-producing matter, and under conditions exactly similar to
those in which it is used in practice. Thus a disinfectant which does
not kill fungi would be of no use in contagious skin diseases, whilst
one which did not destroy bacteria would be inefficient in diseases
caused by these organisms. The author has investigated the action of
disinfectants on bacteria. In these experiments, he has taken great
care in the cultivation of bacteria, selecting those which are seldom
found in the air. Experiments on the development of bacteria were
made on solid nutritious substances. The chief points observed are —
1. If all the organisms are killed. For this it is sufficient to note the
action on the most persistent, viz., the bacilli spores. 2. The facility
with which the development of micro-organisms in favourable nutri-
tive solutions is prevented.
Carbolic acid is almost without action on spores of Anthrax hacUU,
e.g., the bacilli spores retained their vitality after being five days in a
2 per cent, solution, and in another experiment 15 days in a 1 per
cent. It is, however, destructive to the living micro-organism, for
1 gram of pure carbolic acid can completely prevent the development
of Anthrax bacilli in 850 c.c. of a nutritive solution, and even shows a
marked effect in 1250 grams. Its action on other bacteria is less
marked. Carbolic acid in the form of vapour does not affect the
germinating power of bacilli spores at the ordinary temperature, even
after being in contact with them .1^ months; but at 55°, in half an
hour many of the spores are destroyed, in three hours scarcely any
VOL. XLIV. s
2e50 ABSTRACTS OF CHEMICAL PAPERS.
germinating power is discernible, whilst after five or six hours their
destruction is complete. Raising the temperature does not increase
the activity. Carbolic acid vapour can only be conveniently used for
small objects.
The above results are obtained with aqueous solutions of carbolic
acid. Solutions in oil or alcohol do not show any antiseptic proper-
ties ; this is also the case with other disinfectants, e.g., salicylic acid,
thymol, &c., except when they are used with substances containing
water, such as flesh, &c., when some of the disinfectant becomes active.
Sulphurous acid, either alone or mixed with water or steam, does not
disinfect dry objects. If, on the other hand, the object is first
moistened with sulphurous acid and then treated, brisk action is
observed ; it does not, however, destroy all germs. Its disinfecting
action is thus uncertain, and is not to be depended on.
Amongst many others, zinc chloride and glycerol are proved to be
without effect. In fact the only effective disinfectants (see above)
besides chlorine, bromine, and iodine, are corrosive suhlimate, osmic acid^
and potassium permanganate. The last-mentioned only acts in strong
solutions (6 per cent.). Bromine and osmic acid are too expensive.
Corrosive sublimate is very poisonous ; its action, however, is so very
quick that it could be used for solid substances, which could then be
washed well with water.
Substances effective in checking the germination of spores are corrosive
sublimate, some essential oils, thymol, and amyl alcohol.
D. A. L.
Effect of the Presence of Sheet Zinc in Boilers, and a
Method for Preventing Explosions. By Tr^ve (Compt. rend., 95,
522 — 524). — When sheet zinc is placed in iron boilers, galvanic action
is set up, and the water is slowly but continually decomposed. The
oxide of zinc which is formed neutralises the fatty acids in the feed
water, producing zinc soaps, which surround the boiler tubes and
prevent the adherence of salts deposited by evaporation. The con-
tinuous evolution of hydrogen might be expected to assist ebullition
and prevent superheating of the water. Since, however, it sometimes
seems to fail in producing this effect, the author proposes to inject into
the water in the boiler a stream of air or a non-oxidising gas, such as
carbonic anhydride, in order to keep up ebullition and prevent super-
heating, which is undoubtedly the cause of many boiler explosions.
C. H. B.
Industrial Value of Crude Alunite. By P. Guyot (Compt.
rend., 95, 693 — 695). — The crystallised portions of the alunite from
the Tolfa Mines contain as much as 32 per cent, of the base, but the
average composition of the mineral is —
AI2O3. SO3. K2O. H2O. Fe. SiOj.
27-60 2974 7'55 11-20 120 2271 = 100-00
When the mineral is gradually broken up, the fine powder is richer
in alumina and potash than the coarser fragments. In the following
table of analyses the numbers indicate the degree of fineness, the
finest powder having the highest number : —
TECHNICAL CHEMISTRY.
251
First crushing.
( '
1. 2.
Calcination 23-00 3760
Crude mineral.
Alumina 17-81 25*40
Potassium sulphate .... 8"40 12*20
Calcined mineral.
Alumina 23'13 4070
Potassium sulphate. . . . 10*91 19*50
Second crushing.
r *
I. II. III.
Calcination 22*40 24*40 33*90
Crude mineral.
Alumina 17*80 28*67 31*75
Potassium sulphate 8'51 11*95 15*31
Calcined mineral.
Alumina 22*93 31 '31 48*04
Potassium salphate 10*92 15*92 23*16
3.
41*00 per cent.
31*00
15*30
44*90
22*17
IV.
34*60
32*29
15*40
49*40 „
23*56 „
C. H. B.
GutzkofF 's Process for the Separation of Gold in California.
(Chem. Ceutr., 1882, 508 — 509.) — The principal materials for separa-
tion are — 1. Gold bar, containing 2 parts gold and 3 parts silver;
this is granulated before being dissolved. 2. Silver plates with 2 to
10 per cent, of gold. 3. Silver plates mixed with copper; before dis-
solving, fine silver is added to these to reduce the percentage of
copper to 12 to 8.
The alloys are treated with boiling sulphuric acid in covered
vessels of cast iron (containing 2 to 4 per cent, of phosphorus, so as
to better resist the action of the acid), capable of holding a charge of
100 to 150 kilos, of alloy. The pots being partially filled with acid
(the acid reservoirs are so arranged that the pots can be easily filled)
and boiled, the charge is put in ; after 15 minutes the necessary
additional quantity of acid is a^ded, and the whole boiled for three to
four hours. The hot liquid is then syphoned off by means of a vacuum
arrangement into shallow iron tanks, capable of holding five charges,
in which there is sulphuric acid of 58° B. in the proportion of 0*5 cm.
for every 100 kilos, of alloy at 110" C. ; here the liquid remains at
this temperature until clear. The gold remains behind in the pots ;
there is also some deposited along with graphite and lead sulphate in
the tanks. The hot clear liquid containing silver, copper, and iron
sulphates is run into vessels and cooled to 30 — 40° by means of a
current of water, when silver sulphate crystallises out ; the copper sul-
phate is syphoned back into the tank. The silver sulphate crystals
when drained are ladled into wooden vats lined with lead, having a
252 ABSTRACTS OF CHEmCAL PAPERS.
•
false bottom with a tap underneath. A hot saturated nentral soltition
of ferrous sulphate is poured over the crystals, and ultimately run
out by the tap. The copper sulphate is dissolved first ; the liquid is
therefore blue ; the silver sulphate is then reduced, the liquid becoming
brown, and at the end of the operation it is green ; the reduction
occupies 3 — 4 hours. The liquids are separated ; the brown one holds
in solution 2^ per cent, of silver ; the (green) ferric solution is treated
with scrap iron, and is returned to the ferrous sulphate store tank.
The gases and vapours given off during the dissolving are condensed
in leaden chambers, towers, and shafts. A figure is necessary for an
efficient and clear description of the apparatus employed.
D. A. L.
Deplastering of Wines. By Blaeez {J. Pharm. CUm. [5], 6,
267 — 270). — The author confirms the opinions of Calles (Abstr., 1882,
1336) on the deplastering of wines, maintaining that from a hygienic
point of view the deplastering is more injurious than the plastering —
(1) owing to the use of poisonous barium salts, and (2) because in the
decomposition of the potassium sulphate by the barium chloride the
potassium chloride is injurious. L. T. O'S.
Application of Strontium Chloride in Purifying Syrups.
By G. KoTTMAN (Dingl. polyt. J., 245, 395). — The juice obtained by
diffusion or pressure is treated with calcium chloride until the acids
forming insoluble calcium salts have been precipitated. The filtrate
is then saturated with lime and again filtered. To the solution a
sufficient quantity of strontium chloride is added, when a further
separation of acids in the form of insoluble strontium compounds is
effected. The author recommends to precipitate with calcium chloride
in the first place, add strontium chloride after removing the calcium
precipitate, and finally saturate the mixture with lime. Strontium,
chloride may be employed also for the purification of svrups.
D. B.
Recovery of Sugar from Molasses by means of Strontiimi
Hydroxide. By C. Scheibler (Ding, poli/t. J., 245, 430 — 433,
465 — 469, and 506 — 508) . — The author has recently patented an im-
proved process for the recovery of sugar from molasses by means of
strontium hydroxide, according to which molasses is diluted with
water, the degree of dilution depending on the composition and the
percentage of sugar contained in the solutions, and mixed with stron-
tium hydroxide in the proportion of 3 mols. to 1 of sugar. The solu-
tion is then heated, and the strontium saccharate separated in the form
of a heavy sandy precipitate. By diffusing this through warm water
it splits up into a less basic saccharate and strontium hydroxide. The
filtrate from the saccharate precipitate contains only from 0'3 to 0*8
per cent, of sugar. The composition of the saccharate is represented
by the following formula: Ci2H220ii,2SrO,aH20. On throwing it
into water it suffers the following decomposition : —
3Ci2Ha20ii,2SrO,«H20 = 4H2SrOo,8H20 + 3Ci2H220n,2SrO +
(ie-9)H30,
i
TECHNICAL CHEMISTRY. 253
The paper, which is of considerable length, gives full particulars
relating to the entire method of working, and describes in detail the
preparation of the strontium hydroxide. D. B.
Preparation of Brown and White Cellulose. (Dingl. polyt. /.,
245, 520.) — According to Rasch and Kirchner, the steamed blocks of
wood are broken up into pieces of the size of a pea by means of a
chopping machine ; they are then crushed between rollers, and the
fibres disintegrated in a centrifugal rag-engine. The product thus
obtained is used for the preparation of pasteboard and coarse kinds of
paper. D. B.
Preparation of the Homologues of Phenol, Naphthol, and
Resorcinol. (Dingl. polyt. J., 246, 201.)— Equivalent quantities of
a phenol and an alcohol are heated with zinc chloride until two
layers form, and the oil is then rectified. The reaction takes place
thus : —
CeHg.OH + Et.OH = CeHiEt.OH + H^O.
A. K. M.
Becker's Creaming Process. By W. Fleischmann and R,.
Sachtleben (Bied. Gentr., 1882^ 770). — The authors find that no
special advantage is gained by employing the above process, as the
amount of cream removed is no greater than that obtained by the
older methods, and moreover it is uncertain and of long duration.
One advantage is, however, gained — that the coagulum formed by
the rennet is not in thick lumps, but in fine flocks, which is the more
digestible form of casein. E. W. P.
Jakobsen's Testing-churn. By W. Fleischmann and R. Sachtle-
ben (Bled. Centr., 1882, 763). — The results obtained by the use of
this apparatus (ibid., 1876, 400, and 1877, 224) are not trustworthy,
as the percentage of butter yielded falls- with the weight of milk ex-
perimented on, and the greatest yield is- obtained by the more rapid
rotation of the apparatus. Sour milk gave the most trustworthy
results. E. W. P.
On Creaming. By D. Gabel (Bied, Centr., 1882, 626).— The
author adheres to his opinion, previously expressed, that it is quite
unnecessary to cool milk before creaming. E. W. P.
Preservation of Milk, &c. By Barff and others (Bied. Centr.,
1882, 627 — 630). — Barff preserves milk, &c., by the addition of a
solution of boroglyceride in water (1 : 20 — 60). Le Bon employs a
calcium and sodium compound of boroglyceride. Mayer and Portele
find that salicylic acid must not be added to milk or butter, as it im-
parts an unpleasant taste. To preserve milk for transport, A. Meyer
keeps it at 60° by steam for three hours, introducing sodium benzoate
(0"8 gram per litre), or half as much boric acid with or without sodium
chloride. He believes the benzoate to be harmless, but cannot say as
s 2
254 ABSTRACTS OF CHEMICAL PAPERS.
much for the boric acid, which, however, only costs a sixth as much
as the benzoate. E. W. P.
Preservation of Milk. By B. Dietzell (Bied. Centr., 1882, 789).
— The method proposed is almost identical with that proposed by
Scherfe (Abstr,, 1882, 1016). E. W. P.
Preservation of Milk. By Bcsse (Bied. Centr., 1882, 789).— To
every litre of milk 1 — 2 teaspoonfuls of hydrogen peroxide is to be
added. Butter made from milk containing hydrogen peroxide remains
for a long time without becoming rancid. E. W. P.
Preserved Milk, &c. By W. Fletschmann (Bied. Centr., 1882,
771 — 773). — In this report from the Experimental Station in Raden,
the composition of milk is reported as follows : —
Morning. Evening. Mid-day.
Dry matter .... 11-332— 12852 11-203- 12694 11-376-12-557
Fat 2-816— 4-015 2-276— 3-858 2-820— 3-790
The composition of two samples of Swiss condensed milk without
added sugar, but with added benzoic acid, was : — Water, 52-315 ; fat,
13-090; albumin, 12-130; lactose, 17*434; ash, 2-788; benzoic acid,
1-740. Loss, 0-503.
Comparisons of estimation of milk by the gravimetric process with
those obtained by the use of Soxhlet's method and the lactobutyro-
meter (Schmoger's modification) yielded good results, but Mittelstrass'
optical method gave results varying between +0'37 and —0-26.
Pepsin causes casein to separate more rapidly from milk than when
rennet is used, but there is no perceptible difference in the appearance
of the curds thus formed. E. W. P.
On Milk. By M. Scheodt and others (Bied. Centr., 1882, 625).—
Schrodt finds that the addition of saltpetre to milk which tastes of
turnips does not remove that unpleasantness, as has been stated.
Leze placed milk in contact with several odorous gases, which com-
municated their taste to the milk ; ammonia rendered milk gelatinous
and thick. It occasionally happens that butter during churning
appears as a flocculent coagulum. H. Schultze's analyses show that it
consists of 12 per cent, water, 11 per cent, casein, and 75 per cent, fat ;
the cause is probably the presence of excess of acid in the cream, due
to carelessness, &c. E. W. P.
Preservation of Butter. By W. Hagemann (Landiv. Versuchs.-
Stat., 28, 201 — 227). — The peculiar smell and taste of rancid butter
is generally assumed to be due to the presence of free butyric acid, of
which only a very small quantity is required to give fresh butter
similar properties to those of rancid. In approaching the question as
to the origin of the free acid, two theories present themselves : either
it arises from a butyric fermentation at the expense of the lactose or
glycerol, or else is the product of chemical changes, and is set free
from certain glycerides in the butter. In carrying out experiments
TECHNICAL CHEMISTRY. 255
suggested by the former of these views, bacteria were obtained from
a mass of cane-sugar undergoing butyric fermentation; these were
introduced into quantities of pure butter fat which had been washed
and freed from water, salts, and lactose : nutriment was added in the
form of lactose, and ammonium and other salts necessary for the growth
of the cells. The conditions of experiment were varied greatly, but
in no instance was the fat turned rancid, even after standing many
weeks : and the addition of a small quantity of rancid to fresh butter
did not appear to accelerate the process. Analysis also showed that
the quantity of glycerol in fresh and rancid butter was as nearly as
possible the same, hence the presence of free acid could not arise from
a decomposition of the glycerol. From these facts the author con-
cludes that the rancidity of butter is not due to butyric fermentation.
In testing the reaction of fresh and rancid butter with litmus-paper,
it was noticed that the former gave reddish spots in all cases when the
cream from which it was prepared had become sour owing to lactic
fermentation of the milk-sugar : rancid butter, however, gave in all
cases a most powerful reaction. About half a per cent, of undecom-
posed lactose is contained in fresh butter, and its fermentation appears
to proceed further as the butter becomes rancid : the question then
suggested itself whether this rancidity was not actually due indirectly
to the lactic acid formed, and the action of this on fresh butter was
therefore studied. Experiments made at the close of autumn showed
that fresh butter when mixed with lactic acid becomes rancid very
quickly, and at a temperature too low for the growth of bacteria.
Pure butter fat was dissolved in ether, a few drops of lactic acid were
added, and the whole allowed to stand over night : the ether was then
driven off at a low temperature, and the residual fat proved to be
strongly rancid. In order rightly to comprehend these results, the action
of lactic acid on mono- and tri-butyrin was studied ; and it was found
that butyric acid was in every case set free, as shown by its smell and
reaction with litmus-paper : the amount varying with the tempera-
ture, and being greater with tri- than mono-butyrin ; these results
indicate that the rancidity of butter is due to the formation of lactic
acid by a process of fermentation from the milk-sugar contained in
the butter.
The liability of butter to become rancid might be prevented either
by removing the glycerides of the volatile acids, by creaming milk
fresh from the cow with the addition of a small quantity of caustic
soda, or by removing the milk-sugar itself ; but at present no success-
ful practical methods of performing either separation have been
described : washing with water gives a tolerably stable product, but,
if pushed too far, the aroma is lost. The ferment which acts on the
lactose appears to be organic, and not a chemical ferment such as
diastase, myrosin, &c., as its activity is entirely restrained by chloro-
form ; the amount also of acid formed does not vary with the quantity
of the ferment, and increases instead of diminishing the longer the
ferment remains in the lactose solution. This behaviour can only be
due to the presence of some organised bodies which increase in num-
bers as the fermentation proceeds, the amount of acid increasing in
like proportion. * J. K. C.
256 ABSTRACTS OF CHEMICAL PAPERS.
Cheese, Oleomargarin-cheese, &c. By P. Vieth and others
(Bied. Centr., 1882, 764i). — The following is the composition of
spurious American cheeses made fi*om grease and oleomargarin : —
Grease. Oleomargarin.
Water 38-26 37'99
Fat 21-07 23-70
Casein, &c 35-55 34 65
Ash 612 3-66
100-00 100-00
The extracted fat contained —
Insoluble fatty acids 90-46 91-82
Butter fat 63*00 46-00
Foreign fat 37*00 5400
Schmoger reports that some cheeses made from milk that has passed
through a centrifugal machine become blue throughout the whole
mass. Gabel has noticed the same appearance, and attributes it to
unclean vessels which retain some organisms to which the production
of the blue colour is due. E. W. P.
Injurious Action of a Cupriferous Oil used in Turkey-red
Dyeing. By E. Schaal (Dingl. ^ohjt. /., 245, 516). — In dyeing
vegetable fibres with alizarin, the yarn is subjected to a preliminary
mordanting process, consistiug in treating it with soda or soluble glass,
drying, and bringing it into a bath of Turkey-red oil (Jiuile toumante),
potash-ley, and sheep's dung. After drying, the yam showed a
number of places full of holes. On examination, it was found that the
destruction was due to the presence of copper in the oil, the iron tank
used for storing the warm oil being fitted with a gun-metal cock.
When this was replaced by an iron stopcock these appearances were
no longer visible. D. B.
Fixation of certain Artificial Colouring Matters by means
of Metallic Mordants. By M. H. Koechlin {Chem. News, 46, 179).
— A long list of colouring matters is given which have been fixed by
aluminium, magnesium, calcium, and chromium acetates, or a mixture
of these. It is frequently necessary to use a mixture in order that the
colour produced shall be "fast," and compound mordants have a
greater resisting power as regards acids and alkalis, and are therefore
suitable for colours which are either acid or alkaline. A short historical
account of the introduction of compound mordants is also given.
E. W. P.
Preparation of Aluminium Thiocyanate. {Dingl. polyt. /.,
245, 306.) — Lauber and Haussman obtain aluminium thiocyanate in
the following manner : — In the preparation of thiocyanates by means
of carbon bisulphide and sulphuretted hydrogen, there is obtained in
the first place a ley containing ammonium thiocyanate and sulphuretted
TECHNICAL CHEMISTRY. 257
hydrogen ; if after driving off the latter, the ]ej is decomposed in suit-
able vessels bj a definite quantity of lime, a solution of calcium thio-
cyanate is obtained, which is free from iron, and sufficiently pure for
the manufacture of aluminium thiocyanate. The latter is prepared as
follows : — 5 k. aluminium sulphate are dissolved in 5 1. boiling water,
250 g. chalk added, then 11*5 1. calcium thiocyanate solution of 20° B.
The mixture is stirred well, allowed to settle, filtered, and the clear
solution used. D. B.
Application of Baeyer's Artificial Indigo. By H. Schmid
(Dingl. polyt. J., 245, 302 — 305). — Orthonitrophenylpropiolic acid
is brought into commerce in the form of a yellow paste containing
25 per cent, dry matter. A weak reducing agent, when allowed to act
in an alkaline solution at a temperature of 31^, develops the blue, and
fixes it on the fibre. The receipt originally given by the Baden Aniline
and Soda Works consists of 40 g. propiolic acid in the form of paste,
10 g. finely pulverised borax, 70 g. starch thickening, to which 15 g.
sodium xanthate are added immediately before the printing. After being
printed, the goods are dried and hung in a warm place. The rapidity
with which the colour is developed differs in accordance with the degree
of heat. A passage through Mather and Piatt's continuous fixing
machines suffices to produce the blue, whilst if hung in the cold,
48 hours' time is necessary to effect the same result. In order to
remove the unpleasant smell resembling mercaptan accompanying the
printing colour, the pieces are treated with a boiling solution of 10 g.
sodium carbonate per litre, and soaped at 30 — 40°. For the produc-
tion of lighter shades, a thickening is used containing 100 g.
sodium xanthate. The quantity of borax is calculated to form the
neutral sodium salt of orthonitrophenylpropiolic acid ; in its place an
equivalent amount of sodium carbonate or acetate may be used, whilst
the starch thickening may be replaced by gum tragacanth ; burnt
starch and gum Senegal weaken the colour, although borax coagulates
the former. At a price of 44^. per kilo, of propiolic acid in 25 per
cent, paste, 1 kilo, of indigo blue fixed on the cloth costs 70"45., it
being assumed that the conversion into blue is theoretical. Sodium
xanthate acts at a low temperature without steaming, in fact the latter
is injurious. It is obtained by the action of sulphuretted hydrogen on
alcoholic soda-ley, and forms a yellow crystalline powder. Its prin-
cipal products of decomposition are carbonic anhydride, alcohol, and
sulphuretted hydrogen. The nitrophenylpropiolic acid is therefore
exposed to this weak reducing action, which is frequently used for
reducing aromatic nitro-compounds in alcoholic or alcoholic ammo-
niacal solutions by means of sulphuretted hydrogen. The author
finds that when thiocarbamide is used a higher tempei'ature is needful,
which has the advantage that the printing colour keeps better, besides
being free from smell. The printing colour prepared with sodium
xanthate is decomposed in a very short time, hence it is necessary to
add the xanthate immediately before printing, or the cloth may be
prepared with it, in which case it is padded in a solution containing
from 100 — 300 g. sodium xanthate. The blue obtained from the pro-
piolic acid gives brighter colours than the blue dyed with natural
258 ABSTRACTS OF CHE>nCAL PAPERS.
indigo, and resists rubbing and soaping better. It can be printed in
conjunction with aniline-black and all colours which are developed by
means of oxidation. Owing to its reducing action, sodium xanthate
may be used as resist for aniline-black. The acid contained in the
black liberates xanthic acid, which readily decomposes into alcohol
and carbon bisulphide. The author used this reaction to reserve
indigo-blue under aniline-black. Sodium xanthate forms a yellow
precipitate with copper salts, so that it is possible to produce a green
colour. By adding an excess of sodium xanthate to the propiolic
acid blue, and passing the goods through a solution of copper after full
development of the blue, a bluish-green is obtained, owing to the mix-
ture of the yellow with the blue. The yellow produced with copper
xanthate withstands acids and dilute alkalis, whilst the green resists
soaping extremely well. D. B.
Chemical Theory of Gunpowder. By H. Debus (Proc. Boy.
Soc, 33, 361 — 370). — The author at the outset draws attention to the
fact that notwithstanding the antiquity of the use of gunpowder, no
theory has hitherto been propounded by which the quantities of the
chief products of combustion can be calculated from the known com-
position of a given weight of gunpowder, or of the amount of heat
generated during its metamorphosis.
The potassium nitrate, charcoal, and sulphur are transformed
during the combustion into potassium carbonate, sulphate, bisulphide,
and thiocyanate, carbonic oxide and anhydride, nitrogen, hydrogen
sulphide, methane, ammonia, hydrogen, and water. Of these sub-
stances, the hydrogen and its compounds, together with potassium
thiocyanate amounting to about 2 per cent, of the original weight of
the powder, are merely secondary products, and not direct results of the
explosion of the powder ; potassium thiosulphate has also been found,
but is formed from the sulphide during the analysis by Bunsen and
Schischkoff's method. With regard to the remaining products, the
author proposes to solve the following problems (1) to determine the
reactions- which cause their formation and the order in which they
succeed one another, and to represent the complete combustion of gun-
powder by one equation ; (2) to calculate from the known composition
of a given weight of powder the volume of the gases, the amount of
heat generated, and the relative energies of powders of different com-
position.
The experiments of Noble and Abel (Phil. Trans., 1875, 137) have
shown that the proportions of the several constituents of the solid
residue are dependent upon accidental variations of the conditions of
the explosion, and therefore any attempt to express by a single equa-
tion the metamorphosis in question would be apt to convey an
erroneous idea, and would lead to no important elucidation of the
theory of the explosion of gunpowder. But the author shows that
the differences in the composition of samples of powder of the same
nature, together with the inevitable errors attached to the analytical
operation, are quite sufficient to explain the variations in the propor-
tions of the product of combustion. For instance, 1st, a portion of
the potassium bisulphide is partly converted into the sulphate and
TECHNICAL CHEMISTRY. 259
thiosulphate, and tlius the qnantities of these salts vary in different
experiments ; 2nd, the potassium bisulphide gives up readily a portion
of the sulphur to the steel of the vessel in which the explosion is
effected, and the quantity of ferrous sulphide so produced is dependent
upon the conditions of the explosions.
If the sources of error be taken into consideration, the explosion of
powders in a confined space may be expressed with some degree of
accuracy by the equation I6KNO3 + 21C + 5S = 5K2CO3 + K2SO4
+ 2K2S2 + I3CO2 + 3C0 + 8H2O, whereas the composition of the
powder calculated from the mean results of the analyses of Noble and
Abel can be represented by the symbols I6KNO3 + 21-18C +
6-63S.
The author by the light of the results obtained by Karolyi and those
of Noble and Abel has been enabled to develop a theory of the explosion
of gunpower competent to explain the observations of former experi-
menters, and in harmony with the thermochemical relations of the
reacting substances. According to this theory, gunpowders which
differ considerably in their composition are transformed during the
first stage according to the equation —
IOKNO3 + 8C + 3S = 2K2CO3 + 3K2SO4 + 6CO2 + 5N2 (1),
but as carbonic oxide is produced, the following equation more nearly
represents the nature of the change: —
I6KNO3 + 13C + 5S = 3K0CO3 + 5K2SO4 -f 9CO2 + CO + 8N2 (2).
The oxygen contained in the potassium carbonate and sulphate, and
the carbonic anhydride in equatio^i (1) stand in the ratio 1:2:2,
whereas the heat developed by the formation of the potassium car-
bonate to the sulphate and carbonic anhydride in equation (2) stand
in the relation 1 : 2*05 : 1-04.
But, as a rule, gunpowder contains more carbon and sulphur than is
required by the equations above, so that, in the second stage of the explo-
sion, the carbon reacts on the potassium sulphate, and the sulphur on
the carbonate, thus : 4K2SO4 + 7C = 2K2CO3 + 2K2S2 + 5CO2 and
4K2CO3 4- 7S = K2SO4 + 3K2S2 + 4CO2, while some of the free
carbon reduces carbonic anhydride to carbonic oxide. These latter
reactions are endothermic, are not of an explosive nature, and in
practice are seldom complete.
If X, y, z be positive numbers, and a represents the molecules of car-
bonic oxide formed by the complete combustion of a given weight of
powder, we have the following general equation as representing the
complete combustion of gunpowder : a'KNOs -\- yC -\- zS = ^hi^^ +
Sy - 16z - 4a)(K2C03) + -^VC^Oa^ - 16y + 4z + 8a)(K2S04) +
_?_(_ Wx + 8y + 12^ - 4a)(K2S2) -\- ^{- 4x + 20y + 16z -
24a) (CO2) + aCO + Ja;N2. The correctness of the equation is proved
by the agreement of the calculated numbers with those observed by
Bunsen and Schischkoff, Noble and Abel, and others. But if in this
equation a; = I6and(i = 0 (and this latter value does not materially
affect the main result), we obtain I6KNO3 + i/C -f zS = ^\(64} + 8w
- 16z)iK,C0,) + ^(320 - ley + 4z)(K,s60 + a\(- 160 + 8y -H
i2z)(KSd + A(- 64 + 20y + I6.)(C02) + 8N2.
2 GO ABSTRACTS OF CHEMICAL PAPERS.
If the coefficients of the potassium carbonate, sulphate, and bisul-
phide be taken as 0, the equation (a) 64 + 8y — 16z = 0, and (^)
320 - I6y + 4^ = 0, and (7) — 160 + 8?/ -\- 12z = 0, represent
three sides of a triangle, of which the two sides represented by equa-
tions (a) and (7) intersect at points y = S and ^ = 8, and these values
introduced into the equation above give I6KNO3 + 80 + 8S =
8K2SO4 -f 8CO0 4- 8N2, and finally the two sides represented by
equations (/S) and (7) intersect in points y = 24 and z = 16, hence
I6KNO3 + 240 + 16S = 8K2S2 + 24OO2 + 8N2.
Again, if V represent the volume of gas evolved by the combustion
of a powder containing 16 mols. KNO3, y atoms of caiJbon and z atoms
of sulphur, and W the units of heat developed, then, on the assumption
that a = 0, Y = 152_±_^L±J:i^, and W = 1000[1827-154 -
14
16*925?/ — 8*7882]. Thus the volume of gas becomes greater, and
amount of heat less when y and z are increased, and vice versa ; quan-
tities of KNO2, 0, and S, represented by the symbols I6KNO3 +
80 + 8S, produce the greatest amount of heat and the smallest
volume of gas, while those corresponding to 16X^03 + 240 + 16S
produce the largest volume of gas and the smallest amount of heat.
The products of the equations for V and W divided by 2 x 1000 =
Y_2^JL = 10440-88 - 12-09?/2 + 1208-39w - 15-95w;? + 993-867z -
2000 J i)
5*02222 = J], which may be taken as the relative energies of powder
of different composition. The difference of the values for E is very
small if the powders contain from' 21 — 24 atoms of carbon, and from
8 — 16 atoms of sulphur for every 16 mols. of potassium nitrate.
Equal weights of the mixtures I6KNO3 + 220 + 8S and I6KNO3
-f 240 + 16S give for E the values 16*84 and 16*95 respectively. If
therefore a powder is required which shall possess nearly the greatest
amount of energy, and at the same time contain the smallest amount
of sulphur and carbon compatible with this condition, theory points to
a mixture, I6KNO3 + 220 4- 8S, whereas the gunpowders of most
nations fluctuate about I6KNO3 + 21*20 + 6*8S.
The author finally draws attention to the advantage of the geome-
trical demonstration above for illustrating the qualitative nature, and
the quantitative relations of the products of combustion, the volumes
of the gases, and the amount of heat developed. V. H. Y.
Cause of the Acid Reaction Exhibited by some Kinds of
Paper. By Haerling {Dingl. polyt .7., 246, 195). — It has been
stated by Feichtinger (Abstr., 1882, 1339) that paper sized with resin
exhibits an acid reaction, which he attributes to the presence of free
sulphuric acid. According to the author, the acid reaction is not due
to free acid, but to the presence of aluminium sulphate, which is used
for fixing the size. A. K. M.
261
General and Physical Chemistry.
The Light emitted by Comets. By Berthelot (Ann. Chim.
Phys. [5], 27, 232 — 233). — Arguing from the presence of hydrogen,
carbon, and nitrogen detected by Huggins in the spectra (correspond-
ing to those given by acetylene and hydrocyanic acid) of the Hght
emitted by comets, the author suggests electrical disturbance as a
more probable cause of luminosity than combustion. L, T. T.
Telluric Rays and the Spectrum of Water Vapour. By
J. Janssen {Gomjpt. rend., 95, 885 — 890). — An historical summary.
Spectra of Carbon and its Compounds. By Gr. D. Liveing
and J. Dewar {Proc. Boy. Soc, 34, 123— 130).— The authors, in
former experiments, have traced a fluted band spectrum, which occurs
when carbon poles transmit the arc or spark current in air to the
compound cyanogen (Abstr., 1882, 252 — 253). The present paper
is a continuation of the investigations, which have received fresh
interest from the discovery by Huggins of cyanogen bands in the
comet of 1881.
The arc discharge between graphite poles in carbonic anhydride
shows the cyanogen triple set beginning about A, 4380, with traces of
the fluted bands at 4218 and 3883 ; if the carbonic anhydride is dis-
placed by air, the triple set is weakened, whilst the fluted series is
strengthened. The spark discharge in carbonic anhydride does not
show the cyanogen series ; but it appears when the discharge is taken
in nitrogen. With the arc discharge in hydrogen, the triple set is
well marked, while the series at 4218 disappears, but the hydrocarbon-
group at 4310 comes out strong. When the pressure in different
gases was reduced to 1 inch, the arc in air showed the hydrocarbon
set, the cyanogen series, and the nitrogen series near H. But in carbonic
anhydride, the triple set alone was strongly marked : in hydrogen, the
triple set disappears, but the hydrocarbon-group comes out strong.
The authors give a list of carbon arc-lines from X 2434*8 to \ 2881*1,
when a continuous Siemens current is used ; these seem to prove
that carbon-vapour of a low tension exists in the arc discharge, which
would account for the combination of carbon with hydrogen or
nitrogen under these conditions.
When the spectrum of a magnified image of the electric arc is
examined, all the more refrangible cyanogen-groups are seen near the
positive pole, together with a series of channellings in the red ; the
cyanogen-group is also visible at the negative pole. But if puffs of
air or carbonic anhydride are passed into the arc, the hydrocarbon
lines are produced; the same result obtains if one of the poles is
moistened.
The De Meritens arc in water shows the hydrocarbon spectrum
alone, but if a little nitrobenzene in glycerol be substituted the cyanogen
triplet about 4380 appears.
VOL. XLIY. t
262 ABSTRACTS OF CHEMICAL PAPERS.
The authors have repeated their experimeuts with vacuum tubes,
using those of capillary glass; the tubes containing benzene or a
solution of naphthalene in benzene, show no trace of the cyanogen
spectrum, until, after continued use, there is a leak or crack at the
point where the platinum is sealed into the glass.
In observations by the eye of flames of coal-gas which had passed
through ammonia, no cyanogen spectrum could be observed; similarly,
hydrogen mixed with carbonic anhydride and ammonia gave no
result, but cyanogen can be detected if the ammonia is mixed with
chloroform and other carbon compounds.
As a result of their experiments, the authors consider that hydro-
cyanic acid can always be separated from reducing flames, in which
the free carbon or dense hydrocarbon vapours favour its formation.
In photographs taken by means of a quartz and calcspar train, the
authors could detect in a flame of coal-gas well supplied with oxygen
only the hydrocarbon-groups ; but if the coal-gas is passed through
ammonia, photographs reveal the characteristic cyanogen-groups at
X 3803 and X 4218. Spectrum analysis can then detect the presence
of cyanogen under widely different conditions. In photographs of the
ultra-violet spectrum of a cyanogen flame fed with oxygen, the authors
succeeded in detecting the carbon line X 2478'3, which proves that
carbon-vapour does exist in flames of cyanogen, although to a smaller
extent than in the arc discharge. V. H. V.
The Ultra-violet Spectra of Elements. By G. D. Livetng and
J. Dewae (Froc. Boy. Soc, 34, 122 — 123). — From photographs taken
with a Rutherford grating, the authors have determined the wave-
lengths of 91 of the principal lines in the spark spectrum of iron
between X 2948, the termination of Cornu's map of the solar spectrum,
and X 2327; and 14 of the strongest lines of the spark spectrum of
copper up to X 2135. With these lines as lines of reference, they have
deduced the wave-lengths of 584 more lines in the arc and spark
spectra of iron within those limits.
The authors have further mapped out the ultra-violet lines of the
arc spectra of sodium, lithium, barium, strontium, calcium, zinc,
mercury, gold, thallium, aluminium, lead, tin, antimony, bismuth, and
carbon. They consider that in several cases harmonic relationships
exist similar to those noticed in the visible lines of the spectra of the
alkalis and magnesium. V. H. V.
An Arrangement of the Electric Arc for the Study of
Radiation of Vapours. By G. D. Liveing and J. Dewar (Proc.
Boy. Soc, 34, 119 — 122). — The authors have constructed a form of
apparatus suitable for a study of the reversal of metallic lines; it
consists of a block of lime, perforated by two holes in planes at right
angles to one another, and through which pass the carbon rods con-
nected with a Siemens dynamo-machine. One of these rods is
perforated, and observations are made by projecting with a lens the
light issuing from the tube on the slit of the spectroscope. By intro-
ducing a small rod of carbon into the perforation from the further
GENERAL AND PHYSICAL CHEMISTRY. 263
end, a luminous background can be obtained, and as the walls of the
tube are hotter than the metallic vapours, the metallic lines are
reversed ; an alteration of the position of the carbon rod causes the
lines to disappear, reappear^ or show reversal. Using commercial
carbons, the first lines seen were the potassium lines k 4044 — 6, next
the two aluminium lines between H and K, then the manganese triple
about X. 4034, a calcium line X, 4226, then the calcium lines near M,
the iron line M, and then gradually many conspicuous lines between
0 and h. In the higher region, the continuous spectrum extends
beyond the solar spectrum.. The calcium lines H and K were often
absent, and not even brought out reversed when calcium or its
chloride was introduced into the tube. The lithium lines X- 4603 and
X 4131 are relatively difficult of reversal. If ammonia is passed into
the tube, most of the lines attributed to cyanogen by the authors appear.
As it is known that ammonia reacts on carbon at a white heat to
produce ammonium cyanide and hydrogen, the appearance of the
cyanogen lines offers an independent confirmation of the author's
views. The two indium lines X 4101 and X 4509 are always reversed ;
tin gives flu'tings in the highly refrangible portions of the spectrum,
and silver gives a fluted spectrum in the blue.. Calcium chloride
gives six or seven bands between L. and M ; these are sometimes
bright and sometimes reversed.- V. H. V.
Reversal of Mietallic Lines in Over-exposed Photographs of
Spectra. By W. N.. Hartley {P>roc.. Boy. Soc, 34, 84— 86).— The
author has made a series of comparative experiments in order to
ascertain the exact period of exposure of the sensitive plate to the
rays, in order to bring out the most characteristic lines, without the
diffused rays of the air spectrum.. Over-exposure causes strong lines
to be reversed without materially altering the appearance of the rest
of the spectrum; this is particularly the case with lines of the metals
magnesium, aluminium, and indium : thus in two over-exposed
photographs the magnesium triplet b' between K and L became a
quadruple group by reason of the most refrangible line being split
into two by a reversal. The author considers that the method of
comparative exposures should be employed to confirm the accuracy of
observations based entirely on photographic representations of spectra.
V. H. V.
Researches on Spectrum Photography. By W. N. Hartley
(Proc. Boy. Soc, 34, 81 — 84). — The author has made an experimental
comparison of the spectra of various compounds in solution with those
of the elements they contain. In order to eliminate lines foreign to the
substances examined, the arc spectrum between graphite poles- was
chosen, as producing about 12 insignificant lines due to carbon,
and about 66 easily recognisable line&^ and bands due to air. On
comparing the spectra of solutions of salts with those from metallic
electrodes, it was found that the same lines, with the same graphic
character, were produced in both cases,, but their continuity was
altered. Thus discontinuous but long lines, or, in certain cases, even
short lines, appear as long lines in the solution-spectra. Zinc offers
an exceptional instance of this variation, for the pure metal exhibits a
t
264
ABSTRACTS OP CHEMICAL PAPERS.
series of short lines or dots, "which are absent from photographs of the
spectra from its solutions. Certain discontinuous lines in the spectrnm
of iridium become continuous when moistened with calcium chloride
solution.
The author considers that only -the method of solution is available
for the estimation of the relative proportions of the constituents of an
alloy or mineral ; for most alloys are not homogeneous, whereas the
composition of a solution represents throughout the composition of
the mass dissolved.
Experiments were made in order to examine the sensitiveness of
the spectrum -reaction under various conditions, as the nature of the
element, time of exposure, and intensity of the spark; it was found
that YoVo P®^ cent, of calcium, silver, copper, and ^q^qq per cent, of
manganese, were recognisable quantities. V. H. V.
Atomic Refraction of Sulphur. By R. Nasini (Ber^ 15, 2878
2892). — The author, at the outset, alludes to the dependence of the
atomic refraction of an element on the nature of its combination with
other elements, which has been established by the researches of
Briihl. As the specific refraction of only a few sulphur compounds
has been determined, the author has made a minute examination of
several organic and inorganic compounds, in order to ascertain whether
the atomic refraction of sulphur varies with its valency.
The refractive indices were determined for the hydrogen lines a, (3,
and 7, and the sodium line D, and the specific refraction calculated
according to the empirical formula — ^ , and the formula —-= — — ;
a (ri* f 2)d
on the basis of these formulae, the index of refraction A for a ray of
infinite wave-length is calculated by the aid of "Cauchy's dispersion
formula (/t\ = A-f- —r\ + . « .). The sj). gr. of the liquid used
Ag A/ 4
was taken ai:.20°, and reduced to that of water at 4°.
The following table embodies the author's results : —
Substance.
Ethyl mercaptan, EtSH
Ethyl sulphide, EtaS
Ethyl bisulphide, EtsSg
Isobutyl mercaptan, C4H9SH . .
Isoamyl sulphide, (0511^1)28 . . . .
Carbon bisulphide, CSj
Ethyl ethylsulphonate, Et.SO^Et ,
Sulphuric acid ......
Sulphuric anhydride
t?v
V"a
f^
0-89307
0-83676
0 -99267
0 -83573
0-84314
1 -2634
1 -42769
1-4396
1 -50306
1 -43575
1 -44966
1 -61847
1 -43055
1 -44233
1 -50633
1 43859
1-45238
1 -62037
d\-.
1 -14517
1 -41733
1 -41959
d\\
1 -8273
1-42659
1 -42922
d\o.
1 -9365
1-4077
1 -4C.965
-43788
•44929
-51604
-44547
-45889
•65268
1-4242
1 -43353
1-41484
GENERAL AND PHYSICAL CHEMISTRY.
265
Substance.
«7.
A.
B.
Ethyl mercaptan EtSH
1 -4445
1 -45522
1 -52.407
1 -4511
1-46447
1 -67515
1 -42595
1 -43745
1 -41805
1 -42746
1-4067
1 -42382
1 -43813
1 -5864
1 -41065
1 -41826
1 -39922
0 -34979
Ethyl sulphide EtgS
0 -52362
Ethyl bisulphide EtsSg .-
0-70431
Isobutyl mercaptan, C4H9SH
0 -51456
0-49646
Carbon bisulphide CSo - • .
1 -16098
Ethyl ethylsulphonate, Et.S03;Et
0-28896
0 -36202
0-36924
From the values obtained for the line a in the above table, together
with a few others obtained by Wiedemann, the author has calculated
the atomic refractioa ?-« and r^, r« and ri&, for the line a, and deduced
from the constant A, according to the old and- new formulaa. The
results are contained in the table below : —
Substance. fa-
Ethyl mercaptan 13-8
Ethyl sulphide 14-28
Ethyl bisulphide 14-41
Isobutyl mercaptan ..;... 13'93
Isoamyl mercaptan 14-
Isoamyl sulphide 14-2
Diethyl monothiocarbonate —
Diethyl dithiocarbonate . . —
Mean
14-10
13-43
13-63
13-7
13-31
13-34
13.-47
13-65
13-78
13-53
15-20
Carbon bisulphide 15-61
Diethyl thiocarbonate,
CS(0Et)2 — 14-y8
Mean 15*6
15-09
{n^ + 2)d.
7-8
8
8
7-82
7-84
7-74
7-87
902
9-02
Xa-
7-64
7-72
7-68
7-53
7-55
7-46
7/89
7-7B.
7-65
8-88
8-80
8-84
From this table it is evident that the atomic refraction of sulphuT
varies according as it is combined with two different groupings, by one
affinity each, or with both of its affinities to one carbon-atom ; and further,
the values for r^ and r^ are concordant among themselves, and stand
in relation to one another, similar to that existing between the values
for r^ and Xa- As far as regards the other sulphur compounds examined,
the values for the atomic refraction of sulphur are in accordance with
one another, but differ in a most marked way from the values above ;
they vary according to the hypothesis adopted to express their con-
stitution, i.e., whether the oxygen-atom is combined with the sulphur-
atom by one or two bands.
266
ABSTRACTS OP CHEMICAL PAPERS.
Diatomic snlplmr «
Tetratomic sulplitir
Hexatomic STilphur
fEt.S.O.O.O.Efc.
I OH.S.O.O.OH
Js<?
o
Et.S,O.Et . . .
0
L
Atom.
refraction.
n-1
d '
. 8-91
. 901
8-10
0<Q>0 8-37
8-33
OH.S.O.OH 84-3
0:S:0 6-94
0:S<n 779
Et O
>SC 7-75
Et^ ^O
OH 0
>SC 7-85
/O
O : Sf 6-63
(n« + 2)rf.
5-25
5-24
6-37
5-82
4-52
4-51
4-91
4-59
3-79
3-78
313
These variations in the atomic refraction of sulphnr may arise from
one of two causes, t.e., alteration of valency, or the direct combination
of sulphur with oxygen instead of carbon ; a further examination of
other sulphur compounds alone can decide the question, and the
author proposes to carry on researches for this purpose.
V. H. V.
Electric Discharge in Rarefied Gases. By E. Goldstein
(PM. Mag. [5], 14, 366— 387).— The author has previously shown
that the electrical discharge in rarefied gases cannot be effected by the
actual projection of gas particles, and for the same reasons it cannot be
propagated by particles torn off from the tube, electrodes, &c. A system
of pores in an insulator, or a single aperture of relatively small
diameter, sends out rays with properties precisely similar to those
from a metallic kathode. It is known also that at sufficiently high
exhaustions the positive light has the property of rectilinear propaga-
tion and the power of exciting phosphorescence, and hence it would
GENERAL AND PHYSICAL CHEMISTRY. 267
not be reasonable to adopt an explanation of the kathode light, the
principle of which is not applicable to the positive light.
If two wires, a and b, are inserted in the end of a cylindrical tube,
parallel with its axis, and both are made kathodes of the same dis-
charge, each repels those rajs from the other which pass near it, thus
producing two sharply defined surfaces, one of which receives no rays
from a, whilst the other receives no rays from b. If one of the
electrodes is platinum, it is found that that part of the tube on which
no rays from the platinum kathode fall, is just as thickly covered
with a deposit of platinum as is any other part of the tube. In other
words, the rays of the kathode light are deflected, whilst the particles
projected from the electrode are not deflected. It follows, therefore,
that, contrary to the usual supposition, recently defended by Gintl and
by Paluj, the two cannot be essentially connected. The objections
to the supposition that the discharge is effected through the medium
of particles torn from the electrodes, apply equally well in the case of
particles torn from the walls of the tube.
Since the discharge cannot be explained by the motion of ponder-
able particles, it follows that it must be a process which takes place in
the free ether.
Hittorf found that the resistance of the positive light decreases as
the exhaustion increases, and that changes in the form and magnitude
of the anode are without influence. He also concluded that the resist-
ance of the kathode light, and at the surface of the kathode, increases
as the exhaustion increases, and hence the resistance to the discharge
at very high exhaustions is exerted at the surface of the kathode and
in the space filled by the kathode light. The author finds, however,
that the resistance of the kathode light at very low pressures becomes
comparatively small with respect to the total resistance to the dis-
charge. Hence it appears that the resistance at very low pressures is
exerted entirely at the surface of the kathode. The experiments on
this point were made with a spark micrometer, included in a second
circuit connecting the electrodes of the discharge tube. It was found
that the discharge did not pass exclusively through the tube up to a
certain distance between the balls of the micrometer, and then with a
certain small decrease in this distance exclusively through the air
space between the balls ; but that there are certain positions in which
the spark sometimes takes one path, sometimes the other, and the one
path the less frequently, the closer the approach to the point at which
the other alone is taken. This phenomenon did not affect the accuracy of
the measurements. If the micrometer is included in the branch circuit
of tubes which transmit the discharge at both make and break, it is
found that if the distance between the balls of the micrometer is
gradually diminished, a point is reached at which the current at break
completely leaves the tube and passes only across the air space between
the balls, whilst the current at make continues to pass through the
tube with undiminished luminosity. This phenomenon may depend
on different maximum tension of the current on making and breaking
contact. From these experiments, it is evident that when the discharge
takes place in gases, the division of the current cannot be calculated
by means of Ohm's law. If two similar tubes are placed sidie bj aide.
268 * ABSTRACTS OF CHEMICAL PAPERS.
opposite to each other, in the same induced current, then at a certain
pressure the current does not divide itself between the two tubes in
any definite ratio to the resistance of the tubes, but passes exclusively
through one of them, leaving the other entirely dark. These observa-
tions will slightly, but not materially, affect the accuracy of some
results given in the author's book on a " New Form of Electrical
Repulsion."
By means of a vacuum tube of special form, in which the anode
was placed close and parallel to the plane of a kathode of large
surface, and in which the length of the tube could be altered by slid-
ing an enclosed closely-fitting glass cylinder, the author was able, at
very low pressures, to increase the expansion of the kathode light in
the ratio 1 : 30, without causing the resistance to vary as much as
1 : 1*06 ; hence the resistance of the kathode light is a vanishing
quantity in comparison with the resistance at the surface of the
kathode. It is also evident that the resistance of the gas in the dis-
charge tube becomes less as the quantity of gas decreases, and it
follows that the tube would have the greatest conductivity when the
whole of the gas is removed and the tube is filled only with
free ether, which the author regards as the true medium of the dis-
charge. The motion of the ether cannot be regarded as progressive,
but is best regarded as radiant. Every particle of ether in a pencil
of negative light assumes that form of motion which is excited at the
point of origin of the pencil.
Experiments with a tube filled partly with nitrogen and partly with
sodium vapour, show that the positive light can be displaced without
any corresponding displacement of the gas itself, and experiments with
two tubes connected by a capillary tube furnished with a stop-cock,
show that when the discharge is powerfully deflected by a magnet
against the side of one tube, the stop-cock being open, there was no
actual transport of gas from one tube to the other, or, rather, that the
diflference in pressure caused by such transport, if it did take place,
was less than 0*01 mm. of mercury, a difference which could have been
recognised by alteration in the distance between two consecutive
striae. It has been argued in opposition to the theory that the ether
is the vehicle of the discharge, that if such w^ere tlie case all gases
would give the same spectrum, which is contrary to fact. But the
ether itself has not the power of emitting light. The luminosity of
gas subjected to an electric discharge depends on the molecules of the
gas having a form and period of oscillation necessary for the emission
of visible rays. The phenomena of phosphorescence and fluorescence
show that molecules of matter can take up invisible vibrations of free
ether, and thus become luminous. The author considers that the dis-
charge takes place in free ether, but is itself non-luminous. The
motion of the ether is, however, communicated to the molecules of gas
in the tube, and these then vibrate according to their particular struc-
ture and conditions of elasticity, and in their turn communicate to
the ether transverse vibrations which produce the sensation of light.
In fact, the luminosity of gases traversed by the electric discharge is
a phenomenon closely analogous to resonance. It differs from
fluorescence and phosphorescence in that, in both these cases, the
i
GENERAL AND PHYSICAL CHEMISTRY. 2G9
vibrations of the ether are transferred to the atoms or molecules of
matter, and back again to the ether, without changing their character
as transverse vibrations, whilst in the luminous discharge a motion of
the ether, which does not consist of transverse vibrations, is converted
into such vibrations. Moreover, a temperature-condition is always
associated with phosphorescence, which does not obtain in the
case of the luminous discharge in gases. The assumption that a
vacuum conducts electricity is of the highest importance in cosmical
physics. The author considers that certain terrestrial electric and
magnetic phenomena may be due to currents of electricity radiated
from the sun through interplanetary space. Experiments show that
there is no limit to the expansion of the kathode light, and that it
streams out into space without reference to the position of the anode.
It is therefore not necessary to assume that the earth is one pole of
the solar current, for discharges, both poles of which were on the sun,
might produce negative rays radiating from the sun into space.
II. Two processes are essential to the production of an electric dis-
charge : a change in the condition of the ether preceding the dis-
charge, which produces a certain condition of unstable equilibrium in
the arrangement of its parts (this condition may be called the tension
of the ether) and the restoration of stable equilibrium, i.e., the dis-
charge itself. The tension preceding the discharge is not equally
great at all cross sections of the discharge- tube, even when the tube is
of equal section throughout ; in certain parts of the tube it may even
be zero : it has either finite or maximum values at the surfaces of the
metal poles, and at those points which appear as points of issue of the
separate positive layers or of secondary negative pencils. The so-
called ether- envelopes surrounding the atoms or molecules of a gas
undoubtedly play an important part in the emission of light produced
by the discharge, but their exact function cannot at present be deter-
mined. The forces which are exerted by the particles of matter in.
the production of the ether-envelopes tend to produce an arrangement
of the ether different from that produced by the electrical forces alone,
and consequently the more gas molecules in a given space, the greater
will be the electrical forces necessary to bring about that arrange-
ment of the ether which must precede discharge : hence the resistance
of the space in which the discharge takes place is less the more com-
pletely the gas is removed. The author cannot accept Wiedemann's
view that the ether-envelopes are the real medium of discharge. If
the envelopes suffer deformation without the free ether taking part in
the discharge, then there must be a pure distance-action between the
envelopes.
From the results of the following experiments, the author concludes
that the direction of the negative current from the kathode is the
direction in which the electric discharge is propagated in .the kathode
light and also in the negative pencils and in the positive stratifications.
If a solid body is placed in the path of a pencil of kathode light, or
of secondary negative light, the shadow is cast on that side farthest
away from the kathode, and the shadows formed in the phosphorescent
surfaces excited by the positive light exhibit similar behaviour. The
properties of secondary negative rays, even for a considerable dis-
270 ABSTRACTS OF CHEMICAL PAPERS.
tance, correspond witli the conditions which exist at that boundary of
the negative rays which is nearest the kathode. With higher and
higher degrees of exhaustion, the pencils radiate continually more and
more from the mouth of a narrow tube opening into a wider tube, a
phenomenon which would not occur if the pencil had its origin in the
wider tube and was propagated from it into the narrower tube. If a
sufficiently weak magnet is allowed to act on the end of a long
kathode pencil remote from the kathode, only the end of the pencil is
affected by the magn-et, the rest of the pencil remaining unaltered. If,
however, the magnet is brought close to the kathode, so as to act on
the rays nearest the kathode, then the whole of the pencil is deflected
even to its furthest point, although the distance of the latter from the
magnet is so great that the magnet could not produce any direct
effect. Precisely similar phenomena are exhibited by secondary nega-
tive pencils, and also by the rays of separate positive stratifications.
It is evident, therefore, that in each separate stratification the dis-
charge is propagated from the bounding surface on the kathode side to
the bounding surface on the side nearest the anode. The usual
phenomena of defl.ection may be explained in a similar manner.
III. It is necessary to distinguish between the velocity and direction
of the discharge of a pencil of electrical rays and the velocity and
direction with which the tension preceding the discharge is propagated.
All the observed phenomena indicate that the tension is propagated in
the direction of the negative current ; the tension of separate posi-
tive stratifications is developed in the same order of time as that in
which they follow one another in space from the kathode to the anode.
The position and character of separate complete stratifications, espe-
cially the position of the points from which the separate discharges
formed by the stratifications issue, depend, not on the conditions of the
anode, but on the position and character of the kathode. With high
exhaustion and a sufficiently powerful and regular induction cun*ent,
stratifications can be obtained which are perfectly stationary and equal
in thickness to the diameter of the tube. In a tube arranged so that
the electrodes can be moved along the axis of the tube, any motion of
the anode produces no displacement of the stratification. The layers
passed over by the anode as it approaches the kathode disappear one
by one as if absorbed by the anode. If the anode is moved away from
the kathode, all the previously existing layere retain their original
positions, and new layers appear in the space left by the anode, each
new layer after its formation being perfectly independent of any sub-
sequent motion of the anode in the same direction. If, however, the
kathode is moved towards the anode all the layers in the tube move at
once through exactly the same. distance and exactly in the same direc-
tion as the kathode moves. As the distamce between the electrodes is
diminished, the number of layers possiWe is diminished also, and each
layer disappears as soon as it is pushed up against the anode. If the
kathode is moved away from the anode, all the layers follow the
kathode and new layers appear in the space left between the last layer
and the anode, each layer after its formation following the motion of
the kathode. The interval between every two layers in a tube is
practically the same, so that at a given density of gas and intensity of
GENERAL AND PHYSICAL CHEMISTRY. 271
dlscHarge we may speak simply of the stratification interval. The
number of layers in a tube is evidently the quotient of the length of
the column by the stratification interval. When, as frequently hap-
pens, this quotient is not a whole number, it is found that the layer
nearest the kathode is at the same distance from it for every distance
between the two electrodes, whilst the incomplete layer is in contact
with the anode and shortens or lengthens in proportion to the excess
of the quotient above a whole number. Moreover, consecutive layers
in a column of positive light may show distinct differences in colour
although of the same form and magnitude, a phenomenon especially
marked in the case of hydrogen. The colour of each layer depends
entirely on its position with respect to the kathode, and not at all on
its relation to the anode. Further, variations in the size of the anode
have no effect on the position of the layers, but a variation in the size
of the kathode changes the position of all the positive layers. Other
conditions being the same, the smaller the kathode the greater the
distance between the kathode and the first positive layer ; the intervals
between the successive positive layers are not altered.
It must not be assumed, however, that the conditions of tension and
discharge of the whole stratified column are determined by the kathode,
or the physical conditions at the kathode. The position and proper-
ties of each layer depend mainly, if not entia'ely, on the position and
properties of the layer preceding it on the side next the kathode. The
influence of the kathode on the entire stratified column is therefore
only indirect. The conditions at the kathode determine the properties
of the kathode light ; this determines the position aand properties of
the first positive layer; this the position, &c., of the second layer, and
so on. This view is based on the results of experiments with secondary
negative light. A cylindrical tube provided with a movable kathode,
K, and fixed anode, A, contained a closely-fitting short glass tube, R,
with a small aperture, x, which could be moved along the larger tube ;
the small aperture, x, acting as a secondary negative pole. Any move-
ment of K affected all the layers between K and cc, but had no effect
on the layers between x and A. If K remains stationary while x is
moved, the movement affects all the layers between x and A, just as if
X were a metallic kathode. Then, too, the colours between K and x
depend on the position of K, whilst those between x and A depend
only on the position of a?, and are independent of K. The magnitude
of the secondary pole affects aiU the layers between it and the anode,
just as the magnitude of the kathode affects all tbe layers between it
and the secondary pole. With a tube containing two secondary nega-
tive poles it was found that the position of each layer depends on the
position and character of that secondary negative pole or pencil of
secondary negative light which is nearest to it on the side towards the
kathode.
As a matter of fact, the interval between two consecutive layers in
a simple cylindrical tube diminishes slightly from the kathode to the
anode. If a secondary pole is introduced, the distances diminish from
the kathode up to this secondary pole, then the distance suddenly
increases, and a new series of diminishing intervals is commenced.
With infinitely small changes in the section when the secondary nega-
^72 ABSTRACTS OF CHEMICAL PAPERS.
tive pencil passes into a positive layer, the distance between any two
layers depends on the properties of that component of the pair which
is nearest the kathode. The conditions existing at the point of origin
of each layer always inflaence the layer following next to it on the
side of the anode, but have no effect on the preceding layer on the
side of the kathode. The conditions of formation of the nth layer
stand to the properties of the (n + 1) layer in the relation of cause
to effect. In other words, the propao^ation of electrical tension or the
production of separate layers, is effected in the direction from the
kathode to the anode. C. H. B,
The Leclanchd Cell, and the Reactions of Manganese Oxides
with Ammonium Chloride. By E. Divers (Ghem. Neivs, 46, 259
— 260). — Longi doubts Priwoznik's statement that zinc acts on ammo-
nium chloride and forms zinco-diaramonium chloride, Zn(NH3Cl)o ;
the author has, however, obtained this same substance, and describes
its properties ; in solution it probably exists as a double salt with
ammonium chloride, for when the liquid is heated, much ammonia
appears and a double chloride of zinc and ammonium is formed. The
zinco-diammonium chloride is decomposed by water into a soluble
salt, (ClH4N)2,Zn(NE[,jCl)2, and an insoluble compound, H0-.Zn.NH3Cl,
which latter is probably the same as that found by Davis, and to
which he assigned the formula Zn(OH)2,NH'4€l.
Manganese dioxide is not affected by digestion with ammonium
chloride ; the monoxide, however, is attacked, a portion passing into
solution accompanied by evolution of ammonia and the formation of a
light-coloured body, presumably manganous hydroxy chloride, HOMnCl,
as treatment with water gives rise to the formation of manganous
hydroxide. Intermediate oxides are also attacked in a similar manner. '
Zinco-diammonium chloride, in presence of ammonium chloride, acts
gradually on hydrogen manganite, Mn2H204, manganese passing into
solution, and zinc being precipitated as manganite, but this action does
not occur with native manganite. Solid manganese dioxide is attacked
by zinc in presence of ammonium chloride, both zinc and manganese
going into solution, whilst amuMonia is set free. From these observed
facts, a theory of the action of the Leclanche cell is deduced.
Primary action —
MnaOi + 2HNH3CI + Zn = Mn^O.Ur + (NH3Cl)2Zn.
This zinc compound remains in solution until the liquid is saturated,
and then crystallises out in the usual manner.
Secondary reaction causing polarisation —
MnjO^ + Zn(NH3Cl)2 + Zn = MnjO^Zn + (NH3Cl)2Zn.
The zinc manganite thus formed coats over the manganic oxide, pro-
tecting it from the action of the ammonium chloride.
Secondary reaction causing depolarisation —
MnaO^Zn + 4NH,C1 = Mn02 + 2H2O + MnCl^ + ZnQ^R.Cl)^ -f
GENERAL AND PHYSICAL CHEMISTRY. 273
From this equation we see that the manganese dioxide becomes active
again, but as this action is slower than that which occurs during
polarisation, it is necessary to leave the cell uncircuited for a time in
order that it may recover ite full power after being used.
E. W. P.
Currents Produced by IFused Nitrates in Contact with In-
candescent Carbon. By Brard {Gompt. rend., 95, 890—892).—
Becquerel has shown that when incandescent gas-carbon is plunged
into a bath of a fused nitrate, a powerful current is produced which
passes from the bath to the carbon in the exterior circuit. The author
finds that this takes place with all forms of carbon. The current
rapidly becomes weaker, in consequence of the deposition on the
surface of the carbon of a very compact strongly adhering crust of
salts which protects the carbon from the action of the nitrate. The
fused nitrates become very fluid, and acquire the property of moisten-
ing for a considerable distance the surfaces of heated bodies with
which they are brought into contact. In consequence of this property
it is not necessary to plunge the ignited end of the carbon into the
fused nitrate, but the cool end may be placed in the bath, and the
other end then made incandescent. If a capsule, containing some
grains of fused nitrate, is left for a few minutes on the s.urface of
glowing coals, a current is produced which flows from the bath to the
coals in the exterior circuit, and remains sensibly constant in intensity
so long as the coals continue to glow or any nitrate remains in the
capsule. In this experiment the fused nitrate ereeps over the edge of
the vessel and flow-s down the outside on to the hot coals on which
the capsule rests. The gradual flow of the thin layer of fused nitrate
produces regular chemical action, and thus the current remains
sensibly constant. The current passes ihrough the fire the more easily
the higher the temperature. When a metallic capsule containing the
fused salts is suspended freely above an active fire, a current still
passes from the nitrate to the exterior of the capsule. These currents
are more, feeble than those obtained by the preceding methods, but they
may be increased by surrounding the outside of the capsule with a
layer of black-lead and encasing the whole in metallic gauze. The
best effect is obtained by covering the outside of the capsule with a
layer of asbestos-paper, covering the latter with black-lead, and then
putting on the coarse metallic gauze. The metallic gauze forms the
negative pole of the element, and the capsule the positive pole. A
couple of this kind heated over a Bunsen flame giv-es a remarkably
constant current of 6 to 7 milliamper^s. It is important to place the
capsule just in the point of the flame where the number of incan-
descent carbon particles is greatest, for it is these incandescent
particles which, coming in contact with the fused nitrate absorbed by
the asbestos, produce the .current : the constancy of the current is due
to the fact that with a properly regulated lamp the temperature and
the proportion of carbonaceous products remain practically constant
for a long time. The nitrates which melt at about 200" are very
stable, and only decompose at about 1000° or 1200°. Up to this point
they not only do not attack the vessels in which they arc contained
274 ABSTRACTS OF CHEMICAL PAPERS.
but, on the contrary, appear to prevent or to retard considerably the
oxidising action of the fire. C. H. B.
Determination of High Temperatures. (Chem. Centr. [3], 13,
6&6 — 667.) — Gold and platinum alloys are recommended for this par-
pose. The alloy used is made into balls of 1 to 2 grams ; these are
hammered out to plates about the size of sixpenny-pieces, bent in the
form of an arch, and placed in rows in cupels, which are then arranged
in the furnace so that they can be seen through a peep-hole. The
temperature is reckoned from the melting point, which may vary from
the melting point of silver to that of steel (nearly). The same alloy
may be used over and over again. D. A. L.
Specific Heat and Heat of Transformation of Silver Iodide,
and its Alloys with Cuprous and Lead Iodides. By H. Bellati
and R. Romanese (Proe. Boy. Soc, 34, 104 — 105). — The authors have
made a series of calorimetric investigations on these substances, the
expression and contraction of which Rodwell has stndied (Abstr.,.1881,
495, 465). In the table below ^i and 6^_ are the temperatures between
which the structural change occurs, c the mean specific heat between
t and T for temperatures below 9i, Ci the mean specific heat for tem-
peratures above O2, and X, the heat absorbed by unit weight of the
substance in consequence of modification of structure : —
rormula of
substance. Si- 62. c. Cj* X.
Agl 142 156-5 0-054389 + 0-0000372 (T + 0 0-0577 6-25
CU2I2 + 2AgI 95 228 0-05882 -f (from 16 to 89) 0-068 8-31
CU2I2 + 4AgI 180 282 0-056526 -f 0-000041 (T + t) 0*0702 7*95
CU2I2 + 3AgI 194 280 0-059624 -h 0-000028 (T + 0 00726 7-74i
CU2I2 + 2AgI 221 298 0 061035 + 0-0000295 (T + t} — 7*88
CU2I2 + Agl.. 256 324 0-063099 + 0-000026 (T -|- 0 — 8-67
Pblj +AgL 118 144 0-47458 -h 0-000026 (T -}- 0 0-0567 2-556
V. H. Y.
Direct Determination of the Heat of Combination of
Certain Gases. By F. W. Raabe (Bee. Trav, GMm., 1, 158—166).
— Ammonium Carbonate. — Lecher (Wien. Ahad. Ber., October, 1878)
determined by an indirect method the heat of combination of car-
bonic anhydride and ammonia, and obtained the numbers 38,817 and
36,642 heat-units (gram- degrees) ; mean 37,700. The difference
between these numbers being rather wide, the author has endeavoured
to obtain a more exact result by direct combination of the gases,
bringing them together in a modified form of Bunsen's calorimeter.
The mean value found for the heat evolved when 44 g. CO2 and 34 g.
NH3 unite to form 78 g. ammonium carbamate, (NH3)2C02 or
NH2.CO.ONH4, was 39,300 units. Thomson by an indirect method
found 42,500, and Berthelot 38,100.
Ammonium Chloride. — The heat of combination of NH3 and HCl
has been determined indirectly by Thomson, by Berthelot, and by
Favre and Silbermann, with the following results : —
GENERAL AND PHYSICAL CHEMISTRY. 275
Thoinsen. Berthelot. Favre and Silbermann.
41,899 42,700 43,240
Favre and Silbermann by an indirect method obtained the number
39,970, bat regard this result as less exact than that found indi-r
rectly. The author of the present paper obtained by the method
above indicated the value 44,460. H. W.
Lead Iodide. By Beethelot (Compf. rend., 95, 962 — 955). —
If lead iodide is dissolved in a hot concentrated aqueous solution of
potassium iodide, the liquid on cooling deposits a pale-yellow crys-
talline salt, of the composition Pbl2,2KI,2H20. At a lower tempera-
ture, or by the gradual evaporation of the mother-liquor in the cold,
long pale-yellow needles are obtained, of the composition
4KI,3Pbl2,6H20.
These salts combine together, forming intermediate compounds. The
heat of formation of these double salts was determined by treating
them with a large quantity of water. The following results were
obtained : —
2KI,Pbl2 -\- 2H2O liquid = 2KI,Pbl2,2H20, crystallised
„ „ solid = „ „
2KI + Pbl, 4- 2H2O solid = 2KI,Pbl2,2H20
2KI + Pbia = 2KI,Pbl2 anhydrous
4KI,3Pbl2 + 6H2O liquid = 4KI,3Pbl2,6H20
„ „ solid = „ „
4KI + 3Pbl2 + 6H2O solid = 4KI,3Pbl2,6H20
4KI + 3Pbl2 ■■= 4KI,3Pbl2
The formation of the first salt is exothermic in both the hydrated
and anhydrous condition, whereas the formation of the second salt is
exothermic in the hydrated condition only.
A cold saturated solution of lead iodide yields an immediate pre-
cipitate on addition of a few drops of a dilute solution of potassium
iodide or hydriodic acid. Solution of lead bromide, on the other
hand, is precipitated by hydrobromic acid, but not by soluble bro-
mides, and solution of lead chloride is precipitated by hydrochloric
acid, but not by soluble chlorides. ^ . C. H. B.
Ethylene Oxide. By Berthelot (Bull. Soc. Chim., 39, 484 —
487). — The following heat determinations of ethylene oxide were
made by the author: — Heat of combustion, C2H4O + O5 = 2CO2 +
2H2O (liquid) = 307*5 cal. at constant volume, 308'4 at constant
pressure; heat of vaporisation, 6*1 cal. ; heat of solution, 1*5 cal.;
heat of formation from its elements, C2 (diamond) + H4 -|- O =
C2H4O (gas) = 17*7 cal; heat of formation from ethylene, C2H4 -f
0 = C2H4O (gas) = 33 cal. This last number is practically the
half of the heat of formation of aldehyde from the same constituents,
which may account for the fact that the formation of ethylene oxide
directly from ethylene has not been observed, aldehyde being formed
in preference. , .
talli
Develops.
sed. -f 4-62 cal.
.. -f 1-76 „
.. -f 2-58 „
.. + 0-84 „
.. -f 12-36 „
.. + 3-8 „
..4-2-8 „
.. - 1-0 „
276 ABSTRACTS OF CHEmCAL PAi'ERS.
From the data of the heat of solution of glycol, the following
number is deduced : — C2H4O (liquid + HjO (liquid) = CaHeOj
(liquid) = 19*1, a result comparable with the heat of hydration of
sulphur trioxide (20"4 cal.) and barium oxide (17*6 cal.).
On heating ethylene oxide to redness the volume is doubled, with
formation of carbonic oxide and marsh-gas, C2H4O = CO + CH4, a
reaction which disengages 26*4 cal. A very volatile liquid, probably
aldehyde, is formed as an intermediate product.
The author draws attention to the differences of the heat of forma-
tion of gaseous aldehyde and ethylene ©xide, for Cg (diamond) +
H4 + 0 = C2H4O
In forming gaseous ethylene oxide evolves 17' 7 cal.
,, „ aldehyde evolves .... 50*1 „
Thus ethylene oxide has a greater potential energy than aldehyde,
which explains its ready polymerisation and direct combination with
water and acids. The conversion of ethylene oxide into aldehyde
disengages 32*8 ,cal.^ this isomeric change being accompanied with a
loss of energy. Inasmuch as glycol on dehydration with zinc chloride
furnishes not ethylene oxide, but aldehyde, conclusions as to the
constitution of compounds drawn from their products of dehydration
by zinc chloride must not be accepted as final without an appeal to
the thermochemistry of the compounds in question. V. H. V.
Critical Temperatures of Alkyl Salts. By B. Pawlewski
(JBer., 15, 2460 — 2464). — The author has made a series of determina-
tions of the critical temperatures and boiling points of the alkyl
salts of the CnBiimOz series, the results of which are embodied in the
following table. In the first column are the several boiling points, t;
in the second the difference of boiling point (t — ^i) of two consecutive
salts ; in the third the critical temperature, T ; in the fourth the
difference of critical temperature, T — Ti, of two consecutive salts ; in
the fifth the difference between the boiling point and critical tem-
perature.
Ethereal salt. (t). (t-ti). (T). (T-Ti). (T-^.
Ethyl formate 557 — 238-6 — 182-9
Propyl formate 85'1 294 267-4 28-8 182-3
Isoamyl formate 121-8 36-7 304-6 37-2 182-8
Methyl acetate 57-1 — 239-8 — 182-7
Ethyl acetate 75-0 17'9 2565 167 181-5
Propyl acetate 100-3 25-3 282-4 25-9 182-1
Normal butyl acetate .. 123*7 23-4 305-9 23-5 182-2
Isobutyl acetate 114-6 — 295-8 — 181-2
Methyl propionate 80-0 — 262-7 — 182-7
Ethyl propionate 98-5 18-5 280-6 17-9 182*1
Propyl propionate 122-3 23-8 304-8 24*8 182-5
Isobutyl propionate .... 135-8 — 318-7 — 182-9
Ethyl butyrate 121-7 — 304-3 — 182-6
Propyl butyrate 144-3 22-5 326-6 22-3 382-3
GENERAL AND PHYSICAL CHEMISTRY.
277
Ethereal salt. (t). {t-t{). (T). (T-Ti). (T-t).
Methyl isobutyrate .... 91-7 — 273-6 — 181-7
Ethyl isobuty rate 108-6 16-9 290-4 16'8 181-8
Propyl isobtyrate 133-4 24-8 316*0 25-6 182-6
The following relations are rendered evident by the tabulated
results : —
(1.) The difference between the boiling point and the critical tem-
perature is a constant = 182-3.
(2.) Alkyl salts of the same formula and analogous structure
have approximately the same critical temperature.
(3.) The difference between the critical temperatures of two con-
secutive alkyl salts is equal to the difference between their boiling
points.
(4.) The difference between the critical temperatures of two salts
of the same acid and alcohol-radicals (alkyls) is equal to the difference
between their boiling points.
The author considers that the determination of the critical tem-
perature can be used as a control for the boiling point.
V. H. V.
Critical Point of Mixed Gases. By G. Ansdell (Proc. Boy.
Soc, 34, 113 — 119). — The author, in continuation of his researches
on the physical constants of liquid acetylene and hydrochloric acid
(Abstr., 1882, 266), has investigated the behaviour of two gases in
presence of one another as regards the alteration of the critical point.
Carbonic anhydride and hydrochloric acid were chosen as offering
examples of gases which are easily prepared, and whose critical
points are accurately known ; and further the results are probably
not modified by their mutual decomposition or by the formation of an
addition compound. The author used a Cailletet pump and the same
method of experiment which he adopted in his former researches. The
critical point of the mixture was determined, and then the tensions of
the saturated vapour at different temperatures, together with the frac-
tional volume to which the gas was reduced at the point of liquefac-
tion, and also the relation between the liquid and gaseous volumes at
different heights in the Cailletet tube. Some of the results are
appended below.
Temp, of
Temp, of
mixed gases.
Pressure
mixed gases.
Pressure
r 0
, 15
27-84
r 0
28-86
40-66
1 1.3-8
P. c. of CO2 in J 25-5
mixture 19-37 ^ 38
39-86
P. c. of CO2 in J 27
54-22
52-77
mixture 17-18 ] 37-5
70-28
67-36
46
82-26
44
76-23
Critical point l^ 47*2
92-21
Critical point 1^45 '5
80-52
r 0
3317
17-5
P. c. of CO2 in , 26-6
mixture 45-67 ] 35
32-72
16-3
50-09
50-73
] P. c. of CO2 in ! 25-4
63-98
63-31
mixture 25*48
34
77-02
76-64^
43-2
90-03
I 37-6
7914
;■ Critical point
6 VOL. XLIV.
45-1
—
Critical point ^38
81-35
u
278 ABSTRACTS OP CHEMICAL PAPERS.
Pawlewski, from his experiments on the ethers and alcohols, arrives
at the result that the critical point of mixed bodies is directly pro-
portional to the percentage composition of the mixture when the
co-ordinate origin of temperature taken is that of the body having the
lowest critical point. He infers that the same rule would hold good
in the case of liquid substances which are gaseous at ordinary tem-
peratures ; but as the physical constants of liquefied gases are so
exaggerated as regards their compression and expansion, and as the
variation of their critical points is materially affected by traces of
impurity, it would appear probable that mixtures of such liquefied
gases would not follow Pawlewski's rule. This view is confirmed by
the results of the author's experiments. V. H. V.
Law of Freezing of Solvents. By F. M. Raoult (Compt. rend.,
95, 1030 — 1033). — If A represents the reduction of freezing point
caused by the solution of 1 gram of the substance in 100 grams of
the solvent, M the molecular weight of the dissolved substance
(anhydrous), and T the molecular reduction of freezing point, i.e.,
the reduction caused by the solution of a gram-molecule in 100
grams of liquid, then, if the solution is dilute,
MA = T.
The author has examined solutions of a large number of inorganic
and organic bodies in water, benzene, nitrobenzene, ethylene dibro-
mide, formic acid, and acetic acid, all of which, with the exception of
water, contract on solidificatioti.
Acetic Acid. — All organic and many inorganic bodies produce a
molecular reduction of freezing point between 36 and 40, generally
about 39. Certain inorganic compounds, sulphuric and hydrochloric
acid, calcium nitrate, and magnesium acetate produce a molecular
reduction of about 19, nearly half the ordinary number.
Formic acid behaves in a similar manner; the normal molecular
reduction is 28, the abnormal 14.
Benzene. — Almost all organic compounds and all non-metallic
chlorides produce a molecular reduction between 47 and 51, mean
49. Methyl and ethyl alcohols, formic, acetic, valeric, and benzoic
acids, produce a mean reduction of 25, or half the normal reduction.
Nitrobenzene and ethylene dibromide behave in a similar manner,
the mean molecular reductions with the first-named being 68 and 34,
and with the second 117 and 58. The different reductions are pro-
duced by the same compounds as in the case of benzene.
Water. — The results are not so concordant. The majority of the
inorganic acids, alkaline bases, salts of the alkalis and alkaline
earths produce a molecular reduction between 33 and 43. Barium
and strontium chlorides give about 50. With the greater number
of more than 60 inorganic substances the reduction is about 37.
On the other hand, magnesium sulphate, metaphosphoric acid,
hydrogen sulphide, and all organic bodies without exception give a
much more constant molecular reduction, lying between 17 and 20,
mean 18*5. Here, as in the other cases, one reduction is just double
the other.
GENERAL AND PHYSICAL CHEMISTRY. 279
From the results of experiments with more than 200 compounds
dissolved in these six different liquids, the author draws the following
conclusions : —
All bodies when dissolved in a liquid compound which can solidify,
lower its freezing point. In all liquids, the molecular reduction of
the freezing point due to different compounds approaches two values,
invariable for each liquid, and of which one- is double the other. The
greater value is most frequently met with, and is the no-rmal mole-
cular reduction; the lower value is the abnormal reduction. This
lower value corresponds with those cases in which the molecules of
the dissolved substance are united in pairs.
The normal molecular reduction of freezing point varies vdth the
nature of the liquid, but if each of the molecular reductions is divided
by the molecular weight of the particular solvent, which reduces
the results to the case of a molecule of the substance dissolved in
100 mols. of the solvent ; the quotients, except in the case of water,
are practically the same.
Water.... 37:18 = 2-050 Benzene 49 r 78 = 0*628
Formic acid 28 : 46 = 0*608 Nitrobenzene 70-5 : 123 = 0*600
Acetic acid. 39 : 60 = 0*650 Ethylene dibromide 117 : 188 = 0*623
Water obeys the general law if it is assumed that the physical mole-
cule, at least near the freezing point,, is composed of three chemical
molecules, for 37 : 18 X 3 = 0685. It follows that a molecule of any
compound whatever, when dissolved in 100 mols. of any liquid what-
ever of a different nature, lowers the freezing point of the liquid by a
quantity which is almost constant, and which is about 0*62. This law
is general if it is admitted that physical molecules may be composed
of two, or in rare cases of three, chemical molecules. O. H. B.
Report to the R. Accademia dei Lincei on a Memoir by
R. Schiff "On the Molecular Volumes of Liquids." By P.
Blasebna and S. Cannizzaro {Gazzetta, 12, 488 — 494). — A theoretical
paper, not admitting of abstraction.
Passage of Alcoholic Liquids through Porous Vessels. By
H. Gal (Compt. rend., 95, 844 — 846). — The author has studied the
alteration in composition of aqueous alcohol when placed in bladders
under different conditions. It is generally taught that alcohol placed
in bladders becomes stronger with lapse of time, but the author shows
that this is not always true. When the bladders are exposed to a
comparatively high temperature and dry atmosphere, the alcohol
increases regularly in strength, but when placed in an atmosphere
saturated with moisture and at low temperatures, the liquid loses
strength regularly. The author thinks that those who have previously
studied this subject have assigned too much importance to the part
taken by the membrane used, and have not taken sufficient account of
the effect of the surrounding atmosphere. E. H. R.
Lecture Experiments. By A. W. Hofmann (Ber., 15, 2656 —
2677). — A continuation of experiments previously described.
w 2
280 ABSTRACTS OF CHEMICAL PAPERS.
Electrolysis of Hydrocldoric Acid. — The acid is decomposed in the
closed limb of a XJ-tube, and the liberated chlorine is absorbed by a
solution of potassium iodide, which is admitted through the open end
of the second limb, the volume of the gas being reduced to one-half.
To show that by the union of chlorine with hydrogen no change of
volume takes place, a glass bulb containing the mixed gases is intro-
duced into a large wide-mouthed globe containing dry air. The gaseous
mixture is exploded by means of the magnesium light, the pressure in
the globe before and after explosion being indicated by a manometer.
For showing that the weight of a body is increased by combustion,
magnesium or phosphorus is burned in a globe, the globe and metal
being weighed before the experiment, and the globe together with the
product of combustion after the experiment.
To show that carbonic anhydride has the same volume as the oxygen
it contains, a glass globe fitted with a mercury safety tube is filled
with oxygen. A piece of glowing carbon is then introduced, and the
opening immediately closed. After the combustion of the carbon, the
globe is allowed to cool, when the mercury regains its original level.
Combustion of Oxygen in Hydrogen. — The hydrogen is passed upwards
into a glass globe, and the jet supplying the oxygen is introduced
from above, both ends being closed by corks, through which the supply
tubes pass. In this way the cracking of the globe is avoided which
so frequently took place when, as in the older form of the experiment,
the hydrogen was allowed to burn below it in contact with the air.
To show that aqueous vapour is lighter than air, water is boiled in a
flask, the vapour being made to pass through a horizontal tube, in
connection with which are two vertical tubes, one directed upwards,
and the other downwards. The steam escapes by the upper tube, and
at the end of the horizontal tube, but does not escape by the lower tube.
Relative Volumes of Water in the Liquid and Gaseous State. — A rapid
current of steam is passed through a globe connected above and below
with narrow glass tubes. When full of vapour the upper end is closed,
and the lower end dipped under mercury. The latter rises and fills
the globe, while the condensed water is forced into the capillary tube.
Maximum Density of Water. — In a glass tube containing distilled
water a coloured glass float is placed, the density of which is such that
the body just floats when the temperature of the water is 4°. The
tube is sealed, so that when once adjusted it cannot get out of order.
Decomposition of Water by Sodium. — By placing the sodium on the
end of a long packing needle, and introducing it quickly into the
water under the inverted gas jar, the explosions which sometimes
occur when gauze is used, are avoided.
Alternate Decomposition and Reproduction of Water. — A U-tube,
closed at one end, is arranged with wires for passing the electric
spark, and lower down with electrodes for decomposing water. The
lower part of the U-tube contains mercury, and above this in the closed
limb is acidulated water. A cork is inserted in the open end, and
mercury is run out below, so as to diminish the pressure in the tube.
The decomposition of the water is then started by the current, and as
soon as the evolved gases surround the upper wires, they are caused to
combine again by the passage of the electric spark.
INORGANIC CHEMISTRY. 281
Volumetric Analysis of Ammonia. — One limb (whicli can be closed
at both ends bj stopcocks) of a U-tube is filled with chlorine.
Ammonia solution is poured into the other limb, and about 10 c.c.
admitted into the chlorine. The tube is well shaken, and the excess
of ammonia replaced by dilute sulphuric acid, which is then admitted
into the closed limb. The liquid rises until the volume of the gas
(nitrogen) is seen to have diminished to one-third of the original
chlorine.
Volumetric Belation of Ammonia to the Nitrogen it contains. — The
apparatus described in the last experiment is filled with dry ammonia.
On shaking with a solution of bromine in dilute soda, ihe nitrogen is
set free, and occupies half the original volume of the ammonia.
For showing quantitatively the production of sidphuric acid, the
author employs a U-tube, one limb of which is provided at its upper
extremity with a three-way stopcock, the other limb being open. After
filling the tube with mercury, nitric oxide (40 c.c), sulphurous anhy-
dride (60 c.c), and dry oxygen (30 c.c.) are introduced. On finally
admitting steam, the temporary formation of the characteristic white
crystals may be observed. At the end of the experiment nearly the
original volume of the nitric oxide remains, whilst the sulphuric acid
forms a layer above the mercury.
Demonstration of Dulong and Petifs Laiu. — The apparatus employed
consists of two similar thermometers, the bulbs of which are double
cylinders of glass, so that there is a hollow space in the centre of each
bulb, into which the metal experimented with can be inserted. In con-
ducting an experiment, the two metals whose specific heats are to be
compared are heated to a given temperature, and quickly dropped
into the cavities of the two thermometers.
The equivalent weights of lead and zinc can be shown by suspending
a weighed cylinder of zinc in a solution of lead acetate, and comparing
the weight of the precipitated lead with that lost by the zinc.
Leidenfrosf s Experiment Reversed. — A platinum flask is maintained
at a white heat by a current of oxygen and hydrogen passing into it.
It is then made to dip under water, when the platinum will continue
to glow for some secoy ds. A. K. M.
Inorganic Chemistry.
Oxygen prepared from Potassium Chlorate. By A. Wagner
(Zeits. Anal. Chem., 21, 507 — 510). — It is well known that oxygen
prepared from potassium chlorate frequently contains appreciable
traces of chlorine. The author finds that whilst the absolutely pure
salt yields pure oxygen, the commercial salt never does, owing to
traces of organic matter present in it. Carbonic anhydride decom-
poses even pure chlorate, with formation of chlorine. O. H.
282 ABSTRACTS OF CHEMICAL PAPERS.
Formation of 025one and Hydrogen Peroxide. By S. Kappel
(Arch. Pharm. [3], 20, 574 — 577). — The author, having previously
experimented on the nitrification of ammonia in presence of metals
(p. 286), made experiments of a similar kind with fixed alkalis and
copper in the presence of air, thinking that the nitrogen of the air
would be oxidised to nitrous acid ; he was, however, unsuccessful as
regards the end sought. The test papers which he suspended in the
flasks certainly .became blue, but were immediately decolorised, and
the fluid, on the termination of the experiment, gave no nitrous reaction.
The results indicate the simultaneous production of ozone and
hydrogen peroxide ; the latter probably decomposes the former, which
is again formed, and a continuous process of the kind appears to go
on. The fluid, if tested with potassium dichromate and sulphuric
acid and shaken with ether, does not show the hydrogen peroxide re-
action, but if left for a long time in an open flask, or if a current of air is
passed through it to remove the ozone, the reaction is easily obtained.
J. F.
Activity of Oxygen. By M. Traube (Ber,, 15, 2421— 2443).— A
continuation of the author's researches (Abstr,, 1882, 795).
PAiiT I. — In this paper the author criticises the theory of Hoppe-
Seyler, which supposes the dependence of the life functions of animal
organisms on a process of fermentation whereby hydrogen is evolved,
and the oxygen molecule separated into its constituent atoms, these
at the moment of liberation assuming the active character of ozone, and
effecting the oxidation processes necessary for the continuation of life.
According to the author, this theory fails both on physiological and
chemical grounds, for in the first place the evolution of hydrogen has
only been observed in the alimentary canal, where fermentation
processes are undoubtedly effected by bacteria : further, if the fermen-
tation and life processes were identical, then those organs of the body,
such as the blood and muscles, on which the function of life is depen-
dent, would soon after death show an evolution of hydrogen (in the
absence of oxygen) ; but this is directly contradicted by the researches
of Broech (Annalen^ 115, 78) and those of the author, for fresh
muscle does not reduce dilute nitric acid. Again fermentation
bacteria convert nitrogenous into ammoniacal compounds, but the
animal organs in the absence of such bacteria effect no such change.
Secondly, Hoppe-Seyler based the chemical part of this theory on
experiments which showed that petroleum shaken up with sodium in
the presence of air absorbed oxygen with formation of volatile acids.
Hoppe-Seyler did not however examine whether this result was not
due to the inevitable moisture of the air; and the experiments of
Fudakowski, Schonbein, and others have shown that a number of
organic compounds, as benzene, ether, turpentine, gradually darken in
the air with absorption of oxygen, without the intervention of sodium
or of active hydrogen at the moment of its liberation. Such experiments
cannot serve as examples of the conversion of oxygen into ozone by
nascent hydrogen. The author made some experiments directly bearing
on the point. Dilute sulphuric acid and zinc were shaken up with
air, but no ozone could be detected even by indigo sulphate. Again,
zinc and concentrated ammonia solution, or a mixture of ammonia and
INORGANIC CHEMISTRY. 283
soda, shaken up with air, caused no conversion of oxygen into ozone,
for the ammonia was not converted into nitrons or nitric acids ; there-
fore nascent hydrogen cannot separate from the oxygen molecule active
atoms, which combine together to form ozone. Further, nascent hydro-
gen cannot form hydrogen peroxide with oxygen in the presence of
water ; for although zinc and dilute sulphuric acid shaken up with air
cause a formation of hydrogen peroxide, yet this must be attributed
solely to the water present in the sulphunc acid, for if concentrated
acid be used, no hydrogen peroxide is formed, and nascent hydrogen
by itself reduces hydrogen peroxide.
Schonbein observed that various metals, which with dilute acids
do not cause the formation of hydrogen peroxide, possess this pro-
perty when amalgamated with mercury ; this the author explains by
supposing that the amalgams of these metals have a more feeble
reducing action than the metals themselves, and so do not destroy the
molecules of the hydrogen peroxide. This view receives support from
the fact that the evolution of hydrogen from zinc and sulphuric acid
is considerably modified by the amalgamation of the metal.
Again, Hoppe-Seyler attributes the oxidising action of hydrogen
palladium in presence of water and oxygen to the liberated or
nascent hydrogen, but he completely overlooks the formation of
hydrogen peroxide, which is produced according to the equation —
Pd,
H , OH
H "^ OH
S+ 0.
= 4Pd + 2H2O + H2O2.
The presence of water is necessary for this change, for palladium
hydrogen shaken up with ether in the air, forms no hydrogen peroxide,
but its presence becomes manifest directly a little water is added.
Substituting palladium hydrogen for zinc, the author repeated the
experiments described in his former paper (vide supra), and with the
same results. Palladium-hydrogen must then be classed among those
substances, which like zinc, lead, pyrogallol, &c. (which the author
proposes to name autoxidisahle) , possess the property of attracting
oxygen, so as to combine with the hydrogen of water to form hydrogen
peroxide. In conclusion, the author remarks that this property of
such substances is neither identical nor intimately associated with the
more rare property possessed by some substances of rendering oxygen
active by converting it into ozone.
Part II. — The author, to examine his theory that hydrogen peroxide
is not oxidised water but reduced oxygen, has studied the electrolysis
of acidulated water, the platinum electrodes being separated by a
cylinder of some porous material. No hydrogen peroxide is formed
at the positive pole, but only at the negative pole, when the oxygen
liberated from the opposite pole can come in contact with the hydrogen.
It is thus probable that the hydrogen peroxide is formed by the direct
combination of the nascent hydrogen with the oxygen molecule, 'thus :
H + H + O2 = H2O2 ; in this case, hydrogen peroxide differs in its
chemical character from the peroxides of the heavy metals, which are
formed by oxidation processes at the positive pole. The quantity ot*
hydrogen peroxide is increased when the electrodes are of palladium,
284 ABSTRACTS OF CHEMICAL PAPERS.
but decreased witli electrodes of mercury, silver, gold, and the heavy
metals, and it is nil when the negative pole is of carbon. As a general
result, it is found that those metals which, with dilute sulphuric
acid and air readily form hydrogen peroxide, form this substance
the less readily when they are made the electrodes for the decomposi-
tion of water. Conversely those metals, which form no hydrogen
peroxide in presence of acid and air, but which possess the pro-
perty of retaining hydrogen like palladium, form hydrogen peroxide in
the larger quantities during the electrolysis of water ; but if the
palladium-hydrogen is made the negative electrode, the hydrogen is
completely burnt to water : 2Pd2H + 0 = 4Pd -f- HjO.
Thus the formation of hydrogen peroxide is not caused by active
oxygen, as hitherto believed, but is prevented by it. V. H. V.
Ozone in Presence of Platinum-black. By E. Mulder and
H. Gr. L. VAN DER Meulen {Bec. Trav. Chim., 1, 167 — 172). — By pass-
ing ozonised oxygen over platinum-black at the ordinary temperature,
the authors have obtained results from which, they say, it appears
highly probable that the ozone is thereby converted into ordinary
oxygen ; and they regard this result as the first known instance of the
transformation of an element into an allotropic modification under the
influence of another element, without the occurrence of chemical
action between the two. For the theoretical speculations as to the
manner in which this transformation may be supposed to take place,
we must refer to the original. H. W.
Variations of the Amount of Oxygen in the Atmosphere.
By C. A. Vogler (Chem. Centr. [3], 13, 556— 558).— The author
makes some remarks in support of his theory against the attack on it
by Morley. Both agree as to the fact that the atmosphere varies in
composition vertically and not latitudinally, and therefore that the
variation in the quantity of oxygen is due to vertical air-currents.
Morley is of opinion that the air which sinks down when the barometer
is high is poor in oxygen, and would thus lower the amount of that
element ; and that when the barometer is low, the lower layers of air
are rich in oxygen. The author thinks that when the barometer is
low the air is well mixed by currents, and that therefore there is no
difference in the amount of oxygen found above or below a certain
point ; and that when the barometer is high, the air, being in a state
of rest, resolves itself into bands according to Dalton's law, which
would cause a greater quantity of oxygen to be found in the lower
bands. He urges this by arguments and calculations. Finally, he
welcomes the idea of analysing air from various places under similar
circumstances, for it will settle the point whether the variation in the
quantity of oxygen in the atmosphere is really a regular phenomenon
or simply local. D. A. L.
Carbonic Anhydride in the Atmosphere. By E. H. Cook
(Phil. Mag. [5], 14, 387 — 395). — Taking the polar diameter of the earth
as 7899 miles, the equatorial diameter as 7925*5 miles, and the height
INORGANIC CHEMISTRY. 285
of the homogeneous atmosphere as 26,214 feet (nearly 5 miles), the
cubical content of the homogeneous atmosphere is found to be
591,647,337 cubic miles, or in round numbers 592,000,000 cubic
miles. If the average amount of carbonic anhydride in the atmosphere
is taken as 4 vols, in 10,000, the total volume of the carbonic anhy-
dride is 236,800 cubic miles, and the total weight 4287 billions of
pounds, or 1,913,685,908,480,000 kilos. These numbers differ con-
siderably from those given by Dumas and Boussingault, and from
that given in Roscoe and Schorlemmer's chemistry. The first of these
is nearly 40 per cent, and the second about 33 per cent, too high.
Recent investigations, however, show^ that the proportion of carbonic
anhydride in the atmosphere is not so high as 4 vols, in 10,000. If
the mean of these (Fittbogen and Hasselbarth, 3*4 vols, in 10,000,
Farsky 3*4 vols., and Reiset 2*942 vols,) is taken, the total weight of
the carbonic anhydride is nearly 1545 billions of kilograms. The
average amount of coal raised annually in the world during the last
three years is about 280,000,000 tons. Assuming that this con-
tains 75 per cent, of carbon, 10 per cent, of which is thrown away
with the ash, 182,000,000 tons of carbon are annually converted into
carbonic anhydride, which gives a daily production of 1,800,000 tons,
or nearly 1,800,000,000 kilos. Assuming that one-third more is
produced by the combustion of wood, peat, oil, &c., the total daily
production by combustion is 2,400,000,000 kilos. The present popu-
lation of the world is about 1,500,000,000, and each individual
produces on an average a kilogram of carbonic anhydride in
24 hours. Assuming that twice as much carbonic anhydride is
produced by the respiration of lower animals as by that of man, the
total amount produced by respiration is 4,500,000,000 kilos, per
day. The amount produced by the decay of animal and vegetable
matter may be taken as equal to that produced by the respiration of
man, and the amount sent into the air from subterranean sources may
be fairly assumed to be five times as great as the total amount derived
from all the other sources together. This gives about 40,000,000,000
kilos, per day. Adding all these quantities together, it is found that
the total amount of carbonic anhydride daily added to the atmosphere
is at least 50,000,000,000 kilos., from which it follows that if no
compensating influences were at work the proportion of carbonic
anhydride would be doubled in about 100 years.
The causes which remove carbonic anhydride from the air are
fixation of carbon by plants, removal of the anhydride by zoophytes,
and absorption of the anhydride by inorganic chemical action. In
the first case alone is oxygen returned to the atmosphere ; in the other
two cases the carbonic anhydride is absorbed as a whole. The total
area of the land-surface of the globe is 57,600,000 square miles
(Saunders). Of this 8,200,000 square miles are in arctic and antarctic
regions, thus leaving 49,400,000 square miles on which vegetation
might flourish. A considerable portion of this area is, however,
occupied by barren mountains, cities, and rivers. Estimating the
total area of leaf-surface as 50 per cent, of the area of plant-bearing
land, it follows that 24,700,000 square miles or 63,973,000,000,000
square meters of leaf-surface are engaged in the work of removing
286 ABSTRACTS OF CHE^nCAL PAPERS.
carbonic anliydride. Since each square meter of leaf-surface decom-
poses about 1 litre of carbonic anhydride per hour, it follows that
63,978,000,000,000 litres of the gas are decomposed every hour.
Taking into account the fact that sunlight on the average lasts only
ten hours each day, and allowing 25 per cent, for diminution of the
action in winter, the average amount of carbonic anhydride de-
composed per day is 479,000,000,000 kilolitres, or more than
900,000,000,000 kilos. A considerable proportion of the carbon
thus removed is, however, returned to the air when the leaves decom-
pose in the autumn, and allowance must also be made for the fact
that some plants give off carbonic anhydride in the dark. On
this point, however, there are no data on which to base any calcu-
lation, and the evolution of carbonic anhydride by the nocturnal
respiration of plants may be much greater than is usually supposed.
From the numbers given it would appear that the vegetable life on the
globe is of itself sufficient to maintain the purity of the atmosphere.
This conclusion is, however, based on incomplete data.
The removal of carbonic anhydride from sea- water by low forms of
animal life takes place on a gigantic scale, but the carbonic anhydride
thus removed exists in the sea and not in the atmosphere, and a very
large proportion of it must be derived from submarine volcanic
eruptions. In all probability the influence of this action is felt only
after many years, and so far as the atmosphere is concerned, it cannot
be compared to plant life in point of activity. Large quantities of
carbonic anhydride are removed by inorganic chemical changes, as, for
example, in the conversion of orthoclase into kaolin (Sterry Hunt,
Am. J. Sd., May 1880), but any estimate of the rate of this action is
impossible.
These calculations seem to show that the causes which remove
carbonic anhydride from the air are more powerful than those which
add this gas to the air. Its proportion must therefore be gradually
decreasing, but there are no trustworthy data on which to base any
conclusions on this point. As to the source of the enormous quantities
of carbonic anhydride already fixed in the form of limestone, we have
no knowledge. Either at one time the atmosphere surrounding the
earth must have been much richer in carbonic anhydride than it is at
present, or, as Sterry Hunt supposes, there must be a universal
atmosphere similar to our own from which the carbonic anhydride
now fixed in the earth's crust has been derived. C. H. B.
Nitrification in Presence of Copper and other Metals. By
S. Kappel (Arch. Pharm. [3], 26, 567— 573).— The author was
accustomed to show his pupils, as a class experiment, the production
of nitric reactions when ammonia was left in contact with metallic
copper. Some flasks used in his experiments were left with their
contents, corked, for about a year; on examination he then found
that the fluid had lost its ammoniacal smell, and contained both
nitrites and nitrates, and induced by this observation he made the
experiments reported in the present paper : —
1. A quantity of copper cuttings were placed in a flask connected
with a drying apparatus — a bulb tube containing copper oxide, and an
INORGANIC CHEMISTRY. 287
aspirator — the flask was placed on a sand-bath, and air drawn through
the arrangement for 14 days, at the end of which time the fluid gave
strong reactions of nitrites and nitrates, and the copper oxide was not
reduced ; a second experiment exactly similar, except that it was
made in the cold, gave the reactions plainly, but not so strongly.
2. Copper clippings and ammonia were placed in a flask through
which carbonic acid was passed, and whea as nearly as possible free
from atmospheric air, the mouth was closed by fusion. After six
hours the fluid became intensely blue ; it fchen gradually waned, and
became colourl-ess. When the flask was opened, nitrites and nitrates
were distinctly .present.
3. The arrangement im this experiment was similar to the last, but
the fluid was heated to 60 — 70'' during the process; the reactions
were similar but sharper.
Other experiments were made in which a current of hydrogen was
passed through the arrangement during the process. The results
were variable and inconclusive.
Similar experiments were made with iron and zinc, and it was
found that in all cases nitrification took place, but not with as much
activity ; possibly, the author says, the nascent hydrogen had a reducing
effect on the nitrites at the moment of their formation, a continuous
process of oxidation and reduction proceeding simultaneously. The
author's opinion is that the presence of air is necessary to this
process of nitrification, and that although it proceeds in the cold, it is
facilitated by heat, and he thinks metals other than those mentioned
are capable of producing similar results. J. F.
Conversion of Tricalcium Phosphate into Chlorine Com-
pounds of Phosphorus. By J. Riban (Com-pt. rend., 95, 1160
— 1163; and JBuIl. 8oc. Chim., 39, 14). — When chlorine is passed
over a mixture of tricalcium phosphate and carbon, or when
chlorine and carbonic oxide are passed over tricalcium phosphate
alone heated to incipient redness, a small quantity of calcium
chloride and metaphosphate is formed, but no further change
takes place. If, however, a mixture of chlorine and carbonic oxide
is passed over an intimate mixture of calcium phosphate and carbon
(e.g., bone-black), heated in a glass tube to 330 — 340° in an oil-
bath, phosphorus oxychloride, calcium chloride, and carbonic anhy-
dride are produced. After some time, the calcium chloride formed
interferes with the reaction, but if it is removed by washing, the
phosphate can be completely decomposed. The carbon plays no
chemical part in the reaction, and is found practically unaltered
at the end of the experiment. It is essential to the produc-
tion of the reaction, and probably acts by condensing the gases in
its pores. The reaction takes place in two stages, thus : (1) Ca3P208-h
2C0 + 2CI2 = CaPaOe + 2CO2 -f- 2CaCl2, and (2) CaPaOs + 4C0 -|-
4CI2 = 2POCI3 + 4CO2 + CaCl2. The reaction takes place slowly at
180°, and proceeds rapidly between 330° and 340°. When carbonic
oxide and chlorine are passed over bone-black at this temperature, no
phosphorus oxychloride is at first obtained, the gases being used up
in converting the phosphate into metaphosphate, which is afterwards
288 ABSTRACTS OP CHEMICAL PAPERS.
decomposed in accordance with the second equation. The phosphorus
oxychloride thus obtained is almost pure.
When phosphorus oxychloride is passed over a long column of wood
charcoal heated to redness in a glass tube, phosphorus trichloride is
formed, and carbonic oxide, or a mixture of carbonic oxide and
carbonic anhydride, according to the length and temperature of the
column of carbon, is given off.
This method of reduction by means of a mixture of chlorine and
carbonic oxide in presence of carbon, will doubtless prove valuable in
many other cases. It answers very well for the production of
aluminium chloride from alumina, the change taking place easily at
the temperature of an oil-bath. It may also serve for the production
of phosphorus oxychloride from calcium phosphate on a large scale.
C. H. B.
Volume-weight of Sulphiiric Acid. By A. Scheetel (/. pr,
Ghem. [2], 26, 246 — 249). — If concentrated sulphuric acid is boiled
down to about half its volume, the residue contains 80"40 per cent.
SO3 = 98*50 per cent. H2SO4 : sp. gr. at 0° (compared with wat^r at 0")
= 1*857. If the same acid is distilled until acid of constant composi-
tion passes over, and the last portions of this are collected, they have
the composition 80*54 of SO3 = 98*66 per cent. H2SO4, and are of sp. gr.
1*8575 at 0°. If these acids are mixed with dry or fuming sulphuric
acid, a fall in the volume- weight takes place until the composition of
normal hydrogen sulphate, H2SO4, is reached. On the other hand,
by the addition of anhydride, the volume-weight increases again, as
seen from following table : —
'ercentag
el
■
Correspond
■J Parts.
' H2SO4.
Volume-weight
OfSOg.
ing with
atO°.
80-40
98*50
1-8570
80*54
98*66
1*8575
81*00
99*23
1-8558 •
81*10
99-35
1-8550
81*63
100-00
1-8540
81*86
100*28
1-8548
82*10
100*57
1-8577
82*55
101-13
1-8640
82*97
101-64
1-8722
The acid obtained by distillation with constant composition is the
most concentrated, and has the highest sp. gr. The liquid normal acid
undergoes dissociation even at 0°.
The tables of the volume- weights and composition of sulphuric acid
edited by Bineau, Kolb, and Otto, show a continual increase in
sp. gr. D- A. L.
Argentous Oxide. By W. Pillitz (Zeitsch. Anal Ghem., 21, 496
— 506). — In continuation of his investigation {ibid., 21, 27), the
author has examined the precipitates obtained by the action of alka-
line solutions of antimony trichloride, stannous oxide, or stannous
chloride on silver nitrate. The product obtained by means of the
antimony solution -was proved to consist of a mixture of disodio-
INORGANIC CHEMISTRY. 289
dihydric pyroantimonate (N"a2H2Sb207 + 6H2O), metallic antimony,
metallic silver, and silver chloride, whilst the alkaline tin solutions
furnished a mixture of metallic silver and stannic acid. The pre-
cipitates were quite free from argentous oxide. 0. H.
Aluminates and Basic Haloid Salts of Barium : Notes on
Barium Hydroxide and Haloid Salts. By E. Beckman (/. pr.
Ghem., 26, 385 — 421). — This paper, the first instalment of the
research, gives a description of the barium aluminates.
Action of Baryta-water on Aluminium Compounds. — The result of
this action is the production of a soluble aluminate having the com-
position Al2,03,BaO,Aq, and if the solution of this compound is digested
with excess of aluminium hydroxide, an insoluble aluminate is formed.
The result of mixing baryta-water with aluminum chloride is a preci-
pitate of aluminium hydroxide, but a small percentage of barium is
found in the precipitate, and this is probably due to the formation of
barium carbonate. The solvent action of baryta- water on metallic
aluminium cannot be stated with certainty, as only metal having a
small percentage of silica was obtainable, but at the ordinary tempera-
ture aluminium hydroxide was formed as insoluble crystalline powder,
whilst Ba0,Al2O3 was present in solution. At high temperatures
aluminium foil is attacked by water, but not readily, whilst wire
remains unaltered ; but with baryta- water under like circumstances,
8j solution of monobarium aluminate is formed. It appears then that
barium forms -definite compounds with aluminium, and the author
carefully describes the method of preparation, the analytical re-
sults, &c., and shows that A1^03,BaO,6H20 ; Al203,2BaO,5H20, and
Al203,3BaO,llH^O, exist. The dibarium aluminate is prepared by
boiling together the requisite quantities of baryta- water and freshly
prepared aluminium hydroxide, filtering while hot, and then boiling
the filtrate ; when this liquid is reduced to eight times the amount of
compound present, colourless crystals begin to be deposited, and can
be washed with hot water ; these have the composition of dibarium
aluminate; the crystals are well formed, asymmetrical with an
axial proportion of 0*8545 : 1_: 0'9888, and amongst other faces, have
the following as principal : coPoo, coPco, OP, 2'P2. Dibaiium alumi-
nate is a tasteless powder scarcely soluble in cold water, and is pre-
cipitated from its solutions by alcohol; when heated, the crystals
decrepitate, slowly losing water, but not their form, and do not fuse
at the highest temperature ; as regards the crystalline water, some is
lost up to 125° ; at 155°, 2 mols. H2O are slowly lost, and a third more
slowly still ; a rise of tempej'ature to 250° removes a further quantity,
but the whole of the fourth mol. is not got rid of below 300°, and the
last or 5th mol. only at a red heat. It is probable that this last
mol. is retained by the barium hydroxide, because in the case of
the tribarium aluminate a mol. of water corresponding to each mol. of
BaO is firmly retained up to the last. When dibarium aluminate
is heated in a current of dry gas, the water is rapidly and suddenly
removed, and when it is fused with acid potassium chromate, the
removal is irregular ; this is exactly opposite to what occurs in the
case of barium hydroxide under like conditions.
290 ABSTRACTS OF CHEMICAL PAPERS.
A crystalline precipitate consisting of aluminium and barium
hydroxides, is produced when carbonic anhydride is passed into a solu-
tion of the dibarium aluminate, and baryta-water removes the
alumina from this precipitate; but if the gas be passed into the boiling
solution, short acicular crystals are formed, and baryta- water removes
only alumina from this at a high temperature. Dry carbonic
anhydride does not act on cold solid dibarium aluminate, but if this
compound is ignited, then every mol. absorbs 1 mol. CO2.
Monobarium Aluminate. — The solution of this compound is obtained
by boiling the result of the last-mentioned reaction with water ; the
solution is stable, but if much concentrated deposits the dibarium
compound.
The solid compound is prepared (1) by precipitation from the last-
named solution by means of alcohol ; (2) by allowing the solution of
the monobarium aluminate, whose percentage of alumina corresponds
with that of a concentrated dibarium aluminate solution (1 = 8) to
form spontaneously a granular uon- crystalline deposit; (3) the di-
barium solution will also deposit crystals of the monobarium compound,
and will decompose the more rapidly the more concentrated the solu-
tion. All the preparations of this compound are loose white tasteless
powders, but slightly soluble in cold water, and by boiling with water
form an opaque alkaline liquid. No alteration in appearance is notice-
able when this compound is heated, although it loses crystalline water.
When heated at 110°, nearly 3 mols. H2O remain, analogous to
those present in dibarium aluminate ; of these, 1 mol. is removed at
130°, another at 220°, the last remaining until a red heat is reached:
heated with acid potassium chromate, all the water passes away at
once. Carbonic anhydride causes all barium and alumina to be pre-
cipitated as needles from hot solutions, but the dr}'- monobarium
aluminate only absorbs this gas if an excess of the barium oxide is
present.
Triharium Aluminate. — When 1 part of dibarium aluminate is boiled
in 30 parts of water with 10 parts of barium hydroxide, the solution
filtered hot, and concentrated to 28 parts, colourless crystals of the tri-
harium compound are deposited ; if the concentration is effected over a
lamp, there will be *?\ mols. H2O present, but when an oil-bath is em-
ployed, 11 mols. are found. This substance may also be prepared by
mixing hot dibarium aluminate solution with barium hydroxide dis-
solved in its own water of crystallisation. The crystals are opaque and
brittle, taste alkaline, and dissolve in 15 parts boiling water ; this solu-
tion decomposes when boiled, the dibarium compound being formed.
The first mol. of water of crystallisation is lost by heating at 115°,
5 mols. are lost at 165°, and 6 mols. at 255°, the remaining 1^ mol.
making up the whole 7-J mols., is only lost at a red heat. Fused
potassium dichromate removes that amount of water corresponding to
its own temperature, 2 mols. remaining even after complete fusion.
Microscopic needles containing barium and aluminium are separated
from hot solutions by carbonic anhydride, but the gas is only absorbed
by the solid at incipient redness, every molecule absorbing 2 mols.
CO2. Oxygen is not absorbed by this compound. E. W. P.
INORGANIC CHEMISTRY. 291
Beryllium Hydroxides. By J. M. v. Bemmelen (/. pr.
CJiem. [2], 26, 227 — 246). — From previous researches the author
concluded that those hydroxides which separate from their solu-
tions in a colloid form, such as those of silicon, iron, &c., never have
a constant composition, and are scarcely ever homogeneous. He,
however, thinks it probable that under certain conditions they ought
to be obtained as chemical compounds, and remain constant within a
wide range of changes of temperature. For illustration of this hypo-
thesis the hydroxides of beryllium seemed well adapted. Of these
the author has distinguished two, a, granular, and /3, gelatinous. The
^-hydroxide is precipitated by ammonia from pure beryllium sulphate,
it is washed out of contact with the air with cold water, dried in a
stream of air free from carbonic anhydride and powdered ; its constitu-
tion is then represented by: BeO,l • 61 (H2O), 0-025 (CO2). When washed
and dried in the air, its constitution is BeO,2"63(H2O),0*05(CO2).
To prepare the oc-hydroxide, the solution of the ^-hydroxide in
sulphuric acid is precipitated with potash and redissolved by
excess of the precipitant ; it is then diluted with much water and
boiled. The granular deposit of the hydroxide is washed with boiling-
hot water, excluding air ; it forms a fine white powder, is free from
carbonic anhydride, and has the constitution BeO,H20, which remains
constant up to 200° ; dissociation now commences and reaches a
maximum at 215°, and after two hours' heating at 215 — 220°, the
oxide loses half a mol. H2O, whilst after ten hours' heating
BeOjO'lSHjO remains ; the last y^th mol. H2O is only entirely driven
ofi' at a strong red heat. From air saturated with moisture, the
a-hydrate will absorb as much as ^ — ^ mol. HgO, which, however, is
given off again in the ordinary air. After losing | mol. HoO at 200°,
its constitution is definitely changed, for although it absorbs 1 mol. of
water from moist air at 15°, it gives it up again in dry air. Heated
at 280°, the water is reduced to 0*13 mol., now again it absorbs 1 mol.
H2O, but gives it up only till the residue is reduced to 0*18 mol.
After being heated to redness, it behaves in the same way ; but a strong
red heat changes it altogether ; it then loses all power of absorbing
water, and is only soluble in boiling sulphuric acid.
The y3-hydroxide is a fine powder; at the ordinary temperature it
absorbs a considerable amount of water from moist air, even when it
has been previously heated at 100°. It has no constant composition.
When heated it gradually and constantly loses weight (water) ; between
150 and 180°, the compound BeO,H20 is attained, and remains constant
between 180 and 200° ; above this temperature at about 215° it under-
goes changes similar to the a-hydroxide. When tested with regard to
the power of absorbing salts from aqueous solutions, the |(3-hydroxide
shows this property, the a- does not. Comparative experiments with
hydrated magnesium oxide confirm the results of previous investiga-
tors (Ditto and Rose) ; it retains the composition MgO,H20 even
when heated above 350°, and does not even undergo molecular change
below this temperature ; it loses water of hydration between 350° and
red heat. The author comes to the conclusion that beryllium a-hydr-
oxide resembles those of magnesium and calcium, whilst beryllium
jS-hydroxide resembles those of aluminium, &c.
292 ABSTRACTS OF CHEMICAL PAPERS.
Thus fhe former can be represented by a definite and simple formula,
and is constant within a certain range of changes of temperature, but
smaller than that of magnesia. The changes which the /3-compound
undergoes during heating are similar to those observed bj Berthelot in
ferric hydroxide, for he found that from the time it was precipitated,
it constantly changed molecularly, and at no period conld be repre-
sented by a simple formula. The author considers this peculiarity of
the gelatinons hydroxide to be due to the fact that it is a mixture of
hydroxides, which behave differently at the same temperature, that is,
that each one requires a different temperature to convert it into the
lower hydroxide or anhydride. This view is supported by some observa-
tions which the author has made on the hydroxide freshly precipitated
from aluminium chloride by ammonia. 1. After boiling for 24 hours
with water it has the composition Al^Oajl'GHzO. 2. Washed for some
time with cold water it is AlaOsjl'QHjO. 3. Precipitated from diluted
solution and quickly washed with water it is Al203,2"6H20. 4. After
half a year in contact with water it is AlaOsjS'l HjO. The last-mentioned
is quite constant between 15 and 100°, and even above. Nos. 1, 2, and 3
are mixtures of this with a lower hydroxide. D. A. L.
Atomic Weight of Yttrium. By P. T. Cleve (Oompt. rend., 95,
1225 — 1226). — The determinations of the atomic weight of yttrium
made in 1872 are inexact, since no precautions were taken to sepa-
rate terbium, which at that time was not definitely known to exist.
By fractional precipitation with oxalic acid, the author has obtained
from 3 to 4 grams of yttria with a constant molecular weight. The
mean of twelve determinations of the amount of yttria in the sulphate
prepared from this pure oxide is 48-503 ± 0'00029 per cent. It fol-
lows, therefore, that the atomic weight of yttrium is 89*02 if O = 16
and S = 32, or 88*9 ± 0-027 if 0 = 15'9633 and S = 31'984. Pure
yttria is perfectly white, the yellow colour which it sometimes
has being due to the presence of very small quantities of terbia.
C. H. B.
Lecture Experiments illustrating the Combination of Zinc
with Sulphur. By H. Schwarz (Ber., 15, 2505— 2508).— After
alluding to the common method of illustrating chemical combination
by heating flowers of sulphur with copper or iron filings, the author
suggests the following experiment. Two parts of zinc-dust and one
part flowers of sulphur are intimately and carefully mixed ; on apply-
ing a light the mixture ignites and burns with a green flame, and the
zinc sulphide is deposited on surrounding objects; the mixture can
also be ignited by percussion, and in an explosion apparatus the author
found that the detonating power of the mixture was about an eighth
of that of blasting powder.
The author explains the fact that sulphur does not mix directly
with molten zinc, as a form of Leidenfrost's phenomenon, as the
sulphur vapour prevents the metal coming in contact with the molten
sulphur ; or perhaps a thin layer of zinc oxide or sulphide is formed
between the sulphur and the metal.
If carbon bisulphide vapour, either by itself or mixed with hydrogen
sulphide, be passed over heated zinc-dust, zinc sulphide is formed witb
INORGANIC CHEMISTRY. 293
formation of methane and hydrogen. Similarly, if carbon bisulphide
and ammonia is led over zinc-dust, ammonium cyanide is formed
according to the reaction CS2 + 2NH3 + 2Zn = 2ZnS + NH4.CN + H2.
The author also calls attention to the use of zinc-dust for removing
sulphur from compounds, and adduces as examples the decomposition
of thiocarbanilide into aniline and phenylnitrile [CS.NHPha + Zn =
ZnS + NHjPh -h PhCN], of thiocarboparatoluidide into paratoluidine
and tolylnitrile, and the conversion of allylthiocarbimide into allyl-
nitrile. V. H. V.
Separation of Gallium. By L. de Boisbaudean (Gompt rend.,
95, 1192—1194 and 1332—1334 ; see also this vol., p. 21, and Abstr.,
1882, pp. 897 and IS2S).— From Bismuth.— (I.) The moderately acid
solution of the chlorides is saturated with hydrogen sulphide'; th©
precipitated bismuth sulphide is free from gallium. (2.) The bismuth
is reduced by means of zinc, or much better, by finely divided copper in
a slightly acid solution at a gentle heat. (3.) The gallium is pre-
cipitated by means of potassium ferrocyanide in a solution containing
one-third its volume of strong hydrochloric acid : contrary to the
general statement, the precipitate produced by potassium ferrocyanide
in solutions of bismuth chloride is soluble even in dilute hydrochloric
acid. Bismuth and gallium cannot be separated by means of potas-
sium hydroxide, since the alkaline solution retains notable quantities
of bismuth.
From Copper. — (1.) The copper is precipitated in an acid solution
by means of hydrogen sulphide ; the precipitate is washed with
acidulated water containing hydrogen sulphide. (2.) The copper is
precipitated with excess of potassium hydroxide, and the liquid boiled
for some minutes. (3.) The copper is precipitated by metallic zinc
or, much better, by electrolysis. (4.) The solution is made strongly
alkaline with ammonia, and boiled for some time. If much copper is
present, the precipitate must be redissolved, and the operation repeated
several times. The liquid should contain a moderate quantity of
ammonium chloride. All four methods are good, but the first is
preferable where it can be applied.
From Mercury. — (1.) The solution is strongly acidified with hydro-
chloric acid and saturated with hydrogen sulphide. This method is
rapid and exact, and is to be strongly recommended. (2.) The mercury
is reduced by zinc or, better, by copper. (8.) The gallium is precipi-
tated as ferrocyanide in presence of a considerable quantity of free
hydrochloric acid, and the precipitate is washed with dilute hydro-
chloric acid. Mercury cannot be separated from gallium by means of
potassium hydroxide, as contrary to the usual statement, the alka-
line liquid retains notable quantities of mercury. The precipitated
mercuric oxide is, however, free from gallium.
From Silver. — The silver is precipitated by a slight excess of hydro-
chloric acid in presence of a considerable quantity of nitric acid, or the
silver is precipitated by hydrogen sulphide in a moderately acid
(hydrochloric or nitric) solution.
From Gold. — (1.) The distinctly acid solution is saturated with
hydrogen sulphide. (2.) The gold is reduced by sulphurous acid, and
VOL. XLIV. X
294 ABSTRACTS OF CHEMICAL PAPERS.
the precipitated metal washed with water containing a little hydro-
chloric acid. (3.) The solution is made distinctly acid with hydro-
chloric acid, and the gold reduced by finely divided copper at the
ordinary temperaturCj or at a gentle heat.
From Palladium. — (1.) The solution is strongly acidified with
hydrochloric acid, submitted to long treatment with hydrogen sul-
phide, and then heated at 70° for two hours. The solution should be
somewhat concentrated, and the greater part of the free acid should
be expelled by evaporation before the last treatment with hydrogen
sulphide. (2.) The palladium is reduced by copper in a distinctly
acid solution at 80°, the precipitated metal never containing more
than an insignificant trace of gallium. If zinc is used instead of
copper the precipitated palladium obstinately retains notable quanti-
ties of gallium. Precipitation of the palladium as potassium palladio-
chloride is inexact, since the double chloride is slightly soluble in
alcohol, and the precipitate retains distinct traces of gallium.
From Platinum. — The only exact method is to saturate the dis-
tinctly acid solution with hydrogen sulphide, heat to 70'', and continue
the passage of hydrogen sulphide for several hours. The wash- water
is mixed with the filtrate, evaporated to expel the greater part of the
acid, and again treated with hydrogen sulphide. An approximate
separation is effected by adding ammonium chloride to the solution
made distinctly acid with hydrochloric acid, and mixed with alcohol.
The precipitate appears to be free from gallium, but the liquid
contains small quantities of platinum. Platinum is reduced with
great difficulty by copper, even in a hot solution. It is completely
precipitated by zinc, but the metal retains gallium even more obsti-
nately than does palladium. C. H. B.
Stannous Oxide and some of its Compounds. By A. Ditte
(Ann. Ghim. Phys. [5], 28, 145 — 182). — When a solution of stannous
chloride is treated with potassium or sodium hydroxide, stannous
hydroxide separates as a compact precipitate, which may be easily
washed by decautation as long as an excess of the alkaline chloride
formed in the reaction is present. When the washing approaches
completeness, however, the solution becomes turbid, and the precipi-
tate needs days to settle. The author has made a careful investi-
gation of the behaviour of stannous hydroxide and stannous chloride
in the presence of various reagents. From the results of these experi-
ments, he draws the following conclusions : —
(i.) Stannous hydroxide is transformed into the crystalline anhydrous
oxide by traces of any acid which is capable of forming a stannous
salt, decomposable by boiling water into free acid and oxide, (ii.) The
same change takes place in the presence of salts (such as stannous
chloride, ammonium chloride, &c.) which are partially decomposed by
water, with liberation of small quantities of an acid coming under
head (i). (iii.) This conversion of the hydroxide into the oxide is not
effected by acids forming stable stannous salts (such as nitric acid),
nor by those (such as sulphuric acid) giving stable basic salts in the
presence of water. (iv.) Potassium and sodium hydroxides act on
stannous hydroxide both in the cold and on heating, but the reaction
INORGANIC CHEMISTRY. 295
is complicated, and the resulting' product varies according to the con-
centration and temperature of the solution. According to circum-
stances, an alkaline stannate, a mixture of this latter with stannous
oxide, or a mixture of the stannate with metallic tin, may be obtained,
(v.) Contrary to the statements usually given in text-books, ammonia
not only does not cause the dehydration of the hydroxide, but prevents
it taking place : the author shows that if the anhydrous oxide is
formed, it is only after the ammonia has been expelled by boiling, and
that if care be taken to replace this, and the solution be kept alkaline, no
dehydration will take place, however long the boiling may be continued,
(vi.) Anhydrous stannous oxide may be obtained in several slightly
modified forms, but these modifications are not definite enough to be
termed allotropic. (vii.) At a red heat, stannous oxide partially decom-
poses into stannic oxide and tin, the former uniting with unchanged
stannous oxide to form SusOi. (viii.) The salts of silver, palladium,
and platinum form with stannous salts, stannates or meta-stannates,
according to the relative proportions of the two reagents. From the
decided colours of these compounds, they are very good tests for dis-
tinguishing stannous from stannic salts. L. T. T,
A Higher Oxide of Titanium. By A. Weller (Ber., 15, 2599—
2600). — A higher oxide of titanium, probably TiOa, is produced when
freshly precipitated titanic hydroxide is treated with hydrogen per-
oxide or when ammonia is added to a solution of titanic acid and hydro-
gen peroxide. This oxide has a yellow colour. It is decomposed by heat,
yielding oxygen, water, and titanic oxide. It dissolves in strong acids,
forming a reddish-yellow solution, from which the oxide is reprecipi-
tated by alkalis ; if an excess of alkali is used, titanic oxide is thrown
down. On heating the hydrochloric acid solution, chlorine is evolved.
w. c. w.
Arsenious Sulphide in Aqueous Solution. By H. Schulze
(/. pr. GJiem., 25, 431 — 452). — It is well known that sulphuretted
hydrogen does not precipitate, or only partially precipitates, a pure
aqueous solution of arsenious anhydride. The author has experi-
mented on this fact, and concludes that the water contains arsenious
sulphide in solution. In one experiment, he dissolved 10 cframs of
pure arsenious anhydride in 1 litre, and passed sulphuretted hydrogen
into the solution, which became yellow and turbid, forming very thin
golden-yellow flakes on the surface, which, on agitation, were thrown
down and sank to the bottom in a flocculent state. The remaining
solution was slightly turbid and of a reddish-yellow tint. This tur-
bidity could not, however, be removed by filtration, and on examina-
tion under the microscope no traces of solid matters could be detected,
the solution being clear and yellow. When the solution was rendered
turbid by addition of an acid or salt insufficient to produce complete
precipitation, solid particles in a yellow menstruum were seen under
the microscope. The solution moreover was not turbid when viewed
by transmitted light (e.g., in thin layers between parallel plates of
glass), but only in reflected light, an efiect which the author attributes
to fluorescence. Carbonic anhydride was passed through the above
solution to remove excess of sulphuretted hydrogen, and the arsenic
X 2
296 ABSTRACTS OP CHEMICAL PAPERS.
and sulphur were determined in a portion, and found to be in the
ratio of As2 : S3. This sohition of arsenious sulphide is a colloid, and
cannot he dialysed, although any added arsenious anhydnde can be
rearlily removed from it by dialysis. On evaporation to dryness, an
amount of arsenious sulphide remains proportional to the amount of
arsenious anhydride taken, this solid sulphide being no longer soluble
in water.
There is a limit to the strength of the solutions of arsenious sul-
phide prepared by passing sulphuretted hydrogen through aqueous
solutions of arsenious anhydride on account of the sparing solubility
of the latter, but by passing sulphuretted hydrogen and then dissolv-
ing fresh arsenious anhydride and so on, the author succeeded in
obtaining a 37'46 per cent, solution of AS2S3 (1 pt. AS2S3 in 1*67 pts.
water) ; it was like an intensely yellow milk, but perfectly transparent
under the microscope. The stronger solutions deposit a small quan-
tity of solid matter on prolonged standing ; the dilute solutions are
more permanent, a solution of 1 in 500 being quite unchanged after
standing for three months.
Dilute solutions of arsenious sulphide prepared from stronger solu-
tions by dilution are more turbid than dilute solutions of the same
strength prepared directly, and have a yellow rather than a reddish-
yellow tint.
These solutions are only very slightly influenced by high tempera-
tures; but finely divided animal and vegetable charcoal, acids, and
soluble salts have the power of precipitating the solid sulphide. In
the case of soluble salts, it is found that there is a certain state of dilu-
tion for each salt, at which it ceases to precipitate, and further the
precipitating power of the various salts depends on the metals, and
only slightly on the acids in those salts. The salts of the alkalis have
the least precipitating power ; the ferric, chromic, and aluminium
salts the greatest.
The author infers that we have to deal with a colloYdal modifica-
tion of arsenious sulphide comparable with the colloidal ferric and
aluminium hydroxides, soluble silicic acid, and soluble albumin.
F. L. T.
Formation of Crystallised Uranates in the Dry Way. By A.
DiTTE (Compt. rend., 95, 988 — 991). — If uranoso-uranic oxide, UaOe,
is fused with sodium chloride in a platinum crucible, the bottom of which
is kept considerably hotter than the upper portions, a ring is formed
round the sides of the crucible at the surface qf the fused mass, con-
sisting of a mixture of sodium chloride and brilliant greenish-yellow
plates of sodium uranate, Na2U207, insoluble in water, but easily solu-
ble in dilute acids. If the heating is continued after the removal
of the first ring, a second ring is obtained, smaller than the first, but
soon the fused mass ceases to yield a crystalline deposit no matter how
long the fusion may be continued. The mass is allowed to cool, and
the sodium chloride removed by washing, when a deep green crystal-
line residue is left, which dissolves partially in dilute hydrochloric and
sulphuric acids, leaving a black crystalline residue of uranous oxide.
The portion soluble in acids consists of crystals of the intermediate
oxide, U2O5. When the sodium chloride is heated with the uranoso-
INORGANIC CHEMISTRY. 297
uranic oxide, the latter is decomposed into oxygen whicli unites with
the uranic oxide, forming sodium uranate, and into uranous oxide,
part of which combines with uranic oxide forming the intermediate
oxide, U03,U02, whilst the remainder crystallises. The chlorine of
the sodium chloride is liberated, but at high temperatures, attacks
neither the uranium oxides nor the platinum of the crucible.
If the sodium chloride is mixed with a little sodium carbonate the
same products are obtained; but if the chloride and carbonate are
in about equal proportions, sodium uranate is the sole product. If the
uranoso-uranic oxide is fused with pure sodium chloride, and sodium
chlorate is added in small portions so that the crucible is always filled
with an atmosphere of oxygen, the uranium is entirely, although
slowly, converted into crystalline uranate. If the uranium oxide is
mixed with sodium chlorate, decomposition is accompanied by defla-
gration, and the uraniam oxide is almost instantly converted into
amorphous sodium uranate. The reaction is moderated by the
presence of sodium carbonate, but the product is the same. The
amorphous uranate can be obtained in crystals by fusing it with
sodium chloride.
Any of the alkaline uranates can be obtained in greenish-yellow
plates, insoluble in water, and infusible at a bright red heat, by any of
these three general methods. Sodium uranate is more readily formed
than the corresponding potassium salt. If the green uranium oxide is
fused with sodium and potassium chlorides mixed in equivalent pro-
portions, the crystals deposited are almost pure sodium uranate. The
potassium, rubidium, lithium, and magnesium uranates have been
obtained in crystals by these methods.
When uranoso-aranic oxide is fused in the same way with calcium,
barium, and strontium chlorides, the corresponding uranates are
obtained, CalJzOv, BaUaO?, SrU207. If the uranium oxide is heated
with the chlorates of the alkaline earths, it is entirely converted into
amorphous uranates, but the latter, when fused with sodium chloride,
yield a ring very slowly, and the greenish-yellow plates thus ob-
tained have the composition respectively CaU40i2, BalJiOn, SrUiOjo.
The strontium salts crystallise more slowly than those of calcium,
whilst those of barium, on the other hand, form very rapidly. These
uranates form greenish-yellow plates, insoluble in water, but soluble
in dilute acids. If heated for some time to bright redness, they acquire
a deeper colour, and become less soluble in dilute acids.
C. H. B.
Nitrososulphides and Nitrosocyanides. By 0. Pavel (Ber., 15,
2600 — 2G06). — Fotassium ferronitrososulphide^ K2Fe8(NO)i4S6, is best
obtained by adding 400 c.c. of potassium sulphide, prepared from
44 grams potash, to a boiling solution of 35 grams of sodium nitrite in
400 c.c. water. After the addition of a few drops of dilute sulphuric
acid, 159 grams of ferrous sulphate dissolved in 1200 c.c. water are
slowly poured into the hot mixture. The liquid is heated in a water-
bath for about half an hour, until a deposit begins to fettle on the
sides of the flask. It is then quickly filtered, and dilute potash is
added to the filtrate. After 48 hours potassium ferronitrososulphide
298 ABSTRACTS OF CHEMICAL PAPERS.
crystallises out. It is pnrified by recrystallisation from water at 70",
containing a small quantity of potassium hydroxide. The potassium
and ammonium salts contain 2 raols. H2O. The ammonium salt is less
soluble than the potassium salt, and the rubidium salt is less soluble
than the ammonium salt. The caesium compound is insoluble in
cold water, and sparingly sol able in alcohol and ether. The easily
soluble sodium, lithium, magnesium, calcium, and barium salts are
unstable. TlFe4(NO)7S3 + H2O is sparingly soluble. The salt obtained
by the action of ferrous sulphate on a mixture of sodium thiocarbonate
and sodium nitrite, is sodio-ferrous nitrosulphide, and not ferrous
nitrosothiocarbonate, re4S(NO)6CS2, as stated by 0. Low. These
nitrososulphides are decomposed by heat in presence of air, with
formation of ammonium sulphate, ferrous sulphide, and other pro-
ducts; if air is excluded, no ammonium sulphate is produced. The
free acid, Fe4(NO)7S3H, is precipitated by dilute sulphuric acid from
an aqueous solution of the sodium salt. It is an amorphous unstable
compound, insoluble in water, alcohol, and ether, but soluble in chloro-
form and carbon bisulphide. Sodium ferronitrososulphide is com-
pletely decomposed by hot strong sulphuric acid, by silver oxide or
sulphate, by hydrochloric acid, and by iodine.
A second series of nitrososulphides is obtained by treating the pre-
ceding salts with a warm dilute solution of potash. These salts are
unstable ; they are, with the exception of the iron compound, insoluble
in ether, chloroform, and carbon bisulphide. They are decomposed
by potassium ferricyanide, which does not attack the first class of
nitrososulphides. The composition of the potassium and sodium salts
is represented by the formulae —
K3Fe2(NO)4S2 + 4H2O and ]Sra2Fe2(NO),So -f SH2O.
Ethyl ferronitrososulphide, Et2Fe2(NO)4S2, prepared by the action of
ethyl iodide on an alcoholic solution of the potassium salt, forms large
monoclinic crystals melting at 78°. The dark glistening crystals dis-
solve freely in ether, chloroform, benzene, ethyl iodide, and carbon
bisulphide. This compound is not attacked by potash or by sulphuric
or hydrochloric acids, but it is completely decomposed by nitric acid.
The author considers that the formation of sodium nitro-prusside, i.e.,
sodium nitrosoferricyanide, by the action of nitric acid on sodium
ferrocyanide, takes place in the following stages : —
/ FeCyo^NaCy / FeCy42NaCy / FeCy42NaCy / Fe(NO)2Cy22NaCy
\ FeCy24NaCy t FeCy24NaCy \ FeCy42NaCy \ FeCy42NaCy
w. c. w.
Artificial Production of Iridosmin. By H. Debray (Gomjjt.
rend., 95, 878 — 880). — If iridium is fused with iron pyrites at a high
temperature a regulus is obtained, which, when treated with dilute
hydrochloric acid, leaves a residue of crystallised iridium, mixed with
a light black amorphous sulphide easily soluble in dilute nitric acid.
The iridium retains from 1 to 2 per cent, of iron, and crystallises in
octohedrons, although some flattened crystals have the appearance of
regular hexahedrons. Osmium behaves in a precisely similar manner,
but the crystals obtained retain no sensible traces of iron, and have all
MINERALOGICAL CHEMISTRY. 299
the cliaracteristics of tHe metal obtained by the action of hydrochloric
acid on alloys of osmium with zinc or tin.
When a mixture of one part amorphous osmium with 1, 2, or
8 parts amorphous iridium, is fused with a large excess of iron pyrites,
and the fused mass treated successively with hydrochloric and nitric
acids, a crystalline residue is obtained, which consists of regular
octohedrons mixed with hexagonal plates, closely resembling certain
natural varieties of iridosmin. The crystals have not the composition
of the mixture from which* they are prepared, owing to the partial
conversion of the metals into sulphides ; the relative proportion of
osmium and iridium does not depend on the relative quantities of the
two metals employed, but varies with the temperature to which the
mixture is heated. Three specimens obtained had the following com-
position : —
1. 2. 3.
Iridium 50 59 62*5
Osmium 50 41 37*5
100 100 100-0
In appearance and properties, these alloys are identical with the
natural iridosmin. Since osmium and iridium are isomorphous, and
can crystallise together in all proportions, it is possible that natural
iridosmin may be a true isomorphous mixture belonging to the
regular system, notwithstanding the hexagonal appearance of some of
the crystals. The composition of natural iridosmin is, however, much
more complex than that of the artificial crystals. C. H. B.
Mineralogical Chemistry.
Analysis of the Coal of the Muaraze. By P. Guyot (/.
Pharm. [5], 6, 474 — 475). — This is a short paper, containing an
account of thin beds of coal found in the valley of the River Muaraze,
a tributary of the Zambesi. The volatile matter varies in different
specimens from 20 to 22 per cent., and the coke from about 50 to 55
per cent. E. H. R.
The Thorite of Arendal. By L. F. Ntlson (Compt. rend., 95,
784 — 786). — Nordenskiold found, near Arendal, in 1876, a crystalline
silicate containing 50 per cent, of oxide of thorium, and 10 per cent,
of uranous oxide. He regards the mineral as a variety of thorite.
Later, the same mineral was discovered at Hittero (Norway) by
Lindstrom, and at Champlain (U.S.A.) by Collier, who called it
uranothorite.
The mineral is interesting as containing uranous oxide. Zimmer-
man has shown that uranous oxide has the formula UO2, and the oxide
of thorium having probably the formula ThOa, it is to be presumed
that the two oxides are capable of replacing one another in thorite in
300 ABSTRACTS OF CHEMICAL PAPERS.
variable proportions.' The molecular volumes of the oxides in question
confirm this hypothesis.
The author has obtained pure sulphate of thorium by a new and
simple method. He finds that by saturating 5 parts of water at 0'
with 1 part of crude anhydrous sulphate and then warming to 20°,
thorium sulphate is precipitated as a heavy white crystalline powder,
amounting to two-thirds of the sulphate dissolved. The precipitate is
washed with cold water, the mother-liquors are evaporated to dryness,
and the product is subjected to the same treatment. Proceeding in this
way a solution is finally obtained which, saturated at zero, precipitates
nothing more when warmed to 20°. The solution contains principally
thorium sulphate, and gives, with potassium sulphate, insoluble double
sulphates, while certain double sulphates remain in solution. The
insoluble double sulphates contain thorium, cerium, and didymium,
whilst the others include all the metals contained in the old "erbia,"
and are characterised by their absorption-bands. In examining the
earths precipitated as double sulphates, the author has observed the
following peculiarity : — The anhydrous sulphates of the earths, from
which the didymium has been separated by repeated partial decom-
position of the nitrates, are of a yellow colour. Their solution is also
yellow, but is decolorised by sulphurous anhydride. When the
decolorised solution is evaporated, and the excess of sulphuric acid
expelled, the sulphates reassume the yellow colour, and this can be
repeated as often as desired. The author finds that a mixture of pure
thorium sulphate and cerous sulphate behaves in the same manner.
The yellow colour indicates the presence of eerie sulphate. Hence the
author concludes that the presence of thorium oxide determines the
conversion of the cerous into eerie sulphate by means of the excess of
sulphuric acid.
The author finds that four precipitations of thorium sulphate, in the
manner described above, are sufficient to obtain it in a perfectly pure
state. E. H. R.
Study of " Longrain " and Measure of the Foliation in
Schistose Rocks by Means of their Thermic Properties.
By E. Jannettaz (Compt rend., 95, 996— 999).— The law that
heat is conducted more easily along the plane of foliation than along
the perpendicular direction, holds good in all cases. By means
of experiments made in the manner previously described {Compt.
rend., 78 and 81), the author has constructed the isothermal surfaces
characteristic of schistose rocks. The isothermal surface of these
rocks is an ellipsoid, the three principal sections of which are the plane
of foliation, containing the major and the minor axes, and two others
perpendicular to this and to one another, the one containing the major
and the minor axes, the other the mean and the minor axes. Some-
times the two axes in the plane of foliation are equal, in which case
the eKipsoid is a figure of revolution.
In slate quarries the workmen split up the rock into slabs, by taking
advantage of the ease with which it cleaves in the plane of foliation,
or, as the author terms it, first cleavage, and then cut these up into
smaller slabs along a somewhat more difficult plane of cleavage, which
MINERALOGICAL CHEMISTRY. 301
is locally termed the "longrain," "long," or "fil," and which the
author terms second cleavage. By experiments on a large number of
schistose rocks from diiferent localities and of different composition,
it is found that the intersection of these two planes is parallel with the
major axis of the ellipsoid, and the plane of foliation is perpendicular
to the least axis. In other words, the major axis of the isothermal
surface is parallel with the longrain or second cleavage, and the minor
axis is perpendicular to the plane of foliation or first cleavage. The
author has applied this method to the contorted schistose beds in the
lias in the neighbourhood of La Paute and Venose. The following
table shows the percentages of calcium carbonate and clay in these
beds, with the ratio of the axes of the isothermal surface on sections
perpendicular to the plane of foliation.
Calcium
carbonate. Clay. Eatio of axes.
La Paute 90 lU 1-07
65 35 1-30
50 50 1-42
Venose 25 75 2-00
C. H. B.
Lithium, Strontium, and Boric Acid, in the Mineral Waters
of Contrexeville and Schinznach (Switzerland). By Dieula-
FAIT (Compt.re7id.,Q5, 999 — 1001). — The author's previous researches
have led to the conclusion that the salts existing in different strata
have been derived directly or indirectly from the evaporation of
ancient seas. He also concludes that mineral waters derive their
saline matter from the salt-bearing strata of the permian, triassic,
and tertiary formations, this saline matter itself being derived from
ancient seas. If this conclusion is correct, all the substances which
existed in these seas should be found in the mineral waters. Amongst
the most characteristic are lithium, strontium, and boric acid, and it
follows from the author's investigations of sea water that these sub-
stances should exist in mineral waters in relatively considerable pro-
portions. The lithium spectrum ought to be obtained with the residue
left by the evaporation of 1 c.c, or often even from a single drop, the
strontium spectrum with the residue from 5 c.c, and the boric acid
reaction with the residue from not more than 100 c.c.
Water of Contrexeville. — Lithium exists in relatively considerable
proportion, and the strontium spectrum is obtained distinctly with
the residue from 5 c.c. Deboul failed to find strontium in this water,
because he looked for it in the precipitate produced by boiling, on the
assumption that the strontium is present as bicarbonate, whereas it
really exists as sulphate.
Water of ScJdnzriach. — This water derives its saline matter from
the trias. Contrary to the statement of Grandeau, lithium can be
detected in a single drop, strontium in 4 c.c, and boric acid in 25 c.c.
of this water.
These two waters are therefore not exceptions to the author's law,
but, on the contrary, afford further proof of its accuracy.
C. H. B.
302 ABSTRACTS OF CHEMICAL PAPERS.
Presence of Arsenic in the Waters of Bareges. By M.
SCHLAGDENHAUFFEN (/. Pharm. [5], 6, 475 — 480)" — The author has
detected arsenic in these waters from the different springs. The
quantities vary from 0*000016 to 0'00022 gram per litre. The source
of the metal is the rock through which the water runs. The residue
on evaporation yields only part of its arsenic to hydrochloric acid :
hence the author concludes that the metal is partly present as a
sulpharsenate which is converted bv the acid into insoluble sulphide.
E. H. R.
Origin of Arsenic and Lithium in Waters containing
Calcium Sulphate. By M. Schlagdenhauffen (/. Pharm. [5], 6,
457 — 463). — The author has established the presence of arsenic in the
mineral waters of Schinznach and Baden in Switzerland. According
to Orfila and "Walchner, the arsenic is present in all similar mineral
waters in combination with iron, but it is shown in this paper that the
quantity of arsenic bears no relation to the proportion of iron, and
that the former is often pi-esent when the latter is entirely absent.
Hence the arsenic probably exists in these waters in combination with
calcium. The origin of arsenic is without doubt the sulphide of that
element contained in marls associated with the gypsum, from which it
is dissolved by waters charged with calcium carbonate, being first
converted into sulpharsenate and finally into arsenate of calcium.
The author shows that these marls also contain lithium, and that
this metal can easily be detected by the spectroscope in these mineral
waters. E. H. R.
Glairin or Baregin. By N. Jolt (Compt rend., 95, 1194 —
1195). — The glairin or baregin found in almost all the hot sul-
phuretted waters of the Pyrenees, is a very complex substance, con-
sisting of the remains of animal and vegetable matter, together with
various inorganic substances, such as crystals of sulphur, iron pyrites,
silica, &c. The nitrogenous organic matter which exists in solution
in these waters is apparently derived from the ultimate decomposition
of the various animal and vegetable organisms which live in the waters.
The complex glairin of Luchon is derived almost entirely from the
decomposition of the dead bodies of nais, cyclops, infusoria,, and
sulfurairia. The author has been able actually to watch the gradual
formation of glairin from the decomposition of these organisms.
There can be no doubt that true glairin is an animal product.
C. H. B.
Organic Chemistry.
Relation between Boiling Points and Specific Volumes. By
W. Staedel (Ber., 15, 2559 — 2572). — An examination of the chlori-
nated derivatives of ethane shows that the boiling point (under the
normal pressure) is raised 56'22° when one atom of hydrogen is
replaced by chlorine in the group CH3, e.g., CH3.CHCI2 (b. p. 57*7°),
ORGANIC CHEMISTRY. 303
and CH0CI.CHCI2 (b. p. 113-7°). The introdnction of a second
chlorine-atom into the methyl group raises the boiling point 31*3°, e.g.y
CH2CI.CCI3 boils at 130-5°, and CHCI2.CCI3 boils at 161-7°. The con-
version of the group CHCI2 into CCI3 raises the boiling point 16-04°.
The specific volume of these compounds at their boiling points is
increased 14-2 by the introduction of the first chlorine-atom in the
methyl group, 16-37 for the second, and 19-16 for the introduction of
the third chlorine-atom. Hence it appears that an atom of chlorine
can possess different specific volumes. W. C. W.
Conversion of Organic Chlorides into Iodides by means of
Calcium Iodide. By P. v. Romburgh {Bee Trav. Chim., 1, 151 — 153).
— The transformation of organic chlorides into iodides cannot con-
veniently be effected by heating them with potassium iodide, as the
action is too slow ; aluminium iodide, on the other hand, acts too
rapidly. Hydrogen iodide can be used only at ordinary temperatures,
since at higher temperatures it acts as a reducing agent. Calcium
iodide, on the other hand, appears to be available in all cases, and
effects the conversion more rapidly than potassium iodide, inasmuch
as the difference between the heats of formation of chloride and
iodide of calcium is greater than that which is found to exist in the
case of any of the other metals except aluminium. — Allyl chloride,
heated with calcium iodide in a sealed tube at 100" for six hours, is
completely converted into allyl iodide (b. p. 100 — 101^ ; sp. gr. 1-846
at 15°). — Amyl chloride (b. p. 112"), heated with Cal2 for 24 hours at
100", is almost wholly converted into iodide (b. p. 147° ; sp. gr. 1*499
at 15°). — Ethylene chloride, heated with Cala at 100° for three hours,
yields a small quantity of a crystalline body, melting at 82°, subliming
without alteration, decomposed at a stronger heat with separation of
iodine vapour, and in fact exhibiting all the characters of ethylene
iodide. — Benzyl chloride similarly treated at 100°, yielded a red-brown
liquid, which was decolorised by washing first with water, then with
aqueous potash ; and on distilling the colourless liquid thus obtained,
the temperature soon rose above the boiling point of benzyl chloride,
and at 215° decomposition took place, with separation of iodine- vapour,
the greater part of the product solidifying at the same time. In
another experiment white crystals were obtained, melting at the heat
of the hand. These characters, together with the irritating odour of
the product, pointed to the presence of benzyl iodide, but the author
intends to examine it further. H. W.
Decomposition of Cyanogen. By Berthelot (Gompt. rend., 95,
955 — 956). — Cyanogen decomposes with explosion under the influence
of a discharge of mercury fulminate. This effect is due to the high
temperature developed by the destruction of the first layers of cyanogen
by the detonation, the conditions being favourable to the production
and propagation of an explosive wave. On the other hand the gas is
but slowly decomposed when passed through a red hot tube. Per-
fectly dry cyanogen is completely decomposed into nitrogen and
carbon after about three hours by the continuous passage of induction
sparks. In presence of the least trace of moisture small quantities
of hydrocyanic acid and acetylene are formed. Decomposition under
304 ABSTRACTS OF CHEMICAL PAPERS.
these conditions remains slow, and has no explosive characteristics.
The gas is very rapidly decomposed by the electric arc, the carbon
being partly deposited in a flocciilent condition round the negative
pole. It would appear that decomposition under these conditions
approaches the point at which it becomes explosive. In presence of
hydrogen or a hydrogen compound, some hydrocyanic acid is formed.
C. H. B.
Properties of Normal Cyanic Acid. By E. Mulder {Bee. Trav.
Chim., 1, 191 — 222). — From the experiments detailed in this paper,
and from previous researches, the author draws the following conclu-
sions : — 1. The existence of normal cyanic acid as potassium salt,
CN.O.K, appears to be impossible under ordinary circumstances. —
2. Gyanethollne (corps de M. Cloez) is conveniently prepared by the
action of cyanogen bromide on absolutely anhydrous alcohol (easily
obtained by decomposition of a solution of sodium ethylate in ordinary
absolute alcohol). — 3. By the action of cyanogen bromide dissolved in
ether upon sodium ethylate in presence of alcohol and ether, and sub-
sequent filtration and evaporation of the volatile parts of the filtrate, a
crude product is obtained, which dissolves for the most part in water,
leaving a small residue of cyanetholine, and appears to consist chiefly
of a;(CISr.OEt,C2H60). — The wash-water treated with ether yields
ur ethane, formed according to the equation CN.OEt + HoO =
NH2.C00Et. This water likewise contains normal ethyl cyanurate,
and a very small quantity of ethyl monamidoyanurate, and perhaps
also ethyl diamidocyanurate. It is remarkable that cyanogen bromide,
acting on sodium ethylate in presence of alcohol and ether, gives rise
to normal ethyl cyanurate, even in presence of water, to the amount of
SHjO to EtONa, a result which seems to imply the existence of
EtONa in alcoholic solution, in presence of a relatively large quan-
tity of water, much larger, indeed, than that which would be neces-
sary to decompose EtONa into Et.OH and NaOH. — 4. Cyanetholine,
after drying for some time in the exsiccator, gives by analysis num-
bers agreeing pretty nearly with the formula CN.OEt; it probably
always contains small quantities of ethylic monamidocyanurate and
diamidocy an urate. — 5. This body, after remaining at rest for some
time, gradually deposits crystals, consisting chiefly of normal ethyl
cyanurate, sometimes in well-formed prisms. The crystals deposited
from aqueous solution at low temperatures contain a large proportion
of crystal- water, which is given off with efilorescence at 6°. This
compound melts at about 29°, remaining liquid for some hours, and then
solidifying. Normal ethyl cyanurate may be distilled under diminished
pressure, without being converted into isocyanurate. It is very
slightly soluble in water, and its saturated or nearly saturated solu-
tion becomes thickly clouded when heated nearly to the melting point
of the compound. — 6. Normal ethyl cyanurate is soluble in bromine,
and on evaporating the excess of bromine at a sufficiently low tempera-
ture, there remains an orange-red compound, apparently consisting of
3CNOEt,6Br, which undergoes dissociation. The same is the case
with an addition- product, which separates in yellow needles on adding
bromine-water to an aqueous solution of ethyl cyanurate. Neither
isocyanuric acid, nor its methylic or ethylic ether, forms an addition-
ORGANIC CHEMISTRY. 805
product with bromine, so that the formation of such a product may be
regarded as a reaction characteristic of the normal cjanurates. —
7. Cyanetholine is very shghtly soluble in water ; its solution becomes
very turbid when heated, and in presence of bromine-water behaves
for the most part like that of normal ethyl cyanurate. Ethyl isocyan-
urate, on the contrary, differs from cyanetholine in its behaviour with
bromine- water ; the same is the case also with the aqueous solutions
of these bodies at low temperatures. — 8. Ammonia-gas passed through
the alcohol-etheric filtrate of the preparation does not appear to form
either cyanamide or dicyanamide, which might be expected to form in
presence of N : C.OEt, if cyanamide were regarded as the amide of
normal cyanic acid, N : C.NH2. Cyanamide, moreover, does not com-
bine either with bromine or with cyanogen, whence it is probably a
derivative of isocyanic acid, its constitutional formula being that of
carbodiimide, HN ! C ! NH. H. W.
A Reaction of the Compounds of Normal Cyanuric Acid and
Cyanetholine (corps de M. Cloez). By E. Mulder (Bee. Trav.
Chim., 1, 41). — The compounds of normal cyanuric acid (the free acid
is not known) and cyanetholine (isomeric with ethyl cyanate) form
addition-products with bromine, whereby they may readily be distin-
guished from isocyanuric acid and its compounds, which do not form
such addition-products. For example, an aqueous solution of normal
ethyl cyanurate forms with bromine-water a crystalline addition-
product (CN)303Et3,Br2, very soluble in water, which is not the case
either with ethyl isocyanurate or with isocyanuric acid. Hence the
author infers that the two isomeric acids may probably be represented
by the following formulae : —
NzzC.OH HN~CO
^ '
HO.C N OC NH
II II II
N— C.OH HN— CO
Normal cyanuric acid. Isocyanuric acid.
H. W.
Ethyl Peroxide. ByBERTHELOT (Ann. Chim. Fhjs. [5], 27, 229 —
232). — V. Babo noticed {Annalen, Suppl. 2, 165) that ozone acts on
ether, and states that hydrogen peroxide is produced. Berthelot
finds that this is the case only when the ether employed is wet. If dry
ether is evaporated by passing a dry current of ozonised oxygen over
its surface, a small quantity of a dense syrupy liquid is left. This
liquid is miscible with water, does not solidify when cooled to —40°,
and when subjected to heat, explodes violently as soon as a small
portion has distilled over. It acts as an oxidising agent in a manner
similar to hydrogen peroxide, and gives up 10 — 11 per cent, of oxygen
when treated in the cold with permanganic or chromic acids. The
author ascribes the formula (C2H6)403 to this body, and gives it the
name of ethyl 'peroxide. L. T. T.
Second Anhydride of Mannitol. By A. Fauconnier (Compt.
rend., 95, 991 — 993). — When mannitol is subjected to dry distillation
306 ABSTRACTS OP CHEMICAL PAPERS
in a vacuum, it yields a browniyh-yellow liquid mixed with erapjreu-
matic substances. The liquid is filtered throuo^h a moistened filter
and distilled. It begins to boil at 60° under ordinary pressure. The
fraction which passes over between 160° and 190° under a pressure of
0*03 m., consists partly of the second anhydride of mannitol, CeHjoO*.
When freshly distilled, this compound is a colourless syrup which, if
perfectly pure, forms bulky crystals melting at 87°, and apparently
belonging to the monocliiiic system. It boils without decomposition
at 176" under a pressure of 003 m., and with partial decomposition
at 274° under ordinary pressure. It is very soluble in water and
alcohol, but insoluble in ether, and possesses in a high degree the pro-
perties of remaining in superfusion, and of forming supersaturated
solutions.
This second anhydride of mannitol does' not combine directly with
either cold or hot water, and is not affected by nascent hydrogen. It
is not attacked by bromine in the cold ; but if the two bodies are
heated together alone or in presence of water, hydrobromic acid is
given ofiP, and black resinous products are formed, but cannot be dis-
tilled. When boiled for eight hours with three times its weight of
acetic anhydride, the mannitol anhydride yields a diacetic derivative,
C6H8O4XC9, an almost colourless viscid liquid, which is not altered by
the prolonged action of acetic anhydride ; it boils at 197 — 198° under
a pressure of 28 mm.
The mannitol anhydride is not attacked by phosphorus oxychloride,
but with phosphorus pentachloride it yields a dichlorhydric derivative,
CeHBOaCla, which forms hexagonal lamellae, very soluble in ether,
somewhat soluble in alcohol and benzene, insoluble in water. It melts
at 49°, boils at 143° under a pressure of 43 mm., and can be distilled
in the vapour of water. Not more than two atoms of chlorine can be
introduced into the molecule by the action of phosphorus pentachlo-
ride. When heated in sealed tubes at 120° for four hours with ethyl
iodide and concentrated potash, the anhydride yields a monethyl
derivative, C6H904Et, a colourless somewhat mobile liquid, soluble in
water, alcohol, and ether: it boils at 165° under a pressure of 17 mm.
From these facts it is evident that the second anhydride of mannitol
is a saturated compound containing two alcoholic hydroxyl-groups,
and that there are no double bonds between the carbon-atoms. Its
formula is therefore C6H802(OH)2. The primary, secondary, or
tertiary character of the hydroxyl-groups, and the function of the
two other oxygen-atoms, has yet to be established. C. H. B.
Influence of Mass and Time on the Inversion of Sugar. By
F. Urech (Ber., 15, 2457— 2460).— The author has observed that the
inversion of cane-sugar in the case of a mixture of 16*35 grams cane-
sugar and 11*40 grams hydrochloric acid in 100 c.c. water, is an
exothermic reaction.
Therefore, as the velocity increases with the temperature, no con-
stant can be deduced from the laws of mass action, but only approxi-
mate values for short intervals of time.
In the first half of the reaction more heat is evolved than in the
second, during which smaller quantities of cane-sugar enter into the
ORGANIC CHEMISTRY. 307
reaction. The author has, notwithstanding the experimental difficul-
ties, made a series of observations on the velocity of the reaction by
the polariscope and by a titration method with Fehling's solution.
The experimental tube of the polariscope was kept cool by a current
of water; and in the titration method quantities of the inversion
mixture were taken out at given intervals of time, run into excess of
alkali to stop the reaction, and then titrated.
From the results obtained by these two methods, the author con-
cludes that generally in equal intervals of time, equal quantities of
cane-sugar disappear, while the hydrochloric acid plus water increases
in direct proportion to the decrease of cane-sugar. Large quantities
of hydrochloric acid and water invert more quickly than smaller quan-
tities of the same concentration. Y. H. V.
Formula of Starch. By T. PrEiFFER, B. Tollens, and F. Salo-
mon {Bled. Gentr., 1882, 775 — 777). — Sachsse and I^ageli attribute to
starch the formula CaeHeaOai + 5H2O = GCeHijOe, and ground this for-
mula on the amount of sugar obtained by the action of acid. Pfeiffer
and Tollens, however, consider that the formula should be C24H40O20, or
C24H43O21, deducing this from the composition of the sodium and
potassium compounds, which contain 3'44 per cent. Na and 5'25 per
cent. K; they also think that inulin and dextrin should be repre-
sented by C12H20O10 or Ci2H220ii, and that the molecules of starch and
inulin are not of the same size. Salomon repeated Sachsse's experi-
ments, and proceeding further claims ajCeHioOj as the formula which
more closely represents the composition of starch, for he obtained
111 per cent, dextrin from starch. Combining these two formulae as
suggested by Pfeiffer, Tollens, and Salomon, it appears that we must
adopt 4C6H10O5. E. W. P.
Action of Triethylamine on Symmetrical Trichlorhydrin
and on the Two Dichloropropylenes. By E. Reboul (Compt,
rend., 95, 993 — 996). — When trichlorhydrin is heated with three vols,
triethylamine in sealed tubes for some hours at 100°, the product
becomes almost entirely solid on cooling ; no gas is given off. The
contents of the tube are dissolved in water and evaporated on a water-
bath in order to expel all unaltered triethylamine.
The syrupy mass thus obtained is a mixture of triethylamine hydro-
chloride and the two isomeric chlorides, a-chlorallyltriethylammo-
nium chloride, ClNEt3.CH2.CCl ! CH2, and |S-chlorallyltriethylammo-
nium chloride, ClNEt3.CHCl.CH I CH^.
The triethylamine hydrochloride may bo separated from the mixture
by means of boiling alcohol, from which it separates in silky needles
on cooling. If platinum tetrachloride is added in slight excess to an
aqueous solution of the mixture, an abundant precipitate is formed,
readily soluble on warming. The solution on cooling deposits
cL-chlorallyltrietTiylammonmin platinocliloride in nodular groups of
long thin orange-red needles, only slightly soluble in cold water.
On further concentration and cooling, the orange- red needles are
succeeded by orange-yellow crystals (not needles) of li-chlorallyltri-
ethylammonium platinocJiloridef more soluble in cold water than is
308 ABSTRACTS OF CHEMICAL PAPERS.
the first compound. On further concentration the mother-liquor
yields triethylamineplatinochloride.
When triethylamine acts on trichlorhydrin, it first removes hydro-
chloric acid, producing a mixture of the two isomeric dichloropropy-
lenes, which then unite with the excess of triethylamine, forming the
compounds just described.
If triethylamine is heated with an excess of trichlorhydrin, the
product is a mixture of the two isomeric dichloropropylenes. a-Di-
chloropropylene, CHj ! CCI.CH2CI (b. p. 94°) attacks triethylamine
in the cold ; the action proceeds rapidly at 100°, and after some hours
the whole mass becomes solid. No gas is given off, and the product
consists of a-chlorallyltriethylammonium, without any of the /3-com-
pound, and with only slight traces of triethylamine hydrochloride.
When the mixture of the two dichloropropylenes obtained by the action
of potash on trichlorhydrin is heated with triethylamine, it yields a
mixture of the two ammoniums already described, with mere traces of
triethylamine hydrochloride.
It is evident that symmetrical trichlorhydrin does not simply fix
two molecules of triethylamine, as would be supposed from the exist-
ence of two CH3CI groups, but loses hydrochloric acid, the chlorine of
which is derived partly from a CII2CI group, and partly from the
middle group, CHCl. The two isomeric dichloropropylenes thus
produced obey the same law as the chlorine derivatives of the primary
monhydric alcohols, and simply fix triethylamine. The two tetram-
monium hydrochlorides thus formed are easily decomposed by freshly
precipitated silver oxide, and yield the corresponding ammonium
hydroxides, which precipitate calcium hydroxide from a solution of
calcium chloride. C. H. B.
Glyoxaline and its Homologaes. By B. Radziszewski {Ber., 15,
2706 — 2708). — In a previous communication (Abstr., 1882, 1064) the
author expressed his opinion that glyoxaline has a constitution
CH : N
analogous to that assigned by him to lophine, viz., | >>CH2,
CH : N^
basing this formula on the synthesis of glyoxaline by the action of
ammonia on glyoxal and formaldehyde, just as lophine is formed from
benzil, benzaldehyde, and ammonia. Its solubility in alkalis and its
passive behaviour to nascent hydrogen again suggest an analogy to
lophine. Against Wyss's formula, the author urges its neutral be-
haviour towards the acid chlorides and anhydrides, and also the fact
that it forms no nitroso-derivative. In order to further test the cor-
rectness of his views, the author has substituted other aldehydes for
formaldehyde in the above-mentioned reaction, and has succeeded in
obtaining homologues of glyoxaline.
With acetaldehyde he obtained a body melting at 1.37°, and boiling
at 266 — 268°. It crystallises in needles which readily dissolve in
water, alcohol, and boiling benzene. It is represented by the formula
C4H6N2, and is in fact identical with Wallach and Schulze's paroxal-
methyline (J5er., 14, 426). With bromine it forms the compound
C^HaBraNa (m. p. 258°). The properties of paroxalmethyline show
ORGANIC CHEMISTRY. 309
that it is a true homologae of glyoxaline, and from its synthesis from
glyoxal, &c., the author assigns to it the constitution —
CH : K
I >CHMe.
CH : W A. K. M.
Decomposition of Tertiary Amyl Acetate by Heat. By N.
Menschutkin (Ber., 15, 2512 — 2518). — Tertiary amyl acetate, pre-
pared by the action of acetic anhydride on ethyl dimethyl carbinol, is
slowly decomposed by heat at 125", according to the equation —
C2H3(C5Hii)02 = C5H10 -f- C2H402.
In six days 2*06 per cent, of the acetate is decomposed. At a higher
temperature decomposition proceeds more rapidly. At 155° signs of
decomposition make their appearance two hours after the commence-
ment of the experiment.
The rate of decomposition is at first slow, it then accelerates until
it reaches a maximum point, when it gradually diminishes to zero.
w. c. w.
Tetrasubstituted Propionic Acids. By H. B. Hill and C. F.
Mabery (Amer. Ghem. J., 4, 263 — 272). — Tetrahromopropionic acid,
C3H2Br402, is easily prepared by adding the calculated quantity of
bromine to a solution of tribromopropionic acid in chloroform at
ordinary temperatures, and gradually separates in large well-defined
prisms, the yield being about 90 p. c. of the theoretical amount. The
crystals are triclinic, having the axial ratio a : b : c = 1*507 : 1 : 0"934,
and angle ah = 94° 50' ; ac = 104° 28' ; he = 74° 20'. Observed
forms ooPob, coPc5b, OP, Pco, ooP'. The acid melts at 125—126°;
dissolves very readily in alcohol or ether, readily also in hot chloro-
form, carbon bisulphide, and benzene, and separates in crystals on cool-
ing ; it is sparingly soluble in light petroleum. Under water it melts
at a very low temperature to a colourless oil, which dissolves freely
on heating.
The silver salt, C3HBr402Ag, separates on adding silver nitrate to
a solution of the acid in dilute alcohol in clusters of needles, the
quantity of which may be increased by cautions addition of ammonia.
It is extremely unstable, yielding silver bromide when warmed, and
blackening rapidly on exposure to light. The barium salty
(C3HBr402)2Ba,2H20,
obtained by saturation, separates on spontaneous evaporation in groups
of flattened needles, which give off their crystal-water over sulphuric
acid. The calcium salt, (C3HBr402)2Ca, prepared in like manner, crys-
tallises in anhydrous needles.
The barium salt in aqueous solution is resolved by heat into barium
bromide, carbonic anhydride, and tribromethylene : (C3HBr402)2 Ba =
BaBr2 + 2CO2 + 2C2HBr3. The acid heated with alcoholic potash
is resolved into hydrobromic acid and tribromacrylic acid, C3H.Br302,
melting at 118° (Abstr., 1881, 1125).
a-Dichlorodibromopropionic acid, C3H2Cl2Br202, is prepared by heat-
ing dichloracrylic acid (m. p. 85 — 86°) with 1 mol. bromine for several
hours at 100°, and may be purified by pressing it between paper and
YOL. xLiv. y
310 ABSTRACTS OF CHEMICAL PAPERS.
crystallising it, first from carbon bisulphide and finally from chloro-
form. It crystallises in well-formed triclinic crystals, exhibiting the
faces coPoo, coPc5o, OP, P|co, P|cx), ,P'ob, ,P'cx3 ; frequently also ooP|
and oo|P. Axes a : & : c = 1*02 : 1 : 1*052. Angles ab = 9V ; ac =
70° 31^' ; be = 108° 52'.
The silver salt^ C3HCl2Br202Ag, is obtained by precipitation in
flattened jagged needles, easily decomposed by heat. The barium salt,
(C3HCl2Br202)2Ba, obtained by neutralisation, crystallises in long
branching anhydrous needles. It is decomposed by heat, yielding
products similar to those obtained from the tetrabromopropionate.
0-Dichlorodibromopropionic Acid. — Chlorine gas passed into dibrom-
acrylic acid in ordinary daylight is slowly taken up, and dichlorodi-
bromopropionic acid is formed, but so contaminated with oily products
that its purification is somewhat difficult. If, however, the action be
made to take place in direct sunshine at 100°, it goes on rapidly, and
the process may be stopped when the melted acid becomes solid, from
separating crystals of the addition-product. This product purified by
crystallisation, first from carbon bisulphide and then from chloroform,
forms oblique prisms melting at 118 — 120°, easily soluble in water,
alcohol, and ether, somewhat less easily in carbon bisulphide, chloro-
form, and benzene. The solution in carbon bisulphide deposits well-
defined monoclinic crystals having the axes a:b: c = 2'393 : 1 : 1*731,
and the angle ac = 46° 9'. Observed faces coPc5b, cxjP, + P, + ^Pco.
The silver salt of this acid is precipitated in short thick pointed prisms
on adding silver nitrate to the aqueous acid ; it is easily decomposed by
heat. The barium salt, (C3HBr2Cl202)2Ba + 2H2O, is obtained by
neutralisation, and crystallises by slow evaporation in long radiating
needles, very soluble in cold water. H. W.
Constitution of the Substituted Acrylic and Propionic
Acids. By H. B. Hill (Amer. Chem. J., 4, 273— 276).— a-Mono-
bromacrylic acid can be made from a- and from ajS-dibromopro-
pionic acid, and must therefore have the structure CH2 .' CBr.COOH ;
the tribromopropionic acid made from it by addition of bromine will
-have the corresponding form, CH2Br.CBr2.COOH, and the dibrom-
acrylic acid obtained from the latter will be represented by the
formula CHBr ! CBr.COOH. The dibromacrylic acid of Fittig and
Petri, which, as shown by Mabery and Hill, can be made from
bromopropiolic acid, must have tjie form CBra ! CH.COOH, and the
acids made in like manner, containing two halogens, will be repre-
sented by the corresponding formulae —
CBrI : CH.COOH and CBrCl ! CH.COOH.
The tribromopropionic acid melting at 118° must be represented by
the formula CHBr2.CHBr.COOH, and tetrabromopropionic acid by
CHBr2.CBr2.COOH. H. W.
Crystalline Form of Tribromacrylic Acid. By W. H. Mel-
ville (Amer. Ghem. J"., 4, 277). — This acid forms monoclinic crystals
exhibiting the forms ooPob, 00 P, -j- Pcx), — Poo, ^Pob, the last three
ORGANIC CHEMISTRY. 311
however occurring but rarely, a : b : c = 0*502 : 1 : 0*559 ; Angle
ac = 64° 29i'. H. W.
Addition of Hypochlorous Acid to /3-Crotomc Acid. By P.
Melikoff (Ber., 12, 2586 — 2588). — ^-Crotonic acid unites directly
with hypochlorous acid, forming chloroxybutyric acid. On treating
an alcoholic solution of chloroxybutyric acid with alcoholic potash,
potassium chloride is deposited, and potassium butylglycidate remains
in solution; the excess of potash is precipitated by a current of
carbonic acid, and ether added to the filtrate, when potassium butyl-
glycidate is deposited in oily drops.
ButylglycicUc acid, C4H6Q3, is a mobile liquid forming viscous salts.
It combines with hydrochloric acid,^ yielding chloroxybutyric acid,
C4H7CIO3, which crystallises in prisms melting at 98°, and forms a
zinc salt crystallising in rhombic plates containing 1 mol. H2O. Butyl-
glycidic acid also unites direc-tly with water^ forming butylgly eerie
acid, which has been described by Hanriot {Ann. Ghim. Fhys. [5], 17,
104). W. C. W.
Ethyl Acetoacetate. By A. E. Matthews and W. R. Hodgkinson
(Ber. J 15, 2679). — By the action of potassium cyanide on monochlor-
acetone, Me.CO.CHzCl, the corresponding cyanide Me.CO.CHo.ON is
obtained, and on decomposing this with hydrochloric acid, it yields ethyl
acetoacetate. A. K. M.
Preparation of Methyl Chlorocarbonate. By A. Klepl
(J. pr. Chem., 26, 447). — In preparing the chlorocarbonate by passing
chlorocarbonic oxide into methyl alcohol in the ordinary way, a con-
siderable quantity of methyl carbonate is formed at the same time,
and can only be separated with difficulty. This may be avoided by
diluting the alcohol with ready-formed methyl chlorocarbonate, and
employing chlorocarbonic oxide free from chlorine ; for this purpose
the gas is first passed over a mixture of metallic antimony with frag-
ments of glass, kept at a temperature of 100° to absorb the free
chlorine, and then into a mixture of methyl chlorocarbonate with less
than one-third of its bulk of methyl alcohol surrounded by ice-cold
water. As soon as the chlorocarbonic oxide is no longer perceptibly
absorbed, a fresh quantity of methyl alcohol is added^ and the opera-
tion repeated, taking care that the alcohol added always bears about
the same ratio to the chlorocarbonate already formed. When
successive additions of alcohol have brought up the total quantity of
liquid to about 150 c.c, the operation is stopped, the product washed
with water at 0°, dried over calcium chloride, and distilled ; almost
the whole passes over between 70° and 72°, and one or two fraction-
ations with a Linnemann's tube, render it perfectly pure (b. p. 71 —
71"5°). The same process maybe employed with advantage in the
preparation of ethyl chlorocarbonate. C. E. G.
Action of Chloroform on Sodium Ethylmalonate. By M.
Conrad and M. Guthzeit (Ber., 15, 2841 — 2844). — Oppenheim and
Pfaff have observed that by the action of chloroform and other
V 2
312 ABSTRACTS OF CHEMICAL PAPERS.
chlorine derivatives of raethane on sodium acetoacetate, the ethyl salt
of hydroxynvitic acid is formed ; a reaction which they explain by the
intermediate formation of an ethyl salt of an unsaturated acid of
formula C5H6O4, thus : —
2(CH2l5.COOEt) + CHCl3= 3HC1 +
cooEt.ci:^ : cn.cHXH.cooEt.
The authors have studied a similar reaction in the case of sodium
ethylmalonate, and obtained in the first place a sodium compound,
Cis&oOsNa, crystallising in glistening prisms, whose aqueous solution
gives crystalline precipitates with the chlorides of the alkaline earths
and the acetates of the heavy metals, and a violet coloration with
ferric chloride. On decomposing the sodium compound with hydro-
chloric acid, a substance of the formula C15H22O8 is found. It is a
colourless oil (b. p. 270 — 280°, sp. gr. 1*131) which gives off carbonic
anhydride when heated with hydrochloric acid, and is converted into
a crystalline acid (m. p. 133°) of composition (^sHeOi, which the
authors propose to name glutonic acid, in that it yields glutaric acid
on hydrogenation. The changes described above may be explained by
the following reactions: —
2CNa2(COOEt)2 + CHCI3 = (C00Et)2CNa.CH I C(COOEt)a +
3NaCl
and (C00Et)2CH.CH ! CCCOOEt), + 4Ho.O =
COOH.CH2.GH : CH.COOH -f 2CO2 + 4EtOH.
y. H. V.
Action of Sodium Ethylate on the Sodium Salt of Symmetric
Dibromosuccinic Acid. By E. Mulder and G. Hamburger (Bee.
Trav. CMm., 1, 54 — 55). — Sodium dibromosuccinate (1 g.), treated
with absolute alcohol containing in solution 0*2875 g. sodium, i.e.,
with four times the quantity required by the following equation, yields
a gelatinous mass ; and on treating this mass with a small quantity of
water, filtering, and mixing the filtrate with alcohol, a gelatinous pre-
cipitate is obtained, which when washed with alcohol to remove sodium
bromide, and dried under a bell-jar, forms a bulky hygroscopic mass
consisting of sodium monobromethylmalate, C6H7Br05Na2, formed
according to the equation —
COONa.CHBr COONa.CHBr
i + EtONa = NaBr +
COONa.CHBr COOlSTa.CHOEt.
The formation of this compound in presence of an excess of sodium
shows that the second bromine-atom in the dibromosuccinate is diffi-
cult to replace ; but by acting on the broraethylmalate with sodium
ethylate, the authors hope to obtain the sodium salt of diethyltartaric
acid, CgHuOs = CiHiEtoOe. H. W.
Derivatives of Citraconic Acid. By G. L. Ciamician and M.
Dennstedt {Gazzetta, 12, 500— 502).— Gottlieb (Annalen, 77, 274), by
evaporating to dryness a mixture of citraconic acid with excess of
ammonia, and heating the residue to 180°, obtained an amorphous
ORGANIC CHEMISTRY. 313
resinous mass, which he regarded as citraconimide ; and the authors
of the present paper, by exactly following Gottlieb's directions, have
obtained an amorphous mass of similar character ; but on heating this
substance to a higher temperature, they find that it gives off large
quantities of ammonia, together with a yellow oily distillate solidify-
ing on cooling to a mass of crystals ; and at a still higher temperature
a small quantity of a brown oil which does not solidify, and whose
vapour exhibits the characteristic reaction of pyrroline with a deal
shaving moistened with hydrochloric acid ; finally there remains in
the retort a quantity of shining friable charcoaL
The crystalline body above-mentioned may be freed from adhering
oil by pressure between paper, and further purified by repeated crys-
tallisation from boiling water with addition of animal charcoal, the
solution on cooling depositing groups of splendid colourless needles
which give by analysis 63'90 per cent, carbon, 4*72 hydrogen, and
] 2*92 nitrogen, agreeing very nearly with the formula of citraconi-
mide, C5H5NO2, which requires 54-05 C, 4-50 H, and 12'61 N. This
body melts at 109 — llO'', is volatile and sublimable, slightly soluble
in cold, freely in hot water and alcohol, sparingly in ether. It has a
neutral reaction, and gives with ammoniacal silver nitrate a. compound
sparingly soluble in water. Heated with phosphorus pentachloride at
105 — 110°, it yields a dark brown liquid, which dissolves partially in
water, forming a solution from which ether extracts a chlorinated
body melting at 144 — 145° and subliming in colourless leaflets.
This and other derivatives of citraconimide will form the subject of a
future communication. H. W.
Acetylenedicarboxylic Acid. By E, Batjdrowski (Ber., 15, 2694
— 2698). — Anhydrous acetj^enedicarboxylic acid crystallises from
ether in well-formed four-sided plates, melting with decomposition at
175°. Dimethylacetylenedicarboxylate, C404Me2, is a colourless liquid
(b. p. 195 — 198°) of aromatic but pungent odour.
Ghlorofumaric acid, C4H3CIO4, obtained by the action of'hydro-
chloric acid on acetylenedicarboxylic acid, melts at 178°. It dissolves
very readily in water, alcohol, and ether, and crystallises in microscopic
needles. Hydrogen potassium chlorofumarate, C4H2CIO4K, cryste,l-
lises in sparingly soluble prisms. The silver salt, C4HC104Ag2 + H2O,
forms a white crystalline precipitate, and the lead salt, C4HC104Pb +
2H2O, a flocculent precipitate which, however, soon becomes crystal-
line. From the properties of chlorofumaric acid, the author considers
it as identical with the acid obtained by Perkin and Duppa by the
action of phosphorus pentachloride on tartaric acid {Annalen, 115,
105). Caius's acid, obtained by the action of hypochlorous acid on
benzene (Annalen, 142, 139), appears, however, to be an isomeride.
Bromof umaric acid, prepared by dissolving acetylenedicarboxylic acid
in fuming hydrobromic acid, agrees in all its properties with the acid
described by Kekule and Fittig (Annalen, 195, 63). lodofumaric
acid obtained by the action of hydriodic on acetylenedicarboxylic acid,
is readily soluble in water, alcohol, and ether. It melts at 182 — 184°.
The hydrogen potassium salt, C4H2IKO4, forms small well-formed
crystals, sparingly soluble in water. The lead salt, C4HI04Pb +
314 ABSTRACTS OF CHEMICAL PAPERS.
2H2O, and the silver salt, C4HI04Ag2, are precipitated amorphous,
but soon become crystalline. A. K. M.
Propargylic Acid. By E. Baudrowski (Ber., 15, 2698—2704).—
The potassium salt of propargylic acid has been previously described
by the author (Ber., 13, 2340). To prepare the free acid, C3H2O2, a
solution of hydrogen potassium acetylenedicarboxylate is treated
with dilute sulphuric acid and shaken with ether. After standing for
some hours, the ethereal extract is separated, dried, and evaporated
on a water-bath. On distilling the residue, the principal fractions
obtained are one at 100 — 125 , which after repeated fractioning
yields ethyl propargylate boiling at 117 — 119°, and another at
125 — 154°. The greater part of this fraction distils at 140 — 145°,
but as it decomposes at the same time, a constant boiling point cannot
be obtained. Analysis showed this body to be propargylic acid. The
residue in the flask became partly solid on cooling, apparently from
separation of anhydrous acetylenedicarboxylic acid. Propargylic acid
is a colourless liquid, which solidifies at about 4°, forming long silky
crystals which melt at 6°. It is soluble in water, alcohol, ether, and
chloroform. Its odour resembles that of acetic acid, but is more
powerful. The salts of mercury, silver, and platinum are readily
reduced by this acid. With the alkalis and alkaline earths, it forms
salts very readily soluble in water. On reduction it yields propionic
acid, and by the action of the halogen acids substituted acrylic acids.
Bromine converts it into dibromacrylic acid melting at 85 — 86°.
A. K. M.
Derivatives of Barbituric Acid. By M. Conrad and M. Guth-
ZEIT (Ber., 15, 2844—2850). — The author alludes to the interest
attached to the chemistry of barbituric acid as the central point of the
alloxan group^ and the starting point for the synthesis of uric acid.
In the course of preparation of barbituric acid from malonic acid,
carbamide, and phosphorus oxychloride, the authors obtained as a
bye-product a golden powder of empirical formula C3H3NO2. As this
substance gives dibromobarbituric acid by the action of bromine, it is
most probably acetobarbituric acid, formed according to the equa-
tion—
300<^^;^^>CH2 + 3CH2(COOH)2 + POCls =
30C<^]^;^^>CH.COCH3 + 3CO3 + 3HC1 + H3PO4.
Mhylharhituric acid, OC<t;g"XQ>CHEt, prepared from ethyl-
malonic acid, carbamide, and phosphorus oxychloride, crystallises in
vitreous prisms melting at 190° ; with bromine it forms a white crystal-
line monobrom- derivative. Benzylharhituric acid from benzylmalonic
acid forms prismatic crystals (m. p. 206°) soluble in hot water. The
researches of the authors and others have established that one hydro-
gen-atom is replaceable by metals, the halogens and the nitrosyl
group. In the present paper the silver salt is described. It is
obtained as a reddish flocculent precipitate by the addition of silver
ORGANIC CHEMISTRY. 315
nitrate to the acid ammomum barbiturate. Bimethylharbituric acid,
prepared by heating silver barbiturate with methyl iodide, was
obtained as a red precipitate. The corresponding diethyl compound
is a crystalline compound melting at 182°.
On mixing an aqueous solution of barbituric acid with potassium
nitrite and adding silver nitrate, the silver salt of purpuric acid is
formed. Benzylpurpuric acid, obtained by the action of benzyl chlo-
ride on this silver salt, forms glistening crystals (m. p. 226°). On
saponifying benzylpurpuric acid, benzylnitromalonic acid is obtained,
which shows that the benzyl group (and therefore the silver-atom) is
directly combined to a carbon-atora, thus —
^^<NH.CO>^(^^)-^'^- v. H. V.
Extraction of Asparagine from Liquids. By E. Schulze
{Ber., 15, 2855 — 2856). — The author proposes to separate asparagine
from plant-extracts by precipitation with mercuric nitrate, and de-
composition of the white precipitate by sulphuretted hydrogen. This
method is useful when the presence of soluble carbohydrates pre-
vents the crystallisation of the asparagine.
Y. H. V.
Benzene from Various Sources. By Y. Meter {Ber., 15,
2893 — 2894). — Baeyer has shown that benzene and isatin combine,
when shaken with concentrated sulphuric acid, to form the deep-
blue indophenine (CbHjNOs + 2C6He = H2O + C20H15NO). In the
present communication the authol* points out that the purest benzene
(b. p. 78*8°) from coal-tar oil undergoes this reaction, whereas ben-
zene of the same boiling point prepared from benzoic acid remains
unaltered. The same result obtains whatever be the source of the
benzoic acid, but if the purest benzene from coal-tar be heated for
ten hours with concentrated sulphuric acid, and the unattacked por-
tion separated and purified, the benzene so obtained (b. p. 78*8") will
not react with isatin. This difference in property the author con-
siders to be due to a minute impurity in the benzene from coal-tar,
which assists the reaction, or of an imparity in the benzene from
benzoic acid, which prevents the reaction, or finally the presence of
two modifications of benzene in the liquid obtained from coal-tar.
Y. H. Y.
Trinitro-derivatives of Benzene and Toluene. By P. Hepp
(Annalen, 215, 344 — 375). — To prepare trinitrobenzene, metadinitro-
benzene (4 parts) is dissolved in a mixture of concentrated nitric
acid (12 parts) and pyrosulphuric acid (30 parts); the mixture is
then heated for two days at 80° and two days at 120° ; the resulting
product is poured into water, filtered, washed with water and with
dilute sodium carbonate solution, and then crystallised from alcohol.
The first crystallisation consists nearly exclusively of trinitrobenzene,
which can be obtained quite pure by a single recrystallisation from
water. The trinitrobenzene remaining in the alcoholic mother-liqnor
is best recovered by precipitation with aniline and decomposition of
31 & ABSTRACTS OF CHEMICAL PAPERS.
the resnlting compound with dilate hydrochloric acid. The yield is-
about 50 per cent, of the dinitrobenzene employed.
Trinitrobenzene crystallises from warm alcohol in silky plates or
needles ; by slow evaporation of the cold saturated solution, small
rhombic tables are obtained, giving the axial relations a: 6 : c =
0*954 : 1 : 0*733, and showing combinations of P, oof*co, coPoo, cx>P,
and, seldom and very small, 2P2 and coP2. It melts at 121 — 122°,
can be sublimed in small quantities by careful heating, explodes
when quickly heated, and does not distil with water vapour.
By the action of ammonium sulphide on trinitrobenzene, only a
very small quantity of a dinitraniline (?) was obtained, which resinified
on attempting to purify it. With tin and hydrochloric acid the
double salt C6H3(NH2)3(HCl)3,SnCl2 is obtained in brilliant white
crystals. By removing the tin with sulphuretted hydrogen, the
triamidobenzene hydrochloride may be obtained as a white crystalline
mass. It does not give a blue coloration with ferric chloride, whilst
the triamidophenol of Heintzel and the triamidobenzene prepared from
picric acid (which should be identical with that from trinitrobenzene)
both yield a deep-blue colour with this reagent.
On oxidation with potassium ferricyanide in weak alkaline solution,
trinitrobenzene yields picric acid, the reaction occurring with great
readiness. In order to ascertain what influence the accumulation of
NO2 groups had in accelerating oxidation, the author investigated the
action of the same oxidising mixture on di- and mono-nitrobenzene.
With metadinitrobenzene the reaction was very slow ; after one hour's
boiling, the greater part of the metadinitrobenzene was unaltered ;
the products of oxidation were jS-diuitrophenol and a small quantity
of a-dinitrophenol. Mononitrobenzene was not attacked by this
oxidising mixture.
Addition-products of Trinitrobenzene and Aromatic Amines. — Trinitron
henzene-aniline, C6H3(N02)3,NH2Ph, is precipitated on adding aniline
to an alcoholic solution of trinitrobenzene. It crystallises in long
brilliant orange-red needles which melt at 123 — 124°. It is resolved
into its constituents on long exposure to air, or by treatment with
dilute acids. Trinitrohenzene-dimethylaniline, C6H3(N02)3,NMe2Ph, crys-
tallises in dark- violet needles melting at 106 — 108°. Compounds were
also prepared with ortho- and para-toluidine, both crystallising in long
red needles, and forming violet-black granules with metaphenylene
diamine.
Picramide, on reduction with tin and hydrochloric acid, gave the
hydrochloride C6H2(NH2,HC1)3.0H, crystallising in brilliant white
needles. The corresponding sulphate was obtained by the addition of
sulphuric acid to an alcoholic solution of the hydrochloride. Picramide
also unites with amines (Mertens, Abstr., 1878, 725). The aniline
compound (m. p. 123 — 125°) forms dark-red crystals, the dimethyl^
aniline compound (m. p. 139 — 141°) brilliant dark-blue crystals.
Picryl chloride reacts with potassium iodide in alcoholic solution,
giving a substance crystallising in golden-yellow needles (m. p. 164°),
decomposed by potash into potassium iodide and potassium picrate,
and is therefore trinitro-iodohenzene.
By the nitration of paradinitrobenzene, 1 ; 2 : 4 trinitrobenzene
ORGANIC CHEMISTRY. 31 T
sliould be obtained; but all attempts to separate it from the unaltered
dinitro-bodj were unsuccessful. Its presence was, however, conclu-
sively proved by the formation from the product of the reaction of
a-dinitraniline [1:2:4] by treatment with alcoholic ammonia, of
dinitrodiphenylamine (m. p. 153°) by boiling in alcoholic solution with
aniline, and of a-dinitrophenol by boiling with dilute soda solution.
Trinitrotoluenes. — Two trinitrotoluenes have been described,
a-trinitrotoluene by Wilbrand (Annalen, 133, 178) and Tiemann
(Ber.^ 3, 217 and 213), and 7-triuitro toluene, prepared from 7-nitro-
toluene by Beilstein and Kuhlberg (Annalen, 155, 26). The author's
researches add a third, jS-trinitrotoluene.
oc-Trinitrotoluene, C6H2Me(N02)3, closely resembles trinitrobenzene.
It crystallises in the rhombic system, rt : h : c = 0*7586 : 1 : 0*597,
and shows the faces coP, coPoo, coP2, Poa. It unites with amines,
and these compounds may be prepared in a manner similar to those
of trinitrobenzene, which they closely resemble, ci- Trinitrotoluene-
aniline crystallises in long brilliant red needles melting at 83 — 84°.
The dimethylaniline compound forms violet needles.
f^-Trhiitrotoluene is obtained by the nitration of metanitrotoluene.
It crystallises in six-sided yellow rhombic tables ; axial relations,
a:h'.c = 0*9373 : 1 : 0*6724; observed forms, ooPcx), P, ooP2, 2Pco,
OP. It is sparingly soluble in cold alcohol, moderately soluble in hot
alcohol or hot glacial acetic acid, readily soluble in ether, benzene,
and acetone. The last solvent yields the best formed crystals. It
does not yield simple additive products with aromatic amines.
f^-Binitrotoluidine, C6H2Me(N02)2-NH2, is prepared by the action of
concentrated alcoholic ammonia on 7-trinitrotoluene. It crystallises
in small, hard, well-formed, golden-yellow crystals, apparently of the
rhombic system. It melts at 192 — 193", and is sparingly soluble in
nearly all solvents, dissolving most readily in acetone.
r^-Binitrotolylphenylamine, C6H2Me(N02)2-NHPh, is obtained by the
action of aniline on a hot alcoholic solution of 7-trinitrotoluene. It
crystallises in orange-coloured needles (m. p. 142°), sparingly soluble
in alcohol.
^-Trinitrotoluene is formed, together with 7-trinitrotoluene, by the
nitration of metanitrotoluene. It is obtained in less quantity than the
7-body, from which it can be separated by its greater solubility. It
crystallises in colourless thick prisms of the triclinic system ; axial
relations, a : h : c =_ 06657 : 1 : 0*6228 ; observed faces, coP', cxj'P,
Poo', 'P'co,, ''P,co, P, coPoo, OP. It is sparingly soluble in cold
alcohol, moderately in hot alcohol and glacial acetic acid, readily
soluble in ether, benzene, and acetone ; with ammonia and aniline it
behaves like 7-trinitrotoluene.
^-Dinitrotoluidine, C6H2Me(N02)2.NH2, is prepared by heating
^-trinitrotoluene with alcoholic ammonia for four or five hours in
sealed tubes at 100°. It crystallises in short golden-yellow needles
melting at 94°, and is more readily soluble than the corresponding
7-derivative. A. J. G.
Addition-products of the Nitro. derivatives -with Hydro-
carbons. By P. Hepp {Annalen, 215, 37b— 380).— Trinitrobenzene^
318 ABSTRACTS OF CHEMICAL PAPERS.
benzene, C6H3(N02)3>C6Hfl. — Trinitrobenzene is readily soluble in ben-
zene, crystals of it deliquescing rapidly in benzene vapour; these
solutions, on slow evaporation in the cold, yield hard, compact, bril-
liant, well-formed crystals of the new compound. They only retain
their brilliancy whilst preserved in an atmosphere of benzene vapour,
and are completely resolved into their components by a few hours*
exposure to air.
Trinitrohenzene-napJithalenej C6H3(N02)3,CioH9, separates on mixing
cold saturated solutions of trinitrobenzene and naphthalene ; it crystal-
lises in long white needles which melt at 152°, and can only be
recrystallised from alcohol containing naphthalene. Anthracene and
trinitrobenzene yield a red additive compound.
oi-Trinitrotoluene-naphthalene, C6H2Me(N02)3,CioH8, crystallises in
needles (m. p. 97 — 98^) closely resembling the trinitrobenzene com-
pound. Trinitrotoluene^anthracene crystallises from benzene in red
needles. A benzene-compound could not be obtained.
l3-Trin{trotolue7ie-naphthalene crystallises in yellowish-white needles
which melt at 100°. rj. Trinitrotoluene-na phthalene iorma ^ne yellowish-
white needles melting at 88 — 89°.
Metadinitrohenzene-naphthalene, C6H4(N'02)3,CioHf,, prepared by mix-
ing solutions of its components in benzene, crystallises in long
thick prismatic needles melting at 52 — 53°. Paradinitrobenzene-naph-
thalene forms long white needles melting at 118 — 119°, and is distin-
guished from the last by its ready solubility in alcohol.
Binitrotoluene-naphthalene, C6H3(N02)2Me,CioH8, closely resembles
the metadinitrobenzene-compound, and melts at 60 — 61°.
A. J. G.
Paradiethylbenzene. By H. Aschenbrandt (Annalen, 216, 211 —
223). — This compound is best prepared by mixing dibromobenzene
(25 g.) with ethyl iodide (50 g.), sodium (15 g.), and benzene (20 g.),
and leaving the mixture to itself for about a day and a half, by which
time the reaction comes to an end. 15 g. ethyl iodide are then added,
whereupon further action takes place, and the decomposition is com-
pleted by adding 10 g. more, and heating the mixture in a paraffin-bath
for two or three hours at about 150°. The product still contains
small quantities of bromine-compounds, from which it may be freed
by boiling it in a reflux apparatus with 3 or 4 grams of sodium cut
up into small pieces. 150 g. p-dibromobenzene thus treated yielded
15 to 16 grams of pure j9-diethylbenzene boiling at 181 — 182°.
p-Dietliylbenzenesulphonic acid, C6H3Et2.S03H. — The author, by heat-
ing 5 g. diethylbenzene with 20 g. fuming sulphuric acid on the wat-er-
bath, neutralising with lead carbonate, and decomposing the resulting
lead salt with hydrogen sulphide, obtained this sulphonic acid as a
brown rather viscid liquid which could not be brought to crystallise
even by prolonged exposure to freezing mixtures. Fittig and Konig
{Annalen, 144, 277), on the other hand, describe the same acid as
crystallising in colourless deliquescent laminae. .
The salts of this acid are, for the most part, easily soluble in water,
and (excepting the alkali-salts) are prepared by heating the acid with
the corresponding carbonates. The barium salt, (CioH,3S03)2Ba,4H20,
separates by rapid crystallisation in brilliant nacreous laminae ; by
ORGANIC CHEMISTRY. 319
slower crystallisation in fine rosettes of crystals ; it is but sparingly
soluble in alcohol. The strontium salt (4- 4H2O) separates from a
highly concentrated solution in large shining laminaa ; by slower crys-
tallisation in very fine compact monoclinic crystals. The calcium salt
(-|- 5H2O) crystallises in small laminae, more soluble than either of
the preceding salts. The magnesium salt, (CioHi3S03)2Mg, is less
soluble than the salts of the alkaline earths, and separates from dilute
solution in fine prismatic crystals. The nickel salt (+ 5H2O) is but
sparingly soluble, and separates from a concentrated solution in fine
green laminae. The cobalt salt (+ SHgO) crystallises from dilute
solutions in cruciform groups of red tablets, which, when cautiously
heated on platinum foil, change to a splendid blue, and melt to a deep
blue liquid.
Mercuric Salts. — On boiling the acid with mercuric oxide and con-
centrating the solution, shining yellow crusts separate, probably con-
sisting of a basic salt, whilst the mother-liquor yields the normal
salt, (CioHi3S03)2Hg, in small laminae, which, when once separated
no longer dissolve in water. The potassium salt,
C10H13SO3K + SJHsO,
obtained by precipitating the barium salt with potassium sulphate, is
very soluble in water, and crystallises therefrom in large nacreous
laminae, or by slower separation in thick tablets. The s&dium salt,
CioHiaSOaNa,
prepared in like manner from the strontium salt, is somewhat less
soluble than the potassium salt, and crystallises in large laminae. The
ammonium salt is extremely soluble in water, and crystallises in flat
well-defined plates. The silven^ salt, CloHisSOsAg, obtained by heating
the acid with silver oxide, is even more soluble than the potassium
salt, and separates from concentrated solutions in beautiful shining
tablets, which decompose on exposure to the air, with blackening and
separation of silver oxide.
p-Ethylbenzoic acid, C6H4Et.COOH, is obtained by heating p-di-ethyl-
benzene with dilute nitric acid, and may be purified by steam-distilling
the product which separates on cooling, then converting it into
the sodium salt, decomposing the latter with hydrochloric acid, and
digesting the precipitate with tin and hydrochloric acid to remove
traces of a nitro-acid. The acid thus prepared is identical with that
which Fittig and Konig obtained from a mixture of 0- and p-diethyl-
benzene, and crystallises from hot aqueous solution in bright shining
laminae ; it melts at 112 — 113°, and sublimes in laminae. The residue of
the steam- distillation above mentioned consists of a mixture of mono-
and dinitro-ethylbenzoic acids, together with terephthalic and nitro-
terephthalic acids.
_p-Bthylbenzoic acid is easily soluble in ether, alcohol, benzene, and
chloroform, and separates from these solutions in rhombic tablets and
prisms. The calcium salt, (C9H902)2Ca -|- 3H2O, obtained by pro-
longed boiling of the acid with calcium carbonate in a flask with
upright condensing tube, is slightly soluble in cold water, and crystal-
lises in colourless needles. The barium salt ( 4- 2H2O) obtained by
320 ABSTRACTS OF CHEMICAL PAPERS.
gentle boiling of the acid with barium carbonate, forms thin nacreoad
laminae, easily soluble in water. The strontium salt, prepared in like
manner, is very soluble, and crystallises in small laminae.
Nitro-p-ethi/lbenzoic acid, C6H3Et(N02)-COOH,. is obtained by dis-
solving j9-ethylbenzoic acid in cooled fuming nitric acid, and pour-
ing the resulting solution into cold water, as a crystalline precipitite
which may be purified by filtering, washing, and recrystallisation from
boiling water, and then separates in long shining needles, which turn
yellow when exposed to light, and on keeping split up into small
needle-shaped fragments. It melts at 155 — 156°^ dissolves readily in
alcohol, ether, benzene,, and chloroform, and separates therefrom in
needles or prisms. Its barium salt, [C9H9(N02)02]2Ba, crystallises in
tufts of needles only slightly soluble in water. The calcium salt
(+ 2H2O) is sparingly soluble, and crystallises in broad tufts of
needles. The strontiuvi salt (+ 4H2O) is also sparingly soluble, and
forms small, shining, faintly yellowish laminae. The sodium salt,
C9H8(N02)02Na + 2H2O,
crystallises in shining laminae, very soluble in water. The potassium
salt, C9H8(N02)K -f H2O, is much more soluble than the sodium salt,
and separates from a highly concentrated soluticm in long silky
needles.
p - JBromethylhenzene, C6H4Et.Br, was once obtained, in conse-
quence of using an insufficient quantity of sodium for the preparation
of p-diethylbenzene from p-dibroraobenzene by the process above
described (p. 318), in the form of a heavy liquid, boiling after careful
fractionation at 204". It remains quite colourless on keeping, refracts
light very strongly, has a strong smell of anise, and does not solidify in
freezing mixtures-. H. W.
Camphor-cymene, and the So-called Second Sulphonic Acid
of Paracymene. By P. Spica {Gazzetia, 12, 482— 488).— The state-
ments respecting the sulphonic acids obtained from camphor-cymene
do not quite agree (see Abstr., 1880, 878, 890; 1881, 174, 594, 602 ;
1882, 196). Paterno, in preparing the barium salt of ordinary campho-
cymenesulphonic acid, obtained also a small quantity of a less soluble
salt, which crystallised in white scales containing 1 or \\ mols. water.
Subsequently Paterno and Spica obtained, together with the ordinary
barium cymenesulphonate, a more soluble salt containing 12'02 p.c.
crystal- water. Jacobsen obtained from " isocymene " two sulphonic
acids, the barium salt of one of which, containing 12 p.c. water, was
regarded by Paterno and Spica as identical with the more soluble salt
which they obtained from camphor-cymene, Claus also obtained from
paracymene two sulphonic acids> one yielding a barium salt more
soluble than ordinary barium cymenesulphonate, and containing
3 mols. H2O like the ordinary salt. The sulphonic acid from this
salt melted at 130 — 131°, and yielded a lead salt containing 3H2O,
and a calcium salt containing 2H2O, like the ordinary calcium sul-
phonate; also sodium, potassium, and copper salts crystallising with
1 mol. H2O. To throw further light on the constitution of these
acids, the author has made experiments upon a large quantity of
ORGAXIC CHEMISTRY, 321
cymene prepared by the action of sulphur and red phosphorus on
camphor, carefully purified, and boiling at 175 — 178°. This was con-
verted into sulphonic acids ; these acids into barium salts ; the barium
salt containing 1 mol. H2O was converted into a sodium salt; and
from this latter, by heating it in sealed tubes at 190 — 200° with
strong hydrochloric acid, the corresponding hydrocarbon was obtained.
The examination of this hydrocarbon and its products of oxidation —
details respecting which the author will communicate in a subsequent
paper — showed clearly that the hydrocarbon in question consisted of
me^a-cymene. Hence it appears that when cymene is prepared from
camphor by the action of sulphur and red phosphorus, the paracymene
which forms the chief product is accompanied by metacymene ; and
that the mono-hydrated barium cymenesulphonate prepared from
camphor-cymene, is derived, not irom para- but from weto-cymene.
H. W.
1 4
Paradipropylbenzene, C12H18 = Pr^.CsHi.Pr*. By H. Kornee
(Annalen, 216, 223 — 232). — This hydrocarbon, obtained by the action
of sodium and propyl bromide on j9-dibromobenzene, is a colourless
strongly refracting liquid, having an aromatic odour like that of
sassafras oil, and not solidifying in freezing mixtures. It floats on
water, boils at 218 — 220°, volatilises with aqueous vapour, and bums
with a very smoky flame.
p-Dipropylbenzenesulphonic acid, OiaHigSOa = C6H3(C3H7)2.S03H, is
obtained by gently heating the hydrocarbon with a quantity of fuming
sulphuric acid sufficient to form a compound soluble in water. On
diluting the solution with water, supersaturating with lead carbonate,
precipitating the lead from the filtered solution with hydrogen
sulphide, evaporating the filtrate on the water-bath, and then leaving
it to evaporate in the exsiccator, the sulphonic acid is obtained in
thin colourless needles having a nacreous lustre ; they absorb water
rapidly from the air, and soon deliquesce. The lead salt,
[C6H2<C3H0^SO3],Pb + H2O,
obtained as above, crystallises in concentric groups of silky needles.
The harium salt (+ JH2O) forms slender colourless needles which
slowly give off their water in the exsiccator, and may be heated to
180° without decomposition. The calcium salt (-f- OHoO) crystal-
lises in large, colourless, highly lustrous, orthorhombic prisms, termi-
nated by two dome-faces. On exposure to the air it effloresces, and
quickly loses its lustre. The sodium salt, C6H3(C3H7)2.S03Na + 4H2O,
forms colourless very soluble laminae.
DimtrO'p-dipropylbenzene, Ci2Hi6(N02)3 = C6H2Pr2*(N02)2. — When
p-dipropylbenzene is added, with stirring, to cooled fuming nitric acid,
and the resulting solution is poured into cold water, two nitro-com-
pounds separate, both volatilising with steam, one solid at ordinary
temperatures, the other liquid. The quantity of the liquid compound
was too small for analysis ; the solid body, after washing vdth water,
repeated pressure between bibulous paper, drying, and several recrys-
tallisations from alcohol, exhibited the composition of dinitrodipropyl-
benzene. The crystals. of this nitro-compound are large, colourless,
322 ABSTRACTS OF CHEMICAL PAPERS.
nacreous, rectangular tablets, usaally with truncated summits. It
melts at 65°, volatilises with aqueous vapour, turns yellow in the air,
and dissolves with yellow colour in alcohol.
Dibromo-p-dipropylbenzene, CeHaPrj^Brs, is prepared by dropping
the hydrocarbon into excess of bromine, and removing hydrobromic
acid and excess of bromine by agitation with potash-lye, whereupon it
separates in white flocks which may be purified by washing with
water, pressing, drying, and solution in alcohol, from which the com-
pound separates in shining needles or rectangular plates melting at
about 48°.
p^Propylbenzoic acid, doHiaOz = CeHiPr^.COOH, is prepared by
boiling p-dipropylbenzene with a mixture of 1 vol. nitric acid (sp. gr.
1'3), and 3 vols, water, and separates, after some hours' boiling, in
loose masses of crystals. To purify it, the product is diluted with
3 vols, water, and distilled, with renewal of the water which passes
over; the distillate, after saturation with sodium carbonate, is dis-
tilled with steam to remove any unaltered nitro-dipropylbenzene ; the
residue of the distillation is then evaporated over the water-bath to a
small bulk ; the propylbenzoic acid, somewhat contaminated with
nitro-acid, is precipitated with hydrochloric acid ; and the precipitate,
after being dried and pressed, is treated with tin and hydrochloric
acid to remove the last traces of nitro-acid, and again distilled in a
stream of aqueous vapour.
p-Propylbenzoic acid crystallises from boiling water in small bril-
liant, six-sided, monoclinic prisms. It is insoluble in cold, and only
slightly soluble in boiling water, but dissolves readily in alcohol, ether,
benzene, chloroform, and carbon bisulphide, and separates from these
solvents in long broad needles resembling benzoic acid. It sublimes
undecomposed, volatilises readily with steam, and melts at 140°.
Barium propylbenzoate, (C3H7.C6H.i.COO)2Ba + 2H2O, obtained by
saturating the acid with barium carbonate, crystallises in large colourless
laminae or tablets having a satiny lustre, and less soluble than benzoate
or ethylbenzoate of barium. The calcium salt (-f- SHjO) forms moss-
like groups of fine satiny needles, more soluble than the barium salt.
The strontium salt (2JH2O) forms colourless shining laminae, some-
what sparingly soluble in water. The lead salt (2H2O) forms druses
of slender needles, nearly insoluble in cold, and only slightly soluble
in boiling water.
From the preceding facts, it appears that the jo-propylbenzoic acid
prepared by oxidation of jp-dipropylbenzene is identical with that
which Paterno and Spica obtained from isopropyl-propylbenzene
(Abstr., 1880, 296). By this coincidence, the constitution of the
latter acid is established, supposing that the reaction by which it
was formed was not attended with any molecular transformation of
normal propyl into isopropyl.
Nitro-p-propylbenzoic acid, C6H3Pr*(N02).COOH, separates in yellow
flocks on adding propylbenzoic acid to fuming nitric acid, and pour-
ing the acid solution into a large quantity of water. It is very solu-
ble in alcohol, ether, chloroform, and benzene, and crystallises from
alcohol in large, broad, colourless needles. It is nearly insoluble in
cold water, but melts in hot water to small oily drops, then dissolves in
ORGANIC CHEMISTRY. 323
moderate quantity, and crystallises on cooling in small, colonrless,
shining needles. The harium salt, [C9Hio(N02).COO]2Ba,4H20, crys-
tallises in colourless rectangular plates, sparingly soluble in cold,
easily in hot water. The strontium salt (SHjO) is sparingly soluble in
cold water, and crystallises in tufts of colourless needles. H. W.
A New Hydrocarbon. By E. Louise {Gompt. rend., 95, 1163 —
1164). — 120 grams of mesitylene are mixed with 20 grams benzyl
chloride, heated at 100°, and aluminium chloride gradually added
until evolution of hydrochloric acid ceases. The black product is
gradually added to water, and the yellow liquid which separates out is
distilled. When the fraction boiling between 295° and 305° is purified
it yields a liquid which boils at 300 — 303°. This new hydrocarbon,
henzyl-mesitylene, CeB.2M.ei.C^li^, forms a white crystalline mass with
a slightly yellow tinge, easily soluble in benzene, light petroleum,
alcohol, ether, acetic acid, acetone, &c., from which it separates in
small white needles. Benzyl-mesitylene melts at 31°, and will remain
in a superfused condition for several days, even if cooled repeatedly to
— 25°. When benzyl-mesitylene is dissolved in warm alcohol
saturated with picric acid in the cold, the liquid deposits on cooling
small citron-yellow needles, probably analogous in composition to the
compounds of hydrocarbons with picric acid described by Berthelot.
C. H. B.
The History of the Metanitrils. By W. Staedel (Ber., 15,
2864 — 2865). — A purely controversial paper.
Oxalic Acid Derivatives of Metanitro-paratoluidine and
3—4 Diamidotoluene. By 0. Hinsberg (Ber., 15, 2690—2694).—
On heating metanitro-paratoluidine with oxalic acid at 110 — 130°, the
two bodies, oxalylnitrotoluidide, C202(NH.C6H3Me.]N'02)2, and nitro-
tolyloxamic acid, COOH.CO.NH.CeHsMe.NOz + H2O, are formed.
The former has been described by Rudolph (Annalen, 209, 371). The
latter crystallises from dilute alcohol in yellowish-red plates, which
lose their water of crystallisation at 100°. Its ethyl-derivative
(m. p. 127 — 128°) splits up when boiled with alkalis, yielding nitro-
toluidine, oxalic acid, and alcohol. The sodium salt, C9H7N205Na -f
H2O, and the barium salt, CisHuNiOioBa + 3H2O, both crystallise in
yellow needles. The amido-compound, C202(NH.C6H3Me.NH2)2, ob-
tained on reducing oxalylnitrotoluide, crystallises in small colourless
needles. Heated to 130°, it loses one mol. H2O, and the compound
CieHieNiO is formed. At 300° a second mol. water is given off, with
formation of the anhydro-base —
... / N ^ . N ^
CeHgMe^ >C.Cf >C6H3Me,
which in its properties closely resembles the diamido-compound. On
reducing nitrotolyloxamic acid, water is eliminated and the body
2C9H8N2O2 + H2O is produced ; this is feebly acid and readily soluble in
alcohol, sparingly in water, from which it crystallises in colourless
needles, melting above 300° with slight decomposition. Its salts are
324 ABSTRACTS OF CHEMICAL PAPERP.
decomposed by carbonic anhydride. The author suggests three
formulea for this body, viz. : —
JSTR J^H.CO
I. CeH^Me/ >C.COOH, II. CeH3Me< | ,
^ N ^ ^NH.CO
1SB..C0
III. C6H3Me< I
^N : C.OH
but from its feebly acid properties he considers the last formula as
the most probable. A. K. M.
Crystalline Ciiniidine. By A. W. Hofmann (Ber., 15, 2895—
2897). — The author at the outset alludes to the industrial application
of the method devised by Martins and himself for the introduction of
the methyl-group into a phenyl residue (Ber., 4, 742). In the present
paper, the author describes a cumidine obtained by the action of
methyl alcohol on xylidine hydrochloride. This base agrees in
chemical and physical properties (m. p. 62°, b. p. 234°) with a cumidine
obtained by S chafer from pseudocumene. By the methyl ation of
cumidine, mono- and di-methyl cumidine are formed together with the
tetralcoholic ammonium iodide. Monomethylcumidiney CgHn-NHMe,
melts at 44°, and boils at 287° ; its platinochloride crystallises in
needles. Dimethylcumidine, C9HiiNMe2, is a fragrant oil boiling at
222° ; the methiodide, CgHnNMea, crystallises in prisms. These
compounds when heated yield the last member of the series of
methylated anilines, viz., pentamethyl-aniline, C6Me5.NH2, the pro-
perties of which the author proposes to study. Y. H. V.
The Three Isomeric Phenylenediamines. By E. Lellmaxn
(Ber., 15, 2839 — 2840). — The researches of Hiibner and Ladenburg
have established various differences in the chemical behaviour of the
three isomeric phenylenediamines. In the present communication the
author shows that under similar conditions the dithiocyanates of
these compounds undergo a dissimilar decomposition, for the ortho-
compound gives oi'thophenylenethiocarbamide, but the meta- and
para-compounds give the corresponding dithiocarbamides. Ortho-
phenylenethiocarhamide crystallises in glistening leaflets (m. p. 290°),
having an intensely bitter taste. MetapJienylenedithiocarhamide crys-
tallises from alkaline solutions in microscopic leaflets melting at 215°.
Paraphenylenedithiocarhamide crystallises from aqueous ammonia in
small colourless needles (m. p. 218°), sparingly soluble in alcohol.
V. H. V.
Substitution-products of Azobenzene. By H. Janovskt (Ber.,
15, 2575 — 2579). — Azobenzenemonosulphonic acid, formed by the action
of fuming sulphuric acid on azobenzene at 130°, yields aniline and
amidobenzeneparasulphonic acid on reduction with iron and hydro-
chloric acid. When azobenzene is treated at 150° with Nordhausen
acid containing 25 per cent. SO3, a mixture of three acids is obtained.
On diluting the acid liquid with water, the mixture of the a- and
ORGANIC CHEMISTRY. * 325
/5-disulplionIc acids solidifies to a crystalline mass. They can be
separated by fractional crystallisation of the free acids or of their
barium salts.
OL-Azohenzenedisulplionic acid, S03H.C6H4.!N'!!N".C6H4.S03H [4:1:1: 4],
crystallises in ruby-coloured needles containing 3 mols. H2O. It is
identical with the acid obtained from [1 : 4] benzenenitrosulphonic
acid. The ^-disulpJionic acid [3:1:1:3] forms yellow plates,
which are freely soluble in water. Its salts are more soluble than
those of the a-acid. On reduction with tin and hydrochloric acid, the
/3-acid yields amidobenzenemetasulphonic acid. The third acid, found
in small quantities in the mother-liquor of the a- and /3-acids, yields
aniline and amidobenzenedisulphonic acid on reduction. Its formula
is probably Ph.N2.C6H3(S03)2 [1:2: 4].
Two mononitro-derivatives are obtained by treating azobenzene-
parasulphonic acid with nitric acid (sp. gr. 1*41). The a-acid,
C6H4(N02).N2.C6H4.S03H, resembles azobenzenesulphonic acid in
appearance. It crystallises in golden scales belonging to the rhombic
system. The crystals are sparingly soluble in water, but dissolve
freely in dilute nitric acid. The salts of this acid are colourless. On
reduction, it yields an amidosulphonic acid which crystallises in pale
yellow monoclinic plates. The potassium salt forms rhombic plates.
/3-nitrazobenzenesulphonic acid, C6H4(N02).N2.C6H4.S03H [3:1:1:4],
is very deliquescent. Its salts have a yellow colour. Binitrazohenzene-
parasulphonic acid, prepared by the action of nitric acid (sp. gr. 1*45)
on azobenzenesulphonic acid, crystallises in microscopic needles. The
potassium salt explodes on heating. A trinitro-acid is formed when
nitric acid (sp. gr. 1*5) is employed. Its salts are very explosive.
W. 0. w.
Formation of Anilides. By G. Tobias {Ber., 15, 2866—2876).—
This paper consists of a series of observations on the conditions
attending the formation of the anilides. The author has confirmed
the results of Willm and Girard as regards the formation and pro-
perties of the formyl-derivatives of diphenylamine ; he finds furthef
that ethylaniline reacts with formic acid, but the resultant anilide
cannot be obtained in the pure state. Attention is also drawn to the
fact that formic acid acts more readily than acetic acid to form the
anilide. Thus 15*7 per cent, formic acid heated with the equivalent
quantity of aniline for four hours gave 79 per cent, of the theoretical
yield of the anilide, but 15 per cent, acetic acid under the same con-
ditions gave only 18 per cent, after 36 hours.
The author also criticises the observations of Menschutkin on the
decomposition of acetanilide by water containing a trace of acetic
acid ; he considers that the change is effected by the acetic acid, and
is inclined to maintain the view that pure acetanilide is unaffected by
pure water, and that the same result would hold good with pure
formanilide. Y. H. V.
Formanilide and its Homologues. By G. Tobias {Ber., 15,
2443 — 2452). — The author has made a series of experiments to prove
that aniline reacts more completely and more rapidly with formic than
with acetic acid to form the anilide. Thus, under similar conditions,
VOL. XLIV. z
326 ABSTRACTS OF CHEMICAL PAPERS.
90 per cent, of the theoretical quantity of the formanilide, but only
35 per cent, of the acetanilide was obtained. Traces of mineral acids
and the presence of large qnantities of water exert a material influence
on the preparation of the formanilide. When 1 mol. anhydrous
formic acid acts on 1 mol. aniline, the reaction limit reaches 98 per
cent, of the theoretical quantity.
Formorthotoluide, H.CONH.C6H4Me, from orthotoluidine and
formic acid, crystallises in white glistening leaflets melting at 68°;
formoparatoluide, from paratoluidine, crystallises in compact crystals,
melting at 52° ; oL-najpTitliylformamide, from a-naphthylamine, crys-
tallises in white silky needles, melting at 138"5° ; y3-naphthyl forma-
mide, from /3-naphthylamine, crystallises in glistening leaflets, melting
at 128°. By the action of metaphenylenediamine on formic acid, a
substance was obtained in refractive crystals melting at 155°, soluble
in hot water and alcohol, and giving no reaction with the nitrites of
the alkali-metals unless previously heated with hydrochloric acid.
The substance in question was probably diformylmetaphemjlenediamine,
although the results of the analyses showed that it was not quite pure.
On passing dry hydrochloric acid through formanilide, methenyl-
diphenyldiamine was obtained (a result in accordance with the re-
searches of Hofmanii and others), with considerable evolution of
carbonic oxide. Methenyldiphenyldiamine easily reverts to its two
components, aniline and formanilide. The sodium salts of formortho-
and para-toluide crystallise in glistening leaflets, which rapidly absorb
carbonic anhydride from the air. Y. H. V.
Decomposition of Acetanilide by Water. By N. Menschutkin
{Ber., 15, 2502 — 2505). — After some remarks on the general
concordance of his quantitative results with L. Meyer's quali-
tative experiments on the decomposition of acetanilide with water
(this vol., p. 56), the author takes exception to the observation that
acetanilide is not decomposed by water. Although, when pure water
is heated with acetanilide, no reaction occurs even after an interval of
150 hours, yet if a trace (t^o) of acetic acid is added, a different
result is obtained; about ly"75 per cent, of the acetanilide being de-^
composed when a mixture of 1 mol. acetanilide with 1'103 mols. of
water is heated for some hours. Experiments were also made to
determine the effect on the limit of the reaction, caused by altering
the proportion of water, and the following were the results : —
Proportion of
acetanilide to water. Limit of reaction.
1 : 0-87 86-50 per cent.
1 : 0-88 84-41
1 : 0-9 81-31
These experiments show that acetanilide is decomposed by water,
and that the reactions between aniline and acetic acid on the one hand,
and acetanilide and water on the other, are reversible according to the
conditions of the experiment. The author further shows that an
increase in the proportion of acetic acid is favourable to the production
of the acetanilide — a result which is in accordance with the observation
ORGANIC CHEMISTRY. 327
of Berthelot, that an increase of acetic acid favours its etherification
by alcohol. V. H. V.
Aromatic Arsenic- and Antimony-compounds. BjA.Michaelis
and A. Reese (Ber., 15, 2876— 2877).— The authors show that tri-
phenylarsine is best prepared by the action of sodium on a mixture of
arsenic trichloride, monobromobenzene, and ether. On filtration and
evaporation of the ethereal solution, the compound separates out as a
solid mass, which can be readily purified by crystallisation from
alcohol. By a similar process the corresponding antimony-compound
may be obtained in the form of golden leaflets melting at 48°, soluble
in ether and benzene, insoluble in water and hydrochloric acid. If the
sodium is not in excess, crystalline bromo- and chloro-addition products,
SbPhgBra and SbPhaCL, are formed, but cannot be separated from the
free stibine. The author suggests the above process for the prepa-
ration of the aromatic silicon, boron, and metallic derivatives.
Y. H. V.
New Nitro-derivatives of Phenol. By R. Henrtqu^s (Annalen,
215, 321 — 344). — So far no isomerides of picric acid have been ob-
tained; Bantlin (this Journal, 1875, 6'40) stated that he had prepared
isopicric acid by boiling the dinitro phenols obtained from metanitro-
phenol with nitric acid ; but he found later (this Journal, 1877, ii, 475)
that the substance was trinitroresorcinol (styphnic acid). The author
has re-investigated this reaction, and succeeded in obtaining two new
trinitrophenols.
7-Dinitrophenol is dissolved in three times its weight of concen-
trated nitric acid in the cold, and the solution, after standing for 36 to
48 hours, is poured into water, when an oily mixture separates ; the
free nitric acid is neutralised with ammonia, and the nitrophenols are
extracted with ether. The ethereal solution is evaporated to dryness and
treated with steam to remove unaltered dinitrophenol ; the residue is
dissolved in water, treated with barium carbonate, and evaporated to
dryness ; and the barium derivatives are treated with absolute alcohol.
The residue then consists of barium styphnate, together with a small
quantity of the barium salt of a tetranitrodihydroxybenzene (see later).
The alcoholic solution contains the barium salts of /?- and 7-trinitro-
phenol, which can be separated by fractional crystallisation. The
yield of the trinitrophenols is only about one-sixth of the dinitro-
phenol employed.
Bantlin concluded that 7- dinitrophenol had the constitution
[OH : NOa : NO2 =1:3:5]. As this, however, is in contradiction to its
ready conversion into trinitroresorcinol, in which the two OH-groups
are known to be in the meta-position, the author has re-investigated
the question. 7-Dinitrophenol was heated for a short time at 100° with
methyl iodide and methyl alcohol, when the anisoil of melting point 96*
was obtained. This was heated with alcoholic ammonia at 200 —
210° ; the resulting dinitraniline, on treatment with ethyl nitrite, gave
a readily sublimable mass of m. p. 170°. (Paradinitrobenzene melts
at 171 — 172°, whilst metadinitrobenzene, which should have been
formed according to Bantlin's hypothesis, melts at 90°.) From this,
it is evident that the constitution of 7-dimtrophenol would be
[1:3:6] (OH in 1).
z 2
328 ABSTRACTS OF CHEMICAL PAPERS.
The nitration of e-dinitrophenol [1 : 2 : 3] is best effected by adding
it to well-cooled nitric acid, and, after two or three hours, pouring
into water, the subsequent treatment being similar to that given for
the 7-compound. It yields trinitroresorcinol and 7-trinitrophenol.
o-Dinitrophenol [1:3:4] yields on nitration trinitroresorcinol,
/3-trinitrophenol, and possibly another trinitrophenol in small quantity,
as after the treatment with ammonia, the aqueous solution was found
to contain a dinitramidophenol, apparently not derived from /5-trimtro-
phenol.
The new trinitrophenols closely resemble picric acid ; they have a
bitter taste, readily decompose carbonates, detonate on heating, yield
explosive salts, and give crystalline compounds with some hydrocarbons.
^-Trinitrophenol, C6H2(N02)3.0H. (m. p. 96° uncorr.), being derived
from both d- and 7-dinitrophenols, must have the constitution
[1:3:4:6] (OH in 1). It crystallises in white satiny needles or plates,
is very readily soluble in alcohol, ether, and benzene, moderately
soluble in hot water, sparingly in cold water and dilute acids. The
harium derivative, [C6H2(N02)30]2Ba + 4H2O, crystallises in reddish-
brown prisms, and only completely loses its water on long heating
at 150°; it is moderately soluble in water and alcohol. The potassium
derivative forms anhydrous, brilliant, clear- red crystals of violet reflex ;
it is sparingly soluble in water, nearly insoluble in alcohol. Solu-
tions of the salts of /3- trinitrophenol give a yellow precipitate with lead
salts, which can be obtained crystallised in needles, and a reddish-
brown flocculent precipitate with silver salts. On gently heating it
with nitric acid, ^-trinitrophenol is converted into trinitroresorcinol.
Naphthalene unites with ^-trinitrophenol, giving a compound of the
formula CioIl8,C6H2(NO)3.0H; it crystallises in yellow needles, which
melt at 72 — 73°, and are readily soluble in alcohol. Phenanthrene
does not yield a similar compound.
r^-Trinitrophenol is obtained from 7- and e-dinitrophenol, and there-
fore has the constitution [1:2:3:6]. It crystallises in white
needles (m. p. 117 — 118°), behaves towards solvents like /3- trinitro-
phenol, and is also converted into trinitroresorcinol on oxidation with
nitric acid. The harium derivative, [C6ll2(N02)30]2Ba, crystallises in
clear brown to golden-yellow scales, frequently united in rosettes ; it is
not very soluble in water or alcohol. (In the preparation of 7-trinitro-
phenol from 6-dinitrophenol, barium salts were obtained in small
quantity, crystallising with 1 and 3 mols. H2O, but all attempts to
prepare such hydrates from the anhydrous barium salt were unsuc-
cessful.) The potassium salt crystallises in deep-red anhydrous
needles, readily soluble in water with red colour, nearly insoluble in
alcohol ; the aqueous solution dyes wool and silk of an orange colour.
Solutions of 7-trinitrophenol salts give a dark-yellow precipitate with
lead salts ; a reddish-brown flocculent precipitate with silver salts, and
no precipitate with copper or mercuric salts. With naphthalene, a
compound of the formula CioH8,C6H2(N02)3.0H is obtained in golden-
yellow needles, which melt at 100°.
^'Dinitroamidophenoly C6H2(N02)2(NH2).OH, isomeric with picramic
acid, is obtained, as previously described, by treating the trinitro-
phenols from ^-dinitrophenol with aqueous ammonia j it crystallises in
ORGANIC CHEMISTRY. 329
brilliant red needles, melting at 202°, and subliming readily. It is
nearly insoluble in ether, water, and mineral acids, sparingly soluble
in absolute alcohol, but dissolves readily in solutions of alkalis or
alkaline earths with formation of salts. The potassium derivative crys-
tallises in clear yellow needles, readily soluble in water ; it explodes
feebly on heating.
Tetranltrodihydroxyhenzene, C6(N02)4(OH)2, obtained in small quan-
tity in the nitration of 7-dinitrophenol, crystallises in yellowish or
colourless needles, which melt at 166°, and are readily soluble in alcohol
and ether, sparingly in water. The barium derivative, C6(N'02)402Ba +
6H2O, crystallises in golden-yellow silky needles ; when anhydrous, it
acquires a cherry-red colour. It is sparingly soluble in water, inso-
luble in alcohol.
The constitution of styphnic acid is also settled by these experiments.
It has long been known to be a resorcinol derivative, and being
formed by the oxidation of both (3- and 7-trinitrophenol, it must have
the constitution [OH : NO3 : OH : NO2 : NO2 =1:2:3:4:5].
A. J. G.
Conversion of Tolylenediamine into an Amidocresol and
7-Orcinol. By 0. Wallace (Ber., 15, 2831— 2835).— In order to
determine the constitution of the monacetotolylenodiamine already
described by the author, with a view of deciding between the
formula NH2.C6H3Me.NH5^ [Me : NHo : ^Kl^ = 1:2:4] or
[Me : NHXc : NH2 =1:2:4], the author converted it into an amido-
cresol, and compared it with the amidocresol obtained by Knecht
from nitrotoluidine (Abstr., 1882, 728). By the action of nitrous acid
on monacetotolylenediamine, an acetamidocresol, OH.CeHaMe.NIlAc,
is formed; it crystallises in large leaflets (m. p. 224)°, sparingly
soluble in cold water, soluble in alcohol. When the acetamidocresyl
is boiled with hydrochloric acid, it is converted into amidocresol
chloride, which crystallises in leaflets, soluble in water and alcohol.
The free amidocresol is obtained by precipitating an aqueous solution
of the hydrochloride with potassium hydrogen carbonate ; it forms
needles melting at 15y°, sparingly soluble in cold water. This
amidocresol is not identical, but isomeric with the amidocresol ob-
tained by Knecht from nitrotoluidine, which has the constitution
[Me : NO2 : OH =1:2:4]; it is therefore a derivative of ortho-
cresol, and has the constitution [Me : OH: NO2 = 1 : 2 : 4]. The
author has re-examined the former amidocresol, and finds that its
hydrochloride gives no colour reaction with ammonia as described by
Knecht ; it crystallises in leaflets melting at 138°, sparingly soluble
in cold water.
The amidocresol melting at 159° is converted by the diazo reaction
into 7-orcinol, C6H3Me(OH)2 [Me : OH : OH = 1 : 2 : 4], identical with
the cresorcinol of Knecht. V. H. V.
Synthesis of Indole from Cuminol. By O. Widman (Ber., 15,
2547 — 2553). — Nitrocumic acid can be prepared by the action of
a glacial acetic acid solution of chromic acid on nitrocuminol. When
an alkaline solution of this acid is treated with a concentrated solu-
tion of potassium permanganate, it is converted into nitrohydroxy-
330 ABSTRACTS OF CHExMICAL PAPERS.
jDropjlbenzoic acid, CMe2(OH).C6H3(N03).COOH, which is obtained
as a crystalline precipitate on acidifying the cold solution with hydro-
chloric acid. A good yield of nitroliydroxyprojpylhenzoic acid can also
be obtained by the direct action of potassium permanganate on nitro-
cuminol. This acid is deposited from a hot aqueous solution in colour-
less needles melting at 190°, freely soluble in alcohol and ether.
The ammonium salt crystallises in needles, and the silver salt in
rhombic prisms or plates. The ethylic salt forms rhombic plates,
melting at 96^. It is freely soluble in the usual solvents, with the
exception of light petroleum. It is decomposed by warm hydrochloric
acid, forming nitropropenylbenzoic acid. Sodium azoxypropijlbenzoate^
(CioHioN03!N'a)2 -f IOH2O, is obtained by the action of sodium amalgam
on an aqueous solution of nitrohydroxypropylbenzoic acid, in rect-
angular plates, exhibiting a brilliant red colour. The free acid crystal-
lises in yellow plates, insoluble in alcohol, ether, and benzene. It i«
not decomposed by hot hydrochloric acid.
Nitropropenylbenzoic acid, C10H9NO4, prepared by boiling nitro-
hydroxypropylbenzoic acid with hydrochloric acid (sp. gr. I'lO),
crystallises in colourless needles (m. p. 154°), which dissolve freely in
alcohol and ether, but are sparingly soluble in water. The ammonium
and silver salts of this acid crystallise in needles. The methyl and
ethyl salts are uncrystallisable oils.
On distillation with lime, nitropropenylbenzoic acid yields indole,
C10H9NO4 -h CaO = CSH7N + CaCOa + H2O + CO. W. C. W.
Brominated Derivatives of Toluquinone. By F. Canzonebi
and P. Spica (Gazzetta^ 12, 469 — 475). — Tribromotoluquinone^
CTHsBraOa - CeMeBraOs,
is obtained, as chief product, on agitating toluquinone, in presence of
a little water, with a quantity of bromine rather more than sufficient
to form the monobromo-derivative, the liquid becoming warm and
yielding as it cools a brown viscid mass, from which alcohol removes
a resinous portion, leaving undissolved a yellow crystalline substance
obtainable by repeated crystallisation from alcohol in broad golden-
yellow laminae which melt with slight blackening at 223°. The sub-
stance thus prepared has nearly the composition of tribromotolu-
quinone, but contains only 66"06 to 66*82 per cent, bromine, whereas
the formula of that compound requires 66'85 per cent., the deficiency
being due to the presence of less highly brominated compounds
formed at the same time and very difficult to separate. The pure
tribro mo- derivative may however be obtained by oxidising tribromo-
toluquinol (next page) with ferric chloride, in which case it separates
in rather smaller laminae having the same crystalline form, a bright
golden-yellow colour, and melting at 235 — 236°. It is insoluble in
water, but very freely soluble in ether and in benzene, very sparingly
in cold alcohol ; it dissolves with partial resinification in potash, also
in sulphuric acid, from which it is precipitated by water.
The same tribromotoluquinone is also formed by the action of sul-
phuric acid, manganese dioxide, and potassium bromide on commercial
cresol, and lastly, together with a more highly brominated compound,
ORGANIC CHEMISTRY. 331
by subjecting cresol to the simultaneous action of bromine and iodine.
Being thus obtained by three different processes, it may be reo-arded
as the one of the three possible tribromotoluquinones, which is most
easy of formation.
With regard to its constitution, it may be observed that the tolu-
quinone from which it was prepared, having been formed from ortho-
toluidine, must have the constitution Ce-Me.O.H.H.O.H, and therefore
its tribromo-derivative must be represented by the formula —
Ce.Me.O.Br.Br.O.Br;
and this view is in accordance with its formation from commercial
cresol which, although it contains the three isomeric cresols, is capable
of yielding only one tribromotoluquinone, inasmuch as para-cresol
cannot furnish a quinone at all, and ortho- and meta-cresol must
necessarily yield the same tribromotoluquinone.
Tdbromotoluquinol, C7H3Br3(OH)2 = C6MeBr3(OH)2, is formed by
the prolonged action of sulphurous anhydride on tribromotoluquinone
suspended in water, the colour of the substance changing from yellow
to white. On filtering and treating the residue with cold alcohol,
the tribromoquinol dissolves, the solution when mixed with water
depositing a flocculent precipitate, which when purified by successive
crystallisation from water and from alcohol, yields the tribromotolu-
quinol in white or faintly reddish needles melting at 201 — 202°. The
same product is obtained by reducing tribromotoluquinone with tin
and hydrochloric acid. Its alcoholic solution, treated with excess of
ferric chloride, yields a precipitate of tribromotoluquinone.
The anilide of tribromotoluquinone,
CigHisBraOa = CeMeBrsOa I (NHPh)^,
appears to be formed, together with other anilides, on boiling an
alcoholic solution of the tribromoquinone with excess of aniline, the
product separating on cooling in black shining crystals, infusible and
nearly insoluble in alcohol.
Bihromoboluquinone, CsHMeBraOi. — The alcohol which had been
used for washing the tribromoquinone yielded on fractional evaporation
an additional quantity of the latter, together with products of lower
melting point mixed with resinous matter; and the remaining mother-
liquor, when filtered and left at rest, deposited yellow crystals (m. p.
about 100"^) which, after repeated crystallisation from dilute acetic
acid, yielded, as the constituent most soluble in that liquid, yellow
crystals melting at 85°, and having the composition of dibromotolu-
quinone ; the same substance, mixed with traces of the tribromo-
quinone, is also found in the alcohol which has been used for crystal-
lising the latter, and separates in small quantity on adding water.
The same products were obtained by the use of ether instead of alcohol,
the proportion of dibromotoluquinone thereby produced being however
some^N hat larger. H. W.
Orthamidobenzaldehyde. By P. Friedlaender {Ber., 15, 2572
- — 2575). — Orthamidobenzaldehyde is best prepared from anthranil,
which is obtained from crude nitrobenzaldehyde by the process pre-
332 ABSTRACTS OF CHEMICAL PAPERS.
viously described by the author (Ber., 15, 2105). A mixture of pure
antbranil, ferrous sulphate, and ammonia is gently heated until the
odour of anthranil is no longer perceptible. On distillation in a cur-
rent of steam, orthamidobenzaldehyde is found in the distillate in
shining scales melting at 39°. The crystals are freely soluble in alcohol,
ether, benzene, and chloroform. Amidobenzaldehydo forms a crys-
talline compound with mercuric chloride and with hydrogen sodium
sulphite. Acetorthamidobenzaldehyde crystallises in long needles
melting at 71°. When this compound is heated with acetic anhydride
and sodium acetate, carbostyril is produced. Attempts to prepare salts
of amidobenzaldehyde were unsuccessful.
Quinoline is produced on warming a mixture of this aldehyde with
acetaldehyde and soda solution.
The ready conversion of anthranil into amidobenzaldehyde is in
CO
favour of the view that the constitution of anthranil is C6H4<^ | .
W. C. W.
Bromacetophenone. By R. Mohlau {Ber., 15, 2464— 2466).— After
a description of the numerous difficulties which attend the formation of
bromacetophenone by dropping bromine into a solution of acetophenone
in carbon bisulphide, the author proposes the substitution of acetic
acid for the carbon bisulphide, as being a better solvent of the water
and hydrobromic acid formed in the reaction. Adopting this change,
the author, in a. test experiment, obtained 80 per cent, of the theo-
retical quantity of bromacetophenone. V. H. V.
Action of Bromacetophenone on Phenol. By R. Mohlau
(J5er., 15, 2497 — 2500). — The intoduction of the benzoyl-group into
the molecule of methyl bromide, and the readiness with which the
resultant bromacetophenone reacts with the primary amine, points to
bromacetophenone as possessing the character of an acid bromide. In
order to examine this hypothesis, the author has studied the action of
phenol on bromacetophenone, and finds that no action occurs unless
the hydrogen of the phenol is previously replaced by a metal, when
acetophenone phenyl .ethevy COPh.CH2.OPh, is produced. This sub-
stance crystallises in colourless prisms, melting at 72°, soluble in
alcohol, and decomposed by fusion with potash into phenol and
phenylmethy 1 keto ne .
Acetophenone paranitrophenyl ether,
COPh.CH2.0.C6H4.N02 [0 : NO2 = 1 : 4],
formed by the action of sodium paranitrophenol and bromaceto-
phenone, crystallises in golden prisms melting at 144°, sparingly
soluble in alcohol, insoluble in water, decomposed by molten alkali
into paranitrophenol and phenyl-methyl ketone. Orthonitrophenol
does not undergo a similar reaction. These results show that brom-
acetophenone possesses the character rather of an alcoholic than of an
acid bromide. V. H. V.
Acetophenoneanilide. By R. Mohlau (Ber., 15, 2466—2480;
compare Abstracts, 1881, 262). — The hydrochloride of acetophenone-
ORGANIC CHEMISTRY. 333
anilide, C0Pli.CH2.NHPh,HCl, is obtained by passing hydrochloric
acid into an ethereal solution of the anilide ; it forms glistening pris-
matic crystals, decomposible by water into its constituents. The
hydrobromide forms polysynthetic prisms.
AcetylacetopJmioneanilide, COPh.CHa-NPhS^, crystallises in rhombic
prisms melting at 126°, insoluble in water, sparingly soluble in_alcohol
and ether. Benzoylhromacetophenoneanilide^ COPh.CH^.NPhBz, crys-
tallises in glistening prisms melting at 145°, insoluble in water, soluble
in alcohol and ether.
The product of the action of nitrous acid on acetophenoneanilide
is dependent on the conditions of the reaction ; in presence of alcohol
nitroacetophenoneanilide is formed ; in presence of glacial acetic acid,
nitrosoacetophenonenitr anilide. Nitrosoacetophenoneanilide crystallises
in golden prismatic needles melting at 73°, insoluble in water, easily
soluble in alcohol, ether, &c. ; soluble in potash, with formation
of a red colour. It readily gives Liebermann's reaction for nitroso-
compounds. Nitrosoacetophenonenitranilide crystallises in glistening
leaflets, insoluble in water, easily soluble in ether ; soluble in potash
with a red colour. On boiling an alcoholic solution of this compound
with concentrated hydrochloric acid, it is converted into acetoplienone-
nitraniUde, COPh.CH2.NH.C6H4.NO2, which forms glistening golden,
needles, melting at 167"^ ; it can readily be reconverted into the nitroso-
derivatives by nitrous acid. On oxidation it yields benzoic acid, and
on reduction acetophenone and paraphenylenediamine ; these results
show that the nitro-group is in the anilide radical, and that the nitro-
group is in the para-position to the imido-group.
By the action of fuming nitric acid on acetophenoneanilide, SbdinitrO'
derivative, COPh.CH2.NH.C6H3(N02)2, is obtained, which crystallises
in golden prisms, melting at 171° ; on oxidation it yields benzoic acid,
and on reduction, acetophenone and Will's triamidobenzene
[JSTHa : NH2 : NH2 =1:2:4],
and therefore the constitution of the acetophenonedinitranilide is
[NH : NO2 : NO2 = 1:2:4]. Y. H. V.
Oxidation of Durene by Chromic Acid. — Dinitrodurylic
Acid. By R. Gissmann (Annalen, 216, 200— 211).— When durene,
CeHoMci [1 : 2 : 4 : 5], is subjected to the action of chromic acid
or other powerful oxidising agents, only one of its methyl-groups is
converted into a carboxyl-group, the greater part of the substance
being completely broken up. The oxidation is best effected by treating
durene with the calculated quantity of chromic acid, both dissolved in
glacial acid. On pouring the resulting green liquid into water, part
of the oxidised product separates as a white flocculent precipitate, and
a further quantity may be obtained by precipitating the chromium from
the hot filtered liquid with caustic soda, filtering again, and super-
saturating with hydrochloric acid. The product thus obtained is
durylic acid, C10H12O2 = C6H2Me.COOH [formerly called cumylic acid].
It dissolves very sparingly in cold, more readily in hot water, from
which it crystallises in needles ; with moderate facility in alcohol, ether,
and benzene, and separates from the latter in long thick transparent
334 ABSTRACTS OF CHEMICAL PAPERS.
strongly refracting prisms ; it sublimes between watch-glasses in long
needles, volatilises completely with aqueous vapour, and melts at
150°.
Jannasch (Zeits. f. Chem., 6, 449), by oxidising durene with dilute
nitric acid, obtained, in addition to durylic (cuinylic) acid, a bibasic
acid, C6H2Me2(COOH)2, which he called cumidic acid. The oxidation
of durene by chromic acid in acetic acid solution does not appear to
yield a bibasic, or any more highly basic acid.
Dinitro-durylic acid, CMe3(N02)2-COOH, is obtained by gradually
adding durylic acid (1 pt.) to strong nitric acid (10 pts.), in which it
dissolves immediately, with copious evolution of red vapours. On
pouring the cooled solution into water, a flocculent precipitate sepa-
rates ; and on distilling this with steam, there passes over, together
with unaltered durylic acid, a small quantity of a yellowish low-melting
compound, insoluble in alkalis, which the author regards as probably
consisting of nitrotrimethylbenzene, formed by exciiange of one of
the carboxyl-groups for a nitro-group.
The non-volatile part of the product separates on cooling as a finely
divided precipitate ; and on boiling this with water and pounded
calcspar, a calcium salt is obtained, which, when purified by recrystal-
lisation and treated with hydrochloric acid, yields dinitrodurylic
acid as a yellowish powder, melting at 205°, slightly soluble in cold,
more readily in hot water, and always separating therefrom as an
amorphous deposit. It dissolves very readily in ether, chloroform,
and benzene, but does not separate from either of these solvents in
characteristic crystals. On dissolving it in alcohol, adding just suffi-
cient water to produce turbidity, and boiling the liquid till it becomes
clear again, this clear solution yields large transparent prisms, which
before redissolving melt to a transparent oil. The same compound
was once obtained in very well-defined prisms from a solution of the
dinitro-acid in alcoholic ether. The crystals quickly become cloudy
when dried in the air, and when left over sulphuric acid they entirely
lose their crystalline form, and are reconverted into dinitrodurylic
acid. They probably consist of an unstable compound of this acid
with alcohol of crystallisation. Their formation affords a ready means
of obtaining the acid in great purity.
Calcium dinitrodurylate, [C6Me3(N02).COO]Ca,3H20, obtained by
neutralisation, crystallises from a highly concentrated solution in
radiate groups of shining needles, easily soluble in hot, sparingly in
cold water. It explodes violently when heated on platinum foil.
The barium salt forms slender silky peach-blossom-coloured needles,
likewise containing SHgO, and dissolving in water with moderate
facility.
Monobromodurene, C6HBrMe4, is formed, together with the dibromo-
compound, on gradually adding bromine (2 mols.) to durene (1 mol.),
both dissolved in glacial acetic acid ; and on pouring the contents of
the flask, which are nearly colourless after 12 hours' action, into a
considerable quantity of cold water, a white flocculent precipitate is
obtained, consisting of a mixture of mono- and di-bromodurene, easily
separable by distillation with steam, the monobromo- compound pass-
ing over much more readily than the other. The solution of the dis-
ORGANIC CHEMISTRY. 335
tillate in boiling alcohol yields monobromodurene in thin shining
lamina3, which after several recrjstallisations melt at 61°, while the
mother- liquor deposits a small quantity of another bromine-compound
in needles melting at 199°. This latter, which is obtained in larger
quantity by repeated crystallisation of the residue of the distillate,
bears considerable resemblance in external aspect to monobromopseudo-
cumene.
Bromodurene, obtained as above, crystallises in thin nacreous laminas,
sparingly soluble in cold, readily in hot alcohol, also in ether and
benzene. It volatilises with aqueous vapour, and melts at 61°. It is
the fourth crystalline monobromo-derivative of a benzene-homologue,
the previously known members of the series being parabromotoluene
(m. p. 28*8°), bromoparaxylene (9 — 10°), and bromopseudocumene
(73°). H. W.
ProtocateclmtanniG Acid and Anhydrides of Aromatic
Hydroxycarboxylic Acids. By H. Schiff (Ber., 15, 2588—2592).
When a mixture of phosphorus oxychloride and parahydroxybenzoic
acid is gently warmed at a temperature not exceeding 50"", tetraparoxy-
henzoid, C28H18O9, is produced. It is a white insoluble powder, which
is decomposed by heat without melting. Under similar treatment
met ahydroxy benzoic acid yields dimetomyhenzoid, CuHioOs, aud octo-
metoxybenzoid, C56H34O17. The former compound melts between 130°
and 135°, and is soluble in hot alcohol ; the latter is an amorphous
powder melting at 160 — 165°, insoluble in alcohol, but freely soluble
in chloroform. These condensation-products do not give a coloration
with ferric chloride.
When ether is added to an aqueous solution of protocatechuic acid,
which has been boiled for some hours with arsenic acid, the liquid
separates into three layers, and on evaporating the middle layer,
diprotucatechuic acid, CuHioO? remains as a hygroscopic vitreous mass,
soluble in water and alcohol. This compound produces a green colora-
tion in a solution of ferric chloride, but it resembles tannin in its
other reactions. TetraprotocaiecJmtatinic acid, C28H18O3, obtained by
the action of phosphorus oxychloride on an ethereal solution of proto-
catechuic acid, dissolves slowly in water. It gives a green coloration
with ferric chloride, and bright red with alkalis.
Katellagic acid, CuHioOj, is formed when a mixture of dry arsenic
and protocatechuic acids is heated at 160°. It dissolves in nitric acid,
yielding an orange-coloured liquid. Qallamide, C7H7NO4 -f 1^1120,
prepared by the action of ammonia on digallic acid, forms large colour-
less crystals. Gallanilide is deposited as a crystalline mass when
digallic acid is dissolved in aniline. W. C. W.
Allyloxybenzoic Acids. By S. Scichilone (Gazzetta, 12, 449 —
454). — The methylic and ethylic salts of these acids are prepared by
a reaction analogous to that which yields the corresponding alkyl
salts of methoxy benzoic acid and its homologues, viz., by heating the
methylic or ethylic salts of the three hydroxybenzoic acids in sealed
tubes with, molecular proportions of allyl iodide and potassium
336 ABSTRACTS OF CHEMICAL PAPERS.
hydroxide in alcoholic solution, methylic allylsalicylate, for example,
by heating methyl salicylate (Gaultheria oil) with allyl iodide and
alcoholic potash for nine hours at 120°, the reaction being represented
1 2
by the equation C6H4(OH).COOMe + CaHJ + KOH = H^O +
KI + CeH^COCsHs^COOMe.
Methylic allylsalicylate thus prepared, and purified by treatment
with water, drying with calcium chloride, and repeated fractional dis-
tillation, is a colourless or faintly yellow liquid, having a fragrant
aromatic odour, and boiling at 245°. By saponifying it with excess of
aqueous potash, and treating the product with excess of hydrochloric
acid, allylsalicylic acid, C6H4(OC3H5).COOH, is obtained as a
mass of transparent needles, which after purification by repeated crys-
tallisation, melt at 113°. This acid crystallises well from very weak
spirit, but from stronger alcohol it separates as an oily liquid, and
retains that form even on evaporating the solvent, or leaving it in a
vacuum. It may however be made to crystallise readily by dissolving
it in alcohol, even at ordinary temperature, and quickly diluting the
solution with a large quantity of water, whereupon the liquid becomes
milky, but recovers its transparency after a few hours, and then yields
very beautiful needles of allylsalicylic acid. The author has in
several instances found this method of crystallisation very useful for
purifying substances, which, in presence of foreign matters, tend to
assume an oily consistence.
Allylsalicylic acid is tasteless and inodorous, very soluble in alcohol,
ether, benzene, and chloroform, moderately soluble in water. Its silver
salt, C6H4(OC3H5).COOAg, is crystalline.
1 4
Para-allyloxy'be7izoiG acid, C6H4(OC3H5).COOH. — The ethylic salt
of this acid, prepared from ethyl p -hydroxy benzoate, allyl iodide, and
alcoholic potash, and purified by distillation, boils at 260°, condenses
to a dense, transparent, nearly colourless liquid, having an odour
somewhat like that of acrolein, but not so repulsive, and solidifies on
cooling to a mass of " colourless transparent needles, melting at 109°.
The acid obtained from it by saponification crystallises in transparent
laminae, melts at 123°, dissolves very easily in alcohol, ether, benzene,
and chloroform, slightly also in water.
1 3
Meta-dllyoxylbenzoic acid, C6H4(OC3H5).COOH. — The ethylic salt
of this acid, prepared like that of the para-compound, passes over, after
fractional distillation between 283° and 285°, as a heavy fragrant oil,
which after 15 or 16 hours solidifies to a crystalline mass. By the
action of potash it is converted into meta-allyloxybenzoic acid, which
crystallises in colourless laminae, soluble in alcohol and ether, slightly
soluble in water, melting at 118°. H. W.
Benzoylacetic Acid (Preliminary Notice). By A. Baeyer
(Ber., 15, 2705). — On dissolving ethyl propiolate in sulphuric acid
and pouring the solution upon ice, an oil separates which is ethyl
benzoylacetate. The reaction may be thus expressed : —
CPh i C.COOEt + HoO = C0Ph.CH2.C00Et.
ORGANIC CHEMISTRY. 337
The free acid is crystalline, and is obtained by the saponification of
its ethyl derivative. A. K. M.
Synthesis of some Acids Analogous in Constitution to Hip-
puric Acid. By T. Curtius (/. pr. Ghem. [2], 26, 145— 208).— Kolbe
considered that hippuric acid might be regarded as " amidaceto-
benzoic acid," but as it has been prepared synthetically by Dessaignes
from glycocine and benzoic acid, and by Jasukowitsch from monochlor-
acetic acid and benzamide, it is now generally looked upon as
" benzoylamidacetic acid."
Kolbe, however, is of opinion that this benzoylamidacetic acid is
isomeric and not identical with the natural hippnric acid, and the
author has undertaken the present research with the object of settling
this point. The crude natural hippuric acid is readily purified by
treating the boiling solution with chlorine until it smells distinctly of
that gas and the colour becomes pale yellow. On cooling, the hippuric
acid deposited is recrystallised with aid of animal charcoal, whereby it
is obtained quite pure.
To prepare pure glycocine, hippuric acid is decomposed by boiling
it for 12 hours with four times its weight of strong sulphuric acid
(1 of acid to 2 of water), and after 24 hours the benzoic acid is filtered
off, and the benzoic acid still in solution is removed by agitation with
ether. The solution of glycocine sulphate thus obtained is neutralised
with barium hydroxide or with chalk, filtered, and the excess of barium
removed from the solution by carbonic anhydride (or the calcium by
oxalic acid). On evaporation glycocine is deposited in beautiful crystals,
generally short monoclinic prisms ; the form of crystallisation, how-
ever, is greatly affected by the presence of inorganic matter; thus a
trace of soda produces rhombohedrons, and with a trace of baryta the
crystals are long. Amidacetic acid has a sp. gr. 1'1607, turns brown
at 228°, and melts at 232 — 236" with evolution of gas, and becomes
purple coloured : it does not polarise. Its basic are more prominent
than its acid properties. It does not combine with barium, sodium,
or thallium hydroxides (strong bases capable of attacking the amido-
group), to form salts. With zinc oxide, however, it forms two salts,
(NH2.CH8.COO)3Zn + H2O, and {^'Ki.CU^COO)^ZTi +
CH2(NH2)COOH.
The solution of the former deposits zinc oxide on adding water or
on boiling, the latter salt being left in solution. In the same way
sodium carbonate precipitates zinc carbonate readily from the first
salt, but not from the second. Sulphuretted hydrogen precipitates
both salts. Silver amidacetate : — A concentrated solution (containing
100 grams) of amidoacetic acid is poured on 38 grams of freshly pre-
cipitated silver oxide ; the whole is well stiri-ed and heated nearly to
boiling, filtered, and the filtrate allowed to cool in the dark, when
crystals of the salt are deposited ; the unused silver oxide is again
treated with the mother-liquor, and so on until all the oxide aiong
with 38 grams more is taken up. The crystals are generally small
transparent prisms, but sometimes form large tablets : they soon be-
338 ABSTRACTS OF CHEMICAL PAPERS.
come grey and opaque on exposure to light. This salt is not hygi-o-
scopic, does not contain water of crystallisation, and does not decom-
pose below 100°.
Action of Benzoic Chloride on Amidacetic Acid. — When silver amid-
acetate or free amidacetic acid is heated with benzoic chloride, a
large quantity of resinous matter and benzoic acid are obtained, but
very little of the desired compound, as the silver salt or acid decom-
poses below the boiling point of the benzoic chloride.
On diluting the mixture with benzene, however, reaction soon sets
in with deposition of silver chloride : the whole is kept gently boiling
until hydrochloric acid commences to come off. The benzene is then
distilled off, and the residue after being washed with ether to remove
benzoic acid, is extracted with 30 per cent, alcohol. The alcoholic
extract is concentrated, neutralised with soda, acidified with strongf
hydrochloric acid, and the crystals formed are purified with the aid of
animal charcoal.
The crystalline product is a mixture of three acids, (a) contain-
ing one, (iS) containing two, and (7) containing three atoms of
nitrogen.
1. The a-acid, synthetical hippuric acid, is identical with the hippuric
acid from the urine of Graminivora. It is separated from the mixed
product by extraction with chloroform, in which the other acids are
practically insoluble. If the silver amidacetate and benzoic chloride
are mixed according to the equation, AgC3H402N -|- CtHjsOCI =
C9II9NO3, then only small quantities of the )3- and 7-acids are ob-
tained ; if, however, 2 equivalents of silver amidacetate are mixed
with 1 equivalent of benzoic chloride, and the 2nd equivalent of the
latter added afterwards, then the chief products are the B- and 7-
acids. The mixed product is treated with absolute alcohol, in which
the 7-acid is almost insoluble. The a-acid is nearly all separated from
the alcoholic extract by chloroform, and finally, the iS-acid is puri-
fied by fractional crystallisation from absolute alcohol ; 1st fraction
contains a- and iS- acids, 2nd pure y3, 3rd (3 and 7.
When the aqueous solution of the /3-acid is cooled slowly, it is de-
posited in small transparent colourless rhombic tablets, with satin
lustre, greasy to the touch; when, however, the solntion is cooled
quickly it forms tufts of sharp-pointed microscopic needles. It melts
at 206*5°, and at this temperature decomposes and becomes red. It is
insoluble in cold ether, chloroform, benzene, and carbon bisulphide.
It is sparingly soluble in cold absolute alcohol, somewhat more so
when hot. It is very soluble in 30 per cent, alcohol. Ammonia dis-
solves it immediately, forming a salt. Cold mineral acids have no
action on the |S-acid, but when boiled with them it is decomposed into
1 mol. benzoic acid and 2 mols. amidacetic acid, taking up 2 mols.
water — hippuric acid under similar circumstances produces 1 mol.
benzoic acid and 1 mol. amidacetic acid, taking up 1 mol. H2O. If,
however, the decomposition with warm acid be conducted very care-
fully, avoiding excess of acid, then the y3-acid takes up only 1 mol.
H2O, and breaks up into 1 mol. hippuric acid and 1 mol. amidacetic
acid. From these decompositions, coupled with its method of forma-
tion, the author concludes that this acid is analogous to hippuric acid,
ORGANIC CHEMSTRT. 3e39
NHBz.CH2.COOH, being" amidacetic acid in which one of the hydro-
gens is replaced by the radical of hippuric acid, " hippuryl,
NHB^.CH^.CO,"
It is therefore called hipjjuramidacetic acid,
NHB^.CH^.CONH.CH^.COOH.
With alkalis it behaves in a similar manner : in the cold, salts are
formed, and the acid can be reprecipitated unaltered, but they are
decomposed when warmed, with formation of hippuric acid and
glycocine, and finally of benzoic acid and glycocine. It has no basic
properties, but is a strong monobasic acid ; it does not dissolve metal-
lic zinc with evolution of hydrogen, but forms crystalline soluble
salts with most of the metals. Silver hippurylamid acetate,
forms nodular groups of microscopic needles, insoluble in cold, soluble
in hot water and in ammoniacal liquids. In the moist state it is
blackened by light, but when dry it is not perceptibly coloured, ahd is
perfectly stable at 105°. The thallium saZ^, CnHa]S'204Tl, crystallises
in small hexagonal monosymmetrical tablets. The harium salt,
(CnHuN204)2Ba + 5Ho0 (?), can be obtained in four-sided leaflets, or
in fine hair-like needles, easily soluble in cold water and ordinary
alcohol, sparingly in absolute alcohol. The cojpiier salt,
(OuHu-^.OOaCu + S^H^O,
forms brilliant transparent dark-blue rhombic prisms terminating at
each end in short pyramids. It loses its water of crystallisation at 110°,
becoming bright green. The zinc salt crystallises in drnsy groups of
small transparent needles or tablets, with 1 JHgO, which are driven off
at 110°.
Ethyl hippuramidacetate, C]oHiiN202.COOEt, prepared either by the
action of dry hydrochloric acid gas on a solution of hippuramidacetic
acid in absolute alcohol, or by the action of ethyl iodide on the silver
salt suspended in absolute alcohol. It crystallises from ether in
transparent tablets, from water in large white needles with satin-like
lustre, melting at 117° (ethyl hippurate melts at 60'5°). It is moder-
ately soluble in cold chloroform and cold water, and easily in cold abso-
lute alcohol spirit, and in boiling chloroform and ether and in warm
water. Ethyl hippurate is insoluble in cold water, and very easily
soluble in ether ; this difference can be used to advantage in separat-
ing hippuric and hippuramidacetic acid. On warming it with aqueous
ammonia, ethyl hippuramidacetate is dissolved, and a somewhat
violent reaction takes place resulting in the formation of hippuryl
glycollamide, C10HHN2O2.CONH2, which crystallises in transparent
sharp-edged leaflets melting at 202° (hippuramide melts at 183°),
easily soluble in warm absolute alcohol and hot water, sparingly in
ether and cold water, and insoluble in chloroform and benzene.
Hippurylglycollamide hydrochloride crystallises in yellow quadrangular
leaflets ; it is resolved into its components by the action of water. It
does not form a platinochloride. MonochloFobenzoic acid is formed
340 ABSTRACTS OF CHEMICAL PAPERS.
by the action of chlorine on hippuramidacetic acid. The 7-acid,
CioHi2N304, is deposited from boiling water in brilliant semi-trans-
parent films, which under a powerful microscope are seen to consist of
stellate groups of needles ; when it is dried at 100°, it tarns yellow.
Heated at 230°, it becomes gradually brown, and at a little above
240° it melts with complete decomposition. It is almost insoluble in
cold water and absolute alcohol, and quite so in other solvents. It
is more soluble in 30 per cent, spirit, in ammonia, alkalis, and
concentrated mineral acids. On heating it with soda, ammonia is
evolved.
This (7-) acid is -decomposed on heating it with hydrochloric acid
in sealed tubes. The products are a nitrogenous substance, C9H9NO3,
and benzoic jind amidacetic acids. A quantitative experiment showed
the radical Bz to be contained only once in the molecule of the 7-acid.
With dilute Fehling's solution it gives rise to a carmine coloration,
with strong solution a purple-violet. With phenol and sodium hypo-
chlorite it is coloured dark green-blue, whilst hippuramidacetic
acid is coloured very slightly greenish-yellow, and hippuric acid is not
coloured at all. This acid has a strongly acid reaction, but does not
form simple salts. The silver salt forms a white precipitate soluble in
ammonia, from which it is deposited in small transparent irregular
granules. The author suggests the probable isomerism of this 7-acid
with Griess's uramidohippuric acid. D. A. L.
Triphenyl Orthoformate. By F. Tiemann {Ber., 15, 26S5 —
2687). — On heating an alkaline solution of phenol with chloroform,
and extracting with ether, a neutral oil is obtained which becomes
crystalline after purification. It is triphenyl formate, CH(0Ph)3. It
crystallises in long white needles (m. p. 71 '5°) which are insoluble in
water, but soluble in ether, chloroform, boiling alcohol, and hot ben-
zene, less soluble in light petroleum. It decomposes when distilled at
the ordinary pressure, but passes over unchanged under a pressure of
50 — 55 mm. Acids readily decompose it into phenol and formic acid,
but alkalis do not affect it. A. K. M.
Tribasic Nitrophenyl Orthoformate. By A. Weddige (/. pr.
Chem., 26, 444 — 446). — The action of the alkali salts of ortho- and
para-nitrophenol on chloroform results in the formation of a nitro-
derivative of the tribasic phenyl orthoformate. This substance,
CH(O.C6H4.N02)3, is produced by heating 2 mols. chloroform with 3
mols. potassium nitrophenol and 4 to 6 parts of alcohol at 140 — 150°
for 10 hours. After purification by crystallisation from alcohol, it
forms white needles, which melt at 182°. They are not decomposed
by boiling potash or soda, but are destroyed by distillation. The
ethereal salt prepared in a similar way from para-nitrophenol melts
at 232°. Reduction by tin and hydrochloric acid produces a crystal-
line base, CHCO.CeH^.NHOa.
It will be interesting to see whether this compound yields a dye
under the influence of oxidising agents in a manner analogous to
triamidotriphenylmethane, CH(C6H4.NH2)3. E. W. P.
ORGANIC CHEMISTRY. ' 341
Paradichlorazobenzene-monosulphonic Acid. By A. Calm
(Ber., 15, 2558 — 2659). — The following salts of paradichlorazoben-
zeiie-monosulplionate (Ber., 13, 1183) have been prepared: —
The potassium salt, CeHiCl.Na.CeHsCl.SOaK, forms glistening orange-
coloured plates, soluble in alcohol and in hot water. The silver
salt, Ci2H7Cl2N2.S03Ag, a pale- orange amorphous precipitate. The
harium salt, (Ci2H7Cl2N2.S03)2Ba, and the lead salt are obtained as
crystalline precipitates soluble in hot water. The calcium salt,
(Ci2H7Cl2N2.S03)2Ca, forms lustrous golden scales. The sulpho-
chloride, C6H4CI.N2.C6H3CI.SO2CI, is deposited from an ethereal
solution in orange-coloured needles melting at 161°. W. C. W.
Preparation of Indigo-blue from Orthonitrobenz aldehyde.
By A. Baeyer and V. Drewsen (Ber., 15, 2856— 2864).— By the
action of alkalis on a solution of orthonitrobenzaldehyde in acetone, a
condensation-product is formed, a dilate solution of which yields
indigo if acted on by excess of alkali. This intermediate product is
orthonitro-/3-phenyllactyl methyl ketone. It crystallises in mono-
clinic prisms (m. p. 68°), soluble in ether and alcohol, insoluble in
petroleum. On boiling its aqueous solution, it decomposes with forma-
tion of indigo. This substance is a direct addition-product of nitro-
benzaldehyde and acetone, and probably stands in the same relation
to orthonitrocinnamyl ketone that aldol does to crotonaldehyde.
Its formation may be expressed thus ; — NO2.C6H4.CHO + (CIl3)2CO
= N02.C6H4.CH(OH).CH2.COMe. On boiling one part of this con-
densation-product with acetic anhydride, orthonitrocinnamyl methyl
ketone is formed thus : —
N02.C6H4.CH(OH).CH2.COMe = H2O + NO2.C6H4.CH: CH.COMe.
This ketone crystallises in long flat needles meliing at 58°, soluble in
ether and alcohol, insoluble in petroleum ; it is identical with one of
the nitro-compounds obtained by the direct nitration of cinnamyl
methyl ketone ; and the identity is further established by the forma-
tion of indigo from both under similar conditions. In order to
obtain indigo from orthonitro-y3-phenyllactyl methyl ketone, soda is
added to its aqueous solution, and the precipitated indigo washed
with alcohol and water. The indigo so obtained is perfectly free from
indirubin ; the change may be represented thus : —
2CioHuN04 = CieHioKaOa + 2C2H4O2 + 2H2O.
If aldehyde be substituted for acetone, a similar condensation-
product is formed, which with excess of alkali yields indigo. This
substance is probably analogous to aldol, and is the alcohol of ortho-
nitro-/3-phenyllactic acid, N02.C6H4.CH(OH).CH2.CH2.0H. It crys-
tallises in needles melting at 108° ; it is converted by silver oxide
into an acid (probably orthonitro-y3-phenyllactic acid), which crystal-
lises in monoclinic prisms, melting at 127°.
On saturating a solution of orthonitrobenzaldehyde in pyrotartaric
acid with hydrochloric acid, orthonitrocinnamyl formic acid,
no2.C6H4.ch:ch.cooh,
is obtained in the crystalline form (m. p. 185°), soluble in alcohol and
ether. Its barium salt crystallises in leaflets. Orthonitrocinnamyl
VOL. XLiv. 2 a
342 ABSTRACTS OF CHEMICAL PAPERS.
formic acid is easily decomposed by alkalis, with formation of indigo
and oxalic acid. V. H. V.
Diphenyldiisoindole. By R. Mohlau (Ber., 15, 2480—2490).—
If bromacetophenone is added gradually to boiling aniline, a violent
reaction occurs, and from the crude product diphenyldiisoindole is
obtained. This substance, C28H32N2, is derived from the condensation
of 2 mols. of acetophenone anilide and loss of 2 mols. of water, a
change which may be represented thus : —
NPh
PhC ^^ CH
2(NHPh.CH2.COPh) = + 2H2O.
HC
NPh
CPh
It oflPers the first example of a nitrogen-atom combined with three
different hydrocarbon radicals, belonging to the class of substances
which the author proposes to call paranitriles.
Diphenyldiisoindole crystallises in colourless glistening scales (m. p.
181°, b. p. over 360°), soluble in alcohol and ether, insoluble in water.
It shows some points of resemblance to dimethylaniline in forming a
blue-green colouring matter when heated with benzotrichloride and
zinc chloride, and in giving azo-dyes.
The picrate crystallises in vermillion-coloured prisms melting at
127°, easily soluble in alcohol, ether, and benzene. The nitroso-
derivative, C28H2oN2(NO)2 crystallises in rhombic leaflets melting at
244°. It combines directly with mineral acids to form salts, of
which the hydrochloride, C28H2oN2(NO)2,2HCl, crystallises in prisms,
the nitrate, C28H2oN2(NO)2,2HN03, in needles. The nitroso-derivative
does not give Liebermann's reaction. From the analogy of nitroso-
diphenyldiisoindole to nitrosodimethylaniline in forming azo colouring
matters, the author suggests for it the following formula : —
NPh
PhC ^^ CNO
NOC
^-/CPh
\^h ^- H. V.
Azo-ColoTiring Substances from Diphenyldiisoindole. By
R. Mohlau (Ber., 15, 2490 — 2497). — Biplienyldiisoindolazotrihromhen-
zene hydrocJiloride, C4oH24N6Br6,2HCl, prepared from diphenyldiiso-
indole and tribromodiazobenzene hydrochloride, crystallises in fine
golden needles, insoluble in water and alcohol. On warming it with
sodium carbonate, the corresponding base is obtained, which crystal-
lises in orange-golden prisms melting at 150°. Its alcoholic solution
absorbs all the rays from the green to the violet.
Diphenyldiisoindolazodibromopheiwl, C4oH26N6Br402. — The hydrochlo-
ride of this base is obtained by heating an alcoholic solution of
diphenyldiisoindole and paradiazodibromophenol with hydrochloric
acid. It crystallises in glistening olive- coloured prisms, insoluble in
water, and decomposed by alkalis with formation of the free azo-colour-
ORGANIC CHEMISTRY. 343
ing substance, wliicli crystallises in golden-green prisms melting at 198**.
An aqueous solution of its sodium salt dyes wools of an orange, and
silk of a yellow colour, and absorbs all lines of the green, beginning
from E, and all the blue and violet rays. As the paradiazodibromo-
phenol is convertible into the [6:1: 2] dibromophenol, the diphenyl-
diisoindolazodibromophenol can be represented by the formula
(C6H4.N2.C6H2Br2.0H)2(N2C4)H2Ph2, in which the nitrogen- atoms
and the phenyl-groups are in the para-position to each other, and
[Br : OH : Br = 6 : 1 : 2].
DipJienyldnsoindolazohenzene-sulphon'ic acid, C4oH3o^6S206, from di-
isoindole and diazosulphanilic acid, crystallises in red-brown metallic
glistening scales. Its sodium salt forms golden leaflets, its silver salt
vermillion-red prisms. On reduction, the acid is converted into
diphenyldiisoindole-sulphanilic acid, together with a basic substance
crystallising in colourless prisms, but which was not obtained in a
sufficiently large quantity for a minute examination. V. H. V.
Derivatives of Diphenyl. By E. Lellmann (Ber., 15, 2837 —
2838). — Mononitrodibromodiphenijl, C6H4Br.C6H3Br.NO2. — The author
alludes to the difficulty experienced in introducing one nitro-group
into Fittig's dibromodiphenyl (m. p. 164°), for either no nitro-
derivative is formed or else a dinitro-compound. In order to obtain
a mononitro- compound the dibromodiphenyl is dissolved in acetic acid,
and an equal volume of nitric acid of sp. gr. 1*52 added. After purifi-
cation by alcohol, the compound is obtained as a golden crystalline
mass melting at 127°, easily soluble in alcohol and benzene.
Trinitrodibromodipiienyl, N02.C6H3Br.C6H2Br(N'02)2, obtained by
dissolving dibromodiphenyl in fuming nitric acid, crystallises in small
colourless needles melting at 177°, sparingly soluble in alcohol, easily
soluble in benzene.
DibenzoyldiamidodihromopJienyl, (C6H3Br.NHBz)2, is formed by the
action of benzoic chloride on the corresponding diamidodibromo-
phenyl. Y. H. V.
A Case of Physical Isomerism. By E. Lellmann (Ber., 15,
2835 — 2837). — The dibenzoy Miami dodibromophenyl mentioned in the
preceding abstract crystallises in colourless needles, which melt at 195°;
but if the melting-point tube be suddenly taken out of the hot bath,
the contents solidify as a glassy mass, which melts at 99°, solidifies in
crystals at 125 — 130°, and finally melts again at 195°. This series of
changes can be repeated frequently. If the substance of lower melt-
ing point be dissolved in alcohol, the modification of high melting
point crystallises out. The former could be obtained only as a
vitreous mass, whilst the latter formed distinct crystals.
V. H. V.
Nitro-derivatives of Naphthalene. By V. Merz and W. Weith
(J5er., 15, 2708— 2731).— By the action of fuming nitric acid on
bromonaphthalene, two isomeric bromodinitronaphthalenes are formed.
One of these, called by the author a-bromodinitronaphthalene, melts
at 170'5°, and the other, jS-bromodinitronaphthalene, at 143°. The
former crystallises from benzene in groups of slender needles, and the
2 a 2
344 ABSTRACTS OF CHEMICAL PAPERS.
latter in plates (from benzene) or needles (from alcohol). Both dis-
solve readily in alcohol, benzene, and glacial acetic acid. Boiling with
soda-solution does not decompose them. To obtain more highly
nitrated compounds, the dinitro- derivatives are treated with a mix-
ture of fuming nitric and concentrated sulphuric acids, when the
a-derivative yields bromotetranitronaphthalene, melting at 189 —
189*5°, and the y3-derivative a tetranitro- compound melting at 245°.
On dissolving a-bromotetranitronaphthalene in sodic carbonate solu-
tion, and then acidulating, tetranitronaphthol (m. p. 180°) is precipi-
tated. It forms coloured metallic derivatives, which crystallise well.
They explode slightly on heating. The sodium salt, CioH3(N02)4.0Na
+ 2H2O, crystallises in reddish-yellow scales, the potassium salt,
CioH3(N02)4.0K + 1^H20, in dark-red prisms. The barium salt,
[CioH3(N02)40]2Ba + 3H2O, forms yellowish-red crystalline flocks,
the calcium salt, [CioH3(N02)40]2Ca + 2H2O, yellowish-red needles,
and the silver salt, CioH3(N02)4-OAg + 3H2O, dark-coloured needles.
By the action of aniline and ammonia on a-bromotetranitronaphtha-
lene, tetranitronaphthylphenylamine, CioH3(N02)4.NHPh, melting at
162*5°, and tetranitronaphthylamine, CioH3(N02)4.NH2, melting at
194°, are produced.
From ^-bromotetranitronaphthalene the corresponding tetranitro-
naphthol could not be obtained pure. /3-Tetranitronaphthylphenyl-
amine (m. p. 253°), and /3-tetranitronaphthylaraine (m. p. 202°) were,
however, prepared. When oxidised with dilute nitric acid, both
a-and/3- bromodinitronaphthalene yield ordinary a-mononitrophthalic
acid melting at 212°. By the oxidation of a-bromotetranitronaph-
thalene, a dinitrophthalic acid (m. p. 227°) is obtained, which by
reduction and subsequent distillation with soda-lime yields meta-
liiamidobenzene. /3-Broniotetranitronaphthalene yields a dinitrophtha-
dc acid (m. p. 200*^), from which para-diamidobenzene may be obtained.
The formulae for the two dinitrophthalic acids are therefore
]Sr02:COOH:COOH:N02] = (a) [1 : 2 : 3 : 5] and (/3) [1:2:3:4].
From the oxidation-products, it is evident that both in the dinitro-
and tetranitro-bromonaphthalenes the nitro-groups are equally divided
between the two benzene nuclei. The fact that both bromodinitro-
naphthalenes yield a-nitrophthalic acid shows that in both dinitro-
derivatives one nitro-group must have the position 1', and since it
has been ascertained that in bromomononitrophthalene (from bromo-
naphthalene) the bromine and the nitro-group are in the 1 : 4 position
to one another, it is highly probable that the two dinitro-compounds
are represented by the following formula : — [NO2 : Br : NO2 = 1' : 1 : 4
and 4' : 1 : 4]. A. K. M.
Picrates of a- and S-Naphthol. By C. Marchetti (Gazzetta, 12,
502 — 504) . — These compounds are prepared by dissolving the
naphthol in a small quantity of 85 per cent, alcohol, and the picric
acid in a quantity of the same alcohol sufficient to form a solution
saturated at ordinary temperature, pouring the boiling picric acid
solution into that of the naphthol, then agitating, and cooling. The
liquid then deposits very slender crystals, which are to be collected on
ORGANIC OHEMISTRT. 345
a stictlGn-filter and dried in a vacuum. The filtered liquid when con-
centrated and cooled yields a second crop of crystals, and others may
be obtained in like manner.
The crystals thus obtained gave by analysis 51*43 and bl'S6 per
cent, carbon, 3*07 and 3'35 hydrogen, agreeing nearly with the formula
of naphthol picrate, C6H2(N02)3.0H,CioH7.0H, which requires 61*47 C
and 2-95 H.
OL-Najphthol picrate crystallises from alcoholic solution on rapid
cooling in slender orange-yellow needles, and by slow cooling in
larger needles of an orange-red colour. It melts at 189 — 190° to an
opaque dark-red liquid; dissolves very freely in alcohol and ether, and
crystallises readily therefrom ; sparingly in cold chloroform, some-
what more readily at higher temperatures, and crystallises out on
cooling. It is but very slightly soluble in carbon bisulphide, and in
water either cold or boiling. It is decomposed by ammonia, the
liquid on distillation with steam yielding the a-naphthol in the free
state.
(3-Naphthol picrate crystallises in thin silky orange-yellow needles
of somewhat lighter colour than the a-compound, and melts at 155°
to a dark-red limpid liquid. It is very soluble in alcohol, ether, and
chloroform, less soluble in carbon bisulphide, nearly insoluble in cold,
sparingly soluble in hot water. Ammonia decomposes it, separating the
j8-naphthol, which may be obtained in the crystalline form by heating
the solution and then leaving it to cool. H. W.
Derivatives of Naphthalene Hexhydride. By A. Agrestini
(Gazzetta, 12, 495 — 499). — With the view of preparing Graebe's
naphthalene tetrahydride {G. /., 1873, 1008), the author heated in a
sealed tube at 235", for 7^ hours, 10 g. naphthalene, 3 g. red phos-
phorus, and 98 g. hydriodic acid (b. p. 127°). On decolorising the
resulting liquid with acid sodium sulphite, neutralising with sodium
carbonate, and distilling with steam, then treating the distillate with
ether, drying it with calcium chloride, and again distilling, an oil was
obtained lighter than water ; and on boiling this oil for some time
with pellets of sodium, distilling, and treating the distillate with
picric acid, a crystalline precipitate was formed consisting of naphtha-
lene picrate. The oil separated from this precipitate was then dis-
tilled in a current of steam, dried with calcium chloride and with
sodium, and subjected to fractional distillation, the greater part of it
passing over at 195 — 196° under a pressure of 773*9 mm. The
analysis of this distillate gave, as a mean result, 89*53 p.c. carbon and
10*57 hydrogen, agreeing closely with the formula CioHu or CioH8,H6,
which requires 89*55 C and 10*45 H.
The chief product obtained by the process above described is there-
fore naphthalene hexhydride. It is a colourless, fragrant liquid,
lighter than water, and boiling at 204 — 205°. It does not combine
with picric acid. It is probably identical with the hydrocarbon CioHu
(b. p. 195 — 200°), which was obtained in like manner, together with
others, by Wreden and Znatowicz (Annalen, 187, 164).
Naphthalenehexhydrosulphonic Acids, CioHi3(S03H)8. — Two isomeric
acids, having this composition, are obtained by the action of fuming
346 ABSTRACTS OF CHEMICAL PAPERS.
sulphuric acid on naphthalene hexhydride, and may be separated by
diluting the product with water, neutralising with lead carbonate,
filtering it at the boiling heat, precipitating the lead with hydrogen
sulphide, neutralising the filtrate exactly with potapsium carbonate,
evaporating to dryness, completing the desiccation of the potassium
salt thus obtained in a vacuum, then pulverising and treating it with
boiling alcohol. In this way two potassium salts are obtained, one
soluble in alcohol, the other insoluble, bul both having the composi-
tion of potassium naphthalene hexhydrohisulphonate, CioHi2(S03K)2.
The crystals of the former are anhydrous ; those of the latter con-
taining 1-^ mol. H2O, and are soluble in water. Both these salts,
when fused with potassium hydroxide, yield small quantities of
a phenolic substance, shown by its melting point to consist of
a-naphthol.
Action of Bromine on Naphthalene Hexhydride. — On treating this
hydrocarbon with bromine in molecular proportions, added by succes
sive quantities, a violent action takes place, accompanied by evolution
of hydrogen bromide, and a nearly colourless liquid is obtained
heavier than water, and decomposing when distilled. After purifica-
tion with sodium carbonate, solution in ether, &c., it gave by analysis
37'41 p.c. C, 4-48 H, and 3801 Br, agreeing nearly with the formula
CioHgBr, which is that of monohromonaphthalene dihydride.
H. W.
Some Ethereal Oils. By Beilstein and E. Wiegand (Ber., 15,
2854 — 2855). — Oil of Erecthidis consists of a terpene, CmHie (b. p.
175°, sp. gr. 0*838 at 18*5°), which absorbs a molecule of hydrochloric
acid without the separation of a crystalline compound. The portion
of the oil which boils above 200^ also consists of a terpene.
Oil of JErigeron canadense consists of a terpene (b. p. 176°, sp. gr.
0"8464) ; it absorbs 2 mols. of hydrochloric acid to form a solid di-
hydi ochloride melting at 47 — 48°.
Oil of Majorum. — The portion of lower boiling point consists of a
terpene (b. p. 178°, sp. gr, 8*463) which absorbs 1 mol. of hydrochloric
acid, without forming a compound. The portion boiling from 200 —
220° contains a sesquiterpene hydrate, Ci5H24,H20, which from its
behaviour towards sodium is shown to contain no hydroxyl-group.
V. H. V.
Ledum Camphor. By E. Hjelt and U. Collan (Ber., 15, 2500 —
2501). — In the year 1831, Grassmann obtained from the wild marsh
rosemary {Ledum palustre), a volatile oil, which solidifies on exposure
to form the so-called ledum camphor. The substance has since been
examined by Trapp, who assigned to it a formula, CzsHisO, and by
Ivanoff, who deduced the formula C6H8O2. The author distilled the
oil with water, and obtained the camphor in acicular needles melting
at 101°, and from his analyses deduces the formula C25H44O2. In its
chemical relationship ledum camphor shows no resemblance to the
other camphors. Y. H. V.
Note. — Wright (this Journal, 1875, 1038) assigns to ledum camphor
the formula C20H32O.— Y. H. Y.
ORGANIC CHEMISTRY. '347
Glucosides. By H. Schifp (Gazzetta, 12, 460—469).— ^rii^^m. —
Tlie variations in the amount of crystal-water and in melting
point (142—145°, 162— 168^ and 187°) observed in commercial
arbutin are attributed by the author to the presence of methyl-arbutin
(Abstr., 1881, 610). This latter compound has been prepared
by Michael C Abstr., 1882, 174) by the action of acetochlorhydrose on
the potassium- derivative of methyl- quinol, according to the equa-
tion : —
0 : CH0.(CH.0I:H)4.CH2C1 + KO.CeH^.OMe + 4EtOH
Acetochlorhydrose. Potassium-methyl-
quinol.
= KCl + 4Et05:5 + 0 : CH.(CH.OH)4.CH20.C6H4.0Me
Methyl-arbutin.
When thns obtained it melts at 168 — 169°, i.e., at about the tem-
perature observed by Strecker and others for the melting point of
arbutin, whereas the methyl-arbutin prepared by the author's method,
viz., by the action of methyl iodide and potassium hydroxide on
arbutin dissolved in methyl alcohol, melts at 175 — 176°. The two
products differ also in their amount of crystal- water, the crystals
obtained by Michael's process having the composition 2Ci3HuOn +
H2O, while those obtained by the author's method contain CisHuOn
+ H2O. The smaller amount of water found by Michael was perhaps
due to partial dehydration. Methyl-arbutin may also be obtained in
anhydrous crystals, e.^., from concentrated solutions containing potas-
sium iodide. Supersaturated solutions sometimes also deposit mam-
mellated groups of anhydrous crystals. Methyl-arbutin is moderately
soluble in cold, freely in boiling water, and in alcohol, sparingly in
ether, more freely in a mixture of alcohol and ether; its solutions
give no colour with ferric chloride.
The lower melting point (168°) observed for arbutin by Strecker
and others, and by the author in certain fractions, may perhaps be
attributed to the presence of methyl-arbutin, and may be regarded as
an additional instance of the fact that a mixture may melt at a tem-
perature lower than the melting point of either of its constituents.
Constitution of Helicin. — When hot saturated solutions of heliciu
(5 pts.) and urea (2 pts.) are mixed together, and the mixture is
evaporated in an open vessel, there remains a dense colourless syrup,
which, when left in the exsiccator over sulphuric acid, leaves a nearly
colourless gummy mass, gradually changing to a white crystalline
powder, which is but slightly soluble in absolute alcohol, and may be
freed thereby from uncombined helicin and urea. This compound
dissolves in a large quantity of boiling water, and separates on cooling
in the form of a very white crystalline powder consisting of gluco-
ealicyl-carbamide, (NH2.CONH),CH.C6H4.0.C6H„05. It is dis-
tinguished from its components by being hygroscopic and very soluble
in water. It deliquesces in alcohol of 99 p.c, dissolves readily in
alcohol of 95 p.c, and is not precipitated by absolute alcohol even
from highly concentrated aqueous solutions. The aqueous solution
has a bitter taste, and is not precipitated by nitric acid, but gives a
348 ABSTRACTS OP CHEMICAL PAPERS.
white floccnlent precipitate with mercuric nitrate. The componnd
melts at a high temperature, giving off ammonia, becoming coloured,
and apparently decomposing in a very complex manner.
Glucososalicyl-thiocarbamide,
(NHa.CS.NH)2CH.C6H4.0.CeHii,
prepared by heating together the alcoholic solutions of 1 pt. thiocar-
bamide and 2 pts. crystallised helicin, is also a very white crystalline
powder, even more hygroscopic than the carbamide.
The compounds just described afford additional proof of the alde-
hydic nature of helicin, which is, moreover, confirmed by its power
of combining with organic bases, as with aniline and toluidine. With
tolylene- diamine it forms glucosalicylic tolijlenediamine,
CeHaMe : (N : CH.C6H4.0.C6H50a)2,
which separates in deep orange-coloured crystalline groups when 5 pts.
helicin and 2 pts. tolylenediamine are dissolved together in a small
quantity of hot water. Like most derivatives of metatoluidine, this
substance exhibits a strong tendency to form deep-coloured com-
pounds. Its dilute aqueous solution exhibits a decided red-green
fluorescence. The crystals contain water, which they lose in the
exsiccator, being thereby converted into a vitreous mass, which may
be recrystallised from warm water. It dissolves but slightly in cold
water, easily and with red colour in dilute hydrochloric acid.
Helicin unites readily with hydrocyanic acid, and yields with
Perkin's reagent a mixture of well-crystallised compounds, which,
however, the author has not yet succeeded in separating.
Anhydrous helicin does not absorb dry ammonia-gas, but dissolves
readily in concentrated alcoholic ammonia, forming a solution which
has only the faintest ammoniacal odour, showing that the ammonia
has really entered into combination, though the compound formed has
but little stability, and gives off ammonia even at ordinary tempera-
tures. It is probably an additive aldehydic combination,
C6Hu05.06.C6H4.CH(OH).NH2,
which, however, is not converted into the corresponding hydrosalicyl-
amide under conditions similar to those which give rise to the forma-
tion of salicylaldehyde.
The paper concludes with theoretical speculations as to the consti-
tution of helicin. H. W.
Poisonous Principle of Andromeda Japonica. By J. F.
EiJKMAN (-Bee. Trav. Chim., 1, 224 — 226). — By exhausting with water
the fresh leaves of this plant, well known in Japan for their poisonous
properties, agitating the concentrated and filtered solution with
chloroform, and mixing the chloroform with light petroleum, a pre-
cipitate is obtained which may be dissolved in ether containing
alcohol, and extracted therefrom by agitation with water ; on
evaporating the aqueous solution thus obtained, the poisonous princi-
ple remains in the form of a transparent, colourless, brittle uncrystal-
lisable substance, which the author has not been able to resolve into
more definite constituents.
ORGANIC CHEMISTRY. 349
This substance, which the anthor designates as Asehotoxln, is free
from nitrogen, leaves no ash when burnt, and gave, as the mean of
four analyses, 60-48 p.c. C, 7'40 H, and 32'11 0. It softens at 100",
and melts at 120°. It is more soluble in hot than in cold water, and
dissolves readily in chloroform, common alcohol, and amyl alcohol ;
also in acetic acid and in ammonia, and to a smaller amoant in caustic
potash and soda; in all cases without decomposition. It is but
slightly soluble in pure ether, and nearly insoluble in benzene, light
petroleum, and carbon bisulphide. The aqueous solution is neutral, and
is not precipitated or changed in any way by ferric chloride, cupric
sulphate, mercuric chloride, auric chloride, silver nitrate, or normal
lead acetate, but gives a flocculent precipitate with the basic
acetate. From an alkaline cupric solution it throws down a small
quantity of cuprous hydroxide, but the precipitation is more abundant
if the asebotoxin be previously heated with hydrochloric acid, and the
filtered liquid added to the cuprous solution. Asebotoxin moistened
with hydrochloric acid acquires a splendid blue colour, changing to
red-violet at the heat of the water-bath. Strong sulphuric acid dis-
solves it with red colour, changing after a while to rose-pink, a bluish-
grey substance separating at the same time.
Asebotoxin exhibits the characters of a glucoside, and is extremely
poisonous, a fatal dose for a rabbit by subcutaneous injection being
3 mg. per kilogram of bodily weight.
The poisonous principle of Andromeda japonica has been examined
with similar results by P. C. Plugge, who calls it Andromedotoxin, and
claims priority over Eijkman. H. W.
Hsematoxylin and Haematein. By E. Erdmann and G. Schulz
{Annalen, 216, 232 — 240). — The authors' experiments confirm the
formula of haematoxylin, CieHuOe, deduced by Gerhardt from the
analyses of. 0. L. Erdmann, Hesse, and others. Acetyl-haematoxyliu
has the composition CaeHziOn = CieHgZcsOe [Xc. calc. = 42 per cent. ;
exp. = 4174 to 42-67].
The authors also confirm the formula C16H12O6 assigned to haematein
(the product obtained by exposing an ammoniacal solution of haemat-
oxylin to the air) by O. L. Erdmann, and by Hummel and Perkin
(Trans., 1882, 367), of whose experiments, however, they take
no notice.
By sulphurous acid, and more readily by hydrogen sodium sulphite,
haGmate'in is converted into a colourless liquid, which, however, con-
sists not of haematoxylin, but of an addition-product, that obtained
with the free acid being partially decomposed by boiling, whereas the
product obtained with the acid sodium salt is decomposed only
when heated with an acid, yielding haematein, which when thus
prepared, cannot be reconverted, by any mode of treatment, into
haematoxylin. A similar result is obtained by reducing haematein
with tin and hydrochloric acid.
Reim (Ber., 4, 331 ; C. J., 1871, 541) by treating haematoxylin
with strong nitric acid, obtained an oxidation-product, regarded by
him as identical with Erdmann's haematem, but really isomeric there-
with, inasmuch as it crystallises in brown-red needles much more
350 ABSTRACTS OF CHEMICAL PAPERS.
soluble in boiling water than beematem, and differs from the latter in
many other characters, especially in its behaviour to sulphurous acid,
by which it is immediately reduced to haBmatoxylin, whereas
Erdraann's haematein is not reduced by similar treatment. Lastly,
Reim's oxidation-product is converted by boiling with acetic chloride
in a reflax apparatus into an acetyl-derivative, less soluble in alcohol
than pentacetylhaematoxylin, and crystallising therefrom in spherical
groups of small white needles, melting with partial decomposition at
216 — 219°. No such acetyl-derivative can be obtained from Erdmann's
haematein.
Attempts to split up haematoxylin and hsematem into similar mole-
cules have not hitherto yielded very definite results. Haematoxylin
reduced by hydriodic acid (b. p. 127°) yields at first a red body, not
obtainable in definite form, and afterwards, when heated therewith in
sealed tubes, a mixture of hydrocarbons, a small portion of which
volatilises with steam, while the rest forms a black mass soluble in
benzene.
By heating haematoxylin with strong ammonia at about 180°, a
nitrogenous body is obtained, which has the properties of an ami do-
phenol, and separates on addition of acids as a light red precipitate
soluble in excess of the acid.
The authors confirm the observation made by R. Meyer, that
haematoxylin by dry distillation yields a mixture of resorcinol
and pyrogallol. The two bodies may be separated by prolonged
boiling with benzene, which dissolves pyrogallol more readily than
resorcinol.
Haematoxylin yields formic acid when fused with potassium
hydroxide. H. W.
Compounds of the Pyrroline Series. By G. L. Ciamician and M.
Dennstedt (Ber., 15, 27^9— 268b). —Tetrolur ethane, EtO.CO.N : C4H4,
prepared by the action of ethyl chlorocarbonate (diluted with anhy-
drous ether) on potassium pyrroline, is a colourless oily liquid boiling
at 180°. It is almost insoluble in water, and is resinified by contact
with hydrochloric acid. By boiling with alkalis it is converted into
ethyl alcohol, pyrroline, and an alkaline carbonate. On treatment with
ammonia at llO^'jtetrolurethane yields tet rolcarbamide, 'N H^.CO .l!i '.dHi.
This substance crystallises in colourless plates (m. p. 167°), which can
be sublimed without decomposition. Tetrolurethane is decomposed
by ammonia at 130", splitting up into alcohol, pyrrol, and urea.
Allijl'pyrroline, C4H4 ! NC3H5, obtained by warming potassium pyrrol
with a mixture of allyl bromide and anhydrous ether, is a colourless
oil, which boils at 105° under a pressure of 48 mm., but decomposes
when distilled under the ordinary atmospheric pressure. On exposure
to the air, it acquires a brown colour, and is partially converted into
resin. It is almost insoluble in water, and gives a white precipitate
with mercuric chloride.
TetriodopyrroUne, C4I4HN", is best prepared by cautiously pouring an
ethereal solution of iodine into a flask containing 100 c.c. of anhydrous
ether and 10 grams of potassium-pyrroline. The iodine is added until a
permanent coloration is produced, but a large excess of iodine must be
ORGANIC CHEMISTRY. 351
avoided. After removing the ether from the mixture by distillation,
the residue is exhausted with boiling alcohol to separate the potassium
iodide from the iodopyrroline ; the alcoholic solution is treated with
animal charcoal, and poured into water ; and the precipitated product
is further purified by solution in alcohol, reprecipitation by water, and
recrystallisation from alcohol. Tetriodopyrroline forms long prisms
soluble in ether, acetic acid, and in hot alcohol. The crystals decom-
pose without melting between 140° and 150°. With silver nitrate, their
alcoholic solution gives a white precipitate which rapidly blackens.
Tetriodopyrroline is insoluble in an aqueous solution of potash, but
dissolves readily in alcoholic potash. On evaporating the alcohol, a
white crystalline compound remains, which is soluble in water.
w. c. w.
Substitution-derivatives of Quinoline. By P. Feiedlander
and A. Weinberg (Ber., 15, 2679 — 2685). — The readiness with which
the chlorine in a-chloroquinoline can be replaced by hydroxyl and
other radicals has been already shown by Friedlander and Ostermaier
(Abstr., 1882, 732). The authors find that in the case of |S- and
7-chloroquinoline the substitution takes place with much greater
diflficulty, and that the replacement of hydroxyl by chlorine in
hydroxy-quinolines by means of phosphorus pentachloride takes place
readily only in the case of the a-compound. From these results it is
inferred that the readiness of the substitution depends on the fact
that the carbon-atom on which the substitution takes place is directly
united with nitrogen. /3-chlorocarbostyril, CgHeNOCl, obtained by
heating dichloroquinoline with dilute hydrochloric acid at 120°, is
found to be isomeric with the compound obtained by Baeyer and
Bloem from orthamidophenylpropiolic acid (Ber., 15, 2147), although
both melt at nearly the same temperature, viz., 242° and 246°. The
|S- compound differs from Baeyer's in yielding (with phosphorus
pentachloride) a dichloroquinoline melting at 104°. On melting
/3-chIorocarbostyril with potash, |S-hydroxycarbostyril melting above
300° is obtained ; it is soluble in concentrated hydrochloric acid, and
crystallises from it in slender colourless needles. With alkalis it
forms stable salts.
By the action of bromine-vapours on the ethyl-derivative of
carbostyril in the cold, an unstable addition-product is formed,
which readily gives off bromine and hydrobromic acid, yielding
amongst other products the ethyl-derivative of monobromocarbo-
styril. On heating this with hydrochloric acid, 7-bromocarbostyril
is produced, identical with the body obtained by Baeyer and Bloem
from orthamidophenylpropiolic acid (Ber., 15, 2149). By the action
of fused potash the corresponding hydroxy-compound is produced,
accompanied, however, by small quantities of indole, and by an
isomeric hydroxycarbostyril. The latter is separated from 7-hydroxy-
carbostyril by means of hot alcohol. It forms white concentrically
grouped needles melting at 189°. From the acid properties of this
body, and from the readiness with which one hydroxyl-group can be
replaced by chlorine, &c., it is assumed that one hydroxyl-group is
present in the benzene-ring. In this case the body may be termed
hydroxyquinophenol. The body, CgHsClNO (m. p. 180°), obtained
352 ABSTRACTS OF CHEMICAL PAPERS.
from it by the action of phosphoras pentachloride, possesses properties
similar to those of hjdroxyquinophenol. A. K. M.
Cyanethine and Bases derived from it. By E. v. Meyer (J. pr.
Chem. [2], 26, 337 — 366). — The author has already shown in a pre-
vious paper (Abstr., 1881, 64) that cyanethine probably contains an
ttwicZo-group, which is easily replaced by hydroxy! on treatment with
hydrochloric acid. The hydroxyl is further replaced by chlorine by
the action of phosphorus pentachloride. These bodies may all be
regarded as derivatives of the base cyanconiine which has been already
prepared.
Cyanconiine^ G^xJ^2. — In the perfectly pure state this base is a
colourless oil of about 0'93 sp. gr., and boils at 204 — 205°. With
mercuric chloride it yields a sparingly soluble double salt, which,
dried over sulphuric acid, has the composition HgCl2,C9Hi4N2 + ^H20.
Simple salts*of cyanconiine have not yet been obtained. On heating it
with ethyl iodide at 160°, reaction takes place, and an ethylcyanconiine
is produced, which, however, has not been obtained in the free state.
By treating the product of the reaction, after purification, with
platinic chloride, a platinochloride, (C9Hi3EtN2)2,H2PtCl6, is obtained.
Acetic chloride acts violently on cyanconiine, and a crystalline body
is produced, which appears to be formed by the combination of equal
molecules of the base and the chloride. Bromine- water added to an
aqueous solution of the base causes the separation of an oil which soon
becomes crystalline. This is an unstable polybromide, which, on
standing in the air, gives off some of its bromine. The crystalline
residue on treatment with ammonia yields hromocya7iconiine as a
sparingly soluble oil.
Ghlorocyanconiine (loc. cit.), when treated with zinc and hydro-
chloric acid, yields a double salt of a base containing more hydrogen
than cyanconiine. This salt has the formula
ZnCl2,Ci8H3oN4,2HCl,
and yields cyanconiine on oxidation. The base CisHaoN^ has not been
isolated.
Action of Nitrous Acid on Cyanethine. — When gaseous nitrous acid is
passed into a solution of cyanethine in glacial acetic acid, the follow-
ing reaction takes place : C9H13N2.NH2 + NO. OH = N2 + H2O 4-
C9Hi3N2,OH. The hydroxycyanconiine thus produced is identical with
that prepared in other ways.
By the action of the iodides of the alcoholic radicles at 160° substi-
tuted cyanethines are obtained.
Methylcyanethine melts at 74°, and boils between 257 — 258°. It
dissolves easily in water, forming a strongly alkaline solution, which
absorbs carbonic anhydride from the air. It expels ammonia from its
salts, and forms double salts with mercuric chloride, silver nitrate, &c.
Heated with hydrochloric acid in a sealed tube at 180°, it yields
methylamine and the hydroxy-base above mentioned. Hence methyl-
cyanethine is probably represented by the formula C9Hi;N'2.NHMe.
It undergoes no alteration when treated with nitrous acid as above
described.
ORGANIC CHEMISTRY. 353
Ethyl cyanetJiine forms hard crystals melting at 45*. It boils at
259 — 261°, and closely resembles the methyl-derivative.
By the action of methyl iodide, ethyl iodide, and ethylene bromide at
150° on hydroxycyanconiine, derivatives of the latter are obtained.
Methyl-hydroxycyanconiine, C9Hi3MeN'20, forms snow-white needles
melting at 76*5°. It boils at 275 — 276°. It dissolves in water, form-
ing a slightly alkaline solution, which is intensely bitter and only
slightly poisonous. Its platinochloride crystallises in yellow rhombic
prisms. It also forms a characteristic double salt with mercuric
chloride. The base is insoluble in alkalis, in this respect differing
widely from the parent base.
Etlnjl-hydroxycyanconiine closely resembles the methyl-derivative.
It melts at 43° and boils at 267 — 268°. It is isomeric with the
etlioxycyanconiine formerly described (prepared by the action of alcoholic
potash on chlorocyanconiine) , inasmuch as the latter splits up into
ethyl chloride and the hydroxy-base when treated with hydrochloric
acid, whilst the former remains unchanged.
Ethylene-Jiydroxcyanconnne melts at 153*5°, and is very sparingly
soluble in water, wherein it differs widely from the methyl and ethyl-
derivatives.
By digesting a mixture of hydroxy cyancoiive with alcoholic potash
and ethyl iodide, the chief product is the ethyl hydroxy-base, but a
small quantity of ethoxy-base seems to be also formed. The author
concludes from these experiments that the hydroxycyanconiine and
its silver and ethyl-derivatives must be formulated respectively as
C9H,2N(NH).OH, C9Hi2N(NAg).OH, and C9Hi3N(NMe).OH.
Action of Bromine on Cyanethine. — 50 grams of cyanethine is dis-
solved in from five to six times its weight of dilute sulphuric acid,
and 90 grams of bromine added in small portions at a time, the whole
being warmed and shaken in a strong closed flask. A yellow oil sepa-
rates, which is extracted with ether. The acid solution contains
ammonia, propionic acid, and monohromocyanethine as hydrobromide.
Bromocyanethine, pTrecipitated by ammonia from the solution of its
hydrobromide, crystallises from alcohol, in which it is easily soluble,
in crystals resembling those of cyanethine. It melts at 152 — 153°.
Nascent hydrogen converts it into cyanethine, and nitrous acid into
vnonohromohydroxycyancoiine. The latter forms delicate needles, melt-
ing at 172°. It gives an unstable silver derivative on addition of silver
nitrate and a few drops of ammonia.
The oil extracted with ether is a mixture of several substances. It
dissolves in potash, and the yellow solution contains (besides potas-
sium bromide) the potassium salts of a fatty acid (probably propionic),
of isoadi^pic acid, and of an acid containing nitrogen. The oil, when
treated with twice its volume of concentrated ammonia and allowed
to remain for a time, yields beautiful crystals of the amide of a hutylene-
dicarboxylic acid, C4H8(CONH2)2. From 30 grams of cyanethine about
2 — 3 grams of the body are obtained. On saponification with mode-
rately dilute sulphuric acid, it yields the corresponding acid. It
melts at 192°, and is identical with the (S-hutylenedicarboxylic acid
which Otto andBeckurts obtained irom. a-dich lor opropionic acid, and is
in all probability dimethyls mcinic acid, COOH.CHMe.CHMe.COOH.
354 ABSTRACTS OF CHEMICAL PAPERS.
Behaviour of Hydroxycyanconiine with Bromine and Potassium Hy-
droxide.— The action of bromine alone on hydroxycyanconiine is exactly
similar to its action on cyanethine. The same yellow oil is produced,
and the same products are found in the acid solution. But when
potash is used in addition, the result is different, a colourless solution
being obtained, and this, when distilled by itself, yields, besides
ammonia, a body which, on oxidation with chromic mixture, yields
aldehyde and propionic and acetic acids.
Fused potash decomposes hydroxycyanconiine completely, giving off
ammonia, whilst the " melt " contains the salts of propionic and acetic
acids and potassium cyanide.
The author concludes the paper with some remarks on the constitu-
tion of cyanethine. The experiments described seem to warrant the
conclusion that the body contains both an amido- and an tmic?o-group,
and the formation of dimethylsuccinic acid points to the presence of
the group <CpTT]u^ p • Hence the author formulates cyanethine as
follows:— C9Hi5N3='C6H3lSrMe8(NH)(NH2). E. H. R.
Specific Rotatory Power of Salts of Nicotine. By P.
ScHWEBEL (Ber., 15, 2860 — 2853). — The author has made a series of
observations on the specific rotatory power of dilute solutions of salts
of nicotine. The values for the rotatoiy power [a]p of the hydro-
chloride CioHi4N2,HCl in aqueous solution, varied from + 14*44 to
20"02 (L = 100'15) according to the concentration, and agree with
those calculated from the formula [a]^ = 51*5 —79312 + 0-0042382*.
The values for the acetate varied from + 1-667 to + 4-083, in
accordance with the formula [ajn = 49-68 -0-681992 + 0-0025422^
for the neutral sulphate from -f- 1'483 to + 14'717, according to the
formula [ajc = 19-97 — 0-059112. The molecular specific rotatory
powers of nicotine and the above salts, are given in the table below : —
^ = M.
100
Nicotine -261-71
„ hydrochloride + 102-23
,, acetate +110-29
sulphate + 83*43
It is to be observed that whereas the free base is laevorotatory, its
salts are dextrorotatory, and these values for the molecular rotatory
power bear no relation to one another. V. H. V.
Caffeine, Theobromine, Xanthine, and Guanine. By E.
Fischer (Annalen, 215, 253 — 320). — Derivatives of Caffeine. Chloro-
caffeine, C8H9N4O2CI, first obtained by Rochleder (Jahrb., 1850, 435),
is best prepared by the action of dry chlorine on powdered cajffeine,
the reaction being assisted towards its close by heating to 75 — 80° ;
it can also be prepared by the action of phosphoric pentachloride on
caffeine. It forms white crystals melting at 188°, sparingly soluble in
cold water and ether, more readily in boiling water and hot alcohol.
It is reconverted into caffeine by the action of nascent hydrogen.
ORGANIC CHEMISTRY. 355
Bromocaffeine (Abstr., 1881, 614), when heated with alcoholic am-
irionia for 6 to 8 hours at 130°, is converted into amidocaffeine,
C8H9N4O2.NH2 ; this crystallises in slender needles, melts at above
360°, and can be sublimed. It is sparingly soluble in water and
alcohol, more readily in hot acetic acid. Notwithstanding the entry
of the amido-group, it has less basic power than caffeine. It is also
formed in small quantity by the action of potassium cyanide in dilute
alcoholic solution on bromocaffeine. Bromocaffeine, when boiled with
aqueous potash, does not yield hydroxycaffeine ; with alcoholic potash
it yields etlioxy caffeine, CeH9N402.0Et, crystallising in colourless needles,
which melt at 140° and distil at a higher temperature with but little
decomposition. It has feeble basic properties. If heated with hydro-
chloric acid it is resolved into ethyl chloride and hydroxycaffeine (loc.
cit.) ; this melts at above 345°, and sublimes in considerable quantity
at the same temperature ; it yields unstable salts with bases. The
sodium salt, C8H9N403Na + SHoO, crystallises in slender interlaced
needles. The harium salt, (C8H9N403)2Ba + 3H2O, forms groups of
very fine prisms ; both salts are very soluble in water. The silver salt
is obtained in slender needles by mixing ammoniacal solutions of
hydroxycaffeine and a silver salt, and boiling to expel ammonia ; it is
insoluble in water ; by heating it with ethyl iodide it is converted into
ethoxycaffeine. Hydroxycaffeine, when heated with phosphorus
pentachloride and oxychloride, is converted into chlorocaffeine.
Oxidising agents react readily with hydroxycaffeine ; cont^entrated
nitric acid destroys it even in the cold ; chlorine or bromine, according
to circumstances, gives either dimethylalloxan with small quantities of
apocaffeine, or in concentrated hydrochloric solution in the cold, yields
no alloxan, but a mixture of apo- and hypo-caffeine ; in both cases an
additive-compound of the halogen and hydroxycaffeine seems to be
first formed, and then decomposed by the water present. A compound
of this kind is obtained by the action of bromine on dry caffeine, but
it is too unstable to purify ; as, however, it yields diethoxyhydroxy-
caffeine when treated with alcohol, it would appear to be a dibromide,
C8H9N402(OH)Br2.
Diethoxyhydroxy caffeine, 08119^402(011) (OEt) 2, is best prepared by
the action of bromine on an alcoholic solution of hydroxycaffeine,
cooled by a freezing mixture of ice and salt : the yield is nearly quanti-
tative. It crystallises in triclinic prisms, showing combinations of
coPco, coPcxj, OP coP', and Tco, mostly developed in tables parallel
to ooPco ; the properties of this substance and of the corresponding
methoxy-compound, have been already described (loc. cit.).
Alloc.affeine, C8H9N3O5, is obtained as a bye-product in the pre-
paration of diethoxyhydroxy caffeine ; it forms a sandy powder, melts
at 198°, is nearly insoluble in water, and sparingly soluble even in
boiling alcohol ; it is slowly dissolved by boiling with concentrated
hydrochloric acid, and on evaporation is decomposed into readily
soluble products.
Apocaffeine, C7H7N3O5, is formed together with hypocaffeine (Abstr.,
1881, 614; 1882, 217) by ihe action of hot hydrochloric acid on di-
ethoxycaffeine. It crystallises in monoclinic prisms, having the axial
relations a : h : c = 0-8025 : 1 : 0-6976 ; melts at 147—148°, and is
356 ABSTRACTS OF CHEMICAL PAPERS.
decomposed on further heating ; it is readily soluble in hot water,
alcohol, and chloroform, sparingly soluble in cold water, benzene, and
carbon bisulphide.
Oaf uric acid^^C&'E.^'^zOi, is obtained together with carbonic anhy-
dride by boiling apocaifeine with water; the statement that hypo-
caflf'eine is formed at the same time (Abstr., 1882, 217) is found to be
erroneous, and was due to the presence of hypocaffeine in the apo-
caffeine employed (cf. Maly and Hinteregger, ihid.^ 632). By the
action of hydriodic acid, caifuric acid is converted into hydrocaffuric
acid, CeHgN^Os, crystallising in colourless prisms, melting between
240° and 248"^, and resolidifying at 235°; it is readily soluble in hot
water. On boiling it with baryta-water, methylamine is formed,
together with the barium salt of an acid (methylhydantoincarboxylic
acid ?), stable in alkaline solution, but yielding methylhydantoin when
the barium is precipitated by carbonic anhydride.
Hypocaffeine, C6H7N3O3 (m. p. 182°), is not derived from the decom-
position of apocaffeine as previously stated (Abstr., 1881, 614), but is
formed at the same time and apparently independently of the latter in
the decomposition of diethoxyhydroxycaffeine by hydrochloric acid.
It can be distilled in great part unchanged, and is readily soluble in
hot water and alcohol, sparingly in cold water. The barium salt,
(C6HpN303)2Ba, crystallises in slender white needles, the silver salt,
C6H3N303Ag or Ci8Hi9N909Ag2, in aggregates of plates. On boihng it
with baryta- water, hypocaffeine is converted into caffoline (Abstr.,
1882, 217, 628).
When caffoline is boiled with acetic anhydride, carbonic anhydride
and acetylacecafeine, C6H10N3O2AC, are formed ; this crystallises in
monoclinic forms, showing the combinations 00^00, OP, ooP, ^co,
fPco. It melts at 106 — 107°, is readily soluble in water, alcohol,
chloroform, and benzene, sparingly in ether. On treatment with
hydrochloric acid, acecaffeine hydrochloride is obtained as a crystalline
mass, readily soluble in water, and yielding the free base on treatment
with silver oxide.
Acecaffeine, C6H11N3O2, crystallises in prismatic or tabular forms of
the rhombic system, having the axial relations a :b : c = 0'6707 : 1 :
1*2245, and showing the combination ooP. OP, Pco, and, less fre-
quently, ooPco. It melts at 110 — 112°, distils without decomposition,
and is readily soluble in water and alcobol. On oxidation with
chromic acid, it yields a substance closely resembling cholestrophane.
By the action of chlorine a chloro- derivative is obtained, crystal-
lising in colourless needles. When heated with baryta-water, am-
monia, methylamine, and dime thy Icarbamide are formed.
Theobromine. — By the action of chlorine on theobromine, mono-
methylalloxan and methylcarbamide are obtained. BromotheobroTnine,
C7H7N402Br, is prepared in a manner similar to bromocaffeine, and
forms a white crystalline powder, sparingly soluble in hot water,
nearly insoluble in the cold; like theobromine, it possesses acid pro-
perties, and dissolves readily in aqueous solutions of alkalis, but only
sparingly in ammonia. The potassium salt is nearly insoluble in
alcohol, and does not yield an ethoxy-compound on long boiling with
alcoholic potash. The silver salt is obtained as a crystalline pre-
ORGANIC CHEMISTRY. 357
cipitate by mixing ammoniacal solutions of broraotheobromine and
silver nitrate. On heating this silver salt with ethyl iodide, bromethyC-
theobromine is obtained ; it closely resembles broraocaffeine. By the
action of alcoholic potash, it yields ethoxy ethijltheobromine, crystallising
in needles (m. p. 155°). Hydroxyethyltheobrominej C7H6EtN204.0H,
is obtained on boiling the ethoxy-compound with hydrochloric acid ; it
closely resembles hydroxycaff eine in appearance ; treated with bromine
and alcohol it is converted into diethoxyhydroxyethy It heobr amine (m. p.
152°), which is much more readily soluble in alcohol tban the corre-
sponding caffeine-compound, and is decomposed by evaporation with
hydrochloric acid into methylamine and apoethyltheobromine. This
last, on being boiled with water, gives a substance which, by its
behaviour with basic lead acetate, is undoubtedly a homologue of caf-
furic acid.
Hypoethyltheobromine, C7H9N3O3, is obtained, together with the apo-
compound, by the action of chlorine on a solution of hydroxyethyl-
theobromine cooled to —10°. It forms colourless crystals melting at
142°, and closely resembles hypocafFeine ; it is sparingly soluble in
cold, readily in hot water, and can be distilled unchanged. The author
considers that these results show that the same methylamine-group is
split off in the formation of apo- and hypo-compounds, from both
caffeine and theobromine.
Xanthine. — From the resemblance which xanthine bears to caffeine
and theobromine, Strecker (Annalen, 118, 72) considered that the
three bases formed a homologous series, but was unsuccessful in his
attempts to methylate xanthine.
Xanthine is best prepared from guanine as follows : — 10 grams of
guanine is dissolved in a mixture of 20 grams concentrated sulphuric
acid and 150 grams water, heated to boiling, and after cooling to
70 — 80°, a solution of 8 grams of sodium nitrite is added, the mixture
being well stirred. The yield is nearly quantitative, the xanthine is
only of a pale orange colour, and is free from Strecker's nitro-
body.
By the action of hydrochloric acid and potassic chlorate xanthine
is converted into alloxan and urea.
On heating the lead salt of xanthine with 1^ times its weight of
methyl iodide in closed tubes for 12 hours at 100°, a yellow mass is
obtained, from which, by boiling with water, treatment with hydrogen
sulphide, and evaporation with ammonia, a crystalline powder is
obtained, possessing all the properties of theobromine. To remove all
doubt as to its identity with natural theobromine, it was converted
into caffeine by Strecker's method ; the melting point of the sample
so prepared agreed perfectly with that of natural caffeine.
Constitution of Caffeine and its Derivatives. — The following are the
principal facts to be considered in assigning a formula to caffeine : —
1. Its decomposition by chlorine into dimethylalloxan and monomethyl-
carbamide. 2. The presence of a single hydrogen-atom other than
those contained in the three methyl-groups, and capable of replacement
by chlorine, bromine, or the amido- or hydroxyl-groups. 3. The direct
union with a molecule of bromine, showing a double carbon linking.'
4. The conversion of caffeine by addition of oxygen and successive'
VOL. XUY. 2 b
358
ABSTRACTS OP CHEMICAL PAPERS.
elimination of methylaraine and carbonic anhydride, into caffaric acid,
a substance easily resolved into mesoxalic acid, methylamine, and
methylcarbamide. 5. The ready formation of methylhydantoin from
hydrocaffuric acid, showing the presence in the latter of the group
C.NMe
I \p,^ (6.) It has already been shown (Abstr., 1882, 628) that
OH.CH.NMe
caffoline has the constitution I >C0. From these con-
NHMe.C
N'
/^
Biderations caffeine and its homologues are best represented by the
formulae —
MeN— CH MeN— CH HN— CH
^1 II 1 II II
OC C.NMe OC C.NMe OC CNH
MeN— C=N/^^ HN— C=N/^^ ttxt n_Ar/
Caffeine,
Theobromine.
HN— C=rN^
Xanthine.
Nco
The following formulae are assigned by the author to the more
important caffeine- derivatives.
COOH
HO.C-
NHMe.C=N/
Caflfuric acid.
NMe
^CO
COOH
I
HC— NMe
NHMe.C=N/'^'^
Hydrocaffuric acid.
COO.CH NMe
MeN
COOH
I
COO . C— NMe
' I \co
I I
MeN C=N— /
Hypocaffeine
CO
Apocaffeine.
A. J. G.
Some Derivatives of Morphine. By E. Grimaux (Ann. Chim.
Phys. [5], 27, 273— 288).— The substance of Part I of this paper has
already been abstracted (Abstr., 1881, 829) from the Comptes rendus.
Paet II. — By acting on the sodium compound of morphine with
ethyl iodide, ethylmorphme, CnHigNOgEt, is obtained. This body is
homologous with codeine, itself an ether of morphine, and the author
therefore proposes the generic name codeines for this class of bodies.
Codeine proper would then be codomethyline, the body under discussion,
codethyline, &c. Codethyline crystallises with 1 mol. H.O in plates,
soluble in boiling water, alcohol, and ether. At 83° it fuses to a clear
liquid, which solidifies on cooling to a transparent vitreous mass.
Heated for some time at 100°, it turns brown, and after cooling fuses at
65 — 60°. Its hydrochloride crystallises in groups of needles. Sulphuric
acid does not colour it. Heated to 2C° with sulphuric acid and ferric
chloride, it gives a blue colour, a reaction apparently common to all
ethers of this class, and not, as Hesse suggested, confined to codeine
ORGANIC CHEMISTRY. 359
proper. Dried in the air at the ordinary temperature, codethyline has
the formula Ci9H23N03,H20, but loses ^ mol. of H2O in a vacuum.
This seems to support Wright and Matthiessen's double formula.
Heated with methyl iodide, it forms the addition-product
Ci9H23N03,MeI,
which, if treated with silver oxide, yields a tertiary base fusing at
132°, and giving with sulphuric acid the same reaction as metho-
codeine. Other halogen compounds, such as the alcoholic iodides,
epichlorhydrin, allyl bromide, benzyl chloride, chloromethyl acetate,
ethylene bromide, &c., give similar compounds with the sodium «alt
of morphine.
Ethylene-dimorphine, or JDicodetMne, (C]7HigN03)2C2H4, crystallises in
small colourless needles, insoluble in ether, soluble in alcohol. On
heating, it decomposes below 200°, without fusion. Heated to 20° with
sulphuric acid and ferric chloride, it gives a blue coloration. Its
hydrochloride crystallises in small colourless prisms, easily soluble in
water. With chloromethyl acetate, oxacetijlcodeme, or morphine-
fjlycollic acid, C17Hi8NO3.CH2.AcO is produced. This body, obtained
as a deliquescent gummy substance, drying up in a vacuum to an
amorphous mass, is very unstable, and decomposes on being boiled
with water.
When codeine methiodide is treated with silver oxide, it yields a
compound which seems to be an ammonium base. On evaporating
the product in a vacuum on a brine-bath, an oil is deposited,
partially crystallising on complete evaporation. From this residue
ether extracts a substance of the formula Ci9H23]S'03, crystallising in
bright plates, and having all the properties of a tertiary base ; it
appears to be formed by the dehydration of methylcodeine hydroxide,
and to be analogous to some bodies obtained by Claus from the cin-
chona alkaloids. Methocodeme fuses at 118*5°, and soon turns brown
if kept at this temperature. Codethyline methiodide, if treated with
silver oxide, yields a base analogous to methocodeme, but melting at
132°.
With aldehydes, morphine yields compounds similar to those
obtained by Baeyer with the phenols. If morphine is treated with
raethylal or chloromethyl acetate, it forms a compound apparently
of the formula CH2(Ci7Hi8N03)2- The ethers of morphine forui
similar compounds. Benzaldehyde appears to act in like manner.
L. T. T.
Specific Rotatory Power of Apocinchonine and Hydro-
chlorapocinchonine under the Influence of Acids. By A. C.
OuDEMANS, Jun. (Rec. Trav. Ohim., 1, 173— 185).— This paper gives
the results of a large number of observations leading to the conclusion
that, in regard to variation in specific rotatory power under the influence
of acids, the two bases above mentioned conform to the laws already
demonstrated with regard to the four biacid cinchona-bases (p. 81).
The statement of Hesse that the specific rotatory power of hydro-
chlorapocinchonine is the same in its basic as in its neutral salts, is
regarded by the author as destitute of foundation. H. W.
2 6 2
360 ABSTRACTS OF CHEMICAL PAPERS.
Behaviour of Conglutin from Lupines towards Saline Solu-
tions. By H. RiTTHAUSEN (J.pr. Chem., 26, 422 — 440). — In a prelimi-
nary communication (Abstr., 1881, 1160) it was stated that crude as
well as purified conglutin from lupine seeds was almost entirely soluble
in a 5 per cent, solution of sodium chloride, and a portion remaining
undissolved proved the presence of two sorts of prote'ids present. It
was also shown that on adding water to the saline solution, a portion
of this proteid was precipitated, whilst from the mother-liquor copper
vsulphate separated another portion ; the proportions in which these
substances were present were also different, the more nitrogenous
being present in larger proportion in the soluble part, the less nitro-
genous in the insoluble. The present communication deals more fully
with observations made. The results are, that lupines contain large
quantities of albuminoid matter relatively poor in carbon, but rich in
nitrogen, the composition being, C 50-16^ H 7'03, N 18'67, S I'OV,
0 23*07, corresponding with the formula (C44H74N 14015)38. This albu-
minoid matter is soluble at the ordinary temperature in a 5 per cent,
sodium chloride solution, and by the addition of 4 —5 times the
volume of water, is reprecipitated to the extent of 80 — 90 per cent. It is
likewise soluble in water containing a little potassium hydroxide
without decomposition, and is precipitated by acetic or hydrochloric
acids. In the sodium chloride mother-liquor, a substance remains
dissolved, which is precipitated by salts of copper, and is soluble in
solutions of lime or potash. The body heretofore named conglutin is
divided by sodium chloride solutions into a soluble and an insoluble
substance, the latter being however dissolved by potash -solution, and
consisting of legumin originally present, and not of a product of decom-
position; otherwise the formation of ammonia, &c., in presence of
potash would have been noticed. The composition of the substances,
one precipitated by addition of water to the salt solution, the other
s.eparated from the mother-liquors by potash or copper salts, appears to
be identical, and the properties possessed are those of glutiu, and for
this substance the author retains the name conglutin. Conglutin is
present in larger quantities than legumin, from which it may be
easily separated by treatment with potassium hydroxide, addition of
hydrochloric acid, purification by alcohol, treatment of the dried pre-
cipitate with salt solution, which dissolves the conglutin. The above
ig true for the seeds of the blue or yellow lupines, although the
albuminoid in the blue contains rather less sulphur. E. W. P.
Albuminoids in Peach Kernels and Sesame Cake. By H.
B/iTTHAUSEN (/. _pr. CJiem., 26, 440 — 444). — Peach kernels, when
treated with a 5 per cent, solution of sodium chloride, yield up nearly
all their albuminoid matter, but this substance is reprecipitated only
l?y the addition of acids ; in composition it resembles conglutin and
the albuminoid in hazel-nuts and almonds, but is most probably
combined with potash, seeing that it is precipitated only by acids,
and not by the addition of small quantities of water to its solution.
Treatment of these kernels with sodium chloride causes the pro-
eduction of a larger amount of hydrocyanic acid than water alone.
In, a specimen of sesame cake the author found that the albuminoid
PHYSIOLOGICAL CHEMISTRY. 361
contained 2*36 per cent. S (see Pfliigers Archiv., 21, 92 — 96) ; a later
examination proves that this excess of sulphur is due not to the albu-
minoid, but to calcium sulphate occurring in the ash of the prepara-
tion. E. W. P.
Physiological Chemistry.
Oxidations and Syntheses in the Animal Organism. By 0.
ScHMiEDEBERG {Gliem. Gentr. [3], 13, 598). — The method employed by
the author is the same as in previous experiments, benzyl alcohol,
salicylaldehyde, toluene, and benzene being the substances operated
on ; they undergo but slight changes when oxidised. In the experi-
ments with the kidneys, a canula is tied in the ureter, and the secretion
always again mixed with the blood. The luugs were also made use of
through the pulmonary artery.
Benzyl alcohol is only very slightly oxidised by continued shaking
with blood ; the oxidation is much more energetic if the blood mixed
with benzyl alcohol is passed through the kidneys, contact with the
cells of the organs apparently assisting oxidation.
Salicylaldehyde is not oxidised by blood alone, but when it is passed
through the kidneys along with blood, plenty of salicylic acid is formed ;
on the other hand only a small quantity is formed by passing through
the lungs.
Toluene is not oxidised by passing through organs ; and even in the
living animal only slightly. Two grams toluene were injected in
various places into a dog, and only 2| milligrams of benzoic acid were
found in from 500^600 co. of its blood.
Benzene is converted into phenol in the organism ; appearing in the
urine as phenolsulphuric acid. Phenol is converted into catechol and
quinol, which are likewise found in the urine, combined with sulphuric
acid. The author gave a dog a large quantity of benzene, along with
meat; the oxidation products were phenol and catechol, combined with
sulphuric acid. Another dog that had been fed for three days on pure
fat and starch, received on the fourth day, within 48 hours, 24 grams
of benzene, mixed with the same sort of food ; the urine was at first
yellow, but very soon became dark in the air. It contained
16907 gram of phenol, of which 1"005 gram was combined with sul-
phuric acid, the remainder being in the form of phenylglyconic acid.
The author regards these changes as synthetical, water being eliminated,
and the requisite oxygen being supplied from the blood.
D. A. L.
Decomposition and Sjmthesis in the Animal Organism. By
0. ScHiMiEDEBERG {Ghem. Gentr. [3], 13, 599 — 600). — Benzylamine is
readily decomposed in the organism, yielding benzoic and hippuric
acids and urea. Other experiments show that it is not decomposed by
passing through dogs' kidneys j on the other hand it is readily attacked
86? ABSTRACTS OF CHEMICAL PAPERS.
on passing through pig's kidneys, which also can produce hippuric
from benzoic acid. The organs, and frequently the l^lood of dogs and
pigs, also decompose hippuric acid; blood with hippuric acid passed
through pig's or dog's kidney, when the kidney artery is tied, gave rise
to benzoic acid; this change is due to a soluble ferment, "histozym," and
is not the work of bacteria. The ferment can be extracted by means of
glycerol, and is precipitated by alcohol as a white chalk-like mass.
Thus the two processes of decomposition and synthesis go on side by
side, even in living animals, success depending on the most prominent
agency. The quantity of histozym in the blood or organs is very
variable, the dog's liver and pig's kidneys being the richest. Dog's
kidneys may be rendered active both for decomposition and oxidation
of benzylamine, by the introduction of histozym from pig's kidneys.
Benzyl alcohol is produced when finely powdered pig's kidney or
blood is digested with benzylamine. With regard to the difference
between dogs and rabbits in their power of producing hippuric acid,
the author attributes it to the action of the histozym giving way to
the synthetical process ; with dogs, in the kidneys only ; with rabbits,
on the other hand, in other organs as well ; therefore in the dog the
kidneys alone produce hippuric acid, whilst in the rabbit other organs
also produce it. When histozym is injected into the blood of dogs,
they suffer from fever, symptoms of general sickness, and diarrhoea.
D. A. L.
Experiments on the Poisonous Action of Potato Brandy.
By BiiOCKHAUS {CJiem. Centr. [3], 13, 669). — The following substances
were taken into consideration, aldehyde, paraldehyde, acetal, and
propyl, isobutyl, and amyl alcohols. The author tried the experiments
on himself, and took the substance either (1) in the morning fasting,
with water ; or (2) in the afternoon or evening, with wine or good old
brandy.
The aldehyde in the first case acted violently on the mucous mem-
brane ; in the second on the nervous system. The effect is soon over.
The author attributes the greater intoxicating effect of new wine in
part to this substance. The action of paraldehyde and acetal is of
a similar character to that of aldehyde, but more lasting, the effects
remaining to a slight degree until the next day. The alcohols above
mentioned give rise to burning in the mouth, heat in the head, pain in
the forehead, nausea, sensation of suffocation, intoxication varying in
intensity directly with the increase in the formula of the alcohol.
Amyl alcohol is an extremely violent poison. It is at any rate evident
that the impurities in potato-spirit are very much more injurious to
mankind than ethyl alcohol. The better the material is dissolved, the
stronger the action. The author concludes that the greater part of
the visible drunkenness is due to the consumption of bad spirits. He
further points out that even solutions of pare ethyl alcohol, such as
good wine, and spirits and beer, taken in excess, are likewise harmful
to human health, and the more concentrated the alcohol the quicker
and more violent is the injurious effect. He therefore recommends
the prohibition of the sale of bad spirits, and objects to the drinking
of spirits in any form as a pleasure. D. A. L.
"STEGPTABLE PHYSIOLOGY AND AGRICULTURE. 363
Chemistry of Vegetable Physiology and Agriculture,
Schizomycetic Fermentation. By G. Maepmann (Arch. Pharm.
[3], 20, 664 — 673). — In this paper the author has collected all the
facts known concerning the various kinds of fermentation. Specific
bacteria fermentation is that in which, by reason of the growth of
bacteria, reduction products are formed, whilst oxidation processes by
means of the same agents, such as nitrification, are not fermentation.
Nencki explains the reducing action of bacteria by their power of
decomposing water, one hydrogen -atom of which reduces, whilst the
hydroxyl-group is assimilated by the bacteria.
Glycerol. — Fitz describes three glycerol fermentations : (a) in the
ethyl alcohol fermentation produced by a slender bacillus, probably
identical with B. subtilis, in which neither butyric nor succinic acid,
nor butyl alcohol is formed; neither can this bacillus decompose
calcium lactate ; (b) butyl alcohol alone is produced by a bacillus
O'OOS — 6 mm. long by 0*002 mm. broad ; (c) succinic acid is never
formed by bacilli from glycerol, but Fitz found in blue pus a small
micrococcus, which did act in this way. Schulze has found other
bacteria, which besides forming ethyl and butyl alcohols, butyric and
caproic acids, also produce a phorone of the composition C9H14O.
Tartaric Acid. — According to Gautier, Mediterranean wines under
certain conditions rapidly become thick when exposed to the air ; the
red colour changes to a blue- violet, and a brown deposit is formed, as
also acetic and lactic acids ; the cause of this is a bacillus of varying
length, but 0'0012 mm. broad. Konig found succinic acid amongst
the products of the fermentation of tartaric acid : hydrogen ammonium
tartrate yields butyric acid and ethyl butyrate, under the influence of
Ascococcus Billrothii.
, Sugar. — The mass resembling frog spawn, into which beet-sugar
juice is frequently converted, is due, according to Cienkowski and
V. Tieghem, to Ascococcus mesentero'ides (00018 — 0*002 mm. thick),
whereby sugar is converted into cellulose. The lactic ferment of
sugar consists of a thin scum, built up of cells 0*001 — 3 mm. broad,
and nearly double as long. These cells are active only as long as
oxygen is present : consequently the conversion is indirect. This
ferment described by Boutroux does not produce succinic acid, but
the acid is formed from giupe-sugar by Bacillus amylohacter, fully
described by v. Tieghem. B. amylobacter exists in the cells of all
milky- j uiced plants ; a butyric fermentation of albumin is caused by
B. subtilis.
Nitrogenous Matter. — Normal urine is decomposed by Micrococcus
urece (0*00125 — 0002 mm. broad) with formation of ammonium car-
bonate ; pathological urine is affected by other bacteria. The most
important fermentation of albuminous matter is occasioned by Bac-
terium Termo (0*0015 — 0*002 mm. long), and it is this bacterium
which induces the decay of all organic matter, and to which, as pre-
serving the balance between animal and vegetable, our thanks are due.
364 ABSTRACTS OF CHEMICAL PAPERS,
All the other schizomycetes are in some way or another harmfal to ns.
Ptomaines are produced by bacteria as yet nndescribed, and the same
bacteria also produce phenol, which is remarkable, as phenol is detri-
mental to their existence ; also in salting matter phenylpropionic and
phenylacetic acids, indole, cresol, and scatole, &c., have been found.
Reference is made to various fermentations, and to Dispora caucasicay
which forms " kephir." E. W. P.
Progress in the Knowledge of Bacteria. By G. Marpmann
(Arch. Pharm., 3, 20, 905 — 924), — In this communication the author
reviews the work that has been done in the subject of disinfection.
He points out the great difFerence between antisepsis and disinfection,
which difFerence is not generally taken sufficiently into account
in considering the action of carbolic acid, which at times acts as
an antiseptic when in 2 per cent, solutions, but at other times a 5 per
cent, solution is required. To shield a fermentable substance from
the attacks of schizomycetes is vastly different to destroying a ferment,
and arresting its action when in contact with fermentable matter. In
the first case, a relatively small quantity is necessary as compared
with that requisite in the second case. Again a large quantity of
phenol is necessary to render the air of a room antiseptic, whilst on
the other hand a small quantity distributed through the air is suffi-
cient to preserve healthy substances from the attacks of pathogenous
bacteria.
Kosegarten has shown that potassium chloride is unable by itself to
hinder the formation of bacteria in a mixture of cheese, water, and
urine, but the addition of borax brings about the desired result. The
formation of mildew is more easily prevented by borax than by salicylic
acid. Wernich (Virch. Arch., 8) has examined the action of thymol,
hydrocinnamic, and phenolacetic acids, indole, scatole, cresol, and
phenol on schizomycetes, and finds that the action of the first is far
superior in all respects to that of the last-mentioned substance. Most
investigators consider that the present methods of disinfection are
insufficient to destroy bacteria, and exert only a temporary influence on
their development. There are only two methods of testing the vitality
of those bacteria which cease to move when dead. The first method,
introduced by Engelmann, consists in supplying oxygen by means of
chlorophyll to the bacteria, when, if they are still alive, motion may
be detected. This method is uncertain, however; for the elimination
of oxygen by the chlorophyll cells is caused to cease by the anti-
septics employed to destroy the bacteria. A second and more certain
method is that of Loew-Bokorny (Pfliiger^s Archiv., 25). In this the
reducing action of bacteria on salts of platinum, gold, and silver in
alkaline solutions is taken advantage of. The author then describes
several experiments which he has made, using this reaction as indi-
cative of life remaining in the bacteria. In a dilute solution of
extract of meat, a 2 per cent, solution of hydrochloric acid does not
destroy bacteria, a 5 per cent, only partly, but death occurs with a
10 per cent, solution; the same may be said of sodium chloride.
Goulard water is not fatal to bacteria ; it acts only by retarding or
.preventing development, and keeps wounds clean. Lead w^ater
VE(iETABLE PHYSIOLOGY AND AGRICULTURE. 305
(Ph. Germ. ?) has but little inflaenne ; but if three times the usual
strength be employed, then death ensues : henee this preparation is to
be preferred to Goulard water. An aqueous emulsion of TJng. hydrarg.
cinereum (Ph. Germ.) slowly kills B. termo and crythosporus. A
retarding action on B. termo is noticed when 2 — 5 per cent, solutions
of iodine tincture are employed : whilst the concentrated tincture is
probably fatal ; this then accounts for the observed actions of iodine
(and mercury) on ulcers, &c. Appended is a valuable list of the
literature on the subject which has appeared during 1880 and 1881.
E. W. P.
Direct Fermentation of Starch. By Y. Marcano (Compt. rend.,
95, 856—859; compare Abstr., 1882, 1311).— The Indians of South
America make an alcoholic liquor called chicha, by the fermentation of
Indian corn. The corn is first allowed to soak for from four to six
hours to soften it, and afterwards fermented. The fermentation is not
due in the first instance to the action of a diastase present in the
grain ; because if powdered maize be boiled with water for a quarter
of an hour and then left at rest, fermentation soon sets in. The
effect is produced by a minute organism, which can be detected by the
microscope.
The first action of this organism, however, is to form a diastase,
wliich thus either produces or aids fermentation. This is shown by
the fact that a mixture of maize-starch with water satui-ated with
chloroform, remains almost unaltered : chloroform prevents the action
of those organisms which cause fermentation, but does not interfere
with the action of diastase, whereas a similar solution without chloro-
form is soon found to contain (after being freed from organisms by
filtration through porous porcelain under pressure) matter capable of
producing fermentation. Alcohol precipitates the diastase from the
solution.
The same organism causes lactose, mannite, and dulcite to ferment,
and it may be used to produce koumiss by adding it to milk con-
taining lactose in proportion to the strength required.
The organism which causes maize-starch and starchy grain in
general to ferment, and which is found in the stalks of the Indian
corn, is identical with that which produces the fermentation of the
juice of the sugar-cane in sugar manufactories. The germs are found
in the cells of the stalks of the plant. E. H. R.
The First Product of Plant Assimilation. By A. Mori
(Chem. Centr. [3], 13, 565; compare Abstr., 1882, 243).— The author
detected a substance of aldehyde nature both by nitrate of silver and
rosaniline sulphite in plants containing chlorophyll, which had been
exposed to the sun. If, however, the same plants were left 24 or 48
hours in the dark, so that the first products of assimilation had time
to alter, little or no separation of silver took place. This supports
Baeyer's view, that the assimilation of carbonic acid under the influence
of light gives rise to formaldehyde, thus : CO2 + H2O = CH2O -f O^.
D. A. L.
Function of Resins in Plants. By H. de Vries {Chem. Centr.
[3], 13, 565). — The author is of opinion that the primary function of
3G6 ABSTRACTS OF CHEMICAL PAPERS.
the resins of Coni/erce, and analogous juices of oilier plants, is to render
service in cases of injury, by covering the wound with a protecting
coating, and by favouring the healing of the wound. D. A. L.
Chemistry of the Maize Plant. By H. Leplay (Gompt rend.,
95, 1033-1036, and 1133— 113G).— The maize was analysed at three
different stages of vegetation, viz. : — (1.) July 1st, when the organs of
reproduction have not yet appeared or just begin to appear. (2.)
August 1st, when fertilisation has been effected and the ear and grains
have formed, but when the grains are easily crushed between the
fingers, and yield a milky juice containing but little starch, (3.) Sep-
tember 1st, when the grain is ripe and hard, and no longer contains a
milky jaice, but is full of starch.
Between the first and second stage the stalks, leaves, and roots of
the maize increase in weight, and at the second stage the weight of
the leaves is greater than that of the stalks. Between the second and
third stages, the weight of the leaves and stalks diminishes, until at
the third stage the stalks have lost nearly half their weight, and the
leaves more than half. At this stage the weight of the ear is nearly
the same as that of the leaves, and is but little inferior to that of the
stalks. Between the second and third stages, the weight of the root
remains practically the same.
The total amoant of sugar, without regard to its chemical natune,
increases considerably during the formation of the ear, but diminishes
considerably during the formation of the starch in the grain. W^hen
the organs of reproduction begin to form, the sugar is uniformly dif-
fused throughout the stalks and leaves, but between the first and
second stages it increases from 2*27 up to 1054 per cent, in that
portion of the stalk below the ear, and up to 11'63 per cent, in the
stalk above the ear. It also increases by 4 per cent, in the sheathing
leaves, and by 2*54 per cent, in that part of the leaves which hangs
freely. At the same time sugar is found in the ear and in the support
of the ear, to the extent of 8-72 per cent., and in the milky grains in
smaller amount, about 5'81 per cent. During the ripening of the
grain and the formation of starch, sugar disappears entirely from the
leaves, diminishes in the stalk from 10*54 to 2'36 per cent., in the
support of the ear from 8*72 to 5'81 per cent., and in the grain itself
from 5*81 to 236 per cent.
In the first stage of vegetation, the stalks and the part of the leaves
forming the sheath contain no reducing sugar ; the free portions of the
leaves contain crystallisable sugar to the extent of about one-fourth
the total amount of the sugar. Between the first and second stages, the
saccharose increases in the leaves by 55 per cent, of the original amount,
and in the stalks by 10 times; whilst between the second and third stages
both crystallisable and non-crystallisable sugars disappear entirely
from the leaves ; the non-crystallisable sugar disappears entirely from
the stalk, and the crystallisable sugar diminishes by more than 80 per
cent. It appears, therefore, that the sugar is formed in the leaves
and accumulates in the stalk until the starch begins to form in the
grain, when the sugar travels towards the ear into the support of the
grains, and lastly into the grains themselves, where it is transformed
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 867
into starch. This process goes on nntil the leaves are entirely, and the
stalks and supports almost entirely exhausted. The function of the
sugar is evidently to furnish to the grain the elements necessary for
the formation of starch. Since the sugar remaining in the stalk is
entirely crystallisable, it would appear that the reducing sugars are
the most readily converted into starch. The transformation is ex-
plained by the elimination of 3 mols. H^O from the reducing sugars,
and 2 mols. H3O from the crystallisable sugars, thus : —
Reducing sugars C12H24O12 = C12H18O9 + 3H2O
Crystallisable sugars C12H22OU = CviHigOg + 2H2O.
In the first stage of vegetation, potassium and calcium exist in com-
bination with vegetable acids in the soluble state in the juices, and in
the insoluble state in the tissues in all parts of the plant. After the
first stage, no more potassium is absorbed from the soil. Between the
first and second stages, the quantity of potassium in the stalk dimi-
nishes very considerably, it being transferred to the ear which is in
process of formation, and in which the amount of potassium con-
tinually increases until the grain is ripe. Between the first and
second stages, the amount of potassium in the leaves remains constant ;
but between the second and third stages it diminishes by more than
16 per cent., wliilst the amount in the stalk increases by 25 per cent.
During the development of the grains and whilst they are soft, the
amount of potassium which they contain is five times as great as that
in their support ; but after the grains are ripe, the amounts in the
grains and in the support are about equal.
The distribution of the calcium differs considerably from that of the
potassium. Unlike the potassium, the total amount of calcium in-
creases by 143 per cent, between the first and third stages. Whilst
the potassium diminishes in the stalks between the first and second
stages, the calcium increases by 141 per cent. Between the second
and third stages, the calcium diminishes in the leaves, and still more
in the stalks, but increases in the ear and especially in the grains, in
which, from the time of their formation to maturity, it increases to the
extent of 188 per cent. The leaves and stalks apparently constitute a
reservoir which furnishes calcium and potassium to the grain, with,
however, this difference, that the total amount of potassium in the whole
plant remains constant after the first stage, whilst calcium is conti-
nually absorbed from the soil.
Between the first and second stages, the total potassium existing in
an insoluble form in the juices and tissues diminishes by 75 per cent.,
whilst the total calcium present in an insoluble form increases by
59 per cent. In the stalks, the potassium in an insoluble form dis-
appears entirely, whilst the calcium increases by 41 per cent. In the
leaves, the potassium diminishes by 72 per cent., whilst the calcium
increases by 62*6 per cent.
The potassium and calcium exist in the maize, as in the beetroot, in
combination with vegetable organic acids. The acids are formed from
the carbonic acid absorbed by the roots partly in the form of potas-
sium and calcium bicarbonates and partly in solution in water. The
368 ABSTRACTS OF CHEMICAL PAPERS.
equations which represent the conversion of the carbonic acid into
different organic acids are the same as in the case of the beetroot.
C. H. B.
Chemistry of the White Silesian Beetroot. By H. Leplay
(Compt. rend., 95, 893—895 and 963— 966).— The author concludes
that the organic acids which exist in the beetroot in the form of caU
cium and potassium salts are the result of the transformation of the
calcium and potassium bicarbonates absorbed from the soil along
with water saturated with carbonic anhydride, by the roots of the
plant. The transformation may be represented .by the following
equations : — Conversion of potassium bicarbonate into potassium oxa-
late, K2C03,C02 = K2C2O4 ^- 0 ; conversion of the bicarbonate, car-
bonic anhydride, and water, into potassium acetate, K2C03,C02 +
2CO2 + 3H2O = 2KC2H3O2 + Og ; conversion of the bicarbonate, car-
bonic aiihydride, and water into potassium malate, K2C03,C02 +
2CO2 + 2H2O = K2C4H4O5 + Oe; conversion of the bicarbonate, car-
bonic anhydride, and water into potassium tartrate, K2C03,C02 -h
2OO2 + 2H2O = K2C4H4O6 + O5; conversion of the bicarbonate, car-
bonic anhydride, and water into potassium citrate, K2C03,C02 +
4CO2 + 3H2O = K2C6H6OV + O9.
The tissues always contain a certain quantity of calcium in the
form of an insoluble organic compound, apparently formed from cal-
cium bicarbonate, carbonic anhydride, and water, thus : CaC03.C02 +
IOCO2 + IOH2O = Ci2H2oOio,CaO + O24. The changes which take
part in the transformation of the substances absorbed from the soil
are (1) reduction of the carbonic anhydride with elimination of
oxygen ; (2) condensation or assimilation of carbon ; (3) assimilation
of the elements of water in the same proportion as in water. The
author gives a table showing the relative importance of each of these
three changes in the formation of the various acids. The changes
differ essentially among themselves, and do not follow the same order.
The oxygen which is not used up in the formation of organic acids
and tissues, apparently plays an important part in the formation of
complex nitrogenous compounds.
The nitrogen compounds, such as albumin, nitric acid in the form
of potassium nitrate, &c., existing in different parts of the beetroot,
appear to be produced by the organic transformation of the ammo-
nium bicarbonate absorbed from the soil by the roots of the plant.
Since the juice of the beetroot is never acid, it is evident that the
nitric acid exists only in the form of potassium nitrate, the potassium
having been absorbed by the roots in the form of bicarbonate. It is
probable therefore that the albumin, &c., are formed by the simul-
taneous alteration of the ammonium and potassium bicarbonates. The
forces which take part in the formation of vegetable acids and tissues
differ essentially from those concerned in the production of the
nitrogen compounds. The changes which take place in the formation
of the acids and tissues are reduction of carbonic acid, condensation or
assimilation of carbon, assimilation of the elements of water in the
same proportions as in water, and elimination of oxygen. In the for-»
mation of the nitrogen compounds, on the other hand, there is no
reduction of carbonic acid, no condensation of carbon, no assimilation
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 369
s
of water, no evolution of oxygen, but water is eliminated and oxygen
is assimilated. The two series of changes are complementary. The
conversion of the potassium bicarbonate into vegetable acids and
tissues furnishes the oxygen and potassium necessary for the conver-
sion of the ammonium bicarbonate into albumin, potassium nitrate,
&c., and the production of these compounds liberates in the nascent
state the water required for the formation of the acids and tissues.
Equations are given showing the formati(m of tissues, albumin, &c.,
from the bicarbonates. All the elements contained in the potassium,
calcium, and sodium bicarbonates absorbed by the roots, are found in
the beetroot in the form of tissues, salts of vegetable acids, albumin,
potassium nitrate and nitrite, water, carbonic acid, and nitrogen.
Under conditions unfavourable to the complete conversion of the
bicarbonates into these compounds, secondary organic substances,
such as asparagine, are formed, but these must be regarded as abnor-
mal products, although formed in a similar manner. C. H. B.
Chemistry of the Nymphsea. By W. Gruning (Arcli. Pharm.
[3], 20, 582 — 605, and 736 — 761). — Amongst popular remedies in
Germany, Nym^ihcea alba and Nuphar luteum have long occupied a
prominent place, but were omitted from the officinal list of medicinal
plants in the beginning of the present centurj ; they have since
attracted the attention of chemists on account of their tannin, as a
probable substitute for other tanning materials.
Morin in 1821 published an examination of the rhizome of N. alba,
and Dragendorff in 1879 described an alkaloid obtained from it;
he promised further researches, but did not carry them out ; the
author undertook their examination at his request, and made both
qualitative and quantitative estimations of the constituents of dif-
ferent portions of the two species, N. alba and Nuphar luteum.
Moisture and Ash. — Seeds and stalks dried at 110°, and the residue
ignited; N. luteum showed a richness in alkali which, calculated from
sulphates, equals Na^O, 4'63 per cent., and KjO, 32*15 per cent.
Fat and Resin. — The former, obtained by treating the pulverised
substance with light petroleum, was greenish in colour and thick,
easily saponified with soda. The seeds of N. luteum yielded a fat,
congealing at the ordinary temperature, melting on the hand, and
transparent when cold ; the resin is the residue of the fat operation
treated with ether ; in the case of nuphar an intermediate washing with
water is given to remove the tannin.
Matter soluble in ether should theoretically equal the sum of those
soluble in light petroleum and in ether, but in fact there is a dif-
ference.
Soluble in Alcohol. — After extraction with absolute alcohol, evapo-
ration, drying, and weighing, the residue was treated with water, a
part of the solution again evaporated, the remainder of the aqueous
solution was employed for estimation of tannin by Sackur's process —
precipitation by copper acetate.
Soluble in Water. — 20 grams macerated for one or two days at ordi-,
nary temperatures in 400 c.c. water, a part evaporated, dried and
weighed, and a part precipitated with alcohol, the precipitate dried
370 ABSTRACTS OF CHEMICAL PAPERS.
and ignited — the nitrogen in both estimated by soda-lime ; part treated
with lead acetate for tannin, and freed from lead with sulphuretted
hydrogen ; the remainder was employed to estimate glucose and
saccharose. An examination for vegetable acids other than tannin
showed the presence of citric, oxalic, and malic acids. Tests for
salicylic, tartaric, benzoic, succinic, and fumaric acids yielded nega-
tive results.
Solvhle in Soda Solution. — Part of the residue from the previous
operations was treated with an aqueous solution of 1 per 1,000 of
soda, filtered, the filtrate neutralised with acetic acid and decomposed
with alcohol ; the precipitate after deduction of ash waa called meta-
rabic acid.
Starch.— The residue from the soda treatment, boiled with water,
a small quantity of diastase added, left to digest fonr hours at a tem-
perature of 40°, filtered, 4 per cent, hydrochloric acid added and
boiled in connection with an upright condenser for three hours : the
resulting sugar, estimated by Fehling's solution, was calculated to
starch.
Pararalin. — The residue, after removal of starch, was dicrested for
a day with 1 per cent, solution of hydrochloric acid, quickly boiled
and filtered, the filtrate treated with alcohol, and the precipitate (ash
deducted) reckoned as pararabin.
Wood gum of Thomon was sought, but not found.
Cellulose. — After the various processes described, the portions of
the plants were treated with freshly prepared chlorine-water, and
successively with clean water, dilute soda solution, and again fresh
water ; the loss of dry matter between two weighings, less albuminous
matter, was reckoned as lignin and similar substance.
The following table (p. 371) shows the results of the analysis.
Alkaloids. — The author succeeded in separating an alkaloid from
N. luteum, and also from N. alba. Dragendorff had already isoliited it
in the case of the latter ; the chemical and physical properties appear
to be identical as well as their behaviour towards group reagents, but
in their colour reactions there is a decided difference ; nupharine, as
the alkaloid of JV^. luteum is named by the author, is a whitish, brittle
mass, which on being rubbed sticks to the fingers. It solidifies at 40
— 45° ; at 65" it is of a syrupy consistence ; it is easily soluble in
alcohol, chloroform, ether, amyl alcohol, acetone, and in dilute acids,
but almost insoluble in light petroleum ; the acid solution has a
peculiar and characteristic smell, and is acted on by most of the
group reagents for alkaloids, potassium chromate, picric acid, iodide
of potassium, &c. With trouble the author discovered colour reac-
tions which distinguish it from all other alkaloids. A small quantity
when dissolved in dilute sulphuric acid and warmed on a steam-bath,
assumes a brown colour, which gradually passes into a dark black-
green; the addition of a very few drops of water causes the colour to
disappear, with precipitation of a voluminous yellow-brown substance.
The acid solution when placed over sulphuric acid and lime, after 10
or 12 days, becomes a magnificent green, increasing in intensity for
about another 10 days, until it becomes a dark blue-green ; a few
drops of water causes the colour to disappear immediately with separa-
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
371
Moisture
Ash
Fat
Resin soluble in ether
Resin insoluble and pbloba-
phene
Mucous matter with traces
of albumin
Tannin
Matter not precipitated by
copper acetate
G-lucose
Saccharose
Substances soluble in water
indirectly estimated. .
Metarabin, &c
Soluble in dilute soda solu-
tion not precipitated by
alcohol
Starch
Pararabin
Albumin
Lignin, &c
Intercellular substance
Cellulose
Nuphar.
Rhizoma.
Seeds.
10-30
11-31
5-19
0-89
0-77
0-51
0-60
2-11
1-54
1-97
1-31
0-26
2-27
6-72
0-54
5-93
—
1-21
—
4-40
1-38
2-50
0-86
8-36
0-59
18-70
44-00
3-81
—
3-99
7-08
14-82
6-45
—
3-22
14-11
13-21
Nymphaea.
Rhizoma. Roots. Seeds
10-56
5-47
0-49
1-55
2-52
8-62
10 04
0-03
6-25
1-92
3-26
5-80
20-18
1-80
4-06
14-26
9-36
6-71
10 07
0-59
1-38
0-30
6-94
8-73
1-00
5-62
3-60
6-11
•60
•09
•20
•21
•99
•47
•42
9-06
2 12
106
0-21
0-42
1^47
1-10
0-86
0^94
1^18
0 46
1-51
47-09
9 79
4-78
0^98
11 66
tion of a yellow crystalline precipitate, which when removed from the
filtrate, liquefies in air, or over sulphuric acid, with return of the
green colour. This experiment can be repeated frequently with the
same sample.
The alkaloid is tasteless, but its acid solution is intensely bitter j it
has not yet been obtained crystalline.
The formula given to the alkaloid is N2C18H24O2. The formula re-
quires an equivalent of 300 ; by experiment it was found 285'5 ; the
differences are attributed to impurities in the sample.
The same formula has baen given by Pelletier and Couerbe to
menispermine and paramenispermine ; the three alkaloids are probably
isomeric. With Wild's polariscope nupharine is optically inactive.
Its physiological efFects were tried on cats, with no toxic effect.
The alkaloid of Nymphcea alba does not give the green reaction with
dilute sulphuric acid, but on the contrary, it gives the following, which
are not given by nupharine. Concentrated sulphuric acid and potassium
chromate colour its solution first red-brown, after some hours clear
green. Concentrated sulphuric acid alone produces a red- brown,
which passes into grey. Frohde's reagent colours first red, then dirty
green. The alkaloids are not present in the seeds of N. luteum nor
in the blossoms or seeds of N. alha.
In the second paper the author continues the examination of the
372
ABSTRACTS OF CHEMICAL PAPERS.
two plants of the family, N. alba and Nuphar lutea. As far as exami-
nation of two members of it allows him to come to a conclusion, he
thinks that the tannin contained in them is their most important con-
stituent from a chemical point of view ; after that the alkaloids and
then the starch. The tannins of the two species differ slightly in
their properties, but are closely related in their reactions. They both
differ from tannin derived from other sources in yielding characteristic
secondary products. The insoluble tannin found in them is very
characteristic, but a somewhat similar substance was found by Lowe
in oak-bark, and as methods of examination are now in use which
were not then employed, it is probable that the substance has often
escaped detection, and will be more frequently found in future.
The insoluble tannin of oak-bark is the anhydride of the soluble
acid ; the insoluble acid of Nyraphasa appears to be a hydrate of ic8f
phlobaphene, and the author thinks it more than probable that the
phlobaphene is an intermediate product between the soluble and in-
soluble tannin.
The tannins of I^ympha^a are also notable for yielding many second-
ary products, which have individually been found in other tannins, but
their presence together has not been hitherto noted. Ellagic and
gallic acids are easily obtained ; another substance, which rapidly
absorbs oxygen from the air and passes into a body of the nature of
phlobaphene, and a second substance, which by similar absorption of
oxygen passes into two bodies, or assumes two phases with properties
similar to chlorophyll. Sugar was looked for in consequence of
Strecker and others having asserted it to be one of the derived pro-
ducts of tannin from gall-nuts and oak-bark, but it was not found.
The author's experiments lead him to believe that the molecule of
the tannin obtained from Nymphaea is of a very complex nature.
J. F.
Analyses of Tobacco Ash. By R. Romanis (Chem. News, 46,
248).
Men-jone
Grown on alluvial soil at
X_,J
•-
tobacco on
Karrawaddy.
granite soil
of Mandalay.
Midrib.
Leaf.
Midrib.
Leaf.
K20
17-88
31-49
22-65
32-19
19-02
KCl
—
2-55
—
0-63
0-40
NaaO
4 12
—
4-45
—
—
NaCl
0-74
1-84
1-09
—
—
CaO
27-27
28-93
20-78
37-40
36 51
CaOPA-.
—
—
—
—
8-84
MgO
7-58
6-64
8-90
6-12
7-31
MgOPA . .
—
—
—
11-95
—
FesOgPA--
6-94
12-58
10-27
—
7-76
SO3
10-92
4-40
7 35
4-62
6-50
SiOs
24-53
11-56
24-56
6 19
13-76
99-98
99-99
100-05
99-10
100-10
E. W. P.
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
373
Composition of Different Varieties of Fodder. Cabbage. By
M. DuGAST (Annales Agronomiques, 1882, 226 — 239). — The plants
were grown on two sorts of soil, one rather stony, and belonging to
the niiocene period, the other moor, which had been cleared for some
years. The samples taken represented as nearly as possible the
general characteristics of the crops, and were gathered early in
November and January of the following year. They were then dried
in an oven and ground before being subjected to analysis. The per-
centage of water varied from 90 in the leaves to 70 in the roots, and
was greater in January than November. The following analysis of
the " chou moellier " will give a general idea of their composition : —
Dry substance.
—
Ash.
Leaves.
Stalks.
Leaves.
Stalks.
Roots.
Protein
19-46
14-26
0-32
13 19
14-07
5-35
2 94
8-14
22-27
13-29
14-60
4-Ot
24-98
1417
10-05
0-95
7-85
10 07
Phosphoric acid
6-29
36-11
7-25
*2-17
13-79
11-52
0-04
15-57
6-58
1-99
6-25
20 -85
6-48
2-58
16-03
15-58
0-06
24-41
6 21
1-62
5 05
10 14
Saccharose
Starch
Magnesia
Ferric oxide. . . .
Sulphuric acid. .
Chlorine
Manganese ses-
quioxide
Potash
Soda
8-87
2-72
Cellulose
Pectose
Fat
13-23
6-54
0-05
A-h
Not determined .
20-37
5-08
Silica
The percentage of ash in the roots was 5-93.
Generally speaking, the amount of protein was greater in the leaves
than in the stalks: in the former it varied from 11*9 to 21*2 per
cent., and in the latter from 7*34 to 13-29 per cent. The samples
taken in 1881 were richer in protein than those of the following year.
The percentage of fat was also much greater in the leaves than in the
stalks. The ash was found to vary considerably as regards some of
its constituents. Phosphoric acid ranged from 4'6 to ll'l, and lime
from 46-05 to 21*2 per cent., the latter being found principally in the
leaves, whilst the stalks were richer in potash.
The rule generally followed in practice that it takes 5 or 6 kilos, of
cabbage to replace one of hay, is confirmed when we compare the rela-
tive amount of nitrogenous bodies they contain, as shown by the above
analyses. J. K. C.
Loss and Gain of Nitrogen in Arable Land under the
Influence of Different Systems of Cultivation. By P. P.
D^H^RAiN (Annales Agronomiques, 1882, 321 — 356). — It is evident
that in a perfect system of culture, the land which has received
manures and yielded crops should in the end be as rich as before in
reproductive qualities, or even richer ; taking the nitrogen present for
example, the sum of that originally contained in the soil, together
VOL. XLIV. 2 C
374 ABSTRACTS OF CHEMICAL PAPERS.
with the quantity furnished by manures, should be equal to the
nitrogen left in the soil together with that abstracted by crops. In
practice, however, this is not the case, and a loss of nitrogen, repre-
sented by the difference of the above quantities, always takes place ; to
ascertain this loss under varying circumstances, and how to reduce it
to a minimum, was the object of this investigation.
Three series of four plots of land each received from 1875-77 large
quantities of manures, viz., stable dung, sodium nitrate, and ammo-
nium sulphate ; from 1878 to 1881 different crops were raised without
the addition of fresh manures, samples of soil and crops being taken
and analysed at various stages. One series was left without manure
the whole time.
Four plots were planted exclusively with maize : in 1875 the soil
was found to contain 2*04 grams nitrogen per kilogram ; the quantity
of nitrogen was again determined in 1878 and 1881, and found to be
as follows : —
Sodium Ammonium
Stable dung, nitrate. sulphate. Unmanured.
1878 201 1-79 1-88 1-G7
1881 1-68 1'45 1-62 1-45
It appears, therefore, that from 1875 — 1878 the soil was losing
nitrogen the whole time, although large quantities were being fur-
nished by the manure, while it underwent still greater absolute loss in
the four following years, that plot indeed which had been manured
with sodium nitrate becoming as poor as the unmanured soil. A
calculation was made to ascertain the actual loss of nitrogen incurred
between 1875 — 1878, taking into consideration that furnished by the
manure, and extracted by the crops ; and the result showed that the
plot manured with stable dung was the best, the losses in the other
cases being greater than the quantities supplied by the manure. By
subtracting the nitrogen contained in the crops of the unmanured
plot from that of the crops of each of the three other plots, the
amount of nitrogen supplied by the manure was roughly obtained.
The percentage utilised in the case of the stable dung was 13'5, whilst
in sodium nitrate I'l^ and in ammonium sulphate only 0*5 per cent,
of the nitrogen had been utilised.
From 1878 — 1881 the losses of nitrogen, although still great, were
not nearly so large as in the three preceding years, the annual loss
being only about half; in some cases, however, it was still greater
than the amount of nitrogen in the crops, especially in the case of
sodium nitrate.
Another series of four plots was sown from 1875 — 1879 with pota-
toes, and in 1880 and 1881 with corn, the same conditions with
respect to manure being observed as before ; the quantities of nitrogen
per kilogram of soil are shown below : —
Sodium Ammonium
Stable dung. nitrate. sulphate. Unmanured.
1878 2-08 1-78 1-74 1-74
1881 1-69 1-67 1-54 169
i
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 375
Whilst the soil manured with stable dung contained in 1878 more
nitrogen than at the commencement of the experiments, all the others
had become impoverished, especially in the case of the soil treated with
ammonium sulphate. The absolute loss of nitrogen calculated as
before, from 1875 — 1877, proves also to be greatest in this case, and
is more than double the quantity furnished by the manure. In all
cases the crops contained less than one-third of the nitrogen afiPorded
by the manures, and the percentage of utilised nitrogen was found to
be in stable dung 7'^, sodium nitrate 6"3, and ammonium sulphate
1*5 per cent. only. Tho worst crops- were also obtained with the last,
and the best with the first of these manures, both before and after
1877. The annual loss of nitrogen was greater in the case of the soil
manured with stable dung, after the manuring had ceased, than before,
but the reverse happened with the other three plots. The amount of
nitrogen extracted by the potatoes was much less than by the maize
crops.
The next series of plots was grown with beetroot from 1875 — 1877,
with maize in 18'78, and with hay in the two following years. Lossof
nitrogen was observed as in the previous cases in the first four years,
the soil being impoverished to a far greater degree than was the case
either with potatoes or maize, the final percentage of nitrogen in the
soil in 1879 being much less than before, and varying very little in the
manured plots. In the next three years, crops of hay were raised
containing considerable quantities of nitrogen, but at the end of the
time all the soils were found to have gained appreciable amounts of it,
instead of undergoing loss as in all the former instances. That this
gain was not confined to the upper strata of the soil was shown by
several analyses of samples taken from below at varying depths.
Further experiments showed that a loss of nitrogen in a soil was
accompanied by a corresponding, although much greater, loss of
carbon ; whereas, when the quantity of nitrogen increased, no decrease
in the carbon took place.
The ameliorating effect of allowing land to grow crops of hay occa-
sionally has long been knovra to agriculturists,, and meadow lands
often contain very large quantities of combined nitrogen. The cause
of the loss of the latter in cultivated soils is probably due to the
greater surface exposure produced through ploughing and breaking
up the soil, and consequent oxidation of the organic compounds, the
nitrogen being probably converted into nitrate and washed away with
the drainage-water. J. K. C.
Analysis of a new Guano from Australia. By A. B. Griffiths
(C/iem. Neios, 46, 260).
Nitrogenous matter Phosph. Salts of
and ammonia salts. acid. Lime. alkalis. Sand. Water.
46-721 15021 15-999 1*421 2 714 15918
E. W. P.
Utilisation in Agriculture of the Slag from the Basic
Dephosphorising Process. {Ghem. Centr. [3], 13, 668—669 ;
comp. this vol., 133). — A slag of the following composition —
2 c 2
376 ABSTRACTS OF CHEMICAL PAPERS.
SiOa.
CO2.
s.
PgOfl. FesOg. MnsOa- CaO.
and sand.
6-20
172
0-56
19-33 974 9-50 47'60
2-68
Percentage
liad 10*94 per cent, of its phosphoric, that is 66'6 per cent, of the total
phosphoric acid, soluble in ammonium citrate, and therefore in a form
easily assimilated bj plants.
After treatment with sulphuric acid — (1.) 1000 grams slag with 700
grams 66 per cent, sulphuric acid; the dried mass contained 12'13 per
cent, phosphoric acid, of which 1'15 per cent, was soluble in water,
9'35 in ammonium citrate, and 1'63 in hydrochloric acid. (2.) 1000
grams slag with 1000 grams 66 per cent, sulphuric acid ; superphos-
phate contained 8*07 per cent, phosphoric acid, of which 4'61 per cent,
was soluble in water, 275 in ammonium citrate, and 071 in hydro-
chloric acid; after the lapse of three months matters had altered,
evidently on accouflt of the iron present, and the quantity soluble in
water was now only 0'63 per cent., against 6'b6 per cent, in ammonium
citrate and 0*88 per cent, in hydrochloric acid. It will thus be seen
that conversion with sulphuric acid is not profitable, but as more
than half of the phosphoric acid is soluble in the soil-fluids containing
carbonic anhydride, and hence is rendered available to plant-roots ; the
slag can be used directly as manure. There is an objection to this
application, however, namely, the deleterious effect on plants of the
lower oxides of iron and manganese, and of the hydrogen sulphide
resulting from reduction of the sulphur-compounds ; this gives
rise to the suggestion that the slag should be applied early in the
autumn only to those fields which are not going to be tilled until the
spring, so that the objectionable substances may become harmless by
oxidation during the winter. Moreover, it is advisable to strew the
slag on the straw in the stable, or to place it in layers between the
manure on removing it from the stable ; in this way the oxidation of
the noxious compounds goes on spontaneously, and at the same time
the carbonic anhydride formed by the decomposition of the manure
renders some more of the phosphoric acid available. D. A. L.
Analytical Chemistry.
Microchemical Reaction Methods. By A. Tschiech (Arch.
Pharm. [3], 20, 801 — 812). — The author describes the great advantages
of the microscope in technical chemistry, especially in the examina-
tion of foods, and expresses regret that many chemists consider their
laboratories complete without such an instrument : he enumerates many
examples of its usefulness such as starches, textile materials, &c. ; even
in the domain of pure chemistry, its application is necessary in the
hsematin reaction for the detection of blood- stains, the composition of
urinary deposits, the search for strychnine, atropine, &c.
These advantages led to its more extensive employment in pure
ANALYTICAL CHEMISTRY. 377
chemistrj, and the name of microcliemistry was given to it bj
Dobereiner. The author thinks that microchemistry must always be
distingaished by a series of colour reactions, that in the same manner
as the changes of colour, &c., in experiments on the large scale are
examined in the test tube, so must they be similarly observed on the
slide of the microscope. The actual process is simple. The objects to
be examined must be either in thin sections, fine powder, or as fibres ;
a drop of the reagent is placed on a slide and allowed to flow slowly
towards the object, the operator observing through the instrument :
many physical as well as chemical changes may be thus detected ;
expansion or contraction, refractive changes, commencement of colo-
ration, evolution of gas babbles, solution^ &c. The iodine starch
reaction of Stromeyer was the first to be employed with the micro-
scope ; from it is learned the topograpliy and division of starch in
plants, the way it is stored up, and the process of its conversion ; this
reaction has also taught the difference between pure cellulose and
woody fibre and the nature of intercellular substance. The reactions
with zinc chloride and iodine, and with sulphuric acid and iodine, are
also striking instances of the value of microchemistry, affording an
easy method of distinguishing vegetable from animal fibres, the first
colouring pure cellulose violet, and the second dissolving it with an
intensely blue colour, the lignin encrusting the fibres having been
previously removed by maceration in nitric acid, alkalis, or Schultze's
maceration fluid. Thus sulphuric acid and iodine stain cork dark-
yellow, thereby affording a trustworthy test for all membranes or
sections containing suberin. The solubility of pure cellulose in
"cuoxam" discovered by Schweitzer is also credited to microchemistry:
the reagent may be prepared by digesting copper turnings in concen-
trated ammonia, or by decomposing a concentrated solution of copper
sulphate with ammonia until the precipitated hydroxide is redissolved.
The maceration process of Schultze is a valuable aid to opera-
tions in microchemistry ; the substance is treated with nitric acid and
potassium chlorate either in the cold, or in cases of obstinate samples,
is boiled for a short time, when the cells are isolated by the solution of
the intermediate lamellae. Amongst the instances given of its utility in-
food analysis is the separation of those peculiar cells of radiating
branchial form which exist in the tea leaf, and are not found in other
leaves used for its adulteration (they are, however, found in some of
the camellia family).
This treatment has also the advantage of dissolving the coloured
incrustations of cinnamon, roasted coffee, &c., and leaving the sub-
stances ready for further examination. Potash plays an important
part in microchemistry, as it renders many objects transparent which
are not made so by other reagents ; it was by successive treatment
with potash solution, acetic acid, and iodine that Bohm was able to
perceive in chlorophyll the small particles of starch which had hitherto
escaped observation. The most striking success in the science is that
of Sachs with Trommer's sugar-test which, with slight modifications,
enables the microscopist to identify, and even estimate quantitatively,
cane- and grape-sugar, dextrin, gums, and albuminous substances in
single cells.
378 ABSTRACTS OF CHEMICAL PAPERS.
The author alludes to the tinctorial methods which are employed in
the examination of microbes, but which do not come under the strict
domain of chemistry ; he urges more extensive use of the microscope,
together with the micropolariscope and spectroscope, and the study of
botany and physics among chemists. J. F.
An Instrument for Correcting Gaseous Volume. By A.
Vernon Har€OURT {Froc. Roy. Sac, 34, 166 — 167). — The author has
devised an instrument to facilitate the correction of the observed
volume of a gas, measured at any common temperature and pres-
sure, to the volume the gas would occupy under standard condi-
tions, and thus to dispense with corrections for readings of ther-
mometer, barometer, and tension of aqueous vapour. The instrument
consists of two small glass tubes side by side ; the one is open above
and drawn out, the other terminates in a bulb whose capacity is about
four and a half times that of the tube. These tubes are fixed to an
upright on which a scale is drawn ; they are connected below with a
small cylinder containing mercury, closed above by a leather cap,
which can be pressed down by a button attached to a screw. The
bulb and a portion of the stem are charged with a drop of water, and
then with a quantity of moist air, which occupies 3 J c.c. under
standard conditions ; the stem below this level, which is taken as 1000,
being filled with mercury. To use the instrument, the pressure of the
screw on the mercury is increased or relaxed until the level of the
mercury is the same in both tubes ; the reading of this level on the
scale represents the volume occupied at the actual atmospheric pres-
sure and temperature by a mass of moist air, which, under standard
conditions occupies a volume 1000. Any volume of gas under the
same conditions may be corrected to its true volume under standard
conditions by multiplying by 1000, and dividing by the number read
on the scale of the instrument. The author proposes to name the
instrument an aerorthometer. Y. H. Y.
Improvements of Gas Analysis Apparatus. By J. Geppert
(Ber., 15, 2403 — 2410). — The author at the outset draws attention to
the length of time required, and the numerous readings of barometer
and thermometer and corrections for tension of aqueous vapour neces-
sary for a gas analysis by Bunsen's apparatus. To avoid these diffi-
culties and to reduce the number of readings to two, the author has
devised a form of apparatus consisting essentially of a suspended
eudiometer and barometer tube, enclosed in a water jacket. The
vacuum of the barometer is moistened with a drop of water, by which
the correction for tension of aqueous vapour is dispensed with ; the
barometer is not provided with a scale, for alterations of external pres-
sure affect the mercury level of the barometer and eudiometer equally,
and it is thus only necessary to read, by some external scale, the differ-
ence of these levels. A minute description of the apparatus, which
does not present any further novelties, cannot be rendered intelligible
without the accompanying diagrams. Y. H. Y.
Estimation of Organic Nitrogen as recommended by Ruflle
and Tamm-Guyard. By C. Arnold {Arch, Pharm. [3], 20, 924
ANALYTICAL CHEMISTRY. 379
— 927). — The author finds neither of these two methods (of which the
first is to be found in the Chem. Soc. /., Trans., 1881, 87, and the
other in Abstr., 1882, 773) to be satisfactory ; he quotes analyses
showing the great differences which may exist between the true per-
centages of nitrogen, and that as found by either of these methods. The
best results he has ever obtained were when employing both methods
combined, burning the substance with a mixture of equal parts of
anhydrous sodium acetate, sodium thiosulphate, and soda-lime. For
details, see Bepert. Anal. Chem., 1882, 21. E. W. P.
Estimation of the Halogens in Carbon-compounds. By E.
Mulder and H. J. Hamburger (Bee. Trav. Ghim., 1, 156). — The
authors recommend the method of ignition with pure lime, prepared
by igniting precipitated calcium carbonate in a current of pure
hydrogen. They observe however that in some cases this method does
not yield exact results ; thus an analysis of benzene hexchloride made
by it yielded in four experiments 574, 58*2, 58*5, and 58'4 per cent,
chlorine, whereas the calculated quantity is 73*2 ; but by using a
mixture of lime and potassium nitrate, the percentage of chlorine
obtained was 73-0. H. W.
Analysis of Silicates. By W. Knop (Chem. Centr. [3], 13, 637—
639). — The method is as follows : — 2 grams of the finely powdered
mineral are fused with 10 grams of sodium carbonate ; when cold the
mass is dissolved in water at the ordinary temperature, which opera-
tion lasts 48 hours ; a sufficient quantity of pure ammonium chloride
solution is now added to decompose the dissolved mass, and the whole
is evaporated to dryness. It is now gently boiled with water, which
dissolves manganous chloride and phosphate, lime, and manganese,
whilst the silica and undecomposed silicates of the sesquioxides
remain undissolved, and are filtered off. The filtrate is made alkaline
with ammonia, oxidised with chlorine-water, and after digesting 4 to
6 hours at 50 — 60° on a water-bath, the precipitated manganic oxide
and phosphate are collected on a filter. The filtrate is made up to
200 C.C., and the calcium and manganese are determined in it in the
usual way. The silica and sesquioxide silicates are treated with hydro-
chloric acid, evaporated to dryness, taken up with strong hydrochloric
acid, and the silica is collected on the same filter as the manganese preci-
pitate ; this dissolves the manganese, and the filtrate is again treated
with ammonia, chlorine- water, &c., to obtain the manganese, iron, and
alumina. The iron is estimated in a separate portion by titration with
permanganate. The advantages claimed for this process are : 1, that
the evaporation with ammonium chloride at a temperature 80 — -90°,
can be conducted without the least loss by spirting; 2, that the
calcium and magnesium are removed before the precipitation of the
iron, manganese, and aluminium, thus preventing these precipitates
being contaminated by those substances. As yet only silicates contain-
ing small quantities of calcium and magnesium have been examined.
To recognise and even estimate the fluorine present, the author
recommends the following method. The finely powdered mineral is
warmed at 50 — 60^ C. with concentrated sulphuric acid, the gas
380 ABSTRACTS OF CHEMICAL PAPERS.
evolved being driven over, by means of dry air, into a p^lass cylinder
partially filled with a colourless solution of aniline in equal parts of
alcohol and ether. If fluorine is present, aniline silicofluoride is pre-
cipitated. This can be decomposed with soda, and the soda silico-
fluoride tested. The quantity of fluorine present can be calculated
from the ash of the aniline salt. D. A. L.
Estimation of Phosphoric Acid and of Manganese. By K.
Broockmann (Zeits. Anal. Ghem.^ 21, 551 — 552). — Instead of igniting
the ammonium magnesium phosphate precipitate with the filter,
the author dissolves it in dilute nitric acid, evaporates the solution,
and ignites the residue. O. H.
Volumetric Estimation of Phosphoric Acid. By Kratschmer
and SzTANKOVANSKY (Zeits. Anal. O/tem., 21, 523 — 530). — Silver nitrate
precipitates the whole of the phosphoric acid from neutral or slightly
acetic acid solutions of the alkaline phosphates. If silver nitrate is
added to nitric acid solutions of the earthy phosphates, and the solu-
tion then exactly neutralised with ammonia, the whole of the phos-
phoric acid is precipitated as silver salt. The authors found their
method on this reaction, proceeding as follows : — In a measuring-flask
excess of standard silver solution is added to the acid phosphate
solution to be examined ; ammonia is then added to neutralisation ; the
fluid is heated to boiling ; the precipitate allowed to settle ; and the
excess of silver in the clear filtrate is estimated preferably by Volhard's
thiocyanate method. O. H.
Behaviour of Alkaline Phosphates to Various Indicators.
By G-. Tobias {Ber., 15, 2452 — 2456). — Berthelot and Louguinine, using
litmus as the indicator, have shown that the ratio l'5NaOH : H3PO4
corresponds to the point of neutralisation ; this result is confirmed by
the isolation of sodium and thallium salts, containing this proportion
of alkali to acid which are neutral to litmus. Shlickum, using cochi-
neal, and Joly, using " helianthin," estimated that one equivalent of
alkali requires one equivalent of acid. The author has further examined
these results with the use of litmus, phenolphthale'in, and cochineal
as indicators. In the case of litmus and phenolphthalein, the ratio
2K0H (or 2NaOH or 2NH3) : H3PO4 corresponds with the point of
neutralisation, but in the case of cochineal the ratio, NaOH
(or NH3) : H3PO4 obtains. It is well known that disodium hydrogen
phosphate, in concentrated solution, takes up a further proportion of
alkali, and thus functions as an acid salt, but this fact cannot be
recognised by a suitable indicator. If a red alkaline solution of phenol-
phthale'in be added to disodium hydrogen phosphate melted in its
water of crystallisation, the red colour disappears, but immediately
reappears when the salt is solidified, which shows that the recrystallisa-
tion effects a dissociation into the hydrogen salt and free alkali. The
author draws attention to the uncertainty accompanying the use of
these several indicators. V. H. V.
AXALYTICAL CHEMISTRY. 381
Testing of Silver Nitrate. {Chem. Centr. [3], 13, 666.)— The silver
salt is dissolved in the smallest possible quantity of water and filtered,
hydrofluosilicic acid is then added drop by drop ; a precipitate indicates
the presence of alkalis ; if the solution remains clear it is mixed with
an equal volume of alcohol ; a precipitate shows than an alkali is
present in small quantity. To test for nitrous acid or nitrites, the
liquid is evaporated down and treated with a solution of 1 part
magnesia (?) in 100 parts acetic acid ; a change of colour from
violet to yellow shows the presence of these substances. Free mineral
acids bring about a similar change, but in this case the colour returns
on diluting with water. D. A. L.
Estimation of Titanic Acid in Presence of Iron. By E.
WiEGAND {Zeits. Anal. Chem., 21, 510 — 516). — Pisani has proposed
{Compt. rend., 59, 289) a method for the volumetric estimation of titanic
acid, founded on its reduction in acid solution by means of zinc, and
the oxidation of the titanic oxide formed with, potassium permanga-
nate. As the titanium is oxidised before any ferrous salts present are
affected, the end point of the reaction can be ascertained by means of
a thiocyanate. The author has carefully examined Pisani's method,
and concludes that it is not capable of giving trustworthy results.
0. H.
Detection and Estimation of Titanium. By A. Weller
(Bar., 15, 2592 — 2599). — Titanium may be detected by the coloration
which is produced by a neutral solution of hydrogen peroxide. 1 mgram.
of titanic acid dissolved in 1 c.c. strong sulphuric acid gives an orange
colour, and 0*1 mg. gives a bright yellow colour with a few drops
of hydrogen peroxide. This test cannot be applied in presence of
vanadic, molybdic, or chromic acid. Titanic acid can be accurately
estimated by means of a colorimetric process based on this reaction.
A normal titanium solution is prepared by dissolving pure potassium
titanofluoride in sulphuric acid, and diluting with water. The
colorimetric determination is carried on in two similar four-sided
bottles of 125 c.c. capacity. Two sides of the vessel are cut parallel,
the other two sides are blackened. Light from a narrow slit is allowed
to pass through each of the flasks and fall on a sheet of paper.
w. c. w.
Detection of Arsenic Microscopically. By H. Hager (Chem.
Ceritr. [3], 13, 690 — 691). — This method is founded on the fact that
arsenic and arsenious acids are reduced by oxalic acid or ammonium
oxalate. Sulphuric acid can be tested by simply boiling with pure
oxalic acid ; the pure acid remains colourless ; if it contains arsenic it
turns brown. Dilute acetic acid or vinegar is tested by adding a few
drops of glycerol to 3 or 4 c.c. vinegar or 2 c.c. dilute acetic acid, and
about 1'5 c.c. ammonia, and shaking well; to this mixture 8 drops of
concentrated solution of oxalic acid or 12 drops of ammonium oxalate
solution, are added. Concentrated acetic or hydrochloric acid is
tested by mixing I'S c.c. of the acid, 3 drops glycerol, 0*25 gram
oxalic acid, and a few drops of ammonia (to excess in case of acetic
acid). The test mixture for phosphoric acid is 2 c.c. of the acid,
3 drops glycerol, 025 gram oxalic acid, 6 drops strong potash, ammonia.
382 ABSTRACTS OF CHEMICAL PAPERS.
and then an equal bulk of water. To test sulpbur for antenic, an am-
monia extract is made, and 2 c.c. of this are mixed with an equal
quantity of acetic acid, 4 or 5 drops glycerol, 25 drops of strong
ammonium oxalate solution, or 20 drops saturated oxalic acid. A
drop or so of any of these solutions is put on an object-glass, heated
over a spirit-lamp, until visible vapour ceases to come off, or until the
glycerol has disappeared, and is then examined with a power of about
100 diameters. Brown or black or grey amorphous or crystalline
specks or rings are evidences of arsenic. Should there be doubt, it is
advisable to reheat the glass and examine again. By this means
O'OOOOl of arsenic can be detected. D. A. L.
Examination of Bismuth Subnitrate. By W. Lenz (Arch.
Pharm. [3], 20, 677 — 578). — The tests for this compound, provided
in the German Pharmacopeia, are boiling with acetic acid, precipitation
of the solution with sulphuretted hydrogen water, and dilution of the
filtrate with water ; any residue that may be left is regarded as lime or
magnesia. The author, in an examination of the commercial salt,
found the residue to consist of potash, and it was quite free from
either lime or magnesia. He was unable to make a quantitative
estimation, owing to the smallness of the sample ; but as the other
properties of the substance fulfilled the requirements of the Pharma-
copeia, he does not think there was intentional adulteration. He
thinks that in the original preparation of the salt, potash was sub-
stituted for ammonia for reasons of convenience ; he recommends
pharmacists to bear the substitution in mind. J. F.
New Form of Apparatus for Estimating Ammonia in Potable
Waters. By C. R. Tichbokne (Chem. News, 46, 247— 248).— To
prevent the weak solution of ammonia which distils over during the
estimation of this gas in potable waters, becoming stronger by reason
of ammonia in the air of the laboratory, the receiver should be con-
nected with two bulb-tubes, similar to Liebig's potash bulbs, but with
two pear-shaped bulbs on each side to prevent regurgitation of the
fluid, and three absorption bulbs at the bottom ; the centre bulb of
these three is provided with a glass tap, for filling and emptying the
apparatus. The bulb farthest from the receiver prevents the admission
of any laboratory air to the second set of bulbs, which in its turn
retains any ammonia which might escape from the receiver.
E. W. P.
Determination of Sulphur in Coal-gas. By 0. Kncblauch
(Ber., 15, 2397 — 2403). — The principle of the author's method con-
sists in passing a mixture of 4 — 5 parts of air with 1 part of coal-gas
over heated platinised asbestos, and absorbing the sulphuric and sul-
phurous acid in a dilute solution of potassium carbonate (10 grams in
1 litre). The liquid in the absorption tubes is oxidised by dilute
potassium permanganate, and the excess removed by the addition of
oxalic acid ; the whole is then precipitated by barium chloride.
About 20 litres of gas, the burning of which lasts from 50 — 60 minutes,
are used for a determination. To show the accuracy of the process,
the details of several analyses are given in the paper. Y. H. V.
ANALYTICAL CHEMISTRY.
383
Sulphur in Coal. By T. M. Drown (Dingl. polyt. /., 246, 154).
— With a view of investigating the sulphur compounds contained in
coal, the author used hydrochloric acid mixed with bromine, in order
to determine the amount of sulphur present as metallic sulphide ; the
sulphur volatilised on burning this residue in a current of oxygen was
absorbed in a solution of potassium permanganate, and estimated ;
finally the sulphur remaining in the ash was determined. Among
others the following coal analyses were made : —
Water
Volatile constituents
A.
. . . . 0-75
15-35
B.
3-48
25-25
Coke free from ash. .
. ... 66-10
66-63
Ash
.... 17-80
4-64
The ash contained —
SiOs. AlaOgFeoOa.
A 4774 3417
B 28-89 65-92
CaO. MgO.
7-61 0-98
2-49 0-57
SO3.
5-30
2-02
The sulphur determinations in the samples of coal and the coke
obtained gave the following results : —
i
1
burning the
sidue in oxy-
n.
H
burning the
al direct in
ygen.
i
•5
3
fusing with
da and potas-
nm nitrate.
^
m"^
^ss
A
1
Pf2-s
. f Coal ....
^•' Coke.,..
1 -660
0-640
0 040
2-340
1-983
0-203
2-186
1-940
1-073
0-747
0-065
1-885
1-287
0-477
1-764
—
T. J Coal ....
-"•tCoke....
0-041
0-450
0 031
0-522
0-431
0-058
0-489
0-474
0 034
0-406
0 -060
0-500
0-429
0-087
0-516
0-495
A large portion of the sulphur is therefore present in organic combi-
nation. D. B.
Flashing Point of Petroleum.. By J. T. Stoddard (J5er., 15,
2555 — 2557). — The author suggests the use of the following simpli-
fied modification of Liebermann's apparatus (Abstr., 1882, 1326)
for determining the flashing point of petrc^leum, A glass cylinder
10 cm. high and 2 — 3 cm. wide, is fitted at the lower end with a per-
forated cork, through which is passed a glass tube drawn out to a point.
The cylinder, filled to about one- third of its height with the oil to be
tested, is placed in a suitable water or 'oil-bath, care being taken that
the oil in the apparatus and the liquid in the bath shall be nearly
at the same level. A current of air is forced through the drawn out
tube with sufficient rapidity to produce a foam half a centimeter deep.
The temperature of the bath when the mixture of petroleum vapour
and air ignites is noted. W. C. W.
384 ABSTRACTS OF CHEMICAL PAPERS.
Detection of Sulphurous Acid in Wine. By L. Liebermann
(Ber., 15, 2553 — 2555). — The author points out that the distillate
from a wine may contain ammonia and other volatile bases, in which
case the carbonic, formic, and acetic acids in the distillate would be
precipitated on the addition of silver nitrate. Hence Wartha*s
method (Ber., 15, 1395) for detecting sulphurous acid in wines is
untrustworthy. W. C. W.
Estimation of Fixed Organic Acids in Wine. By C. Schmitt
and C. HiEPE {Zeits.Anal. Chem., 21, 534 — 541). — The authors operate
as follows : — To 200 c.c. of wine, evaporated to about one-half, basic
lead acetate is added until the reaction is alkaline. The precipitate is
washed with cold water, decomposed with sulphuretted hydrogen, and
the solution of the acids thus obtained is concentrated until about
50 c.c. are left; this is exactly neutralised with potassium hydroxide, and
further concentrated. An excess of a saturated calcium acetate solu-
tion is then added, and after 4 — 6 kours the precipitate is separated,
washed until the fluid amounts to 100 c.c, ignited, and the alkalinity
titrated with standard hydrochloric acid. From the volume of normal
acid used, the amount of tartaric acid is calculated, and 0"0286 gram
is added as a correction for the solubility of the calcium tartrate.
The filtrate from the calcium precipitate is again concentrated to
20 — 30 c.c, and 60 — 90 c.c. of 96 per cent, alcohol is added. The
precipitate of calcium malate, succinate (tartrate), and sulphate is
collected, dried at 100*^, and weighed. It is then dissolved in the
minimum quantity of hot dilute hydrochloric acid, the solution ren-
dered slightly alkaline with potassium carbonate, and the precipitated
calcium carbonate separated by filtration. After neutralisation with
acetic acid, the filtrate is concentrated to a very small bulk, and pre-
cipitated hot with barium chloride, the precipitate consisting of barium
sulphate and succinate. From it the barium succinate is extracted with
dilute hydrochloric acid, the barium estimated as sulphate, and from
the weight of the latter the amount of succinic acid is calculated,
233 BaS04, corresponding to 118 of C4H6O4. The weights of the
sulphuric, succinic, and tartaric acids (0'U286 gram tartaric acid),
calculated into the corresponding calcium salts, are subtracted from
the total weight of the lime precipitate, the difference being calcium
malate, 172 parts of which correspond to 134 of malic acid.
O. H.
Detection of Rosaniline Hydrochloride in Wine by Means of
Stearin. By C. H. Wolff {Ghem. Centr., [3], 13, 670).— The wine
to be tested is warmed, and then shaken with a piece of stearin, which
becomes dyed the characteristic colour, if rosaniline hydrochloride be
present; natural wine colour only discolours the stearin. Sodium
rosaniiinesulphonate, which is more frequently used than the rosani-
line hydrochloride for colouring wines, both because the colour is more
stable and more like wine colour, only dyes stearin blue-violet; in
neutral solutions this reaction is not very sensitive. The presence of
the rosaniline hydrochloride on the stearin may be rendered evident by
treating it with amyl alcohol, which on warming becomes coloured red,
ANALYTICAL CHEMISTRl'. 385
and by spectroscopic examination shows tlie rosaniline absorption
spectrum, even when only a very small trace of the dye-matter is
present. D. A. L.
Glycerol in Beer. By C. Amthor (Zeifs. Anal. Chem., 21, 541 —
545). — The amount of glycerol present in pure Strassburg ales was
found to vary from 005 — 0'3 per cent. O. H.
Test for Organic Acids in Phenol. By W. Bachmeyer (Zeits.
Anal. Chem., 21, 548). — Whilst most organic acids destroy the colour
of aqueous Brazilwood solution, phenol is without action upon it.
The author utilises this difference for the detection of organic acids in
phenol. 0. H.
Rapidity of Separation of Cuprous Oxide by the Action of
Invert-sugar on Fehling^s Solution. By F. Urech (Ber., 15,
2687 — 2690). — In his first experiments, the author obtained very irre-
gular results, which he found were due to the varying diameters of
the vessels in which the precipitation took place. The narrower the
beaker the more rapidly does the reduction proceed, other conditions
being the same, but if exactly similar glasses are employed satisfactory
results can be obtained. The solution of invert-sugar employed con-
tained five times the quantity required for the reduction of the copper
solution ; the temperature at which the reaction took place was 13°.
The results show that under such conditions the rate of separation of
the cuprous oxide is directly proportional to the time. When, how-
ever, equivalent quantities of invert-sugar and copper solution are
employed, the reduction takes place more slowly as the operation pro-
ceeds. ' A. K. M.
Detection of Benzoic and Boric Acids in Milk. By E.
Meissl (Zeits. Anal. Chem., 21, 581 — 533). — For benzoic acid, the
author renders 250 — 500 c.c. of the milk alkaline with lime or barvta-
solution, evaporates to about one quarter of the original bulk, adds
gypsum, and dries completely on the water-bath. The dry mass is
finely powdered, moistened with dilute sulphuric acid, and extracted
with 50 per cent, alcohol, in which the benzoic acid is readily soluble,
whilst only traces of the fat are taken up. The alcoholic solution is
neutralised with baryta, concentrated, and after acidulation, shaken
up with small quantities of ether ; from this the benzoic acid crys-
tallises almost pure.
For boric acid, 100 c.c. of the milk are incinerated, after having
been rendered alkaline with baryta. The ash is dissolved in the
smallest possible quantity of strong hydrochloric acid, the solution
evaporated to dryness ; turmeric solution is then added, and a drop
or two of dilute hydrochloric acid. On evaporation on the water-bath
as little as O'OOl per cent, of boric acid in the milk gives a distinct
vermilion coloration. O. H.
Test for Sodium Carbonate in Milk. By W. Bachmeyer
Zeits. Anal. Chem., 21, 548 — 55 L). — The milk to be tested is skimmed,
386 ABSTRACTS OF CHEMICAL PAPERS.
and three separate quantities of 15 c.c. each are mixed in flat basins
with 3, 5 and 10 c.c. respectively of a moderately strong solution of
tannin, the mixture being allowed to stand in a cool place for 8 — 12
hours. Pure milk remains either unaltered, or shows a pale grey colour,
whilst in the presence of as little as 0"03 per cent, of anhydrous sodium
carbonate, a deep bluish-green colour is developed, which on the
addition of a few drops of dilute acetic acid becomes red. The depth
of coloration depends greatly on the proportion of tannin to soda,
hence the use of three separate samples with different quantities of
tannin. O. H.
Sulphocarbometer. By A. and T. Gelis (Compt. rend., 95, 967
— 969). — This apparatus was devised for the valuation of thiocar-
bonates. It consists of two parts ; a flask of about 80 c.c. capacity
provided with a metal collar with a screw thread, and a bulb sur-
mounted by a tube graduated in tenths of a cubic centimeter. This
bulb-tube is fitted with a metal collar and stopcock, which screws
into the metal collar of the flask. The flask is filled with a solution
of sodium or potassium hydrogen sulphite of 35° B. ; 50 grams of the
thiocarbonate are placed in the bulb-tube, the stopcock of the latter
is then closed, and the two parts of the apparatus are screwed together.
The stopcock is then opened, and the reaction between the bisulphite
and the sulphocarbonate is retarded or accelerated by placing the
flask in cold or hot water, as the case may require. The liberated
carbon bisulphide rises into the upper tube, and its volume is read off".
The number of cubic centimeters multiplied by 1-27 (the sp. gr. of
the bisulphide) and by 2 gives the percentage amount of carbon bi-
sulphide in the thiocarbonate. . C. H. B.
New Colour Reactions of the Alkaloids. By B. Arnold (Arch.
Pharm. [3], 20, 561 — 566). — The author describes the behaviour of
various alkaloids with certain reagents ; the most distinctive are the
following : —
Conine. — One drop, when mixed with a few drops of syrupy phos-
phoric acid, and the mixture evaporated in a white porcelain capsule
over a small flame, becomes a fine green to blue-green.
Nicotine similarly treated gives a deep yellow to orange, the residue
is soluble in water ; the same colour. The reaction is more surely
obtained when the mixture is heated for 5 to 10 minutes on the water-
bath. Conine when so heated shows a clearer green.
Aconitine. — The well-known violet colour given by this alkaloid
when evaporated with phosphoric acid, is obtained easily and surely
by agitating a few particles with syrupy phosphoric acid and warming
10 to 15 minutes on the water-bath.
The syrupy acid used as the reagent is obtained by dissolving the
anhydride of the glacial acid in the ofiBcinal phosphoric acid of the
German Pharmacopeia.
The author suggests that the ptomaconine of Selmi should be
tested by this reagent.
Portions of other alkaloids yielded characteristic reactions when
ANALYTICAL CHEMISTRY. 387
rubbed with a few drops of concentrated sulphuric acid and gently
warmed ; (30 to 40 per cent.) alcoholic or aqueous potash solution is
then dropped in by means of a capillary tube with constant stirring
until in excess. Narcotine, morphine, and codeine give the most
striking reactions.
Narcotine in course of heating with the acid takes a yellow, or if
warmed longer a violet colour. On the addition of alcoholic potash,
it becomes a fine orange-red, which on adding water passes to yellow ;
treated with aqueous potash solution, the final reaction shows a gamboge-
yellow, soluble, unchanged in water.
Morphine on the addition of the alcoholic solution becomes yellowish
to dirty red, then turns to steel-blue and sky-blue. The continued
addition of the potash solution causes after a short time a transition
to a fine cherry-red. Water partially dissolves the residue to a red-
violet colour : the residue is a fine blue to blue-green, and dissolves
with that colour on adding water. Treated with aqueous potash solu-
tion it passes from red to a fine moss-green, and on further addition
of the potash solution to a dirty yellow-brown. The more strongly
the morphine is heated with the acid, the more intense is the blue
produced on the addition of alcoholic potash.
Codeine gives no reaction with alcoholic potash : with the aqueous
solution it passes from reddish to pure green, and then to a dirty
white; if it is heated with sulphuric acid until it begins to brown,
it gives all the reactions of morphine, and seems to change into
that body.
Solanine with the alcoholic solution passes from yellow to blue or
red-violet, particularly after standing some time ; with more potash
it becomes whitish-grey. Sulphuric acid dropped into the mixture to
excess causes a cherry-red, which disappears on adding water. Sola-
nine treated with the aqueous potash solution passes from yellow
to violet, then to green, and finally dirty yellow-brown. Sulphuric acid
added as above causes the same reactions, but the process must be
carefully conducted. The cherry-red and its disappearance are very
strongly characteristic of this alkaloid. The reaction is most success-
ful when the substance is dissolved in cold sulphuric acid and warmed,
but not until the solanine becomes brown, as in that case the colour
reactions do not take place.
Another method of examination adopted by the author is to rub
small portions of certain alkaloids with concentrated sulphuric acid
on a white porcelain slab ; to the mixture he then adds a few crystals
of sodium nitrite. Certain changes of colour occur, which again alter
when alcoholic or aqueous potash solution employed in the previous
experiments is added in drops, with constant stirring, until in excess ,
previous warming with the sulphuric acid is not desirable, unless
when specially directed.
Atropine with sodium nitrite shows a deep yellow to orange. Alco-
holic potash produces a splendid red- violet, quickly passing into pale
rose : the more nitrite used, the deeper the colour. Aqueous potash
does not produce a colour reaction.
Narceine with sodium nitrite, first gives a dirty brown-green, then
clear blue margin, the mixture gradually passes to a fine violet, red-
388 ABSTRACTS OF CHEMICAL PAPERS.
violet, and a blood-red. Alcoholic potash changes this to a yellow,
but aqueous potash causes the violet to pass through yellow to a dirty
brown. When the blue margin appears as above, if the mixture is
very gently warmed, it becomes a magnificent blue-violet.
Narcotine with sodium nitrite passes gradually through red, brown,
and green into a cherry-red. Alcoholic potash added changes this to
a dirty orange ; aqueous potash when dropped into the mixture after
the sodium nitrite, shows a green spot after each drop. When it has
been added in excess, all becomes a dirty green ; when narcotine is
warmed with sulphuric acid until yellow, or till the characteristic
violet appears, and sodium nitrite is then added, a fine cherry-red
immediately makes its appearance.
Strychniyie with sodium nitrite gives a dirty yellow. Alcoholic
potash changes it to a fine orange-red, the aqueous solution causes it
to turn brownish-green, and finally dirty red-brown.
Digiialine with sodium nitrite gives a brown to dirty cherry-red
colour, changed by alcoholic potash to a dirty yellow-grey, by aqueous
potash to brown : the reaction with the sulphuric acid and sodium
nitrite is peculiar to this alkaloid.
Two or three samples of each alkaloid were obtained from different
sources. The processes followed in the experiments require considerable
amount of practice, and it is sometimes difficult to exactly specify
the shade of colour, for example, whether one should be called
brownish-green or greenish-brown ; yet with practice the characteristic
reactions can be very accurately produced. J. F.
Quantitative Estimation of Cinchona Alkaloids. By H.
Meyer (Arch. Pharm. [3], 20, 721—736, and 812— 824).— The
author criticises the methods employed by different chemists in the
estimation of the total alkaloids present in cinchona barks, and having
examined several, proposes certain alterations which he believes to be
improvements. Having carried out most carefully the processes re-
commended by Prollius, Hager, Moens, and De Vrij, repeatedly and
on the same sample of bark, he found differences of no unimportant
character in the results, both between experiments made by the same
method and between different processes with each other. In the
method proposed by Prollias, the fatty wax, always more or less pre-
sent in bark, is estimated as alkaloid. De Vrij does not extract the
whole of the alkaloid by his method, but calculates as if the undis-
solved alkaloid in each sample examined always bears the same ratio
to the dissolved portion : this the author believes not to be the case.
The system of Moens presents difficulties in the way of filtration
and removal of the separated alkaloid. Johnson (Pharm. Zeit. Uiiss.^
1880) found in three analyses of Bolivian bark by this method 2-93
per cent., 2*67 per cent., and 3*08 per cent., whilst in the residual
gypsum, acid fat, &c., he found 7*42 per cent., 7*89 per cent, and 7*4 per
cent., more than double the quantities first obtained. To avoid trouble-
some washing and facilitate the process generally, the author devised
the following method. Into a tared flask he brings 10 grams of finely
powdered bark and 12 grams of freshly prepared calcium hydroxide
with 180 c.c. of 90 per cent, alcohol, and boils on the water-bath for one
ANALYTICAL CHEMISTRY. 389
hour. When perfectly cool, the contents of the flask are made up to
190 c.c. with 90 per cent, alcohol ; it is then carefully shaken, allowed
to settle, and 100 c.c. filtered off. The sp. gr. of the filtrate will
average 0'84; the quantity taken represents the alkaloids contained in
5 grams of the original bark. It is placed in a dish previously rinsed
with alcohol; 20 c.c. of 1 per cent, diluted sulphuric acid is added ; it is
then warmed on a water- bath ; and the alcohol is evaporated with con-
stant stirring. The quinovine and quinovic acid with the waxy fat
remain suspended in the fluid, which now amounts to about 10 c.c. ; after
cooling, 10 c.c. distilled water is added, and the whole filtered into
a separating funnel of about 150 c.c. capacity. Dish and filter are
repeatedly washed with distilled water until the filtrate gives no pre-
cipitate with picric acid : 50 c.c. of chloroform are now added, and
caustic soda solution to strong alkaline reaction. The liquid is well
shaken up, and after the mixture clears, the chloroform is allowed to
run off" into a tared flask, and is removed by distillation ; and the flask
after being heated in an air-bath for an hour at 100°, is cooled in an
exsiccator and weighed. This shaking up with chloroform is repeated
as long as any weighable residue is found. Three operations are
generally sufficient. The sample of the same bark which treated by
Moens' method gave 4*9 per cent, alkaloid yielded in this way 5*4 per
cent.
The author then proceeds to examine the methods of Hielbig and
Eykman ; the chief feature of both is maceration of the bark for 24
hours previous to the treatment with lime and alcohol. Five experi-
ments were made, and their results show that maceration in acid does
not exert any influence on the yield of alkaloid, but only tends to
lengthen the process. The method of ProUius consists in treating
the finely divided bark with a mixture of alcohol, chloroform, and
ammonia ; the infusion obtained is of a wine-red colour, the colouring
matter is precipitated by calcium hydroxide, the filtrate is of a wine-
yellow tint ; an aliquot part is taken and evaporated to dryness, and
the dry matter reckoned as alkaloid. This method is defective in that
the fat and some other alkaloids remain in the residue. The author
introduced modifications with a view to improve the process, but
finally condemns it as untrustworthy.
De Vrij's process is fully described by him in " Haaxmans tyd-
scrift,'^ and criticised by Eykmann in the same journal. Its distinc-
tive feature is percolation of the infusion until the percolate gives no
precipitate with caustic soda solution. The author employs picric
acid, and the difference is important, beca,use the solubility of the
alkaloids in water and soda-solution is far greater than in picric acid ;
and in an experiment made it was found that a percolate which yielded
no precipitate with the soda-solution, was rendered strongly opalescent
on addition of picric acid. Two experiments made by this method on
bark of the same kind as that previously used, and yielding 5"4 per
cent, of alkaloid, gave only 4*6 per cent, and 4*35 per cent, by this
method. The loss is caused apparently by the tannates of the cin-
chona bark being precipitated in the course of the process. De Vrij's
method is pronounced defective because it does not extract the
whole of the alkaloids ; the author treated residues from the process,
VOL. XLIV. 2 d
390 ABSTRACTS OF CHEMICAL PAPERS.
and found in them appreciable quantities of alkaloids ; the quan-
tity so left is variable, not bearing a fixed proportion to the quan-
tity extracted, the process is also tedious, taking five days to carry out.
Eykman's own method is the following: A maceration fluid is
prepared by mixing 15 c.c. chloroform and 4 c.c. glacial acetic acid ;
the finely powdered bark is carefully mixed with it in a test tube, the
lower end of which is drawn out to a fine point and sealed ; in this
lower end is placed a plug of lint or shredded linen ; the mixture is left
for at least 24 hours, and then the fine point is broken ofp; the liquid
is allowed to flow off, and then displaced with 98 per cent, alcohol ; and
the extract is quickly evaporated on the water-bath with a steady heat
until it becomes thick. It is then, whilst warm, rubbed up with 5 c.c.
hydrochloric acid of 10 per cent. ; after cooling an equal quantity of
water is added ; the liquid filtered in a separating funnel, and the
residue is washed. The method, owing to the small quantity of alcohol
used, and its comparative rapidity, caused special attention to be given
to it ; but the author condemns it as not being more trustworthy than
De Vrij's ; he found the quantity of alcohol far too small for perfect
deplacement, and the time occupied in that part of the process to be
eight hours instead of five, as stated by Eykman, besides which the total
alkaloids are not extracted ; the comparative results will be found in the
accompanying table. The process of v. Hager was next examined, and
is quickly dismissed as yielding results much too low. That of Gunning
was the last method taken into consideration. 10 grams of powdered
bark is mixed with a potash solution (6 grams in 12 of water) and
kneaded to a homogeneous mass, which is left at rest for three hours,
then mixed with 10 grams of gypsum, and dried. The dry mass is
next extracted with amyl alcohol until no more alkaloid is taken up, and
evaporated ; the dry residue gives the alkaloid contents. This method
is the only one which employs strong potash-solution, with a view not
only of extracting the alkaloid from its combinations, but also, by
partially destroying the bark itself, to obtain perfect extraction ; the
author, however, prefers his own process, and believes that treatment
with lime and alcohol is sufficient to extract all the alkaloid present in
the bark. The following are some of the general conclusions drawn
by him from his investigations: — (1.) All the alkaloid passes into
solution on boiling the finely pulverised bark with calcium hydroxide
and 90 per cent, alcohol for one hour. (2.) Previous maceration with
acid or acidified alcohol is without beneficial influence. (3.) The
separation of the alkaloid is effected more readily by agitation than by
precipitation. (4.) The separation of quinovic acid, quinovine, and
the waxy fats can be done without loss by treating the alcoholic infu-
sion previous to evaporation with dilute sulphuric acid in excess, and
then cautiously evaporating with stirring. (5.) That repeated boil-
ings and displacement of the lime is necessary to obtain the total
alkaloids. (6.) That the author's method allows the total alkaloids to
be obtained in 12 hours if necessary, or taking into account other
laboratory work, in parts of two days. (7.) All other methods are
incorrect, in that they do not extract the whole of the alkaloids,
(8.) except those of Gunning and Prollius, which yield high results in
consequence of extracting matters which are not alkaloids. i
ANALYTICAL CHEMISTRY.
391
The following table shows the comparative results of different
methods ; the figures are the mean of several experiments, and were
made on samples of absolutely dry bark.
Method.
Cort. cinch, succirub.
Javanens.
Cort. cinch,
offic.
Hager
ProlHas, unmodified . .
Prollius, modified, without previous
acid maceration
ProUius, modified, with previous
acid maceration
De Yrij
Eykman, chloroform, &c
Gunning, unmodified
Grunning, modified
Meyer
Meyer, maceration, with 2 per cent.
sulphuric add
Meyer, maceration with H2SO4
containing 90 per cent, alcohol . .
Meyer, maceration with 50 per
cent, alcohol
Pure alkaloid per cent.
6-33
3-75
3-76
—
4-14
3-7 '
8-12
4-77
4-60
4-72
5 16
5-4
4-17
3-86
3-9
4-6
—
5-42
4-59
—
5-38
4-61
—
5-4
4-57
5 12
5-54
5-85
5-81
6-57
6-67
6-65
J. F.
Estimation of Tannin. By A. Gawalovski (Zeits. Anal. Chem.^
21, 552 — 553). — Instead of igniting the precipitated copper tannate
(Fleck- Hager' s method), and multiplying the resulting cupric oxide
by 1*034, the author dries the cupric tannate precipitate, weighs,
ignites, and subtracts the resulting oxide from the total weight, the
difference being the weight of the tannin. O. H.
Estimation of Tannin. By F. Simand (Dingh polyt. /., 246,
133 — 140). — The author has abandoned the use of Lowenthal's im-
proved method (ibid., 228, 53) of estimating tannin, as he found that
the percentage of tannin in the same material was subject to certain
variations. A series of experiments was therefore made, the object
being to replace the gelatin used by Lowenthal by a substance capable
of absorbing tannin. The method was founded on oxidation with
potassium permanganate or calcium hypochlorite, with indigo solution
as indicator in presence of sulphuric acid. The first substance experi-
mented with was powdered skin, which Hammer and Lowenthal had
used some time ago for extracting tannin from solutions. Although
more satisfactory results were obtained than with gelatin, tlie
absorption of the tannin was a slow operation, requiring often 24
hours' agitation or more, and even then tannic acid was present in the
filtrate ; moreover, the difficulty experienced in preparing the skin
rendered this method impracticable. The author then tried the gela-
tinous tissue of bones. Tubular bones were treated with dilute hydro-
2 d 2
392
ABSTRACTS OF CHEMICAL P.VPERS.
chloric acid, and after removing the lime salts the residue was washed
and used for extracting tannic acid from infusions. The results were
as satisfactory as those obtained with powdered skin, whilst the
absorption of the tannin was efPected more readily. Later on, when
Miintz showed that tannin is absorbed by nitrogenous vegetable sub-
stances, the author, assuming that all nitrogenous animal substances
softening in water are capable of absorbing tannin, used horn
shavings after removing the lime salts, with equally good results. In
the original paper, the method pursued by the author in his laboratory
for preparing the skin powder, extracted bones, and horn shavings is
described in detail, and numerous tannin estimations with these sub-
stances are given. D. B.
Detection of Adulterations of Flour with Rye-meaL By
WiTTMACK (Bied. Centr., 1882, 790). — The method depends on the
difference of the microscopical appearances presented by the husk,
gluten cells, and starch grains.
Wheat. Bye.
mem. mem.
Thickness of husk 43—50 31—40
Length of epidermis cells of
husk 116—160 136—400
Breadth of ditto 20—28 26—32
Thickness of the cell walls . . 6-8— 6'0 4-3- 5-8
Glandular markings on the cell v€ry close and not so close.
well defined.
Length of the cells underlying
the epidermis of the husk. . 114—192 72—90
Breadth of ditto 14—17 11—14
Thickness of cell walls 5-8— 87 3-3- 5'0
Glandular markings on the cell very close and not so close,
well defined. often undefined.
Long diameter of gluten cells. 56 — 72 40 — 64
Shorter, ditto 32—40 24—40
Diameter of isodiametrical
gluten cells 40—48 32—36
Diameter of starch grains, . . . 28 — 35 42 — 52
These differences, however, are sometimes of little use, as careful
milling removes all traces of husk, and as the difference between the
starch grains and gluten cells of the two flours is so slight, no great
reliance can be placed on their indications. However, there are
always remains of the hairs which grow from the end of the seeds, to
be found in flour, and by their means the presence of rye in wheat
meal can be detected. Measurements are as follows : —
Wheat. Rye.
mem. mem.
Thickness of wall of the hairs .... 7 3 — 4
Breadth of lumen 1-4— 2*0 7
Seldom to 5 0
■ To aid detection of the hairs when mixed with flour on the micro-
ANALYTICAL CHEMISTRY. 393
scopic slide, the starch should be brought into solution by soda or
potash. E. W. P.
Creasote from Beechwood Tar. By A,. Gtratzel (Arch. Pharm.
[3], 20, 605 — 610). — This substance, discovered by Reichenbach, and
highly esteemed for its medicinal properties, is not a simple body, but
a mixture of numerous homologous phenols — guaiacol (b. p. 200°),
creosol (b. p. 219°), and small proportions of products boiling at about
232°, and resembling the others in their reactions ; the proportions in
which they exist are variable, and in great measure dependent on the
quality of the tar employed, which in turn varies according to the
treatment given to the timber in the wood- vinegar factories where it
is produced. The rough creasote, in addition to pyrogallic dimethyl
ether and methylpyrogallic dimethyl ether examined and described by
Hofmann, contains another substance, recently isolated by the author
and named by him coeruUgnol.
This possesses so strong and dangerously astringent properties that
a single drop on the tongue causes bleeding ; creasote must therefore
be absolutely freed from it ; its absence can be very accurately known
by the barium hydroxide test.
Beechwood tar creasote boiling between 195*^ and 235° is of a wine-
yellow colour ; in flasks of large diameter it is of a deep-yellow, similar
in appearance to a solution of potassium dichromate, and if pure
should possess the following properties : —
1. The addition of an equal measure of saturated solution of soda
should leave the mixture quite clear, or at most with the yellow
colour described, and the addition of 10 to 20 times the bulk of dis-
tilled water should not cause any opacity ; if there is opacity, it is
caused by the presence of lime in the water, or the presence of cc©ru-
lignol, or some neutral oil.
2. Its aqueous solution, when treated with aqueous solution of ferric
chloride, should give a blue colour, rapidly passing into brown.
3. From aqueous solutions, zinc chloride should throw down a white
precipitate, soluble in excess of the reagent.
4. Mixed with an equal quantity of glycerol of 1*250 sp. gr., it
should not dissolve, but after warming the mixture should take up
50 per cent, of the glycerol, the remainder separating clear.
5. With an equal, or less than equal, bulk of collodion solution, it
should not form any gelatinous compound.
6. With strong ammonia, after 24 hours, it ought to show an olive-
green colour, not blae.
7. Baryta- water with alcoholic solution of creasote, should not show
any colour whatever, either blue or passing to red.
8. 1 part of creasote is soluble in 30 parts of boiling water; on cool-
ing so much of it should separate that but 1 part should remain dis-
solved to 80 parts of water. Water containing carbonic acid dissolves
creasote less readily ; therefore in an aqueous solution left exposed to
the air separation takes place and the solution is troubled.
The remainder of the paper contains information on cases in which
creasote may be usefully employed in medicine and surgery, its effects
and modes of application, and is not of chemical interest- J. F.
394 ABSTRACTS OF CHEMCAL PAPERS.
Properties of Chlorinated Organic Gases and Vapours. By
Berthelot (Ann. Chim. Phys. [5], 27, 227— 229).— In testing for
the presence of volatile chlorinated compounds dissolved in the blood
or other animal fluid, by passing their vapour, mixed with air and
steam, through red-hot tubes, and leading the resultant gases into a
solution of silver nitrate, the possible generation of acetylene and
hydrocyanic acid forms two serious sources of error. The author pro-
poses to eliminate these by leading the gases issuing from the heated
tube into water, and boiling this for some time. Hydrocyanic acid
and acetylene are thus driven off, whilst the hydrochloric acid remains
dissolved, and may be tested for as usual by acidifying and adding
silver nitrate. L. T. T.
Estimation of Haemoglobin in Blood by Optical Means.
By E. Branley (Ann. Ghim. Phys. [5], 27, 238— 273).— In the first
part of this paper the author discusses the relative accuracy of the
results obtained with various instruments for the above purpose. He
has obtained the best results by the combined use of the spectroscope
and polariscope. In the instrument which he recommends — a modi-
fication of those used by Trannin and Violle — the cell containing the
substance under examination is divided horizontally, and between
this and the spectroscope a Wollaston double refractor, and a polari-
scope are introduced; the double refractor, giving two images of
each half cell, is so arranged that the ordinary image of one half
and the extraordinary of the other are thrown on to the prism of
the spectroscope, so as to give spectra in juxtaposition. The part
©f the spectrum observed is that between the bands D and E. The
•substance under examination is introduced into one half cell, the
standard of comparison into the other, a lime (or magnesia) light
being used as the source of light. By turning the Nicols prism, the
two spectra are brought to the same brightness, and the absorption of
light reckoned from the angle of rotation. In this apparatus it is
only necessary to compare a standard solution of haemoglobin once for
all with water, all estimations afterwards being made against water.
With this apparatus, the author has made a large number of careful
determinations. He has experimentally verified the law of absorption
for a coloured liquid, Ii = la% where I is the intensity of the light
incident on the slit, a is the coefficient of expansion, and e the thick-
ness of the layer of liquid ; and also the law of the proportion between
-the absorption and the quantity of colouring matter dissolved in a
given volume. The author has examined human blood in various
pathological states, and also the blood of the ox, dog, horse, cock, and
carp, and haemoglobin prepared from the blood of the dog and horse,
and finds that the haemoglobin in all of them is identical. The
colouring matter of blood changes very rapidly. At temperatures
near the ft^ezing point, no change takes place for three or four days,
but at 15° decomposition sets in within about 24 hours, and at higher
temperatures within a much less time; when frozen, it does not
change. Haemoglobin, treated with carbonic oxide, shows no appre-
ciable variation in absorptive power. The author also gives a number
of determinations of the haemoglobin in blood taken from persons and
TECHNICAL CHEMISTRY. 395
animals in various stages of disease, &c., and points out tlie patho-
logical value of such determinations. L. T. T.
Technical Chemistry.
Cleansing of Glass Laboratory Vessels. By A. Muller (Arch.
Pharm. [8], 20, 841 — 844). — The use of sea or river sand is injurious,
as the sharp fragments of quartz scratch the surface of the glass.
Lead shot, which is an excellent mechanical cleanser, is condemned,
because it leaves part of its substance on the glass, which has to be
removed by dilute nitric acid. Its use is strongly condemned for
cleansing beer and wine bottles. Clean wood-ash is recommended for
domestic use, as it acts both mechanically, and chemically by its
potash. Powdered rock-salt is also used. For glass vessels used in
the laboratory, the author recommends a piece of india-rubber cut
into the form of a tongue or other convenient shape, and fastened to
a flexible wire as a handle. When great cleanliness is required, he
rinses the vessels and dishes with potassium dichromate and sulphuric
acid. The acid from the desiccators mixed with the dichromate from
estimation of nitric acid answers the purpose. J. F.
Preparation of Silver Bromide Gelatin- emulsion. By J. B.
Obernetter (GJiem. Oentr. [3J, 13, 687). — The author dissolves gelatin
and silver nitrate together in water, filters, and leaves the liquid to
solidify. The jelly is cut into convenient pieces, washed (thus far opera-
tions may be conducted in daylight), and then, in the dark, immersed
in a solution of a bromide. After an hour or so, the pieces are well
washed. Thus prepared, the emulsion is very efficient for photographic
purposes. It can be applied by melting and pouring on the plate ; or
may be preserved any length of time after being treated with alcohol.
D. A, L.
Antiseptic Properties of Carbonic Anhydride. By H. Kolbe
(J.pr. Ghent. [2], 26, 249— 250).— The fact that putrefying meat has
an alkaline reaction led to experiments on the effect of exposing meat,
in suitable vessels, to the action of the vapour from the spontaneous
evaporation of hydrochloric, nitric, and aqueous sulphurous acids
respectively, the result being that meat was well preserved, but at
the same time lost its original flavour, acquiring a taste similar to
meat kept in vinegar. The author was thus led to try experiments
with carbonic anhydride. The apparatus employed consists of a
tinned-iron cylinder, at the top of which and outside is a channel par-
tially filled with glycerol, into which the rim of the cover dips ; in the
side of the cylinder near the bottom and in the top of the cover tubes
are soldered, which can be closed. The tube in the cylinder serves for
the admission of carbonic anhydride, whilst the one in the cover is for
the escape of the air. The meat is suspended on a tinned-iron hook, and
a porcelain plate is put below the meat to catch whatever falls from it i
396 ABSTRACTS OP CHEMICAL PAPERS.
the cylinder is then filled with carbonic anhydride, and the tubes
closed. A lump of beef, with fat alone weiglung from 2 to 5 kilos.,
was experimented on at varying temperatures. After eight days, the
meat had the same colour and odour as fresh meat ; it had a slightly
but decidedly acid reaction; the broth made from it had the same
odour and taste as that made from fresh meat, and the cooked flesh
was tender and soft. After 14 days, the outside had become grey;
the interior, however, was red and juicy, and the meat was good.
After three weeks, the meat was as good as after 14 days, but was
softer and required less time for cooking and making broth. After
five weeks, the meat was not quite free from putrid flavour. Carbonic
anhydride therefore prevents putrefaction in beef to some extent,
but this is not the case with mutton, veal, fish, lobster, oysters, and
vegetables, which undergo change in carbonic anhydride after a
short time ; thus mutton, after eight days in the gas, began to be
tainted.
A mixture of carbonic anhydride and carbonic oxide, such as that
given off when oxalic acid is decomposed by sulphuric acid, acts also as
an efficient antiseptic for beef ; in fact, in this case the meat does not
even become grey, but retains its red colour throughout. Small white
spots of mould, however, are formed ; but the meat underneath them
is of the same red colour as the parts unaffected. D. A. L.
Sinidor. (Chem. Gentr. [3], 13, 576.) — This is prepared by heating
magnesium acetate with magnesia until the mass becomes slimy, or it
can be made less pure by adding caustic alkali to a solution of neutral
magnesium acetate. It is a basic magnesium acetate, and it is
proposed to use it for destroying bad odours and for disinfecting and
preserving organic substances. D. A. L.
Carlsbad Salts. By E. Haenack (Chem. Gentr. [3], 13, 670—
671). — The preparation of the so-called " Sprudelsalz " has been
conducted very imperfectly, the usual preparation being, in fact,
principally crystalline Glauber salts. This state of things is now
being improved, and the process employed is this : — The spring water
is boiled, and the precipitate (iron, manganese, calcium, magnesium,
and silica) filtered off, the filtrate is evaporated and saturated with
carbonic anhydride from the spring to reconvert the carbonate into
bicarbonates. The salts then have the following constitution, nearly
approaching the natural proportions : —
Sodium bicarbonate 35-95 1 ^^.^^ ^^^^
Lithium bicarbonate 0*39 J ^
Sodium sulphate 42"03 1 ^5.98
Potassium sulphate .... 3*25 J "
Sodium chloride 18" 16 „
Sodium fluoride 0"09 „
Sodium borate 0'07 „
Silica 0-031 O.Q.
Ferric oxide O'Ol / ^ ^*
A litre of the water yields h\ grams of salts ; they form a pure
TECHNICAL CHEmSTRY. 397'
white very fine powder, containing very little moisture and no water
of crystallisation. It is very soluble in water ; a heaped-up tablespoon
(about 5^ grams) dissolved in a wine bottle (litre) of water, gives
approximately the concentration of Carlsbad-spring water.
The author recommends the following proportions for the artificial
preparation of the salt, the other ingredients having no therapeutic
value in his opinion.
Sodium bisulphate 100 parts, sodium bicarbonate 80 parts, sodium
chloride 40 parts. The German Pharmacopoeia gives 44, 36, and
18 parts respectively of these ingredients, besides 2 parts potassinm
sulphate. 6 grams of this mixture should be dissolved in 1 litre of
water. D. A. L.
Bauxite. By A. Ivan (Ghem. Centr. [3], 13, 575— 576).— The
author does not consider French bauxite superior to the Austrian .
The former in the crude form contains 43 to 64*5 alumina, 1*5 to 40
ferric oxide, 0*0 to 0*45 chalk (calc. carb.), 4 to 38 silica and titanic
acid, and 11 to 16 water.
The practical value of bauxite depends on the high amount of
alumina in proportion to the silica ; it is this which, after ignition,
makes it hard and fire-resisting. Ignited bauxite constitutes artificial
emery, which differs from the natural only in its containing less iron,
which constituent can be extracted by acids from the former, but
not from the latter. Natural bauxite should be exposed for 3 or 6
months to weathering influences, and should then be treated with hydro-
chloric acid to remove iron. As a powder, it does not bind readily,
and also contracts considerably when heated to redness ; to overcome
the former defect it is mixed with some sort of cement, whilst the
latter is remedied by mixing it with burnt bauxite powder (artificial
emery). For the preparation of fire-resisting material it is mixed with
fire-clay ; for grindstones or millstones with clay ; mixed with dolomite
or magnesite, it forms an extremely solid and hard fire-resisting material.
It may also be mixed with silicates, borax, lime, metallic chlorides,
gypsum, &c. Besides the nses already mentioned, it may be used for
plastering, for roofs, for all kinds of crushing, grinding, or polishing
stones, &c., for tiles, fire-bricks, retorts, crucibles, and such like, and
in several chemical industries. D. A. L.
Calcination of Alunite. By P. Ghyot (Compt. rend., 95, 1001
— 1003; compare this vol., p. 250). — When powdered alunite is
roasted, the free alumina first loses its water and thus becomes soluble
in acids. The alum and basic aluminium sulphates require more pro-
longed heating to render them soluble in water. The best results are
obtained with about three hours' roasting at a temperature of 800°.
Under these conditions there is a minimum loss of alumina rendered
insoluble in acids by the action of heat. C. H. B.
Glass, Enamels, Porcelain, Stoneware, and Refractory Clays.
By G. Wagener (Dingl. polyt. J., 246, 30—37, and 84— 90).— (7(w^.
position of Porcelain Enamels. — In former communications (Abstr.,
1882, 563 and 1245), the author mentioned that enamels which
fuse at the temperature of the porcelain or Bohemian glass furnace,
398 ABSTRACTS OF CHEMICAL PAPERS.
are of anentral character, and consist of the silicates K2(N'a2)0,6Si02,
Ca(Ba)0,2Si02,Mg(l^e,Mn,&c.,)0,Si02,Al203,3Si02,K2(Na2)0,5Si02,
and CaOjSiOa. This opinion has been confirmed by the analysis of
many enamels which contain practically the theoretical amonnt of
SiOa for the formation of these compounds. The relative amounts of
these silicates are capable of much variation, the quantity of alkaline
silicate, however, must be sufficient to completely fuse the mixture
into a shining transparent mass without traces of devitrification.
Porcelain may be considered as a difficultly fusible glass, being
rendered opaque by the presence of crystalline or non-crystalline sub-
stances, such as Al203,2Si02, Al203,3Si02, and Al203,Si02. The first
refers to the Meissen, Sevres, and Parian wares, containing 23 — 35 per
cent. AI2O3 and 64 — 11 per cent, Al203,2Si02; they require a high
temperature, and only yield glass with the greatest difficulty. The
author calls these alumina-porcelain. The second series, comprising
Berlin and similar porcelains, consists of glass free from alumina
25 per cent. ; Al203,3Si02 73 per cent. ; and free silica 2 per cent.
It is more easily fusible than the former, and owing to the difficulty
of separating the enamel and mass, Berlin porcelain vessels will
resist sudden and extreme variations of temperature without cracking
on the surface. This type the author proposes to call glass or silicate-
porcelain. Bohemian and Japanese, as well as most of the porcelains
of commerce, belong to the third group; they contain an excess of
SiOs, can be burnt at lower temperatures, and may be called silica-
porcelain. The composition of stoneware closely resembles that of
silica-porcelain, but the coloured varieties are different.
In conclusion, the author tries to establish a method for determining
the degree of refractoriness to heat shown by various earths from their
chemical composition. As the compounds Al203,3Si02, Al203,2SiOa,
and Al203,Si02, are only fused with difficulty, the proportion of these
to that of the other silicates present, gives some indication as to the
refractoriness. D. B.
Weather-proof Cement Work. By C. Puscher (Chem. Centr.
[3], 13, 573 — 574). — An object is soaked for 24 hours in solution of
ferrous sulphate (1 part in 3 of water), and then dried in the air.
The ferric oxide produced is chemically combined in the cement, and
makes it denser, harder, heavier, and weather-proof, filling up most of
the pores, and giving it an ochre colour. Ornamental cement work is
brushed over with the solution four times, and allowed to dry. The
cement work can be rendered extremely resisting by warming and
then coating with a hot mixture of equal parts of paraffin and paraf&n
oil. By treating twice with a 5 per cent, soap solution, drying and
polishing, the surface is made efficient for oil painting. Chalk
objects and room walls treated in this manner will stand any amount
of washing. Light ochre colour can be obtained by adding alum to
the ferrous sulphate ; and various shades of green by painting with
chrom-alum. D. A. L.
Application of Electricity in Metallurgy. By F. Fischer
(Dingl. ]Jolijt. /., 246, 27 — 30). — The successful application of thermo-
TECHNICAL CHEMISTRY. 399
electricity for the determination of metals sngg-ested its nse for metal-
lurgical purposes. Thus, Bunsen (Annalen, 82, 137 and 128, 154)
prepared magnesium electrolytically from magnesium chloride, by the
aid of his zinc- carbon elements, whilst for the preparation of magne-
sium by means of sodium, Sonstadt {ibid., 170, 115 ; 174, 439)
recommends the use of the double salt KMgCla, the metal being sub-
sequently purified by distillation in a current of hydrogen. For a
similar purpose, Reichardt {ihid., 176, 141, and 188, 74) uses the
mineral carnallite, and other investigators tachydrite, the former
being specially suitable for the electrolytic preparation of magnesium.
The production of aluminium, according to Bunsen (ibid., 133, 273),
by electrolising the double chloride of sodium and aluminium, melt-
ing at 200°, is of great importance. The practical difficulty of sepa-
rating the deposited aluminium from the saline mixture is said to be
surmounted by properly regulating the temperature ; it is moreover
essential to use vessels made of lime or magnesium, where possible, as
aluminium absorbs silicon from clay vessels, and is rendered brittle.
D. B.
Toughened Glass. By T. Lubisch (Chem. Centr. [3], 13, 687).
— In this process the red hot object is dipped into a warm bath, con-
sisting of water and starch, or gum, kept at 100°, and is taken out
again when the red glow has almost gone ; it is then allowed to cool
in an oven, kept at a slightly lower temperature than the object.
Any glass object can be treated by this method; and the glass can be
cut by a diamond or ground, &c-, with sand, and is quite as tough as
glass prepared by the " oil-process." D. A. L.
Bromine Amalgamation Process. By H. Aenold (Dingl
loohjt. /., 246, 154). — The silver in combination with sulphur,
antimony, and arsenic is converted into silver bromide by means of
bromine. The pounded ore is heated with steam in closed pans, and
after the addition of bromine, the action is continued for a few hours.
The mixture is then subjected to amalgamation by the usual pan or
vat process. Experiments made at Leadville gave a yield of 82 per
cent, silver, whilst by the ordinary amalgamation process only 46 per
cent, is obtained. This process is said to be specially suitable for ores
containing both silver and gold. D. B.
Roasting of Zinc-blende and Neutralisation of the Evolved
Gases with Calcium Sulphide Solution, By Kosmann {Chem,
Centr. [3], 13, 668). — In certain blends which contain as much as
20 per cent, of sulphur, it is not advisable to absorb the sulphurous
anhydride evolved in roasting by Schnabel's process with zinc oxide,
for then 25 parts of ore would require 12J parts of zinc oxide, render-
ing the process too costly. A better method is to send a spray of
calcium sulphide solution into the gases from the furnace by means of
steam under 5 atmospheres pressure ; in this way from 50 to 58 per
cent, of the sulphurous anhydride is absorbed. With improved
appliances better results may be obtained. It is recommended first to
400 ABSTRACTS OF CHEMICAL PAPERS.
absorb the sulphurous acid by Freytag's method by sulphuric acid,
and then to treat with calcium sulphide. D. A. L.
Roessler's Method for the Separation of Gold, Silver, Lead,
and Copper from Sulphides by Air-blast. (Chem. Ceidr., [3], 13,
543.) The sulphides are melted in a graphite crucible in a blast
furnace ; by means of a suitable arrangement of tubes air is blown on
to the surface of the molten mass ; the sulphur bums off as sul-
phurous anhydride (which is converted into sulphuric acid), and a
mixture of gold and silver is precipitated and removed in the first place ;
by further treatment an alloy of copper and silver, or lead and silver.
These simple alloys are treated in the usual manner for the separation
of the metals. Complicated alloys are mixed with an excess of sulphur,
and treated as sulphides. This process may be used for the extraction
of lead or copper from sulphurous ores, and in fact for many purposes.
A blast furnace is not positively necessary, any suitable arrangement
will do. Any volatile metals or products can be collected in a cooling
chamber. D. A. L.
Separation of Copper from Lead by Refining in Freiberg.
(Chem. Centr. [3], 13, 570— 571.)— The first separation is by the
Pattinson process, a lead of the composition " a " yielding 5"1 per cent,
of dross of the composition " fe."
Ag. Pb. Cu. Bi. As. Sb. Sn.
a . . 0-544 — 0-940 0-066 0-449 0-82 0-21
h . . 0-17 62-40 17-97 — 2-32 0-98 0-04
Ni and Co. Fe. Zn. S. O. Slag, &c.
a .... 0-055 0-027 0-022 0-2 — —
h .... 1-09 0-43 0-07 4-0 1-87 8-66
The dross is fused with borax, by which means a regulus consisting
of three layers is obtained, containing respectively per cent. —
S.
Ag.
Cu.
Pb.
Ni.
As.
c ....
0-34
1-79
96-50
0-08
0-75
d ....
—
37-60
25-68
8-60
27-0
6
—
47-70
32-80
0-25
115
17-72
The author is of opinion that the separation of the copper depends
on the amount of sulphur and arsenic with which it combines, and
not on the formation of a lead-copper alloy. D. A. L.
Modification of the Hunt- Douglas Process for the Extrac-
tion of Copper. (Chem. Gentr., 13, 684— 686.)— By the Hunt-
Douglas process about two-thirds of the copper is extracted as cuprous
chloride, thereby greatly diminishing the amount of iron required for
its precipitation, whilst the remaining third is in the state of cupric
chloride: theoretically therefore the amount of iron required to
precipitate a given weight of copper is only two-thirds that used in
other processes, but in practice it is much less, from the absence of
TECHNICAL CHEMISTRY. 401
ferric salts; moreover, a still further saving of iron is effected by
reducing the cupric chloride in solution to cuprous chloride by the
action of copper sulphide, and the silver can then be precipitated by
metallic copper. The process has its drawbacks however, inasmuch
as in treating the ore with the ferric chloride solution, ferric hydroxide
is precipitated, which chokes the filter ; moreover, before the silver can
be precipitated, the whole of the cupric chloride in solution must be
reduced to cuprous chloride, which occasions much loss of time ; and
if the ore is rich in copper, the quantity of liquor in this case is
necessarily very large, on account of the sparing solubility of cuprous
chloride : Claudet's method of precipitating the silver with an iodide is
not applicable, as insoluble cuprous iodide is formed.
In order to overcome these difficulties, Sterry Hunt has modified
his process in the following manner: — The copper sulphate solution
obtained by extracting roasted pyrites or by the treatment of copper
ore with dilute sulphuric acid is mixed with sodium chloride in the
proportions of somewhat less than 1 mol. NaCl to 1 mol. CUSO4,
sulphurous acid is now passed into the solution, when almost the
whole of the copper is precipitated as cuprous chloride, the reaction
taking place in two stages, thus : —
2CUSO4 + 2NaCl = CUSO4 + CuCla + Na2S04;
CUSO4 + CuCl2 + SO2 + 2H2O = CU2CI2 + 2H2SO4.
The excess of sulphurous acid is removed by some of the prepared
copper solution, and after the cuprous chloride has been separated,
the dilute sulphuric acid is used for extracting copper from suitable
ores or from copper slags. If the ore contains zinc, nickel, or cobalt,
these gradually accumulate in the sulphuric acid liquor, and may be
recovered when this is rich enough. The cuprous chloride is washed
and reduced by iron, or where economical reasons prohibit the use of
iron, the cuprous chloride may be converted into the oxide by boiling
with milk of lime and then smelted. The ferrous or calcium chloride
formed can be used instead of sodium chloride in the treatment of a
fresh quantity of copper sulphate solution. The sulphurous acid is
obtained by the roasting of pyrites ores.
If the ore contains no silver, it is of no moment whether the
sodium chloride is in such proportions as to decompose one-half of the
copper sulphate present or more ; in the latter case excess of cupric
chloride is formed, and on treatment with sulphurous acid, hydro-
chloric acid goes into solution as well as sulphuric acid. If silver is
present, however, this is partly dissolved by the excess of cupric
chloride, and is again precipitated with the cuprous chloride, causing
the amount of silver extracted from the residue of the ore to be less
than it should be.
The advantages of this modification of the process are that the
silver is not dissolved along with the copper, no ferric hydroxide is
formed, the copper is purer, and the amount of iron used is consider-
ably diminished, less than 50 pounds of iron being required for each
100 pounds of copper produced. The one drawback is the large
quantity of sulphurous anhydride required, which is costly when not
derived from the ore itself. C. E. G.
402
ABSTRACTS OF OHEiOCAL PAPERS.
Improvements in the Manufacture of Iron. (Dingl. polyi. /.,
246, 99.) — This paper gives an outline of the improvements made
in the production of iron during the past 20 years. D. B.
Iron Industry. (Dingl. polyt J., 246, 95—99, and 148—162.)—
Referring to the preparation of puddled iron of second quality,
Tiemann mentions that roasted spathic iron ore is not used, black
band, mill furnace-slag, and bog-iron ore being worked very largely,
whilst calcareous iron-stone from the oolites of Lorraine is but little
used. The liseder-Hiitte produces pig-iron from the oolitic iron-ores
occurring in great abundance in the neighbourhood of the foundry ;
it is chiefly worked into puddled iron and steel. The following is the
composition of the most important of these ores : — ^
Fe.
Mn.
Si02.
AI2O3.
CaO.
MgO.
PA-
T.
4078
5-27
1070
4-76
6-09
0-44
1-2— 1-82
II.
43-91
3-68
4-87
1-00
8-96
—
—
III.
30-80
3-40
3-90
1-00
21-61
—
—
The iron industry of Lorraine and Luxemburg has been developed
during the last 15 years owing to the abundant occurrence of oolitic
calcareous iron-stones belonging to the Jurassic formation. These
ores contain 26 — 50 per cent, iron, 0*15 — 0-6 manganese, 3 — 22 silicic
acid, 2 — 40 lime, and 0-3 — 0-8 phosphorus.
Liirmann's form of slag worked in a furnace with closed front (ibid.^
194, 106, 475 ; 217, 460), and the introduction of Whitwell and
Cowper's apparatus {ihid., 197, 315; 205, 98; 229, 246) maybe
regarded as novelties in the production of puddled iron.
According to Schilling, the manufactare of spiegeleisen on a large
scale was not commenced .until the introduction of the Bessemer and
Siemens-Martin processes. After discussing the production of
spiegeleisen and the progress made in working it. Schilling mentions
that for the preparation of spiegeleisen containing a large percentage
of manganese (19 — 21 per cent.) the same process as that for ordinary
spiegeleisen is used. The progress made in the German manufacture
of specular iron and ferromanganese is due to the improvements in
the working appliances, whereby a product of uniform composition
is obtained. Hilgenstock discusses the preparation of Bessemer pig-
iron for the last 17 years. The following table gives the composition
of Grerman Bessemer iron from various localities and at different
times : —
January, 1867. . .
April, 1867
September, 1868
October, 1868 . .
March, 1871 . . .
April, 1871
Si.
4-216
1-842
4-383
3-689
3-800
2-000
Mn.
6-195
3-450
6-115
5-970
7-130
10 -580
S.
0-029
0-045
0-060
0-097
0-124
0-088
0-085
0-078
0 110
C.
2-850
0-550
3 -217
. 0 -760
3-500
0-780
Cu.
1 0-220
1 0 -181
1 0-080
TECHNICAL CHEMISTRY.
403
May, 1871
February, 1872 ,
November, 1873.
October, 1874. . .
October, 1874. . .
September, 3 875,
November, 1875.
November, 1875,
September, 1877
January, 1878 . ,
Si.
•218
6-
•500
2-
•050
5^
•360
3-
•390
4-
•700
7-
•520
5^
•990
4^
•920
3-
•220
3-
Mn.
•336
•870
•650
•384
.'920
•100
•810
•010
;-890
•370
S.
0-029
trace
0-010
0 030
0^040
0-065
0^240
©•076
0^083
0-102
0^090
0-055
0-085
0-093
4-069
Cu.
0 176
0-220
0-180
Referring to the preparation of pig-iron according to the Thomas-
Gilchrist process, Hilgenstock mentions that not only is the furnace
room required less per ton of iron, but the cost of production is much
below that of Bessemer pig-iron.
In conclusion, it is stated that, with due regard to the great progress
in the iron industry during the last 15 or 20 years, the question under
what conditions the largest yield of white iron is obtained from the
blast furnace still remains unsolved. D. B.
Influence of Charcoal on the Amount of Phosphorus in Pig-
iron. (Dingl. polyt. /., 246, 101.) — It is well known that iron pre-
pared with charcoal from ores containing small quantities of phos-
phorus shows a larger percentage of phosphorus than corresponds with
the amount in the ore employed. By the use of charcoal, Tamm found
that the percentage of phosphorus was increased by O'Ol, whilst
Sarnstrom recently analysed two samples of wood charcoal containing
O'OIG and 0'005 per cent, phosphorus respectively. D. B.
Steel from Pig-iron containing Phosphorus, at Creusot. By
Delafond (Chem. Centr. [3], 13, 667 — 668). — Steel can be readily
made from iron containing phosphorus, either in the Bessemer pot or
in a reverberatory furnace, by using a lining of lime mixed with mag-
nesia. By this means the phosphorus is got rid of as much as
possible ; the silica is almost entirely eliminated, and large quantities
of the sulphur are driven off. The process is most successful in a
reverberatory furnace. This " basic " steel is purer and more homo-
geneous than " acid " steel, and its tenacity is more uniform than that
of the latter. Samples from both show them to be statically and
dynamically alike. There are, therefore, two processes for the manu-
facture of steel — one with acid the other with basic lining. The latter
is the best when a reverberatory furnace can be used ; in the con-
verter, however, it gives way to the former, for the alkaline coating
cannot deal with large quantities of silica. Some of the analytical
results are given below ; —
404 ABSTRACTS OF CHEMICAL PAPERS.
Per cent. Per cent. Per cent.
Constituents. in crude iron. in " acid" steel. in " basic" steel.
Carbon S'O 0'40 043
Silicon 1-30 O'SO trace
Manganese 1-5 to 2 0-66 076
Phosphorus 2-5 to 3 0-075 0'060
Sulphur 0-2 0-040 0*029
In slag from In slag from
decarbonising, dephosphorising. Basic lining.
Silica 22-0 12-0 I'l
Magnesia j \ 35*8
Manganese and iron oxides .... ll'O 11-0 —
Phosphoric acid 12-0 16-0 —
Sulphuric acid 5-0 5-0 —
D. A. L.
Influence of Sulphur and Copper on the Working of Steel.
By Wasum (Chem. Gentr. [3], 13, QQQ). — The author finds that steel
is not made red-short, even when it contains as much as 0-862 per
cent, copper, besides 0-233 carbon, 0'091 silicon, O'OSO phosphorus,
0*709 manganese, and 0-060 sulphur. Neither do copper and sulphur
together make it red-short, unless the amount of the latter is suffi-
cient by itself to do so ; O'l per cent, sulphur may be regarded as
harmless. D. A. L.
Galvanising and Nickeling of Iron in Cleveland, Ohio.
{Chem. Gentr. [3], 13, 541 — 542.) — The sheets of iron are washed in
dilute sulphuric acid, and then with water ; any inequalities are thus
removed, and the plates are immersed in ordinary hydrochloric acid,
after which they are dried in a hot oven. The zinc is melted in a
large iron pan, along the middle of which an iron screen is fixed, so
that it just dips into the bath and extends about 3 inches above the
rim ; the surface of the zinc is thus divided into two sides — in the one
is placed ammonium chloride, in the other wet sand. The iron plates
hot from the oven are dipped one at a time perpendicularly into the
ammonium- chloride side, and are pushed under the iron screen into
the other side, whence they are drawn out by tongs and pulleys. Drops
of zinc are removed by touching with an iron rod. When they are com-
pletely removed from the bath, the sand is wiped off and the plate is
finished. The nickeling is conducted in wooden tanks lined with
asphalt ; the solution used consists of f lb. nickel-ammonium sul-
phate dissolved in 1 gallon of water. The object to be nickeled, after
it has been made perfectly clean by washing respectively with potash
and dilute hydrochloric or sulphuric acid and scouring with pumice-
stone, is suspended in the bath by means of thin iron wire from a cop-
per bar which is connected with the negative conductor of a dynamo-
electric machine, whilst from another copper bar, connected with the
positive conductor, a nickel plate is suspended in the bath, care being
taken that the nickel plate does not touch the object. After 10 — 15
minutes under the influence of the current, the object becomes suffi-
TECHNICAL CHEMISTRY. 405
ciently nickeled, and is withdrawn, washed first with cold and then with
warm water, and subsequently well dried. Care must be taken to
regulate the current, as if it is too strong the deposited nickel will be
dull, whilst if it be too feeble the deposit will be granular. The
polisher is a disc of wood covered on the surface with a piece of
leather which has been immersed in thin lime-water, rolled in emer^?
powder, and dried. D. A. L.
Argentine. By C. Pascher (Ghem. Gentr. [3], 13, 540).— Argen-
tine is reduced tin used for stamping fabrics and paper. A very
dilute — 60 litres of water to 120 grams of the salt — and strongly acid
solution of a tin salt is reduced by metallic zinc, and the spongy tin is
collected, without pressing, on a sieve, well washed with water, and
dried at a gentle heat. It is then rubbed fine in a pestle, put
through a hair sieve under water, and mixed with the necessary
quantity of starch-paste, when it is ready for nse. The same water
may be used several times for the solution and precipitation, and the
zinc chloride solution when sufficiently concentrated may be used for
soldering, or to clean iron ware before tinning. Finely divided anti-
mony can be prepared in a similar manner. To tin metals, except
lead, the precipitated tin, without starch, is stirred into a hot concen-
trated solution of ammonium chloride to a magma, and this is spread
on the metal, which is then heated until the tin melts ; in about a
minute the tinning is complete, and the article is washed with water
and polished with chalk. By nsing a mixture containing from 5 to 10
per cent, of the precipitated antimony, and 5 per cent, of ammonium
chloride, along with the argentine made into a magma with water, a
white covering of Britannia metal can be obtained. Zinc goods may
be tinned by painting with concentrated solutions of tin-salts contain-
ing 5 per cent, ammonium chloride, then drying and heating until the
reduced tin fuses, and so on until the tinning is complete, which is
rendered evident by a grey instead of a bright deposit forming. A
mixture of zinc-dust, tin, and ammonium chloride may be used for
tinning iron. D. A. L.
Application of Aluminium Pahnitate. By K. Liebek (Dingl.
polyi. /., 246, 156). — Basic aluminium palmitate has the property of
thickening ethereal or fatty oils, and has therefore been recently used
for chemical cleaning and for the preparation of lubricators. As
a cleaning agent it facilitates the application of benzene, prevents
its rapid volatilisation, and decreases the risk of fire. It forms an
excellent materia] for converting easily meltf d lubricating oils into
solid lubricators at a small cost, and that without affecting the lubri-
cating property of the oil. D. B.
Preparation of Thiocarbonates for the Destruction of Phyl-
loxera. By F. Sestini (Gazzetta, 12, 476— 482).— The nse of potas-
sium thiocarbonate as a remedy against phylloxera is preferable to
that of iyee carbon bisulphide, inasmuch as the latter is very injurious
to the vine itself, but the high price of the potassium salt has hitherto
VOL. XLiv. 2 e
406 ABSTRACTS OF CHEMICAL PAPERS.
stood in the way of its extensive application. Varions cheaper snb-
stitutes have, however, been proposed, and the anthor of the present
paper recommends a mixture of the thiocarbonates of potassium and
calcium, prepared by agitating together in a reflux apparatus at the
temperature of 60° C, 200 g. CSj, 200 K2CO3, 1000 water, and 200
quick-lime previously slaked with 100 g. water. After agitation for
10 hours the liquid is left to cool, and is then found to contain 1050 g.
K2CS3, holding in combination 80 g. CS2 and 650 g. CS2 containing
150*55 g. combined CS2. The product is pasty and may be kept in
earthen jars and transported in wooden casks, like those used for the
carriage of petroleum. The cost of preparing 100 kilos, solution of
K2CS3 containing 8 per cent. CS2 and 65 kilos. CaCSa containing
107 per cent. CS2, is 25 lire (= 16s. 8d.). H. W.
New Dyes. (Dingl. polyt /., 246, 200— 201.>— By the action of
diazo-compounds on resorcinol and its homologues, compounds of the
general formula R.N2.C6H3(OH)2 are obtained, from which by the
further introduction of a diazo-group, compounds of the formula
Il.N2.C6H2(OH)2.N2.Il can be produced. They form anhydrous yellow
and brown dyes.
For the preparation of azo-dyes from methylnaphthalene, the latter
is converted into amidomethylnaphthalenesulphonic acid, and then
into the corresponding diazo-compound. By the action of y3-naphthol
and its sulphonic acids on this, dyes are obtained. Yellowish-red dyes
can also be obtained from methylnaphthalene by converting it into
methylnaphthol, and acting on this with diazosulphanilic acid, diazo-
naphthalenesulphonic acid, or with amidoazobenzenedisulphonic acid.
Methylnaphtholsulphonic acid gives red dyes with the diazo-com-
pounds of the hydrocarbons.
A blue dye is obtained by heating methyl orange with an excess of
hydrogen ammonium sulphide at 105 — 110°, and subsequent oxidation
of the product with ferric chloride. A. K. M.
Meat Extract from South America. By Niedekstadt (Arch.
Pharm. [3], 20, 680 — 582). — Extract of meat prepared under
Liebig's directions has been followed by various similar preparations ;
the sample examined by the author is from St. Elena, in the Argen-
tine Republic, an establishment under the direction of Dr. Kemmerich.
The extract has a fine meaty smell, and the taste of freshly roasted
meat ; it dissolves in water to a clear brown liquid, and is free from
fatty and gelatinous matters, which the author believes assists its
keeping properties. The nitrogenous and protein matters consist of
creatine, syntonine, sarcosine, fibrin, &c., and, in the author's opinion,
directly available for the formation of blood, muscle, and nerve sub*
stance. Analyses by three chemists are given.
TECHNICAL CHEMISTRY.
407
Freseniua.
Organic matter 61'13
Inorganic (ash) 20'99
Moisture 17-88
Nitrogen 9*55
Fat and gelatin absent
Soluble in alcohol 68*43
Insoluble in alcohol —
Composition of Ash.
Ferrous oxide trace
Lime 0-43
Magnesia 2*86
Soda 11-63
Potash 44-26
Chlorine 8-34
Sulphuric acid 1*77
Phosphoric acid 32-35
Silicic acid 0*24
Deduct oxygen for chlorine
101-88
1-88
100-00
BischofF.
Niederstadt.
62-42
66-07
20-69
20-08
16-89
13-85
8-30
8-02
absent
absent
72-98
69 60
~~~
16-55
0-22
0-32
0-52
1-76
' 3-89
2-03
11-51
11-32
41-79
44-04
9-46
8-36
1-54
1-62
32-55
32-12
0-82
0-31
102-30
101-88
1-88
100-00
J. F.
American Storax. By F. A. Fluckigee and W. v. Miller (Arch,
Fharm. [3], 20, 646—648, and 648— 651).— Fliickiger considers that
the storax from Asia Minor is identical with that from the Mexican
Liquidamhar styraciflua, but when growing in the United States the
tree does not give so good a yield. The gum then appears in the market
as " sweet gum," is mixed with benzoic acid, and is harder than the
ordinary Styrax liquidus. Miller has made analyses of American storax,
and found it to contain a styrolene, whose bromine compound melted at
73°; besides the styrolene, oxygenated compounds were present, viz.,
styracin and phenylpropyl cinnamate. E. W. P.
Alteration of Synip of Tolu. By Malenfant (/. Pharm.
[5], 6, 466 — 473). — Syrup of tolu, when prepared by heating the
balsam with water for four hours in the water-bath, is perfectly odour-
less at first, but after a time acquires a benzene-like odour. The
author shows by experiments that this is due to the decomposition
of the ethereal cinnamates present, these yielding first cinnamic acid,
which is then further decomposed into cinnamene and carbonic anhy-
dride. Cinnamic acid when boiled either with distilled or with ordi-
nary water for several hours, shows no sign of decomposition, but if
left at rest for a month or six weeks, it acquires the persistent odour
above referred to. If, however, the acid is simply left in contact
with cold water for the same time, without previous boiling, no altera-
tion takes place. E. H. R.
408 ABSTRACTS OF CHEMICAL PAPERS.
Adulteration of Cochineal. By J. Lowe (Dingl. polyt. ./,, 246,
90 — 92). — According to the mode of killing the insect, cochineal is
found in commerce either in the form of white dusty or of brownish-
black shining granules. Both qualities are often adulterated to a con-
siderable extent, the former, however, being more generally adulterated.
The addition of mineral matter is detected by an ash determination,
real cochineal containing not more than 0*5 per cent. In order to
retain their natural appearance, samples of cochineal when adulterated
are exposed to the action of moist air, whereupon they swell up and
become sticky. The adulterant is then dusted over the granules in
quantities of 10 — 12 per cent. After re-drying, the original appearance
returns, and without chemical investigation it is impossible to distin-
guish these samples from the natural colouring matter. D. B.
Prevention of Boiler Incrustation. By Baddet (Ghem,
Ceritr. [3], 13, 576). — A mixture of 15 pts. sodium thiosulphate,
10 pts. rain-water, and 10 pts. glycerol, is added to the water.
D. A. L.
Liquid Carbonic Anhydride as a Fire Extinguisher. Bv
W. Ratdt (Ghem. Gentr. [3], 13, 671— 672).— The author's apparatus
consists of an iron cylinder filled with liquid carbonic anhydride, and
a large water vessel which is connected with the carbonic anhydride
reservoir in such a way that the gas when set free must pass through
and force out the water, and thus a solution of carbonic anhydride can
be directed on the fire. It has been found efficient. Liquid carbonic
anhydride occupies 450 times less space than the gas, therefore a
100-litre cylinder would hold 45,000 litres of carbonic acid gas.
D. A. L.
Analysis of Petroleum-coke. By A. Lidoff (Jour. Biiss. Ghem.
Soc, 1882, 323 — 324). — In the manufacture of gas for lighting, pur-
poses by distillation of crude petroleum, a peculiar kind of hard, very
difficultly combustible glistening coke of a steel-grey colour is found
in the retorts. Its sp. gr. is r829. This coke has the following
percentage composition : — Water (hygroscopic) = 0'24 per cent.,
hydrogen = 0*65, carbon = 94*27, ash = 4*52. The ash contains in
100 parts :— ^
FesOg. CaO. SiOg (sand).
76-71 5-48 15-07
besides a little soda and carbonic acid. From these data it will be
seen that this coke is purer, denser, and less combustible than ordi-
nary coke from coal, and the author recommends it for the manufac-
ture of carbon electrodes, especially for electric lighting purposes.
The presence of ferric oxide is due to the corrosive action of petro-
leum vapour at high temperatures on the cast-iron retorts. B. B.
409
General and Physical Chemistry.
Electromotive Force of a Daniell's Element. By E. Kittles
(Ann. Phys. Ghem. [2], 17, 865— 897).— In the introduction, the
author remarks on the uncertainty arising from the use of a Daniell's
element as the unit of electromotive force (E.M.F.), on account of the
various components, as dilute sulphuric acid, zinc sulphate, or the
chlorides, used for its construction. The researches of Fromme and
Svanberg tend to establish that the E.M.F. of the combination
Zn|ZnS04|CuS04|Cu increases with dilution of the zinc sulphate, but
decreases with concentration of copper sulphate; but, on the other
hand, those of Baumgartner appear to show that the E.M.F. decreases
Avith the proportion of copper sulphate. Again, Poggendorff, Svan-
berg, and Baumgartner have shown that in the combination
Zn|H2S04|CuS04|Cu, the E.M.F. is increased in proportion to the
strength of the acid, while J. Thomsen liuds precisely the reverse. The
E.M.F. of a Daniell's element is a function of the difference of
potential of the liquids at the point of contact, which varies according
to the concentration of one or the other liquid. As then in the com-
bination Zn!ZnS04|CuS04|Cu solutions of two salts come in contact,
which would follow Volta's law as regards the difference of potential,
yet in the combination Zn|H2S04|CuS04|Cu the difference of potential
is dependent on the chemical and heat changes involved.
For the measurement of the E.M.F., the author used an Edelraann's
cylinder quadrant electrometer, the aluminium needle of which was
charged by a Zamboni's dry pile. Instead of the ordinary clay cells,
the author used a glass syphon, bent at right angles, and terminating
in a capillary tube, so that only small surfaces of the different liquids
came in contact. The copper and zinc used were chemically pure,
and the strength of the acid and salt solutions were determined by
their specific gravities and by analysis.
The normal element used consisted of zinc in sulphuric acid of
sp. gr. = 1"075 at 18°, and copper in concentrated copper sulphate
solution of sp. gr. 1"19, the E.M.F. of which was shown to be constant
during 6 — 8 hours, and decreased only 0*6 per cent, after 20 hours.
Further, no change was observed with a variation of 6'5 degrees. The
E.M.F. 's of the Latimer Clark cell (the English unit), the normal cell,
and the cell Zn|ZnS04|CuS04|Cu, stand in the relation 886: 1000 : 1217 ;
but the normal cell has the advantage over the Latimer Clark in
being more independent of the temperature.
The author made a long series of experiments to ascertain the
dependence of the E.M.F. of the Daniell's cell on the degree of con-
centration of the acid. Solutions were used varying from sp. gr. 1"357,
to that containing one drop of sulphuric acid of sp. gr. 1*075 in a litre
of water.
The tabulated results show.that the E.M.F. of a Daniell's element,
in which the copper is surrounded by a concentrated copper sulphate
solution, increases with the proportion of the sulphuric acid, up to a
VOL. XLIV. 2 /
410 ABSTRACTS OF CHEMICAL PAPERS.
certain limit; the maximum value corresponded to a sp. gr. 1-186 —
1-222 (25—30 per cent. H2SO4), above which the E.M.P. decreases.
The author explains the sudden decrease of E.M.F. in the case of the
more concentrated acid by the increased dissolution of the zinc, and
the formation of zinc sulphate. Experiments, in which the concen-
tration of the acid was varied as before, and also the strength of the
copper sulphate solution, established that the E.M.F. increases with
the degree of dilution of the copper sulphate solution, and is at its
maximum when the copper is surrounded with pure water. (Thus the
E.M.F. of a cell of Zn|H2S04 sp. gr. = l-076|H2O|Cu is to the E.M.F.
of the normal cell in the ratio 1076 : 1000.) This, however, holds
good only for concentrated acid; with dilute acid, the E.M.F. de-
creases with the degree of dilution of the copper sulphate solution.
Hence there exists a degree of concentration of the acid for which
the E.M.F. of the Daniell's cell is the same, whatever be the strength
of the copper sulphate solution ; this acid is of sp. gr. = I'OOll at 16°,
and consists of 750 c.c. H2O and 100 c.c. H2SO4 of sp. gr. = 1-007.
The author made observations of change of E.M.F. of various elements
with the time of contact, which proved that with the same time of
contact the E.M.F. decreases the more rapidly the more dilute the
copper sulphate solution, and the stronger the acid. The E.M.F. of
the ordinary Daniell's cell is somewhat less (1000 : 940) than that of
the author's normal cell, and this difference is traced by experiment
to the use of the clay cylinder; the E.M.F. also decreases much more
rapidly, for even after 20 minutes' contact, a difference of 1-0 per cent,
was observed. The substitution of a copper cylinder for the copper
plate had no effect, but an amalgamated zinc cylinder, instead of
chemically pure zinc, caused a great decrease of E.M.F.
The E.M.F. of the normal cell is equal to 1-195 volts, or in
absolute units = 1-195 x lO^M^LIT'^ the E.M.F. of the cell
Zn|ZnS04|CuS04lCu = 1-089 volts; the E.M.F. of the Latimer
Clark = 1-437 volts ; and the E.M.F. of the ordinary Daniell's cell =
1'14 volts. In a note the author adds some results obtained with the
combination of amalgamated zinc, sulphuric acid, and copper. These
show that the E.M.F. of this cell increases at first rapidly with con-
centration of the acid ; then slowly until it reaches a maximum, which
corresponds to the same degree of concentration of acid as that used
in the normal Daniell element. The E.M.F. of the former then stands
to that of the latter in the ratio 929 : 1000, but this varies according
to the quality of the copper. V. H. V.
Galvanic Polarisation. By F. Streintz (Ann. Phys. Chem. [2],
17, 841 — 858). — In the course of some experiments on the decompo-
sition of water by the Leyden jar discharge, the author was led to a
study of galvanic polarisation. As a result, it is proved that the
difference of potential between a platinum electrode covered with
hydrogen and an electrode free from gas undergoes a reversal after a
short time. This phenomenon can be observed in the case of other
metals as palladium, platinum, gold, silver, and aluminium. In the
course of his memoir, the author observes that two strips of platinum,
although cut from the same piece of foil, are not electrically indifferent
GENERAL AND PHYSICAL CHEMISTRY. 411
when placed in acidulated water; this difference of potential is
practically unaltered by heating the strips in a flame, or in boiHng
acid. Again, if one strip is heated in the flame or acids, or in an
electric circuit, it becomes electro-negative to a strip which has not
been so treated. The same observations hold good in the case of
platinum and palladium. From the tabulated results, the following
conclusions are arrived at : —
(1.) The E.M.F. of hydrogen polarisation is dependent on the
nature of the electrode ; it is largest for gold,, and smallest for alumi-
nium (Fromme).
(2.) The values for the E.M.F. are characteristic for each metal, and
vary with its nature. In all cases there is a great decrea.se of E.M.F.
immediately following the breaking of the circuit. But if oppor-
tunity is afforded to the hydrogen-occluding metals of taking up a
larger quantity of gas, the decrease of E.M.F. is only about 15 per
cent, of the initial value ; the percentage loss for gold and silver is far
greater, and aluminium loses all its E.M.F. In the next place, the
value for the E.M.F. for palladium remains the same, but decreases
in the case of other metals. Aluminium plates show a reversal of
electric condition on breaking the circuit, after it has been closed for
a long or short time ; but this phenomenon occurs with platinum or
palladium only after a short close of the circuit.
Experiments are described in which a current from four Daniell
cells was passed through a voltameter with palladium electrodes.
Immediately after the closing of the circuit, a rapid evolution of oxygen
took place from the anode, while not the smallest trace of hydrogen
was evolved from the kathode. After some time bubbles appeared,
and subsequently increased. On breaking the circuit, the evolution
of oxygen ceased at once, but that of the hydrogen decreased gradually,
and had not entirely ceased after the lapse of half an hour. These
observations offer an independent confirmation of Graham's expe-
riments. If the palladium kathode is made the anode, the evolution
of gas ceases and no difference of potential can be observed. On
increasing the electric current, gas bubbles are formed at the anode,
and the increase of oxygen polarisation increases, while that of the
hydrogen decreases. On breaking the circuit, the oxygen polarisation
rapidly disappears, and gives way to the hydrogen polarisation. The
author explains these phenomena by supposing that the oxygen evolved
from the surface of the pole is burnt with the hydrogen, also at the
surface of the plate. Subsequently the hydrogen inclosed in the inner
layers of the metal reaches the surface and is there burnt. If the
process is interrupted, the remaining hydrogen molecules cause the
decrease of the oxygen polarisation, and consequently the increase of
the hydrogen polarisation.
In some further experiments, the author shows that the smaller the
resistance offered by the circuit, the greater, the difl'erence of potential
between the electrodes. As the oxygen polarisation increases with
decrease of resistance, it appears that the electrolysing circuit gives
up some of its energy to the voltameter. This would necessarily
follow from the separation of water into oxygen and hydrogen, in
accordance with Joule's law. V. H. V.
2/2
412 AllSTRACTS OF CHEMICAL PAPEKS.
Amalgamation Currents. By H. Haga (Ann. Phys. Ghem. [2],
17, 897 — 901). — -The researches of Moser on the electric currents
produced by the amalgamation of zinc led Obaoh to examine whether
such currents were not thermo-electric currents due to a change of
temperature accompanying the amalgamation. Exner has, however,
remarked that Obach's experiments were not decisive ; for either the
sum or the difference of the thermic and the amalgamation current
might have been observed. The author has re-examined the question
with a form of apparatus which permitted the measurement at once,
of a change of temperature by a thermo-electric needle, and of a com-
parison of the current produced with a possible amalgamation current.
If the observations by these methods agreed, then there is no amalga-
mation current proper, but only a thermo-electric current due to the
change of temperature involved. This was found to be the case, thus
offering a confirmation of Obach's original suggestion.
V. H. V.
Electricity of Flame. By J. Elster and H. Geitel {Ann. Phys.
Ghem., 16, 711). — Referring to a former communication (t6., 16, 193),
the authors state that Hankel's views on the electricity of flames,
published in 1859, but only recently come to their knowledge, have
been confirmed by their experiments, which show that galvanic ele-
ments may be formed of heated gases and metals, without the use of
flame. R. R.
Actinoelectric and Piezoelectric Properties of Quartz, and
their Relation to the Pyroelectric. By W. G. Hankel (Ann.
Phys. Ghem. [2], 17, 163 — 175). — The author has previously observed
the direct transformation of light into electricity in quartz, a phe-
nomenon which he calls actinoeledricikj (cf. Abstr., 1880, 838), as
distinguished from pyroelectric ity or the transformation of heat into
electricity. J. and P. Currie have observed that in the case of hemi-
morphous crystals, increase or decrease of pressure in the direction of
the hemimorphous axes causes a difference of potential at the ends of
the axes. This phenomenon the author proposes to call piezo-
electricity. In the present communication, the author discusses
these several phenomena in relation to the crystallographic habitus of
quartz.
Pyroelectricity . — The author has made a series of observations on the
difference of potential caused by heating an edge or surface of a
quartz crystal in a miniature oven to 120° ; he shows that the crystals
have generally three polar electric axes, viz., the three secondary axes
of the crystals. Those ends of the axes which terminate in rhombi or
trapezia are the positive poles, whilst the opposite ends are negative, if
the temperature of the crystal is falling, but with rise of temperature
the electro-polarity is reversed. In perfectly normal crystals, both
ends of the primary axes are positively electrified.
Actinoelectricity . — If the rays from the sun, or electric light, or a
flame be made to traverse a quartz crystal, then all the six edges are
electric poles, alternately positive and negative according to the direc-
tion of the light rays. Thus, one end- of every secondary axis is
Potential diffei
+ 18-7
+ 28-5
4- 34-5
+ 37-5
+ 39-5
+ 41-0
GENERAL AND PHYSICAL CHEMISTRY. 413
positively, the other negatively electrified ; and in this respect the
phenomenon of actinoelectricity resembles pyroelectricity.
At the commencement of the radiation, the increase of potential
difference is greatest, but it diminishes in the course of time, as shown
by the following experiments : —
Time after commencement.
5'
10
15
20
25
30
On removal of the source of radiation, the actinoelectricity dis-
appears again at first quickly, then slowdy. The radiation from the
electric light causes a difference of electric potential seven times
greater than that gsaused by a fish-tail burner at the same distance ;
the effect of thiB sun in May is equal to that of a flame at 244 mm.
distance from the crystal.
Piezoelectricity. — If pressure be exerted in the direction of the
secondary axes, their ends which terminate in rhombi or trapezia
show negative electricity on increase of pressure, but positive with
decrease of pressure. By these facts the connection between the
phenomena of pyro-, actino-, and piezo-electricity is brought out, and
also their relation to the crystallographic axes. V. H. V.
Electrical Energy and Chemical Action. By F. Braun (Ann.
Phys. Ohim. [2], 16, 561 — 593). — The paper describes an investigation
instituted to test the truth of W. Thompson's theory, according to
which the chemical energy, or heat of combination, due to the action
in a galvanic battery, is wholly converted into electrical energy. The
author's conclusion is that a part only of the heat of combination is
transformed into current energy, the rest remaining in the cell, and
forming part of what has been regarded as beat due to secondary
actions. He asserts also that certain galvanic elements, from which
polarisation is absent, supply more electricity than the equivalent of
the heat due to their chemical actions. He likewise refers to cases in
which endothermic chemical actions may produce galvanic currents,
and thus constitute another diiliculty for Thompson's theory. The
values of the fractions representing the maximum electromotive effect
of certain combinations are stated in the paper ; thus, for example,
only 83 per cent, of the heat of the combination ZnSOi, and 68 per
cent, of that of CUSO4, can possibly be transformed into electrical
energy. R. R.
Specific Conductivity of Sulphuric and Pyrosulphuric Acids,
and the Specific Gravity of Concentrated Sulphuric Acid. By
W. KOHLRAUSCH (Ann. Phys. Chem [2], 17, 69—85). — The author
draws attention to the interest attached to determinations of the
specific conductivity of mixtures of water and sulphuric acid, as offer-
ing starting points for conclusions on the dependence of electric con-
414 ABSTRACTS OF CHEMICAL PAPERS.
duciivity on temperature coefficients, viscosity, chemical constitution,
temperature of solidification, &c.
Experiments in elucidation of these points have previously been
made by F. Kohlrausch Mid Grotian ; the former of whom came to
the conclusion that the hydrates, 2H20,S03 and H20,S03, correspond
with the minima of specific conductivity. In order to decide the ques-
tion, the author has examined the specific conductivity of sulphuric
acid of various degrees of concentration, as a function of its percentage
composition and the temperature of its solution.
The method adopted by the author consists in measuring the
resistance of a Wheatstone bridge, with alternating currents, the
electromotive force being supplied by a battery of four Leclanche's
cells ; observations were made by a telescope, mirror, and scale on
Kohlrausch's electro-dynamometer. The necessary corrections were
made for the self-induction of the resistance bridge. The sulphuric
acid was contained in glass cells fitted with platinum electrodes, the
capillary ends of which were connected with a drying apparatus filled
with phosphoric anhydride and calcium chloride ; these cells were
heated in an oil-bath, the temperature of which was accurately ascer-
tained. Determinations were made of the specific resistance of these
glass cells. The percentage composition of the sulphuric acid was ascer-
tained by mixing it with a known weight of water, and determining
the composition of the mixture by its sp. gr. or by precipitation with
barium chloride. If kis X 10^ be the specific conductivity of the acid
at 18°, deduced from that of quicksilver at 0°, multiplied by 10^, a
the temperature coefficient of the first order, (3 the coefficient of the
second order, then the specific conductivity at the temperature t is
represented by the formula kt = hs[l + a(^ - 18) -\- ^ (t — 18)2].
From the tabulated results, the author concludes that the specific con-
ductivity of sulphuric acid at 18° decreases from 7837 per cent. SO3 to
81*43 per cent. SO3; then increases until it reaches a maximum at
833 per cent. SO3, and from this point again decreases. It does not,
however, reach a minimum at that concentration, which corresponds
with the constitution of pyrosulphuric acid, but at that of pure sul-
phuric acid, S03,H20. A slight addition either of water (Q'Vl per cent.),
or of sulphuric anhydride (0*2-5 per cent.) to the hydrate SOsjHaO,
increases its conductivity. F. Kohlrausch has observed that the mini-
mum of conductivity does not strictly coincide with the hydrate
H20,S03 ; this the author attributes to a partial dissociation of the
acid into sulphuric anhydride and water; but the lower the tem-
perature of observation, the less is the error due to the dissociation.
The crystallised acid is a very bad conductor, and more perfect crys-
tallisation corresponds with more imperfect conductivity.
F. Kohlrausch's experiments have previously established that the
temperature coefficient is dependent rather on the specific conductivity
than on the percentage composition of the acid ; for the smaller the
specific conductivity, the greater the temperature coefficient. The
author in the main confirms these results, but remarks that for higher
percentage composition the values for a increase when the specific
conductivity remains constant.
Most remarkable is the fact that with change of concentration of
GENERAL AND PHYSICAL CHEMISTRY. 415
the acid from 98*75 to 99 '75 per cent. H2SO4, the value for a increases
from 0-028 to 0-04, that of ^ from 0*0002 to 0*0004, whilst the specific
conductivity decreases by about a sixth of its amount. Taking into
consideration the fact that the solid acid is practically a non-conductor,
that those hydrates which have the highest melting point have the
lowest specific conductivity, the conclusion drawn by Wiedemann
and Kohlrausch is inevitable, that there is an intimate relation between
the viscosity or internal friction and electric resistance.
The author made several determinations of the sp. gr. of sulphuric
acid of various degrees of concentration ; from his results it follows
that the sp. gr. of sulphuric acid reaches a maximum with a concen-
tration of 97 per cent. (sp. gr. = 1*8385), then slowly decreases to a
minimum with concentration of 99*5, and from this point again
increases.
In a note the author adds some results of the specific conductivity
of rain-water collected in the Tyrol, and kept in glass vessels for about
four months ; the values for A;10^*^ varied from 3*3 to 4-1, which differ
considerably from that (fclO^^ = 0*7) obtained by F. Kohlrausch with
water distilled with careful exclusion of glass. The contact with the
glass increases its conductivity. V. H. Y.
Particles of Matter in the Electric Spark. By F. Wachtee
(Ami. Phijs. Ghem. [2], 17, 903— 927).— In the spark discharge from
statical electric apparatus the author, in conjunction with Keitlinjen,
has observed that the surface dissipation takes place from the positive
electrode, while on the other hand, the researches of Pliicker, Gassiot,
and others have shown that under certain conditions the dissipation
takes place from the negative electrode. (It is to be observed that
no such discrepancy of statement exists with regard to the spark from
the current or dynamic apparatus, for all observers are agreed that
the stream of particles flows from the positive to the negative elec-
trode.) The object of the present paper is to explain the above-men-
tioned discrepancy by observations of the conditions on which depend
the passage of particles through a gaseous medium from the positive
or negative pole, and also of the difference of properties exhibited
between these two different electric streams. The author arrives at
the following results : —
(1.) The passage of particles from the anode takes place in atmo-
spheric air under pressures of 4500 to 10 mm. ; but from the kathode
only under pressure of 63 to 0*005 mm.
(2.) The quantity of particles dissipated from the anode in the same
time and under the same conditions decreases, but that from the
kathode increases with decrease of pressure.
(3.) The particles from the anode are driven off through a wider
space than those from the kathode.
(4.) The particles from the anode start from a relatively small
surface, independently of the atmospheric pressure ; those from the
kathode start from a large surface, which increases with decrease of
pressure.
(5.) The particles from the anode are separated from that part of
416 ABSTRACTS OF CHEMICAL PAPERS.
the anode which lies nearest to the kathode ; those from the kathode
are separated from the whole of its surface.
(6.) The separation of particles from the anode is favoured by a
constriction or by a pointed shape of the electrode ; that from the
kathode by a chemically pure or unoxidised surface.
(7.) The direction of the particles from the anode is in the direction
of the line of least electric resistance ; the direction of those from the
kathode is always normal to its surface, and is independent of the
position of anode and the direction of the electric current.
(8.) The particles from the anode follow all manner of paths,
while those from the kathode move only in a straight line.
(9.) The particles from the anode are diverted by a magnet as
diamagnetic substances ; those from the kathode resemble paramag-
netic substances.
(10.) The particles from the anode are dissipated, not only in the
luminous, but also in the non-luminous discharge ; those from the
kathode only in the non-luminous discharge.
(11.) The quantity of matter dissipated from the anode is measnre-
able, and seems to depend on some mechanical impulse ; those from
the kathode seem to arise from a process of evaporation.
(12.) Heating the kathode influences mosfc markedly the passage
of particles ; but the same phenomenon could not be observed in the
case of the anode.
(13.) The particles from the kathode bring about the passage of the
current from the electrode by the molecules of the gas ; but this is not
the case with those from the anode.
(14.) The passage of particles from the anode requires a greater
difference of potential, and they follow one another after longer inter-
vals than those from the kathode.
All these facts confirm the author's view that the difference between
positive and negative electricity is a difference not of quantity, but of
quality. V. H. V.
Electric Shadows. By P. Riess (Ann. Phys. Chem. [2], 17,
901 — 903). — The author remarks at the outset that no satisfactory
explanation has hitherto been given of the electric shadows; he
adduces descriptions of some phenomena on which their explanation
may be based.
An electrified surface is illuminated in an ordinary atmosphere at
those points where there is an opposing electrified air-current ; if the
interposing body be a conductor, this surface is not illuminated, but
there appear upon it shadows, the forms of which are dependent on
that of the interposing body and the discharged air-current. If this
current be not discharged, but only diverted by a non-condacting air-
current, there appear no shadows, on account of the repulsion exerted
by a part of the current being sent back in its former direction.
When the interposing body is merely an imperfect conductor, the
shadows appear or disappear according to the power of the machine.
The fact that a conducting strip causes almost the same shadows,
whether its surfaces or edges are opposed to the air-current, shows
that in either case the amount of discharge is the same, and proves
GENERAL AND PHYSICAL CHEMISTRY. 417
that the quantity of the discharge of an electrified air-current is
greater the smaller the an^le with which it falls upon the surface of
the interposing body. In a rarefied atmosphere a positively electrified
surface] remains dark before a negatively electrified air-current, and
only a negatively electrified surface is illuminated when in contact
with a positively electrified air-current. Y. H. V.
Specific Heat of Gaseous Compounds of Chlorine, Bromine,
and Iodine with one another and with Hydrogen. By K.
Strecker (Ann. Fhys. Gliem. [2], 17, 85—103). — The author has
made a series of observations on the specific heat of these compounds
in the apparatus and by the method of experiment described in his
former paper (Abstr., 1881, 784). In order to arrive at more exact
results, the haloid acids were prepared by various methods, and their
purity was carefully ascertained ; specimens of iodine mono-chloride
and bromide were prepared and purified by fractioual distillation. As
Lowig found the vapour-density of hydrobromic acid to be 2" 71 — a
number which diffiers from the theoretical value, 2*8 — the author de-
termined its vapour-density at various pressures, the results of which
show that at ordinary atmospheric pressures the vapour-density ap-
proaches the theoretical value, but that for other pressures it differs
in a most marked way from Mariotte's law.
Pressure.
Yapour-density.
Pressure.
Yapour-density.
690 mm.
2-788
216
■2-698
622 „
2-789
211
2-706
512 „
2-795
204
2-708
In the original paper there are tabulated for the above compounds
a series of determinations of —
ir ^ specific heat of the gas at constant pressure,
specific heat of the gas at constant volume,
and of the kinetic energy of their molecules ; the values obtained are
identical, whatever the method adopted for the preparation of the
substance.
The author draws the following conclusions : — Gases whose mole-
cules consist of 2 atoms are separable into two groups, the one con-
taining oxygen, nitrogen, carbonic oxide, nitrous oxide, hydrochloric,
hydrobromic, and hydriodic acids, the other containing chlorine, bro-
mine, iodine, chlorine and bromine iodides, and probably bromine
chloride. The atoms of the molecules of the first group differ from
these of the second group in their reciprocal action (cf. snpra).
V. H. Y.
Relation between Pressure and Temperature in the Satu-
rated Vapours of Water and Carbonic Anhydride. By A.
Jarolimek (Monatsh. Ghem.y 3, 835 — 837). — Zeuner gives for the rela-
tion between the pressure and value of saturated water-vapour the
expression jp®*^''^^^ orpv'"*^*^ 1-764). Substituting this expression
in Zeuner's equation of condition for aqueous vapour :
:pv = 0-0049287T - 0-187815p*.
418 ABSTRACTS OF CHEMICAL PAPERS.
the equation for the relation between the pressure and temperature of
saturated water- vapour becomes —
T = 33477V«««« + SS'lOep'"'^ (1),
which gives exact results only for pressures between 1 and 8 atmo-
spheres. Compared with the results of Regnault's well-known experi-
ments, the values of T, given by equation (1) for pressures between
p = 2 and j9 = 7, are too large, while for p = 0*0004 to 1 and j9 = 9
to 28, they are too small.
The author now proposes a formula which gives very exact results
for all values of j9, viz., from 0*0004 to 28 atmospheres (and, therefore,
between the temperatures —32° and -f- 230°). This formula is —
T = 326*7/*^^»» + 46*3jp«'«»* (2).
He also proposes another formula which gives exact results only for
the higher pressures, viz., from 9 to 28 atmospheres, but, on the other
hand, has the advantage of great simplicity. Putting t — 100 =
T — 373 = X] 9^ — p = y and 94 = r, this second formula is 3^ + y*
= r\ which is the equation of a circle, and may also be written in the
form —
^ = 100 + 2 x/942-(95-p)» (8).
A table is given showing the values of t corresponding with the various
pressures as deduced from the formulae (1), (2), and (3), also those
calculated from Zeuner's formula, and those determined by the ex-
periments of Regnault,
If the relation between pressure and temperature be represented
graphically, it will be found that the curve for saturated water- vapour
likewise holds good for the vapour of carbonic anhydride, provided
that, while the degrees of temperature in the axis of abscissae have
the same values as for water- vapour, they be reckoned, no longer from
the boiling point of water (t = 100°), but from that of carbonic
anhydride ( — 7 8' 2°), and that the ordinates representing the pressures
have 4*3 times the values of those for water-vapour. Hence it ap-
pears that, at any given distance from the boiling point, the excess of
pressure of the vapour of carbonic anhydride above that at the boiling
point is f times as great as in the case of water- vapour. H. W.
Absorption of Gases by Liquids under High Pressure. By
S. V. Wroblewski (Ann. Phys. Chem. [2], 17, 103— 128). — The
author's researches have shown that gases in their diffusion through
caoutchouc membranes follow Graham's law. Stefan's experiments
( Abstr., 1879, 347) would seem to show that the rate of diffusion of
gases, as carbonic anhydride, through liquids is in accordance with this
law ; but the author criticises the results and their interpretation. The
author has made a number of experiments on the absorption of gases
by liquids under high pressures, and the present paper contains a
description of the apparatus used, and the methods of experiment for
a study of the behaviour of carbonic anhydride with, water. It has
for a long time been assumed that carbonic anhydride forms with
water a definite hydrate, the properties, composition, and curve of
GENERAL AND PHYSICAL CHEMISTRY. 419
critical pressure of which the author has minutely examined. Ex-
perimental results are given to prove the correctness of Clausius's
formula, C = YJ*k, for determining at 0° C. the relation between pres-
sure and volume of a gas which does not follow Marriotte's law (C is
a constant, P = pressure, V = volume, Ic a coefficient, which is a
function of temperature and pressure, and dependent on th6 nature of
the gas) ; for any temperature t, the formula becomes C = ^j -r^^'
Observations were made at temperatures 0° and 11 "3°, and the results
are in accordance with these formulae within the limits of experimental
error.
If water is introduced into a eudiometer tube filled with carbonic
anhydride, cooled to 0°, and the pressure increased, the carbonic an-
hydride begins to liquefy at a pressure of 35 atmospheres ; the liquid
carbonic anhydride, however, does not mix with the water, and, on
gradually diminishing the pressure, it is found that the only difference
due to the compression consists in the water containing a larger
quantity of carbonic anhydride in solution. If, on the contrary,
the pressure be released suddenly, but not allowed to sink below
12*3 atmospheres, there appears on the inner surface of the eudiometer
tube and on the surface of the water a thin opaque rime. The author
proves this to be not frozen water, but the hydrate of carbonic anhy-
dride, and its formation is dependent on the following conditions : —
1. At 0° and at higher temperatures the hydrate can be obtained
only at the critical pressure for the liquefaction of carbonic anhy-
dride.
2. After a preliminary compression, an expansion is necessary which
causes a momentary sinking of temperature.
3. At pressures greater than the critical, the hydrate remains solid,
but it disappears below this pressure to reappear again when the
pressure is increased.
4. The hydrate is decomposed at pressures far below the critical.
The following results were obtained for the critical pressure of the
hydrate at various temperatures : —
Pressure in
Pressure in
Temperature.
atmospheres.
Temperature.
atmospheres.
0-48
127
61
23 3
27
167
6-8
26-1
5-3
21-8
These numbers, however, must be regarded merely as approximate,
and the author proposes to repeat the experiment in a more refined
apparatus. The composition of the hydrate wa,s determined by taking
such a volume of carbonic anhydride that at 0° it exerted a pressure
of 16 atmospheres; after the pressure was exactly ascertained, the
whole of the water was converted into the hydrate, and the remaining
gas brought to the same volume and its pressure reascertained. The
quantity of carbonic anhydride entering into combination can be ex-
pressed by the formula Q = V(P^ — P' k') in which k and k' are
the coefficients corresponding with the pressures P and P'. The mean
results of the analyses show that about 8 molecules of water are
420 . ABSTRACTS OF CHE>nCAL PAPERS.
required for 1 molecnle of carbonic anhydride. The composition of
the hydrate, therefore, is not C0<>,H20 as formerly assumed.
V. H. V.
Osmose of Salts. By J. E. Enklaar (Eec. Trav. Chim., 1, 252 —
270). — The apparatus employed consists of a bottle of about 150 c.c.
capacity, the neck of which is fitted with a cork through which
passes a capillary tube. The bottom of the bottle is removed, and
over the carefully ground edges is stretched a membrane of hare's
or rabbit's bladder. This bottle is suspended in a beaker containing
distilled water, and the beaker is placed in a large glass cylinder
provided with a well-fitting glass stopper, and resting on legs in the
middle of an iron vessel containing water, which should be kept at a
constant temperature by means of a Bunsen burner furnished with an.
automatic regulator. The water must completely surround the cylinder
containing the diffusiometer. Special precautions are taken to keep
the liquid inside the bottle at the same level as the liquid in the
beaker, both when introducing the bottle into the beaker and when
withdrawing it at the end of the experiment. The experiments de-
tailed in this paper are confined to solutions of the chlorides of the
alkalis and alkaline earths. 50 c.c. of a solution of the particular
chloride of known strength was placed in the bottle, and the latter
was suspended in 100 c.c. of distilled water contained in the beaker.
After six hours, the duration of each of the experiments, the amount
of chlorine which had passed through the membrane into the water
was determined by standard silver solution. In most of the experi-
ments the temperature was 30'5''.
The hare's or rabbit's bladder forms a very thin transparent mem-
brane which, if carefully purified by prolonged treatment with water,
alcohol, and ether, is far superior to parchment paper. The mem-
brane acquires its maximum transmissive power only after it has been
used several times, and this maximum is apparently reached with
different degrees of rapidity for different salts. Drying the mem-
brane exerts considerable influence on the results : a hare's bladder
which had been dried for a long time at the ordinary temperature was
used in three successive experiments, in each of which the solution in
the bottle contained 1"4615 gram NaCl; the amounts of chlorine
which passed through in the three experiments were respectivelv
0-4716, 0-4858, and 0-5071 ; after the third experiment the i-ate of
osmosis became constant. If the experiments are to be comparable,
it is necessary to employ animal membranes of the same kind and of
the same age, to take care that the membrane is at a constant distance
from the bottom of the beaker in which it is suspended, and to pay
special attention to the tension of the membrane.
Experiments with potassium, sodium, ammonium, calcium, and
magnesium chlorides prove that the law that " the rate of diff'usion of
molecules of salts in water is proportional to the density of the saline
solutions," or, in other words that, other conditions being the same,
the quantity of a salt which passes through the membrane is propor-
tional to the amount of salt dissolved, is strictly accurate, and not
merely an approximation, as Beilstein supposed.
A series of experiments with different mixtures of any two out of
GENERAL AND PHYSICAL CHEMISTRY. 421
the five chlorides previously mentioned showed that in the case of
mixed solutions of sodium, potassium, and ammonium cblorides each
of the salts retains its own rate of diffusion. The resnlts obtained
with mixtures of calcium chloride with alkaline chlorides are not so
conclusive, but the differences between the observed and calculated
values are not greater than the errors of experiment. Mixtures of
magnesium chloride with potassium or ammonium chloride in mole-
cular proportion obey the general law, but mixtures of potassium
chloride and magnesium chloride in the proportion of 2 mols. of the
former to 1 mol. of the latter, show differences between the observed
and calculated values which are considerably greater than errors of
experiment. It is well known that magnesium chloride forms well-
defined double salts with the alkaline chlorides, and the author
concludes that in the above mixtures the different salts unite in the
proportions in which they are mixed, forming double salts, the rates of
diffusion of which are inversely proportional to their molecular weights.
This supposition is supported by the experimental results. In the
case of mixtures of either calcium or magnesium chloride with alka-
line chlorides, it is possible that double salts are formed which, how-
ever, allow just as much chlorine to pass through the membrane as
would have passed through if the salts had remained uncombined and
each had retained its own rate of diffusion.
Numerous experiments were made with a View to ascertain the accu-
racy or inaccuracy of the statement, that the rates of diffusion of salts
from their solutions into pure water are in the inverse ratio of tlieir
molecular weights. The experimental results are fairly in accordance
with this law, especially if the salts are grouped according to the
number of chlorine-atoms in the molecule ; bat it would appear that
although the molecular weight is the main factor which determines the
rate of diffusion of a salt, other causes, such as influence of heat, the
form of the molecules, and the nature of the membrane, exert an
appreciable influence. Experiments were also made with a view to
test the value of the rate of diffusion as a means of investigating the
constitution of mixtures of various salts in solution. The solutions
actually employed were mixtures of potassium nitrate with chlorides
of the alkalis and alkaline earths. The results obtained showed that
complete decomposition took place, with formation of potassium chlo-
ride and a corresponding quantity of nitrate of the other metal. In
the case of magnesium chloride, however, the results indicated that
complete decomposition of the magnesium chloride does not take place
unless the potassium nitrate is in considerable excess. This is pro-
bably due to the formation of the relatively highly stable double
chloride of magnesium and potassium.
When a mixed solution of sodium chloride and hydrochloric acid
passes through a membrane, the rates of diffusion of the two com-
pounds are lower than when each passes alone through the membrane ;
it follows, therefore, that in the mixed solution they do not pass
through independently of each other. This retarding influence is
exerted by a very small quantity of the free acid, and is but slightly
affected by the actual quantity of acid present. The quantity of
hydrochloric acid which passes through the membrane into pure water
422 ABSTRACTS OF CHEMICAL PAPERS.
from a solution of sodium chloride of known strength is proportional
to tlie amount of hydrochloric acid originally contained in the solu-
tion.
Tables giving details of the experimental results are given in the
original paper. C. H. B.
Constitution of Liquid Compounds. By H. Schroder (Arm.
Phys. Chem. [2], 16, 660 — 693). — This paper, a continuation of
former ones (ibid., 11, 997—1016, and 14, 653—670), relates to the
molecular volumes of liquid compounds taken at their boiling^ point.
To each class of compounds is assigned a " structural formula," vs^hich
has always an extremely simple relation to the ordinary atomic
formula.
The present paper discusses the steres of several classes of compounds,
and concludes with a table of 120 compounds, showing that the sura
of the steres in the " structural formula " has a nearly constant ratio
(1 ; 7) to the molecular volume at the boiling point. R. R.
Rupert's Drops. By I. Taylor (Chem. News, 46, 253).— Rupert's
drops may be successfully prepared by dropping the molten glass into
a cold saturated solution of ammonium chloride in a cylinder about
18 inches long. D. A. L.
Explosion of a Tube containing Liquid Carbonic Anhydride.
By L. Pfaundler (Ann. Phys. Ghim. [2], 17, 175 — 176). — In the course
of the solidification of liquid carbonic anhydride in a sealed glass
tube, a violent explosion took place. The tube in question had often
been heated to 31" without injury. The author attributes the explo-
sion either to a disintegration of the glass at the low temperature, so
that it was no longer able to withstand the tension of the liquid car-
bonic anhydride, or more probably to the sudden expansion of the
carbonic anhydride in its solidification, Y. H. Y.
Inorganic Chemistry.
Action of Platinum and Palladium on Carbonic Oxide and
Hydrogen. By M. Traube (Ber., 15, 2854 (compare this vol., p. 150).
— Palladium, whether hydrogenised or not, and platinum, in pre-
sence of water and oxygen, oxidise carbonic oxide to carbonic anhy-
dride with intermediate formation of hydrogen peroxide. Platinum
foil or wire when shaken up in water in an atmosphere of hydrogen
and air, causes the formation of hydrogen peroxide in large quantities.
The author proposes to carry on further researches on the problematical
catalytic action of platinum and palladium. V. H. V.
Researches on the Hyponitrites. By Beethelot and Ogier
(Comjpt. rend., 96, 30 — 35, 84 — 88). — The authors have prepared
INORGANIC CHEMISTRY. 423
silver typonitrite by Divers' method, and state that in order to obtain
it pure, it is necessary to dissolve the crude product in dilate nitric
acid, and reprecipitate by neutralising exactly with ammonia. They
ascribe to the salt thus obtained the formula ^^4^405, and not AgNO.
The latter formula was founded on analyses of the salt dried at too
high a temperature. The percentage of silver found increases with
the temperature at which the salt has been dried : hence the authors
dried their product in a vacuum at the ordinary temperature, and in a
dark place. Under these conditions it retains a small quantity of
water, but no reduced silver. The analyses agree better with the
formula Ag4N405, than with the old formula AgNO. By the action of
heat under different conditions, of dilute acids, of oxidising agents,
more especially bromine and potassium permanganate, and estimation
of the products of the reactions or of the quantities of oxidising agent
used, the authors bring further evidence in support of the new
formula.
From the results obtained by oxidation with bromine, the heat of
formation of silver hyponitrite is calculated to be — 9*3, and that of
hyponitrous acid — 38'6 calories. The instability of the acid is in
accordance with this result.
The authors further deduce the heat given out in the oxidation of
this body by bromine and permanganate, and the heat of neutralisa-
tion of hyponitrous acid by the alkalis. E. H. R.
Nitrogen Selenide. By Yeeneuil (Bull Soc. CMm. [2], 38,
548 — 550). — Wohler's method of obtaining this body by the action of
gaseous ammonia on strongly cooled selenium tetrachloride gives very
variable results. The author has, however, obtained a body of con-
stant composition, NSe, bypassing gaseous ammonia into bisulphide of
carbon in which selenium tetrachloride is suspended. A mixture of
ammonium chloride and nitrogen selenide is thus obtained. The
former is removed by washing with water, and the residue purified by
boiliug with carbon bisulphide. Thus prepared it is an amorphous
orange-coloured substance, insoluble in water, ether, and alcohol, very
sparingly soluble in bisulphide of carbon, benzene, and glacial acetic
acid. When dry, it explodes as easily as silver fulminate if struck or
heated to 230°. Potash decomposes it with evolution of ammonia and
formation of selenide and selenite of potassium. Hydrochloric acid
acts in a similar manner, ammonium selenite and chloride being
formed. Cold water has no action, but at 100° it causes very slow
decomposition. E. H. R.
Pyrosulphuric Chloride. By J. Ogier (Compt rend., 96, 66 —
68). — This paper is a reply to Konowaloff {Compt. rend., 95, 1284),
who found the vapour- density of the above compound to be that
required by Avogadro's law for the formula S2O6CI2, whilst the author
found it to be one-half less. From repeated experiments, the author
concludes that his previous determinations were correct, that the sub-
stance used by him was not contaminated with impurity to an appre-
ciable extent, and that the body does not undergo dissociation.
E. H. R.
424 ABSTRACTS OF CHEMICAL PAPERS.
Mechanical Properties of Aluminium. By W. H. Barlow
(Chem. Centr., 1882, 777). — From observations made on a bar 3 feet
long and ^ inch square, the specific gravity of alamininm is found
to be 2'688 ; its tenacity about 12 tons for ^ inch ; its elasticity coejffi-
cient, 10,000. The ductility of a piece 2 inches long was only 25 per
cent. ; the metal can, however, be improved in this direction. When
its strength is compared with its weight, it gives a mechanical value
almost equal to steel. D. A. L.
Potash Alum from Felspar. By H. Pemberton, Jun. {Chem.
Neivs, 1883, 5). — The author is of opinion that Spiller's suggestion
for the manufacture of potash alum from felspar by treatment with
sulphuric acid and a fluoride will not answer in America; firstly,
because of the large quantity of sulphuric acid required ; and secondly,
if fluorspar be the fluoride employed, because of the large amount of
calcium sulphate formed, whilst if cryolite is used, it will be necessary
to purchase and introduce the potash, and then enormous quantities of
sodium sulphate will be formed. With regard to the utilisation of the
evolved silicon fluoride as silica and hydrofluosilicic acid, there is no
market for such quantities as would be produced. D. A. L.
Double Chloride of Potassium and Thallium. By C. Bammels-
BEEG {Ann. Phys. Chem. [2], 16, 709). — The paper gives the analysis
and crystalline properties of a new double chloride of potassium and
thallium, 2KC1,T1C13 + SH^O. R. R.
Thallium and Lithium Phosphates. By C. Rammelsberg
{Ann, Phys. Chem. [2], 16, 694 — 709). — The paper contains analyses
of the following salts, with some details relating to their preparation
and chemical and physical properties : — Trithallium phosphate,
TI3PO4 ; monothallium phosphate, H2TIPO4 ; a compound of mono- and
di-thallium phosphates, HTlsPOi + 2H2TIPO4; isomorphous mixtures
of thallium and ammonium phosphates, corresponding with H2RPO4,
in which Tl : Am = 1 : 2, and with HR2PO4, Tl : Am = 1 : 36;
phosphates of higher oxides of thallium, Tl2P208,Tl2H606, and
3Tl2P208,Tl2H606 ; triiithium phosphate, Li3P04 ; monolithium phos-
phate, H2Li2P04 ; an acid phosphate of lithium, HsLiPaOg. All
attempts to obtain HLi2P04 failed. R. R.
Compounds of Tin with Bromine. By K. Reis and B. Ratmanh
{Chem. Centr.,, 1882, 77^^). — Tin tetrahroTnide. — The product from the
action of ordinary Stasfurt bromine on tin is subjected to fractional
distillation. The fraction boiling at 181 — 190** consists of SnClBra.
The fraction 202 — 203° is pure SnBr4. Tin tetrabromide forms a
white iridescent mass at the ordinary temperature ; it crystallises from
its solution in SnClBra in clear colourless crystals which deliquesce in
the air. It melts at 33°, and boils at 203'0° (corr.) ; its sp. gr. at
35° is 3*349 ; it dissolves in water without perceptible decomposition,
but on heating the solution, tin hydroxide is precipitated. Fused tin
tetrabromide dissolves iodine and sulphur readily. The vapour of
tin tetrabromide does not decompose readily when passed through a
INORGANIC CHExMISTRY. 425
red-hot tube even when mixed with air, oxygen, or carbonic oxide.
Ammo7nostannic hromide. — When tin tetrabromide is warmed in an
atmosphere of ammonia it readily absorbs the gas, forming a white
mass of no constant composition. When this product is heated,
ammonia is given off, the mass becomes yellow, and a yellow subli-
mate of the constitution SnBr4,2NH3 is deposited. Bromostannic acid,
H2SnBr6,8H20, can be prepared by the action of tin tetrabromide and
bromine on amyl alcohol, or by the direct action of hydrobromic acid
on tin tetrabromide. It forms small colourless crystals. The sodium,
calcium, strontium, manganese, and iron salts have 6 mols. H3O, the
nickel salt 8 mols., the magnesium and cobalt salts 10 mols. A
hydrate of tin tetrabromide is produced when tin tetrabromide is exposed
to moist air, or when it is dissolved in a small quantity of water, and
then allowed to evaporate over sulphuric acid ; it forms colourless,
transparent, brilliant crystals which fume in the air ; their constitu-
tion is thus represented : SnBr4,4H20. Tin oxybromide wsis ohtamed
by accident whilst preparing barium bromostannate ; the mixed solu-
tions of SnBr4 and BaBrg became coloured by free bromine, and in
order to overcome this inconvenience metallic tin was added. On
evaporating the solution, barium bromide crystallised out first, but was
succeeded by crystals of the formula Sn3Br60,12H20 ; these are decom-
posed by water even in the cold ; this decomposition is explained by
the equation SngBrgO + 2H2O = HsSnOg + 2SnBr2 + 2HBr. From the
mother- liquor of these crystals another oxy bromide, SnBr8O2,10H2O,
is deposited. D. A. L.
Preparation of Stannic Oxide from Sodium Stannate. By P.
T. Austin (Chem^. News, 46, 286).— Stannic oxide, SnOo, is precipi-
tated when a solution of sodium stannate is boiled with sodium hydro-
gen carbonate, or when a current of carbonic anhydride is passed
through a strong solution of sodium stannate containing an excess of
soda. D. A. L.
Uranyl Potassium Chromate. By Wiesner (Chem. Gentr., 1882,
'J'J^). — According to Berzelius, the body U02.Cr04 is precipitated
from uranium nitrate by potassium chromate. The author did not
succeed in obtaining it in this manner, but found instead the following
series of double salts : —
U02.Cr04,K:2Cr04 + H2O ; 3(U02.Cr04),2K2Cr04 + 7H2O ;
4(U02.Cr04),3K2Cr04 + 7H2O ; 3(U02.Cr04),K2Cr207 + I4H3O.
The last of these forms silky golden-yellow crystals. They are all
decomposed by water. The author regards them as the products of
the decomposition by water of some body formed during the precipi-
tation. D. A. L.
Natural Formation of Manganese Dioxide, and some Reac-
tions of Peroxides. By Berthelot (Gompt. rend., 96, 88—90). —
Manganese dioxide seems to be formed naturally from the carbonate
by the oxidising action of the air, either free or dissolved in water.
VOL. XLiv. 2 g
426 ABSTRACTS OF CHEMICAL PAPERS.
The carbonate, at the moment of its separation from waters surcharged
with carbonic anhydride, becomes oxidised to dioxide. The author
shows, from a consideration of the heats evolved in the reactions
MnO f CO2 (dissolved) = MnCOg and MnO 4- 0 = MnOj, that the
results are in accordance with thermochemical theory, and that the
same is true of the formation of ferric oxide from ferrous carbonate,
which is supposed to take place in nature in a manner exactly similar
to that described above.
The inverse reaction should and does take place between barium
dioxide and carbonic anhydride, and further, thermochemical data
indicate, what is true as a matter of fact, that hydrogen dioxide
cannot be formed by the action of acids on manganese dioxide or ferric
oxide, whilst it can easily be produced by the action of acids on
barium dioxide. In the former case an absorption of heat would take
place, whereas in the latter case heat is developed. E. H. R.
Mineralogical Chemistry.
Silver Amalgam from the Sala Mines. By T. Nordstrom
{Jalrh. f. Min., 1882, 2, Ref., 361— 362;.— The silver amalgam found
at Sala, in dolomite with quartz and blende, has the following compo-
sition : —
Zn. Pb.
Insol.
Ag.
Hg.
Fe.
\. J
CaCOg.
gangue.
Total.
46-30
51-12
0-81
trace
0-21
1-01
99-45
With this exception, silver amalgam has never been found in Sweden.
B. H. B.
A Remarkable Platinum Nugget. By P. Collier (Jakrb. f.
Min., 1883, 1, Ref., 27).~This was found near Plattsburg, New York.
It was 4 cm. long, 3 wide, and 2 high, and weighed 104-4 grm. ; it con-
sisted of a naixture of 46 per cent. Pt with 54 per cent, chrome-iron.
The former had a sp. gr. 17'35, whilst that of the mixture was only
10-446. The analysis of the chrome-iron gave the following result: —
54-944
EeO. AI2O3.
31-567 5-690
SiOs.
3-731
CaO.
3-405
MgO.
0-941
Total.
100-278
The
platinum
had the following composition ;
:—
Pt.
82-814
Fe.
11-040
Pd. Ir.
3-105 0-627
Rh.
0-286
Cu.
0-397
AI2O3.
1-953
CaO.
0-062
Mg.
0-030
Total
= 100-314.
Osmium was present, but the amount could not be estimated. The
nugget was somewhat magnetic. B. H. B,
MINERALOGICAL CHEMISTRY. 427
Substance Resembling Dopplerite from a Peat Bog near
Scranton, Pa. By H. C. Lewis (Jahrh. f. Min., 1888, 1, Ret'., 31—
32). — This substance occurs in irregular veins. When exposed to the
air, it becomes more elastic. It is black, and burns slowly without
flame. It is soluble only in caustic potash, and gives a dark brown
solution. From this solution it is thrown down by acids as a reddish-
brown precipitate. When completely dried, the substance is brittle
and almost as hard as coal (H. = 2*5) ; it also acquires the lustre
and conchoidal fracture of genuine coal. It burns with a yellow flame.
Sp. gr. = 1-032. Streak dark-brown. The dried substance has the
following composition : —
C. H. O + N. Total.
30-971 , 5-526 63-503 100
corresponding with the formula C10H22O16. It resembles dopplerite in
its physical characters, but differs from the latter by the small per-
centage of carbon and the large amount of oxygen it contains. The
author is of opinion that it is an intermediate product between peat
and coal, and proposes the general name Phytocollite for all similar
substances of variable composition. B. H. B.
Idrialite. By R. Scharizee (Jahrh. f. Min., 1883, 1, Ref., 31).—
In the quicksilver mines of Idria a green resin has been found ; this
consists of idrialite in a tolerably pure state. It is a massive, pista-
chio-green mineral containing idrialin, C80II56O2. Its sp. gr. is greater
than 1, but less than 1-85. It has a hardness of 1 — 2, and an uneven
fracture. When dissolved in hot concentrated sulphuric acid, it gives
a deep indigo-blue solution, and on distillation gives a straw-yellow
product which is pure idrialine. The dark-coloured mineral formerly
described as idrialite contains only a very small amount of idrialin.
B. H. B.
Artificial Production of Mellite. By C. Friedkl and M.
Balsohn (Jahrh. f. Min., 1882, 2, Ref., 30 — 31). — By allowing solu-
tions of mellitate of sodium and of an aluminium salt to mix very
slowly for about a fortnight, crystals may be obtained of sufficient
size to examine crystallographically ; they had all the properties of the
natural crystals. H. B.
Cryolite, Pachnolite, and Thomsenolite. By C. Klein (Jahrh.
f. Min., 1882, 2, 89 — 90). — Brandl, in a recent paper before the
Bavarian Academy, described the analyses of specimens of the above
minerals, which had been crystallographically determined by Groth.
Their formulae are AlF„3NaF; AlF3,CaF2,NaF, and AlF3,CaF2,ISraF,H20
respectively. The author, whilst admitting the service done by
Brandl in determining the true composition of pachnolite, points out
that the composition of cryolite and of thomsenolite was already
determined with certainty, as in 1877 he showed that the crystals
examined by Wohler were in reality cryolite, that the crystals of
thomsenolite also examined by Wohler — who then called it pachno-
lite— had all the properties ascribed to it by Kreuner, and re-analysed
2g 2
428 ABSTRACTS OF CHEMICAL PAPERS.
wave the formula adopted by Wohler, which is the same as that given
by Brandl. H. B.
Minerals Found near Massa in the Apnanian Alps. By A.
d'Archiardi {Jahrh. f. Min., 1882, 2, Ref., 353— 354).— In the Fidgida
valley, near Massa, not far from the celebrated Carrara marble
quarries, a lode comes to the surface. It consists of iron spar with
quartz and copper pyrites, together with magnetic pyrites and a dark-
grey metallic mineral, which the author believes to be coppite. Blende
is also occasionally fonnd, and a grey fibrous mineral not yet investi-
gated. The copper pyrites contains 26 — 30 per cent. Cu, and has a
sp. gr. of 4*1. . The magnetic pyrites consists of
S. Fe. Ni.
39-65 58-18 2'17 per cent.,
thus indicating the formula {FeNi)7S8.
To the grey mineral, the author gives the name of Frigidlte. It rarely
occurs crystallised, being usually in granular masses. Sp. gr. = 4*8.
H. = 4. Before the blowpipe, it acts like tetrahedrite, which it very
much resembles in appearance. The analysis gave the numbers under
I : the results obtained, after subtracting the impurities and reducing
to 100, are shown under II —
s.
Sh.
Cu.
Fe.
Ni.
Ag-
Zn.
SiOg.
Total.
I.
29-60
25-59
19-32
12-67
7-55
0-83
trace
2-20
96-96
11.
31-23
27-00
20-39
13-37
7-97
0-04
trace
—
100-00
III.
27-01
29-61
30-10
13-08
—
—
—
—
99-80
It is, therefore, not Becchrs coppite, the composition of which is given
under III.
The above composition may be interpreted in various ways, and aU
the interpretations agree equally well with the analysis.
The mineral may be regard-ed as a mixture of nickel tetrahedrite
with copper pyrites, as a somewhat diflferent tetrahedrite with uUman-
nite and iron pyrites, or lastly as a mixture of tetrahedrite with anti-
mony-nickel. There is, however, no doubt that frigidite is an impure
tetrahedrite. B. H. B.
Galena with Octohedral Cleavage. By A. Brun (Jahrb. f.
Min., 1883, 1, Ref., 9—10). — In the Glacier de Lochant (Chaine du
Mt. Blanc) the author found a fine twin crystal of galena ; the twin
face was O, and the crystal was formed by the faces of the octohedron
and the cube. The octohedral cleavage was very distinct. Sp. gr. =
7-67. It contained some bismuth and a little iron. This is the third
known example of galena with an octohedral cleavage ; the other two
are from the Habach valley and from Pennsylvania respectively.
B. H. B.
Analysis of Miargyrite from Pribram. By J. Bumpf {Jahrh.
/. Mill., 1882, 2, Ref., 17).— The analysis gives 21-68 S, 41-15 Sb,
36*71 Ag, agreeing well with the accepted formula, AgoS. 81)283.
H. B.
MINERALOGICAL CHEMISTRY. 429
Alaskaite, a New Bismuth Mineral. By G. A. Konig (Ja/irh.
f. Min., 1883, 1, Ref., 25 — 26). — Alaskaite occurs with tetrahedrite
and copper pyrites in Colorado. The colour is lead-grey to white;
the lustre metallic. The mineral is soft and has a sp. gr. of 6'878.
It decrepitates on being heated, and melts without the formation of a
sublimate. It is decomposed by hot hydrochloric acid, leavino^ a
residue of silver chloride with copper pyrites and heavy spar. The
analysis gave the following results : —
Sb.
Bi.
Pb.
Ag.
Cu.
Zn.
S.
I.
51-49
12-02
8-08
3-00
0-26
15-72
II.
0-51
46-87
9-70
7-10
2-85
0-64
15-07
III.
—
51-35
17-51
3-00
3-74
0-20
16-21
The ratio of R : Bi : S is here 1:2:4; the formula is then RBiaS^,
or (PbZnAg2Cu2)S + BigSg. B. H. B.
Compact Magnetic Iron Ore from Cogne, Valley of Aosta.
By M. ZECCHmi {Jahrh. f. Min., 1882, 2, Ref., 386).— With this ore,
a small quantity (about 6 per cent.) of an apparently rhombic mineral
is found. Analysis I gave the composition of the magnetic iron ore ;
Analysis II that of the accompanying mineral : —
Insoluble silicates
H2O.
I. 0-60
II. 11-19
and free SiOa. FegOg. FeO. MgO.
CaO.
5-54 18-09 73-47 1-65
0-55
SiOa 43-15 4-10 — 40-31
trace
Nickel and chromium
CoO. oxides. Total.
I. 0-21 trace 10011
II. — — 98-75
B.
H. B.
Occurrence of Iron Ores at Taberg in Smaaland (Sweden).
By A. E. ToRNEBOHM {Jahrh. f. Min., 1882, 2, Ref., 66— 67).— The
ore is associated with a variety of hyperite, rich in olivine and mag-
netite, and the whole forms together an immense lense-shaped mass.
Its period of formation is more remote than that of most other
Swedish ores. A somewhat similar mass occurs at Launghult
(Kronoberg). Analyses of the ores from these localities are given,
and also that of a similar ore from Rhode Island. H. B.
A Manganese Mineral from Upsala. By Gr. de Geer (Jahrh.
f. Min., 1882, 2, Ref., 361). — This mineral has the following compo-
sition : —
Gangue. CuO. MnjOg. HjO. Total,
7-24 117 73-19 16-27 9787
The formula is then Mn304,4H20, and the author suggests for it the
name manganese-ochre. B. H. B.
430 ABSTRACTS OF CHEMICAL PAPERS.
Pseudom Orphic Senarmontite Crystals. Bj C. Htntze (Jahrh.
f. Min. 1883, 1, Ref., 32). — Several senarmontite crystals from South
Ham, in Canada, have a dark roa^h surface. On closer investigation,
it was found that only the kernel of the cryst-als consisted of senar-
montite, whilst the outer layer was antimonite ; so that the crystal
is a pseudomorph of antimonite after senarmontite. The kernel has,
however, not been converted directly into antimonite, but first into
an aggregate of valentinite fibres, which were afterwards converted
into antimonite. B. H. B.
Artificial and Natural Gay-Lussite. By A. Arzruxi (Jahrb. f.
Mill., 1882, 2, Ref., 17, 18) ; and Reproduction of Gay-Lussite.
By A. Favre and C. Soret {ihld., 18, 19). — From the clarified soda
liquors there are deposited crystals of gay-lu.ssite at a temperature of
40° on the bottom of the vessel, and also in the carbonising tower,
where the gases from burning coke are passed through the solution ;
these crystals were examined and compared with natural crystals. They
contain from 32 — 36 per cent. NagCOa, while the formula Na^COa -h
CaCOs + 5H2O requires 35'8 per cent. The predominating faces are
coP and ^00, -^P and OP being more subsidiary. All faces in the zone
ooP, ^co, ^P are striated parallel to the zonal axis. A table em-
bracing all published and also new measurements is given ; those of
the artificial crystals agree very well with those of the natural
crystals. Their optical behaviour agrees with Des Cloizeaux's obser-
vations.
A snail and a piece of wood, after being immersed in a solution of
sodium silicate for 27 years, were examined. The shell was eaten
away and the wood covered with a crust containing silica, soda, water,
and alumina, and with a thin skin of organic matter ; between the two
were small crystals of gay-lussite. They had the chemical and physical
properties of this mineral. Measurement showed the following
forms to possess almost the interfacial angles of the native mineral : —
coP . -^P . ^00 ; cd^co is probably also present. H. B.
Composition of Dawsonite. By C. Friedel, M. Chaper, and
J. Harrington (Jahrb. f. Min., 1883, 1, Ref., 16 — 16). — This Canadian
mineral was discovered by J. Harrington in 1874, and a mineral of
similar chemical composition has now been observed by Chaper in
Tuscany. It occurs there in small, white, finely fibrous bundles in
crevices in a dolomitic marl. When the substance is heated strongly in
a closed tube, it gives up water ; it is infusible before the blowpipe, and
is coloured blue by cobalt solution. Friedel's analyses gave the fol-
lowing results (I) : —
COs. AI2O3. NaaO. H.O. OaO. MgO. Total.
1. 29-09 35-b9 19-13 12-00 042 1-39 97-92
thus indicating the composition Al203,]S"a20,2CO-.>,2H20. Friedel
regards the compound as an aluminium hydroxide, in which one atom
of hydroxyl is replaced by the monad radicle NaCOa, thus leading to
the formula Al(OH)2(NaC03).
II and III are Harrington's original analyses. He has also analysed
MINERALOGICAL CHEMISTRY. 431
the mineral which he recently found, together with calcspar, dolo-
mite, iron pyrites, galena, and a small quantity of a manganese
mineral, in the Montreal Reservoir (IV).
CO3. AI2O3. NajO. H2O. CaO. MgO.
II. 29-88 32-84 20-20 ll'Ol 5-95 trace
III. 30-72 32-68 20-17 (10-33) 5-65 0-45
lY. 32-23 2471 1564 906 1685 trace
K2O, MnOa. SiOg. Total.
II. 0-38 — 0-40 101-56
III. — -. — 100-00
lY. — 0-23 0-84 99-56
On subtracting the accidental impurities, the analyses correspond
very well with the composition demanded by the formula :
I. II. III. IV. Calculated.
CO, 29-27 27-96 29-06 27-78 30-49
AI2O3 37-88 3642 36-70 36-12 35-55
ISTagO 20-19 22-41 22-65 22-86 21-48
H2O 12-66 13-21 11-59 13-24 12-47
Harrington determined the specific gravity to be 2-40. The Tuscan
dawsonite is accompanied by dolomite, cinnabar, calcspar, iron pyrites,
fluorspar, and bitumen. B. H. B.
Strontianite in Westphalia. By E. Venator (Jahrh. f. Min.,
1883, 1, Ref., 28). — Numerous veins of strontianite occur in the
Senonian marl between Hamm and Miinster ; and in order to obtain
the mineral, more than 1200 miners are employed. The minerals
filling the veins consist of strontianite, calcspar, marls, and sometimes
iron pyrites. The thickness of the veins is very variable, the maximum
being three metres. Faults are exceedingly rare. B. H. B.
Turquoise of New Mexico. By B. Silliman {Jahrh. /. Min.,
1883, 1, Ref., 27). — The paper gives an account of the occurrence of
turquoise in the augite trachyte of the Cerillo Mts. The rook is
quite altered by hot springs, and in the yellowish- white product of this
action small concretions of bluish-green kalaite are found which oc-
casionally pass into the azure-blue variety valued as a precious stone.
B. H. B.
Artificial Production of Phosgenite. By C. Friedel and E.
Sarasin {Jahrh. f. Min., 1882, 2, Kef., 31). — By heating a mixture of
lead carbonate and chloride in a closed flask at 1 80" in presence of
water, small quadratic crystals were obtained ; they always contained
much of the ingredients and were not suitable for analysis, but the
author believes that the optical behaviour demonstrates it to be phos-
genite. H. B.
Natural Barium Nitrate. By P. Groth (Jahrh. f. Min., ^ 883,
1, Kef., 14). — This new mineral was found in an old coUecciou of
432 ABSTRACTS OF CHEMICAL PAPERS.
Chilian minerals. The crystals are 4 mra. in size ; they are colonrless
and consist of octohedra. Twin crystals similar to those of spinelle
also occur. B. H. B.
Examination of the Ores from Amberger and of the accom-
panying Phosphates. By J. B. Schober (Jakrb. f. Min., 1882, 2,
B/ef., 20 — 21). — The bulk of this paper is of technical interest. The
sparingly occurring phosphates, wavellite, vivianite, and cacoxene are
described in an appendix ; analyses of the last two are given ; the last
one has been much changed, and has lost most of the phosphoric acid.
H. B.
Existence of Apatite in the Pegmatite of Lyons. By F. Gon-
NARD (Jahrb. f. Min., 1882, 2, Ref., 352). — Apatite occurs in the
eruptive rocks in the neighbourhood of Lyons, partly in microscopic,
partly in macroscopic crystals. It occurs in gneiss at Beauraan with
dumortierite, a mineral recently discovered there, also with garnet,
near Greillon, and in pegmatite in the Roche Garden and Sainte Foy.
B. H. B.
Mineralogical Notes. By A. Weisbach (Jahrb f. Min., 1882, 2,
Mem., 249 — 259). — 1. Apatite. — In the collection of the School of
Mines in Freiberg is a short columnar crystal of apatite from the tin
lodes of Ehrenfriedersdorf. It appears to be a combination of the
pyramid, ^P, with the hexagonal prism and the basal plane. It has,
however, been found that the latter is not a true basal plane, but an
extremely flat pyramid having the symbol roPf- ^^^ middle edges
form an angle of 1° 23^ the polar edges 179° 18'. It is the flattest
pyramid which has yet been observed in any mineral species.
2. Lautite. — Under this name a mineral from Lauta, near Marien-
berg in Saxony, has recently been introduced. It is composed of Cu,
As, and sulphur, and its chemical formula was asserted to be CuAsS.
The author is of opinion that it is not a true mineral species, but a
mixture of native arsenic and a copper sulpho-salt. The latter he
determines to be CugAsSs. The so-called lautite is a mixture of 71
per cent, of this sulpho-salt and 29 per cent, arsenic.
3. Bronzite. — The crystals of this mineral, which was found inthe
meteorite of RiUersgriin, had the following form : — cxjP, OP, ooPoo,
tx)Poo, ooP3, ooP2, ooP2, iPoo, Pf, P2, P4, 4P2, iP, fPf.
4s. Keramohalite. — By many dealers a mineral from Schwarzenberg
in Saxony, is frequently sold under the name of tectizite. This is,
however, not an iron but an aluminium sulphate, as the analysis
roves —
AlA-
12-69
FeO.
6-46
CaO.
0-14
H2SO4.
34-26
H2O.
46-70
Total.
99-25
The formula is thus Al6S8033,48H20, which differs but very slightly
from that of keramohalite.
5. Bismuth carboimte, from Guanajuato in Mexico, contained 91*68
per cent, bismuth oxide and 8'29 per cent. CO2. Total 99-97. This
corresponds exactly with the composition of the Schneeberg variety.
MINERALOGICAL CHEMISTRY. 433
6. DomeyMte, from Zurickan, gave on analysis the following
results : —
Cu.
Fe.
m.
As.
0.
Residue.
Total.
65-08
0-64
0-44
20-45
2-49
3-84
98-94
The presence of oxygen is owing to a copper arsenate, a product of
the decomposition of the domeykite. The " residue " consists of
porphyry.
7. Eulytine. — Among the colours assigned in the text-books on
mineralogy to this mineral (bismuth silicate), black is not mentioned.
A series of examples possessing this characteristic exist, however, in
the Werner Museum at Freiberg.
8. Winhlerite. — Analysis of this mineral from Almeria in south
Spain gave the following results : —
H2O. O. SiOg. BiO. CuO. AS2O3. FeO.
12-12 4-11 0-29 1-70 1501 20-50 0*71
C02O3. NisOj. CaO. Total.
23-80 12-98 9-27 100-49
The mineral analysed was associated with olivenite in such a way that
it was impossible to separate them perfectly. On subtracting the con-
stituents which may be regarded as impurities in the above analyses,
we obtain —
H20.
0.
C02O3.
NioOa.
Total.
10-6
41
23-8
13-0
51-5
20-6
8-0
46-2
25-2
100-0
a composition which may be represented by the general formula —
R203,2H20, or Co4Ni209,2H20.
9. Uranium Ochre. — This was found at Johanngeorgenstadt. It
gave on analysis the following result (sp. gr. = 3-953) : —
CaO. UO. H2SO4. H:20. Residue. Total.
2-08 77-17 3-18 16-59 0-39 99*41
This leads to the formula CaUi6S203i + 25H2O. B. H. B.
Relation between the Chemical Composition and Optical
Characters in the Group of Pyromorphites and Mimetesites.
By C. Jannettaz and L. Michel (Jahrb. /. Min., 1882,' 2, Ref., 347 —
348). — Pure pyromorphite is uniaxal, pure mimetesite biaxal. Crystals
occur in which the centre is pyromorphite and the exterior is mimete-
site, and chemical analysis now shows that crystals occur with uniaxal
centre and biaxal exterior, which contain no AS2O3. For such cases
the authors suggest that the apparently biaxal interference figure is
caused by non-parallel aggregation of uniaxal individuals.
B. H. B.
Dietrichite. By A. Arzruni (Jahrb. f. Min., 1882, 2, Bef., 19).—
The author considers the formula to be ZnO,Al203,4S03 + 22H2O,
434 ABSTRACTS OF CHEMICAL PAPERS.
instead of -1-23320, as ^ven by Dietrich. The analysis by Dietrich
gives RO : H^O = 1 : 20-3, R2O3 : H2O = 1 : 230, SO3 : H^O =
4 : 21 '9, and hence the point cannot be considered as definitely settled.
This mineral is doubly refractive, the depolarising direction being
parallel to the length of the fibres. H. B.
Thenardite from Aguas Blancas. By C. Baeewald (Jahrb. f.
Min., 1882, 2, Bef., 19 — 20). — The crystals are clear and transparent,
but in the air soon become covered with a white crust. Measurements
gave the axial relations a : b : c = 0*4771 : 1 : 0'7984. Plane of the
optical axis is coPob, the axis a is acute bisectrix ; double refraction -|- ;
dispersion weak p>v; 2V = 89° 59' for Li, 90° for Na, and 90° OJ'
for Tl light. Analysis gave —
NaaO. SO3. CaO. H2O.
41-91 53-34 2-66 0-93 = 99-84
The author supposes the calcium to be present in some unknown form,
and not as glauberite. H. B.
Arsenates from Laangban. By W. Lindgken (Jahrb. f. Min.,
1882, 2, Bef., 362 — 363). — 1. Berzeliite. — Honey -yellow colour, waxy
lustre, translucent, fracture imperfectly concho'idal, brittle, H. = 5,
sp. gr. = 4*09 — 4-07. It melts before the blowpipe to a brown
globule. Soluble in hydrochloric and in nitric acids. It occurs as
small granules in limestone.
2. Doubly -refracting Berzeliite. — No distinct cleavage, doubly re-
fracting, crystalline system unknown, yellowish colour, H. = 5, sp. gr.
= 3-89 — 4*04. The analysis gave —
PbO. FeO. Insol.
A82O3. CaO. MgO. MngOa. ^^ , ' residue. Total
62-00 20-00 12-81 4-18 trace 0-68 99-67
The formula is therefore 3(Ca,Mg,Mn)0,As205.
3. Karyinite. — Doubly refracting, not pleochroic. The analyses are
not trustworthy, as it is never free from berzeliite.
4. A calcite occurring with the karyinite gave on analysis the fol-
lowing results : —
CaCOg.
MgCOa.
MnCOa.
ZnCOg.
Total.
92-64
4-18
2-80
1-09
100-71
B. H.
B.
Analysis of Columbite. By E. D. Hallock {Jahrb. f. Min.,
1883, 1, Bef., 26).— Columbite from Middletown, Conn., with the sp.
gr. 6" 13, gave on analysis —
Acids.
FeO.
MnO.
CaO.
82-64
11-77
4-95
4-93 = 104-29
82-56
12-08
0-50
0-45 = 95-59
The high sp. gr. of the fused precipitate of the mixed acids indicates
a large percentage of Ti02. B. H. B.
MINERALOGTCAL CHEMISTRY. 435
Crystalline Form of Sipylite. By J. W. Mallet (Jahrh. f. Min.,
1883, 1, 28). — This mineral has already been described by the author
{Amer. J. Sci.^ 1877, 15, 397). He now determines the crystalline
form to be a tetragonal pyramid, the polar edgres of which form an
angle of 100° 45', and the middle edge 127°. Cleavage is parallel to
the pyramid faces. Sp. gr. = 4-883 at 18°. B. H. B.
Wulfenite. By S. Koch (Jahrh. f. Min., 1883, 1, Ref., 11—13).—
The author examined a large series of crystals of wulfenite from
Juma County, Arizona: from Utah, Mexico, Phenixville, Bleiberg,
and Rucksberg in Banat. From the angular measurements he calcu-
lated for wulfenite a general ratio of the axes, a : c = 1 : 1*57767.
Twenty-nine crystal forms altogether occur in wulfenite, of which
seven were first obsei-ved by the author (-fP, ^P, ^-^Poo, yV^co, f Pco,
ooP|^, ^P|-). Pyramids of the second order, and prisms form the
majority of the faces. Hemimorphism was never observed.
B. H. B.
Anatase and Xenotime from Burke Co., N. Carolina. By
W. E. Hidden (Jahrb.f. Min., 1883, 1, Bel, 14). — Anatase occurs in
the form of greenish-yellow crystals, in the gold sands near Brindle-
town, together with monazite, xenotime, fergusonite, samarskite,
zircon, and brookite. The crystals have the combination OP . P.
The xenotime is yellowish-grey, and is combined with zircon in such
a way that the two minerals have the same principal axis.
B. H. B.
Pseudobrookite. By A. Schmidt (Jahrh. f. Min., 1882, 2, Ref.,
24 — 25). — To the already known forms the author adds coP^, accept-
ing the first proposals of Groth (Zeitsch^ f. Kryst., 3, 306). New
measurements gave the angles ooPdb : cx>P2 = ISS"* 23' — 163° 51', and
ooPc5b : Pdb = 138° 30^—138° 57', from which
a : 6 : c = 0*992 : 1 : 1-130.
A discussion follows on Groth's proposal to interchange the a and h
axes, whereby the form approaches much more nearly to that of
brookite. This alteration the author does not accept. No fresh
analysis is, however, given. H. B.
Tin Ores, Aventurine Glass, and Green Aventurine Quartz,
from Asia, and Krokydolite Quartz, from Greenland. By H.
Fischer (Jahrh. /. Min., 1882, 2, 90— 98).— The author discusses the
interest attaching to a correct knowledge of the localities whence the
ancients obtained their minerals, whether ornamental stones, as the
turquoise and lapis lazuli, or as metallic ores. Besides the localities
mentioned in mineralogical lists, a number have been collected together,
and appeared in Gurlt's Berghau-und Huttenkunde, 1877, 9 ; the know-
ledge of these localities of the East is of great historic interest, and
the author by drawing attention to them wishes to make them better
known. The aventurine glass offered for sale in Allahabad and North
India generally, is not of Venetian origin; the articles are brought
in by the Afghans (Cabulis), who are practised in the production of
436 Abstracts of chemical papers.
artificial stones ; it is, however possible that they are only middlemen,
for Badakschan is the only known locality where this glass is made. In
Delhi the Venetian product is used. The author suggests that Marco
Polo, who visited Central Asia in the 13th century, learnt the art of
making this glass from some native tribes, and brought it to Venice ;
in these districts chalcedony and agates are still cut, polished, and
bored, and it is possible that this is the source of the Assyrian and
Babylonian cylinders and talismans, and of the agate and other beads,
&c., found in ancient Roman and German tombs. Sections of the
cut aventurine quartz ornaments showed the presence of a number of
thin plates, with their long axes for the most part parallel ; they are
beautifully dichroic, varying from emerald-green to blue-green ; they
are chromium mica. In a collection of stone axe-heads from Athens,
some were found made of a remarkable rock ; its section showed a
ground-mass of red quartz, in which groups of fine needles of a pure
blue were thickly imbedded ; they are probably glaucophane. Other
specimens appeared to have come from the emery districts of Asia
Minor, but no satisfactory sections could be obtained. H. B.
Composition of Minerals of the Chondrodite Group. By H.
Sjogren (Jahrb. f. Min., 1883, 1, Ref., 23 — 24). — The author accepts
the opinion of Kammelsberg and Groth, that water is present in the
three members of the chondrodite group, and being of the opinion that
the differences in the analyses prove them not to have the same com-
position, he adopts the following formulae : —
Clinohumite = MgsCMg^^^'jJ^CSiOJa.
Hnmite = Mg3[Mg(^^^')]2(SiO02.
Chondrodite = Mg4[Mg('^^)]4(Si04)3.
B. H. B.
Iron Glance and Augite, from Ascension. By G. v. Rath
(Jahrh. /. Mi7i., 1883, 1, Ref., 16— 17).— On a plate of iron glance,
90 mm. in diameter, with the faces OR, + R, — ^R, fPa, coP2, and
— jR, small reddish-yellow crystals of augite, 1 mm. long, were
developed. The augite had the following faces: h P, + ^^5, — P,
cx)P, — ooP3, + Poo, ooPoo, co^co. From this it is proved that the
augite was formed by sublimation. B. H. B.
Nephrite or Jade of Siberia. By E. Jannettaz and L. Michel
(Jahrh. f, Min., 1883, 1, Ref., 29— 30).— In the bed of a stream in the
Bagoutal Mountains, near the Chinese frontier, Alibert found loose
blocks of a jade-like substance. They were greenish-white to emerald-
green, had a greasy lustre, and were more or less translucent, accord-
ing to the colour. Fracture splintery. Hardness, 6-5. Sp. gr. 3*08 —
3*2. Before the blowpipe, it melted easily to a light-green globule.
The chemical analysis gave —
MINERALOGICAL CHEMISTRY. 437
SiOg.
MgO.
CaO.
Fe,03.
Al,03.
H2O.
Total.
56-60
23-04
13-45
2-38
1-37
303
99-87
I.
11. 55-13 19-67 14-13 8-5 31 10053
I. Analysis of the light-coloured variety. II. The green variety.
B. H. B.
Jadeite Axe from Rabber, Hanover. By A. Arzruni (Jahrb. f.
Min., 1883, 1, Ref., 30). — The axe in question is 12 cm. long, has a
cutting edge 5 cm. broad, and on the opposite side has a somewhat
flattened conical point, 2 em. in diameter. Under the microscope a
thin section showed the confused fibres, characteristic both of nephrite
and of jadeite, but in places rhomb-shaped crystal sections could be
seen, with cleavage planes cutting each other at angles of 87 — 89°, and
93 — 91°. As this angle agrees with the results obtained by Descloizeaux
with jadeite from Thibet, the author concluded that the axe was made
of the same mineral, and that this belonged to the pyroxene group :
consequently jadeite must belong to the monoclinic system.
B. H. B.
Danburite, from the Scopi, in Granbiindten. By E. Ludwig
{Monatsh. Ghem., 3, 819 — 821). — This mineral occurring, surrounded
by earthy chlorite, in a rock-cleft on the Scopi, agrees in composition,
chemical characters, primary form, and optical properties, with dan-
bnrite, from Bussel, in New York (Chem. J., Abstr., 150 — 151), but
differs from the latter in the mode of development of its crystals.
Sp. gr., 9-85« Analysis gave —
SiOg. B2O3. CaO. MgO. AlaOa.FesOajMnaOa.
48-52 2877 23-03 0-30 traces
The mineral may be regarded as the calcium salt of a borosilicic
acid, Si^BaHaOs. H. W.
Helvite, from Virginia. By R. Haines (Ghem. News, 1883, 6). —
The mineral is found mixed with orthoclase, with pale-red topazolite, and
a variety of garnet. The helvite crystals were shown to be isometric
by the polariscope, but were not sufficiently perfect for angular mea-
surements. H. is about 6 ; colour sulphur-yellow ; lustre somewhat
resinous, partially translucent ; fusibility about 4, to a brown glass.
The mineral gives no water in closed tubes ; wirh fluxes, it gives the
reactions for manganese ; is soluble in hydrochloric acid, with evolu-
tion of hydrogen sulphide, and separation of gelatinous silica. Sp. gr.
3-29. Analysis yields the following results : —
Silica insoluble in acid and in sodium carbonate, 9-22.
Total
SiOs- BeO. AI2O3. MnO. FeO. CaO. K2O. NaaO. S. Moisture.
32-32 11-47 2-68 45-38 1 85 064 0-39 0-92 4-50 0*30
Second
deter.
32-49 —.__--_ — — _. —
2-25 is to be deducted for oxygen replaced by the sulphur.
D. A. L.
438 ABSTRACTS OK CHEMICAL PAPERS.
Melanite from Lantign6 (Rhdne). By A. Lacrotx (Jahrh.f.
Min., 1882, 2, Ref., 352—853). — In a bed of ma^etic iron ore near
Lantigne the author found specimens of two different varieties of
garnet. Both occur in crystals and in compact aggregates. In both
cases the forms 202 and coO occur. Sp. gr. 3'66 for the first, and 3-62
for the second variety. The garnet gives up water when heated in a
closed tube, and melts before the blowpipe to a magnetic globule.
The second variety gives the manganese reaction when melted with
borax, and when treated with soda and nitre on platinum foil. From
the analysis, the formula 3CaO,Fe203,3Si02 is deduced. Marcasite,
quartz, galena, cerussite, malachite, and iron glance also occur in the
same locality. B. H. B.
Change of Colour in Felspar under the Influence of Light.
By E. Erdmann (Jahrh. f. Min., 1882, 2, Ref., 363).— Green felspar
(Amazon stone) from pegmatite veins at Ammeberg, when first taken
from the mine, is of a greenish-grey colour, but after exposure to the
air for some time, it assumes a bright emerald-green colour. By
placing fragments in variously coloured glass tubes, and submitting
them to the action of light for 11 months, the author came to the
conclusion that light alone effects the change, air and moisture having
no influence. When the dark-green felspar is heated, it again loses its
colour. B. H. B.
Bechi's so-called Picranalcime from the Monte Catini Mine,
Monte Caporciano. By E. Bamberger (Jahrh. f. Min., 1882, 2,
Ref., 22). — Crystals of this picranalcime were examined crystallo-
graphically, optically, and chemically. In all these properties it
agrees with analcime ; it is nothing but analcime, and " picranalcime '*
must be removed from mineralogical lists. Magnesia is not contained
in it.
SiOa. AI2O3. NaaO. KjO. H^O.
57-08 21-51 13-63 0-32 832 = 100-86
H. B.
Spodumene and the Products of its Alteration. By G. J.
Brush and E. S. Dana (Jahrb. f. Min., 1882, 2, Ref., 355—358).—
This paper gives the results obtained in a study of the spodumene
from Branch ville, Connecticut, and of the various minerals derived
from its alteration.
The unaltered spodumene occurs in crystalline masses, with albite, a
little quartz and mica, apatite, lithiophilite, columbite, garnet, urani-
nite, &c. In addition to this massive variety, spodumene also occurs,
unaltered, as nuclei of distinct pseudomorphous crystals. The fresh
spodumene is perfectly transparent, sometimes colourless, sometimes
pink. It shows the prismatic cleavage with unusual perfection. The
analysis gave the following results : —
SiOa. AI2O3. FesOg. LigO. Na<jO. K2O. Loss. Total.
64-25 27-20 0-20 7-62 0*39 trace 0-24 99-90
Sp. gr. 3-193. The formula is then LigAloSi^Oiz.
MINERALOGICAL CHEMISTRY. 439
Alteration of the Spodumene. — As the results of the alteration, |8-
spodumene and cjmatolite were found. The following independent
minerals were also found : albite, microcline, muscovite, and killinite.
The ^-spodumene is compact, appa,rently homogeneous, havins;' a
rather indistinct fibrous structure. H. = 5"5 — 6. Sp. gr. = 2*644 —
2-649. Colour, white to greenish-white. The results of the analysis
were as follows : —
SiOo. AI2O3. LigO. IS'asO. K^O. Loss. Total.
61-51 26-56 3-50 8'14 0-15 0-29 100-15
The ratio obtained, RjO : II2O2 : Si02 =1:1:4, is the same as
that of spodumene, in which, however, half of the lithium has been
removed and its place taken by sodium. The formula is then
(LiNa)2Al3Si40i2.
It is not entirely decomposed by treatment with hydrochloric acid,
67" 56 per cent, remaining insoluble. The analysis gave the following
results, I being the soluble, II the insoluble part : —
SiOa. AI2O3. LisO. NaaO. KoO. Total.
1.48-13 40-50 10-90 — 0-47 100-00
II. 68-18 20-07 — 11-74 — 100-00
The insoluble part closely resembles albite, !N'a2Al2Si60i6, while the
soluble part has the composition Li2Al2Si208. This the author calls
Eucryptite.
The /3-spodumene is therefore a mechanical mixture of eucryptite
and albite. The microscopical examination of thin sections confirms
this view.
Eucryptite crystallises in the hexagonal system with basal cleavage.
Sp. gr. = 2-647. In form and composition, it resembles nepheline.
Cymatolite has a fibrous structure. Sp. gr. = 2*692 — 2*699. Colonr
white to pink. Chemical analysis gave —
S102.
AI2O3.
CaO.
Na^O.
KaO.
H3O.
Total.
59-38
26-67
0-62
7-68
3-51
2-01
99-87
The ratio obtained is R2O : AI2O3 : Si02 = 1:1:4. The formula is
therefore (Na,K,H)2Al2Si40i2. It is derived from the /3-spodumene,
and is also a mechanical mixture.
Albite occurs pseudomorphous after spodumene. An analysis
gave —
SiOg. AI2O3. MgO. NagO. K2O. Loss. Total.
67-60 20-09 0-15 11-69 0-11 0-14 90-78
tlms corresponding to the formula Na2Al2Si60i6.
Microcline arises from the alteration of the spodumene. The com-
position is shown by the following analysis : —
SiOa- AI2O3. NaaO. KjO. Loss. Total.
64-55 19-70 0-58 15*62 0*12 100-57
440 ABSTRACTS OF CHEMICAL PAPERS.
Killinite probably consists of very finely divided mica, impregnated
with more or less amorphous silica. The want of homogeneity renders
the analysis very variable.
The cymatolite is often further changed into an impure kaolin, and
associated with this is a pink clay-like mineral resembling mont-
morillonite. The analysis of which gave —
SiOs- AI2O3. FeO. MnO. CaO. MgO. Li.^O. NasO. KgO.
51-20 22-14 trace 0-18 3-53 3-72 trace 0-18 0-38
Loss. P2O5. Total.
17-08 1-42 99-83
The authors suggest that this is the result of the further alteration
of the cymatolite. B. H. B.
Hiddenite, an Emerald-green Variety of Spodumene. By J.
L. Smith, E. S. Dana, and L. Smith {Jahrh. /. 3/m., 1882, 2, Ref.,
345 — 346). — This mineral occurs, together with quartz, mica, rutile,
beryl, and orthoclase in the gneiss and mica slates of Alexander Co.,
N. Carolina. The following 18 crystalline forms occur: ooPob, OP,
coPf, ooP, ooP2, ooP3, 2P, P, ooPc^b, 4P, fP, -6P3, -8P|, -4P2,
AP2, 4P2, 3P|, 6P|. Among these, the last 10 are new for the
species. Twin crystals are more frequent than simple ones. The
cleavage is parallel to ooP. Sp. gr. = 3*152 — 3*189. The analysis
gave the following result : —
810.2. AI2O3. FesOg. LigO. Na^O. Loss. Total.
64-35 28-10 0-25 7-05 O'SO 0*15 100-40
B. H. B.
Analysis of Petalite from Utb'. By K. Sond^n (Jahrh. f. Mln.,
1882, 2, Ref., 363— 364).— The following analytical results were
obtained : —
SiOs.
AI2O3.
Li^O.
NagO.
CaO.
P2O5.
Loss.
Total.
76-91
16-85
415
0-73
0-27
0-31
0-84
100-06
From this the formula Li20,Al203,8Si03 was calculated.
B. H. B.
Analysis of Scapolite. By L. Sipocz (Jahrb. f. Min., 1822, 2,
Ref., 22). — 1, from Malsjo ; 2, from Arendal; 3, Gouverneur.
SiOs.
AI2O3.
FeO.
MgO.
CaO. ]Sra.>0.
K2O.
I.
52-48
25-56
0-39
—
12-44 6-52
0-79
IT.
52-57
24-24
0-26
—
11-57 719
0-42
III.
52-65
25-32
0-11
0-23
11-30 6-64
I08
H2O.
CO2.
SO3.
CI.
I.
0-61
0-14
0-58
0-27 = 99-78
II.
0-69
0-39
0-90
0-23 = 98-46
III.
0-42
—
0-14
0-33 = 98-72
Scapolite fi*om Rossie gave 010 per cent. SO3, and that from
Vesuvius 0*22 per cent. H. B.
MINERALOGIOAL CHEmSTRY. 441
New Face on Stilbite (Desmin). By M. F. Heddle (Jahrb. f.
Mm., 1882, 2, Ref., 25).— The face is 3P3 (rhombic) or cx3^3 (mono-
symmetrical), as shown by approximative measurement and zonal
relationships. The localities are Loch Humphrey and Long Cray in
Dumbartonshire, and also Farrugaric-Wuardi in Australia.
H. B.
Crystalline Form of Idocrase (Vesuvian). By G. Doltek
(Jahrb. f. Min., 1883, 1, Ref., 8). — The author examined a series of
idocrase crystals from Ala, Vesuvius, the Banat, Maine, and Pfitsch, in
order to determine whether the mineral really belonged to the tetra-
gonal system. The results he obtained agreed very satisfactorily
with those obtained by Zepharovich :
OP : P = 142° 45' 29"
P : P = 12r 19' 39"
Several of the best measurements agree also with the values obtained
by V. Kokscharoff :
142° 461' and 129° 21'.
Crystals occur, however, in which the results differ by several minutes
from the above normal values, but the author arrives at the conclusion
that the deviation is not of such a character as to support the theory
that idocrase does not belong to the tetragonal system.
B. H. B.
Minerals from Fritz Island, Pennsylvania. By B. Sadtlek,
Jounr. (Amer. Chem. J., 4, 356 — 357). — These minerals were found
associated with thomsenite and calcite, and more rarely with a
zeolite which has been analysed by Genth (Mineralogy of Pen7isylvan{a,
p. 110). (1.) Ghahazite forming well-developed rhombohedral crys-
tals, colourless, having a vitreous lustre. Sp. gr. = 2"3 and hardness
= 4. (2.) MesoUte, in globular concretions or tufts of fine white
fibres. Hardness = 2'5 and sp. gr. 2'4. The analytical numbers
show the composition of the mineral after deduction of about 0'2 per
cent, of calcite, which could not be completely removed. (3.) ApophyllUe
occurring in tetragonal tablets, modified by octohedral planes. The
crystals are colourless with pearly lustre. The analytical results are
as follows : —
SiOg. AI2O3. FegOj. CaO. MgO. KgO. NaaO.
(1.) 50-28 17-83 trace 6-96 0-22 2*40 2-43
(2.) 43-29 24-02 trace 1215 — — 3-40
(3.) 51-02 — 1-49 24-40 — 5-87 —
H2O. F.
(1.) 20-21 — = 100-33
(2.) 16-01 — = 99-87
(3.) 16-75 0-40 = 99-93 H. W.
Prehnite from Tuscany, &c. By A. Coesi and E. Bechi (Jahrb.
f. Min., 1882, 2, Ref., 26 — 29). — Prehnite from Impruneta. — The form
and behaviour of the specimen was normal ; the analysis of Corsi (1)
and of Bechi (II) gave —
VOL. XLIV. 2 h
442 ABSTRACTS OF CHEMICAL PAPERS.
SiOg.
AI2O3.
FesOg.
CaO.
MgO.
NajO.K^O. H2O.
I. 42-35
24-67
0-92
25-77
0-45
— 4-81 =
= 98-97
II. 43-80
23-90
0-70
24-60.
1-70
3-8 0-30 =
= 98-80
Corsi's analysis leads to the generally accepted formula
HaCazAlzSiaOia,
and he believes that Bechi's analysis is for some reason incorrect.
Specimens from Impruneta are pseudomorphs of prehnite after
analcite.
An analysis of specimens from Figline (Prato) is given nnder III.
Bechi has described and analysed a mineral resembling prehnite from
Monte Catini, but the analysis (IV) of Corsi shows it to be nothing
bnt prehnite. No. V is the analysis of a sample from Monte Perrone,
Elba.
Bechi, in replying, gives three analyses of prehnite from Monte
Catini, which agree with those of other observers ; they are Nos. VI,
VII, VIII ; his analysis ISTo. II is therefore incorrect.
SiOa.
Al,03.
Fe^Os.
CaO.
MgO.
H2O.
Mn304.
N.
III.
42-36
24-14
1-10
26-87
0-30
4-85
—
— = 99-62
IV.
42-86
24-20
0-99
27-03
—
4-96
—
— = 100-04
V.
44-03
23-20
2-05
26-24
—
4-90
—
— = 100-42
VI.
43-41
23-64
1-03
24-54
—
5-09
1-87
0-22 = 99-80
VII.
44-00
24-79
1-53
23-98
—
5-06
1-03
0-20 = 100-59
VIII.
43-63
23-39
2-40
26-08
—
4-30
—
— = 99-80
H. B.
Prehnite and Laumontite from Monte Catini. By E. Becht
(Jahrh. f. Min., 1882, 2, Ref., 29— 30).— The following analysis is
given of small globules of a zeolite supposed to be laumontite : —
SiOa.
ALO3.
FesOa.
CaO.
MgO.
H2O.
53-78
19-28
3-13
. 8-34
0-52
15-00 =
100-05
H. B.
Epistilbite. By C. 0. Teechmann {Jahrh. f. Min., 1882, 2, Mem.,
260 — 268). — This mineral was found in basalt near Hartlepool
among the fragments of " whinstone," used as road metal. As there
is no rock in the neighbourhood resembling this basalt, it seems pro-
bable that it was originally brought there by ship as ballast, and
afterwards utilised for road- making. The analysis gave the following
results : —
SiOa.
ALO3.
CaO.
Na^O.
H2O.
Total.
I. 56-54
19-17
8-75
1-25
15-68
101-39
II. 56-76
18-20
8-61
1-69
15-52
100-78
Sp. gr. = 2-247 ; hardness, 4 to 4-5. The following forms occur in
the crystals :— ooP, OP, cx)P<^, P<5o, + JP. B. H. B.
Epistilbite and Heulandite. By P. Jannasch {Jahrl f. Min.,
1882, 2, Mem., 269 — 280). — This paper gives the results of analyses
of heulandite and epistilbite from Iceland : —
MINERALOGICAL CHEMISTRY. 443
Analysis of Heulandite (Beruf jord).
SiOs. AI2O3. CaO. SrO. LigO. K2O. NaaO. HgO. Total.
6772 16-47 7*00 049 trace 0-44 1-63 16-91 100*66
Sp. gr. = 2-216.
Analysis of JEpistilhite (Beruf jord).
SiOg. ALO3. CaO. LisO. KgO. NasO. H2O. Total.
57-57 17-49 7-98 trace trace 1*69 15"29 100-02
Sp. gr. = 2-255. B. H. B.
Zinc Aluminite, a New Mineral Species. By E. Beetband
and Damour (Jahrb. f Min., 1882, 2, Ref., 351— 352).— This mineral
occurs, with other zinc minerals, at Laurium, in the form of greenish-
white hexagonal tablets. The angle does not always measure 120°,
123° and 124° having been observed. The sp. gr. is 2-26; the hard-
ness is less than 3. Heated in a closed tube, it gives up water. It
is soluble in nitric acid, leaving 5 to 7 per cent, of clay as residue.
The analysis gave
Si02.
AI2O3.
ZnO.
CuO.
HoO.
Total.
12-94
25-48
34-69
1-85
25-04
100-00
from which the formula 6ZnO,3Al,03,2S03 -f I8H2O is deduced.
B. H. B.
Chlorophyllite from Loquidy, near Nantes. By Baret
{Jahrh. f. Min., 1882, 2, Ref., 30). — Notice of and mode of occurrence
at the above locality. H. B.
Chemical Composition of Epidote. By E. Ludwig (Jahrh. f.
Min., 1882, 2, Ref., 22—23) ; Chemical Composition of Epidote
from Quenast. By A. Renard {ibid., 23). — Ludwig, in criticising
the work of Laspeyres, upholds the correctness of previous analyses
of epidote, and refers more especially to one of his previous analyses
of Sulzbach epidote {Jahrh. f. Min., 1873, 89), showing that it is per-
fectly free from quartz and giving fresh analyses of it. The mean of
two analyses agrees well with the formula Si(Al,Fe)6Ca4H2026, calcu-
lating for 70 per cent. Al-epidote and 30 per cent. Fe-epidote. He
further holds that most other analyses agree with this formula, and
considers it unnecessary to have resource to Laspeyres's hypothesis,
that the iron existed originally as ferrous oxide, and became con-
verted in course of time into the ferric condition.
Renard gives the following analysis made on microscopically tested
material : —
SiO^. AI2O3. FegOg. FeO. CaO. H2O.
38-26 24-75 11*07 0-56 23-63 2-26 = 100-53
Considering the ferrous oxide as isomorphous with the lime, the
formula given by Tschermak and Ludwig is deduced. The mineral is
2 h 2
444 ABSTRACTS OP CHEMICAL PAPERS.
easily decomposed by heating it in a sealed tube with hydrochloric
acid at 125—130°. H. B.
Hornblende and Anthophyllite after Olivine. By Becke
(Jahrh. f. Min.^ 1883, 1, Ref., 32 — 33). — Near Rosswein, in Saxony,
the author found blocks of a rock containing green patches, with a
radial structure. These patches contain a hard black kernel of olivine,
which is surrounded by a radiated layer, 5 — 6 mm. thick. This cover
consisted of two zones ; an inner one, which is of a brown colour, con-
sisting of anthophyllite with grains of magnetic iron ore, and an outer
one, which is leek-green, formed by hornblende together with granules
of a spinel-like mineral. Clinochlore occurs as a secondary constituent
in the hornblende zone, and serpentine in the oliv^ine kernel.
The author is of the opinion that the formations described above
result from a reciprocal action of the silicate of the felspar and the
olivine. B. H. B.
Gedrite in the Gneiss of Beaunan, near Lyons. By F.
GONNARD (Jahrh. f. Min., 1883, 1, Ref., 27). — This mineral occurs in
gneiss in almond-shaped masses, which have a lamellar or fibrous
structure. The colour is straw-yellow to brown ; the other distinctive
characters coincide with those of an anthophyllite containing alumina.
B. H. B.
Bole from Steinkirchen, near Budweis, in Bohemia. By
G. Starkl (Jahrb. f. Min., 1882, 2, Ref., 21).— After drying at 100",
it contained —
H2O. SiOg. AI2O3. FegOg. CaO. MgO. KgO. MnO.
10-53 46-734 26-166 12-345 1-641 1-315 0-9/8 0280 = 99-989
It fills clefts in granite. H. B.
Polyhydrite from St. Christoph Mine, Breitenbrunn, in
Saxony. By G. Starkl {Jahrh. f. Min., 1882, 2, Ref., 21—22).—
Colour chestnut-brown, streak ochreous yellow ; brittle when fresh ;
lustre glassy. H. = 2—3, G. = 2-1272—2-2012. Soluble in hydro-
chloric acid. The amount of water contained varies with the moisture
of the air ; but when fresh, it is 34-604 per cent. After drying at
100°, it gave :—
HgO. SiOg. CaO. AI2O3. FeaOg. MnO. MgO.
16-749 34131 4-236 8-867 32-656 3-308 0422 = 100-369
whence the formula CazMnSiaOg + FesAliSigOae + I8H2O. Further
examination is necessary, and it is especially necessary to show that
the mineral is homogeneous. H. B.
Chromic Tourmalin and the Deposits of Chrome-iron in
the Urals. By A. Cossa and A. Arzruni {Gazzetta, 12, 520 — 535). —
The chrome-iron ore of the Ural mountains occurs most frequently in
MINERALOGIOAL CHEMISTRY.
445
miniite granules disseminated througli serpentine, bnt occasionally
also in kidney-shaped masses, and in beds of varioas thickness.
The wide diffusion of chromic oxide, CrgOs, as a constituent in small
quantity of various silicates, and especially of fuchsite, talc, emerald,
and diallage, in which its presence is revealed by the characteristic
green colour, renders it highly probable that this oxide is the original,
or at least the most ancient form in which chromium occurs. Its
combination with ferrous and ferric oxide in the chromites is an
occurrence of later date, probably due to the substitution of CraOa for
an equivalent quantity of Fe203 in magnetite — a view which is sup-
ported by the presence of nests of magnetite iu chloritic and talcose
schists and in serpentine, at distances of a few meters from beds of
chromite. Moreover, it is impossible to overlook the simultaneous
action of chromium and other modifying agents, e.g., water and car-
bonic acid, on the rocks which enclose the deposits of chrome-iron ore.
Simultaneously with the partial transformation of talc and serpentine
into mesitine, brucite, and texasite, with traces of nickel derived from
the so-called noble serpentine, the action of chromium manifests itself
in the formation, by epigenesis, of many chromiferous silicates at the
expense of serpentine, talc, and chlorite.
These chromiferous minerals are uwarowite ; an adamantine garnet
containing calcium and iron with traces of chromium {demanto'id) ;
chromiferous clinochlore or kocuhejite ; chromiferous pennine, or kdm-
mererite and rhodochromite ; and two minerals hitherto unexamined,
viz., a chromiferous mica of fine emerald-green colour, and a dark-
green chromiferous tourmalin. These two minerals were found in a
mine of chrome- iron ore situated four kilometers to the north-east of
the village of Syssert on the left bank of the Kimenka, which is a
small affluent of the River Syssert.
The tourmalin, which occurs also in a few other localities, forms
prismatic crystals belonging to the rhombohedral system and having
the axes a:c = l: 0'45149, this value of c being greater than has
hitherto been observed in tourmalins. The chromic tourmalin differs
also from other tourmalins by its optical properties. It has a strong
dichroism. When viewed by daylight, the rays which vibrate parallel
to the optic axis exhibit a yellowish-brown colour, while those which
vibrate at right angles to that axis are bluish-green.
When heated before the blowpipe in thin fragments, this mineral
fuses readily to an opaque greyish-white non-scariaceous globule. With
borax, it gives a deep emerald-green, and with phosphorus salt a green
glass, enclosing a skeleton of silica. Quantitative analysis gave the
following results : —
Fluorine
SiOa . . . .
B2O3 . . . .
AI3O3 . . .
CraOa . . .
0-65
36-79
9-51
30-56
10-86
FeO, with trace of MnO. .
MgO
CaO
Na20, with trace of K2O .
Water
2-91
4-47
0-72
1-36
2-25
100-08
Assuming that the chromic oxide replaces part of the alumina, the
446 ABSTRACTS OF CHEMICAL PAPERS. •
chromic tourmalin of the Urals may be placed in Rammelsberg's third
group (JJandbach der Mineralchemie^ 2te Auflage, p. 644).
The chromates of the Urals occur in talcose and chloritic schists,
amongst which may be specially mentioned a variety of talcose schist
(called by the miners litwyanite), distinguished by the green colour of
its talc, and including spathic fragments of mesitine, together with
iron pyrites and magnetite. The most abundant chromate of the
Urals is crocoite, or chromate of lead. H. W.
Dioptase from the Corderillas of Chili. By M. Bauer (Jahrb.
f. Mm.^ 1882, 2, Ref., 24). — The crystals obtained were small and
transparent, and were recognised by their characteristic form,
ooP2.— 2R.
Sp. gr. 3*325 ; H. = 5. Qualitative analysis showed only copper,
silica, and water. The statement of Dana, " reported as found in the
Duchy of Nassau, between Oberlahnstein and Braubach," is due to a
confusion between " smaragdochalcite " and dioptase. H. B.
Chemical and Microscopical Researches on Italian Rocks
and Minerals. By A. Cossa {Jahrh. f. Min., 1882, 2, Ref., 47—49).
— This publication is a collection of the author's papers, arranged
chronologically. The description of the Iherzolite, from Piedmont, is
very complete; many analyses of the rocks and of the contained
minerals are given. The examination of rocks from many localities
is fully detailed. H. B.
The Granite Hills of Konigshain, in Oberlausitz, with especial
regard to the Minerals found therein. By G Woitschach {Jahrh.
f. Min, 1882, 2, Ref., 12 — 17). — The granite makes its appearance at
mfiny points, but is otherwise covered with diluvial deposits or clay
schists. The texture of the granite varies from porphyritic to coarsely
granular, and to granite of normal appearance. Potash mica is absent.
The upper layers contain cavities, in which are the crystals of various
minerals, either attached or broken, and imbedded in a clay-like mate-
rial. These various minerals amount to 31 in number.
MicrocUne, crystals composed of albite and microcline laminae, after
the manner of perthite. Crystals of pure microcline were also identified
optically. The crystals are either simple or twins, according to one or
more of the well known laws. Albite^ crystals or shapeless masses.
Quartz, mostly darkly coloured. Mica, meroxene and zinnwaldite of
Tscherraak. Chlorite, small plates. Aphrosidei'ite.
The analysis gave —
SiOj. AlA- FesOg. FeO. MgO. CaO. P2O5. HjO.
27-06 19-56 11-71 28-91 1*18 038 trace 9-73 = 98-73
whence (Fe,Ca.Mg)5(Fe)2Si50i8 + 2AI2H6O6. Diaspore, probable.
Cassiterite occurs in the felspar. Hcematite, in small amount. Anns-
tase, one crystal. Pyrite, wolfranite, at Mengelsdorf, in large quantity,
as veins. Molybdenite, in small quantity. JJagnetite, in usual forms,
and also pf^eudoinorphous after mica. Fergusonite, ceschynite, zircon.
MINERALOGICAL CHEMISTRY. 447
and melacon occur in various conditions ; analysis of partially decom-
posed crystals is given ; water 5*024 per cent. Thorite, xenotime, jluorite,
beryl, epidote, all in small quantities only. Tourmalin^ hyalite^ psilome'
la tie f frequent. Calcite, rare. H. B.
The Rapakiwi Granite, from Finland. By T. v. Ungern-
Sternberg (Jahrb. f. Min., 2, Ref., 882 — 383). — This rock is an
amphibole-biotite- granite, with accessory zircon, magnetite, ilmenite,
apatite, and triphyline. The analysis gave the following results : —
SiOs.
TiOa.
AI2O3. FesOa. FeO. MnO. CaO. MgO.
I.
70-329
1-030
11-828 3-730 2-376 trace 2-547 0-200
[I.
71-008
—
11-861 3-921 2-312 — 1235 0-257
K2O.
Na^O.
HoO. CO2. P2O5. Ca. F. Total.
I.
3-085
2-410
1-377 0-135 0-515 0'144 0-136 99-842
[I.
3-020
2-585
0-929 0-092 0-848 0*882 0*928 99-878
B. H. B.
Phyllite from Rimogens, in the Ardennes. By E. Genitz
{Jahrb. f. Min., 1882, 2, Ret, 67— 68).— This rock is a crystalline mix-
Uire of quartz, green mica, tourmalin, and yellowish-brown microliths.
These microliths were regarded as zircon, but the author shows that
this is erroneous, the form being that of rutile, and further, of the
isolated particles, 76-3 per cent, is made soluble by fusion with hydro-
gen potassium sulphate, and then yields 59-64 per cent, titanic acid.
Small lense-shaped collections of biotite (?) around a magnetite or
pyrites crystal occur in the phyllite ; they are not a secondary pro-
duct. H. B.
Micaceous Porphyrite of Morvan. By A. Mtchel-L^vy (Jahrb.
f. Min., 1883, 1, Ref., 37 — 41). — The chemical analysis of a rock from
Goie, in Morvan, which the author describes as " micaceous andesite
porphyrite," in which the augite has become converted into chalcedony,
gave the following results : —
SiOs.
AI2O3. FesOg. CaO.
MgO. Na«20.
K2O.
H2O.
P2O5.
Total.
67-55
15-00 5-00 3-00
1-10 1-40
6-10
0-60
trace =
= 99*75
This analysis would indicate an orthophyr rather than a porphy-
rite. B. H. B.
The Melaphyres of the Little Carpathians. By G. E. Stein
(Jahrb. f. Min., 1882, 2, Ref., 59). — The rock occurs in isolated or
connected bosses, in the red sandstone. The predominating consti-
tuents are plagioclase, augite, and augite microliths, and decomposed
olivine. There are also present magnetite, picolite, apatite, and occa-
sionally bronzite and orthoclase in the varieties rich in augite.
Secondary products are delessite, quartz, calcite, iron oxides, and silica.
The magma is partially or completely devitrified. The structure varies
from irregular to fluidal porphyritic or mandelstein. A variety from
Peterklin contains globules 3—30 mm., formed by the decomposition
of the rock. H. B.
448 ABSTRACTS OF CHEMICAL PAPERS.
The so-called Andesites of South and Central America. By
C. W. GuMBEL (Jahrb. f. Min., 1882, 2, Ref., 59— 63).— These eruptive
L'ocks, generally classified according to the amounts of augite, or
hornblende and quartz they contain, are to be divided into two groups ;
those of the first are lighter coloured trachytic rocks, containing much
silica (over 57 per cent.), those of the second group being darker, more
resembling basalt, and contain less silica — under 57 per cent, when
quartz particles are absent ; the rocks of the second group are also the
older. If this division is supported by an examination of the rocks
in situ, the author would propose to retain the name andesite for the
lighter more acid rocks, while he would class the others as olivine-free
felspar basalts. Detailed descriptions are given, together with the
analyses of specimens collected by Wagner, in 1870. H. B.
Examination of Ophites from the Pyrenees. By J. Kuhn
(Jahrh. f. Min., 1882, 2, Bef., 63 — 64). — The examination of speci-
mens from over 100 localities has resulted in the harmonising of
various results obtained by other authors, whose examinations have
not been so extended. The essential constituents of an ophite are ordi-
nary augite, " diallage-like-augite," diallage, uralite, viridite, felspar,
epidote, titanic iron ; as accessories are magnetite, pyrites, haematite,
apatite, hornblende, quartz, calcite, and biotite. Bj? the expression
" diallage-like augite " is to be understood ordinary augite, which has
become fibrous by decomposition. H. B.
The Clay Ironstone of Rheinhesse. By Tecklenburg (Jahrh. /.
Min., 1882, 2, Bef., 50). — These deposits lie directly on tertiary lime-
stone ; they are accompanied by various clays and marls. The author
supposes them to have been formed from, and by the disintegration of,
a superincumbent bed of limestone containing 1 — 2 per cent, mag-
nesium carbonate, and 0'3 — 2*5 per cent, iron and manganese carbonates
and hydrates. By the percolation of water, this upper layer was acted
upon, and the solution penetrating further, gave rise to the formation
of numerous cavities. Those cavities lying above the general water
level became filled with air, and when again the solution found its way
into them, the iron and manganese were deposited as hydrates, and the
liberated carbonic acid, acting on the walls of the cavities, enlarged
them, thus allowing of the further growth of the contained nodules by
the periodic recurrence of these processes. H. B.
The Lake Deposits of Kolsnaren, Viren, and HSgsjon, Soder-
manland, Sweden. By A. W. Ceonquist {Jahrb. f. Min., 1882, 2,
Ref., 51). — The result of the author's examination is that these deposits
are of no technical value. The deposit lies 2 — 3 meters or more
below the lowest water level, and either forms a band 3 — 300 meters
wide following the shore, or else is more generally deposited ; the
thickness does not exceed a few millimeters. The mean percentage
of ferric oxide is 52-4 — 54 ; sulphur, 0'07 — 0*06 ; and phosphorus,
0012— 0-93. H. B.
Artificial Formation of Various Rocks. By F. Fouqu^ and
A. MiCHEL-L^VY {Jahrb. f. Min., 1882, 2, Ref ., 64— 65).— The authors
ORGANIC CHEMISTRY. 449
in continuing their researches have succeeded in preparing samples
having all the characteristics of basalt and diabase. A mixture of
2 parts olivine, 1 augite, and 2 of labradorite, fused for 48 hours at a
white heat, deposited well-defined olivine and magnetite crystals ;
after another 48 hours at a bright red heat, there were formed lense-
shaped labradorite crystals, augite microliths, a second generation of
magnetite, and picotite octahedra ; but little of the glassy magma
remained, the whole exactly resembling many natural basalts. Employ-
ing a mixture of anorthite and augite, lense-shaped plagioclase was
obtained at a white heat, and after several days at a bright red heat,
irregular augite crystals cementing the felspars together had formed,
the characteristic structural appearance of the ophites. On replacing
the anorthite by labradorite, the augite separated in microliths, owing
to the small difference in fusibility of the ingredients; the sections
resembled those of a trachyte. H. B.
Meteorite of Louans (Indre-et-Loire). By A. Daubr^e (Jahrb.
f. Min., 1882, 2, Ref., 30).— The stone fell 25th January, 1843, and
buried itself half a meter in the soil. It weighed 3 kilos.
H. B.
Analysis of a Spring Water from Rindo, near Stockholm.
By A. W. Cronquist (Jahrb. f. Min., 1882, 2, Ref. 51).— The water
contains in 100,000 parts : —
COg. FeO. CaO. MgO. SO3. CI.
26-5 19-5 2-4 22 6-5 17
H. B.
Organic Chemistry.
Isomeric Monochlorallyl Iodides. By P. v. Romburgh (Bee.
Trav. Ghim., 1, 233 — 238). — Dilute solutions of aluminium iodide and
allylidene chloride in carbon bisulphide react very violently at 0°,
with liberation of iodine and production of a carbonaceous mass, but
no allylidene iodide is formed. Aluminium chloride alone reacts
violently with allylidene chloride, with evolution of torrents of hydro-
chloric acid.
AllyUdene chloride was heated with excess of dry potassium iodide
at 100° for 24 hours, the product treated with water, and the dense
liquid thus obtained was dried over calcium chloride and distilled. The
purified product has the composition C3H4CII, and boils at 162° with
partial decomposition. It is a colourless liquid, with a penetrating
odour and very acid taste; its sp. gr. at 15° is 1*977. The same pro-
duct is obtained when allylidene chloride is heated with calciam
iodide at 100°, but the reaction proceeds more quickly, and the yield
is greater. Calcium iodide is, however, without action on the
analogous compound, ethylidene chloride, and hence it appeared
probable that the product C3H4CII is not CHo : CH.CH ! ClI, but that
450 ABSTRACTS OF CHEMICAL PAPERS.
the allylidene chloride has been converted by intermolecnlar displace-
ment into CHCl ! CH.CH2I, just as concentrated hydrochloric acid
converts allylidene chloride into y3-chlorallyl chloride. This chlorallyl
iodide combines readily with mercury, forming a compound very
soluble in boiling alcohol, from which it separates in small white
plates, which rapidly become yellow when exposed to air and light :
this behaviour also would indicate that the iodine compound is a
chloro-derivative of allyl iodide. Moreover it appears to be identical
with the following compound.
8-chlorailyl iodide, C3H4CII, is obtained by heating dry calcium
iodide with /3-chlorallyl chloride at 100°, treating the product with
water, decolorising the dense liquid thus obtained with spongy copper,
drying over calcium chloride, and distilling. It boils at 162° with
partial decomposition, and is a colourless liquid with an irritating
odour and a sharp taste ; its sp. gr. at 18° is 1"97. It rapidly decom-
poses and becomes coloured, ^-chlorallyl iodide combines readily
with mercury, forming white plates, which are very soluble in alcohol,
and rapidly become coloured when exposed to air and light. It
reacts readily with silver nitrate and with potassium cyanide. When
treated with potassium hydroxide, it yields y3-chlorallyl alcohol, which
the author has previously described {Bull. Soc. Chini., 36, 557).
a-Ghlorallyl iodide, C3H4CII, is obtained by heating a-chlorallyl
chloride with calcium iodide at 100°. It boils with decomposition at
about 150° under ordinary pressure, or at 95° under a pressure of
40 mm. ; sp. gr. at 15° = 1'918. This iodide also combines with
mercury. When heated with dilute potash or with silver oxide, it
yields oc-chlorallyl alcohol, a colourless liquid, with a slightly aromatic
odour; it boils between 186° and 140°, and does not act violently on
the skin like the /S-derivative. a-chlorallyl iodide reacts readily with
silver nitrate forming a-chlorallyl nitrate, a heavy, almost colourless
liquid insoluble in water ; it boils at about 140°. When heated with
potassium cyanide, the iodide forms a yellowish liquid, with an odour
resembling that of the nitrils; when boiled with potash soluti£>n, it
evolves ammonia. C. H. B.
Trimethylene Glycol and Trimethylene Bases. By G.
NiEDERiST {Monatsli. Chem., 3, 838 — 849). — Trimethylene bromide
(m. p. 161 — 163°) is decomposed by heating with water much more
quickly than ordinary propylene bromide, yielding trimethylene
glycol, OHCH2.CH2.CH2.OH, identical with that which Reboul and
Geromont obtained by saponification of trimethylene diacetate
(C. /., 1871, 697, and 1874, 1153). This glycol becomes viscid at
— 30°, and when exposed to the temperature of a mixture of solid
carbon dioxide and ether, becomes very viscid, and soon deposits
warty groups of needle-shaped crystals, finally solidifying to a silky
crystalline mass. The crystals quickly deliquesce when taken out of
the freezing mixture.
Action of Ammonia on Trimethylene Bromide. — When this bromide
and alcoholic ammonia are left to act on one another in sealed tubes
at ordinary temperatures, a saline mass is formed, containing, together
with a large quantity of ammonium bromide, an amorphous body
ORGANIC CHEMISTRY. 451
insoluble in water, together with the hydrobromides of certain non-
volatile bases very slightly soluble in alcohol, easily in water. One of
these hydrobromides (a) forms a sparingly soluble doable salt with
cadmium bromide, the other (6) with auric bromide. The same
hydrobromides treated with strong potash-lye, yield the free bases.
The alcoholic solution filtered from the saline mass above mentioned
yields on evaporation large qtiantities of a body identical with the
amorphous insoluble substance which separates in the tubes. If the
tubes are heated, the formation of this insoluble body is limited to
the quantity which separates in them, and the resulting ammonium
bromide is found to be drenched with a thick liquid, very sparingly
soluble in alcohol, and containing a large quantity of the hydro-
bromides precipitable respectively by cadmium bromide and auric
bromide.
The insoluble substance which collects in the tubes, and is obtained
in the distillation of the alcoholic solution, forms, after washing with
hot water, a very balky jelly, insoluble in all the ordinary solvents,
and not altered by boiling with strong acids. By boiling with strong
potash-lye, it is converted into a non-brominated body which likewise
resists the action of all ordinary solvents, and shrinks up when dried
in a vacuum over sulphuric acid.
The brominated body in the dry state is a white to yellowish, horny,
strongly hygroscopic mass, which quickly softens when exposed to
the air, and swells up in water to the original volume, perhaps 20
times as great as that of the dried substance. The non-brominated
compound in the dry state is white and friable ; heated in a vacuum,
it melts and decomposes at about 260°, giving off ammonia and methyl-
amine, and yielding as distillate a mixture of very hygroscopic bases,
which have an odour of pyridine, fume in the air, and form crystal-
lisable platinochlorides.
The above-mentioned cadmium salt of the hydrobromide (a) sepa-
rates in the first instance as an oily mass, which may be purified by
repeated solution in hot water, reprecipitation by hydrobromic acid,
and final washing with alcohol. Under absolute alcohol, it hardens
after some time to a white porcelain-like mass easily pulverised under
alcohol. The white powder thus obtained is highly hygroscopic, and
dissolves readily in hot water, but if heated for some time in a vacuum
at 100°, it becomes insoluble in water, and swells up to a transparent
jelly. On adding soda-lye to its very dilute solution, the cadmium is
precipitated, and the concentrated filtrate treated with stronger soda-
lye yields the free base in white flocks, gelatinising when heated, and
not volatilising with aqueous vapour. Its solution in hydrochloric or
hydrobromic acid is precipitated by the chlorides of zinc, mercury,
gold, and platinum, also by tannin and by iodised potassium iodide.
All the double salts thus obtained are amorphous.
The analysis of the cadmium salt leads to the empirical formula
Ci6H42N4Br6Cd, but on the supposition that the trimethylene group in
the base remains intact, this formula must at least be trebled to give
the molecular formula.
The aurobromide, obtained on adding auric bromide to the solution
of the hydrobromide (6), after separation of the oily cadmium salt,
452 ABSTRACTS OF CHEMICAL PAPERS.
separates in brick-red flocks, and forms, after drying in the exsiccator,
an amorphous, transparent, brittle, pomegranate-red mass, which dis-
solves readily in hot water, but is decomposed by prolonged heating,
with separation of metallic gold. Its analysis leads to the formnla
(C3H6)4N3H7,4HBr,4AuBr3. By decomposing this salt with hydrogen
sulphide, the hydrohromide CzHasNsBri is obtained, as a white amor-
phous deliquescent mass, sparingly soluble in alcohol, and precipitated
thereby from its concentrated aqueous solution in white flocks ; and
this hydrohromide treated with potash-lye yields the free base in white
flocks, easily soluble in water, and not volatilising with aqueous
vapour. H. W.
Action of Anhydrides on Aldehydes, Ketones, and Oxides.
By A. P. N. Franchimont (Bee. Trav. Chim., 1, 243—251). — Ordinary
aldehyde when heated with benzoic chloride on a sand-bath for six
hours, yields a pitchy mass which contains crystals of benzoic acid, but
from which no other substance could be isolated. Paraldehyde gives
a precisely similar result. Valeraldehyde when treated in the same
way yields hydrochloric acid and benzoic acid, together with liquid
products which boil at a high temperature with partial decomposition.
Acetone yields large quantities of hydrochloric acid, together with
benzoic acid and the ordinary condensation-products of acetone. The
same result is obtained when the acetone and benzoic chloride are left
in contact for a long time at the ordinary temperature. When benzoic
bromide is left in contact with acetone for a long time at the ordinary
temperature, it behaves in a precisely similar manner, and does not,
as Claisen has stated, form a crystalline addition-product. Ace-
tone when heated with acetic chloride, or when left in contact with
this compound for several months at the ordinary temperature, yields
hydrochloric acid and the ordinary products of condensation, notably
mesityl oxide. This observation has been confirmed by Beilstein and
Wigand (Bull. Soc. Chim., 38, 167). When acetone is heated with
acetic bromide at 125° in sealed tubes, the tubes are invariably
shattered, but if the two liquids are left in contact at the ordinary
temperature for several months, a thick dark-coloured liquid is formed,
which evolves large quantities of hydrobromic acid. When this liquid
is distilled, about half passes over below 120^, but it decomposes if
heated to a higher temperature. Acetone, as Geuther has stated,
does not combine with acetic anhydride.
Ethylidene acetochloride, the addition-product formed by the com-
bination of aldehyde with acetic chloride, can be obtained in a state of
purity by heating aldehyde or paraldehyde with an equivalent quantity
of acetic chloride on the sand-bath for about six hours, and fraction-
ating the product. Whether obtained from aldehyde or from
paraldehyde, it is an optically inactive liquid which boils at 121*5°
under a pressure of 74i& mm. ; sp. gr. at 15*^= 1*114. When distilled,
it decomposes very slightly into aldehyde and acetic chloride, and
consequently no satisfactory determinations of the vapour-density
could be obtained. It is rapidly decomposed by water, and the
chlorine was determined by heating the liquid in a sealed tube with
water and silver nitrate. The method of Carius is not applicable,
ORGANIC CHEMISTRY. 453
since the action of the strong nitric acid produces chloropicrin, which
is only oxidised with difficulty.
By fractionation of that portion of the original product which boils
above 125°, ethylidene diacetate was obtained (b. p. 167" at 744 mm.;
sp. gr. at 15° = 1'073). 25 grams of this compound were obtained
from 176 grams of aldehyde. The diacetate is formed only in very
small quantity, when paraldehyde is heated with acetic anhydride in
sealed tubes at 160 — 170° for six hours, although a large proportion
of the paraldehyde is depolymerised. It can, however, be obtained by
heating either aldehyde or paraldehyde with acetic anhydride for
12 hours at 183° in stout tubes which contain only a small quantity of
the mixture ; the ordinary aldehyde apparently gives the best yield.
The diacetate has a feeble not unpleasant odour resembling that of
the other diacetins ; it has not the onion-like smell described by
Geuther, and, contrary to the statement of the same chemist, it does
not decompose when distilled. Determinations of the vapour- density
by V. Meyer's method gave 5*08 and 5*13 (calculated, 5'069).
That portion of the crude product obtained by heating the aldehyde
with acetic chloride which boils below 120° is very small. It consists
mainly of aldehyde and acetic chloride, but apparently contains no
ethylidene chloride.
Compounds of the same class as ethylidene acetochloride, which are
formed by the union of two anhydrides, show a greater or less ten-
dency to bplit up under the influence of heat into more stable com-
pounds, frequently into the original substances. This tendency
apparently reaches a maximnm in the case of the ketones. The same
tendency is exhibited in different degrees by the componnds of the
acid halides with the aldehydes, and reaches a maximum in the case
of carbon oxychloride, which apparently will not combine with aldehyde
under ordinary conditions. Mixed anhydrides, such as butylbenzoic
anhydride, behave in a similar manner. C. H. B.
Paraldehyde. By A. P. N. Feanchimont (Bee. Trav. Chim., 1,
239 — 242). — The generally accepted view of the constitution of par-
aldehyde would indicate that it is related to the ethers, since it contains
oxygen united with two carbon-atoms which are not themselves in
direct union with one another. It is, however, well known that phos-
phorus pentachloride acts on paraldehyde in a very different manner
from its action on ethers.
Perfectly pure and dry paraldehyde may be boiled for several
hours with metallic sodium, out of contact with air, without the metal
being attacked. It can indeed be purified by distillation with sodium.
It is also known that paraldehyde forms no aldehyde resin when
boiled with even very strong solutions of potassium hydroxide ; it
does not reduce an ammoniacal solution of silver nitrate even when
boiling, and does not combine with ammonia or with alkaline bisul-
phites at the ordinary temperature. When heated, it dissolves mer-
curic chloride, which is deposited on cooling ; it also dissolves mercuric
iodide, although to a less extent. Mercuric bromide is but very
slightly soluble in paraldehyde at the ordinary temperature, and the
two compounds may remain in contact at 16° for two days without
454 ABSTRACTS OK CHEMICAL PAPERS.
any trace of ordinaiy aldehyde being formed, but when heated toabont
90° the paraldehyde is evidently depolynierised, the liquid boils
rapidly, and pure and dry aldehyde distils over.
When paraldehyde is mixed with dry acetic chloride in equivalent
proportions, there is at first a considerable reduction of tempera-
ture (in one case from 20° to 10° in three quarters of an hour, the
temperature of the room being 16°), but after some hours the liquid
acquires the temperature of the room and is now found to contain
ordinary aldehyde. This is the first experimental proof that the de-
polymerisation is attended by absorption of heat. When paraldehyde
and acetic bromide are mixed in equivalent proportions with similar
precautions, the temperature is at first reduced even more rapidly,
in one case from 20° to 5° in three minutes, but it afterwards rises
with very great rapidity, and in a few minutes reaches 92°, when the
mixture begins to boil and evolves large quantities of ordinary alde-
hyde. If heated to 100° or higher, it forms in both cases the same
products as ordinary aldehyde. When acetic anhydride is mixed with
paraldehyde, there is no reduction of temperature, and the two liquids
may remain in contact for two days without any ordinary aldehyde
being formed. Even at 100°, no depolymerisation takes place, but at
132° aldehyde is given off.
The reduction of temperature is also observed with benzoic chloride,
hydrochloric acid (with the dry gas the temperature rises), and sul-
phuric acid. This fact may be shown as a lecture experiment by
putting into one test-tube some aldehyde, and into another some par-
aldehyde, placing a thermometer in each tube, and then adding some
strong sulphuric acid. With the aldehyde there is evolution of heat,
but with the paraldehyde there is absorption of heat, and these changes
can be rendered evident by throwing the images of the thermometers
on to the screen. C. H. B.
Non-saturated Acids (Part VI). By R. Fitttg (Annalen, 216,
26 — 29). — The results of the researches of Gottstein, Young, Jayne,
Penfield, Hjelt, and Beer, afPord evidence in favour of the author's view
II
that the ring =C<^pQpv>C= is characteristic of all lact-ones and
laetonic acids. W. C. W.
Two New Caprolactones. By L. Gottstein (Annalen, 216,
29—3S).—a.Methylvalerolactone, CHMe<^^>CHMe, is obtained by
the action of sodium amalgam on crude ^-acetisobutyric acid prepared
from ethyl a-bromopropionate and ethyl acetoacetate by the process
described by Conrad and Limpach (Annalen, 192, 153). The alkaline
solution is acidified with sulphuric acid and boiled for a few minutes.
When cold, it is neutralised with potassium carbonate and extracted
with ether. On evaporating the ether, the lactone remains as a colour-
Jess liquid which boils at 206° and does not solidify at —17°. It is
soluble in 20 — 25 times its volume of water ; when the cold saturated
solution is warmed, a portion of the lactone separates out, but is re-
dissolved when the temperature reaches 80°.
ORGANIC CHEMTSTRY. 455
The formation of the lactone takes place in two stages : (S-acetoiso-
butyric acid unites with a molecule of hydrogen, yielding the unstable
a-methyl-7-hydroxyvaleric acid, which loses a molecule of water and
forms symmetrical caprolactone. The barium salt of a-niethyl-7-hy-
droxy valeric acid, CeHnOa, is obtained by boiling the lactone with
baryta- water.
^-Methylvalerolactone, CH2<^ pqo ^^HMe, has not been obtained
in a state of purity. It is formed by the action of sodium amalgam
on an aqueous solution of ^-acetobutyric acid prepared from ethyl
acetosuccinate (Annalen, 192, 153). The crude lactone boils between
205° and 212°. W. C. W.
^-Lactone of Normal Caproic Acid. By L. Wolff (Annalen,
216, 127— lS8)~rf. Acetohuti/nc acid, COMe.CCHOs-COOH, is formed
when ethyl acetoglutarate is boiled for several hours with hydrochloric
acid diluted with twice its bulk of water. It is a thick liquid boiling
at 275°, miscible with water, alcohol, and ether. It solidifies in a
freezing mixture to a crystalline mass melting at 1.3°, which absorbs
moisture from the air, forming the hydrate CeHioOs + HgO. This
compound crystallises in monoclinic prisms (a : h : c = 0"769l :
1 : 0-8845, (3 = 75° 20') which melt at 36°. The acetobutyrates of
calcium, zinc, and potassium are crystalline salts freely soluble in
water. Calcium acetobutyrate crystallises with 1 mol. H2O. The
needle-shaped crystals of the silver salt, AgCeHgOs, are soluble in hot
water.
^- Acetobutyric acid is converted into the <5-lactone of normal caproic
acid by the action of sodium amalgam on its aqueous solution at 30°.
The lactone, CH2<2pQQ >CHMe, forms thin colourless crystals
melting at 18°, boiling at 230*", soluble in alcohol, ether, and water.
The aqueous solution of the lactone changes into ^-hydroxycaproic acid,
and conversely a solution of r^-hydroxycaproic acid undergoes partial
decomposition into the lactone and water. When the ^-lactone is dis-
solved in boiling baryta- water, the barium salt of ^-hydroxycaproic
acid, Ba(C6Hii03)2, is obtained as an amorphous mass. On adding
silver nitrate to a solution of the barium salt, a gelatinous precipi-
tate is thrown down, which dissolves in hot water, but separates out
again on cooling. If the jelly is separated from the mother-liquor, it
slowly changes into a crystalline mass. W. C. W.
Hepto- and Octo-lactones. By S. Young (Annalm, 216, 38 —
CH
45). — a-Ethyl-valeroladone, CHEt<[^QQ>CHMe, obtained by the
action of sodiam amalgam on an aqueous solution of the a-ethyl-
/3-acetopropionic acid, described by Thorne (this Journal, Trans., 1881,
336), is a colourless liquid which does not solidify at 18°, and boils at
219-5°. Its sp. gr. at 16° is 0-992.
Barium, hydroxijheptylate, Ba(C7lIi303)2, is obtained as a gummy
amorphous mass when ethyl-valerolactone is dissolved in boiling
baryta-water. The silver salt, CvHiaOaAg, is deposited in crystals
456 ABSTRACTS OF CHEMICAL PAPERS.
from a warm saturated solution on cooling. Hydroxyhepfcjlic acid
cannot exist in the free state.
The ethyl salt of methylethylacetosuccinic acid is produced by the
action of an excess of sodium ethylate and methyl iodide on ethyl
y3-ethylacetosuccinate. On treating the free acid (prepared by saponi-
fying this compound with hydrochloric acid) with water and sodium
CHMe
amalgam, a,-ethyl-f^'methylvalerolactone, CHEt-<^ POO /^CHMe, is
obtained. This lactone boils at 226*5° ; in other respects it closely
resembles ethyl valerolactone. It dissolves in hot baryta- water, yield-
ing barium hydroxyoctylate. Silver hydroxyoctylate is crystalline.
w. c. w.
Lactones from AUylmalonic, Diallylmalonic, and Diallyl-
acetic Acids. By E. Hjelt (Annalen, 216, 52 — 77). — An account
of most of the compounds described by the author has already aj»-
peared in this Journal (Abstr., 1882, 946—948).
CH
Carhovalerolactonic acid, COOH.CH<]p^A^CHMe, prepared by
boiling a solution of allylmalonic acid in fuming hydrobromic acid
with water, is a thick syrupy liquid sparingly soluble in ether, but
freely miscible with water. The free acid is decomposed by heat at
200'', splitting up into carbonic anhydride and valerolactone.
Barium carbovalerolactonate, (C6H702)2Ba, crystallises in anhydrous
scales. When carhovalerolactonic acid is treated with hot solutions of
SL[ksd\s,Jiydrox]i/propyl7nalonates are produced. Barium hydroxy propyl-
malonate, CeHgOsBa, forms needle-shaped crystals which are less
soluble in alcohol and in water than barium carbovalerolactonate.
The crystals are also less soluble in hot than in cold water. Silver
hydroxypropylmalonate and the calciwin salt have been previously
described (loc.cit.).
Nonodilactone, CHMe^QQp>-C.C<^PQQ]>CHMe, prepared by the
action of water on a solution of diallylmalonic acid in hydrobromic
acid, crystallises in needles or thin plates (m. p. 105°) belonging to
the rhombic system. It is soluble in warm alcohol and hot water.
The lactone boils above 360° with slight decomposition. It dissolves
in warm baryta- water, forming a barium salt, BaCgHuOe, which de-
composes on warming its solution, yielding barium carbonate, a hygro-
scopic salt, Ba(C8Hi504)2, and a lactone, CgHuOa. The hydroxylac-
tone is a thick liquid which does not solidify at —13°. It is freely
soluble in water, and sparingly soluble in ether.
When dibromononodilactone is treated with baryta- water, a barium
salt of the acid CgHigOs is first formed, which is decomposed by
boiling with water, yielding barium carbonate and a trihydroxylactone,
CsHuOs. W. C. W.
Peculiar Decomposition of the Ethereal Salts of Substituted
Acetoacetic Acids. By S. Young {Annalen, 216, 45 — 52). — On being
distilled, ethyl iS-ethylacetosnccinate undergoes partial decomposition,
splitting up into alcohol and ethyl ketolactonate, C10H20O5 = CioHuOi
-f- C2H6O. When the fraction boiling above 265* is saponified by
OKGANIC CHEMISTRY. 457
boiling with dilate hydrochloric acid, hetoladonic acid (m. p. 181°)
crystallises out. This acid is sparingly soluble in cold water. It
forms crystalline silver and barium salts having the composition
CgHgAgOi and Ba(C8H904)a + 2H2O. It also forms a second series
of salts, e.g., CgHioAgaOo. The barium salt of this series is obtained
in an impure state by adding baryta- water to the acid and precipi-
tating the excess of barium by carbonic acid. The sparingly soluble
silver salt may be obtained by double decomposition with silver nitrate.
Both these salts decompose at 60°. When ketolactonic acid is boiled
with baryta-water, an amorphous salt, having the composition
Ba(C7Hii03)2, is produced.
The constitution of ketolactonic acid may be represented by the
formula —
/C(COOHX. CH(COOH)^
CHEt< >CMe or CHEt/ \C ! OH3.
^— COO— ^ \ COO ^
W. C. W.
Decomposition of Formic Acid by the Silent Discharge.
By Maquenne (Gompt. rend., 96, 63 — 66). — Monohydrated formic acid
submitted to the action of the silent discharge in Berthelot's apparatus,
is decomposed, with formation of carbonic anhydride, carbonic oxide,
and hydrogen. The greater the pressure, the less is the volume of
carbonic oxide produced, its place being taken by carbonic anhydride
and hydrogen in nearly equal volumes. The variation in the manner
of decomposition is not due to diflference of pressure only. The first
reaction is expressed by the equation CH2O2 = CO + H2O, and the
formation of carbonic anhydride and hydrogen is due to a secondary
reaction between the first-formed products, viz., carbonic oxide and
water. The author has proved this to be the case by direct experiments
on moist carbonic oxide. E. H. R.
Sjmthesis of Optically Active Carbon Compounds. By E.
Mulder {Bee. Trav. Chim., 1, 231 — 232). — Several years ago, before
Pasteur and Jungfleisch had discovered that optically inactive tartaric
acid can be converted into the optically active varieties by the action of
heat, the author advanced the idea that optically active compounds
might be obtained by the action of ferments, and, later, by the action
of heat and light on compounds prepared synthetically. He considers
that in the experiments of Lebel and Lewkowitsch (who have recently
shown that optically active compounds are produced by the action of
Penicillium glaucum and other moulds on inactive amyl alcohol, and on
amygdalic acid obtained by synthesis), the optically active bodies are
formed by the splitting up of the original substances, with destruction
of the lasvorotatory portion. In order to decide this point, it will be
necessary to ascertain whether inactive tartaric acid yields dextro-
tartaric acid under the influence of Penicillium glaucum, or, better, to
make a chemical separation of the arayl alcohol or amygdalic acid, as
Pasteur has done in the case of uvic acid. C. H. B.
Itamalic, Paraconic, and Aconic Acid. By A. Beer (Annalen^
216, 77 — 97). — Itamalic acid, CsHsOs, cannot exist in the free state,
VOL. XLIV. 2 i
458 ABSTRACTS OF CHEMICAL PAPERS.
but calcmm itamalate, CsHeOs + H2O, is obtained by boiling an
aqueous solution of itamonobromopyroracemic acid for six hours in a
flask fitted with a reflux condenser ; the acid liquid is extracted with
ether, and the liquid which remains on distilling off the ether is boiled
with chalk. The bulky precipitate which is thrown down on the addi-
tion of alcohol to this solution of the crude calcium salt, is digested
with alcohol, and afterwards treated with small quantities of hot
water, in order to remove calcium bromide. The pure salt forms a
white chalky powder, sparingly soluble in water. Silver itamalate,
CsHeOsAga, decomposes at 50°. Paraconic acid is produced whenever
an itamalate is decomposed by an acid. This acid can best be pre-
pared by boiling itamonobromopyroracemic acid with water, and
removing the hydrobromic acid from the product by means of silver
oxide. Its formation may be represented thus : —
CH2Br.CH(COOH).CH2.COOH= CH^: C(C00H).CH2.C00H -h HBr
Itabromopyroracemic acid. Itaconic acid.
= CH,<^^^p^^^^>>CH. + HBr.
COO
Paraconic acid.
Paraconic acid, C5HBO4, melts at 57°, and is exceedingly deliquescent.
Calcium paraconate, Ca(C6H504)2 + SHgO, crystallises in small white
needles. It is converted into calcium itamalate by boiling with
calcium carbonate. These results do not agree with those obtained
by Swarts (Bull. Acad. Belg. [2], 18, 21; 24, 25). When itadibro-
mopyroracemic acid, prepared by Kekule's method {Annalen, Suppl. 1,
339), is boiled with water for two hours, aconic acid, C5H1O4 (m. p.
163°) is obtained; by prolonged treatment with water, this acid is
decomposed, yielding oily products. Sodium aconate is obtained in
beautiful triclinic tables \^a ih : c =■ 0*538 : I : 0*6985], when excess
of itadibromopyroracemic acid is boiled with a solution of sodium
carbonate.
Aconic acid does not yield a bromine addition-compound. The pro-
duct of the action of nascent hydrogen on aconic acid has not yet been
identified. W. C. W.
Ferrous Citrate and its Double and Secondary Salts. By
R. Bother {Pharm. J. Trans. [3], 13, 629— 630).— i^errrms citrate,
FeHCi, is best prepared by heating until action ceases (about three
hours) excess (60 pts.) of fine iron filings with 210 pts. of citric acid,
and 1500 parts of water; thus prepared, it is a dingy white sparingly
soluble salt. When prepared by the action of citric acid on ferrous
hydrate or carbonate, it dissolves rapidly in the ferric citrate formed
by atmospheric oxidation, hence ferrous citrate has been considered
deliquescent. Sodioferrous citrate, FeNaCi, obtained by the action
of one equivalent of sodium hydrogen carbonate on one equivalent
of ferrous citrate, forms very soluble apple-green scales. When
ferrous citrate is acted on by two equivalents of the carbonate,
sodioferrous hydroxy citrate, NajCiFe.OH, is formed, a very soluble
ORGANIC CHEMISTRY. 469
grass-green amorplious substance. Ferrous citrate is not entirely
dissolved by sodium phosphate, a green solution, however, is ob-
tained, which, with citric acid, gives a green gelatinous precipitate,
requiring large quantities of sodium citrate for solution. Sodium
phosphate precipitates ferrous phosphate from ferrous sodium citrate
and ferrous sodium hydroxy citrate ; the precipitate is redissolved
by the addition of citric acid, or if that acid is present before-
hand, precipitation is altogether prevented. The emerald-green
solution thus produced contains two amorphous salts, one a double
citrate of sodium and iron, FeNa^HzOia ; the other a citrophospha,te
of these metals, FeNa^HoCiPOi. Phosphoric acid, when added to any
of these salts in sufficient quantity, discharges their colour ; the solu-
tion is apparently permanent, but with small quantities of acid,
ferrous phosphate is formed. Sodioferrous citrate behaves rather
peculiarly with insufficient phosphoric acid, for if the addition of
acid is stopped so as to leave the solution pale green, an abundant
precipitate of triferrous phosphate, Fe3(P04)2,8H20, is produced, which
requires for its solution much more phosphoric acid. Ferrous citrate
may be converted into ferric citrate by carefully evaporating to dry-
ness with 45 parts of nitric acid. D. A. L.
A Metacymene and a New Isomeride of Thymol. By P.
Spica (Gazzetta, 12, 543 — 654). — In a former paper (p. 321 this vol.),
the author stated that the monohydrated barium salt of the sul-
phonic acid obtained from camphor-cymene is a derivative of meta-
cymene. In the present communication he describes several other
derivatives of this hydrocarbon, and examines its constitution more
fully.
The hydrocarbon CioHu, obtained by converting the barium salt just
mentioned into a sodium salt, heating the latter with hydrochloric
acid, and distilling the product with steam, is converted by gentle
oxidation with dilute nitric acid into metatoluic acid, and by further
oxidation with chromic acid mixture into isophthalic or metaphthalic
1 3
acid, a result which shows it to be a metacymene, CH3.C6H4.C3H7 ;
but whether it contains normal propyl or isopropyl, or in other words
whether it is a normal cymene or an isocymene, is a question to be
decided by further experiment. With this view the sulphonic acid
obtained from the hydrocarbon in question was compared with those
prepared by Claus and Stiisser from normal cymene (Abstr,, 1880,
632), and by Kelbe from isocymene (ibid., 878, and 1882, 299). This
acid, separated from its lead salt by hydrogen sulphide, forms a syrupy
liquid, which crystallises by evaporation under reduced pressure,
in groups of prisms, deliquescent, and moderately soluble in alcohol,
ether, chloroform, and benzene. Its sodium salt, CioHi3.S03Na,H20,
crystallises in large transparent nacreous scales ; the potassium salt,
C10H13SO3K, in stellate groups.
The sulphocMoride, C10H13.SO2CI, obtained by treating the sodium
salt with phosphorus pentachloride, is a heavy uncrystalHsable oil,
having an ethereal odour, decomposing when heated, and thickening
but not solidifying in a mixture of ice and salt. Heated with alcoholic
2 i 2
460 ABSTRACTS OF CHEMICAL PAPERS.
ammonia, it yields the sulphonamide C10H13.SO2NH2, which on addition
of water separates as an oil, but afterwards solidifies to a crystalline
mass, and is deposited from its solution in dilute alcohol in transparent
plates, melting after purification at 75 — 75'5°. Now the a-sulphonic
acid obtained by Kelbe from me^a-isocymene yields a sulphonamide
which melts at nearly the same temperature, viz., at 73°, and an
uncrystallisable sulphochloride ; whereas the corresponding acid
obtained by Klaus and Stiisser from normal we^acymene, yields a crys-
talline sulphochloride melting at 175°, and a sulphonamide which
has not yet been crystallised, whence it appears most probable
that the cymene obtained by Spica is identical with that of Kelbe,
viz., meto-isocymene ; but on the other hand the sulphonic acid ob-
tained from Spica's me^acymene agrees in the solubility of its barium
salt and the characters of its copper and potassium salts, more nearly
with that of Glaus than with that of Kelbe. The constitution of the
cymene obtained by Spica must therefore be regarded as requiring
further investigation.
The potassium salt of the sulphonic acid obtained from this hydro-
carbon is converted by fusion with potassium hydroxide into the corre-
sponding phenol, C10H13.OH = CeHgMePr.OH, which is a new
isomeride of thymol, forming a colourless liquid, slightly soluble in
water, miscible with alcohol and ether, thickening but not solidifying
in a mixture of ice and salt. It has a sp. gr. of 1 '001 22 at 0°,
and 0-91971 at 100°; boils at 227'5— 229'5°. Its aqueous solution
does not colour ferric chloride. Its ethyl salt, CioHi3.0Et, is a colour-
less liquid, smelling somewhat like orange oil, insoluble in water,
volatilising with steam. Sp. gr. 0*93866 at 0°, 0'85758 at 100° ; b. p.
227-2— 229-2°. H. W.
Pour Metameric Benzanisethyl-hydroxylamines. By R.
PiEPER (Annalen, 217, 1 — 23). — According to present theoretical
views, the replacement of hydrogen in hydroxylaraine, NH3O, or
NH2.OH, by benzoyl (CHsO = Bz), anisyl (CsH^Oa = AH), and
ethyl, may give rise to three metameric compounds, viz. : —
NB^Aii(OEt), NAiiEt(OBi), NBiEt(OAH).
Eiseler, moreover, obtained two ethylic ethers of this class, distin-
guished by the names ethylic anisbenzhydroxamate and ethylic benz-
anishydroxamate (this Journal, 1875, 76(S); and the author of the
present paper has prepared two other bodies having the same percent-
age composition, but differing in their chemical behaviour both from
each other and from Eiseler's compounds.* Moreover it appears that
Eiseler's ethyhc benzanishydroxamate can exist in two different modifi-
* To account for the isomerism of these and other derivatives of hydroxylamine,
it is supposed that the three H-atoms in that base possess different functions, and
the several isomerides are distinguished by formulae in which the substituted radi-
cles are numbered and arranged according to the order in which they have been
introduced into the molecule, thus —
1^ 2. 3^
Benzanisbenzhydroxylamiue N Bz Jn Bz O
Dibeuzanishj'droxylaraine N Bz Bz An O
Anisdibenzhydroxylamine N An Bz Bz O. — H. W.
ORGANIC CHEMISTRY. 461
cations (a and /3), analogous to tlie two ethylic dibenzhydroxamates
described by Giircke (Annalen, 205, 279), that is to say, chemically
alike, but differing greatly in their physical characters.
I. Eiseler's Compounds. — oc-Ethylic Benzanishydroxamatey
NB^SOEt.
The a-modification of this ether, prepared by the action of ethylic
iodide on the silver salt of benzanishydroxamic acid, melts according
to Eiseler at 69°. Pieper, however, finds that it melts at 74° (nncorr.
like all the following), and supposes that Eiseler obtained a different
modification, just as two modifications of ethylic dibenzhydroxamate
are known to be obtained by the action of ethylic iodide on silver
dibenzhydroxamate. The modification melting at 74° forms mono-
clinic crystals, having the axes a : & : c = 1 : 51813 : 0*66584, and exhi-
biting the forms coPco, cx)P, — P, + P, + P(5o. Plane of optic axes
perpendicular to the clinodiagonal principal section. This ether,
heated with potash-lye, yields anisic and a-ethylbenzhydroxamic acids
(m. p^4°), according to the equation NBzAnEtO + HoO = CgHgO-j
+ NBzH.EtO. By hydrochloric acid_it is resolved into ethyl_benzoate,
anisic acid, and hydroxylamine : NBzAnOEt + 2H2O = BzOEt +
AnOH + NH3O.
^-Ethylic Benzanishydroxamate is formed by the action of anisyl
chloride on ethylbenzhydroxamic acid dissolved in aqueous potash :
NBzHEtO + AhCl = HCl + NBzAnEtO. The insoluble portion of
the product was triturated with aqueous sodium carbonate, then
washed and recrystallised from ether. This ether differs from the
a-modification both in melting point (89°) and in crystalline form.
The crystals are monoclinic. Axes a : 5 : c = 0*748118': 1 : 0'802848,
j8 = 75" 21' 15''. Forms P, ooP, coPob, coPcxj. Plane of optic axes
parallel to the clinodiagonal principal section.
The analogy of this ^-modification to ethylic ^-dibenzhydroxamate
is shown by the fact that, like the latter, it is decomposed by potash,
with formation of |S-ethylbenzylhydroxamic acid, melting at 67 — 68°.
Decomposition of Ethylic Benzanishydroxamate by Heat. — This ether,
when heated above its melting point, decomposes suddenly, with evo-
lution of aldehyde, leaving a residue from which aqueous sodium car-
bonate extracts nothing but anisic acid, while benzonitril remains
undissolved. The decomposition is represented by the equation
N(CO.C6H5)(C8H702)(C2H50)0 =: NCCeH^ + CsH^O^.OH + C0.H4O.
In this case, therefore, as in the distillation of the dibenzhydroxamic
acids, the acid radicle which first enters the molecule suffers decom-
position.
Ethylic Anishenzhydroxamate^ NAnBzEtO, prepared by Eiseler {loo.
cit.), forms triclinic crystals which have not yet been examined.
II. Benzethylhenzhydroxylamine, Benzethylanisliydroxylamine^ and
Anisethylhenzhydroxylamine. — The first of these compounds,
NB^.EtBzO,
which Lessen obtained by the action of benzoic chloride on the silver
compound of ethylic benzhydroxamate (this Journal, 1877 [ii], 328),
may be prepared more simply by acting on the same ether in alkaline
462 ABSTRACTS OF CHEMICAL PAPERS.
solution with benzoyl cbloride. When pnrified by washing with aqneous
sodium carbonate, and recrystallisation from ether and light petro-
leum, it forms transparent colourless rhombic crystals, melting at 48 —
49°, easily soluble in alcohol and ether, insoluble in water. Axes,
a : 5 : c = 0-6242293 : 1 : 2-5873036. Forms OP, P, ^Pdb. Plane of
optic axes parallel to ooPc>b.
Benzethylanishydroxylamine, NBzEt5nO, obtained by the action of
atiisic chloride on ethylic benzhydroxamate, crystallises in triclinic
prisms, having the axes a : b : c = 0 7727191 : 1 : 1-08549157. Forms
ooPco, CO Poo, OP, ,P, P„ co|P, 'P,do. The crystals are moderately
soluble in ether and alcohol, insoluble in water and in light petro-
leum, and melt at 64°.
This compound is but partially decomposed, even by prolonged heating
over an open fire with strong potash-lye (1 : 1), the product consisting
of ethylic benzyhydroxamate (m. p. 67°), which separates on passing
carbonic anhydride into the filtered solution, and anisic acid, which
may be precipitated from the liquid, after a second filtration, by hydro-
chloric acid. The decomposition by potash may therefore be repre-
sented by the equation NB^EtXnO -f H2O = NB^EtHO + GeHsOg.
Benzethylanishydroxylamine (2 g.) heated for two hours in a sealed
tube at 100°, with hydrochloric acid of sp. gr. 1*12 (9 c.c.)2_is resolved
into ethylhydroxylamine, benzoic acid, and anisic acid : NBzEtAnO-j-
2H2O = NHEtHO + C7H6O2 + CsHgO,. By very gentle action of
very dilute hydrochloric acid, however, the first products obtained are
ethylic ^nzhydroxamate^d anisic acid, the same as with potash-lye :
NBzEtAnO + H2O = NBzEtHO + CsHgOa.
By dry distillation, benzethylanishydroxylamine is completely re-
solved, after fusion, into phenyl cyanate and ethyl anisate :
N(COPh)Et(aH702)0 = TSr(CO)Ph + CsHvO.OEt,
whereas the metameric body, ethyl benzanishydroxamate, similarly
treated, yields phenyl isocyanide, anisic acid, and aldehyde :
N(COPh)AnEtO = NCPh + CsHsOa + CoH^O.
Ethylic Anishydrox am ate, NAnEtHO, prepared by the action of anisyl
chloride on a solution of ethylhydroxylamine hydrochloride in excess
of sodium carbonate, crystallises in well-formed tabular crystals, melt-
ing at 84°, insoluble in water, slightly soluble in ether, readily in
alcohol. By heating with strong hydrochloric acid, it is converted
into anisic acid and ethylhydroxylamine. Like ethylic benzhydrox-
amate, it exhibits the characters of a weak acid, being converted by
potash-lye into a potassium salt.
Anisethylbenzhydroxylamine, GnHisO^ = NAnEtBzO, best prepared
by adding benzoic chloiide to a solution of ethylic anishydroxamate in
an equivalent quantity of potash-lye, forms transparent crystals, less
soluble in ether and alcohol than benzethylanishydroxylamine, inso-
luble in water and in light petroleum ; resolved by heating with excess
of potash, chiefly into benzoic acid and ethylic anishydroxamate, a
small quantity of anisic acid being, however, produced at the same time,
probably by further decomposition of ethylic anishydroxamate formed
in the first instance. By heating with hydrochloric acid, anisethyl-
ORGANIC CHEMISTRY. 463
benzhydroxylamine is converted, first into benzoic acid and etbylic
anishydroxamate, which latter is then farther resolved into ethyl-
hydroxylamine hydrochloride and anisic acid. — The decomposition of
anisethyl benzhydroxylamine by hydrochloric acid takes place much
less readily than that of benzethylanishydroxylamine, a fact which is
analogous to that observed by Lessen with regard to trisubstitution
products of hydroxylamine containing three different acid radicles,
viz., that those in which the third hydrogen-atom is replaced by
benzoyl are less easily decomposed by hydrochloric acid than those
in which the same hydrogen-atom is replaced by anisyl.
The decomposition of anisethylbenzhydroxylamine by heat is less
simple than that of benzethylanishydroxylamine, and cannot be repre-
sented by a definite equation. Considerable quantities of gas are
evolved, smelling like aldehyde, but not containing either combustible
gases or carbonic anhydride. The distillate smells of phenyl cyanate,
deposits on standing a body melting at 224°, and yields, after removal
of these two, a liquid smelling like anisic ether, and convertible by
saponification into anisic acid. H. W.
Three new Phenols : Isopropyl-, Di-isopropyl-, and Dipropyl-
metacresol. By G. Mazzaea (Gazzetta, 12, 505 — 511). — The author
has already shown (Abstr., 1882, 838, 1198), that when a mixture of
metacresol and propyl- or isopropyl-alcohol in molecular proportion is
heated in sealed tubes with anhydrous magnesium chloride, propyl-
and isopropyl-metacresol are formed, together with their propylic
ethers ; and by further experiments he finds that the same reaction
also gives rise to tetrasubstituted derivatives, viz., dipropyl- and di-
isopropyl-in-cresols. The two phenols last mentioned are insoluble in
dilute aqueous potash, but dissolve in the concentrated lye, and sepa-
rate therefrom unaltered on addition of water, a property which, the
author thinks, may have some relation to the nature and number of
their lateral chains.
Isopropyl-m-cresol, CioHuO = CeHaMe.Pr^.OH, is a colourless or
faintly yellowish liquid which boils at 237 7°, and does not solidify in
a mixture of ice and salt. It has a faint phenolic odour, dissolves
sparingly in water, freely in alcohol and ether, giving no characteristic
reaction with ferric salts. Its nitroso-derivative,
C6H2(NO)MePr^.OH,
crystallises in yellowish needles, melting with decomposition at 155 —
167°, very soluble in alcohol, sparingly in benzene, but more freely
than nitrosopropylmetacresol. It is very unstable. The methylic
ether, CeHsMePi^.OMe, is a colourless liquid, lighter than water, boil-
ing at 215—220°.
Vi-isopropyl-metacresol, C13H20O = C6H2Me(Pi'^)2.0H, is a faintly
yellowish syrupy liquid, having a slight phenolic odour and boiling at
251°. It dissolves in alcohol and ether, and is very soluble in water ;
it does not solidify in a mixture of snow and salt. Its acetyl-derivative,
C15H23O2 = C6H2Me(Pr^)2.0Ac, obtained by the action of acetic
chloride, is a very limpid liquid, having an acetic odour, soluble in
alcohol and ether, not solidifying in snow and salt, boiling at 255 —
260°. The methylic ether, C6H2Me(Pr^)2.0Me, is a colourless, very
4()4 ABSTRACTS OF CHEMICAL PAPERS.
mobile liquid, lierhter than water, having a somewhat nnplcasant
odour, boiling at 242—245°.
Dipropyl-metacresol, CeHsMePrj^.OH, yields an acetyl-derivative in
the form of a mobile liquid, having an acetic odour and boiling at
255—260°. H. W.
Action of Nitrous Acid on Guaiacol. By J. Herzig (Monatsh.
Ghem., 3, 825 — 834). — When nitrous gas is passed into an ethereal
solution of guaiacol (10 g. to 100 — 130 c.c), the liquid turns brown,
and deposits a considerable quantity of a crystalline body ; and on
decanting the ethereal solution, agitating it with well cooled water,
and neutralising the resulting aqueous solution with an ice-cold solu-
tion of sodium carbonate, it soon deposits a yellow crystalline powder
consisting of the sodium salt of carboxytartronic acid,
C0H(C00H)3
(Ber., 1879, 504; Abstr., 1879, 643).
The body already mentioned as separating in crystals when the
ethereal solution is shaken with water, partly remains dissolved in the
ether, and may be separated therefrom by repeatedly agitating the
ether with water till it is all dissolved. This body is dinitroguaia-
col, C6H2(OMe)(OH)(N02)2- It may be purified by repeated crystal-
lisation from dilute alcohol, in which it is moderately soluble when
warm, and is deposited therefrom on cooling in splendid flattened
needles having a golden lustre very much like that of picric acid, and
nearly the same melting point as the latter, viz., 122 — 123°.
By the action of tin and hydrochloric acid, dinitroguaiacol is con-
verted into the tin salt of diamidoguaiacol,
CeH^COH) (OMe) (NH2)2,2HCl,SnCl2,
which retains 1 mol. H2O at 100° ; and on separating the tin with
hydrogen sulphide, and treating the resulting diamidoguaiacol hydro-
chloride with a solution of ferric chloride, the liquid acquires a
splendid violet- red colour, and deposits brown-red metallically lustrous
leaflets which dissolve in water with a fine red colour. The crystals
thus obtained are so extremely soluble in water and in alcohol that
they cannot be purified by washing. They appear, however, to con-
sist of di-imi do guaiacol, the reaction being analogous to that by
which triamidophenol is converted into the corresponding imido-com-
pound.
Weidel and Gruber (Ber., 10, 1137), by treating triamidophenol
with bromine and water, obtained bromodichromazine, and as final
product, hexbromacetone, CaBreO. A similar action takes place on
treating a dilute solution of diamidoguaiacol hydrochloride with
bromine and water, the liquid acquiring first a red, then a brown,
and on addition of excess of bromine, a light yellow colour, and yield-
ing a crystalline precipitate, which dissolves in chloroform and sepa-
rates therefrom in crystals having the form and melting point (I08 —
109°) of hexbromacetone. At the same time, there is formed a
body having nearly the composition and properties of bromodichrom-
azine, but the quantity of it obtained was not sufficient to admit of
satisfactory purificaticn.
ORGANIC OHEMIiSTRY. 465
The analogy between the action of bromine and water on diamido-
guaiacol and triamidophenol renders it probable that only the two
amido- groups and the HO-group of the former are concerned in the
reaction above described, this analogy being probably due to the simi-
larity of the position of the two NHa-groups and the HO-group of the
former to the three NH2-groups in the latter. Diamidoguaiacol will,
therefore, be represented by the formula C6H2(OH)(OMe)(]N'H2)2, in
which [OH : OMe : NH2 : NH2 = 1:2:4:6]. H. W.
Quinones and Quinols. By R. Ntetzki (Annalen, 215, 125 —
172 ; see also p. 146). — The preparation of quinone has already been
described (Abstr., 1878, 794). In order to prepare quinol, sulphurous
anhydride in excess is passed through the crude mixture containing
the quinone, and the quinol is extracted from the filtered liquid by
ether. For further purification of the quinol, Eckstrand recommends
boiling with animal charcoal in presence of sulphurous anhydi-ide.
The Combinations of Quinone with Phenols. — The formulae of quin-
hydrone and of the combinations of quinone with phenol and
resorcinol have already appeared in this Journal (Abstr., 1878, 146 ;
1879, 464 ; and 1880, 247).
Nitro- derivatives of Quinone and Quinol. — In the cold, quinone is
dissolved unchanged by the strongest nitric acid, but on warming,
complete decomposition takes place, oxalic acid and hydrocyanic acid
being formed. Quinol, on the other hand, decomposes in the cold
solution : the nitration of the latter proceeds readily if the hydroxyl
hydrogen has previously been replaced by an alcohol or acid
radical.
Nitro-anilic Acid. — A notice of this compound has appeared in the
Berichte (see Abstr., 1878, 425). The potassium salt, C6N2O8K2, is
best obtained by neutralising the acid with potassium hydroxide solu-
tion ; it crystallises in yellow needles resembling iodoform. The
barium salt, C6N208Ba, is prepared by adding a solution of barium
chloride to any solution of the acid, even in the presence of nitric acid
or hydrochloric acid ; the crystals resemble those of lead iodide. The
ammonium salt, C6N208(NH4)2, is obtained by neutralising a solution of
the acid with ammonia. The sodium salt forms greenish scales, and
is slightly more soluble than the potassium salt. The calcium, silver,
and lead salts are also yellow crystalline precipitates. The author
finds that the best way of preparing nitro-anilic acid is to treat 1 part
of dinitro-quinol with a well cooled mixture of 3 parts of strong nitric
acid and 6 parts of glacial acetic acid. A violent evolution of red
fumes takes place. After a few minutes, the mixture is diluted with
water, and an excess of potassium hydroxide solution added. On
cooling, the potassium derivative separates out, about 50 per cent, of
the dinitro-quinol employed being obtained.
On heating with sulphurous anhydride at 100° in a sealed tube, tbe
acid yields a colourless body, not yet obtained in a crystalline form.
By incomplete reduction with tin and hydrochloric acid, violet-coloured
needles are obtained, which by further reduction yield a colourless
solution. With ferric chloride this solution gives a very insoluble
green crystalline precipitate resembling quinhydrone. It appears as
466 ABSTRACTS OP CHEMICAL PAPERS.
if a diamido-tetroxybenzene were formed, which on oxidation gives
dioxydiimidoquinone.
Dinitro-quinol, C6H2(N02)2(OH)2, is prepared from diacetyl-qninol
by the action of fuming nitric acid and decomposition of the resulting
dinitro-diacetyl-quinol with potash (Abstr., 1878, 499). It dissolves
sparingly in cold, but readily in hot water, also in ether and alcohol.
It forms two series of salts, of which the primary yields dark yellow,
and the secondary violet solutions.
Nitro-derivatives of Diethyl quinol. — (Comp. Abstr., 1878, 866, and
1879, 464). — Mononitro-diethylquinol is best prepared by dissolving
1 part of diethylquinol in 4 — 5 parts glacial acetic acid, allowing
the mixture to cool, and then treating the crystalline mass with its
own volume of nitric acid of sp. gr. 1*3. The nitro-body generally
separates as an oil, but becomes crystalline in a short time. It crys-
tallises from 60 per cent, alcohol in yellow needles 1 inch long (m. p.
49°). Reduced with tin and hydrochloric acid, it yields the corre-
sponding amido-body, which forms well crystallised salts.
Dinitro-diethi/lquinol, C6H2(N02)2(OEt)2, is formed by suspending
diethylquinol in 5 times its weight of glacial acetic acid, and pouring
it into an equal volume of fuming nitric acid 1*48 sp. gr. The product
contains two isomeric bodies which can be separated by repeated
crystallisation. The a- compound melts at 130°, and the y3-, which is
less soluble, at 176°. Both form sulphur-yellow needles, which are
soluble in alcohol, ether, benzene, and acetic acid. On reduction,
they yield amido-compounds which form crystalline hydrochlorides.
If the a-compound be reduced and treated in an aqueous solution
with 3 mols. of hydrochloric acid and 1 mol. of sodium nitrite, a grey
precipitate separates out, which, on boiling with alcohol and animal
charcoal, yields a colourless body. Recrystallised from glacial acetic
acid, it can be obtained in needles 1 cm. long (m. p. 233°) of the
composition C10H13N3O2. The body is similar to that obtained by
Hofmann by treating nitrophenylenediamine with nitrous acid, and
that by Ladenburg from various orthodiamines. It has scarcely any
basic properties, being precipitated by water from its solution in
hydrochloric acid. It behaves with alkalis like a weak acid, and forms
salts which are decomposable by carbonic anhydride.
Trinitro- diethylquinol, C6H(N02)3(OEt)2, is best prepared by adding
the mononitro-compound gradually to a well cooled mixture of H2SO4
and HNO3. It crystallises from alcohol in long yellow needles melting
at 130°. It is more soluble in alcohol, ether, and benzene than the
dinitro-compounds. When heated with alcoholic ammonia for some
hours under pressure at 110 — 120°, it yields red crystalline scales.
One of the ethoxyl- and one of the nitro-groups are replaced by ammo-
nia groups. If trinitro-diethylquinol is acted on by aniline instead of
ammonia, the nitro-groups alone are attacked. In addition to amido-
a.zobenzene, a body crystallising from alcohol in red needles (m. p. 133°)
is obtained. It is a diethoxy-dinitrodiphenylamine, CieHnNsOe- On
boiling it with alcoholic potash, the aniline-group is separated and
probably replaced by a HO-group. The product is a monobasic acid,
and crystallises from alcohol in golden-yellow needles melting at 152*.
The potassium salt has the composition 06H(N02)2(OEt)2.0K,
ORGANIC CHEMISTRY. 467
JTydrotoluquinone.-^TLolnqumone is easily reduced if suspended in
water through which a current of sulphurous anhydride is passed.
When all is dissolved, the hydrotoluquinone is shaken out with ether.
It is purified by crystallising from high-boiling benzene, from which
it separates out in mother-of-pearl plates melting at 124°. It forms a
diacetyl-derivative melting at 52°. Hydrotoluquinone can be obtained
by the oxidation and subsequent reduction of orthotoluidine.
Methyl Mkers of Hydrotoluquinone and their Gondensation,-products
(comp. Abstr., 1878, 868).— The dimethyl ether, C7Hfi(OMe)2, is a
colourless liquid boiling at 214 — 218°, and solidifies to colourless crys-
tals which melt at 15°. By the action of chromic acid it yields the
quinone of a dioxymethylditolyl of the composition C16II16O4,
.aH,(OMe).0
'^'^^C7H5(OMe).0^-
It is almost insoluble in water, but dissolves easily in alcohol, ether,
benzene, and glacial acetic acid. On reduction, it yields the cor-
responding quinol (loc. cit.).
On heating this compound for several hours at 180 — 190°, with
concentrated hydrochloric acid in a sealed tube, a crystalline mass is
obtained, mixed with small quantities of a black substance which
dissolves in alcohol with a violet colour. The latter is formed in larger
quantities when the tube is heated to a higher temperature or for a
longer period. On opening the tube, methyl chloride is evolved. The
black substance crystallises from benzene in long needles (m. p. 232") ;
the author considers them to be an anhydride of tetroxy-ditoluyl,
probably having the constitution<^p'TT^/QTT^^O. When distilled
with zinc-dust it yields a semi-liquid hydrocarbon.
Xyloquinone, C8H8O2. — The conversion of xylidine into the quinone
is performed in two ways, either by the direct oxidation of the base or
by decomposition of the amidazo-compound. On oxidation with
chromic mixture, xylidine behaves differently from its homologues.
The intermediate product which is of a light brown colour, does not
exhibit the characteristics of aniline-black : on further oxidation, a
precipitate always remains suspended in the liquid. The quinone
resembles its homologues in most of its properties, but differs from
them in its sparing solubility in hot water, as well as in being less
readily reduced by sulphurous anhydride. Like tolu- and benzo-
quinone it is very volatile, and sublimes in golden-yellow needles
at 125°. It can be reduced to a quinol. With hydrochloric acid, it
yields a chloroquinol.
Xyloquinol, C8H10O2. — Xyloquinone is best reduced by heating it at
100° in a closed flask with an aqueous solution of sulphurous anhy-
dride. The quinol thus obtained is very slightly soluble in cold, but
readily in hot water, and crystallises from it in plates with a pearly
appearance (m. p. 212°). It oxidises rapidily, even by standing in
the air, and becomes re-converted into xyloquinone. J. I. W.
Action of Melting Potassium Hydroxide on Benzoic Acid.
By L. Baeth and J. Schreder (Monatsh. Chem., 3, 800 — 818). — The
4()8 ABSTRACTS OF CHEMICAL PAPERS.
experiments described in this paper confirm and extend the results
obtained by Earth in 1872 {Annalen, 144, 138 ; and this Journal, 1872,
1013), showing that the products obtained by fusing benzoic acid at a
high temperature with potash are much more complex than those pro-
duced in like manner with soda, and that the action consists of- —
(1.) Direct oxidation (or hydroxylation), whereby parahydroxybenzoic
acid is obtained, together with a small quantity of salicylic acid.
(2.) Hydroxylation and carboxylation, resulting in the formation of
a-hydroxy-isophthalic acid, C6H3(OH)(COOH)(COOH) [1:2: 4].
(3.) Reduction and condensation, resulting in the formation of two
diphenylcarboxylic acids, C13H10O2 or C12H9.COOH, together with yellow
and brown condensation-products.
Of the two diphenyl-carboxylic acids thus obtained, one forms a
soluble, the other an insoluble barium salt. To separate them, the
mixture was dissolved in dilute ammonia, the excess of the latter
driven off by heat, the cooled and diluted solution precipitated with
barium chloride, and the precipitate decomposed by hydrochloric acid.
The organic acid thereby separated and purified by repeated crys-
tallisation from alcohol, crystallises in tufts of anhydrous needles
melting at 216 — 217^, yields diphenyl when heated with lime, and
exhibits all the properties of p-diphenylcarboxylic acid.
The second diphenyl-carboxylic acid, separated by hydrochloric acid
from the filtrate of the barium p-diphenylcar boxy late, forms a fl.oc-
culent crystalline precipitate, and is obtained by repeated crystallisation
from alcohol in dazzling white leaflets, likewise anhydrous, and
melting at 160 — 161°. Heated with lime, it yields a large quantity
of diphenyl. As it is distinct from the p-acid, and does not agree in
its properties with the o-acid described by Fittig and Ostermayer, it
must be me^a-diphenylcarboxylic acid, and is probably identical with
the acid which Fittig and Schultz obtained {Annalen, 203, 132) by
oxidation of isodiphenylbenzene.
m-Diphenylcarboxylic acid is easily soluble in ether, benzene,
xylene, light petroleum, and glacial acetic acid, sparingly in water.
Its aqueous solution, like that of the para-acid, gives a white preci-
pitate with lead acetate. Its ethylic ether, Ci3H902Et, is a colourless
somewhat viscid non-crystallising oil, boiling at a rather high tem-
perature. The barium salt, (Ci3H902)2Ba,3jH20, forms tufts of needles.
The calcium salt, (Ci3H902)2Ca, is a white powder, containing in the
air-dried state 3 mols. water, which is given off at 200°. The copper
salt is a light greenish-blue flocculent precipitate; the silver salt, a
white flocculent precipitate, not very sensitive to light. The ammonium
salt is very unstable. The sodium salt is obtained as an indistinctly
crystalline mass, drying up in the air to a white powder, containing
2 mols. water, which is given off at 130° ; it is partly decomposed on
agitating its aqueous solution with ether, the solution afterwards
exhibiting a strongly alkaline reaction. The sodium salt of ^-diphenyl-
carboxylic acid is decomposed by ether in the same manner.
The diphenylcarboxylic acids obtained as above were accompanied
by very small quantities of two other bodies, one having the compo-
sition of a diphenylcarboxylic anhydride, but not agreeing in pro-
perties therewith, inasmuch as it was precipitated unaltered by acids
ORGANIC CHEMISTRY. 469
from its solution in potash-lye, even after prolonged boiling ; the
other melting at 187°, and apparently consisting of di-diphenyl,
C24H20, isomeric with benzerythrene and triphenyl-benzene.
The other condensation -products above mentioned, as resulting from
the action of melting potash on benzoic acid, were not obtained in
sufficient quantity for satisfactory examination. H. W.
Monobromopseudocumic Acid and Dibromomesitylenic
Acid. By H. SiJssenguth (Annalen, 215, 242 — 252). — Preparation
of Monohromopseudocumene, CeHaBrMca. — Monobromopseudocume (m.p.
72°) was first obtained by Beilstein and Kogler from coal-tar oil. In
order to purify the crude oil, the author shakes it with tolerably
strong soda-solution, and then pours off the upper layer of liquid, thus
removing the phenol. After drying the liquid, it is fractionated, and
the portion which boils constantly between 161° and 169° is treated
with the theoretical quantity of bromine; the product, when washed
with dilute soda-solution and distilled, yields a fraction which boils at
220 — 240°, and contains large quantities of monohromopseudocumene.
On cooling the distillate by ice, it partially solidifies, and the crystals,
after being drained and crystallised from alcohol, melt at 72°.
Monohromopseudocumic acid, CeH.2BrM.e2.COOH, is obtained by warming
bromopseudocumene dissolved in acetic acid with twice its weight of
chromic acid. It is easily soluble in alcohol, and dissolves in water on
continued boiling, crystallising from the solution, on cooling, in small
needles, melting at 172—173° ; it can be sublimed. The author has
not succeeded in obtaining salts of the heavy metals in a crystalline
state. The calcium salt, (06H2BrMe2COO)2Ca + 2H2O, is obtained by
boiling an aqueous solution of the acid with finely-powdered Iceland
spar. It crystallises in fine colourless needles, soluble in water. The
barium salt, (C6H2BrMe2.COO)2Ba + 6II2O, crystallises in groups of
needles, soluble in water. The potassium salt, C6H2BrMe2.COOH,
crystallises in fine concentric groups of needles or prisms, which
effloresce in dry air.
Preparation of Bromomesitylenic Acid from Bromomesitylene. — On
treating monobromomesitylene dissolved in acetic acid with chromic
mixture, it readily undergoes oxidation. Bromopseudocumic acid
differs from its isomerides in its easy solubility in alcohol and boiling
water. Its salts are also more easily soluble than those of the cor-
responding bromomesitylenic acid, whose melting point is 212°. The
calcium salt, (C6H2BrMe2.COO)2Ca + 6H2O, forms long needles. The
author has not obtained salts of the heavy metals, as they undergo
decomposition in a hot solution.
JDihromomesitylene from Coal-tar Oil. — In preparing monohromo-
pseudocumene, a large quantity of a substance boiling at 250° was
obtained. On fractionally distilling it, a portion boiling constantly at
277 — 278° was isolated, which solidified on cooling. After purification
from alcohol, it was obtained in colourless crystals 1 inch long,
having all the properties of dibromomesitylene. The boiling point,
277—278° and melting point, 64°, differed greatly from former
observations. In order to decide whether the body was a derivative
of mesitylene or of pseudocumene, or of the third possible trimethyl-
470 ABSTRACTS OF CHEMICAL PAPERS.
benzene, the author prepared dibromomesitjlene from pure mesi-
tylene, and found that it exhibited the greatest similarity (b. p.
276 — 278'\ m. p. 64°) to the brominated compound obtained from
coal-tar oil.
Dinitro-monohromomesitylene, C6Br(N02)2Me3. — On boiling dibromo-
mesitjlene with fuming nitric acid, an oily and a solid compound are
formed. The solid body, after repeated crystallisation from alcohol,
is obtained in colourless needles, melting at 194**. One bromine-atom
is replaced by a nitro-group.
Dibromomesitylenic acid, CeHBrgMez.COOH. — The author finds that
chromic acid acts too violently on dibromomesitylene ; the temperature
rises rapidly, and the compound is destroyed and bromine liberated.
Hoogewerff observed a similar phenomenon with dichloromesitylene.
In the case of the bromine compound, a third atom of bromine enters
into combination, as the product of the reaction on crystallisation
from alcohol yields lar^e quantities of tribromomesitylene. By em-
ploying potassium dichromate and acetic acid, the oxidation proceeds
well, and on adding water to the mixture when the reaction is com-
plete, the dibromomesitylenic acid is precipitated. On recrystallisa-
tion from water, it is obtained in small colourless glittering needles,
melting at 194 — 195°. They are soluble in alcohol, and can be sub-
limed between watch-glasses. The calcium and barium salts are easily
soluble in water, and crystallise well ; the salts of the heavy metals
decompose in a warm solution. The calcium salt crystallises in needles
and in rectangular tables. The barium salt forms short prisms, which
are soluble in water.
The author has not succeeded in obtaining oxidation-products of
the tribromo-derivative of the isomeric trim ethyl benzene. Chromic
acid and potassium permanganate in weak solutions have no action,
and, when concentrated, decompose the compound. J. I. W.
Guaiaconic and Guaiaretic Acids (Preliminary Notice). By
J. Herzig (Monatsh. Chem., 3, 822 — 824). — The author has already
shown that guaiaconic acid, treated with hydrochloric acid, yields
methyl chloride and catechol — together with bodies not yet examined
— and has hence inferred that the guaiacol given off in the dry distil-
lation of guaiacum resin pre-exists therein (Abstr., 1882, 593). This
conclusion, however, is by no means unassailable, since we cannot be
sure that the methyl evolved as chloride was directly connected with
the catechol. Subsequent experiments have, however, distinctly
shown the existence of a guaiacol residue in guaiaconic acid. In fact,
when this acid dissolved in ether is treated with nitrous acid, and the
resulting solution is shaken up with ice-cold water, there remains dis-
solved in the ether a body which, after repeated crystallisation from
alcohol, melts at 122 — 123°, and exhibits the composition and pro^
perties of dinitroguaiacol, C7H6(N02)202.
Guaiaretic acid, treated in like manner with hydrochloric acid, like-
wise yields methyl chloride and catechol, together with a body which
resembles pyroguaiacin in melting at 183 — 185°, but differs from that
compound in not subliming readily under ordinary pressure, in imme-
diately turning brown in contact with potash, and in not turning blu0
ORGANIC CHEMISTRY. 471
with sulphuric acid. Guaiacol is likewise resolved by the action of
hydrochloric acid into methyl chloride and catechol.
The author is continuing his experiments. H. W.
Phenylhydroxypivalic Acid. By R. Fittig and H. W. Jatne
(Annalen, 216, 115 — 119). — When a mixture of sodium isobutyrate,
isobutyric anhydride, and benzaldehyde is heated at 100° for four
hours, phenylhydroxypivalic acid, CHPh(0H).CMe2.C00H, is pro-
duced. This acid crystallises in glistening needles (m. p. 134°),
soluble in alcohol and ether. At a temperature slightly above the
melting point, it splits up into carbonic anhydride and butenylbenzene,
C10H12. This property of the acid accounts for the fact that Perkin
(this Journal, Trans., 1879, 136) only obtained butenylbenzene by the
action of benzaldehyde on a mixture of sodium isobutyrate and
isobutyric anhydride. W. C, W.
Ethoxymetatoluic Acid. By P. H. Broun (Amer. Chem. /., 4,
374 — 377). — Remsen and Kuhara have shown that the nitrotoluic
acid obtained by the oxidation of ordinary nitroxylene with chromic
1 2 4
acid has the constitution C6H3(N02)Me(COOH) Abstr., 1882, 607).
The corresponding diazo-compound is easily converted into the
hydroxy-acid by boiling with water ; but when boiled with alcohol, it
yields, not metatoluic acid, as might be expected, but another acid,
described as insoluble in cold and only slightly soluble in hot water,
crystallising from alcoholic solution, volatilising with steam, and
subliming in light flakes. The analysis of this acid did not yield
satisfactory results, on account of the smallness of the quantity
obtained ; but the author of the present paper has succeeded in pre-
paring it in larger quantity and in determining its constitution.
In preparing the amido-acid from the nitro-acid, it is advisable to
use as little hydrochloric acid as possible ; and the nitric acid used in
converting the amido-acid into the diazo-acid must be very dilute.
On boiling the dried diazo-com pound with nearly absolute alcohol
(99 p. c.) and diluting the product with water, the acid under investi-
gation is thrown down with all the properties ascribed to it by
Kemsen and Kuhara. The analysis of its calcium salt gave numbers
agreeing with the formula (CioHii03)2Ca,2H20 or
[C6H3Me(OEt)COO]2Ca,2H20,
showing that the acid in question is ethoxymetatoluic acid. Its forma-
tion may be represented by the equation NOa.N ! N.CeHaMe.COOH +
EtOH = NO3H + N2 -H Etb.CeHgMe.COOH. H. W.
Coumarin. By G. Ebert (A7inalen, 216, 139 — 161). — Coumarin
dissolves in boiling baryta-water forming an unstable compound,
which has not been isolated. Coumarin is also dissolved by a hot
solution of potassium carbonate ; an unstable compound is produced
which is soluble in alcohol and water. A hot alcoholic solution of
sodium ethylate also has the power of dissolving coumarin.
The properties of ethylcoumarinic acid, EtO.C6H4.CiI '. CH.COOH
472 ABSTRACTS OF CHEMICAL PAPERS.
(a-ethylorthoxyphenylacrylic acid), have been previously described by
Parkin (this JoTirnal,'Tran8., 1881,409). The calcium salt, rCnHu03)2Ca
H- 2H2O, crystallises in glistening needles. 100 grams of the saturated
solution at 21° contain 2'15 grams of the anhydrous salt. Calcium
ethylcoumarate also forms needle-shaped crystals containing 2 mols.
H2O. 100 grams of the saturated solution at 21° contain 0'43 gram
of the anhydrous salt. Barium ethylcoumarinate is deposited from an
alcoholic solution in silky needles containing 2 mols. HjO. Barium
ethylcoamarate forms crystals containing 4 mols. H2O. It is very
soluble in alcohol, but is left as a gummy mass on evaporating the
solution. Both ethyl coumarinic and ethylcoumaric acids yield ethyl-
salicylaldehyde and ethylsalicylic acid on oxidation with potassium
permanganate. These acids are both converted into ethylmelilotic
acid, EtO.C6H4.(CH2)2.COOH, by the action of sodium amalgam on
their aqueous solutions. The author also finds that the bromide,
CiiHi2Br203 (m. p. 155°), obtained by the action of bromine on a
solution of ethylcoumarinic acid in carbon bisulphide, is identical with
the bromine-compound derived from ethylcoumaric acid. This state-
ment does not agree with Perkin's observations {loc. cit.).
Coumaric acid stands in the same relation to coumarinic acid, that
angelic acid bears to tiglic acid. W. C. W.
Phenylbutyrolactone and Phenylparaconic Acid. By H. W.
Jayne (A7malen, 216, 97 — 114). — A mixture of phenylparaconic acid
and isophenylcrotonic acid is obtained by heating equivalent propor-
tions of sodium succinate, benzaldehyde, and acetic anhydride at
125 — 130° for four hours in a flask fitted with an upright condenser.
The product of the reaction is dissolved in water and extracted with
ether. The extract is treated with sodium carbonate, and on adding
hydrochloric acid to the alkaline liquid isophenylcrotonic and para-
conic acids are precipitated. After the precipitate has been dried, it
is treated with carbon bisulphide, which dissolves out isophenylcro-
tonic acid, and leaves phenylparaconic acid undissolved. A further
yield of phenylparaconic acid is obtained by adding hydrochloric acid
to the aqueous solution of the crude product after it has been treated
with ether.
Isophenylcrotonic acid, CHPh ! CH.CH2.COOH, crystallises in
needles or prisms, which dissolve freely in alcohol, ether, and carbon
bisulphide. The acid melts at 86°, and boils at .302°.
Barium isophenylcrotonate, Ba(CioH902)2 + 3H2O, forms large crys-
tals, freely soluble in water. Ca( 010^900)2 + 3H2O is also very
soluble.
Isophenylcrotonic acid unites with hydrobromic acid, yielding
phenylbromobutyric acid, CioHiiBr02 (m. p. 69°). This acid is decom-
posed by a dilute solution of sodium carbonate, ioTmmg phenylbutyro-
lactone, C13.o<^^^X^CJIPh. This compound crystallises in rhombic
needles (a : & : c = 0'6106 : 1 : 0*426) soluble in alcohol, ether, carbon
bisulphide, and hot water. It melts at 37°, and boils at 306°, but
begins to volatilise at 100°. It is converted into a salt of phenyl-
hydroxy butyric acid by boiling with an alkali.
ORGANIC CHEMISTRY. 473
Barium phe7iylh/droxijhutyrate, Ba(CioHn03)2, is an amorplious
body, soluble in water and in alcohol. The free acid, C10H12O3, forms
transparent crystals (ra. p. 75°), soluble in alcohol, ether, and carbon
bisulphide. It also dissolves in water, but at 80° the solution decom-
poses yielding the lactone.
Isophenylcrotonic acid unites with bromine to form phenyldibromo-
butyric acid (m. p. 138°), which is converted into phenylbutyrolactone
or sodium phenylhydroxybutyrate by the action of sodium amalgam on
its aqueous solution.
Phenylbutyric acid, CH2Ph.(CB[2)2-COOH, obtained by treating the
isophenylcrotonic acid with nascent hydrogen, resembles benzoic acid
in appearance. It melts at 47*5°, boils about 290°, and dissolves in
ether, alcohol, and water. The barium salt of this acid is crystalline,
the calcium salt amorphous.
Phenylparaconic a>cid, CB[2<^ POO _]!>CJHPh, crystallises in
glistening needles containing J mol. H2O melting at 99°, soluble in
ether, alcohol, chloroform, and hot water. The melting point of the
anhydrous acid is 109°. At 150°, the acid begins to decompose into
phenylbutyrolactone, carbonic anhydride and isophenylcrotonic acid.
Barium phenylparaconate, Ba(CiiH904)a 4- SHgO, forms colourless
crystals soluble in water. The caleium salt contains 2 mols. H2O. It
is converted into calcium isophenylcrotonate by heating at 140°.
Phenyl itamalates are produced when paraconic acid is boiled with
an alkali. W. C. W.
Phenylhomoparaconic Acid. By S. L. Penfield (Annalen, 216,
119— 127). —Phemjlhomoparaconic acid, CHMe<^^^^J^>CHPh,
is obtained by heating a mixture of equivalent quantities of benz-
aldehyde, sodium pyroracemate, and acetic anhydride at 130° for nine
hours in a flask provided with an upright condenser ; the contents of
the flask are then dissolved in hot water and extracted with ether.
The extract contains small quantities of phenylhomoparaconic and
cinnamic acids. A third acid is also present. On adding hydrochloric
acid to the aqueous solution from which these acids have been ex-
tracted by ether, phenylhomoparaconic acid is precipitated. The
pure acid forms glistening needles melting at 177°, soluble in hot
water, alcohol, and ether.
Silver phenylhomoparaconate, Ci2Hn04Ag, forms small crystals
soluble in water. By the action of calcium carbonate on a hot solution
of phenylhomoparaconic acid, calcium phenylhomitamalate,
CisHiaOeCa + 3H2O,
is obtained in sparingly soluble needle-shaped crystals. BaCi2Hi205 -|-
2H2O resembles the calcium salt in its properties. Ag2Ci2Hi206 is
insoluble in water.
Phenylhomoparaconic acid does not combine with bromine, but it
dissolves slowly in strong hydrobromic acid, forming the unstable
compound Ci2Hi3Br04. This body melts with decomposition at 149°.
It is soluble in alcohol and ether. On warming the aqueous solution,
VOL. XL IV. 2 k
474 ABSTRACTS OF CHEMICAL PAPERS.
carbonic anliydridis is evolved, and crystals of an acid having the
composition CnHigO-j are deposited on cooling.
Phenylhomoparaoonic acid is' decomposed by heat at a temperature
slightly above its melting point, yielding phenylbutylene (b. p. 177°),
benzaldehyde, and other products. The phenylbutylene appears to be
identical with the hydrocarbon which Aronheim {Annalen., 171, 219)
obtained by the action of allyl iodide on benzyl -chloride.
w. c. w.
Coumarilic Acid. By R. Fittig and G. Ebert (Amialen, 216,
162 — 171). — Coumarilic acid, CgHcOa, prepared bv the action of
alcoholic potash on coumarin dibromide, melts at 190'5°, boils between
810° and 315° with very slight decomposition, and possesses the pro-
perties ascribed to it by Perkin (this Journal, 1870, 360; 1871, 37).
The barium salt, Ba(C9H503)2 + 4H2O, crystallises in plates, soluble
in boiling water, whilst the calcium salt, Ca(C9H50a)2 + 3HjO, is
deposited from a hot aqueous solution in needles. The crystalline
silver salt is sparingly solnble in hot water^
Coumarilic acid is not attacked by bromine. On fusion with
potasli, it yields salicylic and acetic acids. It unites directly with
nascent hydrogen to form hydrocoumarilic acid, CgHgOa, wbich crystal-
lises in pearly leaves, soluble in alcohol, ether, and water. This acid
melts at 116*5°, and boils about 299° with decomposition. The forma-
tion of hydrocoumarilic acid shows that coumarilic acid is not hydroxy-
flienyl'pro'piolic acid, as stated by Beilstein. Barium hydrocoumarilate,
Ba(C9H703)2 + 2H2O, forms tabular crystals, which dissolve freely in
water. The calcium salt bears a close resemblance to the barium salt.
It readily forms supersaturated solutions. AgCgHvOa is very slightly
soluble in water. Ethijl hydrocoumarilate, C9H703Et (m. p. 23°, b. p.
273°), is insoluble in water.
Coumarilic acid splits up into coumarone, CsHeO, and carbonic
anhydride when distilled over lime. Coumarone is a colourless oil,
heavier than water. It remains liquid at —18°, and boils at 169°.
It is insoluble in water and soda-lye. It is not attacked by nascent
hydrogen, but it unites with bromine, yielding a dibromide, CgHeBraO
(m. p. 86°), which slowly decomposes at the ordinary temperature.
Hydrocaumarilic acid does not yield a hydrocouraarone on distil-
lation with lime, but is decomposed with formation of phenol.
From tte result of these experiments the authors propose the
following formulae : —
Coumarilic acid. Coumarone. Hydrocoumarilic Acid.
CeH/ \C.C00H C^/ \CH ^CeH/ ^CRCOOH.
,^CH^ ^CH^ ^Ch/
Action of Sulphuric Acid on Cinnamic Acid. By E. Erd-
MANN (Annalen, 216, 179 — 199). — Cinnamic acid is completely decom-
posed by prolonged boiling with dilute sulphuric acid, splitting up
into distyrenic acid, distyrene, and carbonic anhydride.
The relative yield of hydrocarbon and acid varies with the strength
ORGANIC CHEMISTRY. 475
of the STilphnric acid employed, the more dilute the acid the larger being
the yield of hydrocarbon. Good results are obtained by boiling cinnatnic
acid for 3J hours with five times its weight of strong sulphuric acid
diluted with an equal volume of water. The mixture of distyrenic
■acid and distyrene forms an oily layer on the surface of the liquid.
This is collected, diluted with ether, and repeatedly shaken up with a
solution of sodium carbonate. The ethereal solution contains the
hydrocarbon, and the alkaline liquid distyrenic acid, which is precipi-
tated on adding hydrochloric acid. The acid is best purified by con-
version into the insoluble calcium salt. The pure acid, CnHieO,, is
amorphous, and forms amorphous salts. It is freely soluble in ether,
alcohol, and glacial acetic acid. It melts about 50°, and boils without
decomposition. The acid is monobasic. On oxidation with chromic
mixture, it yields benzoic acid, but it is neither attacked by bromine
nor by nascent hydrogen.
Distyrene, CieHje, is a colourless liquid exhibiting a blue fluorescence,
which gradually disappears. The hydrocarbon has no action on
polarised light. Its sp. gr. at 15° is 1*016, and it boils at 311°. On
oxidation with chromic mixture, benzoic acid is produced. The crys-
talline dibromide, CieHieBra (m. p. 102°), obtained by the addition of
bromine to a mixture of distyrene and carbon bisulphide, is freely
soluble in ether, benzene, carbon bisulphide, and in hot alcohol,
glacial acetic acid, and light petroleum.
Distyrene is decomposed by prolonged boiling, yielding toluene,
styrene, and isopropyliienzene. W. C. W.
Imides of Bibasic Acids. By M. Landsberg (Annalen, 215, 172
— 213). — The author has endeavoured in his research to obtain a more
complete knowledge of the imides of bibasic acids, in order to be able
to determine their real constitution. His principal object has been to
ascertain whether a hydrogen-atom in these imides can be replaced
by metals other than silver or mercury, and, if possible, starting from
the imides themselves, to prepare ethyl derivatives which yield ethyl-
amine with elimination of water. The present paper is limited to an
investigation of the properties of phthalimide and succinimide.
Phthalimide. — The phthalimide employed was prepared by Laurent's
method, viz., by subliming ammonium phthalate. The sublimate was a
snow-white mass consisting of very small plates melting at 228 — 229°.
Phthalimide is precipitated from solutions of its metallic derivatives on
adding an acid. The potassium derivative, CgHiOgNK, is precipitated
from an alcoholic solution of phthalimide, when it is treated with the
theoretical quantity of potash in alcohol. It forms white plates which
are almost insoluble in alcohol and ether. The sodium derioative^
CsFr402NNa, is prepared in a similar manner. It is precipitated on
adding ether. The barium derivative, (C8H402N)2Ba + ^HgO, is pre-
pared by decomposing the potassium compound with barium chloride.
It forms a glittering white precipitate, which decomposes when heated
to 100°. The magnesium derivative, (C8H402N)3Mg, is formed when
the potassium compound is decomposed by magnesium sulphate. It
is obtained as a white powdery precipitate easily soluble in water.
The silver derivative is a white cheese-like precipitate which, when dried
2 A; 2
476 ABSTRACTS OF CHEMICAL PAPERS.
over sulphuric acid, has the composition CsHiOjNAg + ^HjO. After
drying at 100° for several days it is obtained in an anhydrous state.
Laurent prepared the silver derivative by treating an ammoniacal solu-
tion of phthalimide with silver nitrate. He states that he obtained
three different precipitates consisting of silver phthalimide, silver
a.mmoniam phthalimide, and silver amidophthalate. The author
finds on repeating the experiments, that the powdery precipitate
described by Laurent consists of silver phthalimide, and he considers
the compound crystallising in needles to be a mixture of silver
phthalimide and phthalimide. The mercury derivative, (C8H402N')3Hg,
is prepared by decomposing the potassium compound with mercuric
chloride. The copper salt is obtained as a bluish- white precipitate on
mixing equivalent quantities of potassium phthalimide and copper
sulphate. The author was unable to obtain the salt free from sul-
phate. Assuming that the salt obtained was a mixture of copper
phthalimide and copper sulphate in varying proportions, and deduct-
ing the latter, from calculations based on the determinations of sul-
phuric acid, he obtains the formula (C8H402N)2Cu + H2O for the
copper salt. He endeavoured to prepare the salt from copper chlo-
ride, but was equally unable to obtain it free from chloride. The salt
obtained from the chloride crystallises with 2 mols. HoO. On pre-
cipitating lead nitrate with potassium phthalimide a mixture of lead
phthalimide with varying quantities of phthalimide is obtained.
Uthyl-phthalimide is obtained by treating anhydrous silver phthal-
imide with the theoretical quantity of ethyl iodide and a small
quantity of anhydrous benzene, and allowing it to stand for some
days ; on evaporating, phthalimide separates at first, but from the last
mother-liquors, well-formed plates melting at 90° are deposited,
which, after repeated crystallisation from alcohol, melt at 90 — 94°, and
have the composition C10H13NO4. The author had not sufficient mate-
rial to make further investigations of its properties.
Salts of Amidophthalic Acid. — The potassium salt,
CONH2.C6H4.COOK,
is obtained when potassium phthalimide is boiled with water. It
crystallises from an aqueous solution in clear rhombic plates. The
silver salt is obtained in pearly- white flakes on adding silver nitrate to
an alcoholic solution of potassium amidophthalate. On treating the
silver salt with the theoretical amount of hydrochloric acid and
filtering, a solution of the free acid is obtained. On evaporation in the
cold, they are decomposed yielding nothing but ammonium phthalate.
The harium salt is easily soluble in water, and, on addition of acids,
yields no phthalimide. The author endeavoured to obtain the free
acid from this salt, but only obtained ammonium phthalate.
Succinimide, C4H5O2N. — The succinimide employed was obtained by
distilling ammonium succinate. The metallic derivatives are all more
or less soluble in water, and, on treatment with acids, yield succinimide.
They possess the characteristic property of forming the correspond-
ing salt of amidosuccinic acid by taking up water. The potassium
derivative is obtained by treating an alcoholic solution of succinimide
with the theoretical quantity of potassium hydroxide dissolved in alco-
ORGANIC CHEMISTRY. 477
hoi, and then adding ether ; it consists of small needle-shaped crystals,
or a pure white powder, according to the amount of ether added. The
crystalline form is anhydrous, whilst the powder contains half a mole-
cule of water, C4H4O2NK -f- JHgO. Both forms are easily soluble in water
and alcohol. The sodium derivative^ C4H402N]Na, crystallises in small
needles. It is very hygroscopic. The barium derivative is obtained by
acting on a solution of succinimide in absolute alcohol with barium
ethylate ; the compound, which is easily soluble in water, crystal-
lises with 2| mols. H2O. The silver derivative can be prepared
either by decomposing potassium succinimide with silver nitrate,
when it is obtained as a white powdery crystalline precipitate,
C4H402NAg + JHaO, becoming anhydrous at — 80°, or by adding
ammonia to an alcoholic solution of succinimide, boiling, and then
adding the theoretical quantity of silver nitrate. On cooling, the salt
crystallises in long silky needles containing water. If only a trace of
ammonia be present, the compound is obtained anhydrous, but the
whole is not precipitated. Silver succinimide is very slightly soluble
in cold water and alcohol. The mercury derivative, (C4H402N)2Hg, is
obtained by dissolving mercuric oxide in a hot alcoholic solution of
succinimide, and is deposited on cooling in small glittering needles
which are easily soluble in water and alcohol : it can also be obtained
by decomposing sodium succinimide with mercuric chloride. A basic
copper derivative is obtained when sodium succinimide is treated with
copper acetate. It is easily soluble in water. When dried at 100°, it
has the composition C8H804N2Cu,Cu02H2,2H20.
Ethyl- succinimide. — The author dissolved succinimide in absolute
alcohol, and treated the solution with the theoretical amount of
sodium ethylate and ethyl iodide. As soon as a considerable amount
of sodium iodide was formed, carbonic anhydride was passed into the
mixture until no further precipitate was obtained. The solution was
then filtered and the filtrate distilled. On fractionating, a portion
was isolated which boiled constantly between 232 — 234°, and re-
mained liquid at —12°. When distilled with potassium hydroxide, it
yields ethylamine. Menschutkin found the boiling point of ethyl
succinimide, obtained by distilling ethylamine succinate, to be 234°.
J. I. W.
Constitution of some Azobenzenedisulphonic Acids. By P.
RODATZ {Annalen, 215, 125 — 172). — The methods employed for pre-
paring these acids are : — 1. By reducing nitro-acids with sodium
amalgam or zinc-dust and sodium. 2. By oxidising amido-acids with
potassium permanganate. 3. By dissolving azobenzene in fuming
sulphuric acid. The first two methods yield azo-acids whose com-
position may be known with certainty, provided that the nitro- or
amido-acids employed be known. The third method, on the other
hand, gives azo-acids of unknown constitution.
By heating azobenzene with fuming sulphuric acid, two azoben-
zenedisulphonic acids are formed — a and ji. The former probably
has the composition SO3H.C6H4.N2.C6H4.SO3H [SO3H : SO3H = 4:4],
as it is also obtained by oxidising paramidobenzenesulphonic acid
with potassium permanganate. This is confirmed by its behaviour
478 ABSTRACTS OF CHEMICAL PAPERS
when treated with hydrochloric acid at 150°, wheii it yields an amido-
ncid. On heating the potassium salt or the chloride (m. p. 222°)
with hydrochloric ncid at 150" in a sealed tube, paramidobenzene-
sulphouic acid is obtained. When the chloride of iS-azobenzcnedi-
sulphonic acid (m. p. 120'^) is heated with hydrochloric acid in a
similar manner, it yields paramido- and metamido-benzenesulphonic
acids. The former is the less soluble. The latter separates from an
aqueous solution in thin white needles containing water of crystal-
lisation and effloresce on exposure to the air ; their solution becomes
red when evaporated. When treated with bromine, it yields dibrom-
araidobenzenesulphonic acid : with excess of bromine, it forms brom-
aniline. The acid, therefore, which is formed along with paramido-
benzenesulphonic acid must be metamidobenzenesulphonic acid, and
the composition of the azobenzenedisulphonic acid probably
SO3H.C6H4.N2.C6H4.SO3H [SO3H : SO3H = 3:4].
The same acid is formed by the oxidation of a mixture of equal parts
of the potassium salts of meta- and para-amidobenzenesulphonic acids.
In the same manner other similarly constituted azo-acids can be pre-
pared. The author, from want of material, was unable to make
experiments with the ortho-acid. J. I. W.
Brominated Azobenzenedisulphonic Acids. By P. Rodatz
{Annalen, 215, 217 — 227). — The acids were prepared from bromi-
nated amidobenzenesulphonic acids of known constitution by oxida-
tion with potassium permanganate.
Tetrabromazohenzenedistdphonic acid, Ci2H4Br4N2(S03H)ol4HoO
[SO3H : Br : Br : SO3H : Br : Br = 3 : 4 : 6 : 3 : 4 : 6]. The di-
bromamidobenzenesulphonic acid from which it was prepared was
obtained by acting on metamidobenzenesulphonic acid with bro-
mine. Its constitution is 06H2Br2(NH2).S03H [NH2 : SO3H : Br: Br
= 1:3:4:6]. A dilute aqueous solution of the potassium salt was
gradually mixed with a 5 per cent, solution of potassium perman-
ganate at 45°. In order to convert the amido-acid into the azo-com-
pound it is necessary to employ about four times the theoretical amount
of potassium permanganate, a part of the amido-acid undergoing
further oxidation.
Tetrahromazobenzenedisulphonic acid, prepared by decomposing the
barium salt with, sulphuric acid, separates from the concentrated
solution in thin red needles which are soluble in water and alcohol.
The potassium salt, Ci2H4Br4N2(S03K)2,3H20, forms small regular hex-
agonal plates of a red colour, easily soluble in hot water. The barium
salt, Ci6H4Br4N'2(S03)2Ba,H20, is precipitated from a solution of the
potassium salt on adding barium chloride as a heavy flesh-coloured
insoluble mass of small needles. The calcium salt^
Ci2H4Br4N2(S03)2Ca,4H20,
is prepared in a manner similar to the barium salt ; it forms yellowish-
red plates. The lead salt, Ci2H4Br4N2(S03)2Pb,2|H20, forms a heavy
red crystalline precipitate insoluble in water.
ORGANIC CHEMISTRY. 479
Tetrabromazobenzene disulpkochloride, Ci2H4Br4N'2(S02Cl)2, is pre-
pared by heating the potassium salt with phosphorus chloride and
treating the mass with water. The chloride remains undissolved as
a red powder, which is slightly soluble in ether, but more soluble
in benzene, from which it crystallises in fine red needles melting at
233°.
Tetrahromazohenzenedisulphamide, C6H4Br4N'2(S02N'H2)3, is prepared
by digesting the chloride for some time with concentrated ammonia.
The amide is very slightly soluble in water. It crystaUises from
alcohol in yellowish-red microscopic needles.
Tetrabromazobenzenedisulphonic acid loses its colour when heated
with stannous chloride solution, and yields slender white needles of
the dibromamidosulphobenzoic acid from which the azo-acid was pre-
pared. A hydrazo-acid could not be obtained in this manner.
Tetrahromh^jdrazohenzenedisulphonic acid has been prepared by
Jordan by treating hydrazometabenzenedisulphonic acid with bromine
and water. The author finds that when treated with potassium per-
manganate solution, it yields the potassium salt of tetrabromazoben-
zenedisulphonic acid. The barium salt and the chloride cannot be
obtained in a crystalline form.
By oxidising dihromorthannidohenzenesulphonic acid the author was
unable to obtain the potassinm salt crystalline, resinous matters being
formed.
Tetrabromazo'henzenedisulpli07iicacid,0i^^^v^'i{^0^)2,'^^20. — The
acid obtained by Schmidt from paramidobenzenesulphonic acid whose
composition is CcH2Br2(NH2).S03H [SO3H : Br : NH3 : Br= 1:3:4:5],
yields the above acid on oxidation. Its structure is
SO3H.C6H2Br2.N2.C6H2Br2.SO3H [Br : SO3H : Br = 2 : 4 : 6].
The free acid prepared from the barium salt crystallises in glittering
red plates, soluble in water and alcohol. The potassium salt,
Ci2H4Br4N2(S03K)2,2H20,
forms long plates of a dark red colour, slightly soluble in cold water,
more freely in hot. The barium salt, Ci2H4Br4N2(S03)2Ba,3H30, forms
a heavy flesh-coloured precipitate consisting of fine microscopic needles,
insoluble in water. The calcium salt, Ci2H4Br4N2(S03)2Ca,4H20, pre-
pared by treating a solution of the potassium salt with calcium chloride
solution, crystallises in red rhombic plates easily soluble in hot water.
The lead salt, Ci2H4Br4N2(S03)2Pb, forms a brownish-red precipitate
consisting of small groups of crystals.
Tetrabromazobefizene disulphochloride, Ci3H4Br4N2(S02Cl)2, is obtained
by melting the potassium salt with phosphorus chloride. It forms a
brown powder which is slightly soluble in ether, but freely soluble in
benzene, from which it crystallises in yellowish-brown plates melting
at 258— 262^
Tetrabromazobenzenedisulphamide, Ci2H4Br4!N'2(S02N'H2)2, is obtained
by heating the chloride with concentrated ammonia for some time. It
crystallises from ammonia and alcohol in long silky violet needles.
On boiling the tetrabromazobenzenedisulphonic acid with stannous
480 ABSTRACTS OF CHEMICAL PAPERS.
chloride, a dibromamidobenzenesulphonic acid is obtained. A hydrazo-
acid could not be detected.
Hexbromazobenzenedisulphomc acid, Ci2H2Br6N2(S03H)2,H20, is
prepared from tiibromamidobenzenesnlphonic acid (derived from
metainidobenzenesulphonic acid). It therefore has the constitution
[Br : Br : SO3H : Br = 2:4:5:6]. Potassium permanganate only-
acts on a solution of the potassium salt of the amido-acid at 70 — 80°.
The free acid prepared from the barium salt forms thin yellow needles
extremely soluble in water and alcohol. The potassium saltj
Ci3H2Br6N2(S03K)2,3H20,
crystallises in silky lemon-yellow thin needles which are slightly
soluble in cold water and easily dissolve in hot wafer and alcohol. The
harium salt, Ci2H2Br6N2(S03)2Ba,2H20, forms large yellowish-red
prisms, slightly soluble in hot water. The ealcmm salty
Ci2H2Br6N2(S03)2Ca,7H20,
crystallises in red-pointed plates slightly soluble in cold water. The
lead salt, Ci2H2Br6N2(S03)2Pb,4H20, is prepared by neutralising the
acid with lead carbonate. It forms yellow hexagonal pyramids slightly
soluble in cold water.
Hexhromazohenzene disidpho chloride, Ci2H2Br6N2(S02Cl)2, is pre-
pared by acting on the potassium salt with phosphorus chloride. It
forms a red powder which crystallises from benzene in deep violet
plates (m. p. 222 — 224°). Hexhromazobenzene disiLlphamlde,
Ci2H2Bre]S"2(S02NH2)2,
forms yellowish-brown crystalline masses, slightly soluble in hot water
and alcohol. On boiling it with stannous chloride solution, the acid is
converted into an amido-acid. A hydrazo-acid could not be obtained.
J. I. W.
Jaflferabad Aloes. By W. A. Shenstone (Pharm. J. Trans. [3],
13, 461 — 462). — The author has found the alo'in extracted from
Jafferabad aloes to be similar to Tilden's zanaloin, the crystalline form
and most of the reactions being alike. The author suggests a scheme for
naming aloins. Thus he divides them into two classes : 1. Natalohi^,
like that obtained from Natal aloes, which yield only picric and oxalic
acids by treatment with nitric acid and are not reddened even on
heating with it. 2. Barbaloins, which yield chrysamic, aloetic,
picric, and oxalic acids, and are reddened by nitric acid, a- Barb aloins
from Barbary aloes are reddened in the cold by ordinary strong nitric
acid. ^-Barbaloins from Socotrine, Zanzibar, and Jafferabab aloes
are coloured only on heating by ordinary, but in the cold with fuming
nitric acid. D. A. L.
Certain Substances obtained from Turmeric. By C. L. Jack-
son and A. E. Menke (Amer. Chem. /., 4, 360 — 368). — In a former
paper (Abstr., 1882, 1107) the authors described the preparation
ORGANIC CHEMISTRY. 481
and properties of onrcnmin, the yellow colouring matter of turmeric^
and showed that it may be represented by the formula
CuHu04 = C6H3(CH.C5H5.COOH)(OMe)(OH).
In the present paper they describe the products obtained from it. by
the action of nascent hydrogen and of bromine.
Cur cumin Bihydride, Ci4Hie04, obtained by the action of sodium-
amalgam and water on curcumin, is a brownish- white powder, melting
near 100°, insoluble in water, freely soluble in alcohol and glacial
acetic acid, slightly in ether, insoluble in benzene and light petroleum.
It dissolves in strong sulphuric acid with reddish-brown colour, in
caustic soda and sodium carbonate on warming ; the latter solution,
however, depositing a brown precipitate as it cools.
An Anhydride of Curcumin Dihydride, C28H30O9 = (Ci4Hi504)20,
obtained by heating curcumin with acetic acid of 85 per cent, and a
large quantity of zinc-dust, at a temperature below the boiling point of
the acetic acid, is a dirty white powder closely resembling the dihy-
dride, and melting gradually near 120°. It is nearly insoluble in
ether, light petroleum, and benzene, slightly soluble in chloroform,
more soluble in alcohol and glacial acetic acid, from which it is
deposited on evaporation as a varnish. It dissolves with yellow colour
in aqueous potash, and with brown colour in a boiling solution of the
carbonate, but without forming a definite potassium salt.
When diethylcurcumin, obtained as described in the authors' former
paper, is treated with acetic acid and zinc-dust, it yields a mixture of
di- and mono-ethylcurcumin dihydride, which is slowly oxidised by
potassium permanganate, yielding ethylvanillic acid, together with
a small quantity of ethylvanillin, indicated by its characteristic smell.
Teb'ahromocurcumin, Ci4HioBr404, is formed by the action of bromine
in excess on curcumin dihydride dissolved in acetic acid. The liquid
left over night turns black, and on addition of water yields the tetra-
bromo-compound, as a red amorphous precipitate which does not melt
below a red heat, but seems to decompose without melting. It is
insoluble in water, light petroleum, and benzene, very slightly soluble
in alcohol and ether, more freely in glacial acetic acid ; not acted on
by strong sulphuric acid, but vigorously attacked by boiling aqueous
potash, forming a red solution, from which acids precipitate a black
tarry body nearly free from bromine, whence it may be inferred that
all the bromine in the original substance is situated in the side-chain.
Curcumin Tetrabromide, Ci4Hi4Br404, is formed on leaving curcumin
suspended in carbon sulphide in contact with excess of bromine for
some hours, and is left, as the solvent evaporates, as a whitish amor-
phous substance, melting with decomposition near 185°, insoluble in
water, soluble with decomposition in alcohol and glacial acetic acid,
very slightly soluble in ether, chloroform, and carbon bisulphide, in-
soluble in light petroleum and benzene. Potassium hydroxide and
silver oxide convert it into vanillin; aniline and metallic zinc act
•opon it, the former with considerable evolution of heat.
Fentahromocur cumin Bihroviide, Ci4H9Br704, is obtained by treating
curcumin dissolved in glacial acetic acid with excess of bromine, or the
482 ABSTRACTS OF CHEMICAL PAPERS.
solid tetrabromide with bromine, as a red amorphotis substance melting
near 120°, insoluble in water and in light petroleum, soluble in alcohol,
ether, and glacial acetic acid, slightly soluble in benzene. Strong
sulphuric acid acts on it but slowly. When heated alone, it gives off
bromine and hydrobromic acid, leaving a black tar from which alcohol
extracts a yellow, substance containing bromine. Sodium hydroxide,
sodium carbonate and water, and sodium ethylate and water all act
upon it, but no smell of vanillin has been observed in either case. The
same is true of the action of several oxidising agents, and this would
seem to indicate the presence of part of the bromine in the benzene-
ring. It is remarkable that this substance is but very slowly attacked
by chromic acid mixture and by potassium permanganate, both of
which act vigorously on curcumin. H. W.
Turmeric Oil— Turmerol. By C. L. Jackson and A. E. Menkb
(Amer. Ghem. J., 4, 368 — 374). — This oil, to which turmeric (and
therefore curry-powder) owes its aromatic taste and smell, was ex-
tracted from Bengal turmeric with light petroleum, and after being
freed from the higher-boiling portion of that solvent by heating to
150° in a flask, formed a thickish oily yellow liquid having a pleasant
aromatic odour. It was purified by fractional distillation under
diminished pressure, and was thereby separated into three portions,
the first boiling JdcIow 193°, the second at 193 — 198°, and the third
consisting of a viscous semi-solid residue. The middle portion con-
sisted of nearly pure turmerol ; the first, of that compound contami-
nated with hydrocarbons from the petroleum. The middle fraction,
after further purification by distillation in a vacuum, gave, as a mean
result of several analyses, 83*62 per cent, carbon and 10*42 hydrogen,
agreeing nearly with the formula CigHogO, which requires 83'8l C
and 10-29 H.
Turmerol is a pale yellow oil having a pleasant, moderately strong
aromatic smell, and a density of 0*9016 at 17°. It is optically dex-
trogyrate, [a]D = 33'52. Under ordinary pressure it boils at
285 — 290°, but decomposes at the same time, yielding a substance of
lower boiling point. Under 60 mm. it boils at 193 — 198^, still however
with slight decomposition. It is essentially insoluble in water, but
mixes readily with all other ordinary solvents. It does not unite
with acid sodium sulphite.
Turmerol is an alcohol, and is converted by heating at 150° with
strong hydrochloric acid into turmeryl chloride, C19H27CI, which is
a pale brownish fragrant oil decomposed by distillation. The same
compound is formed, but less definitely, by treating turmerol with
phosphorus trichloride ; the pentachloride appears to act partly in the
same manner, but at the same time to add chlorine. By treating tur-
meryl chloride with boiling water, and with alcoholic solution of
sodium acetate, potassium cyanide, or ammonia, substances are
obtained having the characteristic odours of the classes to which they
belong, but they have not yet been obtained pure. Turmerol treated
with sodium yields a semi-solid mass having the composition of sodium
turmerylatej Ci9H270Na.
Isohutyl turmerylatey C19H27.OC4H9, prepared by boiling the sodium
ORGANIC CHEMISTRY. 483
compound with isobutyl iodide in a reflux apparatus, is a heavy
yellowish fragrant oil. The ethylic ether is a similar substance.
Oxidation of Turmerol. — By the action of a hot aqueous solution of
potassium permanganate in excess, turmerol is oxidised to tere-
phthalic acid. With a cold solution of the same salt, not in excess,
it appears to yield some new acids, with the study of which the authors
are at present occupied. H. W.
Hypochlorin and its Formation. By A. B. Frank (Bied. Centr.,
1882, 856). — Certain observations made go to prove that hypochlorin
is the result of the action of acids on the decomposition products of
chlorophyll ; and Pringsheim's reaction may always be obtained in an
acidified alcoholic extract of dead green plants. E. W. P.
Nature of Pringsheim^s Hypochlorin Crystals. By A. Meyer
(Bled. Centr.y 1882, 857). — The author agrees in the conclusions
arrived at by Frank (preceding abstract) ; he considers hypochlorin
to be identical with Hoppe-Seyler's chlorophyllan. Perfectly dry
glacial acetic acid is a better reagent than hydrochloric acid for hypo-
chlorin, as it dissolves chlorophyll more readily. E. W. P.
Researches on Pyridine. By H. Weidel and M. Russo (Monatsh.
Chem.^ 3, 850 — 885). — Anderson, by heating pyridine with sodium,
obtained a base which he regarded as diiiyridine, CioHmNa, together
with other products. The authors of the present paper, following
Anderson's process, with some modifications, for which we must refer
to the original paper, have also obtained dipyridine, but they find that
the chief products are : a base, CioHgO?., isomeric with the dipyridyl
which Skraup and Vortmann obtained by distilling dipyridyl-car-
boxylic acid, Oi2H8N"204, with lime (p. 85 of this volume), and isonico-
tine, C10H14N2.
The base, CioHgNj, thus obtained is distinguished by the authors as
" 7-dipyridyl."* It may be purified by crystallisation from boiling
light petroleum, from which it separates in crystals on cooling ; and
distilling it in a current of steam. It dissolves very readily in alcohol,
ether, benzene, and chloroform, somewhat less in ether, and is nearly
insoluble in cold, but easily soluble in hot water. When heated, it
melts and sublimes in long needles. Small quantities of it volatilise
with vapour of water. The aqueous solution has a faintly alkaline
reaction. The base has a bitter taste, no smell at ordinary tempera-
tures, but when heated it gives off faintly odorous cough-exciting
vapours. It melts at 114° and boils at 304-8° (bar. 760 mm.).
These are the properties assigned by Anderson to his dipyridine,
CioHioNa. The authors, however, find that the base in question gives,
as a mean of several closely agreeing analyses, 76*87 per cent. C,
5*18 H, and 17"95 N, leading to the formula C10H8N2, which requires
* The designation of an organic base by a name ending in yl (a termination
usually applied to alcoholic or acid radicles) is somewhat anomalous j a better- name
would perhaps be dehydrodifyridine. — H. W.
484 ABSTRACTS OF CHEMICAL PAPERS.
76-92 C, 5-13 H, and 17-96 N. This formnla has farther been con-
firmed by the analysis of several salts.
The anhydrous crystals of 7-dipyridyl absorb wat«r from the air
with great avidity, the meltiDg point of the hydrated substance thus
formed, sinking, according to the time of exposure, to 107°, 104°, 96°,
and finally to 73°, which last is the melting point of the crystals
deposited from aqueous solution. The hydrate, CioH8N2,2H30, thus
obtained, gives off the greater part of its water at 100°, the remainder
only on distillation.
r^'Dipyridyl Methiodide, CioH8N2,2MeI, is formed on adding methyl
iodide in excess to a solution of the base in methyl alcohol ; and sepa-
rates on evaporation over sulphuric acid, in large, yellow-red, highly
lustrous, monoclinic crystals, OP . ooP. Treated with potash-lye or
silver oxide, it does not yield the corresponding base in definite form.
The reaction above described shows that 7-dipyridyl has the character
of a tertiary amine.
Oxidation of (^-Dipyridijl. — This base in the free state offers great
resistance to the action of oxidising agents, but in the form of sul-
phate it is easily oxidised by potassium permanganate, yielding pj/W-
dine-TYionocarboxylic or isonicotinic acid, according to the equation
20ioHg]^2 4- 230 = 2(C6H4lSr.COOH) -\- 8CO2 + SH^O + N2. This
acid, after purification, forms a white crystalline mass melting at 307°,
and identical in every respect with that which Weidel and Hiibner
obtained by oxidation of nicotine (this Journal, 1873, 508).
Action of Nascent Hydrogen. — 7-Dipyridyl treated with tin and
hydrochloric acid takes up 6 at. hydrogen, and is converted into
isonicotine: CioHgNa + 3Sn + 6HC1 = 3SnCl2 + CioHuNz. This
base, separated from the product in the usual way, and purified by
drying in a vacuum at 150", and subsequent distillation in hydrogen,
forms a colourless oil, which solidifies on cooling to a mass of slender
needles, and turns yellow in the air, especially in the fused state. It
is extremely hygroscopic, deliquesces in water, alcohol, or wood-spirit,
and dissolves readily in ether, light petroleum, and benzene. It has a
strongly alkaline reaction, and cauterises the skin like caustic potash.
When pure, it is nearly scentless at ordinary temperatures, but when
gently heated, it emits a faint odour somewhat like that of commercial
opium ; at higher temperatures, it emits a pungent vapour. It
has an aciid alkaline taste, and acts on the animal economy as a
poison, like nicotine, but much less strongly. In aqueous solution,
and especially when neutralised with sulphuric acid, it is easily oxi-
dised by potassium permanganate to isonicotinic acid. Its salts are
deliquescent, and crystallise with difficulty, even from the most con-
centrated solutions. The methiodide, CioHuN2,2MeI, crystallises from
its solution in methyl alcohol by spontaneous evaporation, in monoclinic
or triclinic crystals.
Isonicotine, as already observed, is also found among the products
obtained by the action of sodium on pyridine; and its formation,
together with that of 7-dipyridyl and dipyridine, is supposed by the
authors to take place by two stages, the first consisting in the forma-
tion of sodium- pyridine, CsHiNaN, and certain products formed there-
from by addition of hydrogen ; the second in the action of the air on
ORGANIC CHEMISTRY. 485
these products. This series of actions may, perhaps, be represented
by the following equations : —
I. 2C5H5N' + 2Na = 2C6H4]SraN + H^
CsHiNaN + H2 = CaHeNaN
CsH^NaN + He = CsHioNaN.
II. 2C5H4NaN + O = NaaO + doHsN,
y-Dipyridyl.
CsHeNaN + C5H4NaN + 0 = Na^O + CioHioN^
Dipyridine,
CjHioNaN + CsHiNaN + 0 = Na^O + CoHuNa.
Isonicotine.
Certain resinous and oily products of no decided basic character,
formed at the same time, are probably due to the further action of the
sodium on the dipyridyl or on the sodium-pyridine. H. W.
The Trapezohedral Hemihedry of Strychnine Sulphate.
By H. Baumhauee (Jahrb. f. Min., 1882, 2, Ref., 30) .—Although the
crystals show circular polarisation, yet they show no trapezohedral
faces ; on the basal planes, water or alcohol produces etching figures,
formed by the primary pyramid ; but dilute hydrochloric acid pro-
duces a series of furrows crossing each other at right angles, and
inclined 16° to the edges OP : P ; on the opposite basal plane the
furrows are similar, but inclined in the opposite direction. This beha-
viour proves the trapezohedral hemihedral nature of the crystals.
H. B.
Hydropiperic and Piperhydronic Acids. By E. Buri (Annalen,
216, 171 — 179). — When the action of nascent hydrogen on potassium
piperate takes place in a strongly alkaline solution, /3-hydropiperic
acid is produced, but if care is taken to keep the solution nearly
neutral, only a-hydropiperic acid is obtained. The ^-acid forms
needle-shaped crystals (m. p. 130°), which are somewhat less soluble
in water, ether, chloroform, alcohol, and carbon bisulphide than the
crystals of the a-acid (m. p. 78°). To separate the two acids, the
greater solubility of the ammonium salt of the /3-acid is made use of ;
a-hydropiperic acid is converted into its isomeride by solution in warm
soda-lye.
a-Hydropiperic acid unites with bromine, yielding a dibromo-addi-
tion-product, CiaHiaBraOi, but when the )3-acid is treated with bromine
it forms a monobromo-substitution-product, CiaHuBrOi (m. p. 170°).
Pijperhydronic acid, C12H14O4, obtained by the action of sodium-
amalgam on a warm aqueous solution of /3-hydropiperic acid, or
preferably its monobromo-derivative, is deposited from an alcoholic
solution in colourless plates (m. p. 96^) soluble in the solvents for
hydropiperic acid.
When calcium piperhjdronate J (Ci2Hi304)2Ca -f H2O, is treated with
hot water, a portion dissolves, and the remainder melts.
w. c. w.
486 ABSTRACTS OF CHEMICAL PAPERS.
Action of Invertin. By A. Mayer {Bied. Centr., 1882, 850).—
There seems to be no relation between the action and the amount of
invertin in a solution. Invertin is not destroyed by its own action.
Temperatures which have no efPect on invertin when active, are
destructive to it when it is alone and quiescent. Neither bacteria nor
light have any influence on this ferment. E. W. P.
Physiological Chemistry
Behaviour of Ozone with Blood. By C. Binz (Chem. Gmtr.,
1882, 810). — Traces of ozone introduced into the blood give rise to
the formation of metahsemaglobin, the ozone being itself quickly and
completely destroyed by admixture with blood ; this is the accepted
view, which is now disproved by the author's experiments.
When a continual current of ozonised air, strong enough to produce
irritation of the throat and chest within a minute, is passed through
400 — 500 CO. of defibrinated calf's or sheep's blood, after one hour the
blood has undergone no apparent chaiige, either spectroscopically or
microscopically. Its alkalinity, however, is greater than that in a
check sample acted on by air alone. By prolonging the action the
colour corpuscles are ultimately attacked. The ozonised blood Yery
quickly undergoes the usual changes incident to blood. Smaller quan-
tities (5 — 30 c.c.) of blood, treated in a similar manner, soon become
dark, and after an bour resemble strongly reduced blood, whilst air
alone does not change the colour. In the spectrum there are oxygen
bands, along with which, on the following day, are metahaemoglobin
bands, similar to those seen in blood treated with iodine. The microscope
reveals, amongst other things, fragments of red corpuscles, all of
them being puffed up and globular. Fresh dog's blood (30 c.c.) mixed
with 30 c.c. of a 7 per cent, salt solution, and subjected to the ozonised
air treatment is not coagulated after 90 minutes, but dark red oxygen
bands are evident ; the corpuscles are distended. With further treat-
ment, the blood becomes thick as treacle, red-brown in colour, and
metahasmoglobin bands develope. After a day, the corpuscles disappear
and tbe metahaemoglobin increases. A specimen of this ozonised blood
kept in a closed vessel had no putrid odour even after some weeks.
The blood which does not come in contact with the current of gas
remains red. Solutions of crystalline oxygenated haemoglobin treated
with ozonised air become turbid and brown in less than 10 minutes,
and finally separate itito a yellowish liquid with acid reaction, and a
dirty grey fibrous albumin. Soda retards the decomposition of the
hsemoglobin. Ozonised air was passed through 350 c.c. of blood in a
column 15 cm. high, and also through another 300 c.c. of blood 42 cm.
high ; in both cases ozone could be distinguished by odour and by starch
paper when the bubbles on the surface were pricked, or even when they
were left to burst by themselves, being thus enclosed in the blood film
for some minutes. These tests were continued an hour with the same
PHYSIOLOGICAL CHEMISTRY. 487
results ; no hydrogen peroxide is formed. The blood was changed in
the same way as described above. The author estimates the ozone by
a new method. A measured quantity of the ozonised air is shaken
with mercury, which becomes oxidised at the expense of the ozone ;
the mercuric oxide is dissolved out with acetic acid, converted
into chloride, precipitated with sulphuretted hydrogen, and weighed
as sulphide. From this weight, the amount of ozone is easily calcu-
lated. D. A. L.
Digestibility of Casein from Warmed Milk. By M. Hoffmann
(Chern. Gentr., 1882, 811). — Rennet precipitates casein in compact
masses, both from raw and warmed (short time at 50 — 70°) milk.
Slight concentration of the rennet solution or the previous warming
of the milk simply retards the curdling. If, however, the milk is boiled,
or kept for two hours at 70° (Becker's method of milk preservation), a
fine flocculent curd forms. Digestion experiments were tried with
artificial gastric juice, and the amount of peptones formed determined
colorimetrically show that Becker's preparati(m yields most, boiled milk
comes next, and raw milk least in quantity of peptones. Becker's
milk does not turn sour, but after a few days decomposes with an
unpleasant odour. D. A. L.
The Digestive Pluids and Digestion of the Horse. By Ellen-
BERGEE and HoFMEiSTER (Bled. Gentr., 1882, 805 — 810). — In a previous
communication (Abstr., 1882, 1119), the properties of the various
fluids which form saliva were stated. In the present article the
physiological action is more extensively considered and examined
experimentally. The mixed saliva contains a powerful diastatic fer-
ment, which completely converts a small quantity of starch into achroo-
dextrin and sugar within a quarter of an hour, also the action com-
mences immediately ; but if coarsely powdered starch is used, then a
short time elapses before the commencement of the conversion. Potato-
starch is not converted into sugar in the mouth, yet a small portion
of the starch of oats and barley is there converted. Both the parotid
and submaxillary fluids contain a saccharifying ferment, and the action
of these fluids when mixed is equal to the sum of their action when
alone. A small amount of a diastatic ferment is found in the blood,
in most of the organs, and in the watery portion of the excrement.
Slightly acidifying the saliva, and mixing it with artificial acid gastric
juice does not destroy its power, although a large addition of acid
causes the action to cease, without, however, destroying the ferment ;
in fact the action is stronger when the fluids are acid than when
neutral. Cane-sugar is but slowly altered. The parotid secretion
contains a trace of a peptonising ferment ; the mixed salivas have no
effiect on cellulose, nor on fat, save that with it they produce an emul-
sion, especially the parotid secretion. So far these statements refer
only to the reactions in the mouth, the next portion of the experiments
dealt with the changes occurring in the stomach. The digestion of
horses continues from one feeding time to another, for if a feed is
omitted, the digestion still goes on, but slowly, and food may be found
in the stomach even when 24 hours have elapsed between the feeds.
488 ABSTRACTS OF CHEMICAL PAPERS.
The contents of the stomach, when oats are sapplied, Is a crambly
mass containing 60 — 70 per cent, water ; with hay the contents con-
tain 75 — 80 per cent, water, and at all times have an acid reaction, the
percentage of the acid in the liquid portion seldom exceeding 0'2 pef
cent., being lowest, 0*08 per cent., immediately after eating ; thus it
appears that the acidity of the stomach of the horse is below that of
the Carnivora. The acids present are lactic acid, followed by hydro-
chloric acid, the former never failing, and being most abundant with
oats, whilst, with hay as fodder, hydrochloric is the principal. There is
likewise found in the stomach an albuminous and lactic ferment, also
a ferment which dissolves starch, and one which coagulates milk.
The conversion of the starch occurs for the most part in the stomach ;
if food has been freely given, the conversion is but slow, and lasts
longer; this happens because at least two-thirds of the fluids present
consist of alkaline saliva, and so a considerable time must elapse before
sufficient acid is secreted to prevent the conversion ; the percentage of
sugar present is 0*2 — 1*0. Vegetable albumin is rapidly digested, and
converted into peptone ; the process commences slowly, and increases
rapidly, but the intensity is dependent on the amount of food given,
for frequently there will not be enough pepsin and acid present to
convert a large feed. In such a case, if another feed is given, the first
is in part lost, as it is passed on into the intestines in an undigested
state. After oats, 0*3 per cent, of peptone is present, which later on
increases to 1*5 ; the absolute quantity may be at times 40 grams, but
after hay the quantity is much less, being only 0'26 per cent., or
5 grams. E. W. P.
Hygienic Action of Maize as Fodder. By M. Chatin (Bied.
Centr., 1882, 803). — This article was written in consequence of a
notice published by Fua, on the raising of a large-grained early-ripen-
ing variety of maize. By reason of its pleasant-tasting oil, and easy
digestibility, maize forms a valuable food for man and beast; and
where it is much eaten by men, diseases of the bladder, epilepsy, and
phthisis are unknown. But maize may at times be harmful, and then
it will be found to be a bearer of penicillium, aspergillus, &c. Diseased
grains contain a reddish oil, and also a neutral alkaloid ; where cheap
and therefore probably diseased maize is used, pellagra is prevalent,
hut this disappears if the grain be previously dried in ovens.
E. W. P.
Alkalinity and Diastatic Action of Human Saliva. By R. H.
Chittenden and J. S. Ely (Amer. Chem. J., 4, 329 — 333). — The
authors' experiments were made upon saliva obtained from 14 different
persons, all, with one exception, being men between the ages of 20 and 30.
The secretion of the saliva was accelerated by chewing a piece of pure
india-rubber. The saliva was collected generally an hour or two after
breakfast, and was at once filtered through paper in an atmosphere
free from ammonia. A portion of the filtered liquid was then at once ,
neutralised with standard acid, to determine the alkalinity, while
another portion was used to determine the diastatic action of the saliva
by its power of converting starch into sugar. The experiments, the
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 489
numerical results of which are given in tables, led to the following
conclusions : —
1. Saliva from different individuals may show a constant difference
in alkalinity, although in the majority ot" cases the alkalinity varies
only within narrow limits. — 2. Saliva secreted by the same individual
at different times has within certain limits a constant degree of alka-
linity.— 3. While saliva from different individuals shows in several
cases a decided and constant difference in alkalinity, there is no corre-
sponding difference in diastatic action which is at all constant.
Hence it appears that the variations of alkalinity are comprised within
limits too narrow to exercise any appreciable influence on the diastatic
action of the saliva. H. W.
Chemistry of Vegetable Physiology and Agriculture.
The Test for Life. By L. Keetzschmar (Bied. Gentr., 1882,
830). — Loew and Bokorny's reagent (alkaline silver solution), which
they recommend as a test for living or dead albumin, is untrust-
worthy ; the protoplasma of living or dead spirogyra is blackened by
the silver, so that no distinction could be drawn between the two.
Also cells which had been exposed to the solution containing no silver
became grey, and the alkali itself kills the protoplasma. The author
finds no difference between the actions of strong and dilute silver
solutions. Loew states that living cells are only slightly blackened
by the strong solutions, for the cells are rapidly killed.
E. W. P.
Influence of Oxygen on Fermentation, By F. Hoppe-Seyler
(Bied. Gentr., 1882, 860). — Cane-sugar in the presence of ferment
and oxygen is inverted, but not fermented to alcohol ; acid is formed
at the same time, and the microscope shows the presence of much
micrococcus and mycelium.
Animal matter in the presence of oxygen is readily altered, and the
more easily, the larger the supply of oxygen, reduction-products such
as sulphuretted hydrogen being formed. E. W. P.
Contributions to the Dissociation HypotL>esis. By W. Detmeb
(Bied. Centr., 1882, 831). — The action of dilute phosphoric acid and
of chloroform on diastase and on germination has been studied, and it
appears that certain substances, such as chloroform, do not destroy
the action of the ferment, but do destroy plant cells; on the other
hand, some substances, such as phosphoric acid, arrest the power of
the ferment, but do not destroy the plant cells.
From these observations, the author infers that the fermentation
theory as a starting point for the explanation of the origin of life pro-
cesses is untenable. E. W. P.
VOL. XLIV. / 2 I
490 ABSTRACTS OF CHEMICAL PAPERS.
Effect of Steeping and Drying on the Germination of Seeds,
as also the Value of Sprouted Grain for Seed. Bj H. Will
(Bied. Centr., 1881, 821 — 826). — Samples of the usual agricultural
Reeds of Swedish origin were steeped for 12 and 24 hours, and then
dried. Another set of samples were soaked for 12 hours, and then
allowed to germinate between sheets of moist paper, and these latter
were then sown at different stages of germination. The observations
made show that steeping for 12 hours has no effect, whilst soaking for
.24 hours is detrimental to germination. Some seeds are unable to
endure the interruption in the germination, but in this case adventi-
tious roots and axillary buds are formed; the further germination has
proceeded, the more prone are the seeds to rot during their subsequent
growth. Monocotyledons are more hardy than dicotyledons. Of the
first, barley and oats are the most delicate ; of the second, buckwheat
and peas, and especially maize. E. W. P.
Part played by Lime in the Germination of Seeds. By A. v.
Ltebenberg (Ghem. Centr., 1882, 806 — 809). — Previous experiments in
this direction have been made by Bohm and by Raumer and Keller-
mann; the experiments were, however, only made on one kind of
plant, phaseolus muUiflorus, the result indicating that lime is actually
necessary for the growth of the young plant. The author has set
himself to answer the questions : Are these experiments on phaseohcs
muUiflorus correct ? Is lime necessary for other plants also ? Are not
other minerals also useful to the young plant ? What function does
lime perform in the growth of the plant ?
To this end several series of cultivations of seeds of various plants
were very carefully conducted in distilled water, in well water, in
water containing lime, in Knop's nutritive solution, and in many other
solutions of single salts, the concentration being always, equal to that
of Knop's nutritive solution. The apparatus employed consists of
glass vessels, which had been boiled in water for some days, covered
with a piece of tulle, previously washed with hydrochloric acid ; the
germinated seed when the young roots were 10 to 20 mm. long are
placed upon the net. The results arrived at are as follows : — 1. In
order to effect the consumption of the reserve nutritive matter of the
seed during the germination, an addition of lime is alsolutely necessary
in the following cases: — Phaseolus muUiflorus, Phaseolus vulgaris,
Pisum sativum, Vicia sativa, Ervumleiis, Ervum ervillay Medicago sativa,
Blcinus nfricanus, Soja hispida, Cucurhita pepo, Gucumis sativa,
Brassica oleracea, Gannahis sativa, Helianthus annmis, Zea mays,
2. The addition of lime is not necessary with Brassica napus oleifera,
Sinapis alha, Papaver somniferum,, Garum carvi; it is, however,
advantageous to Poly go7iumfagopy rum, Linum usitatissimum. 3. Com-
plete foods favour the development of the very young plant of PoZy-
gonum fagopyrum, Brassica oleracea, Brassica napus oleifera, Picinus
africanvs, Gucurhita pepo, Sinapis alba, Papaver somniferum, Helianthus
annwis^ Zea mays, Carum carvi. 4. Nutritives without lime promote
the development for a short time of Polygonum fagopyi-um and Zea
mays. 5. Medicago sativa requires other substances besides lime.
The greater number of the cultivations were conducted in the dark in
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 491
order to avoid assimilation ; some few were conducted by light as check
experiments. From time to time, the distilled water or solutions were
changed.
From these results, it is evident that some plants do require lime in
order that the reserve nutritive matter in the seed may become useful.
Some experiments have been conducted on plants requiring lime to
see if it is the root or the plant which is injured by the absence oi
lime. In the absence of lime, the roots appear to grow all right,
but the stems attain a certain height and then die off. The- roots
suffer partial plasmolysis both in solutions free from and containing
lime. If the roots are cut off, the young plant thrives in solutions
containing lime until all reserve food is exhausted, whilst it dies
in solutions free from lime. Again, if the seeds are first soaked in
water containing lime, and are then cultivated in distilled water, the
resulting plants are much stronger, and the reserve food is better
utilised than when they are not steeped. From these facts, it is
manifest that the roots are not injured by the absence of lime. The
author is of opinion that seeds of some plants do not contain sufficient
lime for the growth of the young plant, although after the plant is
dead, lime can still be found in the seed; it is,, however, not enough,
and not easily assimilable.
With regard to the function of lime, the author has come to no
positive decision. He, however, observes that when the plant becomes
sickly lime is always wanting in the parts immediately affected^ and if
these parts be treated with dilute lime solution the death of the plant
is avoided, and the whole of the reserve food is utilised.
Moreover, the falling off commences in- all cases at those- parts of the
plants where the growth has been most vigorous, that is, where the
cells have become stretched ; it would seem from this that lime has
something to do with the formation of the cells. D. A. L.
Researches on the Growth of the Maize Plant. By R. Horn-
BERGER and E. v. Raumer {Bied. Geniv., 1882, 837 — 8M). — Each
separate portion of a maize plant, viz., roots, leaves, &c.^ was examined
for ash, nitrogen, &c., plants of different ages being employed in each
case. In preparing the ash, Strecker's^ method for the prevention of
the formation of pyrrophosphate by means of baryta was made use of,
and Stutzer's directions for the estimation of nitrogen in the forms of
albumin and amides were followed. The percentages given are on
100 grams of dry matter in each portion af the plant, also the absolute
quantities calculated on 1000 plants are referred to. In the original
{Landw. Jahrhucher, 1882, 359) these figures are given in full, as well
as tables of curves representing the increase of each component as
affected by growth.
During the first two weeks of germination, the seed suffers loss
principally in mineral matter (phosphoric acid and potash), whilst of
the organic matter only fat and nitrogen are lost. During the second
week, amides are produced from the albuminoids, but in the third
week the loss in nitrogen, organic matter, phosphoric acid, is greatest,
whereas but little potash is removed. The greatest increase of the
plant occurs immediately after blossoming, and ceases some weeks
2 I 2
492 , ABSTRACTS OF CHEMICAL PAPERS.
before the grain is ripe ; tTie maximum increase occurs 14 weeks after
sowing, a second maximum occumng also three lyeeks earlier, at the
commencem^ent of the formation of the spadix. From the period of
blossoming and onwards, the stems increase in weight sevenfold,
whilst the leaves alter but little, and att the time when the grains fill
most rapidly, the stems and leaves lose dry matter. As regards
crude fibre, the increase goes side by side with the production of dry
matter, being for the first 14 weeks one-fourth of the dry matter, but
in the 15th week only one-thirteenth.
The highest relative amount of fibre is in the roots, then the
blossom, and lowest in the grain, the greatest absolute quantity being
found before blossoming in the leaves, later on in the stems. Before
the completion of the setting of the grain, the plant is relatively poor
in fat, aftor which an increase is observed; the seed contains the
greatest amount of fat, the stems less than the leaves, but both stems
and leaves finally yield up this fat to the seed- The non-nitrogenous
extractive matier increases with the fat up to the time of ripening; it
is present in the stems to the amount of 50 per cent, migrating after-
wards to the grain. The total nitrogen decreases gradually during
the whole period of growth, being at ripening time only one-third of
what was present during the fourth wee^k ; up to blossoming, the
leaves contain the principal quantity, later on the stems. The relation
to one another of the two forms in which nitrogen appears is very
varying, but generally they, like the total nitrogen, diminish in per-
centage up to the penultimate week of growth. In the last (16th)
week, the amides diminish largely owing to an increase in albuminoids,
at the same time, because of the absolute diminution of nitrogen,
albuminoids are formed from amides. The highest relative amount of
amides, 43 per cent, of the total nitrogen, was found in the 14th week
of the observations, viz., at the time when the maximum absorption
of nitrogen occurred ; albumin is found principally in the leaves,
stems, and seeds, whereas the spadix and stalk contain for the most
part amides. The maximum absolute increase in protein takes place
when the grain is forming (10th and 11th week) ; there is also a
second maximum during the 14th week, but at this period amides are
produced. It is evident that the subsidiary organs draw their supplies
of nitrogen from the stem in the form of non-albuminoid matter,
which is only transformed into albumin by the increased energy of
the later stages of growth. The author also considers that amides
are first formed from the assimilated nitrogen, then the albuminoids.
In the young plant, the percentage of ash is higher than in the old.
The leaves are richest in ash, which becomes more siliceous with age ;
this statement is also true for the stems. All the organs of the
plant, except blossom and spadix, are relatively poor in sulphuric
acid ; phosphoric acid likewise decreases with age, and the highest
absolute amount is found in the grain and spadix, but it continues to
be absorbed even after the dry matter no longer increases. The
leaves contain most lime where it increases during blossoming, whereas
it decreases in all the other parts.
There seems to be a definite relation between the lime and the
carbohydrates, for after the first assimilation maximum (11th week)
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
493
a redaction of both occurs in the 12th week, which is followed bj a
rise in the 13th.
Magnesia resembles lime in many points, but is; present in larg-est
quantities in the stem and grain, and not in the leaves. Potash
appears up to the blossoming period principally in the stem, and is
absorbed up to the time of maximum production af dry matter ; the
largest relative quantity is found in the young spadix. The observations
show that there is in the plant during its later stages- a less quantity
of potash than was originally present, which seems to indicate a
downflow of this substance back to the soil. The leaves contain
nearly all the soda, whilst in the stems is found the greatest amount
of the iron, whose assimilation seems to be irregular.
Attention is called to certain analogies between the various consti-
tuents : at the time of setting the ratio of phosphoric acid to potash
is 1 : 3, from that date the ratio is widened. Potash to nitrogen from
the 9th week onwards bears a ratio of 1 : 1*25 to one another. Lime
and magnesia bear a constant proportion towards each other, and it
seems probable that these two bases are indispensable for the forma-
tion of cellulose and carbohydrates. E... W. P.
Development of Wheat. By P. P. D^h^rain and Meyer (Ann.
Agron., 1882, 23 — 43). — This paper contains the authors' first year's
(1881) observations on the development of wheat, intended to be
supplementary to the researches of Pierre. They give detailed proxi-
mate analyses of the entire plant, the roots, the stems^ and the
heads at different phases of development, paying more attention to
the distribution of the organic constituents than to that of the ash
constituents. Their results are embodied first in a series of tables of
percentage composition of the various parts at the various dates, and
then in tables giving the weight in kilograms per hectare of the sub-
stances determined. The latter series of tables is reproduced here.
Entire Plant (excluding Boots) .
Mean total weight . . .
Mean total dry
weight
Water
Nitrogenous sub-
stances
Fat, chlorophyll, &c. . .
Cane-sugar
Glucose
Starch
Cellulose
Ash
Nitrogen
i^^O,
3l8t May.
kilos.
10,200
3,223
6,977
382
164
10
135
268
783
288
61
25
13th June.
kilos.
12 937
3,872
9,065
387
78
298
55
333
1,270
248
62
15
16th July.
kilos.
10,400
5,598
4,802
391
108
143
55
1,157
1,428
279
62
28
23rd July
(harvest) .
kilos.
7,425
5,974
1,451
399
86
30
52
1,847
1,911
289
64
28
30th July.
kilos.
5,090
4,311
779
306
48
39
8
1,374
1,228
241
49
24
494
ABSTRACTS OF CHEMICAL PAPERS.
Stems.
3l8t May.
13th June.
16th July.
23rd July
(harvest).
30th July.
Mean total weight. . . .
Mean dry weight ....
Water
kflos.
10,567
3,223
7,344
382
10
135
164
268
782 ,
288
61
25
kilos.
11,016
3,403
7,213
310
279
51
66
279
1,127
223
49
15
kilos.
5,655
3,207
2,448
184
71
26
51
546
1,191
167
29
14
kilos.
4,481
3,735
746
156
none
8
48
622
1,565
202
25
9
kflos.
3,085
2,634
451
Nitrogenous sub-
stances
Cane-sugar
134
none
GHucose
none
Fat, chlorophyll, &c.. .
Starch
29
415
Cellulose
1,074
167
Ash
Nitrogen
21
P„0-
7
Ears.
3l8t May.
13th June.
16th July.
23rd July
(haryest) .
30th July.
Mean total weight ....
Mean dry weight
Water
kilos.
kilos.
1,792
467
1,125
53
13
24
4
54
143
25
80
15
kflos.
4,645
2,389
2,256
211
57
70
24
1,031
236
102
34
12
kflos.
3.063
2,207
856
243
43
30
44
1,220
251
86
39
16
kilos.
1,944
1,676
268
Nitrogenous sub-
stances
Fat, chioropyhll, &c.. .
Cane-sugar
178
54
15
Grlucose
8
Starch
953
Cellulose
Ash
154
74
Nitrogen
28
PoO,
14
It was of course impossible to ascertain the total weight of roots per
hectare, but the percentage composition is given in the annexed
table : —
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
495
Roots {"per cent, of Dry Matter).
31st May.
13th June.
16th July.
23rd July
(harvest).
30th July.
Nitrogenous sub-
stances
Fat
kilos.
6-31
0-50
2-60
traces
9-31
38-24
13-50
1-01
6-41
0-86
kilos.
4-87
0-97
2-10
0^21
10-71
36 -80
7-29
0-78
4-71
0-34
kilos.
3-18
0-72
1-90
none
10-36
36-65
7-66
0-51
2-07
0-16
kilos.
2-50
0-63
1-03
none
9-87
38-24
7-80
0-40
1-39
0-11
kilos.
2-12
0-47
Cane-suffaiT
0-90
Glucose
none
Starch
9-25
Cellulose
40-40
Ash
7-86
Nitrogen ^ . .
0-34 .
P.2O5 per «ent. of ash. .
P.2O5 „ roots
1-43
Oil
The authors sum up thus : — (1.) In 1881, at Grignon, the total dry
matter of the wheat increased in weight up to the harvest. It was
only in those plots which were allowed to stand after the harvest that
a loss in dry matter was observed. This loss was considerable, and
demonstrates the advisability of reaping as soon as possible after
maturity. (2.) The gain in dry weight from 31st May to 23rd July
consisted of starch a,nd cellulose, the albuminoids and ash remaining
stationary during these last two months of growth. (3.) The ces-
sation in the assimilation of nitrogen and minerals appears to have
been due to the peculiarities of the season. Bright days favoured the
assimilation of carbohydrates, whilst drought hindered the assimila-
tion of nitrogen and minerals by the roots. J. M. H. M.
Comparative Effect of two Metameric Bodies on the
Growth of Nicotiana Longiflora. By J. E. Reynolds (Chem.
News, 46, 271). — In this paper, experiments and results thereof are
described, the subject being the action of ammonium thiocyanate and
its metameride, thiocarbamide, respectively on the growth of a variety
of the tobacco plant (Nicotiana longiflora). For the experiments, several
sets of three healthy plants were selected, the members of each set
being alike as regards height, number of leaves, and strength of stem.
The plants, potted singly in rather poor very sandy mountain loam,
were under glass, and so placed as to receive equal light and to prevent
excessive drawing up or splinding. Each set received the following
treatment : — No. 1 plant was watered, when necessary, with Vartry
water only. No. 2 was watered twice a week with a 0*2 per cent,
solution of pure thiocarbamide ; at other times was treated similarly
to No. 1. No. 3 was sometimes watered twice a week with a 0"2 per
cent, solution of ammonium thiocyanate. Following the changes of
one set, it was observed that No. 3 was the first to be visibly affected ;
for after the third treatment, not only was the growth checked and
development stopped, but the plants shrank in a curious manner, the
leaves began to droop, and became sickly in colour. A fourth appli-
496 ABSTRACTS OF CHEMICAL PAPERS.
cation made matters worse ; therefore the thiocyanate treatment was
stopped, and the soil well washed out by percolation with pure water.
The plant recovered somewhat; the treatment and washing were
repeated and continued for nearly three months. Plants have been
killed by continued doses of thiocyanate. No. 2 plant was soon
affected, but in a very different manner to No. 3 ; the stem did not
elongate much, but the leaves developed in length, breadth, and sub-
stance, and had a healthy deep-green hue. This development was
less satisfactory when the thiocarbamide was used alone, than when
the soil was washed with water between the doses, which is easily
accounted for from the fact that some of the thiocarbamide becomes
converted into thiocyanate, which then exerts its deleterious effect.
No. 1 plant soon outstripped the others in height, but its stem and
leaves were poor and thin as compared with No. 2. The condition of
each of the plants, after three months' (1st December, 1881) treat-
ment, is here tabulated: —
Plant Plant Plant
No. 1. No. 2. No. 3.
Total height in inches from surface of soil. 31 23 12
Number of leaves 15 14 13
Maximum length of leaf in inches 9^ 15;^ 8
Maximum breadth of leaf in inches 4^ 6 2^
Number of seed pods in any stage of de- 9 15 none
velopment
Number of seed pods well developed 1 11 none
Corresponding results were obtained with the other sets. The
quantity of nicotine is to be estimated on some future occasion, when
more material is at hand. Thus it is evident that the ammonium
thiocyanate is a plant-poison; whilst its metameride thiocarbamide is a
distinct plant-food, and were it not for its tendency to revert to the
thiocyanate, might be regarded as a good organic manure for tobacco.
The author concludes — (1.) That the particular elements of which
bodies are composed exert less influence on their physiological activity
than the extra-molecular grouping of the component atoms. (2.) That,
in some instances at least, differences of physiological activity between
metameric bodies can be easily detected by the aid of plants.
^ ^ ^ D. A. L.
Growth of Plants under Special Conditions. By A. B.
Griffiths (Ghem. News, 47, 27). — A patent manure, consisting chiefly
of animal charcoal, phosphates, and ferrous sulphate, having shown
remarkable properties in aiding the growth of plants, the author
undertook experiments to find out the reason, &c., of this. For the
experiments three very young Savoy cabbages, all nearly of the same
weight and in healthy condition, were chosen. No. I cabbage was
planted on a piece of land, and not manured. No. II cabbage was
planted on the same piece of land near to No. I, and received a
weighed quantity of the manure. No. Ill cabbage was placed on a
different piece of land, received the same quantity of manure as No. II,
but grew more in the shade. All the plants were placed in the ground
on the same day, and grew from February to December. They were
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
497
then taken up witli their roots attached, and after removal of all
adhering soil by washing, were weighed. No. 1 weighed 4 lbs. 2^oz8. ;
No. II weighed 9 lbs. 3 ozs. ; No. Ill 8 lbs. 6 ozs. Leaves and stems
of each plant were carefully burnt, and the ashes analysed with the
following results : —
No
. L
No.
II.
No.
III.
Leaves.
Stalk.
Leaves.
Stalk.
Leaves.
Stalk.
Potash
33-951
15-665
2-523
8-323
4-936
12 -931
8-613
7-994
4-999
41 -231
13-601
4-296
1-502
6-210
14 -463
9-619
6-781
2-294
31 -634
14-210
1-825
12-290
3-128
16-210
7-641
7-310
5-631
39 -223
13 -583
2-360
3 -521
6-000
18 -944
8-916
4-200
3-121
31 -521
14 -310
1-917
11-832
2-921
16 123
7-592
7-400
6 -265
38-929
13-621
Soda
1-813
Iron (FegOs)
Magnesia
Phosphoric acid
3-005
5 -942
18 -891
8-922
4-319
Silica
4 -468
99 -935
99 -997
99-879
99-868
99 -881
99 -910
The conclusions the author draws from these experiments are : —
(1 .) That plants, when grown in a soil containing iron and phosphoric
acid in a soluble form, are healthier and larger than if they are grown
in a soil wanting in these soluble compounds. (2.) The plants grown
in soils containiijg this manure appear to absorb larger quantities
of soluble iron and soluble phosphates than when not so treated.
(3.) Sunshine and rain appear to favour the absorption. The author
attributes the superiority of Plants II and III over Plant I to the pre-
sence of the soluble iron salt and phosphates, and he therefore con-
siders a fairly large proportion of soluble iron and soluble phosphates
in a soil favourable to the growth of plants which devplop a large
amount of chlorophyll cells, like the varieties of cabbage.
D. A. L.
Chlorine as a Plant Food. By Parskt (Chem. Centr., 1882,
809). — Chlorine is a very important plant-food, and to all appearances
potassium chloride in this respect is more valuable than potassium
nitrate, provided only that a certain quantity is not exceeded. Too
much potassium chloride reduces the quantity of chlorophyll, makes
the plants ripen sooner, and developes oxalic acid. This effect is well
marked when hydrochloric acid is used. D. A. L.
Contribution to the Knowledge of the Interchange of
Material in Amylaceous Plant Organs. By H. Muller (Bied.
Centr.y 1883, 832 — 836). — The generally accepted idea concerning the
freezing of potatoes is, that during that process a portion of the starch is
converted into sugar. This subject has been carefully studied, and at
the outset it was found that the sweetening of potatoes has nothing to
do with the actual freezing of the tuber, but rather that the low tern-
498 ABSTRACTS OF CHEMICAL PAPERS.
peratnre exerts a peculiar influence on the interchange of material in
the tuber. The most important results are as follows : — By rapid
freezing, no formation of sugar occurs ; but if the tuber is slowly
frozen, then sugar appears. Before the formation of ice occurs in the
potato, its temperature must sink to — 3° ; when slowly frozen, a con-
siderable time elapses before the temperature sinks from 0° to — 2".
Sweetening is not caused by freezing, because the temperature remains
for some time at 0° ; thus potatoes which were not frozen, but whose
temperature was for 15 days at —1° and —2°, contained 2 per cent,
sugar. The percentage of sugar does not increase in potatoes when
frozen and kept in the frozen state. At low temperatures, more sugar
is formed by fermentation than the protoplasma present requires ;
consequently, the proportion of sugar increases. The increase of
sugar is at first slow, gradually increasing, but finally decreases. A
high- percentage of moisture in the potato is advantageous to the for-
mation of sugar. In other parts of a plant containing starch the
greatest change occurs at 0°. The storage of sugar being greater at
0'' than at 20° is not to be attributed solely to the less expiration
which occurs at lower temperatures, but the change is also induced by
a ferment. If potatoes which are sweet at 0° be warmed, the sugar
rapidly disappears, and this is because at high temperatures expiration
is more energetic. Potatoes exposed to the open air rapidly cool ;
but if the temperature rises before they have cooled to —2", then they
are not frost-bitten nor sweet ; but should the temperature sink below
•—3°, then they are frozen hard, but at the same time not sweet; this
is because the cooling down is rapid. It is otherwise when potatoes
are kept in cellars, when the change is but gradual. A long time
is required for the fall from +5° to —2°. During this time sugar
acc^umulates, and they become sweet, not frozen hard ; when the tem-
perature has reached —3"^, they are sweet and frozen hard. This
sweetening is a loss, as a portion of the starch is first converted into
sugar and then expelled as gaR, but the whole of the albuminoids
remain. To enable sweetened potatoes to be eaten, they must be kept
warm for several days, so that the sugar may be lost by expiration.
Washing does no good, for all the sugar is not removed, and some of
the p-lbumino'ids are. Sweet potatoes can germinate. E. W. P.
Respiration of Plants. By E. Godlewski (Amu Agroru, 9, 37 —
43, from Jahrb. f. Weis. Bot. de Prinsheim, 13, 3). — By a modification
of Mayer's apparatus (which is, however, unfavourably criticised by
the translator), the author has observed the proportion between the
volume of oxygen absorbed and carbonic anhydride emitted during the
germination of certain oily seeds.
Daring the first stage, that of swelling, which (at 15 — 20°) lasts
about two days, the proportion CO3 : O is nearly 1, showing that at
first it is the small quantity of carbohydrates contained in these seeds
which is oxidised. During the second stage the proportion of oxygen
increases, and about the fourth day the proportion is CO2 : O = 60 : 100 ;
this proportion remaining nearly constant up to the eighth or tenth
day in the case of radish, hemp, flax, and lucerne seeds. It is during
this stage that the greater part of the oil is consumed, the complete
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 499
combustion of olein, e.g., requiring tlie proportion CO2 : 0 = 57 : 80.
From the constancy of the proportion CO2 : 0 = 60 : 100, the author
constructs the following alternative equations, showing a transitory-
conversion of part of the oil into starch : —
(1.) C57H104O6 + 66O2 = 4C6H10O5 + 33CO2 + 32H2O
CO2 : 0 = 59 : 100.
(2.) (C,8H3302)3C,H5 + 3H2O = 3C18H34O2 4- C3H,05
3C18H34O2+ 52102 = 4CeHio05 + 3OCO2 + 3IH2O
CO^-, 0 = 57-1 : 100,
During the third stage of germination a part of the starch is con-
verted into cellulose, and another part is burned, the proportion CO2: O
again becoming unity. The respiration of seeds containing a large
amount of starch is characterised by the oonstancy of the proportion
C02:0 = l.
The effect of reducing the pressure of oxygen is to render the
respiration less active, but the proportion of carbonic anhydride is not
disturbed until the oxygen present falls below a certain minimum,
when intramolecular respiration takes place, some of the proximate
principles of the seeds absorbing oxygen at the expense of others.
During the ripening of oleaginous seeds, the proportion CO2 : 0 is
greater than unity (128 : 100 in the case of castor-oil seeds), showing
that the oil is formed by reduction of the carbohydrates.
J. M, H. M,
Composition of Ivy Berries. By A. Jandous (Chem. Centr., 1882,
806). — The fleshy part of the fruit contains 70 per cent, of water; also
a dark red colouring matter soluble in alcohol and water, and turned
greenish by ammonia, light red by hydrochloric acid ; besides this,
grape-sugar is present and a resinous substance of greenish-yellow
colour, sweet at first, but afterwards sharp and bitter ; hydrochlo- ■
ric acid turns it a beautiful green ; and finally gum, albumin, and
mineral matters. The seed contains albumin, inorganic matter, and
a fat oil, with a characteristic herbaceous and irritating taste, only
slightly soluble in water, precipitated by lead acetate, and slightly by
lime water, and coloured green by ferric chloride. The poisonous pro-
perties of this fruit are neither due to the resinous^ ^matter in the flesh
nor to the oil in the seeds. D. A. L.
The Ice Plant (" Mesembrianthemum Crystallinum"). By
H. Mangon (Gompt. rend., 96, 80 — 83). — The author has analysed the
leaves of this plant cultivated by himself under various conditions.
He finds that of the dried plant about 43 per cent, on an average con-
sists of salts of potassium and sodium. Calculating from the mean
yield per square meter, the author finds that a hectare would give 588
kilos, of potash capable of yielding 863 kilos, of potassic carbonate.
He therefore raises the question whether the plant might not be pro-
fitably cultivated, under certain conditions, as a source of potassium,
and whether it might not be employed to remove from the saline soils
of the Mediterranean coasts the excess of alkaline salts which render
those soils so barren. E. H. R.
500 ABSTRACTS OF CHEMICAL PAPERS.
Influence of Fallen Snow on the Temperature of the Air.
By R. BiLLWiLLEii (Bied. Centr., 1882, 851). — Meteorological observa-
tions are quoted to show that when the ground is covered with snow,
the temperature of the lower strata of the atmosphere is lower than
when there is no snow, because this snow cuts off all communication of
heat from the soil to the air. It follows that the soil in winter
being always warmer than the air, when snow is on the ground, the
air is deprived of its source of heat. E. W. P.
Influence of the State of Aggregation on the Temperature of
and Moisture in a Soil. By E. Wollny {Bied. Centr., 1882, 793—
795). — A soil whi©h has laid long uncultivated, or has never been
cultivated, finally assumes a condition in which the particles lie too
closely together ; on the other hand, in a soil which has been fairly
treated, the particles do not lie evenly side by side, but being bound
together by clay, humus, &c., into lumps, interstices are formed suffi-
cient for the free passage of air and water..
Experiments as to the effect of these two conditions on the tempera-
ture and moisture have been made in zinc boxes placed in the open
air, with the following results: — The proportion of water increases
with the fineness of division, and consequently is highest in a soil in
a very fine state of division, because a greater number of capillaries
are formed which draw up the bottom water, and prevent the down-
ward flow of atmospheric water. Evaporation is greatest from finely
divided soils ; permeability is in a direct ratio with the size of the
particles ; it may happen that evaporation and permeability stand in
indirect proportion to one another in a soil whose particles are of very
varying size, so that a balance is maintained, and the amount of water
present remains the same.
During the warm season, the coarse-grained soil is the warmest, but
only up to a certain extent, for a further increase in the size of the
grains causes a fall in temperature ; the cause of this is the specific
heat of the water present. Moreover, the cooling of the soil at night by
the entrance of cold air is greater, and. the conductivity for heat is so
much less the larger the particles.
The differences in the temperatures of the two kinds of soil is so
much the less the smaller th-e amount of water present; it is also
lower when the evaporation is reduced, consequently during cold
seasons, when the air is still and moist, this difference is at its mini-
mum. E. W. P.
Irrigation of Meadows by Waste Water from Beet-sugar
Factories. By Teuchert {Bied. Centr., 1882,851).— Crops irrigated
by the above waste waters were greatly improved, nearly all the
organic matter being removed from the water, which afterwards con-
tained neither algse, bacteria, nor vibrios. E. W. P.
Manurial Value of " Dissolved Wool." By A. Petermann
{Ann. Agron., 1882, 77 — 86). — " Dissolved wool " is made by treating
woollen refuse with high pressure steam, evaporating the resulting
liquid to dryness, and powdering the residue. It is a dark brown,
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 501
hygroscopic powder, witb. an odour like that of caramel, and almost
entirely soluble in water. It contains nitrogen as ammonia, as soluble
organic compounds, and a very little in the insoluble condition in which
it exists in wool. The author has made comparative trials of its
manurial value against crude woollen refuse and nitrate of soda, with
and without the addition of precipitated phosphate of lime. His
trials were made with wheat plants growing in pots in a greenhouse,
and upon a field crop of beet growing in the loamy soil of Gembloux.
Experiments were also made on plants growing in earthenware cases
liolding a cubic metre of soil, to ascertain whether any loss of the
soluble nitrogenous compounds of the dissolved wool occurred by
drainage.
The action of the dissolved wool was very favourable on both
wheat and sugar-beet, raising the yield of the former by 25 per cent.,
and of the latter by 30 per cent. It was more efficacious than crude
woollen refuse, but less than nitrate of soda. No sensible loss of
nitrogen by drainage occurred. J. M. H. M.
Chemical Manures and Farmyard Manure. By K Outllaume
(Ann. Agron., 9, 30 — 37). — Having previously shown that the addi-
tion of phosphates to the soil of Harauoourt and Villepreux, a soil
naturally very poor in phosphoric acid, does not produce remunerative
results, the author has now extended his experiments to the use of
superphosphates, and has also instituted a comparison between chemical
manures and farmyard manure. All the results are summed up in
the annexed table (p. 502), the chief points of interest being the fol-
lowing : —
Haraucourt^ — Superphosphate gave better results than phosphate
with wheat and oats ; both raised the produce, but not to a sufficient
extent to pay the cost of the application. The summer of 1882 being
wet, the yield of green maize was very large, and the superiority of
superphosphate over insoluble phosphate is strikingly shown. Potatoes
succeeded best without any manure ; farmyard manure in wet seasons
seems to encourage disease. On beet, superphosphate produced better
results than mineral phosphate.
Villepreux. — The soil is slightly calcareous, effervescing with acid,
and contains 0'204 per cent. IS". Phosphate and superphosphate alone
produced good results with potatoes and sogina ; farmyard manure
and nitrate of soda with maize and mangold. The sogina seed was
imported from Italy, and succeedjed very welL
502
ABSTRACTS OF CHEMICAL PAPERS.
^rn
m ^
I "I
a
m O
o
W
Ci^
O
8
o
- _ _ lO
fl O (M OO
o o o o
O O O O-
CSJ (M (M (N
o o o o
la o" z6 CO
i5^ r
Cl4
00
O
wTicTo'co'"
,^3
O <D CO
5 2 a>
2 i=^
S o o
03 O
o2
p o
o s
S|
-I
W
CO 2
e3 O
2-5
W
C5 S
^ CO
M
"* "* ec N (M
O C O Ci o
O O viZr l^ CO
t^ uO l^ N O
O O O Q
§888
888
o o o
U5 W Q W O
XO t^ O 00 i-i
O O O O O
o-o o ko lo
CC (M_^ O^ 0_ i-J^
o c> o o o
»o Q O w: O
^ ^ ^ ^ ^
2
S
s
^4
>^ CL, 57 -w
r^S C m o g
p e*_, Ph on fl
c Q O O O
5 10 i-Ti-T
p;5
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 503
Reduction of Nitrates in the Soil. Bj P. P. D^h^rain and
Maquenne (Ann. Agron., 9, 7 — ^21).— Schloesing^ in 1873, found that
when 12 kilos, of soil mixed with 7*5 grams nitre were placed in a
flask with a confined portion of air, the whole of the nitrate disap-
peared, a part of the nitrogen being converted into ammonia, and the
rest being evolved as free nitrogen.
The following experiments and observations, of the authors appear
to show that this reduction of niti*ates by soil is due to a fermentation
carried on by Anderobia.
A handful of garden soil is placed in a litre flask, the flask is then
filled with a 7 or 8 per cent, solution of sugar, fitted with a delivery
tube dipping into mercury, and maintained at 35° in a water-bath. In
about 15 hours fermentation sets in, aTid an evolution of gas is. pro-
duced which lasts about 30 hours ; the action then slackens, but may
be renewed by adding a little chalk to neutralise the acidity of the
solution. The evolved gases consist of carbonic anhydride and
hydrogen, and the solution contains butyric acid. The fermenting
liquid contains vibrios similar to the butyric ferment discovered by
Pasteur, but the authors have reason to believe that the Bacillus amyl-
ohacter of Van Tieghem is present also, perhaps in greater quantity
than the butyric vibrio. In order to connect the existence of this
anaerobic ferment in the soil with the reduction of nitrates, the
authors cite the following observations : —
(1.) The reduction of nitrates takes place only in atmospheres de-
prived of oxygen. If some garden mould and a little saltpetre are
placed in a sealed tube, the air of the tube will after a time be found
to contain no oxygen, and at the same time no nitrate wiH be
detected in the soil. The nitrogen contained in the tube is found to
have increased.
(2.) The reduction of nitrates takes place only with soil rich in
organic matter. A soil poor in organic matter (containing O'l per
cent, nitrogen) may, however, be rendered active by adding to it
glucose which has been treated with potash.
(3.) If the saltpetred soil be heated in the sealed tubes at 120 —
125° for some hours, and afterwards kept for a months the nitrate
does not disappear.
(4.) The addition of a few drops of chloroform to the contents of
the tube also prevents the reduction of the nitrate, even when kept
for several months ; 'the oxygen of the enclosed air nevertheless disap-
pears, being replaced by carbonic anhydride.
(5.) Soil which has been heated at 120° for some hours regains its
power of reducing nitrates when it is mixed with a very small
quantity of fresh soil and placed in another tube. Often the mere
transference from one tube to another is sufficient, without any addi-
tion of fresh soil.
(6.) In an experiment with a saltpetred soil in contact with a solu-
tion of sugar, the gas evolved during fermentation was found to con-
sist of CO2, 67'3 ; H, 31*5 ; N, 1*2. When the sugar is omitted, or
when the fermentation is less active, the reduction of the nitrate is
not so complete, and nitrous oxide is evolved as well as nitrogen ; in
two cases cited by the authors, the nitrogen was mixed with 11"5 and
504 ABSTRACTS OF CHExMICAL PAPERS.
95 per cent, of nitrous oxide. In another case, when saltpetred soil
and sugar solution were used, the gas consisted of CO2, 85*5 ; N2O,
8-2; N, 11-8.
The authors consider that the reduction of the nitrate is a secondary
action, effected by the nascent hydrogen resulting from the butyric
fermentation, and they compare the evolution of nitrous oxide in this
case with its production when zinc is dissolved in dilute nitric acid.
In connection with these results, the authors discuss the impoverish-
ment in nitrogen of arable land bearing cereal crops, and the compa-
rative richness in nitrogen of pasture land — some of the Rothamsted
pasture soil, for instance, contains 0*25 — 0*28 per cent. N, whilst
the wheat-growing plots, although receiving more nitrogen in manure
than the pasture, contain only 0'12 — 0*18 per cent. N.
Well-worked arable soils, freely aerated, lose nitrogen by nitrifica-
tion, the produced nitrates being carried away in the drainage water.
In the soil of a pasture, however, the nitric fermentation proceeds
very slowly because of the deficient supply of oxygen; on the other
hand, there is probably always enough oxygen present in the soil to
prevent the occurrence of the anaerobic fermentation, which would
give rise to reduction of nitrates and loss of free nitrogen and nitrous
oxide. Incidentally, the authors remark that the only certainly known
causes of the continuous enrichment of soil in nitrogen are : (I) the
fixation of free nitrogen observed by Berthelot, and (2) the fixation
of ammonia observed by Schloesing. Both of these processes require
a soil rich in organic matter, and in order that the gain of nitrogen
may be permanent, the supply of oxygen and consequent nitrification
must be limited. J. M. H. M.
Analysis of Materials used in the Preparation of Composts.
By A. Petermann (Ann. Agron., 1882, 135—140).
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
505
bfi
•
s ©
'a,
g
- be
la- 33
CM
o
r^
rflrd
.113
© ©
o
^
fl fl
o o
?*
o
rfl^
i3
-Ti
fl
fl
^ ^
O
Ti TS
Fl
H
© ©
p
s
:; M H
[^
^
1^^
O ©
pug
if
©^
p^ <I ptH
rfi ?-^
03 ^
CO (M
00
r-i CO
O
^ I
I I
>0 05
CO CO
^ 00
o o I o o
li I
00 05 CO CO ■<?' OS
(N CO a> r-( CO T?
o o o o o o
I I I
) N © IX) r-
iiHgO IrHrHr-IOOtH
. CO 00 05 00 I>
I ■* (M "* O C*
O O O O iH O O O O I O O O .S rH o
OOOOOiHOOOO
2 s
lO-*O0i05CDl0l0.-IC0(W00CC ©OIX35W5— '
(M— IM(M»pi-ltHO(MrH(Mii5(N Ct^rf(CqO"<!f<
OOOOOOOOOOOOO flOOOOO
CO >0 ^ CO 00
OS Oi I I N O 00
iH O O rH fH
(3 is
5l
I I
r I
CO ■^
CO .-I I
' ':^§5
.2 o
CqCOCO'*iOG<J»OCO'<fiOCCiMO5r>.(M00O5
<>3l0C0i0'^rHCqO'HrHt*05(Mi001C0p
COCOiH(N(MCOOS(M'-IOOOOOO(N<iiOO'*^ I IcOCOOStJIOO
(M(M TffC<T tJ) tJ(iOtJ(,-I (M r-ICOCOi-lr-(
I I
§
a
.la
If5
ii
fe a =
o ©
O &I
O "
e3 o
a "
s
CM
©
. o
: «
. o
. ©
• e3
^a
"^ " § s ^ J! B I
i-l(MCO-^iaC01>X050i-*(MCO-^lOCOt>0005Cr-l(NCOTfl\OCOt>Q'"050
r-irHrHTHTHiHiHi-lrHiHN(N0a<NC<l(NN<M<M(NCO
VOL. XLIY.
506 ABSTRACTS OF CHEMICAL PAPERS.
Artificial Manuring of Sugar-canes. By G. Riffaed (Bied.
Centr., 1882, 797— 803).— An average crop of canes (50,000 kilos,
canes, and 10,000 kilos, leaves) removes per hectare, of nitrogen 41'3
kilos., phosphoric acid 27'7, sulphuric acid 34*4, lime 50'0, magnesia
35*9, and potash 72'2. Of this ash, bnt very little is returned to the
soil in any form ; the leaves are used as fodder, as is also the scum
from the pans, but the rest is lost to the ground. As manures, guano,
farmyard ma/uure, and Yilles' No. 5 have been employed, but no
marked difference in the yields was noticed; the canes absorb alkaline
chlorides readily, as much as 42'7 of the ash of the cane, and 26 per
cent, of the ash of the leaves may consist of potash if they are
manured with potassium chloride, which has a bad effect on the plants
the canes gradually becoming yellow.
The author has made experiments, using 12 per cent, superphos-
phate, saltpetre, guano, potassium chloride, and ammonium sulphate,
and finds that stable manure produces the best results ; although the
yield is not the best, yet the amount of uncrystallisable sugar per
100 kilos, juice is the lowest. It still remains to be proved whether
the use of potassium sulphate in preference to the chloride is to be
recommended ^or not, as lowering the percentage of uncrystallisable
sugar. E. W. P.
Analysis of Gas-lime. By A. Mater and F. Clausnitzer (Bied.
Centr., 1882, 852). — ^Water = 30'1, calcium hydroxide 326, carbonate
17*5, sulphate and sulphite 20*2, sulphide traces; thiocyanate traces;
ammonia 0*01 . Total = 100-4.
Gas-lime must therefore be used as if it were slaked lime, and not
as sulphate ; it cannot be used in manure heaps or on moor or sandy
soils, but must be long exposed to the air before use. E. W. P.
Ajnalytical Chemistry.
Asbestos Filters. By P. Casamajor (CAm. News, 1883, 17).—
The author recommends the following method for the preparation of
asbestos filters.
Of the different kinds of asbestos, the Australian is the best for
rapid filtration ; it is first rubbed through a brass sieve (10 openings
to the inch), and the dust and fine particles are removed from the sifted
material by washing it with water and stirring well in a No. 25 or
No. 30 sieve until the water comes through clear ; the washed asbestos
is then boiled for half an hour with a solution of hydrochloric acid,
1 part of fuming acid to 4 parts of water; after this treatment,
ANALYTICAL CHEMISTRY. 507
the pulp is well washed until free from acid and then strongly
heated in a platinum dish. It may be kept in a wide-mouth bottle
until required for use, when it is made into a thin paste and poured
on to the perforated platinum disc. D. A. L.
Influence of Hygroscopic Condensation in Glass Vessels on
the Determination of the Density of Aqueous Vapour. By D.
Macaluso and G. Grimaldi (Gazzetta, 12, 535 — 543). — If an unsatu-
rated vapour conformed to the laws of Boyle and Gay-Lussac, its
density, as compared with that of air or any permanent gas, would
remain constant for all pressures and temperatures. With regard to
aqueous vapour, Hegnault found (Etudes sur VHygrometrie) that,
although its density may be calculated according to these laws for
pressures and temperatures remote from the point of saturation, its
value becomes much greater as the vapour approaches that point, in
consequence either of abnormal condensation, or of a deposition of
liquid on the inner surface of the vessel, which can be prevented only
by keeping the vapour far above the point of saturation. It therefore
becomes of interest to determine whether such deposition really takes
place, and, if so, to what amount. Regnault suggested, as an ap-
proximative method of determining this point, the use of glass vessels
of different forms, so that the ratios of their surfaces to their capa-
cities might also be different; and this suggestion was adopted by
Wiillner and Grotrian in their memoir on the density and tension of
saturated vapours (Wied. Ami., II, 545) ; they found, however, no
appreciable difference in the results of their experiments with dif-
ferent vessels, and thence inferred that the surface- condensation
in question does not take place. Macaluso and Grimaldi, on the
other hand, consider that these experiments are not conclusive,
inasmuch as the ratios of surface to volume in the vessels employed
in them differed but little from each other. They have, therefore,
endeavoured to determine the matter by the use of vessels to
which this objection does not apply, and they infer from their
experiments that a condensation of water on the surface of the
glass vessels really takes place, which, although small at the tem-
perature of 108°, is plainly appreciable, and would probably be
much greater at temperatures nearer to the point of saturation. They
consider, however, that this surface-condensation is not the sole cause
of the difference between the experimental value of the vapour-
density and the values calculated according to the laws of Boyle and
Gay-Lussac. H. W.
A Modified Process for the Estimation of Chlorine in
Bleaching-powder. By J. W. C. Harvey {Chem. News, 47, 51). —
The original process is that in which the chlorine in bleaching-
powder is determined from the number of c.c. of a bleaching solution
of known strength required to convert a solution of ferrous chloride
containing a weighed quantity of pure iron into ferric salt. The
modification proposed does away with the weighing of the iron and the
making of ferrous chloride from it. The basis of the method consists
in adding a measured quantity of a dilute solution of stannous chlo-
2 m 2
508 ABSTRACTS OF CHEMICAL PAPERS.
ride to excess of a solution of ferric chloride, the amonnt of ferrous
salt thns formed beinp^ determined by standard potassium dichromate ;
by this means, therefore, a known quantity of ferrous chloride can be
formed immediately. The estimation is thus worked : the same quan-
tity of stannous chloride as in the test experiment is added to excess
of ferric chloride ; and the diluted solution is titrated with the
bleachin^-powder solution until all the ferrous is converted into ferric
chloride. The amount of chlorine is calculated from the ferrous iron
found by the dichromate, &c., &c. Required solutions are : 1. Stan-
nous chloride, dissolve 60 ^ams in hydrochloric acid, and make up to
1 litre : 5 c.c. of this solution suffice for an experiment. The amonnt
of ferrous chloride to which it corresponds should be determined
before each series of estimations. 2. Ferric chloride, which must be
free from ferrous salt. 3. Standard dichromate, 30 grams in 2 litres.
D. A. L.
Estimation of Chlorides, Bromides, or Iodides in Presence
of Sulphuretted Hydrogen. By H. Topsoe (Zdts. Anal. Ghem.,
22, 5 — 10). — By the addition of an excess of potassium permangan-
ate solution acidified with nitric acid, the sulphuretted hydrogen is
oxidised to sulphuric acid, the liberated bromine or iodine converted
into the corresponding hydro-compound by aqueous sulphurous acid,
the excess of permanganate being reduced by the same agent, and
in the solution now free from sulphuretted hydrogen the haloids are
determined by the usual methods. 0. H.
Modification of Scheibler's Azotometer. By K. So\DE^^ (Zeits.
Anal. Ghem., 22, 23 — 27).— The author describes an apparatus for
he measurement of gases, the volume being constant and the pressnire
of the gas being variable. O. H.
Estimation of Nitric Oxide and Nitric Acid. By C. Boehmer
(Zeits. Anal. Ghem., 22, 20 — 23). — The author has some time asro
(ibid., 21, 212) pointed out that chromic acid absorbs nitric oxide with
great facility. He now utilises this fact in the gravimetric estima-
tion of nitric oxide (and of nitric acid) in Schlosing's method, bv
parsing the gas through Liebig's bulbs filled with strong chromic acid
solution, and ascertaining the increase of weight. O. H.
Estimation of " Half Soluble " Phosphoric Acid. By H. v.
Ollech (Bied. Gentr., 1882, 853). — Instead of employing \ percent,
solution of citric acid, a f per cent, solution was used ; the phosphates
examined were in various states of aggregation, finely- powdered,
coarse, and medium-srrained ; also in one set of experiments, the phos-
phoric acid was precipitated directly, in the other only after the organic
matter had been destroyed. But little difference was noticed whether
the phosphates had been ignited or not ; the more finely divided the
substance, ihe higher was the percentage of dissolved acid ; the con-
centrated citric acid dissolved less than the diluted ; it matters not
how magnesia mixture is added to the solution from which phosphori ^
acid is to be thrown down, so long as the mixture is not in too great
excess. E. W. P.
ANALYTICAL CHEMISTRY. 509
Separation of Strontium and Calciam. By D. Sidersky
(Zeits. Anal. Chem., 22, 10 — 14). — The principle upon which the
method is based consists in the observation, that if a mixture of am-
monium sulphate and oxalate is added to a solution containing both
strontium and calcium, the whole of the strontium is precipitated as
sulphate, and the whole of the calcium as oxalate.
The author extracts the mixed precipitate with dilute hydrochloric
acid, weighino" the residue as sulphate, and precipitating the calcium
oxalate from the solution by ammonia.
Satisfactory test experiments are quoted. O. H.
Detection of Strontium. By F. "Ransom (Pharm. J. Trans. [3],
13, 626 — 627). — Solutions of strontium nitrate varying from 1*25 per
cent, upwards are precipitated or rendered turbid by the addition of
a 5 per cent, solution of potassium chromate. A 1'25 per cent, solu-
tion does not alter until boiled, when a precipitate forms : boiling
accelerates precipitation in all cases. Descending to weaker solutions
and applying heat, turbidity is obtained until, with a 0'25 per cent,
strontium solution, only a slight cloudiness can be observed. Free
acetic acid prevents this precipitation in the cold, for even a 20 per
cent, solution is not affected until boiled, and then is merely rendered
turbid. This state of things is not altered by neutralising the free
acid with ammonia, for, even then, strontium nitrate solutions are
only rendered turbid by the potassium chromate instead of being
precipitated as they are when the strontium salt is pure. Calcium
salt solutions, even when strong, are not precipitated by 5 per cent,
potassium chromate solution ; sometimes, however, a turbidity may be
obtained ; the small precipitate causing calcium turbidity remains dif-
fused in the liquid, whilst that of strontium nitrate turbidity aggregates
in circular discs adhering to the glass. From these facts, it is evident
that potassium chromate may be used to detect strontium ; further, it
should be observed that plenty of free acetic acid ought to be used
when barium is to be separated with potassium chromate previously to
testing for strontium. D. A. L.
Weil's Method for the" Determination of Copper, Iron, and
Antimony. (Chem. News, 46, 284.) — The necessary solutions are :
— (1.) Normal copper solution, 19'6675 grams of pure po>\dered
crystalline copper sulphate, which has been dried between white
blotting-paper, are dissolved in water and made up to half a litre.
(2.) Is a similar solution containing 7*867 of copper sulphate.
(3.) Standard tin solution, 4*5 to 5 grams of tin crystals (stannous
chloride), dissolved in water, and 30 grams of hydrochloric acid, are
made up to half a litre, with water acidified with about 40 per cent,
hydrochloric acid. This solution is standardised with solution No. 1.
10 c.c. of solution No. 1 are mixed with 25 c.c. hydrochloric acid,
boiled, and the tin solution to be standardised is run in until the green
colour disappears.
Estimation of Copper. — 5 grams of substance are dissolved in hydro-
chloric or sulphuric acid, and made up to 250 c.c. 10 c.c. of this sola-
510 ABSTRACTS OF CHEMICAL PAPERS.
tion are taken, 25 c.c. hydrochloric acid added, and then titrated as
above.
Estimation of Iron. — When there are 2^ vols, of free hydrochloric to
1 vol. of the ferric solution, no indicator is necessary, and the standard
tin solution is run in until the iron solution is colourless ; in this way
the quantity of iron is obtained in terms of copper. Of solutions con-
taining 2 grams of the sample in 250 c.c, 10 c.c. are evaporated in a
po Cilain capsule, with 10 c.c. of the copper solution (No. 2) ; to the
concentrated mixed solution large excess (about 75 c.c.) of hydro-
chloric acid is added, and this is titrated with the tin solution as
before ; of course the tin required for the copper used must be deducted.
The copper is nsed as an indicator, and is not required with substances
containing more than 2 per cent, of iron.
Estimation of Iron and Copper. — 5 grams of ore in 250 c.c. Titrate
as above. In another, 10 c.c. of solution, precipitate the copper
with zinc, filter, reconvert the ferrous into ferric salt by means of
potassium permanganate, and titrate the iron again.
Estimation of Antim.ony. — In making up the 250 c.c. in this case, it
is necessary to use aqueous solution of tartaric acid to prevent precipi-
tation of antimony. The solution of antimonic chloride is mixed with
normal copper solution, and a large excess of hydrochloric acid then
titrated ; the c.c. standard tin solution used indicates the sum of the
copper and antimony. If the mixed solution of cuprous and antimo-
nious chloride is allowed to remain some time, the copper becomes re-
oxidised, but the acid does not, therefore a second titration gives the
quantity of copper only ; this is scarcely required when strength and
quantity of copper solution added is known. Antimony, copper, and
iron, when together in same sample, are thus determined. 5 grams
substance is dissolved in nitric acid, evaporated down, and filtered.
The filtrate contains iron and copper, which are determined as above
directed. The precipitate contains all the antimony ; it is dissolved
in hydrochloric acid, treated with potassium permanganate, and the
antimonic chloride determined as directed.
This process depends on the reducing action of stannous chloride.
It is therefore necessary to get rid of extraneous oxidising influences,
such as free chlorine, nitric acid, or excess of permanganate, &c.,
before titration ; this is effected by evaporating to dryness, taking up
with hydrochloric acid, and repeating, until the solution or vapour
evolved on boiling ceases to turn starch-paper blue. D. A. L.
The Thiocyanate Reaction for Iron. By H. Wekner {Zeits.
Anal. Ghent., 22, 44).— Chlorides, and to a less extent nitrates, of the
earth-metals are said to interfere with the above reaction.
O. H.
Analysis of Iron. By A. Tamm (Ghem. Gentr., 1882, 766).— In
this paper the various methods of iron analysis at present in use in
different countries are discussed.
The total carbon is determined in England, Sweden, and many parts
of Germany, by dissolving the iron in ammonium copper chloride,
collecting undissolved carbon on an asbestos filter, and finally burning,
ANALYTICAL CHEMISTRY. 511
and weighing as carbonic acid. In Freiberg tbe carbon is not bnmt,
but oxidised with chromic acid. In France this iron is dissolved in
mercuric chloride (Boussinganlt's method). The English method is
quicker than the Swedish iodine method. For graphite determination,
at Dowlais the iron is dissolved in nitric acid, the graphite and silica
remain undissolved; the first is burnt, the second weighed. Daily-
tests of the furnace metal are universally made by Eggertz's colori-
metric method. Silica is generally determined in England by dis-
solving the iron, either in aqua regia or in hydrochloric acid, diluting
with sulphuric acid ; others dissolve in nitric, diluted with sulphuric
acid. At Creusot and Terrenoir the pulverised iron is moistened
with nitric acid, ignited, and oxidised in a mufile, heated in oxygen,
and then converted with dry hydrocbloric acid into ferric chloride,
which is volatilised, leaving pure silica behind. Phosphoric acid is
mostly weighed in the form of the ammonium molybdate precipitate.
The iron is dissolved either in nitric acid, with subsequent addition of
bydrochloric acid, or in a mixture of the two acids, or seldom in nitric
acid alone ; the first is the best solvent. Pattinson works on 3 grams of
iron ; Stead with 2. At Creusot 1 gram is used. The precipitation
is conducted in acid, alkaline, or neutral solution. Thus Eggertz's
acid solution is in use in the Lowther Works, in Landore, and at
Creusot. Ammoniacal solution (Snelus's method) is in vogue at
Dowlais, and is used by Pattinson, whilst Stead uses a neutral solu-
tion, and Riley employs the magnesium method. Altogether the acid
method is the best, and is in fact the only one available for iron con-
taining arsenic. Sulphur is estimated in various ways. At Dowlais,
Snelus, Stead, and others dissolve the iron in aqua regia, turn the
sulphur into sulphuric acid, and precipitate with barium chloride, &c.
In other methods, the sulphur is converted into hydrogen sulphide.
In Freiberg, the gas is passed into solution of bromine in hydrochloric
acid, and the sulphuric acid determined with barium chloride. Pattin-
son passes the gas into an ammoniacal cadmium chloride solution, and
oxidises the precipitated sulphide with bromine, and then treats with
barium chloride, &c. In other places, the gas is passed into lead
acetate, or sulphate of copper or- silver nitrate solutions. RoUet at
Creusot ignites the pulverised iron in a stream of gas, consisting of
three-fourths of hydrogen and one-fourth carbonic acid; the gas is
led into silver nitrate solution, and when only small quantities of
sulphur are present, the gas is passed through a series of flasks, each
flask containing silver solution representing 0*01 per cent, of sulphur,
thus the number of flasks precipitated gives directly hundredths per
cent, of sulphur. Manganese is determined in England and Belgium
with ammonium acetate ; in France, Germany, and Sweden by means
of sodium acetate. Pattinson's titration method only gives approxi-
mate results. Various colorimetric systems are in use : thus, Osmond's,
in Devain and Creusot ; Dehayes, in Terrenoir. These methods are
not very good. Sarnstrom's volumetric method is very good. Iron is
determined in England with potassium dichromate ; in France, Belgium,
and Germany, with permanganate. At Landore, when titanic acid is
present, reduction is effected with sodium sulphide. D. A. L.
512 ABSTRACTS OF OHEMTCAL PAPERS.
Reduction of Ferric Salts. By P. T. Austin and G. B. Hurfp
(Chem. News, 46, 287). — The authors suggest the use of a saturated
solution of sodium sulphite for the reduction of ferric to ferrous salts
previous to titration of the iron with permanganate. The sodium sul-
phite solution is added to the acid ferric solution in small quantities at
a time, until it is colourless ; the reduced solution is then boiled out
of contact with the air, until all the sulphurous anhydride is driven ofE.
Satisfactory results have been obtained by this method.
D. A. L.
Estimation of Sulphur in Iron and Steel. By G. Craig
(Cheyn. News, 46, 272). — In answer to Rocholl (next Abstract), the
author states that he has, in test-experiments with magnesium sul-
phate, obtained all the sulphur precipitated as barium sulphate in pre-
sence of large quantities of ferric and potassium chlorides. Rocholl
was under the impression that such a precipitation was not possible
under the given conditions. Several experiments have also been made
with the hydrogen peroxide evolution process, all the sulphur being
given off, not a trace of sulphur being found in the residue by Rocholl 's
process. On two occasions, however, when the residue was fused with
potassium nitrate and sodium carbonate, a small quantity of sulphur
was found, thus: —
S in residue.
Cu in iron.
S evolved.
f
Liquid.
Sohd.
Per cent.
S evolved.
1. 0-50
0-063
0
0 *
100-0
2. 0-50
0-065
0
0*002t
97-0
3. 0-50
0-064
0
0-003t
95-4
The author suggests that the difference between his and RochoU's
results is probably due to the fact that he (the author) boils his solu-
tion for about 15 — 20 painutes after the evolution of gas has become
sluggish. D. A. L.
Estimation of Sulphur in Pig-iron. By H. Rocholl (Chem,
News, 46, 236). — The author does not approve of Craig's method (this
vol., p. 121) ; neither does he agree with the sta/tement "that the residue
left on dissolving pig-iron in strong hydrochloric acid is free from
sulphur, even when the metal contains much copper."
The author has dissolved several samples of iron in hydrochloric
acid in the usual way, passing the hydrogen evolved through a 5-bulb
tube containing weak ammoniacal silver nitrate. The silver sulphide
is oxidised with bromine- water, filtered, and precipitated with barium
chloride ; results obtained are given in table below under " Sulphur A."
The residue in the flask is filtered, and the solid portion washed into a
basin, evaporated, and successively heated with nitric and hydrochloric
acids, dried, redissolved, and filtered. From the filtrate, barium chlo-
ride always produces a precipitate representing a second portion of
" Sulphur B." No other precipitate with this reagent is obtained.
The following are the results : —
* KochoU'a process. f Fusion process.
ANALYTICAL CHEMISTRY.
513
Sulphur B
Name of iron.
Copper,
Total S.
Sulphur
A.
Sulphur
per cent, of
total
sulphvir.
1. Cleyeland pig-iron ....
None
0-075
0-069
0-006
8
2, Ordinary Bessemer pig
0 -02 (about)
0-045
0-041
0-004
9
3. ,5 » 55
0 -02 (about)
0-026
0^021
0-005
19
4. Cupriferous „ „
0-02
0-065
0-050
0-015
23
5. 55 55 55
0-23
0-017
0-011
0-006
35
6.
0-26
0-061
0-029
0-032
52
•• 55 55 55
0-26
0-064
0-027
0-037
58
8-
0-26
0-026
0-009
0-017
65
9. 55 55 55
0-27
0 041
0-026
0-015
36
10.
1-09
0-071
0 046
0-025
35
D. A. L.
Volumetric Estimation of Manganese Dioxide. By J. W. C.
Rauyey (G hem. News, 188.3,2). — The requisite solutions are: — 1. Stan-
dard potassium dichromate, 30 grams of pure salt in 2 litres ; so that
1 c.c. = 001 7 Fe = 0-013205 MnOa. 2. Stannous chloride solution: dis-
solve 180 grams in hot hydrochloric acid, and, wlien clear, make up to
1 litre with water. 3, Ferric chloride solution containing 60 grams of
iron per litre. To work the process, 1 gram of the finely powdered
manganese dioxide is warmed with 10 c.c. of the stannous chloride
solution and 15 c.c. hydrochloric acid until the oxide is dissolved ;
excess of ferric chloride is now added, and the whole heated again ;
finally the amount of ferrous chloride formed by the residual stannous
chloride is determined with potassium dichromate. This being done,
10 c.c. of stannous chloride solution are heated with excess of ferric
chloride, and the amount of ferrous salt is determined with the di-
chromate. From the difference between this and the former deter-
mination, the manganese can be calculated. An analysis occupies
15 minutes. The stannous chloride should be tested against the di-
chromate if any length of time elapses between the determinations.
The method has been tested against Fresenius and Will's process,
and has always yielded better results. D. A. L.
Separation of Vanadic Acid from Metals. By W, Halbeestadt
(^Zeits. Anal. GheTn., 22, 1 — 4), — The hydrochloric solution is evapo-
rated to dryness and the residue extracted with a saturated ammonium
oxalate solution to which a few drops of acetic acid have been added.
The solution thus obtained is, while hot, very gradually mixed with
acetic acid as long as oxalates are precipitated. The filtrate is evapo-
rated, the residue ignited, heated in a current of oxygen, and weighed
as vanadic pentoxide.
The method is applicable to the separation of vanadium from barium,
calcium, zinc, and lead, but not suited to that from cobalt, nickel,
manganese, magnesium, bismuth, copper, or cadmium. O. H.
Test for Arsenic. By W. A. H. Naylor and J. O. Bratthwaite
{Pharm. J. Travis, [3], 13, 464 — i65 ; compare this vol., p. 381).— In
514 ABSTRACTS OF CHEMICAL PAPERS.
this paper, a series of experiments is described, intended to clear
np the question whether oxalic acid, when boiled with a solu-
tion of sodium arsenate, exercises a reducing action upon it, either
alone or with sulphuric acid or hydrogen sulphide. To this end,
1 gram of sodium arsenate and ^ gram oxalic acid or ammonium
oxalate were dissolved in 60 c.c. of water and boiled for half an hour ;
no reduction was observed. Moreover, a mixture of oxalic acid and
sodium oxalate solutions may be boiled for some time without the
evolution of carbonic acid ; thus oxalic acid alone exerts no reducing
action on arseniates. With regard to any reduction which takes place
when oxalic acid and sulphuretted hydrogen act simultaneously on
sodium arsenate, the authors found that sulphuretted hydrogen, when
passed through a solution of oxalic acid, gave rise to a powerful
reducing agent, probably formic acid, which substance, however, does
not reduce sodium arsenate to arsenite. The authors conclude that
oxalic acid cannot be credited even indirectly with the reduction of
arsenates. D. A. L.
Examination of Water and Air for Sanitary Purposes, with
Kemarks on Disinfection. By R. Hitchcock {Chem. News, 1883,
7). — The author points out that although it is not possible to ascertain
by chemical means whether a water contains contagious disease-germs
or not, nevertheless chemical analysis is very valuable, for by it the
source of any impurity may be traced, and the possibility of the water
becoming a vehicle of disease may be indicated. In the same way with
air, although the bad gases alone would not produce disease, never-
theless disease-germs would grow and multiply better in gases from
decomposition of animal matter than in pure air ; and, besides, the
germs will be very readily disseminated by the rising gases. Air
charged with germs can be filtered through gun-cotton, which can be
dissolved in ether, when the germs remain behind and can be micro-
scopically examined. The author attaches great importance to this
point. He considers ordinary aerial disinfection utterly useless ; the
only efficient plan for purifying a sick room is to immediately disin-
fect all refuse, and to have thorough ventilation. D. A. L.
Anmionia-process for Water Analysis. By C. W. Maesh
(Chem. News, 1883, 19 — 20). — In this paper, a statement made by
Remsen is confirmed, to the effect that when free ammonia and albu-
minoid ammonia are determined by Wanklyn's process, the amounts
of the two added together are found to be much smaller than the total
ammonia found when the oxidising mixture is added without previous
boiling. Results obtained from the analysis of 26 samples of various
waters (well, cistern, canal, distilled, spring, surface) tend thus ; the
analysis for free and albuminoid ammonia being made as Wanklyn
directs : in one case only did the sum of the free and albuminoid
ammonia exceed the total ammonia, and this result the author attributes
to error from the high colour of the solution Nesslerised ; in three cases,
the amounts were identical, due to the fact that no volatile nitrogenous
substances escaped during the distillation part of the process ; in the
remaining twenty-two the sum of the free and albuminoid ammonia
ANALYTICAL CHEMISTRY. 515
was less than the total ammonia. These results prove conclusively
that some volatile substance escapes conversion into ammonia ; and
from a series of ten experiments out of which six support the view,
the author comes to the conclusion that the volatile substance is a
condensable nitrogenous organic compound which passes over and is
condensed along with the "free'' ammonia distillate. The experi-
ments consist in redistilling the " free " ammonia distillate with
potassium permanganate, so that the free ammonia is obtained plus
the ammonia produced by the decomposition of the nitrogenous
organic compound ; for example, in experiments Nos. 2 and 3 : —
1.
2.
3.
4.
5.
Sum of free
Free
Albumin.
Sum of
Total
and regained Sum of
ammonia.
ammonia.
1 and 2.
ammonia.
ammonia. 2 and 5.
2. Well water 005
0-10
0-15
0-16
0-06 0-16
3. „ „ 0-05
0-08
013
017
0-09 0-17
The results of all the experiments are tabulated. D. A. L.
Determination of Nitrites. By E. W. Davy (Pharm. J. Trans.
[3], 13, 4!66 — 468). — The proposed method is based on the reaction
which takes place between nitrous acid or soluble nitrites and gallic
acid, of the nature represented by the equation : —
CtHbOs + 2HNO2 = C6H4O3 + CO2 + 2N0 + 2H2O.
Gallic acid. Tanno-melanic
acid.
This change is always accompanied by a coloration of the solution.
The colouring matter thus formed is unajffected by dilute sulphuric,
nitric, and hydrochloric acids, or even by concentrated solutions of
organic acids, oxalic, acetic, and tartaric ; moreover, the coloration is not
affected by the presence of saline and earthy salts, or small quantities
of organic matter or of nitrates. The intensity of the colour produced
is in direct proportion to the amount of nitrite reacting on the gallic
acid ; the process can therefore be applied quantitatively in a manner
similar to the Nessler test. Thus it would only be necessary to com-
pare the colour produced in the liquid under examination with that
produced with a definite quantity of standardised nitrite solution.
The standard nitrite recommended has double the strength of that
described by Frankland for use with Griess's test ; the gallic acid test
solution is a concentrated aqueous solution of the acid which, if
coloured, can be decolorised by treatment with animal charcoal; this
solution is made strongly acid, so as to prevent the very rapid change
of colour which gallic acid generally undergoes. The process is well
adapted for water analysis ; its application is very simple : 25 to 50 c.c.
of the water are boiled with 1 or 2 c.c. of the gallic solution and a
few drops of sulphuric or hydrochloric acid ; the colour produced is
then compared with the standard in the usual way. If iron salts are
present, they should first be removed by ammonia and filtmtion. The
author has been able to detect 1 part of nitrous acid in 20,000,000
parts of water. Compared with Griess's method this process does not
516 ABSTRACTS OF CHEMICAL PAPERS.
give so deep a colour when there are large quantities of nitrites
present, but with smaller quantities it is equally efficient, and, from an
economical point of view, has a decided advantage. D. A. L.
Preparation of Alkaline Potassium Permanganate Solution
for Water Analysis. By J. Stapleton (Chem. News, 46, 284).— The
great difficulty has been to prepare alkaline potassium permanganate
solution free from ammonia; the author considers that most likely the
potash is the cause of this difficulty. The process now recommended
by him consists in (1) the purification of the potash by a sort of
" Clarke's process," and (2) the distillation by steaming of the mixed
solutions of alkali and permanganate. It has been used for two years
and has proved satisfactory. It is thus worked : the potash is dis-
solved in a hard water containing dissolved calcium carbonate, and
the precipitate of calcium carbonate is allowed to subside 24 hours or
so, carrying down with it a large proportion of the nitrogenous organic
matter. The clear potash-solution is now mixed with the solution
of potassium permanganate; the mixed solution is warmed by a
Bnnsen, and is subjected to a current of steam from water free from
ammonia ; the vapours are condensed ; and the steaming is continued
until the distillate, when Nesslerised, shows only 0'005 mgrm. per litre
of ammonia ; this occupies about one hour, and the solution is practi-
cally free from ammonia. It is advisable to have the neck of the retort
inclined slightly upwards, to fill it only to one-third, to put in some
small pieces of pumice, and to support it on wire-gauze on a tripod in
such a manner as to be able to syphon off the liquid. D. A. L.
Preparation of a Volumetric Solution for Determining the
Hardness of Water. By C. R. C. Tichborne (Chem. News, 46,
2.35). — Since the time of its introduction, Clarke's process for deter-
mining the hardness of water has undergone, with the exception of
some minor changes, no improvement. As the preparation and stan-
dardising of the soap-solution is troublesome, the author thought the
usual method might be improved. It was thought that by taking a
definite fatty acid (^ oleic) and neutralising with standard soda, a trust-
worthy soap-solution could be obtained in which the sodium would
represent its equivalent of the calcium constituting the hardness.
When soda is added to oleic acid, it gives a neutral reaction with
phenol-phthalein as indicator, when the quantity required for the
formula M'Ci8H3302 has been added, assuming the sp. gr. of oleic acid
as 0915 ; if another equivalent of soda be now added, the aqueous
solution of the sodium oleate becomes a solid jelly, and, if the action
of the soda be pushed further, additional compounds are formed.
The mono- and di-sodium oleates are permanent compounds, and, as
the fatty acid is the measure of hardness, either can be used for the
determination.
Method of preparation : — 5 c.c. oleic acid are dissolved in 50 c.c.
alcohol, 2 drops of phenol-phthalein are now added, and a volumetric
solution of soda is run in until a pink tinge is produced. If gela-
tinous salt is required, another equal quantity of soda is run in. The
author prefers this salt when it can be easily prepared, which is not
ANALYTICAL CHEMISTRY. 517
always the case. The sodium oleateis made up to the required strength
bv the addition of equal parts of rectified spirit and water. Each 15*.5 c.c.
of soda used in the first neutralisation equals 820 c.c. of volumetric
soap solution. Such a solution is in Clarke's original scale ; it is not
necessary to titrate against a calcium solution, as the soda is quite as
definite. The author has always found that 5 c.c. of oleic acid (pure
or commercial) require 15'5 c.c. of soda : 82 c.c. of the solution when
operating on 100 c.c. water represent 16° hardness per gallon by
Clarke's scale. The advantages claimed are that the soap-solution may
be made in five minutes, requires no titration against a standard water,
and is more permanent than those made from ordinary soaps.
D. A. L.
Estimation of the Fertility of a Soil. By A. Yogel {Bied.
Centr., 1882, 852). — If a sample of a soil treated with acetic acid
gives no indication of phosphoric acid after having been in contact
with ammonium molybdate for 24 hours, the percentage of phosphates
is abnormally low.
Organic matter may be roughly estimated by boiling 10 grams of
the soil with water, and adding to the solution potassium perman-
ganate until a permanent coloration is produced. E. W. P.
Determination of the Plashing Point of Petroleum. By J.
T. Stoddard (Chem. News, 1882, 297). — The author suggests a niodi-
fied form of Liebermann's flashing point apparatus. It consists of a
cylinder 2 to 3 cm. in diameter, and 10 to 12 cm. long, closed at the
bottom by means of a cork through which just passes a small tube
drawn out to a jet. This tube is bent round and up along the outside
of the cylinder, and is connected with a supply of compressed air by
means of india-rubber tubing, which is furnished with a screw clip for
regulating purposes. To use the apparatus the cylinder is filled to
about one-third with oil ; it is then plunged into a water-bath up to
the level of the oil, and can be secured in this position by means of a
clamp. Air is admitted through the tube at a rate suJEcient to keep
about 0*5 cm. of foam on the surface. A small flame or match is
used to test for the flashing point. D. A. L.
Estimation of Coke and Volatile Products in Coal. By
R. Galloway (Chem. Centr., 1882, 767).— About 500 grains of the
powdered coal are weighed in a tared porcelain crucible, which is then
placed in a larger clay crucible, the bottom of which is covered with
powdered wood-charcoal, the space round and above the smaller
(crucible is filled up with lumps of wood- charcoal, and after the cover
is on, the whole is heated at a bright red heat in a furnace. This
done, it is allowed to cool, and the porcelain crucible is weighed.
The total weight, less weight of crucible, is coke, whilst the loss repre-
sents the volatile products. Previous methods have always given the
amount of coke too low, because part is generally burnt away by the
air. The charcoal in this process prevents access of air, and also keeps
the smaller crucible in the proper position. D. A. L.
518
ABSTRACTS OF CHEMICAL PAPERS.
Estimation of Alcoholic Liquors. By J. Nessler and M.
Barth (Zeits. Anal. Chem., 22, 33 — 43). — A considerable number of
various brandies (cherry, pi tim, &c.) have been examined by the authors,
and tested specially for copper and hydrocyanic acid. The metal was
found in varyinj^ amounts, up to 18 m^rm. per litre, in most, and the
hydrocyanic acid in the whole of the samples in quantities from
3 to 17 mgrms. per litre. O. H.
Relation between the Glycerol and Alcohol in Wine. By
E. BORGMANN (Zeits. Anal. Chem., 22, 58 — 60). — From a number of
experiments, the author concludes that the proportion of glycerol to
alcohol is never less in pure wines than 7'8 : 100. 0. H.
Analyses of Pure Wines. By R. Fresenitjs and E. Boegmann
(Zeits. Anal. Chem., 22, 46 — 58). — The results may be tabulated as
follows : —
100 c.c. contain Grams.
Red
Main
wines.
White
Main.
Hocks.
White
French.
Bed
French.
Moselle.
' Maximum .
9-51
10-15
10-39
9-84
9-32
8-72
Alcohol . . .
Minimum .
9-49
8-90
6
42
9-05
7-99
7-04
Average. . .
9-50
9-52
8
77
9-44
8-56
8-08
Maximum.
3-30
2-78
3
00
2-62
2-67
2-44
Extractives
Minimum .
2-70
2-16
1
86
2-47
2 17
1-92
Average. . .
3-00
2-43
2
32
2-54
2-44
211
Mineral
■ Maximum .
0-35
0-20
0
30
0-28
0-27
0-20
Minimum .
0-29
0 17
0
16
0-24
0-21
0 15
matter
_ Average. . .
0-32
0 19
0
22
0-26
0-25
0-18
■ Maximum .
0-62
0-80
1
01
0-71
0-58
0-95
Acidity . . .
Minimum .
0-54
0-54
0
-48
0-54
0-48
0-64
Average. . .
0-58
0-69
0
66
0-62
0-54
0-79
" Maximum .
1-23
1-34
1
28
1-00
0-99
0-85
Glycerol . .
Minimum .
116
0-86
0-
64
0-88
0-75
0-66
_ Average. . .
1 19
1-10
0
92
0-94
0-86
0-73
Sulphuric
acid
' Maximum .
0-082
0-069
0
050
0-019
0-027
0-018
Minimum .
0-070
0-027
0
045
0-015
0-006
0-OOfi
Average. ..
0-076
0-044
0
047
0-017
0 013
0-012
Phosphoric
acid
' Maximum .
0-065
0-051
0
048
0 046
0-037
0-056
Minimum .
0-065
0-033
0
026
0-023
0-023
0 039
_ Average. . .
0 065
0-039
0-040
0-034
0-027
0 047
The mutual relations of the different constituents are on the
average as follows : —
Alcohol : glycerol = 100 : lO'S
Extract : acidity = 1000 : 16'6
Acidity : mineral matters = 10 : 3'4
Mineral matters : extractives = 1 : 11 '2
Phosphoric acid : mineral matters =
6-8.
O. H.
ANALYTICAL CHEMISTRY. 519
Estimation of Sugar by Alkaline Copper Solutions. By
P. Degener and F. Allien (Bied. Cenir., 1882, 845 — 84-7). — Because
of the uncertainty whicli exists in the usual process for the estimation
of sugar, Degener proposes a solution consisting of 80*2 grams copper
tartrate, 400 c.c. solution sodium hydroxide made up to 500 c.c. with
water; 12*5 c.c, 25 c.c, or 50 c.c of this are then mixed with a solu-
tion of Rochelle salt, and boiled with the sugar solution for half an
hour. The author states that only 6 mols. cuprous oxide will be
formed for every molecule of grape-sugar, whether the copper be in
excess or not. AlHhn, on the contrary, finds that the quantity reduced
varies, so that there is no advantage gained by the use of this method.
E. W. P.
Pyrolein. ByJ. Arbos (Pharm.J. Trans. [3], 13, 624— 626).— When
certain fixed oils are distilled with glycerol, both substances undergo de-
composition, the distillate being in two layers, the lower one consisting
of acrolein, whilst the upper is generally an oily, limpid, acid liquid,
insoluble in water, greasy to the touch ; this contains what the author
calls pyrolem. It is completely soluble in a small quantity of alcohol,
but on adding more alcohol an oil separates out, which is soluble in
ether and in. excess of pyrolein. The alcoholic solution forms an
emulsion with lead acetate, and a precipitate with copper sulphate.
Results obtained by distilling separate mixtures containing (1)
2 parts of glycerol and 1 of olive oil ; (2) 20 parts glycerol, 9 parts
olive oil, and 1 of oil of sesame ; (3) 20 glycerol, 10 olive oil, and 1 of
cotton-seed oil, along with observations, are tabulated below : —
520
ABSTRACTS OF CHEMICAL PAPERS.
,
1
^ fc
^-^ E
1
1
1 ^ .o' -^T 3
1 ."= -1-3 !>• . a ^ o . .
1
Does not foam.
Penetrating, irr
ing the throa
24 hours, m. p. 7
Buff coloured.
Reddish-yellow
G-olden-yellow.
Very small quai
of solid yello
oil after 48 h
Blackish.
Black.
Yellowish.
Bright carmine
Bright scarlet.
Dark yellowish-
brown.
Reddish.
Greenish.
Olive-brown.
: :
;og, 1 i
: ^ :2
d
o
: ^
:-^" sl :
©
: N
:-i2r=i §3 :
^ .^
1
; ^
reenisl
it
ddish-
rS
DQ
I p-^
. " 'C Tfl •*i ,00
CM
1
^TJ
§
^
a
i 2 21
-i
d yelloi
;s after
^sh, and
yellow
y-red. .
if.
red; g
ted ligl
;-groen
dark re
§
1^
1 iiilriillllli
Dark
flee
Bottlt
Very
: _ • • • • t-.Tf<
! ^
:'3 f^j M
: ^
ut sligh
d, after
48 hour
d
: 3
CD
■-"/lo
o
©
: ^
c
aratea
nd tu
lains i
rC
T
O
«fH
dish-yell
jh oil Sep:
)loured a
ours, ren
0
1
>
. 1
bJD42
ii
1
I I-i3 i
:
. -U) bo .
.rc:;:^ ,
^
bfr^ •
'ib
. ;^ © •
:2-
'-'^•■^ ''
.£pT3
•^ a :
-- ®
11
9. «
00 . t" +3 •
Ji c
p. g" .-;3 ©
. II
ft
1
;:3
m
TS
^
^1-
f
5
i
1 :
1
become
which
4 hours
ers, the
1
CD •
^ :
'^ gj - :
onia.
iquid
he oil
fter2
0 lav
1 •
3 •
S ^ 1 1 a :
1
U.2
1:
ises at
if liqui
c solui
with a
tricac
•oduce
Si
ystalli
lour c
coholi
eated
ithni
CI,, PI
. ^
II
S
■13
O
6
c
o
r-H
S
^
^
p
^
1
ANALY'i^'ICAL CHEMISTRY. 521
The author is of opinion that these reactions will be useful in the
examination of fixed oils. D. A, L.
Milk Analysis. By E. Ppeiffek {Zeits. Anal.jChem., 22, 14 — 20).
— The author's remarks as to the estimation of casein and albumin
contain nothing new. He points out, as Hoppe-Seyler and others
have done long ago, that milk contains a considerable amount of
nitrogenous matter apart from the casein and albumin, this albu-
minous matter being precipitable by tannin. In human milk it
varies between 0*3 and 0'5 per cent., in cow's milk it is about 0*7 per
cent. 0. H.
Adulteration of Butter. By E. Schmitt (Ann. Agron.^ 8, 544 —
655). — The conflicting evidence of analysts in a case of suspected
butter adulteration led the author to examine the different published
processes for the analysis of butter.
The density of butter is, according to the author, too variable and
too difficult to determine exactly either by sp. gr. flask or by the
margarimeter, so as to allow of definite conclusions being drawn. It is
moreover easy to imitate exactly the density of genuine butter. The
same remarks apply to the fusing and solidifying points, which vary
according to the method adopted to determine them, and with the
quantity of water contained in the butter.*
The microscopical examination proposed by Juillard yielded results
which were untrustworthy, and discordant from those of the chemical
examination.
The proximate analysis (water, fat, casein, ash) does not distinguish
between pure butter and mixtures of butter with oleomargarin.
Husson's process (Jour. Chim. Pharm.^ 1878, 100), depending on the
relative solubilities of the natural fats in glycerol, alcohol, and ether
under special conditions, was also tried. This gave, for a butter
subsequently proved to be genuine, margarin 36, olein 46, butyrin and
caprin 3, = 85 ; these figures are at variance with the composition af
genuine butter. Lechartier's process (Ann. Agrun., 1, 456), based
on saponification with alcoholic potash, distillation of the soap
with tartaric acid, and estimation of the distilled volatile acids by
titration or conversion into barium salts, did not give concordant
results. The same sample of butter gave 83*84, 82"25, 89' 70, and
85*54 per cent, of fixed insoluble fatty acids.
Hehner and Angell's process was the only one found to give correct
and concordant results ; three independent determinations by different
operators giving 88*25, 88*00, and 88*13 per cent, of fixed fatty acids
in the same butter-fat. The author recommends the determination of
the melting point of the fixed fatty acids separated by this process ; for
genuine butter-fat this should be 36 — 38°. Some analyses made in
this way are subjoined : —
* Note hy Abstractor. — Some of the uncertainty which the author complains of in
his determinations of density and fusing point, appears to be due to the fact that he
operated on crude butter, and not upon butter-fat, us is customary in England. —
J. M. H. M.
VOL. XLiv. 2 n
522
ABSTRACTS OF CHEMICAL PAPERS.
M.p.
butter.
Per cent.
fixed
fatty acids.
M. p.
fixed
fatty acids.
1. Butter seized by Public Prosecutor (genuine)
2. Flemish butter (warmbruehig)
3. -Best Lille butter
4. Butter (Saint Amand)
5. Oleomargarin
6. " Dutch butter " (2 fr. 60 per kilo.)
7. Lard
8. Butter 75 per cent., lard 25 per cent
9. Maize oil (sp. gr. 0-919)
33-5°
37-5
36 0
36 0
37-0
370
31-5
37-0
•25
•80
•89
•72
•0
•32
•17
•25
•67
39-5°
39-5
39 0
40-2
41 0
41 5
42-5
40-5
26 0
The standard proportion of fixed acids contained in genaine bntter-
fat has been variously fixed by different chemists. Hehner and
Angell give 87"5 percent., Pierre Apery 88 — 89*5 (for Siberian butter),
Bischoff 88 — 88'36; Fleischmann and Vieth from analyses of 185
German butters give 89 '73 as maximum, E-ussian chemists adopt
90'00 as maximum, Ralli 85-6, and Girard 87'96. J. M. H. M.
Estimation of Salicylic Acid in Milk and Butter. By A.
R^MONT {Bull. Soc. GUm. [2], 38, 547— 548).— 20 c.c. of milk are
taken, two or three drops of sulphuric acid added, and the whole
agitated so as to break the coagulum and produce a nearly homo-
geneous mass, which is then agitated with 20 c.c. of ether and left at
rest for a time ; 10 c.c. of the ethereal solution are then decanted and
evaporated in an ordinary test-tube, marked to indicate a volume of
10 c.c. The residual butter is then boiled with 10 c.c. of alcohol and
left to cool. A solution is thus obtained equal in volume to the milk,
and containing all the salicylic acid originally in it. 5 c.c. are filtered
off into a graduated tube of 1 5 mm. diameter, and two or three drops
of a 1 per cent, solution of ferric chloride added ; the intensity of the
colour is then compared with that given by a pure milk to which O'l
to 0*2 gram of sodium salicylate per litre has been added.
Butter is examined in a similar manner, 10 grams being taken and
boiled with 50 c.c. of alcohol, and the liquid tested colorimetrically.
E. H. R.
Genesis of Ptomaines. By F. Coppola (Gazzetta, 12, 511 — 520).
— These bases were originally regarded by Selmi (Bendiconti delV
Accad. di Bologna, 1874), and afterwards by Schwanert (Ber., 1874,
1332), as exclusively products of cadaveric putrefaction. Selmi, how-
ever, afterwards modified his opinion so far as to admit that, in cases
of serious pathological alterations, they might be produced in the
animal organism during life, a conclusion fully confirmed by Spica
(Abstr., 1881, 294). Finally the question was further modified by
the experiments of Paterno and Spica (Abstr., 1882, 741) on blood
and on egg-albumiu, and by those of Gautier on normal urine, all of
which showed that reactions similar to those above alluded to may
be exhibited by perfectly healthy animal fluids.
TECHNICAL CHEMISTRY. . 523
To throw further light on this question, the author has made a
series of experiments on the physiological action of bases extracted
from the blood of a healthy dog ; and his conclusions are that alka-
loids extracted from healthy animal fluids, carefully protected from
putrefactive alteration, may exhibit strong toxic properties, and that
consequently whatever idea may be formed of the nature of the putre-
factive process, the albuminoids must be capable of undergoing certain
transformations, which may give rise to the formation of poisonous
alkaloids. This being the case, it becomes a question whether among
these transformations should be included those which albuminoidal
substances undoubtedly nndergo in the extraction of alkaloids by
Dragendorif 's process ; for if this be the case, it might be alleged that
the ptomaines are merely products of the decomposition of the albu-
minoids, brought about either by chemical reagents or by putrefac-
tion, either during life or after death ; and until some process of
extraction shall have been devised, incapable in itself of giving rise
to the production of such alkaloids, no satisfactory proof can be given
of their presence in the normal animal organism. H. W.
New Method of Detecting Dyes in Yarns or Tissues. By
J. JoFFRE (Ghem. Ney^s, 46, 211, 250, and 260). — The reagents which
serve to distinguish the various dyes are nitric acid, potassium
hydroxide, hydrochloric acid, ammonia, ferric sulphate, and stan-
nous chloride. Full details of the effects produced by these reagents
on a very large number of dyes are given, but for these reference
must be made to the article itself. E. W. P.
I
Technical Chemistry.
Flameless Combustion. By T. Fletcher (Dingl. polyt. J., 246,
293 — 295). — In experimenting with gas and air burners, the author
found that the smaller the flame produced, the greater the heating
efl'ect which could be obtained from the consumption of a given
quantity of gas. This result led him to reduce the flame as much as
possible, and ultimately it was proved that under the most favourable
conditions the flame would disappear entirely. If, for instance, a ball
of iron wire be heated in the flame of a gas blowpipe, and the supply
of air be gradually increased, the jet of flame will become shorter and
the temperature will gradually rise. Then if after the ball has become
heated, the gas tube be pinched for an instant so as to extinguish the
flame, it will be found that there is a sudden increase of heat, and that
the iron will be melted. A similar increase of heat during the flame-
less combustion is shown if a lump of fireclay be substituted for the
iron wire, and petroleum vapour may be used in the place of coal-gas.
The author's experiments are still in their infancy ; it is hoped, how-
ever, that they will be the means of effectually utilising much of the
heat at present wasted. D. B.
2 n 2
524 ABSTRACTS OF CHEMICAL PAPERS.
Removal of Fixed Glass Stoppers. (Ohem. News, 46, 286.)
To remove these, tap and then unscrew with a wooden wrench,
made of a piece of wood about 3'5 inches long and 1 inch in breadth
and depth, with a piece morticed out large enough to admit the flat
part of the stopper. If this and all ordinary means fail, soak the
neck of the bottle and stopper in water. D. A. L.
Explosion of a Zinc Gasometer containing Oxygen. By
L. Pfaundler (Ann. Phys. Chim. [2], 17, 176). — On testing with a
spill a sample of oxygen gas which had been kept for six months in a
zinc gasometer, a violent explosiou took place. As the introduction of
hydrogen or coal-gas was precluded by the column of water within the
gasometer, the author considers that this water gradually absorbed the
acid vapours of the laboratory, which thus acted upon the zinc, and
liberated hydrogen. This view was confirmed by the observed corro-
sion of the zinc. In order to prevent this, the author suggests that
the surface of the zinc should be preserved by a coating of varnish.
V. BL V.
Recent Progress in the Soda Industry. By G. Lunge (Dinql.
polyL /., 246, 334—343, 383—390, 416—423, and 520— 532).— In
the introduction to this extensive paper, the author mentions that
although most of the subjects have already been published elsewhere,
the information is in many cases so imperfect, that it was thought de-
sirable to discuss this important question more minutely. In the first
place attention is called to the want of uniformity in specific gravity
tables, a question which affects, not only the soda industry, but almost
all other branches of technical chemistry. Messel has compiled a
table showing the wide differences in the specific gravity of sulphuric
acid and ammonia obtained by various investigators. Squire calls
attention to the fact that the tables published in books are drawn up
for pure substances, and are therefore often useless for commercial
products. The author cannot agree with Messel, who states that the
differences can hardly arise from impurities in sulphuric acid made
from sulphur.
Referring to gas generators, the author quotes as a novelty, Wilson's
gas producer, used in England for steel furnaces, copper-smelting
furnaces, glass and porcelain furnaces, and applied to Mactear's
decomposing furnace.
As to the progress made in the manufacture of sulphuric acid from
pyrites, it is mentioned that the so-called shelf-burners, which are
generally used in Germany, are now coming into extensive use in
England. The process of Benker and Lasne, based upon the intro-
duction of sulphurous anhydride and steam into the chamber exit
gases before they reach the Gay-Lussac tower, does not appear to have
given satisfactory results. The use of potassium nitrate in the form
of an aqueous solution has also been abandoned.
Lovett, in a paper on the testing of noxious vapours, describes a
number of absorption-apparatus and several forms of aspirator (J.
8oc. Ghem, hidustry, 1882, 20y).
Referring to Hurter's dynamic theory of the manufacture of sul-
TECHNICAL CHEMISTRY. 525
pharic acid, the anthor points out that it irmst be considered a most
valuable research in pure cbemistry. Hnrter attempts to show,
according to mathematical principles, the connection which exists
between the dimensions of the chambers, the composition of the
gases, the intensity of the reaction, and the consequent temperature
in the chambers, as depending on the method of combining single
chambers into sets. He thinks he has been successful in finding a
law applicable to more complicated reactions, which he expresses in
the following words : — " The rate of chemical change depends on and
is proportional to the facility with which groups of molecules favour-
able to the particular change can form in the system in which the
change occurs." Hurter does not give the deduction itself, but merely
a differential equation based thereon, into which he introduces the
amount of sulphurous anhydride, oxygen, water, and nitrogen com-
pounds, in order to find the dynamic equation representing the rate
of the formation of sulphuric acid in the chambers. He obtains the
following results : —
1. As the chamber space is increased in arithmetic progression, the
amount of sulphurous anhydride not converted into sulphuric anhy-
dride decreases in geometric progression.
2. The chamber space for a given fixed loss of sulphur is propor-
tional directly to the velocity of the gas, or, what is the same thing,
to the amount of sulphur burnt.
3. The chamber space is inversely proportional to the nitrogen
compounds and aqueous vapour present.
Hurter's conclusions as to temperature show that the excess of tem-
perature of the chambers over the surroundings for successive cham-
bers decreases in geometric progression, and that the temperature of
the leading chamber depends on the number of chambers which are
connected into one system.
In discussing the manufacture of sodium sulphate. Lunge mentions
that the substitution of machine power for manual labour is becoming
more and more of an accomplished fact. In England the processes
of Jones and Mactear are competing with each other. Since the con-
struction of the furnace devised by Jones and Walsh has been altered,
this furnace is said to work satisfactorily, although it is less generally
employed than Mactear's salt cake furnace. In general construction
this furnace is very similar to Mactear's carbonator, there being, how-
ever, no central opening, but a central division or pot, into which the
salt and acid are continually fed. This pot serves as a mixing vessel,
irom which the thin pasty mass flows over into the first division of
the bed, where the first stage of the process is completed. It then
passes successively through the other division until it reaches the
outer circumference of the furnace, where it passes into the delivery
trough which runs all round the furnace, and is luted to prevent
escape of gas. The materials are mixed by means of an agitator
placed between the two flues, through which the acid vapours mixed
with the products of combustion pass away to the condensers. The
heating of the furnace may be carried out as most convenient, care
being taken to obtain thorough combustion, so as to prevent soot being
passed on into the condensers. The great advantage of this continuous
526 ABSTRACTS OF CHEMICAL PAPERS.
system of decomposing salt is to be found in connection with the con-
densation of the hydrochloric acid. The salt-cake as it is withdrawn
is almost entirely free from smell or acid vapour ; there is no difficulty
in making sulphate of 97 per cent, from common white salt. The
advantages may be summarised as follows : — Reduced cost of labour
and fuel, and economy of sulphuric acid. Complete condensation
without wash-towers, no weak acid being produced. Hydrochloric
acid formed of greater strength than by an open furnace, and equal
to the best form of close farnace. Complete removal of nuisance
caused by escapes of acid vapours during the working or discharging.
Small amount of wear and tear, and low cost for repairs. Better
quality of salt cake, rendering it specially suitable for glass-making
purposes. Ability to use rock salt alone. Less outlay for plant to
decompose a given amount of salt and condense all the acid. Re-
ferring to the decomposition of salt in hand-furnaces, Deacon's fur-
nace has been introduced into most works using muffle furnaces.
According to Weldon, the preparation of anhydrous sodiam sulphate
from crystallised Glauber salt by Pechiney's process, is effected on a
large scale in the following manner : — At the salt- work of Giraud,
the mother-liquor left after the salt has crystallised from the salt
water when subjected to cooling, deposits large quantities of sodium
sulphate, associated with 10 atoms of water. Pechiney adds to
Glauber salt a certain proportion of " sels mixtes," i.e., a mixture of
sodium chloride and magnesium sulphate, which is deposited during
the concentration of the mother-liquor to 35° B. by sun heat. The
mixture is then introduced into iron cylinders, and heated to 70 — 80".
When a temperature of 35° has been attained, the contents of the
cylinders are found to have become a mixture of anhydrous sodium
sulphate with a saturated solution of " sel mixte," the latter having
dissolved in what was the water of hydration of the sodium sulphate.
The whole is then machined at a temperature not under 35° (hence
Pechiney's object in heating to 70 — 80°), when the full quantity of
anhydrous sulphate corresponding to the hydrated sulphate treated is
obtained. The whole process is performed in a very short time, and
its only cost is for a small amount of labour and steam. The solution
filtered from it is employed for the production of more hydrated sul-
phate.
Parnell has made a series of trials on the action of potassium nitrate
in the manufacture of caustic soda, the results of which confirm the
conclusion previously arrived at, namely, that the ammonia evolved
from the boiling liquors in the Leblanc process is due to cyanide, and
does not arise from the decomposition of the nitrate.
Referring to the improvements in the manufacture of chlorine,
Lunge mentions Strype's process of purifying hydrochloric acid from
sulphuric acid by means of calcium chloride. This method, which is
worked successfully at Wicklow, consists in adding to the hydrochloric
acid in the cold about 20 per cent, of its volume of the solution of
calcium chloride, obtained as a bye-product in the Weldon process.
Thus almost the whole of the sulphuric acid originally present in the
hydrochloric acid is precipitated, and may be separated by filtration.
In the manufacture of potassium chlorate, as at present ordinarily
TECHNICAL CHEMISTRY. 527
conducted, there is a loss of* from 15 — 25 per cent, of the total chlorate
produced. According to Pechiney's improved method, this loss is
reduced to below 5 per cent. The improvement in question was de-
vised for the purpose of reducing the cost of preparing sodium chlo-
rate, now extensively used in the printing of aniline-black. Pechiney,
in investigating the solubility of a mixed solution of sodium chlorate
and chloride, found that, not only does the solubility of sodium chlorate
increase with the temperature, but it increases to such an extent that
mere concentration by evaporation of a mixture of these salts will cause
practically the whole of the sodium chloride to fall down, leaving
sodium chlorate alone in solution. The disadvantages of this process
are : the large amount of sodium sulphate required by the reaction
CsiCWe + 5-5CaCl2 + C-SNa^SOi = 2NaC103 + 2NaCl -|- 6-5CaS04 ;
the unavoidable loss of sodium chlorate ; its separation from the large
amount of calcium sulphate ; and the expense of evaporating the wash
waters. The presence of so large a proportion of sodium chloride
was a further cause of loss of chlorate. Pechiney surmounted these
difficulties by removing the 5'5 molecules CaClz, which are unavoidably
formed in the preparation of 1 molecule CaCl206, and thereby reducing
the quantity of calcium sulphate and sodium chloride considerably.
The method consists in evaporating the crude chlorate liquor until its
density is 48° B. The liquor is then cooled to 12°. Of its 5*5 mols.
of calcium chloride, 4*3 mols. are thus caused to crystallise out as
CaCl2,2H20. The concentrated solution must be cooled to at least
12°, or this proportion would not be separated ; it must not, however,
be cooled below lO'', or calcium chlorate would be deposited as well.
The crystals obtained between these limits of temperature are free
from calcium chlorate, and are of a nature permitting them to be sepa-
rated completely from their mother-liquor by means of the hydro-
extractor. The mother-liquor consists of 1 mol. CaCl206, and 1'2 mol.
CaCl2. It is diluted with its own volume of water, treated with three
times 1*2 mol. lime, and heated to 80°, to determine the formation of
calcium oxy chloride. It is then cooled and filtered. The filtrate con-
sists of a solution of 1 mol. calcium chlorate and only 0'3 mol. calcium
chloride, and thus contains one-eighteenth of the proportion of calcium
chloride originally present, so that the above-mentioned loss is con-
siderably reduced.
In conclusion, the author discusses the recovery of sulphur from
soda-waste. At Salindres, Pechiney simply injects air into the liquor
by the aid of a Korting's injector, and then when oxidation has just
reached the point at which treatment of the product by an acid would
not cause evolution either of sulphuretted hydrogen or of sulphurous
anhydride, he decomposes the product by hydrochloric acid. During
the operation of oxidising the liquor, there occurs a considerable preci-
pitation of lime, in a peculiarly dense state, and readily separable.
Owing to this separation, the quantity of hydrochloric acid is appre-
ciably reduced. Kingzett recommends to dry the soda-waste in the
air, then grind it, and finally melt it with coal-tar pitch, for the pur-
pose of asphalt- making. After referring to Mond's sulphur recovery,
Lunge describes and discusses at length the process invented by
Schaffner and Helbig, as recently reviewed by Weldon (/. Soc. Chem.
528 ABSTRACTS OF CHEMICAL PAPERS.
Industry, 1882, 45), and Chance (/. Soc. Arts, 1882, 727; and /. Soc.
Chem. Industry, 1882, 264). D. B.
Improvements in the Preparation of Alkalis. (Bingl. polyt.
J., 246, 279—285.)
Analytical Methods. — In dissolving iron pyrites or similar snlphur
ores. Lunge nses nitric acid of a density not exceeding 1*42, and to
avoid the separation of sulphur and facilitate the oxidation, J vol. of
hydrochloric acid is added to the mixture. The same investigator
recommends the use of phenacetolin instead of the barium chloride
method for determining carbonated in the presence of caustic alkalis.
The barium chloride method was found to give satisfactory results
when the quantity of carbonic anhydride present was small ; in the case
of caustic liquors, however, inaccurate results were obtained ; phena-
cetolin is preferable, although there is a certain amount of doubt in
determining the end reaction. With crude soda-liquors containing
much sodium carbonate, and only a small amount of caustic soda, the
barium method is almost useless. When phenacetolin is used, the
titration should be continued until a red colour is produced, which
indicates the complete saturation of the sodium hydroxide. Sodium
sulphide does not interfere with the reaction, so that solutions con-
taining it can be titrated direct for alkalinity ; ammonia, however,
behaves differently, giving a red colour immediately after its addition.
For titrating the oxidisable sulphur compounds in crude soda-liquors
with iodine. Lunge recommends to dilute 5 c.c. to 200 c.c, then add
starch solution, acidify with acetic acid, and titrate as rapidly as
possible with iodine solution. In titrating alkaline f errocyanides with
copper sulphate according to Hurter's method (ibid., 243, 489),
depending on the oxidation with calcium hydrochlorite, it is better to
add a concentrated solution of calcium hypochlorite or bromine-water
from a burette, until the mixture ceases to give a blue colour with
iron chloride. A second portion is then treated with the same quan-
tity and titrated with copper sulphate, until a distinct pink coloration
is produced, with a dilute solution of ferrous sulphate. In calculating
the results according to Schaeppi's formula, only 84" 1 per cent, of the
quantity actually present is obtained, due to the fact that Schseppi,
instead of basing his calculation on the molecular weight of cnprio
oxide (79), assumed the atomic weight of copper (63).
Combined Process of Leblanc and Ammonia- Soda Manufacture. — •
According to Schaffner and Helbig, the soda residues obtained in the
Leblanc process are treated with magnesium chloride. The magnesium
hydroxide formed and that precipitated by the addition of slaked lime
or dolomite to the magnesium chloride are used to evolve ammonia
from the ammonium chloride liquors of the ammonia-soda manufacture,
magnesium chloride being again formed. According to Solvay the
bicarbonate obtained in the ammonia-soda process always contains
water, and on heating becomes pasty, forming troublesome deposits in
the apparatus used. This diflSculty is overcome by adding a certain
quantity of calcined soda to the bicarbonate. It is further recom-
mended to utilise the natural basic phosphates in the manufacture of
soda and potash by the ammonia process. The cmdo phosphates are
TECHNICAL CHEMSTRY. 529
ground, waslied with water, in order to remove the calciam carbonate,
burnt, and used for the recovery of ammonia from the ammonium
chloride.
Korndorff has patented a process for recovering potassium chloride
by means of calcium chloride or solutions containing it, in dissolving
carnallite raw salts, instead of using water, or solutions of magnesium
chloride containing potash. Thus the magnesium sulphate is pre-
vented from being dissolved, the result being that the solution on
crystallisation yields a purer potassium chloride.
According to Meyer, potassium sulphate is prepared from schoenite
in the following manner : — The separation of both salts is effected by
boiling a hot saturated aqueous solution of schoenite with an excess of
schoenite salt, potassium sulphate being separated, whilst a corre-
sponding quantity of magnesium sulphate is dissolved. On evapora-
tion, crystals of schoenite are obtained, and subsequently crystals of
magnesium sulphate, which are separated from the mother-liquor at
25 — 30°. If allowed to cool below this temperature, the potassium
sulphate contains schoenite.
Griineberg extracts schoenite from ka'inite by means of a saturated
solution of sodium chloride. The latter dissolves at 80 — 100°, nearly
one-half its weight of schoenite from kainite. From this solution
schoenite crystallises almost completely on cooling. The mother-liquor,
if not too rich in magnesium chloride, may be used for a further extrac-
tion. It suffices to lixiviate the mass three times, or the process may
be made to work continuously. The greater portion of the magnesium
chloride is contained in the first extract, and is used either in the
manufacture of potassium chloride or recovered on evaporation.
Wittgen and Cuno have patented a process for preparing potassium
carbonate from potassium chloride by forming carbonate of zinc and
potassium, and decomposing it with water. D. B.
New Mineral Manure Deposits. By P. Grigorjeff (Chem.
Centr., 1882, 809). — In many districts in Russia there are extensive
deposits of the so-called Ancella-Schicht. The author has examined
the green sandstone and the sand of this deposit from four places in
the Rjazansehen Gubernie. The sandstone contains (besides a small
quantity of clay) 57'91 — 62*59 per cent, of a cement consisting of
calcium phosphate and carbonate and brown haamatite ; the sand
Contains 1803 — 27*04 per cent, of the cement. The sandstone is com-
posed of 47*13 — 50*41 per cent, calcium phosphate (which forms
75*49 — 86*63 per cent, of the cement.), 19*18 — 24*96 per cent, glaukonite,
and 5*2 — 14*5 per cent, quartz. The sand contains 40*12 — 42*23 per
cent, glaukonite. These are very valuable manures, especially the
sandstone, which contains easily decomposible silicates containing
8 per cent, potash. D. A. L.
Production of Pozzolana. By L. Demarchi and 0. Fodera
(Dingl. pohjt. J., 246, 540). — In the Journal of Engineering and
Mining, 34, 45, the occurrence and production of pozzolana at Rome
and Naples is described. The following is the composition of pozzo-
lana occurring near San Paolo : —
530 ABSTRACTS OF CHEMICAL PAPERS.
Alkalis
and volatile
SiOs- AI2O3. MgO. FejOg. CaO. HoO. substances. Sand.
47-66 14-33 , 3-86 10-33 1-m 703 4-13 500 = 100*00
From 15 — 45 per cent, of lime is added, the quantity depending on
the subsequent application of the cement, e.g., for the production of
hydraulic cement, an addition of 18 per cent, lime is required.
D. B.
English Cement. {Bingl. polt/t. /., 246, 539).— The following
are analyses of samples of cement from the Folkestone (I and II,
taken in March, 1880, and September, 1881, respectively) and Thames,
(III, taken in 1881) Cement Works : —
Insoluble. SiOj. ALjOg. FeaOg. CaO. MgO.
1 1-260 20-990 8-869 4-998 61-350 0-669
II 2-566 18-917 8-763 4412 62472 0841
III 2-894 21-307 6-593 5386 61459 0-449
SO3. K2O. NasO.
1 0-886 0-978 — = lOO'OOO
II 0-929 1-100 — = 100-000
III 1-422 0-437 0-429 = 100-376
D. B.
Portland Cement and its Adulteration. By W. Michaelis
(Dtngl. polyt. J., 246, 390 — 391). — The author has made a series of
experiments as to the effect of additions of trass, Roman pozzolana,
blasb-furnace slag, glass and flint, on the tenacity and durability of
cement, which show that these substances by no means always pro-
duce a beneficial effect, and that some of them only set very slowly
with lime, and harden very gradually. How far such addition may be
made depends on the composition of the cement itself, and on the body
chosen for admixture with it.
The practice of German cement manufacturers to adulterate their
finely powdered Portland cement with foreign and less valuable sab-
stances, such as blast-furnace slag, trass, chalk, or limestone, and to
sell this mixture as Portland cement, having been carried too far, it
was resolved, at a meeting of the Society of German Cement Manu-
facturers, to consider the sale of cement adulterated with foreign
bodies of less value as a fraud on the buyers, unless the nature of the
mixture be made clearly known on sale and delivery. Additions up
to 2 per^ cent, of the weight which are made with the object of im-
parting especial properties to the cement, are not to be regarded as
adulterations. D. B.
Process for Rendering Cement and Lime less subject to
Atmospheric Influences. By E. Puscher (Dingl. polyt. J., 246,
539). — The author recommends that the cement materials should be
allowed to remain in a cold solution of 1 part ferrous sulphate in 3 parts
of water for 24 hours, after which they are dried in the air. The com-
pound of iron hydroxide formed renders the cement firmer and
harder, and less subject to atmospheric influences. D. B.
TECHNICAL CHEMISTRY. 531
Tellurium in Copper. Bj T. Egleston (Chem. News, 47, 51—
52). — The author has examined a sample of copper which was " red-
short," and in the process of refining gave off dense white fumes,
which " poisoned " the furnaces, rendering them anfit for refining
purposes. The cold metal is tough and malleable. The cause of this
mischief is the presence of tellurium, of which substance the " matte "
contained 0'12 per cent., the " black copper " 0*095 per cent., the
'* refined copper " 0'083 per cent. The copper as it comes from the
mould has every appearance of being good, but if repeatedly heated
and left to cool in the air, it becomes covered with tellurium oxide.
This, the author thinks, is the first time tellurium has been detected in
commercial copper, and he is surprised that such small quantities
should make the metal red-short. ^ D. A. L.
- Novelties in the Iron Industry. (Dingl. polyt. /., 246, 433—
438, 474—483, and 508— 513).— At the meeting of the Iron and Steel
Institute recently held at Vienna, a paper was read by G. J. Snelus " On
the Chemical Composition and Testing of Steel Rails." The author
refers to the investigations of Smith and Dudley, who conclude that
soft steel rails, i.e., rails with low tensile strength and considerable
extension are the most durable. For such rails, Dudley gives the fol-
lowing composition: — Carbon, 0'300; silicon, 0'040 ; phosphorus,
0*100 ; manganese, 0*350. In spite of the apparently conclusive proofs
as to the superiority of soft steel rails, the North Eastern Railway
Company, among others, uses a harder material having the following
composition: — Carbon not under 0*3 or over 0'45 per cent. ; silicon,
0'06 ; phosphorus, 0'06 ; sulphur, 0*06. Besides these substances, the
steel should contain only iron and manganese. The author is of
opinion that as hard rails break more easily, it is best to use the softer
kinds. He, however, objects to Dudley's formula as being difficult to
work to and very expensive. He considers the production of sound
castings free from porous and blistered places to be the most important
point, and mentions that with the use of Dudley's formula it would
scarcely be possible to obtain this result. Sound castings can be pro-
duced only by using more carbon, silicon, or manganese.
Referring to the question as to the presence of phosphorus in steel,
all evidence shows that it is a most vital one.
The author recommends the following formula : — Carbon, 0*35 ;
silicon, 0*10 ; phosphorus as low as possible, but not above 0*075 ;
manganese, 0*75.
In conclusion, some remarks are made in connection with the test-
ing of steel rails.
In a paper read by G. L. Bell on blast-furnace practice with coke
and with charcoal, the author states that the comparison of blast-
furnace statistics is a difficult matter, as there are so many quantities
variable — ore, flux, fuel, and temperature — that it requires the greatest
possible caution to enable the effect of any one single change to be
really identified. Nevertheless, it is clearly proved that Austrian
charcoal furnaces are worked with much less fuel per ton of pig iron
made than coke furnaces in England. Whereas also in Cleveland a
532 ABSTRACTS OF CHEMICAL PAPERS.
blast furnace produces about 30 tons of grey iron per week per 1,000
cubic feet ca])acitj, and in Luxembourg with similar ore about 50
tons, and in England with heematite 50 — 55 tons ; in Vordemberg, the
charcoal furnaces are driven so as to produce 73 to 93*5 tons white
iron, and in America even still more heavily. The paper examines
minutely the probable causes and efEects of these different methods of
working.
The most notable paper read during the meeting at Vienna was
that by J. Gjers, on the rolling of steel ingots with their own initial
heat without the use of fuel, by means of the so-called soaking pits.
Bessemer in 1856 showed that it was possible to produce malleable
steel direct from liquid cast iron without the expenditure of any fuel
except that which already existed in the fluid metal. The author has
supplemented this work by devising a method which enables him to
roll such steel into a finished bar with no further expenditure of fuel.
It is known that the fluid metal poured into the mould contains a
larger amount of heat than is required for the purpose of rolling or
hammering. This heat is composed not only of the high temperature
of the fluid metal, but also the store of latent heat in the same, which
is liberated when solidification takes place. All attempts hitherto
made with a view of utilising this heat of the ingot have proved
failures. The difficulty depends on the fact that a steel ingot when
newly stripped is far too hot in the interior for the purpose of rolling,
and if it be allowed to cool the exterior becomes too cold to enable it
to be rolled successfully. The author introduced his new mode of
treating ingots at the Darlington Steel and Iron Company's works
in June, 1882.
It is carried out in the following manner. A number of npright
pits are built in a mass of brickwork sunk in the ground below the
level of the floor. These pits are in connection with an ingot crane.
Each pit is covered with a lid at the floor level, and after having been
well dried and heated to redness, is ready for operation.
As soon as the ingots are stripped they are transferred one by one
and placed separately, by means of the crane, in the previously
heated soaking pits and covered with the lid to exclude the air. In
these pits, the ingots are left to stand and soak, i.e., the excessive
heat of the interior becomes uniformly distributed throughout the
metallic mass. Comparatively little heat being able to escape, as the
ingot is surrounded by red-hot brickwork, the surface-heat of the
ingot is greatly increased, and after the lapse of from twenty to thirty
minutes, the ingot is lifted out of the pit and swung round to the rolls
by means of the crane. The advantage gained is that the ingot is
always certain to be at least as hot in the centre as it is on the sur-
face. Every ingot when cast contains a considerably larger store of
heat than is necessary for the rolling operation; this surplus from
successive ingots going into the brickwork of the soaking pits tends
continually to keep the pits at the intense heat of the ingot itself.
During the soaking operation, a quantity of gas exudes from the
ingots and fills the pit, thus entirely excluding the air. This gas
being composed of hydrogen, nitrogen, carbonic oxide, and carbonic
anhydride, protects the ingots from oxidation. D. B.
TECHNICAL CHEMISTRY. 533
Tungsten Steel. (Chem. Centr., 1882, 783).— When tungsten is
mixed with steel during the final stage of preparation, a very charac-
teristic alloy is obtained. Steel with 10 to 12 per cent, tungsten is so
hard that it cannot be worked at the lathe nor can it, be filed ; it may,
however, be forged and polished. Steel with 5 to 6 per cent, is still
hard, but can be worked. Tungsten steel can be highly magnetised,
and magnets made from it show extraordinary power. Mu chefs
patent steel contains tungsten. Tools made from tungsten steel are
forged into form and then ground, and are extremely hard. Steel is
improved b}'' the addition of small quantities of tungsten.
D. A L
Composition of Pirwood Charcoal. By L. Einman (Dingl.
polyt. J., 246, 472). — One gram of the charcoal contained 0*053 water.
Composition : —
c.
CO2.
CO.
CH4.
H.
H2O.
Ash.
81-5
4-8
4-9
1-8
0-7
5-3
1-0
About 0*5 per cent, nitrogen and air may be considered as adhering
to the charcoal. By excluding the water and ash we obtain for
100 parts of charcoal the following numbers : —
c.
0.
H.
C:
. . . 87-0
87-0
—
—
CO2 . . . .
... 51
1-4
3-7
—
CO
. . . 5-3
2-3
3-0
—
CH4....
... 1-9
1-45
0-45
H
... 0-7
—
—
0-70
100-0
92-15
6-7
1-15
D. B.
Examination of Galician Petroleum. By A. Naweatil
(Dingl. polyt. /., 246, 328—334, and 423— 429).— The author has
investigated 18 varieties of Galician petroleum, obtained direct
from the springs. The following are the properties of the samples
analysed : —
1. Petroleum from Klenczany. Colour light reddish-yellow, with
■green fluorescence, transparent. Sp. gr. at 15° 0-779.
2. Petroleum from Ropa. Brownish-red with green fluorescence,
transparent. Sp. gr. 0'808.
3a. Petroleum from Ropa. Transparent, reddish-brown with green
fluorescence. Sp. gr, 0*800.
36. Petroleum from Ropa. The same as 3a. Sp. gr. 0-853.
4. Petroleum from Wojtowa. Non-transparent, greenish-black.
Sp. gr. 0-820.
5. Petroleum from Wojtowa. The same as 4. Sp. gr. 0-836.
6. Petroleum from Libusza. Greenish-black. Sp. gr. 0*837.
7. Petroleum from Senkowa. Greenish-black. Sp. gr. 0-837.
8. Petroleum from Libusza. Greenish-black. Sp. gr. 0-842.
9. Petroleum from Starunia. Greenish-black. Sp. gr. 0-845.
10. Petroleum from Siary. Blackish-brown. Sp. gr. 0-847.
11. Petroleum from Pagorzyn. Brownish-black. Sp. gr. 0*849.
12. Petroleum from Lipiniki. Greenish-black. Sp. gr. 0*850.
534
ABSTRACTS OF CHEMICAL PAPERS.
13. Petroleum from Siary. Brownish-black. Sp. gr. 0*853.
14. Petroleum from Mencina. Greenish -black. Sp. gr. 0'853.
15. Petroleum from Klenczany. Dark green. Sp. gr. 0*870.
16. Petroleum from Kryg. Brownish-black. Sp. gr. 0*876.
17. Petroleum from Harklowa. Brownish- black. Sp. gr. 0*898.
18. Petroleum from Harklowa. Brownish-black. Sp. gr. 0*902.
These oils were subjected to fractional distillation, and the results
are tabulated. The table, which is too long for insertion here, gives
the sp. gr. of the fractions obtained at 50° to 100°, 100° to 150°, 150°
to 200°, 200° to 250°, 250° to 300°, 300° to 350°, 350° to 400°, and
above 400°, with the percentage proportions of gum, coke, and loss.
The following table, which is a condensation of the first, gives the
percentages of the products separated, including coke and loss : —
Sample.
Light oils,
distillates up to
150°.
Petroleum dis-
tillates from
150°— 300°.
Heavy oils,
distillates above 300°
+ gum.
Coke and
l0S3.
1
2
3a ....
U
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
43-5
26-6
27-5
11-4
12-4
13-6
19-0
22-0
13-3
10-9
20-0
9-8
20*9
11-3
19*6
3-4
8-0
6-7
5-7
33-5
42-0
34-2
39*8
43*6
50-3
29-2
37-4
32-8
34-9
31-2
45-4
30-3
31-9
33 1
38*6
32-6
28-2
29-1
22-85
30-40
37 -00
46*50
41-50
34-30
47-10
30-10
49-40
50-90
43*3
40-6
41 0
52-3
42-9
54-5
53-2
58*2
56-7
0 15
100
1*30
2-30
2-50
1-90
4-80
2-50
4-00
3-30
5*5
4-2
4*8
4-5-
4-4
3 5
6-2
6-9
7 5
D. B.
New Source of Benzene, Naphthalene, and Anthracene.
(Bingl. polyt. /., 246, 429 — 432). — According to Liebermann, the
manufacture of benzene, naphthalene, and anthracene, from petroleum
residues, is worked on a large scale bj Nobel Brothers, of Baku.
Although the quality of the anthracene and naphthalene compares
fa,voarably with the same products derived from coal-tar, the benzene
boiling between 80° and 85° contains large quantities of foreign hydro-
carbons, and is not suitable for the preparation of nitrobenzene. It is
proposed to purify it by freezing out the benzene. The residues at
Baku are heated in red-hot iron retorts filled with pumice stone, the
gas produced being used for heating and lighting purposes. As bye-
product, a tar resembling coal-tar, is obtained. 1000 kilos, naphtha
residues yield about 500 cubic meters of gas, and 300 kilos, tar con-
TECHNICAL CHEMISTRY. 535
taming 4 — 5 per cent, benzene and toluene, and 0*6 per cent, crude
anthracene. D. B.
Carbon Bisulphide. By L. H. Friedburg (Ghem. News, 47, 52).
— The author gives some facts in addition to those already published
(Ber.j 8, 1016). Binitrohenzene (m. p. 84°) is formed amongst other
products when bisulphide of carbon, charged with nitric peroxide, is
mixed with pure benzene. When this same mixture is exposed to
direct sunlight, the inside of the glass above the liquid becomes covered
with small white crystals, which decompose when brought in contact
with the air, yielding nitric peroxide and benzene. The author sug-
gests that they are possibly nitro- addition products of the character
of benzene hexchloride, C6H6(N02)4 or C6H6(N02)6- When carbon
bisulphide charged with sulphurous anhydride, and the same medium
charged with nitric peroxide (not free from nitrous acid), are
brought together in a cool dry beaker, white crystals form in con-
siderable quantities ; these are nothing but lead-chamber crystals of
the sulphuric acid works. Carbon bisulphide which has been cleansed
with fuming nitric acid, has sp. gr. 1"266 at 15°, and b. p., at
760 mm., 47'4°. The author has always detected nitrobenzene as one
of the products of this treatment of crude bisulphide with nitric acid :
he therefore considers that benzene is one of the products formed
during the manufacture.
The author recommends that, in extracting oils with bisulphide,
excess of the latter should be avoided, and that a mixture of oils and
bisulphide should never be run into a still containing oil freed from
this substance. D. A. L.
Preservation of Wine by Salicylic Acid. By D. Denuc^
{Bled. Gentr., 1882, 859).— The addition of 10—40 grams of salicylic
acid to every hectolitre of wine is not deleterious. E. W. P.
Amount of Carbonic Acid in Beer. By T. Langer (Bingl.
polyt. J., 246, 487). — Beer, rich in carbonic acid, is obtained by
using a wort rich in maltose, and containing a small amount of
peptones. It is also necessary to work with strong yeast, a propor-
tionate quantity being introduced into the casks : the fermentation
should not be allowed to go too far, whilst the temperature should
be kept as low as possible. The brewer's task therefore is to pro-
duce, absorb, and preserve, carbonic acid in beer, whilst the publican's
business is to handle the beer with the utmost care, to avoid aU
possible loss of gas. D. B.
The Ferment of Chica Beer. By Griessmayer (Bied. Geyitr.,
1882, 861). — The formation of this beer from maize in South America,
is due to a ferment situated on the epidermis of the grain (comp. this
vol., p. 365). The ferment can affect unripe starch, and resists a tem-
perature of 95°. When the grains germinate, the vibrio developes in
its interior. Eurotium belongs to the same category of ferments, being
capable of saccharifying and fermenting. E. W. P.
536 ABSTRACTS OP CHEMICAL PAPERS.
The Strontia Process for the Separation of Sugar from
Molasses. By C. Scheibler (Bied. Centr., 1882, 848).— This is a
more detailed account of the process previoasly described. Molasses
are dissolved in water with 3 mols. crystallised strontium hydroxide
per 1 mol. sugar. After heating, the strontium saccharate,
Ci2H23C)ii,2SrO,
is thrown down ; this precipitate, after filtration and washing with
10 per cent, strontium hydroxide solution, is treated with water,
whereby it is decomposed, and the filtrate after evaporation yields
crystalline sugar. To prepare the crystallised hydroxide, the carbonate
is ignited at a somewhat higher temperature than that required for
calcium carbonate, and then boiled with water, from which on cooling
Sr(OH)2,8H20 crystallises. The deficiency of strontianite in the
market is a bar to this process, but it is hoped that caelestin, of which
there is a large supply obtainable from Sicily, may in time be made
use of. E. W. P.
Action of Dibromonaphthol on Amines. By R. Meldola
(Chem. News, 47, 27). — The dibromonaphthol (m. p. 111°), obtained
by the action of bromine on a-naphthol, acts as a powerful oxidiser
when heated with certain amines; thus it converts diphenylamine
into diphenylamine blue. The author has tried its action with various
other amines. Thus when dibromo- a-naphthol is dissolved in aniline
and heated at 140° for about 30 minutes, an orange colour is
developed, and on adding alcohol a basic substance separates out in
large orange needles. Similar bases are obtained from paratoluidine
and iS-naphthylamine. These bases are soluble in hot dilute acids
with a crimson colour ; they form well characterised salts and bronzy
crystalline platino- and zinco-chlorides.
In the course of the author's present research, he has observed the
following colour-reactions with dibromonaphthol and other haloid
derivatives of phenols. With a-naphthylamine and with cumidine
dibromonaphthol gives colours dissolving in alcohol with magenta-red ;
withresorcinol, it gives a reddish-brown. When monobromo-|S-naphthol
is heated with a-naphthylamine, it gives a red ; tetrabromo-3-naphthol
readily gives diphenylamine blue ; and with a-naphthylamine a violet.
Tribromophenol gives diphenylamine-blue with diphenylamine ; with
a-naphthylamine a red, with y3-naphthylamine a violet. Some of
these compounds are now being investigated. D. A. L.
Luting for Conduct-pipes. (Chem. Gentr. 1882, 784.) The
material recommended can be used for steam, water, or gas, for pipe-
joints, and is much cheaper and more efficient than red lead. It con-
sists of equal quantities of burnt lime, cement, potter's clay, and loam.
These are well dried, ground, sifted, and intimately mixed and kneaded
up with linseed-oil varnish. For water-pipes, it is well to use more
cement, in order to make the material still more resisting.
D. A. L.
587
General and Physical Chemistry.
Photometric Intensity of the Lines of the Hydrogen Spec-
trum. By H. Lagarde (Compt. rend., 95, 1350— 1352).— The
relative intensity of the various lines in the spectrum of a gas is not
constant, but varies with the temperature and pressure. The author
has determined the intensity of the lines of the hydrogen spectrum
under varying conditions by means of Crova's spectrophotometer
(Comjpt. rend., 93, 512). The results obtained up to the present are
given in the following table. R is the length of resistance- wire
introduced into the circuit to vary the tension, and therefore tem-
perature of the electric spark : p is the pressure of the gas expressed
in mm. of mercury. The numbers are only relative, being compared
with the intensity of the corresponding parts of the spectrum of the
particular lamp used by the author, taken arbitrarily as 1000.
65 mm.
Line.
r
"\
E.
^a-
V
Hy.
14
3-6
6-5
17-2
10
6-2
7-5
181
6
7-5
12-4
19-6
2
9-5
22-6
36-7
14
8-8
25-8
65-8
10
12-9
34-2
861
6
28-3
72-5
140-2
2
49-4
1521
240-9
14
12-6
39-3
110-9
10
17-8
65-0
133-8
6
38-5
94-9
176-4
2
761
183-2
289-6
L. T.
0-542
0-010 mm.
Stokes^s Law of Fluorescence. By E. Hagenbach (Ann. Phys.
Chem. [2], 18, 45 — 56). — By former experiments, the author esta-
blished the universality of Stokes's law of fluorescence, but his results
have been criticized by Lommel and Lubarsch. In the course of the
present paper the author elucidates the following points : —
(1.) An oblique instead of a normal position of the spectrum
apparatus to the surface of the fluorescent liquid does not cause an
increase of intensity of light within the apparatus.
(2.) The intensity of light in the field of the spectroscope is
independent of its distance from the fluorescent liquid, provided that
the illuminated surface fills the angle of aperture of the collimator.
(3.) As regards the dependence of the colour of the light on the
degree of concentration of the fluorescent liquid, the author objects
to Lommel's view that with increase of concentration the more
strongly absorbed constituents are more refracted than those which
are less strongly absorbed.
VOL. XLIY. 2 0
538 ABSTRACTS OP CHEMICAL PAPERS.
The author has repeated his experiments and those of Lommel and
Lnbarsch, using sunlight, the electric light, and sodium light, and has
confirmed his former results in every way, V. H. V.
Dependence of Molecular Refraction of Liquid Carbon
Compounds on their Chemical Constitution. By H. Scheodee
(Ann. Phys. Ghem. [2], 18, 148 — 175). — This paper is an enlargement
of a preliminary communication (Abstr., 1882, 910 — 911), and con-
tains in a series of tables the values deduced according to Lorenz's
formula of the molecular refraction for the lines Ha and Hy, and for
a ray H of infinite wave-length. These values confirm the results
noted in the former paper.
I. The Refraction equivalent in the case of Homologous Substances
increases with Molecular Weight. — An increase of CH2 causes an in-
crease of about 4*5, of 0 about 1*5, and of chlorine replacing hydrogen
about 4-7.
II. Metameric Substances at the same Temperature have not identical^
but only approximately, equal Molecular Refraction. — Thus, according
to Lorenz's formula, the molecular refraction of the acids of the
acetic series is somewhat less than the ethereal salts metameric with
them, bat according to the old empirical formula of Landoldt the
reverse is the case. Again, the normal compounds possess a somewhat
smaller refraction-equivalent than the isomeric iso-compounds, and
this relation is also reversed by the adoption of the old formula.
III. The Atom Refraction of the Elements Carbon, Hydrogen, and
Oxygen stand in a simple relation. — (1.) In every compound CO has
the same eff'ect as CHj. Thus the molecular refractions of propionic
acid and propyl alcohol, of butyric acid and butyl alcohol, &c., are
identical. (2.) In acids and ethereal salts O2, and in alcohols HOH,
have the sam.e efiect on the molecular refraction as CH2. (3.) The
atom-refraction of 0 in OH has one-third the effect of CH2. (4.) The
doubly-bound carbon-atom has an atom-refraction twice as great as
the singly-bound carbon-atom.
For examples the reader is referred to the former abstract (vide
supra).
IV. Aromatic Compounds. — The peculiar dispersive power of the
aromatic compounds has been noticed by Briihl and others. The
author shows that on comparing aromatic compounds containing the
same number of hydrogen- and oxygen-atoms, but differing from one
another by four carbon-atoms, differ by ten refraction steres thus : —
Mr.A2.
Phenol, CJ^HJO} 2672 = 19 x 14
Ethyl alcohol, C|HJ01 12-47 = 9 x 1-386
Benzoic aldehyde, C}^H«0? 30-29 = 21 x 1-442
Acetone, C|H«0? 13-71 = 11 x 1428
Ethyl benzoate, CJ^H}SOf 40-72 = 28 X 1-455
Methyl butyrate, CIR'M 20-29 = 18 x 1-46
Ethyl hydrocinnamate, C^HltOi 50-85 = 34 x 1495
Ethyl valerianate, C?HltO^ 35-98 = 24 x 1-499
GENERAL AND PHYSICAL CHEMISTRY. 539
Again, on comparing the molecular refraction of the aromatic
hydrocarbon and the paraffinoid alcohols containing the same number
of hjdrogen-atoms, a difference of molecular refraction of nine stores
is observed.
Mr.A2.
Benzene, Q^HS 2499 = 18 X 1-388
Ethyl alcohol, C^H^O} 12-47 = 9 x 1-386
Mesitylene, Q^H}| 39-05 = 27 x 1-446
Amyl alcohol, QH||01 26-09 = 18 x 1-449
These values show that six carbon-atoms of the phenyl grouping
have a refraction constitution Cg^, but that the refraction-equivalent
increases with decrease of refrangibility of the ray.
Chlorine. — A chlorine-atom combined with a carbon-atom has the
same effect on molecular refraction as the grouping CH3. Thus
ethyl chloracetate has the same refraction- equivalent as the ethereal
salts of the formula O5H10O2, and ethylene chloride as propyl chloride.
The author proposes in a future communication to bring out further
relationships between the molecular refractions of the carbon com-
pounds. Y. H. V.
Lnminosity of Flame, By W. Siemens {Ann. Phys. Chim. [2],
18, 311 — 316). — The luminosity of burning gases is a secondary
phenomenon dependent on the separation and incandescence of solid
particles suspended in the flame. Gases from which no such particles
are separated, burn with a feebly luminous flame, and this luminosity
is assigned to the incandescence of the gases themselves. No experi-
ments have hitherto been made to ascertain whether pure gases heated
to a high temperature really emit light. In order to examine this
point, the author's brother made a series of observations with a
Siemens regenerative oven of the form used in the hard glass manu-
facture, whereby a temperature of the melting point of steel, 1500 —
2000° C, could easily be attained. By a suitable contrivance the
interior of the oven could be examined, and it was thus found that,
provided the experimental room was kept perfectly still, the heated
air in the oven emitted no light. The introduction of a luminous
flame into the oven caused its interior to be only feebly illuminated.
As a result of these experiments, it follows that the supposition that
the luminosity of the flame is due to the incandescence of the gas is
incorrect. In order- to determine the temperature at which luminous
flames become non-luminous, the author suggests a repetition of the
above experiments with a more refined apparatus.
The author further demonstrates that the heat-rays emitted from
hot gases are very small in number as compared with those emitted
from equally hot solid bodies.
Observations on the behaviour of flames themselves prove equally
that the luminosity of flames is not due to the incandescence of the
products of combustion. If the gases to be burnt are more quickly
mixed, the flame becomes shorter, since the process of combustion is
accelerated, and hotter, since less cold air is mixed with the burning
gas. The same phenomenon occurs if the gases are strongly heated
2 0 2
540 ABSTRACTS OF CHEMICAL PAPERS.
before they are burnt; but since the ascending products of com-
bustion are maintained for a short time only at the temperature
of the flame, the above phenomenon would be reversed were the
gases self-luminous. The luminous part of the flame is separated by
a line of demarcation from the products of combustion, and is coin-
cident with the termination of chemical action, which is probably the
cause of the emitted light. If it be assumed that the gas molecules
are surrounded with an envelope of ether, then a chemical combination
between two or more of these molecules will cause a vibration of the
ether particles, which becomes the starting point of the light and
heat waves. The luminosity of gases when an electric current is
passed through them can be explained in a similar manner, and the
author has already observed that all gases are conductors of electri-
city when their point of so-called polarisation maximum has been
reached. V. H. V.
Constitution of Electrolytes. By A. Bartoli (Gazzetta, 13,
27 — 34). — A theoretical paper not admitting of abstraction.
Electrolysis of Water and of Solutions of Boric Acid. By A.
Bartoli and G. Papasogli (Gazzetta, 13, 35 — 37). — The authors find,
contrary to Bourgoin (Ann. Ghem. Phys. [4], 15, 56 [1868]), that pure
water and pure aqueous boric acid are both capable of electrolytic
conduction. Bartoli showed (Nuovo Cimento, 1879) that pure water
may be decomposed by the current of a single Daniell's element, and
from experiments mentioned in the present paper it appears that a
solution of boric acid saturated at 80° conducts better than water, and
exhibits easily visible decomposition with a battery of a small number
of Bunsen's elements. H. W.
New Experiment in Electrolysis. By E. Semmola (Gompt.
rend., 96, 336 — 337).-^The apparatus consists of a voltameter having
three electrodes arranged in the form of an equilateral triangle, with
a tube over each electrode. One of the electrodes, c, is connected
with the positive pole of the battery, the other two, a and i, being
connected with the negative pole by means of a commutator, which is
so arranged that the current can be sent entirely through a or h, or
can be bifurcated and sent partly throngh a and partly through b.
The sum of the volumes of hydrogen collected in the two tubes, when
the current is thus bifurcated, is equal to the volume collected in a
single tube when the current is sent entirely through one of the
electrodes a or h, thus proving by means of a single voltameter that
the same quantity of electricity always produces the same amount of
chemical decomposition. C. H. B.
Thermoelectric Properties of Minerals belonging to Various
Systems. By W. G. Hankel {A7in. Phys. Ghem. [2], 18, 421—428).
An examination of the thermoelectric properties of the topaz has
convinced the author that Hauy's view, according to which only
hemimorphous crystals show a difference of potential with change of
temperature, is too restricted, since experiment shows that most
GENERAL AND PHYSICAL CHEMISTRY. 541
minerals, provided that they may be obtained in sufficiently well crys-
tallised individuals, possess this property, and in the present com-
munication the author describes the position of the thermoelectric
poles in relation to the crystal lographic axes in minerals belonging
to various systems.
(I.) Regular System. Helvin crystallises in tetrahedrons ; on cool-
ing, the large tetrahedral faces are positively, the small faces nega-
tively, electrified. This polarity is opposite to that observed in
boracite, which crystallises in the' same form. In helvin, the larger
faces are more glistening than the smaller, the reverse being the case
with boracite : hence it appears that the more glistening face
becomes electrified positively, the less glistening face negatively.
(II.) Tetragonal System. Mellite resembles apophyllite and ido-
crase in its thermoelectric behaviour ; for the ends of the primary
axes become electrified positively, and the terminal edges and prismatic
side-faces negatively.
(III.) Hexagonal System. Pyromorphite and Mimetesite resemble
apatite, which is isomorphous with them in that the ends of the
primary axes are electrified positively, whilst their prism-faces are
negatively electrified. But in individuals of mimetesite, if the prism
faces are overgrown, they frequently show an electropositive potential.
The author formerly observed a similar reversed polarity in specimens
of the beryl.
Fhenacite crystallises in the rhombohedric tetratohedral modification
of the hexagonal system ; the terminations of the primary axes and the
rhombohedral faces are electrified positively, the prismatic side-faces
negatively. The reverse is, however, the case with pennine. Some
specimens of dioptase resemble phenacite in their thermoelectric poles,
whereas others resemble pennine, but observations were rendered
difficult from the imperfect form of the crystals.
(IV.) Rhombic System. Strontianite, Luthenite, and Cerussite. The
ends of the primary and brachydiagonal axes become the positive
poles, but those of the macrodiagonal are the negative poles.
(V.) Monoclinic System. JE/itcZase resembles gypsum in its thermo-
electric properties ; the ends of the vertical and clinodiagonal axes
are the positive, the ends of the orthodiagonal axes the negative poles.
The same position of the poles is observed in titanite ; in this mineral
the surfaces OP, and part of the surfaces |Pco and Poo are positively,
and the remaining portions of the surfaces |Pcx) and Poo are nega-
tively electrified. The author observed in 1840 that the electric
polarity of crystals of titanite as of boracite undergo reversal at 112°.
This phenomenon can best be observed by heating the crystals to 210° ;
at the commencement of cooling the ends of the orthodiagonal axis
have an electronegative potential' which reaches a maximum, then
diminishes, and finally undergoes reversal. V. H. V.
Specific Heat of Water. By F. Neesen {Ann. Phys. Chem. [2],
18, 369 — 386). — The author begins his communication with a com-
parison of the relative value of the methods available for determi-
nation of specific heat. Of the three methods, (I) the method of
mixture, (II) the method of melting of ice, (III) the method of cool-
542 ABSTRACTS OF CHEMICAL PAPERS.
ing, tlie latter involves a source of error in the supposition that all
sides of the cooling body, at every moment of time, are at the same
temperature, a supposition which is never fulfilled. The author has
devised a form of apparatus to obviate this source of error, and in
order to render the results of observation by it more exact, he has
made a series of experiments on the dependence of the specific heat
on the temperature. As regards the variation of the specific heat of
water with the temperature, Regnault and others observed a small
increase of specific heat with rise of temperature, whilst Pfaunder
and Flatten found a decrease under the same circumstances, and
Rowland observed a decrease from 0 — 30'^, and from that point an
increase.
In the present paper the author has re-examined this question with
the aid of a Bunsen's ice calorimeter ; full details are given of the
form of apparatus, method of observation, determination of the specific
heat of platinum and glass. It appears as a result of the experiments
that the mean specific heat of water at first increases, and then
decreases, but the maximum point varies according as the tempera-
ture was observed by mercury or air thermometer; with the former,
the maximum is at 12°, with the latter at 20°. The author
endeavoured to reduce his observations in terms of the formula
D = a(b — ty, but the values deduced from this formula did not
agree satisfactorily with the observed values ; he puts forward with
reserve the empirical formulae D = 14 + 8*063 (^ — 2), from 0 — 20°,
and D = 167 4- 777(« — 21) above. The results of the author's
observations agree qualitatively with those of Rowland obtained by
the method of mixture, and a table is given in which the observations
are compared. Y. H. V.
Measurement of Pressures developed in Closed Vessels by
the Explosion of Gaseous Mixtures. By Vieille {Compt. rend.,
95, 1280 — 1282). — The author has made experiments to show that
the manometric results calculated from the displacement of a piston
of known diameter and mass, inserted in the wall of the vessel, gives
results as good as those obtained with the usual static manometers,
and is more suitable for the measurement of pressures of very short
duration. L. T. T.
Momentary Pressures produced during the Combustion of
Gaseous Mixtures. By Mallard and Le Chatelier (Compt. rend.,
95, 1352 — 1355). — In a former communication (this vol., 148) the
authors, during the combustion of gaseous mixtures, noticed the pro-
duction of pressures of exceedingly short duration, but of much
greater intensity than would normally be expected. They have now
very carefully measured, by means of Depretz's plan of registering the
displacement of a piston, the pressures produced in closed vessels.
With mixtures of hydrogen and oxygen, momentary pressures of 20
atmospheres have been obtained, the normal pressure calculated rela-
tive to the temperature of combustion being but 11 atmospheres.
The authors propose the following explanation. The first portion of
the mixture in exploding compresses the adjoining layer. If now the
I
GENERAL AND PHYSICAL CHEMISTRY. 543
velocity of propagation of iguition is sufficiently rapid, this adjoining
layer of the explosive mixture will be ignited before an equalisation
of pressure can take place, and hence the pressure due to this
explosion will be superimposed on that derived from the first portion
of the mixture. This will be repeated, the pressure in each succeed-
ing wave becoming greater, and the momentary pressure due to one
of these explosive zones will be that registered by the piston. This
hypothesis is supported by the fact that the excess of pressure above
the normal increases with the velocity of propagation of ignition
of the mixture experimented with. This hypothesis would also ex-
plain the formation of the explosive wave discovered by Berthelot
and Yieille : for supposing the pressure to increase from layer to
layer, a point would be reached where the rise in temperature due
to the compression would be sufiicient in itself to cause ignition of
the mixture, and this would then be propagated with the velocity of
the propagation of the pressure. The fact that the velocity of this
explosive wave is greater than that of sound under ordinary circum-
stances, is probably due to the intensity of compression and tempera-
ture in the exploding mixture. The duration of these excess pressures
is less than one ten-thousandth of a second, and it is therefore proba-
ble that the observed excess pressure is much below the actual, since
the motive action of even very large pressures acting on a piston for
so short a time is exceedingly small. A pressure of 100 atmo-
spheres acting for one-thousandth of a second on a piston 1 gram in
weight and of 1 cq. section would displace the piston only ^oVo ^"^*
L. T. T.
Thermochemical Investigation on the Chlorides of Iodine.
By J. Thomsen (Ber., 15, 3021— 3022).— When a molecule of solid
iodine unites with a molecule of gaseous chlorine to form liquid iodine
chloride, the heat of combination is 11650 cal. The heat evolved by
the union of a molecule of iodine monochloride with a molecule of
chlorine to form the solid trichloride is 15660 cal. The heat of forma-
tion of the trichloride I + CI3 = ICI3 is 21490 cal. W. C. W.
Thermochemical Investigation on the Chlorides of Sulphur,
Selenium, and Tellurium. By J. Thomsen (Ber., 15, 3023—3025).
— The heat of formation of sulphur chloride, S2CI2 (from rhombic
crystals of sulphur), is 14260 cal. ; of selenious chloride (Scj -f CI2)
22150 cal., and selenic chloride, SeCU, from amorphous selenium,
46160 cal.; of telluric chloride, TeCh, from metallic tellurium,
77380 cal. The heat of formation increases therefore with the mole-
cular weight. W. C. W.
Method of Estimating the Heat of Formation of diflft-
cultly combustible Volatile Carbon-compounds. By J. Thomsen
(Ber., 15, 2996— 3000).— The heat of formation of compounds of
carbon and chlorine, or of carbon, hydrogen and chlorine, may be
determined by milling the vapour of the substance with hydrogen, and
burning the mixture in oxygen. The volume of hydrogen used is
measured, and the weight of hydrochloric acid, water, and carbonic
544
ABSTRACTS OF CHEMICAL PAPERS.
anhydride produced is also determined. The operation is conducted
in an apparatus described by the author in his recently published
book on " Thermochemical Investigations," 2, 339. W. C. W.
Heat of Formation of the Chlorides of Phosphorus and
Arsenic. By J. Thomsen (Ber., 16, 37—39).
Reaction.
Heat.
Explanation.
P,CL
75300 cal.
104990 „
29690 „
65140 „
123440 „
71390 „ •
17580 „
1 Direct formation of chlorides from pho8-
J phorus.
PCls from PCI3 and CL.
P,Cl5
PCL.CL
PCI3 : Aq
• Heat of solution.
Direct combination of arsenic with chlo-
iPCL : Aq
A8,Cl3
AsClgrAq
rine.
Heat of solution.
A. K. M.
Heat of Formation of the Chlorides and Oxides of Anti-
mony and Bismuth. By J. Thomsen (Ber., 16, 39—42).
Reaction.
Heat.
Explanation.
Sb,Cl3
91390 cal.
104870 „
13480 „
7730 „
8910 „
35200 „
167420 „
117890 „
228780 „
148570 „
•30680 „
90630 „
88180 „
7830 „
- 6350 „
+ 14180 „
137740 „
103050 „
- Heat of formation.
SbClg from SbClg and Clj.
Sb.CL
SbCl3,Cl2
SbCl3: Aq 1
SbClg : Aq
Complete decomposition.
Formation of Sb405Cl2.
Complete decomposition.
1 Production of Sb03H3.
I Production of Sb04H3.
Sb2,0„3H20
Sb,02,H,H20
Sb2,05,3H20
Sb,03,H,H20
SbOgHgjO
Bi,Cl3
y Heat of formation.
Formation of BiOCl,HoO from Bia,.
BiOgHa from BiCl3.
BiOCl.HoO from BiOsHj.
1 Production of BiOaHg.
Bi,0,Cl,H20
BiCl3 : H20,Aq ....
BiCla : 3H20,Aq
Bi03H„HClAq ....
Bi2,03,3H20
Bi,02,H,H20
A. K. M.
Heat of Formation of Carbon Tetrachloride and Ethylene
Perchloride. By J. Thomsen (Ber., 15, 3000— 3002).— The heat
evolved by the union of an atom of amorphous carbon with four atoms
of chlorine gas to form a molecule of carbon tetrachloride vapour, is
21030 cal., and for liquid carbon tetrachloride 28320 cal.
The heat of formation of methane is 21750 cal., and of carbon oxide
GENERAL AND PHYSICAL CHEMISTRY. 545
29000 cal. Hence it appears that the affinity of chlorine and hydrogen
for carbon is equally strong. The heat of formation of ethane is
—2710 cal., and of gaseous ethylene perchloride — 1150 cal. For
liquid ethylene perchloride the heat of formation is + 6000 cal.
w. c. w.
Volume-change of Metals on Fusion. By F. Nies and A.
WiNEELMANN (Ann. Phijs. Chem. [2], 18, 364— 365).— The results of
the experiments made by Roberts and Wrightson show that the
density of most metals is less in the liquid than in the solid state.
These results are apparently in direct contradiction to those of the
authors, which show that metals when liquid at their point of fusion
occupy a smaller volume than when solid at the same temperature.
This discrepancy is, however, only apparent, for in Roberts and
Wrightson's experiments the density of the metals in the solid state
were taken at the ordinary temperature, whereas those of the metals
in the liquid state were taken at their point of fusion. The values so
obtained are not directly comparable. But some results of Wrightson,
in the case of iron and steel, agree with those of the authors. For the
former physicist found that in the conversion of iron from the solid
state the density of the solid metal 6*95 decreases to 6*5, the density of
the plastic metal, and then suddenly increases to 6" 88, the density of
the liquid metal. V. H. V.
Distillation in a Vacuum. By A. Schuller (Ann. Phys.
Chem. [2] 18, 317 — 325). — The author at the outset calls attention
to the advantages of the automatic mercury pump ; by its aid he
has devised a form of apparatus to study fractional distillation and
sublimation in a vacuum, and the separation of metals from impurities
with which they are contaminated. In the course of his experiments
the author arrives at the conclusion that sufficient attention is not paid
to the substance used for lubrication, and to the so-called anhydrous
phosphoric acid used as a desiccating agent ; the latter contains phos-
phoric anhydride, P2O6, which sublimes at 50° in large translucent
crystals. The author considers that the best substance for lubrication
is a mixture of wax and vaseline, and for desiccation metaphosphoric
acid. Of the elements examined, selenium, tellurium, cadmium, zinc,
magnesium, arsenic, and antimony, are easily sublimed, but the
fusible metals, bismuth, lead, and tin, distil only with difficulty. The
author's observations on this point differ from those of Demar9ay,
but he explains this discrepancy by supposing that the metals
used by Demar9ay were contaminated with impurities, which, accord-
ing to his observations, caused the volatilisation of the metals in ques-
tion ; but if the distillation be frequently repeated, these impurities
are separated. Secondly, it is found that sodium, selenium, tellurium,
cadmium, zinc, arsenic, and antimony, distil so readily in a vacuum
that this process may be used for their purification. Thirdly, during
the first distillation of these metals, there is an evolution of gas, but
this ceases after the process has been repeated. Fourthly, it is found
that many metals require to be heated slightly above their point of
sublimation to effect their distillation ; this phenomenon the author
attributes to the slight difference of pressure caused by the rise of
e546 ARSTRAOTS OF CHEMICAL PAPERS.
temperature, whicli causes a more or less mechanical impulse to the
metallic vapour. Fifthly, organic substances, as tallow, wax, colo-
phony, distil in a vacuum without decomposition, and can thus be
separated from impurities; but crude sugar, dry grape-sugar, and
quinine sulphate, decompose during or even before distillation.
Caoutchouc distils in two separate layers, of which the more volatile
has the smell of caoutchouc, whilst the less volatile has but little
smell, and is of the consistency of fresh caoutchouc. In conclusion,
the author recommends this process of fractional distillation in a
vacuum for purification of organic substances. Y. H. V.
Velocity of Solidification of Bodies in a State of Super-
fusion. By D. Gernez (Gompt. rend., 95, 1278— 1280).— The experi-
ments were made with columns of melted phosphorus 60 — 70 cm.
long, enclosed in U-tubes of diameter 1*4 — 2*7 mm., the walls of
which did not exceed 0*2 mm. in thickness. The surface of the phos-
phorus was protected from the air by a thin layer of water. The tube
was plunged for a short time into a bath of a temperature above the
melting point of phosphorus, and then suspended in a bath of water
kept at a constant temperature and agitated by a current of air. The
solidification was caused by touching the surface of the phosphorus
in one limb of the tube with a piece of solid phosphorus, and register-
ing the time taken before solidification reached the surface in the
other limb. The solidification proceeds quite uniformly, and the
author calls the length of the column solidified in one second the
velocity of solidification. He has heated the phosphorus to 100°, 140°,
200°, and 215° before cooling, but the velocity of solidification was not
influenced.
The following are a few of the numbers obtained, reduced to a
column of phosphorus at its melting point, 442° : —
Temperature 43-8° 43-5° 421)° 42-1° 41-4° 40-6° 39° 38°
Velocity of "I
solidification ^ I'lG 2-63 8-78 24-1 56-9 88-3 159-7 243-1
in mm. J
Temperature.. 36° 342° 33° 31-2° 29° 27-4° 24-9*=
Velocity of
solidification > 353*35 538*9 628-9 675-7 800*0 952-4 1030-9
in mm.
}
L. T. T.
Dissociation of Chlorine and Bromine. By C. Langer and V.
Meter {Ber., 15, 2769 — 2775). — Previous experiments in this direc-
tion have been successful only with iodine, the diminution of pressure
reducing the density from 8*8 to 4*4, or half the theoretical numbers,
below which it could not be brought by reduction of pressure and in-
crease of temperature. With both the other halogens, it has only
been proved that their molecules are dissociated under a higher tem-
perature than iodine, but the lowest density obtained for chlorine was
2-05 instead of the normal 2-45 : no constant figure has yet been
obtained for bromine.
The authors instituted a fresh series of experiments in order to try
GENERAL AND PHYSICAL CHEMISTRY. 547
if they could reduce the figures to one-half their normal value, as in
the case of iodine, using V. and D. Meyer's apparatus for removal of
gas pressure, and discarding platinum chloride and bromide, using the
halogens themselves in a state of the greatest possible purity. Hitherto
the heat obtained was limited by the yielding of the Bayeux porcelain
employed ; and platinum was considered unsuitable; the authors, there-
fore, instead of raising the temperature, decided on diluting the heated
vapour with an indifferent gas. The apparatus was that used by
V. Meyer for estimating the density of permanent gases. A horizontal
tube with capillary openings in both ends is brought to the tempera-
ture of the experiment, filled with the gas under examination (in the
present case chlorine or bromine) mixed with a large excess of air or
nitrogen ; when the mixture has reached the required temperature, it
is forced by a current of pure carbonic anhydride, introduced through
one of the capillary openings, into an absorption apparatus containing
potassium iodide solution, and from thence into a gas-measuring tube
containing an alkaline solution. The halogen remains in the iodide,
and is estimated volumetrically ; the gas mixture used for dilution is
measured, the operation is checked by the measurement of air, with-
out the halogen, before and after the actual experiment ; the presence
of such active bodies as chlorine and bromine necessitated certain
precautions which are detailed. The temperatures at which the work
was carried out were 14°, 100°, 900° with Fletcher's oven not using
blast, 1200° with the same oven using blast. Some of the results with
chlorine are given —
Undiluted at 100° 2'50
Diluted with 5 vols, of air .... 2*51
Diluted with 15 „ 2-46
Undiluted at 900° 2'49 2'46 2-41 2-46
Undiluted at 1200° 2-41 2*42 2-45 2-47 2-44
These figures agree tolerably well with the normal value of CU,
2-45.
The behaviour of bromine at a low temperature and greatly diluted
is interesting — at the ordinary temperature, 60° under its boiling
point ; when diluted with 10 volumes of air, its density is closely that
of Bra, namely, 6*52.
1 part Br vapour 10'5 parts air, temp. 13'5°, density 5*51.
1 „ „ 101 „ „ 13-5 „ 5-54.
1 „ „ 101 „ „ 14-0 „ 5-45.
1 „ „ 10-3 „ „ 14-0 „ 5-46.
The authors promise further information on other experiments at
high temperature and greater dilution. J. F.
Dissociation Heat of the Water Molecule and the Electric
Luminosity of Gases. By E. Wiedemann (Ann. Phys. Chem. [2],
18, 509 — 510). — In former researches, the author has shown the
quantity of heat derivable from an electric discharge, which is neces-
sary to convert the band into a line-spectrum, is independent of the
548 ABSTRACTS OF OHEmOAL PAPERS.
pressure of the gases and the cross section of the tnbe ; its valne is
about 128,300 cal. From theoretical considerations, the author,
starting with the view that the band-spectrum arises from an oscilla-
tion of the molecule, and the line-spectrum from a similar motion of the
dissociated atoms, shows that a gram of water requires 126,000 cal.
in order to effect its decomposition into its atoms. Thomsen in his
" Thermochemische Untersuchungen " has put forward the proba-
bility that the atoms of nitrogen are firmly attached to one another.
The author has established experimentally that if the same capillary
tube be filled under the same pressure successively with hydrogen and
nitrogen, and the gases subjected to the same discharge of the same
intensity, then the line-spectrum is revealed in the hydrogen, but not
in the nitrogen. In order to bring out the line-spectrum in nitrogen,
a condenser must be included in the circuit. Hence it follows that
the molecule of nitrogen requires a greater dissociation heat than the
molecule of hydrogen. Siemens (this vol., p. 540), as well as the
author, has observed the luminosity of gases under the influence of the
electric discharge. The author has established that in charging the
electrodes, a dielectric polarisation is induced, so that the ethereal
envelopes of single gas molecules are distorted, and undergo an
, orientation : if a discharge takes place, the ethereal envelope is set
into motion, and there is a passage of free electricity from the elec-
trodes from molecule to molecule. The author has more fully examined
this motion, and has proved that it can be so powerful as to effect the
resolution of the molecules into the atoms. Siemens would ex-
plain the luminosity of gases by this oscillation of the ethereal
envelope. V. H. V.
Ammonium Hydrogen Sulphide. By Isambert {Compt. rend.,
95, 1355 — 1358). — The author has examined the vapour of ammonium
hydrogen sulphide in order to determine whether this substance
volatilises unchanged or splits up into ammonia and hydrogen sul-
phide. Dialysed by means of a porous porcelain tube, the gas which
passes through contains more than its proper proportion of ammonia ;
thus proving at least partial dissociation. The author then made
determinations of the compressibility of its vapour at 35 — 40°, and
under pressures varying from 720 mm. to 1030 mm. Regnault's de-
terminations gave for ammonia ^^ = 1*01881, and for hydrogen sul-
pv
phide ^^ = 1-01083. For a mixture of equal volumes of the two
pv
gases, this ratio would therefore be a little less than 1*01482, or at 40°
about 1*01, whereas that of the vapour of an easily condensible gas has
been shown by Herwig to be about 1*1. The author obtained numbers
varying between 1*007 and 1*008, showing that no appreciable
quantity of the undissociated compound could be present.
He has also determined the heat of liquefaction, and found it to
be 23, a number far above the average, but almost identical with the
heat of formation of ammonium hydrogen sulphide. He therefore
concludes that in the form of vapour complete dissociation has taken
GENERAL AND PHYSICAL CHEMISTRY. 549
^ etce, and tliat in liquefying a reformation of the sulphide is brought
about. L. T. T.
Constant of Capillarity of Liquids at their Boiling Points.
By R. ScHTFF (jBer., 15, 2965 — 2975). — The apparatus employed by
the author in this research consists of a capillary U-tube, tbe two
limbs having different diameters. The apparatus containing some of
the liquid to be examined is suspended in a glass vessel, which is
filled with the vapours given off by boiling some of the same sub-
stance ; when the temperature of the apparatus is constant, the height
the liquid in each limb of the tube, and the height of the meniscus is
read off by means of a cathetometer. From these data the constant
C can be calculated.
Let d = the diameter of the narrow limb and d' the diameter of the
wider limb of the U-tube, h = the observed difference in the height
of hquid in the two tubes, he — the height corrected for the meniscus,
n = the rise in a normal tube of 1 mm. diameter, r = the radius of
the narrow, and R of the wide tube, let / and F represent the height
of the menisci, p and p the radius of the curves of the menisci, S^ the
specific gravity of the liquid at t°, and G = nSf =■ 2ah. C also =
Quioike's a x 4.
The correction for the meniscus is made by means of the following
- + -^
3 8
formula : lic=h -\ ^ • -^^ ^ ^^^ ^' represent the corrections
for t(he meniscus, then he = h -^ ni — m'.,
r _ R / _ F
and
/.^_R/_F\
dd' I S 3 "^ 3 3 ).
^==-drzrd\ 2 /
I
The following values for C were obtained : —
Methyl alcohol, 7-635 ; ethyl alcohol, 7-059 ; propyl alcohol, 7-002 ;
isopropyl alcohol, 6 '808 ; chloroform, 9-121 ; carbon tetrachloride,
8-160; ethylene chloride, 9-719; benzene, 8-646; toluene, 7*383;
xylene (chiefly ortho), 6-698 ; metaxylene (pure), 6*718 ; paraxylene,
6-662 ; paracymene, 6*686. W. C. W.
Passage of Alcoholic Liquids through Membranes. By H.
Gal (Compt rend.., 96, 338— 340).— The degree of dilution which
alcohol experiences when exposed to a moist atmosphere in contact
with a membrane (this vol., p. 279), is independent of the temperature ;
but the rate at which dilution takes place is materially affected by the
temperature, and is much more rapid at 30^" and 60° than at — 10°.
Dilution takes place whether the membrane is in contact with the
liquid or with its vapour. The latter fact is explained by the dif-
ference between the vapour- tensions of water and alcohol at all tem-
peratures, and by the fact that the alcohol vapour diffuses out into the
atmosphere, which contains only a trace of alcohol vapour, whilst the
water vapour diffuses into an atmosphere already more or less saturated.
Dilution takes place whether the membrane be goldbeater's skin,
bladder, or parchment, but is much more rapid with the first and much
550 ABSTRACTS OF CHEMICAL PAPERS.
slower with the last, than it is when bladder is used. The author's
previous results are confirmed by Bidaud. C. H. B.
Mutual Displacements of Bases of Neutral Salts in Homo-
geneous Systems. By Menschdtkin (Gompt. rend., 96, 348 — 350).
An aqueous solution of triethylamine gives a purplish- violet colora-
tion with a few drops of phenol phthalein solution, but the colour is
destroyed by alcohol even in presence of a large excess of triethyl-
amine. On addition of one drop of a solution of an alkali, the colour
is restored, but is not so intense, and has a bluer tinge.
A standard aqueous solution of potassium hydroxide, and a standard
alcoholic solution of sodium hydroxide respectively were added to
solutions of triethylamine chloride and acetate, the above reaction
being used to indicate the presence of free alkali. When the potas-
sium hydroxide was used, the liquid was mixed with a volume of
alcohol equal to four times the volume of the potash solution. It was
found that triethylamine is entirely displaced from its salts by an
equivalent of sodium or potassium hydroxide.
The chemical mass of the triethylamine exerts no influence on its
displacement, for if that were the case, the displacement would not be
complete in presence of the liberated triethylamine.
These facts are contrary to the law of Berthotlet ; but in perfectly
homogeneous systems the chemical mass of the triethylamine may
exert influence, and the law of BerthoUet may or may not be true.
C. H. B.
Nature of Solution. By W. L. Goodwin (Ber., 15, 3039—3051).
— The author draws the following conclusions from his experiments
on the solubility of chlorine in water : — The chlorides of calcium,
cobalt, iron, magnesium, and strontium prevent the formation of
solid chlorine hydrate. The solubility of chlorine in water is increased
by the presence of hydrochloric acid or lithium chloride. With mixed
chlorides, the solubility is generally the mean of that for the separate
salts. The influence of chlorides on the solubility of chlorine is
chemical at low and mechanical at higher temperatures.
w. c. w.
Inorganic Chemistry.
Crystallisation of Chlorine Hydrate. By A. Ditte {Gompt.
rend., 95, 1283 — 1284). — Chlorine hydrate containing excess of water
is introduced into a long bent tube and strongly sealed. The limb
containing the hydrate is then heated, when the chlorine evolved
becomes condensed in the cold limb by the pressure of its own
vapour. If the whole apparatus be now allowed to cool slowly, chlorine
hydrate reforms on the surface of the water in fine fern-like crystals.
INORGANIC CHEMISTRY. 551
If the limb containing the hydrate and water be immersed in water
and the whole allowed to rest for some time, the crnst of hydrate
crystals gradually increases until it entirely shuts off communication
between the water and chlorine. Chlorine then gradually condenses
above the hydrate, which thus is enclosed between a layer of water
and one of chlorine. On standing some time, the fern-like shapes
disappear, and isolated crystals about 2 — 3 mm. long are formed of a
greenish-yellow colour, highly refracting, and belonging apparently to
the regular system. L. T. T.
Variation in the Amount of Oxygen in the Air. By C. A.
VoGLER (Bied. Ce7itr., 1882, 851). — The author considers that at
meteorological sf:ations the percentage of oxygen in the air should be
regularly determined, as he believes that the percentages of oxygen are
closely conuected with some of the barometric changes.
E. W. P.
Oxidation of Sulphur in the Air. By A. Basaroff (Jour,
Buss. Chem. Soc, 1882, 396 — 398). — In order to suppress the vine-
disease caused by O'idium Tuckeri, flowers of sulphur are often dusted
over the plants; but although this method has been used for more
than 20 years, the mode of action of the sulphur has not yet been
clearly ascertained.* The author has investigated the question anew,
by passing about 250 litres of air, collected about 1^ meter over the
vineyard ground which was treated wifch flowers of sulphur, first
through cotton wool, and subsequently through a solution of pure
soda. After oxidation by chlorine, BaSOi was obtained, corresponding
with 9*6 c.c. of SO2. The air contained, therefore, 0"004 per cent,
by volume, or 0*009 per cent, by weight of sulphurous anhydride, and
this quantity of so strong a disinfectant is, in the author's opinion,
quite sufficient to produce the efiect mentioned above.
B. B.
Reactions between Sulphur, Sulphur Oxides, Carbon, and
Carbon Oxides. By Berth elot (Compt. rend., 96, 298 — 304). —
Carbonic oxide is decomposed into carbon and carbonic anhydride at a
bright red heat, and even at the softening point of glass, but the
amount of decomposition is very small. Sulphurous anhydride, as
Buff and Hofmann have stated, is decomposed by the electric spark
into sulphuric anhydride and sulphur. No oxygen is set free;
part of the sulphur unites with the platinum electrodes ; the re-
mainder combines with the sulphuric anhydride to form a viscous
liquid, which absorbs a certain quantity of sulphurous anhydride.
This is the intermediate product of the reaction. It is decomposible
in the reverse direction, and the tensions of the sulphuric and sul-
phurous anhydrides which it gives off limit the decomposition of the
sulphurous anhydride. When sulphurous anhydride is passed over
purified charcoal heated to redness in a porcelain tube, carbonic oxide,
* The author is evidently unaware of Pollacci's experiments (this Journal, 1876,
ii, 540), -who found that sulphured grapes gave off hydrogen sulphide, and that
this gas rapidly kills the o'idium. — C. E. Q-.
552 ABSTRACTS OF CHEMICAL PAPERS.
carbon oxysulphide, and carbon bisulphide are formed in proportions
indicated by the equation 4SO2 4- 9C = 6C0 + 2C0S + CS,, and a
small quantity of sulphur is set free. Probably the carbon combines
with the oxygen of the sulphurous anhydride, liberating sulphur
which then unites partly with carbon, and partly with the carbonic
oxide formed. When electric sparks are passed for a long time through
a mixture of equal volumes of carbonic anhydride and sulphurous
anhydride, the residual gas has the composition SO2, 31 ; CO2, 30 ;
CO, 20 ; decrease, 19 = 100. Each gas decomposes independently,
and the oxygen liberated from the carbonic anhydride combines with
sulphurous anhydride to form sulphuric anhydride, which condenses.
The sulphurous anhydride is apparently somewhat more stable than
the carbonic anhydride. When a mixture of equal volumes of sul-
phurous anhydride and carbonic oxide is passed through a narrow
porcelain tube heated to redness, the issuing gas has the composition
SO2, 37 ; CO2, 20 ; CO, 43 = 100. Sulphur is liberated, but neither
carbon oxysulphide nor carbon bisulphide is formed in notable quan-
tity. The carbonic oxide evidently reduces the sulphurous anhydride,
thus 2C0 + SO2 = 2CO2 + S, but the reduction is not complete. If
a mixture of 2 vols, carbonic oxide with 1 vol. sulphurous anhydride
is subjected to the action of electric sparks, the sulphurous anhydride
is partially reduced, but a portion of it decomposes independently
without giving up oxygen to the carbonic oxide, and forms a compound
of sulphur, sulphurous and sulphuric anhydrides, which condenses on
the sides of the tube. In presence of mercury, the sulphurous anhy-
dride is completely decomposed, and the residual gas has the com-
position CO2, 24; CO, 75; 0, 1. The mercury absorbs the sulphuric
anhydride produced, forming a basic sulphate. Sulphurous anhydride
has no action on potassium sulphate at a bright red heat, but at a red
heat it converts the carbonate into sulphate, with a trace of sulphide.
If the current of the gas is slow, the proportion of sulphide increases.
A slow current of dry carbonic anhydride has no action on boiling
sulphur, but if sulphur vapour and carbonic anhydride are passed
through a porcelain tube heated to redness, a slight but distinct re-
action takes place. The issuing gas contains 2'5 per cent, of a mixture
of 1 vol. carbon oxysulphide, 1 vol. carbonic oxide, and 0'5 vol. of
sulphurous anhydride. The carbonic anhydride probably does not
directly attack the sulphur, but first dissociates into carbonic oxide
and oxygen. Carbonic anhydride has no action on potassium sulphate
at a bright red heat. When it is passed over the sulphite, the latter is
converted into sulphate and polysulphide, with a small quantity of
carbonate. The acid sulphite gives the same products, but this salt
dissociates even when heated in a current of an inert gas, such as
nitrogen. Carbonic anhydride acts on potassium polysulphide at a
red heat, sulphur being liberated and a mixture of carbonic oxide,
sulphurous anhydride, and carbon oxysulphide being formed, together
with a small quantity of carbonate. This reaction is probably due to
the dissociation of the carbonic anhydride.
Sulphur can be distilled off potassium sulphate below a red heat
without any reaction taking place, but in a porcelain tube heated ta
redness sulphur vapour reduces the sulphate, forming sulphurous
INORGANIC CHEMISTRY. 553
anhydride and a polysulphide, thus: K2SO4 + 5S = K2S3 + 2SO2.
The action of sulphur on potassium carbonate is well known.
The importance of these reactions in the study of the decomposition
of gunpowder is evident. C. H. B.
Pyrosulphuryl Chloride. By D. Konovaloff (Compt. rend., 95,
1284— 1286).— Ogier (Abstr., 1882, 694) obtained for this body the
anomalous vapour-density 3*72. The author has repeated these
experiments with chloride prepared very carefully according to
Schiitzenberger's directions (Compt. rend., 69, 352). Thus obtained,
pyrosulphuryl chloride boils at 153° at 752 mm. pressure, and is a
colourless liquid, fuming in the air, of sp. gr. 1*872 at 0°, and having
a high coefficient of expansion. In contact with water, it decomposes
very slowly at ordinary temperatures, very rapidly at hicrh tempe-
ratures. The vapour- densities were made by Y. Meyer's method. At
the temperature of aniline vapour (183'7°),the numbers obtained varied
between 7'23 and 7'41, with nitrobenzene vapour (210°), 7'27. Theory
for S2O5CI2 = 7*43. The author believes the previous low numbers
obtained to be due to the presence of impurities, probably S02(0H)C1
(differing only slightly in percentage composition). A mixture of
S2O5CI2 and S02(0H)C1, boiling at 140—146°, gave A = 4-01. Pure
S2O5CI2 heated with about 4 per cent, of water gave a liquid boiling at
139—140°, and giving A = 47. L. T. T.
Crystalline Form, Specific Heat, and Atomicity of Thorium.
By L. F. NiLSON (Compt. rend., 96, 346— 348).— Brogger finds that
the hexagonal crystals of thorium obtained by reducing the double
chloride of thorium and potassium by means of sodium are really a com-
bination of the regular octohedron and tetrahedron, and are therefore
identical in form with the crystals of silicon. The density of pure
crystallised thorium is 11 "230 ; that of the amorphous form is 10*968;
mean = 11*099. It follows, therefore, that the atomic volume of
thorium is 20*94, a value approaching that of zirconium, cerium,
lanthanum, and didymiura. The atomic heat of the oxygen in thoria
is equal to 4*08, a value almost identical with the atomic heat of the
oxygen in the oxides of zirconium, cerium, titanium, and tin, and in
zircon and manganese dioxide. The specific heat of thorium is
0*02757, and its atomic heat is therefore 6*41 (Th = 232*4).
These facts, together with facts and analogies previously observed,
show conclusively that thorium is quadrivalent and that thoria is a
dioxide, Th02. C. H. B.
Atomic Weight of Lanthanum. By P. T. Cleve (Bull. Sac,
Chim. [2], 39, 151 — 155). — About 1*5 kilos, of the mixed oxides of
lanthanum and didymium obtained from cerite, gadolinite, orthite, and
keilhauite, were converted into nitrates, the nitrates partially decom-
posed by ignition, and the residue extracted with water. The solu-
tion, which was free from cerium and thorium, was fractionally pre-
cipitated with ammonia. The first fraction consisted of didymium oxide,
almost pure, the seventh and last fraction of almost pure lanthanum
oxide. The lanthanum oxide was then converted into sulphate, which
was purified and separated into fractions by repeated crystallisation,
VOL. XLIV. 2 p
554 ABSTRACTS OP CHEMICAL PAPERS.
and the amount of lanthanum oxide in the sulphate was determined by
ignition. The mean of 12 determinations gave 57*480 + 000395 per
cent, of LaaOg. If SO3 = 80, then La = 138-22 ; or if O = 15-9633,
and S = 31-984, then La = 138-019 + 0-0246. These results confirm
those of Brauner {Monats. Chem.,3, 493); the difference between them
and earlier determinations is probably due to the difficulty of expelling
all free sulphuric acid from the sulphate without causing decomposi-
tion, and to the fact that lanthanum oxide absorbs a small quantity of
oxygen at a dull red heat, but gives it off again at bright redness ; the
oxide is, moreover, somewhat hygroscopic. No element intermediate
between didymium and lanthanum could be detected. C. H. B.
AUotropic Arsenic. By R. Engel (Compt rend., 96, 497 — 499).
— Hittorf and Berzelius observed that in the condensation of the
vapour of arsenic in an inert gas, three forms of the metal are obtained,
viz. : (1) crystalline arsenic in the warm part of the apparatus ;
(2) black amorphous arsenic ; and (3) in the cooler part a grey powder.
This latter modification is more readily oxidised by nitric acid than
either of the former, but it is generally considered that this property
is due to a difference of cohesion. Bettendorf found tha6 both black
and grey amorphous arsenic have a density of 4*7, and that when heated
to 360" they are transformed into crystalline arsenic (sp. gr. 5" 7).
He regarded these forms as three distinct allotropic modifications, and
he suspected that the yellow powder which precedes the deposition
of the grey arsenic was a further modification, but he was unable to
isolate it.
The author has examined the form of arsenic precipitated by various
reducing agents from solutions of arsenious acid. Whatever be the
precipitant employed, the resultant metal was of a velvety brown or
black colour ; its sp. gr. was 46 — 47°, and on heating to 360° it is con-
verted into ordinary crystalline arsenic. The author considers . that
Bettendorf's yellow coloration was due to the yellow vapour of arsenic,
and not to any solid form. The grey powder results from the sudden,
and the black powder from the slow, solidification of the vapour.
There are thus only two well-defined allotropic modifications : 1st, the
amorphous form obtained in the dry way, or in the wet way of precipi-
tation ; 2nd, the crystalline form obtained by the condensation of
vapour of arsenic at 360°, or slightly higher temperature.
V. H. V.
Reduction of Tungsten Compounds. By 0. v. Pfordten
(Ber., 15, 2975— 2976).— A question of priority.
Chemistry of the Chromammonium Compounds. By S. M.
JoRGENSON (/. pr. Chem. [2], 25, 398—430). — A continuation of the
author's researches on this subject (Abstr., 1880, 10 ; 1882, 468,
1169).
VI. Normal Erythrochromium Salts. — Erythrochromium nitrate,
HO(Cr2,10NH3)oNO3,H2O, is prepared by treating 5 grams of the
rhodo-chloride with 50 c.c. of water and 35 c.c. dilute ammonia ; the
solution, at first deep blue, changes to deep crimson, and contains
basic erythrochromium chloride ; on addition of 4 — 5 volumes of dilute
INORGANIC CHEMISTRY. 555
nitric acid, a crimson precipitate of impure erythrochromium nitrate is
obtained, and may be purified by repeated treatment with dilute nitric
acid, solution in water, repreeipitation with nitric acid, and washing with
alcohol, and is finally dried in the dark. It forms a crimson powder,
composed of microscopic octahedrons ; it is not very stable, undergoing
slow spontaneous decomposition, even in the dark. At 100° it decom-
poses, becoming first dark green, and finally black. On ignition, it
decomposes rather violently, red fumes being evolved, and a greenish-
black voluminous residue of chromium oxide left. It is insoluble in
alcohol, but moderately soluble in cold water with a crimson colour ;
on boiling the solution, chromium hydroxide separates. On boiling a
solution acidulated with a few drops of nitric acid, it is converted
into roseochromium nitrate. The erythro-nitrate is insoluble in dilute
nitric acid, bat dissolves slowly in strong acid to a violet liquid, and
after a time is resolved into chromium and ammonium nitrates. On
boiling the solid erythro-nitrate with dilute hydrochloric acid, it is con-
verted into chlorpurpureochromium chloride. An aqueous solution of
the erythro-nitrate gives the following reactions : — Dilute nitric acid
precipitates the salt; dilute hydrochloric acid gives no precipitate;
concentrated acid after some time precipitates chlorpurpureo-chloride ;
concentrated hydrobromic acid precipitates red needles of the erythro-
bromide ; hydrofluosilicic acid a rose-red non -crystalline precipitate ;
hydrogen platinochloride gives no precipitate, but on adding alcohol a
crystalline chocolate-brown precipitate is produced ; hydrogen platino-
chloride and magnesium sulphate give a red precipitate of microscopic
needles ; potassium ferricyanide, a precipitate of long dark-red needles ;
potassium ferrocyanide, a voluminous violet-red precipitate, which
slowly becomes crystalline ; mercuric chloride gives no precipitate,
but sodium mercuric chloride and potassium mercuric bromide give
voluminous precipitates of pale violet-red needles ; hydrogen auro-
chloride and stannous chloride give no precipitates ; solid potassium
iodide, a brownish-red crystalline precipitate ; sodium pyrophosphate,
a clear violet precipitate, soluble in excess of the reagent ; potassium
chromate, no precipitate ; potassium dichromate, a reddish-yellow pre-
cipitate, even from dilute solutions.
Erythrocliromium bromide^ HO(Cr2,10NH3)Br5,H2O, is prepared by
the action of concentrated hydrobromic acid on an ammoniacal solu-
tion of the rhodo-chloride. It crystallises in microscopic crimson
needles, loses 1 mol. HgO over sulphuric acid, but suffers no further
loss on heating at 100° ; after 24 hours, however, it is found to be
nearly completely converted into rhodochromium bromide. It is very
readily soluble in cold water with crimson colour and neutral reaction ;
the solution gives similar reactions to those of the nitrate, except that
it is readily precipitated by hydrogen platinochloride ; the salt is pre-
cipitated unaltered on adding 2 vols, of concentrated hydrobromic
acid ; boiling the aqueous solution with a few drops of hydrobromic acid
converts it into the roseo-bromide, whilst on heating a mixture of the
salt with concentrated hydrobromic acid at 100°, it is rapidly converted
into bromopurpureochromium bromide. Addition of silver nitrate in
the cold precipitates all the bromine, and on shaking with freshly pre-
cipitated silver chloride, all the bromine is replaced by chlorine ; from
2 p 2
55B ABSTRACTS OP CHEMICAL PAPERS.
this all the bromine-atoms would seem to be of equal value ; solution
in ammonia, however, and precipitation with alcohol, gives basic
erythro-broraide, in which one-lifth of the bromine has been removed.
A xantho-salfc could not be obtained by addition of sodium nitrite to
the erythro-bromide, subsequent addition of hydrobromic acid gives an
orange-yellow crystalline precipitate, apparently a perbromide. The
erythro-bromide when shaken with silver oxide and water, gives a red
alkaline liquid containing erythrochromium hydroxide^ which, however,
was not isolated.
Erythrochromium sulphate, (HO,Cr2,10NH3)2-5SO4, is obtained as a
pale crimson precipitate on adding dilute sulphuric acid and alcohol
to a concentrated solution of erythrochromium bromide.
Erythrochromium chloriodide, HO(Cr2,10NH3)ClT4,H2O, is obtained in
short microscopic prisms on adding concentrated hydriodic acid to an
ammoniacal solution of the rhodochloride. Tt loses 1 mol. H2O over
sulphuric acid, and on then heating at 100° is converted into the
rhodo-salt. A corresponding bromiodide is obtained by the action of
potassium iodide on a concentrated solution of the erythro-bromide.
Erythrochromium platinochloride, HO(Cr2,10NH3)2,PtCl6,10H2O, is
obtained by the addition of hydrogen platinochloride and a little
alcohol to a solution of the erythro-nitrate as a chocolate-brown pre-
cipitate of very small thin needles ; it is nearly insoluble in cold water.
The erythro-chloride behaves differently with hydrogen platinochloride,
being precipitated without addition of alcohol in cinnabar-red crystals,
which when washed with water, are slowly converted into the choco-
late-coloured needles of the platinocyanide. The red precipitate is in
all probability a double chloride and platinocyanide.
VII. Basic Erythrochromium Salts. — Basic erythrochromium bro-
mide, HO(Cr2l0NH3)Br4(OH),H2O, is prepared by dissolving erythro-
chromium bromide in ammonia, and adding alcohol, when the basic
salt slowly crystallises out. It forms violet-red plates, loses 1 mol.
H2O on standing over sulphuric acid, and decomposes at 100°. It
dissolves very readily in water, with crimson colour and faintly alka-
line reaction. It is converted into the normal bromide by treatment
with hydrobromic acid, but not by ammonium bromide, thus differing
from the basic rhodo-salts, which expel the ammonia from ammonium
salts. An aqueous solution of the basic erythro-bromide gives the
following reactions : — It is precipitated by alcohol ; is nearly com-
pletely precipitated as dithionate by sodium dithionate ; is completely
precipitated as a lilac-red crystalline powder by potassium ferrocyanide ;
gives no reaction with potassium ferricyanide alone, but on addition of
dilute ammonia gives a reddish-yellow crystalline precipitate ; it does
not react with potassium chromate ; with potassium mercuric bromide,
it gives a thick precipitate of lilac-coloured needles, and with sodium
platinochloride a cinnabar-red granular precipitate.
Basic erythrochromium nitrate, HO(Cr2l0NH3)4NO3(OH),3JH2O,
prepared in a manner similar to the bromide, forms long crim?on
six-sided rhombic tables. When kept it slowly decomposes, with loss
of ammonia.
Basic erythrochromium dithionate, HO(Cr2l0NH3)2S2O6(OH),2H3O,
is obtained by adding sodium dithionate to normal or basic erythro-
INORGANIC CHEMISTRY, 557
chromium nitrate or bromide. It crystallises in brilliant dark violet
needles, united in fan-shaped groups. At 100°, the air-dried salt loses
2 mols. H2O and 2 mols. NH3, without change of shape ; the product
dissolves in cold dilute hydrochloric acid, and the violet-red solution
deposits the tetraminechromium chloride of Cleve on standing.
VIII. Basic Roseo-salts. — Basic roseocohalt dithionatey
Co2l0NH3(OH).,(SA)2,4H2O,
is prepared by boiling nitratopurpureocobalt nitrate with dilute
ammonia, mixing with sodium dithionate, and adding two drops of
alcohol (of 90° Tr.) to 10 c.c. of this liquid, when a crystalline precipi-
tate of the basic dithionate is obtained ; this is now returned to the
main portion, when after brisk stirring, and about one hour's standing,
the dithionate separates as a crimson-red precipitate, consisting of
rhomboidal tables or monoclinic octahedrons. It is sparingly soluble
in water, the solution having a violet-red colour, and is converted into
normal roseo-salt by dilute hydrochloric acid ; it dissolves in solution
of ammonium chloride in the cold with evolution of ammonia.
Basic roseochromium dithionate, Cr2l0NH3(OH)2(S2O6)2 + 4H2O, is
prepared in manner similar to the above, which it closely resembles
in appearance and properties.
The remainder of the paper consists of speculations as to the pro-
bable constitution of the chromammonium compounds,
A. J. G.
Ammoniocobalt Compounds. By Maquenne (Compt rend., 96,
344 — 345). — When ozonised oxygen is passed through an ammoniacal
solution of cobalt sulphate, the liquid first becomes brown, then green,
and finally deposits deep green microscopic prismatic plates on the
sides of the vessel. If the chloride is used, the crystals are slender
needles. These compounds can be more easily obtained by passing a
rapid current of air through a mixture of 100 c.c. ammonia with 10 c.c.
of a saturated solution of cobalt sulphate for about two hours. The
precipitated crystals are collected, dried rapidly between filter- paper,
and thrown, in small portions at a time, into 25 c.c. of a cooled mix-
ture of equal volumes of sulphuric acid, alcohol, and water, when the
brown substance becomes rose-coloured. On adding an excess of
chlorine- water, the rose-coloured compound becomes green, and the
liquid, if heated to boiling and left to cool, deposits prismatic
crystals which are sometimes as much as 5 mm. long, and can be
obtained larger by recrystallisation from dilute (5 per cent.) sulphuric
acid. These crystals are dark green, almost black, quadratic prisms,
of the composition Co202CS04)2(NH3)io,S04H2 + H2O. They are but
slightly soluble in water, by which they are decomposed with evolu-
tion of oxygen, but they dissolve easily in dilute acids without sensible
decomposition, even at 100°, if the operation is conducted rapidly. By
prolonged ebullition with acids, this compound is converted into a
roseocobalt salt. It is entirely decomposed by the fixed alkalis, with
evolution of oxygen and precipitation of black cobaltic oxide.
If this salt is dissolved in boiling dilute hydrochloric acid, and the
solution mixed with strong hydrochloric acid, green shining plates,
558 ABSTRACTS OF CHEMICAL PAPERS.
with a greasy and somewliafc nacreous Instre, are precipitated. Thej
have the composition Co202Cl4(NH3)io,HCl -f SHjO, are somewhat
stable, and dissolve in water, or better, in water acidulated with hydro-
chloric acid. If the acid solution of the sulphate is mixed with
alcohol instead of with strong hydrochloric acid, a pale green magma
of interlaced slender needles is precipitated. This compound is a
chloride undoubtedly identical with that obtained by treating an
ammoniacal solution of cobalt chloride with ozone. It is far less
stable than either of the other compounds ; it is decomposed rapidly
by cold water, and, if left to itself after drying, is transformed in
a day or two into a red mass which consists mainly of roseocobalt
chloride.
These compounds may be regarded as the acid salts of the oxy-
cobalt-ammonium of Fremy. The nitrate is somewhat unstable, and
crj'stallises in green microscopic needles. With solutions of these com-
pounds, especially on agitation, ammoniacal sodium phosphate gives
a green crystalline precipitate, which is deposited more readily on the
rubbed portions of the sides of the vessel, like ammonio-magnesium
phosphate. C. H. B*
Manganese Sulphite. By A. Gorgeu (Compt. rend., 96, 341 —
343). — Manganese sulphite, MnSOsjSHsO, can be obtained in mono-
clinic crystals by the evaporation at ordinary temperatures of a solu*
tion of manganese sulphite in a concentrated aqueous solution of
sulphurous acid, or of a solution obtained by adding an alkaline sul-
phite to a large excess of a solution of a manganese salt until a
permanent precipitate just begins to form. This salt has a pale rose
colour ; dissolves in 10,000 parts of cold or 5,000 parts of hot water ;
is rather more soluble in strong solutions of manganous salts ; and
dissolves Somewhat easily in a strong aqueous solution of sulphurous
acid. It oxidises slowly in dry air, more quickly in ordinary air, and
rapidly in moist air or in contact with aerated water, especially if
finely powdered. In presence of water, chlorine, bromine, and iodine
convert it into sulphate.
Another hydrate, MnS0;^,H20, is obtained by precipitating the man-
ganese sulphite at 100°. It forms rose-coloured crystals belonging to
the rhombic syistem, and does not lose its water below 150°. It rapidly
takes up water in the cold, especially in presence of sulphurous acid,
forming the hydrate Mn 803,31120.
The trihydrated salt begins to lose water at 70°, and oxidises some-
what rapidly. When calcined at a bright red heat, it leaves a
residue of trimanganese tetroxide. Both hydrates when heated out
of contact with air give oif sulphurous anhydride and leave a residue
of manganese monoxide, sulphate, and sulphide. Heated gradually to
redness in a current of hydrogen, manganese sulphite leaves a residue
of 87 parts manganese monoxide and 13 parts manganese sulphide.
Manganese sulphite combines easily with the alkaline sulphites,
forming double salts which crystallise well. C. H. B.
MINERALOGIOAL CHEMISTRY. 559
Mineralogical Chemistry.
Occurrence of Smaltite in Colorado. By. M. W. Iles (Jahrh.
f. Min., 1883, 1, Ref., 194). — Smaltite and erythrite occur with a little
iron pyrites, native silver, and calcite, in a mineral vein near Gothic,
Gunnison Co., Colorado. A sample of smaltite from the surface
croppings gave —
Co. Fe. As. SiOa. Pb. S. Bi. Cu. '
11-59 11-99 63-82 2-60 2-05 1-55 1-13 0-16
m and Ag traces. Total = 94-89
A purer sample yielded 15 per cent, cobalt. B. H. B.
Brazilian Specimens of Martite. By 0. A. Derby (Jahrh. f.
Min., 1883, 1, Ref., 194). — The opinion has recently been advanced
that the octohedral crystals of martite are due to the transformation
of pyrites, but a recent examination of a great number of crystals
from various Brazilian localities indicates that they should rather be
considered as produced by the alteration of magnetite. B. H. B.
Analysis of a Variety of Siderite. By E. Classen {Jahrh. f.
Min., 1883, 1, Ref., 194). — This variety of siderite occurs on haematite,
in the Lake Superior district, either in crusts or in single crystals."
It is often associated with calcite, and has a light green colour. It
contains —
FeO.
CaO.
MgO.
MnO.
CO2.
Total.
41-115
15-883
2-567
trace
40-428
99-993
B. H. B.
Silica and Lithium Silicates. By P. Hautefeuille and J.
Margottet (Jahrh. f. Min., 1883, 1, Ref., 195— 196).— The authors
have succeeded in obtaining artificially three lithium silicates, of which
two are analogous to the magnesium iron silicates ; Li4Si04 and
LizSiOa, resembling (Mg,re) 28104 (olivine) and (Mg,Fe)Si03 (hyper-
sthene) respectively : they agree in many points, but with regard to
Li2Si50u no natural mineral is known resembling it. All these com-
pounds were obtained by the action of lithium chloride on silicates.
Li4Si04 behaves like olivine before the blowpipe. It is somewhat
soluble in hot water; the angle of the rhombic prism measured 119''.
The salt Li2Si03, analogous to hypersthene, has the same angle and
crystal system as the preceding. It is not attacked by dilute acid.
The most acid salt, LiaSisOn, belongs also to the rhombic system.
Quartz and tridymite were also formed by means of lithium chloride,
the former at the melting point of silver, the latter at a bright red
heat. The formation of these bodies is explained by the theory that
lithium chloride contains an oxychloride which renders the crystalli-
sation of the silicic acid possible. B. H. B.
560
ABSTRACTS OP CHEMICAL PAPERS.
Relation between the Optical Properties and Chemical
Composition of Pyroxene and Amphibole. By F. J. Wiik
(Jahrb.f. Min., 1883, 1, Ref., 187— 188).— The author measured the
clinopinakoid angle of a great number of pyroxenes and amphi boles
from Finland, and investigated the relation to the percentage of FeO
in the former and AI2O3 in the latter. The results are given in the
annexed table.
Angle.
FeO per cent.
Analyst.
1
2
8
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
A. Pyroxene Group,
Malacolite (dark)
„ (yellow)
„ (light coloured)
„ (grejish-green)
Diopside (green)
Malacolite (grey)
„ (green)
„ (green)
„ (green)
Pyroxene (green) ,
Augite (black)
„ (black)
„ (black)
Malacolite (red)
(black)
36° SO'
37°
38°
39°
38—40°
39° 30^
39° 30^
41°
42° 30'
42° 30'
43—44°
43° 30'
45° 30'
46°
48°
•08
•99
•52
68
•81
•00
•97
•00
•38
•29
•04
•75
•31
•44
•50
H. Eose.
Bonsdorff.
F. Lemstroa*
E. Moberg,
Castren.
HjelmmaiK
Hjelt.
Landzett.
Castren.
Wiik.
Kudematsch*
Fagerlund.
Sjogren.
Berzelius.
Castren.
Angle.
AI2O3 per cent.
B. Amphibole Group,
Actinolite (green) ,
„ (green)
„ (dark green) . ,
Hornblende (black)
Amphibole, anthophyliite.
Hornblende (black)
„ (green)
„ (green)
16—18°
17°
18° 30'
18° 30'
20°
24° 30'
26° 30'
27° 30'
2-83
1-69
5 10
4-98
7-9
11 92
15 37
20^10
Aakerstedt.
Michaelson,
HofFren.
Wasz.
Tammelin.
Rammelsberg.
Kajander.
Njlander.
The increase of a degree in the angle, with pyroxene, represents an
increase of about 2 per cent, of FeO, or of 10 per cent, of the silicate
(Ca,Fe)Si03. B. H. B.
Artificial Production of WoUastonite. By L. Bourgeois
{Jahrh, f. Min., 1883, 1, Ref., 196— 197).— Wollastonite was obtained
by melting together the required amounts of lime and silica at a
bright red heat, and slowly cooling for two days in the furnace.
A mass of acicular crystals was obtained which appeared transparent
and colourless under the microscope. As the optical properties do
not coincide with those of the natural mineral, the author is of opinion
that the compound is dimorphous. He regards the artificial crystals
as biaxial with an extremely small axial angle.
MINERALOGTCAL CHEMISTRY. 561
Meionite. — The constituents were melted together at a bright red
heat, in the proportions indicated by the formula —
5CaO,Na20,4Al203,9Si02.
In order to obtain a meionite free from soda, the materials 6CaO,
4AI2O3, 9Si02, were melted together. The mixture became fluid at a
dark red heat. The author believes that the product thus obtained
is not meionite but anorthite. B. H. B.
The so-called Ersbyite from Pargas. Bj F. J. Wiik (Jahrh. /.
Min., 1883, 1, Ref., 189). — The author contradicts his former state-
ments with regard to ersbyite (Naumann's Mineralogie, 1881, p. 672),
and he now, after an exhaustive investigation, determines the genuine
ersbyite to be microcline, the analysis being as follows: —
SiOg. AI2O3. CaO. KoO. NaaO. Total.
66-18 19-52 0-36 13-03 091 100
Sp. gr. = 2-67
The colourless felspar formerly mistaken for ersbyite is a variety of
andesine, the analytical results being as follows : —
Loss on
SiOg. AI2O3. CaO. NaaO. ignition. Total.
59-59 26'U 6-23 7-12 0-61 99-99
Sp. gr. = 2-67. B. H. B.
Emerald from Paavo, in Finland. By F. J. Wiik (Jahrh. f.
Min., 1883, 1, Ref., 189). — The emerald was surrounded by a zone of
radiated red albite, this again by a thin layer of muscovite. The
analyses gave the following results : —
SiOs.
AI2O2.
aio.
Total.
I. 66-37
19-29
1401
99-67
II. 66-10
•18-59
14-18
99-87
B. H. B.
Diorites of Montreal. By B. J. Harrington (Jahrh. f. Min.j
1883, 1, Ref., 247 — 248). — Numerous dykes of diorite occur near
Montreal. Their character is very variable ; their colour is light to
dark grey, and sp. gr. 2*92 — 300. The analysis of a typical specimen
gave —
biOs. AI2O3. FejO.,. MnO. Ti02. CaO. MgO.
40-95 16-45 13-47 0-33 339 10-53 6*10
K2O. Na20. I^sOs. Loss on ignition. Total.
1-28 4-00 0-29 3-84 100-63
B. H. B.
Monazite and Zircon from the Quarries of Nil- St. Vincent.
By A. Renard (Jahrh. f. Min., 1883, 1, Ref., 183— 184).— Monazite
occurs in this locality in the form of small tabular crystals with a
greasy lustre and amber-yellow to red colour. The forms of the crys-
562 ABSTRACTS OF CHEMICAL PAPERS.
tals are 4* P, ^oo, ooPoo, ooP, — Poo. The measurement of the angles
gave the following results : ^co : P = 141° 20' 21", cxjPoo : ^co =
100° 16'. The chemical analysis gave 28 — 29 per cent. P2O5 as usual.
The metals cerium, lanthanum, and didymium were qualitatively de-
termined. Together with monazite, crystals of zircon 0-5 mm. long
were formed, which gave on analysis 32*56 per cent. SiOj and 67-29
per cent. ZrOs. B. H. B.
Vanadium in the Leadville Ores. By M. W. Iles (Jahrh. f.
Min., 1883, 1, Ref., 194).— At the Evening Star and ^tna Mine
an orange-coloured substance was discovered, which gave the follow-
ing analytical results : —
SiOg.
PbO.
ZnO.
V2O5.
FeaOg.
H,0.
CO2.
Total.
36-86
38-51
9-07
9-14
2-59
2-41
0-48
99-06'
The author thinks it probable from these results that the mineral is
a dechenite. B. H. B.
Occurrence of Aerenite. By J. Macpheeson (Jahrh. f. Min.,
1882, 2, 98). — This mineral, described by v. Lasaulx, has been found
in the Pyrenees associated with ophite, at Tartaren, in Catalonia, and
at Caserras, in Aragon. It occurs in the rock in small veins. The
sections on being heated become opaque through loss of water, but
transparent again on moistening with that liquid. H. B.
Serpentine from the Alps. By E. Hussak (Jahrh. f. Min., 1883,
1, Ref., 252 — 253). — The serpentine rocks investigated have been
partly described by Drasche (Jahrh. f. Min., 1872, 322). They prove
to be altered slate rocks rich in augite. Salite and diallage were the
original constituents, and have not, as Drasche states, yielded bastite,
but antigorite, which, as a rule, is accompanied by talc.
Analyses were made of the green serpentine slate from Sprechen-
stein (I) ; of the compact serpentine from the same locality (II) ; of
the antigorite isolated from the slate by means of Thoulet's solution
(III) ; and of the chlorite rock resembling serpentine (IV).
The analyses (I — III) agree very well with Drasche's analyses of
serpentine from Heiligenblut and Windisch-Matrei.
I.
II.
III.
SiOa.
40-90
40-55
41-14
29-62
FePa.
7-68
10-40
3-01
AiPa-
2-U8
2-70
3-82
J
CaO.
0-30
4-40
0-40
0-30
MgO.
37-45
33-59
39-16
18-23
H2O.
12-15
9-32
11-85
1034
Total.
100-56
100-96
99-38
w.
41-92
100-41
B. H. B.
Metamorphism of Massive Crystalline Rocks. By J. D.
Dana (Jahrh. f. Min., 1883, 1, Ref., 242— 245).— The rocks investi-
gated occur at Cortland, in Westchester county, New York. The
facts observed appear to sustain the following conclusions. These
rocks, although they include soda-granite, norite, augite, diorite,
hornblendite, pyroxenite, and different chrysolitic rocks, are not
MINERALOGICAL CHEMISTRY. ' 563
independent igneous rocks erupted from great depths. They are
metamorphic in origin, and differ from the other Westchester county
rocks, because the metamorphic process had to do with sedimentary
beds that differed in constitution.
These rocks underwent an upheaval through subterranean move-
ments, and in the course of it they became metamorphosed. The
number of these rocks does not impl}'- widely different ingredients in
the original strata, for they are all alike in containing the same bases
in nearly the same proportion. B. H. B.
Melaphyres of Lower Silesia. By A. P. Coleman (Jahrb. f,
Min., 1883, 1, Ref., 248 — 250). — The melaphyres investigated occur
in the neighbourhood of Waldenburg and Lahn. They consist prin-
cipally of triclinic felspar, probably oligoclase. The presence of
orthoclase is doubtful. Augite occurs in all, and with it is frequently
found a rhombic pyroxene, generally altered to bastite. Brown horn-
blende occurs in the rocks from Waldenburg ; the melaphyre from
Guckelberg also contains biotite. Olivine occurs in variable quantity,
and in many specimens is entirely absent. The melaphyre from Rosen-
thal contains round granules of quartz.
Analyses were made of the rock from Rosenthal near Johannis-r
berg (I), from Lower Schonau (II), and from Kunzendorf near Lahn
(III), the results being as follows : —
SiOj.
AI2O,. FesOg.
FeO.
CaO.
MgO.
KgO.
L 58-93
1547 7-71
—
5-84
3-14
3-17
IL 52-49
15-52 10-99
—
7-26
4-82
3-31
IIL 5512
14-43 —
Loss
9:11
6-60
5-88
4-03
Na^O.
on ignition.
Ti.
Total.
Sp.gr.
I. 4-97
2-34
—
101-57
2-7166
II. 3-62
3-36
trace
101-08
2-7492
IIL 3-64
1-85
trace
100-66
2-7052
B. H. B.
Analysis of a Mineral Spring at Salzbrunn. By T. Poleck
(./. pr. Chem., 27, 45 — 48). — The " Kronenquelle " at Salzbrunn in
Schlesien proceeds from a basin 75 cm. in diameter and 3-3 meters
deep. Its flow is at about the rate of 530 litres per hour. The water
which was collected by the author was 10-5° when the temperature of
the air was 17-3°, and was colourless and without smell.
It possessed a slight chalybeate taste, and was slightly alkaline. Its
sp. gr. was 1-00216.
In 1000 grams of the water there were found the following: —
564
ABSTRACTS OF CHEMICAL PAPERS.
Carbonates
a« bi-carbonstet,
grams.
grams.
grams.
Sodium chloride
0 05899 calculated as sulphate
0-07160
0-05899
Potassium sulphate . .
0 -04086
) 1)
0 -04086
0-18010
Sodium sulphate . . . .
0 -18010
> tt
0-18010
0 -04085
Sodium carbonate
0-55060
> a
0 -73763
0 -87264
Lithium carbonate . . .
0 -00620
1 n
0 00922
0 -01140
Calcium carbonate
0 -43990
i >>
0 -69826
0 -71264
Magnesium carbonate
0 -23288
) >t
0 -33268
0 -40477
Strontium carbonate. .
0 -00198
t >i
0-00246
0-00280
Manganese carbonate .
0-00118
> »
0 -00155
0 00181
Alumina
0 -00047
0 -00156
0 00913
Ferrous carbonate . . . .
0 -00595
„ ferric oxide 0 00370
0 00036
Aluminium phosphate.
0 -00036
, as such . . .
0-00036
0 00047
Silicic acid
0-03460
„ as such . . .
0 03460
0-03460
Total 1-55407
2 -01458 2 -33057
Residue on evaporation
dried at 180° 1 -56300 sulphate found direct 2 -01500
Traces of bromine, iodine, boric acid, barinm and nickel were
detected. The free carbonic anhydride in 1000 c.c. water was found
to be 849-4 c.c. at 10-5° and 740 mm. J. I. W.
Organic Chemistry.
Chlorination of Hydrocarbons from Caucasian Petroleum.
By W. Maekownikoff and W. Ogloblin {Jour. Buss. Chem. Soc., 1882,
354) . — On chlorinating the hydrocarbons of the series CnHon from the
above source, they give chlorides CnHan-iCl, several isomerides being
formed simultaneously. Some of these are easily decomposed, with
formation of hydrocarbons of the general formula CnHon- 2- They re-
semble the chlorides of saturated hydrocarbons, in giving ethereal
salts of acetic acid by double decomposition. The presence of aromatic
hydrocarbons in crude Caucasian petroleum has been confirmed, and
diethyltoluene and pseudocumene were identified, in addition to those
mentioned in previous communications. B. B.
Formation of Dibromodinitromethane and of Villiers' Tetra-
nitroethylene Bromide. By S. M. Losanitsch {Ber., 16, 51—52).
The author has shown (Abstr., 1882, 954) that dibromodinitrome-
thane is produced by the action of nitric acid on tribromaniline. He
has since observed that it is also formed from other bodies belonging
both to the aromatic and fatty series (and amongst these ethylene
bromide) when they are heated with concentrated nitric acid. Accord-
ing to Villiers (Abstr., 1882, 815), the action of fuming nitric acid
on ethylene bromide yields tetranitroethylene bromide, forming an
explosive potassium salt, C2(N02)4Br2,2KOH. The author finds that
I
ORGANIC CHEMISTRY. 565
Villiers' compound is identical with, dibromodinitrometliane, the
potassium derivative having the formula CBrK(N02)2' The latter
explodes at 147 — 150° (according to Yilliers at 145°).
A. K. M.
Conversion of the Propyl into the Isopropyl Group. Bj G.
GusTAvsoN {Jour. Buss. Chem. Soc, 1882, 354 — 355). — Normal propyl
bromide is converted into isopropyl bromide not only on boiling it with
aluminium bromide, as observed by Kekule and Schroter, but the
conversion takes place at the ordinary temperature. This conversion,
however, does not take place during the synthesis of hydrocarbons by
Friedel's and Craffts' method. " B. B.
Direct Combination of Hydrogen with Ethylene. By Ber-
THELOT (Bull. Soc. Ghim. [2], 39, 145). — The author has previously
shown that at a dull red heat hydrogen combines directly with hydro-
carbons, especially with ethylene, the combination being limited by
the dissociation of the hydrides formed. This dissociation varies
rapidly with the temperature, and at the softening point of glass, about
550°, only 51 per cent, of the ethylene is converted into ethane. At a
lower temperature, however, with longer time, as much as 70 per
cent, of the ethylene is converted into ethane, and probably at a still
lower temperature, with sufficient time, the conversion would be com-
plete. C. H. B.
Stability of Trimethylcarbinol. By B. Pawleski (Ber., 15,
3034 — 3036). — Trimethylcarbinol boils at 83° under a pressure of
760 mm. At the temperature of its critical point, viz., 234'9°, it is
perfectly stable. A determination of the density of the vapour of this
substance at 337°, which was conducted in an atmosphere of carbonic
anhydride, agreed with the theoretical results. W. C. W.
Schwarz's Process for preparing Pure Grape-Sugar. By
WoRM-MuLLER and J. Otto (Bled. Centr., 1883, 68). — An excess of
crude sugar is slowly introduced into a mixture of 600 c.c. 80 per
cent, alcohol, and 20 c.c. fuming hydrochloric acid at 25°, then filtered
and set aside to crystallise. Purification is further attained by wash-
ing and by recrystallisation from alcohol. The alkaline mercuric
cyanide process for estimating dextrose is accurate when the solution
is diluted with 3 vols, water and the sugar solution contains about
1 per cent, sugar. E. W. P.
Saccharin and Saccharic Acid. By H. Kiliani (Ber., 15, 2953 —
2960). — Saccharin is most conveniently prepared by treating a solu-
tion of 1 kilo, of invert cane-sugar in 9 litres of water with 100 grams
of slaked lime. After the liquid has remained 14 days in a closed
vessel, 400 grams of slaked lime are added, and the mixture is pre-
served for one or two months until the clear liquid exerts only a feeble
reducing action on an alkaline solution of copper sulphate. After the
mixture has been filtered, the filtrate is saturated with carbonic acid,
and the lime which remains in solution is exactly precipitated by oxalic
SiyQ ABSTRACTS OF CHEmCAL PAPERS.
acid : on evaporating the filtrate, saccharin is slowly deposited. Sac-
charin in aqueous solution slowly changes into saccharic acid, the
presence of free oxalic acid is favourable to this reaction. On the
other hand, saccharic acid is partially converted into its anhydride by
boiling the aqueous solution.
Fotassium saccharafe, CeHnOfiK, crystallises in thick monoclinic
plates, a:b:c = 1'2893 : 1 : 1-8861, ^ = 85° 25'. The calcium and
zinc salts are amorphous. Copper saccharate^ Cu(C6Hn06)2 + 4H2O,
forms blue crystals. By the action of nitric acid (sp. gr. 1'375) at
35°, saccharin is slowly converted into oxalic acid and a new acid,
ObHioOt; after removing the oxalic acid by boiling with calcium
carbonate, the new acid is obtained in rhombic plates or prisms
\_a : h '. c •=■ 0*6903 : 1 ; 0*528] which closely resemble crystals of citric
acid in appearance. The crystals are soluble in water and warm ether,
and the aqueous solution is feebly laevogyrate. This body acts not
only as a monobasic acid bnt also as a lactone. W. C. W.
Some Oxides of the Ethylene Series and their Action on
Water. By A. Eltekoff (Journ. Buss. Chem. Soc, 1882, 355 — 396).
— In the present paper the author gives an account of some of the
known compounds of the formula C»H2«0.
Amylene or Trimethyl-ethylene oxides CgHioO, or McaC — CHMe, was
O
first obtained in 1861 by Bauer (Annalen, 115, 91) by the action of
hydrochloric acid on amylene glycol and subsequent treatment of the
product with potash. On repeating Bauer's experiments with pure
amylene glycol (b. p. 176 — 177°) the author obtained a compound,
C5H10O (b. p. 94 — 95°), which, however, was found to be no "oxide,"
but pure methyl-isopropyl Jcetone, formed apparently by the dehydrat-
ing action of hydrochloric acid on the glycol. According to Carius
(An7ialen, 126, 199) a compound, identical with Bauer's, is obtained
by the action of potash on the corresponding chlorhydrin ; this, how-
ever, the author finds to be the true amylene oxide. It boils at
75 — 76°, and has a sp. gr. of 0*8293 at 0°. It enters into direct com-
bination more readily than the lower oxides of the same series, for it
is completely converted into the glycol by the action of water, even at
the ordinary temperature, in half an hour. Isopropyl-ethylene oxide,
CjHioO or CHMe2.HC — CH2, isomeric with the above compounds, was
\/
O
obtained in an analogous way. It boils at 82°, and combines very
slowly with water, complete conversion into the glycol taking place
only after the mixture has been heated for 50 — 60 hours at 100°. The
third isomeric compound, methyl-ethyl-ethylene oxide, C5H10O or
EtHC — CHMe, obtained from the corresponding hydrocarbon by the
O
method described above, is a liquid (80°) which combines with
water to form the glycol (b. p. 187 — 188°) only after continued heat-
ing at 100°. It is seen from the above that of the three isomeric
ORGANIC CHEMISTRY. 567
compounds, one enters very readily into direct combination where
the combination takes place on a " tertiary " carbon-atom. The beha-
viour of the isomeric oxides described below is analogous to this.
Isohutylene oxide, M-Q^C — CH2, obtained by the action of potash on the
O
chlorhydrin prepared by the direct union of isobutylene with hypochlo-
rous acid in aqueous solution, is a colourless liquid of sp. gr. 0'8311 at 0°,
boiling at 51 — 52°. It combines directly with water at the ordinary
temperature with considerable development of heat, to form isohu-
tylene glycol (b. p. 176 — 178°). The isomeric hutylene oxide ov sym-
metrical dimethyl-ethylene oxide, MeHO — CHMe, was obtained from
0
the corresponding hydrocarbon. A mixture of isobutylene and di-
methyl-ethylene was first prepared by the action of sulphuric acid on
isobutyl alcohol, and from this the first hydrocarbon was removed by
agitation with dilute sulphuric acid (IH2SO4 : IHgO) in which it dis-
solves, leaving pure dimethyl-ethylene. Butylene oxide is a colour-
less liquid boiling at 56 — 57°, and having a sp. gr. of 0*8344 at 0°. It
takes up the elements of water much less readily than isobutylene
oxide, and is only completely converted into the glycol (b. p. 183 —
187°) by heating it at 100° for eight hours.
M ethyl -jorojpy I- ethylene oxide, PrHC — CHMe, obtained in the same
0
way from hexylene (from mannitol), boils at 109 — 110°. It is con-
verted into the glycol (b. p. 206 — 207°) only when heated with water
at 100 — 110° for a considerable length of time.
Hexylene oxide fj;etramethyl-ethylene oxide) , Me2C — CMca. The tetra-
O
methyl- ethylene, which formed the starting point for its preparation,
was obtained by heating methyl iodide and lead oxide or amylene
(trimethyl-ethylene) in sealed tubes at 220 — 230° for eight hours.
In this reaction, some ethyl oxide is formed by the action of the lead
oxide on the methyl iodide, some amylene remains unchanged, and the
rest (about one-third) is converted into a mixture of hexylene (tetra-
methyl-ethylene) (b. p. 73°) and heptylene (unsymmetrical me thy 1-
butyl-ethylene) CMcs-MeC ! CH2 (b. p. 78—80°), as was shown by the
reaction of the products of transformation of these hydrocarbons.
After conversion into the chlorides, the two hydrocarbons were
separated by fractional distillation and obtained in the pure state.
The conversion of amylene into hexylene by the above method takes
place thus : CMcz ! CHMe + Mel = CMcz '. CMcz f HI, but the
author has hitherto been unable to understand the formation of the
' heptylene which takes place simultaneously. Hexylene, obtained as
above, was first converted into the chlorhydride CMe2Cl.CMe2.OH
(m. p. 55°), and this, by the action of potash in presence of a little
water, into hexylene oxide (b. p. 95 — 96°). It combines with water
with the evolution of a considerable amount of heat forming the
568 ABSTRACTS OP CHEMICAL PAPERS.
corresponding glycol, pinacone. This combination takes place so easily
that, on distilling hexylene oxide with potash, no oxide at all is formed,
but crystals of the hydrate of pinacone, C6H,402 + GHjO (m. p. 46°),
are formed in the receiver. The facility with which hexylene oxide
becomes hydrated is explained by the circumstance that the oxygen is
linked to two tertiary carbon-atoms. In contradistinction to this,
propylene oxide, MeHC — CH2, containing no tertiary carbon-atom,
O
combines with difficulty with water, and cannot be converted com-
pletely into the glycol, even after being heated with it for eight hours
at 100°. The author proceeds to investigate the mode of addition of
different acids to the above oxides, the thermal phenomena taking place
at the same time, and the heats of combustion of the oxides, as com-
pared with those of the isomeric aldehydes and ketones. B. B.
Aldehyde-ammonium Bases. By G. Meyer (Ber., 16, 207 —
208). — By the action of sodium ethylate and methyl iodide at the
ordinary temperature on a concentrated aqueous solution of acetalde-
hyde-ammonia, a crystalline mass of isocholine, OH.CHMe.NMe3.OH,
is produced. The salts of this base are very unstable, and act as
powerful reducing agents. The iodide, CsHuNOI, forms needle-shaped
crystals which are freely soluble in dilute alcohol. The platinochloride,
CioHasNaOajPtCle, is insoluble in ether. W. C. W.
Thiocyanopropimine. By J. Tcherniac and T. H. Norton
(Compt. rend., 96, 494 — 497). — By the action of monochloracetone
on ammonium thiocyanate in alcoholic solution, thiocyanacetone is
formed, which reacts with the excess of the ammonium salt to produce
the thiocyanate of a new base, C4H6N2S, which the authors propose to
name thiocyanopropimine. The changes may be expressed thus: —
NH4.SCN + MeCO.CH^Cl = NH4CI -f MeCO.CHo.SCN and
MeCO.CH^.SCJSr + NH4.SCN = H^O + (SCKCH2.CNHMe)HSCN.
The thiocyanate of this base crystallises in bulky straw-yellow
crystals melting at 114°, soluble in alcohol and hot water; the nitrate,
C4H6N2S.HNO3, obtained from the preceding salt by the action of
silver nitrate, crystallises in large colourless needles melting at 183° ;
the acid sulphate forms small white needles, the platinochloride a
yellowish brown powder.
The base thiocyanopropimine, obtained from the thiocyanate by the
action of concentrated potash, forms hygroscopic crystals which display
in a most marked way the phenomenon of superfusion, for they melt
at 42°, but solidify only at 28°. This compound boils at 136° under a
pressure of 30 — 40 mm. mercury.
Acetylthiocyanopropimine, SCN.CH2.CMe !NZc, prepared by the
action of acetic anhydride on the above base, crystallises in delicate
silky needles, having a diamond-like lustre ; it melts at 130°, but re-
solidifies at 91°.
Methyltliiocyanopropimine hydroiodide, SCN.CHj.CMe INMe,HI,from
the free base and methyl iodide, forms transparent brown crystals melting
at 157°, soluble in hot, sparingly soluble in cold water. V. H. V.
ORGANIC CHEMISTRY. 569,
Isonitroso-compounds. By Y. Meyer (Ber., 16, 167 — 170). —
Since benzylbydroxylamine yields benzyl alcohol and not benzylamine
on reduction, the benzyl-gronp in this compound must be attached to
an oxygen, and not to a nitrogen atom. It will consequently have the
formula NH2(OC7H7) and acetoxime will be CMco !N.OH.
It further appears that only bodies containing carbonyl, e.g.^
acetones, aldehydes, yield isonitroso- compounds when acted on by
hydroxylamine. Laevulic and pyrotorebic acids form isonitroso-com-
pounds, but ethylene oxide and glycidic acid do not.
This reaction is therefore capable of affording valuable aid in arriv-
ing at the constitution of certain compounds. W. C. W.
Aldoximes. By J. Petraczek {Ber., 15, 2783— 2786).— The
present paper is preliminary, and is in continuation of the researches
of V. Meyer on the reactions of aldehyde with hydroxylamine, and
the formation thereby of volatile nitrogenous products.
Ethylaldoxime, C2H5NO. — An aqueous solution of hydroxylamine
chloride is decomposed by an equivalent of soda; to the cooled
mixture, acetaldehyde, diluted with water, is added, the mixture is
left for 12 hours, exhausted with ether, dried with calcium chloride,
and the ether is expelled : a fluid remains which has a constant boiling
point of 114 — 115° ; it is miscible with water, alcohol, and ether in all
proportions, and has a weak smell of aldehyde.
Propylaldoxime, C3H7NO, is prepared from propaldehyde by Przy-
bytek's method (Beilstein Org. Ghemie, p. 232), and very closely
resembles the original aldoxime in its properties.
Isohutylaldoxime, C4H9NO, prepared by Fossek's method (Monatsh.
Chem., 11) from isobntyl alcohol and chromic acid mixture ; it is a
colourless liquid not miscible with water, but partially soluble therein ;
its boiling point is about 139°.
Benzylaldoxime, C7H7NO. — Benzaldehyde is added to an aqueous
solution of hydroxylamine chloride and excess of soda, and then suffi-
cient alcohol to clear the solution ; to prevent oxidation the vessel is
filled with carbonic acid. After 24 hours the mixture is shaken with
ether, which is driven off, and the residual oil dried over sulphuric
acid. The product boils about 200° with partial decomposition ; small
portions may be distilled unaltered, but if a few grams are used, the
mass assumes a brown colour, disemgages ammonia, and deposits
crystals whi(?h are either pure benzylaldoxime or an isomeric modifi-
cation.
Solid benzylaldoxime forms white crystals similar to those of ben-
zoic acid, slightly soluble in water, easily in alcohol and ether, and
melting at 161*5" ; prolonged boiling with hydrochloric acid decom-
poses it. The behaviour of benzaldehyde towards hydroxylamine
does not differ from that of aldehydes of the acetic series.
As to the general constitution of aldoximes, ethylaldoxim.e for
example, there are three possible formul89 :
CMeH2.NO; CHMelN.OH; and CHMe<5J^>
J. F,
VOL. XLIV. 2 q
570 ABSTRACTS OF CHEMICAL PAPERS.
Condensation-products of Aldehydes and their Derivatives.
By A. LiEBEN and S. Zeisel. (Second Memoir.) Methylethyl-
acrolein and its Derivatives (Movatsh. Chem., 4, 10— 87).— In a
former memoir (Abstr,, 1879, 615), the authors showed that the
action of sodium acetate on propaldehyde gives rise to a conden-
sation-product, CeHioO = 2C3H6O — H2O ; and the experiments
described in the present paper lead to the conclusion that this body
consists oi propylidenepropaldehyde or a-meihijl-fi-ethylacroldn
CMeHz.CH : CMe.CHO,
and that its formation takes place by the union of the oxygen of one
of the propaldehyde molecules with the H2 of the other, the water
thus formed being eliminated, thus :
CMeH,.CHl 0
CMeiilJcHO = ^^^ "^ CHjMe.CH: CMe.CHO.
Methylethylacrole'in is an unsaturated aldehyde, oxidising in the air,
and forming with hydrogen sodium sulphite a crystalline compound,
which is not decomposed by sodium carbonate, but combines directly
with HCl or Br-z, the latter compound uniting readily with hydrogen
sodium sulphite and forming a body having the composition
C6HioOBr2,S03HNa + 3H2O.
By reduction in alcoholic solution with zinc-turnings and sulphuric
or hydrochloric acid, or better with iron and acetic acid, methyl-
ethylacrole'in is converted into caproic aldehyde, hexyl alc6hol, and
an unsaturated alcohol, CeHigO. The aldehyde and the hexyl alcohol
yield on oxidation a hexoic or caproic acid, viz., m ethyl pr opy la cetic
acid, CHMcPr.COOH, together with methyl propyl ketone and Jiexyl
caproate, CsHu.COOCeHia.
The unsaturated alcohol, C6H12O, forms with bromine an unstable
compound, CeHi-O.Bro, which is decomposed by heating under reduced
pressure, and when boiled with water yields, as chief product, hexenyl
glycerol, C6Hn(OH)3, and the unsaturated aldehyde CeHioO.
The hexenyl- glycerol,
C6Hu(OH)3 = CH2Me.CH(OH).CMe(OH).CH2(OH),
purified by conversion into the corresponding triacetin, and separated
therefrom by boiling with barj'-ta- water, agitation of the watery
liquid with ether, and evaporation under reduced pressure, is a thick
colourless liquid, slightly volatile at ordinary temperatures, and dis-
tilling under 53 mm. pressure between 170"^ and 170°. Heated with
excess of hydriodic acid in a sealed tube at 100°, it yields a hexyl
iodide, CeHisI, distilling at 154—160°. The triacetin, CeTln(OJ^),,
is a colourless, thickish liquid, having a faint odour and aromatic
taste, heavier than water, and not miscible therewith.
Oxidation of Methylethylacrolem. — By oxidation with free oxygen,
chromic acid mixture, or moist silver oxide, this aldehyde yields
propionic, acetic, formic, and carbonic acids, a slightly soluble
ORGANIC CHEMISTRY. 571
"nnsatTirated acid, viz., methylethylacrylic acid, CeHmOs, a soluble non-
volatile crystalline acid, viz., dehydroxycaproic acid, C6H12O4, accom-
panied by a non-crystalline acid, and finally methyl-propyl ketone,
CH3.CO.C3H7.
The formation of these bodies may be represented by the following
equations, from which it will be seen that the oxidation takes place
partly at the aldehyde-group, whereby methylethylacrylic acid is
formed, partly at the doul3le linking, whereby the molecule is split up,
with formation of propionic, acetic, and formic acids, while the for-
mation of dihydroxycaproic or methyl-hydroxypropyl-hydroxyacetic
acid may be explained by oxidation at both these places simul-
taneously, and that of m-ethyl propyl ketone by the successive action
of water and oxygen : —
(1.) CHaMe.CH : CMe.CHO + 0 = CHsMe.CIi: CMe.COOH
Methylethylacrylic acid.
C2.) CHaMe.CH ! CMe.CHO + O4 + H^O = CH,Me COOH +
Propionic acid.
Me.COOH + H.COOH
Acetic acid. Formic acid.
(3.) CH^Me.CH ! CMe.CHO + O2 + H^O =
CHijMe.CH(OH).CMe(OH).COOH
Dihydroxycaproic acid.
(4.) CH2Me.CH: CMe.CHO + H2O = CH2Me.CH3.CMe(OH).CHO
and CH2Me.CH2.CMe(OH).CHO + O2 = H^O + CO^ +
CH2Me.CH2.COMe
Methyl propyl ketone.
Methylethylacrtjlic acid crystallises in large colourless monoclinic
prisms, having the axes a : b : c = 1*4807 : 1 : 0'3847, and the angle
ac = 104° 38'. Observed forms ooP . Pcxj. Habit, prismatic in the
direction of ooP. Melting point 24*4°. Sp. gr. of fused acid at 25"
(corr.) = 0'9812, referred to water at the same temperature. Boiling
point 213° (corr.) under a pressure of 760 mm. reduced to 0°. The acid
has a characteristic, rather agreeable, scarcely sour odour, quite differ-
ent from that of the lower fatty acids, but somewhat resembling that
of methylpropylacetic acid. The calcium salt, Ca(C6H902)2 + 4H2O, is
much more soluble in hot than in cold water or aqueous alcohol, and
crystallises, sometimes in hard hemispherical nodules adhering to the
sides of the vessel, sometimes in well-defined prisms or slender silky
needles, often in radiate groups. The silver salt, AgC6H902, obtained
by digesting the free acid with a large quantity of water and excess
of silver carbonate, crystallises on cooling in needles and laminae.
The solution of the calcium salt gives white precipitates with nitrate of
silver or lead ; with cupric acetate a sky-blue precipitate soluble in
excess of calcium acetate ; with zinc acetate a white, and with ferric
\loride a red precipitate, oily when first separated.
2^2
572 ABSTRACTS OF CHEMICAL PAPERS.
By reduction with hydrobromic acid nnd zinc, or with hydriodic
acid, methylethylacrylic acid is converted into a caproic acid, dUnOtf
identical with that which is obtained by oxidation of the above men-
tioned hexyl alcohol and caproic aldehyde, that is to say, methyl propyl-
acetic acid.
Methylethylacrylic acid unites directly with bromine, forming the
compound CeHioOgBrs = EtCHBrMe.COOH.CBr, which separates in
large fine crystals, is reconverted by nascent hydrogen into methyl-
ethylacrylic acid, and is decomposed by excess of water at 100°,
yielding hydrogen bromide, bromamylene, methylethylacrylic acid,
methyl propyl ketone, dihydroxycaproic acid (apparently identical
with that which is obtained by oxidation of methylethylacrole'in), and
carbon dioxide. H. W.
Constitution of Nitroso-compounds. By V. Meyer and M.
Ceresole (Ber., 15, 3067 — 3074). — By the action of benzyl chloride on
an alcoholic solution of the sodium compound of nitro.soacetone, a
crystalline body is obtained which is isomeric with benzylnitroso-
acetone (7?er., 15, 1876). It forms colourless plates melting at 45**,
freely soluble in ether, chloroform, alcohol, and light petroleum. It
is sparingly soluble in water, and insoluble in alkalis. The formation
of this body instead of benzylnitrosoacetone (m. p. 81°) is further
evidence in favour of the view that nitrosoacetone does not contain
the NO-group, and that its constitution may be represented by the
formula CH3.CO.CH I N.OH.
The aathors are of opinion that true nitroso-compounds are pro-
duced only by the action of nitrous acid on the CH-group, and that
isonitroso- derivatives, C ! NOH, are formed by the action of nitrous
acid on the CH2-group. W. C. W.
Nitrosoketones. By P. P. Treadwell and B. Westenberger
(Ber., 15, 2786 — 2789). — Referring to previous communications on
ketines by one of the authors (Abstr., 1881, 805; 1882, 166), they
announce that in their experiments, occupied with preparation of
nitrosoacetone, they allowed the prepared solution to remain un-
noticed for the space of a week. On proceeding to extract it with
ether, they found, instead of nitrosoacetone, the acetoximacid,
NHO.CMe : CH.NHO, already obtained by V. Meyer and Janny by
the action of dichloracetone on hydroxylamine. It melts at about
153°, gives colourless solutions with alkalis, and sublimes in white
needles. The authors point out certain advantages of this mode of
preparing the substance in question. A nitrosoisobutylketone was
formed by a similar reaction; it crystaUises in the form of white
leaves, melting at 42°, and easily sublimed, soluble in ether and
alcohol, easily in warm, but sparingly in cold water. The authors
note the lowering of the melting point of the nitrosoketones in pro-
portion as their molecular weights increase.
C4H7O2N. C5H9O2N. CgHiiOoN. C;H,30oN.
74° 54° 49-5°. 4:i°.
ORGANIC CHEMISTRY. 573
Tlie primary nitrosoketone, C3H5O2TT, does not follow the rule, its
melting point being 65°. J. F,
Isonitrosoketones. By C. Schramm {Ber., 16, 177—180),—
When isonitrosomethylketone, MeCO.CMe ! N.OIT, is decomposed by
boiling with strong hydrochloric acid, the sole products are hydroxyl-
amine hydrochloride, acetic acid, and a small quantity of ethylmethyl'
acetoxlmic acid, OHN ! CMe.CMe I NOH. This acid is easily prepared
by the action of hydroxylamine hydrochloride on an aqueous solution of
isonitrosomethylketone. It crystallises in white needles, which sublime
about 215°, and are sparingly soluble in water. W. C. W.
Action of Nitric Acid on Ethyl Acetoacetate and Chlor-
acetoacetate. By M. Propper (Ber., 16, 67). — According to a previous
communication (Abstr., 1882, 1193), the author obtained ethyl nitro-
soacetate and chloronitrosoacetate by the action of concentrated nitric
acid on the abovementioned ethereal salts. A further study of these
bodies has led him to infer that they are really oximido-bodies in
accordance with the view of Meyer and Ceresole (Ber., 15, 3067). In
support of this, he urges the fact that ethyl acetoacetate and chlorace-
toacetate yield oxalic acid and the two bodies C4H7O3N" and CiHeClOsN'
respectively, whilst ethyl dichloracetoacetate is not attacked; this
being easily explained on the assumption of the dtad oximido-group :
whereas if the monad nitroso-group is present, a similar body should
also be producible from the dichloracetoacetate. Boiling with hydro-
chloric acid decomposes ethyl oximidoacetate into hydroxylamine
hydrochloride, oxalic acid, and ethyl chloride; whilst boiling with
water decomposes the chloro-derivative into hydroxylamine hydro-
chloride, oxalic acid, and alcohol. A. K. M.
Brom-addition-derivatives of the Crotonic Acids and of
Methacrylic Acid. By C. Kolbe (J.pr. Chem., [2], 25, 369—398).—
The constitution of the isomeric crotonic, isocrotonic, and methacrylic
aoids being still uncertain, although it is known that the two former
are derivatives of normal butyric acid, and the latter of isobutyric
acid, the author in the hope of settling the question has investigated
the brom-additive compounds of these acids.
Methacrylic acid was dissolved in carbon bisulphide, and the cal-
culated quantify of bromine slowly added. The resulting dihrorrdso-
hutyric acid crystallises in long prisms melting at 48°. On heating it
with 10 parts of water in a vessel provided with a reflux condenser,
decomposition commences at the boiling temperature, carbonic anhy-
dride being copiously evolved. The solution then contains a small
quantity of acetone, hydrobromic acid, ordinary bromomethacrylic
acid, bromhydroxyisobutyric acid, aaid very small quantities of prop-
aldehyde, and an oil whose amount was too small for further inves-
tigation. The same products are obtained with aqueous solution of
sodium carbonate, but acetone is formed in large quantity, whilst the
yield of bromomethacrylic acid and of hydroxy bromisobutyric acid is
very small.
Bromhydroxyisobutyric acid^ CMe(CH2Br)(0H).C00H, crystallises
574 ABSTRACTS OP CHEMICAL PAPERS.
in groups of fine white needles melting at 100 — 101°, soluble in ether
and benzene, insoluble in carbon bisulphide and chloroform; it does
not distil with steam. No salts could be obtained, as in presence of
bases it is decomposed with formation of metallic bromides ; on heating
it with water, a very slow decomposition ensues. By treatment with
nascent hydrogen, it is converted into the ordinary hydroxyisobutyric
acid.
On adding dibromisobutyric acid to a moderately concentrated solu-
tion of sodium hydroxide, it dissolves, with evolution of heat, and is
completely converted into bromomethacrylic acid.
From these results, it follows that methacrylic acid must have the
constitution CH2! CMe.COOH, as originally suggested by Frankland ;
for by the formula ZZCH.CHMe.COOH, proposed by Fittig, the dibro-
mide would have the constitution CHBr2,CHMe.C00H, and on boiling
with water -and treatment with nascent hydrogen, should yield, not the
known hydroxyisobutyric acid, CMe2(0H).C00H, but an isomeric
acid of the formula CH2(0H).CHMe.C00H.
Crotonic and isocrotonic acids, when treated with bromine, both
yield the same dibromobutyric acid, which when boiled with water or
solution of sodium carbonate, is decomposed into /3-bromopropylene,
monobromocrotonic acid and bromhydroxybutyric acid, together with
carbonic anhydride and hydrobromic acid.
Bromhydroxyhutymc 'acid was obtained as an oily substance, not
solidifying on standing for many weeks under an exsiccator. Salts
could not be obtained, as it is decomposed by bases, with formation of
metallic bromides. On boiling it with water for eight hours, a dihydroxy-
butyric acid was obtained, whose barium salt, [C3H5(OH)2.COOj2Ba,
was not crystalline. On treating dibromobatyric acid with sodium
hydroxide, monobromocrotonic acid was alone obtained. In conclusion,
the author entirely fails to confirm the statement of Erlenmeyer and
Miiller (Abstr., 1882, 598), that ordinary monobromocrotonic acid
is a mixture of two isomeric acids. The acid was prepared by three
methods, and in each case proved to be one substance only.
A. J. G,
New Method for preparing Carbonic Oxide. By E. Noack
(Ber., 16, 75 — 7G). — When carbonic anhydride is passed over heated
zinc-dust contained in a combustion tube, it is almost completely
reduced to carbonic oxide, the last traces of carbonic anhydride being
easily removed by passing the gas through soda solution.
A. K. M.
Carbonic Hydroxide. By M. Ballo (Ber., 15, 3003—3007).—
Aqueous solutions of potassium and sodium bicarbonates, as well as
solutions of carbonic anhydride, dissolve metallic magnesium with
evolution of hydrogen. Solutioi s of the normal carbonates of sodium
and potassium have no action on magnesium : hence the author con-
eludes that in an aqueous solution, the carbon dioxide exists in the
form of a hydroxide.
An aqueous solution of sulphur dioxide also has the power of dis-
solving magnesium with evolution of hydrogen. W. C. W.
ORGANIC CHEMISTRY. 575
Action of Acids on Acetamide. By W. Ostwald (/. pr. Ghem.^
27, 1 — 39). — The author has studied the action of various acids on
acetamide at certain temperatures, in order to determine the relative
intensities of their chemical actions. By observing the amount of the
amide decomposed in a given time, or vice versa, he has obtained
numbers which represent the rate of decomposition by the acids
under examination. The intensity of the reaction was determined
by estimating the amount of ammonium salt formed, the salt being
decomposed by sodium hypobromite and the nitrogen measured.
The author finds that the presence of acetamide along with the am-
monium salt in the nitrometer yields free nitrogen, in excess of that
which would be evolved; but he has made corrections for the
amount of acetamide present. The observations were made at 65°,
the boiling point of methyl alcohol, and at 100°. The rate at
which the acetamide is decomposed is directly proportional to the
strength of the acid present. The reaction commences quickly ; but
the further it proceeds, the smaller is the amount of decomposition in
equal intervals of time. The author has tabulated the results obtained
with solutions of acetamide of given strength in various intervals
of time. From the different times required to decompose successive
varying quantities of acetamide, the author has calculated the time in
minutes at which the reaction would be half completed in the case of
each acid. The results are shown in the following table : —
65°. 100°. Proportion.
1. Hydrochloric acid 72-1 4-98 14-48
2. Nitric acid 75-2 5-35 14'06
8. Hydrobromic acid 74-0 5*14 14-39
4. Trichloracetic acid 112'8 — —
5. Dichloracetic acid 433-7 — —
6. Monochloracetic acid 4570-0 — —
7. Formic acid 28950-0 2138'0 13-55
8. Lactic acid 293i0-0 2128-0 13-HO
9. Acetic acid — — —
10. Sulphuric acid ISO'O 14-1 12-77
11. Oxalic acid 1516-0 1 18 6 12-80
12. Tartaric acid 13660*0 929-0 14-71
13. Malic acid 35310-0 — —
14. Succinic acid — 7976*0 —
15. Citric acid 44810-0 3088-0 14-53
16. Phosphoric acid — 3880-0 —
17. Arsenic acid — 4005*0 —
By dividijftg the intervals of time in the table of results by the
above values at the respective temperatures, comparable figures are
obtained. The author has drawn the curve representing the theoretical
progress of the reaction, according to the formula — ^ = C^: where a
a—y
is the substance taking part in the reaction, and y is the amount
decomposed in time t, C being a constant. Alongside the curve are
placed dots representing the results of experiments, and showing the
576
ABSTRACTS OF CHEMICAL PAPERS.
amounts of ammonia formed in various intervals of time in presence
of different acids.
The dots representing the reaction in presence of hydrochloric,
nitric, and hydrobromic acids, show that during the decomposition
there is an accelerating moment. Former researches (ibid., 23, 209)
have shown that monobasic acids in certain cases have a more powerful
action in the presence of their neutral saUs. It is, therefore, evident
that in this case the variation is due to the presence of the neutral
ammonium salts. In the case of trichloracetic acid, however, a
retarding action is evinced : it is possible that this is due to the
tendency to form the corresponding amido-acid. The bibasic acids
act less rapidly towards the end of the reaction. There is no doubt
that this is due to the formation of the acid salt. In the case of the
tribasic phosphoric and arsenic acids, the retarding effect is still more
marked.
The curve representing experiments made at 65° is almost identical
with that formed from those at 100°, except that in the case of bibasic
and tribasic acids, towards the end of the reaction, the latter is lower
than the former, showing that a rise in temperature promotes the
formation of the acid salt. If the time for each acid of the semi-
completion of the reaction be divided into that for hydrochloric acid,
the relative velocities are obtained, referred to HCl = 1.
The author shows that the affinities of bodies vary as the 4th root
of the velocity of the reaction in which they take part. The relative
velocities and their 4th roots representing the relative affinities are
given in the following table. Those under a are from experiments
made at 65°, those under b from those at 100°, and those given under c
are the results of former experiments (ibid., 18, 362) made by the
method of equivalent weights : —
Hydrochloric acid . . . .
Nitric acid
Hydrobromic acid . . . .
Trichloracetic acid. . . .
Dichloracetic acid . . . .
Monochloracetic acid. .
Formic acid
Lactic acid
Acetic acid
Sulphuric acid
Oxalic acid
Tartaric acid
Malic acid
Succinic acid
Citric acid
Phosphoric acid
Arsenic acid
Relatire Velocities.
65°.
0000
9588
9743
6393
•1663
01687
■002663
•002628
0005466
4283
•05086
0005644
•002184
•00065
•001608
100
98
98
80
40
13
5
5
2
65
22
7
4
2
4
100°.
1-0000 100-0
0-9327 97-0
0 -9690 98 -0
0 -002330
0-002340
4-83
4-85
0-3532 59-4
0 04199 20-5
0-005360 7-32
0 -0006244 2 '50
0 001612 4-01
0-001284 3-58
0 001244 3-53
Relative Affinities.
100
98
98
80
40
13
5
5
65
22
7
4
2
4
b.
100
97
98
2
59
20
7
2
4
3
3
98-0
100 0
95 0
80-0
33 0
7-0
3 9
3-3
1-23
66-7
5-2
2-82
1-45
J. I. W.
ORGANIC CHEMISTRY. 577
Action of Aluminium Chloride and Bromide on Hydro-
carbons. By G. GusTAVSON {Joyr. Muss. Chem. Soc, 3882, 354). — On
shaking the compound AlBrajSCeHs with toluene, the latter combines
with a part of the aluminium bromide, and benzene is set free. In like
manner cyraene displaces some of the benzene from the same compound.
Aluminium bromide is therefore distributed between aromatic hydro-
carbons, and by this circumstance the great effect of reaction with only
small quantities of halogen-compounds of aluminium is explained.
B. B.
Oxidation of the Nitro-toluenes by Potassium Perricyanide.
By W. A. NoYES {Ber., 16, 52 — 54). — The author has examined the
action of an alkaline solution of potassium ferricyanide on ortho- and
paranitro-toluene with the view to ascertain whether, with this oxidis-
ing agent, the or^/io-nitro-group has the effect of hindering the oxida-
tion of the methyl-group, as is the case when chromic acid is used, or
whether both ortho- and para-groups are oxidised alike, as in the case
of alkaline permanganate. He finds that hoth of these nitro-toliienes
are oxidised to the corresponding nitro-benzoic acids.
A. K. M.
Derivatives of Mesitylene. By G. Robinet (Compt. rend., 96,
500). — By the chlorination of mesitylene at a temperature not ex-
ceeding 215°, a mono- and a di-chloromesitylene are obtained. The
former, C6H3Me2.CH2Cl, is a colourless liquid, which boils from 215 —
220°, and does not solidify at —17° (the monochloromesitylene,
already known, boils at 204—206°) ; the latter, C6H3Me(CH2Cl)o, crys-
tallises in delicate white needles, which melt at 41° and distil at 260°
(the dichloromesitylene of Kahn crystallises in prisms, melting at 59°,
boiling at 243°). Dibromomesitylene, C6H3Me(CH2Br)2, prepared by
treating the vapour of mesitylene with bromine, crystallises in delicate
white needles melting at 66°, having a pungent odour, soluble in ether.
The dibromomesitylene, CsHBroMes, already known, melts at 60°.
Mesitylenic acetate from monochloromesitylene and sodium acetate, is
a colourless liquid, which distils in a vacuum at 242° ; on heating a
mixture of this compound with a further quantity of monochloro-
mesitylene and concentrated nitric acid there are obtained mesitylenic
acid and mesitylaldehyde. The latter, C6H3Me2.CHO, is a heavy oil,
forming a crystalline compound with sodium hydrogen sulphite.
V. H. V.
Benzoylmesitylene. By E. Louise {Compt. rend., 96, 490—500).
— By the action of aluminium chloride on a mixture of benzoic
chloride and mesitylene (Friedel and Crafts' reaction), benzoyl-
mesitylene, C6H2Me3Bz, is formed. This compound forms transparent,
colourless, voluminous crystals, soluble in ether, alcohol, &c. It melts
at 29°, but exhibits in a most marked way the phenomenon of
superfusion, for it can be cooled to —40° without a trace of crystal-
lisation. V. H. V.
Metanitriles. By .0. Wallach {Ber., 15, 6 — 7).— This is an
answer to Staedel (Ber., 15, 2864) on the history of this class of bodies.
A. K. M.
578 ABSTRACTS OF CHEMICAL PAPERS.
Methylation and Ethylation of Aniline and Toluidine.
By H. Reinhardt and W. Staedel (Ber., 16, 29— 31).— When the
hjdrobromides and hjdriodides of aniline and toluidine (see p. 579)
are heated with methyl or ethyl alcohol, secondary and tertiary bases
are formed. In the case of the hydrobromides, a temperature of 145 —
150°, continued for eight hours, is employed, in that of the hydriodides
1 25°, also for eight hours. In preparing the tertiary bases, an excess of
alcohol is to be employed, viz., 5 per cent, of methyl alcohol, and 5 —
10 per cent, of ethyl alcohol. The following bases and derivatives
have been prepared in this way : — Methylaniline (b. p. 192° at
754 mm.) and its acetyl derivative (m. p. 101°), which crystallises in
prisms. Dimethylaniline (b. p. 192°) and its platinochloride,
(C8H9N)^H2PtCl6,
forming large, four- sided, reddish-yellow anhydrous plates, or deep
ruby-red prisms, with 2 mols. H,0. Ethylaniline (b. p. 202—204")
forming an acetyl-derivative which melts at 54'5°, and boils at
248 — 250°. It crystallises in splendid monoclinic prisms. Diethyl-
aniline (b. p. 211 — 211*5°) gives a platinochloride in yellowish-
red crystals. Methylorthotoluidine (b. p. 207°) yields an acetyl-
derivative boiling at 250 — 251°. Dimethylorthotoluidine (b. p. 183°)
forms a platinochloride crystallising in flat reddish-yellow needles.
Ethylorthotoluidine (b. p. 213 — 214°) yields an acetyl-derivative boil-
ing at 254—256°. Diethylorthotoluidine (b. p. 208—209°), the
platinochloride of which forms large reddish-yellow rhombic plates.
Dimethylparatoluidine (b. p. 208°) gives a platinochloride crystal-
lising in sparingly soluble plates. A. K. M.
Hydrobromides and Hydriodides of Aromatic Bases. By
"W. Staedel (Ber., 16, 28 — 29). — Aniline hydrobromide and hydriodide
have already been described by Hofmann. The following analogous
compounds have been prepared by the author : — Ortliotoluidine hydro-
bromide, C7H9]S',HBr, crystallises in large rhombic prisms, and the
hydriodide, C7H9N,HI, in thin rhombic prisms. The latter is partly
decomposed by water, with separation of orthotoluidine. The ht/dro'
bromide and hydriodide of 'paratoluidine form white crystalline plates.
From commercial xylidine two hydrobromides can be obtained, one of
which is derived from the [Me : Me : NHo = 1:3:4] xylidine, and
crystallises in slender needles, whilst the other forms large rhombs.
The constitution of the latter has not yet been determined. Meta-
chloraniline hydrobromide, CeHeClNjHBr, crystallises in large bright-
red shining plates, and parabromaniline hydrobromide, CeHeBrNjHBr +
JH2O, in large white efflorescent prisms. Metanitraniliue hydrobromide,
C6H6(N02)N,HBr (?), forms yellow plates which rapidly effloresce and
give off hydrobromic acid. Ortho- and para-nitr aniline also dissolve
in hydrobromic acid, the latter yielding a hydrobromide, crystallising
in large prisms. Metamidophenetoil forms a hydrobromide,
EtO.C6H4.NH2,HBr (.?),
crystallising readily in soluble plates. A. K. M.
OKGANIC CHEmSTRY. 579.
Nitrotoluidines from Liquid Dinitrotoluene. By A. Bernthsen
(Ber., 15, 3016— 3019).— When the mixed bases obtained by the
reduction of liquid dinitrotoluene are dissolved in hot dilute hydro-
chloric acid, the hydrochloride of a base melting at 91*5° first crystal-
lises out. The benzoic derivative of this nitrotoluidine is deposited
from an alcoholic solution in prisms melting at 167°. The mother-
liquor from the hydrochloric acid solution just mentioned contains
orthonitrotoluidine hydrochloride. The free base melts at 78°, and its
benzoic derivative crystallises in flat prisms melting at 171*5°.
A complete separation of these nitrotolaidines may be effected by
the action of benzoic chloride on the ethereal solution of the mixed bases,
as the ortho-compound is attacked before its isomeride. The ortho-
benzoic derivative is separated from the hydrochloride of the other base
by treatment with hot dilute hydrochloric acid, which dissolves the
latter compound. The benzoic compounds may also be separated by
recrystallisation from hot alcohol, in which the substance melting at
167^ is more freely soluble than that melting at 171'5^.
These results differ in many respects from those obtained by
Cunerth (Annalen, 172, 223), who describes a nitrotoluidine melting
at 94*5°, which forms a benzoic derivative melting at 145°.
w. c. w.
Ethylnitraniline. By A. Weller (Ber., 16, 31— 32).— Ethylacet-
anilide is treated with 4 parts of cold nitric acid (sp. gr. 1'52), and,
when dissolved, the product is poured into cold water and well
shaken. Ethylacetonitranilide, C6H4(N02).NEtZc, separates out in
small white plates, and is easily purified by crystallisation from water,
in which it is sparingly soluble. It is insoluble in light petroleum and
carbon bisulphide, sparingly soluble in ether, readily in alcohol and
benzene. It melts at 117'5°. When boiled with potash solution, it
is converted into ethylnitraniline, NO2.C6H4.NEtH, which can be
purified by crystallisation from alcohol, and then melts at 95 — 95*5°.
This body is very sparingly soluble in water, light petroleum, and
carbon bisulphide, readily in warm alcohol, ether, and benzene. It
crystallises from alcohol in large prisms. A. K. M.
Dimethylxylidines, Dimethylmetachloraniline, and Di-
methylmetamidophenetoil. By H. v. Baur and W. Staedel
(Ber., 16, 32 — 33). — On heating the two hydrobromides obtained
from commercial xylidine (see p. 578) with methyl alcohol (2 mols.),
two isomeric dimethylxylidines are obtained, one of which,
[Me : Me : NMe-, = 1:3:4] (he. cit),
boils at 203 — 205°. It is a colourless liquid, forming readily soluble
salts. The isomeride obtained from the second hydrobromide boils at
200 — 202°, and is very similar to the former. Bimethylmetacldoraniline,
C6H4Cl.NMe2, obtained from metachloraniline hydrobromide and
methyl alcohol, is a colourless liquid boiling at 231 — 233°. Its salts
crystallise well ; the hydrobromide in plates, the oxalate in white
plates, the hydrochloride in slender needles, and the platinochloride
in delicate yellow needles. A nitroso- derivative has also been pre-
pared, the hydrochloride of which crystallises in gold- coloured plates.
580 ABSTRACTS OF CHEMICAL PAPERS.
BimethyhnetamidopTienetoil, OEt.C6H4.NMe2, can easily be obtained
by the same reaction. It is a colourless liquid forming crystalline
salts. Its nitroso-derivative also yields a hydrochloride crystallising
in gold-coloured plates. ^ A. K. M.
Preparation of the Base doHisN (obtained from Benzenyl-
isodiphenylamidine) from Benzoyldiphenylamine. By A.
Bernthsen {Ber., 15, 3011 — 3016). — When a mixture of benzonitril
and diphenylamine hydrochloride is heated at 180— 190^ benzenyl-
isodiphenylamidine, NPhj-CPh ! NH, is produced ; but at a hiofher
temperature (230 — 250°) a totally different base is obtained, which
has the composition C19H13N. The same compound is formed by the
action of zinc chloride on benzoyldiphenylamine at 27o°. It is
deposited from benzene in yellow prisms, containing 1 mol. benzene,
which effloresce on exposure to the air, and also in monoclinic plates
(m. p. 180°), which are free from benzene. The hydrochloride,
CigHisNjHCl, forms sparingly soluble golden-yellow prisms, which dis-
sociate when brought into contact with pure water. The yellow-
coloured platinochloride is almost insoluble in water.
The constitution of the base has not yet been definitely ascertained ;
its mode of formation seems to indicate that it is nitrilotri^phenylmethayie,
CeH/l >CeH4.
^CPh"^ W. C. W.
Acetoximes. By A. Janny (J5er., 15, 2778— 2783).— DimethyU
acetoxime, CMej ! NHO (Abstr., 1882, 1047), is easily soluble in water,
alcohol, and ether; melts at 59 — 60°, and boils unaltered at 134*8°;
its formation from acetone and hydroxylamine is instantaneous.
Ethylmethylketone and hydroxylamine in aqueous solution left for
24 hours, yields ethylmethylacetoxime, which may be extracted by ether ;
it is purified by distillation, and boils between 152 — 153" ; it does not
solidify in a mixture of ice and salt; its sp. gr. is 0"9i95 at 24°; it is
miscible in all proportions with alcohol and ether, and dissolves in
10 times its volume of water ; when decomposed with concentrated
soda solution, it yields a crystalline sodium derivative ; with hydro-
chloric acid, it yields hydroxylamine.
Methylpseadobutylacetoxime, CMea.CMe ! NHO, is obtained from
methylpseudobutylketone and hydroxylamine. The substance crys-
tallises in fine colourless needles melting at 74 — 75° ; they are easily
soluble in alcohol and ether and the ordinary solvents, also in warm
water, sparingly in cold water. It is volatile with steam, tastes of
camphor, and sublimes unchanged.
MethylpJienylacetoxime^ CMePh ! NHO, is formed from hydroxyl-
amine and acetophenone. It forms colourless silky needles melting at
59°, easily volatile with steam ; the vapour has a very agreeable smell,
but attacks the eyes. It is easily soluble in the usual solvents, and
also in acids and alkalis.
Diphenylacetoxime, CPha ! NHO, is obtained from benzophenone and
hydroxylamine, but the mixture must be left at rest for a week
•before extracting the substance; the crystals melt at 139 — 140°, and
ORGANIC OHExMISTRY. 581
are easily soluble in ether and acetone, less so in benzene, cbloroform,
and light petroleum, sparingly in cold water. It is soluble in alkalis,
from whence it is precipitated by hydrochloric acid ; it is also soluble
in concentrated hydrochloric acid, but is precipitated on diluting with
water. J. F.
Acetoximes. By A. Jannt (Ber., 16, 170—177). — DimefhyU
acetoxime decomposes into hydroxylamine and acetone when boiled with
strong hydrochloric acid, CMcz ! NOH + H2O = ISTHjO -f Me.C02Me.
Acetic anhydride and acetic chloride readily attack acetoxime, but
the product of the reaction was not investigated. On mixing benzoic
chloride and acetoxime, a crystalline mass is produced, which on being
heated gives off hydrochloric acid, and leaves a benzoic derivative,
CioHuNcX; this substance crystallises in transparent colourless
plates (m. p. 41°), which dissolve freely in alcohol and ether. It is
decomposed by heating with acids, with liberation cf hydroxylamine.
Acetoxime hydrochloride, CsHvNOjHCl, prepared by passing dry
hydrochloric acid gas over solid acetoxime or into a solution of
acetoxime in absolute alcohol, is a white hygroscopic powder soluble
in alcohol and water, but insoluble in ether. The aqueous solution
slowly decomposes at the ordinary temperature, hydroxylamine being
formed. The hydrochloride melts at 98 — 101°, and at a higher tem-
perature splits up into hydrochloric acid and acetoxime. A platino-
chloride could not be obtained.
When ether is added to an alcoholic solution of acetoxime and
sodium ethylate, a white crystalline salt is precipitated, which contains
19'49 per cent. Na, and probably has the composition CaHeNONa +
EtHO. This compound is insoluble in alcohol and water. Acetoxime
is not reduced by nascent hydrogen. It is completely destroyed by
potassium permanganate or ferrocyanide.
Benzylacetoxime, CMco '. NOC7H7, is formed by the action of benzyl
chloride on an alcoholic solution of acetoxime and sodium ethylate.
The brown oil which separates out when the crude product is diluted
with water is extracted with ether, and distilled in a current of steam.
Pure benzylacetoxime is a colourless oil, soluble in alcohol and ether.
It boils at 190° with decomposition. On boiling with hydrochloric acid,
it splits up into acetone and benzylhydroxylamine. Benzylacetoxime
hydrochloride is an oily liquid. It is decomposed by moisture, benzyl-
hydroxylamine hydrochloride being deposited in crystalline scales,
which are soluble in alcohol and water. On reduction with hydriodic
acid, benzylhydroxylamine yields benzyl iodide, showing that the
benzyl-group in this compound is attached to the oxygen- and not to
the nitrogen-atom. The constitution of benzylacetoxime and benzyl-
hydroxylamine may be represented by the formulse CMcs ! N.OC7H7
and NH2.OC7H,. W. C. W.
So-called Nitrosomethylbenzene Compounds. By S. Gabriel
(Ber., 15, 8057 — 3064). — Nitrosomethylorthonitrobenzene or orthonitro-
henzylaldoxime can be prepared by the action of hydroxylamine hydro-
chloride and sodium carbonate on an alcoholic solution of orthonitro-
benzaldehyde. Metanitrobenzylaldoxime can be prepared by a similar
582 ABSTRACTS OF CHEMICAL PAPERS.
reaction. By the action of methyl iodide in presence of methyl
alcohol and potash on this compound, a methylated derivative,
C6H4(N02).CMe ! NHO, is obtained, which crystallises in colourless
needles (m. p. 63°). This substance is freely soluble in most solvents.
It is decomposed by hydrochloric acid at 160° into methyl chloride,
metanitrobenzoic acid, and ammonia.
By the action of hydroxy lamine on metanitroacetophenone, meta-
nitrophenylmethylacetoxime is produced. This substance forms needle-
shaped crystals melting at 131 '5°, freely soluble in alcohol, ether, acetic
acid, and chloroform, but sparingly soluble in carbon bisulphide and
light petroleum. It yields a methyl- derivative, C6H4(NO)2.CMe I NMeO,
which crystallises in needles melting at 63**.
The fact that the methyl- derivative of metanitrobenzylaldoxime is
not identical with the compound obtained by the action of hydroxyl-
amine on metanitroacetophenone shows that the so-called nitroso-
methylmetanitrobenzene is not a true nitroso-compound, and that it
does not contain the group NO. W. C. W.
Phenacylethylanilide. By A. Weller (Ber^ 16, 26— 27).— The
action of bromacetophenone on dimethylaniline has been described by
Staedel and Siepermann (Abstr., 1880, 639). By the action of
bromacetophenone (phenacyl bromide) on diethylaniline, the author
has obtained a new base to which he gives the name phenacylethyl-
anilide. It crystallises from alcohol in slender needles of a pale
greenish colour, melting at 94 — 95°. It is insoluble in water,
sparingly soluble in alcohol, more readily in ether, benzene, and
carbon bisulphide. In its reactions, it strongly resembles the alkaloids.
Its solution in hydrochloric acid gives white precipitates with potas-
sium mercury iodide, and tannin, yellow precipitates with picric acid
and phosphomolybdic acid, a yellowish- white precipitate with platinic
chloride, and a brown precipitate with a solution of iodine in potassium
iodide. The addition of a drop of dilute nitric acid produces a
beautiful red coloration, or if enough base is present a red precipitate ;
this reaction strongly resembles that for brucine. On heating this
new base with methyl iodide at 100°, the phenacyl-group is split off,
forming iodacetophenone. A. K. M.
Action of Iodine on Mono- and Di-nitrodiphenylthiocar-
bamide. By S. M. Losanitsch (Ber., 16, 49 — 50). — When iodine is
added to a hot alcoholic solution of metadinitrodi phenyl thiocai'bamide
and the alcohol distilled off" by a current of steam, a solid and an
aqueous residue are obtained, the latter containing trinitrotriphenyl-
guanidine hydriodide and metanitraniline, whilst the former consists
of nitrophenylmonothiourethane and dinitrodiphenylcarbamide. Fron"
iodine and metanitrodiphenylthiocarbamide, nitraniline, phenv^
carbimide, metanitrophenyl mono thioure thane, and metanitrotri
guanidine are obtained. Metanitrophenylmonothiourethane,
EtO.CS.NH.C6H4.NO2,
is also obtained, together with CS(NH.C6H4.N02)2, by boiling n
•nitraniline with a slightly alkaline alcoholic solution of carbon bis-
ORGANIC CHEiMISTRY. 583
phide. It forms large yellow prisms melting at 115°, readily solnble in
alcohol, but insoluble in water. Metadinitrodipbenylcarbamide,
CO(NH.C6H4.N02)2, crystallises from alcohol in bright yellow needles
melting at 233°. Metatrinitrotriphenylguanidine,
CeH^CNOa)^ : CCNH.CeH^.NOa)^,
forms yellow shining plates melting at 189°, soluble in hot alcohol and
in potash with decomposition. Metanitrotriphenylguanidine,
PhN : C(]SrHPh).NH.C6H4.N02 or CeH^CNOa)^ I C(NHPh)2,
crystallises from alcohol in yellow plates (m. p. 159°). (See also
Ber., 7, 1236.) A. K. M.
Azo-derivatives. By C. Giraro and A. Pabst (Bull. Sac. Ohim.
[2], 39, 119 — 120). — The diazo- derivative of sulphanilic acid yields
with methylaniline, y3-naphthol, diphenylamine, &c., compounds giving
various shades of orange. The diazo-derivative of naphthylamine-
sulphonic acid yields compounds giving various shades of red, and
diazodinitrophenol yields compounds giving various shades of dark
red and brown. It would appear that azo-compounds have less
tinctorial power the greater their molecular symmetry. The intro-
duction of a conjugate sulphonic group inclines the shade of the
colour towards orange-yellow, whilst the addition of methyl in the
phenol or amido-group slightly inclines the shade towards red.
C. H. B.
Azo- and Diazo-derivatives of Phenylenediamine. By O.
Wallach and E. Schulze (Ber., 15, S020—S021).—Mo7iacetometa-
phenylenediamine hi/drochloride^ NH2.C6H4.NHAc,HC1, is prepared by
boiling phenylenediamine (1 mol.) with glacial acetic acid (2 mols.)
for two hours, and treating the product with hydrochloric acid. The
crystals (m. p. about 280") are soluble in water, but insoluble in a
mixture of alcohol and ether. The free base is obtained in crystalline
scales by treating an aqueous solution of the hydrochloride with
potassium bicarbonate, and extracting the mixture with ether.
Phenolazoacetometamidobenzene, NHAc.CeHi.Nz I C6H4.OH, prepared
by the method previously descpbed by the author (Ber., 15, 2825),
has a brick-red colour, and melts at 208°. On boiling with 10 parts
of hydrochloric acid (25 per cent.) it is converted into phenolazoamido-
henzene hydrochloride, NH2.C6H4.N'o.C6H4.0H,HCl. The free base
crystallises in brownish-yellow scales melting at 168°.
Benzene diazophenol^ CQiiiQ^i-Gs^i.OH)^^ exists as a dark powder,
soluble in soda-lye. W. C. W.
Parazophenol. By R. Bohn and K. Heumann (Ber., 15, 3037 —
3039). — Parazophe7iol, prepared by fusitig potassium parazobenzene-
disulphonate or potassium hydroxyazobenzene-sulphonate with potash,
is identical with the parazophenol obtained by Jager (Ber., 8, 1499)
from paranitrosophenol, and by Weselsky and Benedikt (Annalen,
196, 340) from paranitrophenol and also from diazophenol.
584 ABSTRACTS OF CHEMICAL PAPERS.
On nitration, parazophenol yields dinitrophenol [1:2: 4], which
nif'lts at 112°. By the action of fuming sulphuric acid parazophenol
is converted into a crystalline sulphonic acid,
HS03.C6H3(OH).N"2.C6H4.0H,|
"W^hich has a golden-green metallic lustre. The barium salt of this
acid forms brownish-red crystals. W. C. W.
New Azo- and Diazo-compounds. By O. Wallace (Ber., 15,
2825 — 2830). — Two methods have heretofore been used for obtaining
these compounds, either by the consecutive introduction of two diazo-
residues into a phenol, or by the action of a diazotised monamidoazo-
compound with a phenol. If R be a carbohydrogen radicle, and Ph
any phenol residue, the following formulae will represent the
bodies:— NoB.Ph.NaR and NaPh.R.NgR.
A new process would be found if one could diazotise successively
the two amido- groups in a diamine and pair these diazo- derivatives
with phenols, forming compounds of the type NgPh.R.NgPh, bodies
which have no representative amongst the known azo-compounds.
Efforts in this direction have not as yet been successful. The author
has, however, made an attempt with the metadiamines, and describes
the process.
Tolylenediamine (m. p. 99°) is transformed into the monacetyl-
derivative by Tiemann's method, dissolved in 2 mols. of hydrochloric
acid, and when carefully cooled with ice is treated with a solution
of 1 mol. of sodium nitrite, and afterwards with an alkaline solution
of 1 mol. of phenol. The solution becomes red, and on adding an
acid deposits a flocculent yellow body, which may be purified by
resolution and reprecipitation. It is sparingly soluble in alcohol, and
very difficult to recover from its solution ; sometimes it is obtained
therefrom in crystals, sometimes in flakes, and appears to exist in two
modifications. The crystals are in the form of golden- to red-yellow
plates, melting at 252 — 253°. The analysis gave figures correspond-
ing with the formula NHAcC6H3Me.N2.CfiH4.OH.
In order to remove the acetyl-group, the substance is boiled some
time in a reflux apparatus with excess of 20 per cent, hydrochloric
acid in connecion. As soon as a deep red clear solution is obtained
the solution is cooled, when crystals of the hydrochloride of an amido-
compound separate ; these are collected and decomposed with sodium
carbonate, when the free amido-com pound NHz.CfiHgMe.No C6H4.OH
is obtained as a yellow precipitate. It crystallises from dilute alcohol
in fine yellow-brown needles melting at 172°, easily soluble in acids
and alkalis, alcohol, and ether, but only sparingly in cold water.
J. F.
Compound of Phenol with Carbonic Anhydride. By A.
Klepl (/. pr. Chem. 25, 464). — By heating salicylic acid, paraoxy-
benzoic acid, or a mixture of the two, at 260° for two hours, they are
decomposed into phenol and carbonic anhydride. During cooling the
contents of the tube solidify in crystals resembling pyramids, with
ORGANIC CHEMISTRY. 585
step-like faces of common salt. These crystals melt at 37°. On
opening the tubes, much carbonic anhydride is evolved, and the crys-
tals become white and opaque. On gently heating, or on covering
with alcohol, ether, chloroform, or water, carbonic anhydride is
copiously evolved and phenol remains. A. J. Gr.
Compound of Phenol with Sulphurous Anhydride. By A.
HoLZER (/. pr. Ghem. [2], 25, 462 — 464). — This compound is prepared
by heating sodium phenylate in sulphurous anhydride, or by passing
the latter into dry phenol and distilling, when a yellow oil passes over
at 140°, solidifying on cooling to large well-formed rhombic tables.
It melts at 25 — 30° if precautions are taken to prevent loss of sul-
phurous anhydride. It readily loses sulphurous anhydride in a
vacuum or on exposure to air, and is decomposed by heating in a
stream of carbonic anhydride, whilst in a stream of sulphurous anhy-
dride it can be distilled through tubes heated to dull redness without
suffering much decomposition. The analytical results, although not
very accordant, owing to the instability of the substance, show a com-
pound of 1 mol. of sulphurous anhydride with 4 — 5 mols. of phenol.
A. J. G.
New Ethereal Derivatives of Phenols. By W. Staedel and
others (Annalen, 207, 40 — 49). — Ethyl orthocresyl ether, CvHy.OEt,
is best prepared by heating on a water-bath a mixture of potassium
cresolate, alcohol, aud ethyl bromide, and after the removal of the
potassium bromide and alcohol, the cresyl ether is extracted with
ether, dried with calcium chloride, and rectified. Ethyl orthocresyl
ether is a colourless liquid (b. p. 180 — 181° uncorr., sp. gr. 0*9577),
with a pleasant ethereal odour. JEthylene orthocresyl ether^
(071170)2! C2H4,
is prepared in a similar manner ; it is a white crystalline mass melt-
ing at 79°. Methyl a-naphthol ether, OioH7.0Me, prepared from
potassium a-naphtholate and methyl iodide, may be purified by steam
distilling. It is a yellowish oily liquid (b. p. 258°, sp. gr. 1-0974),
soluble in alcohol, ether, chloroform, and benzene. Methyl (i-n>aphthol
ether forms large white brilliant leaflets (m. p. 72°), of pleasant
aromatic odour, soluble in ether, chloroform, and benzene, insoluble
in water. It is volatile with steam. Benzyl phenol ether, OeHj.OOHgPh,
from potassium phenylate and benzyl chloride. The phenol is converted
by soda into phenylate, and together with the potassium chloride is
dissolved out with water, the benzyl phenyl ether remaining undissolved.
li crystallises in brilliant white plates (m. p. 39°), greasy to the touch,
and when warmed evolving a pleasant aromatic odour. Benzyl para-
cresyl ether, 07H70.0H2Ph, from potassium paracresolate and benzyl
chloride, separates from its alcoholic solution either in white scales
and plates with silky lustre, or in colourless hexagonal transparent
prisms. It melts at 41°, has a pleasant odour, is greasy to the touch,
burns with a smoky flame, and is soluble in alcohol and benzene, but
insoluble in water. Benzyl orthocresyl ether is, a colourless viscid oil,
gradually becoming yellow ; it does not solidify in the cold. It boils
at 285 — 290°, but does not distil without decomposition, and has an
YOL. XLIV. 2 r
586 ABSTRACTS OP CHEMICAL PAPERS.
■ntipleasaiit candle-like odour. It is soluble in alcohol and ether, bat
not in water. Benzyl metacreayl ether. — The metacresol used was pre-
pared from thymol. The ether forms white satiny tablets (m. p. 43°,
b. p. 300 — 305° without decomposition), soluble in alcohol, ether, and
benzene, insoluble in water. Benzyl f3-naphthyl ether^ CioH7.0CH2Ph,
crystallises in brilliant white odourless leaflets melting at 99°, soluble
in alcohol, ether, benzene, and chloroform, insoluble in water, and not
volatile with steam. Benzyl x-naphthyl ether could not be obtained pure,
as the oily product decomposed when an attempt was made to distil it.
D. A. L.
Appendix to the Paper on Cholesterin. By E. Schulze (/. pr,
Chem., 25 [2], 458— 462; comp. Abstr., 1882, 1202).— When paracho-
lesterin and the two cholesterins obtained by the author from lupine
shoots are shaken with chloroform and sulphuric acid of sp. gr. 1*76,
they give the same colour reaction as ordinary cholesterin. Isocholes-
terin, even in considerable quantity, gives after 10 — 15 minutes only
a faint red tinge to the chloroform layer (0'03 — 0'04 gram isocholes-
terin giving a less intense coloration than 0'002 gram cholesterin).
After some hours, the coloration changes to intense brown, the sul-
phuric acid layer showing a brownish-yellow colour and a faint fluor-
escence. The author has repeated his experiments made to ascertain
if isocholesterin is a single chemical substance or a mixture, and con-
firms his previous view as to its individual nature. A. J. G.
Isomeric Nitrobenzaldehydes. By F. Tiemann and R. Ludwig
(Ber., 15, 3052 — 3057), — The 7-nitrometahydroxybenzaldehyde (m. p.
138°) described by the authors (this vol., 189) is found to be a mix-
ture of a- and /3-nitrometahydroxybenzaldehydes, which melt at 125°
and 166° respectively. Both a- and j(5-nitrometahydroxybenzaldehyde
are sparingly soluble in light petroleum ; the former is precipitated in
glistening plates on addition of light petroleum to its solution in
benzene. A blue colouring matter closely resembling indigo in
many of its properties is produced by the action of acetone and dilute
soda-lye on /3-nitromethylmetahydroxybenzaldehyde, but pure a-nitro-
methylhydroxybenzaldehyde does not exhibit this reaction. The
a-com pound is also less soluble in hot light petroleum and less
volatile in a current of steam than its isomeride. The slender
crystals of the a-derivative, obtained by distillation in a current of
steam, melt at 104 — 105°, but more compact crystals of the same
substance melt at 107°. W. C. W.
Bromacetophenone and Acetophenone Derivatives. By W.
Staedel (Ber., 16, 22 — 26). — Bromacetophenone (see also Abstr.,
1880, 659) crystallises from ether in splendid rhombs, apparently
isomorphoas with chloracetophenone. The formation of the base
NMePh.CHj.COPh, by the action of bromacetophenone on dimethyl-
aniline has already been described (Abstr., 1881, 722). It can also
be obtained from bromacetophenone and methylaniline, or from
methyl bromide and acetophenone-anilide. New bases have been
obtained by the action of ethyl- and diethyl-aniline on bromaceto-
phenone (this vol., p. 582). By the action of bromacetophenone on
ORGANIC CHEMISTRY. 587
qfiiinoline a solid mass is formed, for the most part soluble in cold
water ; the aqueous solution yields, first long thick prisms, and sut-
sequently short thick prisms. Solutions of both forms of crystals
give splendid carmine- coloured precipitates with ammonia, soluble
in hydrochloric acid. The author has also made experiments with
some of the homologues of acetophenone. The bromine- derivative of.
phenylacetone reacts violently with ammonia, yielding a body crystal-
lising in splendid thick prisms. The dibromide from phenylbenzyl
ketone gives a body crystallising in long slender needles, which are
very sparingly soluble in alcohol. The bromine-derivative of dibenzyl
ketone (ra. p. 47°) gives two compounds, one forming long silky
needles soluble in alcohol, and the other six-sided plates sparingly
soluble in alcohol. From the bromine-derivative of isopropyl phenyl-
ketone a body containing no nitrogen was obtained indirectly. It
crystallises in splendid rhombic prisms.. A. K. M.
Ethyl Orthonitrocinnamylacetoacetate. By E. Fischer and
H. KuzEL (Ber., 16, 33 — 37). — Bonne (Annalen, 187, 1) has shown
that acetophenone is formed by the saponification of ethyl benzoylace-
toacetate. This may be explained either by assuming that acetic acid
and ethyl benzoylacetate are first formed,, the latter then splitting up
into carbonic anhydride, alcohol, and acetophenone, or that benzoyl-
acetone is first formed, and then decomposed into acetic acid and
acetophenone. In order to decide which series of reactions is correct,
the authors have experimented with ethyl orthonitrocinnamylaceto-
acetate. On boiling this with dilute sulphuric acid, they have suc-
ceeded in obtaining the intermediate product, orthonitrocinnamyl-
acetone, NOa.CeHi.CH I CH.CO.CHg.COMe, which by the continued
action of the acid decomposes into acetic acid and orthouitrocinnarayl
methyl ketone. The ethyl orthonitrocinnamylacetoacetate is obtained
from orthonitrocinnamic acid by converting it into the chloride, which
is then added, in ethereal solution, to ethyl acetosodacetate suspended
in ether: the mixture is warmed to complete the reaction, the
ether distilled off, and the residue after being washed with water
is crystallised from boiling alcohol. The ethyl oithonitrocinnamylaceto-
acetate thus purified forms yellow prisms melting at 120*5°. It is
readily soluble in chloroform, sparingly in hot alcohol and in ether.
The saponification is effected by boiling 20 — 30 grams with five times
its weight of 30 per cent, sulphuric acid. After five hours' heating,
the product was allowed to cool, when it solidified to a crystalline
mass, which was found to contain unaltered substance, nitrocinnamic
acid, nitrocinnamylacetone, and nitrocinnamyl methyl ketone. On
treating the mass, after filtration from the sulphuric acid, with an excess
of cold soda solution, the orthonitrocinnamyl methyl ketone remains
undissolved, and can be extracted by ether and purified by crystallis-
ing it from dilute alcohol. It forms long silky needles melting at 60"",
and is identical with the body described by Baeyer and Drewsen
(Ber., 15, 2858). The nitrocinnamylacetone is recovered from the
soda extract by precipitation with hydrochloric acid, dissolving in
carbon bisulphide, and finally crystallising from boiling alcohol, when
it is obtained in yellow prisms, which softea at 105°, and melt at
2 r 2
588^ ABSTRACTS OP CHEMICAL PAPERS.
112 — 113°. It is readily soluble in liofc alcohol, sparingly in cold
alcohol, carbon bisulphide, and ether. Boiling with dilute sulphuric
acid converts it for the most part into nitrocinnamyl methyl ketone.
A. K. M.
Ethyl Orthocinnamylacetoacetate (Part II). By E. Fischer
and H. Kuzel (Ber.,lQ, 163 — 167). — The ethylic salt of orthonitrocinn-
amylacetoacetic acid splits up on boiling with dilute sulphuric acid,
yielding alcohol, carbonic acid, and orthonitrocinnamylacetone. By
the action of stannous chloride on a concentrated alcoholic solution of
ch:ch.c.ch:ch
nitrocinnamylacetone, acetonylquinoline, | || |
CH : CH.C.N : C.CHj.COMe
is produced. This base crystallises in golden needles (m. p. 76°),
which are sparingly soluble in hot water, forming a yellow solution
which dyes silk and wool yellow. On heating with strong hydro-
chloric acid at 160°, it yields methylquinoline, which forms a beautiful
pink platinum salt (C9H6NMe)2H2,PtCl6 (m. p. 226—230°), and a crys-
talline picrate sparingly soluble in alcohol and water. The same body
is obtained by the reduction of orthonitrocinnamyl methyl ketone by
stannous chloride, and it also appears to be identical with the quinal-
dine of Dobner and von Miller {Ber., 15, 3075).
An acid solution of stannous chloride slowly dissolves ethyl ortho-
cinnamylacetoacetate, with evolution of carbonic acid and production
of methylquinoline, Acetonylquinoline is not formed by this reac-
tion.
Ethyl cinnamylacetoacetate forms pale yellow crystals melting at 40°,
soluble in alcohol and ether. It is decomposed by boiling with dilute
sulphuric acid into carbonic acid and the compound
C6H^C2H2.CO.CH(COMe).COOEt.
w. c. w,
Conversion of Phenyl Ethers of Carbonic Acid into Salicylic
Acid. By W. Hentschel (/. pr. Ghem., 27, 39— 45).— The author
shows that when sodium-phenol is acted on by carbonic anhydride,
sodium phenyl carbonate is first formed ; and in presence of another
molecule of sodium-phenol this is decomposed with formation of the
sodium salt of salicylic acid. The intermediate product is best pre-
pared by passing dry carbonic anhydride into a solution of sodium
phenol in absolute alcohol ; the resulting body is a mixture of equal
parts of ethyl and phenyl sodium carbonate. When heated with
sodium-phenol it yields salicylic acid.
The author has prepared phenyl sodium carbonate in large quantities
by passing carbonyl chloride into an aqueous solution of sodium
phenol. After purification, it was obtained as a white crystalline
mass which distilled at 301 — 302°. The mode of preparation is of
general application. The author has likewise prepared the ortho-
nitrophenyl- compound, which crystallises from alcohol in silky rhombic
plates.
Ethyl phenyl carbonate obtained by the action of ethyl chlorofor-
mate on potassium-phenol, can also be converted into salicylic acid.
Analogous methods of preparation yield a series of substituted ethyl
ORGANIC CHEMISTRY. 589
ethers of phenyl carbonate. A parachlorophenyl, a tribrominated, an
orthonitro- ether of phenyl carbonate, and finally the corresponding
thymol compounds, have been obtained.
Conversion of EtTiijl Phenyl Carbonate intO' Salicylic Acid. — On heat-
ing ethyl phenyl carbonate with sodium-phenol in equivalent propor-
tions, the following reaction takes place : —
HO.C6H4.COOEt + OeHg.ONa = OH.06H4.COOISra + CsHj.OEt.
The author considers that carbonic anhydride in this case exerts
first an etherifying action on sodium-phenol, and that the phenyl
sodium carbonate thus formed only yields salicylic acid on coming into
contact with a second mol. of sodium-phenol. In Kolbe's process, it
is possible that the conversion of the phenyl salt into salicylic acid
might be produced by some other method such as warming. The
author was unable to obtain salicylic acid by digesting ethyl phenyl
carbonate, or diphenyl carbonate, with sodium or an alcoholic solution
of sodium.
The Conversion of Diphenyl Carbonate into Salicylic Acid is best per-
formed by distilling the salt with dry sodium ethylate in a current of
hydrogen gas. The reaction
COCO.CeHe)^ -h EtO.m = OH.C6H4.COOI^a + CeHg.OEt
takes place. When distilled with sodium hydroxide, the diphenyl
carbonate yields sodium salicylate and phenol. The reaction proceeds
so readily that the author suggests the possibility of a commercial
process being made out of it. J. I. W.
Sulphamic Acids and Hydroxy-acids derived from Pseudo-
cumol. By 0. Jacobsen and H. Meter {Ber., 16, 190 — 193). —
Sulphonamidoxylylic acid, C6H2(COOH)Me2.S02NH2 [1 : 2 : 4 : 5],
prepared from pseudocumolsulphonamide by oxidation with potassium
permanganate in dilute alkaline solution or by chromic acid mixture,
crystallises in long needles melting at 268°, freely soluble in alcohol and
sparingly soluble in hot water. The potassium salt forms rhombic plates
containing 1 mol. HgO, and freely soluble in water. The ammonium
salt containing 2^ mols. H^O crystallises in delicate needles. The acid
is decomposed by strong hydrochloric acid at 210°, yielding xylylic
acid and metaxylene. Xylylic acid is also produced when it is fused
with potash. On further oxidation with potassium permanganate,
Bulphonamidoxylylic acid is converted into sulphonamidoxylidic acidf
C6H2(COOH)Me(COOH).S02NH2 [1:2:4:5].
The product of this reaction is filtered, and the filtrate after concen-
tration acidified with hydrochloric acid to remove unaltered sulphon-
amidoxylylic acid. The filtrate is then evaporated to dryness, and
the residue treated with strong hydrochloric acid and extracted with
ether. The acid contained in the extract is purified by conversion
into the barium salt C9H504Ba.S02NH2. From a hot solution, the
barium salt is deposited as an anhydrous crystalline powder, but on
evaporating the aqueous solution at the ordinary temperature prisms
containing 2^ mols. H2O are obtained. The free acid is exceedingly
soluble in alcohol and ether. It is deposited from an aqueous solution
690 ABSTRACTS OP OHEMIOAL PAPERS.
in needles or prisms, which melt with partial decomposition between
295 — 300°. It is decomposed by strong hydrochloric acid at 250°,
forming xylidic acid, and on fusion with potash yields hydroxy-xylidic
■acid, C6H,(C00H)Me(C00H).0H [1:2:4:5]. This acid crystal.
lises in prisms soluble in alcohol and ether. It melts at 285 — 290°,
and even below this temperature slowly decomposes iuto paracresol
and carbonic anhydride. The non-crystalline normal potassium hydr-
oxyxylidate is very soluble. The acid salt is thrown down as a crys-
talline precipitate on the addition of acetic acid to the aqueous solution
of the normal salt. The zinc salt is more soluble in cold than in hot
water. Ferric chloride produces a dark red coloration with the free
acid and also with its salts.
On further oxidation with potassium permanganate, sulphonamido-
xylidic acid yields the potassium salts of sulphotrimellic acid and
sulphonamidotrimellic acid. The precipitate thrown down on the
addition of lead acetate to the solution of these two salts is decom-
posed by sulphuretted hydrogen. On evaporating the filtrate, potas-
smm sulphotrimellate, C6H2(COO)3.S03K, is deposited in transparent
prisms. The mother-liquor contains free sulphonamidotrimellic
acid. When the potassium salts of these acids are fused with potash,
hydroxy trimellic acid, C6H2(COOH)3.0II [1:2:4:5], is produced.
This substance forms transparent prisms containing 2 mols. H2O. It
is soluble in water, alcohol, and ether. The anhydrous acid*melts at
240—245°. The barium salt, (C9H307)3Ba3 + 5fl20, crystallises in
small transparent prisms. The silver and copper salts are sparingly
soluble in hot water. The lead salt is insoluble. Hydroxytrimellic
acid is decomposed by strong hydrochloric acid at 230°, forming car-
bonic anhydride and metahydroxy benzoic acid. On distillation w^th
lime, phenol is produced. W. C. W.
Acetoximic Acids. By 0. Schramm (Ber., 16, 180—183);—
Methylpropylacetoximic acid, OHN \ CMe.CEt \ NOH, is deposited in
white needle-shaped crystals melting at 170°, when hydroxylamine hy-
drochloride is added to a hot aqueous solution of isonitrosoethylketone.
Metkylhenzylacetoximic acid, OHN I CMe.C(C7H7) I NOH, prepared by
the action of hydroxylamine hydrochloride on a hot alcoholic solution
of isonitrosobenzylketone, crystallises in needles which melt at 181°.
Both these acids are soluble in alcohol and ether. They sublime at
temperatures below their melting points. They dissolve with difficulty
in ammonia, and they are soluble in strong solutions of potash and
soda, forming colourless solutions. Isonitrosoketones dissolve in
alkalis, producing an intense yellow coloration. Dimethylacetoximic
acid forms a silver salt, OHN! CMe.CAg! NOH, but the homologous
acids do not. Now, since all the acids of this series form sodium
salts, it follows that the sodium must replace an atom of H in the
NOH-group, whereas the silver-atom is directly attached to the carbon-
atom. W. C. W.
Electrolysis of Solutions of Hydrofluoric Acid and of Potas-
sium Antimonate, with Carbon Electrodes. By A. Bartoli and
G. Papasogli {Oazzetta, 13, 22 — 27).— (1.) Electrolysis of Hydro-
ORGANIC CHEMISTRY. 591
fluoric Acid. — When wood-charcoal or gas-retort carbon, after purifi-
cation by chlorine, is used as the positive electrode in the electro-
lysis of aqueous hydrofluoric acid, it is partly disaggregated, swelling
up in the immersed part, and becoming so brittle that after a while it
splits up by its own weight into rather large fragments, whereas the
carbon at the negative electrode remains quite unaltered. On re-
peatedly washing the altered carbon till the wash- water is no longer
acid, then drying it at 100^, reducing it to impalpable powder,
repeatedly boiling it with hydrochloric acid, and once more thoroughly
washing it with water, it exhibits the following properties. 1. It
dissolves partially, with dark-red colour, in strong sulphuric acid.
2. It is attacked by a hot solution of sodium hypochlorite, yielding
sodium fluoride, mellic acid, and the usual derivatives of the latter.
3. In addition to carbon, hydrogen, and oxygen, it contains fluorine,
amounting to about 3 per cent, of the disaggregated carbon, and not
due to electrolysis of mineral matter, inasmuch as the carbon used in
the experiment did not yield on ignition any perceptible quantity of
ash.
When graphite is employed as positive electrode in the electrolysis
of strong aqueous hydrofluoric acid, the immersed portion swells up,
becomes pappy, and quickly disintegrates; and the disintegrated
portion, when purified in the manner above described, forms a black
powder, which swells up considerably when heated, is insoluble in all
solvents, and contains carbon, oxygen, hydrogen, and fluorine.
(2.) Electrolysis of Potassium Antimonate. — When a solution of this
salt, obtained by heating the acid antimonate in large excess with
caustic potash-lye, is decomposed by a battery of eight Bunsen's ele-
ments, the positive electrode being formed of wood-charcoal or retort-
carbon, large quantities of gas are evolved at the negative electrode, and
only a small quantity at the positive, which at the same time is strongly
attacked, while the electrolyte becomes deep black, and deposits a
black sediment, O, soluble in a large quantity of water. On filtering
the liquid, adding the black wash-waters of the precipitate Q, then
concentrating on the water-bath, and adding excess of hydrochloric
acid, a copious precipitate, B, is formed, which, after washing and
drying, contains only traces of antimony, and exhibits the following
properties. 1. After drying at 100° it contains carbon, hydrogen,
oxygen, and antimony. 2. It dissolves in water and in alkaline
hydrates, forming deep black solutions, from which it is completely
precipitated by mineral acids. 3. It dissolves with rise of temperature
in aqueous potassium hypochlorite, forming mellic acid and other
benzocarboxylic acids, togcjther with potassium antimonate. This
substance being analogous in modes of formation and in properties to
mellogen, the authors distinguish it by the name Stibiomellogen.
When graphite is used as positive electrode in solutions of potas-
sium antimonate, large quantities of gas are likewise evolved at the
negative, and very little at the positive electrode. At the end of
the experiment, the graphite is found to be much disintegrated,
and a copious black deposit Q is found at the bottom of the volta-
meter, surmounted by a nearly colourless liquid containing small
quantities of mellic acid and its derivatives. The deposit Q, after
592 ABSTRACTS OP CHEMICAL PAPERS.
washing and drying, is found to consist of a mixture of graphite and a
new compound of carbon, hydrogen, oxygen, and antimony, which the
authors designate as StibiograpMc acid. Its composition and proper-
ties will form the subject of a future investigation.
From the results obtained in this and in preceding investigations,
the authors infer : (1 .) That in the electrolysis of nitric, phosphoric,
arsenic, and antiraonic acids and their salts, the first and third yield
with electrodes of wood-charcoal or retort-carbon, mellogen free from
nitrogen and arsenic — whereas with graphite electrodes they yield
graphite free from nitrogen or arsenic — and that the second and fourth
give with charcoal or retort-carbon electrodes, phospho- and stibio-
mellogen respectively, — whereas with graphite electrodes they give
phospho- and stibio-graphitic acid. H. W.
Electrolysis, with Carbon Electrodes, of Solutions of Binary
Compounds and of Various Acids and Salts. By A. Bartoli
and G. Papasogli (Gazzetta, 13, 37 — 55). — In this paper, the authors
describe the results obtained by electrolysing (a) with electrodes of
wood-charcoal or retort-carbon ; (3 with electrodes of graphite, — solu-
tions of the following compounds.
1. Hydrochloric, hydrobromic, and hydriodic acids and their potas-
sium salts. 2. Potassium cyanide. 3. Sulphuric and nitric acids
and their salts. 4. Arsenic acid. 5. Boric acid. 6. Alkaline hypo-
chlorites, permanganates, bichromates, and chlorates of alkali- metals.
7. Chromic acid. 8. Mellic acid. 9. Oxalates, formates, acetates,
&c. 10. Hydrogen and sodium sulphite. 11. Sodium pyrogallate.
Analyses are also given of mellogen obtained by electrolysis of
sulphuric, mellic, and boric acids ; of the benzocarboxylic acid ob-
tained by oxidation of mellogen; of pyromellic acid obtained by
electrolysis of potassium hydroxide with carbon electrodes ; and of
hydromellic and hydropyromellic acids.
From the results of these experiments, and of those detailed in
the preceding, and in former papers relating to the same subject
(Abstr., 1882, 58, 406, 850), the authors draw the following general
conclusions : —
1. In liquids whose electrolysis is not accompanied by evolution of
oxygen at the anode, wood-charcoal, retort-carbon, and graphite are
not disintegrated, and do not suffer any appreciable loss of weight.
2. On the contrary, in liquids whose electrolysis gives rise to
liberation of oxygen at the anode : wood-charcoal, retort- carbon, and
graphite, employed as positive electrodes, are partly disintegrated
and partly oxidised to CO and CO2 (the relative quantities of which
depend upon the strength of the cui'rent and the superficial area of
the positive carbon) together with other products varying according
to the nature of the carbon.
3. Graphite used as positive electrode in these liquids never colours
the electrolyte, whereas retort-carbon and charcoal, previously purified
by the action of chlorine at a high temperature, colour the liquid
deep black, both in alkaline solutions and in those of certain acids and
their salts.
4. Charcoal or retort-carbon employed as positive electrode in
OKGANIC CHEMISTRY. 593
solutions of acids or of neutral salts whose electrolysis gives rise to
evolution of oxygen at that electrode, forms chiefly, or rather almost
entirely (besides CO and CO2), a black substance — called by the
authors me Ho gen, — whose composition is represented by the formula
C14H2O4, or a multiple thereof, together with mere traces of benzo-
carboxylic acids ; whilst in solutions of phosphoric acid, hydrofluoric
and potassium antimonate, a substance is formed, analogous to mel-
logen in its properties, but containing phosphorus, fluorine, or anti-
mony, according to the electrolyte employed.
Graphite, on the other hand, employed as positive electrode in the
same liquids, produces — in addition to gaseous CO and CO2 — chiefly
graphitic acid, CuHjOa, or an analogous compound containing
phosphorus, fluorine, or antimony according to the nature of the
electrolyte.
5. Wood- charcoal and retort-carbon, as well as graphite, used as
positive electrode in alkaline electrolytes, yield mellic acid, C12H6O12,
pyromellic acid, doHeOg, hydromellic acid, C]2Hi20i2, and another
body, which is either hydropyromellic acid, CioHioOs, or an acid
isomeric therewith. H. W.
Amidometaxylenesulphonic Acid. By O. Jacobsen and H.
Ledderboge (Ber., 16, 193 — 195). — Amidometaxylenesulphonic acid
[1:3:4:6], prepared by the action of fuming sulphuric acid on
commercial xylidine at 140 — 150'"', crystallises in long flat prisms.
One part of the acid dissolves in 362*3 parts of water at 0°, and in
136'3 at 100°. . The crystals char without melting. The potassium
salt, NHa.CgHe.SOaK -h H2O, and the sodium salt crystallise in large
transparent rhombic plates, which dissolve freely in water. The
barium salt, (NH2.C8H8.S03)2Ba + HgO, forms very soluble microscopic
needles.
On oxidation with potassium permanganate, metaxylenesulphomo
acid is converted into azo-xylenedisulphonic acid,
N2 : (C6H2Me2.S03H)3 [1:3:4:6].
The potassium salt, N2 ! (C8Hp.S03K)2 + 4H2O, crystallises in rhombic
plates, which resemble iodoform in appearance. On the addition of
hydrochloric acid to the solution, the acid salt,
HSO3.CsH8.N2.C8H8.KSO3 + 4H2O,
is precipitated in golden prisms. It is sparingly soluble in dilute
mineral acids, but dissolves freely in pure water. Most of the salts
of this acid are crystalline. The free acid crystallises in plates of a
yellowish-red colour, which dissolve readily in water. By the action of
stannous chloride, azoxylenedisulphonic acid is converted into amido-
xylenesulphonic acid. W. C. W.
Glycocines, Glycocine Ethers, and Oxethylenecarbamides
of the Toluyl and Xylyl Series. By A.Ehrlich {Ber., 16, 204—
206). — The author confirms the accuracy of Staat's description Abstr.,
1880, 387) of the properties of orthotolylglycocine. Orthotolyl-
glcocinetoluidide, C7H7.NH.CH2.CO.NH.C7H7, is obtained when a mix-
594 ABSTRACTS OF CHEMICAL PAPERS.
tare of ethyl chloracetate (1 mol.) and ioluidine (2 mols.) is heated
in a flask with a reflux condenser, for half an hoar. The contents
of the flask are then heated with hydrochloric acid and poured into
water. The crystalline deposit is washed with water, dried, and
dissolved in the minimum amount of alcohol. It is re precipitated
by the addition of strong hydrochloric acid to the alcoholic solution.
From dilute alcohol, this compound is deposited in long pointed
crystals melting at 91°, soluble in alcohol and ether. EthyLorthotolyU
glycocine is an oily liquid (b. p. 272 — 278°) which does not solidify
at —10°. a,-Metaxylijlglijcocine is prepared by mixing ethereal solutions
of a-metaxylydine (2 mols.) and chloracetic acid (1 mol,). The
crystalline product is boiled with water for half an hour and the
solution filtered ; on cooling, xylylglycocine crystallises out in trans-
parent prisms melting at 133°. It dissolves freely in alcohol, ether,
hydrochloric and glacial acetic acids. Ethyl-d-metaxylylglycocine is a
non-crystallisable oil resembling the corresponding derivative of
orthotoluidine. Xylylglycocinexylidide, CgHg.NH.CHo.CO.NH.CgHg,
forms glistening needles (m. p. 128°), soluble in alcohol, ether, and
glacial acetic acid. W. C. W.
Primary and Secondary Naphthylamines. By G. Benz
(Ber., 16, 8— 22).— Merz and Weith (Abstr., 1880, 813) have shown
that the action of ammonia and aniline on the phenols is much
assisted by the presence of a dehydrating agent, such as zinc chloride.
From |S-naphthol and ammonium zinc chloride they obtained princi-
pally dinaphthylamine mixed with a little mononaphthyl amine. The
author finds that on heating |S-naphthol with calciammoniura
chloride, /:J-naphthylamine is the principal product, the best results
being obtained (viz., 80 per cent.) when the mixture of naphthol
(1 part) and calciammonium chloride (4 parts) is heated for two
hours at 230—250°, and then for six hours at 270—280°). Di-
naphthylamine is formed in much smaller quantities, the highest per-
centage (16) being obtained when anhydrous calciammonium chlo-
ride is employed, and the heating carried on for eight hours at
260 — 270°. Similar results were obtained from a-naphthol. When
zinc ammonium chloride is employed, the yield of primary amine is
much smaller, whilst a large yield of dinaphthylamine can be obtained,
viz., 65 per cent, from a-naphthol, and 80 per cent, from iS-naphthol.
To obtain the dinaphthylamine, naphthol (5 grams), naphthylamine
(5 grams), and calcium chloride (10 grams), are heated together for
eight hours at 270 — 280° in the case of the |S-compound, and at 260°
in that of the a-compound. When a-naphthylamine (1 part), iS-
naphthol (1 part), and calcium chloride (2 parts), are heated for eight
hours at 280°, a-8-dinaphthylamine is produced. It crystallises in
prisms readily soluble in warm benzene, ether, and alcohol. It melts
at 110 — 111°. This body is not obtained when /S-naphthylamine and
a-naphthol are employed. With picric acid, it forms a compound of
the formula NH(CioH7)2 + 2[C6H2(N02)3.0H], crystallising in groups
of brownish-black needles, and melting at 172 — 173**. With acetic
chloride, it forms the compound (CioH7)2NAc, crystallising in needles
melting at 124*5 — 125°. a- Dinaphthylamine forms with picric acid
ORGANIC CHEMISTRY. 595
a coraponnd melting at 168 — 169°, and crystallising in small black
needles. The acetyl -derivative melts at 217°, and forms groups of
yellowish needles. The picric acid compound from y3-dinaphthylamine
melts at 164 — 165°, and crystallises in groups of long slender needles.
The acetyl- derivative crystallises in small colourless needles melting
at 114—115°. A. K. M.
Synthesis of a-Naphthol. By R. Fittig and H. Erdmann
{Ber., 16, 43 — 44). — By the action of heat on phenyl paraconic acid,
Jayne obtained isophenylcrotonic acid and phenylbutyrolactone. The
authors find that on distilling phenylparaconic acid but little iso-
phenylcrotonic acid is formed, the decomposition going further, whilst
a-naphthol is produced. Experiment also shows that the action of
heat on isophenylcrotonic acid is to decompose it into a-naphthol and
water. The authors point out that this reaction is a further confirma-
tion of the generally accepted formula for naphthalene.
H H
CH ca c c
HC C CH HC C CH
I II I I II I
HC CH CH3 HC C CH
%/ / v^^
C COOH C C.OH
H H
Isophenylcrotonic acid. o-Naphthol.
A. K. M.
a-Naphthoic Cyanide and its Derivatives. By P. Boessneck
(Ber., 15, 3064^—3066).— d-Naphtkoic cyanide, CioHx.COCN, is pre-
pared by the action of mercuric cyanide on naphthoic chloride. The
crude product is treated with water and ether, and on evaporating the
ethereal solution, the naphthoic cyanide is deposited in beautiful
yellow needle-shaped crystals melting at 101°. By boiling with water
or dilute alkalis it is decomposed into hydrocyanic and naphthoic
acids. Ammonia or aniline converts it into naphthoylamide and
naphthanilide respectively. The cyanide dissolves slowly in acetic
acid which has been saturated with gaseous hydrochloric acid, and on
pouring the solution into water, oL-naphthijlglyoxylamide,
CioHr.CO.CONHa,
is deposited. This substance crystallises in long white needles (m. p.
151^), soluble in alcohol. By the action of alcoholic potash, it is con-
verted into potassium tx-naphthylglyoxylic acid, C10H7.CO.COOH. The
free acid crystallises in colourless plates ; the silver salt is amorphous.
w. c. w.
a-Chloronaphthylsulphonic Acid. By K. E. Abnell (Bull.
Soc. Ghim. [2], 39, 62—63). — The action of sulphuric acid on
a-chloronaphthalene apparently yields only one derivative, oc-chloro-
naphthalenesulphonic acid, C10H7.SO2CI, which forms large crystals
melting at 95*'. When heated with excess of phosphorus penta-
596 ABSTRACTS OF CHEMICAL PAPERS.
chloride, this compound yields )S-dichIoronaphthalene melting at 68°.
Since this /3-chloronaplithalene is an a-derivative containing two
chlorine-atoms in the same benzene nucleus, it follows that a-chloro-
naphthalenesulphonic acid has the constitution SOaH : CI = 1 : 4.
The a-bromonaphthalenesulphonic acid, obtained by the action of
fuming sulphuric acid on a-bromonaphthalene, has an analogous con-
stitution. C. H. B.
Nitronaphthalenedisulphonic Acids. By J. E. Alen (Bull.
8oc. Chim. [2], 39, 63 — 64). — When a-naphthalenedisulphonic
chloride is treated at the ordinary temperature with a mixture of con-
centrated nitric and sulphuric acids, it yields a mixture of two nitro-
derivatives which can be separated by taking advantage of the
difference in their solubility in benzene. The first, mononitro-naphtha-
lenedisulphonic chloride, N02.CioH5(S02Cl)2, crystallises from benzene
in large yellowish tabular crystals, which contain benzene but
gradually give it ofi" and become opaque. It crystallises from acetic
acid in small yellowish needles which melt at 140 — 141°. The
second compound, dinitro-naphthalenedisulphonic chloride^
CioH4(N02)2(S02Cl)2,
crystallises from benzene in flattened needles, which melt at 21 8' 5 —
219*5°. It is less soluble in benzene than is the mononitro-derivative.
jS-l^aphthalenedisulphonic chloride, when treated with a mixture of
concentrated nitric and sulphuric acids, yields a mononitro-derivative
N02.CioH5(S02Cl)2, which crystallises in short yellowish prisms melt-
ing at 185— 187^
The mononitro-derivative of naphthalene-a-disulphonic acid is
obtained by digesting the chloride with water in sealed tubes at 150°.
It is a very soluble compound and crystallises in flexible needles. The
ammonium, calcium, and lead salts are very soluble ; the barium salt
is much less soluble.
When the chloride is treated with aqueous ammonia, two products
are obtained, viz., the amide,N02.CioH5(S02NHo)2, which is only slightly
soluble and crystallises in almost colourless flattened needles melting
at 285° with decomposition, and a somewhat soluble compound, pro-
bably N02.CioH6(S02NH2).S03NH4. C. H. B.
Addition of Acetone under the Influence of Caustic Alkalis.
By F. R. Japp {Ber., 16, 282). — In consequence of the appearance of a
paper by Baeyer and Drewsen (Ber.^ 15, 2856 ; this vol., 341) in
which the formation of an addition-product of acetone and orthonitro-
benzaldehyde by the action of caustic alkalis is described, the author
published a note stating that he has for some time past been engaged
on the study of similar reactions, in which, by the action of caustic
alkalis or ammonia, diketones may be made to combine directly with
1 or with 2 mols. of acetone. The first compound of this class,
acetone-phenanthraquinone, described in a former communication
(Japp and Streatfield, this Journal, Trans., 1882, 273), was prepared by
decomposing acetone-phenanthraquinonimide (obtained by the action
of ammonia on phenanthraquinone and acetone) with acids. The
ORGANIC CHEMISTRY. ' 597
antlior now rejects tlie constitution ascribed to tTiese compounds in
the first paper, and prefers to formulate them —
C6H4.C(OH).CH2.COMe C6H4.C(OH).CH2.COMe
II II
C6H4.CO and C6H4.C(NH)
By substituting potash for ammonia in the above reaction, diacetone-
phenanthraquinone,
C6H4.C(OH).CH2.COMe
C6H4.C(OH).CH2.COMe
is obtained. By the spontaneous evaporation* of its acetone solution
this compound is deposited in short oblique prisms, fusing with decom-
position at 187°. The monacetone addition-product is also formed in
small quantity in the reaction.
Benzil seems to react with acetone and potash in a similar manner.
The above reactions are still under investigation. F. R. J.
Action of Concentrated Sulphuric Acid on Dinitroanthra.
quinone. By C. Liebermann (JBer., 16, 54 — 58). — The action
of concentrated sulphuric acid on dinitroanthraquinone has been
described by Liebermann and Hagen (this volume, p. 72). In con-
tinuing his experiments, the author finds that the nitration of anthra-
quinone takes place with much greater difficulty than has hitherto
been supposed, and that much mononitro-derivative is produced
together with the dinitro-compound. It is probable therefore that
the composition of the dye-stuff (loc. cit.) may vary with the amount
of mononitro-derivative mixed with the dinitroanthraquinone, and
hence the want of agreement between the author's analyses and those
of Bottger and Petersen (Annalen, 160, 147). Dinitroanthra-
quinone, as prepared by Bottger and Petersen, is also wanting in
homogeneity, and so is the dye-stuff derived from it.
By the action of concentrated sulphuric acid on a-nitroanthra-
quinonesulphonic acid, Claus (Ber., 15, 1521) obtained two bodies
to which he assigned the formulae [Ci4H4(OH)(N02)02.S03H]20 or
0 : CuHiCNOOO^.SOaH, and S03H.CuH4(OH)(N02)02.0.S03H or
S03H.CuH4(N02)02 : (OS03H)2.
The author considers these formulse by no means established, and
assigns to the former compound the more simple formula
NH2.CuH4(OH)202.S03H,
i.e., according to him the nitro-group, is reduced and hydroxyl intro-
duced. A. K. M.
* This paper was forwarded to Berlin in English. The words of the English
manuscript " by spontaneous eyaporation " have been transformed by the German
translator into " unter freiwilliger Erwarmung " ("with spontaneous rise of tem-
perature").— F. E. J.
508 ABSTRACTS OF CHEMICAL PAPERS.
Madder Colours. By A. Wuetz (Gompt. rend., 96, 465 — 471). —
This paper is a report drawn up by Wnrtz on a memoir of Rosenstiehl
on the colouring matters of the madder root. From this root
live separate colouring substances can be extracted : alizarin, pur-
purin, madder-orange, pseudopurpurin, and pui^uroxanthin. The
researches of Graebe and Liebermann have fixed the constitution of
the two former, whilst Rosenstiehl has studied more especially the
three latter substances. He has shown that purpuroxanthin is iso-
meric with alizarin, and can be converted into pnrpurin by fusion
with potash ; and inversely pnrpurin can be reconverted into purpuro-
xanthin by the action of reducing agents, but if the action be pro-
longed, hydropurpuroxanthin is formed. Rosenstiehl has also devised
a new method of formation of purpurin. On heating the madder
root with sulphurous acid, Kopp obtained a product known as com-
mercial purpurin ; as this substance is useless for dyeing purposes, it
has been customary to heat it to 180° with glycerol to convert it into
solid purpurin. This rationale of the process Rosenstiehl has ex-
plained ; the " commercial purpurpin " contains pseudopurpurin, which
possesses no tinctorial properties, but is easily decomposed into
carbonic anhydride and purpurin ; this latter dyes a brilliant madder-
red. Rosenstiehl has succeeded in separating the pseudopurpurin,
and shows that it is a monc-carboxyl-derivative of purpurin, thus:
purpurin, CuH502(OH)3, pseudopurpurin, Ci4H402(OH)3.COOH.
This fact has thrown an unexpected light on the practical industry
of the madder ; for it has long been observed that madder of Avignon
gave a more solid dye-stufP than the madder of Alsace. It is now
shown that this fact is due to the greater quantity of lime in the
Avignon soil, which serves to eliminate the pseudopurpurin as a lime
compound, and prevents it being fixed to the tissue of the root.
It has also been customary in Alsace to add small quantities of
chalk to the dye-baths ; this also prevents the fixation of the pseudo-
purpurin which passes into the residues, where it may be decomposed
by sulphuric acid and converted into useful purpurin. Rosenstiehl has
also studied madder-orange, identical with the munjistin of Stenhouse,
and has shown that it is a monocarboxyl-derivative of purpuro-
xanthin, bearing to it the same relation that pseudopurpurin does to
purpurin. These researches also show that the madder root contains,
besides alizarin existing as such, three glucosides, viz., one which
gives pseudopurpurin or purpurincarboxylic acid, a second which
gives alizarincarboxylic acid, and a third which gives munjistin or
xanthopurpurincarboxylic acid. The memoir presented to the
Academy contains a full account of the various substances obtained
from madder, and their physical properties as absorption-spectra.
Y. H. V.
Physical Isomerism of Monochloro-camphpr. By P. Caze-
NEUVE {Gompt. rend., 95, 1358 — 1361). — From the mother-liquors of
the monochloro-camphor obtained by the action of dry chlorine on an
alcoholic solution of camphor (this vol., 214), the author has suc-
ceeded in isolating another monochloro-camphor, differing in physical
properties from the first. This compound is soft, like camphor,
whereas the normal body is hard and brittle, and is. much more solu-
ORGANIC CHEMISTRY. 599
ble in cold alcoliol than the latter. It mixes with boiling alcohol in
all proportions, and on cooling crystallises in microscopic needles. It
is insoluble in water, and has an odour resembling that of camphor.
It liquefies in contact with choral hydrate. Its specific rotatory
power is [a]y = -f 57°. It softens at 95°, melts at 100°, and distils
with very slight decomposition at 244 — 247°. It is not decomposed
by alcoholic solution of silver nitrate ; but on boiling with alcoholic
potash, it is converted into the normal monochloro- camphor. Taking
this latter reaction into account, the author believes this to be a case
of physical and not chemical isomerism, and that the isomeride bears
the same relation to the normal body as is ihe case with the dichloro-
camphor previously described (Abstr., 1881, 738 and 1107).
L. T. T.
Products of the Distillation of Colophony. By A. Renard
(Compt. rend., 95, 1386 — 1387). — The author has examined that
portion of the product of the destructive distillation of " rosin " which
passes over below 100°. Besides some aldehydes which he has not yet
examined, he has obtained two principal fractions boiling at 30 — 40°
and 67 — 70° respectively. The former consists of a mixture of ordi-
nary and normal amylenes, together with small quantities of a
pentane boiling at 33 — 38°. The fraction 67 — 70° consists princi-
pally of isomeric hexylenes, but contains a little hexane.
L. T. T.
Action of Cyanogen Chloride on Potassium Pyrroline. By
G. L. CiAMiciAN and M. Dennstedt (Ber., 16, 64 — 66). — The potas-
sium-derivative of pyrroline was suspended in absolute ether, through
which a current of cyanogen chloride was passed until the liquid
smelt strongly of chlorine, the mixture being kept cool with water.
After filtration from the potassium chloride, the ether was evaporated
on a water-bath and the residue fractioned. No constant boiling
point could be obtained, the temperature rising gradually from 130° to
210°, whilst the small residue left behind solidified on cooling to a
crystalline mass. The different fractions yielded crystalline preci-
pitates with silver nitrate, which, however, are so readily decomposed
by light, that no trustworthy analysis could be made. After long
standing, the different fractions became crystalline, and the crystals
from each fraction were found to be identical. After crystallisation
from boiling alcohol, long white needles were obtained, melting at
210°. The analytical results correspond with the formula C4H4N.CN,
but the properties of the substance indicate that it is a polymeride,
probably 3C5H4N2. It is insoluble in water, almost insoluble in cold
alcohol, and sparingly in hot alcohol. It volatilises above 300° with
decomposition. Hydrochloric and dilute nitric acids do not decompose
it, concentrated sulphuric acid producing a reddish-brown coloration,
which becomes black on warming. Aqueous potash has no action,
whilst alcoholic potash decomposes it into pyrroline, and probably
cyanuric acid. Heated with solid potash, pyrroline, carbonic anhy-
dride, and ammonia are formed. It seems probable that the first
product of the action of cyanogen chloride on the potassium-derivative
of pyrroline is really C5H4N2, which gradually becomes converted into
the polymeric variety. A. K. M.
600 ABSTRACTS OF CHEMICAL PAPERS.
Action of Chloroform and Iodoform on Quinoline. B\r O.
Rhoussopoulos (Ber., 16, 202 — 203). — Methane-triquinoil hydriodide,
CH(C9H7NT)3, is deposited in the form of a crystalliDe precipitate
(m. p. 65°), on mixing ethereal solutions of iodoform (1 mol.) and
quinoline (3 mols.)- This compound forms transparent colourless
needles, which are soluble in ether, benzene, ethyl acetate, light petro-
leum, &c. Chloroform does not act on quinoline at the ordinary tem-
perature. At 300° a non-crystalline chloride is formed, which yields a
non-crystalline platinochloride. W. C. W.
A New Class of Colouring -matters. II. By E. Besthorn
and O. Fischer (J9er., 16, 68—75). — Some time ago Fischer and
Rudolph (Abstr., 1882, 1066) investigated " flavaniline," at the same
time expressing their opinion that it is a quinoline derivative.
This view is now confirmed by the following observations: — The
vapour- density of flavoUne is in accordance with the formula CieHiaN
previously given ; this body, when warmed, emits an odour resem-
bling that of the quinoline bases. On nitrating flavoline, a mononitro-
body is produced, which on reduction yields amidoflavoline, identical
with flavaniline. This identity was confirmed by means of the hydro-
chlorides, and also by the conversion of amidoflavoline into flavenol.
Acetylflavenol is obtained by boiling flavenol with an excess of acetic
anhydride for an hour, diluting with water and neutralising with
alkali. It crystallises from alcohol in long needles melting at 128°.
By the oxidation of flavenol (1 part), in alkaline solution, with potas-
sium permanganate (6 parts), an acid is obtained, melting at 182°
with violent evolution of carbonic anhydride, and yielding an oily dis-
tillate which has the characteristic odour of the quinoline bases. This
distillate is probably lepidine, and the acid, lepidinecarboxylic acid. If
nine parts of permanganate are used instead of six, picolinetricar-
boxylic acid is produced. It crystallises from water in colourless
shining needles, with 2 mols. H2O. From these facts, the authors con-
clude that flavoline is represented by the formula CioHgN.Ph (phenyl-
lepidine), that flavenol is the hydroxy- compound C10H8N.C6H4.OH,
and flavaniline the corresponding amido-derivative. They explain
the formation of flavaniline from acetanilide by assuming a molecular
change, by which the latter yields amidoacetophenone. It is then
easy to see how flavaniline could result by abstracting 2 mols. of
water from 2 mols. of orthoamidoacetophenone —
C6H4(NH2)CO.CH3 ^CMe I CK
= CeHZ >C.C6H4.NH2 -f 2H2O.
CeHiCNHO CO.CH3 ^ W
By interrupting the reaction of zinc chloride on acetanilide as soon
as the colouring-matter begins to be formed, the authors have further
succeeded in obtaining a small quantity of an oil having the odour and
other properties of orthoamidoacetophenone. Flavaniline can also be
obtained by the action of acetic chloride on aniline sulphate or on
acetanilide in the presence of zinc chloride. Propionanilide also gives
a yellow dye, whilst formanilide yields colourless derivatives.
The base C^HuN previously mentioned as having been formed from
ORGANIC CHEMISTRY. 601
diphenylamine and glacial acetic acid, has been obtained in a pnre
condition, melting at 92 — 94". The hydrochloride crystallises in
yellow plates. Its dilute aqueous solution shows a splendid blue-
green fluorescence. A. K. M.
Paraxan thine, a New Constituent of Human Urine. By G.
Salomon (Ber., 16, 195 — 200). — 1'2 grams of paraxanthine were ob-
tained from 1200 litres of human urine by the following process: —
Ammonia is added to the urine, and after 24 hours the clear liquid is
separated from the precipitated phosphates by decantation. The pre-
cipitate which is obtained by the addition of silver nitrate is first
thoroughly washed and then decomposed by sulphuretted hydrogen.
On evaporating the filtrate from the silver sulphide, a precipitate of
uric acid is first deposited, and the addition of ammonia to the mother-
liquor causes a further separation of uric acid in the form of ammo-
nium urate. Nitrate of silver is added to the filtrate ; the precipitate
is dissolved in hot nitric acid (sp. gr. I'l), and after 24 hours the
nitrate of hypoxanthine silver is removed by filtration. The silver
salt, which is thrown down on the addition of ammonia to the mother-
liquor, is decomposed by sulphuretted hydrogen, ammonia is added to
the solution, and, on concentrating the liquid, xanthine separates out,
while paraxanthine remains in solution. Paraxanthine crystallises in
colourless six-sided plates, belonging to the monoclinic system : the
crystals are insoluble in alcohol and ether, but dissolve in hydrochloric
and nitric acids, in ammonia, and in hot water ; they do not melt at
250°, but decompose at a higher temperature. The silver salt is depo-
sited from its solution in hot nitric acid, in silky crystals. Picric acid
gives a yellow crystalline precipitate, with a hydrochloric acid solution
of paraxanthine. The addition of potash or soda to a concentrated
solution of paraxanthine produces a crystalline precipitate, which dis-
solves on the addition of warm water, but crystallises out again
when the liquid cools : this reaction distinguishes paraxanthine from
guanine, xanthine, and hypoxanthine. Analyses of this compound
show that its composition is represented by the formula C16H17N9O4.
w. c. w.
Cuprea Bark. By 0. Hesse (Ber., 16, 68—63).— The author has
previously shown (Ber., 4, 818) that this false cinchona bark contains
cinchona alkaloids, and that it answers to the same tests as the
genuine barks (Annah^i, 166, 218). It has several times appeared in
the market, and is now found in enormous quantities in London. A
microscopic examination has satisfactorily shown that it is derived from
Bemijia ped^mculata, as stated by Triana. It contains quinine, quini-
dine, cinchonine, and amorphous bases, but no cinchonidine or pari-
cine. By the action of permanganate in acid solution on the quinine,
quinidine, and cinchonine, small quantities of the hydro-bases are pro-
duced. On boiling the amorphous bases with water, cincholine is
obtained, and also diquinidine, C40H46N4O3; the platinochloride of
this base, C4oH46N403,2H2PtCl6 + 4H2O, forms a dense yellow powder.
Certain other barks have at different times appeared under the name
of cuprea barks, as for instance Buena magnifolia, Uemijia purdicana,
&c. The base contained in cuprea bark, which in composition and
YOL. XLIY. 2 s
(302 ABSTRACTS OF CHEMICAL PAPERS.
certain properties resembles cusconine, differs from the latter in the
following properties : — It melts at 144° (instead of at 110°), crys-
tallises with 1 mol. H2O (cusconine with 2HoO), dissolves with greater
difficulty in cold alcohol, and turns the plane of polarised light to the
right, cusconine being laevorotatory. This concusconine therefore bears
the same relation to cusconine that quinidine does to quinine. The
base previously assumed to be aricine is found to be a distinct body,
and of different composition, C19H24N2O. It melts at 184°, is dex-
trorotatory, and turns red litmus blue. Its solution in sulphuric acid
does not fluoresce ; with chlorine and ammonia, no green coloration is
produced. The platinochloride, (Ci9H24N20)2,H2PtCl6, forms a yellow
flocculent precipitate. The normal sulphate, (0191124^20)2,62804,
crystallises in prisms, sparingly soluble in alcohol, readily in water.
The body formed by oxidation with acid permanganate is probably
identical with Arnaud's cinchonamine. Another base contained in
cupreabarkis concusconidine, C23H26N2O4, correspondingto cusconidine.
It melts at 124°, and is an amorphous yellowish- white powder. The
platinochloride, (C23H26N204)2,H2PtCl6 + 5H3O, forms an amorphous
flocculent precipitate, A. K. M.
Hydroconquinine and Conquinine. By 0. Hesse (Ber.j 15,
3008 — 3011). — Hydroconquinine sulphate, (C2oH26^20)2H2S04, is de-
posited on evaporating its aqueous solution at 30 — 50° in slender
needles containing 2 mols. HaO. 92*3 parts of water at 16° dissolve
one part of this salt. On exposing a solution saturated at 20° to a
temperature of 10°, the sulphate is deposited in thick monoclinic
prisms or rhombic plates containing 8 mols. H2O. One part of this
salt dissolves in 81'1 parts of water at 16°.
Conquinine may be easily separated from hydroconquinine by re-
crystallising the neutral hydrochloride or acid sulphate from water or
alcohol. W. C. W.
Quinaldine. By 0. Doebnee and W. v. Miller (Per., 15, 3075—
3080).— The following salts of quinaldine {Ber., 14, 2812) have been
prepared. The hydrochloride, nitrate acetate and sulphate are freely
soluble in water ; the picrate and dichromate are sparingly soluble.
The picrate, CioHgN + C6H3N3O7, forms yellow crystals soluble in hot
alcohol; the dichromate, (CioH9N)2H2Cr207, crystallises in beautiful
yellowish-red needles soluble in hot water, and resembling quinoline
chromate in appearance. Quinaldine is not attacked by an aqueous
solution of chromic acid, but it is completely decomposed by a solution
of chromic acid in acetic acid. On oxidation with potassium perman-
ganate, it yields acetylanthranilic acid, COOH.C6H4.NH.COMe, whicli
was obtained by Bedson and King (this Journal, 1880, 752) from
orthoacetotoluidide. Strong nitric acid converts quinaldine into
N : C.COOH
nitroquinolinecarboxylic acid, N02,C6H3/^ | . This acid
^CH : CH
forms colourless crystals soluble in hot water. The sparingly soluble
silver salt, doHsAgNoO^, is crystalline.
I
PHYSIOLOGICAL CHEMISTRY. WB
The formation of these acids from quinaldine shows that this base
N : C.CH3
has the formula C6H4<^ |
^ch:ch w. c. w.
Formation of Peptone and its Conversion into Albuminoid
Substances. By A. Poehl (Jo2ir^ Bms. Chem. Soc, 1882,. 353 —
354). — The author has established the occurrence of peptone in urine
bj analyses. Moreover, many animal and vegetable tissues were
found to exhibit' the properties of peptones, so that many physiological
and pathological processes^ hitherto unexplained, become clear. In
order to investigate the relation of peptones to albumin, the author
has studied the conversion of peptone into albumin. The conversion
of albumin into peptone is, according to his view, due to the swelling
up of the colloid of albumin. The inner constitution of peptone re-
mains the same as that of albumin unaltered in this process of swellr
ing up, as has been found by the study of the optical, phenomena
occurring during the peptonisation of albumin., B. B.
Physiological Chemistry,.
Tissue-waste- in the Fowl during Starvation. By F. Kuckein
(Zeits. Biol., 18, 17 — 40). — Voit has already shown by his-^ experi-
ments in regard to the influence of abstention from food on tissue
consumption in cats and dogs, that the destruction of albuminoids is
determined not only by the size of the organ but by the amount of
fat present. The more the fat, so much less the destruction of albu-
min (ibid. ,1866, 307). Lateir, Rubner confirmed these conclusions in
the case of herbivorous animals, such as rabbits (ihid.^ 1881, .214); the
decrease of fat was correlated to an increased consumption of albumin,
which was longer delayed as the animal happened to be rich in fat,
but in lean animals was manifest in a few days, albumini alone being
ultimately destroyed. On a priori grounds, therefore, the author of
this paper expected that the same law would hold good for other
animals, and, in the case of birds, was likely to be well marked by
reason of their more active tissue expenditure and consumption of
oxygen. At the same time, Schimanski's researches {Zeitschr. f.
Physiol. Chem., 1879, 396) in this direction, showing the existence of
very small quantities of nitrogen in the excretions, and the fact that
the domestic fowl commonly receives an inconsiderable amount of
nitrogenous as compared with unnitrogenous constituents in its food,
were apparently opposed to this view. The author briefly reviews the
work of previous experimenters, Chossat, Boussingault, Regnault,
and others, by none of whom, however, had the simultaneous deter-
mination of excreted nitrogen and carbon, essential to the insight into
the true nature of the tissue-changes going on within the body, been
made.
2 s 2
G04
ABSTRACTS OF CHEMICAL PAPERS.
Kuckein's experiments were carried out upon two fowls, the bird in
each instance being confined in a cage so arranged that the head and
tail projected, allowing thereby the collection of the whole of the
voided excretions. The method of analysis consisted in the estima-
tion of nitrogen by Will and Yarrentrapp's method, in the excrement
previously dried at 100°, after addition of tartaric or oxalic acid, whilst
the carbonic acid exhaled was determined by Yoit's modification of
Pettenkofer's method which allowed of the introduction of bird and
cage into the apparatus.
In both instances the birds were provided with water, the author
remarking that small quantities have no perceptible influence over the
tissue destruction.
In the first experiment, Fowl No. 1 described as lean and wanting
in fat, died on the ninth day after deprivation of food. On section, no
fat was visible in the subcutaneous cellular tissue nor in the peritoneal
cavity, and the body weight had suffered a reduction from 1884*G
grams to 1240*3 grams, or 34"19 per cent.
In the following table are given the results of the progressive
destruction of albumin and fat in the organism, the nitrogen being
reckoned as albumin (with 15'5 per cent, of nitrogen) or as tissue
(with 3'4 per cent, nitrogen), and the carbon in the breath and excre-
ment after deduction of that belonging to the albumin or tissue
(12*52 per cent,) as fat (with 76*5 per cent, of carbon) : —
Mean
Albumin
Tissue
Fat
In 1 kilogram of body weight.
Day.
body
weight.
used
up.
used
up.
used
up.
Albumin,
Tissue.
Fat.
CO3
in
breath.
2
1753
20-35
92-78
_
11-61
52 -93
3
1686
19 -61
89-41
3-23
11-63
53-04
1-91
21-73
4
1605
19 -61
89-41
—
12-22
55-71
—
—
5
1509
17*33
78-99
2-86
11-84
52-35
1-88
21-47
6
1410
17-33
78-99
—
12-29
56-04
—
—
7
1335
17 -71
80-72
1-32
13-27
60-47
0-99
21-43
8
1290
17-71
80-72
—
13-72
61-01
—
—
*9
1257
12*19
55-59
—
9-70
44-23
—
—
Fowl No. 2, of average fatness, died on the 12th day of starvation.
The body weight had diminished from 997 grams to 607*5 grams, or
39 per cent. On section it was found that the fat had entirely dis-
appeared, save in the axillary region, where patches of adipose tissue
could still be seen.
The results are here tabulated as in the first instance.
* Including only 12 hours of the ninth day.
PHYSIOLOGICAL CHEMISTRY.
605
Mean
Albumin
Tissue
Fat
Of body weight per kilogram.
Day.
body
used
used
used
CO2
weight.
up.
up.
up.
Albumin.
Tissue.
Fat.
m
breath.
1
984
2-01
9-17
2-04
9-32
_
_
2
3
4
958
931
900
2-01
9-17
8-58
2-10
9-57
8-96
28-23
3 09
14-06
8-78
3-43
15-62
9-76
32-17
5
868
4-13
18-81
4-75
21 -67
—
—
6
836
5-19
23-67
8-26
6-21
28 -31
9-88
36-43
7
804.
6-58
29-99
—
8-18
37-30
—
—
8
770
6-58
29-99
7-18
8-&4
38-96
9-32
38-17
9
734
7-59
34-61
—
m34
47-15
—
—
10
698
9-05
41-28
4-49
12-97
59-14
6-43
36-27
11
682
10-27
46-81
—
15-05
68-63
—
—
12*
626
6-89
31-43
1-99
11-01
50-20
3-18
24-42
As regards the unequal lengths of time for which fowls thus de-
prived of food survive, Kuckein concludes from the above data and
those of other experimenters, that the fat present in the system is the
determining factor. The same has been observed in the case of cats
by Voit, of dogs by ¥. Hofmann, and of rabbits by Rubner. The
varying excretion of nitrogen noticed in all these cases is similarly
accounted for.
In fowls which survive longest, the nitrogenous excretion at first
diminishes slowly, then remains for some time unchanged, rising again
at the end, and usually in excess of that at the outset. In the case of
those fowls surviving for shorter periods, a marked increase takes place
within a few days, ultimately amounting to perhaps even five times
the early excretion. Hence it is impossible to arrive at any average
estimate of the amount of decomposed albumin for any kind of
animal, uidess the state of the system, especially in relation to the
fat constituents, is taken into account.
The author cites one of Schimanski's experiments, in which a fat
fowl survived until the 32nd day. The increase of nitrogenous
excretion was nevertheless very small, owing, the author explains, to
the abundance of fat present as found upon post-mortem examination,
death resulting not from want of fat, but from exhaustion of the
albuminous principles essential for the phenomena of vitality.
In contrast with this result were those of experiments in which fowls
were of average fatness. At first the disintegration of albuminoids
was exactly as in the former case, but in 6 — 11 days an increase
occurred to the extent of from 5 — 8 times this amount.
Thirdly and lastly, in the case of lean fowls, the albumin decom-
posed amounted already on the second day of starvation to the same,
viz., 5 — 8 times the quantity decomposed in the others at the same
period, and equal to that of the later period of starvation.
* Less three hours.
606 ABSTRACTS OF CHEMICAL PAPERS.
The influence of the fat he assumes to be exerted in restraining the
solution and circulation of albuminoids and the consequent smaller
chance for their disintegration, this being chiefly effected by the fat
present in the juices and in the organs where albumin disintegration
occurs, and not by the fat stored up in the subcutaneous cellular tissue,
peritoneal sac, &c. Regarding the common assumption of a more active
tissue change in the case of birds than of other animals, Kuckein, from
a comparison of his results and those of Rubner and others upon
mammals of equal weight, shows that there is no essential difference
b3tween ithem when the influence of the fat is eliminated, as in the
last stage of the process of starvation. Apparent discrepancies are
thus accounted for. In birds, it is probable that there is, under equal
conditions as to fat, more of the latter in circulation than in other
animals.
The carbonic anhydride eliminated gives no insight into the indivi-
dual changes going on, or measure of the extent of tissue consump-
tion, for whilst CO2 in 24 hours varied in five experiments from 25'3
to 30*4 grams only, and the fat consumed to a corresponding degree,
the disintegration of albumin increased to fourfold or even fivefold
its original amount. In conclusion, Kuckein agrees with Voit, that
the domestic fowl affords the best subject for experiments of this
kind. D. P.
Decrease in Weight of Individual Organs in Children Dying
from Atrop^hy. By W. Ohlmuller (Zeits. Biol, 16, 78— 10:J).—
The author refers 'to earlier experiments upon animals by Chossat,
Schuchardt, Bidder, and Schmidt and others, and gives a resume of
their results.
His own were undertaken to verify the conjecture of H. Ranke,
that in children dying from wasting diarrhoea, atrophy of the various
organs will be found to have occurred just as in animals dead from
starvation.
The bodies of four infants were the subjects of his observations,
but complete investigation was attainable in two only; these were
both infants of 56 days old; one dying from diarrhoea of 2^ weeks'
duration, the other of capillary bronchitis after only four days' illness,
and so taken as representing as nearly as possible the normal weight
of health.
I. Alterations iri Weight of Organs in Proportion to Body WeigJit. —
The several organs do not decrease in weight in equal ratios, but some
more than others. The most striking differences are exhibited in the
instance of the bones, the brain, and the skin. The two former lose
much less weight than the other organs, and consequently form a
larger proportion of the total body weight in the atrophic than in the
normal infant. The skin, on the other hand, decreases considerably
in relative weight, owing to the complete disappearance of the adipose
tissue.
Atrophic infant.
•rganic percentage
of body weight.
20-20
4-38
0-98
23-61
25-53
12-21
105
0-28
3-57
PHYSIOLOGICAL CHEMISTRY. 607
Normal infant.
Organic percentage
of body weight.
^™''" ^"^1 12-75
fepmal cord j
Liver 3*41
Heart 0-66
Muscles 25-82
Bone 16-99
Skin 31-16
Kidneys 0-78
Spleen 049
Lungs , 2*56
II. Alterations in the Percentage of Water and Fat in the several
Organs. — The percentage of water in the organs of the normal and
of the atrophic infant does not greatly vary, decreasing proportion-
ately with decrease of the solid constituents, save in the case of the
skin when an increase, due to the extraordinary loss of fat, takes
place.
In the atrophic infant, there is a decrease of fat in the several
organs save in the brain and heart, apparently dependent in the latter
on fatty degeneration of the muscular tissue, and in the brain either
on more active nutrition or on decrease of the grey and relative
increase of white substance.
III. Absolute Decrease of Organs in Solid Constituents and Fat in
Atrophy. — The normal infant contains 40 per cent, of solid consti-
tuents and 60 per cent, of water ; the atrophic 74 per cent, of water
and only 24 per cent, of solids : the relative increase of water being
due to the less amount of fat constituents, which are only 3 per cent,
in comparison with 21 per cent, in the normal infant. The skin loses
97 per cent., the liver 70 per cent., the bones 66 per cent., and the
muscles 64 per cent, of original fat. The loss in albuminous and
gelatinous constituents amounts to 49 per cent, in the case of the
skin, the intestines and muscles, but only to 23 per cent, for the heart,
18 per cent, for the brain, 16 per cent, for the liver, and 9 per cent,
for the bones. To the total loss of fat the skin contributes 91 per
cent., the muscles 5 per cent., and the bones 'Z per cent. ; the remain-
ing organs contributing altogether only 2 per cent. To the total loss
in albuminous and gelatin-yielding constituents, the muscles contribute
49 per cent., the skin 31 percent., the intestines 17 per cent., and the
remaining organs only 13 per cent.
In the atrophic child the loss in solid constituents (minus fat) of the
heart, brain, liver, and bones, is much less, therefore, than that of the
skin, intestines, or muscles. The former may possibly, up to a
certain point, continue to receive nutrition at the expense of the
organic albuminoids which, becoming fluid, enter the circulation and
for the most part are consumed.
In conclusion, the author draws attention to the probability that the
active organs of the body upon which the maintenance of life de-
pends, are protected from decrease by nutrition in this way at tlie
608 ABSTRACTS OF CHEMICAL PAPERS.
expense, so to speak, of the less active organs. Only when this
supply becomes insufficient do they begin to suffer loss of substance,
and from this condition a long period of recovery is then needful.
Especially is this the case when the loss is brought about, not by
simple inanition, but by long- continued fever. D. P.
Coagulation of the Blood. By K. Hasebrock (Zeits. Biol., 18,
41 — 59). — Vierordt's method (Archiv. f. Heilkunde, 19, 193) was
employed ; it has the advantage of requiring a minimum quantity
of blood, and may shortly be described. A drop of blood from
a prick with a needle of the finger pulp or other part of the body
is taken up in a capillary tube, into which a horsehair deprived of fatty
matter is then slowly inserted from the empty end. As soon as a
coagulum has formed the hair is withdrawn, and this procedure re-
peated so long as coagula can be brought away. The number of seconds
elapsing between the withdrawal of the blood from tlie body and the
formation of the first and last coagula respectively gives approxi-
mately the times of the beginning, end, and duration of the coagu-
lation.
In the author's experiments, blood obtained by pricking the tip of
the finger in his own person, was withdrawn in a pipette of 12*9 cm.
capacity, mixed in a watch-glass with measured amounts of the re-
agents experimented with, and then taken up in capillary tubes as
explained.
The end reaction was found to be more definite than the beginning
of coagulation.
I. Influence of Water. — Additions of water up to one-half the
volume of the blood hastened coagulation ; larger quantities hin-
dered it.
A maximum of rapidity was reached when the added water was
equal to four-tenths of the volume of the blood.
II. Influence of Sodium Chloride. — Solutions of different densities
were prepared, so that equal volumes might be employed.
When added to the blood in proportion of one-half its volume,
coagulation was delayed in proportion to the concentration of the salt
solution ; when this amounted to one-half, a trifling coagulum formed,
and when saturated, coagulation ceased to take place. Weak solutions
of "sir ^o Y5-6 aeted similarly to equal volumes of water, but with
this difference, that while the termination of the process is hastened
and the outset correspondingly delayed by the salt solution, in the
case of water both beginning and end of the reaction are hastened.
III. Influence of Holding the Breath. — The results showed that for
shorter periods coagulation was hastened, but delayed at a later stage.
Hasebrock refers to this difference as accounting for discrepancies of
statements by authors as to the influence of carbonic anhydride on
coagulation of the blood, by the explanation that while small amounts
of the latter promote coagulation large amounts delay it.
IV. Influence of Increased Frequency of Respiration. — In these experi-
ments coagulation was hindered.
V. The Influence of Temporary Arrest of Circulation. — Vierordt's
experiments in his own case, by applying a ligature to the finger for
YEGETABLE PHYSIOLOGY ANl) AGRICULTURE. 609
some minutes, and upon the paralysed limbs of a hemiplegic patient,
showed that the blood coagulated sooner than that taken from the
unligatured and sound members. The author obtained similar results,
showing, according to his view, that want of oxygen hastens, whilst
richness in oxygen delays coagulation, and explaining thereby the
rapid coagulation witnessed after venesection, when the loss of oxygen
is absolutely as well as relatively decreased.
The slower coagulation of venous than of arterial blood is dependent
not on want of oxygen, but on richness in carbonic anhydride ; for on
continued ligature of the finger, when all oxygen was permanently
given off by the haemoglobin, delay in coagulation likewise was
noted.
In conclusion Hasebrock alludes to his observations during the
course of the series of experiments on the collateral influence of tem-
perature on blood coagulation, which is the more rapid accordingly as
the temperature is high ; but further experiments are wanting upon
this point. D. P.
Occurrence of Crystals of Ammonium-Magnesium Phosphate
in Urine. By H. Weiske (Ber., 16, 63— G4).— Schwanert (Abstr.,
1882, 637) has mentioned the occurrence of large crystals of ammo-
nium magnesium phosphate in human urine supposed to be 100 years
old. The urine examined by the author was fresh, had a strong
acid reaction, dark yellow colour, and rapidly deposited a consider-
able quantity of ammonium urate. On standing in a beaker, a fungoid
growth appeared on the surface, the liquid becoming strongly alka-
line, whilst crystals of ammonium magnesium phosphate were formed,
the largest of which measured 9 mm. A. K. M.
Chemistry of Vegetable Physiology and Agriculture.
Reduction of Nitrates to Nitrites. By U. Gaton and G.
DuPETiT. — In a former paper, the authors described a microbe having
the property of decomposing alkaline nitrates with evolution of
nitrogen. They now find that a great many microbes have the power
of reducing nitrates to nitrites. Some of these are very hardy,
even living in chicken broth saturated with potassium nitrate, and
reducing considerable quantities of nitrate. Four species of such
microbes specially examined reduced respectively 9*6, 2"8, 6'8, and
5'6 grams of potassium nitrate into nitrite per day. On the other
hand, experiments with the microbe of chicken cholera, the carbuncle
bacteria, and the Vibrio septica, obtained in a state of purity by
Pasteur, showed that these latter reduce nitrates but very slowly. The
authors consider that the presence of these microbes explains in great
measure the presence of nitrites in soils. L. T. T.
f)lO ABSTRACTS OF CHEMICAL PAPERS.
Butyric Ferment in Arable Soils. By P. P. D^h^rain and
L. Maquenne (Bull. Soc. Chim. [2], 39, 49 — 52). — Arable soil rich in
organic matter contains a ferment which acts as a powerful reducing
agent, and decomposes the nitrates in the soil with evolution of
nitrogen. If such a soil, charged with nitrates, is sealed up in a tube
with exclusion of oxygen, the nitrates will completely disappear in a
few weeks, or sooner if the temperature is kept at about 35°. In pre-
sence of chloroform, or if the soil has been heated for at least an
hour at 120 — 125°, the reduction does not take place. On adding
a small quantity of fresh soil to the heated soil reduction again
begins. The reduction is always accompanied by a rapid absorption
of oxygen and evolution of carbonic anhydride, and is due to the action
of the butyric ferment which is contained in the soil. If some of
the soil is added to an aqueous solution of sugar, previously sterilised
by prolonged boiling, and kept at a suitable temperature, butyric acid
is rapidly formed. Solutions of sugar mixed with potassium nitrate
are reduced by the ferment, butyric acid being formed and nitrogen
and nitrous oxide evolved, but no hydrogen is given off. Reduction
also takes place in presence of ferric hydroxide, which is converted into
ferrous butyrate. Nitrogen and nitrous oxide are apparently the sole
products of the reduction of nitrates by the butyric ferment.
The ferment appears to exist in the soil in a very pure state and
the fermentation of sugar by means of such soil may be employed
for the preparation of butyric acid. After fermentation, the liquid,
which still contains a considerable quantity of unaltered sugar, is
evaporated to dryness, and distilled several times with small quantities
of water and an excess of boric acid. In a paraffin-bath at 160°
almost the whole of the butyric acid is rapidly obtained in the distil-
late, which is exactly neutralised with sodium bicarbonate, evaporated
to dryness, and the sodium butyrate recrystallised from alcohol.
The importance of the destruction of nitrates in soils caused by this
butyric ferment is obvious. It is found, however, that the fermenta-
tion does not take place in presence of lime, even in small quantities.
O. H. B.
Reduction of Sulphates by " Sulfuraires," and Formation
of Natural Mineral Sulphides. By Plauchud (Compt. rend., 95,
1363 — 1365). — In n former paper (this Journal, 31, 704) the author
proved the hydrogen sulphide present in water containing vegetable
matter to be due to the action of some species of Go7ifervce (i.e.,
beggiotoa, osclllat-ia, ulothrix^ &c). These algae, which are vaguely
designated " sulfuraires," have the power of reducing sulphates. The
author's present results confirm those of Etard and Olivier (Compt.
reiid.j 95, 846). Small quantities of chloroform or phenol arrest the
activity of these algae ; phenol in larger quantities kills them. Life-
less organisms have no reducing influence on sulphates. The granules
of sulphur often deposited in the cells of "sulfuraires" are sulphur.
Some "sulfuraires" hermetically sealed between plates of gypsum and
left for some months, gave in one instance a few granules of sulphur.
The author believes the formation of natural mineral sulphides to be
due to the reducing action of this class of algoe. L. T. T.
VEGETABLE PHYSIOLOGY AXD AGRICULTURE. 611
Influence of Chemical Agents on the Assimilative Capacity
of Green Plants. By T. Weyl (Bied. Centr., 1883, &h).—Elodea
canadensis was employed in this research. A 1 per cent, solution of
phenol suppresses the expiration of gas, and in 20 minutes turns the
plant brown, whilst 0*5 and 0*25 per cent, solutions only reduce the
quantity. Saturated solutions of salicylic acid and thymol act more
rapidly and effectively than phenol. Strychnine nitrate turns the
plant yellow, and hinders the expiration of oxygen, bnt dilute solu-
tions of morphine hydrochloride and veratrine have no effect. Strong
solutions of sodium chloride, even if sodium phosphate is present, and
dilute sodium hydroxide solutions are harmful. On the other hand,
in a one per cent, solution of acid sodium carbonate, more oxygen is
evolved than in plain water. E. W. P.
Assimilation by Hsematococcus. By T. W. Engelmann {Bied.
Centr., 1883, 36). — Rostafinski has stated that hsematococcns was
able to decompose carbonic anhydride without the assistance of
chlorophyll. This the anthor shows to be incorrect, and that the red
hsematococcus, although apparently unaccompanied by chlorophyll, is
not so, but that the latter is present, although to- a small extent.
E. W. P.
Presence of Formic and Acetic Acid in Plants. By E.
BoRGMANN (Bied. Centr., 1883, 65). — In a great ntim be r of plants, and
in various parts of those plants, whether chlorophyll is present or
absent, formic and acetic acids have been detected. In chlorophyll-
bearing plants, the percentage of acids rises when assimilation is re-
pressed by removal of light, -so that it would appear as if the
substances were the product of regressive metamorphosis. Below
the minimum temperature of growth, the acids are not formed, and
since there is no respiration, acetic and formic acids are evidently
dependent on respiration for their formation. E. W. P
Occurrence of Coniferin in the Woody Structures of the
Beetroot. By E. O. v. Lippmann {Ber., 16, 44 — 48). — It has been
previously shown by the author (Abstr., 1880, 646) as well as by
Scheibler (Abstr., 1880, 467) that vanillin is present in certain kinds
of raw beetroot sugar, but ifs origin -has not been explained. The
author shows that it comes from the decomposition of coniferin, but
from the difficulty with which the latter is extracted by water, the
coniferin cannot exist in the free state in the beetroot, but is probably
in combination with the lignin. A. K. M.
Poisonous Principle of Edible Mushrooms. By G. Dupetit
(Gompt. rend., 95, 1367 — 1369). — The author finds that all mushrooms
contain a poisonous substance when uncooked. The fresh sap of the
Boletus edulis administered to rabbits, guinea-pigs, and rats, by sub-
cutaneous injection caused their death. The sap of Amanita ccesarea,
Amanita vaginata, Amanita ruhescens, Agaricus campestris, &c., has a
similar action. The sap of Amanita ruhescens is poisonous to frogs,
whilst that of the others is not. The poisonous action is due to some-
thing in solution, and not to extraneous microbes, as sterilisation by
612 ABSTRACTS OF CHEMICAL PAPERS.
means of a Pasteur's filter does not render the liquids innocuous. The
active principle is insoluble in ether, chloroform, alcohol, &c., and is
precipitated from the sap by the addition of alcohol, tannin, &c. It
thus resembles the soluble ferments and not the known alkaloids. A
temperature of 100° renders all these mushrooms innocuous. The
author has also obtained two alkaloids, apparently nevrin and
ptomaine. L. T. T.
Diseases of Plants and their Prevention. By C. Niessinq
and others (Bled. Centr., 1883, 51 — 54). — Barberry plants growing in
hedges should be removed, as they harbour the germs of " rust " {Puc-
cinia graminis), which germs are developed most readily during damp
summer evenings at a temperature of 12"5 — 15°. Plants of Mahonia
aquifolium bear Aecidium berberidis, the first generation of Puccinia,
they should therefore also be removed from the neighbourhood of
fields of grain. This also applies to the blackberry and buckthorn.
According to Kiihn "smut" (Ustilago carbo) on barley and oats may
be avoided by pickling the seed for 12 hours in dilute sulphuric acid
(1"5 : 100). Copper sulphate is active against "smut" as against
wheat bunt (Tllletia caries and T. Icevis), but it may injure the
germinating power of the seed. Prilleux describes the mode of action
of Feronospora Schachtn, which, although well known in Germany, has
but just commenced its attacks on the beets in France. Drechsler
recommends treating beet seeds and the beets themselves with crude
phenol dissolved in 100 parts water, to preserve them from the
attacks of insects — Julus guttulatus and Atomaria linearis. This
treatment has no deteriorating effect on the seeds or root.
E. W. P.
Poisoning of Plants. By C. Krauch {Bied. Centr., 1883, 46—49).—
It is well known that certain solid and gaseous substances act destruc-
tively on plants ; in this article we have additions to the literature of
the subject. Ammonium thiocyanate (0"25 gram and upwards per
litre) is a powerful poison to germinating as well as to developed
plants. Solution of zinc sulphate (O'l gram per litre) kills barley
and grasses, previously causing brown spots to appear on the leaves,
but what the action is remains unknown. Sodium chloride, in small
quantities, acts as a manure, but when its concentrated solutions are
applied to grasses, they die, and their ash contains an abnormal
percentage of this compound. In practice, manuring with salt may
produce undesirable results if the weather be dry, for then its solutions
became concentrated, and, moreover, chlorides of calcium, magnesium,
and potassium are formed, and washed away as well as phosphates,
which are rendered soluble by sodium chloride. E. W. P.
Cultivation of Cereals. By Strebel and others (Bied. Centr.,
1883, 41 — 44). — Reports from Hohenheim and elsewhere on the yield
of varieties of wheat, barley, &c. E. W. P,
Cultivation and Feeding Value of some Varieties of Vetches.
By W. DoHN and F. Nobbe {Bied. Centr., 1883,30— 32).— The kind of
vetch grown by Dohn is not clearly stated, but it appears to have
I
^^:GETABLE PHYSIOLOGY AND AGRICULTURE. 613
been either a variety of the ordinary field pea or Vicia sativa dura,
hut the yield was good, and the straw was nourishing and palatable.
Nobbe reports on the cultivation of tufted vetch ( V. cracca), bush
vetch ( V. sepium) , and meadow vetching (Lathyrus itratensis) on a
sterile soil which was useless for the growth of clover. The com-
position of red clover is compared with that of tufted vetch, and we
find that the latter is much richer in protein, poorer in fat and fibre
than the former. The yield also was double that of clover. The seeds
of wild vetches frequently fail to germinate, even after long steeping
in water; this is due to the very hard outer coating; to remedy this,
it is recommended to shake the seeds in a sack with sand, which pro-
cess, although damaging some of the seeds, raises the percentage of
germination. E. W. P.
Comparative Feeding Value of Symphytum Asperrimum.
By H. Weiske and others (Bied. Gentr., 1883, 33 — 35). — The composi-
tion of this fodder-plant was : albuminoids, 19"88 ; fat, 2*69 ; fibre,
13*19 ; extractive, 42-39 ; ash, 21 "85 per cent. ; and of this a South-
down merino, when fed with it and an equal weight of hay, digested —
Dry matter. Org. matter. Albumin. Fat. Fibre. Extract. Ash.
5-21 69-27 58-3 71-1 18-05 84-64 4-9
Or, making allowances for admixture of sand, the comfrey contains of
digestible albuminoids 11-59 per cent. ; fat, 1-9 ; fibre, 2-38 ; extract,
35-88. Stutzer finds only 0*66 per cent, of the fresh leaves to consist
of digestible albuminoids, whose nitrogen is present in the following
forms: — 25-79 per cent, of digestible albuminoids, 26-76 as amides,
47'35 as indigestible nuclein, so that this fodder is less valuable than
good hay. The editor adds a note, in which it is shown that if
Stutzer's percentages are referred to total dry matter, comfrey appears
to be much richer in protein than meadow-grass, and to contain more
digestible protein, as well as wholly digestible amides. E. W. P.
Cultivation of Gombo. By T. Gr^goire (Bied. Gentr., 1883, 44).
— This plant (Hibiscus esculenfus), known in Marseilles as "gombo,"
is recommended for cultivation on account of its nourishing properties.
No analysis is given. E. W. P.
Removal of the Leaves of Roots. By P. Geibel and others
(Bied. Gentr., 1883, 39), — The leaves of turnips are frequently used as
green fodder ; but their removal acts prejudicially on the weight of
the crop. Experiments on sugar-beet show that not only is the
quantity reduced, but the quality likewise, the sugar being reduced by
3' 7 per cent. The leaves are also less nourishing than young grass.
E. W. P.
Biological Researches on the Beetroot. By B. Corenwinder
(Gompt. rend., 95, 1361 — 1363). — The author has cultivated beet
under three different conditions : a, in pure sand, watered with
chemical manure free from carbonates and organic matter ; b, in a
field prepared in the ordinary way ; c, in highly manured mould. After
about ihree months, the percentage of sugar in samples taken from each
614 ABSTRACTS OF CHEMICAL PAPERS.
section was : a — 5'4o ; h = 2*85 ; c = 4-10. After 6 — 7 months,
a = 12-26 ; 6 = 9-0; c = 10'60. The weight of the beet prepared
under condition c was, however, more than double that of the others,
and therefore the total quantity of sugar produced was much larger.
From these experiments, the author concludes that in soil deprived of
organic matter the beet obtains all its carbon through its leaves from
the carbonic acid of the air ; in soil of average fertility the greater
part of the carbon is still assimilated through the leaves ; in soil of
great fertility, a great deal is also derived from the organic matter of
the soil. L. T. T.
Employment of Dried Potatoes. By Kohne and others (5/e(Z.
Gentr., 1888, 69). — Potatoes are to be sliced by a machine and then
dried in a chicory kiln, whereby 64 — 65 per cent, of their weight is
lost. A mash made from such dVied potatoes ferments normally ; it is
expected that this process might be employed with advantage, should
there be any great outbreak of potato disease. E. W. P.
Comparative Meteorological Observations in: Forests. By
Eankhauser (Bied. Centr., 1883,^. 6 — 9). — The observations, carried
out in^ the Canton of Berne during 13 years, take cognizance of
the temperature of the soil and air inside and outside the forests,
also of the temperature of trees, moisture of" air, &c. The yearly
mean temperatui-e of the same parts of the upper soil is generally
the same, it is lower in the forest than in the open, a difference
also is noticed between by soils overshadowed by evergreen or
deciduous trees ; the greatest difference of temperature occurs in the
summer. The mean temperature of the air is lowest in the forest, the
greatest difference occurring in summer. The highest parts of the
trees are the warmer, and the interior is colder than the surround-
ing air. In spring and summer the trees are warmer, in autumn
and winter colder than the soil. The air of the forest is moister than
that of the plain. In the whole year, the soil of the forest receives
15' 9 per cent, less rain than the open country. These results agree
with those obtained and published by Ebermayer. E. W. P.
Influence of Climate and Weather on the Amount of Car-
bonic Anhydride in Terrestrial Air. By E. Wollny {Bied.
Gentr.j 1883, 9 — 12). — The amount of carbonic anhydride which is so
necessary to vegetable life, depends on the quantity produced in the
soil, and on the amount which passes off into the atmosphere ; the
factors which affect the production are temperature, moisture, and
aeration, and these factors do not all act in the same direction, but in
varied and complicated combinations when the air-pressure, direction,
and force of wind remain the same. The evolution is dependent on
the resistance presented by the particles of the soil, for when the soil
is dense, consisting of fine particles, and the interstices are filled with
water, then the resistance is increased.
In consequence of all these conditions, the percentage of gas in the
superior layers is very variable, and in such a climate as that of
Munich, where the rainfall is fairly constant, but the temperature
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 615
very varying, the amount of carbonic anhydride found in the soil
alters very considerably. When the air of the soil is warmer than
the external air, then atmospheric air enters, and the carbonic anhy-
dride is diluted. A horizontal wind current also lowers the percent-
age, thus in a mixture of peat and sand the percentage was reduced
from 1"92 to 1*69, in humous chalky sand from 3'42 to 3"08, and in a
compost from 2*94 to 2-39. When a soil is covered with vegetation,
then the rainfall has great effect in regulating the percentage present,
whilst in bare soils it is the temperature that exerts most influence.
E. W. P.
Rise of Temperature induced in Soils; by the Condensation
of Liquid and Gaseous Water and ctf Gases. By A. Stellwaag
{Bled. Ceritr.f 1883, 12 — 14). — Different soils were submitted to the
action of water in properly constructed appaiiatus. The rise of tem-
perature was the higher the drier the original state of the soil, the
finer its condition, and the lower tlie outside temperature ; a humous
chalky sand was raised 8*33°, ferric hydroxide 6*60°, and clay 5'57° ;
when the water contained plant food, the rise was less. When the soil
condensed water vapour, the rise was more remarkable, humus rising
12'25°, and fferric hydroxide 93% kaolin 2*63°. When dry carbonic
anhydride was condensed, the increase was but slight ; but when this
gas was moist, then the rise was more remarkable (peat 11*80°, ferric
hydrate 11*80°) ; dry ammonia gas caused a rise in the temperature of
humus of 28-3°, of ferric hydroxide of 18-05°. E. W. P.
Decomposition of Nitrogenous Animal Manures. By A.
Stutzer and W. Klingenberg (Bied. Gentr., 188S; 14 — 17). — ^Morgen
and Petermann have investigated the solubility, deqomposition, &c.,
of the nitrogenous matter of animal manures; But the authors have
investigated the actual power to produce effects by determining the
amount of soluble and insoluble (nucle'in) albuminoid matter by
means of hydrochloric acid solutions of pepsin ; this solvent acts in an
analogous, although not identical, manner to the ferments present in
the soil. All animal and vegetable matter contains nuclein, even
peat and coal. A table is appended which gives the percentage of
soluble and insoluble nitrogen in various waste products : blood meal
contains 89' 7 per cent, of its total nitrogen, soluble leather meal, on
the other hand, only 39 per cent. ; nearly all the nitrogen of wool
waste is insoluble, and part of that ia bones is rendered insoluble by
steaming. E. W. P.
Evaporation of Water from the Soil. By P. Masure (Bied.
Centr., 1883, 1 — 6). — The soils submitted to experiment were Loire
sand, chalky soil consisting of sand 1*6 per cent., chalk 96 per cent.,
clay 2*3 per cent. ; clay soil, consisting of sand, 4 per cent., clay 95*6
per cent. ; garden soil, consisting of sand 61 per cent., chalk 12*6 per
cent., clay 20 per cent., stable manure 5'3 per cent. The following
table shows the effect of the character of the soil on the amount of
moisture retained, &c. : —
G16
ABSTRACTS OF CHEMICAL PAPERS.
1 CUD
1
1
1
•
,d
B
^
^
£
^CDCO
'^O
•Sf^
^
? 1?
> -l^o °o
«
•^«
0
§ lO o
5 f rd 00
^ '-co t^
^ •
1
|o^
1-
^
o
1
1-^
^
a
1
1
1
2qO;S
1?.
- 1?
^o
00 5 c
■> ^05 0
V
X. «
-g X. 00
^o b
• ^ O t-H
1-K
1
fs
1
-gob
1-
1
a
b ^0-
1
i-H
1
^ o
'bJcT'
^2
nS
r^O O
'^^O
> 1?
■3
i>
• |c
' •&?
> °o
^
o
o
S^-r^
.St^cr
.«>
^ ^r
< t»
fH
1
F
03
^ bo
crW
—1 o
rd
*"
>
1 ^c
) o
1-1
^
■§
rM OJ>
-^-^^
js ^
^
s
^ ®c
^ V.
°o
V
00
gMCO
•§?»c.
5 W^O
§>
a
5 ^ <X
> uj-r
(N
iH
1-1
1
^ o o
&.^
^O
-^
c
> cS^
^ c
3
I
• '-^.— ^
• ,^~x^
o
?
.
. .
■M
■73
: F
d
S
t4
ill
^
• ©
•5
'3
be
"d^w
■TS
,c|
c
: a
j^
o
;*— V
— '
c
1
'a
^
-73
d
d
o
; a1
1
■4^
5 (-(
©
I
d
1
%
1
■^
S.2
£ i
1
g
J
u
©
o
2
a"
o
2
-5
Ci.
T!
c3
1?
g
bO
-
fe2
o
II
II
A
"2
E
Id
o
1
i
-2
1
1
S2
i
?51
PermeabiUty estimated in the m
Ratio between the days on w
remaining period
1
1
1
1
■J
1
DQ
1
o
o
a
t
ti
1
a *"
|-3
CM O
£
d
1
a
©
II
■^1
0 ■§
1 I
Drying after ai
Rapidity of ev
Duration of dr
1 Density. Mec
drying
Belative amoui
.2 §
§-1
t?l
© S
^ a
2 ©
11
■^3
bD
1
3
a ^
1}
S
3
e
w;
^
CD
s
e
3
1
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 6l7
The deductions to be made from examination of this table are of
considerable importance ; sand retains bnt little water and soon dries,
on account of its porosity and density; a small supply of water is
retained in the lower layers, and its hygroscopic power causes a suffi-
cient condensation of water to take place on its surface. Farmyard
manure must be added plentifully to render cultivation satisfactory.
Chalky land is less dense, absorbs less water, becomes less hot when
exposed to the sun, and is more easily aerated ; such a soil must be
cultivated like a sandy soil, but is more productive. Clay soils hold
much water and dry slowly, and their high hygroscopic power pre-
vents them from becoming too dry, and as they are easily heated by
the sun, manure rapidly decomposes, also the amount- of oxygen which
they are capable of absorbing, greatly aids plant growth. Farmyard
manure retains the greatest amount of water, yet by reason of its
porosity it soon loses the excess of water, but from its hygroscopic
power still retains sufficient moisture ; when on the surface it readily
absorbs dew, carbonic anhydride, ammonia, and nitrates.
E. W. P.
Manuring Experiments in Holland. By G. Reinders {Bied.
Centr., 1883, 17 — 27). — These experiments, commenced in 1870 on
different farms, were conducted on the principles recommended by Ville,
in which artificial manures containing all the ingredients necessary
for plants are to be used. On one plot, therefore, a complete mixture
was used, whilst to the others the same mixture, less one or other of
the ingredients, was added. With oats and wheat, the omission of
nitrogen resulted in a reduction of straw, and the omission of phos-
phates, a reduction in the yield of grain. Compared with the artificial
manure, farmyard manure produced much lower yields. The absence
of phosphoric acid in all cases was most detrimental to the crop, then
next the absence of nitrogen (Chili saltpetre), and finally potash;
superphosphate mixed with Chili saltpetre produced the highest
results. When the crop was rape, the absence of phosphates and
nitrogen was equally harmful. The advantage of phosphates to
red clover and vetches was undoubted, whilst potash at one time
seemed to influence the grain, at another the straw, although it seems
to exert the greatest effect on those plants, as beans and wheat, whose
ash is rich in potash. The highest net value of the crops was
obtained from those plots which had received no magnesia, as this
element was given in a pure and expensive form. In one case when
ammonium sulphate was used, the value of the increase in the crop
did not cover the expense of the manure ; but when Chili saltpetre
was employed, a profit was made, and this last result was obtained
at more than one of the stations. There was only one case in which
a crop manured with Chili saltpetre was unsatisfactory, namely, clover
sown together with rye, but this was most probably due to the
choking of the one crop by the other. E. W. P.
Manuring of Forest Trees. By M. E. Muel (Bied. Centr., 1883,
27 — 30). — Young oaks, beeches, firs, and pines were manured with a
complete mixture, also with a mixture containing no nitrogen, and
VOL. XLIY. 2 t
()18 ABSTRACTS OF CHEMICAL PAPERS.
witli ammonium sulphate. The resnlts do not seem to he very satis-
factory; the complete manure did not produce effects suflBcient to
compensate for the expenses incurred, and nitrogen was harmful.
On the other hand, the incomplete manure (containing no nitrogen)
was more advantageous to the growth of the young seedlings than to
that of the other plants. E. W. P.
Analytical Chemistry,
VapoTir-density Determination. By Y. Meyer (Ber.^ 15, 2775
— 2778). — The author offers some remarks on his system of vapour-
density determination now so generally adopted by chemists, but
draws attention to the fact that when first introduced, it was recom-
mended as applicable to the determination of the vapour- den si ties of
bodies whose boiling point is higher than 440°, which attack mercury
or Wood's metal ; for other substances, various suitable methods were
already known, and the method which most sharply and accurately
gives the results in each case is the most suitable for use with that
particular substance. If the air displacement method gives generally
satisfactory results, and is in some cases the only method that can be
employed, the author does not himself think that at lower tempera-
tures it possesses the almost absolute freedom from error of the
methods of Dumas, Gay-Lussac, and Hofmann, or of the author's pre-
viously described system of displacement by mercury or Wood's
metal.
In the vapour determinations of new substances during last year,
those made by the air displacement method did not differ from the
theoretical numbers more than those made according to other methods,
but too much importance should not be attached to this, as those new
substances may contain impurities, the quantity at the disposal of the
operator may be insufficient, &c. For the purpose of comparison of
methods, only known and quite pure substances should be used, as in
the author's published determinations of naphthalene vapour : by the
mercury method he obtained the figures 4*41, by the air displacement,
4" 52, theory demanding 4*43, the former agreeing well with theory,
the latter being 0*09 too high, and the author thinks that under ordi-
nary circumstances this method yields results slightly too high.
Pettersson and Ekstrand assert the contrary, and say the results are
too low, but they work under different conditions. These variations,
however slight, should be avoided, and the older and more exact
methods employed when practicable, the air method being reserved
for cases such as it was originally intended to meet. Thus restricted,
there is a large field for its employment in new determinations, such
as the dissociation of iodine, &c.
For bodies which boil about 260°, and bear to be heated 30° over
ANALYTICAL CHEMISTRY. 619
their boiling point, he advises his own mercury process as being
simple and exact, provided the substance does not attack mercnrj. It
requires but about 35 cm. mercury, and is rapid.
For substances which do not vaporise unaltered at atmospheric
pressure, or do not bear heating beyond their boiling point, if they do
not boil higher than 310°, and are neutral to mercury, Hofmann's
method is recommended.
For bodies which volatilise with difficulty, do not attack metals, and
boil between 260° and 420°, the. author's method with the use of
Wood's alloy is suitable.
For substances with a higher boiling point, and which attack
metals, the air displacement system is suitable.
In rare cases, when a body vaporises with difficulty under diminished
pressure, Dumas's method modified by Habermann is recommended.
J. F.
Manufacture and Correction of Burettes. By W. Ostwald
(/. pr. Ghem., 25 [2], 452—458). — The author calls attention to the
almost invariable inaccuracy of the graduation of burettes as obtained
from the instrument makers, and to the necessity of a careful calibra-
tion of each instrument. He has frequently found the error due to
the graduation to be many times that of the analytical process.
A. J. G.
Storage of Oxygen in Zinc Gasholders. By J. Loewe (Ann.
Phys. Ghem. [2], 18, 176). — In order to store oxygen in zinc gas-
holders with safety, and to guard against explosions such as that
experienced by Pfaundler (vide p. 524), the author has adopted the plan
of hanging a linen bag filled with slaked lime in the water near the
tube through which the water flows into the gasholder. The lime-
water thus formed absorbs all the carbonic anhydride and acid vapour.
The lime does not require renewal even after several years' use.
Estimation of Phosphoric Acid in Arable Soils. By P. de
Gasparin (Gompt. rend., 96, 314—315). — Twenty grams of the soil,
finely powdered and passed through a hair sieve, are treated in a por-
celain capsule with dilute hydrochloric acid (1:4) until effervescence
ceases, 80 c.c. of aqua regia added, the mixture evaporated on the
water-bath to a syrupy consistence, diluted with cold water, filtered,
and the residue washed with hot water. The filtrate is mixed with
ammonia in excess, and the precipitate which forms is collected, dried,
calcined in a platinum capsule at a cherry-red heat, and powdered.
It is then digested in the cold with dilute nitric acid (1 in 40), and
the liquid filtered. The filtrate contains the whole of the phosphoric
acid, free from lime, iron, and silica. It is concentrated on the
water-bath, precipitated with ammonium molybdate, the precipitate
washed once, dissolved in ammonia, and the phosphoric acid precipi-
tated with magnesia mixture.
This method gives higher results than the old method, which en-
tailed loss. After the concentration of the dilute nitric acid solution,
2 t 2
620 ABSTRACTS OF CHEMICAL PAPERS.
tlie phospliorus is present entirely as tribasic phosphoric acid, having
probably been brought into this condition by ignition with the ferric
oxide, &c. C. H. B.
Estimation of Phosphoric Acid in Manures. (Divgl polyt. J.^
247, 85 — 93, and 125 — 130). — Wagner has made a series of experi-
ments as to the extraction of superphosphates by water, and concludes
that in the case of double superphosphates and Lahn-phosphorite
superphosphates it is necessary to digest for 24 hours, whilst for
other superphosphates it suflBces to digest for two hours. It is
further stated that ammonium citrate extracts larger quantities of
phosphoric acid from normal phosphates than " citrate " solution
containing free ammonia or ammonium carbonate does, and that
addition of ammonia to the alkaline citrate solution does not materially
alter the results obtained.
At a meeting held at Halle to consider the methods for estimating
different forms of phosphoric acid, the following conclusions were
arrived at. For the estimation of soluble phosphoric acid, 20 grams
of superphosphate are mixed with water in a mortar, and transferred
to a litre flask. The mixture is made up with water to the mark, and
allowed to digest for two hours, the flask being shaken from time to
time. The volume of the undissolved residue is disregarded in the
subsequent calculation. For the separation of iron and aluminium
phosphates in superphosphates containing about 20 per cent, phos-
phoric acid, 200 c.c. oi the filtrate are treated with 50 c.c. ammonium
acetate (100 grams pure ammonium acetate and 1 00 c.c. concentrated
acetic acid per litre). The precipitate is filtered off, washed three
times with hot water, ignited, weighed, and one half calculated as
phosphoric acid. For superphosphates containing more than 20 per
cent, of phosphoric acid, 100 c.c. of the above filtrate are diluted with
100 c.c. of distilled water and treated as above described. The
volumetric estimation of phosphoric acid is applicable to all super-
phosphates which do not contain more than 1 per cent, phosphoric acid
in combination with ferric oxide or alumina. A solution of uranium
nitrate is used, its normal strength (1 c.c. uranium = 0'005 phosphoric
acid) being obtained by dissolving 1000 grams pure uranium nitrate in
28"2 litres water, and neutralising any free nitric acid which may be
present by adding 100 grams ammonium acetate. The solution is
standardised with a solution of superphosphate as above prepared, or
with tricalcium phosphate dissolved in the theoretical quantity of
sulphuric acid, the phosphoric acid in these solutions having been
previously determined by the molybdate method. For the titration,
50 c.c. of the superphosphate filtrate are taken, the end reaction being
determined by potassium ferrocyanide.
The gravimetric determination of phosphoric acid is effected by the
known methods, and it is also recommended to use the condensed
method proposed by Wagner. For this purpose, 25 c.c. of phosphate
solution free from silicic acid and containing 0*1 to 0*2 gram phosphoric
acid are treated with ammonium nitrate and molybdate solution, so
that the total liquid contains 15 per cent, ammonium nitrate, and for
0*1 gram phosphoric acid, 60 c.c. molybdate solution. After heating it
ANALYTICAL CHEMISTRY. 621
to 80—90°, and allowing it to settle for an hour, tlie solution is filtered
and washed with weak ammonium nitrate. The precipitate is dis-
solved in ammonia (of 2*5 per cent.), so fcliat the total quantity of
liquid amounts to 75 c.c. To this solution 10 c.c. magnesia mixture
of the usaal strength is added for O'l gram pkosphoric acid. The
precipitate is allowed to stand for two hours and filtered off. Refer-
ring to the phosphoric acid soluble in citrate solution, it is recom-
mended by Petermann to mix 6 grams superphosphate with 100 c.c.
citrate solution; the mixture is transferred to a 250 c.c. flask,
agitated for an hour at 40'', and filled with water to the mark. The
phosphoric acid is then determined in the filtrate. In estimating bone
jblack, ignition, especially of fermented bone black, is objected to, and
in its place wet oxidation by means of potassium chlorate is recom-
mended. Fish guano, animal excreta, and similar raw materials, are
treated in a like manner. D. B.
Estimation of Sulphurous Acid in Wine. By Y. Waetha
(Ber., 16, 200 — 201). — A continuation of the discussion between the
author and Liebermann on this subject.
Mechanical and Chemical Analysis of Soils. By A. Orth
(Ber., 15, 3025 — 3034). — By means of sieves, the soil is separated into
particles of 5, 2, 1, 0'5 and 0'2 mm. diameter. A further division of
the more finely divided portion is effected by taking advantage of the
■time required by the different sized particles to be deposited from a
stream of running water. The author points out the necessity of
making a separate analysis of that portion of the soil which is present
in particles of less than O'Ol mm. diameter, in order to form a correct
opinion of the true value of the soil. W. C. W.
Separation of Nickel from Cobalt. By G. Vortmann (Monatsh.
Chem.j 4, 1 — 9). — The author, after pointing out the defects of all the
ordinary methods of separating these metals, suggests the following
process, depending on the oxidation of cobalt salts in ammoniacal
solution by sodium hypochlorite. When such a cobalt solution mixed
with sal-ammoniac is treated with this reagent, complete oxidation
takes place, even at ordinary temperature, the liquid assuming a red
colour. The reaction is accelerated by boiling, the solution in a few
minutes assuming a deep reddish-yellow colour, and then containing
the cobalt chiefly in the form of a luteo-cobaltic salt. On diluting
with water after cooling, and adding a small quantity of potash-solu-
tion, the liquid, if it contain nothing but cobalt, will remain clear
even after standing for several hours, but nickel if also present will
be deposited in a short time as hydroxide. In this manner, mere traces
of nickel may be detected in a cobalt solution, and likewise a very
small quantity of cobalt in presence of nickel. A blue ammoniacal
solution of nickel containing a very small quantity of cobalt usually
exhibits, after treatment in the cold with sodium hypochlorite, a dis-
tinct red-violet colour ; but even if the quantity of cobalt present is
too small to produce this effect, the liquid, after dilution with water,
622 ABSTRACTS OP CHEMICAL PAPERS.
addition of potash-lye, and filtration from precipitated nickel hydroxide,
will exhibit a faint yellow colour ; and if the quantity of cobalt be too
small to produce even this faint coloration, its presence may be detected
by the black precipitate formed on addition of ammonium sulphide.
If the quantity of cobalt present is sufficient to give the solution a
strong red colour, the cobalt-ammonium compound contained in it
will be decomposed on boiling, with separation of brown cobaltic
hydroxide. As nickel hydroxide "is dissolved in small quantity by
ammonia, even in presence of potash or soda, care must be taken in the
first stage of the process not to add too large an excess of ammonia,
as it would then become necessary, in precipitating with potash, to
dilute the liquid to a considerable extent, which would interfere with
the subsequent operations.
The author gives the details of a number of experiments made by
this method, showing that in many cases it gives results more exact
than those which are obtained by the use of potassium nitrite or potas-
sium cyanide. H. W.
Analyses of some Moscow Waters. By P. Geigoeefp {Jour.
Buss. Ghem. 8oc., 1882, 328 — 340). — Moscow is at present very badly
supplied with water. Good water .comes chiefly from the sources of
Mitischtschi and Sokolniki, and from the Cholodinsk wells, but in
such small quantities that only a few gallons per diem are available
per head of the population. About 15 times as much had water is
drawn from the old wells and from the rivers laousa and Moscow. In
order to find new sources of good water, and to compare the quality
with that of the water used at present, the author has analysed eight
different kinds of water, and for this purpose he used chiefly methods
recommended by Kubel and Tiemann. The results of the analyses of
the following samples are given in the tables below. (1) and (II) water
from Mitischtschi wells, (III) from Sokolniki, (lY) from the source
of the E/iver laousa, (Y) from the junction of the same river with the
River Moscow, (YI) from the well of Chodynsk, (YII) from an arte-
sian well, (YIII) from an artificial well. The first table gives the
direct results of analysis ; in the second table the quantities of salts
were calculated from the data obtained in the first table. The quan-
tities given in both tables refer to 100,000 parts of water.
ANALYTICAL CHEMISTRY.
623
ifl O O CO O
1> iH N X> OS O
m tH
« (MX>
CD
CD
1
M*
1— 1
Tfl ^ Cq r^ 05 iH ip in cp O CO ^^
tracei
6-6
1-6
60-4
107-9
wsoo-^tHih iTHTjiiiaocbi) 1 go
P
t^ O CO Cq <N •* i-H rH +3
J> 00
T? 00 U5 CO CC 00 ■* ■<# CO 00 O O CO iO
(MOkni>.0 1 OiHCO(N>OOi(NO(N
traces
0-40
0-10
23-90
42-68
M
;>
OOqiOOt^ OiH(M00(NrHOO00
00t> 03 iH iH
'^
l§^?^?l^?^^^ I§i
W5 (M COi>
M
1 00 <N Tfi i>
>
O iH l> i-l (M O iH rH (H iH O tH O 05
o o -^ o
eo <M fH
fH (M
Tfioo-^00 STfiooo-*t>oo Soocc
,S?g^S
>■
(N«5rH0S>p Or-l9(N900r? OCOCC
THOCOOG<lJoNOS<MtHfH^Oj^
^^ss
IflCO-^USi^ 1> i-H '^ lO rH T? O C
iHO-^OOO ItHeHrHCpoOOOi-l l"^
i??3?
>■
M
o o 00 o o o o CO o o o b c
I— 1
CO tH -**>
OJCOt^kO-^ OS iH VO 1-1 fH O S '^ O t> jH CO
(NQDrfOTp lOOOSOTflCOipo |t» c^WSCOCO
OXC0(NO OONOOO^ CO (N b(M -*
M
1— (
1— 1
00
(M m CO
iHOOCOeO(MOO(Mt^iMOOOoOO 05eO"05VO
1—1
Cq«r:^(NOCOrHCNI(M9lNCpo99 j00(NCO9
O "^ rH iH O O O O lO iH O O is O CO O O CO i-i
M
fH iH "^
fH
CO
00 t^
00 O lO O -^ fH (N ff5 ^ OS 05 N O O O CO « CO CO 1
M
fHI><p(NOCq—liH"*J<07-OTH9r-
t* iH '3i TP 1
O '^ <M rH O O O O lO fH O O O O CO ' O O CD 22
•H iH iH
/—
s • »-
"I
* O
!=
:|
^ « 1
o
1
i
I t3 o ^ M
S C3
itter .
atl)
calci:
0
led for 0
same pu
French
s^s
t
'^1^
«
• ^ « «
a
1
> 2
1
2a
11
J
If
i
f^
'it
>
=
624 ABSTRACTS OF CHEMICAL PAPERS.
Table II.
I.
II.
III.
IV.
y.
VI.
VII.
VIII.
KCl
0-25
0-05
0-92
0-20
2-28
9-18
0-46
0 15
0 03
0-10
1-20
0*46
0-94
0-32
2-14
8-58
0-70
0-25
0-02
1-23
0-50
0-94
0-13
0-66
0-29
3-30
0-59
2 05
0-22
0-13
0-26
0-48
1-36
5-45
0-27
0-10
0-85
2-95
111
2-05
0-96
3-61
16-42
1-33*
0-94
0-58
1-76
0-96
2-73
2-18
19-30
0-24
2-22
0 05
1-40
2-39
1-98
27-25
24-78
8-04
16-11
0-12
0-20
0-76
25-52
NaCl
16-23
MgClg
3-34
K2SO4
^8^804
MgS04
CaS04
K2CO3
Na2C03
MgC03
CaC03
Ca3(P04)3
Ca(N03)2
NH4NO3
Fe203 + AI2O3..
SiOo
27-79
22 72
44-98
32 15
1*13
Total
14-82
14-64
8-46
9-12
29-37
31-42
81-63
173 -86
B. B.
Examination of Molasses for Dextrin Syrup. By C. H.
Wolff {Bingl. polyt. J., 247, 228). — The author dissolved blackish-
brown cane-sugar molasses in water, agitated the solution with lead
acetate, then with a solution of alum and animal charcoal, and filtered
the mixture. The colourless 10 per cent, solution was placed in a
200 mm. tube, and produced a rotation of +7°, hence its specific
rotatory power amounted to +35**. A 10 per cent, solution of pure
dextrin syrup rotated 25'6°; its specific rotatory power therefore
equalled +128°. Two samples of light brown molasses showed a
specific rotatory power of +97° and +88°: hence they contained
Q6'6 and 57 per cent, dextrin syrup respectively. D. B.
Estimation of Starch in Grain. By G. Feancke (Bied. Centr.,
1883, 37 — 39). — The method of conversion of starch by a glycerol
malt extract at 140° is inaccurate ; the result is always low. Analy-
tical figures are quoted to prove that modifications of this process do
not yield very satisfactory results; neither could good determinations
of starch in rye, maize, and dari by means of hydrochloric or sul-
phuric acid be made, and the author states his opinion that for the
present the method of conversion by water or lactic acid at high
temperatures must be retained. E. W. P.
Genesis of Ptomaines. By F. Coppola (Oazzetta, 13, 11 — 14). —
The author, in continuing his experiments on this subject, already
noticed (this vol., p. 522), arrives at the following conclusions: —
1. Arterial blood in its normal state does not contain any substance of
alkaloidal nature. 2. In the decompositions which albuminoids
* i.e., 9 -20 NH^NO^, and 1 '13 (NHJ^SO^,.
TECHNICAL CHEMISTRY. 625
undergo dnritig tlie process of extraction by tlie methods of "Dragen-
dorff and of Stas-Otto, toxic principles are formed which exhibit the
reactions of alkaloids. — These conclusions throw great doubt on all
experiments hitherto made on the genesis of ptomaines, since the
extraction of these bodies either from cadaveric substances or putrefac-
tion products, or from liquids pathological or physiological, is always
effected by one or other of these processes, or by some method chemi-
cally equivalent thereto. Moreover it is impossible to say how far the
formation of such products is influenced by putrefaction, cadaveric or
ordinary ; and indeed, notwithstanding the conclusions of Gautier and.
£]tard (this vol., p. 100), it may even be regarded as doubtful whether
putrefaction alone is capable of giving rise to the production of
ptomaines. H. VV.
Examination of Wine coloured by Aromatic Sulphonic
Derivatives. By C. Thomas {Bied. Gentr., 1883, 68).— 100 c.c. of
the wine mixed with excess of baryta-water is boiled, filtered, and
the excess of barium precipitated by ammonium carbonate. The
filtrate is afterwards evaporated down in a platinum basin, and the
residue ignited. The ash is to be dissolved in acidulated water, and
from this solution sulphuric acid may be tested for in the usual
manner. E. W. P.
Technical Chemistry,
Photo-electric Battery. By Borgmann (Dingl pohjt J., 247,
46). — The author places a number of U-tubes in a black box having
removable sides, and fills the tubes with a 2 per cent, solution of sul-
phuric acid, the light being excluded. Silver plates, iodised on the
surface by electrolytic means, are immersed in th© acid. On exposure
to light, an electric current is set up. D. B.
Practical Application of Thermo-electricity. By F. Fischer
(Dingl polyt. /., 246, 324— 328).— In 1823, Seebeck made the obser-
vation that on heating the points of junction of two metals so that
the temperature of one of the points is different from that of the
other, an electric current is excited ; but although Nobili used this
reaction for determining slight differences of temperature, apparatus
for producing powerful thermo-electric currents have not been de-
vised until recently. The author briefly refers to the thermo-electric
batteries of Mure and Clamond and Noe, which are said to have
been superseded by a new form of battery constructed by Koch,
and resembling Clamond's battery. It consists of 144! elements,
which with a consumption of 220 litres of coal-gas per hour produce
660 c.c. oxyhydrogen gas from a small water-decomposing apparatus.
With two copper electrodes having a surface of 30 sq. cm., and being
62Q ABSTRACTS OF CHEMICAL PAPERS.
placed in a solution of cupric sulphate 6 mm. apart, 1'691 gram of
copper was precipitated per hoar, but after the introduction of two
of the above decomposing cells the quantity was increased to 2*278
grams. The combustion-products escaping at a temperature of 480°
contained 6'8 per cent, carbonic anhydride and 6'5 oxygen. The
author points out that this apparatus is capable of being improved,
and recommends its construction of larger dimensions in order to
utilise the heat of the combustion-products more completely. As
the strength of the current for low heats increases in proportion to
the difference of temperature of the points of junction, whereas for
higher heats the electromotive power increases at a slower rate than
the difference of temperature, it seems more advisable to cool the
temperature of the outer points of junction than to heat the inner
ones. The author concludes by stating that the application of thermo-
electricity cannot be carried out successfully on a large scale until it is
possible to convert a larger percentage of heat used into electricity.
D. B.
Fuel to Produce Electricity. By Beard (Dingl. polyt. J., 247,
94). — The electric current is formed by the combustion of coal at a
high temperature and in the presence of potassium or sodium nitrate.
The fuel is shaped into bricks, which are 150 mm. long, 35 mm. wide,
and 25 mm. deep. The outside is covered with asbestos paper, whilst
the interior consists of a coal and saltpetre prism separated by a thin
sheet of asbestos. The bricks contain a large number of holes, which
serve to facilitate the combustion and increase the number of points
of contact with the saltpetre. A copper or brass wire is introduced
into the coal and saltpetre prisms, the ends of which form the poles
of the element. One brick is capable of working an electric bell.
D. B.
Plameless Combustion. By F. Fisch-er (Dingl poJyt. /., 247,
32 — 35). — The author has repeated Fletcher's experiments on flame-
less combustion (ibid.f 246, 293) with the view of investigating the
combustion-products. For this purpose iron wire was wound round
the end of a thin clay pipe, so that a ball 6 to 8 cm. thick was pro-
duced. This was heated as suggested by Fletcher, and whilst the ball
was at its most intense heat, a sample of gas was withdrawn from the
interior, the gas being drawn through the clay pipe and examined
over mercury. The experiments corresponding to the samples of gas
I, II, were made with the ordinary gas pressure, in experiment III the
pressure was increased, whilst the pressure in experiment IV was
still greater. The ball in experiment II was made of very thin wire,
in experiments I and III the wire was 1 mm. in thickness, and in
experiment IV the ball consisted of a mixture of both wires : —
CO. CH4. H.
1-08 traces 0*32
C02.
I
511
II
5-03
Ill
6-60
IV
772
0.
N.
6-26
88-63
3-34
91-63
4-98
88-42
traces
90-88
TECHNICAL CHEMISTRY. 627
The composition of the gas corresponds with that of the gaseous
mixture at the point of the flame of a blowpipe or Bunsen burner ;
the smaller proportion of oxygen, however, shows that part of it is re-
tained by the iron ; moreover, it was found that when thin wire was
used, one half of the fused mass consisted of ferrosoferric oxide. Re-
ferring to the practical application of flameless combustion, the author
considers that it is not available for solid fuels. D. B.
Manufacture of Sodium Sulphide. By W. Weldon (Pharm.
J. Trans. [3], 483 — 484). — Some years ago the author observed that
when " alkali- waste " is digested with water under a pressure of
about 5 atmospheres, the following change takes place : — 2CaS +
2H2O = 2CaH202 + CaH2S2, and that the hydrogen calcium sulphide
thus produced can be converted into a sodium salt by means of the
action of sodium sulphate, thus : — ^.CaH2S2 + Na2S04 = CaS04 +
2NaHS ; the subsequent conversion of this hydrogen sodium sulphide
into sulphide could of course be effected by treatment with caustic
soda, but this is out of the question as a manufacturing operation :
Helbig has lately overcome this last difficulty by making use of what
he calls " a passing formation " of caustic soda. This chemist heats,
by means of steam injection, a mixture of black ash, alkali- waste, and
water, in iron digesters furnished with mechanical agitators kept in
motion during the operation ; when this digestion is complete, the
resulting solution of sodium sulphide is filtered, concentrated to
32° B., any salts separating out during evaporation are fished out, and,
finally, the concentrated liquid is allowed to cool, when it yields crystals
of the hydrate Na2S,9H20. The chemistry of the process is explained
in this manner: the calcium hydroxide and calcium hydrogen sul-
phide being formed as above described, the sodium carbonate of the black
ash then reacts with the calcium hydrogen sulphide and with calcium
bydroxide, producing the corresponding sodium salts, which in their
turn react on one another in this manner : NaHO + NaHS = Na^S -h
H2O. Contrary to the statement of the text-books, anhydrous sodium
sulphide does not fuse in closed vessels made of material upon which
it has no action, and the hydrated sodium sulphide crystals prepared
by the above process absorb oxygen from the air only very slowly ;
this Helbig attributes to the fact that they are quite free from caustic
soda. D. A. L.
Analysis of Clay from LSthain. By H. SmER (Dingl. polyt. J.,
247, 185). — The colour of the clay is light brownish-grey. Its com-
position and that of the clay substance is as follows : —
H2O and
SiOg. AI2O3. FeaOg. CaO. MgO. K2O. org. matter.
Clay 64-51 31-41 0-68 0-04 0-43 0-55 12*37
Clay substance 45'53 37-68 0*82 0-05 0-51 0-52 14-89
corresponding with the formula Al2Si207H20. Owing to its white
colour, refractoriness, and great cohesive power, this clay may be used
628 ABSTRACTS OF CHEMICAL PAPERS.
with advantage as a substitute for blue clay in the manufacture of
stoneware. D. B.
Analysis of Puzzuolanas and Estimation of their Com-
parative Values. By E. Landrin (Compt. rend., 96, 491—494). —
In order to obtain some insight into the constitution of puzzuolanas,
the author proposes to treat them with hydrochloric acid, at a tem-
perature of the water-bath, for two hours, in order to effect a separa-
tion into a soluble and insoluble portion. The following^ are his results
of analyses of four samples of puzzuolana, two of which came from
Reunion, one from Italy, and one an artificial specimen from Paris :—
Portion Soluble in Hydrochloric Acid.
Eeunion. Italy. Paris.
Silica 1-9 1-15
Alumina and ferric oxide 23'80 31*90
Lime 2-6 TS
Magnesia 1'4 O'SS
Alkalis, loss, &c 0-75 0-12
Portion Insoluble in Hydrochloric Acid.
Silica 41-7 37-8
Alumina and ferric oxide lO'G 7'56
Lime 6-05 3'2
Magnesia 1-29 3-05
Alkalis, loss, &c. .,,... 1-16 0*49
From these analyses, it is shown that by far the greater part of the
silica present is in the insoluble portion. But a determination of
this proportion of silica cannot be considered as a final indication of
the value of the puzzuolana as a hydraulic cement, without recourse
to the method of Girard and Vical, which consists in agitating the
sample with standard lime-water, and ascertaining the quantity of lime
absorbed.
The following results were obtained by this process, 3 grams of
the sample being used for each determination : —
Lime absorbed after
24 hours.
Puzzuolana from Reunion (I) 0*0017
Insoluble portion from ditto O'0224i
Puzzuolana from Reunion (II) 0*0051
Insoluble portion from ditto 00396
Puzzuolana from Italy 0*0017
Insoluble portion from Italy 0*0404
Puzzuolana from Paris 0*0017
Insoluble portion from Paris 0*0025
These two methods, that is, treatment with hydrochloriG apid, and
III.
IV.
0*45
0*25
25*85
4*53
5*6
2*25
2*5
0*6
0-75
0-12
44*7
74*8
2*25
13*8
4*05
1*8
1*36
0*06
0*74
0*44
TECHNICAL CHEMSTRY. 629
estimation of lime absorbed are, in the aathor's opinion, sufficient to
fix the value of a sample of puzzuolana. Y. H. V.
Crystals in Cementation Steel. By L. Stoltler (Compt. rend.,
96, 490). — The bars of steel obtained by the cementation process in
the works at XJnieux frequently contained, in those portions exposed
to the hottest portion of the furnace, blebs surmounted by crystals.
Des Cloiseaux has examined these crystals, and finds that they belong
to the cubic system ; he considers it probable that they are regular
octohedra, like those of cast and wrought iron. Y. H. Y.
Presence of Gold in German Standard Silver Coins.
(Bingl. polyt. /., 247, 186). — Dannenberg, in preparing silver nitrate
from 12 marks in 50 pfennig pieces, obtained 5 to 6 mgrm. gold. His
statement that when the mark coinage was introduced into Germany,
the gold contained in the silver was not removed, is erroneous, as after
the introduction of the wet process in 1825, the Hamburg parting
works refined more than half the silver coins collected, whilst the
others were worked up at Frankfort-on-the-Main, Munich, Karlsruhe,
and Stutgart. D. B.
Examination of Illuminating Gas. By 0. v. Than (Ber., 15,
2790 — 2802). — It is well known that when illuminating gas is mixed,
in a closed space, with air, it becomes dangerously explosive ; the
author's experiments were made to discover the proportions in which
the mixture is most liable to explosion. The apparatus employed was
a graduated glass tube, 50 cm. long and 3 cm. in diameter, closed
at one end. Fifteen experiments were made with percentages of gas
to air, varying from 4 to 40 per cent. : when the amount of gas was
under 5 per cent., the mixture was not inflammable ; from 5 to 20 per
cent, the explosions became more violent in proportion to the gas
present ; from 25 to 30 per cent, they gradually decreased, and between
30 to 40 per cent, the mixture burned at the mouth of the tube quietly
and without explosion.
The chemical composition of the gas has an undoubted influence on
the explosiveness of the mixture.
The rapid discovery of leakages in gas fittings is a matter of great
importance, and the author criticises Ansell's indicator, which is sup-
posed to give an alarm when dangerous leakages occur ; he considers
it untrustworthy, and describes an invention of his own, which he calls
a diffusometer. It consists of a porous earthen cell, such as is em-
ployed in galvanic batteries, inverted, closed with a perforated india-
rubber plug, through which it is connected with a manometer, the
lower limb of which is bent, and contains a little water coloured with
litmus ; the cell stands on a small table capable of holding a bell-
glass cover — this bell-glass is filled with air to be examined and
nlaced in position, the mixture of gas and air diffuses into the interior
of the cell, and causes an alteration of level in the coloured fluid.
Tj.e author graduated the instrument with measured volumes, and
found that its indications were very trustworthy ; attention must be
paid to differences of temperature ; if the instrument is brought into
6.S0 ABSTRACTS OF CHEMICAL PAPERS
a room where there is an escape of gas, it will very closely point ont
whether the escape is within the dangerous limits or not. Various
applications of the instrument are given, such as drawing samples of
air from the higher parts of theatres, public buildings, &c., for the
purposes of examination. The precise locality of leakage is often
difficult to find, the ordinary plan of using a light being dangerous.
The author has constructed another little apparatus for the purpose,
which he calls diffusioscope, which may be described as a very flat
glass funnel, closed about half way from the edge with a very thin,
circular, porous earthen plate. The stem of the funnel is provided
with a tap to admit air to equalise the pressure on a miniature mano-
meter, which is connected with the stem of the instrument. The por-
tion containing the porous plate is placed over the suspected spot and
the tap closed, when, if there is leakage, the rise of the column in the
manometer is instantaneous. The apparatus is so sensitive, that when
an argand burner is gradually turned down until it will no longer
ignite, and the instrument held over it, the manometer rises 7 cm. in
four or five seconds, held over an ordinary burner, letting so much gas
out as will just kindle, the fluid rises very rapidly, and is almost
ejected from the tube. If the manometer be graduated to millimeters,
one half percent, of gas can be detected in a room. An instance is given
of a case of sickness, which in the opinion of the physician was due
to gas poisoning, but could not be traced, as there was not a service of
gas in the house. The instrument was used, when it was found that a
pipe, distant 3 meters from the house, had burst underground.
A somewhat similar instrument is described ^by Weyde (Dingl.
polyt /., 196, 513). J. F.
Manufacture of Spirit from Wheat. (Dingl. polyt. J., 247,
228.) — According to Maciejewsky, it pays better to manufacture over-
grown wheat into spirit than to use it for bread-making. The best
results are obtained from unbruised wheat. The value of 100 kilos,
sprouted wheat to the distiller is estimated at 16*20 marks, a price
which sprouted wheat ordinarily does not attain. D. B.
Simultaneous Employment of Potatoes and Grain in Spirit
Factories. (Bied. Centr., 1883, 69.) — A mixture of two-third potatoes
and one-third maize may be satisfactorily mashed in steamers under
pressure. E. W. P.
Purification of Alcohol prepared from Molasses or Beet-
root. By L. Salzer (Bied. Centr., 1883, 70). — According to this
patent, 70 — 80 grams pure potassium hydroxide are to be added to
every hectolitre of 90 per cent, alcohol in tinned iron vessels. During
the first 24 hours, the mixture is to be stirred with glass or highly-
polished iron rods, then left to itself for 12 hours; after which 10 per
cent, water is to be added, and the stirring repeated. After filtration,
200 grams tartaric acid per 100 grams potash are to be added, and
after 12 hours, 10 litres water for every hectolitre alcohol, and the
whole filtered and distilled. E. W. P.
TECHNICAL CHEMISTRY,
631
Analyses of Markgrafler of different Districts and Vin-
tages. By H. Wachter (Bied. Centr., ]883, 59).— The results of 64
analyses of Markgrafler made in the years 1868 — 1881 show that
sugar was present in quantities less than 0*1 per cent. In three
specimens, glycerol occnrred to the amount of 1*6 — 0-86 per cent. ; in
three old wines SO3 to the extent of 0-0724, 0*069, 0'0583 per cent.
E. W. P.
A New Alcohol in Wine. By Henninger (Bied. Centr., 1883,
69). — Ethylene glycol (b. p. 197°) occurs in wines, and up to the
present time has always been estimated with the glycerol present.
E. W. P.
Influence of Foreign Matter on the Conversion of Starch
by Diastase. By W. Detmer (Bied. Centr., 1883, 71).— Carbonic
anhydride hastens the conversion, so do small quantities of citric acid ;
in large quantities however, the latter destroys the action of the
diastase. The same may be said of phosphoric and hydrochloric acids ;
whilst fairly large quantities of phenol have only a very slight retarding
action. Addition of an alkali, even in very small amount, prevents
the change of starch from taking place. E. W. P.
On Malt. (Dingl pohjt. J., 247, 82—85 ; 168—173, and 214—
218.) — With a view of ascertaining the influence of different kinds of
waters in steeping, Michel and Jaeckel-Handwerk have made a series
of experiments, using Bohemian barley of sp. gr. 1*1994, containing
15*01 per cent, water, 2*55 ash, and 63*75 extract. In Experiment I,
50 grams of barley was steeped in 60 c.c. distilled water ; in II 60 c.c.
water containing 1 per cent, common salt was used ; and in Expe-
riment III 60 c.c. well water (1 litre = 425 mgrms. residue on evapo-
ration, of which 120 mgrms. was organic matter), was taken. After
25 hours, the first steeping water was replaced in all three trials by
60 c.c. of the original water used, and this operation repeated after 20,
and again after 29 hours' steeping. The following table illustrates
the results obtained, calculated on 100 grams barley : —
First soaking.
Time : 25 hours.
Second soaking.
Time : 20 hours.
Sample.
Water
absorbed.
Extracted matter.
Water
absorbed.
Extracted matter.
inorg.
org.
inorg.
org.
I
CO.
42
38
42
g.
0 129
0*087
0 131
g-
0 109
0 130
0*121
c.c.
13-6
12 '8
8*0
g-
0-070
0-650
0-067
g-
0-064
II
0*109
Ill
0-077
G32
ABSTRACTS OF CHEMICAL PAPERS.
'Third soaking.
Time : 29 hours.
Total—
74 hours.
Sample.
Water
absorbed.
Extracted matter.
Water
absorbed.
Extracted matter.
inorg.
org.
inorg.
org.
I
c.c.
8
6
10
g-
0 053
0-324
0-043
g-
0-048
0-040
0-043
c.c.
63-6
56-8
60 0
g-
0-252
1-061
0-241
g"
0-221
II
0*279
III....
0-231
It was found that the addition of salt to the water retards the ger-
minating process. Barley tinges the water in which it has been
steeped of an orange-yellow colour, and imparts to it a slightly acid
reaction. The water used for steeping contains two albuminoids, one
precipitable by metaphosphoric acid in the cold, the other on heating.
The former may be retained in the grain by the addition of gypsum to
the water. The repute which the Burton water has is confined to the
presence of nitrates, which promote the germinating process. In
order to prevent the loss of extract in steeping barley, it is recom-
mended to trea^. the latter with O'l per cent, gypsum, and add a small
quantity of calcium nitrate to the mixture. For determining the
value of barley for brewing purposes, it is proposed to allow about
1 litre of the grain to germinate and make it into malt. The following
table gives the results of eight malting tests ; the barley was steeped,
germinated, and dried under the same conditions in each expe-
riment : —
1
h.
i
i
a
"3
a
2
u
a
2
Sample.
a
1^
i 2
a
S
11
11
a
1^
+J cS
«- ^
axi
s-^ —
2-r-w-
«-
-u a
.
l-o
V o
^^
tr^
0
vn
« fc«
6
ii^-S
t. 2
sH
SQ
i^
^■s^
^a
S3 -a
Jz;
Pm
<
Ph
H
H
o
o &-
w (2
P4
Ph
,
85 -87
87-03
84-65
86-31
82-35
86-56
86-70
81-69
37-64
38-02
41-17
44-50
47-40
43-60
38 -65
39-93
0-73
0-44
1-28
0-82
1-40
0-56
1-34
1-14
75
92
79
74
95
73
94
92
11-0
9-4
8-9
8-9
10-25
9-33
9 -25
11-05
41
34
47
38
57
48
46
92
148-1
153-1
157-3
151-9
146-4
153-7
158-2
152-9
83-2
84-4
81-0
83-3
78-5
83-3
80-8
79-6
5-79
6-55
4-80
5-40
4-72
5-42
5-07
4-85
91-27
9
Slavonian
90-62
R
91-09
4
Bohemian
91-30
fi
Franconian
90-82
6
91-01
7
Moravian
89-17
8
94 -86
The amount of nitrogen contained in the barley and malt obtained
therefrom, and the percentage composition of the ash of the barley and
malt, is illustrated hj the following table : —
TECHNICAL CHEmSTRY.
633
Barley.
1.
2.
3.
4.
5.
6.
7.
8.
Nitrogen
Ash
1-809
2-690
0-599
1-010
0-056
0-009
1-629
2-640
0-671
0-790
0-059
0 013
1-877
2-850
0-656
1-078
0-065
0-016
1-809
2-570
0-651
0-923
0-082
0-062
0-231
0-015
0-315
1-859
2-810
0-826
0-798
0-147
0-059
0-229
0-007
0-608
1-696
2-860
0-579
0-817
0-037
0-216
0-013
0-528
1-750
2 -650
0-645
0-804
0-640
0-009
1-605
2 -630
Silicic acid ....
Phosphoric acid
Sulphuric acid.
0-711
0-767
0-107
0-067
Magnesia. .....
Ferric oxide . . .
Potash
0-224
0-003
0-592
Malt.
1.
2.
3.
4.
5.
6.
7.
8.
Nitrogen
Ash
1-625
2-480
0-598
0-929
0-029
0-091
0-253
0-022
0-468
1-600
2-390
0-711
0-868
0-054
0-072
0-266
0-018
0-363
1-857
2-440
0-677
0-904
0-012
0-087
0-236
0-019
0-470
1-798
2-300
0-644.
0-708
0-029
0-077
0-219
0-014
0-367
1-729
2-420
0-725
0-779
0-012
0-084
0-239
0-017
0-385
1-568
2-350
0-556
0-784
0-019
0-096
0-239
0 011
0-417
1-733
2-320
0-770
0-830
0-031
0-085
0-219
0-015
1-413
2-310
Silicic acid ....
Phosphoric acid
Sulphuric acid .
0-651
0-693
0-058
0-082
Magnesia
Ferric oxide . . .
Potash
0-212
0-015
0-407
In the remaining portion of the paper, various processes of kiln-
drying are described. D. B.
Manufacture of Sorgho- and Imphy-sugar in the United
States. By F. Bockmann (Ann. Agron., 1882, 146 — 155; from
Deutsche Industriezeit., 1881, 12 and 43). — True sorgho from Chinese
seed was imported into the United States in 1855 ; imphy, the variety
from African seed, in 1857. The cultivation of sorgho for sugar
making has not hitherto taken root in Europe, but in the States of
Ohio, Iowa, Illinois, Missouri, &c., considerable progress has been
made, the production of sorgho sugar in America reaching 640,000
lbs. in 1875. For the same year the total production of sugar-cane
sugar is estimated at 63,000,000 lbs., and of beet-sugar 20,000,000 lbs.
There are certain difficulties attending the growth of sorgho, but it
presents the advantage of flourishing in a climate too cold for the
sugar-cane and too warm for the sugar-beet. The quantity of cane-
sugar contained in the plant is at its maximum when the seed begins
to ripen; the colour of the plant then changes from apple-green
touched with red to citron-yellow. When this point is reached, the
plants are deprived of their leaves, the stems cut ofE a few inches
VOL. XLiv. 2 n
634
ABSTRACTS OP CHEMICAL PAPERS.
above the ground, and immediately crashed between large vertical or
horizontal rollers. If this operation is delayed, a portion of the cane-
sugar reverts to glucose ; e.^., a sample of sorgho containing 15*47
per cent, cane-sugar and 1*71 per cent, glucose the day it was cut,
contained 45 days later 6 32 per cent, cane-sugar and 15' 73 per cent,
glucose. The proportions of the two varieties of sugar contained in
the plant at different stages of growth were, in the crops of 1863,
1865, and 1866, as follows: —
Cane-sugar.
GHucose.
1. When the ear was half out of the sheath.
2. Just before the fall of the stamens
3. When the ears commenced to turn colour
4. Completely ripe
0 -23— 4 91
2-89- 6-54
7-84— 11-78
9 -24—13 -57
3 -32—6 -37
3 -26—5 -26
2 16—6 -04
1 -19—4 -05
An analysis of sorgho juice gave — water, 80 per cent. ; cane-sugar,
15 — 17 per cent.; glucose, 1 per cent.; starch, gum, pectic acid,
albumin, red colouring-matter, ash, &c., undetermined. The most
primitive method of defecating the juice consists in heating it to
70 — 80"^ and adding lime ; at this temperature, the starch swells and
diffuses throughout the liquid, and subsequently prevents the evapora-
tion being carried to the point necessary for the crystallisation of the
cane-sugar. A better method is to carefully filter the juice through a
series of filters to remove impurities which promote fermentation,
hinder evaporation, and impart a colour to the product. After filtra-
tion the juice is mixed with lime, and allowed to stand at the ordinary
temperature for a certain time ; the clear liquid is then evaporated.
A still more complex method proposed is to mix the juice from the
mill with lime, magnesia, and its own volume of alcohol of 84 per
cent. ; to decant the clear liquor after settling, and to press the residue
into cakes for feeding, or for the production of alcohol ; to distil the
alcohol off from the purified solution, and continue the evaporation of
the latter to the crystallising point. F. L. Stewart's process of
defecation proceeds by heating the juice to 82° with lime in copper
vessels, ^Z^erm^, and evaporating with the addition of an acid liquid,
the composition of which is not published. The evaporation of the
defecated liquid is conducted in a very primitive fashion in the
States. Four kettles of diminishing size are used, each being divided
into several compartments to moderate the ebullition ; the syrup is
transferred from one kettle to another by a long-handled bowl,
skimmed from time to time, and when sufficiently concentrated filtered
through canvas.
The refining is conducted in a simple cylindrical vessel packed with
animal charcoal and sand or gravel. The only analysis of sorgho
sugar known to the author gave — water, 1*72; cane-sugar, 93*05;
glucose, 0*41; ash, 0*68; organic matter, 4*14. J. M. H. M.
Changes occurring in Preserved Milk. By 0. Loew and
others {Bied. Centr.^ 1883, 57). — A specimen of milk, sealed up after
TECHNICAL CHEMISTRY. 635
heating to 101° by Nageli in 1872, was fonnd to have become brown
and slightly acid when opened in 1880 ; the taste was bitter, and the
milk-sugar was converted into lactose and dextrose, the albuminoids
being all converted into peptone, leucin, tyrosin, and ammonia. Other
specimens of preserved milk had all changed. It is evident that
heating to 120° under a pressure of 2 — 4 atmospheres is insufficient to
destroy organisms. Scherff's process only preserves for about a year.
E. W. P.
Oiling and the Operations connected therewith in Turkey-
red Dyeing. By F. Schatz (Bingl. polyt. /., 247, 38— 43).— By
soaking cloth in oil and dyeing in an alizarin bath without previously
mordanting with a metal (aluminium, iron, &c.), no colour is pro-
duced. The oil does not take the part of a mordant, but effects the
precipitation of alizarin in the presence of a mordant, the fatty acids
contained in the oil forming insoluble compounds with the mordant.
If, therefore, the oiling is abandoned, the mordant being soluble is
washed out, and the fabric is not dyed. In dyeing, the alizarin com-
bines with the alumina of the alumina soap, the fatty acids forming
as it were a cover, which protects the aluminium alizarate molecules.
In this respect, the oil imparts fastness to the colour. In the remaining
portion of the paper the author discusses the changes occurring in
Turkey-red dyeing, more especially with regard to the influence of
steaming on cloth, after oiling, mordanting, and dyeing. D. B.
Process for Preparing Crocin-scarlet and Crocin-yellow.
(Bingl. polyt. J., 246, 348.) — For the preparation of crocin-scarlet,
50 kilos, amidoazobenzenemonosulphonic acid are diazotised by means
of hydrochloric acid and sodium nitrite. The diazobenzenesulphonic
acid is introduced into a solution of 75 kilos. |S-naphthol-a-snlphonic
acid in 500 litres water and 150 kilos, ammonia (10 per cent.).
S03H.C6H4.T^2.C6H4.N2.C1 4- ONa.CoHe.SOgNa -f 2NH3.
S03NH4.C6H4.N2.C6H4.N3.(ONa)CioH6.S03Na + NH4CI.
When free amidoazobenzene is used, the dye-stuff has a yellowish
tinge. The homologues of amidoazobenzene form bluish-red colour-
ing-matters, diazobenzene and its homologues give reddish-yellow
dyes, a-diazonaphthalene forms a bluish-red colour, and i(3-diazonaph-
tiialene a brick-red dye-stuff. With nitric acid (50 per cent.) at
40 — 50°, the new )3-naphtholsulphonic acid gives nitro-products,
whose alkaline salts are readily soluble in water, and form yellow
colouring-matters. D. B.
Alizarin-blue. (Dingl. polyt. J., 246, 92— 95.)— In the Bulle-
tin de Bouen (1882, 13 and 243) Mattauch, Schmidt, Blondel, and
Balanche make observations as to the unstable character of soluble
alizarin-blue brought into commerce by the Badische Anilin und
Soda Fabrik. This colouring-matter is prepared by mixing alizarin-
blue (in 10 — 12 per cent, paste) with sodium bisulphite of 25 — 30° B.,
allowing the mixture to stand for 8 — 14 days, and filtering from un-
converted alizarin-blue. The new dye-stuff is obtained from the
filtrate either by evaporation or by precipitation with salt. Its solu-
636 ABSTRACTS OF CHEMICAL PAPERS.
tion is decomposed by sulphuric or hydrocUoric acid with precipita-
tion of ordinary insoluble alizarin-blue ; it forms lakes with aluminium,
iron, and chromium, and yields shades which resist the action of
light, soap, and chlorine as well as indigo. The best shades are pro-
duced with chromium lakes, a neutral or acid chromate being the
most advantageous, as it is reduced by sodium bisulphite. The colour
is developed by steaming, no mordant being required. To overcome
the difficulties raised by Balanche and others as to the instability of
this compound, the Baden works recommends to dissolve the colour-
ing-matter in cold distilled water, and to avoid contact with acid
fumes and iron vessels. D. B.
New Coal-tar Colours. (Dingl. polyt. /., 247, 130—136 and
173 — 178.) — A process for preparing yellow, red, and violet coloaring
matters by the action of diazo-compounds of amidobenzene and its
homologues, as also of the sulphonic acids of these bodies, on phenols,
naphthols, and dioxynaphthalene, and their sulphonic acids, has been
patented by Kriigener. In order to produce a red dye-stuff equal
in shade to cochineal, 50 kilos, amidazobenzenesulphonate or
47 kilos, of the hydrochloride are gradually introduced into 230
kilos, fuming sulphuric acid (14 per cent, anhydride), cooling the
vessel during the operation. The mixture is then heated slowly on a
water-bath at 60" to 70° until it is perfectly soluble in water, amido-
benzenedisulphonic acid being produced. From its sodium salt,
diazo-azobenzenedisulphonic acid is prepared by treatment with
sodium nitrite in a hydrochloric acid solution. 29 kilos, of |8-naph-
thol are then dissolved with 16 kilos, sodium hydroxide in sufficient
water so that all the naphthol remains in solution on cooling. The
mixture is cooled and the diazo-azobenzenedisulphonic acid poured
gradually into the same. The colouring matter is immediately
formed. It is treated with salt, filtered, pressed, and purified by dis-
solving it in water. The homologues of amidazobenzene give
similar dye-stuffs. Instead of /3-naphthol — a-naphthol, phenol and
dihydroxynaphthalene may be used. Amidazonaphthalene treated
in like manner also gives a red colouring matter. The phenols may
be replaced by their mono- and di-sulphonic acids. Again, mixtures
of amidoazo-compounds may be used ; e.g., aniline is converted into
diazobenzene chloride by treatment with an equivalent quantity of
sodium nitrite and hydrochloric acid, and an equivalent quantity of
xylidine is added ; in this way diazobenzamidoxylol is formed, which
is converted into the isomeric amidoazo-compound by the action of
xylidine hydrochloride. The preparation of the sulphonic acids of the
mixed amidazo-compounds is analogous to the preparation of the
disulphonic acids of amidazobenzene. The mono- and di-sulphonic
acids of the mixed amidazo-compounds yield, when diazotised with
sodium nitrite and hydrochloric acid, diazo-azo bodies forming with
naphthols, dihydroxy naphthalenes, and phenol, yellow, red, and violet
dye-stuff's. From Graessler's amidazobenzenemonosulphonic acid
(ibid., 234, 422) and its homologues red and violet colours are obtained
by diazotising and acting on a- and /3-naphthol, phenol, and dihydroxy-
naphthalene.
TECHNICAL CHEMISTRY. 637
Graessler has improved the above patent by diazotising his amid-
azobenzenesulphonic acid and acting on resorinol or orcinol with
diazoazobenzenesulphonic acid. He has also patented dye-stuffs
obtained by the action of diazoazobenzene hydrochloride on naphthols,
resorcinol, orcinol, dihydroxynaphthalene, and their corresponding
sulphonic acids.
For preparing paranitro-compounds from the colouring matters
obtained by oxidising the condensation-products of benzaldehyde with
primary, secondary, and tertiary aromatic monamines, Bindschedler
and Busch effect the nitration by introducing the nitrate into concen-
trated sulphuric acid, or dissolving the colour base in sulphuric acid
and adding a nitrate, or allowing a mixture of nitric and sulphuric
acid to flow into the sulphuric acid solution. For preparing para-
nitro-compounds from the leuco-bases obtained by the condensation of
benzaldehyde with aromatic monamines, Bindschedler and Busch
introduce the nitrate of the leuco-base into concentrated sulphuric
acid, or dissolve the base in sulphuric acid and treat with nitric acid
or a nitrate. By reducing and oxidising the nitro- bodies obtained,
rosaniline colouring matters are produced.
For the preparation of dye-stuffs from the rosaniline group, GreifE
proposes to allow nitrobenzoyl chloride to act on aniline, or toluidine,
or their salts, in presence of oxidising agents such as iron, its oxides or
salts.
For the manufacture of colouring matters by the action of nitroso-
compounds or chloroquinonimides on aromatic monamines, Witt adds
to 1 mol. of an aromatic monamine — especially a secondary or tertiary
base — in a hot acetic acid solution 1 mol. of nitrosodimethylaniline
nitrate. The colouring matter which is contained in the solution as
acetate is transformed into the hydrochloride by the addition of
hydrochloric acid. Dimethylaniline and similar bases give violet,
diphenylamine and its homologues blue and green, naphthylamine and
its homologues, as well as the naphthylphenylamines, give red and
violet colouring matters.
For the preparation of dye-stuffs obtained by the action of nitroso-
dimethylaniline hydrochloride on tannin, tannic acid, or gallic acid,
Koechlin dissolves 2 parts of tannin and 1 part of nitrosodimethyl-
aniline hydrochloride in 10 parts of water, and heats the mixture. It
is then poured into a large quantity of water, and the solution pre-
cipitated with salt. Other tannic acids, gallic acid, and other aro-
matic hydroxy-acids yield similar dye-stuffs. They dissolve in alkalis
with reddish to bluish-violet colour. With alumina or tin mordants,
violet shades are produced.
Jacobsen has patented a method for the preparation of red and
violet colouring matters, by the action of benzotrichloride on pyridine
and quinoline bases. The product of the continued heating at 130° of
equal volumes of quinoline and benzotrichloride is treated with cold
water to dissolve that part of the base which has not been con-
verted, and the residue is extracted with boiling water; the deep
red-coloured base is then precipitated from this solution by an
alkali. It is insoluble in ether, and sparingly soluble in water, but
dissolves readily in alcohol. The solution of the base, like that of its
638 ABSTRACTS OF CHEMICAL PAPERS.
salts, is of a purple colour, and exhibits a strong reddish-yellow
fluorescence, which is also imparted to wool and silk dyed with the
colouring matter. For quinoline, its homologues can be substituted,
as well as pyridine and its homologues.
Geigy prepares dye-stuffs by the action of 1 mol. of an amidazo-
compound on 4 mols. of a phenol or quinone at a temperature of
130 — 200". The colours formed are mostly soluble in alcohol, and are
purified by washing with acidulated water and subsequent treatment
with dilute alkali. By the employment of amidazo-compounds with
more than one amido group, colouring matters are obtained, soluble in
water, from the sulpho- or nitro- derivatives of the amidoazo-com-
pounds, or from the polybasic phenols bodies are obtained soluble in
alkalis. Amidazobenzene yields a blue with phenol, with naphthol a
grey, with paranitrophenol a violet, and with salicylic acid a pearl-
grey colouring matter, and so on.
According to Casella and Co., the colouring matters described as
indophenols are formed also by the direct action of nitroso-compounds
or chloroquinonimides on phenols. These colouring matters are
obtained also by the oxidation of mixtures of paran^ido-phenols and
monamines.
According to the Farbwerke, formerly Meister Lucius and Briining,
in melting the anthraquinonesulphonic acids with alkali, lime, or the
lime salt of the sulphonic acids, is used. Thus, the calcium compound
of alizarin is produced, from which the alkaline liquor is removed by
filtration, and the caustic alkali recovered. The alizarin lakes are
decomposed with acids, or treated with alkalis to remove impurities,
and subsequently precipitated with acids. According to the Farb-
werke, the salts of paraleucaniline and its homologues are converted
into colouring matters of the rosaniline-group by heating them with
the hydroxides of iron, manganese, and copper. The acetyl-com-
pounds of primary or secondary aromatic bases form colouring matters
per se or when mixed with a salt of an aromatic base by heating them
with dehydrating age7its. A yellow dye is obtained by heating
acetanilide with zinc chloride at 230 — 250°. The methyl, &c.,
derivatives of these dye-stuffs and the sulphonic acids are prepared in
a similar manner.
For the preparation of azo-colouring matters, Oehler combines
metadiazosulphobenzene withdiphenylamine; for the formation of the
former, metamidobenzenesulphonic acid is diazotised with sodium
nitrite in a weak acid solution. The diazo-compound is then treated
with an equivalent quantity of diphenylamine in an alcoholic solution
at as low a temperature as possible. The acid formed is filt-ered off,
treated with alkali, and the salt dried down or precipitated with
sodium chloride.
For the preparation of colouring matters from paranitrobenzalde-
hyde, Fischer allows 2 mols. of aniline to act on 3 mols. of nitrobenz-
aldehyde ; an intermediate product is thus obtained which, after
long continued boiling with strong acids, is converted into nitrodi-
amidotriphen^dmethane. Aniline salts of easily volatile acids be-
have in a similar manner. If, however, salts of the primary
aniline bases with heavv or non- volatile acids be used, then 2 mols. of
TECHNICAL CHEMISTRY. 639
aniline act on 1 mol. of nitrobenzaldehyde, and form at once the
nitroleuco-base. By the condensation of paranitrobenzaldehyde with
secondary and tertiary aromatic amines, nitroleuco-bases are formed,
which are converted into derivatives of leucaniline by reduction of
the nitro-group. These derivatives form colours by direct oxidation.
Methyl, ethyl, benzyl, or phenyl may be substituted either before or
after oxidation. Leuco-bases as well as the colours may be trans-
formed into sulphonic acids. Paranitrobenzaldehyde and diphenyl-
amine, for instance, yield a nitroleuco-base, from which diphenyl-
paraleucaniline is obtained by reduction according to the following
equations : —
C6H4CN02).COH + 2NHPhC6H5 = N02.C6H4.CH(C6H4.NHPh)3 +
H,0;
N02.C6H4.CH(C6H4.NHPh)2 + 6H = 2H2O -f
NH2.C6H4.CH(C6H4.NHPh), ;
oxidation of the latter produces diphenylrosaniline, C31H27N3O. A
mixture of 5 parts paranitrobenzaldehyde, 12 parts diphenylamine,
and 12 parts zinc chloride is heated at 100° until the aldehyde has
disappeared ; on boiling the product with dilute hydrochloric acid, th&
zinc chloride is removed and a greenish-yellow substance left. Th©
nitro-group is then reduced with a solution of stannous chloride, the
whole precipitated by water, and the amido-base purified. By oxida-
tion, diphenylparaleucaniline yields a violet colour. According to Kalle
and Company, rosaniline forms very unstable acid sulphates, which at
a higher temperature are transformed into the disulphonic acid. For
the preparation of the sulphonic acids of rosaniline, alizarin, &c., by
the combined action of sulphuric and metaphosphoric acid, Kalle and
Company use a mixture of 1 part of vitreous metaphosphoric acid and
2 parts of common sulphuric acid. This is said to act quite a^i
strongly but more evenly in the formation of the sulphonic acids thau
sulphuric acid containing from 25 to 30 per cent, of anhydride.
Espenschied prepares a blue colouring matter from tetramethyl-
paradiamidoazoxybenzene by treating the cold solution of the latter
in hydrochloric acid with sulphuretted hydrogen, or such sulphides aa
evolve this gas when brought into contact with an acid, and then
oxidising with ferric chloride.
According to the Farbwerke, formerly Meister Lucius and Briining,
artificial indigo is prepared by nitrating monobenzylidenacetone.
From the alcoholic solution of the nitro-bodies the para-compound is
separated, whilst from the mother-liquor the orthonitro-compound is
obtained. This, on treatment with alcoholic soda-ley, forms a sub-
stance which is acidified and extracted with ether. By heating the
aqueous solution of the extract, or treating it with alkali, indigo is
produced. D. B.
Manufacture of Thiocyanates. By J. Tcherniac and Lauber
and Hausmann (Dingl.polyt. /., 246, 533 — 536). — Referring to Lauber
and Haussman's process (this vol., p. 256) for preparing aluminium
thiocyanate by means of calcium thiocyanate liquor, Tcherniac men-
640 ABSTRACTS OF CHEMICAL PAPERS.
tions that the method of converting sulphuretted ammonium thio-
cyanate liquors into calcium thiocyanate by decomposition with a
definite quantity of lime, worked in suitable vessels, was patented by
him in conjunction with Giinzberg (ibid., 245, 214). The paper
mainly discusses questions of priority between Tcherniac and Lauber
and Haussman. D. B.
Dressing for Driving-bands. (Chem. Centr., 1882, 768.) A half
kilo, of india-rubber is melted with a half kilo, of turpentine, in an
iron pot, 400 grams of rosin are now mixed in, and then 400 grams of
yellow wax, stirring well all the time. This mixture, whilst still
warm, is mixed with a solution of half a kilo, of tallow in 1^ kilo, of
jBsh oil. When used, it is put on with a brush, in a warm place. India-
rubber refuse can be used ; it must, however, be boiled with soda- lime,
and instead of 600 grams 625 must be taken. D. A. L.
Ergot. By C. S. Hallbeeg (Pharm. J. Travs. [3], 13, 628—629).
— In order that ergot may be obtained in a condition so that it may
be kept without becoming worm-eaten, &c., so that its most valuable
medical constituent may be retained, whilst the useless substances are
removed, and, finally, so that it may be worked up into pills, &c., with
facility, the author recommends the following treatment: — Light
petroleum (sp. gr. 0"716) which has been purified by shaking with
sulphuric acid, washing, and distillation, is allowed to percolate through
coarsely powdered ergot ; this removes the fixed oils ; it is then
extracted with strong alcohol, which displaces the petroleum and
takes up 2 to 3 per cent, of resinous matter and the poisonous alkaloid
ergotine. During this process, the ergot loses 25 to 30 per cent, in
weight, and the prepared ergot is therefore stronger than the crude drug.
This coarse powder, when pulverised, may be administered as such.
Oil of ergot, constituting 25 to 30 per cent, of the ergot, is very heavy,
dark brown, and almost odourless ; pearly stellate tufts (cholesterin ?)
sometimes separate from it. The oil yields an orange-yellow soap,
which has been recommended in skin diseases ; the oil is an excellent
lubricator for machinery. Tested for alkaloids by treatment with
dilute sulphuric acid, caustic soda, and, finally, citric acid, the oil
yielded a crystalline substance, not an alkaloid, but probably sclero-
crystallin. An attempt to extract the alkaloid from the alcoholic
extract, proved fruitless. The remainder of the paper relates to
various pharmaceutical preparations, such as fluid ergot, made by
extracting the prepared ergot with water by maceration, &c. : alcohol
is subsequently added; the author is of opinion that not more than
25 per cent, of alcohol ought to be added, this quantity being quite
sufficient to precipitate the gummy matter, whilst a larger quantity
would remove some valuable constituents. For pills, powders, &c., the
fluid ergot extract is evaporated down and mixed with milk-sugar.
D. A. L.
i>^
641
General and Physical Chemistry.
Origin of the Hydrocarbon Flame Spectrum. By G. D.
LiVETNG and J. Dewak {Proc. Boy. Soc, 34, 418 — 429). — In former
researches, the authors traced characteristic spectra to carbon asso-
ciated with nitrogen, magnesium with hydrogen and water, of
which the two former, according to the simplest interpretations of
the results, emanate from cyanogen and a compound magnesium
hydrogen molecule (Abstr., 1882, 252). In the course of their
examination of the spectrum of carbon, they wore led to assign a
peculiar flame spectrum to acetylene, a view which receives support
from the fact that carbonic oxide forms a distinct spectrum of a cha-
racter similar to that of the flame spectrum. In order to exhaust this
question, a study was made of the ultra-violet spectrum of carbon (this
vol., 261), by which it was shown that seven marked spark lines of
carbon occur in the spectrum of the arc discharge, and that the strongest
ultra-violet line of carbon occurs in the flame of cyanogen fed with
oxygen. As it seems probable from these observations that the same
kind of carbon molecule exists in the arc and in flame, further experi-
ments were made regarding the origin of the flame spectrum. By a
method similar to that adopied by Wesendonck, the authors have
succeeded in perfectly drying vacuous tubes, and the gases introduced
into them, and thus eliminating the inevitable traces of hydrogen.
The general results of the observations for such tubes prove that the
channelled spectrum of the flame of hydrocarbon, is not necessarily con-
nected with the presence of hydrogen. A tube filled with hydrogen
containing a small percentagce of cyanogen, and then exhausted, gave
only a trace of the brightest green line of the spectrum of the hydro-
carbon flame ; tubes filled with carbonic oxide exhibit the hydrocarbon
flame spectrum when the exhaustion is commencing, but as the
exhaustion proceeds the carbonic oxide spectrum appears, and finally
supersedes the hydrocarbon spectrum. These results were confirmed
b}^ other modifications of the above experiments. In the spark taken
between poles of graphite in hydrogen, the spectrum of the hydro-
carbon flame is seen, but if carbonic oxide be substituted for hydrogen
under ordinary atmospheric pressure, the spectra of carbonic oxide
and of the hydrocarbons appear; if the pressure is increased, the
former grows fainter, the latter brighter, and the line spectrum of
carbon is also visible.
The authors prepared with great care specimens of liquid cyanogen
free from traces of moisture; this, when burnt in oxygen, gave all the
hydrocarbon flame sets; but with air only the single green line
appeared faintly. Thus the hydrocarbon flame spectrum requires a
higher temperature for its pioduction in the combustion of cyanogen,
than that which is sufiicient to produce the special cyanogen molecule
spectrum. Now, cyanogen and acetylene, of all carbon compounds,
give the highest temperature on combustion, and the authors infer
that these flames may reach a temperature of 6000 — 7000". A further
VOL. XLIY. 2 X
642 ABSTRACTS OF CHEMICAL PAPERS.
evidence of the high temperature of the flame of cyanogen is afforded
by the occurrence in the spectrum of the flame, when burnt in oxygen,
of a series of flutiugs in the ultra-violet, commencing approximately
at X2718, X2588, \2479, and \2373, which are in all probability due to
nitrogen.
The authors have further noticed some slight differences in their
observations of the electric discharge between carbon poles in different
gases, when graphite is substituted for ordinary carbon poles (comp.
this vol., 261). In carbonic anhydride, channellings are seen through
the whole length of the spectrum, the triple set of cyanogen flame
spectrum remained strong, when all the cyanogen groups in the violet
had disappeared. On displacing the carbonic anhydride by hydrogen,
the hydrocarbon and hydrogen lines and one of the strongest lines of
carbon appear in the same field of view. The arc in carbonic oxide
shows the triplet and the usual sets of the hydrocarbon flame spectrum,
without any traces of the carbonic oxide spectrum. V. H. V.
Sulphuric Monochloride. By J. Ogier (Comptrend., 96, 646—
648). — Sulphuric monochloride, S02(0H)C1, is easily obtained by the
action of hydrochloric acid gas on solid sulphuric anhydride. Its
specific heat between 15° and 80° is 0282 ; the heat of vaporisation is
12*8 cal. ; heat of solution in water 40 '3 cal. It follows therefore
that —
SO3 sol. + HCl gas = SO3HCI, liquid, develops + 14-4 cal.
SO3 gas + HCl gas = SO3HOI, gas „ -f 18-4 „
This value is of the same order as the heat of formation of analogous
compounds, such as the compounds of hydrocarbons with hydracids.
From the above data, it would follow that pyrosulphuric chloride
can be converted into sulphuric monochloride by the action of water,
for —
S2O5CI2 + H2O = 2S03(0H)C1 would develop + 54 cal.
This change takes place slowly when pyrosulphuric chloride is
exposed to an atmosphere containing a limited quantity of moisture.
Inversely sulphuric monochloride can be converted into pyrosulphuric
chloride by the action of a powerful dehydrating agent, such as phos-
phoric anhydride.
The vapour-density of sulphuric monochloride at 180° and 216° is
2'40 ; the calculated value is 4*03. It is evident that the compound
dissociates at this temperature, although possibly at a temperature
nearer its boiling point its vapour- density would approach more
closely to the calculated value. C. H. B.
Heat of Formation of Chromic Acid. By Berthelot (Compt.
rend., 96, 536 — 542). — Chromic Sulphate. — The heat of formation of
this compound was determined by decomposing chrome-alum with an
equivalent quantity of potassium hydroxide —
CraOa, pptd. -+- 3H2SO4, dilute, at 8° develops -f- 47*0 cal.,
or -|- 156 cal. for each mol. H2SO4, dilute. The actual heat of for-
I
GENERAL AND PHYSICAL CHEMISTRY. 643
mation will depend on the molecular condition of the chromic oxide,
the difference from this cause amounting in some cases to 4*6 X 3 =
13*8 cal. If the chrome- alum is decomposed by an excess of potas-
sium hydroxide, instead of by an equivalent quantity, the heat of
formation of the chromic sulphate becomes + 41 "40 cal., the differ-
ence, 5*6 cal., being due to the different molecular condition of the
chromic oxide. With an excess of potassium hydroxide, the precipitate
is darker in colour, and apparently denser than when an equivalent
quantity is employed. With anhydrous chromic oxide, and especially
with the varieties produced by ignition, the differences would doubt-
less be greater, but no method of dissolving ignited chromic oxide
in the cold is yet known.
Chromic Chloride. — The heat of formation was determined by de-
composing chrome-alum by means of barium chloride —
CraOs, pptd. + 6HC1, dilute, at 8-4° develops -|- 87-0 cal.,
or 6*2 cal. for each mol. HCl. In this case also, the heat of forma-
tion will depend on the condition of the chromic oxide.
The addition of sulphuric acid to chrome-alum develops a sensible
quantity of heat, and in this respect chromic sulphate differs, from the
alkaline sulphates, but resembles ferric sulphate. Chromio oxide, in
fact, belongs to that group of weak bases,- the salts of which are
partially decomposed by water, but are brought back to their original
condition by addition of an excess of acid. Thermochemical measure-
ments show that dilate hydrochloric acid and stannous and stannic
chlorides have no action on chromic chloride, any thermal disturbance
being simply due to the dilution of the solutions.
Chromic Anhydride. — The heat of formation of this compound was
determined by the action of hydriodic acid and stannous chloride
respectively, on potassium chromate and potassium dichromate.
When stannous chloride is the reducing agent, the ptresence of a con-
siderable excess of hydrochloric acid is essential. The mean value of
several concordant determinations, is —
CrjOg pptd. H- O3 + water = 2Cr03 dilute, de^lops + 10*2 cal.
From this result the following numbers can be calculated : —
Develops.
anWride } ^""^^^ PP*^' + ^^ = 2Cr03, crystallised . . H- 6*2 caJ.
'CraOa pptd. + O3 + 2K20,.dil., = 2K2Cr04,
dil.at8° -I- 61*4 „
Potassium . CraOs pptd. + 03+ 2K2O, dil., = 2K,Cr04,
chromate j solid -f- 71*8 „
I CrzOa pptd. + O3 + 2K30, sol., = 2K2Cr04,
L solid +101-8,,
rCraOa pptd. + O3 + K2O, dil., = KaCrgOT,
dil.at8e +37*8,,
Potassium ! CraOs pptd. + O3 + K2O, dil., = KzCraO;,
dichromate ] solid + 54*8 „
I CroOa pptd. + O3 + K2O, sol., = KjCraO,,
I solid +113*0 „
2 JP 2
644 ABSTRACTS OF CHEMICAL PAPERS.
Develops.
rCraOapptd. + O3 + 2NH3, dil., + H2O, liq.,
Ammonmm J = (NH4)2Cr,07 dil. at 12° + 34*6 cal.
dichromate ) CraOg pptd. + O3 + 2NH3, dil., + H^O, liq.,
I = (NH4)2Cr207 cryst + 47-0 „
These values onght to be increased by Q, tbe heat developed by the
conversion of precipitated chromic oxide into the ignited variety.
The decomposition of ammonium dichromate —
(NH4)2Cr207 = CraOa -|- N2 + 4H2O, gas, will develop -f- 78 cal. + Q,
and, from the known specific heats of the products, it follows that
the heat thus developed would raise their temperature to about
1150° + — , a fact which explains the explosive nature of the decom-
position and the incandescence of the chromic oxide formed.
C. H. B.
Heat of Formation of Solid Gly collates. By de Foecrand
(Gompt.rend., 96, 64<9— 662).— Potassium glycollate, 2C2H3O3K + HoO,
crystallises in slender needles which become anhydrous at 120"^. Heat
of solution of hydrated salt — 4't)6 cal., of anhydrous salt — 1*64 cal.
Heat of formation from C,H403 -f- KHO = -f 26-52 cal.*
Sodium glycollate crystallises from hot solutions in anhydrous
rhombic prisms ; from cold solutions in brilliant plates of the com-
position 2C2H303Na + H2O. Heat of solution of hydrated salt
— 8-52 cal. of anhydrous salt —2-56 cals. Heat of formation from
C2H4O3 4- NaHO = 4- 24-64 cal.
Acid sodium glycollate, C2H303Ka +• C2H4O3, obtained in silky
needles by evaporating a solution of the normal glycollate mixed with
an equivalent of acid. Heat of solution — 8-02 cal. ; heat of forma-
tion from 2C2H4O3 + NaHO = -+- 27-52 cal.
Ammonium Glycollate. — An acid salt, C2H3O3.NH4 -|- C...H4O3, is ob-
tained by evaporating a solution of glycollic acid neutralised exactly
with ammonia. Heat of solution — 9-66 cal.; heat of formation from
2C2H4O3 -f- NH3 gas = + 25-39 cal. The normal salt is obtained in
crystals by passing a current of ammonia gas into a cold concentrated
solution of glycollic acid. Heat of solution — 3*23 cal. ; heat of
formation from C2H4O3 + NH3 gas = + 21-51 cal.
Barium glycollate forms anhydrous monoclinic prisms. Heat of
solution — 5-08 cal. ; heat of formation from 2C2H4O3 -|- BaH202 =
+ 40-44 cal.
Strontium glycollate, an anhydrous salt. Heat of solution — 1*20
cal. ; heat of formation from 2C2H4O3 -|- SrH202 = i- 36-16 cal.
Calcium glycollate crystallises from cold solutions with 5H2O. If
precipitated from an aqueous solution by adding an equal volume of
alcohol of 90°, the crystals contain 3H2O ; both hydrates lose their
water at 110°. Heat of solution of (C3H303)2Ca + SH^O - 7-8 cal.;
* In every case, with exception of the ammonium salts, the value given is the
heat of formation of the solid anhydrous salt from the solid acid and solid base.
The heats of solution were determined between 8° and 10°.
INORGANIC CHEMISTRY. 645
of (C2H303)2Ca + 3H2O, - 7-06 cal. ; of (aH303)2Ca, - 1-62 cal.
Heat of formation of anhydrous salt from 2C2H4O3 + CaH202 =
-J- 26-98 cal.
Magnesium glycollate crystallises with 2H2O. Heat of solution of
hydrated salt, — 1 52 cal., of anhydrous salt, + 4'4 cal. Heat of
formation from 2C2H4O3 + MgO = -f- 18'92 cal.
Zinc glycollate also crystallises with 2H2O. Heat of solution of
hydrated salt, — 406 cal. ; of anhydrous salt, + 0*66 cal. Heat of
formation from 2C2H4O3 + ZnO = + 15-98 cal.
Copper glycollate, anhydrous salt. Heat of solution, — 1-62 cal. ;
heat of formation from 2C2H4O3 + CuO = + 12' 74 cal.
Lead glycollate, anhydrous salt. Heat of solution, — 5-80 cal. ; heat
of formation from 2C2H4O3 + PbO = + 16*82 cal.
In every case, the heat of formation of the glycollate, both solid and
in solution, is intermediate between the heats of formation of the
corresponding acetate and oxalate, the heat of formation increasing as
the quantity of oxygen in the acid increases. C. H. B.
Vapour of Carbamide. By F. Isambert (Compt. rend., 96, 840 —
341). — The vapour of carbamide at 61 — 62"^ behaves under changes
of pressure exactly like a mixture of carbonic anhydride and ammonia
gas. Moreover, the condensation of the vapour is accompanied by a
development of heat = 39-8 cal., a number identical with the heat of
formation of carbamide. It is evident, therefore, that the volatilisa-
tion of carbamide is a case of dissociation, and the limiting tension at
a given temperature is the sum of the pressures of ammonia gas and
carbonic anhydride (in the proportion of 2 vols, to 1 vol.) which
limit the dissociation at that temperature. Solid carbamide may be
regarded as formed by the simple addition of carbonic anhydride to
ammonia. C. H. B.
Supersaturation. By S. U. Pickering (Chem, News, 47, 85). —
The author has observed a case of supersaturation in the presence of
some of the solid substance. On cooling a filtered boiling saturated
solution of copper sulphate, a considerable crop of crystals was formed
on the sides of the beaker, and on a glass rod ; as soon as the latter
was disturbed, a sudden and copious separation of small crystals of
copper sulphate took place. L). A. L.
Inorganic Chemistry.
Oxyacids of Chlorine. By C. W. Blomstranp (^^r., 16, 183—
189). — The author does not consider that his views on the conshitn-
tion of the oxyacids of chlorine are rendered untenable by the results
of Spring's experiments {Bull. Acad. Belg., 39, 882) on the action of
phosphorus pentachloride on chlorates and perchlorates.
W. 0. w.
646 ABSTRACTS OF CHEMICAL PAPERS.
Hydroxylamine Hydrochloride, By V. Meyee (Ber., 15, 2789
— 2790). — Small quantities of chemically pure hydroxylamine are
easily produced by Dumreicber's method, but the case is different
when large quantities are required. If some few hundred grams of
it are to be made, a large weight of tin must be precipitated with sul-
phuretted hydrogen. An unmanageable quantity of tin sulphide has
to be filtered and washed, and perhaps a hundred litres of hydrochloric
acid filtrate to be evaporated ; the method besides being troublesome
and tedious on the large scale, does not yield a pure product, and the
impure salt is difficult to keep, whilst if chemically pure it may be
preserved unaltered for a long time. As a small quantity of ammonium
chloride left in the salt is not so injurious as ferric chloride or free
hydrochloric acid, the author gives a method by which a very white
and stable substance can be prepared tolerably free from ammonium
chloride. The acid liquid obtained in the Dumreicher process, which
contains chlorides of iron and sometimes of other heavy metals,
calcium chloride, &c., &c., is strongly concentrated, and when well
cooled supersaturated with soda ; all the heavy metals, together with
calcium, are precipitated and removed by filtration ; the filtrate is
then carefully acidified with hydrochloric acid and evaporated. The
residue consists of sodium and ammonium chlorides, and the hydroxyl-
amine chloride, which is extracted by hot alcohol and crystallises out
on cooling in shining white crystals containing about 90 per cent, of
the pure substance in a very durable form, and available for most
purposes. It is only when a chemically pure substance is required
that the removal of the remaining ammonium chloride is necessary,
which may be effected by platinum chloride. J. F.
Dissociation of Phosphine Hydrobromide. By F. Isambert
(Gompt. rend., 96, 643 — ^46). — The vapour of phosphine hydro-
bromide is a mixture of equal volumes of hydrogen phosphide and
hydrobromic acid, and the compound obeys the vsame law of dissocia-
tion as ammonium bisulphide (Gompt. rend., 95, 1355). It splits up
into hydrogen phosphide and hydrobromic acid until the tension of
these gases reaches a certain limit, which is constant for the same
temperature, but increases at first slowly, and afterwards more rapidly,
with the temperature. C. H. B.
Pyrosulphuric Chloride. By J. Ogier (Gompt. rend., 96, 648—
649). — The author has redetermined the vapour-density of this com-
pound, using a specimen distilled twice over phosphoric anhydride in
order to remove all traces of sulphuric monochloride, S02(0H)C1.
The pure product boils at 140'5° (corr.). Its vapour-density at 185**
was 3-53 and 3-65; at 215° 3*59 and 3-81, mean = 3-72. (See also
this vol., 423.) C. H. B.
Potassium Sesquicarbonate. By C. Rammelsberg (Ber., IS,
273 — 275). — According to Bauer, potassium sesquicarbonate is formed
by the evaporation and crystallisation of large quantities of the bicar-
bonate : it neither deliquesces nor effloresces. Analyses made by Bauer
and by the author are in accordance with the formula 2K2C03,H2C03 -h
SHoO, A. K. M.
INORGANIC CHEMISTRY. 647
Constitution of " Liquor Sodse Chloratae." By W. R. Dun-
STAX and F. Ransom (Pharw. J. Trans. [3], 13, 667—668). — Liquor
sodoi chloratce of the British Pharmacopoeia is prepared by passing
chlorine through a solution of sodium carbonate, and is generally sup-
posed to contain sodium hypochlorite and chloride, and sodium hydro-
gen carbonate, but from observations of Williamson and some experi-
ments of their own, the authors concluded that this preparation con-
tained free hypochlorous acid and not sodium hypochlorite ; this
conclusion is now confirmed by the results of the experiments described
in this paper. After several experiments with various reagents- ether
was found to be an excellent solvent for hypochlorous acid, therefore
some liquor sodce chloratce, B.P., was prepared and extracted with
ether. The ethereal extract had the strong odour of hypochlorous
acid, and readily bleached litmus ; when neutralised with soda, how-
ever, and mixed with nickel ous chloride, it gave a precipitate of green
nickelous hydrate only as long as the ether was present, but as soon
as this was driven off a precipitate of black nickel hydrate was ob-
ained. This anomaly is explained by the fact that ether readily
reduces black nickel hydrate to the green nickelous hydrate. Cobalt
hydrate is also reduced, but not nearly so readily as nickel ; in fact,
this reaction can be used as a distinguishing test for these metals.
The residual liquid from liquor sod(B chloratce, after extraction with
ether, contains sodium chloride and sodium hydrogen carbonate ; on
keeping it, sodium chlorate is formed. Some samples of commercial
liquor sodce chloratce were alkaline to test-paper, contained sodium
hypochlorite, but no free hypochlorous acid and traces of calcium. It
is evident that they were prepared by decomposing bleaching powder
with sodium carbonate. D. A. L.
Action of Chlorine on Solutions of Sodium Carbonate. By
W. R. DuNSTAN and F. Ransom (Pharm. J. Trans. [3], 13, 668— 66^).
— The chlorine employed in these experiments was purified by passing
it through copper sulphate solution : when the chlorination was com-
plete, excess of chlorine was driven out by a current of air before testing
for hypochlorous acid with ether, &c. (preceding Abstract).
In the first series of experiments, a 25 per cent, sodium carbonate
solution was employed, and several quantities of 50 c.c. of this
solution were treated with varying quantities of chlorine. If the
chlorine is not in excess and the solution is still alkaline, it
contains no free hj'pochlorous acid, but sodium hypochlorite in quan-
tities varying directly with the chlorine ; the gas evolved consists of
chlorine and carbonic anhydride. When chlorine is passed until the
solution is only faintly alkaline, it bleaches powerfully, and contains
both sodium hypochlorite and free hypochlorous acid. The small
quantity of gas evolved in this stage of the reaction consists of carbonic
acid. On continuing to pass chlorine, a further small quantity of
carbonic acid is evolved, the solution has the physical properties of
liquor sodce chloratce, and contains sodium hydrogen carbonate, sodium
chloride, and free hypochlorous acid, but no sodium hypochlorite.
Beyond this point, carbonic anhydride is given off with effervescence,
and if the treatment with chlorine is continued until this ceases, the
648 ABSTRACTS OF CHEMICAL PAPERS.
solution contains hypochlorous acid, sodium chloride, and some sodium
chlorate. Exactly similar changes occur in a saturated solution of
sodium carbonate; at first, however, more carbonic aiihj<iriHe is g-iven
ofE than in the case of the more dilute solution. In the next sta^e,
sodium hydrogen carbonate is precipitated, and when this precipita-
tion ceases, the solution contains hypochlorous acid, sodium chloride,
and some chlorate ; effervescence then sets in, and the precipitate
disappears, leaving the solution as in the previous experiment. When
the reaction is conducted at 0°, the changes are the same ; at 100°
the products are sodium chloride and chlorate. The action of chlorine
on sodium hypochlorite gives rise to the production of hypochlorous
acid, sodium chloride, and chlorate. With a mixture of equal parts
of hypochlorite and sodium hydrogen carbonate, cdorine causes no
effervescence at first, and just before it commences the solution is
like the liquor sodce chloratce of the B.P. ; finally, all the carbonate dis-
appears in the manner already described. From these results the authors
represent the changes thus: — CU -f- NaaCOs = NaClO + NaCl -H CO2;
CO2 + OH2 -f ISTaoCOs = 2NaHC03 ; NaClO -f CI2 + H^O = NaCl
+ 2HC10; CI2 + NaHCOa = NaCl -|- HCIO -f- CO2, and the forma-
tion of chlorate by the equation NaCl + 6HC10 = NaClOg + BClz -h
3H2O, whilst they explain the reaction in boiling solutions in the fol-
lowing manner, ^NaaCO^ •+■ SCla = oNaCl -|- NaClOg + SCOj. They
are studying the action of chlorine on certain metallic oxides and
carbonates, and have already obtained some interesting results.
D. A. L.
Production of Brom-apatite and Bromo-wagnerites. By A.
DiTTE {Gompt. rend., 96, 575 — 577). — When a mixture of calcium
phosphate with sodium bromide is heated from one to two hours at a
temperature a little above the melting point of the latter salt, the
calcium phosphate is converted into brom-apatite, CaBr2,3Ca3P208,
which forms regular transparent hexagonal prisms often terminated
by hexagonal pyramids. The products of the reaction are brom-
apatite and sodium phosphate. The proportion of the latter increases
with the amount of calcium phosphate employed, and when it reaches
a certain amount a condition of equilibrium is established between
the reaction of the sodium bromide on the calcium phosphate and that
of the sodium phosphate on the brom-apatite. If tne quantity of
calcium phosphate used is small, it is completely converted into brom-
apatite, but if large the conversion is incomplete, for the sodium
phosphate formed acts on and decomposes the apatite. Indeed apatite
heated with sodium bromide and sodium phosphate in certain propor-
tions is converted into a double phosphate of calcium and sodium.
The corresponding wagnerite, CaBr2,Ca3P208, cannot be obtained
under these conditions, since it is at once decomposed by fused sodium
bronide with removal of calcium bromide and formation of apatite.
This decomposition ceases, however, when the fused mass contains a
very large proportion of calcium bromide, and if a small quantity of
calcium phosphate is heated with pure calcium bromide it is converted
into long slender needles, sometimes terminated by elongated pyra-
mids. These crystals have the composition CaBr2,Ca3P20e. With
a larger amount of calciaiu phosphate, a mixture of wagnerite and
IXORGANIC CHEMISTRY. 649
apatite is obtained, whilst if the amount of phosphate is very large,
apatite is the sole product.
Similar compounds are obtained and similar phenomena are ob-
served with calcium arsenate and calcium vanadates. In the latter
case, a portion of the vanadic acid is sometimes reduced to dark-
coloured lower oxides which remain mixed with the crystals of
chlor- vanadate, &c.
In all cases it is necessary to keep the fused mixtures as much as
possible out of contact with the air. It is evident that the brom-
apatites and bromo-wagnerites are formed and decomposed under the
same conditions as the corresponding chloriae compounds (Gom.pt.
rend., 94, 1592). C. H. B.
Basic Halogen Salts of Barium. By E. Beckmann (/. pr, Chem.
[2], 27, 126 — 147). — A continuation of the author's paper (Abstr.,
1882, 141). These basic barium salts were obtained by crystallisation
of mixed concentrated solutions of barium hydroxide and the halogen
salt ; a varying excess of barium hydroxide beyond that required by
the formulae given by the author was always observed. Basic barium
chloride, BaCl(OH),2H20, crystallises in plates of fatty lustre ; it
readily loses four-fifths of its water at J 20", the remaining one-fifth is
not given oif below the fusing point of the s»lt, and requires several
hours' heating to redness in a stream of hydrogen for its complete
removal. Basic barium bromide, BaBr(OH),2H20, resembles the
chloride in appearance and behaviour on heating. On adding alcohol
to mixed solutions of banum bromide and hydroxide, the basic salt,
BaBr(OH),3H20, was obtained. Basic barium iodide, BaI(OH),4H20,
crystallises in short thick needles.
Crystallised barium hydroxide, Ba(OH)2,8H20, loses 8 mols. HjO on
long heating at Ib"^ , or on heating for two hours at 100° (not 7 mols.
only as generally stated) ; and the combined water is expelled on heating
to redness in a current of hydrogen. Crystallised barium chloride loses
more than 1 mol. H2O when dried over sulplmric acid, and is rendered
anhydrous by heating for some hours at 75°. Crystallised barium
bromide, BaBr2.2H20, loses 1 mol. H2O at 75°, the second at 120°.
Barium iodide, BaJ2,7H20, loses 6 mols. H^O at 125°, the remainder is
not expelled until above 150'^. A. J. G.
Barium Aluminates. By E. Beckmann (/. pr. Chem. [2], 26,
474 — 503). — On adding aluminium chloride to barium hydroxide
solution until a permanent precipitate of alumina is produced, filter-
ing and boiling, the compound Al203,BaO,3BaCl2 + 61120 separates
in the crystalline state. The same compound is formed from mono-
or di-barium aluminate (Abstr., 1882, 141) and barium chloride.
It crystallises in hard rhombic tablets, is but little soluble in cold,
readily in hot water.
The author also describes the compotind Al,03,BaO,BaCl2 H- IIH2O,
obtained from the mono- or di-barium aluminate or the previous salt,
and analogous bromides and iodides. O. H.
Specific Heat and Valency of Thorium. By L. F. Nilson
(-Be>., 16, 153—103). — The specimens of metallic thorium used in
650 ABSTRACTS OF CHEMICAL PAPERS.
these experiments contained 2*4 per cent, of oxygen and 084 of iron.
The sp. gr. of the metal varies from 10-968 to 11-230. The specific
heat of thorium is 0 02787, the atomic weight 232"4, and the atomic
heat 6-41. Thorium also resembles the tetravalent elements, Zr,
Ce, La, and Di, in its atomic volume = 20-94, and silicon in its
crystalline form. Thoria is isomorphous with the dioxides of tin,
zirconium, and titanium, and the molecular volume of thoria agrees
with the molecular volume of Ce02 and UrOa. The molecular beat
of thoria is the same as the molecular heats of the dioxides of zirco-
nium, cerium, titanium, manganese, and tin. The thorium double
fluorides correspond to the double fluorides of zirconium. The platino-
chloride corresponds to the platinochlorides of tin and zirconium.
Thorium attacks platinum, forming a fusible alloy. The close re-
semblance between thorium and the tetravalent elements as exhibited
by the above facts shows that thorium is tetravalent, and that its only
known oxide is a di-oxide, ThOo. W. C. W.
Formation of Arsenides by Pressure. By W. Spring {Ber., 16,
324 — 326). — When a mixture of zinc and arsenic in the proportions
to form Zn3As2, is subjected to a pressure of 6500 atmospheres, the
resulting block powdered, and the opei*ation repeated, a homogeneous
mass is obtained showing crystalline structure. It dissolves in dilute
sulphuric acid with evolution of arseniuretted hydrogen, leaving but
a small black insoluble residue. In a similar manner, lead arsenide^
PbaAs^, tin arsenide^ SuaAso, cadmium arsenide, CdsAsa, copper arsenides^
CugAso, Cu6As2, and Cu]2As2, and silver arsenides, AgsAs and AgeAs,
can w4th more or less difficulty be obtained. When amorpJious ai-senic
(sp. gr. 4- 71) is subjected to a pressure of 6500 atmospheres, it assumes
a metallic lustre, whilst its sp. gr. becomes raised to 4-91 ; as the sp.
gr. of crystalline arsenic is 5*71, it is assumed that one quarter is
converted by pressure into the crystalline variety. (For previous
investigations see Abstr., 1882, 921.) A. K. M.
Tungsten Compounds. By G. v. Knoere (.7. pr. Chem. [2], 27,
49 — 98). — Tungsten Bronzes. — Only a s,va.^\Q potassium tuvgsten bronze
can be obtained by the reduction of the acid potassium tungstates by
heating in hydrogen, by fusion with tin, or by electrolysis. It has the
formula K2W4O12, and crystallises in prisms of reddish- violet colour ;
when finely powdered it assumes a fine blue colour; the powder when
suspended in water gives a liquid, blue by transmitted, greenish by
reflected light. Its sp. gr. is 7-09 when prepared by heating in hydro-
gen, and 7-135 when prepared by electrolysis. The author could not
obtain the bronze K2W6O10 described by Zetnow {Fogg. Ann., 130,
262).
By fusing a mixture of equal mols. of 5K20,12W03,11H20, and
5Na20,12W03,28H20, and then heating to low redness in a stream of
hydrogen, the sodium potassium bronze, 5K2W40,2,2Na4W50i5, is
obtained crystallising in dark purple-red quadratic (?) prisms. Its
sp. gr. is 7-117. The powder is blue. The same mixture of acid
tungstates gave on another occasion a bronze of darker red colour than
the preceding, and of the formula 3K2W40i3,2Na2W309.
ORGANIC CHEMISTRY. 65l
Ko bronzes could be obtained by the reduction of the acid lithium
tungstates, tungsten dioxide being formed. Bj the action for a short
time of tin on fused 5Li20,12W03, a body of the approximate formula
Li2W50i6 was obtained. (The sodium bronzes have been described by
Phillip, Abstr., 1882, 930.)
Tungstates. — The acid sodium salt, 5Na20,12W03,28H20, is de-
composed on fusion according to the equation 3(5Na20,12W03) =
yNaaWiOia + SNaaWOi. Contrary to Scheibler's statement (/. pr.
Chem., 83, 291) the salt, Na2W40i3, dissolves on continued treat-
ment with cold water ; but, in agreement with Scheibler, the author
finds that the unignited salt dissolves in water at 13-5°, the solution
giving the reactions of sodium metatungstate.
Sodium ditungstate, NagWzOv, is obtained by fusion of the mixture
Na20 + 2WO3, and separates on cooling in long needle-shaped
crystals. It dissolves completely on heating it for some hours with
water at 130 — 150° ; the alkaline solution does not recrystallise, and
contains tungstate and metatungstate.
Sodium pentatiingstate, NaaWeOie, is obtained by fusion of the mix-
ture ]S'a2W04 + 2WO3, or by heating sodium paratungstate to in-
cipient fusion. On extracting the fused mass with cold water, it is
left in very brilliant plates or scales. When heated for three hours
with water at 150°, but little dissolves, the faintly acid liquid containing
tungstate and metatungstate, the latter in by far the larger quantity.
Sodium octotungdate, Xa2W8025, is obtained by fusing sodium meta-
tungstate, or Na2W40i3, and after extraction of the fused mass with
water, is left crystallised in brilliant scales or plates. It is attacked
with difficulty by acids or alkalis.
The author has endeavoured to prepare the ditungstate,
Na2W207,6H20, described by Lefort, but, although exactly following
the method of the latter, finds the product to be the ordinary acid
salt, 5Na20,12W03,28H20. "With the potassium salt, an exactly similar
result was obtained. A. J. G.
A Phosphide of Nickel. By E. .Tannetaz {Jahrh. /. 3/iw., 1883,
1, Ref., 198). — This compound, N5P, was obtained by melting together
calcium phosphate, powdered charcoal, and metallic nickel (or, better,
nickel oxide). On cooling slowly, cavities lined with acicular crystals
were formed in the mass. The crystals are long rectangular prisms
belonging to the tetragonal system. They are of a pale-yellow colour,
have a hardness of 5'5, and a sp. gr. of 7'283. B. H. B.
Organic Chemistry.
Normal Paraffins. By C. Schorlemmer and T. E. Thorpe
(uinnalen, 217, 149 — 152). — In a previous commnnioation, the authors
stated their intention of investigating the heptane of Pinus sahintana^
the subject of the present paper. When treated with chlorine, this
^02 ABSTRACTS OP CHEMICAL PAPERS.
heptane yields a mixture of monochlorides (b. p. 143 — 157'5®), from
which are obtained alcohols (b. p. 150 — 168" and 165 — 170°) yielding
on oxidation mathyl perifyl ketone and oenanthylic or heptoic acid. The
ketone when lurther oxidised — with chromic acid solution in sealed
tubes at 100° — gives valeric and acetic acids. By treatment with
alcoholic potash, the mixture of chlorides yields heptyJene and a
mixture of ethi/l heptyl ethers. When left in contact with fuming
hydrochloric acid for six weeks in a dark place, only 10 per cent,
of the pine heptyleiie (b. p. 98'5°) is chlorinated, whilst under
similar circumstances hexylene from mannitol is entirely converted
into secondary hexyl chloride, and heptylene from petroleum is half
converted into heptyl chloride. On allowing the unattacked portion
of the olefines to remain in contact with the acid for several months,
the pine heptylene combines almost completely with the hydrochloric
acid, whereas only a small additional quantity of the petroleum hep-
tylene enters into combination. From these results it is evident that
treatment with hydrochloric acid in the cold is not an eflBcient means
for the separation of isomeric olefines. By oxidation with chromic
acid mixture, this heptylene breaks up into valeric and acetic acids ; it
can therefore be represented by the formula C4H9.CH ! CHMe, and is
hutylmethylethylene. From these and previous results, the authors
conclude that by chlorinating normal paraffins, not several but only
two chlorides are produced, viz., the primary and one secondary, con-
taining the group — CHClMe. Bromine acts in a similar manner
{Annalen, 188, 249, and Ber.j 13, 1649) with petroleum paraffin.
D. A. L.
Hydrocarbons from Peat. By E. Durin (Compt. rend., 96, 652
- — 653). — The author has previously found that the solid products
obtained by distilling peat in a current of superheated steam in a
vacuum consist largely of fatty acids (Compt. rend., 188i). He now
finds tliat a waxy substance, giving the same reactions as the fatty
acids from peat, is obtained by applying the same treatment to fresh
moss resembling that from which the peat has been formed. It
would appear, iheiefore, that these fatty acids are not formed during
the decomposition of the vegetable matter, but exist in the fresh moss.
Analyses of the fatty acids from peat lead to the empirical formula
C47H47O2, but in all probability the acids were not perfectly purified.
C. H. B.
Maltose and Isomeric Gluconic Acids. By A. Herzfeld {Bied.
Centr., 1883, 127 — 129). — Maltose prepared from potato-starch has a
rotatory coefficient of [ajo = 140'6°, and combines with calcium,
barium, and strontium with 1 mol. water ; neither alkaline compounds
nor a compound with borax have been obtained, but an acetyl deriva-
tive, CioHjiOiaXcg, having a rotatory coefficient [ajo = 81" 18° has
been prepared. It is well known that maltose reduces Fehling's solu-
tion to the extent of two-thirds of the copper suboxide, but if this
suboxide be filtered off and the filtrate acidified with hydrochloric
acid, it will when warmed reduce a further quantity of Fehling equal
to about half of the original quantity, the total quantity being equal
to that reduced by an equivalent of grape-sugar. Lactose behaves in
ORGANIC CHEMISTRY. 653
a like manner. Dextrinic, maltoic, and j^luconic acids, prepared by
the action of bromine and water on dextrin, maltose, and grape-
sugar, are shown to be identical, and not capable of reducing Feh-
ling's solution. E. W. P.
Action of Zinc-ethyl on Amines and Phosphines. By H.
Gal (Gompt. rend., 96, 578 — 580). — Frankland obtained the compound
NiPh^HoZn by the action of zinc-ethyl on aniline, and Drechsel and '
¥inkelstein obtained the analogous compound (PH2)oZn by pas-^ing
hydrogen phosphide through an ethereal solution of zinc-ethyl. The
author finds that similar compounds are obtained by the action of
zinc-ethyl on dry ammonia, (NH2)2Zn, ethylamine, (NHEt)2Zn, and
tolnidine, (NHC7H7)>Zn. It would appear, therefore, that when zinc-
ethyl acts on anamraoniacal derivative in which all the hydrogen has
not been replaced, a metallic derivative is formed and ethane is given
off in accordance with the following equation, where Am represents
any primary or secondary amine : —
2Am + ZnEtg = (2Am - H2 -f Zn) + 2C2H6.
A similar reaction takes place with the phosphines. As a rule, these
reactions are very violent, and ib is better to use an ethereal solution
of zinc- ethyl.
Tertiary amines and tertiary phosphines, such as triethylamine,
dimethylanilme, methyldiphenylamine, and triethylphosnhine, do not
react with zinc-ethyl under ordinary conditions. The reaction
described above consequently furnishes a ready means of distinguish-
ing between a primary or secondary amine or phosphine on the one
hand, and a tertiary amine or phosphine on the other.
Zinc-ethyl has no action either on nicotine or on quinoline. These
compounds appear, therefore, to contain no hydrogen replaceable by
zinc.
The majority of the alkaloids containing oxygen are, however,
readily attacked by zinc-ethyl with formation of metallic derivatives
which alter slowly when exposed to air, and are rapidly decomposed
by water with reproduction of the alkaloid and formation of zinc
oxide. . C. H. B.
Cyanmethine. By E. v. Meyer (J. pr. Chem. [27], 152—156). —
Cyanmethine is best prepared by treating sodmm (1 part) with dry
methyl cyanide (6 parts) under a pressure of about 10 cm. of mer-
cury; the gas evolved during the reaction is pure methane, not
ethane as stated by Bayer (Ber., 2, 319). Cyanmethine dissolves in
5*25 parts alcohol at 18°, and in 064 part of water at 18°, thus
differing widely from cyanethine, which requires 1870 parts of water
at 17° for solution. Mixed in aqueous solution with solution of silver
nitrate, a voluminous white precipitate of the compound
(C6H,N3)2,AgN03,
is obtained ; this crystallises from hot water in colourless rhombohe-
drons. An aqueous solution of cyanmethine also gives amorphous
voluminous precipitates with lead acetate, mercury, and barium chlo-
654 ABSTRACTS OF CHEMICAL PAPERS.
rides, &c. Treated in glacial acetic acid solution with nitrons acid, it
exchano^es the amide- for the hydroxj-group, being converted into the
corresponding hjdroxj-base, whose nitrate, C6H8N20,N03H, separates
on cooling as a crystalline mass, readily soluble in water, sparingly
in cold alcohol, more readily in hot, from which it recrystallises in
tufts of long brilliant needles.
The free base, CeHvNaCOH), obtained by the action of soda on the
nitrate, crystallises in white needles melting at 194°. On adding
silver nitrate and ammonia to the nitrate, a flocculent voluminous
precipitate of the silver derivative, CeHvAgNgO, is obtained: this
crystallises from ammonia in thin plates. Bromine acts more readily
on cyanmethine than on cyanethine, yielding bromocyanmethine ; but,
contrary to expectation, succinic acid could not be obtained from the
products of the reaction (comp. cyanethine, this vol., 352, and also
Abstr., 1881, 54). From bromocyanmethine the bromhydroxy base,
CeHvBrNaO, and its silver derivative, CeHgBrAgNzO, have been pre-
pared, and are being submitted to further examination.
A. J. G.
Thiocyanacetone. By J. Tcherntac and R. Hellon (Compt.
rend., 96, 587—589 ; and" Ber., 16, 348— 359).— Barium thiocyanate
is the only thiocyanate which yields thiocyanacetone in satisfactory
quantity (compare this vol., p. 568). This salt is very soluble in
alcohol; at 20° the saturated solution contains 30 per cent, of the
anhydrous salt, and boiling alcohol dissolves 32'8 per cent.
To prepare thiocyanacetone, 175 grams crystallised barium thio-
cyanate are dissolved in 525 grams alcohol and mixed with 100 grams
monochloracetone ; barium chloride is precipitated, and after some days,
when precipitation of this salt is complete, the liquid is filtered and
the filtrate evaporated on the water-bath. The syrupy residue is
boiled with 10 times its weight of water, the solution allowed to
stand 24 hours, the clear liquid decanted from the layer of tarry sub-
stances which separate out, filtered, and evaporated on the water-
bath until the volume of the oil which is gradually deposited is equal
to the volume of the aqueous solution. The oil is then separated
from the aqueous liquid, washed with a small quantity of distilled
water, and dried in a vacuum over sulphuric acid.
Thiocyanacetone, SCN.CH2.CO.Me, is an odourless liquid almost
colourless when pure, but becoming deep red by long exposure to air.
Its sp. gr. at 0° is 1*209; at 20°, 1*195. It is slightly soluble in
alcohol, ether, &c. It cannot be distilled without decomposition, even
in a vacuum, and it is not sensibly volatile in a current of steam. If
dry, it does not lose weight when exposed over sulphuric acid in a
vacuum, a fact which would indicate that it is a polymeric modifica-
tion. It dissolves rapidly with development of heat in a concentrated
solution of an alkaline bisulphite, and can be separated from this solu-
tion by the ordinary reagents, though only in an impure condition.
When heated on the water-bath for some hours with an equivalent
quantity of ammonium thiocyanate, thiocyanacetone yields a con-
siderable quantity of thiocyanopropimine tJdocyanate identical with that
obtained bv the action of ammonium thiocyanate on monochloracetone.
ORGANIC CHEMISTRY. 655
This fact confirms the general view of the constitution of thiocyano-
propimine. C. H. B.
Decomposition of a-Fluoboracetone by Water. By F. Landolf
(Compt. rend., 96, 580 — 582). — a-Fluoboracetone is a liquid which
boils at 120°, and does not solidify at — 15°. It is immediately de-
composed by water with separation of boric acid and formation of
gaseous and liquid products, all of which dissolve in water and have
an agreeable ethereal odour.
Acetone monohydrofluoride, CaHeOjHF, a liquid which boils at 55°,
has an agreeable odour, is very soluble in water, and burns with an
almost invisible bluish flame.
Acetone dihydrofluoride, C3H60,2HF, is a gas which has a strong
ethereal odour, burns with an almost invisible bluish flame, and is
very soluble in water, from which it is expelled by a slight rise of
temperature. It can be liquefied by means of a mixture of ice and
salt, and the liquid boils at from — 15° to — 12°. The vapour-
density of the compound, 1'72, is somewhat more than half the calcu-
lated value, 3'18. The author regards this compound as not merely
an addition-product, but as a true chemical compound, in which car-
bon is hexatomic. He considers that it will be possible by means of
these fluoboro-compounds, to obtain what may be called supersaturated
compounds. The compounds of boron fluoride, with organic substances,
furnish a simple and certain method of obtaining any required fluorine
derivative.
The vapours of these compounds when inhaled, produce strong
nervous irritation, with somewhat high fever. Salivation increases
considerably, and the skin of the gums of the lower maxillary is
strongly attacked and partly corroded. These efiects last for some
time. C. H. B.
New Method for Preparing Carbonic Oxide. By H. Jahn
(Ber.,16, 308).— A reply to Noack (this volume, p. 574).
Insoluble Residue from the Distillation of Castor- oil. By
A. R. Leeds (Ber., 16, 290— 293).— The residue obtained in the pre-
paration of oenanthaldehyde from castor-oil was examined by Stanck
(/. pr. Chem. 63, 138), but its nature has not been determined. The
author distilled castor-oil under diminished pressure (100 mm.), and
obtained a residue which when cold had the consistence of caoutchouc.
On washing it with alcohol and afterwards with ether, it lost its
stickiness and its elasticity almost entirely disappeared, the colour
changing from brownish-red to yellowish-grey. Its composition,
C42H68O5, agrees with that given by Stanck. When the caoutchouc-
like residue is saponified with potash, the solution filtered hot and
hydrochloric acid added, an oil is obtained lighter than water, and of
a brownish-red colour. It is very readily soluble in alcohol and ether,
but insoluble in water. Its composition agrees with Stanck's
formula, CaeHsgO?. It decomposes w^hen heated, yielding a distillate
boiling between 110° and 250", the difierent fractions of which yield
no salts with the alkalis. By exposure to light and air, they absorb
056 ABSTRACTS OF CHEMICAL PAPERS. ,
oxyoren, and darken in colour. No nitrogen could be detected in any
of the oils. The author does not agree with Stanck as to the con-
stitution of the body, C42H68O5, as he is unable to obtain acraldehyde
from it ; neither does he think that the compound, Csr.HgftOT, can be re-
garded as CaeHseOz plus water of crystallisation, its formula being
more probably CaeHeaOi. A. K. M.
Addition of Bromine to Ethyl Acetoacetate. By C. Duisbero
{Ber., 16, 295— 297).— A repk to Lippmann and Conrad. The
author doubts the existence of Lippmann's ethyl acetoacetate dibro-
mide (Abstr., 1882, 177). A. K. M.
AUylsuccinic and Carbocaprolactonic Acids. By E. Hjelt
(Ber., 16, 333 — 335). — By the action of sodium ethylate and ethyl
chloracetate on ethyl malonate, ethyl ethenyltricarboxylate is obtained,
and by the introduction of an allyl-group into the latter, ethvl allyl-
ethenyltricarboxylate (b. p. 282—283°). The free allylethenyltHcar-
boxy lie acid dissolves readily in the ordinary solvents, but forms
insoluble calcium, barium, and silver salts. With hydrobromic acid,
it forms a crystalline body melting at 159°. The acid melts at 151"
with evolution of carbonic anhydride and formation of allylsuccinic
acid, COOH.CH(C3H5).CH2.COOH, the latter crystallising in plates,
which melt at 93 — 94°. It is isomeric with terr>conic acid, to which
it bears much resemblance. It forms an anhydride when heated, and
in its reactions it resembles propylsuccinic acid (Annalen, 214, 58).
It dissolves in fuming hydrobromic acid, but not easily, and on adding
water to the solution, boiling, and finally extracting with ether, an
oily acid is obtained which crystallises in a vacuum. After recrystal-
lisation from alcohol, carbocaprolactonic acid, C7Hin04, melts at 68 —
69°. It decomposes but slightly on heating, and distils at about 260*.
It is isomeric with terebic acid. A. K, M.
Meconic Acid and some of its Derivatives. By E. Mennel
(/. pr. Chem. [2], 26, 449 — 473). — Meconic acid, as Liebig has
shown, yields three different silver compounds, and has therefore
been considered to be a trihydric acid. All attempts to prepare the
three corresponding ethyl salts have, however, proved abortive, only
mono- and di-ethylic ethers being known. The author, suspecting
that the acid was only dibasic, the third replaceable hydrogen-at-om
not belonging to a carboxyl-group, undertook the study of the methyl
and ethyl salts of the acid, which have also been examined by How
(Ann., 83, 350).
If a current of dry hydrochloric acid gas is passed into absolute
alcohol containing in suspension half its weight of meconic acid (dried
at 120°), the meconic acid dissolves, and crystals soon begin to form.
The current of hydrochloric acid is then stopped, and the crystals are
washed with absolute alcohol, crystallised from the same solvent, and
lastly from boiling water.
Monethjl meconate, C6H0o(0H)(C00H).C00Et, is thus obtained
in large colourless needles, melting at 179°. Sometimes from the
alcoholic mother-liquors monethijl comenate (m. p. 126'5°) separates
ORGANIC CHEMISTRY. 657
in well-formed crystals, meconic acid readily losing" carbon dioxide
with formation of comenic acid. If the current of hydrochloric acid
^as is continued until the crystals formed at first have again passed
into solution, and the syrupy liquor is then poured into water, diethyl
meconate, C5H02(OH)(COOBt)s, at once separates in anhydrous
laminar crystals, melting at 111*5°. From a more dilute solution
the compound crystallises with | mol. H2O.
When argentic diethylmeconate, prepared by precipitating a hot
solution of diethylmeconic acid with silver nitrate, and carefully
neutralising the fluid with ammonia, is heated for 4 hours with ethyl
iodide, it yields triethyl meconate^ melting at Q7°^ and crystallising
readily from alcohol. It is but very sparingly soluble in water,
readily so in alcohol, ether, or chloroform. It does not give a red
coloration w^ith ferric chloride (as do the two other ethylic compounds),
and does not therefore include any hydro xyl -group.
The author considers the formation of this ether as a conclusive
proof of the dibasic nature of meconic acid, to which he assigns the
formula C5B[02(COOH)2.0H. That this conclusion is correct is
further demonstrated by the fact that two isomeric monethylic com-
pounds exist, etUylmeconic acid, C5H02(COOH)2.EtO -f H2O, being
obtained on boiling the triethylic compound for several days with
water in a flask with reflux condenser. The acid separates from the
solution in small white prisms, melting at 200°, with copious evolution
of carbonic anhydride. The aqueous solution is strongly acid, and
does not colour ferric chloride. It does not precipitate any metallic
solutions, even after neutralisation, with the exception of those of
copper and lead. Lead ethylmeconate crystallises with IJ mols. H2O.
As stated above, the acid loses carbonic anhydride at 200", leaving
ethylcomenic acid, C5H202(COOH).EtO ; this crystallises readily
from hot water or alcohol, and melts at 239 — 240°. Silver ethyl-
comenate crystallises with 2 J mols. H2O.
On adding ammonia in excess to a solution of monethyl meconate
in hot water, and allowing it to cool, a voluminous yellow precipitate
separates, consisting of diammonic meconaminate,
C5H02(COXH2)(COOI^H4).ONH4,
from which monomeconamic acid, 05H02(CONH2)(COOH).OH, is
readily obtained. On evaporating a solution of meconaminate, it loses
ammonia, and yields meconate.
On adding bromine to solutions of meconic acid, carbonic anhydride
is given off, even at very low temperatures, and bromocomenic acid
is formed, and this when treated with another molecular weight of
bromine gives rise to hromoxy bromocomenic acid,
aHBr02(C00H).0Br -I- SH^O,
in which the hydrogen of the hydroxyl-group is also replaced by
bromine. It is readily soluble in water and alcohol, less so in chloro-
form, ether, or benzene. Its aqueous solution gives a characteristic
reaction with barium chloride, as follows : barium chloride alone
produces no effect, but on the addition of ammonia a yellow precioi-
VOL. xiiv. 2 y
658 ABSTRACTS OF CHEMICAL PAPERS.
tate is formed, whicli with excess of ammonia becomes volnminous,
and of an orange colour.
By treating monethyl meconate with bromine, the ethylic salt of
bromoxybromocomenic acid is obtained. 0. H.
Dry Distillation of Tartaric and Citric Acids with Excess
of Lime. By Freydl (Monatsh. Chem., 4, 149 — 152). — Dried
Rochelle salt, when distilled with an equal weight of quicklime, yields
much gas, consisting almost entirely of hydrogen, together with a
distillate separating into an oily and an aqueous layer. In the aqueous
solution only acetone could be found, whilst in the oily layer benzene
occurs in small quantity.
The aqueous layer of the distillate from tlie distillation of sodium
citrate contains acetone. This was tested for isopropyl alcohol by
Linnemann's method, with negative result. A. J. G.
Biuret Dicyanamide. By F. Resinski (/. pr. Chem. [2], 27,
157 — 159). — Baumann having shown (this Journal, 1874, 793 ; 1875,
446) that dicyanodiamidine is formed on fusing carbamide with
guanidine carbonate, the author endeavoured to ascertain if substi-
tuted ureas behaved in a similar manner. Acetyl-carbamide was mixed
with two and a half times its weight of guanidine carbonate, and the
mixture slowly heated at 140 — 150°, until the fused mass resolidified.
The product was boiled with water, and on cooling, the filtrate de-
posited an amorphous white precipitate of biuret dicyanamide. This
is soluble in alkalis and mineral acids, being reprecipitated from its
solutions in the latter by addition of ammonia. It has only weak
basic properties, its salts being readily decomposed by water. The
nitrate, CiHTN^OajHI^Oa, crystallises in anhydrous rhombic needles.
A. J. G.
Glutamine. By E. Schulzb and E. Bosshaed (Ber.^ 16, 312 — 315).
— The existence of an amide of glutamic acid in the sap of the beet-
root and pumpkin-shoots has been previously shown (Ber., 10, 85 and
199) ; the authors have succeeded in isolating this body {glutamine),
and show that it is a homologue of asparagine. Fresh beetroot sap is
precipitated with acetate of lead, and then a neutral solution of mer-
curic nitrate is added to the filtrate. The white flocculent precipitate
thus obtained is decomposed with hydrogen sulphide, and the filtrate
neutralised with ammonia and evaporated. Glutamine then separates
in slender white anhydrous needles, readily soluble in boiling water,
insoluble in strong alcohol. With cupric hydroxide, it forms a crystal-
line compound very similar in appearance to the corresponding
asparagine compound. When glutamine is heated with alkalis or
with baryta-water, half the nitrogen is given oil as ammonia, whilst a
salt of glutamic acid is formed. From the analogy which glutamine
bears to asparagine, the authors assign to it a similar constitution,
COOH.OsHsCNHO.CONHj. From 1 litre of beetroot sap 07— 09 gram
glutainine was obtained.
Similar results have been obtained with pumpkin-shoots, but in this
case the isolation of the glutamine is more difficult, apparently from
ORGANIC CHEMISTRY. 659
the presence of other substances which interfere with its crvstallisa-
tion. A. K. M.
Action of Chlorine on Sulpho-derivatives and Organic Oxy-
STilphides. By W. Spring and C. Winssinger (Ber., 16, 326—330).
— In continuation of pre^vious experiments CAbstr., 1882, 938), the
authors find that pure propylsulphonic acid (like ethylsulphonic acid)
completely resists the action of chlorine, showing that the sulpho-
group exerts an influence over the entire molecule. By the action of
iodine trichloride (2 mols.) on the sulpho-acid (3 mols.) at 150 — 160°
in sealed tubes, the following reaction is supposed to take place : —
22ICI3 + 33C,H7S03H = 6[C3H6C1S03H + 3(C3H7.SO,H)] +
9C3HgCl3 + 9S02(OH)Ci + 24HC1 + III2. The ehloro-sulphonic
acid first formed becomes further chlorinated with displacement of
the sulpho-group, sulphonic acids in which more than one hydrogen-
atom is replaced by chlorine being incapable of existing in the pre-
sence of iodine trichlbride. If propylsulphonic acid (1 mol.) is heated
for three days witli iodine trichloride (6 mols.),, the chlorination goes
much further, CsClg being probably first formed, but finally converted
into C2CI6 and CCI4. If the heating is carried on only half as long,
the chief product is an acid, the barium salt of which has the formula
(C3H7.S03.Ba.S03.C3H6Cl)2,H20. By the action of chlorine on propyl-
oxysulphide in aqueous solution, dipropylsulphone, chloroppopyl-
sulphonic acid, and trichloro- and tetrachloro-propane are prodnced.
Since neither C3H7SO3H, (C3H7)2S02 nor C3H7SO2CI is acted on by
chlorine, the authors assume that monochlorodipropyloxysulphidB,
C3H6CI.SO.C3H7, is first formed, and then the chloride C3H6Cl.S02Ch
Since ethyloxysulphide does not yield similar results, it seems pro-
bable that in the latter compound the SO-group exerts an influence
over the whole molecule, preventing substitution. A. K. M.
Amylbenzene. By F. W. Dafert (Mmatsh. Chem., 4, 15S—165).
— By the action of zinc-ethyl on benzotrichloride, the author has
obtained, not as he expected, a heptyl-benzene of the formula Ph.CEta,
but ethylene and Lippmann and Louguinine'samylbenzeaevPh.CHEta.
A. J. G.
CEnanthal-aniline, CEnanthal-xylidine, and CEnanthal-
naphthylamine. By A. R. Lbh:ds (Ber.^ 16, 287— 288).— To pre-
pare these compounds^ cenanthaldehyde is gradually mixed with the
amine in molecular proportions, and the whole heated for six hours
with reflux condenser : the product is purified by dissolving it in
glacial acetic acid, heating the solution for somo hours on a water-
bath, and largely diluting with water ; the precipitate is finally
washed with water until free from acid. OEnanthal- aniline,
C6H;N,C,HuO,
nnd cenanthal-xylidine, C8HnN,C-HuO, are perfectly similar mobile
liquids of agreeable ethereal odour. CEnanthal-naphthylamine,
CioH9N,C7HuO,
fiOO ABSTRACTS OF CHEMICAL PAPERS.
is similar to tne above, bnt has a more decided odour, resembling that
'of the pine-«app]e. These bodies are stable, and can be sublimed with
partial decomposition. A. K. M.
Diazo-derivatives of " Symmetrical " Tribromaniline. By
H. SiLBERSTEiN (/. pr. Gkem. [2], 27, 98— 125).— When tribrom-
aniline [1:2:4:6], half dissolved, half suspended in alcohol, and
well cooled, is treated with a rapid stream of the gas obtained by
heating a mixture of arsenic trioxide and nitric acid, the main pro-
duct is a yellow body, tribroniodiazobenzene nitrate, a pale coloured
compound, hexbromofliazoamidobenzene being obtained at the same
time. If a slow stream of the gafl, obtained without heating from a
mixture of arsenic trioxide and nitric acid be employed, the latter
compound is obtained with only a very small admixture of the yellow
body.
Tribromodiazohenzene Nitrate^ C6H2Br3.N2.XO3, crystallises in yellow
rhombic tables, readily soluble in water and hydrochloric acid,
sparingly in glacial acetic acid, more sparingly in alcohol. It is
moderately stable in the dry state, but soon decomposes in presence
of moisture. It explodes sharply when rubbed strongly, or when
heated to 85". It is decomposed with evolution of nitrogen by treat-
ment with solution of caustic soda, ammonia, or potassium cyanide.
Heated with alcohol, it yields tribromobenzene (m. p. 119"^), nitrogen,
nitric acid, and aldehyde. No nitrogen is evolved on boiling it with
water. A cold aqueous solution of tribromodiazohenzene nitrate decom-
poses after a time with formation of tri- and tetra-bromobenzene,
together with other products not yet identified. On heating it with
glacial acetic acid, a violent reaction takes place, nitrogen and
oxidation products are evolved, and tribromobenzene (m. p. 119°) is
formed. On heating tribromobenzene nitrate at 50° with benzene,
nitrogen and reddish- brown vapours are evolved, and an amorphous
body separates. This latter, on treatment with alcohol or water, is
decomposed into nitric acid and dibromodiazophenol,
fCeHjBr/ ^N [.Br : Br :N2: 0 = 2: 6:1:4].
^0^
It crystallises in yellow oblique prisms, is insoluble in cold, but little
soluble in boiling water, readily soluble in hot ethyl or amyl alcohols ;
it explodes when heated to 142°. It possesses weak basic properties,
and forms very unstable salts on gentle heating with concentrated
acids. When heated more strongly with acids, it decomposes, e.g., with
hydroferomic acid, it yields nitrogen and tribromophenoL By oxida-
tion with chromic acid it yields dibromoquinone in small quantity;
on reduction with tin and hydrochloric acid, it is converted int')
ammonia and dibromoparamidophenol. Free dibromodiazophenol is
also formed to some extent in the reaction between benzene and tri-
bromodiazohenzene nitrate,^ogether with tetrabromobenzene (m. p. 98°)
and nitro-benzene.
Tribromediazohenzenesnlfliate^ C6H2Br3.N9.HSO4, is best prepared by
adding nitrous acid to a mixture of sulphuric acid and alcoholic soln-
ORGANIC CHEMISTRY. 661
tion of tribromaniline. It forms nearly colourless prisms, moderately
soluble in water, sparingly soluble in alcohol and glacial acetic acid,
insoluble in ether and benzene. On heating it with alcohol, it is decom-
posed into tribroraobenzene, nitrogen, and sulphuric acid. Boiled with
acidulated water, it does not yield tribromobenzene ; with glacial acetic
acid and also with benzaldehyde, it gives a large yield of tribromo-
benzene. Boiling benzene does not attack the sulphate.
Tribromodiazobenzene chloride was obtained in solution only, but
the corresponding ^erhromide, C6H2Br3.N2.Cl,Br2, is obtained by heating
a solution of tribromodiazobenzene nitrate in concentrated hydrochloric
acid; it separates in clear yellow brilliant prisms, explodes on heating
to 100", yielding tribromochlorobenzene, nitrogen, and bromine. It is
nearly insoluble in most solvents. Heated with glacial acetic acid, it
gives trlbromochlorohenzene, C6H2Br3Cl, crystallising in long silky colour-
less needles (m. p. 80°), readily soluble in ether, benzene,, chloroform,
and hot alcoho-l, and in. glacial acetic acid, sparingly soluble in cold
alcohol or acetic acid.
Trihromodiazohenzeyielmide. C6H2Br3.N<f || , is obtained "by the action
of dilute aqueous ammonia on the perrbromide. It crystallises in
colourless needles melting at 59°. It can be distilled with water
vapour; is insoluble in water, readily soluble in alcohol,, ether, and
chloroform, and is not reduced by zinc and sulphuric acid.
Tribromodiazohe'iizene hromide, C6H2Br3.N2Br, obtained by the action
of hydrobromic acid on the nitrate, crystallises in brilliant golden-
yellow rhombic tables. It explodes- nearly as violently as the nitrate
on heating. It is sparingly soluble in water,, insoluble in alcohol
and ether. The corresponding perbromide, GpHoBrs.Nz-Bra, crys-
tallising in orange-yellow prismatic needles, is obtained by the action
of bromine and hydrobromic acid on the nitrate. Both the bromide
and perbromide yield unsymmetrical tetrabromobenzene (m. p. 98"5°)
when heated with glacial acetic acid.
Hydriodic acid reacts violently with an aqueous solution of the
nitrate, yielding tribromiodohenzene, C6H2Br3L. This crystallises in
colourless needles melting at I03"5°, sublimes readily, is insoluble in
water, sparingly soluble in cold alcohol, ether, chloroform, and ben-
zene.
Hexahromodiazoamidohenzene, C6H2Br3.N'2.NH.C6H2Br3, is obtained as
previously mentioned by the action of nitrous anhydride on tribromo-'
benzene. It crystallises in small colourless needles (m. p. 158°), which
.ire insoluble in water and alcohol, very sparingly soluble in ether,
more readily in chloroform, and readily in benzene.
lVibroinodiazoaviidobe7izene, C6H2Br3.N2.NHPh, is obtained on adding
so'Md tribromodiazobenzene nitrate (1 mol.) in small quantities to an
alcoholic solution of aniline (2 mols.), the resulting yellow precipitate
being recrystallised from alcohol. It forms brilliant yellow triclinic
prisms, melts at 104°, is insoluble in water, readily soluble in benzene,
ether, and hot alcohol. Heated with glacial acetic acid, it yields tri-
bromaniline.
JJimethijlamidoazotribromobenzene, C6H2Br3.N2.C6H4.NMe.., prepared
Q62 ABSTRACTS OF CHEMICAL PAPERS.
by the action of dimethylaniline on tribromazobenzene nitrate, crystal-
lises in red plates, melting at 161° ; it is insoluble in water, sparingly
soluble in hot alcohol, readily soluble in glacial acetic acid. It gives
crystalline salts with acids ; the chloride crystallises in golden-yellow
plates.
Methylphenylamidoazotribromehenzene, CeHaBrs.Nz.CeHi.NMePh, is
prepared by means of methyldiphenylamine in a manner similar to the
above, which it resembles in so»lubilities. It crystallises in red-brown
plates (m. p. 138°),-aind has no basic properties. A. J. G.
Substitution-products of Ethereal Derivatives of Phenols.
By W. Sta«}I)El (Anrialen, 217, 24—40). — This, paper is mainly a
catalogue of work done by various authors on the substitution-pro-
ducts of various phenols, and serves as an introduction to the author's
publications, which are statements of experimental facts, intended to
support future theoretical considerations. D, A. L.
Nitrocresols. By W. Staedel (Annalen, 217, 49 — 54). — Nitw-
orthocresol is prepared by Hofmann and v. Miller's method {Ber.y 14,
567), and from it the ethyl derivative, C6H3Me(N02).OEt [1 : 2 : 3] is
made, which is a liquid. The residue from the preparation of nitro-
orthocresol contained dinitro-paracresol. Wheoi metacresol dissolved
in glacial acetic acid is acted on by nitric acid likewise diluted with
acetic acid, two products are obtained, one of which is volatile in
steam, and crystallises from benzene in compact yellow crystals (m. p.
56°), readily soluble >in 'ether, alcohol, and benzene, but only slightly in
water. The potassiwm •derivative is a very soluble stable red crystal-
line substance. The ammonium derivative iorms soluble needles, which
on evaporation lose ammcmia and nitrocresol. The silver derivative is
red. This nitrocresol is probably C6H3(OH)(N02)Me [1:2:3]. The
second prodtuct is not volatile, crystallises from water in slender white,
or in long ^^ick brownish needles. It melts at 129°, and is soluble in
ether, alcoliol, and benzene, from which solutions it cannot be crystal-
lised. It dissolves in potassium carbonate solution with evolution of
carbonic anhydride. The potassivm derivative forms yellow leaflets,
the ammonium derivative yellow needles, and the silver derivative a
yellow precipitate. This nitrocresol is probably C6H3(OH)(N02)Me
[1:4: 8]. When paracresol is treated with nitric acid by Hofmann 's
and V. Miller's method, a mixture of meta- and dinitro-paracresol is
obtained The author washes this mixture with water, dissolves in
potash and filters h A , whilst potassium dinitroparacresolate soon sepa-
rates out, and when the mother-liquor is evaporated it deposits the
mononitroparacresolate, from which the nitrocresol is easily obtained.
Ethyl 7iitroparacresolate is a pale yellow liquid, boiling at 275 — 285'',
with partial decomposition. It has an aromatic odour.
D. A. L.
Bromonitro- and Bromamido-anisoils and -phenetoils. B^^
W. S'JAEDEL {Anvalen, 217, 55 — 74). — Monohromorthonitronitranisoil,
C6HaBr(N02).OMe, is the product of the action of methyl iodide on
silver (or potassium) monobromonitrophenate ; it crystallises in long
needles melting at 88°, easily soluble in ether and hot alcohol, sparingly
ORGANIC CHEMISTRY. 663
in cold alcohol, and insoluble in water. MonohromorthomtrophenetoU,
C6H3Br(ISr02).OEt, obtained by the action of methyl iodide and alcohol
on potassium monobromorthonitrophenate, is crystalline (m. p. 43°),
and soluble in alcohol and ether. DibromorthonitrophenetoUy
CeH^Br^CNOO-OEt,
is produced when ethyl iodide and alcohol act on silver dibromortho-
nitrophenate. It melts at 46°, is insoluble in water, soluble in alcohol,
benzene, and ether. By similar reactions, the paranitro-derivatives
have been obtained. Monobromoparanitroaniso'il crystallises in white
needles melting at 106°, easily soluble in hot alcohol and ether, mode-
rately so in hot water, and insoluble in cold water. Monohromopara-
nitrophenetoil forms large pale yellow needles melting at 98°, soluble in
alcohol and ether. Vihromo-paranitropheyietoU crystallises in needles
melting at 108°; when the solution contains ethyl iodide, the crystals
are long quadratic prisms. The respective amido-derivatives are ob-
tained from these nitro-products by reduction with tin and hydrochloric
acid. Monobromorthoanisidine, C8H3Br(NH2).OMe, crystallises in white
leaflets melting at 97 — 98°, soluble in benzene, ether, and hot alcohol.
The hydrochloride forms white needles, soluble without decomposition
in alcohol, but resolved into monobromanisidine and hydrochloric acid
by water ; if the water is acidulated, this decomposition is prevented.
The sidphate forms silvery needles, soluble in hot alcohol without, and
in hot water with decomposition. The oxalate forms flat white needles,
similar in properties to the other salts, and when heated decomposes
with evolution of gas. Monobromorthophenetidine, C6H3Br(NH2).OEt,
is obtained in flat needles with oblique ends melting at 57°, soluble in
benzene, ether, and alcohol. The hydrochloride, the sulphate, and the
oxalate crystallise in small white needles, are all soluble in alcohol,
and are decomposed by water. Dibromorthanisidine,
C6H2Br2(NH2).OMe,
is a brownish oil, soluble in alcohol, ether, and dilute acids, insoluble
in cold, and only sparingly soluble in boiling water. The hydrochloride
and sulphate crystallise in silvery white needles, and behave in a similar
manner to the salts described above. The sulphate melts at 177", with
partial decomposition. The oxalate forms white needles or leaflets,
which are decomposed by water, and when heated at 147 — 148° melt,
giving off gas with the formation of a crystalline sublimate. Dibrom-
orthophenetidine, C6H2Br2(NH2).OEt, crystallises in brilliant quadratic
crystals melting at 92", soluble in alcohol and ether. The hydrochloride,
sulphate, and oxalate crystallise in small brilliant needles, and have
the abovementioned properties. Monobromoparanisidine is a red-brown
oil, soluble in alcohol, ether, and benzene, and soon becomes tarry. Its
three salts form white leaflets, with usual properties ; the oxalate
decomposes at 170°. Monobromoparaphenetidine is also an oil ; dibromo-
paranisidine is crystalline (same as that of Korner), and dibromopara-
/>/ieneh'(/me crystallises in needles melting at 67° ; their salts are crystal-
line, and have usual properties. Dibromoparanisidine oxalate browns
at 190°, then becomes black, and melts at 196°, when it decomposes.
D. A. L.
661 ABSTRACTS OF CHEMICAL PAPERS.
Hydroxybenzoic Acid. By A. Klepl {J. pr. Chem. [2], 27,
159 — 160). — On heating 2 mols. of metahydroxybenzoic acid witli
3 mols. of barium hydroxide at 360°, no phenol is formed, the hydroxy-
benzoic acid remaining unchanged, but on increasing the amount of
baryta to 7 mols. decomposition occurs, and the product of the
reaction when treated with hydrochloric acid and distilled with
steam yields nearly the theoretical quantity of chemically pure
phenol. A. J. G.
Products of the Distillation of Calcium Parahydroxybenzoate.
By G. GoLDSCHMiEDT (Monatsh. Chem., 4, 127 — 130). — In a former
communication on this subject in conjunction with Herzig (Abstr.,
1882, 617), mention was made of a substance insoluble in alkalis,
smelling like diphenylene oxide, crystallising from alcohol in white
needles, melting at 99°, but obtained in quantity too small for com-
plete examination. These crystals have now been prepared in larger
quantity, and found to be a mixture of diphenylene oxide and car-
bonyldiphenyl oxide. A. J. G.
Products of the Distillation of the Salicylic Anhydrides.
By G. GoLDSCHMiEDT (Monatsh. Chem., 4, 121 — 126). — Marcker states
(Annalen, 124, 249) that salicylic anhydride on dry distillation yields
phenol and a body C6H4O, crystallising in silky needles melting at
103°, whilst Limpricht, who had previously investigated the subject,
describes CeHiO as crystallising in small white needles melting at
156^. Frequent reference to the body C6H4O is also made by Kraut,
Schroder, and Prinzhorn {Annalen, 150, 1), but no melting point is
given. The author has made numerous experiments, but failed to
obtain a compound of the formula C6H4O. He has distilled trisalicylo-
salicylic acid, Schiff's tetrasalicylide, and the anhydride obtained by
the action of phosphorus oxychloride on sodium salicylate, and in
each case the only definite products were phenol, salicylic acid, and
jVIerz and Weith's carbonyldiphenyl oxide (diphenyl oxide ketone)
(Abstr., 1881,264). A. J. G.
Acroleinureide and Condensed Ureides. By A. R. Leeds
(Ber., 16, 293— 295).— A reply to Schiff (Abstr., 1882, 1195).
Oxidation of the Bases obtained by the Action of Halogen
Compounds on Thiocarbamide. By R. Andreasch (Monatsh.
Chem., 4, 131 — 148). — By the oxidation of thiohydantoin, the author
obtained an acid, which, from its reaction with nitrous acid, he re-
garded as carbamidoacetosulphonic acid (Abstr., 1880, 877; 1881,
257) ; he now confirms that view by showing that on boiling the
potassium salt with baryta- water, carbamide and barium sulphon-
acetate are formed.
By oxidation of diphenylhydrothiohydantoin with potassium
chlorate and hydrochloric acid, phenyltaurine and diphenyltauro-
carbamic anhydride are obtained.
Diphetiyltaurocarbamic anhydride^ C16H11N2SO3, crystallises in bril-
ORGANIC CHEMISTRY. QQo
liant thin plates, or in tufts of very brilliant colourless needles ; it
melts with decomposition at 186 — 187°. It is insoluble in water,
ether, and chloroform, moderately soluble in boiling alcohol, readily
in glacial acetic acid, even in the cold. When boiled with baryta-
water, it is converted into barium carbonate, aniline, and barium
phenylamidoUethio'nate. The latter crystallises in groups of plates, is
readily soluble in water, moderately soluble in dilute, but insoluble in
strong alcohol. It does not give precipitates with solutions of the
ordinary metallic salts, but reduces silver nitrate. The potassium salt
crystallises in thin brilliant plates very readily soluble in water.
FhenylamidoLsethionic acid or phenyltaurine, SO3H.CH2.CH2.NHPh,
crystallises in colourless plates of strong silvery lustre, which meH at
about 260° ; it is soluble in water, the solution having a strongly
acid reaction, but is insoluble in alcohol and ether. It is distinguished
from taurine by its pronounced acid properties, decomposing car-
bonates and forming salts.
In the expectation of obtaining hydrothiohydanto'in, the author
investigated the action of ethylene bromide on thiocarbamide, but
finds the product of the reaction to be ethyleneirriidotMocarbamate
hydrobromide, C2H4[S.C(iNH).NH3Br]2; this crystallises in broad
white prisms resembling thiocarbamide in appearance, or in stellate
groups of thin needles. It is soluble in cold, more readily in hot
water, less soluble in alcohol. It gives a precipitate of silver bromide
on treatment with silver nitrate ; with sodium hydroxide it gives a
white flocculent precipitate, probably the free base ; on digestion
with excess of silver chloride, it is converted into the hydrochloride,
C4H12N4S2CI2, which crystallises in groups of slender needles, and is
much more soluble in water than the hydrobromide. On oxidation
with potassium chlorate and hydrochloric acid, ethylene disulphonic
acid and carbamide are formed. A. J. G.
Molecular Weight of Isoindole. By F. P. Treadwell and
V. Meyer (Ber., 16, 342— 344).— The fact that ketine, CfiH8N2, is
produced by the reduction of isonitrosoacetone and not amidoacetone
/CH2
or its anhydro-derivative, MeCc^ | , seems to point to the instability
N
of such bodies, and it led the authors to doubt the correctness of the
.CH2
formula PhC^ | for isoindole, as produced by the action of ammonia
N
on bromacetone. The fact that isoindole is odourless, sparingly
soluble in the ordinary solvents, and far less volatile than indole, also
indicates a higher molecular weight for the former compound.
Vapour-density determinations made in sulphur vapour, the air in the
apparatus being replaced by nitrogen, are perfectly in accordance
with this view, and show that isoindole is related rather to the ketines
than to indole, its formula being CieHuNj. In Stadel's determinations,
the air was not replaced by nitrogen, and the partial decomposition
of the isoindole under these circumstances would account for his
abnormal results. A. K. M.
666 ABSTRACTS OP CHEMICAL PAPERS.
a-/5-Hydroxynaphthobenzoic Acid. By H. Walpee (Ber., 16,
299 — 307). — In a previous communication (Ber., 15, 2177), the author
announced the formation of an acid of the formula C18H12O4 by the
action of alkaline permanganate on /3-dinaphthol. The iS-dinaphthol
is dissolved in dihite soda solution, and the calculated quantity of
permanganate gradually added, the whole being gently heated on a
water-bath; the solution is then filtered, hydrochloric acid added,
and the precipitate collected. It can be purified by means of animal
charcoal and repeated crystallisation, when it is obtained in prisms
melting at 256°. It dissolves readily in the alkalis and alkaline
carbonates, also in alcohol, ether, benzene, acetone, and glacial acetic
acid, but is almost insoluble in water. With concentrated sulphuric
acid, it forms a fluorescent solution, from which it is reprecipitated on
the addition of water. The sodium salt, Ci8Hii04Na, forms a white
crystalline powder readily soluble in hot water, the barium salt,
(Ci8Hii04)2Ba + 2H2O, a white gelatinous precipitate nearly insoluble
in water, and the silver salt, CisiiuOtAg, an insoluble white gelatinous
precipitate. The methyl-derivative, CigHnOiMe, is best obtained by
boiling the silver salt with methyl iodide, distilling off the excess of
the latter, and extracting the residue with warm benzene. It crys-
tallises in prisms melting at 199°. The ethyl-derivative, Ci8Hn04Et,
forms white silky needles melting at 206'^. It dissolves readily in
hot alcohol and benzene, sparingly in ether and wood-spirit. The
ocetyl-derivative, C18H11O4XC, forms small shining prisms melting at
170". When heated with melted potash, the acid, Ci8Hi204, splits up
into phthalic acid and (S-naphthol, showing that it must be a hydroxy-
naphthobenzoic acid, thus : —
COOK.C6H4.CO.Ci„H6,OK + KOH = C6H4(COOK)2 + CioHv.OK.
On heating it with red phosphorus and fuming hydriodic acid at
190 — 200°, hydroxy7iaphthotolmc acid, Ci8Hu03, is formed, crystallising
in prisms. It melts at 261°, is almost insoluble in water, sparingly
soluble in alcohol and in ether, but readily in hot glacial acetic acid.
Its silver salt, CisHisOsAg, is obtained as a flocculent precipitate. By
the action of zinc chloride (4 parts) on /i-hydroxynaphthobenzoic acid
(1 part) at 210 — 2.30°, a dark red mass is produced, from which a
crystalline body, 0(CioIl6.CO.C6H4.COOH)2, can be obtained, melting
at 146°. It is readily soluble in boiling alcohol, in chloroform, in the
alkalis and alkaline carbonates. When hydroxynaphthobenzoic acid
is distilled, carbonic oxide is evolved, and a body of the formula
C16H12O (m. p. 108"") is formed, crystallising in yellowish plates which
are almost insoluble in sodium carbonate, but dissolve readily in
sodium hydroxide solution. If the heating is effected in sealed tubes
at 270 — 300°, a compound is produced melting at 114°, and crystal-
lising in plates. Its probable formula is CnH^Oo. From /S-hydroxy-
naphthobenzoic acid and resorcinol a compound can be formed crys-
tallising in small prisms with metallic lustre. It dissolves in alkalis to
a splendid cherry-red solution, from which it is reprecipitated by acids.
A. K. M.
Action of the Chlorides of Phosphorus on Phenanthra-
quinone. By B. Lachowicz {Ber., 16, 330 — 333). — By the action of
ORGANIC CHEMISTRY. 667
phosphorus pentachloride on phenanthraqainone at 150°, Schultz
(A7inalen, 196, 10) obtained a red resinous substance which he was
unable to crystallise. The author finds that equivalent quantities of
the above-mentioned substances react violently when warmed on a
water-bath, or in a few minutes without warming. After the action
has ceased, the product solidifies to a crystalline mass, which after
crystallisation from chloroform yields characteristic bright yellow
rhombic prisms. The constitution of this phenanthradichloruketone is
C6H4.CCI2
probably | | . If double the quantity of pentachloride is taken,
O6H4.CO
the same body is produced, but at the same time a larger quantity of a
red resinous substance. Phenanthradichloroketone melts at 165°, is
readily soluble in chloroform and in benzene, less so in ether, and
sparingly in cold alcohol. Alcoholic pota,sh dissolves it, and on shaking
the solution in contact with air, a phosphorescent light is emitted,
dependent on the oxidation of phenanthraquinone to diphenic acid.
A crystalline body is also obtained by the action of phosphorus tri-
chloride on phenanthraquinone, but its study is incomplete.
A. K. M.
Chloronitrocamphor. By P. Cazeneuve {Gom^t. rend., 96, 589 —
592). — Monochlorocamphor is dissolved in four times its weight of
fuming nitric acid, heated gently, and the temperature gradually
raised to about 115", As soon as the weight of the liquid is equal to
the weight of the chlorocamphor employed, the heating is stopped, the
product treated several times with cold water to remove excess of
nitric acid, and the yellowish pasty precipitate agitated with a
large excess of concentrated ammonia, which acquires a red colour,
and leaves chloronitrocamphor in the form of a pulverulent white
mass. The chloronitrocamphor is then dissolved in boiling alcohol, from
which it separates in large prismatic needles on cooling,
Chloronitrocamphor, CioHuCl(N02)0, is insoluble in water, soluble
in chloroform, carbon bisulphide, and ether, moderately soluble in
cold alcohol, very soluble in hot alcohol. It is remarkably white, has
an odour more feeble than that of chlorocamphor, and a slightly-
sharp taste. It melts at 95°, and if heated above 100° decomposes
completely, with evolution of acid vapours and formation of carbo-
naceous products. Chloronitrocamphor has a leevorotatory power for
[alj = —6*2, whereas monochlorocamphor has a dextrorotatory power
for [a,]j = +90.
This chloronitrocamphor is analogous to the bromonitrocamphor
obtained by R. Schiff (Ber., 1880, 1402), and is formed under similar
conditions. Like the bromo-derivative, it is reduced to nitrocamphor
by nascent hydrogen, and in all probability the chloro- and bromo-
derivatives have a strictly analogous constitution. C. H. B.
Action of Phthalic Anhydride on Quinoline. By M. C.
Traub (Ber., 16, 297— 299).— Fischer (Ber., 9, 1753) showed that a
phthalein-derivative could be obtained from phthalic anhydride and
dimethylaniline. The author has experimented with the pyridine and
quinoline bases, and finds that on heating phthalic anhydride with
668 ABSTRACTS OF CHEMICAL PAPERS.
quinoline for 3 — 4 hours at 150', and tlien removing the excess of
base by means of hydrochloric acid, a semi-soUd pasty mass is
formed, which can be purified by crystallisation, from glacial acetic
acid, and finally from benzene. It is, however, not qninoline-phthalem,
its formula being C17H9NO2 (quinophthalone), and the reaction corre-
sponds with that by which anthraqninone is formed. Quinophthalone
is almost insoluble in water, sparingly soluble in alcohol, ether, chloro-
form, and light petroleum, readily in hot benzene and glacial acetic
acid. It melts at 235°, and can be sublimed with partial decomposi-
tion. Heated above 250° with potash, quinoline is given off, whilst
benzoic acid is found in the residue. Fuming sulphuric acid converts
it into a sulphonic acid. A. K. M.
Phenolquinoline. By E. Grimadx (Compt. rend., 96, 584—585).
— In Skraup's method of preparing substituted quinolines, the glycerol
employed is first converted into acraldehyde. It appeared probable,
therefore, that substituted quinolines would be obtained by replacing
the glycerol by phenylacraldehyde (cinnamaldehyde).
A mixture of aniline, nitrobenzene, sulphuric acid, and oil of cin-
namon is heated at 170 — 180°; the black mass thus obtained is
extracted with water, and the solution filtered. On adding potas-
sium hydroxide, the filtrate gives a black resinous precipitate, which
is partially redissolved by ether. The ethereal solution on evapora-
tion leaves a soft black confusedly crystalline mass, which is distilled
ill a, current of air, when a yellow liquid passes over and solidifies to
a crystalline mass on cooling. This product is purified by washing
with a very small quantity of ether, and recrystailising twice from
three or four times its weight of bo-iling alcohol. The phenolquinoline,
CgHfiPh.N, thus obtained forms while slender needles, which melt at
84°. It is very soluble in ether, slightly soluble in cold alcohol, soluble
in three or four times its weight of boiling alcohol, slightly soluble in
boiling light petroleum. The hydrochloride, sulphate, and platino-
chloride are crystalline salts ; the first two are partially decomposed
by a large excess of water.
From its mode of formation, this base is a phenolquinoline contain-
ing the phenyl-group on the pyridic side of the quinoline, and in the
para-position with respect to the nitrogen. It is isomeric with the
phenolquinoline obtained by La Coste {Ber., 1882, 55) by the action of
glycerol and sulphuric acid on paramidodiphenyl. In this compound,
the phenyl-group is on the benzene side of the quinoline, as shown by
the following formulae : —
CH CH CH CPh
PhC C CH CH C CH
' I II I I II I
CH C CH CH C CH
CH N CH N
La Coste's phenolquinoline. Grimaux's phenolquinoline.
C. H. B.
ORGANIC CHEMISTRY. GGO
Cryptidine. By A. R. Leeds (Ber., 16, 289— 290).— When dry
powdered acralxylidine is carefully distilled, ammonia is evolved,
and an oil and water pass over, leaving a porous carbonaceous mass
in the retort. The crude oil has an unpleasant odour and very bitter
taste. It forms crystalline compounds with sulphuric, hydrochloric,
and other acids, and is best purified by means of the hydrochloride,
which can be crystallised from water, and finally decomposed by
potash. The purified oil has a reddish colour and a disagreeable
odour, and boils at 270^. In composition it corresponds with crypti-
dine, CiiHiiN. The hydrochloride forms slender colourless tabular
crystals, which can be sublimed with partial decomposition. The
platinochloride forms slender yellow crystals, soluble in water and in
alcohol. A. K. M.
Creatine-compounds of the Aromatic Group. By P. Griess
(Ber., 16, 336 — 339). — A new method for preparing these com-
pounds consists in the action of cyanocarbimidamidobenzoic acid
on the aromatic amines and diamines. Phenylhenzoglycocy amine,
NHPh.C(NH).NH.C6H4.COOH + H,0, is obtained on adding cyano-
carbimidamidobenzoic acid to 3 — 4 parts of boiling aniline, and heat-
ing until hydrocyanic acid ceases to be evolved. On mixing the
product with alcohol, the above compound is precipitated. It is puri-
fied by washing thoroughly with alcohol and crystallisation from
boiling water, in which it is sparingly soluble. It crystallises in indis-
tinct needles or plates, is almost insoluble in ether, but dissolves
readily in dilute mineral acids and in potash solution. Its taste is at
first slightly bitter, then sweet. The hi/drochloridei
CuHi3N30„HCl,H20,
is very readily soluble in water, from which it crystallises in nodules.
The author thinks it possible that Traube's phenylbenzocreatine (this'
vol., p. 193) is identical with phenylbenzoglycocyamine. (3-Nap7ithyl-
henzoglymcyamine^ CioH7.NH.C(NH).NH.C6H4-COOH, is prepared in
a manner analogous to the above compound, using a large excess of
naphthylamine. It forms small white crystalline nodules, very slightly
soluble in hot water or in alcohol, insoluble in ether and chloroform.
When dry, it is almost tasteless, whilst its aqueous solution tastes
slightly bitter at first, then faintly sweet. The Jiydrochloride,
Ci8Hi6Sl"302,HCl, is very sparingly soluble in water, from which it
crystallises in thin six-sided plates. Amidopkemjlbenzoglycocyaminp,
NH2.C6H4.NH.C(ISrH).NH.C6H4.COOH, is obtained from cyanocarbi-
midamidobenzoic acid and paradiamidobenzene. It crystallises in
small grey-coloured pointed prisms. In solubility it resembles phenyl-
benzoglycocyamine. The hydrochloride, Ci4Ha4Nj02,2HCl, forms small
nodular crystals, readily soluble in cold water. Amidophenylbenzo-
glycocyamine yields a diazo-compound which combines with amines
and phenols to form azo-compounds. A. K. M.
Strychnine Derivatives. By Hanriot (Gompt. rend., 96, 585—
587). — Diuitrostrychnine, differing from that obtained by Clans and
Glassner (Abstr., 1881, 748), is obtained by dissolving 60 grams of
670 ABSTRACTS OP CHEMICAL PAPERS.
strychnine in 300 grams fuming nitric acid, cooled to —10°, and
pouring the solution into 2 litres of water. The crystals of dinitro-
strychnine nitrate, which separate out, are drained, redissolved in
water, and the solution precipitated with ammonia. Binitrostrychnine^
C22H2oN202(N02)2, crystallises with some difficulty, but can be obtained
in long transparent amber-yellow prisms by dissolving it in chloro-
form, adding twice the volume of alcohol, and allowing the liquid to
evaporate spontaneously. It is soluble in alcohol and in boiling water,
slightly soluble in cold water, very soluble in chloroform. It does not
melt, but decomposes at about 202°. It readily undergoes alteration
under the influence of heat, especially in presence of excess of
ammonia.
The salts of dinitrostrychnine are slightly soluble in water, but dis-
solve in strong acids, and are reprecipitated from these solutions on
adding water, especially if the liquid is agitated. This fact may be
utilised for the detection of strychnine in presence of colouring
matters which interfere with the ordinary tests. A drop of fuming
nitric acid is placed in a watch-glass, mixed with a small quantity of
the substance to be tested, and, when solution is complete, one or two
drops of water are added and the liquid agitated, when the cha-
racteristic crystalline precipitate is thrown down.
Dinitrostrychnine nitrate crystallises in thin plates from its solu-
tion in boiling water. The hydrochloride forms a curdy mass ou
agitating a s-olution of dinitrostrychnine in boiling water with hydro-
chloric acid. This curdy mass melts at about 40", and on cooling
deposits needles of the anhydrous chloride.
Diamidostrychnine is obtained by dissolving dinitrostrychnine in
dilute hydrochloric acid, adding a large excess of tin, and heating the
liquid at 50° for 24 hours, after which time it is filtered, more tin
added if the reduction is incomplete, and the tin removed from the
solution by treatment with hydrogen sulphide, the filtrate boiled,
precipitated by ammonia, and the precipitate purified by repeated
crystallisation from chloroform. By slowly cooling the chloroform
solution, the diamidostrychnine is obtained in prisms, which become
opaque when dried. From aqueous solutions, ammonia throws down
a very bulky precipitate. Diamidostrychnine is slightly soluble in
water, soluble in alcohol, and very soluble in chloroform ; almost
insoluble in ether. It does not melt, but begins to decompose at
about 225°. With a neutral solution of the hydrochloride, sodium
hypochlorite throws down a greenish precipitate, which forms a
green, then blue, then violet solution, with increasing quantities of
hydrochloric acid. Sulphuric acid and potassium dichromate do not
give the characteristic violet colour given with strychnine, but this
colour is produced on adding a small quantity of water. Ferric chlo-
ride gives a red coloration on boiling. C. H. B.
Constitution of Atropine. By A. Ladenburg (Annalen, 217,
74—149). — In this paper, the author has collected together the various
facts on this subject, mostly already published and abstracted, and
thus gives an historical sketch of this interesting research. When
tropine had been recognised as a tertiary base, the author proceeded
OKGANIC CHEMISTRY. 671
to synthesise atropine from its products of decomposition, tropine
and tropic acid, which he succeeded in doing by the action of dilute
hydrochloric acid on tropine tropate (Abstr., 1879, 733). This
being accomplished, he next prepared various other alkaloids, called
by him tropeines, by a similar method; thus, from tropine man-
delate he obtained homatropin or phenylgly colic trope'ine (Abstr.,
1880, 410, 715, and 815, and 1881, 420), and measurements of the
crystals and the following additional observations are now given : the
hydrochloride crystallises from concentrated neutral solutions after seme
time ; it is very soluble in water ; the sulphate can be crystallised from
water, and forms needles with silky lustre ; solutions of the hydro-
chloride give a white curdy precipitate with potassium mercuric
iodide, a white oil with mercuric iodide, and a crystalline platino-
chloride with platinic chloride. From tropine atrolactate, atrolactic
tropeme is obtained (Abstr., 1882, 984). Additional remarks ; this
substance crystallises in needles (m. p. 119 — 120°), very sparingly
soluble in cold, but more readily in hot water, and easily in alcohol.
It is isomeric with atropine, and its mydriatic action is equally re-
markable. The hydrochloride, hydriodide, hydrobromide and sulphate,
have not been obtained in crystals. The platinochloride forms reddish-
yellow crystals, very soluble in water and alcohol. The aurochloride,
CnHzsNOsjAuCUH, crystallises in yellow needles, which melt under
water, but when dry, melt at 112 — 114°, sparingly soluble in cold
water. Salicylic iropeine, CisHigNOa, is obtained from tropine salicylate
(Abstr., 1880, 410 and 714) ; it does not act on the pupils of the eye ;
the platinochloride has the composition (Ci5Hi9N03,HCl)2,PtCl4, the
aurochloride, Ci5Hi9N03.HCl,AuCl3. Hydroxyhenzotropeme (Abstr.,
1880, 714) can be partially distilled without decomposing, whilst the
remainder is carbonised. It has a slightly alkaline reaction, and is
soluble both in acids and in soda. It crystallises without water of
crystallisation. It does not act on the eye as energetically as atro-
pine. The nitrate is moderately soluble, and is coloured yellow when
boiled with excess of nitric acid. Iodine gives rise to a crystalline
mixture of tri- and pent-iodide. The mercuro- and stanno- chlorides
have been obtained, the former in colourless leaflets, the latter in tufts
of white needles. Other precipitates are formed with tannic acid,
potassium mercuric iodide, potassium ferri- and ferro-cyanide, and
phosphomolybdic acid. The simple salts of parahi/droxyhenzotropeine,
C15H19NO3 (ibid.),B,re mostly soluble, the nitrate crysisilhsiiig in prisms
only sparingly soluble; this salt is turned yellow by boiling with
nitric acid. It gives precipitates with all the various reagents men-
tioned above ; the mercurochloride, HgCl2,Ci6lIi9N'03,HCl,H20, crystal-
lises in needles.
Benzotropeine, C15H19NO2 (Abstr., 1880, 714). Additional remarks;
it distils without leaving a residue. The nitrate is sparingly soluble,
and is turned yellow by boiling with nitric acid. The aurochloride
forms microscopic needles, slightly soluble in water, easily in alcohol.
It gives precipitate with the usual reagents. Fhenylacetotropeme,
C16H21NO2 (Abstr., 1882, 784), sulphate forms colourless needles.
Cinnamyl tropeme^ Ci7ll2il^02 (Abstr., 1880, 714), can be prepared
either from cinnamic acid, tropine, and hydrochloric acid, or by treat-
()72 ABSTRACTS OF CHEMICAL PAPERS.
inq; phenylacetic acid in a similar manner. It has scarcely any my-
driatic action, but is a powerful poison. Atrojpyltnypeine and phthalyl-
trope'ine (ibid.), are the last of the series of the compounds described in
this paper. The author then passes on to his work on the constitution
and synthesis of tropic acid (Abstr., 1880, 472; 1881, 171), from the
results of which he arrives at the constitution CH2(0H).CHPh.C00H
for that acid . "With regard to the constitution of tropine, the author finds
that when it is heated with soda- lime, methylamine and a hydrocarbon
like tropilidene, C7H«, stand prominent among^st the products, so
that the principal reaction may be represented by the equation
CpHisNO = NH0.CH3 4- C7H8 + H2O. When tropine is decomposed
with acids, it gives rise to fropidine (Abstr., 1879, 733 ; 1880, 675) ;
the best method for the preparation of this base is to heat a mixture
of tropine (2 parts), glacial acetic (12 parts), and concentrated sulphuric
acid (46 parts). In addition to the properties, &c., already given (loc.
cit.), the vapour- density has been determined, and found to be 118.
Tropidine is soluble in acids, in ether, and alcohol, scarcely soluble in
soda ; its aqueous solution has a strongly alkaline reaction. Tropidine
hydrochloride forms hygroscopic crystals, soluble in water. The hydro-
bromide is similar, but not quite so hygroscopic. The picrate crystal-
lises in yellow needles, very sparingly soluble in cold, somewhat more
so in hot water- The periodide forms brown prisms (m. p. 92 — 93°),
soluble in alcohol. With methyl or ethyl iodide, tropidine yields a
mono-methyl or ethyl-derivative, which is crystalline and forms well-
defined crystalline platino- and auro- chlorides. The action of hydriodic
acid and phosphorus on tropine results in the formation of hydro-
tropine iodide (ra. p. 115°) (Abstr., 1881, 263); if, however, during
the reaction, the tube be heated to 150° or above, tropidine and its
periodide are the products, owing to a secondary dehydrating reaction
resulting in the conversion of tropine into tropidine. The formation
of metatropine from hydrotropine iodide is then discussed (Abstr.,
1881, 263 ; 1882, 984), and the conclusion arrived at is that tropine
is a nitrogenous alcohol of which the tropeines are the ethereal deriva-
tives. This view is supported by the author's work on alkines
(Abstr., 1882, 165 and 1193), which are a class of bodies quit«
analogous to the tropeines. Then follow detailed accounts of the
following experiments: — Decomposition of dimethyltropine by heat
(Abstr., 1882, 216) ; the production of tropilene from methyl tropidine
iodide and tropiledene from dimethyltropine iodide (ibid.) ; the de-
composition of methyltropine, methyltropine chloride and iodide by
potash, the principal products being large quantities of di' and small of
fri-methylamine ; the oxidation of tropilene into adipic acid (Abstr.,
1882, 983), and finally the decomposition of tropidine by bromine
(Abstr., 1882, 984 and 1206), by which ethylene dibromide and dibromo-
methylpyridine are obtained. The inferences there deduced (ibid.) are
enlarged upon, and the formula C5H7(C2H40.CO.CHPh.CH2.0H)NMe,
proposed for atropine. D. A. L.
Colchicine and Colchiceine. By S. Zeisel (Moimtsh. Chem., 4,
162 — 164). — By the action of hydrochloric or sulphuric acid on a
very dilute solution of colchicine, it is known that in addition to
ORGANIC CHEMISTRY. 673
colchiceine, another base is formed in small quantity. By heating
colchiceine with strong hydrochloric acid at 110 — 120°, it is com-
pletely converted into the new base (termed ajpocolchice'iiie by the
author) and methyl chloride. Apocolchiceine is obtained as an
amorphous flocculent yellow precipitate on adding sodium carbonate
to its solution in acids ; it is sparingly soluble in cold, more readily in
hot water ; the hot aqueous or dilute alcoholic solutions solidify on
cooling to a gelatinous mass. It is readily soluble in caustic alkalis
or acids, the solutions in the latter being of an intense yellow colour,
and leaving yellow varnishes on evaporation ; contrary to the state-
ment of Hertel, the hydrochloride does not lose hydrochloric acid by
repeated evaporation to dryness. On addition of powdered potassium
nitrate to a solution of apocolchiceine in concentrated sulphuric acid,
the yellow colour changes to indigo, then to violet, finally to reddish-
yellow, addition of alkali causing a fine red coloration. Apocolchi-
ceine hydrochloride gives amorphous precipitates with picric acid,
potassium iodide, bromine-water, potassium bismuth iodide, phospho-
tungstic acid, and phosphomolybdic acid ; with ferric chloride, it gives
a brownish-green precipitate dissolving in hydrochloric acid to a
green solution. A. J. G.
Behaviour of the Bile Acids with Albumin and Peptones,
Antiseptic Action of the Bile Acids. By R. Maly and F. Emich
(Monatsh. Chem., 4, 89 — 120). — On mixing solutions of peptone, or
of propeptone and taurocholic acid, a white milk-like precipitate is
obtained in such a fine state of division as to readily pass through
filter-paper and to require some days to settle to the bottom of the
precipitating vessel, where it then forms a resin-like layer. It is
readily soluble in alkaline liquids, even in sodium hydrogen bicar-
bonate solution saturated with carbonic anhydride, or in blood serum ;
addition of hydrochloric or acetic acid to these solutions reprecipi-
tates it. It is insoluble in common salt solution. It dissolves in
alcohol, and the solution gives merely a faint red coloration with
potash and copper sulphate, showing that the precipitate can contain
but little peptone ; the precipitate appears to consist essentially of tauro-
cholic acid which is precipitated by the peptones in a manner similar
to its precipitation by sodium chloride. Glycocholic acid is not pre-
cipitated by the peptones.
On mixing solutions of albumin and taurocholic acid, a white
flocculent precipitate is obtained consisting of albumin and a small
quantity of taurocholic acid, the latter being in all probability
merely held mechanically by the albumin ; the precipitation of the
albumin is so complete that no reaction is given in the filtrate with
tannic acid or phosphotungstic acid, although the latter reagent,
according to Hofmeister, can detect 1 part of albumin in 100,000 parts
of water. From these results taurocholic acid is regarded by tha
author as a reagent of great importance, precipitating albumin and
syntonin, but not peptone and propeptone, whilst all the other deli-
cate reagents for albumin also precipitate the peptones. Glycocholic
acid precipitates albumin but very partially.
The antiseptic properties of bile have been long known, although
VOL. XLIY. 2 z
♦374 ABSTRACTS OF CHEMICAL PAPERS.
no researches have been made as to which constituent the antiseptic
action was due ; the authors show that taurocholic and glycocholic
acids, and especially the former, are powerful antiseptics, that the
addition of 02 per cent, solution of either acid will prevent the putre-
faction of flesh (with pancreas a 0*5 per cent, solution of taurocholic
acid or a 1 per cent, solution [suspension] of glycocholic acid was
required to prevent putrefaction). The fermentation of sugar by
yeast was prevented by the addition of 0*5 per cent, of taurocholic
acid, but the addition of glycocholic acid, on the contrary, appears
to accelerate the fermentation. The lactic fermentation is prevented
by addition of 0*25 per cent, of taurocholic acid ; glycocholic acid
although not stopping the fermentation makes it proceed very slowly.
The digestive action of pepsine is prevented by 0*2 per cent, of tauro-
cholic acid, 1 per cent, of glycocholic acid has, on the contrary, no
action. The conversion of starch into sugar by trypsin is prevented by
the addition of 0*1 per cent, of either acid, by ptyalin by the presence
of 0'2 per cent, of taurocholic acid or of 1 per cent, of glycocholic
acid. The decomposition of amygdalin by emulsion is prevented by
•0-5 per cent, of taurocholic acid ; 1 per cent, of glycocholic acid is
without influence on the reaction. A. J. G.
Oxidation of Kynurine and Kynurenic Acid. By M.
Kretschy (Monatsh. Ghem., 4, 156 — 161). — Both kynurine and
kynurenic acid when oxidised with an alkaline solution of potassium
permanganate yield kynuric acid ; the yield being 95 per cent, from
the former and 65 per cent, from the latter substance.
Kynuric acid, C9H7N05,H20, isomeric with carbostyrilic acid, crys-
tallises in very brilliant slender needles ; it loses its water of crystal-
lisatioa at 100°, and, on further heating in an open capillary tube, it
gives a white sublimate at 183 — 185" ; at 188 — 189° it intumesces
without being in clear fusion, and, after the intumescence ceases, the
walls of the tube are covered with a microcrystalline deposit which
does not again fuse on heating up to 250°. The acid has a strongly
acid reaction and a faintly bitter taste. It is sparingly soluble in
cold water, moderately soluble in hot water, soluble in alcohol and
ether. A dilute solution gives a pale crimson coloration with ferric
chloride ; in concentrated solution, it is precipitated. Its compounds
with the heavy metals are almost insoluble in water. The silver salt,
C9H6N05Ag2, is obtained as a gelatinous precipitate on adding silver
nitrate to the ammonium salt ; when dry, it forms microscopic pris-
matic crystals. The acid is readily precipitated by addition of
mineral acids to its soluble salts, more slowly by acetic acid. It does
not give any odour of pyridine when heated with excess of lime.
A. J. G.
Action of Potash on Albumin. By G. S. Johnson (Ghem. News,
47, 87). — The author is of opinion that potassium tetrathionate, and
not sulphide, is formed when albumin is boiled with potash. He has
observed that lead sulphide is always formed when white of eggy
filtered or othervyise, or pure albumin is boiled with lead hydrate dis-
solved in dilute potash ; also when fresh white of egg is boiled for a
short time, cooled, and tested with lead acetate, a red colour is pro-
PHYSIOLOGICAL CHEMISTRY. 675
-duced whicli might be mistaken for sulphide. When, however, white
of egg filtered through charcoal, or pure albumin, is boiled with
potash solution (sp. gr. 1'08) alone, no indication of sulphide is ob-
tained with lead acetate, and, if the boiling has been prolonged, no
sulphide is formed, even on boiling in the presence of lead. The
author objects to this result being attributed to the oxidation of sul-
phide formed in the first instance ; firstly, because the same result
(the non-appearance of sulphide after prolonged boiling of albumin
with dilute potash) was obtained in an experiment conducted in an
atmosphere of pure hydrogen ; secondly, because a solution of albumin
after being boiled with potash until it gave no indication of sulphide,
and then mixed with concentrated potash (sp. gr. 1*3) and again
boiled, yielded an abundance of sulphide. These phenomena are
accounted for by the author's hypothesis of the formation of tetrathio-
nate. This salt yields no sulphide when boiled with dilute potash,
but yields large quantities with concentrated potash. D. A. L.
Legumin. By H. Ritthausen (J.pr. Chem. [2], 26, 504—512).—
By treating legumin prepared from peas, vetches, broad beans, and
other leguminous seeds with solution of chloride of sodium, a con-
.siderable fraction passes into solution. This portion has essentially
the same composition as that dissolved by very dilute alkali.
O. H.
Physiological Chemistry.
Exhalation of Nitrogen-gas during the Respiration of
Animals. By J. Reiset (Gompt rend.^ 96, 549 — 553). — A historical
and critical summary. C. H. B.
Feeding Calves with Skim-milk. By G. A. Paul (Bied. Centr.,
1883, 108). — A statement of the loss and gain experienced by feeding
three calves with skim-milk, to which was added malt-combs and
earth-nut cake. In the case of the first calf, 80 kilos, live weight
vv^ere produced at the cost of 63 marks, whilst the milk produced by
the cow was 187 marks, of which the calf only received 56 marks'
worth ; 42*5 kilos, live weight of second calf cost 38 marks, the cow's
milk was valued at 79 marks, of which the calf received 36 marks'
worth ; to obtain 34*5 kilos, increase in live weight in the second calf,
52 marks were spent, cow's milk valued at 119 marks, of which the
calf received 47 marks' worth, so that there was a saving of about
67 marks., E. W. P.
Distribution of Peptone in the Animal Body. By P. Hof-
MEiSTEE (Zeitschr. Physiol. Chem., 6, 51 — 68). — Nothing has as yet
been accurately determined in regard to the way in which nitro-
2 z 2
676 ABSTRACTS OF CHEMICAL PAPERS.
genous nutritive principles absorbed from the alimentary- tract are-
disposed of in the system.
Peptone has always been looked upon with special interest amongst
the products of the digestion of albumin, and Schmidt and Miilheim
(D?t Bois Beymond^s Archiv. fur Physiol., 1879, 39) have established by
their observations the fact of the transformation in chief part of
albumin into this body. It has generally been believed that peptone,
being relatively of easy diffusibility, passes through the alimentary
mucous membrane into the blood-vessels, and is then carried to the
place of its assimilation. Support to this view was given by the ob-
servations of Drosdoff and Plosz and Gyergyai, who found peptone in
the blood of the portal vein. The quantity was, however, very small.
Two different modes of explanation of these facts present themselves ;
either very little unchanged peptone reaches the blood through the
intestinal mucous layer, or the peptone undergoes transformation
immediately after its passage, losing its Own characteristic properties,
and so ceasing to be recognisable. This latter view has, hitherto,
been chiefly adopted, some observers ascribing the place of change to
the muscular tissue, and especially to the liver and other cellular
organs, while others have deemed it to occur in the blood itself.
The author does not agree with either of these views, owing to the
circumstances that when peptone is introduced into the circulation in
some other way than by absorption from the intestine, by direct injec-
tion for instance, the greatest part escapes unchanged in the urine..
This would point to the •intestinal mucous membrane itself as the
place of actual transformation.
In the first place, it was necessar}^ to ascertain the normal distribu-
tion of peptone in the bocJy at successive stages of the process of
digestion, so as to exclude the possible influence of other organs
besides the intestine and the blood, on the destiny of peptone.
The experiments were made upon dogs fed upon flesh, which was
killed at different periods of the digestive process by means of blood
letting. The amount of peptone was then determined in the various
organs. The blood, heart, lungs, stomach, large and small intestines,
liver, pancreas, spleen, mesenteric glands, mesentery, kidneys, and brain
were severally examined. The method followed by the author is
given in the present and also in a previous memoir (4, 264), to which
the reader is referred for details.
The results of these experimental observations showed that only in
one locality was peptone to be constantly found, in the intestinal
mucous membrane. The proportions varied in different parts of the-
alimentary tract.
In the stomach the amount of peptone did not appear to have any
ratio to the progress of digestion, save that in the case of long depriva-
tion of food it sank to the limits of recognition. In the small intes-
tines, on the contrary, a regular increase in the amount of peptone up
to the eleventh hour after food was given was observed, followed by a
diminution; the formation of peptone in the small intestine was
pari passu with its absorption by the mucous layer. These observa-
tions agree with those of Schmidt-Mulheim, and likewise with those
of Panum and Falck, in which the excretion of urea in flesh-fed dogs^
PHYSIOLOGICAL CHEMISTRY. 677
.attained its maximura at the same period. This analogy between the
formation of peptone and excretion of nrea would favour the accept-
ance of the view that much of the absorbed peptone is at once broken
up into its final products.
The total amount of peptone in the alimentary walls, including
■stomach and intestines, is more than double that present in the blood
as a whole. The proportion of peptone found in the walls of the
small intestine was 14 times greater than that in the walls of the
stomach. On the other hand, the proportion of peptone in the gastric
cavity was 15 times that present in the gastric mucous membrane.
Either the stomach plays a much less part in the absorption of
peptone than the intestine, or the absorbed peptone disappears more
.quickly from its mucous membrane.
Next to the intestinal tract, the blood exhibits a pretty regular
proportion. Schmidt-Miilheim had already shown that in the case of
'dogs 24 hours after being fed, the blood contains no peptone.
Although in the majority of cases the blood is found containing
peptone, yet on three occasions out of eleven, negative results were
yielded from four to six hours after food. It would appear that the
'Circulation of unchanged Ipeptone is not indispensably necessary to
nutrition. The peptone present in the blood is never of significant
.amount, ranging from 0*029 to 0"055 per cent, with a well marked
maximum seven hours after food. Experiments tend to establish the
fact that the peptone in the blood is not dissolved in the serum, but
is associated with the red corpuscles.
When peptone was absent from the blood it was never present in
the spleen. Contrary to the results of Plzos and Gyergyai, peptone
•could not be detected in the liver or mesenteric glands.
From the above observations it is inferred that the transformation
•of peptone takes place either in the mucous membrane itself or imme-
.diately after reception by the blood. D. P.
The Proportion of Peptone in the Gastric Mucous Mem-
brane. By F. HoFMEiSTER {Zeitschr. FhysioL Chem., 69 — 73), —
During the act of digestion, the stomach of the dog is opened along
itlie smaller curvature, spread out and then divided by a suture carried
from the pylorus to the cardiac end into two halves as nearly as
possible symmetrical. It might be anticipated that when the viseus
was carefully freed from adhering contents, both portions would
yield equal proportions of peptone. This however, is true only
when both are simultaneously immersed in boiling water. Should
•one be left undisturbed for a time, its peptone will be found to
■diminish in a remarkable manner, and even wholly disappear.
This disappearance of peptone is a vital act, taking place according
ito the stage of digestion with unequal rapidity, and arrested by heat-
ing for a few minutes to 60° C. If the stomach, previously extracted
and wiped dry, be placed in the moist chamber for one or two hours
•at 40", the mucous membrane is further observed to secrete a fresh
layer of mucus, and the muscular contraction to restore the stomach
tto its original condition.
678 ABSTRACTS OF CHEMICAL PAPERS.
Siiice the transformation of peptone also takes place in the stomach
of bled animals, it follows that the blood has no share in the result.
The cause is to be sought for in chemical changes which have their
seat in the gastric mucous membrane. An explanation is thus afforded
of Salvioli's experiments (Archiv. f. Physiol., von Du Bois Beymond,
1880, Supplement Band 112), in which it was observed that peptone
introduced into the intestine disappeared in a few hours without being
detected in the efferent venous blood, whilst no such disappearance
took place when blood injected with peptone circulated through the
intestinal vessels. It also proves that the property of assimilating
peptone belongs not merely to the stomach, but is a common charac-
teristic of the intestinal mucous membrane.
Whether this assimilation is accompanied by a re- formation of albu-
min or by a complete disintegration, or in what part of the mucous
layer it takes place, whether in the epithelial cells of the glandular
portion, or the lymph cells of the adenoid tissue, has not yet been
determined. But to this the author hopes shortly to proceed.
D. P.
On the Oxygen Pressure under which at a Temperature of
35° the Oxyhsemoglobin of the Dog begins to give up its
Oxygen. By G. Hufner (Zeitschr. Physiol. Chem., 6, 94—111).—
From the experiments of J. Worm Miiller, it appeared probable that
the highest limit of oxygen pressure at which a solution of oxyhaemo-
globin yields its loosely combined oxygen did not exceed much more
than 20 mm. of mercurial pressure.
To decide this question, further experiments were undertaken in
which the method adopted differed from that of Worm Miiller so far
that equal quantities of freshly prepared, and as nearly as possible-
equally concentrated, solutions of haemoglobin were employed. These
were thoroughly saturated with oxygen, and then under similar con-
ditions of time and temperature shaken with double the volume of a
mixture of nitrogen and oxygen, in which the proportions of the
latter gas ranged systematically from 0*0 per cent, to 4 per cent.
It was to be expected that the amount of oxygen given off during
agitation under otherwise equal conditions, would decrease in propor-
tion to the amount of oxygen present in the mixture of gases, so that
it appeared possible by varying this latter amount to find the value of
the pressure beyond which a solution of oxy haemoglobin of certain^
concentration ceases to yield its oxygen.
For a figure and description of the apparatus used, as also of the
process, the reader is referred to the paper itself. It is highly pro-
bable that when oxyhaemoglobin and free absorbed oxygen are simul-
taneously present in a solution, it is only the latter which is used
up in oxidation, and not directly the molecule combined with the
haemoglobin. Hence, in a concentrated solution of oxyhaemoglobin,
the haemoglobin may be in combination with oxygen, while the
aqueous medium itself is no longer saturated with the latter. When
such a solution is shaken with a mixture of gases, the oxygen pressure-
of which exceeds a certain limit, a diminution of this pressure takes-
place.
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 67^
The substances which may consume the absorbed oxygen in such a
solution of oxyhaemoglobin are not far to seek. Well purified colour-
ing matter of blood may contain nevertheless traces of fat or lecithin,
even particles of albumin, and it is possible that ultimately the oxy-
haemoglobin may as an albuminate itself, be seized upon by the free
oxygen. In the author's experiments such oxidation actually did take
place, as the production of small quantities of carbonic anhydride
(0'2 to 0*4 per cent.) showed.
The results proved that at a definite temperature of say 35°, only a
smEill fraction of the amount of oxyhaemoglobin mixture present under-
goes dissociation.
According to the theory of probabilities, assuming that other con-
ditions remain unchanged, this fraction should be always the same,
however the total amount of colouring matter present might change.
Consequently the amount of oxygen yielded should increase with in-
creasing concentration of the solution, and therefore likewise the
limit of pressure at which dissociation ceases. Why does the latter
not exceed a maximum ? In the author's experiments the limit of
pressure was as high and even higher in the case of a 6 per cent, solu-
tion as in one of 10 per cent. Solutions of greater concentration
cannot be prepared on account of the slight solubility of the colouring
matter and its instability in concentrated solution.
A diagram is given, in conclusion, showing the several proportions
of oxygen which are retained at 35° by 100 cm. of the blood of the
dog under different increments of pressure of the absorption of
oxygen employed. It illustrates at a glance the vanishing proportion
which the simply absorbed oxygen bears to the loosely chemically
united oxygen of the blood. D. P.
Chemistry of Vegetable Physiology and Agriculture.
A Denitrifying Ferment in Soils. By Gaton and others (Bled,
Centr.^ 1888, 82 — 84). — A ferment exists in the soil which deoxidises all
nitrates in the presence of organic matter : at a temperature of 35 —
40°, this action being most energetic ; it differs from the nitrifying
ferment in that it only acts when air is absent. From sewage- water,
nitrogen, ammonia, amido-compounds, and from soils, nitrous and
nitric oxides and nitrates were produced. Schlosing and Muntz find
that the reducing action ceases at 100° and under the influence of
chloroform vapour, and that sterilised soil recovers its power on the
addition to it of fresh soil. According to Rodionoff "blooming" of
black Russian earth is due to an organism which forms fine threads
in the soil ; in such a condition, the soil is light, fertile, and retains
moisture well. E. W. P.
680 ABSTRACTS OF CHEMICAL PAPERS.
Reduction of Sulphates by Algae. By A. :^vrARD and others
{Bied. Gentr., 1883, 84 — 86). — The reduction of sulphates by the cells
of beggiatoa has already been noticed. The same observations have
been made with Osdlleria and Ulothrix, and there is little doubt but
that these three algae possess the power of reducing sulphates and
forming free sulphur and sulphuretted hydrogen. This will account
for the formation of sulphur waters by another theory than that
formerly held to be the true one, viz., the reduction of sulphates by
dead organic matter. Plauchud states that this property of reduc-
tion is hindered by chloroform, and destroyed by phenol ; he also
accounts for the presence of sulphur in soils (the subsoil of Paris) by
this theory. E. W. P.
Cristalline or Glaciale (" Mesembrianthemum cristalli-
num.^' By E. Heckel (Gompt. rend., 96, 592—594). — The annual
variety of Gristallinmn growing in Provence has the composition:
sodium chloride 7, organic salt of potassium 9, organic matter 5, water
80 = 100. According to Mangon (Gompt. reyid., 96), plants of the
same species growing in Normandy contain water 96'8, salts 1*39,
organic matter 2*0 = 100. The differences in composition are ex-
plained by the fact that the climate of Provence is very dry, whilst
that of Normandy is very humid. The author finds that the calyx,
corolla, and ovary of Gristallinum contain a somewhat large proportion
of sodium. This plant therefore forms an exception to Contejean's
statement that sodium is never found in the flowers or fruits of
marine plants. C. H. B.
Phylloxera and Means for its Destruction. By E. A.
Carri^res and others {Bied. Gentr., 1883, 116 — 117). — Carrieres
refers to a method proposed by Mandon for the destruction of phyl-
loxera, by introducing a 1 per cent, solution of phenol between the
bark and wood of the vine whereby the insect is killed, whilst the
grape is in no way harmed. Balbiani recommends for the destruction
of the Qggi a mixture of 9 parts coal-tar with 1 part heavy coal-tar oil.
E. W. P.
Cultivation of Potatoes. By F. Schulze and others {Bied.
Gentr., 1883, 111 — 115). — Schulze finds of the early potatoes that
Cattel's Advancer is the highest in starch, but Rotterdamer Diinen
gives the highest yield; of medium potatoes, Aurora is highest in
starch, Richter's Schnee Rose the largest cropper ; whilst of late
potatoes, Richter's Imperator is best as regards starch and yield.
Tobisch finds Imperator produces the largest amount of dry matter,
but is most disposed to disease. Several other authors report on the
cropping quality of many varieties. E. W. P.
Feeding Value of Fresh and Dried Diffusion Residue. By
A. Morgen {Bied. Gentr., 1883, 105 — 107). — By experiment it is
shown that the residue suffers no harm by being dried according to
Blossfield's method. E. W. P.
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 681
Influence of the Percentage of Moisture in Peaty Soils on
Vegetation. By R. Heinrich {Bied. Gentr., 1883, 109). — Peaty soils
were employed, and the moisture present varied from 10 — 100 per
-cent, of the total amount which could be absorbed ; it was found that
when grass seeds were sown, the largest number germinated in
those soils in which 60 per cent, of the total water was present,
whilst with only 10 per cent, none germinated. These results coin-
cide with those obtained by Hellriegel on barley, when the maximum
yield was obtained with 40 — 60 per cent, of water. E. W. P.
Retentive Capacity for Plant Food Possessed by Soils. By
L. Dumas {Bied. Centr., 1883, 136). — A certain quantity of nutritive
material is retained, which cannot be removed by plants. Well
cultivated soils retain more manured matters than those which are
badly cultivated. There is a limit to the retentive capacity. It is
unnecessary to add more manure than is requisite to replace the
material removed. E. W. P.
Manuring with Sulphuric Acid. By M. Marcker (Bied. Centr.,
1883, 137). — Marcker points out the danger of manuring with sul-
phuric acid, as has been recommended by Zeroch. The object of
euch manuring was to render phosphates soluble, but in soils poor in
phosphates, carbonates, zeolites, and humates are attacked.
E. W. P.
Action of Manures on the Quantity and Quality of a Wheat
Crop. By W. H. Jordan (Bied. Ce7itr., 1883, 96— 99).— The experi-
ments were made in Pennsylvania on one-eighth acre plots which had
been cropped with potatoes in the preceding season ; the manures
were farmyard manure and artificials, so arranged as to present one
or more constituent to the plant. It was found that fine charcoal
superphosphate increased the yield the most ; addition of potash, or
potash and nitrogen to superphosphate, raised the yield of grain and
a,lso of straw. Heavy manuring with nitrogen, in conjunction with
phosphoric acid and potash, produced no better effects than when
nitrogen was absent ; a full supply of artificials was better than farm-
yard manure ; lime and gypsum were of no value. The weight per
hectolitre of grain was highest in those plots manured with phosphates.
Nitrogen in the manure did not increase that in the grain.
E. W. P.
Researches as to the Behaviour of Insoluble Phosphates in
Peaty Soils and in Dilute Solvents. By A. Konig, R. Kissling,
and M. Fleischer (Bied. Centr., 1883, 87 — 96). — A short account of
these experiments has already been published {ibid., 1882, 422), and
in this communication we find more exact details of the work done,
as well as analysis of the various moorland soils employed. The
general outcome of the experiment is that it is more advantageous to
apply insoluble phosphates rather than superphosphate on humous
soils, as they are capable of bringing insoluble into a soluble condition ;
this applies, however, only to peaty soils, as the presence of lime
hinders this action. E. W. P.
682 ABSTRACTS OF CHEMICAL PAPERS.
Analytical Chemistry.
Glycerylphosphoric Acid. By H. Fleming (Dingl pohjt. J.,.
247, 95). — By dissolving vitreous phosphoric acid in anhydrous-
glycerol, a strongly hygroscopic, syrupy substance is obtained, which
absorbs a larger amount of water in a definite time than sulphuric
acid. (4*4 per cent, against 37 per cent.) It is thought that this
solution may be of some use for analytical or other purposes.
D. B.
Litmus, Methyl-orange, Phenacetolin, and Phenol-pMhaleiny
as Indicators. By R. T. Thomson (Chem. News, 47, 123—127).—
In this paper, the results of experiments are described, which have
been carried out with a view to testing the eflBciency of these various
indicators, used in the estimation of alkalis, &c., in the presence of
various impurities. The tests were made in such a way that the
solution measured about 100 c.c. at the termination of the reaction.
The strength of the indicator solutions (0'5 c.c. was used for every
experiment) was so arranged that the intensity of the colour was
about the same in each case at the completion of the experiment.
I. The delicacy of indicators in absence of hiterfering agents is tested
by adding 0*5 c.c. of the indicator solution to 100 c.c. of distilled
water, and trying how much decinormal acid or alkali is required to-
change the colour. In the following table the results of the experi-
ments are summarised : —
Grams of solid Amount of decinormal acid
matter per litre of or alkali required to
Name of indicator. indicator solution. change colour of indicator.
Litmus 20'0 0*5 c.c. sulphuric acid. .
Methyl-orange 0*15 0'5 „ „
Phenacetolin 2*0 O'l „ sodium carbonate.
Phenol-phthalein 0*5 O'l ,, sodium hydroxide.
II. Application of the Indicators to the Betermiyiaiion of Soda existing^
as Hydrate in the presence of a small proportion of Carbonate. — For
this purpose 50 c.c. of a normal solution of caustic soda was employed
for each experiment containing 1'55 gram of available soda, of which
0'024 gram was as carbonate estimated by precipitation with barium
chloride. The experiment with litmus was conducted as usual ; when
almost finished a single drop only was required to effect the end
reaction. With methyl-orange the end reaction is not very certain, for it
requires from 0*15 c.c. to 0*25 c.c. of normal acid, according to strength
of soda and methyl-orange solutions, to fully develop the changed
colour. The author shows subsequently that this uncertainty is due
to the salts formed; the point he adopts for the end reaction is that
at which the first decided change in colour is apparent. The amount
of indicator solution used must vary according to the volume and
colour (if any) of the solution under examination. Phenacetolin is
used for the determination of both sodium as hydroxide and as car-
ANALYTICAL CHEMISTRY. 683^
bonate in the same solution. For the hydroxide, acid is added until a
permanent rose colour is produced ; for the determination of carbonate
the addition of acid is continued until the rose colour, which at first
becomes more intense, turns to golden-yellow ; the end reaction is
rendered sharper by boiling off the carbonic anhydride when estimating
the carbonate. Phenacetolin does not answer when there are small
quantities of hydroxide in the presence of large quantities of car-
bonate. Phenol-jphthalem is also used for determining both hydroxide
and carbonate. In using this indicator, care must be taken not to
allow carbonic anhydride to escape before the colour is discharged,,
which happens when the hydrate is neutralised, and when the car-
bonate has been converted into the hydrogen carbonate, then the number
noted at this point shows all the sodium as hydroxide, and half that
as carbonate. The titration is continued, boiling thoroughly after
each addition of acid to decompose the sodium hydrogen carbonate,,
and thus bring back the red colour. It is best to add excess of normal
acid, and to titrate back with normal caustic soda. The more car-
bonate there is present the less delicate is the end reaction. This
method is not trustworthy for the determination of small quantities of
sodium hydroxide in presence of large quantities of carbonate. The
results of this series of tests are as follows : —
Soda employed = 1*55 grams, consisting of 1'526 grams as hydrate
+ 0'024 as carbonate.
G-rams of total G-rums of soda as G-rams of soda as
Indicator. soda found. hydrate found. carbonates found.
Litmus 1'55 — 1*55 — —
Methyl-orange .. 1'55 — 1*55 — —
Phenacetolin .... 1-5.5— 1-55 1-523— 1'526 0-027—0-024
Phenol-phthalein . 1-55— 1-55 1-526—1-526 0-024— 0024
III. The estimation of jpotasli in caustic j)otash can be conducted in
the same way and with as great accuracy as in the case of soda.
IV. For the estimation of ammonia, 50 c.c. of a solution containing
0-547 gram of ammonia was employed for each experiment. When
litmus, methyl-orange, or phenacetolin were used, 0*55 c.c. of ammonia
was found ; the end reaction being in all these cases as delicate as
with caustic soda. Phenacetolin produces the dark pink colour cha-
racteristic of its reaction with sodium or potassium carbonate, and not
the yellow, as with the hydroxide of those metals, it therefore cannot
be used as indicator for the determination of the proportions of
ammonia free and as carbonate. Phenol-phthalein gives results much
too low, on account of the colour being affected by the ammonium
salts produced in the reaction. The results are tabulated below : —
Ammonia, NHg, employed for each test, 0*547 gram.
c.c. of normal acid
aramofNHj
Indicator.
consumed.
obtained.
Litmus
32-4
0-550
Methyl-orange . . .
32-4
0-550
Phenacetolin
32-4
0-550
Phenol-phthalein
.. 31-5-31-4
0-535- 0-533
<)84: ABSTRACTS OP CHEMICAL PAPERS.
Richter's process for the estimation of alkalis by dichromats
(Ghem. News, 47, 19) is fully described. The author obtained good
results for soda and potash, with ammonia, however, the results were
much below the truth. In the appended table, results by Richter's
dichromate and the ordinary acid methods are compared, phenol-
phthalem being the indicator.
01550 gram soda, 0'2355 gram potash, and 0*0850 gram ammonia,
were respectively used for each test : —
C.C. ^^ C.C. ^Q
dichromate Gram alkali acid con- Gram alkali
Alkali. consumed. obtained. sumed. obtained.
Soda (Na^O) .... 50-1 01553 50-1 01553
.... 50-0 0-1550 50-1 0-1553
Potash (K2O) .... 50-1 0-2359 50*1 0-2359
.... 50-2 0-2363 50'0 0-2355
Ammonia (NH3).. 46-0 0-0782 47-1 0-0800
.... 45-7 0-0777 46-9 0-0797
V. Determination of Alkali as Carbonate and Bicarbonate. — The
5use of litmus for this purpose is well known. Soda and potash in these
forms may be determined directly, whilst for the determination of
ammonia carbonate or bicarbonate, excess of acid is used, the car-
bonic acid expelled by boiling, and then titrated back with alkali.
PJienacetolin is used in a similar manner. Methyl-orange can be used
for alkaline carbonates, but does not yield good results with ammonium
carbonate. Phenol-phtlialein is not recommended in this case.
VI. Behaviour of the Indicators with the Neutral Salts of the Alkalis.
— In the presence of sulphates, nitrates and chlorides of potassium,
sodium and ammonium, the delicacy of the litmus and phenacetolin
are unaffected, the end reaction with methyl-orange is affected to the
extent above mentioned, whilst the phenolphthale'in is unaffected by
the metallic salts ; the ammonium salts, however, retard development
•of the colour considerably, they must therefore be excluded on all
-occasions when this indicator is used.
VII. Sodium thiosulphate is neutral to all four indicator.
VIII. Effect of Alkaline Sulphites. — These salts act alkaline to
litmus, phenacetolin, and wethyl-orayige. With the first two the end
reaction is not very distinct, with the last it is very sharp and decided.
The sulphites are practically neutral to pheiiolphthaleia in the cold,
and even after boiling, provided the solution has not a great excess of
acid. Results are as follows : — 3*15 grams of Na^SOa (1-55 grams of
KajO) are used for each test.
c c. normal Gram Na^O
Indicator. acid consumed. found.
Litmus 24-9 0-772
Methyl-orange 25-1 0*778
Phenacetolin 25-1 0*778
-p, , , ,, 1 .. f cold . . 0-2 0-006
Phenol-phthalem | foiled. 4-0 0-124
IX. Normal Alkaline Sulphide. — With these salts litmus, phenace-
r
ANALYTICAL CHEMISTRY. 085
tolin^ and methyl-orange, give excellent results ; it is advisable to boil
off' the hydrogen sulphide when using the first two ; this precaution
is not necessary with the methyl-orange. With phenol-phthalem in
the cold only about half the soda is indicated ; on boiling, however, the-
whole of the soda is obtained, this is evidently due to the sodium
hydrogen sulphide formed during the reaction being neutral to thi»
indicator. Results obtained are as follows : — 0*284 gram NaaS used.
c.c. normal Gram 'Na,^
Indicator. acid consumed. found.
Litmus 7-2 0-280
Methyl-orange 7-2 0-280
Phenacetolin 7-2 0-280
r»i, 1 i^xt, 1 •• i cold . . 3-55 0-138
Phenol-phthalem |^^.j^^ ^,^^ ^ ^.^78
X. Effect of Alkaline Phosphates. — With litmus, the change of colour-
is very gradual, and therefore difficult to ascertain ; with methyl-
orange, the end reaction is as delicate as with sodium hydroxide.
With phenacetolin and normal phosphates, the yellow colour is at first
produced, and then the pink, the mono-acid phosphates give the pink
at once ; normal phosphates, in fact, act with this indicator as a
mixture of a hydroxide and a mono-acid phosphate. Phenol-phthalein
acts in quite another way, the metallic hydrogen phosphates being
neutral to it. The results obtained are as follows : — 2-050 gram of
sodium phosphate, Na2P04 (1-162 NasO), used for each test. 1-775
sodium hydrogen phosphate, NaoHPOi (0-0775 NasO), was used for
each test.
Na3P04. Na2HP04.
f ^ , , ^ ,
c.c. normal Gram
acid Gram Na^O c.c. normal Na^O
Indicator. consumed. found. acid used. found.
Litmus 24-9 0-772 12-4 0-384
Methyl-orange 25-05 0-776 12-6 0-390
^, , ,. j 1st change. 110 0341 — —
Phenacetolin 1 2nd change 24-9 0-772 12-4 0-384
T3t, 1 uxi, 1 •• /cold.. 12-65 0392 025 0-008
Phenol-phthalem [^^-^^^^ 13.7 o-42o 1-4 0-043
By the term alkaline salts, those of sodium, potassium, and ammo-
nium are meant ; salts of the last-mentioned must always be excluded
with phenolphthalein. All the substances used for these test experi-
ments were carefully analysed. D. A. L.
Determination of Nitrogen in Mixtures containing Nitro-
genous Organic Matter, Ammoniacal Salts, and Nitrates. By
H. H. B. Shepherd {Gliem. Neivs, 47, 75 — 78). — The author reviews
some of the processes that have been proposed to replace Dumas's
method for the determination of nitrogen. Grosjean's process {Ghem.
News, 25, 205) is noticed, but more attention is given to the following
methods. With regard to the ordinary soda-lime method, the authm*
proves experimentally its uncertainty and inefficiency when organic
<jSQ abstracts of chemical papers.
matter and nitrates are present ; even the addition of starch or sngar
to the substance previous to burning, or the use of a copper roll in
front of the tube, does not make the method trustworthy. The author
•states that " the chief cause of failure is the disengagement of nitric
ncid from the nitrate, which affects the result bj distilling over and
increasing the quantity of acid originally placed in the nitrogen bulb."
Ruffle's method (this Journal, Trans., 89, 87) is next discussed. The
iiuthor points out the importance of making a blank nitrogen deter-
mination with the several materials used in this process, previous to
using them for an actual experiment, otherwise there may be an error
amounting to 0*2 per cent, when 1 gram of substance is taken for
analysis. In some test experiments with pure potassium and sodium
nitrates, and manurial mixtures, good but rather low results were
obtained. For the Crum method, the author describes a nitrometer,
which consists of a graduated cylinder, fitted at the top with the usual
•cup and stopcock, but bent round and upwards at the lower end, and
connected by means of flexible tubing with a mercury reservoir hong
on a cord working over pulleys ; this arrangement is for levelling the
mercury before reading the volume of gas in the graduated cylinder,
the mercury in the reservoir is arranged 1° higher than that in the
nitrometer for every 8° occupied by the acid, in order to compensate
for the weight of the latter. He also describes an indigo method for
manures. D. A. L.
Note. — With regard to the indigo method, the author retains two
-erroneous ideas (compare Warington, Chem. News, 25,45 and 47; and
this Journal, Trans., 35, 578), viz. : 1, he uses a volume of acid which
does not bear a constant proportion to that of the combined volumes
of the solution to be tried and the indigo used ; and 2, he uses one
standard of indigo for all strengths of nitrate solutions. The agree-
ment of his quoted experiments is probably due to the errors balancing
one another. — D. A. L.
Volumetric Estimation of Chromic Acid in Chromates and
IDichromates. By J. W. C. Harvey (Chem. News, 47, 86).— This,
like some methods already proposed by the author (this vol., 513), is
based on the reducing action of stannous chloride. The dichromate
solution in this case consists of 15 grams of the salt to the litre, and
1 c.c. = 0*017 gram iron = 0*01014 gram chromic acid. The stannous
chloride solution contains 330 grams to 1 litre. The ferric chloride
solution should not be too dilute, about 32 grams of iron to 1 litre.
The process is conducted as usual (loc. cit.). To 1 gram of substance,
10 c.c. of the stannous chloride solution and some hydrochloric acid
are added, the whole heated until complete redaction of the chromic
acid is effected, excess of ferric chloride is then added, again heated,
and the ferrous chloride formed by the residual stannous chloride is
titrated with the dichromate, noting the number of c.c. required.
10 c.c. of the stannous chloride solution are now mixed with excess of
ferric chloride, heated, and the ferrous chloride titrated, noting number
of c.c. required. From the difference between the two readings the
amount of chromic acid is readily calculated. Test experiments with
potassium, lead, and barium chromates give satisfactory results. With
ANALYTICAL CHEMISTRY. 687
1 gram of lead or barium chromate, 5 c.c. of stannous cWoride are
sufficient. The stannous chloride should be tested before each series
of experiments. A determination lasts ten minutes or so.
D. A. L.
t
Methods of Detecting Lead, Silver, and Mercury in the Body
in Cases of Poisoning. By Y. Lehmann (Zeits. Physiol. Ghem., 6,
1 — 42). — After fully discussing the literature of the subject, the
author describes a series of quantitative experiments, in which the
delicacy of various processes which have been employed for the detec-
tion of those metals is put to the test.
As regards lead, the sensitiveness of certain reagents were in the
first place determined.
Hydrogen sulphide proved the most sensitive, giving a precipitate
with lead nitrate in 10,000,000 of water in neutral or alkaline solution,
and with 1 in 200,000 in acid solution.
Sulphuric acid with the addition of alcohol detected 1 in 50,000 of
water, as also did potassium chromate, while potassium iodide snfficed
only to indicate 1 part in 12,500 of water. Hydrogen sulphide in
alkaline solutions is therefore the most delicate reagent for the detec-
tion of lead.
In the examination of the organs of the body and of organic fluids
such as urine, it is necessary first to destroy all organic matters by
hydrochloric acid and potassium chlorate, otherwise the separation of
lead takes place incompletely, or even not at all.
In the separation of lead in this way, electrolysis yielded results
as favourable as those obtained with hydrogen sulphide. The method
employed was to place the solutions freed from organic matter and
acidulated with hydrochloric acid in a bell-jar, closed below by means
of parchment paper, and placed in very dilute sulphuric acid. The
positive electrode from a battery of three small copper-zinc couples
dipped into the solution lying on the parchment diaphragm, on the
other side of which lies the negative electrode. Both electrodes were
of platinum foil. After 24 hours, the lead deposited upon the positive
electrode was dissolved by boiling with dilute nitric acid, the solution
evaporated to dryness, and the residue redissolved in water, with addi-
tion of caustic soda. It was then tested by hydrogen sulphide in the
usual way. Other methods, which it is needless to specify, Mayen^on
:and Bergeret's and Reinsch's, gave incomplete results.
For the quantitative determination of lead under these circumstances,
Lehmann adopts the colorimetric method of G. Bischoff (Zeits. Anal.
Chem., 1879), using hydrogen sulphide in presence of alkali.
After the administration of salts of lead, the metal may be detected
in the urine and all organs of the body; in the case of rabbits to
which lead had been given in doses of 3 — 4 mgrms. daily, traces of it
were found in the urine after the first day. The greater portion of
the lead is deposited in the tissues, and after four or five days, while
mere traces are discernible in the blood, large quantities are found in
the heart, lungs, kidneys, brain, and bones.
For silver, hydrochloric acid is the most sensitive test. The reaction
with hydrogen sulphide is precipitated in solutions containing 1 part
688 ABSTRACTS OF CHEMICAL PAPERS.
of silver nitrate in 200,000 of water, and with potassium chromate
only when 1 in 10,000. Hydrochloric acid, on the other hand, still
gives a visible turbidity, with 1 part in 400,000.
The separation of silver by hydrochloric acid from solutions con-
taining salts and organic matters is not complete, as for instance from
the urine which holds alkaline chlorides in solution, these latter dis-
solving in part silver chloride. In such cases and in the organs of the
body, organic matters must first be destroyed, not by means of potas-
sium chlorate and hydrochloric acid, bnt by fusion with potassium
nitrate and sodium hydrate. From the residue left after extracting the
alts by water, the reduced silver is dissolved in nitric acid, filtered,
evaporated, redissolved in water, and precipitated by hydrochloric aeid.
Other methods of determining silver, such as separation on copper
foil, zinc-dust, and electrolysis, give unsatisfactory results. By the
above method silver was detected in 60 cm. of the urine of a rabbity
under the skin of which 18 mgrm. silver nitrate had been injected.
Similarly, after subcutaneous injection, in eight dogs of 48 mgrm.^
silver was discovered in the urine and liver.
Mercury is fouud in cases of poisoning in all the tissues and secre-
tions of the body. The author considers the methods of Schneider
{Sitzmigsherichte der Kaiserlicli. Akad. der Wissenschaft., Mathemat.-
Naturwissensch. Classe, 40, Nr. 8, Wien, 1860), and of A. Mayer
(Wiener Med. Jahrhucher, 1 Heft, 1877) as alone yielding accurate
results. In Schneider's method, the substance under examination is
freed from organic matters by means of potassium chlorate and hydro-
chloric acid, and the filtrate subjected to electrolysis, the mercury
being best deposited on a gold electrode, which Lehmann found to give
more sensitive results than copper.
The deposited mercury is converted into iodide, for which pui'pose
the electrode is introduced into a glass tube, drawn out in a capillary
bore at one end, and sealed at the other. The latter part being heated,
the resulting sublimate is driven into the capillary portion, which,
with a bulb-shaped part of the wide tube, is then cut off before the
blowpipe. This latter part is opened, and some iodine being intro-
duced is again closed. The iodine vapour penetrates the capillary end,.
and changes the mercurial sublimate into iodide. According to
Lehmann, the sensitiveness of the test is heightened if this reaction
takes place in a slow current of air, while the gold electrode is
cautiously heated, and the mercury volatilised in presence of the
iodine. In this way 0*1 mgrm. HgCla may be detected in 100 c.c. of
urine. Mayer's method, by which the mercury is distilled in presence
of steam, is even more sensitive. Urine, or the finely divided organ,,
diluted with water, is mixed with slaked lime, and solution of potash
in a flask having a capacity of about thrice the volume introduced.
A U-tube filled with glass wool moistened with silver nitrate is con-
nected with the flask, and both are heated in a calcium chloride bath
to 130 — 140°. The glass wool is afterwards inserted in a tube and
converted into iodide as already described. A 2 per cent, solution of
sodium chloride may advantageously replace the water used in this
method, frothing being avoided, and the mercury more rapidly volati-
lised.
ANALYTICAL CHEMISTRY.
By this method 0*1 ingrm. HgCl2 may be detected in 1 litre of
nvine. For details of both processes, the reader is referred to the
original memoir.
After subcutaneous injection of mercuric chloride to the amount of
3 — 4 mgrms. daily for five days in a rabbit, mercury was found in
greatest amount in the heart, lungs, liver, and muscles, least in the
brain, bones, and nrine. D. P.
Ready Method of Estimating the Alkalinity of Limed
Beet Synip. By P. Despeax (Bled. Centr., 1883, 141).— Filter-paper
is soaked in solutions of tartaric acid of various strengths, and a
small quantity of rosolic acid is also added. The immersion of several
of such strips of paper into an alkaline solution gives a rough estimate
of the alkahnity. E. W. P.
Assay of Nux Vomica. By W. R. Dunstan and F. W. Shoet
(Pharm. J. Trans. [3], 13, 665 — 667). — This subject being of great
importance on account of the strychnine and brucine in nux vomica,
the authors have investigated the matter in order to find an accurate
and simple method, Dragendorff's method being too long and intricate.
Experiments were tried in which the nux vomica was made into a paste
with various alkaline solutions, dried, and the dried mass extracted
with chloroform ; in all cases the marc (the mass after extraction)
was bitter, showing that the alkaloids were not wholly extracted, and
therefore that chloroform alone is not an efficient medium for the
purpose : a mixture of alcohol and chloroform (1 : 3), however, com-
pletely extracts the alkaloids from nux vomica. Experiment showed
that it was not necessary to mix the nux vomica with alkali, but that
the powdered seeds could be at once extracted with chloroform con-
taining alcohol as follows: — 5 grams of the finely powdered nux
vomica seeds are extracted for about two hours in an extraction
apparatus, w^ith 40 c.c. of chloroform, containing 25 per cent, of
alcohol : this takes from one to two hours. The extract is well
agitated with 25 c.c. of 10 per cent, dilute sulphuric acid, the chloro-
form separated, and again agitated with 15 c.c. of acid. The mixed
acid solutions should be quite free from chloroform, filtered if neces-
sary, then made alkaline with ammonia, and shaken with 25 c.c. of
chloroform. The chloroform extract is run off, evaporated on a
water-bath, and the residue, consisting of the alkaloids, weighed. It
is sometimes necessary to filter the chloroform after separation from
the alkaline liquid. By this process samples of commercial nux
vomica were found to contain the following percentages of alkaloids : —
2-92, 3-57, 3-32, 3-38, and 2-56.
The authors have successfully employed the mixture of chloroform
and alcohol for the extraction of other alkaloids. J). A. L.
Tests for Resorcinol Dyes. By R. Benedikt (Chem. News, 47,
109). — In the tests recommended, a few drops of the solution of the
colour are treated with ammonia and zinc-dust, by which treatment
all cosines are completely decolorised ; the colour comes back slowly
on exposure to the air, but quickly on boiling. The colourless liquid
VOL. XLiv. * 3 a
690
ABSTRACTS OF CHEMICAL PAPERS.
■11 ii
121
« a;
I'm
4; oa
i§§
.S ".3 .
^ > ^ '
;r fl fe a
•2&
•s§
.S3
4J t<)'d
Nsi
4ii
.111
o ,- « a
P s5 ^
O .0 5,
« s .
Ill
sis
c j: M
& «— c
lit
."2 ^ *!. j= >> g
S 4>> 4> -J
•'<*- «"^ 3
•e o g ^ ■« 3
£ c.c.2g «"
53 1^ c^
S .a ^ 5 .2 «
3 c
Si"* '"tS
IIP 11
lijiiii
|<n .5*= ^.5
3 ".3 ».2.S 3
o- § si;:! g
o .25 § 3 X d .S
o
« = c ^
pi
•3 iS^
"?<«&
tt 3 1. g
-■s&§
c 3 ^c
mi
&:§ = §
a *'«i
1-^
pi
.2 o £;
lili
(U 3
ii-
§0
a-s
11
^'B
11
o g
c <»
i
I =1 •
S S o s
OS a
3 i - O
.2 r-:^
y 3 o<
o"^ .3 w
^ u O be
|3«
ai|
ill
o o <^
a {- «j
5S&
si
^8
""3
S<a
|S
S w
* i I
3 -2 2 « s
o .g^^
>>-3 * «2
£|^"£«
as
Cm
is
.•3 c: o
•2a«
£>.
"sS
^.1
II
■5-3
is
TECHNICAL CHEMISTRY. 691
is boiled until a copious precipitate of zinc hydroxide forms, hydro-
chloric acid is now added to dissolve this precipitate, the solution is
next supersaturated with ammonia, and finally tested with potash
(sp. gr. 1-30). The colour on fabrics is tested by stripping the dye
from the cloth either with water to which a few drops of potash or
ammonia have been added, or with alcohol ; the liquid which comes
off the cloth is tested in the same manner as the solution of a dye.
The author's observations are tabulated on p. 690, D. A. L,
Technical Chemistry.
PurilBcation of Contaminated Waters, By J, Konig (Bled.
Centr., 1883, 75 — 79). — The method employed consists in causing the
water to flow on to wire-netting placed at such an angle that the
water flows over the meshes, thus exposing a large surface to the air.
Thus the water becomes thoroughly saturated with oxygen, and sul-
phuretted hydrogen, &c., is completely oxidised. For every 6 to 7
litres water which passes per minute, 50 cm. of netting is requisite,
E. W. P,
Bronze Implements used by the Miners of Peru. By
BoussiNGAULT (Gompt, rend., 96, 545 — 546). — The author found a
bronze chisel weighing 198 gr£|,ms lying amongst the debris of trachyte
in an ancient quarry in the neighbourhood of Quito, The sp, gr, of
the metal was 8'83, and it had the composition —
Cu. Sn, Pb. Fe. Ag.
95'0 4-5 0-2 0-3 traces ==: 100,
The hardness of the chisel was not appreciably greater than that
of copper, and it could not have been used for working trachyte if
this rock did not offer less resistance when freshly exposed and still
saturated with water than when it has become dry by exposure
to air.
A chisel found by Humboldt in a silver mine opened by the Incas
at a little distance from Cusco, the other extremity of the ancient
kingdom of Peru, had the composition Cu 94, Sn 6 = 100,
C. H. B.
Roasting of Gold Tellurides. ByKiisTiL (Chem. G&ntr,, 1882,
783). — Roasting gold or silver tellurides is sometimes attended with
loss of gold which the author attributes to volatilisation. As an
example of the irregular behaviour of this class of compounds, a
sample of petzite containing 2480 per cent, gold, 40'60 per cent,
of silver was heated on charcoal to 323*^ (m. p. of lead), the bluish- grey
mineral suddenly became yellow without altering its outward form.
692 ABSTRACTS OF CHEiMICAL PAPERS.
Examination under the microscope showed that innumerable small
globules of gold on the surface were the cause of this appearance.
Gold requires a temperature of 1200° to effect its fusion; in this
case it melts at 323°. If salt is used daring the roasting of telluri-
ferous ores, large quantities of tellurium chloride pass off, and perhaps
give rise to the volatilisation of the gold. In an experiment the
author, having added salt during the roasting of one of these ores,
lost 8 per cent, of gold before the ore was actually red hot. It is
therefore indispensable to have the furnace connected with a con-
densation chamber when tellurium gold ores are roasted in it.
D. A. L.
Preparation of Pressed Yeast. By J. Wehmee (Bied. Centr.,
1883, 143). — According to this patent raw instead of steamed potatoes
are used ; they are to be pulped and heated with water at 50", then
mixed with green malt and rye husks, heated and allowed to saccharify,
cooled, and allowed to ferment at 25°. E. W. P.
Influence of Chlorides of the Alkalis and Alkaline Earths
on the Precipitation of Lime Saccharate from Warm Solu-
tions. By P. Degener (Bied. Gentr., 1883, 127). — The precipitation
of the lime as well as sugar is greatly dependent on the proportion in
which these two substances are present in the solution. The tri-
basic saccharate is only precipitated when the solution is saturated
with lime. The presence of chlorides of sodium, potassium, barium,
strontium, or calcium does not hinder precipitation, and may even aid
it if they are present only in small quantities, but when in excess they
are distinctly detrimental, E. W. P.
New Process for the Extraction of Fish Oil. (Pharm. J.
Trayis. [3], 13, 669— 670.)— The tish is sprinkled with 5 per cent,
of its own weight of ferric chloride or sulphate solution (45° B.),
and can then be kept three or four days without undergoing altera-
tion. It is then crushed, made into a paste, and pressed, when a large
quantity of water and oil is forced out. The cake from the press
dries readily, becomes friable, and is easily pulverised. A further
quantity of fatty matter may be obtained from it, either by pressing
between heated metal plates, or by extraction with benzene or carbon
bisulphide. The residue forms an excellent fertiliser. D. A. L.
Uranium Oleate, By W. Gibbons (PJiarm, J. Trans. [3], 13,
737). — This oleate, (Ci8H3302)2U02, can be prepared by adding excess
of uranic oxide to pure oleic acid. The mixture is allowed to solidify
in an atmosphere of hydrogen, and the oleate exti'acted with ether,
crystallised from alcohol, and dried in a vacuum. It is very unstable
in air, and must therefore be kept in hydrogen ; it softens at 85°, and
on raising the temperature becomes viscid and finally decomposes.
For medicinal purposes, it is advisable to mix it w4th vaseline or ozo-
kerine to prevent oxidation. D. A. L.
Composition and Ripening of Emmenthal Cheese. By
M. Weidmann {Bied. Centr., 1883, 118— 124).— The following table
TECHNICAL CHEMISTRY. 693
shows the composition of the dry matter of samples of cheese made at
varions dates extending over a period of six months : —
Albumin
precipitated
Amide
Fat
by acetic
nitrogen
Ammonia
per cent.
acid.
per cent.
per cent.
L.
. . 45-13
42-45
005
0-01
II..
. . 44-96
39-77
0-30
0-09
III..
. . 44-46
38-84
0-53
. —
IV..
. . 44-84
34-20
0-88
—
V ..
. . 45-05
—
—
—
Va..
. . 45-64
32-96
1-08
0-16
V6..
. . 44-66
Nitrogen
in extract free
from albumin
Total
and peptones
nitrogen
Ash
P2O5
ner cent.
per cent.
per cent.
per cent.
I..,
. . ^ 0-06
, —
5-16
2-49
II..
—
—^
5-19
2-1.7
III..
.*. 1-05
:
—
2-48
IV..
., —
—
2-39
V ..
—
7-53
5-44
2-33
Ya ,
1-53
—
—
2-31
Yb.,
—
—
—
2-35
Cholesterin was found in the ethereal extracts to the amount of 0-24 — •
0*32 per cent., and also small quantities of free acid. The residue
after removal of the fat was soluble in ammonia or potassium
hydroxide, and was nearly all precipitated by addition of acetic acid,
and in the filtrate were found tyrosine and leucine; in the residue
there were ammonia and peptones. A substance soluble in hot
alcohol, and which seems to be identical with Ritthausen's glutin,
fibrin, and mucedin was found ; this compound has been called
caseo-glutin. The amount of water decreases as ripening proceeds,
falling from 43*99 per cent, to 32-1 per cent. ; but the percentage of
fat is not perceptibly altered, nor the total nitrogen, although the
albuminoids become gradually soluble, being converted into caseo-
glutin : hence we may conclude that although ripe cheese is more
digestible, it has lost some of its nutritious matter. In the same
manner Roquefort cheese, as ripening proceeds, becomes less and less
nutritious. E. W. P.
Liquid Extract of Cinchona. By B. H. Caul (Phamt. J.
Trans, [3], 13, 737 — 739). — The author shows by quantitative experi-
ments that the method of extraction and preparation of liquid
extract of cinchona recommended by the British Pharmacopoeia is
inefficient, only a very small percentage of the alkaloids and other
medicinal principles of the bark being removed by treatment with
water. Moreover, he points out that the infusion, and even more so
694 ABSTRACTS OF CHEMICAL PAPERS.
the decoction, are pharraaceutically better preparations than the
liquid extract of cinchona. The special defect is that this extract
does not represent the medicinal properties of the bark.
D. A. L.
Technical Aspects of Lignifi cation. By C. F. Cross (a paper
read before the Society of Arts, January 25th). — The object of this
paper is to indicate the theoretical lines of the present development
of cellulose technology, more particularly with regard to the applica-
tion of lignified structures to textile and other purposes. These sub-
stances were formerly employed solely for the manufacture of inferior
goods, but improved processes of treatment — both for the isolation of
cellulose (paper-pulp) and for merely bleaching (textiles), have brought
them into more direct competition with the various forms of cellulose
(cotton, linen, &c.). The standard processes for scouring and bleach-
ing cellulose fabrics, as also for preparing cellulose from complex
plant structures, all involve the employment of alkaline solutions
under conditions of more or less drastic oxidation. The application
of these processes to the treatment of lignified cellulose has given
more or less imperfect results, and the investigation of the causes
underlying these results has served to throw light on the chemistry of
lignification. The main feature of the chemical constitution of lignose
(bastose) in regard to its preparation by chemical processes for the
purposes of the arts, is the presence of aldehydic substances of the
furfural type, and from these are formed, as secondary products, acid
bodies and brown colouring matters. This explains the disintegration
and discoloration produced in the treatment of jute fabrics by the
standard processes, and the protective action of the alkaline sul-
phites dried into the fabrics from solution. The author then dis-
cusses, as the principal subject of the paper, the theory of the various
processes of resolving wood by the action of solutions of the acid sul-
phites which are at present occupying the attention of paper makers.
Experiment has clearly shown that the sulphites fulfil the twofold
function, first, of keeping up a condition of reduction or anti-oxida-
tion, and, secondly, in virtue of their well-known relation to the
aldehydes, of forming stable and freely soluble addition- compounds
with the products of resolution of the woods, and are therefore pecu-
liarly adapted to the work of promoting the action of the hydrolytic
agents. The author discusses the work of Fry, Ekm^n, Tilghmann,
Mitscherlich, and Francke, in developing these processes. While
withholding an opinion as to the value of the pulps produced by the
various processes of sulphite boiling, he indicates the existence of
important difierences in the specific action of the several sulphites.
The following suggestions are ofEered in regard to the criteria of a
wood pulp: — To detect residual lignose the aniline sulphate test
(yellow coloration) has hitherto been considered sufficient, but as the
" reduced " pulp often fails to give the reaction, although containing a
large proportion of residual lignose, the author recommends the
chlorine test, followed by immersion of the chlorinated pulp in a solu-
tion of a neutral sulphite : the development of a magenta coloration,
affords an unfailing proof of the presence of lignose ; and the depth
TECHNICAL CHEMISTRY. 695
of colour is a rough measure of the quantity. A quantitative estima-
tion of cellulose by any of the standard methods is of course essential,
as is also a determination of the loss of weight on boiling in dilute
potash solution under standard conditions, the latter revealing the
presence of hydrated and gelatinous modifications of cellulose, which
render paper hard and brittle.
In conclusion the author briefly discusses the subject of " retting "
in regard to the question of replacing this process by that of boiling
the plants with solutions of the sulphites, and thus obtaining uniform^
and certain results in the isolation of their fibrous constituents.
C. F. C.
Indophenol. By H. Koechlin (Chem. News, 47, 40). — This
substance is obtained by the oxidation of a mixture of amidodimethyl-
aniline and sodium naphtholate. It is insoluble in water, soluble in
alcohol with a blue colour, and in glacial acetic acid. Sulphuric acid
dissolves it with a red colour, but decomposes it. Alkalis are without
action on indophenol prepared from a-naphthol, but decompose that
prepared from ^-naphthol ; on the other hand, mineral acids decom-
pose a-naphthol indophenol, but do not act on that inade from
^-naphthol. Indophenol is easily reduced by sulphides, stannous
chloride, &c. ; the product of the reduction is very soluble in acetic
acid and in alkalis. Indophenol, as the name implies, is an indigo-
blue dye, for fixing it on cotton, the fabric is printed with a mixture
of indophenol and tin acetate, duly thickened, aged, and washed, or
steamed and chromed; or tin nitromuriate, ammonia, and stannous
oxide may be incorporated in the mixture. Directions are given in
the paper for dyeing wool and silk. C. Mayer has obtained a violet
indophenol from resorcinol ; it is of great solidity but wanting in
brightness, and is difficult to apply on account of its sparing solu-
bility. The indophenol from phenol dissolves in sulphuric acid with
a blue colour. D. A. L.
New Process for Preparing Press-cake from Maize, &c. By
F. BuROW (Bied. Centr., 1883, 142). — According to this patent, the
materials for fermentation are previously mashed for two days at 60°
in sufficient water to yield a wort containing about 15 per cent, sugar.
After conversion into sugar, the whole is allowed to become acid until
2 — 2*2 per cent, of acid is present, then cooled, and on the third day
before use 2*5 kilos, yeast free from starch is added, and 100 c.c. sul-
phuric acid. When half the sugar has fermented, then 25 litres of
mash of 24 — 25° are added, and a quarter of an hour later another
200 c.c. acid. The mash is prepared from 300 kilos, potatoes with
100 kilos, maize boiled with 600 litres water ; with this, 70 kilos, green
malt, 100 kilos, rye, and 30 kilos, buckwheat may be mashed. The
percentage of sugar must reach 11'5 — 125 per cent, and that of the
acid 0-4— 0'5. E. W. P.
Preservation of Diffusion Residues from Beet-sugar Manu
facture. (Dingl. polyt, X, 247, 123— 125.)— Marker {Journ. /.
Landw., 1882, 413) having shown that diffusion residues when kept
1)0 G ABSTRACTS OF CHEMICAL PAPERS.
lose considerably in weight, several sugar refiners have undertaken
experiments with a view of obviating this loss. The loss of solid
constituents on keeping these residues from three to thirteen months,
amounted to 13'8 — 54'6 per cent. The cause of this loss is due partly
to fermentation of the carbohydrates contained in the residues, partly
to oxidation, the organic matter being converted into carbonic anhy-
dride and volatilised. To prevent this loss, it is recommended to
utilise as large a quantity of fresh residues as possible for feeding
purposes, and dry the remainder, after which they do not suffer so
much loss. D. B.
Cause of the Acid Reaction Exhibited by some Kinds of
Paper. By Fleichtinger (Dlngl. polyt. J., 247, 218). — In a former
communication (Abstr., 1882, 1339) the author stated that all paper
sized with resin exhibits an acid reaction due to the presence of free
sulphuric acid. Harlin, who confirmed this, states that the acidity is
not due to free acid, but depends on the aluminium sulphate used for
fixing the size. The author has again studied this question, and con-
cludes, from a number of experiments, that free sulphuric acid is
present in paper treated with size made from resin. The acid reaction
is due also to the presence of aluminium sulphate, but whether the
latter is contained in the paper as normal or basic salt cannot be
decided without further investigation. D. B.
697
General and Physical Chemistry.
r
Chlorophyll and the Distribution of Energy in the Solar
Spectrum. By C. Timiriazeff (Compt. rend., 96, 375—376). — In a
previous communicatioii (Compt. rend., May 28, 1877), the author
showed the intimate relation existing between the absorption of light
by chlorophyll and the intensity of the chemical action produced, and
expressed the opinion that this action is dependent on the energy, as
measured by its thermal effect, of the rays absorbed. He now calls
attention to the fact that Langley's measurements with the bolo-
meter justify this opinion, and prove that the point of maximum
energy in the solar spectrum corresponds with the characteristic
chlorophyll band between B and C. The author is now engaged on
researches on the quantitative relation between solar energy absorbed
by the chlorophyll of leaves and that stored up in the chemical work
performed. He finds that, under the most favourable conditions, a
plant utilises 40 per cent, of the energy absorbed. L. T. T.
Luminosity of Plame. By W. Hittorf (Ann. Phys. Chem. [2],
19, 73 — 77). — In this paper, the author claims priority over W. Siemens
as regards the non-luminosity of gases at the temperature of molten
steel (this vol., p. 539) ; for he observed in the year 1879 that a layer
of air surrounding electrodes of platinum, made white-hot by the
passage of a current from 1600 cells, appeared perfectly dark to the
eye. The author has repeated the experiment, substituting iridium
for platinum, and using a battery of 2400 elements, divided into series
of 400, 600, and 800 ; the result arrived at was the same, and though
the white-hot iridium anode was melted, yet the gas media, whether
of nitrogen, hydrogen, or oxygen, remained perfectly dark.
Experiments showed that all gases at this elevated temperature
become good conductors of electricity, even at the lowest difference of
potential, and on passage of the current no longer emit the spectra of
the first order. The temperature at which the non-metallic elements
give the spectra of the second order (or line spectra) is considerably
higher, and is attained by the momentary discharge of the condenser.
Further, it can easily be demonstrated that the luminous gases in
Geissler's tubes are at a low temperature, and that their luminosity is
due to a phosphorescence, for the absorptive power of these gases
differs from their emissive power, and they behave differently from
metallic vapours, which become luminous in the flame. Although the
author claims priority over W. Siemens, he yet points out that Melloni
deduced the same conclusions from the researches of Draper, and
even as early as 1792 Wedgwood noticed that air at the temperature
of a furnace is non- luminous. Y. H. V.
Electric Researches. By C. Fromme (Ann. Phys. Chem. [2], 18,
552 — 578, and 19, 86 — i06). — A continuation of the author's experi-
VOL. XLIY. 3 b
098 ABSTRACTS OF CHEMICAL PAPERS.
ments (Abstr., 1880, 490). These papers contain an account of the
behaviour of platinum, palladium, gold, aluminiam, and gas-carbon,
in chromic and nitric acids.
Part I. — I. Platinum in Chromic Acid (Bunsen^s) Solution. — Pog-
gendorff and Buff observed that if nitric acid be replaced by chromic
acid in the Grove's cell, the E.M.F. is diminished in the ratio 100 : 62,,
whilst the constancy of current is materially affected, for the intensity
increases in a most marked way. But if, on the other hand, the
same change is made in the Bunsen's cell, the E.M.F. is increased,
whilst the constancy of the current is not altered. This phenomenon
was variously explained by the above physicists ; Buff considered it to
be due to the greater surface exposed by the gas-carbon, and in
support of this view he demonstrated that carbon, soaked in wax,
behaved as platinum ; Poggendorff concluded that the position of
metals in a difference-of-potential series was altered by the nature of
the liquid in which they were immersed. The author accepts the
latter explanation, but experience gained in the course of his re-
search showed that by Ohm's method, as used by Poggendorff, results
could only be obtained in the case of a cell presupposed to be con-
stant. For under certain conditions, with the combination Pt | HNO3,
an increase of intensity occurs similar to that observed in the com-
bination Pt I HjCrOi. The form of the cell used has been described in
a former paper ; the electrometer was of Kirchhoff's construction, the
sulphuric acid was greatly diluted, the chromic acid solution prepared
according to Bunsen's recipe, and the nitric acid of sp. gr. 1*4!. In
former experiments, an increase of intensity was observed in the com-
binations Pt I HNO3 and PtH2 | Cr04, a decrease in the combinations
C I HNOa-and C | HaCrO* ; Cu | HaCrO* gave a feeble but perfectly
constant current. If the E.M.F. of a Grove's or Bunsen's element,
containing nitric acid, be taken as 100, the E.M.F's. of these elements,
when containing chromic acid, are 70 and 104 respectively; while the
Cu I H2Gr04 combination is 62. But in later experiments with the
Grove's elements, an increase of E.M.F. was observed, and the author
considers that his former results were possibly vitiated by impurities
on the surface of the platinum. In the present paper, the results of
experiments on the Pt | H2Cr04 combination are given, and the
variations of the E.M.F., under different physical conditions, is
investigated.
As a general rule, it is shown that when a lower intensity is followed
by a higher intensity, the E.M.F. increases until a maximum point is
reached, when it decreases, and conversely when a higher succeeds a
lower intensity, the E.M.F. gradually decreases until it reaches a
minimum, and then again increases without however attaining again
its former maximum value. If the circuit is open, then taking the
platinum plate has no effect. Again, neither change of temperature
of the platinum or chromic acid, nor movement or renovation of the
platinum surface, produces any result. Hydrogen occluded in the
platinum raises the maximum and minimum of the E.M.F., in pro-
portion to the quantity of gas contained in the metal; occluded
oxygen is without effect.
If pure chromic acid solution be substituted for Bunsen's chromic
GENERAL AND PHYSICAL CHEMISTRY. 699
acid, the E.M.F. of the open element is lowered by about 2 per cent. ;
on closing the element, the E.M.F. decreases to its minimum poiat,
the more rapidly the smaller the exterior resistance. If sulphuric?
acid be added to the solution, the E.M.F. follows the same curve of
change as that observed in the experiments above.
II. Palladium in Chromic Acid. — The substitution of palladium for
platinum in the (Bunsen's) chromic acid element decreases the E.M.F.
of the open element by about 3*5 per cent., but in the pure chromic
acid element by S'S per cent. The E.M.F. of a closed Pd | HaCrO^
element is, the conditions being the same, less than a Pt | H2Cr04
element, the diminution in value being proportional to the intensity
of the current.
III. Gold in Ghromic Acid.— The E.M.F. of an open Au | H2Cr04
element is equal to that of the Pt | H2Cr04 element ; if the circuit be
closed, the E.M.F. remains constant, and does not follow the same
variation observed in Pt | H2Cr04 element.
TV. Gas-carhon in Chromic Acid. — The E.M.F. of this element
remains perfectly constant, if the intensity be low, but with high
intensity it decreases until it reaches a minimum, at which it remains
constant. If the element, after being closed with a high resistance,
is closed without resistance, which is gradually introduced, then there
is an increase of E.M.F. until it reaches a value greater than the
maximum value under normal conditions.
V. AUiminium in Chromic Acid. — Aluminium behaves generally
as platinum.
Part II. — The interesting results obtained in the experiments above,
led the author to an examination of the behaviour of the same sub-
stances with nitric acid.
Platinum in Nitric Acid. — In the case of the Pt | HNOs combination,
experiments led to the result, viz., that on the passage from a lower
to a higher intensity, the E.M.F. decreases to a minimum point
and then increases, and conversely if the intensity becomes greater,
the E.M.F. increases to a maximum, and then decreases. With
increase of temperature of the nitric acid and platinum, the maximum
and minimum values are arrived at in a shorter time; at 48° the
E.M.F. is constant from the beginning. In the year 18.35 Schonbein
observed that if platinum foil is made the negative pole of a Volta's
pile, in which nitric acid is used, an evolution of gas is observed from
time to time, especially if the nitric acid be concentrated. The author
has extended Schonbein's observation, and shows (i) that when platinum
in nitric acid is the negative electrode, there is always a temporary
evolution of gas at the moment of closing the circuit, which, after a
certain time, spontaneously ceases or continues ; (ii), that the time of
duration is the shorter the more concentrated the acid and the greater
the intensity at the surface of the platinum, and Schonbein considered
the evolution of gas to be the ordinary condition of the platinum,
whilst the stoppage of the gas he considered to be abnormal. The
author's observations show that one of three conditions may obtain :
(i) no gas is liberated from the surface of the platinum ; (ii), the gas
rises from the surface of the platinum ; (iii), the platinum is covered
3 6 2
700 ABSTRACTS OF CHEMICAL PAPERS.
with gas withont rising from the surface. The second of these con-
ditions may be prevented either by making contact with the positive
pole before introducing it into the acid; (ii), by heating the
negative pole ; (iii), by introducing a third platinum foil into the
acid, and binding it with that portion of the circuit intermediate
between the negative plate and the pole of the pile.
Palladium, Gold, and Aluyniniurii in Nitric Acid. — The E.M.F. of an
open Grove's element is decreased in the ratio 1 : 0'95 — 0'98, when
palladium is substituted for platinum. If the circuit be closed, the
E.M.F. gradually decreases until it reaches a point equal to that of
the open element. Generally speaking, palladium, gold, and alumi-
nium, behave as platinum. The E.M.F. of the combination
Zn I H2SO4 I HNO3 I C,
with low intensity, is consta.nt, but it decreases with higher intensity.
The author proposes in a future communication to give a summary
and comparison of the results obtained in these various experiments,
and to refer them to some simple explanation. Y. H. V.
Modification of the Bichromate Battery. ByTEouv^ (Compf.
rend., 96, 787 — 789). — 150 grams of potassium dichromate are placed
in 1 litre of water, the solution agitated, and 450 grams (one-fourth
the volume) of sulphuric acid added drop by drop. The liquid
gradually becomes hot, the dichromate successively dissolves, and in
this way a solution can be obtained containing 250 grams of dichromate
per litre of water. The solution remains clear and yields no crystal-
line deposit, and chrome-alum does not crystallise out even when the
battery has been in action for several months. Batteries prepared
with this supersaturated solution remain constant for a long time,
and can be used with advantage to work incandescent lamps. The
mean electromotive force of the battery is 2 volts with fresh solutions,
and the intensity of the current at the moment of immersion of the
plates is 118 amperes in short circuit, with a resistance of 007 ohm.
C. H. B.
Observation on Trouv^'s Paper on a Modified Bichromate
Battery. By E. Eeynier (Cumpt. rend., 96, 838).— The first table
in Trouve's paper shows an expenditure of 456 grams of zinc in
12 couples in five hours, or an expenditure of 7'6 grams per couple per
hour, the intensity of the current being 12'G amperes at first, and
gradually descending to 6*3 amperes, or a mean intensity of
9'45 amperes. A current of this intensity however requires the
expenditure of 11*34 grams of zinc per couple per hour.
C. H. B.
Electric Discharges. By H. Heuz (Ann. Fhys. Chem. [2], 19,
78 — 86). — The author describes a series of phenomena accompanying
the electric spark discharge in air and other gases at a moderately
low pressure. A large inductorium was used capable of giving sparks
of 4 — 6 cm. in length ; this was connected with a Leyden jar of
2 square feet area. The sparks were taken in a dra^Ti-out glass tube,
GENERAL AND PHYSICAL CHEMISTRY. 701
in wMcli was introduced fhe positive electrode, the negative electrode
being placed a short distance from the mouth of the tube. When this
apparatus was introduced under the receiver of an exhausting pump
and the pressure reduced to 30 — 50 mm., there appeared on the surface
of the kathode a blue glimmering light, and between it and the anode
a broad dark space, crossed by a red streak of 1 — 2 mm. diameter.
On increasing or decreasing the pressure of the air, this streak dis-
appears. The streak is not affected by a magnet. It evolves a con-
siderable amount of heat, as shown by the rise of 10 degrees of a
thermometer and by the melting of wax introduced into it ; and it
exerts a remarkable mechanical action in setting into oscillation
elastic mica plates and radiometers. The author shows that the forma-
tion of the streak is no momentary flashing phenomenon ; for by
means of a Becquerel's phosphoroscope its time of duration was found
to be about gV second. But all parts of the streak are not illuminated
at the same time ; the under part shines out before the upper, which
in its turn is visible after the lower part is extinguished. A similar
phenomenon occurs in other gases. In oxygen and nitrous oxide, the
streak is golden-yellow ; in nitrogen, dark red ; in hydrogen, indigo-
blue ; and in vapours of turpentine, ether, and coal-gas, greenish-
white. The same streak can also be observed in gases at ordinary
atmospheric pressure ; but under these conditions it is only a few
millimeters long and very faint. It appears that the streak arises from
an illuminated mass of gas arising from the tube, and experiments were
made to ascertain whether it was caused by the expansion of the gas
owing to the rise of temperature in the experimental tube. These,
however, led to a negative result. V. H. V.
Influence of Temper on the Electrical Resistance of Glass.
By G. FoussEREAU (Compt. rend., 96, 785 — 787). — Temper diminishes
considerably the electrical resistance of different kinds of glass.
The resistance of tempered lime-glass was increased by 2*3 times by
reheating and annealing. The resistance of tempered crystal-glass
was increased to 11 times its original amount by similar treatment.
Moderate reheating, sufficient only to partially destroy the temper,
causes an intermediate increase in the electrical resistance. The elec-
trical resistance of glass which has recently been reheated, slowly
increases during some time, as if the glass gradually acquired a con-
dition of stable equilibrium. The resistance of tempered or untempered
glass which has not been heated for some time remains constant.
C. H. B.
Electric Resistance of Psilomelane. By H, Meyer {Ann.
Phys. Gliem. [2], 19, 70 — 71). — The author has been engaged for
some time past in the examination of exceptions to Ohm's law first
observed by Braun in the case of conducting minerals. The substance
selected was psilomelane, which was cut into thin plates. The author's
observations agree with those of Braun in so far as demonstrating
that such plates exhibit a remarkable unipolar conductivity ; but the
relation of the resistance in the one direction to that in the second
direction is shown to be dependent on the intensity of the electric
current ; for on changing the latter the position of unipolar con-
702 ABSTRACTS OF CHEMICAL PAPERS.
ductivity can be reversed. In no case was a change of resistance
observed when the electric current was constant ; but the remarkable
changes displayed when continuous and alternating electric discharges
followed in the same direction are perfectly explained by the unipolar
conductivity of the mineral. But as the difference between Braun's
observations and those of the author may receive some explanation
by supposing a difference of the material examined, the author cat
plates from another specimen of psilomelane from the same source,
and found that the resistance was independent of the, direction, con-
tinuance, and intensity of the electric current. As to the nature of
the difference in the two specimens examined, no explanation is
offered.
The author's observations are in opposition to those of Braun, but
in agreement with those of Dupel as regards the normal behaviour of
pyrites and galena to the electric current. V. H. V.
Radiation of Rock-salt at Various Temperatures. By C.
Baue {Ann. Phys. Chem. [2], 19, 17 — 20). — The radiation of rock-salt
at various temperatures has previ(msly been studied by Melloni and
Magnus. The former arrived at the result that the heat radiated
from rock-salt is not to any extent absorbed by polished plates of the
same material, whilst the latter considered rock-salt to be mono-
thermic, and believed that the heat radiated from rock-salt is perfectly
absorbed by another plate. In Magnus' experiments, the rock-salt
plate was heated to 180°, and an absorbing plate of greater thickness
was placed before the thermoelectric pile. The experiments of the
author do not confirm either the results of Melloni or of Magnus.
The apparatus used consisted of a radiometer, a radiating rock-salt
plate of dimensions 90 mm. X 50 mm. X 8 mm. in a copper frame,
which could be brought to the temperature required by a gas flame,
and whose temperature could be determined by a thermopile of copper
and nickel. A zinc screen was introduced to prevent radiation from
the copper and the gas flame. The heat radiated from the plate was
absorbed by three rock-salt plates, mean thickness 3"4, 5"1, and 13*8 mm.
The author's results demonstrate that rock-salt is the greatest
absorbent of heat radiated from the same material ; that the absorp-
tion increases with decrease of difference of temperature between the
radiating and absorbing plates ; and that the absorption is probably
perfect when the radiating and absorbing plates are at the same
temperature. V. H. V.
Evolution of Heat in the Absorption of Gases by Solids
and Liquids. By P. Chappuis (Ann. Phys. Chem. [2], 19, 21 — 38).
— A few years ago Favre made a series of observations on the heat
evolved in the absorption of gases by charcoal, a phenomenon observed
by Saussaure and other physicists. Favre found that the heat of
absorption is greater than the latent heat of vaporisation, and in the
case of carbonic acid, it exceeds the sum of heat of vaporisation and
solidification. Pouillet observed that on moistening pulverulent or
porous compounds with a liquid, a considerable amount of heat is
liberated, which he considered to be a physical phenomenon, and not
GENERAL AND PHYSICAL CHEMISTRY. 703
due to the formation of a chemical compound ('yi(^e Abstracts). In
order to extend this line of research, the author considers that more
accurate determinations are required — (i) for the heat of absorption of
various gases by solids ; (ii) the heat of evaporation of the gases
used ; (iii) heat developed in moistening porous substances. In the
present communication, the author restricts himself to the first of
these problems.
The apparatus used consists of a Bunsen's ice calorimeter, a mano-
meter, and a mercury exhausting pump. The absorbing substance is
first heated, weighed in a vacuum, and introduced into the tube of
the calorimeter, which is connected up with the manometer. The
whole apparatus is then exhausted, and then there is gradually intro-
duced a quantity of gas whose volume, pressure, and temperature are
accurately known. The mercury level of the calorimeter is observed
from time to time, and the heat evolved calculated from these obser-
vations.
With this apparatus the author has examined the behaviour of the
following gases : — Carbonic anhydride, air,, sulphurous anhydride,
ammonia, and methyl chloride, using for the absorbing material wood-
charcoal, meerschaum, platinum black, and asbestos.
From the experiments, the details of which are given in the paper,
the author shows that a greater quantity of heat is evolved for the
first than for the last portion of the gas absorbed, and that the
increase of pressure corresponding to the absorption of equal quan-
tities of gas increases at first slowly, then more rapidly ; also that the
heat of absorption is separable into two portions, one corresponding
with the heat of vaporisation of the gas in question, and the other to
the heat evolved by the further compression of the liquefied gas. The
latter can be observed separately from the former by liquefying the
gas before it comes into contact with the absorbing material ; but as
the apparatus used did not permit of the condensation of the gas
within the calorimeter, the author conducted some experiments on the
heat evolved by moistening solids with liquids of low vapour-tension.
The cases examined were charcoal with water and carbon bisulphide,
and powdered clay with water. The following results were obtained :
— On moistening 1 gram of charcoal with water, 7425 cal. were
developed; with carbon bisulphide, 24,364 cal. ; and 1 gram of clay
with water, 275 cal. As in all these experiments the porous sub-
stance came in contact with a far larger quantity of liquid than that
required for its complete moistening, only a very small portion of the
liquid contributed to the thermal action. Finally, the author made a
series of determinations of the heat evolved in the absorption of sul-
phurous anhydride and ammonia by water, and of sulphurous anhy-
dride and methyl chloride by black caoutchouc which functions as a
liquid. Generally, the values obtained decrease in proportion to the
quantity of gas absorbed, by a more regular gradation than those
obtained in the absorption of gases by solids ; the heat evolved is con-
siderably less in the former than in the latter case, but is in excess
over the heat of vaporisation of the gases. If the gas be condensed
before it is brought into contact with the absorbing liquid, then by
the mixture of both liquids an amount of heat is set free equal to this
704 ABSTRACTS OF CHEMICAL PAPERS.
excess. Then the phenomenon of the solution of gases by liquids is
merely a pai'ticular case of the mixture of two liquids.
V. H. V.
Thermochemical Researches. By E. Wiedemann (Ann. Phys.
Ghini. [2], 18, 608 — 612). — It is possible to estimate the molecular
heat of solids for their solution in water and other liquids. For if a
molecule of salt of molecular weight M be dissolved in n molecules of
a solvent of molecular weight m, and c be the specific heat of the
solution, then c(M + nm) is the molecular heat of the solution. If 7
be the specific heat of the solvent, mn^/ denotes the molecular heat of
the substance in the solution in question. As the specific heat of a
solution is less than unity, then c = 1 — « where x <^ 1. If the
solvent be water (m = 18), the molecular heat of the solution is
(1 — a3)(M + 18w). Observations have frequently been made to
determine whether this value is greater or less than that of the water
18*2' contained therein, i.e., whether in the equation ( 1 — x)(M. -\- ISn)
— 18/2- + a, the value a = M — £c(M + \Sn), that is to say, the dif-
ference of both molecular heats is greater or equal to nil.
The author has examined the values of c(M -f 71I8), a, x, and
xQJL + nY'S) for solutions of sodium chloride, sulphate, and nitrate, and
of ammonium sulphate in water. In all cases examined, a decreases
with decrease of concentration ; this follows as a necessary deduction
from the equation above, for if n = 0, then a = M — «M, and the
specifi-C heat 1 — x is a positive value, and this is the case for very
small values of n, i.e., for very concentrated solutions. If x decreases as
n increases, so a, must become negative, and the value 18na; must in-
crease in proportion. This is the case for all dilute salt solutions, as
the specific heat is an asymptote to the specific heat of water, as x is
asymptotic to nil. With solutions of greater concentration, a is
positive, and with increase of dilution approximates nil, a then
becomes negative. Then the molecular heat is for solutions of greater
concentration greater than for those of lower concentration, less than
for those of mean concentration equal to that of the water contained
therein.
If a = 0 then M = x(M + 18w), or in other words, if the molecu-
lar heat of a solution be equal to that of the water contained therein,
then the difference x of the specific heat of the solution from unity,
multiplied by the molecular weight (M -f- 18n) of the solution, will be
equal to the molecular weight of the salt. Thus in experiment the
values of x(M. ■\- i'Sn) varied from 57-3 to 62-84 (M = 58'5), for
ammonium sulphate from 120 — 133'1 (M = 132), for sodium sulphate
.^(M + 18^0 = 141-7(M = 142), and for sodium nitrate from 81-57—
94-32 (M = 85). V. H. V.
Alkaline Sulphites. By Berthelot (Compt. rend., 96, 142—
146). — Besides the two classes of acid and neutral sulphites of the
formulae RHSOsand II2SO3 respectively, the salts KaSaOs and NaaSoOs
have been obtained, and have received the name of anhydrosulphites.
From the results of his thermochemical researches, and also from the
chemical behaviour of these two salts, the author considers that they
should be looked upon as metasulphites, and as standing in the same
t
GENERAL AND PHYSICAL CHEMISTRY. 705
relation to the normal sulphites as the metaphosphates do to the
normal phosphates. The following are the thermal results obtained
bj the author.
Heat of solution of sulphurous anhydride in water at 12" ; SO2
= 8-34 cal.
Heat of neutralisation of sulphurous acid by a solution of potassium
hydrate : —
SO2 in solution + KHO in solution at 13° = 16'6 cal.
SO2 „ + 2KH0 „ „ = 31-8 „
I^HSOs „ + KHO „ „ = 15-2 „
A slight additional disengagement of heat takes place with an excess
of potash.
K3SO3 in solution + 2K0H in solution at 12° = 0-33 cal.
Freshly prepared acid, and acid which had been kept several years,
gave like results, although the latter reduced silver salts as noticed by
Stas.
Neutral Sodium Sulphite. — The hydrated salt, KaSOsjHaO, which
loses its water below 120°, was obtained. The heat liberated was less
than that due to the solidification of the water of crystallisation, or
the heat of combination was a minus quantity, — I'l. The heat of
formation of potassium sulphite, K2SO3, from its elements is 272'6.
Double Decomposition. — When a solution of potassium sulphite is
treated with hydrochloric acid, partial decomposition takes place, with
the following thermal results : —
KoSOa in solution + 2HC1 in solution at 18° = —1*8 cal.
K.SOa „ + 9HC1 „ „ = -2-4 „
This shows a division of the base between the two acids, as the
equation K0SO3 + HCl = KHSO3 + KCl would require - 1-7
cal., whereas the total replacement of the sulphur radical by CI
would require — 4*0. But if only a small quantity of hydrochloric
acid (^ HCl to 1 K2SO3) be added, a slight evolution of heat (-f 0-6)
is observable, seeming to point to the immediate formation of the
raetasulphite. Sulphurous acid added to a solution of potassium
chloride, also gives thermal results, proving a division of the base
between the two acids.
Decomposition by Heat. — Raised to a dull red heat in an atmosphere
of nitrogen, potassium sulphite decomposes exactly according to the
equation 4K2SO3 = 3K2SO4 + K2S. Contrary to Muspratt's state-
ment, no evolution of sulphurous anhydride takes place. At 450° no
action has commenced. L. T. T.
PyrosTilphites.* By Berthelot (Compt. rend., 96, 208—213). —
Potassium pyrosulphite (potassium anhydrosulpldte), K2S0O5, crystal-
lises out on supersaturating a solution of potassium carbonate with
sulphurous anhydride, and may then be dried at 120°. This salt
difiers from the normal hydrogen potassium sulphite, KHSO3, in
* Called by the author " Metasulphites."
706 ABSTRACTS OF CHEMICAL PAPERS.
greater stability, heat of formation, power of forming hydrates, and
the way in which it decomposes when heated.
In the formation of hydrogen potassium sulphite, SO2 in solution +
KHO in sol. at 13° liberate 16'6 cal., and the immediate addition of
another mol. KHO to form K2SO3 liberates a further 15'2 cal. If,
however, the solution of the bisulphite be boiled or allowed to stand
for a long time, a further addition of 1 mol. KHO only gives 12*5
cal. That this is due to the conversion of the bisulphite into the
pyrosulphite is shown by the fact that a solution of the crystallised
metasulphite converted into the neutral sulphite also liberates 12'5
cal. In the conversion of the bisulphite into the pyrosulphite there-
fore 2 '6 cal. are liberated, which tallies with the greater stability of
the latter over the former. With potassium anhydrosulphate (pyro-
sulphate) K2S2O7, and hydrogen potassium sulphate, the reverse is the
case, an absorption of heat taking place during the conversion of the
latter into the former, and the hydrogen potassium sulphate being the
more stable salt of the two. The heat of formation of the pyrosul-
phite from sulphurous anhydride and potash is therefore 19"2 cal.
These results have been verified by thermometric observations of the
action of hydrochloric acid on (i) solutions of potassium pyrosul-
phite, (ii) the anhydrous salt, (iii) solutions of hydrogen potassium
sulphite, (iv) neutral potassium sulphite.
Hydrates of Potassium Pyrosulphite. — On saturating, in the cold, a
concentrated solution of potassium carbonate with sulphurous acid,
crystals are formed either spontaneously or on the addition of alcohol.
These have hitherto been considered to be normal hydrogen potassium
sulphite, KHSO3. The author, however, finds on analysis, that the
crystals formed spontaneously correspond with the formula
K2S205,iH20,
those produced by the addition of alcohol to that of K2S205,JH20.
The author considers them to be without doubt pyrosulphites and not
acid bisulphites. At 120° they give off no sulphurous anhydride as
would be the case with bisulphites, but merely lose water and become
anhydrous. The heat of solution of the hydrated and anhydrous salts
is also identical (5*6), pointing to mechanical and not chemical union.
From the above data it may be calculated that the heat of formation
of potassium pyrosulphite is as follows : —
82 + Os + K2 = 379-4 cal.
2SO2 (gas) + K2O (anhydrous) = 66-9 „
SO2 (gas) + K2SO3 (solid) = 13-8 „
Decomposition hy Heat. — The decomposition takes place at a dull red
heat, exactly according to the equation 2K2S2O6 = 2K2SO4 + SO2 + S,
no formation of neutral potassium sulphite taking place even as an
intermediate stage.
The following is a list of some of the potassium salts containing
sulphur, with their heats of formation from their elements : —
Bisulphide, K2S2 + lOG'O cal.
Thiosulphate, K2S2O3 4-267-4 „
GENERAL AND PHYSICAL CHEMISTRY. 707
Pyrosulpliite, K2S2O5 + 3692 cal.
Dithionate or Hyposulpliate, KaSaOe + 411-4 „
Bisalphate (pyrosulphate), K2S2O7 . . 4- 473'2 „
Sulphide, K2S +102-2 „
Sulphite, K2SO3 + 272-6 „
Sulphate, K2SO4 + 342-2 „
Or conformably to the observations of Dumas, with the oxides of
tin: —
O3 + K2S2 = K2S2O3 liberates 3 x 53 6 cal.
O2 + K2S2O3 = K2S2O5 „ 2 X 51-0 „
02 + K2S2O5 = K2S2O7 „ 2 X 52-0 „
O + K2S2O6 ^ K2S2O6 „ 42-6 „
03 + K2S = K2SO3 „ 3 X 56-8 „
L. T. T.
Alkaline Thiosulphates. By Beethelot (Compt. rend., 96, 146
— 147). — It has been proved that the potassium thiosulphate found
amongst the products of explosion of powder is not produced during
the combustion, but during the analytical manipulation by the action
of cupric oxide on the poly sulphides which it is used to eliminate.
The author now finds that zinc oxide has the same effect on potassium
polysulphides, producing, besides zinc sulphide, thiosulphate, sulphate
and dithionate. The author believes that although it has hitherto
escaped notice the latter body is also produced when cupric oxide is
used. Zinc acetate also produces traces of dithionate under similar
circumstances.
The author has determined carefully the point at which dried potas-
sium and sodium thiosulphates are decomposed when heated in
nitrogen. The sodium salt begins to decompose at 400^, the potas-
sium salt at 430°, and in both cases decomposition is complete at 470°.
The heat of solution of these salts is as follows : —
Cal.
K2S2O3, dried in a vacuum (1 pt. in 90 pts. H2O at 10°). . -498
Na2S203 „ at 200° (1 „ 50 „ „ 13-5°) +1-72
„ „ 150° (1 „ 50 „ „ 7-5°) +1-24
„ „ 358° (1 „ 50 „ „ 7-5°) +1-48
L. T. T.
Nitrogen Selenide. By Berthelot and Vieille (Compt. rend.,
96,213 — 214). — The heat disengaged by the explosion of this sub-
stance was determined, and gave lor NSe + 42-6 cal., or corrected
to constant pressure 42 3. Nitrogen selenide is therefore formed
with the absorption of heat (— 42-3) similarly to nitrogen sul-
phide, &c. L. T. T.
Chromates. By Berthelot (Compt. rend., 96, 399 — 405).— From
a careful collation of the thermometric determinations of the solution
and neutralisation of chromates, and of their reactions with acids,
together with careful thermometric determinations made by himself,
where these were previously wanting, the author is enabled to draw
the following conclusions. In solutions of neutral potassium chromate
strong acids cause the total, weak acids the partial displacement of one
708 ABSTRACTS OF CHEMICAL PAPERS.
of the two potassium-atoms, potassium dichromate being at the same
time formed. This displacement is due not so much to the smaller
heat of formation of the chromates compared with other acids capable
of displacing chromic acid, as to the fact that the heat of formation
of the dichromate is much greater than that of the neutral chromate,
and that hence there is always a great tendency to the formation of
the dichromate. This tendency renders the one potassium-atom in
the neutral chromate easily replaceable, and enables much feebler
acids to displace a part of the alkali than would otherwise be the case.
The author has already shown that a similar cause produces a ten-
dency towards the formation of bisulphates, and enables hydrochloric
and nitric acids to cause partial displacement in the solutions of
neutral sulphates. L. T. T.
Heat of Formation of GlycoUates. By D. Tommasi {Comi>t.
rend., 96, 789 — 790). — The heats of formation of glycollates recently
determined by Forcrand (this vol., 644) agree perfectly with the num-
bers calculated by means of the author's law (Abstr., 1882, 1257 ;
this vol., 144). Only in the case of zinc glycollate is there any con-
siderable difference between the observed and calculated values, and a
redetermination of the heat of formation of this salt will probably
show that the first determination is inexact. The author has calcu-
lated the heats of formation of several glycollates which have not yet
been made the subject of direct determinations. C. H. B.
Heats of Formation of Glycollates. By de Foecrand (Compt.
rend., 96, 838 — 839). — A reply to Tommasi (see preceding Abstract).
Mutual Displacement of Bases of Neutral Salts in Homo-
geneous Systems. By N. Menschutkin (Compt. rend., 96, 256 —
259, and 381 — 383). — The author has taken advantage of the fact
that aniline, although a base, does not react alkaline, to investigate the
above subject with respect to aniline hydrochloride, nitrate, and acetate
on the one hand, and potassium, sodium, and barium hydroxides,
ammonia and triethylamine on the other. A weighed quantity of the
aniline salt was dissolved in water, and, after the addition of phenol-
phthalein or rosolic acid as an indicator, titrated with a decinormal
solution of the alkali. It is clear that alkaline reaction sets in at
the moment when the alkali added can no longer displace aniline
from its salt, but remains unneutralised. Each experiment was tried
with a saturated solution and also a decinormal solution of the aniline
salt, and the liquid in all cases remained homogeneous, no precipitation
of aniline taking place. In each case the author found that no alkaline
reaction became visible until sufficient alkali had been added to neu-
tralise the whole of the acid contained in the aniline salt. As these
results are in antagonism to Berthollet's theory of the partition of the
acid amongst the bases, the experiments were repeated with the varia-
tion that a large excess of free aniline was used. The proportions
taken were 4 and 8 mols. respectively of aniline to 1 of acid : but
even then as much alkali was neutralised as w^as theoretically equiva-
lent to the acid present. To be quite sure that the water in which
GENERAL AND PHYSICAL CHEMISTRY. 709
the aniline salts were dissolved had no influence on the results, the
author also experimented with alcoholic solutions, but in all cases
with the same effect. The whole of the aniline is therefore displaced
by the stronger bases mentioned above. This does not accord with
Berthollet's theory, but is in harmony with Berthelot's principle of
maximum work, as the heat of combination of these bases with
hydrochloric acid are : —
KHO.
NaHO.
|Ba(H0)2.
NK3.
N(CH3)3.
C6H5.NH2.
13-7
13-7
13-8
12-3
87
7-4
In the second communication, the author gives the results of his
experiments with ammonia. In a solution containing free ammonia,
phenolphthalem produces a purplish-violet coloration ; but this colour
is at once discharged by the addition to the liquid of about three
times its volume of 95 per cent, alcohol : the colour is, however, re-
produced by a single drop of a solution of a fixed alkali or barium
hydroxide. Making use of this reaction, and using ammonium bro-
mide, niti'ate, and acetate, the author finds that in alcoholic solution
or in solutions where the proportion of alcohol preponderates over that
of water, ammonia is entirely replaced by potassium or sodium hy-
droxide, but that in aqueous solution the replacement is only partial.
Using barium ethoxide, prepared by acting on barium oxide with
absolute alcohol, the following results were obtained : — With an alco-
holic solution of ammonium bromide, the displacement is complete.
With a solution of ammonium nitrate in absolute alcohol, the first
drop of barium ethoxide produces a coloration {i.e., no displacement
takes place), but in a few seconds barium nitrate is precipitated, and
the solution becomes again colourless, and this action is repeated until
all the ammonia has been replaced by barium. With a solution of the
nitrate in 95 per cent, alcohol, no displacement takes place : in a solu-
tion in 80 per cent, alcohol, total displacement results, whilst with
alcohol of QQ> per cent, strength, only 96*8 per cent, of the ammo-
nium is replaced by barium. This case is of special interest as
showing the great influence of physical conditions on mutual dis-
placement.
Sodium hydroxide in alcoholic solution displaces methylamine and
ethylamine from their salts, but not completely ; 94"4 per cent, of the
former and 904 per cent, of the latter being replaced. L. T. T.
A Correction. By M. Traube {Ber., 16, 463).— The author di-
vides oxidisable bodies into two classes, viz., those which are oxidised
by ordinary oxygen, e.g., lead, zinc ; and those which can only be
oxidised by nascent oxygen, e.g., ammonia, alcohol, carbon monoxide.
The former are termed " autoxydabel,'' and the latter " dgsoxijdabel,'^
but as this word is apt to be mistaken for desoxydabel, the author
proposes to substitute the term " hradoxydabel " for the second class
of bodies. W. C. W.
f
710 ABSTRACTS OF CHEMICAL PAPERS.
Inorganic Chemistry.
Density of Chlorine at High Temperatures. By J. M. Crafts
(Ber., 16, 457 — 461). — To determine the density of chlorine at high
temperatures (circa 1300°), the author uses porcelain cylinders which
are enamelled in and outside. Through the neck of the cylinder,
which is only 6 mm. diameter, a capillary tube of enamelled porcelain
passes which reaches nearly to the bottom of the cylinder. By
measuring the volume of chlorine displaced by a known volume of
air, the author finds that the density of chlorine is normal at tempera-
tures below 1200°. W. C. W.
Phosphorescence of Sulphur. By 0. Jacobsen (Ber., 16, 478).
— The peculiar odour which is perceived when sulphur phosphoresces,
indicates the probable existence of a lower oxide of sulphur than
SO2. Attempts to isolate such a compound were unsuccessful.
w. c. w.
Action of Sulphur on Oxides. By E. Filhol and Senderens
(Compt. rend., 96, 889 — 841). — It is well known that when sulphur is
gently heated with sodium or potassium hydroxide an alkaline sul-
phide and thiosulphate are formed. If the substances are in the solid
condition, this change is accompanied by a considerable development
of heat, but if they are in solution the thermal disturbance is practi-
cally nil. If solid sodium or potassium hydroxide is rubbed up with
an excess of sulphur in a mortar, a mixture of polysulphide and thio-
sulphate is obtained in a few seconds, and the same result follows if
the two substances are gronnd up separately and then mixed. On the
other hand, the action of the sulphur on the alkaline oxides is greatly
diminished by diluting the solutions of the latter. A solution con-
taining 4 grams of soda per litre has no action on sulphur in the cold,
even after several months, but attacks it readily at 100^. A solution
of 0*4 gram per litre bas no action on sulphur, even when boiled.
C. H. B.
New Modes of Formation of Pyrosulphuric Chloride and
of Chlorosulphonic Acid. By G. Billitz and K. Heumann (Bei\y
16, 483 — 485). — Pyrosulphuric chloride is formed by heating a
mixture of chlorosulphonic acid and phosphorus pentoxide in a flask
provided with a reflux condenser for some time, and then distilling
the crude product. The portion boiling between 135 — 150° is poured
into water in order to decompose the unaltered chlorosulphonic acid.
Pyrosulphuric chloride absorbs moisture from the air, and is con-
verted into chlorosulphonic acid. This fact explains the discordant
results obtained by different observers in the determination of the
vapour- density of pyrosulphuric chloride. W. C. W.
Pyrosulphuric Chloride. By K. Heumann and P. Kochlin (Ber.,
16, 479—483). — Ogier's statement (Compt. rend., 94, 217) that the
vapour- density of pyrosulphuric chloride is half the value required by
INORGANIC CHEMISTRY. 711
the formula S2O5CI2, is incorrect. The density, between 160° and
442°, varies with the temperature. Near the boiling point, the density-
corresponds with the theoretical value, but at 442° the observed
density is only half the theoretical. W. C. W.
Crystallised Phosphates. By Hautefeuille and Marhottet
(Compt. rend., 96, 849 — 852). — The sesquioxides of aluminium,
chromium, iron, and uranium, or, better, the amorphous phosphates
obtained by adding sodium phosphate to solutions of salts of these
metals, are fused with four times their weight of metaphosphoric
acid. They are thus rapidly converted into crystallised metaphos-
phates of the general formula MiOajSPaOs, or M"'(P03)3, which can
be isolated by treating the cooled mass with boiling water. Ferric
metaphosphate forms transparent pale greenish-yellow rhombic prisms,
terminated by pyramids. Chromic metaphosphate forms rhombic
prisms, which are generally macled, and have a yellowish-green
colour by transmitted light. Urajiic metaphosphate forms emerald-
green rectangular tables, derived from rhombic prisms. Aluminium
metaphosphate forms colourless transparent crystals, the dominant
form of which is a combination of the cube with the octohedron or
triakisoctohedron, the faces being frequently curved. All these
metaphosphates are insoluble in water and in acids.
The crystals of the aluminium compound have a cubical appear-
ance, and are without action on polarised light ; the other three com-
pounds crystallise in the rhombic system. It is possible, however, to
prepare aluminium metaphosphate containing different proportions of
the chromium, iron, and uranium compounds; all the four metals, in
fact, being able to replace one another in any proportions. The
dominant form of these double phosphates is a prism modified by the
hemihedral faces of a tetrahedron. If the proportion of aluminium
is very large, the dominant form of the crystals is a tetrahedron, but
they act on polarised light. If the proportion of aluminium is small,
the hemihedral faces disappear, and the crystals exhibit the macles so
frequently observed on substances which crystallise in rhombic prisms
of nearly 90°. It is evident, therefore, that the presence of small
quantities of uranium, iron, and chromium modifies the optical pro-
perties of aluminium phosphate, although the crystals of the latter
retain their cubical appearance. These metaphosphates in fact
exhibit a case of isomorphism similar to that observed between pure
natural aluminium leucite and artificial leucite containing iron.
Crystallised metaphosphates of nickel, cobalt, the alkalis, and other
metals have been obtained in a similar manner. The alkaline meta-
phosphates, like the others, are insoluble in water. C. H. B.
Barium Potassium Phosphate and Barium Sodium Phos-
phate. By A. DE ScHULTEN (Compt. rend., 96, 706 — 707). — A
mixture of potassium silicate and baryta- water is heated to boiling
and mixed with a solution of potassium silicate containing a certain
quantity of potassium phosphate. On cooling, the liquid deposits
cubical crystals, which dissolve easily in dilute hydrochloric acid,
leaving a residue of silica amounting to about 1 per cent. If the
712 ABSTRACTS OP CHEMICAL PAPERS.
silica be regarded as an impurity, the crystals have the composition
KBaPOi + IOH2O.
The corresponding sodinra compound, NaBaP04 + IOH2O, is ob-
tained in a precisely similar manner, and crystallises in regular
tetrahedrons. The formation of these crystallised phosphates is due
to the slow action of the alkaline phosphates on the double silicates
formed by adding baryta- water to solutions of the alkaline silicates.
If alkaline hydroxides are used instead of alkaline silicates, only
amorphous precipitates are obtained. C. H. B.
Action of Different Varieties of Silica on Lime-water. By
E. Landrin (Compt. rend., 96, 841 — 844). — Hydraulic silica, gelati-
nous silica, and soluble silica absorb lime gradually from lime-water,
the maximum absorption varying in all cases between 36 and 38 parts
of lime for one equivalent of silica. The resulting compound has
approximately the composition 3Si02,4CaO. The combination is most
rapid in the case of soluble silica, but even in this case the maximum
absorption is not effected until after several hours. Silica from hydro-
fluosilicic acid absorbs lime much more slowly than any of the three
previously mentioned varieties. The maximum absorption after 68
days, in the series of experiments quoted, was 24*2 parts of lime per
equivalent of silica. C. H. B.
The Setting of Plaster of Paris. By H. Lb Chatelier (Compt.
rend., 96, 715 — 718). — Marignac has observed that anhydrous cal-
cium sulphate yields with water a supersaturated solution, which
afterwards deposits crystals of the hydrated salt. With plaster of
Paris heated at 140° a solution can be obtained containing 9 grams of
the salt per litre, or four times the amount which exists in solution
under normal conditions. The author considers that the setting of
plaster of Paris is due to two distinct but simultaneous reactions.
The anhydrous calcium sulphate when moistened with water dissolves
and becomes hydrated, forming a supersaturated solution, and this
supersaturated solution deposits crystals of hydrated calcium sulphate,
which gradually increase in volume and unite one with another. This
progressive crystallisation continues so long as any anhydrous salt
remains undissolved. This theory is supported by the fact that in
practice 140° is found to be the best temperature at which to heat the
plaster of Paris, and Marignac found that the most highly super-
saturated solutions are formed by calcium sulphate heated to this
temperature. It is found that the addition of a small quantity of
sulphuric acid or sodium chloride to the water used for moistening
the plaster promotes setting. Both these compounds increase the
amount of calcium sulphate which can exist in the supersaturated
solution.
Similar phenomena of setting, due to deposition of crystals from
a supersaturated solution, are observed on moistening coarsely
powdered anhydrous very soluble salts, such as sodium sulphate and
carbonate, which readily form supersaturated solutions.
This theory is applicable to the setting of all mortars, especially
cements and hydraulic mortars. The solubility of lime is well
INORGANIC CHEMISTRY. 713
known. Tlie anthor has recently shown that calcium aluminate is
soluble, and he hopes to prove that calcium silicate is also soluble.
C. H. B.
Preparation of Cerium Oxidfe.. By H. Debrat (Compt. rend.,
96. 828 — 830). — The cerium, lanthanum, and didymium oxalates are
prepared from cerite in the usualway, and converted into nitrates.
The nitrates are then fused in a porcelain capsule with eight or ten
times their weight of potassium nitrate, and kept in fusion between
300 — 350° ; at this temperature cerium nitrate is decomposed, whilst
the nitrates of didymium and lanthanum are not sensibly affected
even at 350°. After some hours the evolution of nitrogen oxides
ceases, the fused mass is allowed to cool, extracted with water, and
the residue washed! with very dilute nitric acid in order to remove
any traces of basic didymium nitrate ; this residue, which consists of
cerium oxide with traces of didymium and lanthanum, is reconverted
into nitrate, which is again fused with potassium nitrate; the last
traces of didymium and lanthanum are thus removed, and the cerium
oxide is obtained perfectly pure. The aqueous solution of didymium
and lanthanum nitrates with excess of potassium nitrate is evaporated
to dryness and again fused, the temperature being allowed to rise
somewhat above 350°. The small quantity of cerium nitrate pre-
viously undecomposed is now decomposed, and on treating the fused
mass with water after cooling, a solution of didymium and lanthanum
nitrates is obtained free from cerium. C. H. B.
Ammoniobromides and Oxybromides of Zinc. By G.
Andr^ (Compt. rend., 96, 703 — 706). — A 30 per cent, solution of
ammonium bromide is boiled for some time with precipitated zinc
oxide, the liquid filtered, and allowed to cool. The compound
3ZnBr2,6NH3,H20 is deposited in slender white needles, which melt
when heated in a closed tube, and give off water and ammonia gas.
They are decomposed by boiling water, a residue of zinc oxide being
left. When these crystals are heated with water in sealed tubes at
200°, they are decomposed, with formation of brilliant white scales, of
the composition ZnBr2,3ZnO,2NH3,5H20. The ammoniacal chlorides
yield similar compounds. By dissolving zinc bromide in hot am-
monia, and allowing the liquid to cool, Rammelsberg obtained a
compound which he described as anhydrous ; the author finds, how-
ever, that the compound obtained in this way has the composition
ZnBr,22NH3,H20. If the zinc bromide is dissolved in cold ammonia,
and the solution allowed to evaporate, the compound
3ZnBr2,8NH3,2H20
is formed. If ammonia gas is passed into a concentrated solution
of zinc bromide until the precipitate is redissolved, and the solution
is then evaporated, slender needles of the composition
3ZnBr2,10NH3,H2O
are obtained. They are easily decomposed by water, especially if
heated. By treating zinc bromide in the manner described by
Divers for the preparation of 2ZnCl2,10NH3,2H2O, voluminous bril-
VUL. XLIV. 3 6
714 ABSTRACTS OF CHEMICAL PAPERS.
liant crystals are obtained, but 'tbey lose their brilliancy unless kept
in an atmosphere of ammonia. They have the composition
ZnBr2,5NH3.
When heated in a closed tube, they melt and give off ammonia, but
no trace of -wa/ter, and if exposed to the air they give off ammonia
and become covered with a white pellicle. They are easily decom-
posed by water.
When a concentrated solution of zinc bromide is heated with zinc
oxide, filtered, and allowed to cool, nacreous lamellaa of the com-
position ZnBr2,4ZnO,13H20, are deposrt,ed. When a solution of zinc
bromide is precipitated with an insufficient quantity of ammonia,
the compound ZnBr2,4ZnO,19H20 is obtained. By heating 30 grams
of zinc oxide with 100 grams of zinc bromide, and adding a concen-
trated solution of ammonium bromide until the zinc oxide is com-
pletely dissolved, a white powder is obtained which has the compo-
sition ZnBr2,4ZnO,10H2O, and which, when washed with water until
all soluble bromide is removed, yields the compound
ZnBro,6ZnO,35H20.
These two last compounds retain a small quantity of ammonia. If
zinc oxide is heated with a concentrated solution of zinc bromide in
sealed tubes at about 200°, small brilliant crystals of the composition
ZnBr2,5ZnO,6H20 are obtained. C. H. B.
Aluminium Sulphate. By P. Marguerite-Delacharlonny (Compt.
rend., 96, 844 — r846). — Pure hydrated aluminium sulphate crystal-
lises in rhombic prisms, which are not hj'groecopic, but, on the con-
trary, show a marked tendency to effloresce. Analyses of these
crystals, prepared by different methods from different sources, prove
that they have the composition Al3(S04)fl + I6H2O. The formula
Al2(S04)3 -I- I8H2O, generally given to the hydrated salt, has been
deduced from analyses of impure specimens containing ferric sul-
phate. The presence of a small quantity of ferric sulphate in
aluminium sulphate makes the latter hygroscopic. The natural
aluminium sulphate found at Hio Saldana has the composition
MCSOOa + I6H2O.. C. H. B.
Ultramarine. By G. Guckelberger (Dingl. polyt. X, 247, 343 —
848, and 383 — 389). — This paper gives an account of recent investi-
gations on ultramarine. In order to obtain the pure colouring matter,
the manufactured product as it is taken from the furnace is allowed
to soak in cold or lukewarm water (not hot) without being previously
ground. Before it is washed thoroughly, it is treated with caustic lye
until it ceases to produce a black coloration when treated with an
alkaline solution of lead. It is then washed with water containing
ammonium acetate.
From his analyses, the author comes to the conclusion that ultra-
marine-blue is a definite compound of the formula Si6Al4Na6S402o,
agreeing with that of Silber and Hoffmann. The following are the
analytical results : —
INORaANIO CHEMISTRY. 71 5
L
IL
III.
IV.
V.
VI.
Si
. . 19-2
19*0
19-0
19-3
19-3
19-0
Al . . . .
. . 12-6
12-7
130
12-5
12-8
13-0
Ka
. . 16-5
16-8
16-5
16-8
161
15-9
S
. . 14-2
140
13-8
13-9
14-0
14-0
0 ....
. . 37-5
37-5
377
37-5
37-8
381
I — III are samples of nltramarine-blue rich in silicon from tlie
Hirsckberg works, Y and VI from the works at- Marienberg.
The author's results with respect to ultramarine-green agree for the
most part with those of other investigators. He concludes that ultra-
marine-green is a definite compound of the formula Si6AlpN'a8S2024.
He then tries to prove that the different ultramarines may be best
derived from a typical formula with Siis and Naao- Thus, for ultra-
marine containing large quantities of silicon, the formula
blisAha^ a2obi2062
is given, whilst for ultramarines poor in silicon the formula
SiisAlisNaooSeOvo — O73 is assumed, so that the sulphur may vary in
accordance with the proportion of Si : Al. Between Sii8Ali2Si2 and
SiisAligSe there are the intermediate stages Sii8Ali4Sio and SiisAlieSs.
In the original paper the author discusses in detail the hypotheses
of other investigators. D. B.
Separation of Gallium, By L. de Boisbaudran (Compt. rend.,
96, 152—154; see also Abstr., 1882, 897 and 1323, and this vol., 153,
156, 293). — From Rhodium. — i. In very acid hydrochloric solution,
gallium is precipitated by potassium ferrocyanide, whilst the whole of
the rhodium remains in solution, ii. Hydrogen sulphide acts very
slowly on dilute solutions of rhodium chloride in the cold, quickly at
100°. The sulphide precipitated from the slightly acid boiling solu-
tion must be dissolved in aqua regia, the nitric acid expelled, and
reprecipitated by hydrogen sulphide, a-s it contains traces of gallium.
If great exactness is required, the mother-liquors from the first pre-
cipitation must be concentrated and re-treated with hydrogen sul-
phide. The precipitated rhodium sulphide often contains traces of
metallic rhodium, insoluble in aqua regia. iii. Copper precipitates
metallic rhodium from its salts. The solution should be as concen-
trated as possible, slightly acidulated with hydrochloric acid, and
digested at about 90° for several hours, the hydrochloric acid and
water lost by evaporation being renewed from time to time. The
reduced rhodium contains no gallium or at most the merest trace,
iv. Zinc slowly precipitates metallic rhodium, from acid solutions.
The rhodium contains a little gallium.
Some Reactions of the Salts of Rhodium. — The usual text-books give
many incorrect or incomplete data of these salts. Hydrogen ammo-
nium sulphide in excess redissolves the rhodium sulphide first pro-
duced, forming an orange-red liquid : rhodium sulphide is only
reprecipitated from this solution on very long standing. Rhodium
sulphide precipitated from a boiling solution by hydrogen sulphide is
insoluble in hydrogen ammonium sulphide, but the sulphide precipi-
3 c 2
716 ABSTRACTS OF OHEMTCAL PAPERS.
tated on boiling an ammoniacal solution, dissolves readily in that
reagent. The solubility of rhodium sulphide in hydrogen ammonium
sulphide may be nsed to separate that metal from copper, iron, zinc,
&c. If rhodium sulphide be precipitated from ammoniacal solution
by a very slight excess of hydrochloric acid, it is of a light reddish-
brown, partially soluble in concentrated hydrochloric acid ; but in the
presence of hydrogen sulphide and in acid solutions, it rapidly becomes
mucb darker in colour and insoluble in hydrochloric acid. There are
thus two modifications of rhodium sulphide, the one of a chocolate-
brown colour, easily soluble in hydrogen ammonium sulphide, partially
soluble in hydrochloric acid ; the other dark-brown, and insoluble in
those reagents. L. T. T.
Crystallised Stannates. By A. Ditte (Compt rend., 96, 701 —
703). — Calcium Stannate. — When the gelatinous precipitate obtained
by adding potassium stannate to a solution of calcium chloride is
heated to 100°, it is converted into small, colourless, transparent,
apparently cubical crystals of the composition Sn02,CaO,5H20. When
a mixture of stannic oxide, calcium chloride, and a small quantity of
calcium oxide is heated for several hours to bright redness, the mass
allowed to cool, washed with water, and then treated with very dilute
hydrochloric acid, small, transparent, square lamellae are obtained con-
sisting of modified cubes or octohedrons. These crystals have the
composition Sn02,CaO, are not attacked by acids, and undergo but
little alteration when fused with sodium carbonate. If ammonium
chloride is used instead of calcium oxide, no stannate is formed, but
colourless, transparent, slender needles of stannic oxide are obtained.
Strontium Stannate. — The gelatinous precipitate obtained by
addition of potassium stannate to a solution of a strontium salt,
gradually changes at the ordinary temperature into small, transparent,
acute rhombohedrons of the composition 2SnO2,3S2O,10H2O. Similar
crystals are obtained by adding a small quantity of a dilute solution
of potassium stannate to a large excess of a cold saturated solution
of strontium oxide, and allowing the precipitate to stand, or heating
the liquid to boiling.
Barium stannate is prepared in a similar manner from saturated
solutions of barium oxide or chloride. It forms small, brilliant,
nacreous plates of the composition SnO2,2BaO,10H2O.
Nickel stannate is obtained by adding potassium stannate to a con-
centrated ammoniacal solution of a nickel salt until a slight permanent
precipitate is produced. The liquid on standing deposits small, trans-
parent, green, apparently cubical crystals, of the composition
Sn02,NiO,5H20.
Cobalt stannate is obtained in a similar manner. It forms small,
transparent, rose-coloured crystals of the composition Sn02,CoO,6H20.
Zinc stannate is also obtained in the same way. It forms colourless
transparent crystals of the composition 2SnO2,3ZnO,10H2O.
Silver stannate is prepared by adding potassium stannate to a solu-
tion of silver nitrate, dissolving the precipitate which is formed in
ammonia, and allowing the ammoniacal solution to evaporate over
INORGANIC CHEMISTRY. 717
sulphuric acid, when small crystals of the composition SnOajAgjO
separate out. They melt at bright redness to a deep brown liquid,
and are decomposed by potassium hydrogen sulphate.
Copper stannate is prepared by adding potassium stannate to an
ammoniacal solution of copper salt so long as the precipitate re-dis-
solves, and allowing the liquid to evaporate over sulphuric acid; it
forms blue crystals of the composition Sn02,CuO,4H20. If these
crystals are left in the ammoniacal mother-liquor at the ordinary
temperature, they gradually change into deep blue, more bulky crys-
tals of Sn02.CuO,(NH4)20,2H20. These crystals are but slightly
soluble in cold water, which, however, gradually removes their ammo-
nia ; they dissolve in acids forming a solution which gelatinises when
heated.
All these hydrated stanuates are insoluble in water, but dissolve in
the cold in hydrochloric or nitric acid, forming limpid solutions which
gelatinise on heating. When heated, the crystals change colour, lose
their water, and become insoluble in acids in the cold. The anhy-
drous salts are attacked by nitric acid, which dissolves out the base
and leaves an insoluble residue of stannic oxide. C. H. B.
Double Chlorides of Lead and Ammonium and Oxy chlorides
of Lead. Bj Gi. Aj^dr^ {Compt. rend., 96, 435—437). — A saturated
solution of ammonium chloride dissolves lead chloride, and from such
solutions the author has obtained several double salts. If 90 grams
of lead chloride be dissolved in a boiling solution of ammonium chlo-
ride (200 grams of salt to 200 of water), brilliant mother-of-pearl-like
flakes are deposited having the formula 4PbCl2,22NH4Cl,7H20 ; from
the same solution a salt, 4PbCl2,18NH4Cl,5H20, was obtained. 50
grams of litharge, dissolved in a boiling solution of 200 grams ammo-
nium chloride in 400 of water, gave hard crystals of
PbCl2,18NH4Cl,4H20,
and on continued boiling PbCl2,10NH4Cl,B[2O. A solution of ammo-
nium chloride saturated in the cold, heated to boiling and treated
with lead chloride, gave crystals of 2PbCl3,18NH4Cl,3H20. If a
solution of litharge in ammonium chloride be poured into a large
excess of cold water, a white precipitate is produced, which, dried at
100°, has the formula PbCl2,PbO. L. T. T.
Chromic Selenite. By C. Taquet (Compt. rmd., 96, 707—708).
— On adding potassium selenite to a boiling solution of chromic
chloride containing free hydrochloric acid, a bulky pale-green pre-
cipitate is thrown down, which, after drying at about 120°, forms a
greenish-grey mass of the composition Cr2(Se03)3. It dissolves in
hot concentrated hydrochloric acid, and is almost insoluble in water,
but dissolves slightly when boiled with an excess of selenious acid,
probably with formation of an acid selenite. The filtrate from the
first precipitate deposits a further quantity of the same compound on
standing. C. H. B.
718 ABSTRACTS OF CHEMICAL PAPERS.
Double Sulphites of Manganese and the Alkalis. By A.
GoRGEU (Com'pL rend., 96, 376 — 379). — If 3 or 4 grams of manganese
sulphite are dissolved in 100 c.c. of a saturated solution of sulphurous
acid containing 15 to 20 grams of potassium sulphite, and the whole
placed for some time under a bell-jar together with an absorbent for
sulphurous anhydride, hexagonal plates of a double sulphite of the
formula KaSOa^MnSOa are formed. The mother-liquor, concentrated
on a brine-bath, either deposits a further crop of the same salt in
hexagonal prisms grouped into stars, or a second salt is formed of
the formula K2S03,2MnS03, and crystallising in tetragonal needles.
Both salts have a slight roseate tint and oxidise rapidly in moist
air. KaSOsjMnSOa is very stable towards water, in which it is very
slightly soluble. Heated to redness out of contact with the air, both
salts give off sulphurous anhydride, and leave a mixture of sulphates
and sulphides together with manganous oxide ; in contact with air,
the residue consists of sulphates and red mans^anic oxide. The salt,
(NH4)2S03,MnS03, crystallising in regular hexagonal plates of mother-
of-pearl-like appearance, is obtained in an analogous manner to the
potassium salt. It is much less easily oxidised, and withstands a
temperature of 180°, although ammonium sulphite decomposes at 60°.
It is very slightly soluble in cold water. Heated out of contact with
the air, it leaves manganous oxide mixed with a little sulphide ; in
the air, manganic oxide. Sodium manganese sulphite, Na2S03,MnS03
+ H2O', is obtained by mixing a 20 per cent, solution of manganous
chloride with a solution of sodium sulphite saturated in the cold, and
to which a little hydrogen sodium sulphite has been added. The
reaction does not take place in the cold, but does so easily if the solu-
tions are heated to about 80°. With a weaker solution of the alkaline
sulphite, a salt, I>ra2S03,4MnS03, was formed ; it is only very slightly
soluble in cold water. The action of water on the salt, !N'a2S03,MnS03
+ H2O, is peculiar ;^ although boiling water scarcely alters the crystals,
cold water at once decomposes them, crystals of MnSOs + 3H2O being
formed. This, which is identical with the action of water on MnSOa
4- H2O, already described by the author, leads him to consider the
double salt as a compound of anhydrous sodium sulphite with mono-
hydrated manganous sulphate, or Na2SO(MnS03,H20). This com-
pound, like MnS03,H20, only loses its water of crystallisation above
150°. L. T. T.
MINER ALOGICAL CHEMISTRY. 719
Mineralogical Chemistry.
Aluminmm Borate from Siberia. By A. Damour (Compt. rend.^
96, 675 — 677).^ — This mineral was found in the pegmatite of the
Soktoui mountains, near Adoun-Tchilon, in. Eastern Siberia. It occurs
in regular, transparent, almost colourless prisms, with a hardness
between that of quartz and that of felspar ; sp. gr. = 3*28. The crystals
appear to haye no cleavage, and break with a vitreous fracture. In the
blowpipe flame, the mineral becomes white and opaqne, and gives the
green coloration characteristic of boric acid. It dissolves completely
in microcosmic salt or in borax, forming a colourless bead, and it
turns blue when moistened with cobalt nitrate solution and strongly
heated. The mineral is not attacked by nitric or hydrochloric acid,
but after being strongly heated, it dissolves slowly in strong sulphuric
acid at 300", solution being facilitated by the addition of a small
quantity of hydrofluoric acid. When heated to bright redness, it loses
33 per cent, of its weight, but still contains boric acid. The mineral
has the composition B,O3,40'19 ; AI0O3, 65-03 ; Fe2O3,4-08; K2O, 0'70
= 100*00. The oxygen ratio of AI2O3 : B2O3 is 1:1, and the formula
of the mineral is therefore Al203,B203.. The name Jeremerewite is pro-
posed for the new mineral in honour of its discoverer, M. Jeremeiew.
C. H: B.
Melilite and Melilite Basalts. By A. Stelzner (Jahrb. /.
Min^ 2, Beil. Bd., 369 — 439). — In a previous communication, the
author states that a certain constituent of some basalts is not nephe-
line, as previously supposed, but melilite, or at least something very
nearly related to it. In the present paper the details are more fully
recorded..
The imbedded melilite crystals are short quadratic prisms, four- or
eight-sided, with rounded prism faces, but well-formed basal planes.
The crystals show not unfrequently cleavage parallel to the basal
plane ; they are seldom quite fe'ee from inclosures ; colourless or very
pale yellow, some of the darker crystalline granules are slightly
dichroic". Oblique sections show, in patches, a very fine striation
parallel to the basal plane.
By means of a mercuric iodide solution, the melilite was isolated
from a sample of undecomposed basalt. Sp. gr. = 2*29 ; an analysis
gave : —
SiOg. AI2O3. FeiOa. FeO. CaO. MgO. Na^O. KjO. H2O.
4^4i'1Q 7-90 516 1-39 27*47 8-60 2*65 033 1*42 = 99-68
These numbers show that the crystalline mineral of sp. gr. 2 "99,
which is a principal constituent of the basalt from Hochbohl, near
Owen, and which was formerly considered as nephiline, is in reality
melilite. Following are remarks on the accompanying minerals,, and
descriptions of the localities (Swabian Alps, N.E. spurs of the
Bohemian Forest), and modes of occurrence of the melilite basalts.
Melilite occurs also in nephiline and leucite basalts, as in those of
720 ABSTRACTS OF CHEMICAL PAPERS.
Hegan, the Kaisers tuhl, the Fiehtelgebirge, Erzgebirge, the Eifel,
Vesuvius, &c. The author concludes: — The described rocks differ
from the known members of the basalt family, since in them melilite
plays the part usually taken by plagioclase, nephiline, leucite, or a
glassy matrix, and in accordance with Zirkel's nomenclature of the
basalts, should be called melilite basalts. The petrographic character
of the melilite basalts may be described thus : olivine, melilite, and,
lastly, augite, are the predominating constituents ; the olivine and
part of the augite are macroscopically, and part of the melilite
microscopically developed, while most of the augite and melilite forms
the microscopically crystalline ground-mass ; in the latter are also
nephiline, mica, magnetite, perowskite, chromite, and occasionally
apatite and hauyn. Chemically regarded, they are extraordinarily
basic, and are characterised by the action of hydrochloric acid, which
decomposes 92 — 95 per cent, of the rock with separation of gelatinous
siliqa. The name nephelinepicrite is no longer needed, since it is
founded on a false determination of melilite. Melilite basalts occur
mostly as veins or masses in other rocks ; but much more frequent
are nepheline and leucite basalts containing melilite. H. B.
The Volcanic Rocks of the Cape Verde Islands. By C.
DoLTER (Jahrh.f. Min., 1883, 1, Mem., 396— 405).— This paper gives
the results of the author's geological investigations at the islands of
S. Antao, S. Vicente, S. Tbiago, and Mayo. After a topographical
and geological description of the islands, follows a petrographical
description of the various rocks. The older eruptive rocks occurring
are : fozaite, diabase, and diorite. A complete analysis of fozaite from
S. Vicente is given under I. The rock consisted of orthoclase, with
some plagioclase and elaeolite, together with pyroxene, hornblende,
and magnetite, and occasionally analcime. Titanite and hauyn were
absent. An analysis of the felspar is given under II, and of the
pyroxene under III : —
I.
II.
III.
IV. V.
VI.
VII.
VIIT.
SiOa . .
. 5576
67-82
41-08
39-64 50-41
49-66
56-36
47-99
AI2O3
. 21-61
16-99
9-11
16-98 29-00
21-19
2701
13-30
Fe.03
1-65
1-03
17-18
6-61 ~
4-91
017
11-32
FeO ..
4-09
—
15-99
9-31 —
5-37
—
10-39
CaO..
. 2-26
0-19
6-09
10-58 13-41
6-78
8-57
5-14
MgO..
. . 074
—
2-29
6-65 —
2-59
—
6-16
K,0 . .
5-34
7-89
—
v^ ^-^^
ro-81
\ 7-02
0-67
—
:Na^O .
. 6-94
4-11
8-70
8-11
6-60
H2O ..
. 3-49
1-75
—
1-32 0-61
1-32
—
—
Total .
. 101-88
99-78 100-44 100-13 lOO'OO
99-65 100-89 100-90
The diabase described is a dark rock, rich in augite, from S. Vicente.
The complete analysis of the rock is given above (IV). The analysis
of the felspar, with sp. gr. = 27, which forms 60 per cent, of the
rock, is also given (V). The rock described by the author as diorite
consists of QQ — 68 per cent, of plagioclase (analysis VII) and 11 — 13
per cent, of pyroxene (analysis VIII), with 7 — 8 per cent, of biotite
MINERALOGIGAL CHEMISTRY. 721
and 15 per cent, magnetite. Titanite and apatite are accessor j con-
stituents. The complete analysis gave the figures under (VI).
Among the younger eruptive rocks, leucitite, phonolite, tephrite,
basanite, basalt, nephelinite, nepheline basalt, limburgite, and pyro-
xenite, were distinguished.
The leucite consists principally of leucite together with hauyn. A
complete analysis of the rock gave the following results (IX) : — •
SiOs. AlAs. FesOg. FeO. CaO. MgO. KaO.
IX. 48-46 21-81 2-17 3-75 4-58 0-68 5-86
NaoO. ^Oa. CI. Loss. Total.
8-41 2-97 '0-13 2-08 100-90
Phonolite occurs very frequently. The results of an analysis of the
porphyritic variety from S. Thiago are given under X. The analysis
of the portion soluble in HCl (XI), of the interspersed augite (XII),
of the augite of the ground-mass (XIII), and of the felspar (XIV),
are also given. XV is an analysis of hornblende phonolite from
Mayo. The hornblende isolated from it had the composition given
under XVI:—
X.
XI.
XII.
XIII.
XIY.
XV.
XVI.
SiO^. . . .
53-80
47-56
43-99
38-15
62-42
50-05
39-96
AU03. . .
23-59
25-1.7
1401
25-96
18-99
20-98
16-91
Fe^Oa. . .
3-57
2-11
2-09
11-08
trace
2-12
3-42
FeO. . . .
1-88
—
8-84
6-17
—
4-05
8-86
CaO ...
2-26
2-96
19-42
4-53
1-52
4-12
15-94
MgO . . .
0-87
0-84
10-88
1-99
trace
1-65
6-03
K,0....
4-77
4-07
—
—
8-16
6-19
—
Na,0 ..
9-05
12-41
1-09
7-91
8-66
8-43
9-01
SO3 . . . .
CI
H0.O....
tmce
trace
0-30
4-97
—
—
—
1-50
4-88
—
—
—
4-35
-—
Total .. 101-29 100-00 100-62 100-76 99-75 101*94 lOO'lS
The tephrites have a grey colour and a crystalline structure.
Besides the augite, a separate analysis of which is given (XVII),
mica, and less frequently hornblende, occur. Hauyn is frequently
present as an accessory constituent ; titanite very rarely. An analysis
of the rock from S. Antao is given under XVIII : —
SiOo.
AI.2O3. FesOj.
FeO.
CaO. MgO. K2O. NaaO.
H2O. Total.
XVII.
47-44
23-71 6-83
3-53
6-47 1-95 3-34 6-40
1-73 101-40
XVIII.
37-20
16-93 15-42
3-55
14-81 6-89 — 5-06
— 99-51
The basanites. The author distinguishes two groups : — basanite
rich in plagioclase, and basanite rich in nepheline. A representative
of the latter group from S. Thiago, gave the following analytical
results (XIX) : —
SiOa. AI2O3. FegOg. CaO. MgO. KoO. Nap. HjO. Total.
XIX. 4309 17-45 18-99 9*76 463 1-81 5-02 0-33 101-08
722 ABSTRACTS OF CHEMICAL PAPERS.
Basalt. — The analysis of a compact basalt from S. Thiago, gave the
results under XX. The augite (XXI), and the plagioclase (XXII),
were also separately analysed : —
SiOa.
Al,03.
FeaOg.
FeO.
CaO.
MgO.
K,0.
Na^O.
H2O.
Total.
XX.
42-65
15-35
6-46
8-19
11-96
7-14
1-47
5-02
1-28
99-52
XXI.
4215
21-51
3-79
9-43
12-28
7-55
—
298
99-69
XXII.
48-88
28-92
1-52
—
11-29
1-01
0-61
6-79
—
99-02
Nephelinite. — Two varieties of this rock were analysed, a yellowish-
grey nephelinite rich in hauyn (XXI II), and another with pJagioclase
as an accessory constituent (XXIV), both from; the island of S.
Antao : —
SiOs. AI2O3. FeaOg. CaO. Mgp. KjO. Ifa«0.
XXIII. 41-09 18-35 14-89 8-79" 1-78 314 8 79
XXIY. 46-95 21-59 8-09 7-97 2-49 2-04 8-93
SO3. CI. H2O. Total.
XXIII. 2-11 0-45 1-26 100-65
XXIV. — — 2-09 100-15
Nepheline Basalt. — Analyses were made of this rock from S. Antao
(XXV), and of the olivine (XXVI), and the augite (XXVII), isolated
from it : —
SiOs.
A1203.
FesOg.
FeO.
CaO.
MgO.
K2O.
XXV.
40-13
16-17
5-71
8-89
10-99
7-05
1-22
XXVI.
29-37
—
—
20-79
—
26-56
—
s^XVII.
40-81
14-24
7-89
5-95
16-01
14-35
—
NasO.
SO2.
CO2.
H2P*
Total.
XXV.
4-10
—
5-97
0-97
101-20
XXVI.
—
20'52
—
2-68
99-92
XXVII.
0-61
—
—
—
99-86
Limhurgite. — A variety containing plagioclase was analysed
(XXVIII), and separate analyses were made- of the augite (XXIX),
and olivine (XXX) :
Si02.
A1203.
FeaPg.
FeO.
CaO.
MgO.
XXVIII.
41-12
10-17
2 60
9-82
14-90
13-34
XXIX.
46-94
5-67
618
5-43
17-83
14-18
XXX.
39-33
1-24
—
15-63
—
43-88
K2O.
Na^O.
TX)88.
Total.
XXVIII.
2-27
6-61
0-67
101-50
XXIX.
—
1-83
—
98-06
XXX.
—
—
—
100-08
Pijroxenite is the name the author gives to younger eruptive rocks
which consist mainly of augite and magnetite in a glassy basis, but as
this term is applied quite differently by Dana and Sterry Hunt, it
MINERALOGICAL CHEMISTRY. 723
would be desirable to adopt some other name, such as "augitite."
Analyses of this rock from S. Vicente (XXXI), and of the portion
(32 per cent.) soluble in hydrochloric acid (XXXII) are given : —
SiO?.
AlgOg. leaOg.
CaO.
MgO.
K,0.
NaaO.
H2O. Total.
XXXI. 40^)5
24'19 9-51
10-99
511
1-89
5-69
1-62 99-95
XXXII. 42-91
24-06 11-26
12-10
2-01
1-92
4-89
0-85 100-00
The volcanic fragmenfal rochs are not described at any length, the
only analysis given being that of phonolite-pumice f rom S, Antao, the
results obtained being : —
SiOs.
AI2O3.
FePg.
CaO.
K20'.
Na^O.
H2O..
MgO.SOa. Total.
51-61
24-72
1-10
0-49
7-89'
8-35
5-62^
trace 99*78
B. H. B.
The Silurian Rocks of Christiana. By W. C. Brogger (Jahrh.
f. Min., 1883, 1, Mem., 388— 396).— Two principal groups of the
eruptive rocks, in the Silurian district, near Christiana, may be dis-
tinguished . — 1. Hornblende granites, syenites, granitites, and mica
syenites ; 2. Augite syenites and elaeolite syenites. The felspar of
the augite syenite is mostly monoclinic, but in the augite syenite from
Fredericks varn and other localities, and in the elaeolite syenite the
felspar is found optically to be triclinic. The following are the
analytical results obtained : — I being an analysis of the monoclinic
felspar of the augite syenite from Byskoven ; II, the analysis of the
anorthic felspar : —
SiO^.
AI2O3.
Fe^Og.
GaO.
MgO.
K2O.
m,o.
Total.
Sp. gr.
I. 62-42
22-68
0-58
3-23
0-22
4-42
.6-48
100-03
2-623
II. 61-3&
22-37
trace
4-66
0-04
4-97
6-59
99-98
2-63
The eruptive rocks occurring as masses and veins, may be arranged
according to age, as follows: — 1. Quartz-porphyry; 2. Augite por-
phyry ; 3. Augite syenite ; 4. Elaeolite syenite ; 5. Hornblende
granites, granitites, syenites, <fec. ; 6. Felspar porphyry. This order
is not absolute- for the veins, as exceptions seem to occur. As the
oldest eruptive rock, the quartz porphyry, is spread over the faulted
Silurian strata, all the above-mentioned eruptive rocks are not only
younger than the silurian strata, but also younger than the act of their
faulting. B. H. B.
The Eruptive Rocks near Tryberg in the Black Forest. By
G. H. Williams (Jahrb. /. Min,, 1883, 2, Beil. Bd., 585—634).—-
The district petrographically examined forms a circle with a radius of
about 6 miles round Tryberg. Rather more than half of this consists
of gneiss, while the remaining (northerly) portion is composed of
granitite. Both are traversed by numerous veins of a quartz-por-
phyry ; whilst the basic eruptive rocks belong exclusively to the gneiss
district.
No special attention was paid to the gneiss, as it has already been
described by Yogelgesang.
The granitite might be termed the " Tryberg " granitite, as it
724 ABSTRACTS OF CHEMICAL PAPERS.
attains here its most typical development. It is a crystalline mixture
of felspar, quartz, and biotite. The analysis gave the following re-
sults : —
Si02.
60-19
AI2O3. FeoOa.
1412 1-64
FeO. CaO.
1-71 1-58
Sp. gi-.
MgO. K2O.
1-66 8-45
= 2-39.
NaoO.
1-81
0-15
Total.
100-31
The eruptive rocks, traversing the gneiss and granitite, may be
divided into two groups : A. The acid rocks, including (1) the vein
granite, (2) the quartz-porphyry, and B. The basic rocks including
(3) mica-syenite porphyry, (4) mica diorite, (5) nepheline basalt.
1. The vem granite occurs in all varieties of colour and grain, but
the mineralogical composition remains almost constant, being a
mixture of biotite and muscovite micas with felspar and quartz.
2. Q'uartz-poiyhyry. — Whilst the vein granite traverses the granitito
in all directions, the quartz-porphyry occurs in parallel fissures cours-
ing N.N.E. — S.S.W. It has always a compact red ground-mass in which
crystals of quartz and felspar are embedded : the red colour due to
iron is highly characteristic. The results obtained on analysis
were : —
SiOg.
AI2O3. FeaOg. FeO. CaO. MgO. K^O.
Na^O. H2O. P2O5.
Total.
77-08
12-95 0-96 0-37 0-30 0-21 4-37
Sp. gr. = 2-597.
3-18 0-71 trace
100-73
This analysis is thoroughly typical for acid quartz-porphyry, and
agrees very well with that made by Rosenbusch of similar rocks in
the Vosges. The small amount of magnesia and iron oxide proves
that mica and bi-silicates are almost entirely absent, so the rock is
apparently an almost pure mixture of quartz and felspar.
3. Mica Syenite Porphyry. — These basic rocks occur in the gneiss
in the form of veins, but are never met with in the granitite. They
are of a brownish-red to bright grey colour. Under the microscope
the porphyritic structure is very distinctly seen ; the rocks presenting
a reddish ground-mass containing numerous crystals of biotite and
felspar. Zircon and apatite are common, but titanite, so common,
according to Rosenbusch, in the mica-syenite-porphyry of the Yosges,
is not to be found in any of the analogous rocks in the Black Forest.
No conclusion can be arrived at with regard to the nature of the fel-
spar of the ground-mass, as unfortunately the author did not make a
complete analysis, and neither the sp. gr. (2*667) nor the percentage
of SiOz (64-68 per cent.) is sufficient evidence. There can be little
doubt, however, that it is a soda-potash-felspar, of which the system
is not determined, and hence it is also uncertain whether the rock
belongs to the syenites cr diorites.
4. Mica Diorite. — The compact ground-mass of this rock has a
violet-grey colour, and contains hexagonal plates of mica and crystals
of felspar. By means of the microscope, quartz is found in consider-
able quantities ; apatite, zircon, and iron pyrites occur as accessory
constituents. The magnesia mica is especially interesting, as it con-
MINER ALOGICAL CHEMISTRY. 725
tains tlie small needles whicli have attracted the attention of so many
observers. Sandberger has recently proved that similar needles in
the mica of Bodenmais and Ontario (Abstr., 1883, 34) are composed
of pure Ti02. The author examined these needles microscopically,
and arrived at the conclusion that they consist of rutile ; he confirmed
this view by a qualitative analysis, applying Schonn's method {Zeita.
Anal. Chem,., 9, 41), which gave most satisfactory results. A complete
^analysis of the rock gave : —
SiOs.
AI2O3.
FesOg.
FeO. GaO. MgO. Na^O. K2O.
H2O.
Total.
64-94
17-50
0-69
3-94 2-59 2-83 3-44 3-11
1-36
100-40
5. NepJielirie Basalt. — This forms a small vein in the granitite.
The rock consists of a compact grey mass containing crystals of
olivine. Under the microscope, the compact ground-mass appears as
an irregular mass of augite and olivine crystals with magnetite and a
colourless cementing material, consisting principally of nepheline.
Hauyn is entirely absent..
The Porphyry Tuff. — This is quarried at the Kesselberg and used as
road metal. The colour is a reddish to yellowish-grey. The sp. gr.
is 2-619. The analysis gave —
SiOs. AI2O3.
Fe^Og and FeO.
CaO and MgO.
KgO. NagO.
F2O. Total.
82-56 11-57
0-86
trace
0-10 0-10
4-37 99-26
B. H. B.
Manganese in Sea-water and in Certain Marine Deposits.
By DiEULAFAiT (Compt. rend., 96, 718 — 721). — Specimens of sea-
water were collected in each degree between Marseilles and New York,
and were allowed to remain in the bottles for a month, at the end of
which time manganese could easily be detected in the deposit which
had formed. Similar results were obtained with sea- water from the
Indian Ocean, the Red Sea, and the eastern part of the Mediterranean.
The manganese exists in the sea-water in the form of carbonate. At
the surface, where the water is in contact with the air, the manganese
carbonate is precipitated and oxidised. In shallow seas the man-
ganese oxide becomes mixed with the suspended matter in the water ;
but in the deep sea, where there is no other suspended matter, the
manganese oxide sinks slowly to the bottom, and it is at the greater
depths that deposits, concretions, &c., rich in manganese, are found.
The "Challenger" soundings showed that the bottom of the deeper
parts of the Atlantic is covered with a mud closely resembling the
chalk of the Paris basin, and hence it has been concluded that this
chalk is a deep-sea formation. But the calcium carbonate is really
precipitated in the superficial layer of the sea which is in contact with
the atmosphere, and sinks to the bottom under the action of gravity,
the only condition necessary for the formation of chalk with all its
special characteristics being that the calcium carbonate shall be depo-
sited in a part of the sea which remains free from other suspended
matter for a very long interval of time. Now these conditions are
also the most favourable for the accumulation of manganese oxide,
and it might therefore be expected that deep-sea chalk would contain
726 ABSTKACTS OF CHEMICAL PAPERS.
a notable quantity of manganese. The author was able to detect
manganese easily in 0'5 gram of 50 different s-pecimens of chalk from
different parts of the Paris basin, and finds that this chalk contains more
than 50 times as much manganese as the coloured marbles of the
Pyrenees and of Italy. If the fact thus proved for the Paris basin is
equally true for the chalk of all countries, it will no longer be necessary
to ascribe the origin of the manganese oxide at the bottom of the sea
to submarine volcanic exhalations, or to submarine springs. It must
be regarded as separated from the sea-water itself by ordinary chemical
changes. C, H. B.
Organic Chemistry.
Aldehydethyl Chloride and Behaviour of Acetals with Alco-
hols at a High Temperature. By A. Bachmann (Annalen, 218,
38 — 56). — By the action of phosphorus pentachloride on diethylacetal,
a substance is obtained identical in boiling point with the aldehydethyl
chloride obtained by Wurtz and Frapolli on saturating a mixture of
alcohol and aldehyde with hydrochloric acid. The reaction is repre-
sented as follows : C2H4(OEt)2 + PCI5 = CaHiCl.OEt + EtCl + POCI3.
In order to identify the aldehydethyl chloride, the author studied the
action of sodium methylate on it, and obtained methylethylacetal and
dimethylacetal, the latter being produced by the replacement of the
ethyl-group of the former by methyl, thus : C2H4(OMe).OEt + MeOH
= C2H4(OMe)2 + EtOH. It was found that the a,ldehydethyl chloride
obtained by Wurtz 's process underwent the same reaction. Simi-
larly, by the action of phosphorus pentachloride on methylethyl-
acetal, aldehydethyl chloride is formed, according to the equation
CHMe(OEt).OMe + PCI5 = CHMeCl.OEt + MeCl + POCI3, which
was also converted by sodium methylate into methylethylacetal.
Aldehydethyl chloride is decomposed slowly on keeping, but more
rapidly on warming with evolution of ethyl chloride; the author was
unable to obtain any other definite product of the decomposition.
Rose, in the course of his work on the ethereal salts of carbonic
acid, demonstrated that a less complex alcoholic group is replaced by a
more complex group when the ethereal salts are heated with the
alcohols at the temperature of the water- bath.
In the present paper, the author, starting from the above-mentioned
result obtained in the decomposition of aldehydethyl chloride by
sodium methylate, has studied the action of various alcohols on various
acetals, and proves that in this case the more complex is replaced by
the less complex group. Thus methylethylacetal, when heated with
methyl alcohol, yield a considerable quantity of dimethylacetal, whilst
dimethylacetal with ethyl, propyl, isobutyl, and isoamyl alcohols,
yield but traces of the mixed acetal containing t-wo different alcoholic
ORGANIC CHEMISTRY. 727
gronps. Similarly diethylacetal with methyl alcohol is converted for
the greater part into dimethylaeetal, but is practically unaltered by
propyl and amyl alcohols. The following table contains the various
acetals identified by the author : —
Substances. Boiling point. Sp. gr.
Dimethylaeetal, C2H,(OMe)2 65° 0-8655
Methylethylacetal, C2H,(OMe)(OEt) 85 0-8433
Diethylacetal, C2H4(OEt)2 104 0-8210
Methylpropylacetal, C^H^fOMe) (OPr*^) . . 103—105 —
Ethylpropyiacetal, C2H40Et(OPr'^) 124—126 —
Methylbutylacetal, C2H40Me(OC4H9) . . . 125—127 —
DiT3Topylacetal, GoH4(OPr'^)2 142 —
Methylamvlacetal, C2H4(OMe)(OC5H„). 141—144 —
Diamylacetal, C2H4(OC8Hn)2 194—196 0-8012
The author further studied the action of various alcohols on ethyl
oxide and various ethereal salts of acetic and butyric acids, but was
unable to effect the replacement of one alcoholic group by another.
V. H. V.
Vapour- tensions of Ethylamine and Diethylamine Hydro-
sulphides. By IsAMBERT (Compt. rend., 96, 708— 710).— Diethylamine
hydrosulphide was prepared by the direct union of the acid and base
in barometer tubes. The white crystalline hydrosulphide is at once
formed even in presence of excess of diethylamine. The maximum
vapour-tension of this compound is 150 mm. at 10^, and increases with
the temperature in the ordinary manner. Under the same conditions,
diethylamine has a Tapour-tensioii of 120 mm, only. In presence of
excess of diethylamine, the solid hydrosulphide has a vapour-tension
of 120 mm. only, and this equality persists at all temperatures between
6° and 22°, whatever the relative proportions of the solid hydro-
sulphide and the liquid diethylamine. It is evident, therefore, that
the vapour-tension of diethylamine hydrosulphide in presence of
excess of diethylamine obeys the same laws as the vapour-tension of
ammonium cyanide in presence of excess of hydrocyanic acid.
With ethylamine hydrosulphide different results are obtained. The
first bubbles of hydrogen sulphide are absorbed by the ethylamine
without formation of any crystalline hydrosulphide and without any
alteration in the vapour-tension of the ethylamine ; but as the quan-
tity of hydrogen sulphide increases, the liquid becomes viscous, the
vapour-tension diminishes, and eventually, in presence of excess of
hydrogen sulphide, all the ethylamine is converted into a white solid
crystalline hydrosulphide, which can be volatilised in the tube and
condenses in crystals resembling those of ammonium dihydrosulphide,
but having a vapour-tension of only 48 mm. at 13°. An excess of
hydrogen sulphide, in presence of the crystalline hydrosulphide, obeys
the law which the author has proved to hold good in the cases of
ammonium dihydrosulphide and phosphine hydrobromide (Abstr.,
1881, 674).
It is evident that although the vapour-tension of a mixture of a solid
compound with one of its liquid constituents is equal to the vapour-
728 ABSTRACTS OF CHEMICAL PAPERS.
tension of the liquid constituent alone in the case of a solid only
slightly soluble in the liquid, yet where the solid compound is very
soluble in the liquid constituent, the vapour- tension of the mixture
may be much lower than that of the liquid, and in fact resembles the
vapours given off by liquids dissolved in one another in considerable
proportions. C. H. B.
The Hydroxylamine Reaction. By E. Mgelt (Ber., 16, 494—
500). — The following compounds were prepared by adding solutions
of hydroxylamine hydrochloride and soda to an alcoholic solution of
the substance under investigation. If the mixture is turbid, sufficient
alcohol is added to render the liquid clear. After an interval of eight
days, the alcohol is removed by evaporation, the residue is diluted
w^ith water, and extracted with ether. The compound which remains
on distilling off the ether, is purified by distillation or by recrystalli-
sation : —
Mesityloxime, CeHio ' N.OH, is an oily liquid, boiling with partial
decomposition between 180° and 190°. It is insoluble in water, but dis-
solves in alkalis, mineral acids, alcohol, ether, carbon bisulphide,
benzene, and light petroleum. On boiling with dilute acids, it splits
up, liberating hydroxylamine.
Phoronoxime, CgHu '. N.OH, crystallises in plates, which melt at 48°
and boil at 218°. It is soluble in alcohol, ether, benzene, light petro-
leum, carbon bisulphide, and in acids and alkalis.
Allylacetoxime, CeHio '. N.OH, is a mobile liquid (b. p. 187*5°) of
unpleasant penetrating odour. It unites with bromine to form a
dibromide, CeHuBraNO.
Suheroxime, C7H12 ! N.OH, is a pale yellow liquid, which boils
without decomposition. It has an odour like peppermint.
CampJioroxime, CioHie '. N.OH, crystallises in white needles, which
melt at 115° and boil at 249 — 254"^. It resembles camphor in many of
its physical properties. It is not decomposed by strong hydrochloric
acid at 110°.
Hydroxylamine has no action on menthol, borneol, benzyl alcohol,
or benzvl ether.
A crystalline compound, HO.N! CH.CCl ! NOH (m. p. 151°), is
obtained by the action of hydroxylamine on chloral hydrate. It is
soluble in water and in alcohol. W. C. W.
Synthesis of Oxaline Bases. By B. Radziszewski (Ber., 16,
487 — 494). — Glyoxalethyline (paroxalmethyline), C4H6N2, is best pre-
pared by slowly adding an aqueous solution of aldehyde ammonia to a
solution of glyoxal. The mixture must be well cooled. After some
hours the liquid is evaporated on a water-bath and the residue dis-
tilled, the portion boiling above 160° is fractionated. The liquid
which comes over between 260° and 270° solidifies on cooling, and is
obtained in a pure state by recrystallisation from benzene. The
aqueous solution of glyoxalethyline and of the bases derived from it,
resemble the alkaloids in their reactions with tannic, picric, and phos-
phomolybdic acids.
Oxalmethylethyline, CiHsMeNj, prepared by acting on an ethereal
ORGANIC CHEMISTRY. 729
solution of glyoxalethyliiie with metliyl iodide and distilling the
product with potash, is a liquid boiling at 205° ; sp. gr. at 11° =
I'OOSl. It is soluble in water, alcohol, and ether. With copper sul-
phate, it gives a blue precipitate soluble in excess, and it also forms
precipitates with mercuric chloride, silver nitrate, tannic, picric and
phosphomolybdic acids, which are soluble in boiling water. With
zinc chloride and hydrochloric acid, oxalmethyle thy line forms trans-
parent prisms (melting at 137°). It also yields a crystalline platino-
chloride, and forms a crystalline compound with methyl iodide,
C4H5MeN2,MeI.
Oxalethylethyline, C4H5Et!N'2, obtained by dissolving glyoxalethyline
in ethyl bromide and decomposing the solution with potash, is identical
with Wallach's oxalethyline boiling at 212°.
Oxalpropylethyline, C4H5PrN'2, is a colourless liquid (b. p. 224° ; sp.
gr. 0*9641). It forms a crystalline platinochloride and a deliquescent
crystalline compound with propyl bromide.
Glyoxalpropyline, CsHsNa, prepared from propylaldehyde and glyoxal,
crystallises in prisms soluble in alcohol, water, ether, and cold ban-
zene. It melts at 79°, and boils at 268°, and resembles the preceding
bases in its chemical properties.
Oxalmethylpropyline has not yet been obtained. When the product
of the action of methyl iodide on glyoxalpropyline is treated with
soda, the crystalline compound, 05H7MeN"2,MeI, is produced.
Oxalethylpropyline, CsHrEtNa, is a colourless liquid of sp. gr. 0*9813
and boiling at 220°. It is soluble in water, alcohol, and ether, and
yields crystalline double salts with platinum and zinc chlorides.
^-Oxalpropylpropyline, CgHvPrNg, is identical with Wallach's oxal-
propyline. W. C. W.
Preparation of Ethers of Trichloracetic Acid. By A. Cler-
mont (Gompt. rend., 96, 437). — To a mixture of molecular equivalents
of the acid and the respective alcohol, a mol. of sulphuric acid is
added. The mixture becomes heated and coloured. On cooling and
adding water, the ether separates. Propyl tar.ichloracetateho\\& at 187° ;
amyltricliloracetate2i>i2V?°. L. T. T.
Action of Carbonic Oxide on a Mixture of Sodium Acetate
and Sodium Isopentylate. By W. Poetsch (Annalen, 218, 56 —
84). — By the action of carbonic oxide on a mixture of sodium acetate
and isopentylate on hexylmethylketone, the author obtained the sodium
salts of formic, isoamylacetic, and oxyethenylamylacetic acids.
Hexylmethylketone, formed by the action of sodium acetate on
sodium isoamylacetate thus, (CTHuNaOa + C3H3Na02 = COsHasO +
Na2C03), is a transparent, oily liquid, having an ethereal odour (b. p.
208—210°; sp. gr. = 0*8430). Traces of another ketone, probably
dihexylketone, were obtained, possibly formed from two molecules of
isoamylacetic acid, 2C7Hi3]S'a02 = CuH260 + Na2C03.
Iso'pentylacetic acid, obtained by the decomposition of the sodium salt
by sulphuric acid, is a colourless transparent liquid (b. p. 212 — 213° ;
sp. gr. = 0*926), which, as derived from fermentation amyl alcohol is
probably dimethylpropylacetic acid, CHMe2.[CH2]3.COOH. It is
VOL. XLIY. • 3 d
730 ABSTRACTS OF CHEMICAL PAPERS.
probably identical with Grimsliaw's iso-cenatithylic acid. Its methyl
salt is a colourless liquid of pleasant fruity odour (b. p. 166°;
sp. gr. = 884), the ethyl salt a light mobile liquid (b. p. 182°; sp. gr.
= 872) ; the sodium salt crystallises with 1 mol. HjO ; the calcium
salt forms silky glistening crystals with 2 mols. H2O.
Oxyethenylamylacetic acid, C7H13ZCO2, derived from isoamylacetic
acid by the replacement of a hydrogen-atom by the grouping oxy-
ethenyl, CH2*C0H, was obtained as a viscid mass, having a strong
acid reaction; its methyl salt boils about 250°, its sodium salt crystal-
lises in leaflets containing 2 molecules water, its calcium salt is an
insoluble precipitate. Y. H. V.
A Non-saturated Acid Isomeric with Itaconic Acid. By R.
FiTTiG-and F. Roedeti (Ber., 16, 372 — 373). — By the action of sodium
ethylraalonate on ethylene bromide, an ethereal salt is produced, which
on saponification yields a crystalline acid of the composition
CH2:C2H2(COOH)2.
The acid unites with hydrobromie acid to form bromethylmalonic
acid melting at 116''. It melts at 139°, and at a higher temperature
splits up into carbonic anhydride, a volatile acid, and a neutral com-
pound (probably isocrotonic acid, and butyrolactone).
w. c. w.
Tetric Acid. By W. Pawlow (J5cr., 16, 486— 487).— Pure dry
ethyl monobromomethacetoacetate is converted into a crystalline mass
when it is heated at 100° for six hours in a sealed tube. Ethyl bro-
mide and carbonic acid are formed, and t?he crystalline product con-
sists entirely of tetric acid: 15 grams of ethyl methacetate yielded
7-8 grams of tetric acid (m. p. 189° ; b. p. 262°). W. C. W.
Action of Water on Lactones. By R. Fittjg (Per., 16, 373 —
374). — The true lactones, as well as the delta lactones, yield an oxy-
acid when boiled with water. But as these oxy-acids themselves pass
into the lactones on boiling with water, a state of equilibrium is soon
established, and the formation of acid ceases, unless the free acid is
neutralised, and in this way protected from decomposition. The
quantity of acid which is formed from the lactones is very small. It
is larger for lactones of simple structure containing a small number
of carbon-atoms, than it is for the lactones of more complicated con-
stitution, w. a w.
Conversion of Unsaturated Acids into the Isomeric Lactones.
By R. FiTTiG (Ber., 16, 373). — Unsaturated acids are converted into
lactones by boiling for a short time with strong sulphuric acid diluted
with an equal volume of water. On prolonged boiling, a further
change takes place, acids of the same composition, but of a higher
molecular weight, being formed, e.g., pbenylbutyrolactone is con-
verted into a crystalline dibasic acid, C2oH2b04. W. C. W.
Conversion of Nitrils into Imides. Action of Hydrocyanic
Acid and of Ethylene Cyanide on Hydrochloric Acid and
ORGANIC CHEMISTRY. 731
Alcohol. By A. Pinner (Ber., 16, S^2—S6S).— Ethyl formimide,
NH ! CH.OEt, is prepared by passing dry hydrochloric acid gas into
a mixture of absolute hydrocyanic acid diluted with four times its
volume of ether (free from water and alcohol), and the calculated
amount of ethyl alcohol. The liquid, which should be surrounded by a
freezing mixture, is stirred continuously during the reaction. When
fumes of hydrochloric acid begin to escape, the operation is complete. As
the heat evolved during the crystallisation of the substance is sometimes
sufficient to cause its decomposition, it must be thoroughly well cooled
in a freezing mixture and continuously stirred during the solidification
of the hydrochloride. This salt forms beautiful transparent prisms.
On exposure to the air, the crystals decompose spontaneously, forming
ammonium chloride and other products. They are decomposed by
lieat, splitting up into ethyl chloride, ethyl formate, formamidine
hydrochloride, and a small quantity of ammonium chloride. Ethyl
formimide hydrochloride is decomposed by alcohols thus : with ethyl
alcohol it yields ammonium chloride and ethyl orthoformate, CH(0Et)3,
and with methyl alcohol it gives ethyl dimethyl orthoformate,
(MeO)oCH.OEt (b. p. 115— 120°). Amyl alcohol acts slowly on the
imido-ether, forming ethyl diamylorthoformate, (C5HnO)2CH.OEt
(b. p. 255°). Formamidine hydrochloride is produced by the action of
alcoholic ammonia on ethyl formimide hydrochloride, and by substi-
tuting methylamine or aniline for ammonia dimethyl formamidine,
NMeiCH.NHMe, diphenyl formamidine, I^Ph ! CH.NHPh, are ob-
tained. Bimethylformamidine hydrochloride is a deliquescent salt
crystallising in plates which dissolve freely in alcohol and water.
The action of alcohol on ethyl formimide hydrochloride explains
why the author and Klein (Ber., 10, 1870 ; ll, 4, 764, 1475, 1825)
failed in their previous experiments to isolate ethyl formimide.
When hydrochloric acid gas is passed into a well-cooled mixture of
ethylene cyanide and alcohol diluted with three times its volume of
absolute ether, crystals of ethylsuccinimide hydrochloridey
C2H4(OEt)2(NH)2,2HCl,
are deposited. This salt is sparingly soluble in alcohol and ether. It
is decomposed by water into ammonium chloride and ethyl succinate,
and by the action of alcoholic ammonia it is converted into succina-
midine hydrochloride, NH : CH2(NH2).CH2(NH2) ! NH,iiHCl. On
recrystallisation from water, this body splits up into succinimidine
NH : CH.
hydrochloride and ammonium chloride, | ^N"H,HC1 ; snccini-
NH : CW
mide hydrochloride crystallises in colourless plates soluble in water.
It is decomposed by heat. W. C. W.
Colouring Matters of the Safranine Series. By R. Nietzki
(Ber., 16, 464 — 478). — Phenosafranine, C18H16N4, obtained by Witt by
oxidising a mixture of aniline (2 mols.) and paraphenylenediamine
(i mol.) or of equal molecules of aniline and paradiamidodiphenyl-
amine, forms beautifully crystalline salts. The hydrochloride crystal-
lises in flat nei^dles of a green colour which dissolve in hot water, but
S d 2
732 ABSTRACTS OF CHEMICAL PAPERS.
are insoluble in hydrochloric acid. The nitrate, which resembles the
hydrochloride, is insoluble in dilate nitric acid. The sulphate crystal-
lises in steel-blue needles. The platinochloride, (Ci8Hi6N"4)2,H2PtCl6,
forms golden plates. Phenosafranine is coloured green by strong sul-
phuric acid, and blue by hydrochloric or, rather, dilute sulphuric
acid. On reduction with zinc-dust, it is converted into diamidodi-
phenylamine. On heating a mixture of phenosafranine hydrochloride
with sodium nitrate and acetic anhydride, diacetylsafranine hydro-
chloride, C:8Hi4N4Sc2,HCl, is deposited in brown plates possessing a
metallic lustre. This salt is insoluble in the ordinary solvents, and is
decomposed by heat without melting. It dissolves in a weak alcoholic
solution of soda, yielding a violet solution from which it is reprecipi-
tated by acids. On boiling an aqueous solution of phenosafranine
with hydrochloric acid and dilute sodium nitrite solution, the colour of
the solution changes from red to blue, and, when gold chloride is
added, a blue crystalline precipitate having the composition
Ci8Hu(N:NC1)(N3HC1) + 2AuCl3, is deposited. A green diazo-
compound appears to be formed when sodium nitrite is added to a
solution of phenosafranine in sulphuric acid which has been diluted
with water until the blue solution changes to green.
Two diethylsafranrnes, Oi8HuN4Et2, can be obtained, viz., a, by
oxidising a mixture of diethylparaphenylenediamine and aniline
(2 mols.), and 3, by oxidising a mixture of aniline, diethylaniline, and
paraphenylenediamine. The two isomerides bear a close resemblance
to each other ; they are distinguished by the greater solubility of the
hydrochloride of the (3 variety. The hydrochlorides and the platino-
chlorides, (Ci8Hi4N'4Et2)2,H2PtCl6, form green needles. The hydro-
chloride of the acetic derivative, Ci8Hi3EtjN'4Zc,HCl, crystallises in
needles of a brown colour ; these are decomposed by boiling with dilute
sulphuric acid, splitting up into diethylsafranine and acetic acid. The
solution of the diazo- derivative of diethylsafranine has a greenish-
blue colour ; the platinochloride forms black needle-shaped crystals,
Ci8HiiN5Et2,H2PtCl6.
Tetrethylsafranine, Ci8HiiPt4N4j obtained by the oxidation of a mix-
ture of equivalent proportions of diethylparaphenylamine, diethyl-
aniline, and aniline, yields a very soluble hydrochloride and a spar-
ingly soluble zinc chloride crystallising in large golden plates. The
platinochloride has the composition (Ci8Hi2Et4N4;2,H2PtCl6. Tetrethyl-
safranine colours wool and silk violet. It is not attacked either by
nitrous acid or by acetic anhydride. The green colouring matter
which Bindschedler (Ber., 12, 207) obtained by oxidising a mixture of
dimethylaniline and dimethylparaphenylenediamine at the ordinary
temperature, yields a crystalline hydriodide, Ci6Hi9N3,HI, and a platino-
chloride, CieHigNsjHaPtCle. By the action of stannous chloride on the
zinc chloride a crystalline zinc double chloride is obtained, which has
the composition Ci6H2ilN'3H2Cl3 + ZnCl2, pr6bably
HCl,NMe2,C6H4.NH.C6H4.]S-Me2HCl + ZnCla,
tetramethyldiamidodiphenylamine zincochloride. When phenosafra-
nine is heated with 4 parts of strong hydrochloric acid at 170° it splits
ap into ammonia and a substance which closely resembles aniline-
ORGANIC CHEMISTRY. 733
black. Safranine is regarded by the author as a derivative of tri-
phenylmethane, (H2N.C6H4)2N/ |
^NHCl. W. C. W.
Mononitroresorcinol. By A. FIivre (Gompt. rend., 96, 790 —
792). — The action of 1 mol. amyl nitrite on 1 mol. monosodinm-
resorcinol in the cold yields the sodium derivative of mononitroresor-
cinol, and when this is treated with sulphuric acid, mononitroresorcinol
is liberated. It crystallises from dilute alcohol in dull golden-yellow
needles of the composition C6H3(N02)(OH)2 + HjO, which become
brown at 112° and are completely carbonised without melting at 148°.
Mononitroresorcinol is very soluble in alcohol and in acetone ; less
soluble in water, chloroform, and ether ; insoluble in benzene and
carbon bisulphide. It dissolves without alteration in concentrated
hydrochloric and sulphuric acids in the cold. Nitric acid converts it
into trinitroresorcinol. In neutral solutions, it yields an intense green
coloration with ferrous salts and with iron filings. The potassium,
sodium, and silver salts of mononitroresorcinol crystallise with diffi-
calty; the salts of ammonium, calcium, and the heavy metals are
amorphous powders, the colour of which varies from orange-red to
black. When reduced by means of stannous chloride and hydrochloric
acid, mononitroresorcinol yields an amidoresorcinol, apparently iden-
tical with the paramidoresorcinol described by Weselsky ; it would
appear, therefore, that in mononitroresorcinol the N02-group occupies
the para-position. The action of nitrous anhydride on an ethereal
solution of mononitroresorcinol yields dinitroresorcinol,
C6H2(N02)2(OH)2,
which forms small yellow tables melting at about 142*5°. Bromine-
water converts mononitroresorcinol into dibromonitroresorcinol,
C6HBr2(]S'02)(OH)2 -f- 2H2O ; this crystallises in large brilliant yellow
needles which decompose at about 138° without melting. It dissolves
readily in alcohol and acetone, but is less soluble in ether, acetic acid,
and cold water. It is not attacked by alcoholic potash. When di-
bromonitroresorcinol is treated with nitric acid, hydrobromic acid is
liberated and dinitromonobromoresorcinol, C6HBr(N02)2(OH)2, is
formed. This compound, which differs from that obtained by the action
of bromine on the dinitroresorcinol previously described, crystallises
from boiling alcohol in large orange-yellow needles ; these melt at 193°
and are soluble in acetone, but almost insoluble in water, and dissolve
with difficulty in boiling alcohol. With the alkalis and with baryta, it
forms beautiful dichroic crystals which detonate violently when heated.
The acetyl- derivative forms yeHow transparent prisms which melt at
135°.
Nitroresorcinol gives colour reactions with all the phenols. With
resorciuol and sulphuric acid, it yields diazoresorujin, which is pre-
pared commercially at Basle by this method. It also yields coloured
products with the aromatic amines. The compound formed by its
action on dimethylamine is violet, and is closely analogous to the pro-
duct obtained by Meldola by the action of resorcinol on nitroso-
734 ABSTRACTS OF CHEMICAL PAPERS.
dimethylaniline. The action of nitroresorcinol on aniline acetate in
alcoholic solution yields a compound which has the composition
C18HUN2O2, and is formed in accordance with the equation 2PhNH2 +
CeHaCNOXOH)^ = CisHuNgOj + NH3 + H2O. This compound cry s-
tallises from chloroform in small brilliant steel-blue needles which
melt at about 238 — 239°. It does not dissolve in alkalis nor in dilute
acids. It dissolves without alteration in nitric acid or hydrochloric
acid forming a blue solution, and in sulphuric acid forming a green
solution. C. H. B.
An Aromatic Tribromhydrin. By A. Colson (Campt rend., 96,
713 — 715). — When boiling mesitylene is mixed with 6 atoms of bro-
mine, a black oil is produced which is distilled under reduced pressure ;
the fraction which passes over between 210° and 220° under a pres-
sure of O'Ol m. is strongly cooled for some time, the solid portion
separated by filtration, and purified by recrystallisation from boiling
alcohol. The crystals thus obtained are elongated birefractive
needles belonging to the monoclinic or triclinic system. They melt at
94'5°, are very soluble in benzene, dissolve readily in ether, and in
their own weight of boiling alcohol, but are only slightly soluble in
cold alcohol. They have the composition C6H3(CH2Br)3, and are the
tribromhydrin of an aromatic glycerol, the acid corresponding to which
is the trimesic acid described by Fittig. This compound is decom-
posed by prolonged ebullition with 30 times its weight of water
with formation of a very soluble compound, the concentrated solution
of which when distilled with excess of hydrobromic acid, yields the
original bromhydrin.
The action of bromine on mesitylene yields also a monobromo- and
dibromo-derivative, corresponding respectively with an alcohol and a
glycol. The monobromo-derivative, C6H3Me2.CH2Br, boils at 230°
under the ordinary pressure, and forms white elongated birefractive
needles, which probably belong to the rhombic system. They melt at
38' 3°, dissolve readily in ether and in benzene, and are easily saponified
by water. The dibromo-derivative, C6H4Me(CH2Br)2, has already
been described by K )binet. It forms elongated birefractive prisms,
probably belonging to the monoclinic system, and melting at 66'4i°.
When boiled with water, it yields a very soluble compound, in all
probability the corresponding glycol, which is reconverted into the
original bromide by hydrobromic acid of b. p. 125°.
The melting points of the three bromo-derivatives increase by 28*1°
for each atom of bromine introduced.
Melting point. Difference.
C6H4Me2CH2Br 38-31 28*1
C6H4Me(CH2Br)2 6&d
CJ34(CH2Br)3 94-4| 28-1
C. H. B.
Amido-phenols. By F. Kalckhoff (J5er., 16, 374— 376).— Ortho-
hydroxyphenylcarbamide, NH2.CO.NH.C6H4.OH, is prepared by
warming a mixture of orthamidophenol hydrochloride with potassium
ORGANIC CHEMISTRY. 735
cyanate. The crude product is purified by adding a few drops of
stannous chloride to the warm aqueous solution, and passing sul-
phuretted hydrogen through the liquid. On evaporating the filtrate
in a vacuum, colourless prisms of orthohydroxyphenyl carbamide are
deposited. The crystals melt at 154° with decomposition. The sub-
stance is freely soluble in water, alcohol, ether, alkalis, and a jids.
The aqueous solution rapidly decomposes.
Parahydroxyphenyl thiocarbamide is deposited from boiling abso-
lute alcohol in lustrous red plates, which melt with decomposition at
214°. It is sparingly soluble in cold water and cold alkalis, and forms
a crystalline platinochloride.. Parahydroxyphenylcarbamide could
not be prepared by the action of mercuric oxide on the thiocarbamide,
but it is easily obtained from paramidophenol hydrochloride and
potassium cyanate in needle-shaped tabular crystals melting at 165°.
It is soluble in water-, alcohol, alkalis, and acids.
Parahydroxythiocarbanilide, prepared by the action of sodium
hydroxide on an alcoholic solution of paramidophenol hydrochloride
and phenylthio carbamide, melts at 162°. It dissolves freely in strong
sulphuric acid, alkalis, and alcohol. W.. G. W.
Phenyl Salts of Phosphorous Acid. By E. Noack (Amialen,
218, 85 — 113). — The author calls attention to the two structural
formulae proposed for phosphorous acid, the one symmetrical, P(0H)3,
based on the formation of the acid by the action of water on phos-
phorus trichloride, the other unsymmetrical, O.PH(OII)2, which
derives support from the fact that under normal conditions only two
hydrogen-atoms can be replaced by a metallic element. As certain
acids, notably sulphurous, hydrocyanic, and nitrous, form isomeric
ethereal salts, it is probable that phosphorous acid would form such
salts, corresponding with the two above formulae. Phosphenyli com
pounds derivable from the unsymmetrical formulae have been studied
by Michaelis, whilst the author in the present communication describes
derivatives of the symmetrical formulae.
By the action of phenol on phosphorus trichloride in excess of that
required by the equation PCI3 + PhOH = PClz.OPh + HCl, and
separating the products by fractional distillation, mono- and di-
phenylphosphoryl chlorides and triphenyl phosphite are obtained. The
former, PCl2.0Ph, is a colourless strongly refractive liquid, which boils
at 216° with partial decomposition. It fumes in the air, and reacts with
water with formation of a cloud of hydrochloric acid ; sp. gr. = 1*348.
The latter, PCl(0Ph)2,similar in appearance to the above compound,
boils at about 295" under a pressure of 731 mm. ; sp. gr. = 1'221.
The author was unsuccessful in his attempts to obtain by the action of
water on the chloride mono- and diphenyl-phosphorous acids; only
a mixture of phenyl and phosphorous acid in various proportions
was formed. Under certain conditions phenol and phosphorous acid
crystallised out together as a molecular compound similar in appearance
and analogous in composition to the substances formed by the direct
addition of sulphurous and carbonic anhydride to phenol.
Triphenyl phosphite, P(0Ph)3, is best prepared by the action of
1 mol. of phosphorous trichloride on rather more than 3 mols. of
730
ABSTRACTS OF CHEMICAL PAPERS.
phenol, according to the equation PCI3 + 3PhOH = P(0Ph)3 -f
3HC1. It is a colourless, odourless, strongly refractive liquid, boiling
above 3G0°, easily soluble in alcohol and benzene, insoluble in, but
gradually decomposed by water into phenol and phosphorous acid ;
sp. gr. = 1*184. It solidifies into a glassy mass when exposed to the
cold produced by a mixture of solid carbonic anhydride and ether.
Michelhaus has shown that by the action of bromine on triethyl
phosphite no hydrobromic acid, but ethyl bromide and diethyl phos-
phoryl bromide are formed. On repeating the experiment with tri-
phenyl phosphite, it is found that triphenylphosphoryl dihromide is
obtained thus : P(0Ph)3 + Brz = P(OPh)3Br2. This substance crys-
tallises in small right-angled tables, which gradually deliquesce into
an oily mass. It is decomposed by cold water, yielding triphenyl
phosphate [BroP(0Ph)3 -f H2O = O ! P(0Ph)3 + 2HBr], identical
with the product of the action of phenol on phosphorus oxychloride.
The readiness with which triphenyl phosphite combines with bro-
mine and takes up oxygen points to its possessing a symmetrical con-
stitution. The decomposition of the compounds obtained by the
author, especially monophenylphosphorous acid into phenol and phos-
phorous acid, points to the combination of the oxygen to the phenyl-
group, while the isomeric phosphenylic acid decomposes into benzene
and metaphosphoric acid, PhP0(0H)2 = PhH -|- HPO3.
A short comparison of the compoauds obtained by Michaelis and
by the author is appended below.
Michaelis' Compounds.
Phosphenyl oxychloride,
0 : PPhCla, from PPhClz + 0 ;
b. p. 258°, sp. gr. 1-375,
slowly decomposed by water
into phosphenylic acid,
PhPOCl + 2H2O
= PhP0(0H)2 + 2HC1.
Phenol phosphenyl chloride,
0 : PPh(OPh) CI, from PhPOCls
-h PhOH ; b. p. over 360° ;
decomposed by boiling water
into crystalline phenolphosphe-
nylicacid, PhPOCl.OPh -h H2O
= O : PPh(OH).OPh + HCl.
Phosphenylic acid, 0:PPh(0H)2,
from PhPCU + H2O ; crystal-
line stable compound, m. p.
158°, soluble in water, and
crystallising from the solution.
NoacWs Compounds.
Monophenylphosphoryl chloride,
PCI2.OPH, from PCI3 and
PhOH ; b. p. 216°, sp. gr. 1-348,
decomposed violently by water,
OPhPCla + 2H2O
= 0PhP(0H)3 -f- 2HC1.
Diphenylphosphoryl chloride,
P(OPh)oCl, from PCI3 and
PhOH; b. p. over 295°, fuming
in the air, decomposed by ice
thus: (0Ph)2PCl + HoO =
(0Ph)2P(0H) -h HCl.
Monophenylphosphorous acid,
P(0Ph)(0H)2; very unstable,
decomposing at once with water
into phosphoric acid and phenol.
ORGANIC CHEMISTRY.
737
Michaelis' Compounds.
Phenol phenylic acid,
0 : PPh(OPh).OH, from the cor-
responding chloride ; crystal-
line stable substance, m. p. 57°,
sparingly soluble in water.
Diphenyl phosphenylate,
0:PPh(0Ph)2, from PhPCU
+ 3PhOH; crystalline, m. p.
63" 5°, not decomposed by
water.
NoacWs Compounds.
Diphenylphosphorous acid,
P(0Ph)2.0H; very unstable,
decomposed at once by water
into phosphoric acid and phenol.
Triphenyl phosphite, P(0Ph)3,
from PCI3 + 3PhOH; not
crystalline, decomposed by
water into phosphoric acid and
phenol.
The difference of constitution of these compounds is sufficiently
elucidated by their difference of behaviour. Y. H. V.
/S-Naphtholtrisulphonic Acid. By I. Lewinstein {Ber., 16,
462 — 463). — The trisulphonic acid of /3-naphthol is formed by the
action of 4 parts of fuming sulphuric acid on 1 part of naphthol at
135°. Better results are obtained by first preparing the monosul-
phonic acid by the action of chamber acid (2 parts) on naphthol
(1 part) at 70 — 80°. Two parts of sulphuric acid are again added,
and the mixture is heated at 120°. Finally 2 parts of fuming acid
(containing 40 per cent, of trioxide) are added, and the temperature
is raised to 150°. The trisulphonic acid does not form a colouring
matter with diazoxylene, although it produces beautiful dyes with
analogous diazo-compounds. W. C. W.
Dinitroanthraquinone and Diorthamidoanthraquinone : a
New Method of Preparing Anthrarufin. By H. Roemer {Ber.,
16, 363— 374).— The author has recently shown {Ber., 15, 1786) that
a mixture of orthonitranthraquinone and two other nitro- compounds is
produced by the action of nitric acid on a solution of anthraquinone in
strong sulphuric acid. That portion of the mixtare which is least solu-
ble in alcohol consists of [1 : 4] dinitroanthraquinone. This compound
is best prepared by adding 10 g. of nitric acid (sp. gr. 1-48) to 10 g.
of anthraquinone dissolved in strong sulphuric acid. The crude pro-
duct is repeatedly treated with boiling alcohol, until a portion of the
residue gives a pure blue colour on the addition of stannous chloride
mixed with excess of potash [1 : 4]. Dinitroanthraquinone dissolves
readily in boiling nitrobenzene, and is deposited from the solution
on cooling in yellow needles, which melt at a temperature above 300°.
It is insoluble in water, sparingly soluble in alcohol, ether, benzene,
chloroform, acetic acid, and cold xylene. It dissolves in strong sul-
phuric acid at 100°, and is deposited from the solution on cooling. If
the liquid is heated more strongly, gas is evolved, and on pouring the
solution into water a purple precipitate is thrown down, which is
soluble in ether. The dinitroquinone is not attacked by alkalis, but
it is converted into [1 : 4] diortliaTnidoanthraquinone by treatment with a
warm mixture of stannous chloride and potash. This compound does
not melt at 300° ; at a higher temperature it sublimes, forming red
738 ABSTRACTS OP CHEMICAL PAPERS.
needles with metallic lustre. It is sparingly soluble in water, alcohol,
ether, benzene, acetone, and chloroform, bat dissolves in strong hydro-
chloric acid, forming a colourless liquid, which deposits a white crys-
talline salt. It dissolves in dilute hydrochloric acid, yielding a red
solution, which deposits the free amido-compound. By the action of
acetic anhydride and sodium acetate, a diacetio derivative,
CuHeO^CNHi:^)^,
is obtained, which is insoluble in cold hydrochloric acid, but is decom-
posed by boiling with hydrochloric acid, [1 : 4] Dinitroanthraquinone
is also produced by treating a solution of orthomononitroanthra-
quinone in sulphuric acid with strong nitric acid,
Diorthamidoanthraquinone may be converted into anthrarufine by
the diazo-reaction. Water is added to a solution of the diamidoanthra-
quinone in excess of strong sulphuric acid, until the amido-compound
is reprecipitated ; potassium nitrite is then poured into the cold mix-
ture until the precipitate redissolves, and the liquid is diluted with
water and boiled for an hour. The precipitate of crude anthrarufine
thus obtained is treated with hot baryta-water, in order to remove
erythro-oxyquinone, and on decomposing the insoluble barium com-
pound with hydrochloric acid, anthrarufine is obtained as a crystalline
precipitate. In the preparation of anthrarufine, it is not necessary to
use pure dinitroanthraquinone, as the presence of a small quantity of
orthonitroanthraquinone does not interfere with this reaction.
w. c. w.
Occurrence of Methyl Alcohol in the Products of the Dry
Distillation of Colophony. By W. Kelbe and J. Lwoff (Ber., 16,
351 — 352). — The aqueous liquid obtained in the destructive distilla-
tion of colophony contains in addition to acetic acid and higher acids
of the acetic series, small quantities of methyl alcohol. About
50 grams of methyl alcohol were obtained from 150 kilos, of colo-
phony. W. C. W.
Bases of the Pyridine and Quinoline Series. By O. de Coninck
{Ann. Ghim. Phys., 5, 433 — 532). — This long memoir is divided into
three parts. In the first part the author gives a brief account, with
references, of the results of previous researches on the pyridine and
quinoline bases, under the heads : history ; synthesis ; bases having the
same composition ; oxidation products ; hydrogenation products ; phy-
siological action ; isomerism of leucoline and quinoline. The second
part contains an exhaustive resume of the author's researches on the
fractional distillation of crude quinoline ; the oxidation and hydrogen-
ation of y3-lutidine and /S-collidine ; hydrates of the pyridine bases ;
fractional distillation of oils from brucine; and the physiological
action of the pyridine and quinoline bases. Most of these researches
have already appeared in the Oompt. rend, and Bull. Soc. Ghim., and
abstracts of them are contained in this Journal, 1881 and 1882. The
conclusions drawn by the author from these experiments are sum-
marised as follows : —
1. The distillation of cinchonine with potash furnishes two series of
isomeric pyridine bases, amongst which are notably two lutidines and
f
ORGANIC CHEMISTRY. 739
two coUidines. The first fractions contain also methylamine and some
fatty ethers, e.g., amyl acetate.
2. The distillation of brucine with potash furnishes a small quan-
tity of neutral products, and some pyridine bases, amongst others
jB-lutidine and )3-collidine. The lower fractions contain a pyridine
base insoluble in water, probably another lutidine.
3. /3-Lutidine has been separated from its isomeride and obtained
pure by a process generally applicable to the purification of the bases
of these series.
4. /3-Lutidine aurochloride undergoes modifications similar to those
of the pyridine platinochloride, hitherto regarded as characteristic.
By regulated oxidation, this base yields nicotianic acid. )8-Lutidine is a
violent poison, more energetic in its action than (3-collidine.
5. The existence of /3-collidine (b. p. 196°) in the crude quinoline
from cinchonine and brucine goes to prove definitely the isomerism
of the pyridine bases derived from cinchonine and brucine with those
derived from coal-tar and Dippel's animal oil.
6. By partial oxidation, y3-collidine furnishes homonicotianic acid,
CsHsMeN.COOH, analogous totoluic acid. By further oxidation this
acid becomes cinchomeronic acid, C6H3N(COOH)2, hence /8-collidine
may be regarded as methyl-ethyl-jpyridine. By oxidation in hot solu-
tions, i8-collidine furnishes nicotianic acid. iS-CoUidine is an anti-
pyretic, a powerful poison, and has the curious property of preventing
the reflex movements of the cornea.
7. The crude quinoline from cinchonine contains ^e^ra^cZrog'^moZine,
the first instance of a hydroquinoleic base derived from an alkaloid con-
taining oxygen ; its existence confirms Wischnegradsky's hypothesis
that the pyridine and quinoline bases exist in the alkaloids as
hydrides.
8. Tetrahydroquinoline from cinchonine is isomeric with that
formed by synthesis, and, like it, is transformed into quinoline by
very feeble oxidising agents. It constitutes an intermediate term
between the two series of bases formed simultaneously in the destruc-
tive distillation of cinchonine with caustic potash.
9. Quinoline from cinchonine is mixed with tarry products, from
which it can be easily separated. Purified from these products and
from its homologue lepidine, which it retains with much persistence,
it boils at 236 — 237° (corrected) under a pressure of 775 mm. In
certain cases of fever (hectic fever) quinoline acts more powerfully
than quinine.
10. Pyridine appears to be as violent a poison as 3-lutidine. The
author concludes, from a careful review of the formation and proper-
ties of pyridine and quinoline and their homologues, and of their
oxidation-, reduction-, and substitution-products, that all the known
facts are in favour of Korner's theory that pyridine is correctly repre-
sented by Kekule's formula for benzene, (N)'" taking the place of one
of the (CH)'" groups, and that quinoline is similarly related to naph-
thalene, the higher homologues of these bases being formed, like the
homologues of benzene and naphthalene, by the introduction of lateral
chains of methyl, ethyl, propyl, &c., in place of hydrogen.
J. M. H. M.
740 ABSTRACTS OF CHEMICAL PAPERS.
Isomerism in the Pyridine Series. By O. de Contnck (Compt.
rend.^ 96, 437 — 439). — The author has applied Anderson's reaction to
the separation of the isomeric lutidines. The lutidines contained in
crude quinoh'ne prepared from brucine cannot be separated by fractional
distillation. They were therefore converted into the platinochlorides,
the precipitate boiled .for an hour and a half and filtered ; a yellow
precipitate was at once formed, and the filtrate deposited a red salt
slightly admixed with the yellow ; the filtrate from this gave a
homogeneous red salt. The yellow salt fuses at 204 — 205°, and is the
modified salt (C7H9N)2,PtCl4. The red salt fused at 179—180°, and
gave numbers agreeing with the platinochloride of normal lutidine,
(C7H9N)2,H2PtCl6. The platinochloride of y3-lutidine fuses above 200".
The author has also studied the efiect of boiling the platinochlorides of
the quinoline series with water. They are, however, much more
stable than those of the pyridine series.
The isomerides of the pyridine series also appear to be distinguish-
able by the varying rapidity with which they unite with the alcoholic
iodides. L. T. T.
Poisonous Principles contained in certain Lupines. By C.
Arnold (Ber., 16, 461 — 462). — A resinous compound may be obtained
from diseased lupines by digesting them for two days at a temperature
of 40 — 50° in a 2 per cent, solution of sodium hydroxide. The extract
is neutralised with acetic acid and concentrated by evaporation at a
temperature not exceeding 60°. After carefully precipitating the
legumin with strong acetic acid, the filtrate is gently evaporated to a
syrup and poured into 15 times its volume of 90 per cent, alcohol.
The resinous precipitate is slowly soluble in water. A dose of 10
grams of this substance causes cattle to exhibit the usual symptoms of
poisoning by diseased lupines. W. C. W.
Physiological Chemistry
Nutrition by Fat. By A. Lebedeff (Zeitschr. Physiol. Cliem., 6,
139 — 154). — The subject of the absorption of fat has been frequently
worked at, but recently rather from a histological than a chemical
point of view. In regard to the origin and disposal of fats the
researches of Radziszewski, Subbotin, and Hoffmann, especially, have
been accomplished. The author undertook the investigation of the
chemical composition of the fats and fatty tissues of the animal body,
in order if possible to arrive at conclusions as to the nature of the
processes through which by oxidation fats are formed or changed
from one kind into another. He succeeded in devising a new and
exact method of quantitative analysis for fats, details of which are
given in this article, and likewise as regards the fattening of the goose
f
PHYSIOLOaiCAL CHEMISTRr. 741
in arriving at certain facts concerning the nutrition of geese, and the
composition of the fat contained in the maize employed for this pur-
pose. Goose fat obtained from the liver as used in the manufacture of
pate defoie gras yielded in two analysis, per cent. —
l-^}:n oleic acid. fVUPf !-!«'' -^d
2. d1'2 J ,i2'i5 J stearic acids.
Strassburg, it is well known, is the centre of this industry. The mode
of feeding these birds is such as to produce a fatty infiltration and
degeneration of the liver to an extraordinary extent in a very short
time ; the liver is presumably the fat- forming organ. The author has
proved that on feeding with richly nitrogenous matters poor in fat, no
fat is present in the liver. In geese which had fed upon peas for six
weeks only trifling deposits of fat were found in the omentum and
around the intestines, whilst the sliglitly developed liver yielded
lecithin, but no fat. From these results, he conjectures that the fat is
derived from the maize and not from the albuminates of the foods, the
maize fat differing, as shown by comparative experiments, from the
liver fat only in its larger proportion of olein.
Maize fat. Percentage results of two analyses : —
1. 76*5 "I 1 . .-, 12-41 palmitic and
2. 79-9 / °1^"= ''"^- 13-9 / stearic acids.
Peritoneal fat from investment of liver (commercial /oie gras) —
1. 64"31 -, . .-, 24'6 1 palmitic and
2. 66-2 / ^^^'^ ^^'^' 27-3 / stearic acids.
Intestinal fat of geese fed with peas —
1. 66-4 1 1 . .. 29-9 1 palmitic and
2. 63-7 / °^^'° ^^'*^- 31-3 / stearic acids.
Mesenteric fat (suet) of ditto —
687 oleic acid. 21-2 ( Pf '™''« ^.^'^
I stearic acids.
The author gives the results of similar estimations of the con-
stituents of fat derived from various organs and regions of the human
body, and also from chronic fatty liver, lipoma or fatty tumour, and
an acute fatty infiltration of the lung following upon embolism caused
by a compound fracture of the ribs. These lead to the conclusion
that the maximum proportion of oleic acid and glycerid is formed in
rapidly occurring fatty infiltration. The subcutaneous fat is the most
fluid, next the intestinal fat, and most consistent is the fat of lipoma
and of chronic deposits.
An attempt was made by the author to determine the mode of dis-
posal of fats foreign to the organism, by feeding dogs upon tributyrin,
but although tributyrin was digested and absorbed by the system,
it appeared to be deposited in the tissues in such insignificant
proportions that the results, as in the previous experiments of Rad-
ziszewski and Subbotin, were indecisive. So far, therefore, it remains
742 ABSTRACTS OP CHEMICAL PAPERS.
•undemoiistrated whether fats forei^ to the animal body may be
deposited therein. The phenomenon of fat deposit is much more
complicated than might appear at first glance. The process is pro-
bably dependent not merely on the chemical but also on the physical
properties of the fat in question. D. P.
Blue Milk. By J. Reiset (Gompt. rend., 96, 682—685 and 745—
750). — In the dairies in some localities, notably in the district of Caux,
a blue mould not unfrequently forms on the surface of the standing
milk, and the same mould has been observed on the milk of ewes and
goats. This mould forms in deep blue patches at the edges of the
earthern pans in which the milk is kept, and also in the centre.
Sometimes these patches do not increase ; sometimes they develop
rapidly, and after a few honrs the mould covers the entire surface of
the milk, the development taking place more rapidly the higher the
temperature. The blue mould can be cultivated by the usual methods,
but sometimes the cultivated mould is sterile, and a white mould is
developed simultaneously, and appears to crowd out or destroy the
blue mould. Milk on which the mould forms has a distinctly
acid reaction. The freshly formed mould is free from mycelium
growth, and consists of membranous tissue composed of fatty matter
and transparent spherical immobile bacteria. Scattered throughout
the tissue are groups of transparent striated crystalline plates, united
at a common centre. These plates undoubtedly consist of fatty acids.
A white mould which often forms at the same time as, and frequently
more rapidly than, the blue mould, consists mainly of Mucor racemosus
with some Penicillium. The nature of the blue colouring matter has
not yet been determined. It is not affected by acids, and is therefore
not identical with the pyoct/anine of Fordos or the Baderidum cyaneum
of Schroeter (Micrococcus cyaneus of Cohn).
The causes of the formation of the mould are not clearly ascertained.
It is not a result of aphthous fever, for the mould did not form on the
milk of several cows affected with this fever. No beneficial results
were obtained by bleeding several cows which were apparently too fat,
nor by the administration of drinks containing sodium sulphate or
sodium bicarbonate. Marchand considers that its formation is due to
one of the three following causes : want of cleanliness in the dairy and
dairy utensils ; overfeeding ; and absence of a proper proportion of lime
in the soil on which the cows are pastured. The growth of the mould
is, however, more probably due to the too frequent manuring of the
pasturage with animal manure, and to the presence of organisms in
the water drunk by the cows; these organisms are taken into the
bodies of these animals, and pass into the milk, which constitutes a
favourable medium for their development.
The formation of the mould may be prevented by adding 0 5 gram
of glacial acetic acid to each litre of milk at the time when it is put
into the pans. This quantity of acid does not coagulate the milk, and
exerts no effect on the rising of the cream. The milk pans should be
immersed in hailing water for at least five minutes, and the use of
brushes and cloths should be avoided.
As the result of a large number of experiments made with delicate
I
PHYSIOLOGICAL CHEMISTRY. 743
red and blue litmns -paper on milk immediately after it was drawn
from the cow, the author finds that normal milk distinctly reddens
blue litmus-paper, and the colour remains after drying. The same
milk imparts to red litmus-paper a pale blue colour which gradually
disappears on drying. C. H. B.
Influence of Calomel on Fermentation and the Life of
Micro-organisms. By N. P. Wassilteff (Zeifschr. Physiol. Chem.,
6, 112 — 134). — Calomel has always held a foremost place amongst
those remedies which are confidently resorted to in certain gastric and
intestinal disorders, especially of childhood, but the precise nature
of its beneficial effect has heretofore been unexplained. Recent works
on pharmacology pass over the question, and only Kohler refers to the
favourable action of the drug in typhus, cholera, dysentery, and other
diseases, as being due to its germicidal and anti-fermentative quali-
ties. No evidence in support of this view is adduced. Voit, however,
had noticed in 1857 that egg-albumin and blood, when mixed with
calomel, remained for days without undergoing putrefaction. Hoppe-
Seyler also mentions an aseptic influence of calomel, and ascribes to
it the well-known green colour of bowel discharges after an adminis-
tration of calomel.
The author undertook this investigation at the request of Hoppe-
Seyler, first, in regard to the behaviour of calomel towards the so-
called unorganised ferments of* the digestive fluids (enzymes), and
secondly, as to its action on the lower organisms associated with the
processes of fermentation and putrefaction.
The first series of experiments were made in order to determine the
influence of calomel on the normal process of digestion in the stomach.
The results proved that its presence in no way interfered with the
properties of the gastric juice, fibrin being digested in the same time,
whether calomel was present or not.
In the next series, the influence of calomel on the process of pan-
creatic digestion was investigated. It is now known that three
separate ferments exist in the pancreatic secretion by which albumi-
nates, fats, and carbohydrates are severally transformed and fitted for
assimilation in the system. The object in view was to observe the
possible influence of calomel on each of these respective ferments. For
the purpose of experiment a watery extract was prepared from the
finely minced gland, and strained through linen. It was found that
the action of the ferment, by which albuminates become digested, was
in no respect hindered by the presence of the calomel, and further,
that there was a conspicuous absence from the liquid mixture of all
products of putrefaction. In the mixture containing calomel, large
quantities of leucin and tyrosin were found, whilst indol and phenol
were absent. In the mixture without the addition of calomel, the two
latter bodies were both present, but only traces of leucin and tyrosin.
The latter solutions had likewise a putrid smell and a dirty brown
colour, whilst the former was of a dark grey colour and odourless.
In some additional experiments, wherein the process was allowed
to proceed in a Bunsen gasometer, and the evolved gases examined, it
was found that from the mixture containing calomel, hydrogen and
744 ABSTRACTS OF CHEMICAL PAPERS.
hydrogen sulphide were never given off, and carbonic anhydride in
very considerably less amount than from the control mixtures without
calomel.
These results accord with those of Hiifner (/. pr. Chem., 10
and 11), who found in his experiments on artificial digestion
with pancreatic extract, that when by means of a properly arranged
apparatus entrance of micro-organisms was prevented, neither hydro-
gen nor hydrogen sulphide made its appearance, but only carbonic
anhydride. These two first-named gases have therefore nothing to
do with digestion proper, but are the result of putrefactive changes,
brought about by the presence of microzymes in the alimentary canal.
The action of calomel on the ferment of the pancreatic juice, to which
the digestion of fat is due, was next examined. The existence of
such a principle has, until now, been considered highly doubtful,
Paschutin's observations on this head being all that is known of the
subject (W. Paschutin, Ueher Trennung der VerdauimgsfermerUe.
Centralhl. fur die Medicin. Wissensch., 1882).
As in putrid solutions, fats become saponified rather quickly, the
problem became an important one to determine whether the trans-
formation of fat in the alimentary canal was owing to the action of an
unorganised ferment or merely to the putrescent changes going on
there. The experiments made proved beyond a doubt that the action of
pancreatic juice upon fat took place in the complete absence of puti-e-
f action, and the digestion of the fat by the pancreatic extract in pre-
sence of calomel, proceeded precisely as in the instance of the experi-
ments in regard to tt 3 peptic ferment (trypsin) of that gland.
The action of the third and remaining ferment of the pancreas, the
diastatic, upon starch, and the transformation of the latter into g-lucose,
proceeded equally undisturbed in the presence of calomel. Hence it
follows that calomel, by its presence in these experiments on artificial
digestion, allows the actual process of digestion to go on without
injury, whilst it effectually prevents putrefactive change. And this in
the same way as proved for salicylic acid by Kiihn, and in the case of
arsenic by Scheffer and Bohm.
The author also found the action of calomel in the process of butyric
acid fermentation, which sometimes occurs in certain pathological
states of the digestive system, similar to that in common putrefaction,
entirely preventing it.
A further series of experiments, which need only be referred to
here, were carried out to determine the disinfectant action of calomel
in fluids containing bacteria and micrococci, the bacterioscopic
method of Bucholtz-Wernich being used. The results showed that
calomel acted as a true antiseptic and disinfectant in preventing the
development of such organisms in culture fluids, and arresting their
activity when already developed therein.
The difference in the influence of calomel on the process of diges-
tion on the one hand, and on putrefactive and fermentative changes
on the other, is dependent upon a distinct difference of action on orga-
nised and unorganised ferments. Whilst it does not interfere with
the activity of the latter, it destroys the vitality of the former, and
with it the power of inducing subsequent septic changes.
PHYSIOLOGICAL CHEMISTRY. 745
Finally, as regards the green colour of the bowel discharges witnessed
after the exhibition of calomel, this was formerly attributed to the pre-
sence of bile, expelled by virtue of the assumed action of calomel as a
cholagogue ; this appearance was considered by Hoppe-Seyler to be
due to the presence of undecomposed bile, and the author's experi-
ments now confirm this view. Under ordinary conditions, the bile
pigments, bilirubin and biliverdin, become decomposed in the intestine
under the influence of putrescent changes, forming hydrobilirubin.
During the administration of calomel this decomposition does not take
place, and the bile pigments are expelled unchanged.
The author concludes that the therapeutic virtues of calomel are to
be ascribed to its antiseptic and disinfectant properties. D. P.
Physiological Action of Coffee. By J. A. Foet (Gom.pt. rend.,
96, 793 — 796). — From the results of a series of experiments made
upon himself, the author concludes that coiFee acts on the central
cerebro-spinal nervous system. In strong doses, it produces sleepless-
ness by exciting the brain ; and, by exciting the medullary, it also
produces cramp in the muscles, pains in the stomach, and disorder of
the intestines, and disturbs the action of the heart. In moderate
quantities, it exerts a much milder exciting action, slightly stimulating
the brain, which is less inclined to sleep and works with somewhat
greater activity. It also stimulates the spinal marrow, and thus pro-
duces increased activity of the different functions. As an article of
diet, coffee does not diminish the waste of nitrogenous matter, but on
the other hand it does not directly increase this waste, its direct
action being exerted on the central nervous system. C. H. B.
Relative Toxic Power of Metallic Salts. By J. Blake
{Compt. rend., 96, 439 — 441). — Rabuteau gave as the law on this
subject that " the metals are more active in proportion as their atomic
weight is higher and their specific heat lower." The author denies
the correctness of this law, but finds that in the same isomorphic group
the effect is greater the higher the atomic weight. The salt was intro-
duced into the system by subcutaneous injection, and in the annexed
table the third column represents approximately the weight in grams
per kilogram weight of the animal which is fatal.
Fatal dose
Metal. Atomic weight. per kilogram.
Lithium 7 1*2
Rubidium 85 0-12
Cesium 133 012
Silver 108 0-028
Gold 196 0-003
Magnesium 24 097
Iron (FeO) 66 0'32
Nickel 68 0-18
Cobalt 68 0-17
Copper . . 63 017
Zinc 65 0-18
Cadmium 112 0-085
yOL. XLiv. 8 e
746 ABSTRACTS OF CHEMICAL PAPERS.
Fatal dose
Metal. Atomic weight. per kilogram.
Calcium 40 0*5
Strontium 87 0-38
Barium 137 008
Glucinura 14 0'023
Aluminium 27 0-007
Iron (FeA) 56 0'004
Yttrium 90 0'004
Cerium (Ce^Oa) 140 0-005
Cerium (CeO^ 140 0-062
Thorium 231 0034
Lanthanum 139 0025
Didymium 147 0-017
Palladium 106 0-008
Platinum 197 0*027
Lead 200 O'll
L. T. T.
Chemistry of Vegetable Physiology and Agriculture.
Action of Air on Yeast. By D. Cochin (Compt. rend., 96, 852
— 855). — The membrane surrounding yeast cells is penetrated by
glucose solution, and fermentation does not commence until some time
after this endosmose has taken place. If yeast is suspended in water
and aerated by repeatedly decanting the liquid from one vessel to
another, the aerated yeast, when added to a solution of glucose,
exerts simply a diluting effect equal to that which would be produced
by the same volume of water. If, however, the yeast is deprived of
air, by suspending it in recently boiled water, covering the water
with a somewhat thick layer of oil, and heating the liquid at 20° for
periods varying from two hours to several days, the effect which it
produces in glucose solution is different. After eight days' heating,
the yeast is still permeable to the sugar solution, but fermentation
scarcely commences; the yeast has been asphyxiated. After two
hours' heating, the absorption of sugar begins, but it is only after
24 hours' heating that the phenomena are most distinctly observed.
At the end of this time, under the conditions stated, the yeast has not
experienced any alteration : when the yeast, thus deprived of air, is
added to a solution of glucose, the latter is absorbed by the yeast cells to
such an extent before fermentation commences, that the amount in solu-
tion is diminished by one-half. If a quantity of the liquid is boiled,
mixed with an equal volume of alcohol and filtered, almost the whole of
the sugar is found in the filtrate, only a small proportion having been
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 747
converted into alcohol. From these experiments, it is evident that the
transformation of su^ar takes place in the interior of the cells, and that
deprivation of air brings the cells into the condition most favourable
for absorbing the sugar.
Aerated yeast, and yeast deprived of air, also show great difference
in their fermentative power. The former produces an amount of
alcohol much below the normal amount, and decomposes part of the
sugar without converting it into alcohol. C. H. B.
Chemistry of the Maize Plant. By H. Leplay (Compt. rend.,
96, 159 — 161). — The following are the results obtained by the
author : i. The total nitrogen contained in the stalk and leaves of the
maize is greater before the formation of the ear than after the
maturity of the grain, and the quantity in the mature grain is
greater than that in the stalk, leaves, or rachis. The albumin,
potassic nitrate, and vegetable acids contained in the sap probably
derive their origin in a similar way to that already suggested by the
author (this vol., 368) in the case of the sap of the beetroot, ii. The
percentage of phosphoric acid to dried substance is greater in the
grains than in the leaves and stalk, and greater in these latter than
in the rachis. A migration of phosphorus therefore takes place
from root to grain. The quantity of base in combination with mineral
acids is less than that combined with vegetable acids in all portions of
the plant except the grain.
The percentage of base combined is as follows : —
With mineral acid. With organic acid.-
Stalk and leaves 17-00 83'00
Rachis 3-30 9670
Grain .- 51-00 49-00
Of the mineral acids, phosphoric acid forms about 90 per cent., and
of the bases magnesia 49 per cent., lime 6 per cent., and potash 42". per
cent. iii. The nitrogenous and mineral matter, during the vege-
tating period of the maize, passes from the root through the various
organs to the grains in a similar manner as with beetroot. The
author believes these various organic and mineral substances, although
often present only in the minutest traces, to be essential to the proper
discharge of their functions by the various organs ; and that their
presence in the soil in suitable form for assimilation is necessary for
the growth of the plant. (See also this volume, p. 366.)
L. T. T.
Respiration of Aquatic and Submerged Aero-aquatic Plants.
By A. Baeth^lemt (Compt. rend., 96, 388 — 390). — Aquatic plants
placed in a vessel containing air gradually absorb the oxygen. Aero-
aquatic plants (the experiments being carried out with members of
the family Nymph ceacece) growing in a deep vessel produce sub-
merged leaves containing gas absorbed through the roots. One of
these leaves supplied, under water, with water impregnated with,
carbonic anhydride, gave out no oxygen, but became yellow and
transparent at the end of several days. A leaf of the white water-
3e2
748 ABSTRACTS OF CHEMICAL PAPERS.
lily, the stalk of which was introduced under a bell-jar, was exposed
to sunlight in water charged with carbonic anhydride; a large
quantity of oxygen was disengaged, ceasing at the end of about a
couple of days. Under the most favourable circumstances as much as
1 litre was emitted in three hours. The disengagement increased
with the temperature up to a maximum at 35°. Scratches made on
the surface of the leaf arrested the disengagement of gas, the solution
of carbonic anhydride killing the green protoplasma. Two leaves, the
stalks of which were connected with caoutchouc tube, gave no evolu-
tion of gas when plunged into water impregnated with carbonic acid.
The author believes that in submerged plants the decomposition of
carbonic acid ceases as soon as the oxygen liberated in the vessels of
the plant reaches a certain tension, and that the disengagement takes
place only when a leaf becomes detached ; the broken surface allow-
ing the oxygen to escape, and so preventing the increase of tension.
In the case of the Nelumhium, the leaves of which retain a layer of
air over their surface, scarcely any gas is emitted, either from their
leaves or broken stalks, but if the layer of air be removed with a
brush a considerable disengagement of oxygen takes place by the
stalk. The Pcntederiacece emit but very little gas. Tulips, hyacinths,
&c., can be grown in closed vessels, where their leaves obtain no
carbonic anhydride, and their whole nourishment must come from the
bulb. From these and his former experiments (Compt. rend., 1877),
the author believes that in a normal condition the special respiration
of the green parts of plants does not play as important a role in its
life as is generally ascribed to it. L. T. T.
Proportion of Nitrogen in the Form of Amides, Albumin,
and Nuclein in different Feeding Stuffs. By W. Klinkenberg
(Zeits. Fhysidl. Chem., 6, 155 — 165). — In ascertaining the nutritive
value of vegetable foods and feeding stulfs, the quantitative determi-
nation of the different forms of nitrogenous constituents is of great
importance. Some of these, as, for example, nitrates, amides, and
alkaloids, are of subordinate value in this respect, and as A. Stutzer
has shown (Jour, fiir Landwirthsch., 1880, 195, 435), only a certain
amount of the proteids are rendered available for the purpose of
nutrition by -the digestive ferments.
Miescher first demonstrated the existence of nitrogenous matters
insoluble in th>e gastric juice at the ordinary temperature of the body
in the nuclei of pus corpuscles, to which constituent he gave the
name of nuclein. Nuclein combinations may be assumed to exist
generally diffused throughput the animal and vegetable kingdoms;
they contain, in addition to the elements C, H, N, 0 and S, also
phosphorus as a characteristic constituent, and having a different
chemical constitution from albuminates soluble in the gastric juice,
doubtlessly play a perfectly distinct physiological role.
Owing to its insolubility, nuclein is worthless for nutrition, and
hence in determining the value of foods in this respect, a separate
estimation of nuclein from soluble proteids is essential.
In his experiments, the author followed the process of A. Stutzer
(lac. cit., pp. 103, 190). He gives the results arrived at by this
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
749
method in the separate det-ermination of the nitrogenous constituents
of feeding stuffs, such as poppy cake, earth-nut cake, rape and cotton
cake, rice-meal, beer grains, and flesh-meal ; the results are tabulated
below, the numbers showing percentage proportions of nitrogen occur-
ring in different forms of combinations : —
Poppy cake. . . .
Sesame cake . . .
Soja-bean
Earth-nut cake
Linseed
Rape cake, 1. .
2..,
3..
Copra cake ...
Cotton cake. . .
Rice-meal, 1 . .
,, . 2..
Beer grains. . .
Flesh-meal . . .
Not
precipitated
by hydrated
cupric oxide.
6-49
1-50
9-50
4-54
8-50
12 -77
8-33
9-23
6-74
4-35
7-07
5-77
4-53
Precipitated and insoluble
and by gastric juice are
rendered
Soluble.
82
92
86
90
78
74
79
76
85
86
72
77
79
93
17
06
18
91
89
46
33
80
75
97
27
09
83
30
Insoluble.
34
41
29
55
58
77
34
97
51
68
66
14
17
17
D. P.
Loss and Gain of Nitrogen in Arable Land. By r. P.
D^H^EAiN {Gompt. rend., 96, 198 — 200). — The author gives the
results of experiments extending over seven years. The crops raised
were maize (for fodder) and potatoes, the different plots of land being
subjected to different treatment. One series of plots was freely
manured with farmyard manure, another was treated with sodium
nitrate or ammonium sulphate, whilst the third was left totally un-
manured.
Each crop was weighed and a sample analysed, and from the num-
bers thus obtained the quantity of nitrogen contained in the whole
crop was calculated.
The author draws the following conclusions from the results which
he obtained : i. The loss of nitrogen in arable land is due not only to
its removal by vegetation, but also, and in a larger measure, to the oidda-
tion of nitrogenous organic matter : the loss being greater the oftener
the land is tilled, ii. When the land is not disturbed by tillage, the
air penetrates less, oxidation is more restricted, and the gain of nitro-
gen exceeds the loss. iii. A soil is more easily enriched by being
allowed to remain in meadow than by lavishing manure upon it.
L. T. T.
750 ABSTRACTS OF CHEMICAL PAPERS.
Analytical Chemistry.
Estimation of Phosphorus by the Molybdate Method. By
E. Tauber {Landw. Versuchs.-Stat., 28, 333— 341).— The object of this
investigation was to study the action of ammoninm nitrate on the
phosphomolybdate of ammonia. The formula given by Fresenius was
used in preparing the nitro-molybdate solution, and the first point
investigated was whether the addition of ammonium nitrate rendered
the use of more. or less ammonium molybdate necessary. The experi-
ments showed that in every case a considerable saving of molybdate
was effected, and that the precipitate thus produced was more floccu-
lent and less liable to stick to the sides of the glass vessels than phos-
phomolybdate thrown down in the usual way ; the precipitation takes
place much more quickly in presence of ammonium nitrate, one hour's
standing being sufficient for complete precipitation.
The solubility of the precipitate in. ammonium nitrate is very little
greater than in molybdate, and the former can be safely used to wash
the precipitate, the first 100 c.c. of wash- water producing no sensible
error, and being in nearly all cases quite sufficient for the purpose ; a
drop or two of nitric acid may be added with advantage, 100 c.c. of
acidified dilute ammonium nitrate solution (100 grams to the litre)
dissolving from O'l — 0*2 milligram of phosphoric acid.
A gradual addition of the magnesium mixture is to be recommended
in all cases, with continued stirring ; otherwise a small quantity of
magnesium chloride is carried down with the precipitate, and the
results come out too high. After heating the pyrophosphate over a
Bunsen flame, a yellow tinge is generally still observable ; this is due
to the presence of a trace of molybdic acid, which may be completely
driven off by heating over the blowpipe ; the change in weight is, how-
ever, very small, and may almost be neglected. J. K. C.
Examination of Butter. (Dingl poJyt. /., 247, 350—351.)—
For testing butter according to Reichert's method (ibid., 231, 478),
Munier melts the sample on a water-bath, allows the melted mass to
settle, and pours it on a warm filter. 2*5 grams of the filtered butter
are weighed into a flask, and treated with 5 c.c. of a solution contain-
ing; 20 g. caustic potash in 100 c.c. of alcohol (70 per cent.) ; on
warming a soap is formed. The last traces of alcohol are removed
by drawing air through the flask, after which the soap is dissolved
in 50 c.c. water, treated with 20 c.c. dilute phosphoric acid and
distilled, adding a few pieces of pumice to avoid bumping ; 50 c.c.
of the filtered distillate are then titrated with decinormal ammonia
solution. D. B.
Recognition of Suint in Suet and other Pats. By L. Meter
(Dingl pohjt. /., 247, 305— 306).— The author had occasion to
examine suet adulterated with as much as 30 per cent, distilled suint ;
one sample contained nothing but fatty acids from suint, the quantita-
ANALYTICAL CHEMISTRY. , 751
tive determination of glycerol showing only '0"2 per cent. 1 g. of fat
required 169"8 mg., and 1 g. of separated fatty acids 170"8 mg, of
potassium hydroxide for saponification, so that the sample consisted
exclusively of free fatty acids. The fatty acids were separated by
saponification with alcoholic potash-ley, the alcohol being expelled by
evaporation, and the soaps decomposed with sulphuric acid. Their
melting point was 41 "8", solidifying point 40°, whilst the original fat
melted at 42'!°, and solidified at 40°. The presence of cholesterin
contained in the grease of sheep's wool was detected in these samples
in the following manner. The separated fatty acids were saponified
with caustic potash ; the resulting soap was treated with ether, which
extracts cholesterin. The ethereal solution was evaporated and treated
with hydrochloric acid and ferric chloride, when a violet-red colour
changing to blue was obtained, characteristic of cholesterin. For
detecting suint in suet, the latter is saponified, the soap treated with
ether, and the ethereal residue tested for cholesterin. By this method
it is possible to find 5 per cent, of suint mixed with suet or other
fats. D. B.
Examination of Oil-cakes. (Dingl. polyt. J., 247, 351—352.)
— In order to determine whether oil-cake contains mustard seeds.
Dirks recommends the oxidation of the extracted oil of mustard with
an alkaline solution of potassium permanganate, and precipitation of
the sulphuric acid thus formed with barium chloride. Mustard oil
treated in this manner gives 31*1 — 31*6 per cent, sulphur ; 15 grams
oil-cake from black mustard gave 0'4729 barium sulphate, correspond-
ing with 1*34 per cent, mustard oil. Oil-cake from winter rape
yielded 0'17— 0*19 per cent, oil of mustard; the seeds of turnips gave
0*033 — 0*038 per cent., and pressed cake from white mustard seeds
0*018 per cent, mustard oil. D. B.
Microscopic Investigation of Dyed Cotton Fabrics. By R.
Meter (Ber., 16, 455 — 457). — Cotton goods which have been dyed by
means of the albumin process can easily be distinguished from articles
which have been printed with soluble dyes, by means of the microscope.
For example, if a piece of cotton is first treated with a solution of lead
acetate, and afterwards with a chromate, the fibres are uniformly
coloured. But if the goods have been printed with a mixture of pre-
cipitated lead chromate and albumin, and the colour fixed by steaming,
the fibres themselves appear colourless under the microscope, but
patches of coloured albumin are attached to the fibre.
w. c. w.
Estimation of the Reducing Po'wer of Urine, and of the
Extractive Matter which it contains. By Etard and C. Richet
{Gompt. rend., 96, 855 — 858). — In an acid solution, bromine is without
action on urea, creatinine, hippuric acid, and xanthine, but attacks uric
acid and extractive matter. In alkaline solution, bromine acts on all
these compounds, and it is usual to estimate the volume of nitrogen
given off" by this reaction. Since, however, the nitrogenous organic
substances other than urea either give oflP no nitrogen at all, or only a
very small quantity, this method gives no .information as to the total
'752 ABSTRACTS OF CHEMICAL PAPERS.
"amount of organic matter present. Better results are obtained by
estimating the reducing power of these bodies by means of a standard
solution of alkaline hypobromite, which is added in excess, and the
excess determined by means of a standard acid solution of stannous
chloride, potassium iodide and starch being used as indicator. The
difference (which is always considerable) between the reducing action
of the urine on the standard hypobromite and the amount of urea
calculated from the volume of nitrogen given off by the ordinary
method, furnishes some measure of the reducing action of the other
substances in the urine. Titration of an acid solution of the urine by
standard bromine-water, the excess being determined by standard
stannous chloride, gives the amount of uric acid and unoxidised extrac-
tive matter.
The ratio between the reducing action of urine on hypobromite and
its reducing action on bromine- water in acid solution varies greatly
for different individuals, but for the same individual oscillates between
very narrow limits, even during long periods of time. In no case is
it possible to predict the total reducing power of urine from the amount
of urea which it contains. C. H. B.
Technical Chemistry.
A New Photographic Paper. By C. Cros and A. Yeegeraud
(Compt. rend., 96, 254 — 255). — To sensitise the paper, it is steeped in
a bath of 2 grams ammonium dichromate and 15 grams glucose in
100 c.c. water, and dried: the developing solution is 1 gram silver
nitrate, 10 grams acetic acid, and 100 c.c. water. The image is of a
blood-red colour when dried quickly before the fire, deep brown if
dried exposed to the air in bright day- or sun-light, and is blackened by
hydrogen sulphide. Treated with a bath of copper and potassium
sulphites, an intense neutral-black image is obtained. L. T. T.
Preparation and Purification of Carbon for Electric
Lighting. By Jacquelain (Ann. Ghim. Phys. [5], 27, 537—554). —
The author's endeavours have been directed towards the preparation
of carbon having the density and conducting power of gas-carbon
without its earthy and siliceous impurities. To remove these im-
purities, gas-carbon may be submitted to three different processes: —
1. Treatment with dry chlorine gas at a bright red heat for 30
hours. This removes silica, metallic oxides, and hydrogen, and was
the process employed by the author to prepare pure carbon for Dumas'
atomic weight determinations. It is more troublesome on a large
scale.
2. Treatment with fused potash or soda. The alkali must not be
too strong nor the temperature too high ; NaaO with three equiva-
lents of water answers well. An immersion of three hours is gene-
TECHNICAL CHEMISTRY. 753
rally sufficient, after whicli the carbon is washed with water, then with
dilute hydrochloric acid, and finally with water.
3. Immersion in hydrofluoric acid diluted with twice its weight of
water for 24 — 48 hours at a temperature of 15 — 25".
The gas-carbon may be submitted to either of these processes after
being cut into sticks or pencils. In order to restore the carbons,
from which the impurities have been removed, to their original com-
pactness, they are carbonised by being strongly heated for a few hours
in the vapour of some heavy hydrocarbon, a portion of the carbon
from the latter being deposited in the pores.
Pure graphitoid carbon may be prepared directly by passing the
vapour of some heavy hydrocarbon through a fireclay tabe raised to a
temperature of 1000 — 1200° C. Two arrangements of apparatus for
this purpose are described and figured by the author. Hydrocarbons
with high boiling points answer best, and gas tar is the most suit-
able for use on a commercial scale. The author gives a table showing
the comparative results obtained by using purified and unpurified
natural and artificial carbon electrodes for the arc light. The steadi-
ness of the light and durability of the carbons are in direct propor-
tion to their hardness, density, and purity. The best results were
obtained with Siberian graphite (sp. gr. 2"3, whilst gas-carbon is 1'9)
purified by treatment with hydrofluoric acid, by which process the
percentage of ash was reduced from 8*674 and 5*184 to 0*767 and
0*900. J. M. H. M.
Variation of the Amount of Ammonia in Rain-waters. By
A. HouzEAU (Oompt. rend., 96, 259 — 260). — The author points out
that the influence both of light and heat tends to reduce the amount
of ammonia present in waters, and attributes this diminution not to
volatilisation, but to absorption by the organic matter present in the
water. L. T. T.
Preparation and Testing of Cement. (Dingl polyt. /., 247,
257 — 258.) — Roth prepares cement from bauxite by mixing blast fur-
nace slag with the requisite quantity of lime and bauxite, moulding the
mixture into bricks, and burning and grinding the latter. In testing
Portland cement for slag-dust, Heintzel states that the composition
of the cement and impurities, especially blast furnace slag, may vary
as follows : —
Portland cement. Slags.
SiOz 21—25 per cent. 30—35 per cent.
AI2O3 .... 3—8 „ 10—16
Fe^Oa .... 3—4 „ —
FeO — 2—4
Mn203 .... traces —
MnO — traces — 4 „
CaO 58-64 „ 40—50
MgO 1-4 „ 2-6
SO3 1 — 2 „ traces — 1 „
S traces — 0*5 ,, 1 — 2 „
Alkalis .. 1—3 „ 2 „
754 ABSTRACTS OP CHEMICAL PAPERS.
By mixing an average cement with 25 per cent, of average slag, a
mixture of the following composition is obtained : —
SiOa. AI2O3. FeaOaandFeO. MnaOg and MnO. CaO. MgO.
, 25-4 7-4 3-6 O'S 580 3-0
SO3. S. AlkaUfl.
1-4 0-6 2-0
Alfchough the small amount of lime and the comparatively large
percentage of silica, manganese, and sulphur point to the presence of
impurities, the differences in the chemical composition do not sufiBce
to condemn the cement as being adulterated with slag-dust. The
sp. gr. of Portland cement is less than that of slag-dust ; 1 litre
cement shot loosely into the measure weighs 1288 grams, and when
shaken down, 1840 grams, slag-dust 1100 and 1500 grams respec-
tively. Under the microscope, Portland cement forms porous lava-
like grey granules, slag- dust vitreous sharp- edged white or greenish
granules. Pure Portland cement extemporaneously mixed with 33*3
per cent, of its own weight of water forms a liquid paste, whilst slag-
dust requires 40 — 45 per cent.
In conclusion, it is stated that unless all the above-mentioned
points are considered, it is impossible to recognise with certainty the
nature of the impurity. D. B.
Hydraulic Silica and its Functions in Hydraulic Cements.
By E. Landein (Gompt. rend., 96, 156—158 and 379— 380).— If a
solution of potassium silicate be decomposed with an acid, and the
precipitate well washed and ignited at a dull red heat, pure silica, in-
soluble in acids, and to which the author gives the name hydraulic
silica, is obtained. This silica, when mixed with two or three times
its weight of lime, has the property of setting under water. In the
hydraulic cement thus obtained, the silica becomes again soluble in
acids, the quantity becoming soluble increasing with the duration of
immersion. Quartz or any other hard substance may be added to
the mixture without affecting its setting power. This property of the
silica thus obtained is not due to its fine state of division, as the silica
obtained in the preparation of hydrofluosilicic acid, although an
equally fine powder, does not possess this power. Hydraulic silica
plays the part of a puzzolana, removing lime from its aqueous solution,
and the author considers that it is to the presence of this silica that
puzzolanas owe this latter property. The author has detected the
presence of hydraulic silica in many natural cements. Calcium
aluminate when present in cements, although slowly dissolved by
water, and thus not addinpf much to the permanent hardness of hy-
draulic cements, aids very considerably in the setting process by pro-
tecting the cement from the too rapid action of the water.
The second paper is a reply to Le Chatelier (see next Abstract),
upholding the author's own claims to priority, especiallv with regard to
the followiug points : — That hydraulic silica does not owe its peculiar
properties to its fine state of division ; that although insoluble in
acids it is slowly acted on by lime ; that it. possesses the property of
TECHNICAL CHEMISTRY. 755
removing lime from water; and that the puzzolanas owe their
hydraulic properties to its presence. L. T. T.
Hydraulic Silica. By H. Le Chatelter (Compt. rend., 96,
255 — 256). — The author contends that most of Landrin's results (see
last Abstract) have been anticipated by Yicat, de Candemberg, Rivot,
Berthier, &c. L. T. T.
Relative Oxidisability of Cast and Malleable Iron and
Steel. By Gruner (Compt. rend., 96, 195— 197).— The author has
tried the oxidising action of weak acid, sea- water, and moist air on
various kinds of steel and iron. The experiments were made on
plates 1 decimetre square, both surfaces being exposed. The plates
were weighed carefully before and after the experiments. The loss of
weight is given in grams for the 2 square decimeters of surface of the
plates.
In moist air, ordinary steel lost 3 — 4 grams in eight days ; that con-
taining chromium lost more ; that containing tungsten less. All
kinds of cast iron were less oxidised than steels, white specular iron
(containing 20 per cent, manganese) losing least.
In sea-water, cast iron is more strongly attacked than steel, specular
iron being most acted on. In nine days, steel lost 1 — 2 grams;
specular iron, 7 grams ; Bessemer black cast iron, 3*5 grams ; and cast
iron containing phosphorus, 5 grams. Tempered steel is less affected
than annealed ; soft steels than those containing • manganese or
chromium ; and those containing tungsten less than ordinary steels
with the same percentage of carbon. These results show that the
use of iron or steel containing manganese should be avoided for coating
of vessels.
In acidulated- water (0*5 per acid), grey cast iron dissolves more and
white specular iron less rapidly than steel. In three days (the acid
being renewed each day), Bessemer black cast iron (3 — 4 per cent,
manganese and 1 — 2 per cent, silicon) lost 15'9 grams ; grey cast iron
containing phosphorus, 8"9 ; white specular iron, 1*5; pure cast iron,
0*8; soft steel, O'l — 0*4 ; soft carburetted steels, 0*8 — I'l ; manganese
steel, annealed hard, 1'6 ; and the same steel tempered, 4'1 grams.
It is thus clear that the action of acidulated water on irons and
steels does not give a true measure of their power of resisting the
corroding action of the air and sea-water. L. T. T.
Plastering of Wines ; Rapid Estimation of Cream of Tartar.
By P. PiCHARD (Compt. rend., 96, 792 — 793). — In a saturated
aqueous or alcoholic solution of potassium hydrogen tartrate con•^
taining potassium hydrogen sulphate, free tartaric acid can only
liberate a quantity of sulphurdc acid, not exceeding one-twelfth
of the total amount. In similar solutions, potassium sulphate and
chloride precipitate potassium hydrogen tartrate, the amount pre-
cipitated increasing with the quantities of the potassium salts.
The chloride acts more energetically than the sulphate, precipitation
being complete when the amount of the latter approaches saturation.
This property may be utilised for the rapid estimation of cream of
tartar in ordinary non-plastered wines. Sodium chloride produces no
756 ABSTRACTS OF CHEMICAL PAPERS.
precipitate nnder similar conditions, and consequently the addition of
sea-salt or sea- water to wines does not diminish the amount of cream
of tartar which they contain. Calcium tartrate is less soluble in
aqueous or alcoholic solutions saturated with potassium hydrogen
tartrate than in the same solutions from which this latter salt has
been removed. In an aqueous or alcoholic solution, equivalent quan-
tities of free sulphuric acid and potassium hydrogen sulphate dissolve
equal quantities of calcium tartrate. The addition of an excess of
calcium tartrate to a saturated aqueous or alcoholic solution of potas-
sium hydrogen tartrate containing potassium hydrogen sulphate,
converts a portion of the latter salt into normal sulphate, and pro-
duces a precipitate of cream of tartar. The true cause of the
diminution of cream of tartar in plastered wines is the impossibility
of saturating with this salt a liquid containing a certain quantity of
potassium sulphate. C. H. B.
Influence of Barley on the Fermentation Process. (Dingl.
polyt. J"., 247, 350). — According to Thausing, the observation of the
important part which a certain amount of proteids in barley plays is
of comparatively recent origin. E-ichness in starch, conditions pro-
ductiveness of barley, and in order to obtain a wort which will form a
good nutrient for yeast, the presence of a sufficient quantity of
albuminoids is absolutely necessary. During the germination of
barley, the proteids act on the starch, and from them the peptones are
formed. Barley containing little proteid matter gives malt, the starch
in which it is difficult to convert into sugar. According to Lintner,
barley should contain at least 10'5 per cent, proteids to produce a good
beverage. D. B.
Defecation of Beet-juice with Strontium Saccharate. {Dingl.
jpolyt. /., 247, 304 — 805.) — For defecating beet-juice or other
saccharine juice, Scheibler uses strontium saccharate, separated at a
boiling heat, or the solution out of which strontium hydroxide has
separated on cooling. For the saturation, carbonic anhydride is em-
ployed. The separated sludge is made into bricks with sawdust or
small coal, burnt, and the strontium oxide recovered, or it is sub-
jected to dry distillation, ammonia, tar, and combustible gases being
obtained. From the solution, the strontium hydroxide is separated in
the usual manner, the insoluble residue being treated with carbo-
nated alkalis for the removal of phosphoric acid, and converted into
strontium oxide by ignition. In order to prevent the loss of sub-
stances valuable as manures, it is preferable to treat the juice first
with lime, lime sludge manure being produced, and then to defecate
the filtrate with strontium saccharate. D. B.
Action of Certain Metals on Oils. By A. Livache (Compt,
reiid., 96, 260 — 263). — Chevreul has shown that under certain cir-
cumstances metals have a considerable influence on the oxidation of
oils, and that when spread over the surface of a plate of lead, linseed
oil becomes rapidly siccative. The author has investigated the action
on oils of lead, copper, and tin when in a state of very fine division.
TECHNICAL OHEmSTRY. 757
The lead used was precipitated from its saline solution by zinc, washed
with water, alcohol and ether, and dried in a vacuum. Moistened with
oil and exposed to air, an increase of weight rapidly took place, the
increase being greater and more rapid the more siccative the oil em-
ployed, and also approximately proportional (except in the case of
cotton-seed oil) to the increase of weight of their respective fatty
acids when exposed to the air for a long time. This will be seen from
the following table : —
Increase of weight of
Increase of weight. corresponding fatty acid
f " V, exposed to the air for
Oil in contact After two days. After seven days. eight months,
with lead. per cent. per cent. per cent.
Linseed 14-3 — ll'O
Walnut 7-9 — G'O
Poppy 6-8 — 3-7
Cotton-seed 5*9 — O'S
Beech-nut 4-3 — 2*6
Colza — 2-9 2-6
Sesame — 2*4 2*0
Earth-nut — I'S I'S
Eape-seed — 2*9 0*9
Olive — 17 07
That this action is due to the metal and not to the greater surface
exposed to the air, was proved by substituting other powdered sub-
stances for lead, when no increase of action took place, and also by
conducting the experiments with lead out of contact with the air,
when the oil was rendered equally siccative. Cloetz has shown that
all the glycerol is destroyed in the preparation of drying oils. The
author finds that in contact with glycerol precipitated lead becomes
oxidised at the expense of the glycerol, and passes into solution. The
drying oil prepared by the action of lead is much less coloured than
that prepared in the ordinary way, and the author believes that this
process might be advantageously used commercially in the prepara-
tion of drying oils, and^in the detection of adulteration.
L. T. T.
Investigations on Milk. {Dingl. polyt. /., 247, 306—307.)—
Vieth found that when milk is kept for two days at 10 — 15°, it lost
0*3 per cent, dry substance; at 19 — 21° the loss was equal to 078 per
cent., whilst in four days the loss amounted to I'O and 1*92 per cent,
respectively. This loss is probably due to alcoholic fermentation ; it
has not, however, been proved whether and to what extent the other
constituents in milk take part in this rapid decomposition. Referring
to the changes which milk undergoes whilst it is in the hands of the
seller, Vieth states that for all practical purposes the alteration in the
percentage of fat is too small to be taken into account. D. B.
Scherft's Preserved Milk. By W. Fleischmann and A. Moegen
(Landw. Versuchs.-Stat., 28, 321 — 332).— Scherff's method of pre-
758
ABSTRACTS OF CHEMICAL PAPERS.
serving milk consists in heating it under two to four atmospheres
pressure at 100 — 120° for one or two hours. Prepared in this way,
it diflfers from fresh milk in being mach less amenable to the action
of rennet, and on being acidified or becoming sour it does not yield a
coagulum consisting of large compact lumps, but a mass of loose
finely divided flakes. This difference in behaviour has been explained
by assuming that during the heating process part of the albumin has
undergone a change, and been converted into peptone. In order to
ascertain the accuracy of this view, the various samples of ordinary
and prepared milk were made use of, and the amount of albumin
determined in each by Ritthausen's method, both before and after
treatment with pepsin ; the filtrates were also examined for peptones
after coagulation with acetic acid.
The experiments showed that the albuminoi'ds in milk do not
undergo any decomposition when treated by Scherff *s process ; no
bodies of a peptoid character being found in milk' thus prepared : the
latter seems, however, to contain albumin in an already coagulated
state, and casein which cannot be curdled by rennet. The albuminoids
in prepared milk are also less easily acted on by pepsin than those of
fresh milk. J. K. C.
Preservation of Milk. (Dingl. polyt. J., 247, 376—378.)—
According to A. Mayer sourness is accelerated when milk is heated at
45°, but retarded if heated for 24 hours at 55° ; the milk, however,
assumes a burnt taste. Milk treated with boric acid, common salt
or salicylic acid, and preserved at 16°, behaved in the following
manner : —
Sourness after Coagulation after
With 0-02 per
cent
boric acid
30 horn's
47 hours.
„ 0-04
jj
. 35 ,
47 „
„ 0-06
))
. 56 ,
60 „
„ 0-02
salt
. 26 ,
30 „
„ 0-04
26
32
„ 0-06
)5 •• *•
))
. 26
34 „
„ 0-02
>>
salicylic acid .
. 33
58 „
. „ 0-04
55
. 47
82 „
„ 0-06
55
. 144
does not coagulate
after eight days.
Without addit]
Lon .
25 ,
J
28 hours.
Mayer preserves milk by adding 0-08 per cent, sodium benzoate or
0*04 per cent, boric acid, warming at 50° for three houi«, and trans-
ferring the milk to closed vessels. According to Biedert milk can be
preserved for a long time by boiling it for two hours at 100° with
exclusion of air.
Meissl (ibid., 245, 142) mentions that the changes undergone by
milk on keeping are due to tbe long-continued interaction of the sepa-
rate milk constituents, neither decay nor fermentation being observable.
Loew (Ber.j 15, 1482) rejects tbis explanation, because when previously
heated at 120° for some time, milk remains permanently unchanged.
TECHNICAL CHEMISTRY. 759
For tlie preparation of condensed milk, it is recommended to use
partially creamed milk, whicli decomposes less readily. D. B.
Preparation of Blue and Violet Dye-stuflfs. (Bingl. 'polyt. /.,
247, 396.)— According to Casella and Co. (Ger. Pat. 20,850), 'indo-
phenol is prepared by warming a-bromonaphbhol on a water-bath
with an aqueous solution of dimethylparaphenylendiamine, adding
carbonated or caustic soda to the mixture so that the liquid remains
alkaline. A blue precipitate is formed, which is separated by filtra-
tion. The filtrate contains leuco-indophenol, and yields farther quan-
tities of indophenol by introducing air into the solution or adding
oxidising agents. The various processes for preparing indophenol
were applied to the following phenols : Orthocresol, paracresol, resor-
cinol, orcinol, ^-naphthol ; and the diamines, paraphenylendiamine,
monethylparaphenylendiamine, diethylparaphenylendiamine (symme-
trical), dimethylparaphenylendiamine, mono- and di-isobutylpara-
phenylendiamine, mono- and di-amylparaphenylendiamine, parato-
luylendiamine, xylendiamine, and diethylparaphenylendiamine (sym-
metrical) ; the colouring matters formed did not, however, supersede
the typical products in fineness, yield, or cheapness. D. B.
A New Method of Manufacturing Paper-pulp. By G. Arch-
bold (Ber., 16, 350 — 351). — Straw or wood is digested for 12 hours in
dilute milk of lime ; it is then saturated with sulphur dioxide under a
pressure of 4 atmospheres, which effects a complete disintegration of
the mass in one or two hours. The mass is washed with water and
subjected under pressure to the action of 3 per cent, of calcium chlo-
ride and 0"5 per cent, of aluminium sulphate dissolved in a small
quantity of water. After a final washing, the product resembles
cotton wool in appearance, and can be used for the manufacture of the
finest quality of paper. W. C. W.
Cause of the Acid Reaction exhibited by some Kinds of
Paper. By Haerling {Bingl. polyt. /., 247, 382).— The author
rejects Feichtinger's statement (ibid.^ 247, 218) that all papers sized
with resin contain free sulphuric acid, as the method used for sizing
does not admit of the presence of free sulphuric acid in paper. The
method consists in adding resin-soap, prepared by dissolving resin in
soda-ley, to the paper pulp and precipitating with normal aluminium
sulphate, so that the precipitate of alumina in combination with resin
forms the size. In the presence of free acid, resin only would be
precipitated, and the paper not sized, but merely impregnated with
resin particles which would render it useless for writing or printing
purposes. Feichtinger admits the presence of aluminium sulphate,
Wt appears unable to prove, without further investigation, whether
the sulphate exists in paper as normal or basic salt. The author
mentions that this question is answered by the above method, for
when normal aluminium sulphate is precipitated with an excess of
sodium hydroxide, a basic precipitate must be formed. Moreover,
760 ABSTRACTS OF CHEMICAL PAPERS.
the assumption of the simnltaneons presence of free sulphuric acid
and basic aluminium salt contradicts the laws of chemistry.
D. B.
Waterproof Paint for Stones, &c. (Dingl. pol/yt J., 247, 396.)
— This paint is prepared by fusing equal parts of aluminium palmitate
and colophony, or mixing aluminium palmitate with wax, and dissolv-
ing in caustic soda and water. A solution resembling soap is formed,
which is used for wall painting, &c. After drying, the paint is
washed with a weak aqueous solution of aluminium sulphate, which
renders it insoluble. D. B.
761
General and Physical Chemistry.
Spectra of Carbon Compounds. By K. Wesendoxck (Ann.
PJiijs. Chem., 17, 427 — 467). — The paper describes the spectra pro-
duced by electrical discharges through the rarefied vapours of certain
compounds of carbon and hydrogen, or of these elements combined
with nitrogen and oxygen. Common to all of these compounds are
two quite different kinds of spectra, the difference having relation
to the nature of the electrical discharge. Tables of the author's de-
terminations of the positions of the several lines and bands attributed
to carbon are given in the paper. He considers that his researches go
to prove that the spark spectrum of bands described by Swan is due
to carbon itself separated from its compounds in a sufficient quantity
and at a sufficiently high temperature, for which it is necessary that a
comparatively large quantity of electricity shall pass each unit of sec-
tion in the unit of time. On the other hand, the channelled spectrum
(called by Watts the second) must be ascribed to oxide of carbon.
The bands ^ and 0 of Watts are due to a nitrogen -compound of car-
bon, for they never occur except when nitrogen is present.
R. R.
Observations of Infra-red Spectra by Means of Phos-
phorescence. By H. Becquerel (Gompt. rend., 96, 1215—1218). —
The author has continued his observations of the infra-red region of
various spectra by projecting them on phosphorescent substances
{Comjpt. rend., 96). The solar spectrum shows four broad telluric
bands, the mean wave-lengths of which in ten-millionths are 9300,
10,820, 12,300, and 14,700. The last band was observed by Fizeau
and Foucault in 1847. When the sun is low on the horizon, the band
at 9300 is very broad and dark ; the bands at 10,820 and 12,300 are
also intense, and the interval between them is less luminous. The
variations in the band 14,700 are difficult to observe. Near A are the
five bands observed by Brewster and Gladstone, viz., 7620 — 7646,
7850—7900, 7995—8020, 8100—8140, and 8240—8310. The varia-
tions in this region and in the luminous spectrum are less marked
than those of the broad bands in the infra-red.
Water. — With a layer of water 1 mm. in thickness, there is absorp-
tion from the extreme infra-red to about wave-length 13,000, and the
bands are visible at 9300 and 12,300. With greater thicknesses of
water, the bands at 9300 and 12,300 become broader and more intense,
and with a thickness of 1 cm. absorption extends from the extreme
infra-red up to wave-length 10,820, where it terminates sharply, and
the band at 9300 is' still visible. A layer of water 0*5 m. in thickness
gives general absorption of the infra-red up to wave-length 9300.
Earth-metals. — The absorption-spectrum of solutions of didymium
gives in the infra-red three intense bands of wave-lengths 7305 —
7560, 7820—8190, and 8720—8900. With very dilute solutions the
bands are narrower, and have mean wave-lengths of 7430, 7960,
VOL. XLIY. 3 /
762 ABSTRACTS OF CHEMICAL PAPERS.
and 8720. The solutions examined showed other bands in addition
to those of water. Two intense bands at about 10,100 and 11,800
respectively appear to be due to samarium, whilst the origin of two
other weaker bands at 8400 and 9100 is uncertain. Solutions of
erbium and holraiura free from didymium show the band at 8110
attributed to holmium by Soret, and another weaker band at 8900.
Certain solutions of copper salts absorb the whole of the infra-red
region. Nickel chloride absorbs the visible red, but is transparent
to that portion of the infra-red which is not absorbed by water.
The author has also applied this method to the study of radiation-
spectra, and will describe his results in a subsequent paper.
C. H. B.
Lockyer's Dissociation Theory. By W. Vogel (Ann. Fhys.
Chem. [2], 19, 284 — 287). — The author has on a former occasion
taken exception to Lockyer's dissociation theory, and has pointed out
that photographs bring out a fifth hydrogen line very close to the
Fraunhofer calcium line H'. This line was probably confounded by
Huggins with its neighbouring calcium line, and its presence, taken in
connection with the absence of the calcium line H" in the photographs
of the spectra of the so-called white stars, was one of the principal
arguments brought forward by Lockyer. Attention is also drawn to
the researches of Liveing and Dewar, which have conclusively proved
that certain magnesium and calcium lines are brought out only in the
presence of some foreign substance, hydrogen, for example (compare
Abstracts, 1882, 249—252, 253—255) ; therefore any arguments
drawn from the presence of certain iron lines in sun spots and their
absence in the protuberances cannot be regarded as conclusive, in that
the former only may afford a medium for the development of the
lines. Lastly, the author quotes experiments of Hagenbach on the
absorption-spectrum of chlorophyll, and of Kundt on the absorption-
spectrum of gases, which have established the fact that lines are under
certain conditions displaced in the direction of the red end of the
spectrum. The gaseous medium of the sun's envelope might effect
such a displacement of the iron lines, and cause the conclusions drawn
from the observations to be erroneous. Y. H. V.
Molecular Refraction. By E. Wiedemann (Ann. Phys. Chem.,
17, 577 — 580). — The mathematical discussion of the refractive indices
of the several sulphur substitution-derivatives of ethyl carbonate,
003(02115)2, shows that with sulphur, as with oxygen and carbon,
when the several bonds of affinity are engaged by the same carbon-
atom, there is a greater atomic refraction than when they are divided
amongst different carbon-atoms. R. E-.
Variation of the Indices of Refraction of Water and Quartz
with the Temperature. By H. Dqfet {Compt. rend., 96, 1221—
1224). — A transparent solid with parallel faces is placed in a liquid
contained in a vessel with rectangular sides. A beam of parallel
rays is allowed to pass through the liquid, and half of the beam passe ^
through the solid from a slit of suitable width. When the trans-
mitted beam is decomposed by a prism, Talbot's fringes are perceived.
GEXERxiL AND PHYSICAL CHEMISTRY. 763
The position of these fringes varies with the temperature, and from
the variations the difference between the refractive indices of the
solid and liquid at different temperatures can be deduced. Since
the refractive index of the glass from. Saint Gobain does not sensibly
vary with the temperature, this glass was employed for determining
the variations in the refractive index of water, and by substituting
for the glass a plate of quartz, the variations in the index of the latter
could then be determined. The number obtained for the variation of
the ordinary index of quartz between 20° and 40^ was — 0"0000050, a
number almost identical with that obtained by Fizeau, 0'0000055,
between slightly different limits of temperature. C H. B,
Fluorescence of Iodine Vapour. By E. Lommel (A7in.
Phys. Ghem. [2], 19, 356 — 358). — The phenomenon of fluorescence
has hitherto been observed only with liquid and solid substances. The
author has examined several highly coloured vapours, as nitrogen
peroxide, chlorine, bromine, and sulphur, but without result. Iodine
vapour, however, displays a remarkable green fluorescence, which is
best observed when sunlight, concentrated by a lens, is thrown on a
glass globe filled with not too dense vapours of iodine, and the emerg-
ing beam filtered through green glass. If blue glass be used the
fluorescence will be very feeble, and it disappears altogether if red
glass is used. The fluorescent spectrum displays itself in the red,
orange, yellow, and green from the line 35 to the line 60 in the Bunsen
scale, and is most marked in the orange. The author further estab-
lished that iodine vapour does not absorb the ultra-violet rays.
V. H. V
Theory of Phosphorescence. By B. Radziszewski (Ber., 16,
597— 601).— The author has shown {Aimalen, 203, 305) that the
phosphorescence of organic bodies is produced by the action of active
oxygen in alkaline solution. He divides such phosphorescent bodies
into two groups, the first of which contains hydrocarbons {e.g., the
terpenes, &c.) which phosphoresce on the addition of an alkali,
whilst the second group contains aldehydes and bodies which yield
aldehydes when treated with alkalis. In the case of group I the
active oxygen is produced by the action of sunlight, and in the case
of group II by the decomposition of the aldehyde by the alkali. The
phosphorescence of fats is probably attributable to the same cause,
namely, the decomposition of the acids C»I12m_202 into salts of fatty
acids and aldehydes. The author is of opinion that phosphorescence
in organisms is also due to the same cause, and in favour of this view
he mentions the presence of an alkaline basic substance and of a fatty
body in such organisms. He also shows the presence of active
oxygen in such organisms (Felagia noctiluca) by placing them on
porous plates moistened with potassium iodide and starch-paste, and
with tincture of guaiacum. A. K. M.
Researches on Statical Electricity. By Y. Dvorak (An7i.
Ghem. Phys. [2], 19, 325— 340).— The author has made a series of
observations on the electric discharge of Leyden batteries consisting
of glass plates between thin layers of silver. The form of this dis-
3/ 2
7()4 ABSTRACTS OP CHEMICAL PAPERS.
chargo ie dependent not only on the thickness of the silver layer, but
also on the intensity of the charge and the distance of the electrodes.
The first part of the discharge consists of a large number of sharply-
defined ripples, disposed concentrically around the electrode ; the second
portion consists of thin branches containing only traces of silver, and
in the third portion, which is colourless and transparent, silver is
wholly absent. If the silver be coated by a layer of some insulating
material, as varnish or oil, the ripples are generally absent, and the
radiating branches diverge immediately from the electrodes ; the
colour of the discharge is golden or even brown. If the varnish layer
be made too thick the glass plate is frequently shattered by the dis-
charge. On substituting thin layers of graphite for the silver the
discharge took a different form, the ripples were perpendicular to the
direction of the discharge. Layers of a mixture of a pulverulent
conductor, as finely divided graphite, with stearic acid, give a dis-
charge, the form of which the author compares to a series of
needles inserted in the positive pole; olive oil, turpentine, gave
similar discharges.
The author on examination considers Riess's theory as regards the
electric action of flames untenable. According to Riess two different
cases of electrostatic action of flames must be distinguished — first, of
substances which only glimmer, as carbon ; secondly, of inflammable
substances, which form a conducting column of hot gas. In the first
case, the electrostatic action will arise from a series of solid points,
but in the second case from a series of gaseous points.
The author quotes experiments to demonstrate that in the first
case the action is derived from a series of gaseous points in a heated
column. He further proves that the electric repulsions, normal to
the surface of a gaseous column, scatter the electrified particles in all
directions, so that the whole environment of the flame is filled with
electrified particles. This fact offers an explanation of the well-
known phenomena of the removal of electricity from an electrified
body and the charge of a conductor by means of a flame.
V. H. V.
The Units of Electricity and Magnetism. By R. Clausiots
(Ann. Phys. GTiem., 17, 713 — 719). — The author expresses the relation^,
between the unit of magnetism and the electrostatic and electro-
dynamic units respectively by the following general equations, which
are independent of the units of measurement : —
[ma] = [e,LT-i]
[m,] = [e,LT-i]. R. R.
Electromotive Force of certain Galvanic Combinations.
By F. Braun (Ann. PJujs. Chem., 17, 593— 642).— Full details are
given in this paper of measurements of the electromotive force of
galvanic elements formed of dry chlorine, bromine, or iodine, with
platinum for one metal, and zinc, lead, silver, mercury, or aluminium
for the other, also with carbon opposed to silver or platinum. The
experiments furnish data for the determination of the fraction of the
total energy of combination that is converted into current energy in
GENERAL AND PHYSICAL CHEMISTRY. 765
the several cliemical processes concerned, which in the second part of
the paper include cases where the electrolyte consists of aqueous
solutions. The author calls in question the validity of Exner's
experiments and views on the relation between chemical actions and
the production of electricity. R. R.
Reply to the Observations of Reynier on Bichromate
Batteries. By Trouve {Gompt. rend., 96, 1048).— The author
corrects some of the numbers given in his paper (this vol., 700). The
consumption of zinc by the battery of 12 elements was 0'912 kilo., or
double the amount given in the paper, which is the value for
6 elements. Each battery of 6 elements had an intensity of 18 amperes
in short circuit, with a resistance of 0*0016 ohm for each element, when
the solutions were fresh. The E.M.F. given, 1*9 vols., is the value
for one element. C. H. B.
Substitution of Hydrogen Peroxide for Nitric Acid in
Galvanic Batteries. By A. Konig (Ann. Phys. Ghem., 17, 347 —
349). — The author has examined the electromotive force and other
conditions of Grove and Buiisen cells in which a 2'25 per cent, solu-
tion of hydrogen peroxide replaced the nitric acid, as proposed by
Landolt. Their electromotive force is less than that of the ordinary
cells, and their internal resistance four to five times greater, when
the hydrogen peroxide solution is not acidulated ; when it is acidu-
lated, the peroxide is much more quickly consumed. Considering the
present cost of the hydrogen peroxide solution, the author believes that
Landolt's proposal cannot be adopted advantageously. R. R.
Secondary Batteries. By G. F. Barker (Chem. News, 47, 196 —
199). — After a sketch of the history of secondary batteries from the
time of Gautherot, 1801, until the present day, the author proceeds
to explain the construction, the theory, and the chemistry of Plante's
and Faure's batteries, and points out that the latter differs from the
•former in that the lead oxide is " put on " and not formed on, thus
saving time. The power stored in these batteries is represented
by the peroxide formed ; the force obtained is never equal to the
theoretical quantity on account of various interfering influences, su'.sh
as difi'usion, counter-currents set up by the formation of secondary pro-
ducts, e.g., lead sulphate, from the action of the sulphuric acid upon
both the metallic kad and the oxide ; this local action is always going
on. A great detect in batteries of secondary cells, is the inequality of
action and varying storage capacity of the individual cells, and there-
fore care should be taken not to use weak or exhausted charges along
with strong fresh ones. Plante's battery is less liable to local action,
and is more permanent than Faure's. The author describes the
charging of these batteries by means of a dynamo and also a "cut
out " apparatus, which consists of a coil with a moveable core, which,
when the current flows, is drawn in, and presses on a spring, which
then makes the contact between the machine and the secondary
batteries ; if, however, the current from the dynamo becomes weaker
than that from the batteries the reverse action takes place, the spring
766 ABSTRACTS OF CHEMICAL PAPERS.
pushes back tlie core, and the circuit is broken. The secondary
battery is a useful regulator in electrical lighting, for if a battery of
sufficient electromotive force be placed in multiple circuit with the
machine and lamps, it acts as an equaliser, and destroys entirely
pulsations due to inequalities in the working of the motive power;
and should the latter fail altogether, the light would still be supplied
from the stored force of the batteries. The average electromotive
force of a single cell, in the author's battery of 32 cells, was about
2 volts. D A. L.
Electric Researches. By C. Fromme (Ann. Phijs. Chem. [2], 19,
300 — 319). — The author was led to suspect that the peculiar pheno-
mena observed when platinum is the positive pole in a chromic or
nitric acid battery, were possibly due to the property of this metal of
absorbing and of condensing hydrogen (this vol., p. 6*37). He has
accordingly exa>mined the electric properties of platinum and palladium
when containing hydrogen.
Before the experiment, the palladium was freed from traces of oxide
and of hydrogen; the measurements of E.M.F. were made with open
circuit. The ratio of the E.M.F. of the Zn-Pt to the Zn-Pd element
was found to be 1 : 0*93 i.
The first form of the experiment adopted to determine the electric
properties of hydrogenised platinum and palladium, consisted in intro-
ducing the metals into sulphuric acid saturated with hydrogen ; under
these conditions the E.M.F. of the Pt | H2SO4 element had a constant
value of 0'71 Daniell, while that of the Pd | H2SO4 element was at
first 0"92 Daniell, and then it slowly decreased. The difference in
behaviour the author explains by the greater readiness with which
platinum condenses hydrogen on its exterior surface, while palladium
absorbs the hydrogen into its interior.
In other experiments, the metals saturated with hydrogen were
introduced into sulphuric acid, free from the gas ; the E.M.F. of the
combination Zn | H2SO4 | Pt was about 18 per cent, less than the same
combination with the pure metal, after eight minutes the difference,
was only 8 per cent. In the case of palladium the E.M.F., after a
polarisation of short duration, reaches a minimum value of 0"75 Daniell.
The author further examined with a rheostat the E.M.F. of the
combinations Zn | H2SO4 | Pt and Zn | H2SO4 | Pd (the acid and the
metals being free from hydrogen), and established that the relation of
the E.M.F. of Pt and Pd decreased from 1'07, and then increased to 1*14;
when the resistance decreased from 00 to 0 ; if the resistance of the
rheostat be 00, then with greater resistance in the circuit the E.M.F.
of the Pd element, but with less resistance the E.M.F. of the Pt element
is the greater.
The author then proceeds to offer an explanation of the phenomena
of the variation of the E.M.F. in the chromic and nitric acid batteries ;
the well-known property of palladium of absorbing hydrogen is suffi-
cient to account for these variations, but in the case of platinum the
evidence is not so clear. When a Grove's element is first closed, a
layer of hydrogen gas appears at the surface of the metal, but it sub-
sequently disappears ; this hydrogen is subject to two opposing forces,
GENERAL AND PHYSICAL CHEMISTRY. 767
tlie one from the nitric acid tending to oxidise tlie hydrogen, the other
from the platinum tending to condense the gas upon the surface of
the metal, and of absorbing it into its interior. If at the outset the
platinum contains no hydrogen, then the latter force preponderates,
and to a greater extent, the more dilute the acid, and the greater the
intensity. With a greater concentration of acid, or with less intensity
of current, these conditions are reversed. Sometimes the platinum
condenses a portion of the hydrogen, while another portion is oxidised
by the acid, and as a necessary consequence the E.M.F. falls ; when it
reaches a minimum then the thickness of the hydrogen layer no longer
increases, and all the gas is oxidised by the acid. As soon as the
hydrogen condensed on the surface begins to combine with the plati-
num molecules on the surface of the metal, then the E.M.F. increases
in proportion as the attraction of the hydrogen for the platinum
decreases, while that of the hydrogen for the oxygen increases. The
E.M.F. never attains its former value, on account of the hydrogen
absorbed by and combined with the platinum. During the opening of
the circuit the E.M.F. suddenly rises until it reaches a maximum,
while the hydrogen on the surface of the metal is oxidised, and the
combined hydrogen is separated off. Shaking the platinum causes the
hydrogen to be given off from its surface, while a rise of temperature
of the acid diminishes the evolution of the oxygen ; the effects pro-
duced by these changes in the conditions will act in an opposite direc-
tion. The similar phenomena observed in the chromic acid battery
cannot be attributed entirely to the absorptive power of platinuni for
hydrogen. The author supposes that the chromium sesquioxide, the
product of the oxidation of the hydrogen by the chromic acid, forms
a compound with the platinum ; this supposition is not based on any
facts, but it appears to the author that no other explanation is suffi-
cient. When the combination Zn | H2SO4 | H2Cr04 | Pt is closed a
portion of hydrogen is oxidised, while another portion, the quantity
of which is dependent on the intensity of the current, is taken up by
the platinum, as no hydrogen is evolved in the free state. The chro-
mium sesquioxide partly combines with the sulphuric acid, and partly
forms a combination with the platinum, and this latter causes the
decrease of the E.M.F., which again increases when the evolved hydro-
gen turns out the chromium sesquioxide, and in its turn combines
with the platinum. V. H. V.
Researches on the Heat Changes at the Poles of a Volta-
meter. By E. Edlund (Ann. Phys. Chem. [2], 19, 287— 299).— In
the year 1869, the author propounded the view that when a current
passes through an electromotor in the same direction as that of tlie
electromotor, a quantity of heat disappears proportional to the pro-
duct of the E.M.F. by the intensity of the current ; conversely if the
current is in the opposite direction, an equal quantity of heat is pro-
duced. If in a closed circuit a current is formed of one or more E.M.Fs.,
then these forces destroy a quantity of heat equal to the sum of the
heats caused by the resistance of the circuit. The total heat produc-
tion of the current is therefore nU^ inasmuch as on the passage of the
current through the circuit an amount of heat is produced equal
768" ABSTRACTS OF CHEMICAL PAPERS.
to iliat required by the E.M.F. Sir William Thomson, however,
considers that the sum of the heat evolved by the resistance is equal
to the quantity of heat produced by the chemical changes within the
battery ; but if the author's view be accepted these quantities bear no
intimate relation to one another. The author has carried on experi-
mental investigations on this point, and has succeeded not only in
establishing that his proposition satisfactorily explains the observed
phenomena, but also in some cases he has calculated the value of the
heat changes. His work has received further confirmation at the
hands of J. Thomsen, Braun, and Hoorveg. In the present communi-
cation, the author proposes a method by which it is possible to decide
whether the heat consumed by the E.M.F. is greater or less than that
evolved by the chemical changes, without a separate estimation of the
latter. Salts of copper, zinc, silver, cadmium, and lead were used as
electrolytes, and the electrodes were of the same metal as that present
in the salt. Taking for example copper sulphate with electrodes of
copper, and assuming a current of intensity i passed through, then
the heat evolved from the resistance of the liquid is gi^^ where g
is a constant. At the anode, copper sulphate is formed, and an
amount of heat required, which can be expressed by ki, where h is
a constant. But as the anode is the seat of an E.M.F., a quantity
of heat is consumed, expressed by ei where e is the E.M.F. At
the kathode, where copper is separated, there is a heat absorp-
tion equal to —hi, and therefore the sum of the heat changes at tlie
anode is equal to gi^ + hi — ei, and at the kathode, gi? — ki + ei. In
experiment gi^ must be eliminated, and the reading of the instrument
made dependent on the difference between ki and ei, and the current
must pass through the electrolyte only for a short time, in order to
prevent any marked variation in the neighbourhood of the electrode.
If the current be passed through an electrode A, then the rise of tem-
perature at the point of junction with the circuit is equal to
f{gi^ + ki — ei), where / is a constant, and at B is f{gi^ — ki + ei)
where/' is another constant. If the rise of temperature is not the
same in both cases, then the swing of the galvanometer is proportional to
the difference between them, and so/(^i* + ki — ei)—f{gi^—ki -f ei) = a.
If the current be reversed, so that B is the positive pole, then there is
a different swing b in the galvanometer, &of(gi^ + ki — ei) ~f(gi^ —
ki -h ei) = b. Hence it follows that ki - ei = (^L:tl\(f + f). If
a -\- b \q positive, then the heat produced by the chemical change is
greater than that consumed by the E.M.F.; if the sum is negative,
then this relation is reversed. The author proves by his experiments,
the details of which are given in the original paper, that in Daniell's
cell the E.M.F. consumes an amount of heat equal to that produced by
the chemical process. On the other hand, with solutions of silver
nitrate and sulphate with silver electrodes, the E.M.F. between the
metal and the salt solution consumes a greater quantity of heat than
that set free in the formation of the salt, and therefore —^ — has a
negative value ; the same obtains with lead acetate and lead.
V. H. V.
GENERAL AND PHYSICAL CHEMISTRY. 769
Effect of Absorbed Gases on the Electrical Conductivity of
Carbon. Bj J. Probert and A. W. Poward (Chem. News, 47, 157).
The authors have measured the electrical conductivity of specimens of
a porous variety of carbon in different gases at different pressures,
and have observed that the conductivity is not constant for a given
temperature, but varies with the chemical nature and density of the
absorbed gas. Quantitative experiments are in progress.
D. A. L.
Unipolar Conductivity of Solid Bodies. By J. Braijn (Ann.
Fhys. Chem. [2], 19, 340 — 352). — This paper is merely a comparison
of the v^ork of the author and Meyer on the unipolar conductivity of
psilomelane, together with a description of the apparatus used.
y. H. y.
Electrical Conductivity of Silver Haloid Salts. By W.
KoHLEAUSCH {Ann. Fhys. Chem., 17, 642 — 654). — At temperatures
above their melting point, silver chloride, bromide, and iodide conduct
electricity much better than sulphuric acid. The order of conductivity
is chloride, bromide, iodide. The resistance of the chloride and bro-
mide is increased when they solidify, and rises quickly by cooling,
until at 20° it has more than a million times its former value. Silver
iodide, on the other hand, does not on solidifying change its resistance
in the least at first, but the resistance increases rapidly at the tempera-
ture (145°) at which it passes from the amorphous to the crystalline
state. B. B.
Fluidity and Galvanic Conductivity. By C. Stephan {Ann.
Fhys. Chem., 17, 673—701). — The experiments described in this
paper relate to solutions of salts in mixtures of alcohol and water, and
they lead to the following conclusions : — In such solutions of NaCl, KCl,
LiCl, Nal, and KI, the conductivity is determined by the coefficient
of friction. The conductivity increases with increase of the propor-
tion of salt less rapidly than is the case with aqueous solutions. The
temperature coefficients of conductivity correspond nearly with those
of fluidity. The conductivity of the alcoholic solutions may be
expressed by multiplying that of the corresponding aqueous solutions
by a factor depending only on the solvent, and the same for all the
salts. In passing from pure water to a mixture of equal parts of water
and alcohol, the conductivity remains very nearly proportional to the
fluidity of the solvent. With a larger proportion of alcohol, the con-
ductivity is behind. B. B.
Platinum-water Pyrometer. By J. C. Hoadley {Chem. News,
47, 171). — The apparatus here described is for the measurement of
temperatures above the range of the mercurial thermometer up to the
melting point of platinum, by means of the method of mixtures,
platinum and water being the substances employed. The pyrometer
consists of an inner cell (for the water) 4*25 inches in diameter and
height, wdth a bottom in form of a spherical segment of 4*25 inches
radius, made of brass plate 0"01 inch thick, nickel plated and polished
on both sides ; and an outer case 8 inches diameter, 8"5 inches deep, of
770 ABSTRACTS OP CHEMICAL PAPERS.
16 oz. copper nickel plated, in the inside, with a hopper-shaped top of
the same metal. The inner cell is connected with the outer case by
three vulcanite bands screwed together, which also insulate it. The
joints between the metal and vulcanite are made tight with asphaltum
varnish. The cover of the inner cell consists of two nickel-plated
brass plates separated by a ring of vulcanite which both connects and
insulates them ; these plates are bonnd together by a vnlcanite tube.
When this cover is on, the water in the cell is surrounded by polished
nickeled brass insulated from all other metallic connections by vnl-
canite. The space between the inner cell and outer case is filled with
eider-down. Brass tubes pass through the cover for the admission of
a thermometer. The agitator is a perforated concave disc of brass
made to conform with the bottom of the cell, with a narrow rim
turned up all round ; the stem as far as the under side of the cover is
of perforated brass tube, the upper part a vulcanite tube and passes
through the vulcanite tube previously mentioned ; in agitating, it is
not necessary to draw the brass tube out beyond the exterior vulcanite
tnbe of the cover. The thermometer is passed down the internal tube,
and to protect this instrument this tube should be surrounded ex-
ternally with a brass wire cage, and should have a tuft of wool at the
bottom inside ; the thermometer itself should be protected by a small
band of india-rubber. Very accurate thermometers must be used.
The best heat-carriers are platinum balls; the author uses three
varying sizes : one 1*1385 inch diameter weighing 4800 grains ;
another 0*9945 inch diameter = 2800 grains ; and the third 0'7894
inch diameter = 1400 grains. A less expensive beat-carrier made
of iron covered with platinum may be used for temperatures np to
about 1500° F. When in nse, the heat-carriers are placed in small
graphite crucibles, which are placed, for further protection, in a
firebrick case ; two are nsed together, one as a check on the other.
The temperature of the water in the cell is carefully taken, and an
instant before " pouring " the heat- carrier from the crucible, the cover
and agitator are both lifted together, so that the rim of the latter is
on a level with the sloping top of the apparatus ; the agitator then
receives the hot ball without doing injury to the apparatus : as soon
as the temperature of the water is constant, the degree is noted and
the result calculated from tables, &c. Several precautionary measures
have to be taken before making an experiment: thus the calorific
capacity in terms of water of the cell, of the inside plate of the cover,
of the metallic portions of the agitator, of the part of the thermo-
meter exposed to the temperature during the reading, also the amount
of water of certain temperature, must be accurately known, care
being taken to note loss occasioned by contact with air, by radiation,
and by evaporation during the time the water is poured from one
vessel to another; again, the amount of heat communicated to the
eider-down muat not be overlooked. Compared with the mercurial
thermometer, the author believes this pyrometer to be more accurate,
although less convenient. For temperatures up to 900° F, it is only
equalled by a suitable air thermometer. For temperatures np nearly
to the melting point of platinum it is without a rival. The author's
sample of platinum began to melt below 2950° F. D. A. L.
GENERAL AND PHYSICAL CHEMISTRY. 771
Radiation from Silver at the Solidifying Point. By J. Violle
(Compt. rend., 96, 1033 — 1035). — The radiation from molten silver,
as measured by its effect on a tbermopile, remains constant during the
actual process of solidification. It therefore constitutes a convenient
secondary standard for spectro-photometric measurements, &c.
C. H. B.
Specific Heats of Gases at High Temperatures. By Yieille
{Com'pt. rend., 96, 1218 — 1231). — Observations of the pressures de-
veloped by the explosion of a mixture of hydrogen and oxygen, or
cyanogen and oxygen, v^rith certain proportions of nitrogen, oxygen,
hydrogen, and carbonic oxide, show that at temperatures as high as
2700° the molecular specific heats at constant volume of these four
gases are identical, if it is assumed that their coefficients of dilatation
remain constant. The results of some of the experiments seem to
indicate that the specific heats of these gases attain a limit at about
3500°.
The pressures developed by the explosion of mixtures of cyanogen
and oxygen indicate that the temperature of exDlosion of CN + 0 is
3927°, whilst that of CN + O2 is 5320°. This last number is probably
too high in consequence of dissociation ; but the first may be regarded
as accurate, and is nearly 1000° higher than the temperatures which
are generally regarded as actually attainable by combustion.
C. H. B.
Some Relations between Temperatures of Combustion,
Specific Heats, Dissociation, and Pressure of Explosive Mix-
tures. By Berthelot (Compt. rend., 96, 1186 — 1191). — In calcu-
lating the temperature of combustion of an explosive mixture, it is
necessary to take into account the amount of dissociation and the
variation in the specific heats of the gases concerned. It is possible
to calculate the temperature of combustion and the amount of disso-
ciation in the case of gases which combine without change of volume,
if only the total heat of combination and the pressure developed is
known ; or the maximum and minimum possible limits of the tempe-
rature of combustion can be calculated with no other datum but the
pressure developed. Generally, in a reversible system, i.e., a system
in which dissociation tends to reproduce the original constituents, we
have, starting from 0°,
' = 273(5 TrrirTg -0-
where t is the temperature of combustion, P the pressure developed,
H the initial pressure, ^ the ratio of the volume of the products when
completely combined to the volume of the same bodies when com-
pletely dissociated, and k the fraction actually combined. If the
initial temperature t is higher than 0", then P must be replaced by
P( 1 + o^ '• WJien there is no dissociation this formula becomes
73;*
.. = 273(1 1-1)
772 ABSTRACTS OF CHEMICAL PAPERS.
which gives one of the limits of temperature, the other being ob-
tained by making A; = 0 when we have
,, = 273( P - l)
When combination takes place without change of volume, the two
limits are identical, and the temperature is at once obtained from the
pressure developed.
If the heat of combination is divided by the temperature of com-
bustion, the quotient is the mean quantity of heat restored by the
system for each degree between 0° and the temperature of combus-
tion ; this quantity the author terms the apparent specific heat of the
system. If there is no dissociation, it will be the mean specific heat of
the compound, and by comparing it with the specific heat of the same
substance at the ordinary temperature it can be ascertained whether
the specific heat varies, and, if so, what is the amount of variation.
If, on the other hand, there is dissociation, the apparent specific heat
is a complex quantity made up of the specific heat of the compound, the
specific heats of its constituents, and the heat developed by the com-
bination which takes place during cooling. If the specific heats of
the compound and its constituents can be measured in any other way,
then the amount of dissociation can be calculated from this complex
quantity.
The maximum limit of dissociation can be calculated in any case.
The specific heat . of compound gases usually increases with the
temperature, and by multiplying its value at the ordinary temperature
into t, the known temperature of combustion, or tz, the lower of the
two calculated limits, the product is the smallest quantity of heat
compatible with the formation of that proportion of the compound
which gives rise to the observed pressure. The ratio of this quantity
to the total heat of combination gives the maximum limit of dissocia-
tion. It must be borne in mind that all these calculations only hold good
for gases which obey the ordinary laws of expansion and compressi-
bility : they are not applicable to a gas like chlorine, which expands
abnormally at high temperatures. It is also necessary to distinguish
between rtversible systems, in which the compound formed can repro-
duce the original bodies by dissociation, and non-reversible systemSy in
which this is not the case.
In order to apply these principles, the author has made a number of
experiments with combustible isomeric mixtui'es, i.e., mixtures of the
same elements associated in different ways in the initial mixtures, but
producing the same final system by combustion : for example, CH4 +
O4 and CO + 2H2 -h O3, C.He + O7, C2H4 + H2 + 0,, CA + 2H2 +
O7, CaHsO + Oe, and 2C0 + SHo + Og. In calculating the tempera-
ture-limits it is necessary to take into account the dissociation of the
water and carbonic anhydride into hydrogen, oxygen, and carbonic
oxide. If g represents the condensation corresponding with the
formation of these two compounds, the formulae for the temperature-
limits are
273
GENERAL AND PHYSICAL CHEMISTRY. 773
273/^1 ,
C^^)i ,' . J""C^^^
H i-\
U = 273
H g
The results of these experiments will be detailed subseqnentlj.
C. H. B.
Basis of Thermo-chemistry. By L. Metet^ {Annalen, 218,
1 — 12). — No simple connected theory of chemical change has hitherto
been based on thermo-chemical investigations, notwithstanding their
number and the trustworthiness of the constants deduced from them ;
indeed many chemists would even consider that such a generalisa-
tion is for the present not ripe for discussion. For although
many observations are in direct accordance with the mechanical
theory of heat, yet from time to time facts are brought forward
apparently in direct contradiction to it ; as the validity of this theory
cannot be doubted, such discrepancies probably arise from wrong
methods of its applica,tion. According to the author's opinion, the
retention of old and baseless hypotheses hampers the framing of a
thermo-chemical theory ; such, for example, is the conception that
the atoms are particles of mass endowed with a power of attraction
through space, altliough it is least highly probable that attraction,
as we conceive it, is produced by a certain movement of smaller par-
ticles, arising from pressure or impact. The satisfaction of these
attractions or affinities is not then correlated with a conversion of
potential into kinetic energy, but the combinations -and also the sepa-
rations of the affinities are merely a conversion of one form of kinetic
energy into another. Again, it is often tacitly assumed that the
atoms are particles at rest, more especially in the more or less esta-
blished generalisation that in absence of disturbing circumstances the
final result of a chemical change is the combination of those affinities
which evolve the greatest heat in their satisfaction. If, on this
assumption, 2 atoms, A and B, are attracted, and, by their mutual
impact combine with one another, then their potential energy is con-
verted into kinetic, which either wholly or partially assumes the form
of heat. Supposing, then, a third atom, C, whose attraction for A is
greater than that of B, to be brought into such a condition that it can
oust B, then the kinetic energy evolved as heat is equivalent to the
potential energy between A and C diminished by the work done in
the separation of A and B. A decomposition of the compound
AC by B is practically excluded, and also every chemical change
which is associated with a consumption of heat.
But atoms and molecules are not at rest : for, not only is every
molecule in motion as a whole, but each of its constituent atoms is.
likewise moving, the movement of the latter being so far limited that
no individual atom can be separated from the others which form the
molecule.
The form and force of the movement is dependent on the nature
of the substance, temperature, and space occupied by a given quantity
of it. Although no ultimate conclusion can be arrived at as to the
actual form of the motion, yet it can a ^priori be suspected that it is
774 ABSTRACTS OP CHEMICAL PAPERS.
either of such a kind that the vis viva remains the same, or alternately
increases and decreases at the expense of the potential energy. The
former case would obtain when the several atoms describe a circle
around some centre of gravity, the latter when the path described is
an ellipse : if the latter represent the form of motion, then the
readiness of decomposition of the molecule is dependent on the
relative position of the atoms in a given unit of time ; and it is thus
possible that one and the same compound by the action of one and the
same substance is in certain cases decomposed, and in others unaltered
without any perceptible difference in the external conditions, especially
temperature. Then for the decomposition of a componnd AB by C, it
is not even necessary that in any given position the attraction between
A and B should be less than that between B and C, for it is a possible
case that while A and B are indefinitely apart from one another, C
strikes with such velocity on A that it ousts B from the sphere of
action. Whether, after such a decomposition, the kinetic energy of the
system is greater or less than before is dependent upon whether C or
B possesses the greater affinity for A, but /or effecting the decomposi-
tion it is not necessary that B should possess the greater, for C can
compensate a less degree of affinity by a greater vis viva. In ac-
cordance with this view not only the decomposition of AB by C,
but the re-formation of AB from AC and B is possible. Finally, the
possibility and ease of a chemical combination is dependent, not
npon the force of the affinities, but upon other properties of atoms and
molecules and upon external conditions.
The author also remarks that there is no fundamental distinction
between positive and negative heat-change : for the combination of two
atoms could scarcely be dissolved without their kinetic energy taking
some part in work done in overcoming the affinities, but the loss of
energy will be marked by the heat developed in the newly formed
affinities. The final heat-change observed in a chemical reaction is
the mixed result of intimately associated circumstances, and does not
probably afford a trne representation of the energy of the satisfied
or dissociated affinities ; this change, as also change of volume and
refractive index, is dependent not upon the mutual attraction or
affinity of the combining substances, but upon their individual nature
and their relative quantities.
In conclusion, the author considers that the science of thermo-
chemistry requires to be thoroughly reviewed, and the recorded
observations, although of manifestly great service, must not be con-
sidered as affording a final solution of the problems involved.
V. H. y.
Neutralisation of GlycoUic Acid by Bases. By de Forcrand
(Compt. rend. J 96, 582 — 583). — The glycollic acid was prepared by
the action of zinc-dust on a solution of oxalic acid. Its heat of solu-
tion in water is — 2*76 cal. between 8" and 10°. Determinations of
the heats of formation of its salts gave the following results : —
GENERAL AND PHYSICAL CHEMISTRY. 775
Potassmra gljcollate,
2C2H4O3, dissolved + K2O, dissolved
Cal.
+ 27-48
Sodium glycollate,
2C2H4O3,
»
+ Nao.O,
)>
+ 27-20
Ammoniam glycollate,
, 2C2H,03,
jj
+ 2NH3,
5>
+ 24-46
Barium glycollate,
2CaH403,
)5
+ BaO,
))
+ 27-80
Strontium glycollate,
2C3H,03,
n
+ SrO,
>)
+ 28 00
Calcium glycollate,
2C3H,03,
>>
+ CaO,
)>
+ 27-80
Lead glycollate,
2C.H4O3,
))
+ PbO,
solid
+ 15-10
Magnesium glycollate.
2C2H4O3,
)i
+ MgO,
)»
+ 27-42
Copper glycollate,
2aH,03,
J?
+ CuO,
))
+ 15-22
Zinc glycollate,
2C,H403,
J)
+ ZnO,
C.
+ 20-80
H. B.
Salts of Glycollic Acid. By de Eorceand (Compt. rend., 96,
710 — 713). — The author has determined the heats of solution of
glycollic acid and sodium glycollate in varying quantities of water.
The results obtained with glycollic acid may be represented by the
formula Q = — 0-012 , where n represents the number of
n
H2O mols. originally united with the acid : starting with from 18 to 20
H2O, the formula Q = — is sufficient. The results with sodium
n
33'652
glycollate are represented by the formula Q = 0-213 — ToTFTt;'
The heat of combination of the acid and base in concentrated solutions,
calculated from these data, differs but little from the heat of com-
bination in dilute solutions, a result similar to that obtained in the
case of strong acids. Themochemical measurements show that acid
glycollates can be formed even in dilute solutions, and that compounds
can be formed at the expense of the alcoholic function of the glycollic
acid, as in the case of lactic acid. The salts of glycollic acid may be
divided into three groups: (1), neutral salts, stable in presence of
water; (2), acid salts, decomposed to a great extent by water ; (3),
basic salts, which have the characteristics of both neutral salts and of
alcoholates, and which, like the acid salts, are partially decomposed by
water. C. H. B.
Heat of Combination of Glycollates. By D. Tommasi (Compt.
rend., 96, 1139— 1140).— Reply to Forcrand (this vol., p. 708, and
preceding Abstract).
Ammoninm Hydrosulphide and Cyanide. By Isambert
Ann. Gfiim. Phys. [5], 28, 332— 349).— The author, in the course of
his investigations on the substances whose vapours occupy twice the
volume of a molecule of hydrogen, has studied more particularly the
vapour of ammonium hydrosulphide and cyanide, as likely to afford
cases bearing on the general problem.
The author at first measured at various temperatures the tension
emitted by ammonium hydrosulphide in presence of the ammonia
compound of calcium chloride, CaCl8,4N'H3, whose partial dissociation
has already been made the subject of experiment. If at any tempera-
ture T the latter emitted ammonia of tension F, and the former a
776 ABSTRACTS OF CHEMICAL PAPERS.
vapour of tension 2/, then, were the ammonium hydrosulphide
vaporised without decomposition, the tension of the mixture would
be F + 2/; but it would be F + /if the dissociation of the salt were
complete, and an intermediate number in the case of partial decom-
position. But experiment did not confirm any of these d priori
suppositions ; the tension of the mixed vapours was even less than
F + /) which corresponds to the complete decomposition. The author
proceeding to investigate the cause of this phenomenon, found that in
the presence of an inert gas, hydrogen or nitrogen, the pressure
exerted is the sum of the pressures of the gas and the vapour of the
hydrosulphide ; but if ammonia or hydrogen sulphide be substituted
for the inert gas, the same general law does not hold good. For the
total pressure exerted is less than the sum of the tensions, this
diminution being due either to an absorption of the gas, hydrogen
sulphide or ammonia, by the hydrosulphide, or to a diminution of the
tension of the vapour of the salt by the presence of these gases.
Experiments are quoted to confirm this latter view.
The numerical results of the tensions of the vapour of the salt in
the presence of one of its constituent gases, proved that the gases,
ammonia and hydrogen sulphide, exert the same pressure in the
mixture, whether in a state of combination or not, the pressure of one
of the gases being inversely proportional to the pressure of the other.
This empirical law can be expressed by an equation __ = (^ + x)x,
4
in which P is the tension of the hydrosulphide in a vacuum, hy the
pressure of the gas introduced in excess, and 2x the tension of the
hydrosulphide in the presence of this excess h of one of its constituent
gases. This formula has been applied by Horstmann to cases in which
a solid compound, as ammonium chloride, is resolved by heat into
equal volumes of its constituent gases.
Owing to the difficulties presented in the investigation of ammonium
hydrosulphide, the author turned his attention to the study of the
vapours of ammonium cyanide. He made a series of determinations
at the same temperatures of the tensions of vapours of (1), hydro-
cyanic acid; (2), ammonium cyanide; (3), ammonium cyanide in
presence of more or less considerable excess of hydrocyanic acid ;
(4), of ammonium cyanide in presence of a known excess of
ammonia. In the third of these cases, in which the hydrocyanic
acid is in excess, the total pressure is independent of the quantity in
excess of the acid, and in all cases is equal to that which would have
been exerted, had the ammonium cyanide been absent altogether.
This doubtless arises from the non-volatilisation of the ammonium
cyanide in presence of the hydrocyanic acid — a view which has
been put forward by Engel and Moitessier to explain analogous cases ;
or from a diminution of the tension of vapour of hydrocyanic acid in
presence of the cyanide, this diminution being compensated by the
tension of the cyanide. In the presence of ammonia in excess, the
cyanide behaves exactly as the hydrosulphide, and observations on the
tension of the mixed gases agree with those deduced from the formula
given above. In order to decide between the hypothesis of Engel
and Moitessier and that of the author, a small quantity of gaseous
\
GENERAL AND PHYSICAL CHEMISTRY. 777
hydrochloric acid was introduced into the vessel containing the
ammonium cyanide and excess of hydrocyanic acid. "White vapours
were thus produced, which prove that the ammonium cyanide is
partially decomposed into ammonia and hydrocyanic acid. Analyses
of the mixed vapours confirmed this fact. The view propounded by
the author is the more correct, and the tension of ammonium cyanide
in presence of hydrocyanic acid can be calculated according to Horst-
mann's formula. From this study of the vapour of ammonium
cyanide, no conclusion can be drawn as regards the composition of- the
vapour of this salt ; for although certain experiments seem to militate
against the decomposition of the salt when vaporised, yet the whole
investigation is beset with so many difficulties that the conclusions
cannot be considered as final. Y. H. V.
Wave of Explosion. By Berthelot and Vieille (Ann. GTiim.
Phys. [5], 28, 289 — 331). — The authors, in the course of experiments
on explosives, were led to examine the velocity of propagation of
explosion in gases, varying the conditions of the phenomenon, such as
the pressure of the gases, their nature and relative proportion, and the
form, dimensions, and material of the containing vessels. The in-
vestigations have revealed a new kind of undulatory movement, the
wave of explosion, which consists of a certain regular surface, wherein
is developed the chemical transformation and its concomitant altera-
tion of temperature and pressure ; this surface, once produced, is
transmitted layer by layer, throughout the entire mass, by successive
shocks of the gaseous molecules, with a gradual increase of vibration,
due to the heat developed by the chemical combination. The effects
produced are comparable to an exaggerated sonorous vibration,
although it is to be observed that an explosion gives rise to an isolated
characteristic wave, while sound is produced by a periodic succession
of similar waves. The following are the principal characteristics of
the wave of explosion: — (1.) It is propagated uniformly; (2), its
velocity is dependent on the nature of the explosive mixture, and not
on the material of the containing vessel ; (3), its velocity is inde-
pendent of pressure ; these two latter facts prove that the wave of
explosion is regulated by the same general laws as the wave of sound ;
(4), the theoretical relation existing between the velocity of the wave
of explosion and the chemical nature of the gas is difficult to establish,
for the former is dependent upon the temperature and vis viva of the
gaseous molecules, which vary with different systems. However, if
the total energy of the gas at the moment of explosion depends on its
initial temperature and the heat disengaged during the combination,
then these two data determine the vis viva, and consequently the
absolute temperature of the system, which is proportional to the vis viva
\mO^, i.e., the vis viva communicated to the molecule is none other than
the heat energy developed in the reaction. At 0", the gas produced by
the reaction contains a quantity of heat q, equal to 273c (c being the
specific heat) ; at the moment of combination it contains, in addition
to this, a quantity of heat Q, disengaged by the reaction'. The vis viva
of the translation 6 of the molecules = \mO'^^ in the former and latter
VOL. XLiv. 3 g
778 ABSTRACTS OF CHEMICAL PAPERS.
conditions are in the ratio — ?, consequently Oi = Oq \^ ^ ? , a
formula which the authors have verified by experiment.
In order to investigate the properties of this explosive wave, a tube
about 40 m. long was filled with the detonating mixture at known
pressure ; the mixture was ignited at one of the extremities of the
tube by an electric spark, and the flame produced destroyed the con-
nection of two electric circuits. The interval of time elapsing between
the interruption of these two currents was measured by a Le Bonlenge
chronograph. With the aid of this apparatus, which is described at
length in the original memoir, the authors carried on experiments in
order to determine whether the velocity of the explosive wave is
dependent upon the position, length, and material of the tube, when
opened or closed at both or one end, on the initial pressure of the
gaseous mixture, and its composition. It was found in the cases of
mixtures of hydrogen or carbonic oxide with oxygen, that the velocity
is independent of the position of the tube, whether horizontal or
vertical, of the material, whether of lead or caoutchouc, of its
diameter, and also whether one or both ends were closed or opened.
The velocity is also independent of the initial pressure of the gases.
Tables are given of the velocity of the explosion in mixtures of
hydrogen, carbonic oxide, acetylene, ethylene, ethane, methane, and
cyanogen, with the necessary quantity of oxygen, and the experi-
mental results compared with those deduced from the formula
Velocity Velocity
calculated in meters found in meters
Mixture. per second. per second.
Hydrogen and oxygen .... 2831 2810
Carbonic oxide 1941 1089
Acetylene 2660 2482'5
Ethylene 2517 2209-5
Ethane 2483 2363
Methane 2427 2287
Cyanogen 2490 2195
In the case of the hydrocarbons and cyanogen, the velocity found is
less than that calculated according to the above formula ; in the case
of carbonic oxide the formula is not applicable. It is evident that
the velocity is independent of the relation between the volumes of
the combustible gas and tlie oxygen, and of the initial and final
volumes.
Results are also given of experiments with a mixture of two com-
bustible gases with oxygen, of a combustible gas with a gas which
supports combustion, of isomeric mixtures of hydrogen and hydro-
carbons with oxygen, which produce finally the same quantities of
carbonic anhydride and water. The influence of the presence of an
inert gas as nitrogen is also investigated. As a result of these various
forms of experiment, it may be stated generally that the velocity of
translation of the gaseous molecules, which preserves the whole of the
GENERAL AND PHYSICAL CHEMISTRY. 779
vis viva corresponding to the heat disengaged in the reaction, can bo
regarded as the limit of maximum velocity of propagation of the wave
of explosion. This velocity is diminished by the presence of an inert
gas, and in the case of carbonic oxide seems to be dependent upon
another law.
With a slightly different form of apparatus, the authors examined
the conditions necessary for the production of the explosive wave,
and of the state of the gases immediately preceding their detonation.
It is thus shown that the velocity of the wave increases rapidly up to
a point distant about 5 cm. from the point of inflammation of the
explosive mixiture ; from that point the velocity for each interval of
space is practically constant. Experiments with mixtures of carbonic
oxide and oxygen with nitrogen showed that for detonation at least
60 per cent, of carbonic oxide are necessary, but for combustion only
20 per cent. ; and in mixtures of oxygen and hydrogen 22 per cent, of
hydrogen are required for detonation, and 6 per cent, for combustion.
It is farther noticed that a mixture of cyanogen with nitric oxide
detonates violently, when ignited by a spark, but burns quietly when
lit by a match. The various results obtained all point to the con-
clusion that the phenomenon of the explosive wave is quite distinct
from that of ordinary combustion, each being marked by well-detined
limits, which the authors denominate the regime of detonation and of
combustion respectively. The transition from one to the other is
accompanied by violent molecular movements. Y. H. V.
Affinity Values of Carbon. By A. Geuther {Annalen, 218, 12
— 13). — The researches of Rose on the mixed alkyl salts of carbonic
acid (Abstr., 1881, 251) have established that the affinity values of
carbon are equal ; the author with his pupils has carried on inves-
tigations on the acetals, taking as the starting point the so-called
ethylene oxychloride and aldehyde chloride. But it was found that the
latter alone possessed the power of forming mixed acetals, and thus of
affording a basis for the investigation of the " carbonic oxide "
affinities. V. H. V.
Specific Gravity and Chemical Affinities of Elements in
Various Allotropic Modifications. By W. Muller-Erzbach
{Annalen, 218, 113 — 120). — The author would generalise into a law
the well-known facts that elements, when prepared by different pro-
cesses, possess different atomic volumes and chemical affinities, and
thus to bring forward further corroboration of his law of " smallest
volumes " (Abstr., 1882, 137). This law states that chemical reactions
are intimately connected with contraction of mass, inasmuch as the
reactions are the more violent the smaller the volumes occupied by the
combinations resulting from it. In many cases, one form of an element
at a given temperature passes into another, but this molecular change
is a particular case of the interaction of two substances, differing
merely from it in that the reacting bodies are of the same and not of
different kind.
The author in the original paper adduces various examples of the
differences in chemical behaviour and atomic volume of the allotropic
3^2
780 ABSTRACTS OF CHEMICAL PAPERS.
modifications of sulpliur, selenium, phosphorus, carbon, silicon, boron,
arsenic, and tin. Of these eight elements, there are only two, sulphur
and selenium, which do not dispJay a higher degree of chemical affinity
associated with a lower specific gravity ; in the remaining cases, this
conclusion is most marked, and in no case is greater affinity asso-
ciated with higher specifiic gravity.
The author considers that the relation affi^rds a fresh corroboration
of his law that the energy of a chemical reaction is dependent upon
the volumes occupied by the resultant substances ; conversely if by the
combination of two chemically analogous substances allotropic modifica-
tions are formed, the^ the lower its specific gravity the more easily is
it decomposed into another form. V. H. V.
Constitution of Hydrated Salts. By E. Wiedemann (Ann. Phys.
Chem., 17, 561 — 576). — The dilatometrical method has been applied
by the author in an investigation of the changes of volume undergone
by certain hydrated salts when gradually heated in the solid state.
His experiments show that changes of constitution take place before
fusion. Two new modifications of magnesium sulphate may thus be
recognised.
These results have certain relations to other researches. Thus, for
example, before we can determine the tensions, we must first ascertain
whether or not the salt changes in constitution within the given range
of temperature ; and again in researches on the heat of solution, &c.,
it is necessary to know the precise constitution of the salts at the
temperature in question. R. R.
Inorganic Chemistry.
Chlorine Hydrates. By E. Maumen^ {Ghem. News, 47, 145—
146). — The author publishes the following in reply to Ditte's note
(this vol., p. 550). He finds that the hydrate formed by passing a rapid
current of chlorine through water at 5° is of a pale yellow colour, and
after being drained and pressed between filter-paper, has the composi-
tion Cl2,12H20. If this hydrate is enclosed in a bent tube according
to Faraday's directions for obtaining liquid chlorine, deep yellow
crystals may be seen bordering upon the liquefied gas ; these crystals
vary in composition. When formed in presence of excess of chlorine,
they have the constitution Cl2,4H20, whilst when produced in pre-
sence of much of the solution, they have a variable constitution ap-
proximating to CUj^HaO. They are produced and remain as long as
the solution of chlorine is hot enough to prevent an absorption of
chlorine. According to the author's theory, chlorine when in pre-
sence of about an equal weight of water, can combine with an equal
weight of it or 72 parts, the crystals formed being Cl2,4H30. When,
however, the water is in excess, the Cl2,4H20 in its turn combines
with an equal weight or 144 parts of water, e.g., Cl2,12H20.
I
INORGANIC CHEMISTRY. 781
Lastly, these two hydrates can combine together in equal weights,
and the result is that Cl2,12H20 combines witb 2(Cl2,4H20), forming
Cl6,20H2O or C]2,6-67H20, or the hydrate bordering on Cl2,7H20.
From this it will be readily seen how Faraday found a hydrate con-
taining Cl2,10H2O. D. A. L.
Liquefaction of Oxygen and Nitrogen; Solidification of
Carbon Bisulphide and Alcohol. By S. Wkoblbwski and K.
Olszewski (Compt. rend., 96, 1140—1142, and 1225— 1226).— Liquid
ethylene boils at — 102" to 103° under a pressure of one atmosphere,
and not at -- 105° as is generally stated. This temperature is above
the critical point of oxygen, but by the rapid evaporation of liquid
ethylene in a vacuum, a temperature as low as — 136° can be ob-
tained. At this temperature oxygen liquefies under a moderate
pressure, the numbers obtained being as follows : —
Pressure at
Cemperature.
which oxygen liquefies.
- 131-6°
26-5 atmos.
- 133-4°
24-8 „
- 135-8°
22-5 „
Liquid oxygen is colourless, transparent, and very mobile ; it forms
a very distinct meniscus.
Nitrogen does not liquefy at — 136° even under a pressure of 150
atmos., but if the pressure is somewhat slowly released, care being
taken not to diminish it below 50 atmos., the nitrogen liquefies com-
pletely and forms a colourless transparent liquid with a very distinct
meniscus ; it evaporates very rapidly.
Carbonic oxide has been liquefied in a similar manner. It forms a
colourless liquid with a distinct meniscus.
Carbon bisulphide solidifies at about — 116°, and melts at about
— 110°. Alcohol becomes viscous like oil at about — 129°, and
solidifies to a white mass at about — 130'5°.
All these low temperatures were measured with a hydrogen ther-
mometer. C. H. B.
Action of Heat on Sulphuric Monochloride and Dichloride.
By K. Heumann and P. Kochlin (2?er., 16, 602— 608).— The readiness
with which sulphuric dichloride, SO2CI2, is decomposed by phosphorus,
arsenic, and antimony has been pointed out by the authors (Abstr., 1882,
1262). When its vapour is passed through a glass tube at a dull red
heat, it is completely decomposed into sulphurous anhydride and
chlorine. This decomposition is further confirmed by vapour-density
determinations made at high temperatures. In aniline vapour (184°)
normal results are obtained, whilst in sulphur vapour (442°) the dis-
sociation is complete. Many vapour-density determinations of sul-
phuric monochloride, S02(0H)C1, have been made by different
chemists, and difi'erent explanations given of the way in which this
body is decomposed. The authors have experimented at 184° and at
44j2°, and they find that at the latter temperature the vapour-density
782 ABSTRACTS OF CHEMICAL PAPERS.
is 2*09 instead of 4*04, the dissociation being nearly complete at 184".
The decomposition probably takes place thus : —
2S02(0H)C1 = SO2 + CI2 + SO3 + H2O.
A. K. M.
Pyrosulphuric Chloride. By D. Koxowaloff (Gompt. rend., 96,
1059—1062, and 1146— 1148).— A reply to Ogier (this vol., p. 646).—
Pyrosulphuric chloride carefully purified by fractional distillation,
whether prepared from carbon tetrachloride and sulphuric anhydride,
from sulphuric monochloride and phosphoric pentoxide, or from sul-
phuric anhydride and sulphur chloride, boils at 153'^, and has the
density 7*3. It is very difficult to pnrify pyrosulphuric chloride from
sulphuric monochloride by the action of even large quantities of
phosphoric anhydride, and it is better to prepare it from perfectly
anhydrous materials. C. H. B.
Combination of Phosphoric Acid with Silica. By P. Haute-
FRuiLLE and J. Margottet {Gompt. rend., 96, 10-52 — 1054). — Silica
obtained by the decomposition of silicon fluoride by vrater is added to
fused metaphosphoric acid, and the fused mass extracted with boiling
water, when transparent colourless octohedrons are obtained, which,
have no action on polarised light. These crystals are rarely distorted
by unequal development of the faces, but their angles are sometimes
slightly truncated. They scratch glass, have a sp. gr. of 3"1 at
14°, and melt on platinum before the blowpipe to a colourless glass
which does not devitrify on cooling. The crystals have the com-
position Si02, 29*37 ; P2O5, 69'91 ; AI2O3, 057, corresponding with
the formula Si02,P205. Phosphates of zirconia and other dioxides
can probably be formed in the same way. The solubility of different
phosphates in metaphosphoric acid furnishes a method of acting on
these phosphates with silica under conditions favourable to the forma-
tion of crystaUised silicates. C. H. B.
Phosphates. By P. Hautefeuille and J. Margottet {Gompt.
rend., 96, 1142 — 1144). — Orthophosphates, pyrophosphates, and the
intermediate phosphates can be obtained in crystals by fusing meta-
phosphates with metaphosphoric acid mixed with progressively in-
creasing quantities of trisilver phosphate. If this method is applied
to the phosphates of sesquioxides, double salts are obtained contain-
ing both the sesquioxide and silver oxide, the latter being easily dis-
placed by an alkaline base. The formation of double compounds of
the types 2M203,Ag20,4P205, and 2M303,2Ag20,5P205 almost always
accompanies the formation of simple phosphates of the sesquioxides.
Aluminium metaphosphate crystallises in pseudo-cubic crystals
from fused metaphosphoric acid containing a small quantity of tri-
silver phosphate, but if the silver phosphate is present in notable pro-
portion, birefractive crystals which act strongly on polarised light are
obtained in addition to the metaphosphate. These crystals are formed
exclusively by fusing 2 parts alumina with 4*6 parts metaphosphoric
acid and 8 parts silver phosphate, and the same result is obtained
by fusing aluminium metaphosphate with about three times its weight
of silver phosphate. The double phosphate thus obtained has the
INORGANIC CHEMISTRY. 783
composifcion 2Al203,Ag20,4P205, and forms colourless perfectly trans-
parent crystals derived from rhombic prisms. It is not very stable
in the fused mixture, and the presence of a slight excess of meta-
phosphoric a(5id causes the formation of monoclinic crystals of alumi-
nium pyrophosphate, Al303,2P205, free from silver. The presence of
an excess of silver phosphate converts the original crystals or the
pyrophosphate into acute octohedrons, apparently derived from a
monoclinic prism, and having the composition 2Al203,3P205.
Ferric and chromic oxides and the corresponding amorphous phos-
phates yield similar results when treated in a similar manner. The
double salt 2Fe203,2Ag20,5P205 forms highly refractive slightly rose-
coloured rhombic prisms. The salt 2Cr203,2Ag20,5P205 forms deep
emerald-green crystals derived from a monoclinic prism, and macled
in the same manner as sphene. Uranium sesquioxide yields similar
compounds. C. H. B.
Action of Sulphur on Alkaline Phosphates. By E. Filhol
and Senderens (Compt. rend., 96, 1051 — 1052). — Finely divided
sulphur has no action in the cold on solutions of trisodium or tri-
potassium phosphate, but if the solutions are heated, a notable quan-
tity of alkaline polysulphide and thiosulphate is formed. In mode-
rately concentrated solutions, trisodium phosphate is converted in
less than two hours into disodium phosphate, in accordance with the
equation GNaaPOi + 8H2O + S« = 2Na2S« + I^a2S203 + 6Na2HP04.
When a solution containing 5282 grams of disodium phosphate per
litre is heated with sulphur in sealed tubes at 100° for more than
300 hours, it is entirely converted into sesquisodiuni phosphate
(Abstr., 1882, 693). This reaction would seem to indicate that phos-
phoric acid is a sesquibasic acid of mixed function. C. H. B.
Bromapatites and Bromowagnerites. By A. Ditte (Compt.
rend., 96, 846 — 849). — The author has prepared several brom-
apatites in addition to those previously described (this vol., p. 648).
They were obtained by heating the metallic bromide with a small
quantity of ammonium phosphate at the lowest possible temperature,
out of contact with the air. If the apatite is required free from the
corresponding wagnerite, a mixture of metallic iDromide and sodium
bromide must be used. The proportion of sodium bromide must not
exceed a certain limit, otherwise the apatite will be decomposed. In
this way, the bromapatites of barium, strontium, manganese, and lead
were obtained. They all crystallise in transparent prisms or plates
belonging to the hexagonal system, and are readily soluble in dilute
nitric acid. They have the general formula MBr2,3(M3Pis08), where
M represents one atom of a dyad metal.
The corresponding brom-mimetites were obtained by substituting
ammonium arsenate for ammonium phosphate. They crystallise in
transparent prisms or plates belonging to the hexagonal system.
Barium, strontium, and lead bromovanadinitcs were obtained by
adding vanadic acid to the fused bromides, care being taken to avoid
the presence of reducing gases. They crystallise in hexagonal prisms
or plates, and are soluble in dilute nitric acid.
784 ABSTRACTS OF CHEMICAL PAPERS.
Bromarsenio-manganese wagnerite, MnBrajMnaA^-^Oe, is obtained
by adding ammonium arsenate to a large excess of the fused metallic
bromide. It forms rose-brown transparent prisms, easily soluble in
dilute nitric acid. The corresponding phosphate is obtained in a
precisely similar manner. Similar compounds are apparently obtained
from magnesium bromide, but they are always mixed with a large
proportion of magnesia, formed by the decomposition of the bromide.
C. H. B.
lodo-apatites. By A. Ditte (Compt. rend., 96, 1226—1229).—
The iodo-apatites cannot be obtained by means of the iodides of the
alkaline- earths, since these are decomposed when fused, but by em-
ploying double iodides of the alkalis and alkaline-earths, carefully
regulating the proportions of the mixtures, preventing access of
oxygen to the fused salt, and taking care not to prolong the fusion
more than is necessary, the author has succeeded in obtaining iodo-
phosphates, iodoarsenates, and iodo vanadates of barium, strontium,
and calcium, closely resembling in crystalline form and other pro-
perties the corresponding chlorine- and bromine-compounds.
C. H. B.
Antimonious Sulphide in Aqueous Solution. By H. Schulze
(J.jjr. Ghent. [2], 27, 320— 332).— The author has recently (this vol.,
p. 295) pointed out the existence of a soluble colloidal modification of
arsenious sulphide, and nov^ shows that a similar modification of anti-
monious sulphide can be obtained. It can be prepared from antimo-
nious oxide in a manner similar to that described for the arsenic-com-
pound, but, owning to the sparing solubility of antimonious oxide in
water, that method is very troublesome. Good results were obtained
with solutions of tartar emetic, sulphuretted hydrogen giving a deep
red coloration, but no precipation in solutions containing -^^^ of that
salt. The best results, however, were obtained with a solution of
antimonious oxide in tartaric acid (4*3 grams Sb203 per litre =
5 grams Sb2S3). On saturating this solution with sulphuretted
hydrogen, it assumes a very deep nearly blood-red colour, is com-
pletely clear by transmitted light, but appears brownish-red and
turbid by reflected light, and shows strong fluorescence. Strong
solutions when viewed in a thin layer are yellowish-red in colour,
and with dilution the yellow tint becomes more pronounced. The
analytical results show that the dissolved substance is the trisulphide.
The colloidal properties are well marked. It can be readily sepa-
rated from crystalloids by dialysis. The solution is tasteless, and on
evaporation leaves a brownish-red varnish of hydrated antimonious
sulphide. It is much less readily converted spontaneously into the
insoluble form than is colloidal arsenious sulphide, but, like the
latter, is readily precipitated by addition of acids or salts. The
author considers it very probable that many other substances usually
regarded as insoluble may be found capable of existing in solution in
the colloidal form. He is at present investigating what appears to
be a soluble modification of selenium. A. J. G.
Production of Crystallised Vanadates in the Dry Way. By
A. Ditte {Com'pt. rend., 96, 1048—1051). — The reactions which take
INORGANIC CHEMISTRY. 785
place between substances dissolved in fused salts obey tbe same laws
as in other solutions, and just as water can decompose certain double
salts, so a fused salt can decompose the compounds which are formed
in it. For example, in the artificial formation of apatites, &c. (this
vol., p. 648), the particular reaction which takes place is determined
hj the relative proportions of the haloid alkaline salt and the haloid
salt of the alkaline earth, and the proportions necessary for the pro-
duction of a particular compound are different in the three cases of
chlorides, bromides, and iodides. By taking advantage of this fact,
the author has prepared the following crystallised vanadates. Barium
vanadate, BaO,V206, obtained by heating vanadic acid with sodium
bromide and a very small quantity of barium bromide, forms yellowish
brilliant transparent crystals, which melt at a red heat, and are only
slightly soluble in water. Strontium vanadate, SSrOjVaOs, by heating
vanadic acid with a mixture of sodium and strontium iodides, forms
yellowish transparent plates. Lead vanadate, PbO,2V205, obtained in
a similar manner, forms short yellow transparent crystals easily
soluble in dilute nitric acid. Zinc vanadate, 2ZnO,V205, is obtained
in orange-red prisms by fusing vanadic acid with a mixture of 5 parts
sodium bromide and 1 part zinc bromide, and extracting the residue
with water. The crystals are slightly soluble in water, and melt at a
red heat. Cadmium, vanadate, CdO,V206, obtained in a similar man-
ner, forms brilliant transparent slender yellowish needles which melt
at a bright red heat. Manganese vanadate, 2MnO,V203, obtained by
fusing vanadic acid with a mixture of equal parts of manganese and
sodium bromides, and treating the slowly cooled mass with water,
forms large brilliant fragile brown needles, soluble with difficulty in
cold dilute nitric acid, but soluble in the hot acid. Nickel vanadate,
3NiO,V205, obtained by heating small quantities of vanadic acid and
nickel bromide with a large excess of sodium bromide, and treating
the fused mass with water and dilute nitric acid, forms green pris-
matic needles, sometimes much flattened. These crystals do not melt
at a bright red heat, are insoluble in hot nitric acid, and are but
slowly attacked by fused potassium carbonate, but dissolve easily in
hydrogen potassium sulphate. C. H. B.
Reduction of Tungsten Compounds. By 0. Freih (Ber., 16,
508 — 511). — When tungsten trioxide solutions are reduced with zinc,
the final product of the reaction is tungsten dioxide. The reduction
does not proceed as readily as in the case of molybdenum trioxide.
The author finds that it is advisable to employ tolerably strong hydro-
chloric acid (27 per cent.). The solution first becomes blue, then
black, dark green, and finally a dark red.
It undergoes partial oxidation in the air. If titrated according to
Zimmermann's method (Annalen, 213, 304), the dioxide can be very
exactly estimated. In a solution containing oxide equivalent to 6*89
per cent, of oxygen, the mean of six determinations made by the
author was 6*886 per cent. He employs the following method for
estimating small quantities of tungsten trioxide. The solution of the
salt in a small quantity of water, containing not more than O'i gram
WO3, is heated on a water- bath and immediately treated with 70 — 80
786 ABSTRACTS OF CHEMICAL PAPERS.
c.c. of 27 per cent, hydrochloric acid, after which 14 — 15 ^raras of
stick zinc are added. The iron contained in the zinc must be pre-
viously determined. As soon as the red colour is observed, the flask
is cooled, and the contents poured into a porcelain basin containing an
excess of potassium permanganate and manganese salphate (40 c.c.)
and dilute sulphuric acid (70 — 100 c.c). After washing out the flask
the whole is diluted to about a litre, an excess of ferrous sulphate
solution is added, and the solution is titrated with permanganate.
The mean of eight experiments made by the author on solutions con-
taining 78 91 per cent. WO3, was 78*93 per cent. J. I. W.
Borotungstates. By D. Klein (Compt. rend., 96, 1054—1056).—
The addition of concentrated hydrochloric acid to the dense mother-
liquor obtained by the action of boric acid on a solution of neutral
sodium tungstate (Oompt. rend., 94, 1070), precipitates a white
crystalline boroquatuordecitungstate, 14W03,B203, 2Na20,4H20 +
25Aq, which was previously described as a boroduodecitungstate.
It dissolves in water, and on gradual evaporation crystallises in
hexagonal prisms. The corresponding acid could not be obtained.
The tribarium salt, 14W03,B203,3BaO,5H20, and the tripotassium
salt, 14W03,B203,3K20 + 22Aq, crystallise in needles; the trisilver
salt, 14W03,B203,3Ag20,7H20 -f Aq, is amorphous. Some of the pro-
perties of these and of the double sodium barium and sodium strontium
salts, have been described in a previous paper (this vol., p. 23), but
some of the formulae given were inexact. These boroquatuor-
decitungstates, or more briefly, borotungstates, are decomposed by
boiling acids with formation of a tungstoborate, and tungstic
hydrate.
The potassium boroduodecitungstate previously described {Compt.
rend., 91, 495), yields with barium chloride a double salt,
12W03,B203,3BaO,K,0 + 28Aq,
which was erroneously described as a barium boroduodecitungstate;
it forms large quadratic crystals. The mother-liquors from potassium
boroduodecitungstate deposit rectangular tables of the composition
12W03,B203,4K20 -f 21 Aq. They are decomposed by boiling hydro-
chloric acid, and probably belong to a new class of salts. Boroduo-
decitungstic acid, obtained by decomposing the insoluble mercurous
salt with hydrochloric acid and mercury, can only be concentnited by
heat up to a certain limit, beyond which it splits up into tungstoboric
acid and tungstic hydrate.
The action of boric acid on ammonium paratungstate yields a very
dense liquid, which continually loses ammonia when heated, and on
cooling deposits oblique prisms, and a saccharoid crystalline mass
belonging to a new class of borotungstates.
When sodium paratungstate is treated with three-fourths its weight
of boric acid and the solution concentrated, a non-crystallisahle
mother-liquid is obtained, from which another new class of boro-
tungstates can be prepared. The barium salt forms rhombic prisms.
C. H. B.
ORGANIC CHEMISTRY. 787
Organic Chemistry.
Preparation of Paraffins. By B. Kohnlein (Ber., 16, 560—563).
— The author finds that when normal propyl iodide is heated with pure
anhydrous aluminium chloride at 130 — 140'' in a sealed tube from
which the air has previously been exhausted, pure propane is formed.
Isobutyl iodide, when treated in a similar manner, yields pure butane.
Ethyl iodide yields ethane. The method appears to be of universal
applicability for the preparation of the paraffins of the C«H2n + 2 series.
J. I. W.
" Reaction Aptitudes " of the Halogens in Mixed Haloid
Ethers. By L. Henry (Gompt rend., 96, 1062—1064, and 1149—
1152). — The experiments described in this paper were undertaken
with a view to ascertain in what order radicles X, X', X", combined
with the hydrocarbon residue CnH.m, and having equivalent or analogous
functions, are aSected by a foreign body Y, to the action of which they
are susceptible.
Ethylene Ghlorohromide. — The action of various metallic reagents,
such as potassium hydroxide, sodium etbylate, potassium acetate,
potassium thiocyanate, silver nitrate, &c., in equivalent proportions,
resulted in the formation of a metallic bromide, and different organic
compounds. In a few cases only were traces of a metallic chloride
formed, whence it appears that metallic reagents have an exclusive
or almost exclusive preference for the bromine in ethylene chlorobro-
mide. The reaction with silver nitrate is particularly well marked.
The reaction of alcoholic solutions of ethylene chlorobromide and
silver nitrate, in molecular proportion, gives a white bulky pre-
cipitate of pure silver bromonitrate, AgaBrNOa, and a mixture of
ethylene chloronitrate, C2H1CI.NO3, and ethylene chlorobromide, only
half the latter being decomposed ; in order to completely decompose
the ethylene chlorobromide, 2 mols. silver nitrate must be used. This
reaction furnishes an easy method of preparing silver bromonitrate,
and the formation of this compound in this way indicates that the
AgNOa
molecule of silver nitrate is | .
AgNOs
Ethylene Ghloriodide. — The reactions with this compound are
rendered less distinct by the secondary changes, due to the action of
the group CH2CI on the metallic iodide at first formed ; in the
initial reactions, however, metallic reagents shown an exclusive or
almost exclusive preference for the iodine. With silver nitrate,
silver iodonitrate is formed, resembling the bromonitrate in its pro-
j>erties.
Ethylene Bromiodide. — With this compound, the secondary changes
are still more marked, a considerable quantity of iodine being always
liberated, in consequence of the decomposition of the metallic iodide
at first formed, by the action of the group CH2Br which is more
788 ABSTRACTS OF CHEMICAL PAPERS.
active in this respect than the group CH2CI. Metallic reagents show
a marked preference for the iodine.
The experiments with ethylene chlorobromide and ethylene brom-
iodide, show that there is a greater difference between the "reaction
aptitudes" of chlorine and bromine than between those of bromine
and iodine. C. H. B.
Reconversion of Nitro- Glycerol into Glycerol. By C. L.
Bloxam (Ghem. News, 47, 169),— The author has observed that nitro-
glycerol is decomposed by alkaline and alkaline earthy sulphides ; thus,
when an alcoholic solution of nitro-glycerol is shaken with alcoholic
potassium hydrogen sulphide, considerable rise in temperature take
place, the solution becomes red, a large quantity of sulphur separates,
and the nitro-glycerol is converted into glycerol. With potassium
or yellow ammonium sulphide, the reaction is less vigorous ; in the
latter case a qualitative examination of the products of decomposition
proved the presence of glycerol, ammonium nitrite and sulphur, the
reaction can therefore be thus expressed: C3H6(N03)3 + 3NH4HS =
C3H6(OH)3 + SNHiNOa + S3. With calcium sulphide, the reaction is
much slower than in the other cases, and more agitation is required ;
the reduction, however, is complete in a few minutes. D. A. L.
Ethylidene Oxy chloride. By H. Laatsch (Annalen, 218, 13—
38). — Ethylidene oxychloride, C4H8OCI2, first obtained by Lieben by the
action of dry hydrochloric acid on aldehyde, is isomeric with dichlor-
ethyl oxide, one of the products of the action of chlorine on alcohol ; to
the latter, Lieben assigned the formula CHzCl.CHCl.O.CHiMe, and to
the former the constitution (CHClMe)20. The formation of alcohol
and ethyl iodide affords a confirmation of the presence of the ethyl-
group in dichlorether, whilst the production of acetic acid by the
action of water indicates the presence of a methyl-group. To. deter-
mine the constitution of ethylidene oxychloride is the object of the
present communication.
Alcohol forms, with ethylidene oxychloride, aldehyde, hydro-
chloric acid, and aldehyde ethyl chloride, thus, C4H8CI2O +
2C2H50.2(C2H40 + EtCl) + H2O ; sodium ethylate, free from alcohol,
gives alcohol and diethylacetal, whilst sodium ethylate containing
alcohol gives, besides diethylacetal, ethylideneoxyethyl alcoholate,
C4H8(OEt)20, derived from ethylidene oxychloride by the replacement
of 2 atoms of chlorine by two ethoxyl-groups. This latter com-
pound is a colourless liquid (b. p. 153°, sp. gr. = O'SDl), sparingly
soluble in water, and undergoing a gradual decomposition into diethyl-
acetal and aldehyde. Similarly, sodium methylate, propylate, iso-
butylate, and isoamylate, gave their corresponding ethylidene oxy-
alcoholates, the physical properties of which are collected in the
following table : —
Formula. Boiling point. Specific graTity.
Methyl compound. . C4H8(OMe)20 126 0-953
Propyl C4H8(OPr-)20 184 0895
Isobutyl C4H8(OC4H9)20 174 0-879
Isoamyl C^HeCOCjHiOzO 226 0874
ORGANIC CHEMISTRY. 789
The author studied further the action of various alcohols on these
derivatives, and obtained in every case a mixture of two acetals, and
not a so-called mixed acetal. Thus —
C4H8(OMe)20 and amyl alcohol gave dimethyl and diamyl acetal.
C4H8(OC5Hii)20 and methyl alcohol gave dimethyl and diamyl acetal.
C4H8(OPr*)20 and amyl alcohol gave dipropyl and diamyl acetal.
C4H8(OPr'')30 and methyl alcohol gave dimethyl and dipropyl acetal.
C4H8(OC4H9)30 and methyl alcohol gave dimethyl and diisobutyl acetal.
C4H8(OC5H 11)20 and ethyl alcohol gave diethyl and diamyl acetal.
Inasmuch as the action of water on ethylidene oxy chloride gives
aldehyde and hydrochloric acid, it appears that its constitution is
expressed by the formula (CHClMe)20, i.e., that it is the ether of
monochlorethyl alcohol, or the analogue of aldehyde ethyl chloride,
CH3.CH0,EtCl, in which one hydrogen-atom in the ethyl- group is
replaced by chlorine. V. H. V.
Action of Bromine on Amines in Alkaline Solutions. By
A. W. HoFMANN {Ber., 16, 558 — 560). — On treating a solution of a
primary monamine in hydrochloric acid with alkaline bromine, a
nitrogen bromine compound is obtained which contains 2 atoms of
bromine. The amines of the propyl and butyl series yield com-
pounds analogous to the bodies MeNBrg and EtNBr2. Hexylamine
and octjlamine undergo the same reaction.
When a secondary amine is subjected to the same treatment, if it
contains two alcohol-radicles, the primary amine will be formed. If,
however, it contains a divalent alcohol-group, a nitrogen bromine
compound is formed, which contains only 1 atom of bromine. The
formation of piperidine and conine derivatives has been previously
described {Ber., 14, 2725, and 15, *7Q7). If the conine-derivative be
treated with an acid, a base closely resembling conine is formed ; it
differs from it, however, in containing 2 atoms less hydrogen. The
compound, CgHuN, boils at 158°, and is a tertiary base. It also differs
from conine in yielding a picrate which is sparingly soluble. On
treatment with an alkali, the conine-derivative yields a secondary
base, CeHu '. NH, of the same composition as the preceding. It boils
at 173°, and forms a sparingly soluble platinochloride. Reducing
agents convert both this and the preceding base into conine; on
allowing the reduction to continue, the conine is reduced, yielding
octylamine and octane. The new derivatives of conine complete the
series of amines containing 8 atoms of carbon : —
Collidine CgHiiN.
Tropidine CeHigN.
New conine-derivative . . CsHisN.
Conine C8H17N".
Octylamine CsHigN".
When piperidine is treated in the same manner as conine, it yields
bromine and oxygen intermediate products, one of which, CsHyBraNO,
resembles the body CsHaBrgNO, previously described by the author
{Ber., 12, 986). J. I. W.
790 ABSTRACTS OF CHEMICAL PAPERS.
Triacetonamine. By E. Fischer (Ber., 16, 649— 650).— If
Heintz's formula Me.,C<^-^2^>CMe2 (Abstr., 1880, 102) is
correct, this body must be closely related to tropine, and should yield
hydroxytetramethylpiperidine by redaction. By the action of a mix-'
ture of phosphorus pentachloride and phosphorus oxychloride on tri-
acetonamine hydrochloride, a chlorinated basic substance is obtained,
having an odour like that of conine ; ammonia and an oily body being
simultaneously formed. It is readily volatile in steam, and forms a
crystalline platinochloride, sparingly soluble in vrater. When triace-
tonamine is heated with twice its weight of sulphuric acid at 160°,
and the product allowed to cool, a crystalline mass is obtained, from
which on addition of water and alkali, an oil separates which in
its odour resembles piperidine; it consists of a mixture of bases
readily volatile in steam, and forming a crystalline hydrate when
cooled. The hydrochloride crystallises in white needles, melting at
293°, and readily soluble in alcohol. The numbers obtained on
analysis agree approximately with the formula CeHnNjHCl.
A. K. M.
Test for Acetal. By M. Grodzki (Ber., 16, 512). — When acetal is
acted on by acids in presence of water, it yields aldehyde and alcohol.
A dilute aqueous solution treated with normal sodium hydroxide solu-
tion and normal iodine solution yields a clear colourless liquid ; on
acidifying, however, a dense precipitate of iodoform is obtained. 1 c.c.
of a tenth per cent, solution of acetal gives a perceptible amount of
iodoform. J. I. W.
Constitution of Nitrosomalonic Acid. By V. Meter and A.
MtJLLER (Ber., 16, 608 — 611). — In support of Meyer and Ceresole's
formula (C00H)2C ! N.OH for nitrosomalonic acid, the authors state
that they have obtained this body from mesoxalic acid and hvdroxyl-
amine, (C00H)2C0 + NH2.OH = H.O + (C00H)2C ! N.OH. The
mesoxalic acid is neutralised with soda, a solution of hydroxy lamine'
nitrate added in excess, together with the equivalent quantity of
sodium carbonate, and the whole allowed to stand for some days.
Solution of silver nitrate is then added, and the precipitate decom-
posed by hydrochloric acid ; the aqueous solution thus obtained is
evaporated over sulphuric acid or in a current of air, and the nitroso-
malonic acid crystallised from ether. It melts at 120°, and explodes
when heated on platinum foil. When its aqueous solution is warmed,
it decomposes with evolution of carbonic anhydride and formation of
hydrocyanic acid. A further proof of the above formula is afforded
by the reduction of benzylnitrosomalonic acid by hydriodic acid, the
benzyl-group being split off as benzyl iodide, whilst if the formula
(COOH)2C(NO).C7H7 were correct, amidobenzylmalonic acid should
be formed. The conclusions drawn by the authors are, that isonitroso-
bodies are always formed by the action of nitrous acid on the group
CH2, and also on CH when united with easily replaceable radicles,
whilst true nitroso-bodies are formed when CH is united with diffi-
cultly replaceable radicles. A. K. M.
ORGANIC CHEMISTRY. 791
Derivatives of Meconic Acid containing Nitrogen, and their
Conversion into Pyridine. By H. Osr (/. pr. Chem. [2], 27,
257 — 294). — In a previous paper by the author (Abstr., 1879, 708),
two isomeric acids, amidopyromeconic acid and pyromecazonic acid,
were described ; the investigation of the latter acid is continued in the
present paper.
Pyromecazonic acid, C^S. {NO (011)2, is best prepared by the reduction
of oxypyromecazonic acid (loc. cit.) with hydriodic acid ; it crystallises
in well-formed rhombic nearly quadratic tables, having characteristic
striation parallel to the longer axis. It is readily soluble in concen-
trated acids and in alkalis, the latter solutions oxidise with great
readiness on exposure to air ; the acid, when mixed with barium chlo-
ride and ammonia, gives a precipitate, at first colourless, but which
quickly assumes a fine blue colour in contact with air, the reaction
being very delicate. Bromopyromecazonic acid, C5H2BrNO(OH)2, is
obtained as a crystalline precipitate on adding bromine to pyromeca-
zonic acid suspended in water and well cooled. It is insoluble in nearly
all solvents, but little soluble in boiling water ; it dissolves readily in
concentrated hydrochloric acid, from which the hydrochloride crystallises
in long needles ; these lose the hydrochloric acid on treatment with
water, or on heating at 100°. With ferric chloride, silver nitrate, and
ammoniacal barium chloride, the free acid gives the same reaction as
pyromecazonic acid. Diacetylpyromecazonic acid, C5H3NO(OZc)2, is
obtained by long heating of pyromecazonic acid with excess of acetic
anhydride at 150 — 200°. It crystallises in small prisms, melts at 153 —
155°, gives no reaction with ferric salts, and is reconverted into pyro-
mecazonic acid by evaporation with water, or better, with hydro-
chloric acid.
Pyromecazone, CsHsNO '. C2, a quinone-like body, is obtained by care-
ful oxidation of pyromecazonic acid with nitric acid. It is insoluble
in ether, but readily soluble in cold water; it gives no coloration with
ferric chloride, but gives a crimson precipitate with barium chloride
and ammonia. On crystallisation from ethyl alcohol, colourless needles
of the alcoholate, C6li3N'03,EtOH, are obtained ; this and the corre-
sponding methylate, C5H3lSr03,MeOH, lose alcohol on exposure over
sulphuric acid, leaving a brownish-red residue of partially decom-
posed pyromecazone. On boiling with alcohol or water, pyromecazone
is decomposed with formation of brown amorphous products ; on
heating it explodes ; in aqueous solution it imparts a dark violet colour
and most unpleasant odour to the skin. Sulphurous acid readily
reconverts it into pyromecazonic acid.
Nitropyromecazo7ie, C5H2NO(N02)02 + H2O, is obtained, in nearly
colourless compact prisms, by the action of nitric acid on a solution
of pyromecazonic acid in glacial acetic acid. It dissolves readily in
water, the solution on standing or on gentle heating evolves carbonic
anhydride, and deposits yellow crystals of nitropyromecazonic acid ; a
much better yield is obtained, however, by reduction with sulphurous
acid.
Nitropyromecazonic acid, C6H2'N'0(N'02)(OH)2, crystallises from hot
water, in which it is but partially soluble, in golden-yellow plates,
which are not decomposed at 200°. It gives a strong blood-red
792 ABSTRACTS OF CHEMICAL PAPERS.
coloration with ferric cLloride, and has a strongly acid reaction. The
sodium salt, CsHgN'gOslSra., crystallises in anhydrous broad yellow-
needles, and is slowly decomposed on evaporation with water. A cold
aqueous solution of pyromecazone on standing deposits small brilliant
octohedrons, possibly of the hydrate CsHj'N'Oi ; a satisfactory analysis
could not be obtained, owing to contamination by decomposition pro-
ducts.
Hydroxtjcomenamic add, C5H2NO(OH)2.COOH, obtained by
Reibstein (Abstr., 1882, 197) by the action of aqueous ammonia at
150°, on hydroxy comenic acid, can also be prepared by the direct
oxidation of comenamic acid. It must be regarded as a carboxylated
pyromecazonic acid, as it is resolved on heating at above 150° into
carbonic anhydride and pyromecazonic acid ; its reactions with ferric
chloride and ammoniacal barium chloride are similar to those of the
latter.
Bromhydroxycomenic acid, C6HBrNO(OH)2.COOH -\- 2H2O, is
obtained by the action of bromine on an aqueous solution of hydroxy-
comenic acid. It crystallises in very fine needles, is sparingly soluble
in cold water, and reduces silver salts.
Azoncarhoxylic acid, C5H20N(02)''.COOH + 2H2O, is obtained by
the oxidation of an ethereal solution of hydroxycomenamic acid with
nitric acid ; it crystallises in orange-red tables, is readily soluble in
water and hot alcohol, sparingly in glacial acetic acid, and is insoluble
in ether. It imparts a colour to the skin similar to that given by
pyromecazone. Sulphurous acid readily reduces it to hydroxy-
comenamic acid; water partially effects the same reduction, but the
greater part of the substance is resinified.
Coynenaviic acid, C5H3NO(OH).COOE[, is best obtained by heating
comenic acid with aqueous ammonia in an open vessel. It is not
decomposed by boiling with solutions of the alkalis ; fusion with potash
converts nearly the whole of its nitrogen into cyanogen. With ammo-
niacal barium chloride it gives a white precipitate of the hasic salt,
CsHaNO-cC^p^^-v^Ba, which assumes a greenish tint on long standing.
Oxidised with nitric acid, it yields hydrocyanic and oxalic acids ; with
potassium permanganate it gives hydroxycomenamic and oxalic acids ;
and with bromine- water it yields oxalic acid and small quantities of
bromhydroxy comenamic acid. Ethyl comenamate, when heated with
excess of acetic anhydride at 220°, yields an unstable volatile acetyl
compound, and a substance, CsHvNOs, crystallising in small prisms
melting at 261°, and nearly insoluble in water.
PyroGomenamic acid, CsHiNO.OH + H2O, is obtained together with
carbonic anhydride by heating comenamic acid with hydriodic acid at
270°. It crystallises in large colourless needles, is moderately soluble
in water and hot alcohol, insoluble in ether, chloroform, or carbon
bisulphide; it decomposes at above 250°, without previous fusion.
With ferric chloride, it gives an intense violet coloration. It has a
slightly acid reaction, and dissolves in alkalis, but does not appear to
yield crystalline compounds with them. It unites readily with acids ;
the hydrohromide, C5H6N02,HBr, crystallises in prisms, and is readily
soluble in water.
I
ORGANIC CHEMISTRY. 793
Nitrisodipyromeconic acid (Abstr., 1879, 708), after standing for
some months in closed vessels, is partly changed into an isomeric
compound, wliich crystallises in colourless needles with 2 mols. H2O, is
sparingly soluble in hot water, gives an intense dark coloration witli
ferric chloride, and reduces silver salts. Treatment with tin and
hydrochloric acid does not convert it into pyromecazonic acid.
Comenamic acid, when heated with phosphoric chloride in a vessel
provided with a reflux condenser, yields an amorphous substance
(probably C5H3CI3N.COC]), which is reconverted into comenamic acid
by heating with water. By reduction with tin and»hydrochloric acid,
it is converted into the aldehyde of dihydrohydroxypyridinecarhoxylic
acid, C5H5N(OH).COOH, crystallising in anhydrous well-formed short
transparent prisms, or with 1 mol. H2O in long prisms, which effloresce
in air. It is sparingly soluble in cold water, gives the same reaction
as comenamic acid with ferric chloride, and readily reduces ammo-
niacal silver solution. By the further action of phosphoric chloride
on comenamic acid it is converted into a mixture of pentachloro- and
hexachloro-picoline, the reaction having to be assisted towards the
close by heating at 250° in sealed tubes ; small quantities of mono-
chlorhydroxypyridinecarboxylic acid, C5B[3ClN(OH).COOH, and of
an acid, C8H8CINO4, are also formed. Hexchlor-cc-picolinej
C5HCI3N.CCI3,
can be separated from the mixture by fractional solidification and re-
crystallisation from alcohol ; it is formed almost exclusively if a still
larger excess of phosphoric chloride (6 — 7 mols.) and a temperature
of 280 — 290° be employed in the reaction. It crystallises in large
colourless acute-angled prisms, melts at 60°, is readily soluble in hot
alcohol, insoluble in water, acids, or alkalis. It has a faint odour,
not, however, like that of pyridine.
Monochlor-oc-picoline, CeHeClN, is obtained by the action of hydriodic
acid on the mixture of penta- and hexa-chloropicoline ; it boils at
164 — 165° (uncorr.), is readily volatile in steam, ha^ a sp. gr. of 1*146
at 20°, and c an be obtained by cooling in large colourless prisms melting
at 2L°. It has a strong pyridine-like odour, is sparingly soluble in
water, readily in alcohol and ether. It has basic properties, reacts
strongly alkaline, and dissolves readily in acids. The hydrochlonde,
CeHeCUSTjHCl, crystallises in anhydrous prisms, readily volatilises at
100°, and is decomposed into its constituents when heated with water.
The platinochloride, (C6H6ClN),H2PtCl6, crystallises in anhydrous
prisms or needles, and is sparingly soluble in cold water.
Ghloriodopicoline, CeHsClIN, prepared by digesting monochloro-
picoline with iodine and caustic soda solution, crystallises in colourless
prisms, apparently rhombic, is insoluble in water, soluble in alcohol,
and can be distilled in steam. It has basic properties. The hydro-
chloride is sparingly soluble iu water ; the platinochloride crystallises
in plates. By the long-continued action of hydriodic acid at 270° on
chloropicoline, very small quantities of a base richer in hydrogen and
free from chlorine is obtained. It appeared to have the formula
CeHiaN" (methylpiperidine), but could not be obtained in a pure
state.
VOL. XLIV. 3 h
794 ABSTRACTS OF CHEMICAL PAPERS.
By heating the mixture of penfca- and hex-cliloropicoline with 8nl-
phuric acid (80 per cent, strength) for about an hour in a vessel pro-
vided with a reflux condenser, dichloropicolinic acid, dichlorhydroxy-
picolinic acid, and monocblorhydroxypicolinic acid are formed, the
first and third of these being derived from the pentachloropicoline,
the second from hexchloropicoline. They are best separated by pre-
cipitation with water, and treatment of the dried precipitate with
chloroform, in which dichloropicolinic acid dissolves, whilst the nearly
insoluble hydroxy-acids are converted into calcium salts, of which that
of the dichlorhydrexy-acid is sparingly soluble in water, whilst that of
the monochlorhydroxy-acid is readily soluble.
Dichloropicolinic acid, C5H2CI2N.COOH + H2O, crystallises in slender
needles, melts with decomposition at 180°, is sparingly soluble in cold
water and ether, readily in hot water, in alcohol, or in hot chloroform.
It volatilises appreciably at 100°, does not give any coloration with
ferric chloride, nor unite with dilute mineral acids. The sodium salt,
C5H2Cl2N.COONa, crystallises in plates or needles, sparingly soluble
in cold water ; the potassium salt, CaHaCliN.COOK, crystallises like"
the sodium, salt ; the ammonium salt forms rectangular plates ; the
harium and calcium salts are insoluble. Dichloropicolinic acid is readily
reduced by sodium-amalgam ; in alkaline solution, all the nitrogen is
evolved as ammonia ; in acid solution no ammonia is formed ; no
crystalline products are obtained in either case.
Tetrahydromonochloropicolinic acid, C5H7C1N'.C00B[, is obtained as
hydrochloride by the action of tin and hydrochloric acid on dichloro-
picolinic acid. The free acid crystallises in brilliant rectangular
plates, melts at 265 — 270°, previously blackening, and is readily
soluble in water. The hydrochloride, C6Ht,ClN02,HCl, crystallises in
readily soluble acute-angled tables and prisms. The copper salt is
characteristic, precipitating in bundles of blue prisms.
Monochloropicolinic acid, C5H3CIN.COOH + H2O, obtained by the
action of hydriodic acid dissolved in glacial acetic acid on dichloro-
picolinic acid at 140 — 150°, crystallises in acute-angled prisms or
needles. It loses its water of crystallisation and sublimes pretty
readily at 100°, and melts at 168°. It is sparingly soluble in cold
water, readily soluble in hot water and in alcohol, moderately soluble
in ether. It does not unite with acids. The hariiim salt^
(C5H3ClN.COO)2Ba + 2H,0,
crystallises in sparingly soluble plates ; the calcium, copper, lead, and
silver salts are also nearly insoluble.
By heating dichloropicolinic acid with hydriodic acid for three days
at 155 — 160°, it is converted into hexahydropicolinic acid and an acid
agreeing in all particulars with the picolinic acid obtained directly
from picoline by Weidel (Abstr., 1880, p. 268).
Hexhydropicolinic acid, C5II10N.COOH, is the main product of the
action of hydriodic acid on mono- or di-chloropicolinic acids ; addition
of ordinary phosphorus prevents the formation in the reaction of
any of the acids containing less hydrogen. It forms a syrup readily
soluble in water. The hydrochloride crystallises in warts, and is also
very soluble ; the platinochloridey (C6HuN02)2,H2PtCl6 + 2H2O crystal-
ORGANIC CHEMISTRY. 795
lises in orange- to brownish-red apparently rhombic prisms ; it is
readily soluble in water.
Bichlor-cc-Tiydroxypiculinic acid, C5HCl2N(OH).COOH -j- H2O, ob-
tained as previously mentioned, crystallises in fine interlaced needles,
or in small hard prisms. It melts with decomposition at about 282°,
gives a pale yellowish-red coloration with ferric chloride, and has an
acid reaction. Its salts are mostly soluble. The calcium salt,
(C5HCl2N[OH].COO)2Ca, is sparingly soluble in water, either hot or
cold ; it forms pale yellow star-like crystals of silvery lustre. The
free acid is not reduced by boiling with aqueous hydriodic acid, nor
by tin and hydrochloric acid ; sodium-amalgam reduces it to a syrup
soluble in alcobol. By heating at 200 — 210° with hjdriodic acid
dissolved in glacial acetic acid, it is converted into oi-hydroxijpicollnic
acid, C5H3]Sr(OH).COOH; this crystallises with 1 mol. H2O in long
needles, or less frequently in anhydrous short needles, melts at 267°,
is not volatile, dissolves readily in hot water and alcohol, and is in-
soluble in ether. It gives a reddish-brown coloration with ferric salts,
a white precipitate with silv^er salts ; it does not reduce silver salts.
The copper salt is sparingly soluble ; the characteristic barium salt,
(C6H4N03)2Ba + H2O, is precipitated on adding barium chloride to
neutral or ammoniacal solutions of the acid ; it can be crystallised
from hot water in obtuse-angled prisms and needles. The calcium
salt, (C6H4N03)2Ca, crystallises in short prisms or rhomboidal tables,
and is moderately soluble in water ; the basic potassium salt,
CjHaNCOKj.COOK + H2O,
separates in groups of needles on adding ether-alcohol to a solu-
tion of the acid in concentrated potas;h. A hydrochloride crystallising
in slimy needles appears to exist. The further action of hydriodic
acid at above 220° leads to the formation of other acids (richer in
hydrogen ?) and elimination of ammania.
Monochloro-(3-hydroxypicolinic acidy C5H2Cl]Sr(OII).COOH + HoO,
whose preparation has been already given, crystallises in thick needles,
melts with decomposition at 257°, and is more soluble in water
than the dichlor-a-hydroxy acid ,* it i^acts strongly acid and gives a
yellowish-red coloration with ferric salts. The calcium salt,
(C6H3ClN03)2Ca -f 4H,0,
crystallises in hard rhombic tables. Heated at 200° with hydriodic
acid dissolved in glacial acetic acid, it yields (3-hydroxypicolinic acid,
C6H3N(OH).COOH, crystallising with 1 mol. H,0 in brilliant rectan-
gular plates, and melting at 250^. The iS-acid is more soluble in
water and alcohol than its isomeride, is insoluble in ether, and gives a
yellowish-red coloration with ferric chloride, much paler than that
given by the a-acid. It is not volatile. The barium salt,
(CoH4N03)2Ba + 2H2O,
crystallises in small tables ; it is sparingly soluble in water, but is
more soluble than the salt of the a-acid. The hydrochloride crystal-
lises in fine thick prisms.
On heating comenic acid with phosphoric chloride in a vessel pro-
3 h 2
70 i) ABSTRACTS OF CHEMICAL PAPERS.
vided with a reflux condenser, and snlisequently adding water, an acid
of the formula C5HCI2O2.COOH (m. p. 217°) is obtained; at higher
temperatures (280 — 290°) tlie reaction takes another course, hexa-
chlorethane and perchloromecylene being formed, together with oily
products not yet separated.
Perchloromecylene, CaClg, crystallises from alcohol in compact acute-
angled prisms, melts at 30", is readily soluble in alcohol, insoluble
in water, has a camphor-like odour, volatilises slowly in a current
of steam, and boils at 270° with evolution of chlorine. A. J. G.
Oxidising Action of Dilute Nitric Acid on Metaisobutyl-
toluene. By W. Kelbe (Ber.,^ 16, 610— 621).— The author obtains
an acid containing the same number of carbon-atoms as the
hydrocarbon oxidised, so that it must be either metaisobutylben-
zoic acid, CHMe2.CH2.C6H4.COOH, or metatolylisobutyric acid,
C6H4Me.CH2.CHMe.COOH, the latter being in the author's opinion
the more probable. It crystallises from light petroleum in needles
melting at 91—92°. A. K. M.
Symmetrical Tribromaniline. By L. Gattermaxn (Ber., 16,
634 — 636), — It is genera,lly stated that symmetrical tribromaniline
does not form salts. In an attempt to obtain higher substitution
derivatives, the author prepared tribromaniline by the action of bro-
mine on aniline salpbate, dissolved the product in benzene, and added
bromine as long as a precipitate was produced. Hydrobromic acid
was evolved, and a mass of small white needles obtained consisting of
tribromaniline (symmetrical) hydrohromide. It is insoluble in benzene,
xylene, light petroleum, ether, and alcohol, melts at 190° with pa.rtial
decomposition, but can be sublimed unchanged, forming long white
needles. It is moderately stable in dry air, whilst water and alkalis
rapidly decompose it. The same body is also obtained by passing dry
hydrobromic acid into a solution of symmetrical tribromaniline in
benzene. By the action of hydrochloric acid, the corresponding hydro-
chloride is formed crystallising in needles- It is far less stable than
the hydrohromide, and loses the greater part of its hydrochloric acid
by exposure to the air. A. K. M.
Gallocyanins. By Kochlin (Chem. News, 47, 170 — 171).— When
an alcoholic solution of nitroso-dimethylaniline hydrochloride is
allowed to react with the tanuins or gallic acid, colouring matters are
obtained, which the author calls gallocyariins.
These colours resist light and various reagents better than alizarin
violets do. Neither concentrated hydrochloric acid nor caustic soda
(38° B.) changes the tone of the violets fixed with chrome. These
colours are faster against chlorine when the dyed material is prepared
with stannate, whilst they resist light better on unprepared cloth.
Yellow or maize discharges may be produced by printing the violet over
a chrome- orange design saturated with dichromate, and after cleansing,
taking the pieces through lukewarm oxalic acid at 25 grams per litre.
The, addition of alizarin in proportion of 1 — 30 strengthens the colour
ORGANIC CHEMISTRY. 797
without sensibly affecting its tone ; in other proportions, olives and
loutres are produced.
Gallocjanin from gallic acid, gallic gallocyanin, is crystalline with
metallic lustre ; its best solvents are ammonia, soda, and the acid sul-
phites. Hydrogen sodium sulphite in excess, however, decomposes it,
forming an orange colouring matter and an insoluble substance ; at
the best, the solvent action of sodium hydrogen sulphite is very slow.
Gallic gallocyanin dyes woollens and silks violet-blue. This dye, like
alizarin, requires double mordants for fixing it on cotton ; with alu-
minous mordants it dyes violets ; with those of iron blacks. In dyeing,
tin, chrome, cobalt, or nickel may be used ; with the other oxides, the
violet does not stand soaping at a boil.
Catechin gallocyanin gives redder shades than gallic gallocyanin.
It is fixed in the same manner, and dyes violets with alumina and iron
which bear soaping well.
Marine or Morintannic Gallocyanin is green. In printing it is fixed
with chromium acetate. With mordants of chrome, tin, alumina, and
iron, it dyes olives, which are exceedingly fast against soap.
Ammonium hydrogen sulphite easily dissolves and reduces it, thus
forming a vat in which goods may be dyed by immersion and subse-
quent oxidation in the air, precisely as with indigo. D. A. L.
Action of Ethyl Chloracetate on Primary Diamines. By
J. ZiMMERMANN and M. Knyrim {Ber., 16, 514^516). — One of the
authors has previously shown {Ber.,\b, 518) that when metaphenylene-
diamine is acted on by ethyl chloracetate, the ethyl salts of metaphenyl-
enediglycocine and phenylenediamine hydrochloride are obtained.
Since the glycocine could not be obtained by the direct action of
chloracetic acid on phenylenediamine, the authors have endeavoured
to saponify the ethyl salt in order to separate it. On treating ethyl
phenylenediglycocine with strong hydrochloric acid, the authors
obtained the hydrochloride of phenylenediglycocine
CeH^CCHaNH.COOH.HCI),.
They were unable to obtain either the free base or a platinochloride.
The crystals of the hydrochloride are freely soluble in water.
When paraphenylenediamine is treated with ethyl chloracetate, it
yields a product similar to the meta-compound. It crystallises frt)m
water in colourless or brown needles, C6H4(CH2NH.COOEt)2, melting
at 83°. It is easily soluble in hydrochloric acid, and like the meta-
compound, yields a hydrochloride of the glycocoll
C6H4(CH2.NH.COOH,HCl).
It crystallises from hydrochloric acid in colourless plates, and does
not yield a platinochloride.
Orthophenylenediamine when treated like its isomeride yields a
body crystallising in long yellow needles (m. p. 135"), which have not
yet been analysed.
When toluylenediamine is acted on by ethyl chloracetate, it yields
ethyl toluylenediglycocine, which crystallises from light petroleum in
glassy greenish crystals, and from water in bright yellow needles
798 ABSTRACTS OF CHEMICAL PAPERS.
melting at 70°, This salt could not be saponified with hydrochloric
acid. J. 1. W.
Cyanic Acid Derivatives of the Three Isomeric Phenylene-
diamines. By B. Lellmann (Ber., 16, 592— 593).— The author has
shown (this vol., p. 324) that the thiocyanatos of the three phenylene-
diamines, exhibit difPerent chemical changes. He now finds that the
corresponding cyanates are all converted alike into phenylenedicar-
bamides, the action taking place much more readily than in the case
of the thiocyanates. OrtJiopJienijlenedicarbamide, C6H4(NH.CONH2).,
is obtained on mixing solutions of orthophenylenediamine hydro-
chloride and potassium cyanate, and can be purified by crystallisation
from hot dilute alcohol. It crystallises in needles melting at 290°, is
readily soluble in alcohol, water, and in glacial acetic acid, sparingly
in chloroform, benzene, and ether. Metafhenylenedicarhamide has
been described by Warder {Ber., 8, 1180). Paraphemjlenedicarhamide
crystallises in plates having a silvery lustre ; when heated these decom-
pose without melting. A. K. M.
Compounds of the Hydrazines with the Ketones. By H.
Reiseneggee {Ber., 16, 661 — 664). — Fischer {Annalen, 190) has de-
scribed compounds of the hydrazines with the aldehydes ; Meyer and
Petraczek {Ber., 15, 2783) similar compounds of the aldehydes with
hydroxylamine ; whilst Meyer and Janny (Abstr., 1882, 1047) showed
that hydroxylamine likewise formed compounds with the ketones. The
author finds that the hydrazines also combine with the ketones, the
products being unaltered by potash, although readily decomposed by
acids, with formation of the original substances. By the action of
phenylhydrazine on acetone, acetonephenylhijdrazine is produced, and
can be purified by heating on a water-bath to drive off the excess of
the acetone, then shaking with water and extracting with ether ; the
latter is evaporated, the residue dried with potassium carbonate, dis-
tilled in a vacuum, and finally allowed to stand over sulphuric acid to
get rid of traces of ammonia. Its formation is thus shown : — PhNjHs
+ COMca = PhKjHCMea + H2O. It has no action on Fehling's solu-
tion. On adding sodium nitrite to a cold solution in dilute sulphuric
acid, diazobenzenimide, CeHjNa, is precipitated. Acetop/ienonephe^iyl-
liydrazine, PhNaHCPhMe, is obtained by warming a mixture of
acetophenone and phenylhydrazine, washing the crystalline product
with dilute acetic acid, and crystallising from alcohol. It forms
slender white needles melting at 105°, sparingly soluble in water and
cold alcohol, readily in ether. Fehling's solution readily decomposes
it. When a mixture of acetophenone and dimethylhydrazine is heated
for some hours at 100° in sealed tubes, acetophenonedimethylhydrazine,
MeaNjCPhMe, is formed as an oil which does not reduce Fehling's
solution. It distils at 165° under a pressure of 190 mm. On heating
cenanthaldehyde with phenylhydrazine at the temperature of a water-
bath, water is given off with the formation of a body of the formula
PhNaH.CTHu. It is a yellowish coloured oil, boiling at 240° under a
pressure of 77 mm., and not solidifying at — 20". Fehling's solution
has no action on it, whilst boiling with acids decomposes it into
ORGANIC CHEMISTRY. 799
aldehyde and hydrazine. Chloral and phenylhydrazine react very
violently at the ordinary temperature with evolution of hydrochloric
acid and formation of a semi-carbonised product. A crystalline body
can, however, be obtained if the base is dissolved in ether and the
chloral added to the cooled solution which is then evaporated to a
fifth of its volume and precipitated with light petroleum. The slender
white needles obtained are very unstable, so that no analysis has been
made. A. K. M.
Amarine and Furfurine. By R. Bahrmann (7. pr. Chem. [2],
27, 295 — 320). — The author finds the best method of preparing
amarine to be that of Bertagnini (Annalen, 88, 127). The melting
point is 113°, not 100*^, as previously stated. An ethereal solution of
amarine, mixed with an equivalent quantity of acetic chloride, gives
an amorphous white precipitate of amarine acetyl chloride,
C2,Hi8N2,l3Cl.
It is very unstable, a solution in cold absolute alcohol begins to
decompose in the course of a few minutes, diacetylamarine being
precipitated, whilst amarine hydrochloride remains in solution. Di-
acetyl amaiine, C2iHi6(Xc.j)N2, is thus obtained in white flocks consist-
ing of a network of microscopic needles melting at 268°. It is only
sparingly soluble in hot alcohol (0*5 gram in 7 litres), insoluble in
water, ether, benzene, and chloroform. It does not react with
moderately concentrated acids or alkalis. Benzoic chloride and
amarine unite directly in_ ethereal solution, the resulting amarine
benzoyl chloride^ C2iHisN2,BzCl, forms a white indistinctly crystalline
precipitate, which is more stable than the acetyl compound; its
alcoholic solution, however, decomposes on long standing, but amarine
hydrochloride was the only definite compound isolated from it. By
the action of benzoyl chloride on an alcoholic solution of amarine,
amarine chloride and a substance of the formula C2iHi6N2Bz.OEt,
crystallising in small white needles, were obtained. On treating a cold
ethereal solution of amarine with ethyl chlorocarbonate, amarine
hydrochloride and diethyl amarinedicarboxylate, 02iHi6N"2(COOEt)2,
are precipitated and can be separated by crystallisation. The latter salt
is readily soluble in hot alcohol, sparingly soluble in ether, insoluble in
water. The alcoholic solution has a neutral reaction. Heated with
alcoholic ammonia in sealed tubes at 100° for some days, it is converted
into a base of the formula C2,Hi6lSr2(COOEt).CONHEt. This crystal-
lises in small rosettes of silky needles, is very soluble in alcohol, has a
strong alkaline reaction, and gives crystalline salts with acids. The
hydrochloride, C27H27N303,HCl, crystallises in brilliant prisms, and is
readily soluble in hot water or hot alcohol. The platinochloride,
(C27H27Na03)2,H2PtCl6 + HgO,
forms orange-coloured crystals. The author considers that his results
best agree with the constitutional formula assigned to amarine by
Glaus (this vol., p. 204).
Acetic chloride and furfurine unite to form an unstable molecular
compound, quickly decomposing in alcoholic solution into furfurine
hydrochloride and monacetyl furfurine.
800 ABSTRACTS OP CHEMICAL PAPERS.
Benzoylethoxy-furfurine, Ci6Hn02N2Bz(OEt), is obtained by the action
of alcohol on the precipitate formed by addition of benzoic chloride to
an ethereal solution of f urfurine. It crystallises in groups of microscopic
needles, melts at about 290°, and can be sublimed. It is moderately
soluble in chloroform or glacial acetic acid, very sparingly soluble in
alcohol, insoluble in ether or water, and does not unite with acids or
bases. By the action of ethyl chlorocarbonate on furfurine, diethyl
furfurinedicarboxylate, Ci6Hn03N2(COOEt)2, is obtained; it crystallises
in hard brilliant prisms, melts at 124°, is soluble in hot alcohol,
sparingly soluble in water, and insoluble in ether. A. J. G.
Anhydro-compounds. By W. Bottcher (Ber., 13, 629 — 634). —
Hiibner and Stiinkel (Annalen, 210, 384) have described the prepara-
tion of anhydrobenzamidophenol, C6H4<^ ^CPh, by the reduction
or orthonitrophenol benzoate by means of tin and hydrochloric acid,
and subsequent decomposition of the resulting tin compound by
hydrogen sulphide. They did not, however, succeed in obtaining the
intermediate compound, orfchamidophenol benzoate. The author finds
that if hydrogen sulphide is passed into the cold alcoholic solution of
the tin compound, the anhydro-body is obtained nearly pure ; if into
a hot solution, a mixture of the latter with henzamidophenol, C13H11NO2,
is formed, from which the anhydro-compound can be extracted by
means of light petroleum. Benzamidophenol can also be obtained
from the anhydro-compound by heating its alcoholic solution with
hydrochloric acid for two days on a water-bath. The liquid assumes
a red colour, and on cooling deposits reddish-coloured shining plates,
melting at 165°. ThaU;his body has the constitution HO.CeHi.NHBz,
and not NH2.C6H4.OBz, is shown by its ready solubility in alkalis,
from which it can be reprecipitated by acids. It also agrees in its
properties with Hiibner's orthobenzamidophenol. The apparently
anomalous change of position of the benzoyl-group from its union
with oxygen (in orthonitrophenol benzoate) to nitrogen is readily
explained when anhydrobenzamidophenol is regarded as the inter-
mediate product, thus : —
/NO, Is"^ ^NH.COPh
C6H4< , CeH^ >CPh, CeH/
^O.COPh ^O^ ^OH
A. K. M.
Nitro- and Amido-derivatives of Benzenesulphonanilide and
Benzenesulphonparatoluide. By E. Lellmann (Ber., 16, 594 —
597). — Benzenesulphonorthonitranilide, C6H6.SO2.NH.C6H4.NO2, is ob-
tained when benzenesulphonic chloride (1 mol.) is added to a solu-
tion of nitraniline (2 mols.) in a little benzene, and the whole warmed
on a water-bath. The liquid is separated from the nitraniline hydro-
chloride, which is washed with light petroleum. It forms yellowish
coloured plates insoluble in light petroleum and in benzene. In moist
air, it decomposes with evolution of hydrochloric acid, also when
heated to 155° or by contact witb water or alcohol. After heating
I
ORGANIC CHEMISTRY. 801
fhe filtrate from the nitraniline salt to drive off the benzene and
petroleum and allowing it to stand in a desiccator, benzenesulphon-
orthonitranilide is obtained, and can be purified by crystallisation
from hot petroleum. It forms yellow plates melting at 104°, and
readily soluble in alcohol, glacial acetic acid, chloroform, and benzene.
Benzenesul'phonmetanitranilide crystallises in bright yellow needles,
melting at 131 — 132°, readily soluble in alcohol, glacial acetic acid,
chloroform, and benzene.
Benzenesulplionparanitranilide forms yellow crystals melting at 139°,
and is readily soluble in alcohol, benzene, and glacial acetic acid, more
sparingly in chloroform and light petroleum. Benze7iesulphonmeta-
nitroparatoluide, C6H5SO2.NH.C6H3Me.NO2, is obtained by the action
of nitric acid (sp. gr. 1"43) on benzenesulphonparatoluide and pre-
cipitation by water, also by the action of benzenesulphonic chloride
and benzene on metanitroparatoluidine. It crystallises from hot
alcohol in cubes melting at 99°.
Benzenesulphonmetaditdtroparatoluide,
C6H5.S02.NH.C6H2Me(N02)2,
is produced by tbe action of nitric acid of sp. gr. 1*47 on benzenesul-
phonparatoluide. It crystallises from hot alcohol in dense yellowish
prisms melting at 178°, and from hot benzene in wedge-shaped crys-
tals containing 1 mol. benzene. It is readily soluble in hot alcohol
and in benzene, sparingly in cold alcohol. Benzenesulphonorthaniido-
anilide, C6H5.SO2.NH.C6H4.NH2, obtained by the reduction of the
corresponding nitro-compound, crystallises from 50 per cent, alcohol
in long colourless needles melting at 168°, and is sparingly soluble in
water, readily in alcohol, glacial acetic acid, and in chloroform. The
hydrochloride^ C6H5.S02.NH.C6H4.NH2,HC1, separates from water in
large dense anhydrous crystals. Benzenesulphonmetamidoparatoluidey
C6H5.SO2.NH.C6H3Me.NH2, crystallises from dilute alcohol in long
colourless needles melting at 146 5°. It is readily soluble in alcohol
and in glacial acetic acid, sparingly in water. A. K. M.
Metanitrophenylthiocarbimide. By H. Steudemann (Ber., 16,
548 — 551). — When metanitrothiocarbanilide, prepared according to
Losanitsch's method, is dissolved in hot acetic anhydride, and the
solution, after addition of water, is boiled for a short time, metani-'
trophenylthiocarbimide separates as a heavy oil, which solidifies on
cooling. The crystals are pressed between filter- paper to remove
admixed phenylthiocarbimide, and after being distilled by steam are
obtained colourless (m. p. 58°). When solid it has no odour; but
on melting evolves the characteristic smell of thiocarbimides. It
is freely soluble in ether, glacial acetic acid, and alcohol, and only
slightly soluble in water. It can be obtained in fine white needles by
adding water to a solution in alcohol until a precipitate just begins
to form. When an alcoholic solution is heated with aniline, metani-
trodiphenylthiocarbimide is formed. With metanitraniliue, it yields
yellow crystals of metadinitrodiphenylthiocarbimide,
CS(NH.C6H4.N02)2,
802 ABSTRACTS OF CHEMICAL PAPERS.
rneltinj^y at 160°. When treated with alcoholic ammonia, it forms
metanitromonophenjlthiocarbimide crystallising in lemon-colonred
crystals inelting at 157— 158'5°. When metanitrophenylthiocarbi-
mide is dissolved in boiling alcohol, it is converted into nitrophenyl-
ethylurethane (m. p. 115°). Ph enylthiocarbi mi de undergoes a similar
change only when heated in a sealed tube at 110—115°. If methyl
alcohol is employed, the corresponding methyl urethane is obtained in
glittering colourless needles melting at 119 — 120". J. I. W.
Conversion of Phenols into Nitriles and Carboxylic Acids.
By Y. Merz (Ber., 16, 512— 513).— Weith and Merz have shown
(Ber., 10, 746) that the monohaloid derivatives of benzene hydrocar-
bons yield the corresponding nitriles when heated with cyanides of
metals. The conversion of phenols into nitriles has not been investi-
gated since Scrugham's research in 1854 (Jahresher., 605). At the
instigation of the author, Heim has studied the action of potassiun^
cyanide on the neutral phosphates of phenols under the influence of
heat. In all cases nitriles are formed which by saponification yield the
corresponding acids. He has, in this manner, prepared benzoic acid,
ortho- and para-toluic acids, and the two naphthoic acids from tri-
phenyl, ortho- and para-tricresol, and a and /3 trinaphthyl phosphates
respectively. Traces of higher nitriles are formed. J. I. W,
Reduction of Substituted Phenols. By F. Pfaff (Ber., 16,
611 — 616). — With the view to obtain monobromoresorcinol, the author
brominated metanitrophenol, reduced the product with tin and hydro-
chloric acid, and then by means of the diazo-reaction obtained a body
which he found to be resorcinol, and not a bromine-derivative as he
expected. The elimination of the bromine takes place during the
reduction by the tin and hydrochloric acid, and can also be effected by
stannous chloride. By the reduction of the methyl ether of bromo-
metanitrophenol, metamidoanisoil is produced. The potassium-deri-
vative of monobroraometanitrophenol, C6H3Bi-(N02).OK + 2H2O, is
a red body which loses its water of crystallisation over sulphuric acid,
at the same time becoming brown. The sodium-derivative,
C6H3Br(NO,).ONa+HA
is yellowish-red and does not change colour on becoming anhydrous.
By the action of ammonium sulphide on dinitrometaxylene, the author
has prepared nitroxylidine, and from this by the diazo-reaction
nitroxylenol, C6H2Me2(N02).OH. The latter forms yellow crystals
melting at 95°. ' A. K. M.
Phenol-derivatives. By L. Henry (Compt rend., 96, 1233—
1235). — Phenyl monochlorethi/l oxide, PhO.CHz.CHjCl, is obtained by
the action of ethylene chlorobromide on an alcoholic solution of
potassium phenate. It is a colourless solid, with an agreeable phenolic
odour, and a sharp taste. It is quite insoluble in water, but dissolves
easily in alcohol, ether, &c. It melts at 25°, and boils without decom-
position at 221° under a pressure of 754 mm. ; the fused mass on
cooling crystallises in thick elongated hexagonal lamellis belonging to
ORGANIC CHEMISTRY. 803
tlie monoclinic system. Since it contains the group CHaCl, it has the
properties of the haloid ethers, and reacts readily with metallic and
hydrogenised compounds. Alcoholic potash converts it into the com-
pound C,Hi(OC6H5)2.
The corresponding bromine-derivative has been described by Wed-
dige (Abstr., 1881, 1136). It melts at 39° and boils between 250°
and 260° with partial decomposition.
The isomeric ethyl-mononlilor phenyl oxide, EtO.C6H4Cl, was described
by the author some years ago {Bull. Acad. Bruxelles, 1869, 566).
Ethylene fhenyl-ethyl oxide, FhO.CH2.CH2.EtO, is obtained by the
action of alcoholic potash on the preceding compound in sealed tubes.
It is a limpid liquid, insoluble in water, with an agreeable ethereal
odour differing from that of other phenol-derivatives. It boils at
about 230° without decomposition; sp. gr. at 11° = 1"018. This
compound is obtained more easily by the action of alcoholic potash an
phenyl- monobromethyl oxide, but in this case the reaction is not so
simple, a notable quantity of a more volatile liquid boiling at about
170° being also produced. This liquid is colourless, insoluble in water
and in solutions of caustic alkalis, and reacts energetically with
bromine ; it is probably oxyphenyl ethylene, CH2 '. CH.OPh, but has
not yet been analysed.
Pheiiylmonohromallyl oxide, PhO.CH2.CBr ! CH2, is obtained by the
action of alcoholic potassium phenate on mouobromallyl bromide boiling
at 142°. It is a limpid colourless liquid, which becomes yellowish after
some time. It has a feeble phenolic odour, a sharp and bitter taste,
and is insoluble in water. It boils at about 240°, with slight decom-
position : sp. gr. at 11° = 1*4028.
Fhenylpro})argyl oxide or Propargylic phenol, PhO.C3H3, cannot be
obtained from allylic phenol, PhO.C^Hs (Jier., 1872, 455), but is pre-
pared by the action of alcoholic potash on the preceding compound.
It is a colourless liquid, becoming brown after some time, with a
feeble propargylic odour and a sweet sharp taste. It is insoluble in
water, and boils at about 210°, but has no fixed boiling point, and
undergoes alteration on ebullition, being probably polymerised ; sp. gr.
at 6° = 1-246. C. H. B.
Nitro-derivatives of Resorcinol. By R. Benedikt (Ber., 16,
667— 668).— A reply to Typke.
Benzil. By M. Wittenberg and "V. Meyer (Ber., 16, 500—508). —
The constitutions of benzoin and of the bodies nearly related to it
are generally expressed by the following formules : —
Ph.CO.CHPh(OH). CH.Ph.CO.Ph.
Benzoin. Deoxybenzoin.
CHPh(OH).CHPh(OH). Ph.CO.CO.Ph.
Hydrobenzom. Benzil.
There is little doubt that the above formula of deoxybenzoin is
correct, and that it is a mixed ketone of benzoic and phenylacetic
804 ABSTRACTS OF CHEMICAL PAPERS.
acids. The formula for benzil does not explain how the characteristic
d^compositioa into benzilic acid can take place.
Action of Heated Lead Oxide on Benzil. — The ordinary formula
places benzil in close relationship to phenanthraquinone. V/hen
benzil vapour is passed over heated lead oxide benzophenone is ob-
tained. The authors have carefully determined the boiling point of
benzil, and find it to be 346—348'' (corr.).
Action of Heated Lead Oxide on Phenanthraquinone and Benzoin. —
When phenanthraquinone is heated with lead oxide, it yields di-
phenylene ketone (m. p. 83 — 84° C) Benzoin under similar circum-
stances yields benzophenone, as was to be expected, since benzil is
formed as an intermediate product.
According to V. Meyer's rule, it is to be expected that by the action
of hydroxylamine on benzil only such oxygen-atoms as are present in
carbonyl-groups will be replaced by the group =N — OH. The oldest
formula of benzil, PhC^- — -^CPh, does not admit of any reaction
taking place.
Action of Hydroxylamine on Benzil. — By treating an alcoholic
solution of benzil with a concentrated aqueous solution of hydroxyl-
amine, a body crystallising in small white quadratic plates is
obtained melting at 130 — 131°. It has the composition CuHaOzN^ or
Ph.C]S'(OH).COPh. This result puts the formula PhC^l-^CPh
out of the question. It is equally incompatible with the ordinary
formula, because only one oxygen- ^tom has been replaced.
In order to show that the hydroxylamine reaction takes place in
the benzoin series in the san:ie manner as with other ketones, and that
the groups CO — CO are both replaceable like a single CO-group, the
authors have made the following experiments : —
Action of Hydroxylamine on Benzoin. — An alcoholic solution of
benzoin was mixed with an aqueous hydroxylamine solution, and
allowed to stand for a week. The product was a snow-white powder
consisting of microscopic prisms (m. p. 151 — 152°) of the composition
CuHiaNOj. The reaction proceeds according to the equation —
Ph.CO.CHPh.OH + NH^OH = H.O + Ph.CN(OH).CHPh.OH.
Action of Hydroxylamine on Glyoxal. — According to the ordinary
formula benzil may be looked upon as a diphenylated glyoxal.
Glyoxal, however, when acted on with hydroxylamine, takes up two
atoms of nitrogen, therefore benzil cannot be represented by the
formula of a substituted glyoxal. On treating an aqueous solution of
glyoxal with hydroxylamine, a colourless body crystallising in trans-
parent well-formed rhombic plates (m. p. 178°) is obtained. It can
easily be sublimed, and dissolves readily in hot water, alcohol, and
ether. Its aqueous solution is slightly acid. When boiled with acids
it yields hydroxylamine. Its composition is C2H4N0O2. The authors
propose to call it glyoxime. The reaction proceeds as follows : —
I
ORGANIC CHEMISTRY. 805
COH.COH + 2NH2OH = 2H2O + H.C]Sr(OH).CN(OH).H.
Glyoxime bears a close relationship to the so-called acetoxiniic acids.
The authors propose that they should be termed "gljoximes." The
five known members of the series would then be —
Glyoxime H.CN(OH).CN(OH),H, glyoxime.
Acetoximic acid . . Me.CN(OH).CN(OH).H, methylglyoxime.
fMe.CN(OH).CN(OH).Me, dimethvlglyo^ime.
Homologous acet-j Me.CN(OH).CN(OH).Et, methylethylglyox-
. P . , < ime.
oximic acids .. | Me.CN(OH).CN(OH).Bi, methylbenzylgly-
(_ oxime.
When silver nifrate is added to an aqueous solution of gflyoxime,
neutralised with ammonia, a silver salt is obtained, C2l!^202H3Ag. It
is a white powder, which decomposes on heating.
As a result of their investigations, the authors conclude that benzil
contains only one carbonyl-group, and they think that it should
be regarded as a lactone with a formula like
C6H4<_^Q_>0. J J ^
Decomposition of Benzil by Potassium Cyanide. By F.
JouRDAN (Ber., 16, 658 — 660). — By the action of potassium cyanide
on benzil in the presence of alcohol, a brownish -red solution is ob-
tained, becoming semi-solid on cooling. On treating it with water, a
solid body and an oil are obtained, the former being benzoin, whilst
the latter consists of benzaldohyde and ethyl benzoate. If methyl
alcohol is used, methyl benzoate is formed, the other products being
the same. This reaction may be explained by the benzil taking up
the elements of alcohol with formation of benzaldehyde and ethyl
benzoate, the production of benzoin being due to a secondary reaction
between the potassium cyanide and benzaldehyde. The same reaction
takes place if a concentrated solution of sodium carbonate is used in
the place of the alcohol, the benzil decomposing into benzaldehyde
and benzoic acid. All compounds containing the group CO — CO
appear to decompose in the same way, furil yielding a deep bine
coloured liquid, which changes to reddish-brown, the solution con-
taining furfuraldehyde and ethyl pyromucate, the evanescent blue
colour being due to furoin. Isatin is not altered by potassium
cyanide, which fact is against the presence of the group CO — CO,
and in accordance with Baeyer and CEconomides' formula for this
body (this vol., p. 202). A. K. M.
Action of Acetic Chloride on Benzaldehyde in Presence of
Zinc-dust. By C. Paal (Ber., 16, 636— 639).— The author pre-
viously stated (this vol., p. 62) that this reaction yielded a body of
the formula C9H8O2, which gave dibenzyl when treated with amor-
phous phosphorus and hydriodic acid, and stilbene when distilled
with zinc-dnst. By the action of sodium-amalgam on its alcoholic
solution at 70 — 80°, hydrobenzo'in and acetic acid are produced, from
806 ' ABSTRACTS OF CHEMICAL PAPERS.
which it is conclnded that the substance is hydrobenzoin-diacetate,
CHPh(OXc).CHPh(Ol^), the half molecule of which, C^E^O^, differs
but sliofhtly from the formula previonsly given, 2Ph.C0H + 2^C1 +
Zn = ZnCU + CHPh(05^).CHPh(Ol5). It melts at 134—135°, i.e.,
some degrees higher than previously stated. A direct comparison
of this body with hydrobenzoin diacetate prepared from benzoin
shows that the two are identical. A. K. M.
Ethyl Phthalylacetoacetate. By E. Fischer and H. Koch
{Ber., 16, 651 — 652). — By the action of phthalic chloride on ethyl
sodacetoacetate the following reaction takes place even at the ordinary
temperature : —
C6H4(C0C1)2 + 2]^aC6H903 = 2^01 + C^RA +
CeH^ : (C0)2 : CeHsOa.
Ethyl pJitlialylacetoacetate, CeRi '. (C0)2 i CeHgOs, crystallises in
colourless prisms melting at 124° ; it yields phthalic acid when boiled
with dilute sulphuric acid. A reaction similar to the above also
takes place between succinic chloride and ethyl sodacetoacetate.
A. K. M.
Displacement of the Sulphonic group by Chlorine. By
W. Kelbe (Ber., 16, 617 — 619). — The action of bromine on metaiso-
cymenesulphonic acid has been previously described by the author.
He finds that chlorine acts in the same way, although more energeti-
cally. Chlorine is passed into an aqueous solution of cymenesulphonic
acid, kept cool with ice, until a considerable quantity of chlorine
hydrate has formed. The vessel is then well closed and heated to
40° in a water-bath, when the chlorine hydrate disappears, whilst
an oily body is formed, which becomes crystalline on standing. It
can be purified by crystallisation from boiling alcohol, from which it
separates in long needles melting at 158*5°. Tetrachlorocymene,
CeCUMePr, tbus obtained is a very stable body, being only slowly
attacked when heated with concentrated nitric acid in sealed tubes.
Chromic mixture, nitric acid, and potassium permanganate have no
action on it, whilst chromic anhydride in acetic acid completely
oxidises it. Bromine has no action at ordinary temperatures, but at
150° a thick oil is produced solidifying to a resin-like mass. If the
ethereal extract of the latter is treated with potash to remove hydro-
bromic acid, the ether distilled off, the residue dissolved in alcohol,
and an alcoholic solution of potassium acetate added, potassium bro-
mide separates, and a filtrate is obtained which gives a resinous
precipitate on being diluted with water ; this after treatment with
alcoholic potash and oxidation with dilute nitric acid at 150°, yields
an acid, the barium salt of which corresponds with
(06Cl4Me.CoH4.COO)2Ba + 3H2O or (C6Cl4Pr.COO)2Ba + 3H2O.
The liquid separated from the chlorocymene contained trichloro-
cymenesulphonic acid, the sodium salt of which, CeClsMePr.SOaNa,
crystallises in plates. By the action of bromine on an aqueous
ORGANIC CHEMISTRY. 807
solution of the latter a bromine-derivative, probably CeClaBrMePr,
is produced, crystallising in long needles. A. K. M.
Barium Paratoluenesulphonate. By W. Kelbe (Ber. 16,
G2I — 622). — This salt crystallises in two forms, according to the
temperature of the solution from which it crystallises. Above 80° it
separates in anhydrous plates, and below this temperature in needles
containing 3 mols. H2O. A. K. M.
Action of Aluminium Bromide on Symmetrical Dibrom-
ethylene and Benzene. By R. ANscHiJTZ (Ber., 16, 622 — 623). —
Demole has shown (Abstr., 1880, 158) that the action of aluminium
chloride on benzene and dibromethylene (b. p. 87 — 92°) yields un-
symmetrical diphenylethylene. From dibromethylene boiling at
110 — 111°, benzene and aluminium bromide, the author obtains
dibenzyl, which proves the symmetrical character of the higher
boiling dibromethylene. Small quantities of anthracene are also
formed. A. K. M.
Rosaniline Colouring Matters. By R. Meldola (Chem. News,
47, 133 and 146). — The author has succeeded in preparing: —
Tri-^-naphthyl-pararosamUne, (C6H4.!N"H(30ioH7)3C.HO, by heating the
rosaniline base with excess of )3-naphthylamine at a temperature
slightly above the melting point of the latter for 15 — 20 minutes in
presence of a small quantity of benzoic or acetic acid, the rich blue
melt thus obtained can be purified and converted into sul phonic acids
in the usual manner. It dyes silk or wool deep blue. Diphenylpara-
rosaniline, (C6H4.NHPh)2C(HO).C6H4.]S'H2, is formed by the direct
oxidation of a mixure of 1 mol. paratolnidine with 2 mols. diphenyl-
amine. These substances are dissolved in glacial acetic acid, and are
heated with the requisite quantity of AS2O5.
A naphthyl-derivative of rosaniline analogous to diphenylamine-
blue is produced by heating /3-naphthyl-phenylamine, NHPh/SCioH?,
with oxalic acid or any of the oxidising substances which transform
diphenylamine into its blue. This also can be converted into a
sulphonic acid, which dyes silk or wool a green shade of blue.
a-Naphthyl-phenylamine does not readily yield a blue with oxalic
acid, whilst no colour is obtained either with di-a-naphthylamine or
di-y3-naphthylamine by similar treatment. D. A. L.
Derivatives of a-Naphthoic Acid. By P. Boessneck (J5er., 16,
639 — 642). — a-Cyanonaphthalene is prepared by distilling a mixture
of dry sodium naphthalenesulphonate (3 parts) and potassium ferro-
cyanide (2 parts), heating the distillate on a water-bath to volatilise
the ammonium carbonate which is formed, and then fractioning. To
prepare naphthoic acid, the cyanide is mixed with an equal volume
of concentrated hydrochloric acid, and heated in sealed tubes at
200°. The product is treated with ammonia, filtered, the acid then
precipitated by hydrochloric acid, and finally crystallised from
alcohol.
The conversion of a-naphthylglyoxylamide into the correspond-
808 ABSTRACTS OF CHEMICAL PAPERS.
ing acid is best eifected by heating it with dilute hydrochloric acid
for about an hour and extracting with ether. Naphthylglyoxylic acid
(m. p. 113*5°) is readily soluble in water, ether, alcohol, and benzene,
sparingly in light petroleum and carbon bisulphide. With sulphuric
acid, its benzene solution gives a reaction similar to that of phenyl-
glyoxylic acid (Abstr,, 1880, Qi7) assuming a brownish-red coloration,
changing to brown. On the addition of water, the colouring matter
remains dissolved in the benzene, forming a carmine-coloured layer.
a-Naphthoic cyanide and a-naphthylglyoxylamide do not show this
reaction. By the action of sodium-amalgam on a slightly alkaline
solution of a-naphthylglyoxylic acid, oc-naphthylglycollic acidj
CioH7.CH(OH).COOH,
is produced, crystallising in plates. a-Naphthylacetic acid,
C10H7.CH2.COOH,
is formed when a-naphthylglyoxylic acid is heated with amorphons
phosphorus and hydriodic acid for some hours at 160°. It is sparingly
soluble in cold water, readily in hot water, from which it crystallises
in long silky needles melting at 131". It also dissolves readily in
ether, alcohol, glacial acetic acid, and in benzene. a,-Napht7i;/lacet-
amide, C10H7.CH2.CONH2, is insoluble in cold water, but crystallises
from hot water in slender needles melting at 180 — 181°. It is soluble
in benzene, carbon bisulphide, and ether, and readily in glacial acetic
acid. On distilling it with phosphorus pentoxide, a yellowish-brown
oil is obtained which is apparently a-naphthylacetonitrily CioB.7.CH.2.CN,
boiling above 300°. a-Najphtliylethenyldqihemjldiamine,
CioH7.CH2.C(NPh)NHPh,
is obtained by the action of phosphorus trichloride (2 mols.) on a
mixture of naphthyl acetic acid (3 mols.), and aniline (6 mols.). It is
soluble in ether, benzene, light petroleum, and in acids, and crystal-
lises from dilute alcohol in colourless needles melting at 130*5°.
a.-NapJithylmethenyldiphenyldiamine, CioH7.C(NHPh) !NPh, from naph-
thoic acid, forms silky needles melting at 183*5°, and in its solubility
resembles the last-named body. A. K. M.
Synthesis of Dihydronaphthoic Acid. By v. H. Pechmann (Ber.,
16, 516 — 517). — When benzyl acetoacetate is treated with from 8 —
10 parts of concentrated sulphuric acid, to which a small quantity of
water has previously been added, and the mixture, after being allowed
to stand for several hours, is poured into cold water, a fine white
3rystalline powder is thrown down. After recrystallisation from
ether, it gives numbers on analysis which correspond with the formula
CnHio02. The body possesses the properties of a dihydronaphthoic
acid. It dissolves in a dilute solution of sodium carbonate with evo-
lution of carbonic anhydride. It yields a bromine additive compound,
and on oxidation with either nitric acid or potassium permanganate,
it gives phthalic acid. When heated in a test-tube, it distils almost
entirely without decomposition. Distilled with soda-lime it yields
ORGANIC CHEMISTRY. 809^
carbonic anliydride and a liquid hydrocarbon of the composition
CoHio, boiling at 199 — 201° ; this appears to be identical with the
dihydronaphbhalene obtained by Berthelot by the action of hydriodic
acid on naphthalene. J. I. W.
New Synthesis of Anthracene. By R. Anschutz and F.
Eltzbacher (Ber., 16, 623 — 624). — Anthracene is formed by the
action of alaminium chloride on a solution of acetylenetetrabroniide
in benzene. Its formation may be explained by the following equa-
tion : —
Br.CHBr ^CH
CeHe + I + CeHe = CJl/ I NCeH^ + 4HBr.
Br.CHBr ^CH
A. K. M.
I
Liquid Terebenthene Hydrochlorides. By P. Barbier (Compt.
rend., 96, 1066 — 1069). — Laevogyrate terebenthene dissolved in twice
its volume of alcohol was saturated with hydrochloric acid gas,
left at rest for twelve hours, the hydrochloride precipitated by addi-
tion of water, dried over calcium chloride, and distilled in a vacuum
In this way a monohydrochloride is obtained which forms a colourless,
slightly oily liquid, boiling at 120° under a pressure of 0*045 mm. Its
IsDvorotatory power, [ajs = — 6° 51' ; sp. gr. at 0° = 1'016 ; refrac-
tive index for D = 1-4826 at 12*5°. When heated with alcoholic
potash in a sealed tube at 180°, it yields a colourless mobile liquid of
the composition C10H16, with an odour which at first resembles that of
the amyl compounds, but changes to that of lemons after exposure to
air. The l86Vorotatory power of this hydrocarbon, [a]© = — 19° 9';
b. p. = 157° ; sp. gr. = 0-8812 ; index of refraction = 1-4692. When
treated with hydrochloric acid gas, it yields a mixture of liquid and
solid monohydrochlorides.
Laevogyrate terebenthene was treated with hydrochloric acid gas at
100°, and the product fractionated in a vacuum. In this way a per-
fectly colourless liquid hydrochloride is obtained, which boils at about
120° under a pressure of 0-04 mm., and yields no precipitate when
placed in a mixture of ice and salt. Its leevorotatory power [a]p =
— 29°; sp. gr. at 0° = 1-017; index of refraction = 1-4083. When
heated with alcoholic potash in a sealed tube at 150° for twelve hours,
it yields a colourless, very mobile liquid hydrocarbon of the composi-
tion C10H16, with an odour recalling that of lemons. It boils at 157° ;
sp. gr. at 0° = 0-8815, at 12° = 0-87-24 ; refractive index for D =
1-4704; laevorotatory power [ajn = — 40°. When treated with
hydrochloric acid gas, it yields a mixture of a solid and a liquid
monohydrochloride. The solid hydrochloride is dextrogyrate.
C. H. B.
Essence of Angelica Root. By L. Naudin (Compt. rend., 96,
1152 — 1154). — When the root of Angelica offi^cinalis is distilled in
vapour of water, a colourless, mobile liquid is obtained of sp. gr. 0-875
at 0°. It turns yellow on exposure to light, and absorbs oxygen from
the air, being slowly converted into a resin. When boiled, it is poly-
merised, but at higher temperatures the polymerides split up into light
VOL. XLIY. .3 i
810 ABSTRACTS OF CHEMICAL PAPERS.
liquids which have not yet been examined. By fractionation in a
vacuum, a colourless, very mobile liquid boiling at 166° is isolated.
It has the composition of the terpenes, does not alter when exposed to
light, and has a somewhat pungent odour ; sp. gr. at 0° = 0*870. Its
dextrorotatory power for a thickness of 200 mm. is + 5° 29'. Wheu
heated at 100° in sealed tubes for 30 days, its rotatory power sinks
to + 4° 1' ; it becomes slightly yellow and less mobile, and its odour
is more pungent. Ordinary terebenthene treated in the same way
does not alter in rotatory power by 1'. At 160° the terpene from
angelica root becomes viscous in a few hours, especially in presence of
sodium. It yields a liquid monohydrochloride, but no solid mono-
hydrochloride. The author proposes for this terpene the name of
(3-terebangelene, in order to distinguish it from the isomeride obtained
from angelica seeds, which boils at 175°, and is far more readily
altered by the action of heat.
The author concludes that essence of angelica root consists of a
single terpene, which, in the commercial product, is mixed with poly-
merides formed during distillation. The proportion of polymerides
increases with time ; a sample two years old had become viscous in a
closed vessel exposed to light. C. H. B.
Action of Zinc Chloride on Camphor. By A. Reuter (Ber.,
16, 624 — 629). — The author distils camphor and zinc chloride accord-
ing to Fittig's method, treats the distillate with strong soda solution
to separate the phenols, and then with concentrated sulphuric acid,
the mixture being well cooled. From the soda solution, he obtains
orthocresol and other higher-boiling phenols. On mixing the sulphu-
ric acid extract with water an oil separates containing camphor, and
a body probably identical with Schwanert's camphrene {Annaleii, 123,
298). The residual mixture of hydrocarbons was distilled over
sodium, converted into sulphonic acids, and the latter purified by
means of the barium and sodium salts. It contained toluene, pseudo-
cumene, cymene, and laurene, and also some hydrocarbon oil (probably
paraffins) insoluble in sulphuric acid. A. K. M.
Gentian ose. By A. Meyer (Zeits. Physiol. Chem., 6, 135 — 188).
— The roots of Gentiana lutea, pannonica, punctata, and purpurea are
nsed in the preparation of gentian brandy. The freshly sliced roots
are for this purpose added to water, allowed to ferment, and distilled.
The relatively large proportion of alcohol in the product is sugges-
tive of the presence of a considerable amount of some fermentescible
substance in the roots. The author sought for this presumably sac-
charine constituent in the expressed juice of Gentiana lutea, gathered
in September. The roots yielded 50 per cent, of juice. From this
juice was obtained by treatment with 95 per cent, alcohol, fractional
precipitation by ether, and subsequent slow crystallisation, a crystal-
line body which the author names gentianose. It occurs in small
colourless crystals having a faintly sweet taste, easily soluble in water.
Melting point, 210°.
On the addition of yeast fermentation at once begins. Concec-
ORGANIC CHEMISTRY. 811
trated sulphuric acid carbonises the substance, as in the case of cane-
sugar. Fehling's solution is not reduced by it. Analysis gives the
formula CseHBeOsi- The other properties of gentianose would appear
to place it near cane-sugar. D. P.
Nitroquinolines. By W. La Coste (Ber., 16, 669— 677).— The
only nitroquinoline previously known is that described by Koenigs
(Ber., 12, 448), and shown by Bedall and Fischer (Ber., 15, 683) to
be the ortho-compound. The author has attempted to prepare iso-
merides by heating the nitranilines with glycerol, sulphuric acid, and
nitrobenzene. From paranitraniline the corresponding nitroquinoline,
C9H6N.N'02 [JS" : NO2 = 1 : 6] is obtained. It crystallises from water
or dilute alcohol in colourless slender silky needles, melting at 149 —
150°, and subliming without decomposition. It is sparingly soluble
in cold alcohol or water, much more readily on heating, is readily solu-
ble in dilute acids and in benzene, whilst ether and light petroleum
dissolve it but slightly. The platinochloride, C9H6N'.N03,H2PtCl6,
forms a yellow crystalline precipitate. Nitroquinoline combines with
methyl iodide at 100° with formation of the compound C9H6N.N02,MfcI,
which crystallises in groups of reddish-yellow needles, readily soluble
in hot water, less so in warm alcohol. AmidoquinoUne, obtained by
the reduction of the above nitro-compound, crystallises from water
with 2 mols. H2O. It Is readily soluble in alcohol and in ether, more
sparingly in water and in light petroleum. When anhydrous it melts
at 114°, and can be sublimed unchanged. The hydrochloride^
C9H6N,ISrH2,2HCI,
forms large prisms of vitreous lustre, which readily dissolve in water
to a deep yellow solution. The platinochloride,
C9H«]Sr.NH2,H2PtCl4 + 2H2O,
is obtained as a yellow crystalline precipitate. By the action of picric
acid on the hydrochloride, the compound C9H6N.NH2,2C6H2(N02)3.0H
is produced, crystallising in woolly needles. Dimethylamidoqulnoline,
CgHeN.N'Mei, is prepared from dimethylamido-paraphenylenediamine
(from paranitrosodimethylaniline). It melts at 54 — 56°, and boils at
about 335°. It is readily soluble in alcohol, ether, and benzene, but
on evaporating the solution it separates as an oil. With picric acid
it forms a sparingly soluble compound, C9H«N.NMe2,C6H2(N'0.)30H,
crystallising in slender reddish-yellow needles, which melt at 215°,
with decomposition, and explode when suddenly heated. When it is
heated with methyl iodide, C9H6N.NMe2,Me[ is obtained, crystallising
in long red shining needles, and on boiling the latter with silver
chloride and then adding platinic chloride, a yellow crystalline preci-
pitate, (C9H6N2Me3)2PtCl6, is produced. Orthonitraniline yields a
nitroquinoline identical with that obtained by the nitration of quino-
line, whilst with metanitraniline an entirely different reaction takes
place. In the latter case phenanthroline (Abstr., 1882, 11 11) is formed,
together with small quantities of hydroxy phenanthroline, C,2H7(OH)N2.
The Letter melts at 159 — 160°, dissolves readily in dilute sodium
3 i 2
812 ABSTRACTS OF CHEMICAL PAPERS.
hydroxide solution, from which it is reprecipitated by carbonic anhy-
dride ; it is also readily soluble in warm alcohol or benzene, and crys-
tallises from the latter in colourless shining needles. The platino-
chloride, Ci2H7N2.0H,H2PtCl6 + H2O, forms a yellow crystalline
precipitate. A. K. M.
Action of Phthalic Anhydride on Quinoline. By E. Jacobsen
and C. L. Keimer (Ber., 16, 513 — 514). — The authors claim the
priority over Traub in the discovery of a yellow colouring matter pro-
duced by the action of phthalic anhydride on quinoline. They found
that other quinoline bases, such as pyridine, would yield similar colour-
ing matters, and one of them took out a patent for their production in
November, last year. The analytical results obtained by the authors
differed somewhat from those published by Traub. They state that
their experiments have shown that quinoline obtained from coal-tar
differs widely from that prepared by Skraup's method.
J. I. W.
Quinazole-compounds. By E. Fischee and H. Kuzel (Ber.,
16, 652 — 656). — In an attempt to prepare ethylhydrazinciu-
namic acid from nitrosoethylamidocinnamic acid by treatment
with zinc-dust and acetic acid, the authors have obtained an
acid of the formula CioHiiI^2-C300H, which is decomposed by heat
into carbonic anhydride, and a base, CioHiaT^a- The latter (ethyU
quinazole) bears no resemblance to the hydrazines, but in many
reactions shows a similarity to quinoline. To prepare ethylqiiinazol-
carhoxylic acid, CioHnN2.COOH, an excess of zinc-dust is added to an
alcoholic solution of the nitrosamine (Abstr., 1881, 599), and acetic
acid gradually added, the temperature being maintained first at 40°,
and towards the end of the operation at 60 — 70°. The product is
filtered, the solution evaporated, and the residue treated with water
and dilute sulphuric acid. On agitating with ether and evaporating,
an oil is obtained, which, after treatment with dilute sulphuric acid,
gradually becomes crystalline. It can be purified by boiling its chlo-
roform solution with animal charcoal, and adding light petroleum
when the acid separates in dense brown crystals, and after recrystalli-
sation from water forms colourless plates, melting at 131°. It is
sparingly soluble in water, readily in alcohol, ether, and alkalis.
Ethylquinazole is obtained by heating the above in an oil-bath at
180 — 190°, until the decomposition is nearly complete, then at 230°,
and finally distilling, its boiling point being 234 — 235° at a pressure
of 741 mm. When cooled by a freezing mixture, it solidifies, forming
large plates melting at 30°. It is readily soluble in alcohol and in
ether, sparingly in water ; it is volatile in steam, has a penetrating
odour resembling that of quinoline, and a sharp taste. It forms
readily soluble salts, which are decomposed by water ; the sulphate,
CioHi2N2,H2S04, is obtained in long needles on adding ether to its
alcoholic solution ; the platinochlGride, (CioHi2N2)2,H2PtCl6, is sparingly
soluble in water, and crystallises from dilute hydrochloric acid in
orange-yellow prisms; the jpicrate is also sparingly soluble in water
and in alcohol. It yields white crystalline precipitates with silver
nitrate and mercuric chloride, nearly insoluble in cold water. FehUng's
I
ORGANIC CHEMISTRY. 813
solution, mercury and silver oxides have no action on it even on boil-
ing; neither has nitrous acid nor boiling acetic anhydride. The
formation of this base from nitrosoethylamidocinnamic acid is most,
easily explained on the assumption that its formula is I, whilst its
similarity to quinoline suggests either of the formulae II or III : —
HO CH CHCH CHCHj
^\/K ^\/% /X/\
HC C ICHa HO C CH HC C CH
I II I Ml I III II
HC ON" HC C NH HC C N
\/\X \/\/ \/^^
HC NEt CH NEt CH NEt
I. IJ. III.
A. K. M.
Piperidine and Pyridine. By A. W. Hofmann (Ber., 16, 586 —
591). — Previous experiments on the action of bromine on piperidine
(Ber., 12, 984) led the author to assume a relationship between the
latter base and pyridine. This has since been established by Konigs
(Abstr., 1880, 404), who obtained pyridine by the oxidation of
piperidine, and also by Schotten (Abstr., 1882, 983), who obtained
dibromopyridine by the action of bromine on piperidine. The
author, by modifying his former experiments, has succeeded in
obtaining pyridine from piperidine. He combines the latter with
acetic anhydride, and gently warms the resulting compound (1 mot:)
with bromine (2 mols.). Hydrobromic acid is evolved, whilst a
colourless distillate, consisting of acetic bromide and its substi-
tution-derivatives, passes over, leaving a syrupy residue in the
retort. On treating the residue with alkali and steam-distilling, an
alkaline aqueous distillate and an oily layer, together with crystals of
dibromopyridine, are obtained. After recrystallisation from alcohol
the latter melts at 112°, and boils at 222°. On adding potassium
hydroxide to the aqueous distillate, an oily layer separates, consisting
of pyridine mixed with unaltered piperidine. The latter is readily
separated by treatment with acetic anhydride, and then distilling, when
nearly pure pyridine is obtained. The oily portion of the steam dis-
tillate contains monobromopyridine, CsHiBrN, which the author pre-
viously obtained by the bromination of pyridine. It forms a platino-
chloride, (C6H4BrN)2,H2PtCl6, crystallising in flat needles, and an
aurochloride, C5H4BrN,HAuCl, crystallising in plates.
An attempt to reverse the process, and to obtain piperidine from
pyridine, was unsuccessful. Pyridine was heated with concentrated
hydriodic acid, when normal pentane and ammonia were produced.
A. K. M.
Oxidation of Piperidine. By C. Schotten (Ber., 16, 643—
649). — The author has shown (this vol., p. 220) that an acid of the
formula C7H15O2N (for which he now suggests the name coninic acid)
is produced by the action of nitric acid on conylurethane. Under
similar conditions, pipery lure thane (Abstr., 1882, 983) yields piperi'
dinic acid, C4H9O2N, homologous with the latter; its hydrochloride^
C4H902N,HC1, forms dense hygroscopic prisms, readily soluble in water
814 ABSTRACTS OF CHEMICAL PAPERS.
and in alcohol ; its platinochlonde, (C4H902"N')2,H2PfcCl6, forms large
shining prisms. If urea is added to the nitric acid to moderate its
action, nitrodehydropiperylurethmie, C5H7(N02)N.COOEt, is produced,
cpjstallising in yellowish needles or prisms, melting at 51*5^, and
soluble in hot water or in alcohol. It is not readily acted on by acids,
whilst alkalis dissolve and decompose it even in the cold. When it is
treated with tin and hydrochloric acid and the solution is then heated
with concentrated hydrochloric acid in sealed tubes above 100°, an oil
is obtained, which is probably dehydropiperidine. On adding bromine
to its solution in glacial acetic acid, it forms a bromhydroxyl'deri-
vative, C5H7(N'02)N(HOBr).COOEt, which crystallises in pi-isms
melting at 157°. Plpenjlmethylurethane, CjHioN.COOMe, is prepared
in the same way as the ethyl-compound (loc. cit.), and forms a colour-
less liquid (b. p. 201°), having a slight and agreeable odour. It is
hpavier than water, in which it is sparingly soluble, and can be boiled
with alkalis or with hydrochloric acid without decomposition. It
yields a nitrodehydro-denvativp, C5H7(N02)N.COOMe, which crys-
tallises in yellowish needles melting at 102 — lOS'', and by the action
of bromine on this a body is obtained melting at 130°. By the action
of bromine on piperylethylurethane, the compound
C5H7BrN(HOBr).COOEt
is produced, crystallising in short hard shining prisms, which melt at
140°. If twice as much bromine is used as is necessary to form this
body, dibromopyridine is produced. A. K. M.
New Crystalline Colouring-matter in Urine. By P. Plosz
(Bied. Gentr., 1883, 208). — The alkaline fermented urine was acidified
with hydrochloric acid, aerated until it became red, then exti*acted
with chloroform, which removed indigo, as well as red acicnlar crystals
or rhombic plates. This substance is probably a skatole derivative.
E. W. P.
Metahaemoglobin. By F. Hoppe-Seyler (Zeitschr. Fliys. Cheni.,
6, 166 — 174). — The author has already (2, 150) described certain
experiments of his, which he believes to prove beyond doubt that
metahaBmoglobin, a name given by him to a product of the decom-
position of the colouring-matter of the blood, must be regarded as a
compound of albumin and haematin, the view of several observers,
that it is a higher oxidation stage of arterial blood pigment, being
erroneous.
The present article is occupied with a defence of his previous state-
ments against the opinion of A. Jaderholm (Zeitschr. fur. Biolog., 16,
1), that metahaemoglobin is a higher oxide (peroxide). D. P.
Nuclein. By W. Klingenberg and A. Stutzer {Bied. Centr.,
1883, 204 — 206). — Miescher couvsiders that the substance found in
yolk, and the red blood-corpuscles of goose-blood, called nuclein by
Hoppe-Seyler, is a grouping of nuclein compounds, and is not identical
with the nuclein of pus. Klingenberg has investigated the nuclein of
fodder, and by means of the proportion P : N, finds that the nuclein
of poppy, earthnut, rape, and cotton cake is the same, whilst that of
palm nut is very different; the proportion P : N : S (1 : 6'97 : 0*88)
PHYSIOLOGICAL CHEMISTRY. 815
found by Klingenberg agrees witli that found by previous inves-
tigators. Stutzer reports the presence of nuclein in yeast and mildew ;
of 100 parts of the nitrogen in mildew, 40*75 are as nnclein ; whilst in
yeast only 26'09. E. W. P.
Physiological Chemistry
Researches on Digestion in the Stomach. By A. Kietz
{Bled. Centr., 1883, 208). — During the first hour of digestion, lactic
acid is not present in notable quantities, but the acid present is hydro-
chloric ; the appearance, sooner or later, of free acid is dependent on
the quantity and quality of the food, as well as on the idiosyncrasy of
the individual. E. W. P.
Reaction of the Living Mucus-lining of the Stomach. By
L. Edinger {Bied. Centr., 1883, 207). — By injection of sodium-alizarin,
which causes the death of the animal experimented upon, it is shown
that the majority of the glands of the stomach are acid during diges-
tion ; the lining itself is not always acid, and whilst the lumen of a
gland may be acid, the interior parts may be alkaline or neutral.
E. W. P.
Digestibility of Meat. By P. Honigsberg (Bied. Centr., 1883,
208). — Experimenting with artificial stomach juice, the author finds
that of the albumin in raw meat 39-7 per cent, is converted into pep-
tone, in boiled 26*6 per cent., ia roasted meat 48 per cent.
E. W. P.
Digestibility of Casein from Heated Milk. By M. Hoffmann
(Bied. Centr., 1883, 208). — More peptones are formed by the digestion
of casein from boiled than from unboiled milk, and most from casein
obtained from milk which has been subjected to Becker's process.
E. W. P.
Decomposition of Digestive Ferments. By J. N. Langley
(Bied. Centr., 1883, 209). — Hydrochloric acid and gastric juice destroy
the power of the saccharifying ferment of the parotid. Dilute alka-
line carbonates destroy pepsin, and in presence of trypsin, these car-
bonates are more energetic. The ferment of rennet is destroyed by
a 1 per cent, solution of sodium hydroxide and by trypsin ; con-
sequently, neither ptyalin nor rennet ferment can exist in the intes-
tines. A glycerol extract of the pancreas is rendered inactive by
hydrochloric acid, and trypsin in acid solution decomposes pepsin.
E. W. P.
Fattening of Calves. By K. v. Langsdorff (Bied. Centr., 1883,
168 — 170). — Thirty-four sets of experiments were instituted to ascer-
tain whether or not it was most advantageous to feed calves for the
butcher with skim milk (with additional food), or with whole milk.
The results are greatly in favour of skim milk. E. W. P.
816 ABSTRACTS OF CHEMICAL PAPERS.
Feeding of Cattle with Dry Fodder. (Bied. Centr., 1883, 167.)
— Seven oxen were fed from May to end of August on hay and after-
math ; in addition to this from June onwards they received a ration
of oats; the expenses of food and attendance being reckoned at
2396 M, each 50 kilos, live weight was put on for 3*7 M— a satis-
factory result. The average daily gain in weight w^as 1'57 kilos.
E. W. P.
Digestibility of Meadow-hay and Wheat-bran treated with
Hot and Cold Water. By G-. Kuhn and others (Landw. Versuchs.-
Stat., 29, 1 — 2 and 1 — 241). — This voluminous paper contains a
report of numerous experiments carried on by the reporter and various
assistants at the station of Mockern during 1877 to 1881, in order to
ascertain whether the treatment of meadow-hay with hot and cold
water and hot and cold infusions of wheat-bran had any influence on
its digestibility. The subject is considered of considerable importance
in GeiTuany, and the authors enter into very minute details, which
occupy 91 closely-printed tables.
The general idea of the experiments was to analyse the fodder and
excreta, keeping a record of the gain and weight of the six oxen
employed as experimental animals.
The stall arrangements were carefully made, the mangers freely
accessible and moveable, with arrangements for collecting the
uneaten fodder ; the floor of each stall was of asphalt and inclined
towards the centre; a cut stone channel running along all the stalls
was so disposed that it received the solid excrement ; this was care-
fully swept into a receptacle from which samples were daily drawn for
analysis, but the urine was allowed to escape.
The methods employed were simple. The hay, as brought in from
the different sources of supply, was spread in thin layers one over the
other, on a dry clean granary floor, and, when all stored, was well
trodden down ; a section, therefore, was a fair specimen of the whole ;
the daily rations of the oxen were so cut, and then put through an
ordinary chaffcutter and filled into sacks, during the filling of which a
certain number of handfuls were taken to make up the sample for
analysis, which was then dried in the water-bath and exposed to the
air and the proportion of dry matter determined. The bran was
sampled in a similar manner. The dung was well mixed in its
receptacle, and samples carefully drawn and dried with like precau-
tions. The chemical examination of both fodder and dung was con-
fined to the estimation of ash, indigestible fibre, fat, and nitrogen in
the dried samples so prepared, according to usual methods.
Fifty-one tables give the daily variations in the food, drink, and
weight of the animals, their solid evacuations, tempei'ature of stalls,
increase of weight, &c., with remarks as to the progress of the
experiments as affecting each animal.
The most interesting points are : the daily ration of diy hay was
10 kilos, with the occasional addition of 2 kilos, of bran prepared in
various ways, steeped either in hot or cold water in different propor-
tions. The amount of water taken by the animals depended greatly
on the wet or dry state of the fodder, but the amount of dry substance
contained in the daily yield of dung was very regular, In table after
PHYSIOLOGICAL CHEMISTRY. 817
table, the avernge of 10 days is given as 3*5 to 3'6 kilos., quite as
regular, apparently, as the quantity of food given. The percentage
of mineral matter in the dry substance of the hay was 7' 79 to 889
per cent.; in the wheat-bran 6*79 to 7"08 ; and in the dung 12*37 to
1823 percent. The nitrogen in the hay 1*71 to 1'96; in the bran
2"35 to 2*54 per cent. ; and in the dung 1*78 to 231 per cent.
The fatty matter extracted by ether from the hay was 2*69 to 2'98
per cent., from the bran 4.'41 to 5*12 per cent., the dung 3'20 to 4*39
per cent.
The greater part of the remainder of the paper is occupied with
tabular comparisons of the experiments with each other, possible
sources of error from the constitutions of the different beasts, and
similar details, the results of the whole series of experiments being of
a negative character. The conclusions drawn by the experimentalists
themselves will be sufficient : —
1. The mere damping of hay, immediately before feeding, either with
cold water or cold bran infusion, in quantity insufficient to satisfy the
animal's thirst, has no eifect on the digestibility of fodder.
2. The saturation of the bran with 30 kilos, of cold water and the
damping of the hay with the mixture has no effi9ct on the digestion
either of the hay or the bran, if done immediately before the feeding.
3. The steeping of the bran for a period of 24 hours in cold water
does not influence the digestion of the fodder, so long as it has not
been so much moistened that the thirst of the cattle is not more than
half satisfied by it, and that they drink half their usual supply of
water ; if this limit is passed, and the desire of the animals for w^ater
does not induce them to take nearly 50 per cent, of their usual
quantity, the digestibility of the fodder becomes sensibly reduced.
4. The scalding of the bran with boiling water is injurious, and
renders the mixed fodder indigestible, in proportion to the initial
temperature of the water used and the length of time it remains
heated.
6. The use of an infusion of bran as a drink, without previous
admixture with the fodder, does not appear to exercise any influence
on the digestion.
6. The diminution of the digestibility of the fodder, when treated
with boiling water, is attributed by the authors to the action of heat
on the albumin of the bran and not on the raw prote'id matter of the
hay.
The authors conclude by saying, that although the experiments in
question refer only to two kinds of fodder, they believe that similar
results would be arrived at with other foods, but they specially
exempt from their caution not to treat the fodder with water, tlje
case of inferior kinds of food, which by such treatment might be
rendered more agreeable and appetising. J. F.
Results of the Suppression of Perspiration of Animals. By
Ellenberger (Bled. Centr.^ 1883, 173). — It is generally supposed that
when perspiration is partly suppressed by means of a coating of
varnish, the animal dies. Ellenberger has investigated this matter,
employing horses, dogs, &c., as subjects, and finds that the above state-
818 ABSTRACTS OF CHEMICAL PAPERS.
ment is incorrect. Only weakly animals die, as also those from which
the hair or wool has been removed immediately before the varnishing.
Sheep snfFer most from the operation, but the varnishing of one-eighth
to one-fourth of the skin is not dangerous. Swine are bat sliofhtly
affected, as also dogs ; but tar must not be employed, or they suffer by
licking themselves. With horses, the temperature falls 1*5° by removal
of the hair, but after the constitution has recovered itself, no harm
ensues. In six out of seven experiments, an increase of urea was
noticed, but albuminous urine was never observed. E. W. P.
Peptone the Source of Sugar in the Liver. By J. Seegen
(Bled. Centr., 1883, 206). — Feeding with peptone or injection of the
same raises the percentage of sugar in the liver. E. W. P.
Alteration in the Secretion of Milk under the Influence of
Drugs. By Stumpf (Bied. Centr., 1883, 171). — Goats were experi-
mented on. When potassium iodide was administered, the yield of
milk was reduced, while the percentage of fat and sugar was raised ;
salts and albuminoids were unaltered ; reaction became alkaline.
Small doses of lead acetate produced no change of composition or
yield ; the same negative results were obtained with morphine.
Pilocarpin at first only reduced the sugar. Sodium salicylate con-
siderably raised the yield. Alcohol did not alter the yield, but the
solids increased, whilst the sp. gr. decreased. When beer was given,
the sp. gr. fell, but the fat rose in quantity, as did also the sugar.
E. W. P.
Behaviour of Blood when Deprived of Oxygen. By Zweifel
(Bied. Gentr., 1883, 207). — If the oxygen be removed artificially from
the blood, decomposition immediately sets in ; also, blood so treated
acts injuriously on animals. E. W. P.
Observations on a Dog with Biliary Fistula. By F. Rohrmann
{Bied. Centr., 1883, 207). — The presence or absence of fistula had no
effect on the weight of the dog. The absence of bile produced a non-
absorption of fat, yet fat continued to be deposited on the body, so
that it would appear as if bile were absolutely essential for the
assimilation of fat. E. W. P.
Formation and Decomposition of Tyrosine. By C. Blender-
MANN (Bied. Centr. y 1883, 209). — Experimenting on himself, the
author found that tyrosine produced phenol in the urine, but no excess
of oxyacids ; in a rabbit, phenol and oxyacids in large proportions were
found, as also two new derivatives of tyrosine, tyrosine-hydantoin, and
oxyhydroparacumaric acid. E. W. P.
Adipocere. By Erman (Bied. Centr., 1883, 209).— Adipocere
formed during life forms fat, and is not a decomposition-product of
albuminous tissue. E. W. P.
Poisoning of Cattle by Earth-nut Cake. By Anacker (Bied.
Centr., 1883, 210). — Examination showed that the death of the cattle
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 819
arose from the presence in the cake of mildew, sand, small stones,
croton and castor oils. E. W. P.
Insensibility arising from a Deficiency of Oxygen in the
Air. By W. Wallace (Ghem. Neiu.% 47, 158).— The author is of
opinion that the feeling of depression or suffocation resulting from
breathing the air of a badly ventilated chamber is due not so much to
carbonic anhydride as to the diminution in the quantity of oxygen. He
supports this view by figures and by a case of death from suffocation in
a confined space where the oxygen was being quickly absorbed, whilst
carbonic anhydride was simply produced from the breathing of the
victim ; on analysis, the atmosphere in question proved to be principally
nitrogen. D- -^« l^-
Chemistry of Vegetable Physiology and Agriculture.
Chemical Character of Living Protoplasm. By O. Loew
(Bied. Centr., 1883, 211). — The silver reaction for living protoplasm
is not due, as Reinke and Mori suppose, to aldehyde, as it takes place
in the presence of spirog-yra which contain neither aldehyde nor chlo-
rophyll ; neither does this reaction occur with every green or chloro-
phyll-free plant, nor even with the same plant under every circum-
stance of growth. It occurs only when the protoplasm contains a
lecithin compound, whereby the chemical resistance is increased so
that change does not follow immediately after the first attack on the
cells. E. W. P.
Autoxidation in Plant Cells. By J. Retnke (Bied. Centr., 1883,
178 — 181). — The researches of others to which reference is made point
to the following conclusions : In every live cell autoxydators (i.e.,
substances which at low temperatures by the decomposition of water
oxidise themselves by taking up molecular oxygen) are formed ; dur-
ing the oxidation of autoxydators, hydrogen peroxide is formed ;
hydrogen peroxide under the influence of diastase, &c., may act as
energetically as atmospheric oxygen. The locality in colourless cells
where oxidation occurs is in the peripheral layer of the protoplasm ;
here hydrogen peroxide is formed, which, however, does not become
free, but is immediately employed in oxidising hydrocarbons. The first
compounds which it will attack are the readily oxidisable matters
which have been formed by the combined action of water and mole-
cular oxygen on the autoxydators ; this explains the presence of colouring
matters in beet and potato juices, which do not appear so long as there
are living cells; this formation of colouring matter is noticeable
when a potato is grated and exposed to the air. E. W. P.
Colour and Assimilation. By T. W. Engelmann (Bied. Centr.,
1883, 174 — 178). — Former investigations in which the activity of
820 ABSTRACTS OF CHEMICAL PAPERS.
bacteria in the presence of oxygen evolved through the aid of chlo-
rophyll was made the measure of assimilation, showed that for green
cells the disengagement of oxygen was greatest when the red rays
between B and C (Fraunhofer) and the blue near F, were allowed to
fall on those cells. These rays being thus more readily absorbed
by chlorophyll, the question arose as to whether a similar relation-
ship existed between absorption and assimilation when cells contain-
ing plasma or another colour were employed. To answer this question,
yellowish-brown cells (Diatomaceae), bluish-green (Oscillaria) and red
(Floridacese) were introduced into the solution containing bacteria;
it was then found that the maxima of absorption exactly coincided
with the maxima of evolution of oxygen, and vice versa. The details
are as follows : —
Green Cells. — Maximum of assimilation and absorption in the red
between B and C, in the blue at F, whilst the minimum occurs in the
green between E and h.
Yellowish-hrown Cells. — First maximum in the red between B and C,
and again at D ^E, the minimum being found in the orange and
yellow.
Bluish-green Cells. — No absolute maximum is found in the red,
although the absorption is high here, but it is found in the yellow ;
comparatively feeble is the action of the blue and green rays.
Red Cells. — The maximum (in gaslight) occurs in the green, a
second maximum at B, C, and a minimum at C -^D. From these ex-
periments it is evident that chlorophyll is not the only substance
which assimilates. It is not improbable that these colouring matters
(chromophyll) are mixtures of chlorophyll with other assimilating
substances. E. W. P.
Formation of Starch from Sugar. By J. Bohm (Bied. Centr.,
1883, 212). — After reference to previous communications, experiments
on plants are described, which prove that starch may be deposited
in chlorophyll and etiolin cells, which would not otherwise contain
starch, and this will occur if the plant be supplied with cane- or
starch-sugar, the quantity deposited being affected by the concentra-
tion of the sugar solution. Some leaves, as those of Allium and
asphodel, which normally contain no starch, will not convert sugar
into starch. The roots of seedlings also take up sugar.
E. W. P.
Experiments on the Value of Various Fodders for Cows. By
F. Walther (Bied. Centr.^ 1883, 210). — Feeding some cows with
cotton cake meal and others with rye bran, proved the superiority of
the former food for the production of butter. When cotton cake and
grains were compared with cocoanut cake and grains, the first
mixture produced less milk, and somewhat less batter.
E. W. P.
Rice and Earth-nut Meal as Food for Milch Cows. By W.
WoLDE {Bied. Centr., 1883, 170). — Rice meal is here shown to be less
costly, more productive of milk, and more palatable than earth-nut
meal. E. W. P,
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 821
Nitrogenous Constituents of Malt, Wort, Beer, and Bread.
By F. Ullik (Bied. Gentr., 1883, 201— 203).— From the examination
of malt and wort, the author concludes that normal malt contains no
ready-formed peptones, the principal portion of the soluble nitrogen
being present as amides : peptones appear first in the wort, but the
quantity is unimportant ; the quantity of the various nitrogenous
compounds present is dependent on the quality of the malt.
Examination of three kinds of beer showed that amides were in larger
proportion than peptones, and albuminates were absent. Further, the
feeding powers of these three are compared with that of bread. To
obtain the necessary amount of albuminoids (118 grams, Voit), a man
must consume of the weaker beer examined 154*7 litres; or 1 kilo,
bread contains the same quantity of albuminoids as 64i'6 litres beer.
E. W. P.
Fermentation of Cellulose. By F. Hoppe-Setler (Ber., 16,
122 — 128). — Experiments recorded by PopofP (Pflugers Archiv., 10,
113) have already shown the probability that the ferments present in
the mud of cesspools are capable of decomposing cellulose into carbonic
acid and marsh gas. The author has succeeded in proving the reac-
tion.
A small portion of mud from a cesspool, purified by levigation, and
containing a known amount : (1) of total organic matter; (2) of cel-
lulose insoluble in alcohol, ether, dilute hydrochloric acid, and dilute
soda-lye, was placed on a weighed filter, the paper of which contained
a known proportion of cellulose, and enclosed in a bottle containing
distilled water. The evolved gases were collected over mercury. The
arrangement was left so for 13 months, during many of which it was
kept in darkness. Atmospheric air was excluded during the whole
time, and the pressure of the gas in the apparatus was always more
than an atmosphere.
Up to the time of the report, many litres of gas had been obtained,
20 to 25 c.c. being obtained daily at a temperature of 20° C. ; the
evolution still continues. The amount of carbonic anhydride obtained
is more than double the quantity which the organic matter in the mud
alone should yield, and as there is nothing else but the filter-paper
present, it must necessarily be derived therefrom. The evolved gas
consists of about 50 per cent, in volume of carbonic anhydride, 45
per cent, marsh gas, and a little hydrogen.
The author remarks on the very large extent of the earth's surface
in which this process of fermentation must be going on, inasmuch as
all cultivated ground, and all meadow and forest land, where favour-
able temperature exists, must contain the elements necessary for it.
He is at present engaged in researches on the subject in connection
with the reduction of gypsum, the formation of carbonate and sul-
phide of iron, and the production of nitrous acid in presence of
ammonia and oxygen. J. F.
Influence of Organic Manures on the Temperature of the
Soil. By F. Wagner (Bied. Centr., 1883, 150— 152).— The tempera-
ture of the soil is not wholly dependent on the heat derived from the
sun, but also from the heat evolved by the. condensation of aqueous
822 ABSTRACTS OF CHEMICAL PAPERS.
vapour, and the decomposition of organic matter. Concerning this
last source, investigations have been made to ascertain the heating
effect of the fresh and rotten dung of various animals, as also of green
manures and stubble. The rise of temperature is in proportion to the
amount of manure, to a certain extent to the temperature of the soil,
and to the amount of moisture present, but only so far as the evapora-
tion of that moisture does not counteract the heating produced, and so
long as there remains a sufficiency of oxygen in the crevices of the soil.
A fall of the external temperature to 10" arrests the production of heat-.
The more readily decomposition is effected, the greater is the rise in
temperature ; all added material, such as lime, which assists decomposi-
tion, aids in raising the temperature, and it is also requisite that the
manure be evenly distributed. The maximum heating effect occurs
immediately after the introduction of the manure, but heat is gene-
rated for from four to twelve weeks. Bean straw and horse dung are
most effective, there having been an increase in temperature of 2*8°
and 1-0° respectively. E. W. P.
Application of Insoluble Phosphates to Soils. By M. Flei-
scher and R. KissLiNG (Bied. Centr., 1883, 155 — 161). — In the first
portion of this paper we find that the action of moorland soils when
mixed with insoluble phosphates is to render a portion of that
phosphate soluble in water, amounting in one case to 5'5 per cent, of
the total phosphoric acid ; at the same time, a portion is reduced to
the dicalcium salt, and in one compost heap as much as 17 per cent, of
the total acid was brought into this form. The observations also
show that as the ratio between soil and phosphate is widened, so does
the amount of soluble salt increase, and although an increase occurs
as time goes on, yet there is a limit, after which soluble phosphate
becomes " reduced." In the second portion, we find the influence
exerted by added salts as kainite, gypsum, &c., on the solubility of
phosphates in peaty soil. Ammonium sulphate was most energetic,
but the authors put its action on one side, as the sample was crude
and contained free acid. Potassium sulphate was very effective, whilst
Chili saltpetre and kainite were far less so. This assisting action
of potassium sulphate seems to increase with each addition of the salt.
E. W. P.
Ash of Pistia Stratiotes : " Pana Salt." By C. J. H. Warden
(Ghem. News, 47, 133 — 134). — Pistia stratiotes, known as " taka
panna," in Bengalee and Hindoostanee, is found floating on stagnant
pools of water in most parts of India, resembling in appearance half-
grown lettuce plants ; the saline matter obtained from the ash is called
" pana salt." To prepare this salt, the matured plants are dried and
incinerated, the ash thus obtained is percolated with water, and the
saline solution is evaporated to dryness. Pana salt is almost entirely
nsed for medicinal purposes. A specimen of the plant yielded the fol-
lowing results on analysis. The plant was dried at 130°, exposed to a
temperature below redness, exhausted with boiling distilled water,
and the insoluble residue incinerated until free from carbon. Total
ash, 31*4583 per cent.; 6*1426 per cent, being soluble and 25*3463
insoluble. A sample of pana salt was slightly deliquescent, had alka-
VEGETABLE PHYSIOLOGY AND AGRICULTURF. 823
line reaction, and looked like dirty common salt. Dried at 130° it
contained —
Per cent.
Potassium chloride 73-0916
Potassium sulphate. 22-6130
Potassium carbonate traces
Sodium carbonate 0'4727
Calcium sulphate 0*5874
Magnesium sulphate 0'2574
Iron oxide and alumina 0*0982
Sand and silica 0*3673
Organic matter 0*3575
Water 1*8674
Nitrates, nitrites, phosphates, bromine, iodine. . Nil
99*7125
This analysis shows that water- weeds may contain a large amount
of saline matter. It is hence probable that these plants have the
power of removing saline matter from water, as well as indirectly oxi-
dising the dissolved organic matter. For this reason, it is desirable
to allow water- weeds to grow in Indian tanks (which are very liable
to pollution), bub only during the cold season, when direct oxidation
proceeds slowly ; in the hot season, however, it is advisable to
keep the surface of the water clear of weeds, so as to expose it to
the heat, light, and air, in order to facilitate direct oxidation, which is
rapid at high temperatures. In the case of wells in India, the mouths
are generally raised above the level of the ground, so that the water
must percolate through a certain depth of soil and is thus rendered
innocuous ; if sewage does gain access, it retains its virulence for a
long time* the author attributes this to the low temperature of the
water, to the absence of light and plant life, and to the stagnation of
the atmosphere. D. A. L.
Manuring Sugar-beet. By A. Tschuschke {Bied. Centr., 1883,
161 — 163). — Five sets of experiments show that a mixture of saltpetre
and superphosphate brings the highest yield of roots, but that saltpetre
alone produces the heaviest root, whilst superphosphate alone produces
a root having the highest quotient of purity. Of two samples of roots,
Schlesian is better as regards yield, individual weight, and quotient
than Little Wanzleben. E. W. P.
821 ABSTRACTS OF CHEMICAL PAPERS.
Analytical Chemistry.
Preparation of Hydrogen Sulphide from Coal-gas. Bj J.
Taylor (Ghem. News, 47, 145). — " Hydrogen sulphide may be pre-
pared very easily, and sufficiently pure for ordinary anajiytical pur-
poses, by passing coal-gas through boiling sulphur." For this purpose
the sulphur is placed in a retort, through the tubulure of which a bent
glass tube, connected with the gas supply, passes below the surface of
the sulphur, the neck of the retort being inclined npwards and con-
nected with a wash-bottle, to which is attached the flask containing
the solution to be treated. The apparatus is worked by an aspirator
which serves both to regulate the flow of gas and also as a receptacle
for unused gas. The gas-supply tube may be advantageously per-
forated with several small holes at the end dipping under the sulphur.
During working hours the sulphur is kept hot by means of a burner,
so that it can be quickly raised to boiling when required. The author
claims cleanliness, cheapness, and convenience for this method.
D. A. L.
Litmus, Methyl-orange, Phenacetolin, and Phenol-phthalein
as Indicators. By B. T. Thomson (Ghem. News, 47, 135— 137).— A
continuation of the paper already abstracted (this vol., 682).
XI. Effect of Sodium Silicate. — With this substance, litmus and
methyl- orange give good results, and the end-reaction is very distinct
in both cases. Fhenacetolin results are good, but the colour-change is
not so; a dark pink is developed, which becomes yellowish and indis-
tinct towards the end. Phenol-phthalein gives very low results. The
titration of sodium silicate, Na2Si409, gave the following results : —
c.c. of normal Gram ^dt^^O
Indicator. acid consumed. found.
Litmus 15-05 0*466
Methyl-orange 15'10 0-468
Phenacetolin 15-00 0*464
-D, 1 1,4.1, 1 •• /cold 12-70 0-393
Phenol-phthalein | ^^.^^^ ^ ^ ^ ^ ^^,^^ ^^.^^g
XII. Effect of Alumina. — The experiments were made with caustic
soda-solution of average strength, containing about 8 per cent, of
alumina. With litmus, more acid is required than when alumina is
absent, and the end-reaction is not very distinct. With methyl-orange,
no permanent change in colour takes place until the alumina first pre-
cipitated is redissolved, and the results show that almost all the
alumina is estimated along with the soda. With ithenacetolin and
phenol-phthalein, the actual amount of soda is found ; the alumina,
however, renders the end-reaction slightly obscure. The results are
as follows: — For each test 50 c.c. of the solution containing 0-775
gram NaoO and 0-103 gram AI2O3 (= 0186 gram NaaO; was em-
ployed.
ANALYTICAL CHEMISTRY. 825
c.c. normal Gram Na-^O
Indicator. acid consumed. found.
Litmus 25-25 0782
Methyl-orange 30-70 0-951
Phenacetolin 25-05 0-776
Phenol-phthalem 2500 0*775
XIII. Effect of Sodium and Potassium Nitrite. — These salts are
neutral to litmus, phenncetoUn, phefiol-phthale'in ; and with methylr
orange no permanent colour is produced in moderately dilute solu-
tions (1-70 gram KNOg in 100 c.c), probably owing to the decolor-
ising effect of the nitrous acid, and even in a solution containing 0-085
gram of nitrite in 100 c.c. the pink colour disappears in a few
minutes, leaving a pale yellow colour.
XIY. Determination of Soda in Borax. — For this purpose, methyl-
orange is admirably adapted, the final colour-change being sharply
defined, and the results are good. With litmus ?iTLd ph&nacetolin the
change of colour is slow, and therefore the end-reaction is indistinct.
J'henol-phthalem is quite useless. The results obtained were as follows :
— 1-683 gram NagBiO? = 0-516 gramNasO were used for each test.
c.c. normal Grram NajO
Indicator. acid consumed. found.
Litmus 16-65—16-60 0-516—0-514
Methyl-orange 16-70—16-65 0-518—0-516 •
Phenacetolin 16-70—16-60 0-51 8—0-514
cold .... 7-60— 7-80 0-235—0-242
boiled .. 11-00—11-30 0-341—0-350
Phenol-phthalein <
XY. Determination of Free Sulphuric, Nitric, and Hydrochloric
Acids. — From previous experiments (loc. cit., 684) it is obvious that
these acids may be determined by a standard caustic alkali in the
presence of these indicators, excepting, of course, by ammonia with
phenol-phthalein. Sodium carbonate can be used for titration in the
cold with methyl -orange, and a small quantity of carbonate should
always be used with phenacetolin in order to obtain the dark pink end-
reaction.
XYI. Determination of Free Oxalic Acid. — Litmus and phenol-phtha-
lein are well adapted for this purpose, the end-reactions being very
well defined and the results exact. With methyl-orange, the pink
colour is soon completely destroyed, whilst the phenacetolin colour
does not develop well, therefore neither of these two indicators are of
use for the titration of oxalic acid. The results obtained are tabulated
below : — 0-900 gram H2C2O4 for each test.
c.c. normal Gram H2C2O4
Indicator. NaHO consumed. found.
Litmus 20-0 0-900
Methyl-orange IS'O 0 810
Phenacetolin 19*8 0-891
Phenol-phthalein 20-0 0-900
XYIL Determination of Acetic Acid. — The acetic acid solution
employed contained 100 grams of acetic acid (sp. gr. 10472 at 15°
VOL. XLIV. 3 Jc
S26 ABSTRACTS OP CHEMICAL PAPERS.
= 35'02 per cent. C2H4O2) per litre. 50 c.c. were used for each titra-
tion. The caustic alkali used was standardised with normal sulphuric
acid. With litmus^ the final change of colour is uncertain, sodium
acetate being alkaline to this indicator, and can only be ascertained
either by comparing with blue litmus solution of the same strength as
that operated on, or by using paper ; the results are the same in
both cases. Neither methyl-orange nor phenacetolm are adapted for the
titration of acetic acid. Phenol-phthalein,, on the other hand, answers
admirably, sodium acetate is neutral to it, the end-reaction is delicate
and sharply defined, and is not affected by dilution, therefore when
the acetic acid is to be determined in dark- coloured liquids (such as
some vinegars) they may be highly diluted before titration so as not
to interfere with the phenol-phthalein colour. The results are as
follows : —
c.c. normal Gram C2H4O2
Indicator. NaHO consumed. found.
Litmus 29-15— 2915 1749— 174'9
Methyl-orange 3*50 0-210 (printed 2-10)
Phenacetolin 27-80 1*668
Phenol-phthalein .. 29-20- 29-20 1-762—1-752
XVIII. Determination of Tartaric Acid. — With litmus, the result is
good, but the change of colour is slow. Metliyl-orange gives very low
results ; whilst those with phenacetolin are very slightly below the truth.
Phenol-phthalein again is prominent with its delicate end-reaction and
good results. The following are the results obtained, 1*5 grams
CiHeOe being used for each test : —
c.c. normal Gram C4H6O4
Indicator. NaHO consumed. found.
Litmus 20-00—20-00 1-500—1-500
Methyl-orange 16-00 1-200
Phenacetolin 19-85 1-488
Phenol-phthalein .. 20-00—20-00 1-500—1-500
XIX. Determination of Citric Acid. — The solution employed con-
tained 14 grams of citric acid (containing 8-53 per cent, of water,
although carefully dried) per 200 c.c. The normal soda was standard-
ised by normal sulphuric acid, standardising with citric acid being
too laborious, entailing as it does the testing for impurities, and tedious
estimation of water (compare Grosjean, Trans., 1883, p. 332). Litmus
either as solution or as paper, is not so good for the titration of citric
acid when the soda has been standardised with sulphuric acid, sodium
citrate being alkaline to litmus. Neither is methyl- orange or phen-
acetolin of any value for this purpose. Phenol-phthalein, however,
gives good results, and a sharply defined end-reaction. The results
obtained were as follows : — 20 c.c. of the solution = 1-2806 grams
CeHgOv being used for each experiment.
c.c. normal
NaHO consumed.
Gram CgHaOy
found.
197—19-7
9-0
17-2
20-0—20-0
1-2608—1-2608
0-5760
1-1000
1-2800—1-2800
ANALYTICAL CHEMISTRY. 827
Indicator.
Litmus
Metbyl- orange .
Phenacetolin . . .
Phenol-phthal e'in
Some lime-juice was titrated with the following results : —
c.c. normal Grams of
Indicator. soda consumed. CgHgOy per oz.
Litmus 13-00— 13-05 36*40- 36-54
Phenol-phthalein .. 13-25- 13-25 37-10—37-10
In this case, 10 c.c. of the lime-juice were diluted to 150 — 200 c.c,
as the yellow colour would otherwise interfere with the reaction ; as it
is, the colour- change is not quite so delicate as with a colourless
solution, although it can be easily recognised. D. A. L.
Use of Rosoiic Acid as an Indicator ; Additional Notes on
the Use of Phenol-phthalein and Methyl-orange. By E,, T.
Thomson {Gheyn. News, 47, 184 — 186). — This paper is simply an addi-
tion to those which the author has lately published (preceding Abstract
and this vol., p. 683). In the absence of any interfering agent rosoiic
acid is a very delicate indicator, the complete change from pale yellow
to deep pink beirg very sharp. For the determination of alkali in
potassium or sodium hydroxide, carbonate, and hydrogen carbonate, this
indicator is extremely delicate, provided the carbonic anhydride when
present is boiled off. Sodium or potassium sulphate, chloride, nitrate,
sulphite, thiosulphate, and nitrite are neutral to rosoiic acid. In the
presence of ammonium salts, 0'2 c.c. of normal sodium hydroxide are
required to develop f ally the deep pink colour ; it is therefore not
recommended for the titration of free ammonia. In sodium sulphide,
the whole of the sodium can be accurately estimated ; the end-reaction
is very sharp, provided the liberated hydrogen sulphide is boiled off.
Effect of Sodium Phosphate. — The disodium phosphate is strongly
alkaline ; the monosodic salt is neutral to rosoiic acid. The whole of
the alkali in sodium silicate can be determined with this indicator ; but
in order to get a good end-reaction, the experiment must be done with
a boiling solution. With alumina, rosoiic acid behaves in much the
same way, and gives results similar to litmus, Rosoiic acid is not
fitted for the determination of soda in borax. It is, however, an
excellent and delicate indicator for the determination of free sulphuric,
hydrochloric, nitric, and oxalic acids, either by standard soda or potash.
It is not well adapted for determiuation of tartaric acid, and is useless
for the titration of acetic and citric acids.
When phenol-phthalein is used for the determination of citric and
acetic acids, the titration should be done in the cold ; for the sodium
salts of these acids, although neutral in the cold, have a slightly alka-
line reaction when hot. The author again points out that phenol-
phthalein is not trustworthy in the presence of ammonia or ammonium
salts. The author has devised the following method for the valuation
of potassiiim or sodium phosphate and phosphoric acid ; it is based
828 ABSTRACTS OF CHEMICAL PAPERS.
on tlie fact that when normal sodium phosphate is titrated with sul-
phuric acid, the neutral point with methyl-orange is reached when the
monobasic phosphate NaH^POi is formed, whilst the phenol-phthalem
neutral point is the dibasic phosphate NaoHPOi stage. To work the
method, 5 to 10 grams of the sample dissolved in 80 c.c. of water is
mixed with normal sulphuric acid, or, in the case of phosphoric acid,
with soda, until the faintly acid reaction with methyl-orange is ob-
tained ; carbonic acid, if present, is expelled by boiling ; and the cool
solution is now titrated with sodium hydroxide, phenol phthalem being
the indicator, until the neutral (or mono -acid) point is reached: the
result thus obtained is one-third of the total phosphoric acid present.
Good results have been obtained, but somewhat lower than by the
magnesia mixture gravimetric method. D. A. L.
Determination of Caustic Alkalis in presence of Alkaline
Carbonates ; and of Calcium Hydrate in presence of Calcium
Carbonate. By Gr. Lunge (Ghem. News, 47, 188). — The author uses
phenacetolin as indicator, and in the case of the lime determination,
he drops in normal acid until a permanent yellow coloration is esta-
blished. For caustic soda, he proceeds in the manner recommended
by Thomson (this vol., 682). D. A. L.
Determination of Zinc as Sulphide. By R. Macaethur (Chem.
News, 47, 159). — The author proceeds in the following manner: —
The solution to be analysed is nearly neutralised, then rendered alka-
line with ammonia, acidified with acetic acid, and the zinc precipitated
with hydrogen sulphide. The precipitate is washed by decantation
with hydrogen sulphide solution containing ammonium acetate, col-
lected on a filter, dried, and ignited in an atmosphere of hydrogen
sulphide. For this purpose the crucible containing the zinc sulphide
is supported in a No. 6 Hessian crucible, which has two holes drilled
in it ; one at the bottom for the Bunsen burner, and one in the side
for the hydx'ogen sulphide supply, which is kept up briskly during the
ignition. D. A. L.
A New Test for Titanium and the Formation of a New
Oxide of the Metal, By E. Jackson {Chem. News, 47, 157). —
Hydrogen peroxide gives rise to a yellow or orange colour in solutions
of titanic oxide in hydrochloric or sulphuric acid : this reaction is ex-
tremely delicate. By it ^^^00 of a gram of titanium oxide, or
conversely 2W000 ^^ ^ gram of hydrogen peroxide, can be easily de-
tected. This colour is due to a new oxide of titanium ; it is destroyed
by reducing agents, or by potassium permanganate or by heating ; in
the last two cases oxygen is evolved. It is not affected by potassium
chromate. With alkalis, a pale lemouTColoured precipitate is thrown
down ; but on redissolving in dilute hydrochloric acid, the colour is
restored to its original intensity. The reaction does not take place
in presence of much hydrofluoric acid ; ferric chloride should also
be absent, as the yellow colour of the iron salt masks the titanium
coloration. The composition of this oxide has not yet been definitely
determined, the results obtained being discordant. By means of this
ANALYTICAL CHEMISTRY. 829
reaction, titanium has been detected in coal ash, in sawdust, in seed
of French bean, in the ash of cotton-seed cake, and in some soils.
D. A. L.
Water Analysis. Bj L. W. McCa.t (Ghem.. News, 47, 195).—
In using Tidy's permanganate method for estimating the organic
puritj of waters, the author has always experienced a difficulty in
ascertaining the precise moment of the disappearance of the blue
colour of the iodised starch ; to avoid this he has adopted the use of
ammonium ferrous sulphate. The solutions he employs are — (1.)
0"395 gram permanganate in 1000 c.c. pure water. (2.) 4'90 grams
ammonium ferrous sulphate in 975 c.c. water and 25 c.c. concentrated
sulphuric acid. From several experiments, the author is assured that
the method is very good ; the results are not only constant, but also
agree well with duplicate analyses done by Tidy's method. The
advantages claimed for the method are — (1.) The abolition of the blue
colour difficulty. (2.) Saving of time. (3.) Two solutions only are
required. (4.) The amount of chemically pure water necessary is
reduced to a minimum. The ammonium ferrous sulphate solution
keeps very well in the dark. D. A. L.
Sulphuric Acid in Sherry. By E. Borgma.nn (Ber., l6, 601 —
602). — An analysis of a soil producing the best sherry is given. It
contains 0"1578 per cent, sulphuric acid, which is insufficient to
account for the amount of acid frequently found in this wine.
A. K. M.
Estimation of Sugar in Urine. By Worm-Mijller (Bied.
Gentr., 1883, 207). — 5 c.c. of urine in a beaker are boiled, and simul-.
taneously a mixture of 1 — 3 c.c. copper sulphate solution (2*5 per cent.)
with alkaline Rochelle salts (100 grams in 1000 c.c. normal sodium
hydrate) is boiled for the same time in another beaker. After 20 — 25
seconds, the boiling is interrupted, and the two are mixed.
E. W. P.
Employment of Magenta with Sulphurous Anhydride as a
Microchemical Test for Aldehyde. By O. Loew and T. Bockornt
(Bied. Gentr., 1883, 212). — This reagent is uncertain, for when it is
exposed to the air, sulphurous oxide volatilises, and a red solution is
left, the colour being similar to that produced by acetone ; it cannot,
therefore, be safely used for the detection of aldehyde in protoplasm
as proposed by Mori. E. W. P.
New Test for Aldehydes. By F. Penzoldt and E. Fischer
(Ber., 16, 657 — 658). — Pure crystallised diazobenzenesulphonic acid
is dissolved in cold water (about 60 parts) with the addition of a little
soda-solution, and the subntance to be tested (also mixed with dilute
alkali) is added, together with a little sodium-amalgam. After stand-
ing for 10 — 20 minutes, a reddish- violet colour is produced, resembling
that of fuchsine. A liquid containing 1 part benzaldehyde in 3000
will show this reaction. Chloral and benzoin do not give the colour,
whilst acetone and ethyl acetoacetate produce a deep red coloration
without the characteristic violet hue which is, however, produced by
3 A; 2
830 ABSTRACTS OF CHEMICAL PAPERS.
grape-sugar. The colour is destroyed hj long exposure to the air,
and is changed by the addition of an acid. A, K. M.
Estimation of Humus in Soils. By G. Loges (Bied. Centr.,
1883, 147 — 150). — Warington and Peake's results are corroborated.
Although chromic acid oxidises organic matter, yet all the carbon
cannot be estimated as carbon dioxide by its means, seeing that acetic
acid is formed. A table of analytical results shows the wide difference
which exists between the results obtained by chromic acid and by the
ignition process. E. W. P.
Technical Chemistry.
Action of Water on the Lime of Theil. Existence of a New
Compound, " Pouzzo-Portland." By E. Landrin (Compt. rend.,
96, 1229— 1232).— The author has already shown (this vol., p. 712)
that the absorption of lime by hydraulic silica tends to the formation of
the compound 3SiO2,40aO. For this compound he proposes the name
Pouzzo-Portland.
If 1 gram of the lime of Theil is agitated with 2 litres of water
free from carbonic acid for 10 or 12 days by means of a mechanical
agitator, a portion of the lime is dissolved. The composition of the
original lime was : — Carbonic anhydride and water, 4"40 ; part soluble
in water, 41*21 ; part insoluble in water, 54*39 = 100. The composi-
tion of the soluble and insoluble portions was as follows : —
SiOj. and Al^Oj. CaO. MgO.
Soluble portion. . . . 4*70 I'Oo 85-10 036 = 41-21
Insoluble portion . . 21-70 1*95 30-06 0-68 = 54-39
From these figures it is evident that the part soluble in water con-
sists of (1) a large excess of free lime, which in actual practice will
either be converted into carbonate by the carbonic anhydride existing
in the air or water, thus forming a protecting envelope to the mortar,
or will dissolve in the water if the latter contains too little carbonic
anhydride to form calcium carbonate, or if on the other hand it con-
tains sufficient carbonic anhydride to form soluble calcium bicarbo-
nate ; (2) soluble calcium aluminate ; (3) silica held in solution by the
alkali.
. If it is admitted that the alumina is combined with the lime in the
most basic form, the composition of the insoluble portion may be thus
expressed : —
TECHNICAL CHEmSTRY 831
Silica 2170
Lime 26-88
Lime 3*18
Alumina and ferric oxide 1"95
Magnesia 0*68
Pouzzo-Portland.. 48-58
Calcium alaminate 6-13
54 39
This insoluble portion when dried at dull redness has the property
of setting and gradually hardening, like the best Portland cement.
Nodules of very similar composition, but containing a slightly higher
proportion of calcium aluminate, are formed during the roasting of
the lime at Theil, and can be separated after slaking the lime, since
they are not disintegrated by the water. They yield excellent Port-
land cement.
When mixtures of lime with different varieties of silica in the pro-
portion required to form Pouzzo-Portland are heated to bright redness
in a gas-carbon crucible for a time varying with the nature of the
silica, the fused but non-vitrified mass yields an artificial Pouzzo-Port-
land which generally splits up and falls to powder as it cools. It is
completely soluble in hydrochloric acid, and when moistened with the
smallest possible quantity of water and immersed under water, it sets in
from 15 to 16 hours, acquiring a hardness which, however, is scarcely
equal to that of Spanish white. If, however, the water is charged
with carbonic acid, the cement after some hours acquires a hardness
equal to that of the hardest stone. C. H. B.
Hardening of Cements. By H. Le Chatelier (Compt. rend., 96,
1056 — 1059). — Whenever a body occurs in the nascent state in contact
with one of its solvents and in quantity greater than can normally
exist in solution, a supersaturated solution is formed. To this law
there may, however, be exceptions. The author extends to other
cements his theory of the setting of plaster of Paris (this vol., p. 712),
and details experiments which prove that supersaturated solutions are
formed when calcium sulphate is treated with a saturated solution of
potassium sulphate, zinc oxide with a concentrated solution of zinc
chloride, and lime with a concentrated solution of calcium chloride.
When fused calcium aluminates are treated with a large excess of
water, alumina and lime dissolve in varying proportions, generally
different from those in which they exist in the original aluminate.
From hydrated aluminates on the other hand, water dissolves no
alumina. The solutions of aluminates gradually deposit the whole of
the alumina and part of the lime in the form of crystalline hydrated
aluminates of variable composition. The aluminates exist in solution
in a state of supersaturation. The proportion of alumina originally
dissolved is greater the smaller the proportion of lime in the anhy-
drous aluminate; the precipitation of the hydrated aluminates on tlie
other hand is more rapid the greater the quantity of lime contained
in the anhydrous aluminate and consequently in the solution.
When a solution of any aluminate is mixed with an equal volume
of lime-water, precipitation commences in a few seconds, and is com-
832 ABSTRACTS OF CHEMICAL PAPERS.
plete after some hours. The precipitate consists of tufts of elongated
microscopic crystals radiating from a central point; if precipitation is
very slow, the precipitate forms small, compact spheroliths. This
precipitate has the composition Al203,4CaO,12H20 + OHjO, and is
identical in appearance with the crystals formed in the setting of
aluminous cements. It loses 9H2O at 40°. C. H. B.
Cliemistry of the Bessemer Converter. By J. E. Stead (Chem.
News, 47, 159 — 162). — The author points out that the Bessemer con-
verter is by far the most important metallurgical instrument of
modern times, and this importance has been increased by the discovery
of the basic or Thomas- Gilchrist process; for by this improvement
immense quantities of phosphoric pig-iron, previously considered unfit
for making steel, have been rendered available for the Bessemer pro-
cess. In this paper, the chemistry of the converter is discussed, and
the two processes, the acid and basic, compared (compare this vol.,
402—404).
Firstly, for lining purposes, the material must be able to resist a
very high temperature, and must be suflBciently plastic when damp,
so as to hold together when placed in the converter; the ganister
therefore should contain about 6 per cent, of alumina. Potash and
soda should be avoided, as they render the mixture more fusible. The
following figures show the percentage composition of linings : —
SiOg.
AI2O3.
Fe^Oj.
CaO.
MgO.
K2O.
Na^O.
A good mixture for
"acid" lining .. 91-2
6-0
170
0-25
0-25
0-38
0-32
A "basic" lining.. 11-4
4-5
3-46
49-91
30-27
—
—
The " basic " lining is prepared by calcining bricks made from
finely ground raagnesian limestone until all carbonic anhydride is ex-
pelled, and the substance has shrunk to about half the original size;
it is then ground to a rough powder, and mixed with 9 to 10 per cent,
of boiled coal-tar free from water. Water would slake the lime, and
cause the lining to crack. The mixture of tar and basic material may
be thrown in plastic lumps into an annular space formed inside the
vessel by the introduction of an iron cage, within which a fire is
placed. The basic mixture soon becomes hot, melts, fills up the space,
and finally becomes quite hard ; or it may be cast and baked into
bricks in iron moulds, whereupon the tar cakes, and the mixture may
be transformed into solid bricks, which after the removal of the moulds,
are simply built round the inside of the converter.
The following analyses of the metal charged during the " acid "
process show that there is more sulphur now than formerly : —
C. Mn. Si. S. P.
Metal used 1-5
years ago. .
3-5—4-0
0-1-
-1-0
2-0-
-3-0
0-01-
-0-05
0-03-
-0-10
Ditto now . .
3-0-
-4-0
01-
-1-0
2-0-
-3-0
0-05-
-0-15
0-03-
-010
But manganese is now added in larger quantities, and this metal neu-
tralises the injurious effect of the sulphur, which would otherwise
render the steel red short {ibid., 404).
TECHNICAL CHEMISTRY.
833
The primary object of the " acid " converter is to rid the metal
of its carbon and silicon. The following tables are the result of
analyses of samples taken after varying periods of exposure in the
converter : —
P.c. at After After After After After
start. 5 mins. 10 mins. 15 mins. 20 mins. 25 mins.
C 3-50 3-60 3-3 3-25 2-0 trace
Si 2-25 1-00 0-5 0-20 O'l trace
Mn .... 1-00 0-35 02 trace — —
Another sample series —
C 3-50 3-60 3*30 25 I'O trace
Si 3-00 1-75 0-25 0-9 07 0-5
Mn .... 075 0-25 trace — _ _
Generally, then, the manganese is the first to go, the silicon next,
and the carbon last ; and, this being the case, the oxygen towards the
end has nothing else to work on but the carbon, which is quickly burnt,
and therefore the large carbonic oxide flame at the mouth of the vessel
drops suddenly, and the " blower " knows that the operation is com-
plete. When large quantities of silicon are present, as in the second
case above, the rapid oxidation causes great increase of heat (this can
be reduced by putting in cold scrap or pig-iron), and under these cir-
cumstances the carbon is attacked before all the silicon is gone, so that,
towards the end of the operation, the work for the oxygen is divided.
In this case the carbonic oxide flame, instead of falling suddenly,
fades gradually away, and the "blower" knows that silicon is present
in the "bath," and continues to blow until brown fumes (iron oxide)
appear, showing that iron is being burnt. Of course the apparent
increase of some substances in some of the stages in the above figures is
due simply to the decrease of the other constituent or constituents. It
is evident that the proper adjustment of temperature for casting is of
great importance if uniformly solid and homogeneous steel is to be
obtained : for if it be too high, the carbon will be oxidised and blow-
holes will be formed.
The metals for the " basic " process are commonly of the following
composition ; —
C. Mn. Si. S. P.
No. 1.... 3-35 0-60 1-30 0-15 175 p.c.
No. 2 .... 3-50 100 1-00 0*12 275 „
The chief feature is the high percentage of phosphorus. From 15
— 17 per cent, of well-burnt lime is put in with the charge; otherwise
the lining would soon be destroyed by the silicon and phosphoric
anhydride produced : the process is really based on the removal of
these acids by the alkali. The approximate rates of disappearance of
impurities from phosphoric pig-iron during the blow are given
below : —
834
ABSTRACTS OF CHEMICAL PAPERS.
Carbon
Silicon
Manganese .
Phosphorus.
Sulphur . . .
P. c. at
start.
3-50
1-50
0-71
1-57
0-16
After
After
After
After
5 mins. 10 mins. 15 mins. 18 mins.
3-55
0-50
0-56
1-60
0-14
2-35
0-09
0-27
1-43
013
0-07
trace
0-12
1-22
012
trace
trace
0-08
010
Remarks. — Si disappears first ; C next ; Mn next : P does not appear
to be much attacked until the C is all oxidised.
The author explains the action in the converter in the following
manner : The oxygen coming in at the bottom combines with all the
constituents forming a highly basic iron oxide cinder. This cinder
passing upwards through the column of metal which is in violent
agitation, brings about the reactions described in the equations: —
Air + wFe = FeO 4- N, air and iron giving iron oxide and nitrogen ;
2FeO -h Si = Si02 + Fea ; FeO + Mn = MnO + Fe ; 6FeO + 2P =
FeO,P205 + 5Fe; FeO.P^Os + 6C = Fe + P2 + 6C0 ; FeO,?^©^ +
3Si = 3Si03 + P2 + Fe. From these changes it is apparent that in
the ordinary way whilst carbon and silicon are present, phosphorus
cannot be removed ; this can, however, be effected in shallow " baths,"
or if the tuyeres blow on the surface of the molten mass, for then the
cinder comes directly in contact with a quantity of lime which is
ready to combine with the silica and phosphoric anhydride as soon as
they are formed, producing calcium phosphate which is not reduced,
either by the carbon in the iron or by carbonic oxide. In Richard's
process some of the excess of oxygen in the ^ - basic " steel is removed
by adding fluid haematite pig containing silicon. From this point
onwards the two processes work alike. Spiegeleisen is added to the
blown metal to replace the carbon and manganese (and in case of
" acid " steel to remove surplus oxygen) necessary to convert it into
malleable steel. Spiegeleisen analyses gave following results : —
C.
Mn.
Si.
s.
P.
Old German . ,
. 4-50
10-00
0-50
trace
0-10 p.c.
New English .
. 5-20
20-00
0-50
trace
0-10 „
The following equations explain why phosphorus is not removed in
the " acid" converter :—3CaO,P205 -f SSiOa = SCaOjSiO, + P2O5;.
FeO.PaOs + Si02 = P2O5 + FeO,Si02 ; P2O5 + 5Fe = 5FeO + P3
Results from the analysis of the slags from the two processes were as
follows : —
FeO. FejOa. K. AljOj. MnO.
Acid"
Basic
process . .
15-62
9-13
1-57 —
102
2-10
5-33
4-32
"Acid" process . .
♦'Basic" „ ..
SiOa. CaO.
75-70 0-94
16-60 47-08
MgO.
0-09
4-62
S. P2O5.
0-01 Nil
012 16-03
Loss in Bessemer converting is greatly due to projections from the
nose of the vessel being carried away as rubbish. Analysis of several
Bessemer projections yielded results as follows : —
TECHNICAL CHEMISTRY.
835
Fe.
70-30
Fe,03.
14-50
Mn.
0-11
C.
1-01
Si.
0-63
Sand.
13-18
P.
0-05
S."
0-06 p.c.
The amonnt of iron burnt is only 2 per cent ; a certain quantity is
always lost in the slag which, being great in the basic process, occa-
sions a greater loss. The respective yields are about : " acid," 88*5 ;
" basic," 85 per cent, of the metal charged. Analyses of the steels
from —
Fe.
C. Mn.
Si.
s.
P.
Cu.
"Acid" process . ,
. 98-33
0-35 1-11
0-08
006
0-05
0-02
"Basic" „
, 98-46
0-35 1-01
0-03
0-11
0-04
trace
The " basic " process is making rapid progress commercially,
especially on the Continent. D. A. L.
Purification of Molasses. By Gundermann (Bied. Centr., 1883,
215). — A solution of bone charcoal or crude calcium phosphate in
hydrochloric acid is added to the molasses, and then milk of lime in
excess ; the precipitate of calcium phosphate carries down with it all
the organic calcium salts. E. W. P.
Manufacture of Sugar -without the Aid of Bone-charcoal,
Sand, or Sulphurous Anhydride. By H. Pellet and A. Dubaele
Bied. Centr., 1883, 200). — After careful treatment with lime and
carbonic anhydride, the solution is passed through Puvrez's filter,
made of strong sacking 2 m. long and 0-3 mm. broad, which lies
horizontally in a channel ; in the supporting channel or gutter are holes
through which the liquid passes clear and pure. A second evapora-
tion and filtration is necessary. E. W. P.
Prevention of Boiler Explosions. By Treves (Compt. rend.,
96, 1043 — 1046; see also this vol., 250). — Many disastrous boiler
explosions are undoubtedly caused by superheating of the water, which
is frequently due to the fact that the water is kept at the boiling point
during the night in order to economise heat. This prolonged gentle
ebullition expels all the air from the water and brings it into a condi-
tion in which it is particularly liable lo become superheated. The
author proposes to furnish boilers with a T-tube about 4 cm. in
diameter, the horizontal part being about 2 decimeters from the bottom
of the boiler. The under side of the horizontal tube is perforated by
a number of small cups, and, before firing up in the morning, air is
driven into the tube until all the water is expelled, this being effected
when the manometer attached to the air-pump registers a somewhat
higher pressure than the pressure of the steam in the boiler. The
small cups filled with air constitute "surfaces of evaporation," from
which ebullition proceeds regularly. The best plan is to provide each
boiler with a thermo- manometer, in addition to the air-pipe, and to
inject air whenever the temperature of the water rises 5° or 6° above
the temperature corresponding with the pressure registered by the
836 ABSTRACTS OF CHEMICAL PAPERS.
manometer. This latter plan is the only one that can be adopted on
board ship. C. H. B.
Explosive and Dangerous Dusts. By T. W. Tobin (Chem.
News, ^7, 149 — 153). — Amongst many observations and experiments,
the author points out that mill fires or explosions generally take their
rise in the dust-shaft or its vicinity, which is due to the fact that,
month after month streams of dry air are urged through them bearing
along with it the dry flour-dust ; at last a spark comes, ignites it, and
sets fire to the mill.
He shows by an experiment, in which he allows flour to fall down
a hollow shaft 7 feet high, perforated so as to admit plenty of air,
and with a Bunsen burner alight at the bottom, that, as soon as the
flour reaches the flame, instantaneous combustion of the contents of
the shaft ensues. The microscopical appearances of several dangerous
dusts, such as flour, starch, " wheat dust-room " dust, consisting of
minute particles of starch, husk, fractured gluten cells, the beard, &c.,
lycopodium, and wood-dust from axe-handle factory are described, and
experimental illustrations of their dangerous character are given.
The great importance of the humidity of the atmosphere is insisted
on, and, from a series of observations, he shows that whereas the
atmospheres of the grinding and bolting floors are generally moister,
that of the dust-shaft is always drier than the external atmosphere ;
the humidity of the grinding and bolting-rooms is due to the evapo-
ration from the flour caused by the heat of the rollers ; the dryness of
the air of the dust-shaft is caused by the hygroscopic nature of the
flour-dust. Again, the pressure of the atmosphere bears an interesting
relation to the question of dangerous dust, for the higher the baro-
meter the more dust particles will be buoyed up. Finally, he suggests
that dust-rooms should be built of brick, and all communicating doors,
shafts, &c., made of iron. The dry shoots, shafts, and dust-rooms
should be daily, if practicable, charged with steam, and the mill
should be kept free from superfluous dust and flour. The hygrometer
should be used, and its readings attended to. Care should be taken
not to overcharge the air with dust in dry weather when the air is
dense ; and naked flames should never be used in the mill.
D. A. L.
837
General and Physical Chemistry.
Atmospheric Absorption in the Infra-red of the Solar
Spectrum. By W. W. Abney and R. Festing (Proc. Boij. Soc, 35,
80 — 83). — The authors allude to tlie importance attached to a stady
of atmospheric absorption in relation to its meteorological bearings.
They describe observations on the absorptions in the infra-red of
the solar spectrum at London and on the Riffel at an altitude of
8500 feet in relation to atmospheric moisture. On a fairly dry
day the banded absorptions occur principally between X 9420
and X 9800, with a fainter absorption between \ 8330 and X 9420,
only on a cold day with a N.B. wind these absorptions nearly
disappear. When the air is almost saturated with water, no ray
beyond X 8330 can be photographed ; with a difference of 3° between
the wet and dry bulb thermometers, the spectrum extends to X 9420.
Precisely similar absorptions may be produced by interposing between
a source of light giving a continuous spectrum and the slit of the
spectroscope, layers of water 1 foot and 3 inches thick respectively.
From a comparison of the spectra it is quite easy to deduce the mois-
ture present at a given temperature.
According to the accepted view, the presence of vapours of certain
thicknesses give rise to linear absorptions, which increase in intensity
and number until there is finally produced a total absorption. But
in the case of absorption in the solar spectrum a different condition
obtains ; the linear absorptions are not thus increased in number and
intensity, except so far that the blackness of the lines is increased by
the blackness of the banded absorptions. Further, the Fraunhofer
lines from X 9420 to X 9800 are so irregularly distributed that it is
impossible to conceive that they are all caused by water- vapour, yet
they are equally darkened by the absorption-band of water- vapour.
However this may be, the authors' experiments show that the absorp-
tions seem to result from a water-stuff existing in some form in the
atmosphere. V. H. "V.
Note on the Absorption of Ultra-violet Rays by Various
Substances. By G. D. Liveing and J. Dewar (Froc. Boy. Soc, 35,
71 — 74). — The authors have made a series of observations, in addition
to those recorded by Hartley, Soret, and Chardonnet, on the absorp-
tion of the ultra-violet rays. The source of light was the spark of an
induction coil between iron electrodes, as offering an almost con-
tinuous spectrum in the ultra-violet region, with a sufficient number
of breaks and conspicuous lines to serve as points of reference. The
spectra were all photographed.
Chlorine in small quantity shows a single absorption-band from
N (X3580) to T (X 3020), in larger quantities bands from H (X3968)
to X 2755, from X 4415 to X 2665, and from X 4650 to X 2630. Bro-
mine-vapour in small quantity absorbs light up to L (X 3820), with
VOL. XLIV. 3 I
838 ABSTRACTS OF CHEMICAL PAPERS.
large quantities the absorption increases to P (\ 3360) ; liquid bromine
in a very thin film is transparent for a band between \ 36-50 and
\ 3400. Iodine-vapour tolerably dense absorbs all below \ 4300, the
absorption gradually diminishing to \ 4080 ; iodine dissolved in
carbon disalphide transmits light between G and H. Sulphnrons
anhydride produces an absorption-band between B, (\ 3179) and
\ 2630, and a greater absorption extending on the less refrangible
side to 0. Hydrogen sulphide produces complete absorption above
\ 2580 ; carbon bisulphide vapour an absorption- band between P and
T, shading away at each end ; liquid carbon tetrachloride an absorp-
tion-band with a maximum about R, extending from Q (X, 3285) to
S (X 3045). Chlorine peroxide gives a succession of nine shaded
bands at equal intervals between M and S. A plate of mica shows
absorption from S (\3100), increasing above U (\ 2947), and reaching
a maximum at X 2840. A thin film of silver transmits a band of
light between A 3380 and X 3070; a thin film of gold produces a
slight absorption throughout the whole spectrum.
The authors endeavoured to apply the photometric method by
means of polarised light to the comparison of intensities of ultra-
violet rays. On taking photographs of the spectrum of the iron spark
through a pair of Foucault's prisms at various inclinations between
the planes of polarisation of the two prisms, it was found that for the
whole range between the position of parallelism and an inclination of
80° there was no sensible difference of effect on the photographic
plate ; but for inclinations between 80 — 90° there is an increasing
diminution, as the planes of the polariser and analj^ser were more
nearly at right angles. ' V. H. V.
Reversal of Hydrogen Lines. By G. D. Ltveing and J. Dewab
(Proc. Boy. Soc, 35, 74 — 76). — From the concentration of the radia-
tion of hydrogen into a few lines, it is d priori to be expected that
the absorption of light of the same refrangibility would be corre-
spondingly strong, and therefore that the lines would be easily
reversed; but owing to the small mass of hydrogen which can be
raised to incandescence at any time, the reversal of the lines has not
hitherto been noticed.
If a short induction spark be taken in hydrogen between alumi-
nium or magnesium points, no reversal is noticeable, but on increasing
the pressure by half an atmosphere the lines expand, and a dark line
is seen in the middle of F; at two atmospheres the reversal is most
marked. With a dispersion of more than one prism the reversal of
C may also be noticed. The authors have before observed that the C
and F lines are visible in the arc of a De Meritens machine taken in
hydrogen, but in the arc of the Siemens machine only the former can
be detected. If, instead of taking the arc in hydrogen, drops of water
are allowed to fall into the arc taken in air in a lime crucible, each
drop produces an explosive outburst of the hydrogen lines, usually
much expanded, but without reversal. The effect produced resembles
that of an outburst of hydrogen in the solar atmosphere.
y. H. Y.
GENERAL AND PHYSICAL CHEMISTRY. 839
Order of Reversibility of Lithium Lines. By G. D. Livetng
and J. Dewar (Proc. Roy. Soc, 35, 76). — From former observations
the authors have concluded that of the lithium lines the blue is more
easily reversed than the orange. In the present note it is pointed out
that such is not really the case, for when a considerable quantity of
lithium is introduced into the arc, a second blue line is developed
near to, but more refrangible than the well-known blue line, so as to
produce the appearance of a reversal of the latter. Of these lines,
the ordinary line X 4604 is the more readily and persistently reversed.
Hence the order of reversibility is as follows : — red, orange, blue,
green, violet. V. H. V.
Chemistry of Storage Batteries. By E. Frankland (Proc. Boy.
Soc, 35, 67 — 70). — The author at first alludes to the variety of
opinion as regards the chemical changes occurring during the charging
and discharging of storage batteries, some authorities maintaining
that the effects are dependent on the occlusion of oxygen and hydro-
gen gas on the plates, whilst others consider that lead sulphate plays
an important part. To test the former opinion, the author twisted
two plates of lead into a corkscrew form, filling the gutter of the screw
with red lead ; the plates were introduced into dilute sulphuric acid,
and charged in the usual way. On heating these plates, and collecting
the gas evolved, it was found that mere traces of gases were expelled,
thus showing that the occluded gases are not the important agent of
the cell. It was observed, as regards the function of the lead sulphate,
that, in charging a storage cell, a considerable amount of sulphuric
acid disappears, which is accompanied by a deposit of lead sulphate.
The deposit formed is not however suflBcient to account for the total
acid which has disappeared.
As the charging proceeds the strength of the acid ceases to diminish,
and afterwards increases, this change continuing until the maximum
charge has been reached, and oxygen and hydrogen gases are evolved
from the positive and negative plates respectively, derived from the
electrolysis of hexbasic sulphuric acid according to Bourgoin's equa-
tion—
HeSOe = SO3 + 30 + 3H2
On + plate. On — plate.
On discharging the cell the phenomena are reversed, the sp. gr. of
the acid decreasing to the point from which it began to increase on
the charging of the cell. From these observations the author con-
cludes that in charging the battery the following changes occur : —
(1.) The electrolysis of hexbasic sulphuric acid. (2.) The recon-
version of the evolved sulphuric anhydride into the corresponding
acid. (3.) The chemical action on the coating of the positive plate,
PbS04 + 0 + 3H2O = Pb02 + HeSOfi. (4.) The action on the
negative plate, PbSOi + H2 + 2H2O = Pb -h HeSOe- In the dis-
charge of the storage battery the two former changes of the charging
are repeated, while upon the coating of the positive, formerly the
negative electrode, the chemical change is as follows : — PbO^ +
H2 = PbO + H2O, while upon the other, formerly the positive elec-
3 I 2
840 ABSTRACTS OF CHEMICAL PAPERS.
trode, the change occurring is Pb + 0 + HeSOe = PbSO* + SHaO.
According to the author's conception, the real formation of the cell
consists in the more or less thorough decomposition of those portions *
of the lead sulphate comparatively removed from the conducting
metallic nucleus of the lead. Lead sulphate has a low specific con-
ductive power, while the far better conductors, lead peroxide and
spongy lead, seem to bring the outlying portions of the coating
under its influence.
The above experiments indicate a means of ascertaining the amount
of stored energy without discharging the cell ; for if the sp. gr., and
therefore the strength of the acid be known in its uncharged and
charged conditions, it is merely necessary to take the sp. gr. at any
time to ascertain the proportion of the charge. Pi*eliminary experi-
ments showed that each increase of 0*005 in the sp. gr. corresponded
with a storage of 20 amperes per hour obtainable at discharging.
V. H. V.
Scrivanow's Chloride of Silver Element. (Dingl. polyt. X,
248, 128.) — This element, although of great power, is too expen-
sive for practical purposes, as, owing to its rapid exhaustion, it
requires frequent treatment. It consists of a prism made of gas
coal, which is covered with pure argentous chloride over its entire
surface. This prism is contained in a solution of potassium or
sodium hydroxide (1'30° to 1-45*' B.), i.e., dissolved in 30 to 40 per
cent, of water. As active electrode, a zinc cylinder or plate is used,
which is placed within a suitable distance from the carbon electrode.
All loss of silver is prevented by enclosing the carbon in asbestos
paper or fibre. When the element has been used up, i.e., when all
argentous chloride has been reduced, it suffices to immerse the carbon
in a bath consisting of 100 parts by weight of nitric acid, 5 to 6
hydrochloric acid, and about 30 water. Potassium chlorochromate
and nitric or sulphuric acid also forms a suitable mixture for a bath.
This cell is distinguished from other chloride of silver cells by the
use of an alkaline solution. D. B.
Effects of Temperature on the Electromotive Force and
Resistance of Batteries. By W. H. Preece (Proc. Roy. Soc, 35,
48 — 62). — The author gives a brief summary of the experiments during
the last forty years on the influence of temperature on galvanic cells,
and of the various views held as to the causes producing the varia-
tions. Some experimenters, as Faraday, attributed the increase of
intensity to improved conductivity of the liquids in the cell, while
others, as De la Rive and Daniell, maintained that the effect was due
to an increase of chemical energy. But in all the various researches
the influence of temperature upon the E.M.F. has not been quantita-
tively separated from its influence on the internal resistance ; but both
factors must be taken into account, for the variation in intensity may
arise either from a variation of E.M.F. or internal resistance, or from
a mixed variation of both together. The cells experimented with were
the Daniell, two fluid and one fluid " bichromate" and the Leclanche,
being the forms generally used for telegraph ; these cells were intro-
duced into a larger vessel containing water, which could be warmed
GENERAL AND PHYSICAL CHEMISTRY. 841
to the temperature required. A Daniell's cell at 14° C. was taken as
the standard. The following methods were adopted to measure the
E.M.F. and resistance; the charge or discharge of a small condenser
(C = 3 microfarad) through a galvanometer of low resistance is an
accurate measure of the E.M.F., and therefore e = E in which B
and e are the E.M.F.'s of the standard and the examined cell, D and
d the charge deflections. To measure the resistance the charge deflec-
tion d is first noted, and then the cell is shunted through a coil of
resistance, and thus reducing the E.M.F. affecting the condenser,
and a discharge d' is noted ; then if h is the resistance of the cell,
Variation of E.M.F. — Experiments proved that when a Daniell's
cell is heated to a gradually increasing temperature up to 100°, the
E.M.F. decreases at first rather abruptly, but then more gradually
until a point was reached about 64°, when it begins to increase. The
E.M.F., however, remains unaltered on cooling the cell from 100° to
ordinary temperatures. These results are probably due to a thermo-
electric action set up within the battery from the difference of tem-
perature of the inner and the outer cell.
In the " bichromate " cell the E.M.F. decreases gradually with
rise of temperature, and conversely increases with its fall. The
E.M.F. of the Leclanche is practically unaltered by change of tem-
perature.
Variation of Interval Resistance. — The results of the experiments
observed that (i) on heating a Daniell's cell from 0 — 100° the resist-
ance decreases at first abruptly, then more gradually until it becomes
rather less than one- third of its original value ; (ii) on cooling the
cell the resistance increases, but at a greater rate than it decreases
while being heated ; (iii) if the cooled down cell be left undisturbed,
the resistance of the cell gradually diminishes until it arrives at the
same value which it had before being heated up ; (iv) at any tempera-
ture the resistance is less the more concentrated the copper sulphate
solution. In the case of the " bichromate " and Leclanche cell,
the resistance diminishes with the rise and increases with the fall of
temperature.
From these results it follows that changes of temperature do not
practically aft'ect the E.M.F., but only the internal resistance of the
batteries. The results obtained with the Daniell's cell explain the
discrepancies of measurements obtained with it, and the uncertainty
of its intensity when placed in exposed positions. V. H. V.
Electric Resistance of Carbon Contacts. By S. Bidwell
(Proc. Roy. Soc, 35, 1 — 18). — The phenomenon of diminution of
resistance of carbon contacts with increase of pressure has long been
known; in the present communication it is systematically investi-
gated.
The author arrives at the following results with carbon contacts : —
Changes of pressure produce proportionately greater changes of
842 ABSTRACTS OF CHEMICAL PAPERS.
resistance with small than with great initial pressure, and with weak
than with strong currents. Changes of current produce proportion-
ately greater changes of resistance with weak than with strong
currents, and with light pressures than with heavy pressures. The
resistance of carbon contact, reduced by an increase of pressure,
returns to its former value on removal of the pressure. The passage
of a current, whose intensity does not exceed a certain limit, causes a
permanent diminution of resistance, which is greater the stronger the
current ; but if that limit is exceeded, the resistance is greatly and
permanently increased.
In the case of bismuth and probably other metallic currents, with a
given pressure, the weaker the current the higher will be the resist-
ance. Increase of intensity of the current is accompanied by a fall in
the resistance, and if the current be reduced to its original strength,
the resultant change in the resistance will be small. Increased pres-
sure produces a greater diminution in the resistance with small
pressures than with great pressures, and with weak than with strong
currents. In some cases on increasing the^ pressure, the metallic
contacts fused together.
The above observations throw light on the superiority of carbon
over metals in the microphone ; the metallic contacts, unlike those of
carbon, do not recover their original resistance, and the initial effect
of pressure upon resistance is more marked with carbons than with
metals.
A metal microphone might be used, but the fundamental tone
produced would be marked by the superimposed vibrations of its
particles. V. H. V.
Thermometric Measurements. By J. M. Crafts (Bull. Soc.
Ghim. [2], 39, 196—205, and 277— 289).— The author remarks at the
outset that the progress made in the purification and preparation of
chemical substances has not been accompanied by any appreciable
improvement in thermometric measurements. In these communica-
tions the author gives an account of a series of experiments on the
commonly employed methods of fusion and ebullition, with a view of
facilitating the construction of thermometers, of examining their be-
haviour, and of rendering the method of observation precise.
In the thermometers from the best sources the author observed
residual errors of 0*015' — 0*04' degree. When the scale is divided
into tenths of a degree, in ordinary thermometers differences of length
of O'l' — 0*5' degree incontiguoas sections of 25 degrees. As these varia-
tions rarely compensate one another, it is not rare to find thermo-
meters which require corrections amounting to several fractions of a
degree.
In determining the value of a degree from the points 0° and 100"*, it
is most important to follow an invariable order in the observation of
these points. After the point 100° has been fixed, the zero point must
be determined by quickly cooling and placing the thermometer in
pounded ice, or preferably snow, which has remained for some time
in contact with distilled water. But even after adopting all the neces-
sary precautions, the value of a degree may vary owing to the dis-
GENERAL AND PHYSICAL CHEMISTRY. 843
placement of tlie zero point, which causes a change in various propor-
tions of all the constants. In the original paper examples are given
to show that the elevation of zero of 1"24 to 2*6° may cause an increase
in the interval 0 — 100° of 0'04 to O'O degree. On the other hand, a
depression of the zero point may be effected by heating a thermometer
at various temperatures for a prolonged time, and then leaving it to
cool in the air, and these depressions will necessarily increase all the
constants of the thermometer when referred to the zero point. After
such a depression has been effected, the thermometer, slowly at
ordinary temperatures, but more quickly when warmed slightly, tends
to revert to its original readings.
A considerable elevation of the zero point, 10° to 26°, is produced
by heating the thermometer for a week at 355°, which is caused by the
expansion of the glass bulb after it has been blown out and then
suddenly cooled.
The elevation of zero in a thermometer maintained at ordinary
temperatures diminishes gradually and ceases to be appreciable after
five or ten years. Similarly variations produced by protracted heat-
ing tend towards constant limit ; thus, for example, a thermometer
may be heated for several days at 300°, or for several months at 100°
without causing a variation in the effect produced by heating to 355°.
From the facts detailed above, it is necessary to heat a thermo-
meter required for ordinary experiments for a week in boiling mer-
cury, the whole of the stem being enclosed in the vessel ; after this
treatment, the points 0° and 100° will have a permanent value.
The author further remarks that thermometers with a limited range,
from 200° to 300° for example, cannot be graduated with the same
degree of precision, for the determination of the fixed points 0 and
100 becomes impossible, owing to the falling of the mercury within
the reservoir. In order to fix definite points above 100°, the author
suggests the use of naphthalene and benzophenone, substances which
can be obtained in a state of purity; the former boils at 218°, and the
latter at 306° under normal pressure ; in a table in the original
memoir, the boiling points of these two substances under various
pressures are given.
In a thermometer which has been thoroughly deprived of air, the
phenomenon of volatilisation of mercury can be observed at 100° ; the
column of mercury gradually descends, and after about 15 minutes
the variation is about 0*01 — 0*02 degree. If the zero point is rede-
termined after each warming, no error is caused by the descent of the
mercury. In all cases the mercury with which the thermometer is
filled must not only be purified but boiled for a long time to rid the
instrument of bubbles of air which cling persistently to the sides of
the bulb and stem.
The changes of barometric pressure may in ordinary cases be
neglected, but it is necessary to take account of the differences of
pressure dependent upon the horizontal or vertical position of the
column of mercury in the stem of a long thermometer. But this
factor cannot safely be neglected for second determination under
reduced pressures, when the thermometer is immersed in the vapour ;
in these cases it is preferable to introduce a thermometer in a tube
844 ABSTRACTS OF CHEMICAL PAPERS.
sealed at its lower extremity, and communicating directly with the
atmosphere.
In conclusion, the author points out the errors in determination of
boiling and melting points. In the former, errors frequently arise
from a too hasty observation ; to ensure accuracy the whole stem must
be immersed in the vapour, and distillation must be carried on for at
least ten minutes before the whole of the stem acquires the tempera-
ture of its environment.
To determine fusing poinfs it is preferable to plunge the thermo-
meter into the melting substances and to observe the changes of tem-
perature during complete solidification : when the quantity of sub-
stance does not admit of this method of procedure, the usual process
must be adopted.
In the memoirs, tables of corrections are given for converting read-
ings of ordinary thermometers and those with limited scale, into
readings of the hydrogen thermometer. Y. H. V.
Combustion of Gaseous Mixtures. By Mallard and Lb
Chatelier {Bull. Soc. Ghim. [2], 39, 268, 269—277, and 369—377).
— A continuation of the authors' investigations, vide p. 542.
The authors' remark that the curves of their registering mano-
meters do not give, owing to loss of heat, exactly the curves of pressure
produced by the combustion. For the maximum pressure recorded by
the curve is affected by the cooling in the interval of time during
which the combustion is propagated through the cylinder, and while
the manometer arrives at equilibrium. If the combustion be instan-
taneous, this latter factor could be neglected, but as the propagation of
the combustion lasts about -^ second, there is a certain and unknown
loss. As a correction for this loss, deduced from the loss of pressures
observed during cooling after the combustion, gives too high a
value, whilst the maximum of the curves gives too low a value, the
mean of these two limits may be taken as fairly exact. If then the
pressure due to combustion be known, and if it be admitted that at
high temperatures the coefficient of expansion of all gases is the
same, then the temperature of combustion can be calculated from the
T T
formula j— = '— , provided that no dissociation takes place.
In the original paper a table is given of the temperatures of com-
bustion of various mixtures of carbonic oxide and oxygen with excess
of nitrogen, carbonic anhydride, and steam, of hydrogen and oxygeu
with excess of hydrogen, oxygen, nitrogen, and steam, of hydrogen
and chlorine with excess of chlorine, hydrogen and steam, and of
mixtures of cyanogen and air sufficient for the burning of the carbon
into carbonic oxide.
Specific Heats. — From the temperatures of combustion the mean
specific heats at constant volume can be calculated according to the
formula Q = (jnc + m c + . . .){d — ^i). It follows, as a necessary
consequence of the authors' experiments, that the specific heats of
the permanent gases, hydrogen, oxygen, nitrogen, and carbonic oxide,
which are equal to one another at ordinary temperatures, are equal to
one another at 200°, for equal volumes of carbonic oxide, nitrogen and
GENERAL AND PHYSICAL CHEMISTRY. 845
oxygen added to an excessive mixture of carhonic oxide and oxygen,
give the same temperature of combustion j the same result holds good
in mixtures containing hydrogen.
From the temperature attained in the combustion of a mixture of car-
bonic oxide and oxygen, the specific heat of carbonic anhydride can be
calculated, provided that no dissociation takes place. The authors esti-
mate that at a temperature of 2000° about 5 per cent, of the anhydride
is dissociated ; if allowance is made for this, the most probable value
for the mean specific heat of this gas referred to a molecular volume
of 22-22 litres between 1° and 2000°, is 13'2. If the mean specific
heat of carbonic anhydride be known, that of steam at the same tem-
perature can be determined, for it is only necessary to compare the
temperatures of combustion of hydrogen and carbonic oxide each
mixed with such an excess of a permanent gas that the temperatures
produced by the combustions is the same. Experiments give the
number 128 as the value for the mean specific heat of the molecule of
steam at 2000°. Similarly the specific heats of the permanent gases
can be deduced by the same method ; the authors find this value to be
7*5 at 2000°, or 50 per cent, more than the mean specific heat at 0°.
Law of Variation of Specific Heats. — The authors have endeavoured
to establish a law of variations of specific heats by comparing the
values found at 2000° with the values at two lower temperatures,
100° and 200° for example. The equation is of the form Go = a +
he -\- C^^ of which h and c are given by a graphical construction.
For carbonic anhydride the experiments of Regnault and Niedermann
give the constant a, while c is fixed by those of the authors ; the law
of variation of the specific molecular heat is represented by the
formula C^ = 6*3 + 0-0056 + 0-0000011^3. Similarly, the law of
variation of the specific heat of steam is expressed by the formula
Qq = 5-9 4- 0-0087^ + 0-000000156'3, and those of the permanent gases
by the formula C^ = 5 + 0-00062^2.
If the law of variation of specific heat were known for any tem-
perature, the degree of dissociation of a gaseous compound could be
deduced from these data; the authors calculate by prolonging the curve
of variation to 8000°, that 40 per cent, of carbonic anhydride and 10
per cent, of steam is dissociated at that temperature. Their calcula-
tion is in direct accordance with the experiments of Crafts on carbonic
anhydride.
The velocity of propagation of flame varies according to the nature
and proportion of the mixed gases, their temperature, and their
internal agitation. The authors have examined the phenomenon by
three different methods : firstly, by causing the gas to flow through a
minute orifice, igniting the jet of gas, and diminishing the velocity
gradually until the flame passes through the orifice: this method,
provided that the experiments are made under strictly comparable
conditions, gives accurate results. The second method consists in
passing the gas into a tube closed at one end and open at the other,
where it is ignited ; the time required for the passage of the gas
through the length is measured. In the third method the velocity is
measured by an arrangement by which the passage of the flame causes
an electric current to attract an electromagnet, and thus cause a
846 ABSTRACTS OF CHEMICAL PAPERS.
registration to be made on a smoked cylinder. But as this method
only records intervals greater than one-hundredths of a second, a
pneumatic arrangement was substituted whereby the pressures pro-
duced set in motion a Marey's registering drum.
The walls of the tubes and orifices exert a cooling action on the
flame, which diminish its velocity of propagation ; this effect is the
more marked the narrower the tubes, but is independent of the
material of the tube. Vibratory movements produced by the propa-
gation of the combustion alwaj's produce a considerable but irregular
acceleration of the combustion. To eliminate as far as possible this
source of error, measurements of the velocity of transmission should
be made at the anterior portion of the tube. The authors have made
a series of experiments of the velocity of combustion of various mix-
tures of methane with air with or without addition of nitrogen or
carbonic anhydride, of hydrogen and coal-gas with air, of carbonic
oxide with oxygen, of hydrogen with oxygen and chlorine.
An increase of temperature increases the velocity ; thus a detonating
mixture of hydrogen and air having at 20" a velocity of propagation
of 3"50 m., at 100° C. has a velocity of 4'30 m. The authors have
confirmed Schloesing and Montdesir's observations on the enormous
velocity of the combustion when the detonating mixture is ignited at
the closed and not at the open end of the tube ; a velocity of 300 m.
per second was obtained by a detonating mixture of hydrogen and air.
As the method of ignition affects the agitation of the gas, and, con-
sequently, the velocity of the propagation of the flame, an explanation
is offered of different phenomena presented by explosions in coal mines.
For some time the flame travels slowly with no noise or mechanical
effect, while at other times a violent detonation is produced accom-
panied by a wreck of every obstacle in the passage of the flame. The
first of these phenomena would be caused by the ignition of the fire-
damp at the open end of the gallery, while the latter to its ignition at
the bottom or closed end of the gallery.
The authors' experiments give further support to the evidence
brought out in inquiries into accidents in coal mines, that the wire
gauze of the Davy lamp is insufficient to prevent an explosion if the
lamp is placed in a current of air sufficiently strong to blow the
detonating mixture through the gauze.
In certain experiments the authors noticed that the flame of a
detonating mixture which had been lighted at the end of the tube
was sometimes spontaneously extinguished, owing doubtless to a very
violent agitation of the gas within the tube and the admixture of a
sufficient quantity of cold gas to prevent the production of the chemi-
cal change. Probably a similar explanation holds good as regards
the experiment of Schiitzenberger on the combustion in eudiometers
of gases containing a small proportion of hydrogen. V. H. V.
Notice on the Atomic Weights. By A. Butleeow (Bull Sue.
Chim. [2], 39, 263— 268).— A short time ago Schiitzenberger
announced that in the analysis of certain hydrocarbons he obtained
numbers which on calculation led to a sum of hydrogen and carbon
greater than the weight of the original substance. In the present
GENERAL AND PHYSICAL CHEMISTRY. 847
notice tlie author proposes to offer some explanation of the abnormal
result. Rejecting the hypotheses (1) that the absolute mass of the
substance is increased by the transformation of some form of energy
into matter; (2) that the absolute mass remaining the same, its
weight has been increased by an increase of intensity of gravity,
there is then left the conjecture that the absolute value assigned to
the atom varies within certain and probably narrow limits. If it be
admitted, for example, that the value of the atom of carbon descends
temporarily to 11*8, then the molecular weight of carbonic anhydride
will become 43'8, instead of 44. Then there will be about one-
hundredth of carbon in excess, if, starting from a carbonic anhydride
of the former molecular weight, the weight of the carbon be calcu-
lated from the latter molecular weight. The author has undertaken
experiments with a view of determining how far the atomic weight
may vary under different conditions ; the examples selected are white
and red phosphorus, and the formation of mercuric chloride from the
combination of the two elements with or without exposure to light.
Though the investigations of Stas have established that atomic weights
are not expressed by whole numbers, yet as the deviations are so small
it is impossible to consider them accidental, and thus to regard Prout's
hypothesis as devoid of any value. In other cases, as for example the
laws of Boyle and Mariotte, the numbers furnished by experiment,
from which the law has been deduced and expressed in a simple form,
are approximately equal to, but not identical with the numbers
required by the law. The atomic weight of an element is the repre-
sentation of a certain ponderable quantity of matter, the bearer of a
determinate quantity of chemical energy : as in other forms of energy
its quantity is far from being determined exclusively by the mass of
matter, it is at least possible that the same principle may hold good
for chemical energy, although within certain narrow limits. Carbonic
anhydride would not be a compound containing absolutely carbon and
oxygen in the proportion of 31*92 [32] of the latter to 11*97 [12] of
the former, but may contain a relative proportion of carbon varying
from 11*8 to 12. These varieties of carbonic anhydride would up to a
certain point still constitute the same chemical compound ; its general
properties, and especially its chemical functions, would remain the
same.
In conclusion the author asks whether such a supposition, although
bold, is entirely devoid of probability. V. H. Y.
Special Form of Gasometer. By L. G. de Saint Martin {Bull.
Soc. Ghim. [2], 39, 377 — 384). — The author has devised a gasometer
differing from the usual form by a special arrangement of the water
reservoir, which, instead of consisting of a simple cylinder, is formed
of two concentric cylinders of nearly the same diameter. The smaller
or interior, closed at the top, fills the cavity of the exterior nearly com-
pletely, so that between the two there is a small annular space filled
with water or some other isolating liquid.
By this arrangement only a small quantity of water is required, so
that secondary chemical reaction or solution becomes practically im-
possible. The author also describes an arrangement of the gasometers
848 ABSTRACTS OP CHEMICAL PAPERS.
whereby gas from the one can be made to bubble through a purifying
apparatus, and then to pass into the other. Thus to obtain pure
nitrogen air from one gasometer is deprived of its oxygen by passing
through sodium hyposulphite, and the gas nitrogen enters the second
gasometer. By a similar method carbonic oxide can be puriiSed from
carbonic anhydride. The arrangement can also be used for a study of
the chemical changes during respiration, air being supplied to the
patient for inspiration from the one, while the expired gases pass into
the other gasometer. V. H. V.
Inorganic Chemistry.
Activity of Oxygen in Presence of Nascent Hydrogen. By
F. Hoppe-Seyler (Ber., 16, 117 — 123).— The author refers to previous
experiments on this subject (this Journal, Abstr., 1880, 3), whereby
he has shown the energy of oxidation in presence of nascent hydrogen.
His experiments were then made with the alloy of palladium and
hydrogen, and also with metallic sodium, and the conclusions arrived
at were, that hydrogen in that state when brought into contact with
the indifferent oxygen of the atmosphere, causes oxidation of the
most active character, accompanied by the production of water. This
fact is of the greatest importance in physiological researches, account-
ing for many processes in the animal economy. Circumstances pre-
vented continued experiments, but they have lately been resumed. In
the meanwhile Traube has published papers in opposition to the
author's views (this Journal, Abstr., 1882, 795), casting doubts on the
accuracy of his deductions.
Traube brings forward the production of hydrogen peroxide by the
action of palladium-hydrogen alloy on oxygen, and seeks to explain
the blue coloration of potassium iodide and starch solution by some
unknown reaction of the palladium on the hydrogen peroxide. The
author does not lay great weight on the objection, as he simply men-
tioned the hydrogen peroxide in passing, and its presence is unneces-
sary to the reaction. He criticises the failure of Traube to reproduce
his experiments, and repeats that he founds his conclusions respecting
the activity of oxygen (1) on the production of a blue colour by the
palladium-hydrogen compound when in contact with oxygen and
potassium iodide starch solution ; (2.) The power of those substances
to oxidise indigo- carmine solution to yellow. (3.) The oxidation of
oxy haemoglobin to metahgemoglobin. (4 ) Oxidation of ammonia to
nitrous acid. These reactions occur regularly except when ignited
palladium is substituted for the hydrogen alloy of the metal; neither
are they produced with dilute pure and neutral solutions of hydrogen
peroxide, whether palladium is present or not. St. Claire-Deville and
Debray have already briefly described a decomposition of formic acid
by means of rhodium and iridium black, which offers an interesting
parallel to the decomposition of that acid by the mud of cesspools, a
.iiJ'l
INORGANIC CHEMISTRY.
849
little of which, when air is excluded, is capable of breaking np almost
unlimited quantities of calcium formate into calcium carbonate, car-
bonic acid and hydrogen ; the same reaction takes place with rhodium
black ; its behaviour resembles that of a ferment, as it comes out of
the reaction unaltered. The author has convinced himself that in
presence of oxygen the hydrogen from the formic acid gives rise to
increased activity in the oxygen, turning the iodide of potassium and
starch-solution blue, and oxidising the indigo solution ; the presence
of free ammonia or its carbonate completely prevents the reaction.
Rhodium black, obtained by the action of formic acid on rhodium
hexchloride and sodium chloride evidently contains hydrogen, and
resembles the palladium alloy.
Rhodium black decomposes hydrogen peroxide with violence into
water and indifferent oxygen, whether hydrogen is present in the
rhodium or not.
The action of rhodium black as a ferment is the more interesting
because it is an absolutely insoluble substance, and it suggests that
there may exist other insoluble ferments. This is the author's con-
viction, and he thinks that he will soon be in a position to show that
they play a very important part in the living body. J. F.
Specific Gravities of Solutions of Ammonia and Ammonium
Carbonate. (Dingl. polyt. /., 247, 504.) — From a suggestion by
Lunge, J. H. Smith was led to determine the sp. gr. of pure ammo-
nia solutions (standardised with normal hydrochloric acid and methyl
orange) at 14° by means of a pycnometer ; the results are compared
with water and reduced to a vacuum : —
Percentage of ammonia (NH3), according to
Sp. gr. at 14°.
j
_2
1
1
0
i
1
2
i
0 -8933
31-0
31-8
29-9
27-8
24-0
27-6
0-9116
23-8
24-6
23-8
—
23-1
19-5
23-6
0 9246
20-8
20-2
19-7
—
19-4
16-4
19-8
0 -9400
15-1
15-4
15 0
—
14-7
12 9
15-5
0 -9536
11-7
11-7
11-3
11-5
11-3
10-2
11-8
0 -9780
5-1
5-2
4-9
5-2
5-0
4-5
—
Solutions of commercial ammonium carbonate, which contained
31-3 per cent. NH3, 66-6 per cent. CO2, and 12*1 per cent. H2O, cor-
responding approximately with the formula
H.NH4.CO3 + NH4.CO2.NH2
gave —
850
ABSTRACTS OF CHEMICAL PAPERS.
Sp. gr.
at 15°.
Per cent,
ammonia
carbonate.
Change
of the
sp. grs.
for + 1°.
1*
!ri^:
Per cent,
ammonia
carbonate.
Change
of the
pp. grs.
for + 1°.
1
1-005
1-66
0-0002
15
1-075
22-25
0 0006
2
1-010
3-18
0
0002
16
1-080
23-78
0
0006
3
1-015
4-60
0
0003
17
1085
25-31
0
00 6
4
1-020
6-04
0
0003
18
1-090
26-82
0
0007
5
1-025
7-49
0
0003
18
1-095
28 33
0
0007
6
1-030
8-93
0
0004
20
1-100
29-93
0
0007
7
1035
10 35
0
0004
21
1-105
31-77
0
0007
8
1 -040
11-86
0
0004
22
1110
33-45
0
0007
9
1045
13-36
0
0005
23
1115
35-08
0
0007
10
1050
14-38
0
0005
24
1-120
36-88
0
0007
11
1-055
16-16
0
0005
25
1-125
38-71
0
0007
12
1-060
17-70
0
0005
26
1130
40-34
0
0007
13
1-065
19-18
0
0005
27
1-135
42-20
0
0007
14
1070
20-70
0
•0005
28
1-140
44-29
0
0007
D. B.
Formation of Nitrous Acid in the Evaporation of Water.
By A. Scheurer-Kestner (Bull. Soc. Chim. [2], 39, 289).— The
author observes that the formation of nitrous acid in the evaporation
of water, to which attention has recently been called by Warington
(this Journal, Trans., 1882, 351), was noticed many years ago by
Schoenbein. The following characteristic experiment made by
Schoenbein is quoted ; a piece of filter-paper is cut into two parts, of
which one is moistened with water free from nitrous acid, and
allowed to dry. Then this part will give the reactions for nitrous
compounds, whilst the other half will give no reaction.
V. H. Y.
Action of Microcosmic Salt on Various Oxides. By K. A.
Wallroth {Bull. Soc. Chim. [2], 39, 316— 322).— Berzelius and
others have remarked that beads of microcosmic salt, when saturated
with various metallic salts, become opaque on cooling, from sepa-
ration of minute crystals of phosphate of sodium and the introduced
metal. The author has isolated these salts by dissolving the metallic
oxides in microcosmic salt heated to a bright red heat; the glass so
formed is maintained in a state of fusion until the crystals have sepa-
rated out. On cooling, the mass is digested with water, and then
with dilute hydrochloric acid.
Phosphates of Dyad Metals. — Cadmium sodium phosphate, CdNa2P207,
is a white crystalline salt, soluble in dilute acids, melting into a trans-
parent glass. The manganese salt, Mnl^a^P-iO?, forms prismatic
crystals, soluble in acids, melting into an amethyst glass ; the ziiic
salt, ZnNa2P207, crystallises in tables, soluble in acids ; the calcium
salt, CaioNai6(P207)9, is a crystalline powder, melting into a white
enamel; the magnesium ssilt, MgioNai6(P207)9, forms transparent prisms,
melting into a transparent glass; the cobalt salt, CoioNa,6(P207)9,
crystallises in cherry-red prisms, and melts into a transparent blue
glass; the nickel salt, NiioNai6(P807)9, forms yellow prisms, melting
INORGANIC CHEMISTRY. 851
into a brown clear glass ; the beryllium salt, BeNaP04, forms hex-
agonal tables, sparingly soluble in cold acids, and infusible ; the copper
salt, Cu3Na6(P04)4, is a bluish crystalline powder which melts into a
green transparent glass.
Phosphates of Triad Metals. — The bismuth salt, Bi4(P207)3, forms
hexagonal tables, decomposed by water ; it melts into a white enamel ;
the chromium salt, Cr2]*'^a2(P207)2, is a brilliant green powder, infusi-
ble and insoluble in acids ; the aluminium ssilt, Al2Na2(P207)2, crystal-
lises in prisms, insoluble in acids, fusible into a clear glass ; the
cerium, lanthanum, and yttrium salts, of formula M2Na2(P207)2, crys-
tallise in infusible microscopic prisms, insoluble in cold, readily soluble
in warm acids ; the erbium salt, Er2Na2(P207)2, forms rhombic infusi-
ble prisms of a rose colour, sparingly soluble in dilute acids ; the
ytterbium salt, Yb2Na2(P207)2, is a white powder resembling the
erbium salt; the didymium salt forms minute crystals, infusible and
insoluble in acids.
Phosphates of Tetrad Metals. — The thorium salt, Th2N'a(P04)3, forms
clinorhombic prisms, infusible and inslouble in acids ; the tin and
titanium salts have a composition similar to that of the thorium salt.
It will be seen from the above that the dyad metals with the excep-
tion of copper and beryllium, and triad metals with the exception of
didymium, form pyrophosphates, while the tetrad metals form ortho-
phosphates. Y. H. Y.
Specific Gravity of Sulphuric Acid. (Bingl. polyt. J., 248,
91). — Lunge and Naef (Chem. Ind., 1883, 37) give the following
table of the specific gravities of very concentrated sulphuric acids at
15°, the numbers having been reduced to a vacuum and compared
with water at 40°. The numbers markedf have been directly
observed ; the remainder were determined by interpolation : —
Commercial acid from Uetikon.
Percentage of
Pure acid.
H2SO4.
Sp. gr.
90-00
1-8185
t90-20
1-8195
t90-29
—
91-00
1-8241
t91-48
1-8271
92-00
1-8294
t92-83
1-8334
93-00
1-8339
94-00
1-8372
t94-09
—
t94-84
1-8387
95-00
1-8390
t95-26
—
t95-97
1-8406
96-00
1-8406
97-00
1-8410
97-70
1-8413
97-75
—
Sp. gr. Baume.
1-8202 65-r
1-8219 —
1-8254 65-4
1-8306 65-6
1-8346 65-8
1-8374 65-9
1-8375 —
1-8397 66-0
1-8404 66-0
l-8468<i> 66-2
852 .ABSTRACTS OF CHEMICAL PAPERS.
Commercial acid from Uetikon.
Percentage of
Pure acid.
H2SO4.
Sp. gr.
98-00
1-8412
t98-39
l-8406<2)
t98-66
1 8409(3)
99-00
1-8403
t99-47
1-8395
tlOO-00
1-8384
Sp. gr. Baum6.
(1.) Acid from Grieslieim, prepared by direct evaporation on a
large scale.
(2.) Prepared by mixing acid of ordinary strengtb with acid con-
taining anhydride.
(3.) Prepared by direct evaporation. D. B.
Preparation of Selenium on a Large Scale. By H. Born-
TRAGER (Dingl. polyt. J., 247, 505). — It is known that when seleni-
ferous pyrites is used for the manufacture of sulphuric acid, selenium
is found in the various stages of the process. For the recovery of
selenium, the following method is recommended : A set of chambers
is connected with a Grlover tower, besides having the nitric acid cas-
cades. Chamber acid alone runs over the tower, the nitric acid being
introduced by means of the cascades. Thus, a turbid Glover acid is
obtained which has a deep red colour, owing to the presence of sele-
nium. It is clarified in leaden tanks, and after decantation the red
deposit is washed with hot water and dried at 100°. The following
is an analysis of this deposit (from Spanish pyrites of Rio Tinto) : —
FeaOa and SiOs. Se. AsoOg- PbS04.
8-20 12-60 0-13 76-30
The dried deposit is heated to redness in closed clay retorts pro-
vided with receivers, when a black metallic sublimate of selenium is
obtained, which is washed with concentrated soda-ley to remove
arsenious and selenious acids, and finally with water. Pure selenium
dissolving completely in sulphuric acid is obtained. D. B.
Atomic Weight of Didymium. By P. T. Cleve (Bull. Soc
Chim. [2], 39, 289— 330).— The author has determined the atomic
weight of didymium in samples of the oxide separated by fractional
precipitation from lanthanum oxides (cf. p. 553). The pure oxide
thus obtained was converted into the sulphate, and the proportion of
the oxide in the salt was determined. A series of ten" estimations
gave 58-0905 per cent, of DigOs. Another series of seven gave
58-0895 per cent. ; the former value the author considers the more
exact. Adopting for oxygen the atomic weight 15'9633 + 0-0035,
and for sulphur the number 31-984 Hh 0 012, the atomic weight of
didymium is Di = 142124 + 0-0326, a number which may practi-
cally be taken as 142.
The author notes that this value differs from those obtained by
other chemists, and from the number 147, which he himself obtained
INORGANIC CHEMISTRY. ' 853
in 1874. This discrepancy he attributes to the presence in former
samples of didjmium oxide of samarium, the existence of which has
to the present time been unknown. V. H. Y.
Basic Sulphates of Copper. By S. U. Pickeking (Ghem. News,
47, 181 — 184). — In previous communications the author has shown
that the metals, iron and aluminium, do not form as many basic sul-
phates as they were supposed to do. He has now examined the basic
sulphates of a metal belonging to a different class, viz., copper, and
has found not six but only two basic sulphates of this metal. The
one, 6CuO,2S03 + 5H2O, is precipitated in small quantity when a
neutral solution of copper sulphate is boiled, the precipitation being
complete in 10 minutes. In this manner from 0"37 to 2*5 per cent, of
the copper present can be precipitated, the quantity increasing with
the dilution of the solution. The second basic sulphate, 4CuO,S03, is
formed when a solution of copper sulphate is precipitated with less
than 1"5 mol. of potassium hydroxide to 1 mol. of copper sulphate, or
with sodium acetate, or when copper hydrate (dried at 100" C.) or
the precipitate obtained by adding excess of potash to copper sulphate
is digested with a 10 per cent, solution of copper sulphate. This
basic sulphate is very sparingly soluble in water (0*017 gram in
1000 c.Cf). When, however, the solution is boiled, it becomes dark,
owing to the separation of copper hydroxide. It remains unaltered
when exposed to air or boiling water. This latter property serves
as a test for the sulphate 4CuO,S03, for those containing more
CuO soon become blackened when boiled with water. No definite
basic sulphate is formed either by heating normal copper sulphate, or
by diluting an ammonio-copper sulphate solution. D. A. L.
Rehydration of Ferric Oxide. By C. F. Cross {Ghem. News,
47, 239). — The method of experimenting was the same as described
(ibid., 44, 101). From the experimental observation the author
shows that the ferric oxide obtained by drying the ordinary precipi-
tated hydrate at 100°, when exposed to a saturated atmosphere and a
somewhat regular temperature, gradually becomes rehydrated. The
observations extended over 192 days, the temperature varying from
15° to 22". The rehydration does not take place so readily when the
temperature fluctuates, so as to cause evaporation and condensation
from or upon the portion enclosed in the saturated atmosphere.
D. A. L.
Gold Compounds. By P. Schottlander (Annalen, 217, 312 —
380). — According to Weber, hydrogen qold chloride, AUHCI4, crys-
tallises with 3 mols. H2O, and according to Thomsen (Ber., 10, 1633),
with 4H2O. The author who evaporates the aqueous solution con-
taining some free hydrochloric acid over lime and sulphuric acid,
obtains crystals which, after being pulverised and exposed for months
over sulphuric acid, contain 3H2O. On gradually adding silver car-
bonate suspended, in water to a warm solution of hydrogen gold
chloride in excess, carbonic anhydride is evolved and a brown preci-
pitate produced. On heating the filtrate with an excess of silver
carbonate at 100°, a second precipitate is obtained, from which the
VOL. XLiv. 3 m
854 ABSTRACTS OF CHEMICAL PAPERS.
excess of silver carbonate can be removed by means of dilute nitric
acid. Both precipitates contain gold oxide and silver chloride
approximately in the proportion of 1 mol. of the former to 8 mols. of
the latter, besides variable amounts of undecomposed gold chloride.
To prepare potassium gold bromide, precipitated gold (20 parts) and a
solution of potassium bromide (12'5 parts) in twenty-four times its
v^reight of water are brought together in a capacious vessel and
bromine (30 parts) added, the bottle being then well stoppered and
allowed to stand in a warm place until the gold is dissolved ; the
solution is evaporated on a water-bath, and the product recrystallised
from water. It forms monoclinic crystals, readily soluble in water,
sparingly in the presence of potassium bromide. Ether decomposes
it, taking up gold chloride, and leaving a residue of potassium bro-
mide. By the action of sulphurous anhydride on an alcoholic solution
of the dried salt, a gold-coloured solution is obtained, whilst potas-
sium bromide is precipitated together with a little sulphate. When
the filtrate is evaporated in a desiccator containing lime, sodium
hydroxide and zinc chloride, two-thirds of the gold are precipitated,
forming a lustrous layer on the glass, whilst the solution contains
free hydrobromic acid, sulphuric acid, and an oily body, probably
ethyl bromide. By the action of potassium carbonate on a boiling
aqueous solution of potassium gold bromide, a brownish-red preci-
pitate is obtained, which, after being washed with boiling water and
dried at 100 — 108°, has a composition corresponding with the formula
16Au203,3KoO,2KBr,15H20. From the filtrate containing potassium
bromide, an orange-yellow substance is also obtained, to which the
author assigns the formula 20Au2O3,3^K2O,2KBr,«H2O. By the
action of hydrogen potassium carbonate, a bright reddish-yellow
solution is obtained, the colour of which almost disappears on boiling.
The solution contains potassium bromide and carbonate and a bright
yellow amorphous body, which is probably a compound of gold oxide
with potash. By the action of manganese acetate on gold chloride
solution, a black precipitate is produced containing the whole of the
gold. If atmospheric oxidation is carefully avoided during the pre-
paration and drying of this precipitate, it can be dissolved in hydro-
chloric acid without evolution of chlorine. Its composition is not
perfectly definite and its constitution is doubtful. The author assumes
it to be a molecular mixture of metallic gold with manganese dioxide
and monoxide, e.g., 6Au + 9Mn02,MnO,2H20, the gold and manga-
nese dioxide being in the proportion of two atoms of the former to
3 mols. of the latter ; whilst if oxidation has taken place, the propor-
tion of dioxide is greater, 6Au + 10MnO2,H2O, the compound losing
a molecule of water for each oxygen-atom absorbed. Gold can be
extracted from this substance by shaking it with mercury ; concen-
trated sulphuric acid does not dissolve it, whilst a mechanical mixture
of gold and manganese dioxide can be dissolved in this acid ; concen-
trated potash solution takes up nothing even on boiling; concentrated
solution of potassium cyanide dissolves the whole of the gold and part
of the manganese, forming potassium gold cyanide and potassium
manganese cyanide, and leaving a black residue. On boiling with
glycerol and concentrated soda-solution, gold separates out, whilst a
INORGANIC CHEMISTRY. 855
violet solution is formed, from which alcohol precipitates the glycerol
compound previously described by the author (Annale7i, 155, 230).
Aqueous ammonia has no action; nitric acid (sp. gr. 1*4) dissolves
part of the gold and manganese, although no oxidation takes place
On digesting with a concentrated solution of sodium thiosulphate for
some days at about 60°, a part of the gold dissolves, forming the
double salt Au2S203,3(Na2S203),4H20, which is precipitated on adding
alcohol. In sealed tubes at 100° only traces of this double salt are
formed, the solution being found to contain manganese, sulphurous
and sulphuric acids, and the residue to consist of a mixture of gold,
manganese (probably as MnO), and sulphur. By the action of man-
ganese acetate on gold chloride in presence of ammonium chloride
in the cold, the gold is only partially precipitated, and on treating
the precipitate with hydrochloric acid, a bright yellow crystalline
body is produced, containing gold, chlorine, and the elements of
ammonia ; it explodes on heating, though not by concussion or
friction. A hydrated oxide of gold of the formula Au302(OH)2 is
obtained by the decomposition of the sulphate AUSO4 (see below) by
water. In its properties it does not agree with the compound
described by Prat (Compt. rend., 70, 840). It forms a crystalline
black powder, which is not acted on by boiling potash-soluti >n,
whilst hydrochloric acid or nitric acid decomposes it into metallic
gold and trioxide, the latter dissolving and forming a salt. Hyrlrated
gold trioxide has been prepared by the author by different methods,
but in no case has he obtained a product corresponding with the
formula Au(H 0)3 generally given ; the highest percentage of water
obtained corresponds with the formula Au403(OH)6, and the lowest
with AuO.OH ; and he thinks it probable that the latter would
always be formed if the product were exposed long enough in a vacuum
over sulphuric acid, or dried at a somewhat higher temperature. The
compound, HN03,Au(N03)3,3H20, is obtained by mixing gold hy-
droxide with nitric acid (3'6 parts) of sp. gr. 1'492 at 20°, and then
heating on a water-bath until a clear yellow solution is obtained,
which is separated from traces of reduced gold, and finally sur-
rounded by a freezing mixture to promote crystallisation. It forms
large gold-coloured triclinic crystals, which deliquesce in moist air. It
melts at 72 — 73° with evolution of nitric acid, and on further heating,
the normal salt Au(N03)3a3H30 is probably formed. At 100° it
loses 50 per cent, of its weight, with formation of a basic nitrate,
Au406(N03)2,2H20. A third nitrate (auryl nitrate), 5(AuO,N03)
+ H2O (P), is obtained by dissolving gold hydroxide in nitric acid of
sp. gr. 1-4, filtering through asbestos, and evaporating at reduced
pressure over lime and soda. When a solution of gold nitrate and
potassium nitrate in nitric acid is allowed to crystallise, a double salt
of the formula HN03,Au(]S'03)3,2KNO is obtained, crystallising in
plates. A gold sulphate (auryl sulphate), AuO,HS04, is produced by
heating the corresponding nitrate with concentrated sulphuric acid at
about 200°, forming a yellow crystalline powder; it absorbs water
from the air, with production of sulphuric acid and gold hydroxide.
Potassium gold sulphate, KAu(S04)2, is formed when hydrogen potas-
sium sulphate is dissolved in a solution of auryl sulphate, and the
8 m 2
856 ABSTRACTS OF CHEMICAL PAPERS.
liquid evaporated at 200^ ; it forms a bright yellow crystalline salt
which is somewhat more stable than auryl sulphate. A silver gold
sulphate can be obtained in the same way. A gold snlphate of the
formula AuSOi is obtained on evaporating a solution of auryl sulphate
nearly to dryness at 250°, the crystals thus obtained being dried on
porous plates in a lime desiccator ; it forms lustrous scarlet prisms,
which rapidly absorb water from the air, with partial decomposition.
The author is of opinion that the gold in this and in corresponding
salts is a true dyad analogous to mercury, and that such compounds
should not be regarded as combinations containing both monad and
triad gold. A. K. M.
Atomic Weight of Manganese. By J. Dewar and A. Scott
(Proc. Boy. Soc, 35, 44 — 48). — The results of determinations of the
atomic weight of manganese may be divided into two classes ; the
one giving approximately the number 55, the other the number 54.
The former has resulted from analysis of the chloride and carbonate,
and conversion of the monoxide into sulphate, or sulphate into sul-
phide ; the latter from the analysis of the oxalate and reduction of the
red oxide into the monoxide.
The authors discuss the errors inherent in these processes ; the
chloride and bromide are apt to contain traces of a manganic salt, are
very hygroscopic, and ^re liable to retain traces of the halogen acids.
Researches into the oxides of manganese have established that they
are difficult to obtain in a definite form. From the molecular weight
of carefully prepared specimens of the chloride and bromide, the
respective atomic weights of manganese were found to be 54'97 and
54*91. Silver permanganate was finally selected as being readily
freed from impurities by recrystallisation, as anhydrous, and not in
any way hygroscopic, and as not liable to contain excess of any of its
constituents. The first method adopted consisted in reducing the salt
in a current of hydrogen, and weighing the residual silver and man-
ganese monoxide ; but the results showed great variation, the errors
being due probably to the occlusion of hydrogen, and suspension of
the oxide in the oxygen evolved. Better results were obtained by
reducing the salt with sulphurous acid, sodium or potassium formate,
potassium nitrite, and determining the silver by precipitation with
potassium bromide. Rejecting the use of sulphurous acid as causing
the formation of sparingly soluble silver sulphide or sulphate, the
mean atomic weight was found to be 55*038 (O = 16, Ag = 107'93).
Another element is therefore added to those whose atomic weights
have been found to be approximately whole numbers.
MINERALOGICAL CHEMISTRY. Sc^l
Mineralogical Chemistry.
I
Application of Organic Acids to the Examination of Mine-
rals. By H. C. Bolton (Ghem. News, 47, 251— 252).— Id previous
communications (ibid., 34, 249, and Abstr., 1881, 62, 642) the author
has shown that citric acid can decompose minerals almost as well as
hydrochloric acid does ; and has described experiments in which the
finely powdered minerals were exposed to the action of the citric acid
solution sometimes for a few hours in the cold, and at other times for
a few minutes at a boiling temperature. The experiments described
in this paper were conducted at the ordinary room temperature, 60 —
70° F., and the time of exposure was prolonged. Some 200 minerals
were examined, but a few representative specimens only have been
selected for description. The progress of decomposition was noted at
periods varying from a few days up to more than two years. A solu-
tion of citric acid concentrated in the cold was used in all the expe-
riments. The following are the representative observations : —
In the suljphide group chalcocite showed signs of decomposition at
the end of ten days, and at the expiration of several months gave a
partial solution of a green colour. Ullmanite showed signs of decom-
position in two days, and in a month gave a very dark-coloured
solution. Arsenical pyrites was attacked in a few days ; iron pyrites
in eight days ; a month later gave a reddish-yellow solution, with the
reactions for iron and sulphuric acid; copper pyrites behaved in a
similar manner, giving, of course, copper, instead of iron reactions ;
I gram of this mineral lost 11 per cent, of its weight after 14 months'
contact with the acid solution. Smaltite was attacked in eight days,
and sulphuric acid could be detected in the coloured solution. Tetra-
hedrite was strongly attacked in about four months. Cinnabar,
orpiment, argentite, and pyrargyrite completely resisted the action of
the acid solation.
Oxides. — In this group experiments were made only on those
minerals which resisted the acid solation on boiling ; of these, magne-
tite and limonite were strongly attacked in eight days, hematite only
after several months.
Silicates. — Datolite was decomposed after 24 hours, yielding gela-
tinous silica. Hornblende, pyroxene, almandite, epidote, vesuvianite,
and serpentine were decomposed in eight days, and after a month,
hornblende, almandite, and epidote yielded coloured solutions and
slimy silica, whilst serpentine gave gelatinoas silica. After 14 months'
contact with the acid solution, hornblende and pyroxene were com-
pletely decomposed, giving dark brown solutions full of floating
silica; serpentine, on the other hand, yielded a dry gelatinoas mass.
Actinolite is not so readily decomposed as common black horn-
blende.
Oi felspars, labradorite yields the most readily, being decomposed in
eight days ; in a few months slimy silica is formed. Tourmaline and
staurolite are attacked after four or five months, the latter forming a
solution coloured by iron, whilst slimy silica separates. Orthoclase
858
ABSTRACTS OF CHEMICAL PAPERS.
and oligoclase show signs of decomposition after eight months, bnt
the decomposition of albite is doubtful. Talc and kyanite appear to
resist the action, of citric acid. Muscovite and biotite yield very
slowly. After two years' subjection to the acid solution, minute
scales of mica separate, and some slimy silica appears in the slightly
coloured solution.
As these results probably bear important relation to the disintegra-
tion of rocks by the action of the humus acids, the author has gone
somewhat into detail, and finally gives the following rough generalisa-
tion of his observations : —
Table showing a'pproximate relative Disintegration of Bock-forming and
Associated Minerals by Citric Acid in Solution.
Quickly decom-
Slowly decom-
Very slowly decom-
Not decom-
posed.
posed.
posed.
posed.
Carbonates.
Serpentine.
Orthoclase.
Quartz.
Phosphates.
Pyroxene.
Oligoclase.
Corundum.
Prochlorite.
Hornblende.
Albite (?).
Spinel.
Chrysolite.
Labradorite.
Biotite.
Beryl.
Nephehte.
Garnet.
Muscuvite.
Fluorite.
Epidote.
Tourmaline.
Barite.
Vesuvianite.
Staurolite.
Talc (?).
Pyrites.
Heematite.
Kyanite (?).
Limonite ,
Magnetite.
Gypsum (?).
D. A. L.
Separation of Minerals according to the Degree of Cohe-
sion. By BiJTTGENBACH (Blngl polyt. J., 248, 112). — The separa-
tion of minerals on a large scale has hitherto been effected mainly by
the differences in their density, and also by magnetic means. The
author suggests separating minerals or ores by the difference in the
degree of brittleness and firmness. Starting with the well-known
fact that by casting two minerals of different degrees of hardness
against a^solid body, the one is crushed to pieces whilst the other
remains intact or is broken into large pieces, he devised a practical
method of separating ores on a large scale according to their cohesive
degrees. In his experiments pyrites and zinc blende were used. The
mixture was introduced into Vapart's disintegrating mill, in which
the ores are cast three times against the sides of the cylinder before
they leave the apparatus. The mass was then sifted through sepa-
rating drums, when it was found that the particles which passed
through the finer sieves consisted chiefly of zinc blende, whilst the
larger pieces left behind were pyrites. D. B.
Analysis of some Minerals. By A. B. Griffiths (Chem. News,
47, 169 — 170). — The author has found considerable quantities of
tungsten in a sample of ferromanganese ore from the neighbourhood
MINER ALOGIOAL CHEMISTRY. 859
of Casa Branca, Portugal, whilst in two samples of brown haematite
from the same locality, in one he detected traces of titanium (sp. gr.
of ore = 4' 102), in the other traces of both titanium and selenium.
The following is an analysis of a nodule of copper ore from the
northern part of Nova Scotia ; it is found in grey nodules, which
often contain anthracite bands : —
Cu. S. FeaOgjAlaOs. Sand, &c. CaO. MgO. Mn. Total.
64-101 25-639 3-891 5-790 0-201 0-137 0*221 = 99-98
From these results he calculates the formula CusSi or Cu2S(CuS)3;
its sp. gr. = 4-392.
An analysis of a Dresden syenite yielded the following results :—
Si02. AI2O3. K2O. NagO. FeO. MgO. CaO. H2O. PgOg. Total.
60-020 16-663 6*504 2-410 7-207 2-509 3-585 1*100 trace = 99*998
D. A. L.
Magnetic Property of Platinum Ore. By T. Wilm (Ber., 16,
664 — 667). — The author has examined a large number of specimens
of platinum ore, and finds that nearly all are magnetic. From an
ore containing 76-07 per cent, platinum, 55*15 per cent, was sepa-
rated by means of a comparatively weak magnet, and this magnetic
portion contained as much as 69 23 per cent, platinum, so that practi-
cally no purification can be effected in this way ; neither does the
magnet afford any criterion as to the adulteration of platinum ores
with iron. For the latter purpose the author recommends warming
the ore with pure hydrochloric acid, when no gas will be evolved if
the ore is uot adulterated. A. K. M.
An Ammonio-phosphatic Deposit in the Vicinity of Cape
Town. By A. B. Gkiffiths (Chem. News, 47, 239).— The deposit is
browu, in a powdered condition, and contains nodules resembling
ordinary guano in appearance. A microscopical examination revealed
the presence of diatomaceae and a few spongy spicules ; and by a
chemical examination a specimen of the deposit was found to contain
70*21 per cent, ammonium compounds, 17*5 per cent, phosphates, and
3" 3 per cent, nitrogen. 1). A. L.
Artificial Hausmannite. By A. Gorgeu (Compt. rend., 96,
1144 — 1146). — Hausmannite can be obtained artificially by fusing
mauganous chloride for several hours in a moist oxidising atmo-
sphere. This can be effected by filling a porcelain crucible about
3 cm. in height with one-third its volume of anhydrous manganese
chloride, placing this crucible in a larger one about 5 cm. in height,
and covering the latter with a piece of platinum foil, which extends
beyond its edges, but only rests on it at a few points. The crucibles
are then heated over a Bungen flame in such a way that no reducing
gases enter the crucibles. The temperature should be somewhat
high, but not high enough to cause a rapid evolution of vapours of
the chloride. An experiment requires at least five or six hours, and
should not be interrupted, but manganous chloride should be added
860 ABSTRACTS OF CHEMICAL PAPERS.
to make up for loss by volatilisation, &c. When the evolution of
hydrochloric acid has almost ceased, the crucibles are left to cool,
the lighter particles removed by elutriation, and the heavier crystals
washed with boiling water until free from chlorine. The crystals thus
obtained are identical with natural hausmannite in composition, form,
colour, specific gravity, hardness, &c.
The formation of hausmannite is due to the combined action of
moisture and oxidising gases on the manganous chloride. Moist car-
bonic anhydride or dry air yields no hausmannite when it acts on the
fused chloride.
In presence of chlorides of potassium, sodium, calcium, and barium
the crystals obtained are smaller, but they do not contain a notable
quantity of the foreign bases. In such cases, however, the salt must
be fused in a platinum crucible.
Cobalt chloride also yields crystals when treated in a similar
manner. C. H. B.
Organic Chemistry.
A New Product of the Slow Combustion of Ether. By E.
Legler (Annalen, 217, 381 — 386). — When ether vapour is oxidised in
a current of air by means of red-hot platinum, and the products of the
imperfect combustion are condensed, a liquid is obtained which yields
by slow evaporation over sulphuric acid a body forming rhombic
crystals and melting at about 51°. It is soluble in water, alcohol,
ether, and chloroform, with slight decomposition, its solution rapidly
becoming acid, although the crystals themselves have a neutral reac-
tion. It volatilises slowly at ordinary temperatures, detonates
slightly when suddenly heated, and also very faintly when struck.
The constitution of this body is not understood, its formula being
apparently C11H33O21. On the addition of alkalis to its aqueous solu-
tion, hydrogen is evolved, whilst formic acid and methaldehyde are
produced ; with ammonia it yields oxygen, formic acid, and methalde-
hyde, and with ammoniacal lead solution, oxygen and lead dioxide.
It liberates iodine from potassium iodide, especially in presence of
sulphuric acid, and with lead oxide it yields detonating gas. The
dioxides of lead and manganese are reduced, with evolution of gas
and formation of formates of these metals ; with acids however it
shows greater stability. A. K. M.
Action of Carbonic Oxide on Steam. By L. Maquenne (Bull,
Soc. CMm. [2], 39, 308— 309).— The formation of carbonic anhy-
dride observed in the decomposition of formic acid, either by the elec-
tric discharge or by heat, led the author to conclude that carbonic
anhydride and hydrogen are the resultants of the action of carbonic
oxide on steam. This view is further supported by the fact that the
proportion of carbonic anhydride increases with the time of action.
ORGANIC OHEMISTRT. 861
Its diange also follows as a necessary deduction from thermo-
cliemical data, for the heat of combustion of carbonic oxide with
oxygen exceeds that of hydrogen by five heat-units.
In one set of experiments the author sealed up carbonic oxide with
water in tubes through which the electric discharge could be passed,
and found that 96*97 per cent, of the theoretical quantity of hydrogen
and carbonic anhydride were formed. The reaction never becomes
complete, owing to the dissociation of the carbonic anhydride. A
similar result was obtained when tubes containing carbonic oxide and
water were heated at 250 — 275°, and even at as low a temperature as
150° the transformation into carbonic anhydride and hydrogen is
practically complete. From these observations the author concludes
that the system CO2 + H2 is stable at any temperature below that at
which carbonic anhydride is dissociated, and that carbonic oxide is a
more powerful reducing agent than hydrogen. V. H. Y.
Compounds of Benzotrichloride with Phenols and Phenyl-
amines. By A. DoEBNER {Annalen, 217, 228— 269).— Most of the
results described in this paper have already appeared in this Journal
(Abstr., 1880, 239 and 644; 1881, 165 ; 1882, 956). From diethyl-
aniline and benzotrichloride a green dye, C2-H32N2, is produced corre-
sponding with malachite-green. The sulphate, C27H32!N2,H2S04, forms
crystals of a golden lustre, readily soluble in water and in alcohol.
The double salt with zinc chloride, (C27H32N2,HCl)2,ZnCl2,2H20, crys-
tallises in reddish-brown needles or in gold-coloured prisms, readily
soluble in cold water. The free base is slightly soluble in water,
readily in alcohol ; on reduction it yields a leuco-base, C27H34N2 (m. p.
62°), wliich crystallises in large colourless needles possessing a vitreous
lustre ; it is sparingly soluble in water, readily in alcohol, ether, and
benzene; the platinochloride, C27H3iN2,H2PtCl653H20, is obtained as
a colourless crystalline precipitate.
On heating the base C27H32N2 with concentrated hydrochloric acid
at 180°, it suffers a decomposition similar to that of malachite-green,
yielding diethylbenzoylaniline, CeHi.BzNEta, and diethylaniline, the
former crystallising in rhomboidal prisms melting at 78° ; it is in-
soluble in water, sparingly soluble in cold alcohol, but readily in hot
alcohol and in ether.
Similar green dyes have also been obtained by the action of benzo-
trichloride on the following tertiary amines : — Dibutylaniline, diamyl-
aniline, methylethylaniline, methylamylaniline, and methyldiphenyl-
amine. Para -derivatives, such as dimethylparatoluidine, appear not
to yield green dyes. A. K. M.
Action of Nitric Acid on Phenols. By W. Staedel {Annalen,
217, 153 — 181). — Action on Ethyl Orthocresol. — When ethyl ortho-
cresol is slowly added to ten times its weight of well cooled nitric
acid (sp. gr. 1*505), ethyl dinitro-orthocresol is formed. It crystallises
from alcohol in bright orange-coloured needles melting at 51°, which
become dark coloured on exposure to sunlight. They dissolve easily
in benzene, carbon bisulphide, and ether. On treatment with alcoholic
ammonia they are decomposed, dinitrotoluidine being formed (m. p.
862 ABSTRACTS OF CHEMICAL PAPERS.
208°). When nitric acid of sp. gr. 1-48 is employed, ethyl mononitro-
orthocresol is formed. It crystallises from alcohol in straw-coloured
needles melting at 71°. They are soluble in ether and benzene, and
are not attacked by alcoholic ammonia even when heated at 180°.
The mononitro-body is always accompanied by a small quantity of the
dinitro-body.
Ethyl-dinitro-orthocresolfrom Ethy l-mononitro-orthocresol. — When the
mononitro-compound (m. p. 71°) is treated with nitric acid of sp. gr.
1*6°, it is converted into ethyl dinitro-orthocresol. The same substance
is formed when the liquid, ethyl metanitro-orthocresol, is slowly added
to nitric acid (sp. gr. 1*5) and the mixture allowed to stand for three
hours.
Dinitro-orthocresol is formed whenever ethyl orthocresol is nitrated.
It varies in quantity directly with the temperature of the mixture
during the experiment. The barium salt, CuN'40ioHioBa + 3JH2O,
forms fine reddish-yellow needles soluble in hot water. The crystals
were observed to be mixed with a salt in the form of bright yellow
warty masses, which proved to be a salt of ethyl-dinitro-orthocresol.
The barium salt when heated for four hours at 70 — 80° loses its water
of crystallisation, and assumes a blood-red colour. The sodium salt
does not crystallise well. The free acid crystallises from dilute alcohol
in canary-yellow coloured needles melting at 85 — 86°. The ammonium
and magnesium salts form yellow needles which are soluble in water.
The silver salt is a brownish-red, and the lead salt a yellow precipitate.
Ethyl-metacresol. — When ethyl-metacresol is treated with nitric acid
in a similar manner to the ortho-compound, it yields a mononitro-
derivative, which crystallises from alcohol in colourless needles melting
at 54°. It is not decomposed when heated at 100° with alcoholic
ammonia.
Ethyl-paracresol dissolved in glacial acetic acid yields on nitrating
an ethyl mononitroparacresol. A different reaction takes place when
acetic acid is not present, and the ethyl salt is very cautiously added
to small quantities of well-cooled nitric acid. When the reaction is
complete, the mixture is poured into a large quantity of water or,
preferably, on to ice. A yellowish-white precipitate is formed which
gradually agglomerates. On treating it with soda-solution, a portion
dissolves, and the remainder is obtained as a dark-coloured oil v;hich
solidifies on cooling. The soluble portion consists of dinitrocresol.
The insoluble oil crystallises from alcohol in long white opaque needles
which, after drying over sulphuric acid, melt at 72'5 — 75°. They
consist of ethyl-dinitroparacresol, and are turned brown by sunlight.
Binitroparacresol crystallises from alcohol in glittering yellow
needles melting at 85°. It is sparingly soluble in water, more soluble
in alcohol, ether, and benzene. It is precipitated from an alcoholic
solution on addition of water as a yellow flocculent precipitate. The
sodium salt, CvHsNgOsNa, is obtained by neutralising it with sodium
carbonate. It crystallises from an aqueous solution in red needles,
which, on drying over sulphuric acid, lose water and assume an orange-
yellow colour. The barium salt, (C7H5N205)2Ba, is obtained by boiling
the dinitro-compound with barium carbonate. It crystallises in yellow
needles which are very sparingly soluble in water and alcohol. The
ORGANIC CHEMISTRY. 863
potassium salt, C7H5K2O5K, is formed when a solution of the barium
salt is boiled with a dilute solution of potassium sulphate. It crys-
fcallises from water in red iridescent anhydrous needles. The silver
salt, CvHsNgOsAg, obtained by treating the potassium salt with silver
nitrate, crystallises from an aqueous solution in dark-red needles. The
ammonium salt, C7H5N2O5NH4, is obtained by boiling the barium salt
with ammonium sulphate. It crystallises from water in the anhydrous
as well as in the hydrated form. The ethyl salt, CrHsNaOsEt, obtained
by acting on the silver salt with ethyl iodide, crystallises in long
colourless needles (m. p. 75°), soluble in alcohol and ether. It is
identical with the salt obtained direct from ethyl paracresol. The
methyl salt, CvHsNaOsMe, crystallises in nearly colourless needles
melting at 122°.
Nitration of Ethyl- and Methyl-naphthol. — Ethyl-trinitro-a-naphthol,
CioH4(N02)3.0Et, is formed when ethyl-a-naphthol is cautiously added
to ten times its weight of nitric acid (sp. gr. 1*52) which is well
cooled by ice. The nitro-product crystallises from alcohol in glittering
yellow needles which melt at 148°. They dissolve freely in glacial
acetic acid, but only sparingly in chloroform, ether, and benzene.
Ethyl-trinitro-^-naphthol, CioH4(N02)3.0Et, prepared in a similar
manner to the a-compound, crystallises from glacial acetic acid in
large yellow needles melting at 186°. They are only sparingly soluble
in alcohol, chloroform, and benzene.
Methyl-trinitro-oc-najohthol, CioH4(N02)3.0Me, is prepared in a similar
manner to the above salts. It crystallises from glacial acetic acid in
yellow plates which melt at 128°.
Methyl - trinitro - p - naj)hthol, CioIl4(N'02)3.0Me, crystallises from
glacial acetic acid in small colourless needles which melt at 213°, and
are almost insoluble in alcohol, benzene, chloroform, and ether.
Trinitronaphlhylamine, CioH4(N02)3.NH2. — When the above-men-
tioned ethyl and methyl salts are heated in a sealed tube at 50° with
alcoholic ammonia, they yield trinitronaphthylamine. It crystallises
from toluene in small glittering yellow plates which melt between
240° and 266°.
Trinitronaphthalene. — The trinitronaphthylamine, obtained from
ethyl trinitro-/8-naphthol as above, was converted into trinitronaph-
thalene. By decomposing the diazo-compound with hot alcohol in the
usual way the product crystallised from nitric acid gave two kinds of
crystals, one forming glittering yellow plates melting at 210", the
other crystallising in cubes melting at 181°. Trinitronaphthylamine,
obtained from methyl trinitro-|3-naphthol on similar tx^eatment, yields
yellow needles melting at 210°.
Nitro-product of Benzylphenol. — This and the following nitro-bodies
were prepared by the general method. After continued treatment
with ether, it forms a yellowish-greycrystalline powder, which is only
soluble in boiling toluene and glacial acetic acid. It is a mononit^o-
benzyl dinitrophenol, C6H3(N02)2.0.CH2.C6H4.N02. It crystallises
from glacial acetic acid in small orange-yellow needles.
The nitro-product of benzyl-par acresol consists of three substances
melting at 70°, 85°, and ISl"". The first is paranitrobenzyl nitrate.
That melting at 85° is dinitroparacresol. The third forms white
804 ABSTRACTS OF CHEMICAL PAPERS.
needles, and probably is the neutral nitro-prodnct of benzyl paracresol.
The nitro-product of henzyl-orthocresol is raononitrobenzyl dinitro-ortbo-
cresol, C6H2Me(N02)2.0.CH2C6H4.N02. When crystallised from boil-
ing alcohol it forms slender colourless needles melting at 145°.
J. I. W.
Nitrophenols and Nitrocresols. By W. Staedel {Annaleriy
217, 182 — 217). — When mononitrohenzyl-dinitrophenol is heated in a
sealed tube at 100° with alcoholic ammonia for 4 — 5 hours, it forms
paranitrobenzyl alcohol, which crystallises in brown needles melting at
91°. Dinitraniline is also obtained. It crystallises from a mixture of
alcohol and ether in brownish-yellow crystals melting at 174°, and is
orthoparadinitraniliue.
On heating mono7utrohenzi/l-dinitro-orthocresol with alcoholic ammonia
at 120 — 130", dinitrotolaidine and paranitrobenzyl alcohol are ob-
tained. The former is insolable in water, but crystallises from alcohol
and toluene in small yellow needles with a blue fluorescence, and
melting at 209°. The latter crystallises from water in light-yellow
needles melting at 91°.
JEthyl-dinitro-orthocresolis partially decomposed by alcoholic ammonia
in the cold. The reaction, however, is more complete when the
mixture is heated at 140 — 160° in a sealed tube for three hours. A
dinitrotoluidine (m. p. 208 — 209°), identical with that obtained from
mononitrobenzyl-dinitroorthocresol, is formed.
Ethijl-dinitroparacresol is easily converted into dinitrotoluidine by
alcoholic ammonia. It is obtained in yellowish-red crystals melting
at 167 — 168°. The author shows that it is identical with the dinitro-
toluidines obtained by iBeilstein and Kuhlberg (m. p. 166°), and by
Tiemann (m. p. 168°) {Ber., 3, 219). Since, on oxidation with
chromic acid and subsequent treatment wdth ammonia, dinitrotoluidine
yields chrysanisic acid, the constitution of ethyl dinitroparacresol must
be C6H2Me(N02)(OEt)(N02) [1:3:4:5].
Freparation of Symmetric Binitrotoluene. — When a solution of
dinitrotoluidine in absolute alcohol is boiled, with a stream of nitrous
fumes passing through it for 12 hours, it remains unaltered. When it is
heated with amyl nitrite for 18 hours, the dinitrotoluidine is attacked
and nitrous fumes are given off. On adding alcohol to the mixture
when cold, it becomes milky, and a heavy oil gradually separates out.
The filtrate from the oil when distilled yields a dark-coloured liquid
having a smell resembling that of amyl compounds. On distilling
with steam, it passes over in yellow oily drops. It is probably a new
product. The aqueous distillate deposits on cooling yellow needle-
shaped crystals of dinitrotoluene (m. p. 90 — 91°). Beilstein and Kuhl-
berg state that nitrous acid does not act on dinitrotoluidine in
concentrated nitric acid. The author finds that on passing nitrous
acid into a well cooled mixture of dinitrotoluidine and pure concen-
trated nitric acid, a reaction takes place. All unaltered dinitrotolui-
dine can be separated by pouring the mixture into boiling absolute
alcohol, and then cooling quickly. On filtering into twice its volume
of water, the solution deposits a reddish-yellow precipitate which,
after treatment with ammonia and crystallisation from water, yields
bright yellow needle-shaped crystals of dinitrotoluene, melting at
ORGANIC CHEMISTRY. 865
90 — 91°. They are sparingly soluble in light petroleum, freely soluble
in warm alcohol and carbon bisulphide, and in cold chloroform and
ether. They crystallise with 1 ttiol. of benzene, and, when anhydrous,
sublime without decomposition. When treated with chromic mixture
the crystals become colourless, and then melt at 92 — 9.3°. On oxida-
tion with chromic mixture, dinitrotoluene yields dinitrobenzoic acid
melting at 201°, and identical with Cahours's acid. The author states
that the ethyl salt is very readily prepared by dissolving the free acid
in a small quantity of absolute alcohol, adding a few drops of strong
sulphuric acid, heating for a few minutes on a water-bath, and finally-
treating the mixture with water: the precipitated salt crystallises well
from alcohol, and melts at 90°. The above-mentioned derivatives of
paracresol have the constitution —
Dinitroparacresol (m. p. 84—85°), C6H2Me(N02)(OH)(N02)
[1:3:4:5].
Dinitroparatoluidine (m. p. 167— 168°), C6H2Me(N02)(NH2)(N02)
[1:3:4: 5].
Dinitrotoluene (m. p. 91°), C6H3Me(N02)(I^02) [1:3: 5].
Syminetric Dinitrotoluene from Dinitro-orthotoluidine. — When dinitro-
orlhotoluidine is treated in a similar manner to dinitrotoluidine it
yields dinitrotoluene, melting at 91°. The latter is absolutely iden-
tical with that obtained from dinitroparatoluidine.
Si/mmetric Nitrotoluidine, C6H3Me(N02)(ISrH2) [1:3: 5].— When
dinitrotoluene is treated with an alcoholic solution of ammonium
sulphide it is reduced, symmetric nitrotoluidine being formed. It
crystallises from water in red needles, melting at 98°.
Symmetric tolui/lenediamine is produced when dinitrotoluene is
reduced with tin and hydrochloric acid. It forms a tin double salt
with the composition C6H2Me(NH2)2,2HCl 4- SnClo. The author
obtained the free base in the form of a syrupy liquid, boiling at 285°,
but was unable to get it to crystallise. The sulphate forms violet
crystals, soluble in water. The platinochloride crystallises in rusty-
coloured needles.
The knowledge that symmetric dinitrotoluene is formed by re-
moving the amido-group of dinitro-orthotoluidine, leads to the conclu-
sion that the above derivatives of orthocresol have the following
compositions : —
Dinitro-orthotoluidine, C6HoMe(NH2)(N02)(N02) [1:2:3:5].
Ethyl dinitro-orthocresol, C6H2Me(OEt)(N02)(N02) [1:2:3:5].
Dinitro-orthocresol (m. p. 85°), C6H2Me(OH)(N02)(NOa)
[1:2:3:5].
Mononitrobenzyldinitro-orthocresol,06HaMe(OC7H6NO2)(NO2)(N02)
[1:2:3:5].
Ethyl mononitro-orthocresol (liquid), C6H3Me(OEt)(N02)
[1:2: 3].
Ethyl mononitro-orthocresol (m. p. 71°), C6H3Me(OEt) (NOj)
[1:2: 5].
The author states that when the same process of removing the
amido-group is applied in the case of other dinitrotoluidines, different
866 ABSTRACTS OP CHEMICAL PAPERS.
dinitrotoluenes are obtained. A dinitrotoluidine obtained by Herif,
by further nitration of orthonitroparatoluidine, yields a dinitrotoluene.
When the dinitrotoluidine, prepared by Tiemann (Ber., 3, 218), and
melting at 168°, is treated with nitrous acid fumes in nitric acid, it
yields a dinitrotoluene which crystallises from alcohol in glittering
needles, melting at 60—61°. It is probably CeHgMerNOz^CNOj
[1:2: 6].
Paranitrobenzylnitrate, C6H4NO2.CHj.NO3. — When benzylparacresol
is acted on with nitric acid, there is formed, in addition to dinitro-
paracresol, a compound which closely resembles the body termed by
Beilstein and Kuhlberg, dinitrobenzjl alcohol. The author finds that
it yields paranitrobenzoic acid on oxidation, and that it is para-
nitrobenzyl nitrate. He has further prepared the latter body by
acting on paranitrobenzyl chloride dissolved in alcohol, with silver
nitrate. The crystals obtained from an alcoholic solution melt at
70—71°. J. I. W.
Ethyl-amido-cresols. By W. Staedel {Annalen, 217, 217—222).
— Ethyl metamido-ortJiocresol, C6H3Me(OEt)NH2 [1:2: 5], is pre-
pared by reducing ethyl metanitro-orthocresol (m. p. 71°) with tin
and hydrochloric acid, neutralising the mixture with alkali when the
reaction is complete, and finally distilling off the free base with
steam. It forms a dark yellow oil, which is only sparingly soluble in
water.
Ethyl-acetoamido-orthocresol, C6H3Me(OEt),NH5!c, is formed when
the above base is treated with an excess of acetic anhydride. It crys-
tallises from water, ether, and benzene.
Ethyl-amidometacresol is prepared by reducing ethyl nitrometa-
cresol (m. p. 54°). After precipitating the tin with hydric sulphide,
the hydrochloride is obtained in dark-coloured crystals. The free
base is best isolated by distillation with steam. Its salts crystallise
well. The aceto- compound is readily obtained.
JEthyl-wietamidojparacresol. — Ethyl metanitroparacresol is easily
reduced by tin and hydrochloric acid. The hydrochloride forms
needle-shaped crystals. The free base is obtained in the form of
white glittering crystals, melting at 40 — 41°. Ethyl aceto-meta-
amidoparacresol, C6H2Me(OEt).NH5^, melts at 106'5*'.
Mhyl-diamidoparacresol, C6H2Me(NH2)(OEt).NH2 [1:3:4:5], is
formed when ethyl dinitroparacresol (m. p. 75°) is added to a warm
mixture of tin and hydrochloric acid. On cooling, the hydrochloride
crystallises out in fine white silky needles. On adding an alkali to its
solution, the free base is precipitated as a nearly colourless oil.
The following table gives the properties of the salts of the above
compounds : —
ORGANIC CHEMISTRY.
867
Ortho-series.
Meta-series.
Para-series.
Free base
Hydrochloride ....
Hydrobromide ....
Sulnliatft .........
Liquid.
C9HpN0,HCl +
liHsO, silky
plates.
(C9Hi3NO)2H2,S04,
needles.
CgHigNO.HNOa,
slender needles.
(C9Hi3N0)2C204H2,
silvery plates.
(C9H,3N0)2H2PtCl6,
yellow crystals.
Rhombic plates
from water; large
tables from ether
(m. p. 108°).
Liquid.
Broad glittering
plates.
Quadratic plates.
(09H,3NO)2C2O4H2,
red plates.
White needles from
water (m. p. 114°).
White needle-shaped
crystals (m. p. 40 —
41°).
C9Hi3NO,HCl +
nU^O, fine silky
needles.
Long white needles.
(C9Hi3NO)2H2S04
+ 2H2O, fine
needles.
Glittering plates.
Nitrate
Oxalate
Platinochloride . . .
Aceto-compound . .
Golden-yellow
needles.
White glittering
plates from water
(m. p. 106-5°).
J. I. w.
Nitro- and Amido- derivatives of Azobenzene. By J. Y.
JanOVSKY (Monatsh. Ghem., 4, 276 — 283). — By the direct nitration of
azobenzeneparasulphonic acid, two mono-nitro-acids are obtained, of
which the more soluble (metanitro-) acid has already been described
(Abstr., 1882, 831). The less soluble acid is obtained as follows: —
100 grams of azobenzeneparasulphonic acid is placed in 500 — 550°
grams nitric acid (sp. gr. 1'4), and heated at 115° until completely
dissolved. When the violent reaction is over, the liquid is cooled to
8 — 10°, and the crystals separated from the resulting magma by aid
of a filter-pump ; the mother-liquor, after standing for some hours,
deposits a further quantity of the paranitro-acid, whilst the more
soluble meta-acid remains in solution.
Paranitroazohenzeneparasulpho7iic acid, C6H4(N02).N2'C6H4.S03H =
[4 : 4'], crystallises with 3 mols. HjO in broad golden-orange needles
having acute terminal faces ; 3'1 parts of the acid dissolve in 100
parts water at 10°, the solution having an orange-yellow colour ; a
hot saturated solution gelatinises when cooled to about 30°. The
potassium salt, Ci2H8(]S'02)N2.S03K, crystallises in orange-red, rhombic
tables, 100 parts of water dissolve 0'161 part of the salt at 17°, and
1-76 parts at 82°. The sodium salt, C,2H8(N02)N2.S03Na + 2H20,
forms pale-yellow monoclinic tables. The barium salt,
. [Cx2H8(N02)N2S03]2Ba,
crystallises in pale reddish-yellow scales, consisting of concentric
groups of microscopic prisms ; it is very sparingly soluble in water.
The lead and silver salts crystallise in concentric groups of minute
needles, explode readily on heating, and are both anhydrous.
Paramidoazobenzeneparasul/phonic acid, C6H4(NH2).N2.C6H4.S03H ^
[4 : 4'], is prepared by reduction of the nitro-acid with stannous
868 ABSTRACTS OF CHEMICAL PAPERS.
chloride and hydrochloric acid ; it crystallises in pale-yellow inter-
laced, microscopic needles ; 100 parts of water dissolve 0'104 part
of the acid at 15°, and 039 at 97°, the solution having a dirty yellow
colour. The potassium salt, Ci2H[8(NH2)N2.S03K, crystallises in
golden-yellow stellate crystals, sparingly soluble in cold, readily solu-
ble in hot water ; the sodium salt forms long needles ; the barium salt,
[Ci2H8(iyrH2)N2S03]2Ba + 4H2O, forms bronze-coloured rhombic
crystals showing the combination coPco, coPco, Pco ; 100 parts water
at 15° dissolve 0*104 of the salt. The silver salt precipitates in long
needles, and readily decomposes. On complete reduction of either the
nitro- or araido-acid with tin and hydrochloric acid, sulphanilic acid
and paraphenylenediamine hydrochloride are obtained, showing that
the nitro- and amido-groups must be in the para-position.
A. J. G.
Azylines. By E. Lippmann and F. Fleissner (Monatsh. Chem., 4,
284 — 308). — Further investigations have convinced the authors that
the formula R2KC6H3 ". KN ! CeHs.NE-a assigned by them to the
azylines (Abstr., 1883, 55) is incorrect, and that these bodies must be
represented by a formula containing two hydrogen-atoms more, and
therefore belonging to the azobenzenes. The following additional
details are given : —
Dimethylanilineazyline, Ci6H2o^4 = Me2^.C6H4.N ! C6H4 ! lN'Me2, not
C16H18N4 as previously given. The platinochloride, Ci6H2oN4,H2PtCl6,
forms a dichroic crystalline powder, red by transmitted, green by
reflected light.
DietJiylanilineazylifie, C20H28N4, crystals monosymmetric ; a : h : c ^=
1 : 07108 : 0-9493. Observed faces: 100; 110; 101; 501; 321;
321; 427; 010. Sp. gr. 1-107 (approx.) at 15°. The platinocJiloride,
C2oH28N'4,H3PtCl6, forms small, brownish-red, trimetric tables of
copper-green lustre. The ferrocyanide^ C2oH28N'4,H4FeCy6, crystallises
in brown rhombohedral plates. Dipropylanilineazyline picrate,
C24H36N4,[C6H3(N02)303],
forms orange-red crystals insoluble in water. Diamylanilineazyline
picrate, C32H54N4[C6H3(N02)303]2, forms small citron-yellow crystals,
sparingly soluble in alcohol and water. The periodides of the azylines
are precipitated on mixing alcoholic solutions of the azylines and
iodine ; they possess a metallic lustre, are dichroic, insoluble in water,
and are completely decomposed by alkalis, mercuric oxide, and silver
nitrate. Diethijlanilineazyline periodide, 4C10H14N2 + SL, forms
microscopic crystals, apparently trimetric. Dipropylanilineazyline per-
iodide, 4Ci2Hi8lS'2 -|- 3I2, crystallises in brilliant violet needles. JDi-
hutylanilineazijline periodide, 4CUH22N2 + Sl-i, forms dark crystals of
bluish lustre. Diamylanilineazyline periodide, 4Ci6H26N2,3l2, forms
black crystals of violet lustre.
By the action of nitrous acid on dimethylanilineazyline, paranitro-
dimethylaniline is obtained ; from diethylanilineazyline the previously
unknown nitrodiethylaniline was obtained in similar manner, and was
prepared, for comparison, by the oxidation of nitrosodiethylaniline.
It has the formula C6H4(N02).NEt2, melts at ^Q°, crystallises in sul-
phur-yellow needles showing a pale blue fluorescence, is sparingly
ORGANIC CHEMISTRY. 869
soluble in light petroleum, readily in hot alcohol. The crystals are
mouosymmetric, a:h:c = 1*0342 : 1 : 0'8245. Observed faces :
100; 001 ; 110; 101; 010. It is more strongly basic than dimethyl-
aniline, and yields a platinochloride, [N02(C6H4).NEt2]2,H2PtCl6, crys-
tallising in thin asymmetric prisms.
Diethylanilineazyline when treated with hydrochloric acid and stan-
nous chloride yields diethylparaph&iiylenediamine, C6Hi(NH2).NEt2, a
colourless oil, which turns brown on exposure to air, and boils at
260 — 262° ; the same substance was obtained by the action of stan-
nous chloride on nitrosodiethylaniline. The acid platinochloride,
2(N"H2.C6H4.NEt2,HCl)>,H2PtCl6, crystallises in thin yellowish-brown
tables.
By the action of ethyl iodide on diethylanilineazyline, and treat-
ment of the resulting hydriodide with potash, tetraethylphenylenedia-
mine, C6H4(NEt2)2, is obtained ; it melts at 52°, boils at 280" (uncorr.), is
very sparingly soluble in alcohol, ether, chloroform, benzene, and light
petroleum, but can be crystallised from water. The colourless crys-
tals are monosymmetrical with clinoquadratic habit. a : h : c =
099 : 1 : 1-833. Observed faces: 001; 100; 010; 201; Oil. The
platinochloride, C6Hi(NEt2)3,H2PtCl6, forms clear yellow tetragonal
crystals. Observed faces :■ 001; 100; 110. The double chloride,
C6H4(NEto)2(HCl)2,HgCl2, forms reddish-white monosymmetric crys-
tals. _a :&: c = 0-8754: 1 : 0-5655. Observed faces: 100; 110;
101; 101 ; Oil. The periodide, 2C6H4(]SrEt2)2 4- 3l2, crystallises in
black opaque forms, sparingly soluble in alcohol. The base was also
prepared by the action of ethyl iodide on diethylphenylenediamine,
and when so obtained showed identity in properties with that obtained
from the azyline.
Methyl iodide and diethylanilineazyline yield a crystalline hydrio-
dide, C6H4(NMel)2(NEt2), which could not be obtained pure.
Diraethylanilineazyline, heated with ethyl iodide, and subsequently
treated with potash, gives a base boiling at 275°.
Dipropylanilineazyline and ethyl iodide yield an iodide crystallising
in small needles, and yielding on treatment with potash an oil boiling
at 295 — 300°. From the foregoing results it appears that the nitro-
gen in these bodies occupies the para-position, the diethvl-compound
having the constitution EtgN.CeHi.Na.CeHi.NEta = [4 : 4'].
A. J. G.
Pyrenequinone. By G. Goldschmiedt (Monatsh. Ghem., 4, 309 —
324). — By oxidation of pyrene with chromic acid Grabe obtained a
compound, Ci6Hs02, which he regarded as pyrenequinone (this
Journal, 1871, 691) ; this result was disputed by Hintz (Inaug.
Dissert., Strasburg, 1878), who stated that he obtained by this reac-
tion two compounds, the one, CioHeOj, crystallising in red interlaced
needles, insoluble in sodium carbonate ; the other, C15H16O4, forming
short, thick, yellow needles, soluble in sodium carbonate. The author
has therefore re-investigated the question, and although closely follow-
ing the methods described by Hintz, entirely fails to confirm his
results. The red crystals are impure pyrenequinone, and the yellow
product was obtained only in very small quantity, could not be
VOL. xi.iv. 3 n
870 ABSTRACTS OF CHEMICAL PAPERS.
obtained well crystallised, and on analysis showed abont 3 per cent,
less carbon than is required by Hintz's formula.
Fiirenequino7ie, C16H8O2, forms a network of slender needles of yellow
to red colour, according to thickness, and cannot be fused without
decomposition. By careful heating in a vacuum it can be sub-
limed, the greater part, however, suffering decomposition. It is
sparingly soluble in alcohol, ether, benzene, light petroleum, chloro-
form, and acetone, the only good solvent being hot glacial acetic
acid. By heating it with zinc-dust or soda-lime, pyrene is ob-
tained. The products of the fusion of pyrenequinone with potash
are still under investigation. Dibromopyrenequinone, CiBH8Br202, is
prepared by heating a solution of pyrenequinone in glacial acetic acid
with bromine, and separates as a granulo-crystaUine precipitate of a
chocolate-brown colour when purified ; it is very sparingly soluble in
the ordinary solvents. On evaporation the mother-liquors from this
substance yield trihromopyrenGqui7ione, Ci6H5Br302, as a fine red, indis-
tinctly crystalline powder.
Pyrenequinone when boiled with dilute nitric acid (1 part HNO3,
2 parts water), yields citron-yellow microscopic crystals of a compound
whose analytical results agree best with the formula CuH5(N02)04.
By employing nitric acid diluted with acetic acid, there was obtained
in addition a substance crystallising in red needles of the formula
CnHeCNOo.), (?).
Pyrenequinol, Ci4H6(OH)2, is obtained by boiling pyrenequinone
with zinc- dust and dilute ammonia; it is a yellow crystalline body,
soluble in absolute alcohol, the solution having a strong dark blue
fluorescence, and being precipitated by water. It readily absorbs
oxygen from the air, and is reconverted into pyrenequinone. Diacetyl-
pyrenequinol, Ci4H8025^2, obtained by heating pyrenequinol for two
hours with acetic anhydride and sodium acetate, is a pale yellow,
crystalline powder melting at 166 — 167°, sparingly soluble in benzene,
alcohol, and ether. A. J. G.
Chelidonic Acid. (Preliminary N'otices.) By A. Lieben and L.
Haitinger {Monatsh. CJiem., 4, 273—275 and 339— 340).— Chelidonic
acid, when heated to boiling with solutions of the alkalis or alkaline
earths, is completely resolved into acetone and oxalic acid, according
to the equation C7H4O6 + 3H2O = 2C2H2O4 -\- CaHeO. The acid
appears to be dibasic, the neutral tri basic salts of Lerch and the basic
salts of Lietzenmeyer being in reality salts of an acid derived from
chelidonic acid by addition of the elements of water, and distinguished
from it by giving yellow precipitates with lead and silver salts, and a
yellowish-red coloration with ferric chloride ; whilst chelidonic acid
gives white precipitates with lead and silver salts, and a brown colora-
tion with ferric chloride only after long standing. The above-men-
tioned yellow lead salt has the composition Pb2C7H207 + H2O. By
treatment with zinc and acetic acid, chelidonic acid yields a crys-
talline acid melting at 140°. The authors suggest the expression
COOH.C — O — C.COOH, as possibly representing the constitution of
CH.CO.CH
chelidonic acid.
- i
I J
ORGANIC CHEMISTRY. 871
By the action of ammonia on cLelidonic acid, Liefczenmryer obtained
an acid of the formula CvHvNOg, termed by the authors am nnnoheli-
donic acid. Treated with bromine in presence of water it yields a
tribasic crystalline dibromo-acid, which gives a purple coloration
with ferric chloride ; it probably contains only two carboxyl-groups.
The author considers it probable that the nitrogen-atom in ammon-
chelidonic acid is exclusively in union with carbon.
Ammonchelidonic acid when heated with water at 195°, or by dry
distillation, is completely resolved into carbonic anhydride, water,
and hydroxy pyridi7ief C5H5NO ; this> separates from aqueous solution
in fine efflorescent crystals containing water of crystallisation, has a
neutral reaction, but yields a hydrochloride and platinochloride : when
distilled with zinc-dust it yields pyridine^
Bihromhydroxy pyridine, CgHsBrNO, is obtained by the action of
bromine on hydroxy pyridine,, or by heating the brominated chelidonic
acid. It is crystalline, sparingly soluble in water, insoluble in dilute
acids, readily soluble in alkalis, from which solutions it is precipitated
unaltered on addition of acids. It dissolves in concentrated hydro-
chloric acid, and yields with platinic chloride the crystalline platmo-
chloride (C5H3Br20)2,H3PtCl6. An ammoniacal solution gives with
silver nitrate a heavy, crystalline, sparingly soluble silver compound.
It is very probably identical w4th the dibromhydroxypyridine which
Hofmann obtained by the action of bromine on piperidine (Abstr.,
1879, 733). A. J. G.
Preparation of Methyl- and Ethyl-derivatives of Hydroxy-
quinolinetetrahydride, Methoxyquinolinetetrahydride, and
Ethoxyquinolinetetrahydride. (Dingl. polyt. /., 248, 172.) —
Fischer and Bedall have shown that hydroxyquinoline and methoxy-
quinoline prepared from quinolinesulphonic acid can be converted
into tetrahydro-compounds by treatment with zinc and hydrochloric
acid. Hydroxyquinoline and hydroxyquinolinetetrahydride yield azo
colouring matters with bases.
Fischer has found that by the action of the iodides or bromides of
the alcohol radicles on the tetrahydro-compounds, the latter are trans-
formed into methyl-, ethyl-, &c., derivatives. By the action of diazo
salts on these bases yellowish-red and brown colouring matters can
be obtained. Of more importance, however, especially in the case of
a-hydroxyhydromethylquinoline, is the fact that they have strongly
antipyretic properties, and can replace quinine. D. B.
Action of Hydrochloric Acid on Xanthine. By E. Schmidt
(Annalen, 217, 308 — 312). — The decomposition of xanthine by hydro-
chloric acid is perfectly analogous to that of caffeine and theobro-
mine, the products consisting of ammonia, glycocine, carbonic anhy-
dride, and formic acid, C5H4N4O2 + GH^O = 3NH3 + C2H5NO2 -h
2CO2 + CH2O2. A partial decomposition takes place at 180°, but to
decompose the xanthine completely the heating must be carried on
for some hours at 220 — 230°. Xanthine is but very slightly attacked
by long-continued boiling with a saturated solution of barium
hydroxide. A. K. M.
3 n 2
872 ABSTRACTS OF CHEMICAL PAPERS.
Theobromine. By E. Schmidt and H. Pressler (Annalen, 217,
287—306). — To prepare theobromine, the authors mix cacao which
has been freed from oil by pressure, with half its weight of calcium
hydroxide, and boil repeatedly with 80 per cent, alcohol. After re-
crystallising the residue obtained from the evaporation of the alcohol,
the theobromine forms a white crystalline powder. It is anhydrous,
and sublimes at about 290° without melting. Its salts are obtained
by dissolving the base in concentrated acids, and resemble those of
caffeine in their instability, being decomposed by contact with water
or alcohol. The hydrobromide, C7H»N40a,HBr + HaO, forms colour-
less transparent platj crystals, which lose tlieir water at 100°,
together with a part of the hydrobromie acid. The hydrochloride,
C7H8N'402,HC1 -h H2O, crystallises in colourless rosette-like groups of
needles, which lose both water and hydrochloric acid at 100°. The
platinochloride, (C7li8N402)2,H2PtCl6 4- 4H2O, has been described by
Glasson. According to the authors, it sometimes contains 4H2O and
sometimes 5H2O. The aurochloride, C7H8N"403,HAuCl4, forms yellow
tufts of needles. The sulphate has been obtained in small colourless
crystals, but of varying composition. The nitroite, 07118^^402, HNO3,
has been described by Glasson. The acetate, 07H8N4O2,C2H4O2, forms
a white voluminous precipitate, which gradually loses its acid by
exposure to the air. In its behaviour to methyl iodide, theobromine
differs markedly from caffeine (p. 873), for on heating the mixture
either alone or in solution in alcohol or in chloroform, no combination
of the theobromine with the methyl iodide takes place, whilst if
a mixture of theobromine,, alcoholic solution of potash, and methyl
iodide in equivalent quantities is heated at 100° in sealed tubes,
caffeine is produced, identical with the natural bases: O7H8N4O2 +
KOH + Mel = C7H7MeN402 + KI + H2O- On heating theobro-
mine with hydrochloric acid at 240 — 250°, it suffers decomposition
similar to that of caffeine, yielding ammonia, methylamine, sarcosine,
carbonic anhydride and formic acid. The same products are also
formed on boiling theobromine with solution of barium hydroxide,
and attempts to obtain an intermediate product, theohromidiiie
(corresponding with catfeidine) have as yet been unsuccessful. The
bromine-derivative, C7H7BrN402, obtained by the direct action of
bromine, agrees with the compound described by Fischer. When
theobromine is boiled with live parts of eonceaitrated nitric acid
in an upright retort until the greater part of the liquid has been
volatilised, and the residue then evaporated on a water-bath, amalic
acid is obtained. On boiling the latter with concentrated nitric
acid a further decomposition takes place, witii evolution of carbonic
anhydride and formation of methylparabanic acid and methylamine.
Maly and Hinteregger (Abstr.., 1881, 74i7) have shown that, besides
these products, ammonia is also produced when the oxidation is
effected by means of chromic mixture- Caffeine is decomposed by
nitric acid in the same way as theobromine, dimethylparabanic acid,
methylamine, and carbonic anhydride being formed, and in this case
also no ammonia. A. K. M.
ORGANIC CHEMISTRY. 873
Occurrence of Caffeine in Cacao. By E. Schmidt (Annalen,
217, 306 — 308). — In preparing theobromine from cacao (see p. 872),
the last mother- liquors yielded a small quantity of a body crystallising
in long needles, which the author has identified as caffeine. In
quantitative estimations the two bases may be separated from each
other by means of cold benzene, A. K. M.
Action of Hydrochloric Acid on Caffeine. By E. Schmidt
(Annalen, 217, 270 — 287). — It was thought possible that theobromine
might be formed by this reaction with elimination of a methyl-group.
No reaction, however, takes place below about 240°, the caffeine then
decomposing, with formation of carbonic anhydride, ammonium
chloride, methylamine hydrochloride, sarcosine hydrochloride, and
traces of formic acid, CgHioNiO., -f- eH.O = 2CO2 + 2MeNH2 +
NH3 + CH2O2 + C3H7NO2. The reaction is effected in sealed tubes,
the temperature being maintained at 240 — 250° for 6 — 12 hours;
above 260° the product becomes partially carbonised. The caffeine
employed was the pure product obtained from tea. The methyl-
amine hydrochloride is separated and purified by means of its
platinochloride, which crystallises partly in lustrous yellow plates
and partly in orange-red rosette-like groups. The sarcosine was
identified by means of its copper salt, (C3H6N02)2Cu,2H20, sarcosine
obtained by the action of barium hydroxide on caffeine yielding a
perfectly similar salt. These results show that caffeine yields the
same products by the action either of hydrochloric acid or of barium
hydroxide, except that in the former case the intermediate product,
caffeidine, is not produced. Theobromine is decomposed by hydro-
chloric acid, with formation of the same products as in the case of
caffeine, but the proportion of ammonia to methylamine is in this
case two molecules ot the former to one of the latter, showing that
the additional methyl-group in the caffeine must be united with a
nitrogen-atom. The fact that only one of the four nitrogen-atoms in
caffeine can be eliminated as ammonia is in accordance with the
formula given by Fischer {Atinalm^ 215, 314), and Medicus (ihuL,
175, 250), but is not explained by Strecker's formula (ibid., 118,
171).
The author has also very carefully compared artificial caffeine
as prepared by Strecker (loc. cit.) with natural caffeine obtained from
tea. His results confirm those previously obtained by Strecker, a
comparison of the following salts proving that artificial and natural
caffeine are identical. The hydrochloride, C8HioN402,HCl,2H20, forms
colourless monoclinic crystals, which give off hydrochloric acid and
water by exposure to air, leaving pure caffeine, the same change
taking place rapidly at 100°, or by the action of water or alcohol.
The platinochloride, (CHiiio^i02)2,^-iPtC\e, crystallises in small rosette-
like groups of needles, and contains variable amounts of water.
Caffeine aurochloride, C8H,oN'402,HAuCl4,2H-,0, forms lustrous gold-
coloured plates. Caffeine methiodide, C8HioN402,MeI,H20, is formed
when caffeine is heated for some hours at 130° with an excess of
methyl iodide in sealed tubes, and may be purified by washing with
cold alcohol and crjstallisii.g from water, in which it is moderately
874 ABSTRACTS OF CHEMICAL PAPERS.
soluble, aUhough but sparingly so in alcohol, and almost insoluble in
ether. > A. K. M.
Metalbumin and Paralbumin: a Contribution to the
Chemistry of Encysted Fluids. By O. Hammarstkn (Zeitschr.
Physiol. Chein., 6, 194 — 226). — Our methods of examination for
paralbumin and metnlburain in pathological fluids are incomplete and
unsatisfactory, yielding results which have not yet proved of value in
diagnosis. Owing to the physical nature of the fluid contents of
cystic tumours, frequently tenacious, ropy, scarcely possible of filtra-
tion, and brown- coloured, as in ovarian cysts, the investigation is
beset with peculiar difficulties. The author's observations were con-
ducted on the fluid contents of some 40 ovarian cysts, which were
placed at his disposal during the past year. They are to be regarded
as a preliminary contribution to the elucidation of the subject.
Metalbumin. — This name was given by Scherer in 1852 to a
proteid substance which he had discovered in the fluid of an ovarian
cyst. In 1864, Eichwald, in his monograph on the " Colloid Degene-
ration of the Ovaries," ascribed metalbumin a place between serum-
albumin and peptone, being, like paralbumin, a transition stage
between the two, but more nearly allied to peptone. Metalbumin is not,
as stated by Mehn (Arch. -Generales de Med., 2, 1869), precipitable by
magnesium sulphate, whilst paralbumin under certain circumstances
may be. The author describes processes for the separation of
metalbumin and paralbumin, which are preferable to those of Plosz,
inasmuch as by employing fractional precipitation by alcohol they are
obtained free from albumin. Analysis in the case of metalbumin
yielded these results : —
C. H. N. S. O. Ash.
J / 49-44 7-11 10-30 _ _ —
^- \ 49-45 6-91 10-26 — — 1-1
II. 50-0 6-84 10-27 125 31-54 14
He considers metalbumin more closely related to mucin than to
albumin, and that the name metalbumin being misleading, that of
2)sevdomucin might be provisionally bestowed upon it.
In his treatise on "Colloid Degeneration of the Ovaries," Virchow
pointed out that when the colloid tumour becomes cystic a softening
of the colloid substance is effected. Recollecting that he also showed
tliat the alkaline solution of the colloid substance is no longer pre-
cipitable by acetic acid, the presumption is great that Scherer's
metalbumin is only a changed and liquefied colloid.
Paralbumin. — This was also discovered by Scherer in ovarian fluid.
It corresp<mds with metalbumin in many of its reactions, but differs
chiefly in this, that in boiling, as also after the addition of certain
reagents, which fail to throw down metalbumin, but only make the
solution opalescent or milky, paralbumin is precipitated. It is pro-
bable that paralbumin is a mixture of pseudomucin with varying
quantities of albumin. The author prepared it by addition of albumin
to metalbumin (pseudoYnuciu), and analysis confirmed the same view,
affording varying results, as follows: —
PHYSIOLOGICAL CHEMISTRY. 875
C.
H.
N.
S.
1.
50-20
6-79
11-22
—
2.
50-94
6-92
12-00
1-75
3.
61-80
6-93
12-84
1-66
4.
—
—
13-46
1-80
5.
52-34
M9
14-52
—
According to the author's experience, his observations are in
accordance with those of Hoppe-Sejler, that paralbumin is only a
mixture of a mucoid substance, pseudomucin, with varying propor-
tions of albumin, chiefly serum-albumin. So far as he has found,
ovarian fluids contain no specific albumins — the so-called metalbu-
min and paralbumin — but only very small quantities of peptone,
varying amounts of globulin and serum-albumin, besides a never-
failing constituent in the form of a substance allied to mucin,
wliich he has provisionally termed, as above stated, pseudomucin. It
is to this substance that ovarian flaids owe their peculiar property :
when it is found almost free from adherent albumin, then we have
Scherer's metalbumin ; on the other hand, when the proportion of
albumin is greater, the reactions are those of Scherer's paralbumin.
D. P.
Physiological Chemistry
Action of Calcium, Barium, and Potassium Salts on Muscle.
By T. L. Brunton and T. Cash (Proc. Boy. Soc, 35, 63). — It has been
observed by Ringer that calcium salts prolong, but that the subse-
quent addition of potash diminishes the contraction of the frog's heart.
The authors in the present note show that the action of calcium
and potassium salts on voluntary muscles is similar to that which they
exert on the gastrocnemius. Barium salts produce a curve of contrac-
tion resembling in its form and modifications that produced by veratria,
and similarly restored to the normal state by potash. The authors
propose to develop the relations existing between groups of elements
as regards their physiological action in accordance with Mendelejetf's
classification. V. H. V.
Secretion by the Kidney fed -with Defibrinated Blood. By
M. Abeles (Monatsh. Chem., 4, 325 — 336). — In these experiments
the kidney was excised from a recently killed dog which had been fed
with defibrinated arterial blood, diluted with one- third of its volume
of a solution containing 0-6 per cent, of sodium chloride and -jo^^qo ^^
sodium hydroxide ; small quantities of urea, sugar, or glycocine being
added in various experiments. The mixture was heated to 35 — 40°
l>efore use. The general result was to show that when the kidney is
fed with the diluted blood alone, no secretion flows from the ureter,
whilst the addition of urea, sugar, &c., to the blood, leads to the
876 ABSTRACTS OF CHEMICAL PAPERS.
secretion of a liquid in which such crystalloid substances are present
in relatively larger quantity than in the blood employed.
A. J. G.
Formation of Uric Acid in the Animal Economy. By
A. B. Garrod (Proc. Eoij. Soc, 35, 63 — 65). — The author has deter-
mined the solubility of uric acid and its more important salts at the
temperature of the healthy human body, and has investigated the
action of ammonium and sodium urates on their chlorides and phos-
phates, when mixed with each other in various proportions. Obser-
vations were also made on the composition of urinary excretions of
the lower animals, whereby it was shown that in the semi-solid urines
of birds, reptiles, and invertebrata, the urate is in the form of spherule
aggregates, consisting of a number of smaller spherules, united with
or contained in colloid cells.
The author lays stress on the varying amounts of uric acid excreted
by different animals in relation to the elimination of nitrogenous
substances, and the excessively large excretion of uric acid by
birds, reptiles, and invertebrata as compared with the weight of their
bodies. Thus a bird throws out relatively to its weight a thousand
times more uric acid than a man.
It is also shown that whereas in the kidneys uric acid exists as an
ammonium salt, in the blood and different tissues it exists as a sodium
salt.
The results of the investigation show that uric acid is not, as
hitherto supposed, formed in the animal body during the metabolism
of its various organs and tissues, then thrown into blood, and after
filtration through the kidneys eliminated from the system ; but that
it is absolutely formed in the renal organs by the action of peculiar
cells, in which it probably exists as the urate of a compound ammo-
nium, readily decomposed into uric acid and ammonia. As such it is
secreted, by it the ammonium is replaced, and sodium or other metal
when its secretion is obtained by mechanical means or by disease. At
times it is deposited as a crystalline sodium salt in the cartilaginous
and fibrous tissues. Experiments were also made on the decomposition
of uric acid by hippurates and benzoates. Glycine, glucose, and
glycerol have no such effect. V. H. V.
Formation and Decomposition of Tyrosine in the Body.
By H. Blendermann (Zeitschr. Physiol. Ghem., 6, 234—262).—
Tyrosine is a product of the decomposition of albuminoids, from
which, as well as from allied substances, it may be formed by the
action of acids or alkalis at a boiling temperature, and also by the
influence of certain ferments, especially the trypsin of the pancreas.
The constant association of tyrosine in such decompositions of albumin
makes it a priori probable that it is also formed in the animal body on
the breaking up of prote'ids. This fact has already been established
by Kiihne and others. The proportion of prote'id which is thus
changed into leucine and tyrosine to that which is absorbed from the
alimentary canal as peptone is variable and dependent on several
conditions, particularly upon the rapidity of the absorption process,
and the circumstances more or less favourable to an abundant develop-
PHYSIOLOGICAL CHEMISTRY. 877
ment of putrefactive ferments. The qnestion as to whether tyrosine
is to be regarded as a normal product of tissue-change in healthy
organs is an open one. Yirchow long ago referred its presence to
cadaveric changes; Naunyn, Keukomer, and others had found it in
pus, and lately Leyden discovered it in the sputum of a girl suffering
from haemoptysis. Tyrosine has been abundantly found in pancreatic
juice ; but according to Kiihne, not in the fresh secretion. Huber
found it in normal organs, especially in fresh spermatic fluid ; and he
meets Virchow's statement by the results of experiments which show
that on free access of air, cadaveric decomposition of albumin yields
neither leucine nor tyrosine. Radziejwsky's researches are, however,
opposed to these views of Huber'^s. Hoppe-Seyler has expressed
himself of all investigators most decidedly against the occurrence of
tyrosine in the normal organism during life. According to him, it is
a pathological product of cell-albumin, and occurs when too limited
quantities of oxygen are conveyed to the tissues. Thus formed, it
may under certain conditions pass away in the urine. Tyrosine is
found in the organs in different diseases, almost always together with
leucine, and often in considerable quantities. Frerichs has found it
in the liver and in the bile, in smallpox and typhus fever ; Frerichs
and Stadeler in acute atrophy of the liver; Scherer in the liver of a
drunkard dying of typhus ; Huber in the spleen, liver, and kidneys of
leukaemia ; and Sotnischewsky in the lungs in pneumonia. In cases
of phosphorus poisoning, tyrosine has been found in the liver,
kidneys, and blood by various investigators. Pouchet asserts that
it is further present in traces in healthy urine, and numerous obser-
vations accord it, with or without associated leucine, a place in the
urine in various disorders. In the urine of acute yellow atrophy of
the liver, tyrosine with leucine would appear to be constantly present ;
but less frequently in the urine in cases of phosphorus poisoning,
although all observers agree as to its presence in the liver and other
organs. In other diseases tyrosine is rarely present in the urine.
Anderson has, however, asserted the contrary. Several observations
have quite recently been made regarding the fate of tyrosine in the
system. Schultzen and Nencki found increased secretion of urine
after administering tyrosine to dogs, and conjectured that this sub-
stance might be a transition stage in the formation of urea from the
physiological destruction of tissue in man. Brieger found that
after giving tyrosine, the excretion of phenolsulphuric acid was enor-
mously increased. The researches of Baumann have established the
presence of certain aromatic bodies in the normal urine of man and
other animals, which, according to his investigations and those of
Brieger and Weyl, are derived from the breaking up of albumin or of
tyrosine.
The relations of these aromatic bodies to tyrosine may be readily
shown. The now established formula of the latter is
CcH4(OH).aH3(NH2).COOH
(araido-hydroparacoumaric acid). From it by putrefaction are formed
hydroparacoumaric acid, C6H4(OH).(CH2)2COOH ; parahydroxy-
phenylacetic acid, C6H4(OH).CH2.COOH ; paracresol, CsHiMe.OH ;
878 ABSTRACTS OF OHEMIC.VJL P.VPERS.
and phenol, CeHc.OH. The occnrrence of phenol in the urine had been
observed by Stiideler, Lieben, and others ; but its origin was referred
to certaia of the vegetable constituents of food, previously to Baumann
showing that it was likewise present in the urine of flesh-fed dogs,
and that it is a constant putrefactive product of albumin. Brieger
also showed that phenol with other aromatic bodies is a constant con-
stituent of faecal matters. One must, with Baumann and Brieger,
regard albumin as the only source of phenol and paracresol in these
cases. In harmony with this view are the numerous observations of
Brieger in the occurrence of phenol in various diseases ; also those of
Salkowsky, including an increased excretion of phenol after ligature
of the gut. The author also found the same increase in a case of
severe intermittent fever. Weyl first proved that phenol and para-
cresol are formed by the putrefaction not only of albumin, but like-
wise of pure tyrosine. Baumann obtained hydropai'acoumaric acid
and parahydroxyphenylacetic acid from the putrefaction of pure tyro-
sine, the last-named acid being also obtained by E. and H. Salkowsky
from putrid albumin. Both of these acids were further decomposed
by septic ferments, and yielded paracresol and phenol.
The experiments on the putrefaction of albumin and tyi"osiue thus
cited afford simple and clear views of the relations of the substances
occurring in urine to tyrosine. Experiments regarding the excretion of
phenolsulphonic acid, and also of the aromatic hydroxy-acids in arti-
ficial digestion of tyrosine have not yet been made, save the
important observation of Brieger to the effect that in man the admin-
istration of tyrosine is followed by an increased excretion of phenol.
In the author's experiments an attempt has been made to determine
the fate of tyrosine in the system. The formation of yet another
substance from tyrosine was also held in view, hydroxymandelic acid,
which hitherto has only once been found by Schultzen and Riess, and
which undoubtedly stands in close relation to tyrosine, having the
formula C8H6O4. Baumann did not succeed in finding it among the
products of the putrefaction of tyrosine. Tyrosine was introduced
into the system in these experiments in two ways ; either formed in
the system itself by phosphorus poisoning, or administered by the
mouth.
I. Fhosphorus Foisoning. — a. In Man. — In several cases of phos-
phorus poisoning admitted to the Charite Hospital, the examination
of the urine for tyrosine yielded negative results. Two, however,
gave positive evidence of its presence. One of them, a child, had
poisoned herself with lucifer matches, and died on the seventh day,
when the urine was at once examined. Tyrosine crystals were obtained,
yielding all the characteristic reactions, and likewise aromatic hy-
droxy-acids in large amount (580 c.c. urine yielded 0'2475 gram, m. p.
167 — 108° C). The second case w^as of a coachman who had swallowed
some prepared rat poison by mistake for cheese. Death likewise
followed on the seventh day, when the urine, on examination, yielded
tyrosine ; its identity was established by a combustion. Leucine was
also found. No tyrosine had been detected on the sixth day. This
sudden change between the sixth and seventh days was accompanied
by an increase of phenolsulphonates and diminution of the sulphates,
PHYSIOLOGICAL CHEMISTRY. 879
an increase wliich the author ascribes to probable increased excretion
of phenol and paracresol.
h. In the Dog. — The results of two experiments were entirely nega-
tive in regard to the presence of tyrosine. On the other hand, there
was an increase of aromatic hydroxy-acids and of phenol. The increase
of tlie hydroxy-acids would nevertheless point to the formation of
tyrosine, probably from destruction of the tissue of glandular
organs.
JI. Administration of Tyrosine in the food. — c. Id the several series
of experiments carried out upon dogs, men, and rabbits, the author
found the following bodies in the urine, which may be regarded as
products of its transformation : —
1. Phenols in large quantities (man, rabbit).
2. Normal hydroxy-acids in increased quantity (dog, rabbit).
3. Tyrosine hydantoin (rabbit),
4. Hydroxy hydroparacoumaric acid (rabbit).
Those named in 3 and 4 appear only in the urine of animals when
saturated, so to speak, with tyrosine ; so that it is readily explicable
why these should be absent from normal urine. Under 2, the absence
of hydroxy-acids in man is remarkable. An interesting accordance is
observable between the results of administration of tyrosine and of
phosphorus poisoning in the dog, in both instances there being in-
creased formation of normal hydroxy-acids and absence of more than
mere traces at most of phenol. The author concludes his paper with
notes on the detection of tyrosine in the urine. This has hitherto
depended upon its separation by the Frerichs-Stadeler method. The
reactions for the identification of tyrosine are especially those of
Hoffman (red coloration with Millon's test) and of Piria-Stadeler, in
which the sulpho-acid of tyrosine is formed, which, in neutral solution,
gives a blue colour with ferric chloride. This latter test can only be
made with pure tyrosine, and the former gives similar reactions with
other bodies present in normal urine, such as phenols and hydroxy-
acids. Other unknown constituents of urine also give reactions with
Millon's test.
From these considerations he regards Anderson's observations
referred to at the outset of this paper with distrust. He has iurther
to this end examined the urine of patients in the Charite Hospital
under the care of Ehrlich and Brieger, including two consumptives,
a case of pneumonia, of acute articular rheumatism, hydatid of the
liver and carcinoma of the liver, without in any case finding tyro-
sine, much less leucine, in the usual way, although Millon's test, as in
the case of normal urine, gave reaction. Hoppe-Seyler has also failed
to detect tyrosine in a long series of severe cases of typhus fever and
other diseases. D. P.
880 ABSTRACTS OF CHEMICAL PAPERS.
Chemistry of Vegetable Physiology and Agriculture.
Easily Oxidisable Constituents of Plants. By J. Rkinke
(Zeitschr. Physiol. Chem., 6, 263 — 279). — It is a well-known fact
that the juices of many plants become discoloured on exposure to the
air. So, too, sections of stems and roots of leaves and fleshy fruits
which acquire a brown colour on exposure. Little has been ascer-
tained in regard to the physiology of these changes. They obviously
depend upon the oxidation of certain constituents ; this is seen, for
instance, on exposing grated potatoes to the air, when the uppermost
layer assumes a brown colour, which by frequent turning over of the
mass may be communicated throughout. The same is seen in the
case of the expressed juice of the potato. Putrefaction or fermenta-
tion, and reducing agents, such as sulphurous or hydrosulphuric acid,
decolorise these fluids. The juice of the white sugar-beet is even
more sensitive, becoming on exposure to the air immediately of a
dirty wine-red colour, then violet, brown, and finally almost black.
These facts indicate the presence in plants of easily oxidisable bodies,
and inasmuch as the products of their oxidation do not occur within
the uninjured cells, it follows that there is either no free oxygen in
the latter, or that with these oxidisable substances other reducing
substances are concomitant, hindering their oxidation, or ac(ain, that
in the protoplasm oxidation affords other uncoloured products. Upon
which of these three factors the colourless state of the protoplasm and
cell- juice of living plants depends is not yet decided.
In the study of oxidation processes in the living plant-cell, an im-
portant question presents itself, as to whether substances occur in the
cell which at ordinary temperatures unite with atmospheric oxygen
without the essential co-operation in this process of the living proto-
plasm. Difficult as the problem is, the isolation and determination of
constitution of these easily oxidisable substances forms an indispens-
able preliminary step. It may be conjectured that they belong to the
aromatic series. In this connection the numerous hydroxybenzene
derivatives claim attention, of which many are known to be easily
oxidisable. Pyrogallol in alkaline solutions greedily absorbs oxygen
and becomes decomposed into carbonic anhydride, acetic acid, and a
brown body of unknown nature. The dihydroxybenzenes (catechol,
resorcinol, and quinol) are easily oxidisable bodies, and their methyl
derivative orciuol is coloured red by the air. As regards derivatives
of the anthraquinone series, there is the change of indigo-white into
indigo-blue, and the behaviour of Boletiis luridus, the colourless section
of which becomes at once blue on exposure to the air. Lastly, there
is a series of complex plant-constituents, undoubtedly benzene deriva-
tives, although their constitution has not yet been ascertained, which
exhibit many analogies to the discoloration of plant juices. Of these
Brazilin may be named, the colourless aqueous solution of w^ich
becomes first yellow, then reddish-yellow in the air.
The author, in his endeavours to isolate the easily oxidisable con-
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 881
stituents of the sugar-beet and potato to wbicli the discoloration of
their respective fluids is attributable, succeeded in the first instance in
isolating from the beet-root a chroraogen which on exposure to the air
acquired a red colour. This substance he has accordingly designated
Bhodogen. The product of its oxidation he terms beet-red, and he
notes certain remarkable analogies between the absorption-bands of
this substance and of the colouring matter of Anchusa tinctoria,
alkanet-red, the spectrum of each showing three bands occupying
identical positions. These investigations have therefore so far aiforded
proof of the existence in the colourless cells of the sugar-beet of an
easily oxidisable colourless body^ capable of isolation, which by itself,
without the aid of the laving plasma of the plant, can split up the
oxygen molecule, forming a coloured substance.
The isolation of the chromogen of the potato has not succeeded so
satisfactorily. The presence of vanillin in the juice appeared to be
shown by the strong odour of vanilla. Vanillin has been detected by
Scheibler in raw beet- sugar. A substance resembling catechol, but
not identical with it, was also separated. It would seem to be the
same body discovered by Grorup-Desanez in the leaves of Ampelopsis
hederacea. It is undoubtedly an acid, and amongst the known aro-
matic acids most closely corresponds in its reactions with hydrocaffeic
acid. In conclusion, the author suggests the hypothesis that these
easily oxidisable bodies belong, in their physiological relations, to the
retrogressive series, perhaps -originating from the breaking up of
albumin, or formed by the synthesis of the products of such decom-
position, and that in these features they are allied to the process of
respiration. D. P.
Studies on Ripe Grapes. By C. Amthon (Zeitschr. Plnjsiol.
Ohem., 6, 227 — 283). — In a paper on the analysis of wines by
Amthor and Musculus, which appeared in the Zeitzchr. Anal. Chem.
for 1882, it was pointed out that extraordinarily high proportions of
extract and phosphoric acid were present in wines prepared from un-
ripe grapes. The must of these wines, however, not being then at
the author's disposal, this investigation has been made in supplement
to the former, and the must, seeds, and wine resulting after com-
pleted fermentation of purple grapes at three successive stages, viz.,
first stage of ripening, of approaching maturity, and of full maturity,
have been severally examined. The results may be summarised as
follows : —
1. At the beginning of the process of ripening, the grape must
becomes poorer in mineral ash, containing, for example, 28*3 per cent.
less on the 4th of September than on the lOth day of August.
2. The phosphoric acid of the must becomes less in the same pro-
portion, 29" 7 per cent, less on September 4th than on August 10th.
3. After fermentation of the must at the early stage of ripening,
the wine is also poorer in extract ; 33'2 per cent, of extract less on
September 4th than on August 10th.
4. During fermentation phosphoric acid is consumed by the yeast
formation, and the more so in proportion to the sugar which
is present, the loss being at early stages 14' 7 per cent. (August 10),
882 ABSTRACTS OF CHEMICAL PAPERS.
21*6 per cent. (August 22), but after full maturity 47' 5 per cent.
(September 4).
5. The amount of asli- constituents in the seeds or grapestones, and
likewise of phosphoric acid, gradually increases with the process of
ripening.
6. The ratio of phosphoric acid (P2O5) to ash in the must is at all
three stages nearly constant, 1 : 9'5.
7. The ratio of P2O5 to the ash of the stones is also constant at all
stages, 1 : 3*5.
The author concludes that inasmuch as these constants remain un-
affected in spite of the increase of ash and P2O5 during the ripening
of the stones on the one hand, and of their decrease during this pro-
cess in the must, a certain proportion of the mineral constituents of
the grape-juice which is unaccounted for in either must or stones,
must pass into the stems. Also a part of the bases in combination
with the phosphoric acid, chiefly potash, must become free and go
over to another acid. As the tartaric acid of the grape is chiefly
changed to potassium tartrate, this must be the destiny of part of the
potassium. But the whole of the potassium is not present, as Neu-
bauer assumes, to be employed in neutralising the free tartaric acid
during ripening ; but free tartaric acid is present partly in order to unite
with the potassium which had been previously combined with phos-
phoric acid, the latter being taken up by the grape stones or kernels.
D. P.
Influence of Manuring on the Composition of Potatoes. By
YiBRANS (Dingl. pohjt. J., 248, 179). — In order to determine the
influence of nitrogenous manures on the percentage of starch in
potatoes, Vibrans cultivated good sandy loam soil with so-called
" alcohol potatoes." It was found that with sodium nitrate a larger
yield of potatoes was obtained than without the use of manure. From
the composition of the potatoes, however, it was shown that the larger
the amount of nitrate used, the smaller was the quantity of solid
matter and starch contained in* the potatoes, so that it must be
concluded that nitrogenous manures act injuriously on their constitu-
tion. D. B.
Analytical Chemistry.
Estimation of Iron and Steel. {Dingl. pohjt. J., 248, 213 —
216.) — For determining the total carbon in pig-iron and steel, Starr
treats 3 grams of steel or 1 gram of iron with 50 c.c. of a dilute neutral
solution of cupric chloride placed in a small beaker, and agitates the
mixture so as to separate the copper in a spongy form. When the
reaction is ended, 50 — 75 c.c. of a concentrated solution of cupric
chloride, and 10 c.c. concentrated hydrochloric acid are added, and
the whole is heated on a water-bath until the copper has been dis-
solved, and the liquid is finally passed through an asbestos filter. The
ANALYTICAL CHEMISTRY. 883
separated carbon is washed with hot water, then with alcohol, after
which the contents of the funnel are transferred to a combustion tube
and burnt in a current of oxygen, the carbonic anhydride evolved being
absorbed by means of soda-lime.
Eggertz has made a series of estimations of carbon in iron, both by
the iodine method and colorimetrically, and finds that the results
obtained by the two methods agree very closely with one another.
According to Woodcock, the hardness of steel depends on the con-
version of the carbon into a form resembling the diamond. Cementa-
tion steel, as obtained from the furnace, is, in spite of the increased
amount of carbon, as soft as the wrought iron used in its preparation.
If it be then heated and cooled suddenly, it becomes hard, its fractured
surface showing numerous crystals resembling diamonds. Woodcock
assumes that at a red heat the molecules expand, with partial separa-
tion of carbon, which is not re-absorbed when cooled suddenly, but
separates by the aid of a small amount of hydrogen in the form of
diamonds. When, however, the cooling is effected gradually, no
crystallisation, and consequently no hardening, occurs.
According to Goetz, the estimation of manganese in iron is effected
colorimetrically at the Cleveland iron works, Ohio. Ledebur mentions
that this process is recomraendable only for iron containing not more
than 2 per cent, manganese.
For determining silicon in iron and steel. Drown and Shimer dis-
solve the metal in the form of filings in hydrochloric acid, evaporate
to dryness, treat the residue with dilute sulphuric acid, filter, wash
with hydrochloric acid and hot water, dry, ignite, and weigh. For
determining the sulphur in iron and steel, Craig recommends to dis-
solve the sample in hydrochloric acid, and abscjrb the gas evolved in
an ammoniacal solution of hydrogen peroxide, the sulphuric acid
formed being precipitated with barium sulphate. Rocholl states that
the presence of copper interferes with the reaction, as a portion of
the sulphur is retained by the same. D. B.
Determination and Investigation of Drinking Water. {Bingl,
polyt. /., 248, 37— 39.)— According to Mallet {Ghem. News, 46, 63),
the injurious effects produced by drinking polluted water do not
depend on the chemical constitution of the organic matter, but on the
presence and action of living organisms. In the determination of the
organic matter by combustion according to the directions of Frank-
land, there is a loss of carbon and gain of nitrogen, varying in amount
with the dilution of the solutions. The loss of carbon is due to the
volatilisation of butyric acid and other volatile substances during the
evaporation of the water with sulphurous acid ; the gain of nitrogen is
occasioned by absorption of ammoniji from the surrounding atmo-
sphere during evaporation. In conducting the albuminoid ammonia
process in accordance with Wanklyn's instructions, there is a loss,
resulting from the fact that on boiling with alkaline permanganate,
part of the nitrogen is volatilised as amines, and escapes detection by
the Nessler reagent. Concordant results are said to be obtained by
Tidy's method, using the acidified permanganate at the ordinary tem-
perature.
881 ABSTRACTS OF CHEMICAL PAPERS.
Mallefc recommends extending the time durinj^ which the perman-
ganate is allowed to act in the Tidy process to 12 — 24 hours, deter-
minations being made at intervals of three to six hours, in order to
trace the procuress of the oxidation. According to Stapleton (Ghem.
News, 46, 284) the preparation of the alkaline permanganate solu-
tion is effected by dissolving caustic potash in water containing
calcium carbonate, in order to remove all nitrogenous matter present.
The clear solution is then mixed with potassium permanganate dis-
solved in distilled water and heated to boiling, to remove further
traces of ammonia.
For estimating ammonia in potable waters by distillation, Tichbome
uses an arrangement of bulbs which he connects with the receiver,
and fills with distilled water. Any accidental contamination with
atmospheric ammonia is thereby avoided.
For the determination of nitrites in water, Davy (CJiem. News, 46, 1)
recommends the use of an aqueous solution of gallic acid, decolorised
by boiling with animal charcoal, filtering, and treating whilst hot
with dilute sulphuric acid. This solution gives with water containing
nitrous acid a brown coloration, the depth of the colour produced
being in direct proportion to the amount of nitrite reacting on the
gallic acid, so that it affords a ready means for the quantitative deter-
mination of the nitrites. If ferric oxide is present, it must be
removed by precipitation with ammonia.
For the volumetric determination of the carbonates of calcium and
magnesium in water free from calcium sulphate, Houzeau (^Co'ni'pt.
rend., 95, 1064) treats 100 c.c. with a solution of cochineal, and adds
a solution of oxalic acid until the mixture assumes a permanent
yellow colour. The quantity of oxalic acid used is in proportion to
the total amount of carbonates. The precipitate of calcium oxalate
is filtered off and titrated with potassium permanganate. The dif-
ference of the two determinations gives the quantity of magnesia
present. D. B.
Detection of Anhydrous Glucose mixed with Refined Cane-
sugar. By P. Casamajor {Ghem. News, 47, 252— 253).— If ordinary
glucose is mixed wi^h the cane-sugar, and the adulterated sugar is
moistened and stirred with water, the glucose will appear as chalky
white specks in the translucent mass of wet sugar ; if, however,
crystalline glucose is present it cannot be detected in this manner, as
it also becomes translucent when moistened. Washing the suspected
sugar with a saturated solution of glucose in methyl alcohol is not
an efficient method, some of the glucose being dissolved. The optical
saccharometer may be used to determine if starch glucose is present
in a sugar, for by observing the deviation immediately after getting
the solution ready for the saccharometer, and repeating the observa-
tions at sufficiently wide intervals of time, the presence of dextrose in
any notable quantities will be indicated by a decrease in the deviation.
From experimental results the author points out that dextrose does
not prevent good results being obtained by inversion, provided that
the observations both before and after the inversion are made w^hen
the deviation power of the dextrose is constant. The author recom-
AXALYTICAL CHEMISTRY. 885
mends the following as a simple and efficient test for the presence of
either anhydrous or hydrated glucose. Equal quantities of the sus-
pected sugar and of unadulterated refined sugar are respectively put
into two beakers, moistened with water, stirred to get them uniformly
wet, and the beakers are then placed in warm water ; in about ten
minutes the pure sugar will appear more moist than when cold, whilst
the other sugar if it contain sufficient glucose, will have sunk into a
pasty sticky mass. On cooling, the pure sugar will become drier again,
whilst the impure sample will remain sticky. Immersion in warm water
is not necessary, but it makes the effect immediate and more marked.
This test is founded on the property which cane-sugar has of forming
viscid compounds with many substances, among which are anhydrous
and hydrated dextrose. Molasses is an example of these compounds.
As long as a mixture of cane-sugar and dextrose is dry, it looks all
right, but as soon as sufficient water is added, the substances which
form the molasses can combine, and enough viscous syrup is formed to
produce the permanently pasty mass described above. The sugar-maker
knows this, and is always careful to dry his sugar before mixing with
glucose. In fact adulterated sugars always come into commerce drier
than refined sugars of the same grade, which are always sold moist.
Fehling's solution is also a useful indicator for detecting glucose ; an
ordinary refined sugar will rarely show more than 5 per cent, of
glucose, so that any considerable excess over this quantity may be
looked upon as adulteration. D. A. L.
Detection and Estimation of Phenols and Hydroxy-acids in
the Urine. By E. Baumann (Zeitschr. Physiol. Chem., 6, 183 — 194).—
A summary of the several methods employed by tho author in his
previously published researches on this subject, which have proved
best adapted for the separation and estimation of the several urinary
constituents in question. D. P.
Detection of Albumin in Urine. By A. B. Haslam (Chem.
News, 47, 239 — 240). — The suspected urine is mixed with a few
drops of sodium chloride solution, and then some iron chloride is
carefully poured on so as to form a layer ; the appearance of a whitish
cone shows the presence of albumin. If phosphates are present the
urine must be rendered acid with acetic acid before applying the test.
This test is much more delicate than the old nitric acid test.
D. A. L.
Detection of Rice-meal in Buckwheat Flour. (Dingl. pohjL /.,
248, 219.) — On warming 1 gram of meal with 2 c.c. of strong caustic
potash solution until the mixture assumes a pasty consistence, rice-
meal gives a yellow colour which turns white when hydrochloric
acid is added, whilst the paste formed with buckwheat flour has a
dark green colour and turns red with hydrochloric acid. On treat-
ing rice-meal with alcoholic hydrochloric acid, the liquid remains
colourless, whereas it assumes a brownish colour with buckwheat
flour. D. B.
VOL. XL IV. H 0
^86
ABSTRACTS OF CHEMICAL PAPERS.
Technical Chemistry.
Contributions to the Knowledge of Sewer Gases. By F.
Fischer (Dingl. polyt. /., 247, 601— 504).— It is known that the
antagonists to the sewer system maintain that through the gases in the
sewers, epidemic diseases, viz., cholera, typhus, diphtheria, scarlatina,
&c., are propagated, without, however, attempting to prove their
assertions by comparative tests of the gases. The author has made a
series of investigations on the gases from the sewer in the Gustav-
Adolfstrasse in Hanover. He found that during 14 months the pres-
sure of the air in the sewer only in one instance exceeded that of a
water-column 9 mm. in height, whilst the maximum external pressure
towards the sewer amounted to 10 mm., so that a water-column 20 to
25 mm. high would have prevented the entrance of sewer gases into
the houses. The variations of pressure are considerably lessened
when sewers are provided with ventilators. With regard to the com-
position of the gases, the author found CO2 = 0*9 to 1*8 per cent.,
O = 19*3, NH3 and H2S = traces. By comparing these results with
the analyses of the gases from other towns (see Renk, Kanalgase^ p. 13),
illustrated by the following table, it will be seen that the sewer gases
from towns worked by the carriage system are often more contaminated
with noxious impurities than the gases from towns containing pro-
perly constructed sewers : —
Sewers in
CO2.
Per cent.
O.
Per cent.
NH3. Mgri
per lb.
HoS.
Per cent.
London, according to
Letheby
London, according to
Miller
Paddington, according
to Russell
Boston, according to
Nichols
Munich, according to
Beetz
Paris, according to
G-lauboy
Paris, according to
Levy
Hanover, according to
Fischer (winter) . . .
Hanover, according to
Fischer (summer) . . .
0-532
0 -106—0 -307
0-51
0 -082—0 -24
0-217— 0-443
2 -3—3 -4
0-9-1-8
2 -1—3 -53
20 7
17-4
19-3
16 -9—18 -2
much
small amount
7—168
0 09
traces
traces to 50
traces
1-25
0 to traces
traces
Whilst doubting whether the spreading of diseases is at all efFectec
by the sewer gases, the author maintains that the contents of sewers
are at least no more injurious than those of cesspools ; moreover, the
gases ascending from dry closets must be the most harmful.
D. B.
TECHNICAL CHEMISTRY. 887
Working of Sulphuric Acid Chambers. By H. Pemberton,
JuN. {Chem. News, Al, 266 — 267). — The author has made observa-
tions extending over several years, and on chambers which have been
doubled in number and capacity during the time. From numerical
data gathered in these observations, he finds that when the cham-
bers are working well, the percentage of nitre used multiplied into
the capacity in cubic feet per pound sulphur burnt, gives a nearly
constant product — about 280; thus a chamber of 280 cubic feet
capacity per pound sulphur will require 1 per cent, nitre, one with
140 cubic feet 2 per cent., one with 14 cubic feet 20 per cent., and so
on. Therefore the chamber capacity in cubic feet, multiplied by the
per cent, nitre used, and divided by the number of pounds of sulphur
burnt daily, should give near about 280 (or better still 300) if the
chambers are working well, and any number much lower than this
would indicate a low yield of acid. The nitric acid introduced into
the Glover tower is taken into account in these remarks. These
results are from the author's experience with this set of chambers
only. D. A. L.
Notes on the Soda Industry. By A. Scheurer-Kestner {Bull,
Soc. Chim. [2], 19, 409—423).—!. Loss of Sodium in the Le Blanc
Process. — Eleven years ago the author established that the loss of
sodium experienced in the Le Blanc process is proportional to the
quantity of chalk employed. It is thus to the interest of the manu-
facturer to avoid excess of chalk, but at the same time to use a quantity
sufficient to ensure perfect whiteness of the finished product. The
author put forward the hypothesis that the loss is occasioned by the
formation of a sparingly soluble calcium-sodium carbonate ; this view
has been confirmed by the researches of Jurisch, Watson Smith, and
Liddle and Reidemeister. The latter has found in the lixiviating vats
crystals of the composition of gay-lussite, Na2C03,CaC02,5H20, a
compound insoluble in sodium carbonate and hydrate, mixed in the
proportion in which they occur in the crude lye ; it dissolves slowly
in water, the crystals becoming opaque from the ready dissolution of
the sodium carbonate.
Reidemeister has further shown that gay-lussite is formed not
only in the lixiviating vats, but also in the anhydrous state in the soda
pans during fusion ; it probably also occurs in the residues, and the
deposit of the caustification process, but its state of division prevents
its detection and isolation.
II. Fresence of Vanadium, Fluorine, and Phosphorus in Crude Soda-
lyes. — In 1864 Rammelsberg detected the presence of vanadium and
of sodium phosphate, N'a3PO4,10H2O, in crude soda-lyes; Baomgarten,
a short time after, found fluorine existing as a double sodium phos-
phate and fluoride, NaF2Na2P04,I8H20. From the red mother-liquors
in the manufacture of the carbonate and hydroxide, Rammelsberg
separated crystals, either white, or red from the presence of iron,
which proved on analysis to be identical with Baumgarten's com-
pound ; they also contained about 1*2 per cent, of vanadic acid. It
is probable that the chalk and coal furnish the vanadium and phos-
phorus ; the origin of the fluorine is quite uncertain.
888
ABSTRACTS OF CHEMICAL PAPERS.
• ITI. Loss of Sodium in Caiistification. — The author has previonsly
shown that the loss of sodium in caustification arises from the same
cause as the loss of sodium in the Le Blanc process, i.e., the formation
of a double sodium calcium carbonate. Analyses by Jurisch (Chem.
Indust.^ 1880, 377) would lead to the conclusion that this loss is less
the greater the excess of lime ; but this statement is in direct con-
tradiction to experience. According to Jnrisch, the density of the
liquor for caustification should not exceed 14° Baume ; the author,
however, points out that under ordinary atmospheric pressure it is
impossible to caustify denser liquors than these, for the reaction
became incomplete owing to a commencement of a reverse chemical
change. The author also criticises Jurisch's statements as regards
the amount of combustible substance required for the evaporation of
caustic soda of various densities.
In the remainder of the paper no new chemical facts are detailed ;
the author quotes, and offers some critical remarks upon Weldon's
statements as regards the extraction of ammonia from coal, the use
of pyrites from Rio Tinto for the manufacture of sulphuric acid, and
the total production of sodium carbonate from the Le Blanc and the
ammonia processes throughout the world. Y. H. V.
Analyses of Bauxite. By L. Mayer and O. Wagxee (Dingl.
folyt. /., 248, 213). — The samples of bauxite, Nos. 1 to 8, were taken
from Feistritz in the Wochein, No. 9 from Pitten near Wiener-
Neustadt. The latter, though resembling bauxite in physical pro-
perties, is in reality clay-ironstone : —
.2
n
11
1
a
11
6
6
i
d
q
s
S
d
6
1-
d
p. c.
p. c.
p. c.
p. c.
p. c.
p. c.
p. c.
p. c.
p. c.
3
2-33
13-86
29-80
3-67
44-76
2-75
0-8i
1-47
2
1-03
27-85
43-22
14-39
10-43
—
1-61
—
113
3
0-84
27-61
38-38
18-29
12-32
—
1-66
—
0-79
4
0-79
26-80
40-60
22-70
6-66
—
2-10
—
0-35
5
1-30
27-70
50-38
11-68
8-34
traces
traces
traces
0-61
6
1-34
23 12
33-86
25-69
12-41
2-42
traces
—
0-53
V
1-31
23-81
46-18
22-05
4-82
—
0-89
0-66
8
0-95
20-83
62-10
6-11
5-06
2-01
3-20
traces
traces
9
117
4-75
21-80
3-75
60-10
"~~
6 06
2-49
traces
Bauxite No. 1 had a white colour, Nos. 2 to 5 were pale yellow, and
Nos. 6 to 9 red. D. B.
Clay and Earthenware Goods. {Dingl. 'pohjt. /., 248, 167—
171.) — Some specially selected specimens of best American clays were
investigated by Bischof. According to Cock, State Geologist, New
Brunswick, they had the following composition : —
TECHNICAL CHEMISTRY.
889
No. of sample.
4.
5.
AI2O3
SiOo
Sand ,
MgO
CaO
FesOg
K2O
Loss by ignition. . ,
Hygroscopic water,
TiOs
41-10
38-66
3 10
0-74
0-46
13-55
1-00
1-20
40-72
34-10
6-50
0-39
2-49
1-91
12-35
1-35
40-09
43-93
0-60
0-88
0-20
13-80
0-50'
39-14
44-20
0-20
0-45
0-25
14 05
0-90
1-05
38-81
44 14
0-80
0-11
trace
114
0-17
12-97
1-23
1-30
38-34
42-90
1-50
0-86
0-M
13-50
110
1-20
No. of sample.
AI2O3
SiOs
Sand
MgO
CaO
FeoOg
K2O........
Loss by ignition . . ,
Hygroscopic water,
TiOg
38-24
43-90
1-10
0-11
trace
0-96
0-15
14 10
0-70
1-30
8a..
37-02
42-95
3-85
0-88
0-20
12-60
0-80
1-70
8b.
1-14
9a.
36-35
40-10
0-40
0-13.
0-15
0-14
22-60
9b.
38-38
45-45
0-77
0-07
013
0-18
0-22
15-00
No. 1. Sayre and Fischer's ISTo. 1. Fire clay. Brownish-grey.
Refractoriness (R.) above 50 per cent.
No. 2. Hokessin, Delaware. Washed kaolin clay. White with
brownish tint. R, approaching 60 per cent.
No. 3. Evens Mine, Howard County, Missouri. Crnde clay. Light
brown, hard, and firm. R. above 50 per cent.
No. 4. E. F. and P. M. Roberts, selected fire-clay. Brownish.
R. above 50 per cent.
No. 5. H. Cutter : ware clay. Bluish-grey. R. above 50 per cent.
No. 6. Geo. Such : washed clay. Brownish-green. R. above 30
per cent.
No. 7. H. Butter : fire-clay. Bluish-grey, very hard. R. above 50
per cent.
No. 8. Hawe's flint clay. Johnstown, Penn. Bluish-grey. R.
partly under 20 per cent., and not much more than 10 per cent.
No. 9. Huron : porcelain clay. Lawrence County. White, with
yellow spots. R. above 60 per cent.
By subjecting these clays to the melting heat of platinum, Bischof
found that, with the exception of No. 8, all retained their form, exceed-
ing therefore the standard of 50 per cent, in refractoriness. The
character of clay No. 8 did not coincide with the American analysis
(8a). Bishof therefore analysed samples 8 and 9 (8b and 9b), and
his results differed widely from the numbers given by Cock. It is
3 0 2
890 ABSTRACTS OF CHEMICAL PAPERS.
questionable, therefore, whether the remaining analyses are altogether
correct.
Seger has made an extensive series of experiments on glazes. He
finds that quantitatively the glaze is out of all proportion as compared
with the clay mass, so that its properties are affected to a great extent
by the composition of the clay substance forming the under layer.
The extreme limits of the composition of the various glazes employed
are for common earthenware, and the fine French Faience R-0,l"5Si02
to ROjSSiOj. For the harder German and English materials the
limits may be expressed by the formulae E;O,0*lAl2O3,2'5SiOa to
RO,0*4iAl2O3,4-5SiO2, whilst for porcelain glazes the formulas
RO,0-5Al2O3,6SiO2 to RO,l-25Al203,12Si02,
may be assumed. The main difficulty experienced in the preparation
of a faultless composition of glaze and clay substance lies in the dif-
ferences of expansion by heat.
In order to obtain coloured glazes, the material is treated with
coloured metallic oxides ^ or the colourless fluxes used in the prepara-
tion of the glazes are replaced by equivalent quantities of coloured
metallic oxides. D. B.
Process for Preparing Bichromates. (Dingl. pohjt. /., 248,
90.)- — According to Pontius, the melt obtained by treating chrome-iron
ore with lime and potash is lixiviated with the mother-liquor of
preceding operations, which contains sufficient potassium carbonate
to convert the calcium chromate in the melt into the potassium
salt.
This liquor is then treated with carbonic anhydride in closed iron
vessels at a pressure of several atmospheres, potassium dichromate and
bicarbonate being formed : 2K2Cr04 + 2CO2 + H2O = KjCrzOT +
2HKCO3. The sparingly soluble dichromate is allowed to settle and
separated from the mother-liquor. The latter is then used for lixi-
viating further melts of chrome-iron ore. The melt can be treated
also with warm water in closed agitators, carbonic anhydride being
pumped in. Thus the normal potassium chromate produced is con-
verted into the dichromate, with simultaneous formation of potassium
carbonate, whilst the normal calcium chromate is changed into the
dichromate, which in the nascent state is transformed together with the
potassium carbonate into calcium carbonate and potassium dichromate.
The latter is separated in the usual manner. Sodium and calcium
dichromates may be obtained in a similar way. Magnesium dichro-
mate is produced from the calcium salt by adding the corresponding
amount of magnesium hydroxide or carbonate, and treating the mix-
ture with carbonic anhydride. D- B.
Scale of Hardness of Metals. (Dingl polyt. J., 248, 41.) —
GoUner has determined the hardness of the principal metals which
are technically useful, made in the following manner. The various
test pieces were provided with a polished surface, and a hardened pin
of cylindrical form, and drawn out to a conical point, was moved to and
fro an equal number of times, the pressure and distance being the same
TECHNICAL CHEMISTRY. 891
in all trials. The action of the pin on the polished surface was then
observed.
The following table gives the succession of metals arranged accord-
ing to their hardness : Refined lead, pure tin, slag lead, soft copper,
refined copper (cast), soft bronze (85 Cu, 10 Sn and 5Zn), cast-iron
(tempered), wronght-iron (fi^brous), cast-iron (granular and light
grey), cast-iron (re-cast with 10 per cent, malleable iron in the rever-
beratory furnace), soft ingot iron (0*15 per cent. C), ingot steel (not
hardened, 0'45 per cent. C), ingot steel (not hardened, 0*96 per cent.
C), crucible steel (hardened, blue), crucnble steel (hardened, violet to
orange-yellow), crucible steel (hardened, straw-yellow), hard bronze
(83 Cu -f 17 Zn), and crucible steel (chilled). D. B.
Extraction of Lead from Ores occurring in the Upper Hartz.
(Dingl. polyt. J., 248, 124 — 128.) — These ores are treated at the
Altenau works. If the percentage of lead is small, the ores are asso-
ciated with comparatively large quantities of quartz and zinc blende,
and cannot be treated by the precipitation method usually adopted in
the Upper Hartz.
Clausbruch has successfully introduced the following process. The
ore to be treated, containing 54 to 55 per cent, lead, 0*08 silver, 0'9
copper, 7 to 8 zinc, and 14 to 18 silicic acid, is roasted in reverbera-
tory furnaces with single hearth and provided with 15 working doors
on each side, of which 13 are used for working the ore, the remainder
communicating with the pit and the fire-place. The hearth is 19 m.
long and 3 m. wide, and the crown of the arch is located 0*5 m. above
the bottom of the hearth, which has a rise of 10 cm. from the fire bridge
to the flue. Between the flue and the chimney a system of condens-
ing chambers is arranged. The fire-bridge and hearth pit are cooled
by air-flues. The smelting of the roasted ore is effected in pit fur-
naces having two tuyeres, the back of the furnace being surrounded
by a cold water-jacket, which protects it from the corrosive action of
the basic charge. The furnace, which is admirably adapted for smelt-
ing these ores, is described in detail, as also the working of the same
and the fluxes most profitably used. It may be mentioned that this
process effects a saving of 6'51 marks per five tons of material
operated on, whilst 98*5 per cent, of the total lead introduced into the
furnace comes out in the form of furnace lead without the use of a
blast. Owing to the regular division, and the delivery of the furnace
gases at a considerable height, the injurious action of the fumes on
the surrounding forests is lessened to a great extent, a circumstance
which is of extreme importance to the smelting industry in the
Hartz. D. B.
Process for Preparing Litharge and Red Lead. (Dingl. polyt.
J"., 248, 220.) — According to Lewis, the fumes from lead smelting
furnaces are mixed with carbonate or caustic soda and roasted or
boiled. The whole is then allowed to settle, washed to free it from
sodium sulphate, and smelted to form either litharge or red lead. If
the fumes contain zinc, the latter must first be dissolved out with
sulphuric acid. D. B.
892 ABSTRACTS OP CHEMICAL PAPERS.
Spontaneous Combustion of Coal. (Bingl. pohjt. J., 247, 506).
While Durand explains the spontaneous ignition of coal in the pit by
the presence of pyrites which, becoming heated, gives rise to combus-
tion, Fayol maintains that the first and main cause of spontaneous
inflammability is the absorption of oxygen by the coal, accelerated
by fine division and high temperature. The ignition of fuel in the
form of dust occurs at the following temperatures: Lignite, 150°;
Cannel coal, 200° ; coking coal, 250°, and anthracite, 300° and over.
It is shown that coal absorbs oxygen and becomes heated more readily
than pyrites, and that the addition of the latter to coal does not aid
the ignition of coal-dust. D. B.
Italian Red Wines. (Dingl. polyt. J., 248, 219.)— Three kinds
of red wines from the Chianta Valley in Tuscany, known as " Chianti
wines," were analysed by Kayser, viz., Stra Vecchio of 1878 (Al),
Vecchio of 1880 (B), and Vino Nuovo of 1881 (C). 100 c.c. con-
tained—
A. B. C.
Alcohol 9-5 c.c. 11-6 c.c. 117 c.c.
Extract 2-15 g. 2-52 g. 2*50 g.
Mineral ingredients 0-21 0'21 0 24
Acidity, calculated on tar-
taric acid 0-532 0'600 0-63
Pyroracemic acid 0-024 0-027 0*029
Tartaric acid — — —
Sulphuric acid 0-014 0*013 0*014
Phosphoric acid 0-028 0*030 0*031
Lime 0-007 0*008 0*008
Magnesia 0*022 0*020 0*022
Potash 0*087 0*084 0*090
Sugar 0-105 0-240 0-200
Glycerol 1*000 1*200 1*400
The absence of tartaric acid, which appears to be replaced by pyro -
racemic acid, is remarkable. D. B.
Contribution to the Problem of Frothy Fermentation.
By P. Pampb {Dingl. polyt J., 248, 76—83 and 128— 133).— Several
efforts have recently been made to solve the question of the frothing
which occurs in the fermentation of potato mash, and to suggest a
ready means of preventing the same. In 1879 an extensive investi-
gation was conducted by the German Society of Distillers ; the
results, however, were not very satisfactory. It was recommended to
change the mashing material, to add oat malt, and treat the mash
with steamed maize at a high pressure, but the reason of the frothing
was not explained. The author has studied this subject very
minutely, and the result of his experiments may be summed up as
follows : —
When the frothing occurs, the cohesion of the fermented liquid
is considerably less than is the case when the normal conditions
of fermentation exist. The main reason of this lies in the peculiar
I;
TECHNICAL CHEMISTRY. 893
form in whicli the nitrogenous compounds are present, also in the
amount of the latter. This peculiarity may be due to the fact that
the nitrogenous compounds were contained in the raw material in
such a form as to diminish the cohesive power, and served, therefore,
as direct yeast nntidment (asparagine and other amides). By the
steaming process the nitrogenous compounds are transformed so as
to be no longer suitable as direct nutrients. When potatoes are
steamed imperfectly, which takes place when they are frozen, frothy
fermentation at once sets in, as this transformation has not occurred.
In addition to this, the nitrogenous compounds are brought into the
diffusible condition by special ferments. In most cases, however, the
frothing is due to the circumstance that the constitution of the yeast
is not in relation to the remaining conditions in the distillery ; either
the formation of yeast is too large, and sugar is unnecessarily consumed
for the production of yeast-cells, or it is too small, in which case
sugar remains in the mash in an unfermented state. D. B.
Process for Preparing Orcinol. By A. Winther (Dingl. pohjt.
J., 248, 133— 135).— Orcinol {Ger. Pat, 20713, Oct., 1881) can be
produced from those derivatives of toluene containing substituted
groups in the meta-position, which are convertible into hydroxy 1-groups,
For the preparation of orcinol from metadinitrotoluene, the latter is
first transformed into raetanitrotoluidine by means of alcoholic ammo-
nium sulphide, precipitation by water, solution in hydrochloric acid,
and reprecipitation by ammonia. The metanitrometatoluidine is then
dissolved in a warm mixture of equal volumes of sulphuric acid and
water, and cooled down, when the sulphate crystallises out. A solu-
tion of potassium nitrite is now added until all the sulphate has been
redissolved. The solution of the diazo-compound thus obtained is
diluted with water and heated, metanitrometacresol being formed,
which by crystallisation from the separated oil, as well as from the
ethereal extract by water, is obtained in the pure form. It is reduced
by tin and hydrochloric acid, and the metamidometacresol is con-
verted into the dihydroxy-compound by means of the diazo-reaction.
From the solution the orcinol is obtained by evaporation or by extrac-
tion with ether. D. B.
Adulterated Soaps. (Dingl polyt. /., 248, 92.)— A firm in New
Isenberg has recently introduced into commerce, at a profit of from
300 to 1200 per cent., a heavily weighted palm-oil soap, which dries
up to a small residue. A soap of English make has been recently
imported into Germany under the name of " Sinclair's cold water
soap," at a cost of 80 marks per 100 kilos. It is described as equal
in efficiency to thrice its weight of ordinary soap. Borcheot has
analysed this soap, and finds that it consists of about 70 parts tallow,
30 parts bleached palm oil, and 25 resin, boiled together, then mixed
with 3 to 6 parts Venice turpentine. Two days after about 8 per
cent, sodium silicate is added. Other analyses showed 1 per cent, talc
instead of sodium silicate. The soap known as " Army blue mottled
soap " consists of palm and cocoanut oils, coloured with ultramarine,
and heavily loaded with lyes. D. B.
894 ABSTRACTS OF CHEMICAL PAPERS.
Use of Soap in Dyeing. By Lauber and A. Steinheil (Bingl.
polyt. J. J 247, 507 — 508). — For the preparation of soap, the follow-
ing process is successfully being worked at the Zawiercier works : —
360 litres of water and 69 kilos, of ley at 36° B. are boiled, and
140 kilos, of oleic acid added, with constant agitation, until a
uniform mixture has been obtained. 3120 litres of water are then
added, and the whole is well stirred until a clear soap solution has been
obtained. Using the above proportions, the oleic acid was in some
cases found to be in excess, and more soda had to be used. In
Bull, de Mulhouse^ 1882, 142, Scheurer has published an interesting
article on oleic acid soap and its influence as a clearing agent on
colours. A soap used for clearing purposes should produce a per-
fectly white ground, on which the colour then appears much more
brilliant, and should not attack the colour. On comparing the dif-
ferent soaps of commerce from this point of view, Scheurer had to
give the preference to Marseilles soap. He was further able to prove
that the so-called alkaline soaps obtained with oleic acid simply con-
tain free oleic acid and alkali, because the saponification has not been
completed, owing to insufficient boiling. Oleic acid soaps are always
more alkaline than others, a circumstance which is due to the fact
that owing to the strong affinity of oleic acid, the saponification is
effected in less time than in the case of soaps from other fatty acids.
Consequently these oleic acid soaps were not treated sufficiently long
to effect a perfect union of the acid and soda. This combination may
be hastened by an increase of temperature or pressure. D. B.
Mordants used for Fixing Artificial Colouring Matters.
(Dingl polyt /., 248, 39.)— Kochlin (Bull, de Mulhouse, 1882, 266)
discusses the application of various mordants for fixing artificial
colouring matters, with the following results : —
Phloxine gives bad results with aluminium acetate, a bright cherry-
red colour with a mixture of aluminium and magnesium acetate, a
pink with calcium and aluminium acetates, and an amaranth-red with
chromium and magnesium acetates.
Ponceau 3. Bright red with a mixture of aluminium and magne-
sium acetate, red resembling garancine with chromium and magnesium
acetates.
Primrose. Pink with blue shade, resisting soaps when fixed with
chromium acetate.
Magenta. The best result is obtained with chromium acetate.
Safranine. The same.
Eosine. Dark red colour with chromium acetate, not permanent if
fixed with aluminium acetate.
Picric acid. Yellow with a mixture of aluminium and magnesium
acetate, does not stand soaping ; no result with aluminium or chro-
mium acetates.
Orange No. 2 is fixed by chromium and magnesium acetat:es ; chro-
mium acetate per se gives a brown colour, magnesium acetate per se
does not fix the colour.
Phosphine gives with aluminium acetate a buff colour, not attacked
by hot soap baths.
TECHNICAL CHEMISTRY. 895
Blue 6 B gives a deep blue with chromium acetate, a lighter colour
with magnesium and chromium acetates, resisting soaps.
Methylene blue. Dark colour with chromium acetate ; stands soap-
ing if fixed by magnesium and aluminium acetates.
Indigo carmine requires aluminium acetate, but is not permanent.
Malachite green. The finest shades are obtained with a mixture of
aluminium and magnesium acetate.
Coerulem, Violet Poi,rrier, and Orseille. With chromium acetate.
Roccellin. Aluminium acetate or a mixture of chromium and
magnesium acetates gives a brick-red colour, which is attacked by
soaps.
Dinitronaphthol does not dye.
Bismarck brown gives a stable colour with chromium acetate.
Grey coupier and induline require chromium acetate, or the latter,
mixed with magnesium acetate. D. B.
Novelties in Dyeing and Calico-printing. (Dingl. polyt. /.,
248, 83— 86.)— Scheurer {Bull, de Mulhouse, 1882, 42) fixes colour-
ing matters by reducing potassium chromate with sodium thiosul-
phate or sulphite. The following is the strongest colour which it is
possible to prepare ; it is, however, not durable, and can be thickened
only with difficulty : — 200 grams normal potassium chromate, 380
sodium thiosulphate, and 420 starch paste. To fix the colour it is
treated with a mixture of 50 grams normal potassium chromate,
95 sodium thiosulphate, 755 thickening, then printed, steamed, and
washed. Schafer (ibid., 43) draws attention to a peculiar incident
which occurred at DoUfus, Mieg, and Co.'s works in oxidising by
the hanging process. The goods dyed with garancin exhibited
streaks and coloured spots after hanging, showing they had under-
gone an accidental mordanting operation. This peculiarity is attri-
buted to the soot collected on the roofs of the dye house, which was
blown through the spaces between the tiles by the wind.
Kochlin (ibid., 63) mentions that when aniline-black is developed
at a temperature above 70°, it does not grow darker, irrespective of
the mordant used as oxidising agent, provided however that the
amount of the latter and the time during which the temperature is
maintained are sufficient. All goods developed in the cold undergo a
subsequent darkening.
Lauth recommends to complete the dyeing with aniline-black by
passing the fabric through hot solutions of salts of chromium, copper,
iron, mercury ^er se or in conjunction with chlorates, ferrocyanides, or
chromates. Schmidt (ibid., 97) produces chrome yellow or orange
by steaming. Barium chromate is readily decomposed by lead
nitrate when the mixture is heated ; a steam colour may therefore be
obtained from a thickened mixture of lead nitrate and barium chromate,
prepared by precipitating normal potassium chromate with barium
chloride. Although the conversion is imperfect, and the colour not
intimately fixed, it is possible, owing to the fact that one of the re-
agents exists in an insoluble form in the dye, to obtain a good yellow
which strongly resists soaping, by employing concentrated colours
of perfect smoothness and homogeneity, e.^., 250 grams gum traga-
896 ABSTRACTS OF CHEMICAL PAPERS.
canth (200 grams per litre), 250 lead nitrate, 550 barium cliromate
(50 per cent.), and 50 water. To prepare chrome-orange, Schmidt
adds to lead nitrate a certain quantity of lead acetate. The following
receipt is given for chrome-orange: — 500 grams gum tragacanth
(200 grams per litre), 500 lead nitrate, 750 lead acetate, and 1400
barium chromate (50 per cent.). By reducing the quantity of lead
acetate, yellower shades are produced.
Kochlin uses finely-divided coal fixed with albumin for calico-
printing, in place of lampblack. D. B.
Utilisation of Battery Residues. (Dingl. polyt /., 248, 89.) —
The residues from the batteries used in the telegraph department of
the German Empire are sold annually by public tender. The pur-
chaser takes possession of the residues at fixed prices without guarantee
as to the percentage of metals (zinc, lead, and copper) contained in
residues. Experience has shown that the proportion between the
amounts of copper and zinc recoverable from the residues is within
narrow limits. Previous to the delivery, which takes place twice a
year, the residues are washed in river or rain-water, to remove all
salts mixed therewith. The sale is said to realise 22 per cent, of the
total expenditure of battery materials. D. B.
Preparation of Terra Cotta Lumber. (Dingl. polyt. /., 248,
179.) — Gillman mixes 1 part pure clay with 1 to 3 parts sawdust and
the requisite amount of water, presses the mass into large blocks,
dries the latter and burns it for two days. The blocks are then cut
with circular saws into the desired forms. Terra cotta lumber is in-
combustible ; resists acids and atmospheric influences ; is a bad con-
ductor of heat, sound, and electricity; has only half the weight of
bricks, can be sawn, cut, and planed ; and combines intimately with
lime, gypsum, &c. D. B.
Polychrome Varnish for White Metal. (Dingl. polyt. /., 248,
220.) — According to Puscher, 30 grams of crystallised cupric acetate are
ground to a fine powder and kept in thin layers in a warm place until
the water of crystallisation and a large proportion of the acetic acid
have been volatilised. The light brown powder is then mixed with
100 grams of gum copal, and heated to 75°. This mixture is painted on
white metal and the colour developed by heating in a drying box. In
consequence of the reduction of the dissolved cupric oxide to cuprous
oxide, green, yellow, orange, or reddish colours can be produced,
according to the temperature and time of heating. D. B.
Process for Preparing Printing Ink. (Dingl. polyt. J., 248,
1)2.) — Schmidt Brothers recommend manganese dioxide instead of
lampblack for the preparation of printing and marking ink. Waste
paper which has been printed with this ink is said to be suitable for
the manufacture of white paper. D. B.
i
897
General and Physical Chemistry.
Electro-dynamic Interference of Alternating Currents. By
A. Oberbeck (Compt. rend., 96, 1498 — 1499). — A claim for priority.
Distortion of Polarised Electrodes. By Gout (Compt. rend.,
96, 1495 — 1497). — ^When a narrow band of thin gold foil varnished
on one side is used as the positive electrode in the electrolysis of a
solution of copper sulphate, the negative electrode being of copper,
the positive electrode becomes polarised, and the gold foil is distorted
and becomes concave on the unvarnished side. Similar phenomena
are observed with a narrow riband of gold coiled into a helix. If the
current is broken, the electrode returns to its former position. The
distortion commences immediately the current is completed, and
attains its maximum in less than a second. The introduction of a
great resistance into the circuit slightly retards the polarisation and
distortion. If the gold is previously covered with a film of copper,
there is no distortion until all the copper has dissolved away. Similar
distortion is observed with electrodes of other metals in other solu-
tions. It is particularly well marked in the electrolysis of man-
ganese nitrate, and if the circuit is broken and the two electrodes are
put into communication with each other, the curved electrode returns
to its original position, and then curves in the opposite direction. In
this case there is a deposit of manganese dioxide on the positive
electrode.
If a metal is deposited on an electrode, or if a deposit is dissolved
away, the electrode experiences a displacement which is doubtless due
to the mechanical action of the deposit, C. H, B.
Pyroelectricity of Quartz. By C. Friedel and J. Curie (Compt.
rend., 96, 1262—1269, and 1390— 1395).— These papers are mainly
a resume of results previously obtained (Bull. Soc. Min., 1879, 31),
and a criticism of Hankel's papers (this vol., 412, 540). The authors
have repeated Hankel's experiments, and have been unable to
recognise the vortical distribution of electrical tension on the faces of
the crystals, and they find that the rhombic axes instead of being
neutral points, are electrified positively. They also find that when a
crystal is surrounded with metallic filings, and heated in a metallic
case, the metallic filings cool more rapidly than the crystal, and
exercise a cooling effect on the latter, which consequently cools irre-
gularly ; the outer layer of the crystal being cooled most rapidly,
contracts and exerts pressure on the interior, which is at a higher
temperature than the mean temperature of the crystal, and also on
the uncovered faces, which are compressed laterally, and consequently
expand in a direction at right angles to the compression, i.e., in the
direction of the lateral axis of the prism. The positive electricity
developed on the rhombic faces, and the negative electricity developed
on the opposite faces, as observed by Hankel, are due to expansion
VOL. XLIY. 3 p
898 ABSTRACTS OF CHEMICAL PAPERS.
along the axes of hemimorphism, produced by the pressure resulting
from irregular cooling. The production of internal tensions under
these conditions is proved by heating a cylinder of glass in the same
way, and examining it with polarised light. When a qaartz crystal
is heated and then allowed to cool gradually and regularly by exposure
to air, there is no development of electricity. The authors' results
agree with those of Rontgen. C. H. B.
Specific Heats of Gases at High Temperatures. By Vieille
(Compt. rend. J 96, 1358 — 1361). — The temperature calculated from
the maximum pressure developed in closed vessels by the explosion of
cyanogen and oxygen in the proportions necessary to form carbonic
oxide, constitutes an inferior limit of the temperature of combustion.
A small quantity of the carbonic oxide is decomposed into carbon and
carbonic anhydride, and another small quantity reduces the water
vapour present in the gases. Analysis of the products, however,
shows how far these changes have taken place, and enables a maxi-
mum limit of temperature to be calculated. The quotient of the
inferior and superior limits of temperature gives a superior limit for
the specific heats at constant volume of the gases nitrogen, hydrogen,
oxygen, and carbonic oxide. By the explosion of mixtures of
cyanogen and oxygen in the proportions necessary to form carbonic
oxide, with varying quantities of nitrogen, the author has obtained
the following maximum values for the mean molecular heats of
hydrogen, oxygen, nitrogen, and carbonic oxide : —
Temperature.
Molecular heat
Ordinary
4-8
3100°
6-30
,3600
7-30
4400
8-10
These values are based on the assumption that the laws of expan-
sion and compressibility hold good at the high temperatures.
C. H. B.
Critical Point of Gases. By J. Jamin (Compt. rend.^ 96,
1448 — 1452). — The author defines the critical point as the tem-
perature at which a liquid and its saturated vapour have the same
density (comp. Abstr., 1862, 267). In the experiments of Gagniard-
Latour the disappearance of the meniscus at the critical point
is due to the fact that the liquid and its vapour have acquired
the same density in consequence of the compression of the vapour
and the expansion of the liquid. There is no interruption of
the general law of evaporation. The liquid remains at its boiling
point and point of maximum vapour-tension, but is invisible because
it mixes with and floats in its own vapour, both having the same
density. As the temperature rises, the vapour-tension increases until
the whole of the liquid is volatilised, and after this point, but only
after this point, the vapour ceases to he saturated, and passes into the
state of gas. Since there is no change of volume at the critical point,
the vapour has no latent heat. In other words, at the critical point
the liquid does not differ from its vapour in tension, density, heat of
GENERAL AND PHYSICAL CHEMISTRY. 899
constitution, appearance, nor in any otber property by which they
can be distinguished. The same explanation holds good in the case of
Andrew's experiments.
In one of Cailletet's experiments a mixture of 1 vol.. air with 5 vols,
carbonic anhydride, was compressed nntil the carbonic anhydride
liquefied, but on increasing the pressure to. 150 — 200 atmospheres,
the liquid entirely disappeared. According to the author's view, the
volume of the liquefied carbonic anhydride undergoes little or no
further diminution, but the volume of the air diminishes continually,
and its density consequently increases until it becomes equal to that
of the liquid, and at this point the meniscus disappears. If this view
be correct, the substitution of hydrogen or some other light gas for
air should render a higher pressure necessary to cause the disappear-
ance of the meniscus. At the author's suggestion Cailletet has made
experiments with mixtures of 5 vols, carbonic anhydride with 1 vol.
air and 1 vol. hydrogen respectively, and the following table gives the
pressures required to bring about the disappearance of the meniscus
at different temperatures : —
Temperature.... 15° 16° 17° 18° 19"' 20° 21°
Carbonic anhy-
dride and air. .. 135. 130 125 120 114 108 102atmos.
Carbonic anhydride
and hydrogen 245 236 227 218 208. 199 190 „
Temperature 22
Carbonic anhydride and air 96
„ „ „ hydrogen . . 181
These results are in accord with the author's theory. Cailletet has
shown that when carbonic anhydride is mixed with a considerable
proportion of air, or a similar gas, its liquefaction is retarded or is
even rendered impossible. This, however, is due to the fact that at
high pressures the volume of the air diminishes more rapidly than
that of the carbonic anhydride, so^ that when the latter has reached
the tension at which it liquefies, its density is equal to or even lower
than that of the admixed air, and the gas appears not to liquefy,
whereas the liquid has only lost its property of collecting at the
bottom of the vessel.
It would appear that if the pressure is continually increased, the
carbonic anhydride will continue to liquefy, and its density will vary
but little, but the density of the admixed air- or other gas will con-
tinually increase, and will at last become greater than that of the
liquid, which will then collect at the top of the tube instead of at the
bottom. C. H. B.
Modification of V. Meyer's Vapour-density Apparatus. By
H. ScHWARZ (Ber., 16, 1051 — 1056).: — The author employs a combus-
tion furnace containing a deep iron trough fitted with a lid. An
ordinary wide combustion tube closed at one end is placed in the
furnace, filled with nitrogen and connected with the apparatus for
3p 2
23°
2.4°
25°
90.
85
79 atmos.
172
163.
153 „
900 ABSTRACTS OF CHEMICAL PAPERS.
collecting the displaced gas. For tlie latter purpose tbe apparatus
used in the estimation of nitrogen is employed (J5er., 13, 771). When
the temperature has become constant, the weighed substance is intro-
duced in a boat into the front cold part of the tube, the cork replaced
and the front end of the furnace raised 20 — 30 cm. The boat is then
made to slide down the tube, the furnace being supported in the in-
clined position. Bubbles of gas begin to collect in a few seconds and
cease suddenly when the volatilisation is complete ; the displa<;ed gas
is then measured in the usual way (loc. cit.). A. K. M.
Air-baths. By L. Meyer (Ber., 16, 1087— 1092).— A description
of some improvements introduced by the author. A. K. M.
Inorganic Chemistry.
Action of Nascent Hydrogen on Oxygen Gas. By M.
Traube (5er.,-16, 1201— 120$).— A reply to Hoppe-Seyler (Ber., 16,
117). The author maintains that his experiments (Abstr., 1882, 795;
1883, 150, 282) prove (1) that palladium-hydrogen does not give ofE
nascent hydrogen; (2) nascent hydrogen does not render oxygen
active ; (3) living tissues do not evolve hydrogen ; (4) the action of
palladium-hydrogen depends :on the formation of hydrogen peroxide,
which acts partly directly, arid also in conjunction with metallic palla-
dium, as an oxidising agent.
The author points out that the use of potassium iodide and starch as
a test for nitrous acid is a source of error, as in many cases the libera-
tion of iodine is due to hydrogen peroxide, and not to nitrous acid.
w. c. w.
Decomposition of Water by Metalloids. By C. Cross and
A. HiGGiN (Ber., 16, 1195 — 1199). — When water containing flowers
of sulphur is distilled, sulphur, insoluble in carbon bisulphide, is
found in the distillate, but if air is excluded from the apparatus, a
clear distillate is obtained. The distillate becomes turbid, and deposits
sulphur on exposure to' the air. It gives a 'white precipitate with lead
acetate, soluble in. acetic .acid, andwith mercurous nitrate a yellow
precipitate, which soon blackens. It bleaches potassium permanga-
nate. Hence it appears that lower sulphur-acids are formed by
the action of water on sulphur. Below 95° no action takes place.
The solubility of arsenious sulphide in boiling water is probably due
to the formation of an oxysulphide of arsenic, as such a compound is
produced by boiling arsenious oxide and sulphide in water.
w. c. w.
Pyrosulphuric Chloride. By D. Konowalow (Bei\, 16, 1127—
1130), — Pure pyrosulphuric chloride, prepared by the action of sul-
phuric anhydride on chloride of sulphur, boils at 153°. The presence
of chlorosulphonic acid lowers the temperature at which the sub-
INORGANIC CHEMISTRY. 901
stance boils. This facfc probably acconnts for the lower temperatures,
viz., 140-5° and 146'', observed by Ogier {Compt. rend., 94, 217), and
bj Heumann (this vol., 710).
The density of the vapour of pyrosulphuric chloride is normal
between 180 and 210°. In conducting the vapour-density determination,
every precaution must be taken to avoid the presence of moisture,
otherwise the pyrosulphuric chloride decomposes, and false results are
obtained. W. C. W.
Phosphorus Sesquisulphide. By Isambeet {Compt. rend., 96,
1499 — 1502). — Sulphur and phosphorus do not combine together
when dissolved in carbon bisulphide, and dry sulphur does not unite
with melted phosphorus at 100°, but at 1.30° sudden and explosive com-
bination takes place. The best method of preparing the sesquisul-
phide is to place 313 grams of carefully dried ordinary phosphorus in
a tubulated retort through which a current of carbonic anhydride is
passing, then add 24 grams of coarsely powdered sulphur, and heat care-
fully in a water-bath with repeated agitation until the mixture is com-
pletely fused. Now add, through the tube through which the carbonic
anhydride passes, 110 grams of fine sand, which has previously been
placed in a tubulated flask traversed by the gas. Agitate vigorously
in order to mix the sand intimately with the fused mixture, and then
heat somewhat strongly over a flame, continuing the passage of the
carbonic anhydride. If the materials are intimately mixed, combina-
tion takes place gradually, and the phosphorus sulphide is afterwards'
separated from the sand by distillation.
Phosphorus sesquisulphide is a yellow crystalline solid, which when
pure melts at 167° to a somewhat darker liquid. It ignites at about
100°, and burns slowly, with formation of phosphorie and sulphurous
anhydrides. Nitric acid and aqua regia attack it but gradually, even
when heated, and chlorine in presence of water converts it into phos-
phoric and sulphuric anhydrides. The sp. gr. of the sesquisulphide at
ll° is 2*00, and it boils regularly at about 380°. Its vapour-density,
determined by Meier's method, is 7*90 (calc. 7*62), and its heat of
formation, determined by the action of iodine on the sulphide in pre-
sence of carbon bisulphide, is P2 4- S3 = -|- I8'4 cals. Since the
heat developed by the conversion of ordinary phosphorus into red
phosphorus is about 20 cals., it follows that red phosphorus and sul-
phur ought not to combine together directly. Red phosphorus and
sulphur, however, combine at 180° ; the tension of transformation of
red phosphorus must therefore be sufficiently high at this point to
convert the red phosphorus into ordinary phosphorus at the moment
of combination. C. H. B.
Analogy between the Allotropic Modifications of Phospho-
rus and Arsenic. By R. Engel (Gompt. rend., 96, 1314 — 1315). —
The author has previously shown that when arsenic is liberated from
its compounds at a temperature below 300° it forms amorphous
arsenic, an allobropic modification which differs from ordinary crystal-
lised arsenic in its specific gravity and point of sublimation. It is
usually stated that arsenic sublimes at 180°, but the author finds that
902 ABSTRACTS OP CHEMICAL PAPERS.
crystallised arsenic does not sublime below 360°, eitber in a vacnum
or in an inert gas, whilst the amorphous variety begins to sublime at
260° in a vacuum, and at 280 — 310° in an inert gas. The sublima-
tion of amorphous arsenic is at first very rapid, bat after some hours
it ceases, and a residue of crystallised arsenic of sp. gr. 5'7 is left. It
follows, therefore, that amorphous arsenic is converted into the crys-
tallised variety at about 310° if the heating is continued sufficiently
long. Crystallised arsenic corresponds with red phosphorus, whilst
amorphous arsenic corresponds with ordinary phosphorus. The sp. gr.
of crystallised arsenic is higher than that of the amorphous variety,
just as the sp. gr. of red phosphorus is higher than that of the ordi-
nary \'ariety ; and just as ordinary phosphorus sublimes at a tem-
perature below that at which it is converted into the red variety,
so amorphous arsenic sublimes at a temperature below that at which
it becomes crystalline. Amorphous phosphorus and crystallised
arsenic respectively do not, however, sublime at these particular
temperatures. The vapour of red phosphorus yields the yellow
variety when condensed at a temperature below the point of trans-
formation, and in like manner crystallised arsenic yields the amor-
phous form when its vapour is condensed below 300°. Moreover, it
is possible to obtain red phosphorus in crystals, and these crystals
are isomorphous with the crystals of arsenic. C. H. B.
Potassmm Carbonate. By F. A. Flucktger {Ber., 16, 1143 —
1144). — An earthenware vessel used as a receptacle for crude pot-
ash, having been washed out and exposed to the sun, became covered
with an incrustation of white needle-shaped crystals, which had the
composition K2C03,KHC03,5H20. Attempts to prepare this salt
artificially were unsuccessful. W. C. W.
Silver Nitrate and Ammonia. By A. Retchler {Ber., 16,
990 — 994). — Two compounds of silver nitrate with ammonia are
known, viz., AgN03,3NH3 and AgN 03,2^113. A strongly acid solu-
tion of silver nitrate is not precipitated by ammonia, whilst from a
neutral or nearly neutral solution the silver is partially thrown down
as hydrated oxide. To redissolve the precipitate, slightly more am-
monia must be used than is required by the proportion AgNOs +
2NH3. If sufficient ammonia is added to produce only a slight pre-
cipitate, and the latter is then separated by filtration, the further
addition of ammonia produces no precipitate. On adding ammonia
in quantity sufficient to produce the maximum precipitate, and
evaporating the filtrate on a water-bath, a brown deposit (AgO ?) is
formed, and silver is precipitated in the form of a mirror, whilst
the concentrated solution crystallises on cooling to a mass of lustrous
needles ; these, after washing with alcohol and ether, should be
dried at a low temperature. The product, silver ammonium nitrate^
NH3Ag.N03, blackens by exposure to light, and is only partially soluble
in water, moderately in alcohol, very sparingly in ether. On dialysing
a concentrated solution of silver ammonium nitrate into water, white
needles are obtained on the lower side of the dialyser, which after
IXORGANIC CHEMISTRY. 903
being washed witli alcohol and ether, and dried at a low temperature,
contain 11 per cent, silver, which approximately corresponds with
silver ammonium hydroxide. Silver ammonium nitrate forms a crys-
talline compound with aldehyde, CH3.CH(0H).NHAg, very readily
soluble in water, moderately in alcohol, and almost insoluble in ether.
It blackens by exposure to light and is decomposed below 100°. On
adding aldehyde to a solution of silver nitrate and ammonia contain-
ing 1 mol. of the former to 2 mols. of the latter, it yields Liebermann
and Groldschmidt's ethylidenimide silver nitrate. A. K. M.
Double Salts of Lead. By G. Akdr^ (Compt. rend., 96, 1502 —
1504). — If litharge is added gradually to a hot solution of ammonium
chloride in its own weight of water and heated at about 100° for some
hours, the liquid on cooling deposits crystals of the composition
PbCl2,6NH4Cl,H-20. This compound is decomposed by water with
formation of an amorphous oxychloride, PbCl2,PbO,H20, and a solution
which, after concentration, deposits small brilliant micaceous lamellaa
of the composition 2PbCl2,IsrH4Cl,6H20.
If a small quantity of the compound PbCl2,6^H:fCl,H20 is heated
with about 50 c.c. of water in a sealed tu'be at about 200° for five
hours, white needles of the oxychloride PbClzjPbOjH^O are obtained.
If some of the mother-liquor from PbCl2,6NIl4Gl,H20 is added to an
excess of water and the mixture heated in a sealed tube at 200° for
about five hours, small slender brilliant needles of the oxychloride
2PbCl2,PbO,2H20 are deposited. When the salt 4<PbCl2,22KH4Cl,7H20
previously described is heated, with water in a similar manner, lead
chloride separates out in slender needles, but no oxychloride is formed.
It would appear, therefore, that the double chlorides obtained by the
action of litharge on a solution of ammonium, chloride contain a
small quantity of oxychloride, which is easily separated by water,
and crystallises under pressure. This oxychloride is probably formed
in accordance with the equation 2PbO -f 2NH4CI = 2NH3 +
PbCl2,PbO,H20.
When lead bromide is added to an aqueous solution of ammonium
bromide until it ceases to be dissolved, the liquid deposits crys-
talline nodules of the composition 7PbBr2,12NH4Br,7H20, which
rapidly alter when exposed to air. The mother-liquor, after evapora-
tion, deposits small lamellee of the composition 2PbBr2,14NH4Br,3H20,
much more stable when exposed to air. By digesting litharge with
ammonium bromide solution, a crystalline crust of the composition
PbBr2,6NIl4Br,H20, is obtained. It is decomposed by water with
formation of an amorphous oxybromide, 2PbBr2,2PbO,3H20. By
treating the double salt PbBr2,6NH4Br,H20, or its mother-liquor in
the same manner as the chlorine compounds, the oxybromide
PbBr2,PbO,Il20 is obtained in slender needles. It would appear that
the double bromides obtained by the action of litharge on ammonium
bromide solution contain some oxybromide ; but the compounds ob-
tained from lead bromide and ammonium bromide yield only lead
bromide and no oxybromide when heated with water in sealed tubes.
C. H. B.
904 ABSTRACTS OF CHEMICAL PAPERS.
Basic Double Salts. By H. Klinger (Ber., 16, 997— 999).— The
author has made experiments with the view to obtain basic lead
cadmium nitrates from cadmium oxide and lead nitrate, and from
cadmium nitrate and lead oxide, and to compare the products. In
both cases insoluble basic salts are formed together with basic lead
nitrate, NOaPbOH, the latter crystallising in white needles. When
hydrated lead oxide is added to a hot solution of cadmium nitrate and
the basic lead salt allowed to crystallise out, the mother-liquor some-
times yields a second salt, basic cadmium 7iitrate, NOaCdOHjHzO,
crystallising in iridescent plates. The latter is also obtained by the
action of heat on cadmium nitrate, or by dissolving hydrated cadmium
oxide in hot cadmium nitrate solution. When mercuric oxide is
added to a boiling solution of calcium chloride and the solution fil-
tered, colourless, lustrous plates of basic 7nercury calcium chloride^
GaCl2,2HgO,4H20, separate, which lose their water at 175 — 178°. It
is decomposed by water with formation of calcium chloride, a small
quantity of mercuric chloride, and an insoluble red amorphous body
containing mercury, calcium, and chlorine. Hydrochloric acid dis-
solves it with difficulty. A basic lead calcium salt has also been
obtained. A. K. M.
Formation of Sulphides by Pressure. By W. Spring (Ber.,
16, 999 — 1004). — This is a continuation of the author's experiments
on the production of compounds by pressure (this vol., p. 650).
A mixture of a. metal with sulphur is subjected to a pressure of
6500 atmospheres, the block so obtained powdered, and the operation
I'cpeated until a unifornL mass is obtained. In this way the following
sulphides have been produced : — Magnesium sulphide, zinc suljphide (in
appearance resembling the natural blende), /errows sulphide, cadmium
sulphide, bismuth sulphide, lead sulphide, silver sulphide, copper sul-
phide, stannic sulphide, and antimonij sulphide.. Only a partial com-
bination could be effected between sulphur and aluminium, the product
yielding with hydrochloric acid an abundant evolution of hydrogen
sulphide. Sulphur and red phosphorus do not combine under the
influence of pressure, neither do sulphur and carbon. A. K. M.
Colloidal Copper Sulphide. By W. Spring (Ber., 16,1142—
1 143). — If copper sulphide, prepared by passing sulphuretted hydrogen
through a dilute solution of copper sulphate in ammonia, is washed
by decantation with water containing sulphuretted hydrogen, until
the precipitate is perfectly free from ammoniacal salts, the copper
sulphide dissolves, forming a dark brown solution. The solution may
be boiled without decomposition, but the addition of small quantities
of metallic salts causes the sulphide to precipitate. On ev^aporating
the solution on a water-bath, the copper sulphide remains as a dark
resinous mass. If the copper sulphide is dried iu vacuo, it loses its
property of dissolving in water. Pure dry copper sulphide has a
dark green colour. Under a pressure of 6500 atmospheres, it forms
a dark blue compact mass, possessing metallic lustre.
Antimony, arsenic, and stannic sulphides, antimony oxide, stannic
INORGANIC CHEMISTRY. 905
oxide, and manganese peroxide, all resemble copper sulphide in their
behaviour with pure water. W. C. W.
Iridmm Potassium Sulphate. By L. de Boisbaudkan (Compt.
rend., 96, 1406 — 1409). — The green iridium potassium sulphate,
which separates out from solutions of the product obtained by fusing
an iridium compound with hydrogen potassium sulphate at a dull red
heat (next abstract), has the composition Ir23S04,3K2S04. It dis-
solves in water or dilute sulphuric acid, but is insoluble in a saturated
solution of potassium sulphate and in dilute alcohol. When deposited
slowly from concentrated solutions, it forms small transparent
crystals, which have no action on polarised light, and are apparently
octahedra, flattened parallel with' one of the faces. An- acid S(jlution
of the salt is not altered by boiling; but if the solution is nearly
neutral and especially if it contains a certain proportion of potassium
sulphate, the green colour rapidly changes to a very pale rose tint,
and potassium hydroxide or ammonia now precipitates the iridium in
the form of an oxide, which dissolves in dilute sulphuric acid, forming
a deep violet solution. With ammonia, the precipitation is incom-
plete, and therefore it is preferable to use potash when testing for
iridium (loc. cit.). An; excess of potash added to the green solution
in the cold changes the colour to pale blue, without any immediate pre-
cipitation; but on heating it, a rich violet colour is quickly developed,
and the iridium rapidly separates out as a blue-violet oxide, soluble
in dilute sulphuric acid ; sometimes the colour produced by potash
is violet-grey, and the precipitate is also violet-grey, but it yields the
same rich violet solution with dilute sulphuric acid.
The green salt is not altered by dilute hydrochloric acid, nor by
hydrochloric acid and iodine, but hot dilute nitric acid changes the
colour to a somewhat feeble blue- violet. Aqua regia decomposes the
salt completely with formation of iridium tetrachloride, and the sul-
phuric acid can be precipitated by barium chloride. If barium chloride
is added to a solution of the original salt, the precipitated barium
sulphate has a deep green, colour, and retains a considerable quantity
of iridium, which is not removed even by aqua regia.
A solution of the green salt in dilute sulphuric acid acquires a pale
blue-violet colour, when, heated with potassium permanganate. If
hydrochloric acid is previously added, the colour produced is very
deep green. A hydrochloric acid solution of the salt also acquires a
deep green colour when heated with potassium chlorate. Sulphurous
anhydride has no action on a hot acid solution of the salt.
C. H. B.
Reactions of Iridium. By L. de Boisbaudran (Gompt. rend., 96,
1336 — 1339). — A. The iridium salt is fused with hydrogen potassium
sulphate at a dull red heat in a gold crucible for some minutes, either
directly or after it has been evaporated with excess of sulphuric acid,
until white fumes are given off ; if the proportion of iridium is not
too great, the residue dissolves completely in hot water, forming a
solution which is usually green, but is sometimes blue or violet.
Concentrated solutions on cooling deposit a deep green crystalline
powder containing iridium, potassium, and sulphuric acid. This salt
90(5 ABSTRACTS OF CHEMICAL PAPERS.
dissolves in water or dilute salphuric acid, but is precipitated by-
potassium sulphate. Without removing the precipitate, the liquid
is nearly neutralised with potash or ammonia, when potassium
sulphate is precipitated and carries down the greater part of
the iridium, which gives it a green colour. The precipitate is
collected on a filter, washed once or twice with potassium sul-
phate solution, and the filtrate and washings mixed and boiled
for lf5 to 30 minutes, when the iridium is converted into a com-
pound which yields a precipitate with potash or ammonia, espe-
cially on boiling. This precipitate dissolves in dilute sulphuric acid,
forming a deep violet solution which appears rose-coloured when
very dilute. The same precipitate is obtained by dissolving the
iridiferous potassium sulphate in hot water slightly acidified with
sulphuric acid, boiling the solution, and then adding potash or ammo-
nia. If the boiling liquid is only very slightly acid, the greater part
of the precipitate separates out before adding the alkali, and is then
much less soluble in dilute sulphuric acid. If the amount of iridium
is very minute, the iridiferous potassium sulphate is not treated sepa-
rately, but the liquid is boiled after partial neutralisation. When
the alkaline filtrate has a faint rose colour it is evaporated to dry-
ness, heated with sulphuric acid, and treated as above. By this
method 0"025 mgrm. of iridium can be detected in 50 grams of
hydrogen potassium sulphate.
In order to separate traces of iron, the solution is neutralised with
ammonia, digested with excess of ammonium sulphide at a gentle
heat for some time, filtered, and the filtrate evaporated almost to
dryness. On boiling the residue with aqua regia, ammonium salts
are destroyed, sulphur separates out, and the iridium tetrachloride is
recognised by its colour, or is examined by the following methods: —
B. The iridium salt is heated with a slight excess of sulphuric
acid in order to expel any chlorine, allowed to cool slightly, and
ammonium nitrate added in successive small quantities. The heating
is then continued, and more nitrate is added, when a deep blue colour
is produced if only 0*001 mgrm. of iridium is present. If the heating
is stopped whilst some nitrate remains undecomposed, the blue sub-
stance dissolves in water without change. Sometimes the substance
has a rich emerald-green tint, but if it is moistened with a little sul-
phuric acid after cooling, and then again gently heated, the green
colour changes to blue. Foreign metals interfere more or less with
this test, but it succeeds well in presence of gold, ruthenium, plati-
num, or rhodium. The blue colour is of course modified by colour
due to any of the other metals : in presence of gold, for example, it is
changed to green.
C. If ammonium nitrate and chloride are added to the cold sul-
phuric acid solution of the iridium salt, and the mixture then heated,
a rose-red colour is produced ; this is destroyed by excess of ammo-
nium salts, but reappears on adding sulphuric acid and heating
gently. If the heating is discontinued before all the ammonium
salts are decomposed, the residue, when treated with water after
cooling, leaves a rose-red powder, soluble in pure water, but insoluble
in a solution of ammonium hydrogen sulphate. The aqueous solu-
ORGANIC CHEMISTRY. 907
tion of the "heated mass appears to contain ammonium iridiochloride.
This reaction is obtained with O'OOl mgrm. of iridium.
By combining method A with the reactions B and C, it is easy to
detect with certainty ()"01 mgrm. of iridium mixed with two million
times its weight of potassium hydrogen sulphate. C. H. B.
Organic Chemistry.
Carbon Thiobromides. By C. Hell and F. Urech (Ber., 16,
1147 — 1149). — By the action of bromine on carbotrithiohexbromide
in presence of water, 2 atoms of sulphur are oxidised to sulphuric
acid, and the third atom escapes in the form of carbon oxysulphide.
When the compound CS2Br4 is diluted with ether and mixed with
alcohol, carbotrithiohexbromide is produced. This body is decom-
posed by alcohol at 120°. With phenol and cresol, the hexbromide
forms red liquids which lose their colour on the addition of an acid.
w. c. w.
Formation of a new Colouring Matter by the Action of
Heat on Carbotrithiohexbromide. By C. Hell and F. Urech
(Ber., 16, 1144 — 1147). — GarhotritJiiohexhromide, C2S3Br6, melts at
125° and decomposes at 180°, whilst free bromine, bromide of sulphur,
and the compound CS2Br4 distil over. If the act of distillation is inter-
rupted when the contents of the retort thicken, carbon tetrabromide
may be extracted from the residue by ether. A blue compound of the
composition C9BriS4,2H20 now remains, which is very slightly soluble
in alcohol, ether, and glacial acetic acid. It dissolves, however, in
strong sulphuric acid or in phenol, forming a blue solution which is
changed to brownish-red by the action of zinc-dust. It is repre-
cipitated as a blue powder from the sulphuric acid solution, on dilu-
tion with water, and from the phenol solution by the addition of
ether.
The authors consider that the blue substance is an aromatic com-
pound, and that it owes its colouring power to the presence of the
group-S— S. W. C. W.
Dicyandiamide, I. By E. Bamberger (JBer., 16, 1074 — 1078). —
Water has no action on dicyandiamide below 150°, but when the
latter is heated with about 12 parts of water for 15 — 20 hours at a
temperature of 160 — 170° in sealed tubes, ammonia is liberated,
whilst the glass becomes coated with a crystalline powder. On
acidulating the ammoniacal filtrate with acetic acid a voluminous
precipitate is obtained which, after being purified and dried over
sulphuric acid in a vacuum, has the composition represented by the
formula C3N4H4O2. The formation of dicijandiamidocarboxylic acid
may be represented by the equations : C2N4H4 + 4H2O = 2CO2 +
4NH3 and 2C2N4H4 + 2CO2 -}- 4NH3 = 2C3]Sr4H402.NH3 + 2NH3.
908 ABSTRACTS OF CHEMICAL PAPERS.
The free acid is an amorphous chalk-like powder which does not melt
when heated, and at elevated temperatures gives off white fumes con-
densing to a crystalline sublimate (dicjandiamide ?), whilst cyanic
acid volatilises. It is insoluble in the ordinary solvents, and dissolves
bat very sparingly in boiling water, from which it separates on cool-
ing in the form of a heavy powder consisting of microscopic aggre-
gates of lustrous prisms. On warming the ammonium salt, the
ammonia is liberated, and the acid obtained in needles. When heated
with water a few degrees above the temperature of its formation, it is
decomposed with formation of ammonia and carbonic anhydride. The
ammonium salt is obtained in the form of slender lustrous prisms,
when a boiling solution of the acid in ammonia is allowed to cool ; it
decomposes on exposure to the air, ammonia being given off. The
barium salt, (C3N4H302)2Ba + 2H2O, crystallises in groups of silky
prisms ; its aqueous solution is decomposed by boiling. The com-
pound, C3lS4H3Ag02,AgN03, separates in white flocks on adding
ammoniacal silver solution to a slightly ammoniacal solution of the
acid. On adding acetate of lead to a boiling solution of the barium
salt, a double lead dicyandiamidocarhoxylate and acetate^
C3N4H302,PbOZ5,
is precipitated as a heavy crystalline powder. When a solution of
the acid in boiling hydrochlbric acid is allowed to cool, crystals of the
hydrochloride^ C3N4H402,HC1, are obtained.
Dicyandiamidocarboxylic acid can be prepared synthetically by
heating dicyandiamide with ammonium carbonate solution for 6 — 8
hours at 120°, and decomposing the ammonium salt thus formed with
acetic acid. A. K. M.
Formation of Amyl Alcohol in. Alcoholic Fermentation.
By J. A. Le Bel {Com^pt. rend., 96, 1368— 1370).— By careful
fractionation of large quantities, the author has been able to separate
several cubic centimetres of arayl alcohol, mixed in all probability
with higher alcohols, from wine, beer, and fermented solutions of
sugar. C. H. B.
Allylamine Derivatives. By C. Liebermann and C. Paal {Ber.,
16, 528 — 534). — The authors have endeavoured to convert ethyl allyl-
amine and its derivatives into piperidine. By the action of concen-
trated sulphuric acid they hoped to introduce a molecule of water into
the compound base, as has been done by Oppenheim (Annalen, SuppL,
6, 367) in the case of allyl chloride. By the subsequent extraction of
a molecule of water, a hydrogen-atom being taken from the ethyl
group, piperidine would be left. The authors have only succeeded in
performing the first part of the operation. They have arrived at no
definite conclusion regarding the second phase of the reaction. They
have, however, observed a curious property of the allyl platin-
aramonium chlorides. They have prepared the ethyl-, propyl-, and
amyl-allylamine bases by the action of the iodides or bromides of the
respective alcohol radicals in the usual manner ; in addition to the
secondary bases, tertiary compounds are generally formed. The sepa-
ORGANIC CHEMISTRY. 909
ration of the mixture requires repeated distillation, in tlie course of
which small quantities of glittering plates separate out, but after-
wards disappear or conglomerate. The authors have not made any
exact examination of their composition. The bases are all colourless
liquids of an odour resembling that of alljlamine. Their solubility
in water decreases with the increasing complexity of the alcohol
radical in combination. Their solutions in hydrochloric acid decolorise
bromine-water, and on adding an alkali even very dilute solutions
become milky from the separation of a yellow oily base. This reac-
tion has been made use of as a test forthe presence of unattacked allyl
groups.
MonethylallyUmine, CgHs-NHEt, boils at 84— 86°.
Ethylallylamine platinochloride, (C3H5]S'HEt)2,H2PtCl6, crystallises
from water in orange- col cured well-formed crystals melting at 154 —
156°. The acid oxalate forms colourless plates sparingly soluble in
alcohol.
Diethylalli/1 amine, CsHg.TiTEta, is stated by E-inne to boil at 100 —
103°. The authors find its boiling point to be 110 — 113°. Its platino-
chloride melts at 128—130°.
Monopropylallylamine, CaHj.NHPr, boils at 110 — 114°. Its sp. gr.
at 18" is 0*7708. The platinochloride forms orange- coloured crystals.
BipropyJallylamine^-CsH.a-^Fr'ij boils between 145° and 150°. Its
platinochloride crystallises from water in fine glittering orange-red
rhombic crystals. When the mother-liquor is allowed to evaporate
in the air, lemon-coloured crystals of a new platinum salt are ob-
tained. The compound can be readily prepared by boiling an aqueous
solution of the ordinary salt. When the liquor becomes concentrated
an oily precipitate forms. After diluting and boiling, the solution
is allowed to cool slowly, yellow needles of the composition
C3H5NPr2,HPtCl3 (m. p. 152—153°) then separating out. All the
above platinum salts yield analogous compounds.
Monethylallyl<imine platini chloride, C^HsNHEtjHPtCla, forms anhy-
drous lemon-coloured crystals melting at 220°.
Diethylallylamine platinichloride, CsHg'NEtajHPtCla, forms groups of
chamois-coloured needles melting at 189°.
Allylamine platinichloride, CaHs.NHajHPtCla, crystallises in ochre-
coloured needles.
The platinochlorides of pyridine and quinoline are not altered by
boiling with water.
Isoamylallijlamine, C3H5 NH.CsHu, boils at 148 — 153°. Its sp. gr. at
18° is 0*777 7. The allylamine bases were all subjected to the action
of concentrated sulphuric acid at 130 — 140°. In addition to quanti-
ties of the unattacked base, allylamine was always found accompanied
by a new base boiling considerably higher than the original one. The
platinochlorides are very soluble in water and alcohol, and diflficult to
crystallise. The bases contain oxygen, and when dissolved in hydro-
chloric acid do not decolorise hydrobromic acid, showing that the
allyl group is saturated.
Hydroxy propylamine, (C3H6.0H).!N'HPr, prepared by the action of
sulphuric acid on propylallylamine, boils at 174 — 177°. Its sp. gr. at
910 ABSTRACTS OF CHEMICAL PAPERS.
18° is 0"9018. At the ordinary temperature it is a colourless liquid ;
but at lower temperatures it forms sleuder needles which melt at 30°.
liydroxy^rojpylpropijlamine platinoch loride,
[(C3H6.0H)NHPr]2,H2PtCl4 -f 2HA
crystallises from water in efflorescent warty masses.
Hydroxypropyldipropylamine, (C3H6.0H)NPr2. The platinochloride
has the composition [(C3H6.0H)NPr2]2,H2PtCl6.
Hydroxypropylethylamine, (C3H6.0H)NHEt, boils at about 160°.
The platinochloride, [(C3H6.0H)NHEt]3,H2PtCl6 + 2H2O, is very
soluble.
HydroxypropyldietJiylamine platinochloride^
[(C3H6.0H)NEt2]2,H2PtCl6,
is also a very soluble salt.
HydrGxypropylamylamine, (C3H6.0H)NH:,.C5Hii, boils at about 200°.
In a freezing mixture it solidifies to needles resembling asbestos, which
melt a few degrees above 0°. It is insoluble in water.
The authors have ascertained that the oxy- bases on further treat-
ment with concentrated H2SO4, undergo a change, and propose to
pursue the investigation thereof. J. I. W.
Imines. By A. Ladenburg (-Ber.,.16, 1149 — 1152). — PentamethyU
enediamine^ C5Hio(NH2)2, is produced by the action of zinc and hydro-
chloric acid on an ethereal solution of trimethylene dicyanide. An
isomeride of piperidine is also formed by this reaction. Soda is added
to the product, and the> free base distilled over in a current of steam ;
in order to get rid of ammonia, the distillate is neutralised with
hydrochloric acid, and the diamine is precipitated by the addition of
a solution of iodine in potassium iodide. The precipitate is then
washed free from ammoniacal salts,, and converted into the hydrochlo-
ride by treatment with silver and silver chloride. The hydrochloride
crystallises in prisms which are slightly hygroscopic. The platino-
chloride, C6Hio(]S'H2)2,H2PtCl6, is deposited from a hot aqueous solu-
tion in golden prisms. The base is not easily decomposed by strong
hydrochloric acid, even at 160°. By the action of soda solution at
260°, it splits up into ammonia and a base of the same composition as
piperidine. The identity of this compound with piperidine, however,
has not yet been established.
The isomeride of piperidine mentioned above, forms a platino-
chloride crystallising in yellow glistening plates. It is less soluble
than piperidine platinochloride. The aurochloride is more soluble
than the corresponding piperidine compound. W. C. "W.
Oxaline and Glyoxalines. By 0. Wallach (Ber., 16, 5.34 —
547). — Having shown in a previous research that oxalmethyline is a
derivative of glyoxaline (Abstr., 1882, 821), the author has now
studied the properties of oxalethyline for the special purpose of
determining the composition of the base from which it is derived.
Ethylglyoxaline, (C3H3N)NEt, prepared by the action of ethyl
bromide on glyoxaline dissolved in alcohol, is a clear liquid boiling at
209—210°, sp. gr. 0-999. It is miscible with water. Its platino-
ORGANIC CHEMISTRY. 911
chloride, (C5H8N2)2,H2PtCl6, crystallises from water. It combines witli
methyl iodide, forming a salt which crystallises in large deliquescent
prisms melting at 74 — 75° ; this forms with cadmium iodide a double
salt which is very insoluble in water, but crystallises from dilute
alcohol in small plates melting at 151 — 152°, and having the compo-
sition (CsHglS' '. ]SrEtMeI)2,Cdl2. The methiodide salt, when shaken
with silver chloride, is converted into the corresponding chloride
Avhich forms salts with platinum chloride and zinc chloride. The
former, (C3H3N I NEtMeCl)2,PtCl4, crystallises well, and melts at
194—195°. The latter, (C3H3N ! NEtMeCl)2,ZnCl2, forms transparent
soluble crystals melting at 157 — 159°.
When ethylglyoxaline methiodide is distilled with potash, no higher
boiling base is obtained ; but a violent reaction takes place, and a
primary amine distils over.
The compound C3H3N '. NEtMel crystallises in deliquescent prisms.
Its derivatives, (C3H3N : NEtMeI)2,,0dl2, (C3H3N' ! NEtMeCl)2,PtCl4,
(C3H3N : NEtMeCl)2,ZnCl2, resemble those of ethylglyoxaline, but
possess somewhat lower melting points. The compound
C3H3N : NEtMel
differs greatly from the corresponding salts of oxalethyline,
C3H2MeE: : NEtHI.
When methylglyoxaline is treated with bromine in a solution of
dilute sulphuric acid, it yields a tribromomethylglyoxaline ; it forms
white crystals melting at 88 — 89*". Ethylglyoxaline, when treated in
a similar manner, yields a tribromo substitution-product melting at
61 — 62°. Oxalethyline forms dibromoxalethylene. Chloroxalethylene
contains only one hydrogen-atom replaceable by bromine. The author
considers from the above facts that oxalethyline is methylethylglyox-
aline, C3H2MeN.NEt. He considers that Badziszewsky's formula for
glyoxaline, considering it to be a tertiary base, is altogether inde-
fensible, since his experiments and those of Wyss have shown that it
is a secondary base, in which 1 atom of hydrogen is easily replaceable
by hydrocarbon radicals. The direct substitution is exemplified by
the formation of benzylglyoxaline on gently heating glyoxaline with
benzyl chloride ; it forms crystals melting at 70 — 71°, and boils at
310°. When glyoxaline is boiled with aniline hydrochloride, ammonia
is evolved. The fact that the boiling point of glyoxaline is lowered
about 70° by the introduction of a methyl group, affords further
evidence of its secondary nature.
The author fiTids that by passing the substituted glyoxalines through
a short tube, heated to redness, they are converted into isomeric com-
pounds. Hydrocyanic acid is produced as a bye-product. Para-
methyhjlyoxaline, so formed, is identical with paroxaline-methyline.
Its platinochloride crystallises in long needles. Paretlujlgltjoxaline,
C5H8N2, melts at 76 — 77°. When heated with propyl bromide at
120°, it forms oxalpropyline (b. p. 229 — 234°). Farapropylglyoxaline
is not so easily prepared as its homologues.
When oxalethyline is passed through a red-hot tube it yields a small
quantity of a higher boiling base resembling paroxalmethyline.
J. I. W.
912 ABSTRACTS OF CHEMICAL PAPERS.
Synthesis of Ketonic Acids (II). — By C. A. Bischoff {Ber., 16,
1044 — 1046). — Ethyl henzomalonate is obtained by the action of
benzoic chloride on ethyl sodomalonate. By the action of aceto-
phenone bromide on ethyl sodomalonate, ethyl fB-benzoisnsuccinate is
produced, and yields on saponification ^-benzoisosuccinic acid^
CH2Bz.CH(COOH)2, melting at 114°. Ethyl orthonitrohenzomalonate^
N02.CfiH4.CO.CH(COOEt)2, is obtained by the action of nitrobenzoic
chloride on ethyl sodomalonate suspended in ether or light petroleum;
it melts at 92°, decomposing at 100°. Ethyl acetylenetetracarhoxylate
is produced when the sodium compound of ethyl malonate is sus-
pended in ether and ethereal solution of iodine added. In the same
way ethyl hutonhexaearhoxylate (m. p. 56°) is obtained from the
sodium compound of cfhyl ethenyltricarboxylate,
2[CNa(COOEt)2.CH2.COOEt] 4- 12 = 2NaI +
COOEt.CH,.C(COOEt)3.C(COOEt)2.CH2.COOEt.
A. K. M.
Correction. By R. Andeeasch (Ber., 16, 1185— 1186).— The
statement that Guareschi (Ber., 12, 682) found that potassium
ethyl enedisulphonate contains 2 mols. H2O is a misprint. Guareschi's
observation agrees with the author's, viz., the salt is anhydrous.
Barium ethylidenedisulphonate contains 3 J, not 2^, mols. H2O.
w. c. w.
Substituted Pyronracic Acids. By H. B. Hill (Bar., 16, 1130 —
1132). — On the addition of bromine to a solution of pyromucic acid
in glacial acetic acid monobromopyromucic acid is formed, together
with carbonic and hydrobromic acids and other bye-products. The
monobromopyromucic acid (m. p. 183°) is identical with the com-
pound described by Tonnies {Ber., 11, 1088) and by Schiff and
Tassinari (Gazzetta, 8, 297). If bromine-vapour is passed into a
vessel containing the acid suspended in 30 times its volume of water,
the acid is decomposed into fumaric, carbonic, and hydrobromic acids,
CsHsBrOa + 2Br2 + 3H2O = C4H4O4 -f CO2 -f- 5HBr. Dibromosuc-
cinic and isodibromosuccinic acids are formed in small quantities. If
liquid bromine is used instead of bromine-vapour in the preceding
experiment, a larger yield of these acids is obtained. Dibromofur-
furanetetrabromide, C4H2Br60, is also produced. CsHaBrOa -|-
3Br2 = C4H2Br60 + CO3 + HBr. It crystallises in colourless prisms
(m. p. 110°), soluble in alcohol, chloroform, ether, carbon bisulphide,
and light petroleum, but insoluble in water. Silky needles of tetra-
bromofurfurane (m. p. 63°) are obtained by the action of alcoholic
potash on dibromofurfurane tetrabromide.
The formation of fumaric acid when monobromopyromucic acid is
treated with bromine-water or hot dilute sulphuric acid, indicates
that the constitutional formula of mouobi-omopyromucic acid is
HC : C.COOH
I
O
I
HC • CBr. W. C. W.
ORGANIC CHEMISTRY. 913
Occurrence of a New Acid in Beet-juice. By E. 0. Lippmann
(Ber., 16, 1078 — 1081). — Besides citric, aconitic, tricarballylic, and
malonic acids, the author has isolated a tribasic acid of the formiila
CeHgOs. It is very readily soluble in water, alcohol, and ether. The
alkali salts are amorphous, and very readily soluble. The harium
salt, (06H508)2Ba3 + 5H2O, is insoluble in water and in alcohol. The
calcium salt has the formula (C6H508)2Ca3 + IOH2O. Pawolleck
(Aniialen, 178, 155) obtained an acid (hydroxy citric acid) of the
same formula by boiling' chlorocitric acid with water or alkalis ; this
acid agrees in its properties with that obtained from beet-juice, the
calcium salt, however, containing, according to Pawolleck, 9 mols.
H2O. The author assumes the two to be identical.
A. K. M.
Metallic Derivatives of Amides : Method of distinguishing
between Monamides and Diamides. By H. Gtal (Gompt. rend.,
96, 1315 — 1317 ; compare this vol., 653). — Acetamide and butyramide
act on an ethereal solution of zinc ethyl at the ordinary temperature
with evolution of ethane and formation of zinc acetamide or zinc
butyramide, as the case may be. These metallic derivatives are
white powders insoluble in ether, and decomposed by water with
regeneration of the amide and formation of zinc oxide. Benzamide
behaves in a precisely similar manner.
Urea acts on zinc ethyl in the cold, with formation of zinc carbamide,
CONaHoZn, probably analogous to Liebig's silver carbamide, Oxamide
has no action on zinc ethyl in the cold, but on heating the mixture,
zinc oxamide, C204N2H2Zn, is formed.
It follows that the action of zinc ethyl on a non-saturated monamine
produces a compound with the general formula 2 (amide) — H2 4-Zn,
which is decomposed by water, in accordance with the equation
[2 (amide) -H^ -f Zn] + 2H2O = ZnH202 + 2 (amide). With
diamides, the formula of the product is amide — H2 + Zn. With
monamides 2 mols. of the amide take part in the reaction, whilst with
diamides only 1 mol. is required. The action of zinc ethyl may there-
fore be used for distinguishing between monamides and diamides.
C. H. B.
Violuric Acid. By M. Ceresole (Ber,, 16, 1133— 1135).— Yio-
luric acid can be prepared synthetically by the action of hydroxyl-
amine hydrochloride on alloxan. Strong hydrochloric acid decomposes
violuric acid with formation of hydroxylamine. Violuric acid is the
only isonitroso-compound which is not decomposed by oxidation, but
is converted into the corresponding nitro-derivative, viz., dilituric
acid.
co<^^;^g>c:NOH + H2O = co<^g;^g>CH.N(OH)2.
C0<^]^;^^>CH.N(0H)2 + 0 = H2O 4- C0<^g;^g>CH.N02.
w. c. w.
Action of Dibromobarbituric Acid on Thiocarbamide and
Thiocyanates. By W. Trzcinski (Ber., 16, 1057— 1061).— When
aqueous or alcoholic solutions of dibromobarbituric acid and thiocar-
VOL. XLIV. 3 q
914 ABSTRACTS OF CHEMICAL PAPERS.
bamide are mixed, a white granular precipitate is obtained identical
with Nencki's thiopseudouric acid, C6H6N4SO3 (Ber., 4, 722) ; it is
insoluble in water, alcohol, and ammonia, but dissolves readilj in the
fixed alkalis; it crystallises from concentrated hydrobromic acid in
slender concentrically grouped needles : C403N2H2Br2 + CSN2H4 =
C503T^4H6S+Br2. On adding an alcoholic solution of potassium thio-
cyanate in slight excess to a cold alcoholic solution of dibromobarbi-
turic acid, a white precipitate is produced, which, after being washed
with alcohol, dried and recrystallised from hot water, has the formula
C4O3N2H2SCNK, i.e.., potassium thiocyanoharhiturate. The ammonium
salt is obtained when ammonium thiocyanate is used, both salts being
nearly insoluble in alcohol^ and crystallising from aqueous solutions
in colourless rhombic anhydrous plates : C403N2H3Br2 + CNSK =
C403N2H2(SCN)K + Biv Potassi-um and ammonium thiocyano-
barbiturates are preeipitated by lead and silver salts with formation
of sparingly soluble salts, which are decomposed on boiling. Free
thiocyanobarbiturie acid has not been isolated, the precipitate obtained
OQ adding hydrochloric acid to its salts decomposing when gently
heated with water into thiodialuric, hydrocyanic, and thiocyanic
acids, and a body insoluble in acids and alkalis. On warming its salts
with dilute potash solution, ammonia, carbonic anhydride, and thio-
dialuric acid are produced. Thiodialuric acid dissolves in nitric acid
to a pink solution, and on warming this a violent reaction takes place
with formation of nitrobarbituric acid. From the fact that thio-
dialuric acid can be obtained from the salts of thiocyanobarbiturie
acid, CO<j^TT*pQ>CH.SC]Sr, and from thiopseudouric acid by sa-
ponification, the author assigns to the latter the constitution —
Jt^H.CO^ /NH
C0< >CH.SCf
^NH.CO'^ ^NHa A. K. M.
Alkyl-NltroTis Acids. By Gr. Chawcel (Gompt. rend., 96, 1466 —
1470). — The author has previously shown that alkyl-nitrous acids are
produced by the action of nitric acid on ketones (Abstr., 1882, 710).
He has now extended his researches to the action of nitric acid on
ethyl acetoacetate and its mono-derivatives. — 5 to 10 c.c. of the aceto-
acetate are gently heated in a flask with a long neck, and nitric acid
of sp. gr. 1*35 is added gradually until the action commences, when
the flask is removed from the source of heat, and more nitric acid
gradually added until its volume is equal to that of the acetoacetate.
When the evolution of nitrogen oxides slackens, the liquid is poured into
water, washed once or twice with this liquid by decantation, dissolved
in twice its volume of alcohol, mixed with excess of alcoholic potash
and agitated, when a crystalline precipitate is thrown down, which is
washed with alcohol and then with ether, and finally crystallised from
boiling water.
Ethyl acetomethacetate yields potassium ethyl-nitrite, CMe(N02)2K,
which forms bulky deep yellow prismatic crystals. They become
deep red when exposed to light, but regain their original colour in the
ORGANIC CHEMISTRY. 915
dark. Like the picrates, this compound detonates violently when
heated or struck. It is only slightly soluble in cold water, but dis-
solves readily in boiling water.
Ethyl acetoethacetate yields 'potassium propijl-nitritey
CH^Me.CCNOO^K^
which forms prismatic crystals of a somewhat deeper yellow than the
ethyl nitrite. When heated on platinum foil it detonates at 140 —
145°, but if heated in a tube it explodes at 106". If heated at 100°
for eight or 10 hours, it loses 42 per cent, in weight, and leaves a
white residue which does not detonate.. If perfectly dry, it may be
kept in a closed vessel for any length of time without undergoing
change. If moist, it gradually gives off nitric oxidje, and leaves a
white crystalline residue.
Ethylacetopropylacetate is obtained by the action of normal iodo-
propane on a mixture of" ethyl acetoacetate and sodium ethylate in
alcoholic solution. It boils at 2"12° under a pressure of 750 mm., and
its sp. gr. at 0° compared with water at 4° is 0'9795. Its sp. gr. at
other temperatures up to- 40° is obtained by means of the formula
D = 0-9795 - 0-000914^. When treated with nitric acid, it yields
potassium hutijl-nitrite,. CH2Me..CH2.C(N02)2K, a yellow compound
which crystallises, according to the strength of the solution, either in
plates, or in long needles which unite into lamellae^ on drying. It
deflagrates when heated, and dissolves in 40'3 parts of water at 0°,
and in 12*2 parts at 40°. Silver butyl- nitrite, C^H.^(N0i)2A.g, is
obtained by adding silver nitrate to a boiling solution of the potassium
salt : it forms deep yellow lamellae. Butyl-nitrous acid, obtained by
decomposing the potassium salt with dilute sulphuric acid, is a colour-
less liquid insoluble in water ; sp. gr-. at 15° compared with water at
0° = 1"205. It boils at about 197°, with partial decomposition.
C. H. B.
Action of Ethyldichloramine on Aromatic Amines and on
Hydrazobenzene. By A. Pierson and K. Heumann (Ber., 16, 1047
— 1050). — When ethyldichloramine is gradually added to a solution of
paratoluidine in light petroleum, a violent reaction takes place which
should be moderated by cooling. Parazotoluene and ethylamine
hydrochloride are produced, 2C7H;.NH2 + NEtCU = NHsEtCl + HCl
+ C^li^.l!!^2^0^1I^. It also reacts violently with aniline, with formation
of dichloraniline (m. p. 63 — 64°) and trichloraniline (m. p. 78 — 79°),
CeHs.NH^ + NEtCU = CeHaCl^.NHj + NHaEt and 2C6H5.NH2 +
3NEtCl2 = 2C6H2CI3.NH2 + BNHaEt. With hydrazobenzene, it forms
azobenzene and ethylamine hydrochloride, 2PhNH.NIIPh -j- NEtClj
= NHsEtCl + HCl + 2Ph]Sr : NPh, and with diphenylhydrazine,
PhjN.N'Hz, a reaction takes place which is not yet understood ; a sub-
stance is obtained crystallising in long white needles, together with a
deep violet-red dyestuff. A. K. M.
Action of Acid Amides on Aromatic Amines. By W. Kelbe.
Anilides can be prepared by boiling the theoretical quantities of amide
and amine in a flask with a reflux condenser until the evolution of
ammonia ceases. The crude product may generally be purified by
372
916 ABSTRACTS OF CHEMICAL PAPERS.
washing it witli ether. In this way the following anilides were
obtained: — Acetanilide (m. p. 114°) from acetamide and aniline, pro-
pionanilide (from propionamide and aniline), forms glistening plates
(m. p. 105°) very soluble in ether. Butyranilide (m. p. 92°) crystal-
lises in cubes. Valeranilide from fermentation valerianic acid melts
at 115°. Capronanilide from fermentation caproic acid is deposited
from light petroleum in glistening needles (m. p. 95°), freely soluble
in alcohol and ether. Orthoacetotoluide melts at 108°, and the para
compound at 147°. Acetamide and xylidine yield acetoxi/lide (m. p.
127°) . Acetonaphthalide from acetamide and naphthylamine melts at
157°. Ac^etoparanitranilide (m. p. 207°), acetoparahromanilide (m. p.
165'5°), diacetylphenylenediamine (m. p. 189''), and diacetyltoluylenedi-
amine (m. p. 223°) were also prepared by this method.
w. c. w.
Nitrobenzaldoxime. By S. Gabriel (Ber., 16, 520— 523).— The
ortho-, meta-, and para-compounds of nitrobenzaldoxime (isonitroso-
methylnitrobenzene) are readily prepared by acting on the correspond-
ing nitrobenzaldehyd^e with the requisite quantity of alkali solution
and hydroxylamine hydrochloride. The author finds that when meta-
nitrobenzaldoxime is boiled with water it is unaltered ; if hydrochloric
acid be present, metanitrobenzaldehyde and hydroxylamine hydro-
chloride are formed. If a mixture of alcoholic solutions of meta-
nitrobenzaldehyde and hydroxylamine hydrochloride be allowed to
stand for a day, nitrobenzaldoxime is formed. When hydroxylamine
and metanitrobenzaldehyde are heated with strong hydrochloric acid to
150 — 160°, ammonia and metanitrobenzoic acid are obtained. This
explains why, after heating the compounds in a sealed tube at 130 —
140°, they were found unaltered when cold, and also explains the
presence of ammonia and nitrobenzoic acid after the tube had been
heated above 140°. The sodiuin salt of metanitrobenzaldoxime,
NO^CeH^CNONa + 2H2O,
forms long orange-yellow needles which decompose when heated at
140 — 150°. An aqueous solution gradually decomposes on standing.
When metanitrobenzaldoxime is acted on with phosphorus penta-
chloride, it yields fine needles melting at 155 — 177°, which possess the
properties of metanitrobenzonitrile, NO2.C6H4.CN. J. I. W.
Methylene-blue. By A. Bernthsen {Ber., 16, 1025—1028).—
The author is examining into the nature of this and allied dyes. The
base of Laut's violet is said to have the composition CioHjoNaS or
C04H20N6S2, and the base of methylene-blue the formula C16H18N4S
{Ber., 12, 592 and 2069). The author finds that on precipitating an
aqueous solution of commercial methylene-blue with potassium iodide
solution and crystallising the precipitate from hot water, bronze-
coloured needles are obtained, to which he assigns the formula —
CeHigNgS.HI (or C32H36N6S2,2HI).
By the reduction of methylene-blue, a leuco-base (methylene-white)
is obtained crystallising from ether in broad needles j it has a slight
ORGA.VIC CHEMISTRY. 917
yellowish colour, but forms colourless salts. It is moderately stable
when dry, but becomes rapidly oxidised when moist. Its composition
agrees with the formula CiellaiNsS (or C32H40N6S2). It yields methyl
and acetyl derivatives, the latter forming a white mass which becomes
slightly blue by exposure to air. When heated with methyl iodide
and methyl alcohol at 100 — 110°, the compound CisHaoMeNaS +
2MeI is formed, crystallising in yellowish needles which are readily
soluble in hot water, sparingly in cold. A. K. M.
Nitro-derivatives of Resorcinol. By P. G. W. Typke {Ber., 16,
651 — 557). — The diacetylresorcinol from which the compounds were
prepared was obtained by acting on resorcinol with acetic chloride ;
in a pure state it forms a clear refractive oily liquid having a faint
odour resembling that of acetamide. When placed in a mixture of ice
and salt it becomes thick. It boils at 278° (uncorr.), with slight
decomposition.
Dinitroresorcinol, C6ll2(N02)2(OII)>, is formed wh^n diacetylresor-
cinol is very gradually poured into 4 — 5 times its volume of well
cooled fuming nitric acid. It separates out as a nearly white
amorphous powder, which is washed with boiling alcohol and then
dried at 100°. After boiling it for half an hour with 30 per cent.,
hydrochloric acid, it is dissolved in a large quantity of boiling water
and filtered; on cooling, the new body crystallises out in slender
needles (m. p. 212'5°), whilst any trinitroresorcinol which is present
remains in solution. The dinitro-body crystallises from ethyl acetate
in large yellow prisms with a vitreous lustre. When gently heated, it
sublimes in spear-shaped needles. It decomposes carbonates, and
forms well crystallised salts with bases. Its solutions colour animal
fibre an intense yellow. When a slight excess of silver solution is
added to a slightly ammoniacal dilute solution of the nitro-body, the
silver salt, C6H2(N02)2(OAg)2, is obtained as a scarlet precipitate, whicb
on standing changes to copper-coloured needles. On dissolving the
nitro-body in an excess of dilute ammonia, the normal ammonium salty
C6H2(N02)2(ONH4)2, is obtained in prismatic needles, which appear
yellowish-brown by transmitted light and bluish by reflected light.
They are sparingly soluble in water.
Hydrogen barium salt, [C6H2(N 02)2(01!) .OJoBa. — When dinitro-
resorcinol is added to freshly precipitated barium carbonate sus-
pended in boiling water, the solution on cooling deposits golden-
yellow needles melting at 212*5°. The normal barium salt,
C6H2(N02)202Ba, is obtained by boiling dinitroresorcinol for a con-
siderable time with the theoretical quantity of barium carbonate sus-
pended in water.
Monobromodinitroresorcinol, C6HBr(N02)2(OH),, is obtained by boil-
ing dinitroresorcinol dissolved in glacial acetic acid with an excess of
bromine. It crystallises in sulphur-coloured needles melting at
192'5°. With bases it forms a series of well crystallised salts.
Diamidoresorcinol hi/drochluride, C6H2(OH)2(NH2)2,2HCl, is obtained
by reducing the dinitro-compound with tin and hydrochloric acid.
It forms transparent vitreous needles having a superficial violet-grey
colour.
918 ABSTRACTS OP CHEMICAL PAPERS.
When a current of air is passed through an aqueous ammoniacal
solution of diamidoresorcinol hydrochloride, an oxidation-product
separates out in glittering scales resembling cuprous oxide. They
appear to consist of a di-imidoresorcinol, (OH)2C6H2(NH)2.
The author was unable to detect a mononitroresorcinol in the
mother-liquors from the dinitro-compound. J. I. W.
A New Homologue of Resorcinol. By F. Pfaff (Ber., 16,
1135 — 1140). — Mort07iitroxylenol, recently described by the autlior
(Ber., 16, 1136), yields the following derivatives: —
The methyl ether, C6H2Me2(N02).OMe, is deposited from an alco-
holic solution in long needles (m. p. 56°), soluble in ether and in
hot water. The potassium-derivative, C6H2Me2(N02).OK + 2H2O, is
a red crystalline compound freely soluble in water and alcohol.
Amidoxylenol hydrochloride, C6H2Me2(OH).]SrH3Cl, is obtained in
lustrous plates when nitroxylenol is treated with tin and hydrochloric
acid. It dissolves easily in alcohol, ether, and water. The free base
is obtained by decomposing an aqueous solution of the hydrochloride
with the theoretical quantity of potassium bicarbonate and treating
the mixture with ether. On evaporating the ethereal solution, amido-
xylenol remains in glistening crystals (m. p. 161°), which are soluble
in alcohol and ether.
Dihydroxy xylene or xylorcinol, C6H3Me2(OH)2, is prepared by
cautiously adding a solution of sodium nitrite to a well cooled solution
of 4 grams of amidoxylenol hydrochloride in dilute sulphuric acid. The
mixture is first diluted up to a litre with water containing 120 grams
of strong sulphuric acid, and then boiled for 2^ hours in a flask with
a reflux ■.condenser. On extracting the liquid with ether, xylorcinol is
obtained as a dark-coloured oil, which solidifies {in vacuo over sulphu-
ric acid) to a crystalline mass (m. p. 125°). The crystals, which have
a bitter taste, dissolve freely in alcohol, ether, and water. Xylorcinol
yields a diacetic-derlvative, C8H2Me2(OAc)2, crystallising in transpa-
rent prisms (m. p. 45°), soluble in alcohol, ether, and in hot water.
When a solution of xylorcinol in glacial a,cetic acid is warmed with
sulphuric acid, a fluorescent condensation-product is formed. The
product of the reduction of bromonitranisol is identical with the meta-
anisidine prepared f i*om metanitroph-enoL W. C. W.
Sulphonic Acids of Paracymene. Bj A. Glaus {Ber., 16,
1015). — A reply to Spica.
Isoindole. By P, Friedlander and J. Mahly {Ber., 16, 1023 —
1025). — By the reduction of ethyl dinitrocinnamate,
C6H4(N02).CH : C(N02).C00Et,
by means of tin and hydrochloric acid in ethereal solution, diaraido-
hydrocinnaraic acid is formed, together with a basic substance,
CsHsNo, which probably belongs to the group of metanitriles. It is
obtained by adding alkali to the product and agitating with ether.
On evaporating the latter, an oil is obtained which becomes crystal-
line on standing. It is sparingly soluble in hot water, from which it
crystallises in large silky plates, melting at 46°, and distilling un-
ORGANIC CHEMISTRY. 919^
changed at 312°. It is slightly volatile in steam, and has a faint
odour resembling that of aniline. Its vapour-density agrees with the
simple formula given. lb forms monobasic salts. The nitrate is
readily soluble in water and in alcohol, and crystallises in large
brownish plates. The hydrochloride forms small plates, readily soluble
in water, and yields a crystalline platinochloride, (C8H8N2)2,H2PtCl6.
The sulphate is more sparingly soluble than the free base, and crys-
tallises in long white lustrous needles. It yields an acetijl-derivative^
crystallising in silky needles and melting at 97°. The probable
formula for the base is l!^H3.C6H4.C2H2N (paramido-a- or y3-phenyl-
amphinitrile). With dry bromine, it forms an addition-compound,
whilst bromine-water added to its solution in hydrochloric acid precipi-
tates a dibromo substitution-derivative. By the action of nitrous acid,
a diazo-compound is produced which yields a red hydroxy-body when
boiled with water, and with alcohol a colourless oil of characteristic
odour, which is probably free amphinitrile. A. K. M.
Action of the Alkyl- derivatives of the Halogen-substituted
Fatty Acids on Aniline. (Preliminary Notice.) By C. A. Bischoff
{Ber., 16, 1040— 1044).— When aniline (1 mol.) is heated with ethyl
chloracetate (I mol.) to above the boiling point of aniline hydrochlo-
ride with an inverted condenser, and the product then distilled, un-
altered ethyl chloracetate first passes over, and afterwards hydrochloric
acid water and aniline hydrochloride, whilst a reddish coloured oil
remains behind, which solidiG^es to a brittle mass on cooling; its
formula is CsHgNO, and it is named by the author dihydro-oxindole.
It dissolves readily in acetone and in hot alcohol, from which it sepa-
rates in an amorphous condition. It is not attacked when heated
with dilute hydrochloric acid or with an alkali. When it is heated to
above 360°, a yellow oil distils, depositing crystals of a substance
melting at 252 — 253°, readily soluble in acetone, insoluble in hot
alcohol. Dihydro-oxindole is soluble in concentrated sulphuric acid,
and on pouring the solution into cold water a flocculent precipitate is
obtained, melting at 120° and decomposing at 175 — 180° with evolu-
tion of gas. A body of the same melting point and decomposing at
the same temperature is also formed by the action of hydrochloric
acid, whilst by the action of nitric acid a substance is obtained de-
composing at 100 — 105°. Alcoholic potash is apparently without
action; acetic chloride reacts violently, yielding an insoluble resinous
mass and a yellowish oil, which is precipitated on adding soda solu-
tion to the liquid portion of the product. By the action of hydriodic
acid, a substance is obtained having a powerful odour resembling that
of pyridine- and quinoline-derivatives. It forms a hydrochloride,
crystallising from alcohol in star-like groups of prisms. A reaction
analogous to the above also takes place between aniline and ethyl
bromopropionate. A. K. M.
Aromatic Nitroso- compounds. By S. Gabeiel (J?er., 16, 517
523). — Nitrosomethylmetanitrobenzene may be regarded either as
metanitrobenzaldoxine (according to Petraczek's nomenclature) or
isonitrosomethylmetanitrobenzene (according to Meyer and Ceresole) ;
920 ABSTRACTS OP CHEMICAL PAPERS.
since it is formed by the action of hydroxjlamine on nitrobenz-
aldehyde, it belongs to the class of isonitroso-compounds, containing
the group — C! N.OH. Nitrosomethylorthonitrobenzene must also be
considered as an isonitroso-compound on account of its analogous
formation from orthonitrobenzaldehyde and hydrozylamine.
Nifrosi'Oxindole, C6H4<^ Utt'_J_]>, has previously been obtained
by treating paramidoxindole with amyl nitrite, and boiling the re-
sulting paradiazonitroso-oxindole chloride with alcohol. It was pre-
pared by Baeyer from oxindole and nitrous acid. The author finds
that the same body is formed when a mixture of 1 mol. of isatin,
1 mol. of hydroxylamine hydrochloride, and ^ mol. of soda is allowed
to stand with water and alcohol for several hours : on adding water,
orange-yellow needles separate out.
Ethyl orthonitrophenyluitrosoacetate, N02.C6H4.CHNO.COOEt, has
been prepared by heating ethyl paramidorthonitrophenylacetate with
amyl nitrite in alcoholic solution (Ber., 14, 825 — 830). If it be an
isonitroso-compound, its formula must be N02.C6H4.CN'OH.COOEt,
which shows that it would probably be formed by the action of
hydroxylamine on ethyl orthonitrophenylglyoxylate,
NO..C6H4.CO.COOEt.
The author has prepared ethyl phenylisonitrosoacetate,
Ph.CNOH.COOEt,
by acting on ethyl phenylglyoxylate (b. p. 257^) with hydroxylamine
hydrochloride. It forms colourless needles, which have a vitreous
lustre, and meltj- at 112 — 113°. When the ethyl salt of orfhonitro-
phenylglyoxylic acid is treated with hydroxylamine in the same
manner, ethyl orthonitrophenylisonitroso-acetate is obtained in long
colourless needles, melting at 163 — 163*5°. It is sparingly soluble in
weak ammonia, more readily in concentrated. It dissolves freely in
potash solution, to which it imparts a yellow colour. J. I. W.
Isobenzil. By H. Kltnger (Ber., 16, 994— 997).— The author
has repeated Brigel's experiments (Annalen, 135, 172) on the forma-
tion of isobenzil by the action of sodium-amalgam on an ethereal
solution of benzoic chloride, and has finally succeeded in obtaining
this body. The benzoic chloride (1 part) is added gradually to the
sodium-amalgam (5 — 6 parts), which is just covered with ether, and
after the spontaneous action has ceased, the whole is heated for 2 — 3
days on a waier-bath. The liquid portion is then decanted, and the
solid residue washed with ether. The solution is agitated with soda,
evaporated, and the residue steam-distilled to get rid of benzoic acid
and benzyl alcohol; it is then treated with soda solution, the residue
dissolved in ether, alcohol added, and the filtrate evaporated. On
repeating this process, again dissolving the syrupy liquid in ether and
then adding alcohol, lustrous scales of isobenzil gradually separate.
The mother-liquor contains ordinary benzil, besides benzoic acid and
anhydride. Isobenzil separates from alcohol in lustrous scales and
needles, and from ether in compact crystals, melting at 155 — 156°.
ORGANIC CHEMISTRY. 921
It gives the benzil reaction with alcoholic potash. By the action of
bromine on its solution in carbon bisulphide, benzil (m. p. 94 — 95°)
and benzoic bromide are produced; (C7H50)4 + Br-^ = CuHioOa
+ 2C6H5.COBr. A. K. M.
Oxidation of Pentachloronaphthalene. By A. Claus and H.
LiPPE (Ber., 16, 1016 — 1019). — Pentachloronaphthalene is best pre-
pared by heating an intimate mixture of a-dichloronaphthaquinone
(1 part) and phosphorus pentachloride (2 parts) in sealed tubes, the
temperature being slowly raised to 250°, and maintained at 200 — 250°
for four or five hours. The product is treated with water and dilute
alkali, and recrystallised from alcohol and ether. The authors find
that the trichloronaphthaquinone obtained by Claus and Spruck
(Abstr., 1882, 1211), by boiling pentachloronaphthalene with nitric
acid is nothing more than a secondary product due to the presence of
a-dichloronaphthaquinone as an impurity in the pentachloronaphtha-
lene, and that it is not connected with the formation of tetrachloro-
phthalic acid. When pentachloronaphthalene is heated with nitric
acid (sp. gr. 1*5) in sealed tubes at 110 — 120° for ten hours, tetra-
chloronaphthaquinone is formed, together with some tetrachlorophthalic
acid, the production of the former as intermediate between penta-
chloronaphthalene and tetrachlorophthalic acid, proving that the
formation of the tetrachlorophthalic acid is due to a primary reaction,
and also that the fifth chlorine-atom in pentachloronaphthalene
occupies the a-position in the second ring. Tetrachloronaphthaquinone
crystallises from alcohol in long lustrous yellow needles, melting at
160°, and subliming without decomposition. It combines with the
alkalis, forming dark red-coloured salts, moderately soluble in water ;
they are decomposed by dilute acids, with separation of yellow needles
of trichlorhydroxynaphthaquinone. With ammonia, aniline, and
toluidine, it forms amido-derivatives, crystallising in lustrous copper-
coloured needles. When heated with phosphorus pentachloride at
200° in sealed tubes, heptacliloronapTithalene is produced, subliming in
small colourless needles which melt at 154°. A. K. M.
Fluorene Derivatives. By J. Holm (Ber., 16, 1081—1082).—
With the view to ascertain whether in the bromine and chlorine sub-
stitution derivatives of fluorene, hydrogen-atoms are substituted in
both phenylene groups or in the methylene group, the author is
examining the effect of oxidation on these derivatives. By the oxida-
tion of dibromofluorene (m. p. 166°), he obtains dibromodiphenylene'
ketone, Ci2H6Br2CO, in two modifications, according to the conditions
of the experiment. When the dibromofluorene is dissolved in glacial
acetic acid and oxidised with the calculated quantity of chromic
anhydride, dibromodiphenyleneketone is formed, crystallising in long
yellow needles, readily soluble in ether and in benzene, and melting at
142*5°. If a slight excess of chromic anhydride is used, the second
modification is produced, melting at 197°; it forms yellow needles,
readily soluble in alcohol, ether, and warm benzene. Both varieties
yield the original a-dibromofluorene (m. p. 166") when reduced with
hydriodic acid and phosphorus. By the action of melted potash on
922 ABSTRACTS OF CHEMICAL PAPERS.
/3-dibromofluoreneketoiie (m. p. 197°), dibromophenylhenzoie acidu,
CizHTBra.COOH, is produced, readily solnble in alcohol, ether, and
benzene, and crystallising in white needles, melting at 212°; the
barium salt, (Ci2H7Br2.COO)2Ba, is insoluble in water, alcohol, and
ether. Tribromofluorene gives the same |3-dibromodiphenyleneketone,
melting at 197°, showing that the third bromine- atom is in the
methylene group.
Triohlorofluorene, C13H7CI3, is obtained by passing chlorine into a
solution of fluorene in carbon bisulphide. It forms white scales,
melting at 147°, and sparingly soluble in alcohol and in ether.
A. K. M.
Coal-tar Quinoline. By E. Jacobsen and C. L. Reimer (Ber., 16,
1082 — 1087). — The authors have mentioned the formation of a yellow
dye obtained by the action of phthaiic anhydride on coal-tar quinoline
(Ber., 16, 513), which was supposed to be identical with Traub's
quinophthalene obtained from quinoline which had been prepared
from cinchonine (Ber., 16, 878). They prepare it by heating the
commercial quinoline, boiling at 235 — 240° (2 parts) with phthaiic
anhydride (1 part) and zinc chloride (1 part) for 4 — 5 hours at 200° ;
the product is dissolved in concentrated sulphuric acid at 100°, and
the solution poured into water, when the dye separates and can be
purified by crystallisation, first from glacial acetic acid and then from
alcohol. It forms slender gold-coloured needles, melting at 234 —
235°, and subliming at higher temperatures. It is insoluble in water,
very sparingly in ether, but more readily in boiling alcohol and in
glacial acetic acid. It dyes silk and cotton, -and resists the action of
light, acids, and alkalis:; it has no basic properties, water separating
it unchanged from its solution in sulplmric acid. The numbers
obtained on analysis agree better with the formula CiftHnNOa than
with CnH9N02, and this led the authors to the supposition that the
formation of this dye might be due to the presence of methylquinoline,
and that it is not derived from the quinoline itself. They prove that
this is the case by showing that after the whole of the methyl-
quinoline has been converted into the dye, the unattacked quinoline
no longer gives the reaction, and also that the yellow dye is decom-
posed by heating with hydrochloric acid into phthaiic acid and quinal-
dine (methylquinoline), and that it can be re-made from the latter,
according to the equation C10H9N -f C8H4O3 = CisHaNOa + H2O.
c.co
Its constitution is probably C6H4<(^ | ^CeH^, i.e., quinal-
^N: CMe.C.CO^
dine, in which two hydrogen-atoms of the pyridine nucleus are re-
placed by the phthaiic radical. Homologues of quinoline containing
methyl groups in the benzene nucleus only do not react with phthaiic
acid, whilst homologues of quinaldine behave in the same way as the
latter substance.
The red dye previously obtained by Jacobsen by the action of
benzotrichloride on coal-tar quinoline can neither be obtained from
pure quinoline nor from pure quinaldine, its formation being appa-
rently dependent upon a mixture of the two. A. K. M.
ORGANIC CHEMISTRY. 923
Quartemary Base derived from Hydroxyquinoline. By A.
WuKTZ (Compt. rend., 96, 1269 — 1271). — Orthhjdroxyquinoline
(m. p. 75°) is heated with three times its weight of ethylene chlor-
hydrin in a sealed tube in a water- bath for ten days. The product is
distilled in a vacuum in order to expel excess of the chlorhydrin, and
the residue is dissolv^ed in absolute alcohol ; this solution is then
mixed with a large quantity of ether, when an abundant precipitate
of a crystalline hydrochloride is gradua-lly deposited. This hydro-
chloride is dissolved in water and precipitated with platinum tetra-
chloride, the precipitate decomposed by hydrogen sulphide, the
platinum sulphide filtered off, and the filtrate evaporated to dryness
on the water-bath.. The residue is dissolved in water, decomposed by
excess of moist silver oxide, and the liquid agitated with ether, which
removes hydroxyquinoline. The red and strongly alkaline aqueous
solution is now acidified with hydrochloric acid and precipitated with
platinum tetrachloride, when a yellow, crystalline, very slightly soluble
precipitate of hydroxy et'li/ylhydroxyquinoline platinochloride,
(CuHi2N02Cl)2PtCl4,
is obtained. The free base is obtained by decomposing the platino-
chloride with hydrogen sulphide. The hydrochloride,
C9H6<0H)NC1.C2H4.0H,
forms yellow anhydrous crystals. With gold chloride it yields an
unstable crystalline yellow aurochloride, and with mercuric chloride
a double chloride crystallising in yellowish lamellse.
In the preparation of the new base, part of the hydroxyquinoline
acts on the ethylene chlorhydrin, liberating ethylene oxide, which
combines with the excess of chlorhydrin. The formation of hydroxy-
quinoline hydrochloride by the displacement of the ethylene oxide
considerably diminishes the yield of the quartemary hydrochloride.
C. H. B.
Pyridinemonosulphonic Acid. By 0. Fischer and C. Riemer-
SCHMiD (Ber., 16, 1183 — 1185). — Pyridinesulphonic acid (Ber., 15,
62) crystallises in pale yellow needles or plates, which dissolve freely
in water, but are only sparingly soluble in alcohol and insoluble in
ether. Most of the salts of this acid are crystalline and soluble in
water, e.g., the salts of ammonium, sodium, nickel, cobalt, copper,
zinc, and silver The barium sulphonate (C5H4N.S03)2Ba -\- 4H2O,
loses its water of crystallisation at 120°. The mercnrous salt is
sparingly soluble. The SO3 group in pyridinemonosulphonic acid is
easily eliminated by reducing agents or by bromine.
/8-P)'ridine dibromide, C5H3Br2N, may be prepared by adding bromine
to a boiling aqueous solution of pyridinesulphonic acid ; the mixture
is rendered alkaline and distilled in a current of steam, when long
needle-shaped crystals of the dibromide (m. p. 164°) collect in the
distillate. The crystals dissolve easily in alcohol, ether, wood spirit,
and benzene, but are only sparingly soluble in water or soda solution.
The platinochloride forms reddish-yellow needles
(C5H3BroN)2,H2PtCl6 + 2H,0,
sparingly soluble in water. W. C. W.
924 ABSTRACTS OF CHEMICAL PAPERS.
Xanthine and Hypoxanthine. By A. Kossbl (Zeitschr. Physiol.
Chem., 6, 422 — 431). — The author has already in previous papers in
this Journal shown that xanthine and hypoxanthine are formed by
the action of dilute acids and water at 1U0° on nucleins, a group of
bodies whose representatives are found everywhere in the active cells
of plants and animals, and which may therefore be regarded as neces-
sary constituents of the developmentally active living tissue. It was
therefore concluded that these products of decomposition of nucleins
have a more universal distribution, and that in the organs which are
known to be the place of their formation, they are produced in larger
amount than has hitherto been assumed. The present paper relating
to some researches in regard to xanthine is in supplement to former
communications upon the investigation and quantitative determina-
tion of hypoxanthine in a series of animal and vegetable structures.
D. P.
Solubility of Strychnine in Acids. By Hanriot and Blarez
(Compt. rend., 96, 1504 — 1506). — Strychnine dissolves with diflBculty
in acids, the solubility being greater the more dilute the acid.
When a concentrated solution of a strychnine salt is slightly
acidified, a precipitate is formed which is most abundant when the
acid added is the same as that contained in the strychnine salt. If
the solution is dilute, the precipitate forms less readily, and its forma-
tion is accelerated by agitation. The precipitate dissolves in an excess
of acid, forming a solution which yields a precipitate when diluted,
and it also redissolves if the solution is neutralised with ammonia.
The precipitate formed by adding s-ulphuric acid to a solution of
neutral strychnine sulphate consists of slender needles of the acid sul-
phate, C22H2,iNi02,H2S04, the mother liquid retaining 1"13 parts of
salt per 1000. The addition of hydrochloric acid to a solution of
strychnine hydrochloride, precipitates the neutral chloride,
2(C22H23N202,HCi),3H20,
in needles, the mother-liquor retaining 4*13 parts of salt per 1000.
Since acid strychnine sulphate is very soluble in water, the formation
of the precipitate is not due to the formation of an acid salt, but rather
to the insolubility of strychnine salts in slightly acid liquids. It is
necessary to bear these facts in mind in testing for strychnine. The
amido- and nitro-derivatives behave in a similar manner.
C. H. B.
Putrefaction Alkaloids, By L. Brieger (Ber., 16, 1186—1191).
— In the first stages of putrefaction of albuminoids, poisonous com-
pounds are produced which resemble curare in their physiological
action : they disappear again after the putrefaction has gone on for
8 to 10 days. To extract the poisonous bases from flesh, the fol-
lowing process is employed: Finely chopped horse flesh is stirred up
with water and exposed to putrefactive fermentation for 5 or 6 days.
The mixture is then boiled and filtered, and lead acetate is added to
the filtrate. The lead salt is decomposed by sulphuretted hydrogen,
and the filtrate after concentration is extracted with amyl alcohol.
ORGANIC CHEMISTRY. 925
Oxy-acids are removed by acidifying with sulphuric acid and extract-
ing with ether. The sulphuric acid is precipitated by baryta, and the
excess of baryta by carbonic acid. The alkaloid is then precipitated
by the addition of mercuric chloride. The precipitate decomposed by
sulphuretted hydrogen, and the filtrate concentrated : inorganic bodies
first crystallise out ; but on concentrating the mother-liquor, a com-
pound is deposited in needle-shaped crystals of the composition
C5H14N2H2CI2. This substance is soluble in water and spirits of wine,
but is insoluble in ether, absolute alcohol, benzene and chloroform.
The crystalline platinochloride is very soluble in water, but is precipi-
tated by alcohol. The pure hydrochloride is slightly poisonous, but
the impure salt has a more powerful action. This substance could not
be prepared from fibrin or albumin, but only from flesh. On treating
the hydrochloride with moist silver oxide, an unstable gelatinous mass
is obtained, which resembles seminal fluid in odour. On distillation
with soda, a mixture of di- and tri-7nethyla7ni7ie is formed.
The filtrate from the mercuric chloride precipitate mentioned above
contains a poisonous base, which forms a platinochloride of the com-
position (C5HnN)3,H2PtCl6. A small dose of the hydrochloride pro-
duces a rapid flow of the saliva, strong secretions from the nose, and
constant flow of watery liquids from the intestines, and finally convul-
sions. W. C. W.
Basic Products of Putrefaction. By E. and H. Salkowski (Ber.,
16, 1191 — 1195). — The authors have continued their research on the
putrefaction of flesh and fibrin (i?er., 12, 648), and find that two bases
are produced. The non- volatile portion of the product is concentrated,
rendered alkaline by the addition of sodium carbonate, and treated
with alcohol. The alcoholic extract is evaporated, acidified with
dilute sulphuric acid, and extracted with ether. A base remains in
the sulphuric acid but has not yet been investigated. The oily
liquid which remains on evaporating the ethereal solution is dissolved
in sodium carbonate solution, and after precipitating the higher acids
of the acetic series with barium chloride, the filtrate is acidified with
hydrochloric acid and extracted with ether. The residue left on
evaporating this extract is purified by solution in absolute alcohol and
conversion into the platinochloride ; this forms orange-coloured crystals
soluble in hot water. The crystalline hydrochloride is very soluble in
water and in alcohol. The aurochloride forms dark yellow monoclinic
crystals, which melt below 100°. The free base obtained by the action
of silver oxide on an aqueous solution of the hydrochloride, is a
white crystalline powder (m. p. 156°) having a peculiar odour. It is
freely soluble in water, insoluble in ether, and only sparingly soluble
in alcohol. It does not appear to have a poisonous effect on animals.
The analysis of the free base, hydrochloride, and gold salt, agree
with the formulae CsHnNOz, C5HuN02,HCl, and
C6H„N02,HCl,AuCl3 + H2O
respectively, but the analysis of the platinochloride corresponds with
the formula (C7Hi5N02)2,H2PtClfi.
926 ABSTRACTS OF CHEMICAL PAPERS.
This seems to indicate that the crystalline substance is a mixture of
homologous bases. W. C. W.
Zymase of Human Milk. By A. B^chastp (Compt. rend., 96,
1508 — 1509). — Human milk contains a zymase which possesses a
much higher rotatory power than the galactozymase from cow's milk,
and liquefies starch and converts it into sugar as readily as diastase.
To extract this zymase in a somewhat impure condition, the milk is
slightly acidified with acetic acid, and mixed with at least three times
its volume of alcohol of 95 per cent. ; the bulky precipitate is washed
with dilute alcohol to remove sugar, treated with ether to extract fat,
digested with water for some hours, and the liquid filtered. The
filtrate possesses in a high deoree the power of liquefying starch and
converting it into sugar. The zymase was obtained from several
quantities of milk drawn successively, and is therefore a prod act of
the function of the milk gland, and is not formed by the alteration of
milk stagnated in this gland. C. H. B.
Peptone. By A. Foehl (Ber., 16, 1152 — 1170). — Peptone prepared
from blood serum and fibrin, is identical in its properties with peptone
from egg albumin. R is thrown down from neutral solutions by
alcohol in the form of a white precipitate. Dried at 100° it forms a
slightly yellow brittle mass, soluble in cold water. The solution is
not changed by boiling. Peptone is not precipitated by the addition
of potassium fierrocyanide and acetic acid ; but is completely preci-
pitated from moderately concentrated neutral solutions by neutral
salts. Tannin produces a brown flocculent precipitate in neutral
or slightly acid solutions, but not in alkaline solutions. Millon's
reagent produces in neutral or slightly acid solutions a brown preci-
pitate, which turns red on warming. By the putrefaction of peptone,
jptomopejptone is produced ; it differs from peptone in that it has no
action on polarised light, is not precipitated by basic lead acetate, and
is decomposed by potash with formation of trimethylamine, and by
sodium hypobromite with evolution of nitrogen. Peptone can gene-
rally be detected in the urine of fever patients. Animal tissue {e.g.,
of the lungs and kidney) converts blood serum and fibrin into peptone
at a temperature of 35^^ : papain, the leaves of Carica papaya, and
other vegetable tissues, have the same property. The artificial forma-
tion of peptone only takes place in the presence of a small quantity of
free acid. Peptone is gradually transformed into albumin by the
action of dehydrating agents, such as alcohol and neutral alkali salts.
In the first stage of the reaction it exhibits the properties of Meissner's
/3-peptone, and is precipitated by acetic acid and potassium ferro-
cyanide. In the next stage it is precipitated by nitric acid (Meissner's
a-peptone). After the action has continued some time, the product
is no longer soluble in cold water (Meissner's metapeptone) ; and in
the last stage the product gives with neutral salts a precipitate which
dissolves in hot water, but separates again on cooling. (Meissner's
parapeptone, propeptone of Schmidt-Miilheim, heniialhuminose of
Kiihne.)
PHYSIOLOGICAL CHEMISTRY. 927
Ptomopeptone does not exhibit these changes when treated with
dehydrating agents.
The specific rotation of peptone is [aj^ = — l^^/Q" when q = 0
{q is the percentage of water in the solution) and [ix]j) = —63' 779°
when q = 100°, i.e., for an infi.nitely dilute solution. The specific
refraction of peptone — -- = 0'4!212 when q = 0^ and 0'33l6 when
a
q = 100. No change in specific gravity, rotary power or index of
refraction takes place in the conversion of albumin into peptone, hence
the author regards the change of albumin into peptone as merely a
transformation into a^ more soluble modification.. W. C. W.
Physialogical Chemistry.
Behaviour of Elastin in Peptic Digestion. By J. Horbaczewski
(Zeitschr. Physiol. Chem.^ 6,. 3 3*0 — 345). — Little has heretofore been
known on this subject, the view obtaining in most of the text-books
being that elastic tissue is not acted on by the digestive fluids.
Recently, however, J. Etzinger has made the observation that the
ligamentum nuclias of the ox is in th-e course of ten days almost com-
pletely dissolved by pepsin and 0'3 per cent, solution of hydrochloric
acid.
The author's experiments, conducted also with elastic tissue, pre-
pared from the ligamentum nucliae (cervical vertebral ligament) of
the ox comports itself similarly to albumin in peptic digestion, and
yields similar products in the reaction. The elastin obtained in the
end by repeated purification of the tissue employed, details of which
are given by the author, was found to be absolutely free from
sulphur, and to yield on ultimate analysis the following percentage
results : —
C 54-32; H 6-99; N 1675; Ash 0-51.
The products of digestion are two substances, which are separable
one from another. One of these, to which the name of hemillactine is
given by the author, is precipitable from its aqueous solution by acetic
acid and potassium ferrocyanide, also by freshly precipitated plumbic
hydroxide and ferric acetate, and behaves somewhat like the hemi-
albumin of Salkowski, or the propeptone of Schmidt-Miilheim. The
other exhibits properties similar to those of albumin peptone, and is
not precipitated by potassium ferrocyanide and acetic acid. It is
named elastin peptone by the author. As regards ultimate analysis
very little difference is perceptible between hemielastin and elastin, as
the following results concerning the former show : — C 54'22 ; H 702 ;
N 16-84 ; ash, 0-48 per cent.
928 ABSTRACTS OF CHEMICAL PAPERS.
Elastin peptone yielded the following percentage composition : —
C 53-57 ; H 8-075 ; N 16-20.
Other details of the properties and reactions of these respective
substances are given in the paper.
By simple heating with vrater at 100° in a closed vessel for about
20 hours, elastin is changed into elastin peptone. Schultze had pre-
viously described the process with superheated steam as essential for
this transformation.
In regard to the physiology of digestion, it is therefore now shown
that elastin is digestible, and doubtless capable of absorption ; although
not holding any prominent position among the constituents of nutri-
tive substances, it nevertheless must be included with those, and in the
form of sarcolemma, neurilemma, and the muscular sheaths, apart
from its occurrence in larger amount in the ligaments and walls of
vessels, is widely distributed, and a digestible constituent of animal
food. The author had an unusual opportunity of testing the digesti-
bility of elastin in the case of a patient under the care of Albert, in
the Surgical Clinique, Vienna, who had a gastric fistula. A small bag
of closely woven silk, containing 1 gram of elastin powder, was intro-
duced into the stomach through the fistula, and its digestion watched.
In 24 hours two-thirds of the elastin had disappeared, some swollen
pulpy elastin remaining behind. This was diluted with water and
filtered. The clear solution showed the reactions of hemielastin.
D. P.
Vegetarianism from a Physiological Standpoint. By T.
Cramer (Zeitschr. Physiol. Chem., 6, 346 — 385). — The author con-
cludes a historical and physiological consideration of this subject,
with the following summary : —
1. The dietary of vegetarianism affords to the system both abso-
lutely as regards total nutriment and the relative proportions of its
constituents, sufficient food for the maintenance of bodily and intel-
lectual functions.
2. This dietary is, however, adequate for the maintenance of life,
only inasmuch as the vegetable portion is supplemented by animal
albumin, in the form of milk and eggs.
3. This dietary, assuming that care be taken not to overburthen
the alimentary system, is too costly for the nourishment of large bodies
of men, as in workhouses, barracks, and prisons, where the cheapest
possible modes of feeding can be employed. It is besides an eminently
impracticable method of alimentation, as for the same cost a much
larger quantity of mixed and profitable food can be procured.
4. Then there arises the question, how will an organism so
nourished comport itself towards disease ? Experience and observa-
tion in regard to prisoners and others living under otherwise equally
favourable hygienic conditions, all point to the conclusion that on vege-
tarian diet the system has less power of resisting the attacks of
disease. D- P.
Comparative Investigations of Intestinal Gases. By H.
Tappeiner {Zeitschr. Physiol. Ghem., 6, 432 — 479). — Investigations into
the nature of the intestinal gases have hitherto been limited in num-
I
PHYSIOLOGICAL CHEMISTRY. 929
ber. Besides the recently published analysis of these gases in herbl-
vorons animals by the author (Ber., 1881), Planer had examined
those of the dog and of man ; Ruge the gases of the colon in man ;
and C. B. Hofmann of the dog and rabbit. Considerable diflPerences
appear, especially in regard to the occurrence of CH4 ; Ruge states
that in man this gas is formed only after exclusively leguminous or
flesh diet, and is absent in a pure milk diet ; neither Planer, Ruge,
nor Hofmann found it in the case of the dog, even after feeding with
leguminous food ; and Hofmann obtained a like result in the rabbit.
No explanation of these differences has so far been given, the want
of which affects the question as to the substances from which, in the
process of intestinal change, CH4 is formed.
The author carried on a series of experiments in regard to this
question in a variety of animals and under different conditions of
nutrition. His results show that CH4 occurs in the intestine of the
herbivora and of omnivorous animals, but not of carnivorous. In the
former it is found in every instance, save after milk diet. Apart from
the stomach, it is formed only in the colon, never in the small intestine,
with the exception of ruminating animals, in which its formation
begins in the ileum.
The abundant formation of CH4, after feeding with legumina and
cabbage, can scarcely have any other source than the cellulose or
mixture of tissues collectively termed woody fibre. But of what sub-
stance, therefore, CH4 in the large intestine is formed by fermentation
cannot with certainty be affirmed, but the probable sources are
albumin and cellulose. D. P.
Sugar from the Lungs and Saliva of Phthisical Patients.
By A. G. PoucHET {Gompt. rend., 96, 1506— 1507).— The saliva, or,
better, an aqueous decoction of the lungs, is acidified with acetic acid,
boiled, the coagulated albuminoid matters filtered off, and the filtrate
exactly neutralised with baryta- water. Barium acetate is added until
a precipitate ceases to form ; the precipitate filtered off ; the filtrate
mixed with neutral lead acetate; boiled, and again filtered. The
filtrate is mixed with a large excess of ammonia, and allowed to stand
48 hours in the cold, when it deposits a bulky dirty grey precipitate
consisting of a lead compound of the sugar mixed with a considerable
quantity of a compound of lead with peptone. This precipitate is
washed with cold water, suspended in water, treated with sul-
phuretted hydrogen at 100", and filtered through porous earthenware.
The filtrate is mixed with tannin to remove gelatin and peptones ;
agitated with animal charcoal ; again filtered, the filtrate concentrated
in a vacuum, and precipitated with alcohol. The precipitate is dis-
solved in a small quantity of water, and purified by repeated precipita-
tion with alcohol. The sugar thus obtained is an almost white
amorphous substance which becomes brown on drying, even in a
vacuum and in the dark. Its solution in boiling alcohol of 25 per
cent, deposits brilliant crystalline scales on cooling. The aqueous
solution, evaporated in a vacuum, yields a vsyrup which will not crys-
tallise, but which, when completely dried, forms somewhat regular
elongated rectangular scales resembling crystals. The sugar is
VOL. xLiv. 3 r
930 ABSTRACTS OP CHEMICAL PAPERS.
hygroscopic and very soluble in water, forming a perfectly limpid
solution, but it is insoluble in strong alcohol, ether, and hydrocarbons.
Its composition is C12H20O10 when dried in a vacuum, and C12HJ8O9
when dried at 120°.
If the aqueous solution of the sugar is mixed with neutral lead
acetate, and alcohol added, a greyish-white precipitate is formed
which, when dried at 120°, has the composition Ci2HuPb09. A con-
centrated boiling aqueous solution yields, with basic lead acetate, a
heavy grey precipitate very slightly soluble in boiling water. It is a
mixture of CigHuPbaOg and Ci2Hi2Pb309 in equivalent proportions.
An alcoholic solution of basic lead acetate, added to a boiling solution
of the sugar in alcohol of 25 per cent., produces a gelatinous precipi-
tate of the compound Ci2HioPb409. Aqueous solutions of the sugar
yield no precipitate with zinc acetate, bat on careful addition of
ammonia a flocculent precipitate is formed which dissolves in boiling
water and is deposited in microscopic needles on cooling. After
drying in a vacuum, this precipitate has the composition
C,2Hi2Zn309.8Zn(OH)2 ; it loses 4H2O at 120°. These metallic deri-
vatives are closely analogous to those formed by various sugars and
dextrins. C. H. B.
Chemistry of Vegetable Physiology and Agriculture.
Diastatic Ferment of Bacteria. By J. Wortmann (ZeitscJir.
Physiol. Ghem., 6, 287 — 329). — Recent investigations have conclu-
sively established the universal occurrence of diastatic ferments in
different parts of plants, and have thrown a new light on the processes
of nutrition and fermentation.
According to earlier observations, the presence of diastase in the
plant was limited to germinating wheat or barley, and knowledge
in regard of its wider diffusion has been advanced by the recent works
of Gorap-Besanez, Will, Kranch, and especially Baranetzky. The
researches of Musculus, E. Schulze, O'SuUivan, and others, have
afforded an insight into the quantitative relations and the modifying
external factors of temperature and acidity concerned in the action of
diastase in the transformation of starch into glucose.
Having in view the action of bacteria as causes of putrefaction or
fermentation in which the destruction of the putrescible or fermen-
tescible body is accomplished by the appropriation for the purpose of
nutrition by the bacteria of constituent nitrogen or carbon, the
question may be asked — can bacteria also obtain their carbon from
starch, just as by the researches of Pasteur and Cohn they have been
proved to be capable of obtaining it, not only from sugar but from
ammonium tartrate ? Are bacteria, by the secretion of a starch-
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 931
transforming ferment analogous to diastase, or in any other but not
clearly defined way, capable of transforming starch into soluble,
diffusible, and nutrient combinations ? Notwithstanding the numer-
ous investigations into the chemical and physiological relations of
bacteria, very little has been made out in regard to their action on
starch — a circumstance from which it may be presumed that the solu-
tion of starch by bacteria can be effected only in certain instances.
In his work, " Ueber die niederen Pilze," Naegeli refers to the
secretion by these organisms of a special energetic ferment capable of
changing milk-sugar into fermentescible sugar, starch and cellulose into
glucose, and of dissolving coagulated albumin and other albuminates,
and Sachsse alludes to the circumstance of starch solution under-
going no change so long as it is protected from the influence of
organic germs by which otherwise it quickly undergoes transforma-
tion.
Some experiments, made by the author in the summer of 1881 with
milky juices, led him to believe that certain appearances of corrosion
exhibited by the starch granules present must be due ta th« action of
bacteria. The result of further precise experiments,, undertaken to
decide this point, led to the conclusion that bacteria are capable of
drawing their supply of carbon from starch,, and that the appearances
of solution or corrosion exhibited by the solid starch granules are
identical with those caused by the action of diastase or saliva.
The method used by the author was as follows : — To about 20 or 25
c.c. a mixture of inorganic salts (sodium chloride, magnesium sulphate,
potassium nitrate, and acid ammonium phosphate) in equal propor-
tions was added to the extent of 1 per cent. The same quantity of
solid wheat-starch was then added, and the liquid then inoculated with
one or two drops of a strongly bacterial solution, shaken, corked, and
allowed to remain in a room at a temperature of 18 — 22°. [Bacte-
rium termo was the predominating organism in the inoculating fluids
employed.] In from 5 — 7 days, the first signs of commencing corro-
sion of the starch grains become visible, the larger grains being the
earliest attacked, and much later, when these have almost completely
disappeared, the lesser granules are attacked.
In a second series of experiments soluble starch was substituted for
the solid form, the. progress of the reaction being watched by the aid
of iodine. Samples taken from time to time exhibited at first the
blue colour, then violet or dark red, passing to wine-red, and, finally,
when the starch had disappeared, underwent no change.
As Baranetzky has shown, the starch granules of different kinds are
acted on with very unequal rapidity by the diastatic ferments of plant
juices, the strongest ferment of all — malt diastase — being well known
to have no perceptible influence, even after long exposure, on solid
potato- starch granules, whilst wheat and buckwheat are dissolved with
facility.
Experiments were made with a view to ascertain whether the action
of bacteria on starch was analogous ; in these, wheat-starch grains are
shown to be by far the most readily attacked by bacteria — in several
instances having even completely disappeared before other sorts of
starch were attacked. Differences were also noticed in regard to the
3 r 2
1)32 ABSTRACTS OF CHExMIOAL PAPERS.
times when palm-starch, canna- starch, turmeric-starch, and iris-
starch were attacked, their degree of resistance being in the order
given. Potato-starch alone resisted attack. When wheat-starch in
the solid state was mixed with starch solution or with starch-paste,
the solution became entirely (and the paste in greater part) changed
before the solid granules were attacked.
With regard to this unequal power of resistance shown by different
kinds of starch, the author concludes from his further observations,
that the difference of rapidity with which a given kind is attacked
and dissolved by a ferment is inversely proportional to its density,
provided always that the granules in question are entire and uninjured
by cracks or fissures. In the same way are explained the differences
in point of time in which granules of the same kind are sometimes
observed to undergo change accordingly as these are intact or
otherwise.
The cause of potato-starch or of bean-starch, and, even under certain
conditions, wheaten starch resisting attack, in spite of the abundant
presence of bacteria, is apparently to be sought for in the fact that
other more easily accessible sources of carbon nutriment were also
present, certain albuminoid constituents of the potato slices or of the
iDcans employed affording this more readily than the starch granules,
just as in the experiments, above cited, with wheaten starch solution,
and solid wheaten starch : the former was preferentially attacked ;
only after all, or at least the chief portion of the albuminoids present,
had been used up was the starch in these cases attacked.
Experiments were also made with the same results in which, after
Cohn, ammonium tartrate was employed along with starch as a
nutrient medium for the bacteria, with the result that so long as even
a trace of this salt was present with the starch, the latter was not
attacked by bacteria in the slightest degree, but, on its disappearance,
appearances of solution became at once visible in the starch granules.
Another point was also established in the course of these experi-
ments, that if air is excluded, no appearances of corrosion or solution
of the starch granules are manifested.
Other researches were made to answer the problem as to whether
the nature of this action of bacteria on starch was such that an
unformed ferment analogous to diastase was secreted by those
organisms to which the corrosive appearances may be ascribed, these
being, as already stated, precisely similar to the resulting action of
diastase itself.
That the starch in the process became changed in part to glucose
was easily ascertained by testing with Fehling's solution, and a
detailed series of experiments, made with a view to eliminating if
possible the ferment itself, yielded evidence showing that bacteria
possess the remarkable property of producing a starch-transforming
ferment only when no source of carbon other than starch is at their
disposal, and this ferment is incapable of changing albumin into
peptone, just as in the case of diastase. It is well known that the
pepsin of gastric juice acts only in an acid medium. The plant juices
which possess a diastatic property exhibit likewise a more or less acid
reaction, so that as Baranetzky assumes, the co-operationof an acidin
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 933
the case of diastase is a necessary condition of its activity. The
solutions in which starch in one or another form was submitted to the
action of bacteria were always slightly acid, due to the presence of
acid ammonium phosphate, and when the solutions were purposely
made neutral, the process of starch transformations went on more
slowly. Detmer some time since has shown that addition of small
quantities of citric acid to a solution containing diastase, hastens its
action on starch. The author's observations are in harmony with
this, but in addition show that the process of starch transformation by
bacteria is capable of going on in the absence of acid, and that the
bacteria do not yield any acid in the process. The results of the
author's researches may be briefly recapitulated.
1. Bacteria are capable of acting on starch, whether in the solid
state, as paste, or in solution, in a manner analogous to diastase.
2. As in the case of diastase, different kinds of starch, are attacked
by bacteria with different degrees of rapidity.
3. The action of bacteria on starch is manifested only in the absence
of other sources of carbon nutriment, and when access of air is not
prevented.
4. The action of bacteria on starch is effected by a ferment secreted
by them, and which, like diastase, is soluble in water, but precipitable
by alcohol.
5. This ferment acts precisely as diastase in changing starch into a
sugar capable of reducing cupric oxide, but not possessed of peptonising
properties.
6. The ferment itself is also capable of acting on starch in the
absence of oxygen.
7. The ferment is secreted by the bacteria also in neutral solution
of starch, and exerts its influence under these conditions.
8. This influence is expedited in slightly acid solutions.
The author concludes his paper with speculations as to the con-
ditions under which bacteria are capable of generating this- amylolytic
(diastatic) ferment, instead of the ordinary peptonising one.
D. P.
Cultivation of the Cacao Tree. By Boussingault (Compf.
rend., 96, 1395 — 1399). — The cacao tree requires a rich deep moist
soil, in shaded localities, close to the sea or to rivers. The tree flowers
when about thirty months old, and the fruit is ripe about four months
after the fall of the flowers. The weight of the fruit varies from
300 — 500 grams, and after picking they are exposed to the sun during
the day, and placed under sheds at night. Active fermentation soon
sets in, but if allowed to proceed too far is injurious. The cacao is
decorticated by careful roasting, which also develops an aroma, due to-
a minute quantity of a volatile oil. Examination of Trinidad cacao
showed the presence of butter, starch, theobromine, asparagine, albu-
min, gum yielding mucic acid, tartaric acid free and combined, solu-
ble cellulose, ash, and indeterminate substances. Decorticated cacao,
slightly roasted and separated from the seeds, forms the basis of choco-
late, which, when genuine, consists only of cacao and sugar. The
superiority of chocolate over tea, coffee, mate, &c., is due to the fact
934 ABSTRACTS OF CHEMICAL PAPERS.
that in addition to theobromine it contains in a small bulk a large
quantity of food materials, and indeed approximates in composition to
milk. C. H. B.
Analytical Chemistry.
Use of Hydrogen Peroxide in Analytical Chemistry. By
A. Classen and 0. Bauer (Ber., 16, 1061 — 1074). — When hydrogen
peroxide is added to a solution of ammonium or sodium sulphide, and
the liquid boiled, the whole of the sulphur is converted into sulphuric
acid. This reaction furnishes a method for the quantitative estima-
tion of hydrogen sulphide, either as gas or in solution, and of the
sulphur in metallic sulphides, the sulphuric acid obtained on oxida-
tion being precipitated in the usual way as barium sulphate. The
method applies also to the estimation of sulphurous acid and
sulphites. To estimate hydrochloric acid in a solution containing
hydrogen sulphide, ammoniacal hydrogen peroxide is added, and the
solution boiled until no more oxygen is evolved ; silver nitrate and
nitric acid are then added, according to the usual method. In esti-
mating hydriodic and hydrobromic acids in the presence of hydrogen
sulphide, the method is the same, except that sodium carbonate takes
the place of the ammonia. Arsenious sulphide in ammoniacal solu-
tion is oxidised by the same reagent to arsenic acid and sulphuric
acid, the former of which can be precipitated as ammonium magne-
sium arsenate, and weighed as pyroarsenate, and the latter as barium
sulphate. Antimonious sulphide is also completely oxidised by hydro-
gen peroxide, whilst in the case of the pentasulphide only a partial
oxidation can be effected. A more convenient method of analysing
sulphides decomposable by hydrochloric acid is to pass the evolved
hydrogen sulphide into the alkaline hydrogen peroxide, a current of
carbonic anhydride being driven through the apparatus, then acidu-
lating the solution with hydrochloric acid, boiling to decompose the
excess of peroxide, and precipitating with barium chloride. The
sulphides of antimony, tin, cadmium, and iron can be treated in this
way. The oxidation and estimation of sulphites is carried out in the
same way as in the case of the sulphides. A. K. M.
Distillation of Wine, By S. Kiticsan (7?«r., 16, 1179—1183).—
The author having repeated Liebermann's experiments (Ber., 15, 154,
438, 2554) on the distillation of wine, finds that the distillate contains
ammonia and formic acid, and that the precipitate produced on
addition of silver nitrate contains organic silver salts ; Wartha's
method (Ber., 15, 437) for detecting sulphurous acid in wines is there-
fore untrustworthy. Old wines contain from 0'0057 — 0*034 per cent,
of ammonia. W. C. W.
ANALYTICAL CHEMISTRY. 935
Estimation of Carbon Bisulphide in Thiocarbonates, By
A. MiJNTZ (Compt. rend., 96, 1430— 1433).— 30 c.c. of the thiocar-
bonate (i.e., 42 grams, since the sp. gr. of the commercial product
is 1"4) is introduced into a flask of 500 c.c. capacity, and mixed
with 100 c.c. of water and 100 c.c. of a saturated solution of zinc
sulphate, and the flask closed with a caoutchouc stopper, through
which passes a long tube bent at right angles and drawn out to a
point at the far end, the upper part being surrounded by a condenser.
The tube dips into a narrow cylinder of 60 c.c. capacity, graduated
in 0*1 c.c. This cylinder contains about 30 c.c. of ordinary petroleum,
the volume of which is accurately read off, and the tube is arranged
so that its extremity is immersed to about two-thirds the total depth
of the petroleum. The flask is agitated, and when the evolution of
gas slackens, the liquid is very carefully heated, the temperature being
gradually raised to ebullition, and the boiling being continued until
10 — 12 c.c. of water has condensed in the graduated cylinder. The
carbon bisulphide which is given ofi" dissolves in the petroleum with-
out contraction. At the close of the operation, the total volume of the
liquid in the cylinder is read off, the volume of the condensed water
subtracted, and 0*2 c.c. added to the increase in the volume of the
petroleum, in order to correct for the small quantity left adhering to
the tube. The corrected increase in volume multiplied by 1*27
(sp. gr. of carbon bisulphide) gives the weight of carbon bisulphide in
the 30 c.c. of thiocarbonate. If the petroleum at the lower part of
the cylinder dissolves so much carbon bisulphide that it becomes
heavier than water, and sinks below the condensed water, the total
volume of the liquids is read off, the cylinder closed with the thumb,
and gently inclined so as to mix the separated layers of petroleum,
and the volume again read oflf after standing about 15 minutes.
Copper sulphate, lead acetate mixed with acetic acid, and recently
precipitated lead sulphate may be used instead of zinc sulphate. The
method gives good results. C. H. B.
Occurrence and Estimation of Free Tartaric Acid in Wine.
By A. Glaus (Ber., 16, 1019— 1022).— The author has previously
pointed out that the presence of small quantities of tartaric acid in
wine is no proof of adulteration. From the examination of a number
of pure but poor wines, he finds a percentage varying from 0"01 to
0'05. Weigelt (Ber., 16, 812) also finds about the same amount, viz.,
0"01 — 0*059 per cent. This is easily accounted for by the fact that
the grapes employed in the manufacture of the wine are not all ripe,
the unripe ones containing the free acid.
To estimate the free tartaric acid, the wine is evaporated to dryness,
and the residue heated in an air-bath at 110°. It is then extracted
with alcohol, and the acid precipitated by means of potassium acetate.
If a known quantity of tartaric acid is added to a wine free from acid
and an analysis is then made, the results obtained will vary according
to the composition of the wine ; the tartaric acid added decomposing
the salts of other acids, part of which are volatilised during the
evaporation, and thus a low result will be obtained. From the
amount of tartaric acid which in this way becomes latent, the author
936 ABSTRACTS OP CHEMICAL PAPERS.
suggests the possibility of devising a method for estimating the value
of a wine. A. K. M.
Examination of Fats. Bj K. Zulkowsky (Ber., 16, 1140 —
1142).— Groger'a modification (Dingl polyt. /., 1882, 244, 303, and
246, 286) of Hausamann's method {ihid., 240, 62) of testing fats
depends on the fact that fatty acids are at once saponified by alcoholic
potash, whereas neutral fats are only saponified on boiling.
Phenolphthalein is added to an alcoholic solution of the fat, and
standard alcoholic potash dropped in until the red coloration disap-
pears. Excess of standard potash is then added, the mixture boiled
for half an hour, and the excess of alkali determined volumetrically.
In this way the amount of fatty acids and of neutral fats is ascer-
tained.
The author points out that the quantity of fat saponified by a litre
of the normal alkali, gives a clue to the nature of the fat, and would
for example distinguish between artificial and natural butter.
The amount of glycerol in fats can be estimated in this way, each
CO. of normal alkali required to saponify the neutral fat corresponding
with 0-030667 gram of glycerol.
If the fat is dry and pure, then the weight of neutral fat F— G
[G = (0'012667t;)] = the amount of fatty acids, when v = the c.c. of
standard potash used.
The molecular weight of the fatty acid can also be ascertained.
w. c. w.
Technical Chemistry.
Modifications of Silver Bromide and Chloride. By H. W.
YoGEL {Ber., 16, 1170 — 1179). — After referring to the researches of
Stas {Ann. Chim. Phys., 1874, 2, 3), Monckhoven, Eder {Theorie und
Praxis der Gelatinemiilsion, 1 Aufl., 9) and Abney (Proc. Roy. Snc.^
1881, No. 217). the author states that only two modifications of silver
bromide exist, viz., one precipitated from aqueous, and a second from
alcoholic solutions. The former is most sensitive to the blue rays of
the solar spectrum (wave-length 450) ; the latter has its maximum of
seusibility in the indigo between 438 and 440.
The formation of these two modifications is neither influenced by
the presence of gelatin or collodion, nor by the temperature at which
the precipitation takes place. The nature of the silver bromide does
not depend on whether an excess of silver salt or of alkaline bromide is
used in the precipitation ; neither does treatment with ammonia change
the particular, modification produced. The variety sensitive to indigo
rays is only produced in solutions containing alcohol of at least 96 per
cent. It cannot be brought into a finely divided state by shaking with
gelatin solution, but this is easily effected if collodion is used. The
TECHNICAL CREMISTRY. 937
variety sensitive to blue rays on the other hand, is easily obtained in
a finely divided state in gelatin, but not in collodion. For photo-
graphic purposes, the silver bromide is always precipitated in presence
of gelatin solution or collodion, in order that it may be obtained in a
very finely divided state.
The modification sensitive to blue rays is more diflSciilt to reduce to
the metallic state than the indigo modification. Collodion plates are
therefore much more rapidly acted on by the "chemical developer"
— ammonium pyrogallate — than gelatin plates. Collodion silver bro-
mide plates are more easily acted on by sensitisers than the gelatin
plates. The variety of silver bromide sensitive to blue rays is 15
times more sensitive to chemical than to physical developers ; the
other modification is only three times more sensitive to chemical
developers. If any excess of bromide is used in preparing the silver
bromide, and the precipitate is heated for some hours in water, the
sensitiveness of the first modification increases, but the variety sen-
sitive to indigo rays is not affected by this treatment. The finely
divided silver bromide sensitive to blue rays has a tendency to adhere
together, forming a compact mass, which is less soluble in sodium
thiosulphate than ordinary silver bromide. Although the indigo
modification is more easily reduced than the blue variety, the latter
is more sensitive to the action of light.
Silver chloride gelatin emulsion is most sensitive to ultra-violet rays
of light between Fraunhofer's lines H" and H', the maximum of
sensitiveness of silver chloride collodion emulsion lies between Gr and
H, about wave-length 410. W. C. W.
Scientific Basis of Antisepsis and Origin of Septic Poison.
By P. ZwEiFEL (Zeitschr. Phijsiol. Ghem., 6, 388-421).— The practical
application by Lister of the principles of antisepsis in surgery, in
aiming at the destruction during operation, and the subsequent exclu-
sion during recovery by appropriate dressings, of pathogenic organisms
or germs believed to enter from the air and external surroundings,
has been successful in preventing the occurrence of putrefaction in
wounds. Hence it has been conjectured that the healthy body itself
must be free from these causes of putrefaction if the above results are
due to the protection of the wound from their access from without ;
otherwise if existing already in the organism, what benefit is likely
to arise from such efforts designed to ward off' bacteria from superficial
parts ?
The earliest experiments concerning the presence of putrefactive
germs in the normal and healthy organism are those of Billroth and
Tiegel, in which the various portions of the body experimented upon
were rapidly removed after the animal had been bled to death by
excision with a knife previously heated to redness, and at once im-
bedded in paraffin. The results were apparently affirmative.
The author repeated the methods of these investigators, and
showed that it was impossible to avoid sources of error, there being
an unavoidable if only momentary exposure to air to begin with, in
the act of removing the organ from the body to the paraffin, and those
viscera which chiefly, without exception, became putrid, were the
938 ABSTRACTS OF CHEMICAL PAPERS.
pancreas, liver, and spleen, precisely tbose to which previons access
of germs from the intestinal canal was most likely to have taken
place.
Burdon Sanderson obtained like results. Similar objections as to
exposure to the air for periods however brief, attach to the method
by which at a later period Nencki and Giacosa sought to establish the
occurrence of bacteria in healthy tissues, in which the organs investi-
gated were at once upon removal plunged into bell-jars filled with
mercury previously heated until mercurial vapours were given off,
and then covered over with a thin stratum of carbolic acid solution.
After the immersion of the organ, the whole apparatus was then
transferred to the culture oven, and kept at a constant temperature of
38 — 40°. All possible precautions were employed by the above-named
experimenters to prevent the access of germs by means of the instru-
ments and other parts of the apparatus.
It is evident that only under rigidly absolute conditions of air
exclusion can the question of the pre-existenee of such germs in
healthy tissues be decided. This is certainly inconceivable as regards
solid structures which cannot be subjected to experiments without
some degree of exposure to the air, and it is only in the case of the
blood which admits of being drawn directly from the artery or vein,
and at once transferred to the previously disinfected mercury, that
these conditions can be met. Blood was accordingly employed by the
author in his crucial series of experiments, being drawn from the
vessel under antiseptic precautions. Thus drawn and maintained at
constant temperatures under mercury, no signs of putrefaction blood
appeared.
The author repeated the experiment with the heart, an organ
admitting of almost instantaneous removal from the body, but in every
instance putrefaction occurred.
Microscopic examination of the blood thus preserved from contact
with air, revealed the constant presence of various coccus forms in
lively movement, confirming earlier observations in this direction,
especially those of Hensen.
To decide whether the difference in results between the two sets of
experiments with blood and with the heart was due to the influence
of air and its germs, another series was made in which air was
designedly introduced by means of a small glass syringe into the blood
under the bell-jar : no putrefaction took place, but when the blood
was first received in a saucer, and then taken up into a syringe and
brought under mercury, all the signs of putrefaction and evolution of
gases occurred. Seeing that the blood to which air had been added
underwent no change, whilst the heart, muscle, and other solid organs,
after short contact with air in removal became putrid, it became appa-
rent that the blood is not adapted as a medium for the development
of bacterial germs. But this could presumably depend only on the
larger proportion of oxygen in the blood, which otherwise is analogous
to the solid tissues, and extremely putrescible under conditions of
warmth and moisture.
Experiments were instituted to determine this point as to the in-
fluence of oxygen, in which the oxygen was removed from its solution
TECHNICAL CHEMISTRY. 939
in the blood by means of hydrogen gas ; and in the other the solid
organs were exposed in an atmosphere of pure oxygen. The results
were remarkable. The blood thus deprived of its oxygen underwent
putrefactive changes, whilst the heart and other organs remained
unchanged. Venous blood reacted in the same way as arterial.
Experiments were made to determine the infectious quality of the
blood which had been withdrawn under antiseptig precautions, and
maintained for days under mercury at a temperature of 38 — 40° 0.
If the presence of oxygen hinders the advent of septic changes,
blood, which with its oxyhsemoglobin has been preserved at 40°,
will not be septic. On the other hand, the mere withdrawal of its
oxygen and the conditions of experiment remaining unchanged, will
make it of septic quality.
The blood in these experiments was injected into the peritoneal
cavity of rabbits. Blood, from which the oxygen had been removed
by displacement with hydrogen alone, showed septic qualities, the
animals dying of septicaemia. The author refers to the circumstance
that in place of fever, a lowering of the temperature was observed ;
but recalls the fact that peritoneal septicaemia may run its course
without elevation of temperature.
Similar results were obtained in experiments in which Potain's
apparatus replaced hydrogen, thus removing any objection as to a
possible noxious influence of this gas. The whole series of expe-
riments establish the fact that blood from which the oxygen has been
removed and for eight days maintained at a temperature of 40°,
becomes of viralent quality through the development of something
analogous to the septic poison. The blood, it is to be noted, had no
positively putrid smell, but was either quite odourless or faintly
mawkish, resembling that of a slaughter-house. As Septicmmia is
derived from septicos, putrid, this term is not an accurate one for
the blood poison, which for the present may be designated " Anoxy-
gerihcemia.''
The author infers from these results that blood from which
oxygen is expelled, and which has been kept at a blood heat for
eight days, becomes, even when it has been derived from a perfectly
healthy animal, virulent, the poison thus generated being the septic
poison or nearly allied thereto, and that the change is effected without
the concomitant presence of atmospheric germs. Tliis poison would
appear to have not a fermentative, but a chemical effect, as it kills
only in a certain somewhat large dose, strong animals being able to
resist and recover from it. The withdrawal of oxygen is the essential
point, and this, with a large amount of blood (taken by the author
from the carotid artery), preservation for eight days, and a tempe-
rature of 38 — 40°, are the conditions of success.
Whether or not two different sorts of organisms exist in normal
blood, of which one cannot undergo development in presence of much
oxygen, but only exhibits its properties in the absence of this gas, is a
crucial point of this problem.
Pasteur has already described, as the result of experiments con-
ducted with Joubert and Chamberland, that the septic bacteria can
940 ABSTRACTS OF CHEMICAL PAPERS.
develop only when oxygen is excluded, as in a vacuum or in carbonic
acid. Kaut'raann, Grossmapn, and Mayerhausen have found that the
rod bacteria were killed by the introduction of pure oxygen. In the
present instance, however, healthy blood has acquired septic pro-
perties upon withdrawal of oxygen. As to whether in the treatment
with oxygen other morphological elements thrive than in the opposite
condition, this is denied by the author. The formation of the virus
is apparently independent of micrococci and a result of purely chemical
influences. D. P.
Hardening of Soft Calcareous Rocks by means of Fluo-
silicates of Insoluble Bases. By L. Kessler (Compt. rend., 96,
1317 — 1319). — The ordinary method of hardening calcareous stone by
means of alkaline silicates has many disadvantages, mainly owing to
the fact that it leaves the stone impregnated with soluble alkaline
salts. The author proposes to treat the stone with a solution of a
fluosilicate of some metal which forms an insoluble oxide, such as
magnesium, aluminium, zinc, or lead. Carbonic anhydride is given
off, and calcium fluoride, silica, and alumina, or the carbonate of lead
or zinc, or magnesium fluoride, are formed, all these compounds being
more insoluble than the stone itself. No soluble salts are introduced
into the stone, and stones treated in this manner do not sufPer from
the action of frost. In order to give a smooth surface to rough stones,
some of the powdered stone is made into a paste with water, applied
to the surface of the stone, and, after drying, treated with the fluo-
silicate solution. The paste soon becomes as hard as the stone itself,
and by mixing the paste with various insoluble colouring matters,
many different effects can be produced. If some coloured fluosilicate,
such as copper fluosilicate, is used, the stone is coloured for a con-
siderable depth, and usually various markings are produced, owing to
the unequal absorption of the colouring matter by different parts of
the stone, which is not homogeneous. C. H. B.
Treatment of the Washings from Wool. By Delattke (Compt.
rend., 96, 1480 — 1483). — The crude potassium carbonate obtained
from the suint which is extracted from wool by systematic washing
has the average composition, K2CO3 = 80 ; K2SO4 = 6 ; KCl = 4 ;
Na2C03 = 3 ; insoluble, 5 ; loss, 2 = 100. After the removal of the
suint, the wool is washed systematically, and the washings are allowed
to run into deep narrow cisterns, where they deposit a heavy sand,
which makes an excellent manure. The liquid is then run into a
larger cistern, at the entrance to which it meets with a jet of hydro-
chloric acid or acid ferric chloride, which liberates a large quantity of
fatty acids. These rise to the surface and are skimmed off, and the
acid liquid is. run into a tub provided with a mechanical agitator,
treated with milk of lime, and run into another cistern where the cal-
careous matter is deposited, the clear liquid being allowed to run
away into the river. The calcareous deposit constitutes a very rich
vegetable soil, or may be used for making bricks. The fatty acids are
compressed at a moderate temperature, and yield an oil which fur-
nishes a good illuminating gas, and a solid cake containing a con-
TECHNICAL CHEMISTRY,
941
siderable proportion of fragments of wool and nitrogenous substances.
This method is profitably applied to the wash-water from 6,^)00,000
kilos, of wool per annum. C. H. B.
Mineral Combustibles. By Boussingault (Gompf. rend., 96,
1452 — 1456). — The following table shows the composition of a number
of combustible substances from South America and other localities : —
1
2
3
4
5
6
7
Carbon
Hydrogen ....
Oxygen
Nitrogen ....
86-82
13-16
0-00
0-02
82-85
13-09
4-06
0-00
85-29
8 24
6-22
0-25
77-84
8-93
11-54
1-70
82-7
10-8
6-5
0-0
71-89
6-51
21-57
0 03
80-96
5-13
12-50
1-41
8
9
87-81
10
93-05
11
12
13
14
Carbon
87-05
92-25
94-83
97-6
97-87
Hydrogen ....
5-00
3-88
3-35
2-27
1-27
0-7
0-37
Oxygen
6-56
7-67
3-43
4-94
3-16
1-7
1-70
Nitrogen ....
1-39
0-64
0-17
0-54
0-74
—
0-06
1 and 2 are analyses of bitumen from the fire pits of Ho-Tsing in the
province of Szu-Tchnan, China. This bitumen is dark green by
reflected light, brown by transmitted light. It is liquid at ordinary
temperatures, but when cooled deposits a crystalline granular mass of
naphthalene. Column 1 gives the analysis of the portion remaining
liquid. Column 2 the analysis of the semi- solid portion. 3. Egyptian
asphalt, which left an ash consisting of ferric oxide. 4. Bitumen of
Judea, found floating on the Dead Sea. 5. Fossil resin, resembling
amber in appearance, from the auriferous alluvium at Giron, near
Bucaramanga, New Granada. 6. Fossil resin from the auriferous
alluvium of Antioqnia, New Granada. 7. Coal from Canoas, plateau
of Bogota ; height, 2800 m. It occurs in grit connected with neocomian
limestone. 8. Fibrous coal from Antioquia. 9. ^^ Fiisain" from
Blanzi. 10. " JT'wsam " from Montrambert, Loire. Fusain is a variety
of coal, resembling wood-charcoal in appearance. Some stalks, the
interior of which is composed of fusain, are covered with a bark which
has been converted into coal. It is apparently the fossil form of wood
which was dried by exposure to air before becoming embedded, and
which has not undergone the same changes as vegetable debris which
decomposes in swamps. 11. Anthracite from Chili. 12. Anthracite
from Muso, New Granada. It occurs in masses in the schists in the
emerald mines. It is hard, brilliant, and takes a very high polish ;
sp. gr. 1-689. 13. Anthracite supposed to come from Brazil. 14.
Graphite from Kaison. C. H. B.
942 ABSTRACTS OF CHEMICAL PAPERS.
Investigation on Boiler Fires. By F. Fischer (Dingl polyt. J.,
248, 73 — 76). — The author has recently examined the flue gases from
a boiler furnace, the evaporation trials being made by Kobus. On the
22nd February, 1883, an experiment was made, which lasted from
9*30 A.M. to 6 P.M. Forty gas analyses and 40 determinations of tem-
perature at intervals of 10 minutes, gave as a mean CO2 = 5*96 per
cent., 0 = 14*55, N = 79'49, and temperature 221" in the gases carried
away. The temperature of the admitted air was 37°. To lessen the
influx of air, the back of the furnace was covered with stones. The
second trial was made on the 27th February, from 10 a.m. to 6 p.m.
The temperature in the boiler-house was 30°. From an average of
41 determinations of the gases carried ofF, CO2 = 9" 50, 0 = 9*90,
N = 80*6 ; temperature 196°. The coal used had the following com-
position : —
C. H. O. N. S (volatile). HgO. Ash.
80-18 6-29 8-10 061 052 1-08 4*22 (O'll S)
corresponding to a fuel value of —
8100 X 80-18 + 34220 x (5'29 - -%^) + 2500 x 0-52 ^ ^,973
100 '
calculated on water at 0° as combustion product. The hydrogen in
1 kilo, coal produces, by combustion, 0*476 kilo, water plus the
hygroscopic water, making a total of 0*487 kilo., so that by taking
water- vapour at 100° as combustion product, 310 or (as the tempera-
ture of the coal is 30°; 295 must be deducted, leaving, say, 7680 as
fuel value. The loss of heat, due to the high temperature of the
flue gases was equal to the following (salphurous anhydride being
disregarded) : —
1 kilo, coal gives. Loss of heat.
CO2 . 1-487 cm. 1-487 cm. 120 105
O 3-630 1-549 208 80
]Sr 19-833 12-616 1118 642
Steam 0*487 k. 0-487 k. 28 22
-f Atmospheric moisture . 0-570 0-401 60 32
1524 881
So that on the first day 20 per cent., and on the second day 11 per
cent, of the f uelvalue was lost. In order to arrive at accurate data for
judging as to the most economical mode of firing, the author thinks as
a rule five or six analyses of the smoke gases suffice to form an
opinion ; if, however, the analyses show wide differences, it is best to
determine the carbonic anhydride and oxygen, say, every five minutes
during one hour. D. B.
Process for Preparing Weatherproof Wall Paintings.
{Bingl. polyt. /., 248, 92). — According to Keim, the ground colour is
TECHNICAL CHEMISTRY. 943
prepared from a mixture of slaked lime, sand, and water, which, after
drying, is polished with rough sandstone and saturated with potash-
water glass. The ground on which the painting is produced consists
of a mixture of 4 parts quartzy sand, 3*5 marly sand, 0*5 infusorial
earth, 1 caustic lime, and the requisite amount of distilled water.
After drying, the painting-ground is saturated with hydroflnosilicic
acid and again dried, when it is ready for use. The picture is washed
with a hot solution of potash water-glass, dried, treated with a solu-
tion of ammonium carbonate, and washed. D. B.
New Substance obtained from some of the Commoner
Species of Marine Algae ; Algin. By E. C. C. Stanford (Chem.
News, 47, 254—257, and 267— 269).— The main object of the present
paper is to introduce a new seaweed industry, the present uses for
this substance being very limited, and in some cases a great loss
of useful material occurs in the preparation of the products for
commercial purposes. In the process recommended by the author,
the sea-weed is first macerated with cold water by was-hing in a num-
ber of vats in turn, by which means about one- third of the weight of
the sea- weed is removed. The weed is now bleached with chlorinated
lime-water, treated with acid^ and washed. To extract the algin, it is
acted on with one-tenth of its weight of sodium carbonate for 24 hours
in the cold, and is then carefully heated, filtered, and evaporated :
the residue on the filter is cellulose, and can be used in the manu-
facture of paper. The result of this treatment of laminaria is the
separation of the sea- weed into the following parts : — Moisture, 20 ;
extracted by water, 30 ; extracted by acid, 5 ; extracted by sodium
carbonate {algin), 35 ; and cellulose, 10 per cent.
When evaporated to dryness the aqueous extract forms a viscid mass,
consisting of the salts mixed with a saccharine matter resembling man-
nite in appearance ; this precipitates Fehling's solution to the extent
of 15 per cent, glucose ; it does not ferment, and would hence be very
useful, but as yet there is no process for separating it from the salts.
The whole mass is therefore carbonised and treated in the usual manner
for separating the iodine and salts. Analysis of mixed samples of the
salts yielded the following results : —
Laminaria Fueus
vesiculosus. stenophylla.
Calcium sulphate 1'69 4'33
Potassium sulphate 11*29 23-62
Potassium chloride 19-90 13-71
Sodium chloride 60-96 58-20
Magnesium chloride 4-35 —
Sodium carbonate 0-53 —
Sodium iodide 1-26 0-12
99-98 99-98
From experiments, it is demonstrated that the extraction is prac-
tically complete after four macerations.
944 ABSTRACTS OF CHEMICAL PAPERS.
The sodium carbonate extract is evaporated, and the residue (the
algin combined with soda) when dry resembles gum in appearance, but
can be obtain( d in thin transparent flexible sheets. The solution is
slightly alkaline ; any great excess of sodium carbonate apparently
destroys the algin, whilst excess of acid gelatinises it so that a solu-
tion of only 2 per cent, becomes semi-solid when acidified. A solution
can be neutralised without the algin being precipitated. The solution
gives the following reactions with various reagents. Dilute mineral
acids generally coagulate it. Boracic acid, however, has no effect; and
it is not affected by acetic, formic, citric, tartaric, or benzoic acids.
Barium, calcium, strontium, copper, zinc, aluminium, tin, antimony,
cobalt, and nickel salts all precipitate it. Ferric chloride gives a dark
brown coagulum ; mercurous nitrate forms a white precipitate, but
mercuric chloride and silver nitrate have no effect. Both basic and
normal lead acetates give white precipitates. It is unaffected by mag-
nesium salts ; by potassium silicate, dichromate, ferrocyanide, and
permanganate ; and by sodium borate, tungstate, stannate, and suc-
cinate; and by tannin. Concentrated sulphuric acid dissolves it; con-
centrated nitric oxidises it, oxalic acid being amongst the products.
From these reactions, it will be seen that it differs from all similar sub-
stances : thus, from albumin by not being coagulated when heated, and
by not precipitating silver nitrate; from gelose, by being soluble in
dilute alkalis, but insoluble in boiling water, gelose is just the reverse ;
from gelatin, by giving no reaction with tannin ; from starch, by not
reacting with iodine ; from dextrin, &c., by being insoluble in dilute
alcohol and dilute mineral acids. The purest form of algin is the
precipitate produced by a mineral acid. It dries to a hard homy sub-
stance.
The composition of this substance is still obscure, for although the
compounds with calcium, aluminium, barium, and lead have been
investigated, no uniform results have been obtained. The sodium
carbonate appears to be unaltered in its compound with algin ; the
carbonic acid is, however, only given off by treating with excess of
hydrochloric acid, and heating. When a solution of algin is precipi-
tated by acid, re-dissolved in alkali, and this treatment repeated,
decomposition seems to go on continually. The author then suggests
various uses for algin, founded on the properties above described ;
mixed with starch it could be used as a stiffener for fabrics, or alone
as a dressing material, or as a mordant. It would also form a useful
food. It can be used to prevent boiler incrustations, for lining wines
and spirits, for insulating electrical appliances, &c. It can also be
used to replace horn for the manufacture of various moulded articles.
D. A. L.
945
General and Physical Chemistry.
Electric Researches. By G. Quincke (Ann. Phys. Chem., 19,
705 — 782). — Dielectric Constants of Insulating Liquids. — Faraday con-
ceived tliafc in every point of an insulating dielectric there is a strain
in the direction of and a stress normal to the lines of force. If P be
the difference of potential, and a the distance between two condensing
plates, k the dielectric constant of the intervening medium, then,
according to Clerk Maxwell, the strain parallel to is equal to the
strain normal to the lines, both being expressed by the equation (1)
^ p2 .
p = ~ — - According to Helmholtz, these values vary with the
nature of the insulating substance.
If a condensing plate of area O be placed in a liquid of dielectric
constant k, then the quantity of electricity collected upon Q = CP =
OP
k- — , where C is the capacity of the condenser. The constant, k, of
47ra
equation (2) is, according to Maxwell and Helmholtz, equal to the
constant, ki, of equation (1), and according to Maxwell equal to the
square of the refractive index for a wave of infinite wave-length.
Helmholtz supposes that two quantities of electricity, E and E',
attract one another with the same force as two quantities, Ey^A;
and El \/k, when separated by a dielectric medium of constant k.
The values of k for different liquids have recently been made the sub-
ject of various investigations at the hands of Silow, Werner Siemens,
Gordon, and Hopkinson. The author has determined for a number
of liquids the constants ki and k according as the stress acts parallel
or normal to the lines of force.
1. In order to determine the dielectric constant kp for a strain
parallel to the lines of force, the author used a form of induction
balance enclosed in a glass vessel filled with air or the liquid to be
examined ; the condensing plates were connected with a Thomson's
screw electrometer. The plates were charged by a Holz' machine or
a Ruhmkorff 's coil. Great care was taken in the introduction of the
liquids within the glass vessel in order to avoid contact with dust and
absorption of water. The various parts of the apparatus are described
at length in the original memoir. The value for kp found for the
strain within the liquid corresponds to ki of equation (1).
2. At the same time the dielectric constant k was determined by
the ordinary method of measurement of the capacity of a condenser
(vide equation 2), formed by the plates of the electric balance when
immersed in air or an insulating liquid.
3. The electric stress ks normal to the lines of force was estimated
by the pressure exerted on an air bubble with the insulating liquid in
which the condenser was immersed. On the lower plates of the con-
denser a vertical metal tube was soldered ; this was connected with a
VOL. XLIV. , 3 s
946 ABSTRACTS OF CHEMICAL PAPERS,
glass tube, on which was fused a U-shaped manometer half filled with
a mixture of carbon bisulphide and ether of sp. gr. 1*2720. Through
this arrangement the bubble of pure dry air was introduced. The
difference of level in the two limbs of the manometer depends on the
height of the liquid in which the condenser is immersed, and the
capillary pressure of the air bubble. On connecting the plates with
a Ley den battery, the electric stress of the liquid acts on that of the
air bubble, causing it to contract : this produces a fall in level of the
Outer branch of the manometer, which is proportional to the difference
of potential of the plates. This difference in level was measured by a
cathetometer microscope, described at length in the memoir. The
value for hs can thus be deduced from equation (1).
The values found for Tii, hp, and hs, and the refractive index no of
some of the liquids examined, are ^given in the table below.
Dielectric constants.
2-396
3132
0-061
2-217
2-669
2-743
2-05
2-325
2-375
2-443
2-385
3-296
1-94
2-259
2-356
1-705
2-138
2-149
Refractive ( * ^
Liquid. index. Je. Icp k^
Ether 1-360 3-364 4-851 4-672
5 vol. ether + 1 vol. carbon bi«
sulphide 1-4044 2-871 4-136 4-392
1 vol. ether + 1 vol. carbon bi-
sulphide 0-9966 2-458 3-539 3392
1 vol. ether + 3 vols, carbon bi-
sulphide 1-5677
Carbon bisulphide 1-6386
Benzene (from benzoic acid). . . . 1-505
Rape-seed oil 1-4743
Turpentine 1-4695
Petroleum 1-4482
Maxwell's theory that values for Ari, Tcp, and A;,, and that of the
square of the index of refraction, are equal, is not confirmed. In most
cases Tcp and hs are approximately equal, and, with the exception of
rape-seed oil, are always greater than h. If a volume Vi of a liquid
of dielectric constant hi, and v^ of a liquid of dielectric constant ho,
be mixed, the mixture has approximately a dielectric constant h =
-^ — ; — — The observed values and those calculated from this equa;-
vi -\- vz • ^
tion are given for various mixtures of carbon bisulphide with ether
and turpentine. Further determinations of h by Siemens* method are
given, the values of which are only approximately equal to those
given above, the discrepancy being explained by differences in the
conditions of the experiment. They prove, however, the inaccuracy
of Maxwell's law.
Electric Double Befraction (comp. Kerr, Abstr., 1880, 599 — 601). —
The author formerly propounded the view that insulating sub-
stances display the phenomenon of double refraction when subjected
at various parts to unequal electric forces; but the hypothesis is
untenable, for Kerr has shown that carbon bisulphide between two
parallel metallic plates becomes doubly refractive when the plates are
GENERAL AND PHYSICAL CHEMISTRY. 947
charged as the coatings of a Leyden jar. Kerr has also proved that
in the case of carbon bisulphide the difference of phase in the rays of
light polarised parallel and normal to the lines of force is proportional
to the square of the difference of potential and inversely proportional
to the square of the distance of the plates.
The author has critically examined the phenomenon of double
refraction induced in various liquids, in an apparatus named an
"" electric liquid condenser," which is described at length. This appa-
ratus consists in the main of a German glass tube containing two
concentric nickel plates, the annular space between which is filled
with the liquid the electro-optic properties of which are to be
determined ; these plates are connected with a Thomson's screw
electrometer, and can be charged by a Holz' machine or a battery
of Leyden jars. If such an electric condenser is introduced between
two parallel or crossed Nicol's prisms whose plane of polarisation is
inclined at an angle of 45° to the lines of electric force, then the layer
of liquid enclosed between the metallic plates, through which the
polarised light passes, displays the same polarisation colours as a
crystal whose optical axis is parallel to the lines of force. In most
cases, the amount of birefringent action was measured by a Babinet's
compensator. Among the liquids examined in the above apparatus
were carbon bisulphide and ether, either alone or mixed in various
proportions ; pure, heavy, and light benzenes ; sulphur dissolved in
carbon bisulphide ; turpentine either alone or mixed with carbon
bisulphide ; and rape-seed oil. The determination of B, the birefrin-
gent action, follows from Kerr's law (vide supra), expressible by the
P I
equation d = B— -—7-, in which B is the difference of phase of the
^2 100
rays of light polarised at right angles to one another, P the difference
of potential, I the length of column of liquid relatively to 100 cm.,
and a the distance in cm. between the plates. If cylinders are used
instead of plates, then the expression R log — must be used instead of
Ivi
a, R2 and Hi being the respective lengths of the radii of the cylinders,
and R their difference. For the same liquid, the value of B is constant
for different values of P, 6, Z, and a, and can be characterised as the
electric double refraction for the liquid in question. In the table below
are given the mean values of B 10® for some of the liquids examined,
nickel plates being used.
Values for
Liquid. B 10^
Carbon bisulphide 32798
3 vols, carbon bisulphide +
1 vol. ether 27'252
1 vol. carbon bisulphide -f-
5 vols, ether 4'422
Pure benzene 3'842
Values for
Liquid. B lO".
Rape-seed oil - 2-273
Ether — 6*4
Turpentine 0*109
From the table above, it will be seen that petroleum and turpen-
tine display practically no birefringent action. In the case of mixtures
3 s 2
948 ABSTRACTS OP CHEMICAL PAPERS.
of liquids the electric double refraction cannot be deduced from an
equation B = , in which Vi v^ are the volumes of liquid in.
v^ -\- v-i ^ ^
the mixture, and Bi B2 their electric double refractions respectively.
The author calls attention to a peculiar phenomenon observed when,
the electric forces within the liquid are subjected to periodic fluctua-
tions by alteration of difference of potential in the charging apparatus.
Simultaneously with the necessary contraction or total disappearance-
of the dark stripes in the Babinet's apparatus, several bubbles rise
from the insulating liquid, and a musical note is heard, whose tone
decreases with the lowering of potential. The notes resemble those
obtained from a Dolbear's telephone.
Change of Refractive Index of Liquids hy Electric Forces. — With the
aid of the liquid condenser apparatus described above, the author has-
made a series of observations on the effect of electric forces on the
refractive index of liquids when charged as the glass of a Ley den jar.
An interference apparatus was used, which the author has constructed
for the examination of the influence of hydrostatic pressure on the
refractive index of liquids. The following are the principal facts
noticed in the course of the experiments : —
1. "With the same liquid, sometimes an increase and at other times a
decrease of refractive index is caused by electric forces, which can be
alternated either frequently or only once. This phenomenon probably
arises from a change of hydrostatic pressure within the liquid caused
by a vortex motion of the electric forces.
2. By the prolonged action of the forces, a decrease of refractive
index is noticed, corresponding to a rise in temperature of 0'0001° to
0"1°, which is increased by a greater difference of potential between
the electrodes and a greater viscosity of the liquid. This is appa-
rently due to a rise in temperature caused by a friction of the particles
within the liquid.
3. The electric current seems to pass intermittently and not con-
tinuously between the metallic plates. V. H. Y.
Theory of Galvanic Circuits. By A. Witkowski {Ann. Phys.
GJiem., 19, 844 — 849). — According to Sir William Thomson, the sum
of the heat evolved from the resistance in an entire circuit is equiva-
lent to the heat evolved in the same time by the chemical changes
produced within the circuit. On the other hand, Edlund (Abstr.,
p. 767) supposes that the amount of heat produced is equal to the
amount consumed by the B.M.F. within the circuit, without reference
to the concomitant chemical changes. In the present paper the author
seeks to reconcile these opposing theories. Imagine a circuit whose
temperature does not differ from its environment, and whose potential
energy is known from the mass of material, composition of solution,
and structure of its solid portion. Let a perfectly constant current
pass through the circuit when closed, and its temperature be kept
constant by the abstraction of heat from some parts and its addition
to others. On opening the circuit and testing the potential energy,
it will be found to be diminished by a quantity equal to the heat con-
GENERAL AND PHYSICAL CHEMISTRY- ,94d
•ducted away to the environment. It may be expressed in the following
equation : i^R = ki + 2X2*' — "SXfi + k\ in which i^B, is the heat
evolved by the resistance, 2X2^, ^^fi the sums of heat absorbed by
the contact surface within and that conducted away by surfaces from
without, ki the difference of chemical potential energy proportional to
the intensity of the current, and k' a change of energy independent
■of the intensity. Taking the latter as 0, then B = A; + 2X,2 — 2\/,
in which E is the E.M.F. Adopting Thomson's view, the equation
becomes E = k, or the E.M.F. is equal to the difference of potential
energy for unit of time and current. Edlund's hypothesis can also
be expressed by the same equation if we write \ = fi — v, in which
jiiov represents the quantity of heat evolved by chemical action ; the
equation becomes of the form E •= 2/t2 — 2/t/, or the E.M.F. is equal
.to the quantity of heat absorbed in the circuit.
According to this latter hypothesis the chemical action within the
battery is of itself of no intrinsic importance, but merely serves to
heat the contact surface causing the E.M.F. ; a thermoelectric pile is
then merely another form of a battery, the E.M.F. being caused by
the chemical processes occurring with the gas flame, which serves to
heat the junction. From the above, it is evident that as regards the
•estimation of E.M.F. both Thomson's and Edlund's hypotheses lead to
practically the same result. Y. H. V.
Difference of Positive and Negative Discharge. By H.
Hellmann (Ajin. Phys. Chem., 19, 816 — 818). — Goldstein for some time
past has investigated the question whether the difference of appearance
between the so-called positive and negative discharge is dependent
vcntirely on the external conditions of the discharge, and not on the
nature of electricity. The author has succeeded with a Crookes's tube,
filled with air, in obtaining simultaneously from both electrodes a dis-
charge of the same form and arranged in alternating striae. The red
-aureole and the concave striae appeared at both electrodes ; in the
middle of the tube were two striae opposed near to one another. The
.striae from the negative pole were farther distant from one another,
of a redder colour, and more curved than those from the positive
pole. The nearer the positive electrode and the greater the oscillation
of the commutator, the more marked were the negative striae. If
the induction apparatus ceased to work, the positive striae disappeared
first, while the negative striae became clearer, and finally disappeared.
V. H. V.
Researches on the Glow Discharge. By H. Herz (Ann.
Phys. Chem., 19, 782 — 816). — The author has investigated several
■questions as regards the phenomenon of the glow discharge in rarefied
gases ; the source of electricity used was a battery of 1000 secondary
Plante's elements, arranged in series of fives. By the aid of this
battery and various forms of apparatus, which are described at length
in the original memoir, the author shows (i) that the electric discharge
in rarefied gases is not, as Gassiot supposed, necessarily a discon-
tinuous phenomenon ; but under certain conditions, i.e., by the use of
;a battery of sufficiently low resistance, it has all the properties of
continuity, (ii.) The luminous rays from the kathode are a con-
950 ABSTRACTS OF CHEMICAL PAPERS.
comitant phenomenon of the discharge, but this cause is not identical
with that of the current ; these rays have practically no electrostatic
or electrodynamic properties, (iii.) The illumination of the gases by
the glow discharge does not arise from a phosphoresence induced
directly from the current, but only from the kathode rays. These
rays are electrically indifferent ; they resemble rays of light most
nearly, and their inflection on the approach of a magnet may be con-
sidered to be analogous to the phenomenon of plane polarisation of
light. V. H. y.
Observations on Thermo- and Actino-electricity of Quartz.
By W. Hankel {Ann. Fhys. Ghem., 19, 811— 844).— The author, after
enumerating the various results obtained in the course of his inves-
tigations on the phenomenon of pyro-, actino-, and piezo- electricity of
quartz crystals (this vol., 412, 640), proceeds to discuss the points
of difference between his results and those of Friedel and Curie (this
vol., p. 897). The latter have observed that pressure or cooling, —
approach of the molecules, — and release of pressure or warming, — sepa-
ration of the molecules, — call forth the same kind of electricity at the
ends of the crystallographic axes. The results of the author are, how-
ever, in direct opposition to this simple rule, and the discrepancy is
attributed by Friedel and Curie to an irregular cooling of the crystal.
Secondly, the latter do not consider actino-electricity to be a particular
phenomenon, but merely to be caused by an irregular heating of the
crystal. In the present paper the author describes various forms of
experiments made both to confirm his previous results, and to prove
that the position of the poles is reversed according as the crystal is
left or right handed. He has also extended his experiments on actino-
electricity, which is shown to differ from pyro-electricity in that,
firstly, the former causes a polarity of crystallographic axes precisely
the reverse of that which would be produced by the latter, were the
ray of light merely a source of heat. Secondly, actino-electricity
reaches its maximum about 40'^' after the commencement of the
radiation, and disappears at about the same interval of time after the
withdrawal of the radiating body ; whilst the pyro-electric difference
of potential is slowly evolved by heating or cooling the crystal.
Thirdly, it is proved that the actino-electricity is not produced by un-
equal heating of the crystal. But if the radiation be long continued,
then from the warming of the mass of the crystal pyro-electricity is
produced, causing ultimately an opposite polarity in the axes. Expe-
riments are also quoted to show that actino-electricity is a reversible
phenomenon, for the approach of a cold body near a crystal causes au
opposite polarity to that produced by a warm body. If Y be the
maximum potential produced by a radiation of given intensity, and y
the time in seconds from the commencement of the radiation, then
Ayjdt = a (Y—y), where <x is a constant. By integration, when
^ = 0, 2/ = 0 the formula becomes 3/ = Y— Ye~"* ; on removal of the
source of radiation, when t = 0, y = Y, then y = Ye""'. Experiments
are quoted to prove the accordance of the values calculated from these
formulae with those obtained directly by experiment. The author has
been unable to detect the phenomenon of actino-electricity in other
GENERAL AND PHYSICAL CHEMISTRY. 951
hemimorphous and symmetrical crystals, with the one exception of
cinnabar, which, like quartz, is hemimorphous in its secondary axes,
and in the direction of its principal axes rotates the plane of polarisa-
tion. In conclusion, the author gives a list of substances, crystallising
in perfectly symmetrical forms, which display the phenomenon of
pyro-electricity. Regular System. Fluorspar. Tetragonal System.
Idocrase, Apophyllite, and Mellite. Hexagonal System. Calcspary
Beryl, Brucite, Apatite, Pyromorphite, Mimetesite, Fhenacite, Pennine,
and Bio'ptase. Rhombic System. Topaz, Heavy Spar, Celestine,
Aragonite, Strontianite, Gerussite, Phrenite, and Natrolite. Monoclinic
System. Gypsum, Diopside, Orthoclase, Scolecite, Batolite, Euclase,
and Titanite. Triclinic System. Alhite, Pericline, and Axinite. The
author has been unable to detect the phenomenon of piezo-electricity
in perfectly symmetrical crystals. V. H. Y.
Determination of Vapour-density. By P. Pawlewskt (Ber.,
16, 1293 — 1297). — In this modification of Dumas's method, a cylin-
drical flask of only 20 — 30 c.c. is used ; it is drawn out to a thick-
walled tube 10 — 12 cm. long and 1 mm. internal diameter; the tube
is bent at 2 — 3 cm. from the flask, and is thickened to a conical form
at the extremity. A small glass tube is provided 10 — 12 mm. long
and 5 — 7 mm. broad, closed at one end, and containing a piece of thick
caoutchouc tubing ; this, when placed over the conical end of the neck
of the flask, makes a perfectly air-tight joint and obviates the neces-
sity of sealing the tube. In cases where many determinations have to
be made, to avoid trouble in cleaning and drying, it is better to
employ a flask having in addition an upright tube 8 cm. long and
1| — 2 mm. internal diameter, widened at the top, and closed by an
accurately fitting stopper. The determination is made as usual, but
the small size of the flask makes a medium-sized beaker a sufficient
bath. By constantly employing the same apparatus, the calculations
can be much simplified. A. J. G.
Relation between the Tension and Temperature of Satu-
rated Vapours. By A. Jarolimek (Monatsh. Chem., 4, 193 — 202). —
The author, in continuation of his researches on this subject already
noticed (p. 417 of this volume), now gives for all vapours the formula
^ = a H- bp^"^ -f -.
The constants are : —
a. h. c.
Water-vapour 8 97 — 5
Carbon dioxide -154-5 63 +13*5
Mercury 175 190*5 - 8
Alcohol - 8-2 90 - 3-5
952 ABSTRACTS OF CHEMICAL PAPERS.
a. b.
Ether -72-5 108
Acetone —56 112'5
Chloroform -68-5 118-5
Carbon bisulphide — 73-5 120
Carbon tetrachloride — 53'3 130
For the last five liquids, c may be neglected. H. W.
Congelation of Aqueous Solutions of Organic Bodies. By
F. M. Raodlt (Ann. Ghim. Phys. [3], 28, 133— 144).— By delicate
apparatus, the author has accurately determined the lowering of the
freezing point produced by dissolving organic compounds in water.
The lowering corresponding with a solution containing 1 part of the
substance to 100 of water he calls the coefficient of lowering^ and this
multiplied by the molecular weight, the molecular lowering. The
molecular lowering is sensibly constant for all organic compounds, and
may be calculated for any compound, as CpH^N^Oa, by the formula —
15j? 4- 15g + 30r + 30g
p -}- q + r + s '
In other words, the m^olecular lowering is the mean of the empiri-
cally calculated atomic lov^ering of the elements of the compound,
which is the same for all organic bodies, having the value 15 for
carbon and hydrogen, and 30 for nitrogen and oxygen.
These results have important practical applications in testing the
purity or strength of a liquid, and, above all, the law is available for
fixing the choice of a molecular formula in the many cases where the
determination of the vapour- density is impr?icticable. R. R.
Inorganic Chemistry.
Liquefaction of Nitrogen and of Carbonic Oxide. By S. v.
Wroblewski and K. Olszewski (Monatsh. Chein., 4, 415 — 416). — The
authors have liquefied these gases by the method previously applied
by them to the liquefaction of oxygen (see p. 781). Their lique-
faction takes place under conditions exactly similar to those required
in the case of oxygen, but is much more difficult. Neither of them
assumes the liquid state at — 136° under a pressure of about 150
atmospheres ; but if the gas be then suddenly relieved from pressure,
a brisk efiervescence of liquid is seen in the nitrogen tabe, like that of
liquid carbon dioxide when the tube containing it is plunged into hot
water. "With carbon monoxide the effervescence is not so strong. If
however the expansion be made not too quickly, and the pressure not
allowed to fall below 50 atmospheres, both nitrogen and carbon mon-
oxide liquefy completely, the liquid exhibiting a distinct meniscus and
INORGANIC CHEMISTRY. 953
volatilising very quickly. These gases cannot however be thus
retained in the liquid state for more than a few seconds : to retain
them in that state for a Jonger time would require a temperature
lower than any that the authors were able to obtain.
Nitrogen and carbon monoxide in the liquid state are colourless and
transparent. H. W.
Bleaching Powder and Analogous Compounds. By Gr.
Lunge and P. Naef (Annalen, 219, 129 — 161). — As Kraut has
recently taken up the subject of the constitution of bleaching powder,
directing a polemical paper against the investigations of Lunge and
Schaeppi (Abstr., 1880, 789), the authors have repeated their former
experiments, and those of Kraut, with a view of establishing the
correctness of the formula Cl.Ca.OCl first proposed by Odling. In
their former paper great stress was laid on the complete and ready
expulsion of all the chlorine in bleaching powder by carbonic anhy-
dride in the presence of a little moisture, as militating against the
presence of free calcium chloride. Kraut has shown that calcium
chloride, when treated with a mixture of hypochlorous anhydride and
carbonic anhydride, forms calcium carbonate thus : CaCla + CUO 4-
CO2 = CaCOs + 2CI2, and concludes from this that calcium chloride
is present as such in bleaching powder. But the authors point out that
this reaction can equally be explained by the intermediate formation of
bleaching powder and its subsequent decomposition thus : CaCl.OH +
HOCl = H2O -i- CaCl.OCl and CaCl.OCl + CO2 = CaCOa •+- CI2. To
prove the correctness of their interpretation, a series of experiments
were conducted in which pure hypochlorous anhydride was passed
over pure calcium hydroxy chloride, CaCl.OH ; and the chloride in
every case the resultant material always contains a considerable pro-
portion of bleaching powder (mixed with unaltered chloride and
traces of chlorate), which can be subsequently decomposed by car-
bonic anhydride. Kraut's experiments are therefore inconclusive.
Secondly, Kraut having established that when lithium hydroxide is
heated with chlorine, only half of it is attacked with formation of
LiCl + LiOCl, draws the conclusion that as the lithium hydroxide is an
integral part of the resultant compound, so calcium hydroxide is an
integral part of bleaching powder. The authors however show that
80 per cent, of lithium hydroxide can be converted into the mixture
LiCl + LiOCl, which is far less stable than bleaching powder in pre-
sence of excess of chlorine, in that it gives off oxygen, the presence of
which could be recognised. On the other hand, the mixture LiCl +
LiOCl is far more stable than bleaching powder towards carbonic
anhydride ; at low temperatures it is practically unaltered, whilst at
higher temperatures the mixture is converted partly into the chloride
and chlorate, and is partly decomposed into the chloride and oxygen.
The gas given off is not chlorine, but hypochlorous anhydride. As
the properties of the so-called chloride of lithia differ so markedly
from those of bleaching powder, a different constitution must be
assigned to each. Arguments drawn from the behaviour of the one
compound have no bearing on the constitution of the other.
The analogous compounds of barium and strontium were also
954 ABSTRACTS OF CHEMICAL PAPERS.
examined ; that of barium is very unstable, whilst that of strontium is
readily prepared, and resembles bleaching powder in its decomposition
by carbonic anhydride. V. H. V.
Spectral Researches on Scandium, Ytterbium, Erbium, and
Thulium. By T. Thal:6n (Ghem. News, 47, 217).— The emission
spectra were obtained with the use of two Leyden jars. The spectrum
of scandium contains a great number of lines. Tables of wave-
lengths for the first three metals are given. The absorption-bands
distinguishing thulium from erbium are broad and intense, their
centres having the wave-lengths \ = 6840 and = 4650. The emission
spectrum given by thulium consists of two bands, the above X = 6840,
and another = 4760. There is no trace of a bright line corresponding
with the dark band 4650, but such a bright line is given by salts of
erbium, hence it is doubtful if the absorption-band 4650 belongs to
thulium. H. B.
Position of Thallium in the Chemical System, and its
Presence in Sylvin. By J. Scheamm (Annalen, 219, 374—384). —
Elements resembling one another in their chemical and physical pro-
perties, and belonging to the same natural group, are generally
associated with one another in nature. The element thallium is
assigned by some to the alkali, but by others to the lead-group. It
has however been found associated with the alkali-metals in specimens
of lepidolite, mica, alum, carnallite, and the mother-liquors of the
Nauheim salt springs. The author has examined with the spectroscope
specimens of carnallite and sylvin from Kalusz, and found the presence
of thallium in both minerals. As thallium is so often associated
with the alkali-metals, and its chloride and potassium chloride
crystallise together, it is exceedingly probable that thallium is to
be classified with these metals, a view which receives great support
from the many points of resemblance of their compounds. The
author reviews these points, and the less distinctly marked points of
difference. The compounds in which thallium functions as a triad
are not so stable as those in which thallium acts as a monad ; many of
them are decomposed by water like potassium tri-iodide, whilst the
greater stability of thallium trichloride is probably connected with
the more sparing solubility of the monochloride. The trisulphides of
thallium and potassium are analogous compounds. The relation of
thallium to the alkalis is the same as that of lead to the alkali-
metals, or of bismuth to the nitrogen-group. The author regards the
presence of thallium sulphide in pyrites not as indicating the associa-
tion of thallium with the heavy metals, but as a relic of the presence
of the alkaline sulphides. V. H. V.
Preliminary Notice. By F. Wilm (Ber., 16, 1298— 1301).— In
the course of the author's investigations on the estimation of the
metals in native platinum, he has come across a peculiar substance
whose nature still remains obscure. A solution of native platinum
after filtration from osmium-iridium was treated with excess of
barium carbonate in the cold, the precipitate dissolved in hydrochloric
MINERALOGICAL CHEMISTRY. 955
acid, heated and saturated with hydrogen sulphide. The precipitate
was reduced in hydrogen, extracted first with nitric acid and then
with aqua regia, and the insoluble residue treated according ta
Wohler's method with sodium chloride and chlorine. The portion
still remaining insoluble was fused with sodium carbonate and ex-
tracted with water, when a snow-white indistinctly crystalline powder
was left, which by its extraordinary indifierence to reagents has sa
far baffled all the author's attempts at its further investigation.
A. J. G.
Mineralogical Chemistry.
Minerals from Upper Silesia. By Kosmann (Jahrh. f. Min.,
1883, 2, 15 — 16). — This paper treats at some length of the minerals
occurring in the ore-deposits of the " Musclielkalk " of Upper Silesia^
more especially in the so-called blende bed, which is a thick bed of
sulphuretted ores from which the upper deposits of oxidised ores have
originated. The minerals described are : Blende, cerussite, zinc spar,
zinc silicate, and manganese ores. Manganite, psilomelane, and man-
ganese ochre are found at Beuthen. Heavy spar is very rarely met
with. In conclusion, the author mentions the discovery of a bed of
asphalt in the deep workings of the Friedrich's mine.
B. H. B.
Hieratite, a new Mineral Species. By A. Cossa {Jahrh. f. Min.,
1883, 2, 11). — This mineral was found among the products of the
volcanic activity of the Island of Yulcano, and derives its name from
Hiera, the ancient name of that island. Grey stalactitic concretions,
enclosing small octohedral crystals, were found near the apertures of
the fumaroles. 3 kilos, gave 200 grams of these crystals, which were
isolated by dissolving the mass in hot water. They crystallise in the
regular system, and have the composition 2KF,SiF4. The mineral is
mixed selenium sulphide, realgar, potassium, caesium, and rubidium
alum, sodium sulphate, sassoline, and compounds of arsenic, iron,
thallium, zinc, tin, lead, bismuth, and copper. Until now, tin, zinc,
and bismuth have never been found as volcanic exhalations.
B. H. B.
The so-called Liebigite from Joachimsthal. By A. Schrauf
{Jahrh. f. Min., 1883, 2, 26). — The mineral forms crusts on the
decomposed uranium ores of Joachimsthal. The crystals are micro-
scopically small or imperfectly developed. The forms observed were :
ooPco, ooP, ooP3, 2Poo, 2P, 2PS. The analysis gave :—
CaO. UrOa. COj. HgO. Total.
16-42 36-29 22-95 23-72 99-38
corresponding with the formula —
2CaC03 + Ur(C03)2 -f IOH3O.
BA.
AlA.
K2O.
NaaO.
CaO.
MgO.
I. 33-93
41-40
12-00
1-62
0-74
0-82
II. 41-49
41-40
12-00
1-62
0-74
0-82
^OQ ABSTRACTS OF CHEMICAL PAPERS.
The author gives this mineral the name of " Uranothallite," and
proposes to reserve the name Liebigite for the compound poor in
lime, analysed by S.nith in 1848. B. H. B.
Rhodizite. By A. Damoue (Jahrh. /. Min., 1883, 2, 5).— Rhodi-
zite, discovered by Rose, is a white mineral crystallising in the form
ooO . f ; it occurs in small crystals on the red tourmaline of Sara-
pulsk and Schaitansk, in the Ural Mountains. By the blowpipe
reactions, this rare substance was thought to consist chiefly of calcium
borate. A complete analysis has now been made for the first time by
the author with material collected by G. Rose himself. A consider-
able amount of alumina was found, whilst the calcium plays only a
subordinate part. The results obtained are given under I : —
VolatUe
¥6303. constituents. Total.
1-93 .2-96 95-40
1-93 — 100-00
"The loss of 4-6 and the 2-96 per cent, volatile constituents are
regarded as boric acid. The analysis then takes the form shown
Tinder II, and from this the empirical formula, R20,2Al203,3B203, is
deduced. B. H. B.
Danburite from Switzerland. By A. Scheauf and others
(Jalirb.f. Min., 1883, 2, 11 — 15). — The crystals of this mineral are
found at Scopi in a fissure filled with chlorite. They are transparent,
odourless, and as hard as quartz. The sp. gr. is 2-986. The pyra-
mid, 2P4, is a very characteristic form of the Swiss crystals. The
ohemical analysis gave the following results. An analysis (d) of the
American variety from Danbury, Connecticut, is added for the sake
of comparison : —
a. b. c. d.
Smith and
Analyst. E. Ludwig. Schrauf. Bodewig. Brush.
SiOj 48-52 48-92 48-66 48-15
B2O3 28-77 (26-88) 28-09 27-15
^Sr:::;::::: =} ^-^^ TJ} 0-30
Mno.Oa — — — 0-56
CaO 23-03 21*97 22-90 22-37
MgO 0-30 — — 0-40
Loss on ignition. — 0-36 — 0*50
Total 100-62 100-00 9996 99-43
Trom these analyses the formula, Si2B2Ca08, is deduced.
B, H. B.
Minerals, mainly Zeolites, occurring in the Basalt of Table
Mountain, Colorado. By C. W. Cross and W. F. Hillebeand
iAmer. J. Sci., 1882, 23, 452, 24, 129).— In the following description
.of the minerals occurring in the basalt of Table Mountain, near
MINERALOGTCAL OHEMISTRr. 957
Golden, Colorado, the order followed is that in which the minerals
have been deposited : —
1. Ghahazite. — This mineral seems to be the oldest of the zeolites
with the exception of a peculiar stratified deposit. It is also preceded
in some places by yellow calcite. A second generation of chabazite-
came after thomsonite and analcime, but the crystals are few and
minute.
2. Thomsonite. — As in the case of chabazite, a second generation of
thomsonite was deposited towards the close of the zeolite formation.
Chemical analyses were made with material of the older as well as of
the more recent growth. In each case they gave an excess of silica,
and the authors believe that the results obtained indicate a greater
variation in the composition of thomsonite than is allowable under
the generally accepted formula.
3. Analcime. — A second generation of analcime was also observed
upon the apophyllite. All the analcime examined was doubly refrac-
tive, but so irregularly that it cannot be used in confirmation of the
observations of Ben-Saude (Abstr., 1882, 285).
4. Apophyllite. — This mineral occurs in well-developed crystals of
the combination coPoo, P, while OP is quite subordinate or entirely
wanting. In chemical composition the apophyllite is quite normal.
The presence of PegOa is owing to minute particles of limonite which
could not be completely removed. A pseudomorph, resembling
albine, has originated by an increase of SiOz, AI2O3 and H2O. Tho
alteration proceeds from without, and the result is a white substance
with a pearly lustre, and finely foliated parallel to the basal plane of
the apophyllite. There is no calcite in the product.
5. Calcite. — Calcium carbonate has had three periods of deposition
in the basaltic cavities — two as calcite and one as arragonite.
6. Mesolite. — This appears in masses composed of exceedingly
delicate needles, the crystal form of which could not be determined
even under the microscope at a high power. The chemical analysis
gave the following results, which correspond exactly to a composition
of 2 mols. of scolecite and one of natrolite : —
SiOa. AI2O3. CaO. NaoO. HgO. Total.
46-13 26-88 8-77 6*19 12*16 100-13
7. In many of the cavities of Table Mountain a reddish-yellow
sandstone -like mineral occurs. In this mass small fissures may some-
times be observed, some of which are partially filled with minute
white crystals, easily recognisable under the microscope as laumon-
tite and stilbite. Chemical analyses of the yellow granular mass
gave the following results ; care being taken to exclude all red
spherules : —
SiOa.
AlA.
FeaOg.
CaO.
K2O.
NasO.
H2O.
Total.
56-37
17-64
0-79
8-52
0-17
1-42
16-27
100-18
This composition is such as would result from a mixture of stilbite
and laumontite.
The reddish spherules gave on analysis the following results : —
<)58 ABSTRACTS OF CHEMICAL PAPERS.
SiOa. AI2O3. FeA- CaO. Na^O. H2O. Total.
40-51 29-21 0-78 1242 4-30 12-79 100.04
These figures agree with the analysis of thomsonite.
B. H. B.
Beryl from Craveggia in Piedmont. By G. Spezia (Jahrh. f.
Min., 1883, 2, 10). — This beryl occurs in loose blocks of a coarsely
granular pegmatite rock. These blocks were probably derived from
& gneiss in the neighbourhood, and contain tourmaline and manga-
nese-garnet in addition to the beryl. The latter is generally found
in the quartz, and never in the felspar. The analysis gave the fol-
lowing results : —
SiOg. AI2O3.
65-12 19-65
BeO.
11-49
FesOa.
0-67
MgO.
0-48
Lobs on
CaO. ignition. Total,
trace 195 99*36
B. H. B.
Garnet and Amphibole Rocks of the Bastogne Region.
By A. Renaed (Jahrb. f. Min., 1883, 2, 68— 71).— The metamorphic
rocks of Bastogne, belonging to what Dumont called the metamorphic
belt of Paliseul, were submitted by the author to a searching micro-
scopical and chemical examination.
The rock described by Dumont as quartzite containing garnet is a
hard black rock containing brownish-yellow crystals of garnet, 1 to
2 mm. large, in a ground-mass saturated with carbonaceous matter.
The sp. gr. is 2-751. The rock is composed of 4*8 graphite, 1-51 apa-
tite, 1-02 titanite, 4-14 garnet, 20-85 paragonite and muscovite, 30-62
quartz, and 1-32 water. The analysis of the rock gave the following
results : —
SiOg.
55-82
TiOa.
0-42
PA.
0-69
AI2O3.
19-67
Fe203. FeO.
0-96 4-18
MnO.
0-61
CaO.
8-42
MgO.
2-21
K.O.
0-39
Na^O.
1-42
H2O. C.
2-29 4-80
Total.
101-88
Tlie
analysis
of the inclosed garnets gave: —
SiOg.
37-58
AI2O3.
20-45
Fe203.
3-21
FeO.
15-53
MnO. CaO.
14-72 10-03
MgO.
0-68
Total,
102-20
Dumont's quartzite and eurite with actinolite and hornblende may be
distinguished from the rock described above by its lighter colour. A
typical specimen of this rock from Ourt gave the following analytical
results : —
SiOa.
AI2O3.
FeaOg.
FeO.
CaO.
MgO.
NaoO.
H2O.
Total.
69-34
12-07
1-88
4-74
7-70
2-96
0-40
1-57
100-66
The rock was composed of 46*73 hornblende, 52*36 quartz, and 1*57
water.
Dumont's phyllite containing garnet is distinguished from the
rocks described by its evidently stratified nature and bluish-black
MINERALOGICAL CHEMISTRY. 959
colour. The enclosed garnets are translucent and of a brownish-
yellow colour. Dumont's classification of these rocks is abandoned,
as garnet and amphibole mostly occur together. Felspar, which the
term " eurite " demands, has not been observed, and the percentage
of silica in the quartzite is not high enough to i-ender that name
suitable.
In conclusion, an analysis is given (I) of a mineral from the quartz
veins of Libramont, called Bastonite by Dumont. The author regards
this as a variety of phlogopite. The sp. gr. is 2-928. An analysis
(II) is also given of the ottrelite from Lierneux, the sp. gr. of which
was 3-266.
SiOg. AI2O3. FesOg. FeO. MnO. CaO. MgO. K2O.
I. 36-91 20-04 20-01 3-73 trace 0-95 7-96 3-07
II. 40-55 30-80 3-82 12-46 6-51 1-29 0-45 —
NaoO. HaO. Total.
I. 0-22 6-98 99-87
11. — (4-12) 100-00
B. H. B.
Diabase from Weilburg. By W. Will and K. Albrecht (Ber.,
16, 1323 — 1327). — This diabase is dark greyish-green in colour; the
ground-mass appearing uniform even when examined with a lens. It
contains roundish dark-green masses of chloritic substances, and
numerous concretions of calcspar which in places give the stone an
amygdaloid appearance ; single crystals of iron pyrites also occur.
Microscopic examination of the ground-mass showed it to be a crys-
talline mixture of triclinic felspar, magnetite, ilmenite, and fine
needles of apatite, the whole being interpenetrated with green chlo-
ritic mass. Analysis of the stone gave : —
SiOs. FegOg. FeO. AI2O3. CaO. MgO.
50-26 1-46 11-61 13*'-53 5-45 3-59
NasO. K2O. TiOa. PA- COg. CI. HgO.
5-34 1-57 0-50 1-14 1-10 0-40 3-38
Sp. gr., 2-796. Loss on ignition, 4-40 per cent.
A. J. G.
Notes on the Occurrence of certain Minerals in Amelia
Co., Virginia. By W.F. Fontaine (Amer. J. Sci. [3], 25, 330—339).
— The minerals in question occur in so-called veins of gigantic granite,
which are not fissure veins but ruptured portions of the country rock
— micaceous gneiss and mica schist, into which the components of the
granite have been introduced, most probably by solution in hot water.
The essential minerals of these deposits, mica, felspar, and quartz,
have crystallised pretty constantly in the same order of succession,
viz., mica first and quartz last. The mica has been worked during
the last few years, and at the outcrop it has been removed in pre-
historic times ; the mica is mostly muscovite, and is sometimes bent,
showing movements in the vein. The felspar is mostly orthoclase,
but albite also occurs, and in such a manner as to clearly show that it
960 ABSTRACTS OF CHEMICAL PAPERS.
is a secondary prodnct after the formation of the mass of granitic
materials ; labradorite and amazon stone also occur. Very large
opaque beryls are found, as are also smaller transparent ones ; they
seem to have crystallised at the same time as the felspar and after the
mica. Fluorite is only found in crystalline masses. Columbite occurs
quite frequently, and often in crystals of groups weighing up to six
pounds ; a variety occurs containing considerably more manganese than
iron, and with the ratio of niobic to tantalic acid 1:1. Garnet —
spessarite — is common ; one variety is intimately mixed with helvite,
which is the last mineral deposited ; the spessarite gave on analysis : —
SiOs. AI2O3. FeO. MnO. CaO. MgO.
36-34 12-63 4-57 44-20 1-49 0-47 = 99-70
Orthite occurs in long thin-bladed crystals, sometimes 15 inches long;
the ends are imperfect, and most of the crystals have suffered partial
decomposition. Microlite occurs between the interstices in tangled
masses of quartz, felspar, and mica. It was formed after the mica
but before the felspar. The crystals are all of good size, and very
large aggregates are sometimes found ; the form is that of a modified
octohedron. Monazite is found only in a couple of localities ; it does
not occur in isolated crystals, but in large aggregates. It is very
much more prone to change than microlite. Helvite is only found in
one locality, in the interstices of spessarite. No crystalline forms
have been observed, and a great deal of the mineral has undergone
alteration. Galena, stilbite, pyrochlore, manganese-tantalite (?),
apatite, tourmaline, and fluocerite (?) occur but rarely. H. B.
The Gneiss of Beura. By G. Spezia (Jahrh. /. 3fin., 1883, 2,
17 — 18). — At Beura, in the Ossola valley, gneiss is quarried to a con-
siderable extent. The rock occurs in several varieties, and contains a
number of minerals, either disseminated through it or crystallised out
in fissures and geodes. These minerals are : quartz, tourmaliue,
chlorite, orthoclase, mica, staurolite, cyanite, laumontite, calcite,
fluorspar, titaniferous iron ore, limonite, iron pyrites, magnetic pyrites,
marcasite, stilbite, titanite, apatite, and anatase. Quartz is the most
frequent. Hornblende has not been met with. All the minerals men-
tioned occur in fissures or geodes, only yellow tourmaline, cyanite, and
staurolite are disseminated through the rock. B. H. B.
Minerals in the Sodalite Syenite of South Greenland. By
J. LOEENZEN (Jahrh. f. Min., 1883, 2, 18 — 21). — The nepheline syenite
containing sodalite, which occur on both sides of the Tunugdliarfik
and Kan ger dinar suk fjords in the Julianehaab district. South Green-
land, is very rich in accessory constituents. The rock is composed of
a greenish-white felspar, probably orthoclase, arfvedsonite, aegirine,
sodalite, nepheline, eudialite, lievrite, calcite, several zeolites, especially
analcime and natrolite, lithium mica, dinigmatite, and steenstrupine.
The first four of these minerals predominate.
Analyses were made of most of these minerals; the results obtained
in the analysis of steenstrupine were as follows : —
OKQANIO CHEMISTRY. 961
SiOj. TaOa. AI2O3. FesOg. ThO. MnO. CeO. LaO. CaO.
27-95 0-97 2-41 9-71 7-09 4-20 10-66 17-04 3-09
KaO. HaO. Total.
7-98 7-28 98-38.
Sp. gr. = 3-38. Hardness, 4. The mineral lias a brown colour and
a white streak. Ainigmatite belongs to the monoclinic system ; the
usual combination being ooP, ooPco, coPoo, with a pyramid and two
clinodomes. It has a black colour and a hardness of 5*5. It may be
distinguished from arfvedsonite by its red streak, and sp. gr. 3*80.
B. H. B.
Organic Chemistry.
CompoTinds of Hydrogen Sulphide with Ethers. By Dr
FoRCRAND (Ann. Ghim. Phys. [3], 28, 1 — 67). — Some properties of
the compound of hydrogen sulphide and water formed at a low tempe-
rature or high pressure, are first described. The tensions of dissocia-
tion at various temperatures from 0-5° to 28-5° are given, a critical
point being found at about 29°. The composition assigned to this
compound by the author is HgS + I2H2O. He then proceeds to
detail the preparation, and the most important properties of a large
number of compounds similarly formed by hydrogen sulphide with
the simple chlorides, bromides, and iodides of radicals of the fatty
series, or with their chlorinated, brominated, or iodated derivatives.
These compounds have all well-defined crystalline forms belonging to
the cubic system, and all correspond with the general formula —
R + 2H2S + 23H2O.
Their dissociation-tensions are constant for the same temperature, as
is also the composition of the vapours evolved, and the tension in-
creases regularly with the temperature. The heat of formation of
these compounds is considerable, but it is mainly due to the change
in the physical state of the water entering into their composition.
The heat of formation of the ethyl bromide compound (37"08 cal.) is
about the same as that of the chloroform compound (37-5 cal.). The
author has also examined a few analogues of these compounds in
which hydrogen sulphide is replaced by hydrogen selenide, and he
finds the closest resemblance in their properties. R. R.
Bromodinitromethane. By J. KL^chler and F. Y. Spitzer (Bcr.,
16, 1311—1312). — By the distillation of a-dibromocamphor (m. p. 61°)
with nitric acid and treatment of the product of the reaction with
alcoholic potash, a yellow crystalline precipitate of potassium bromo-
dinitromethane, CBr(N02)2K, is obtained, whilst on diluting and
heating the alcoholic mother-liquors, carbon tetrabromide distils.
VOL. XLIV. 3 t
962 ABSTRACTS OP CHEMICAL PAPERS.
Losanitsh has stated (Abstr., 1882, 950) that the potassium salt of
this composition yields on treatment with acids dibromodinitrome-
thane ; the authors, on the contrary, find the oil so obtained to give
numbers intermediate between those required for mono- and di-bro-
monitromethane, and as, on gentle heating, carbon tetrabromide
sublimes, it is in all prolDability a mixture of the latter with mono-
bromodinitromethane. A. J. Gr.
Saccharone and Saccharin. By H. Kiliaxi (Annalen, 218,
361— 374).— Scheibler (Abstr., 1881, 149) showed the formula of
saccharin to be CgHioOs, and suggested the constitution
CH2(OH).CH(OH).CH(OH).CH.CH2.CO.
\ /
O
TJie author obtained acetic acid and glycollic acid by the oxidation of
saccharin with silver oxide (Abstr., 1882, 820), and from this result
he assumed it to contain the groups CH3 and CH2.OH. By the oxida-
tion of saccharin with concentrated nitric acid, saccharone, CeHgOc, is
produced, containing carboxyl, COOH, in the place of CH2.OH ; this
compound is slightly Isevorotatory, and forms large crystals of the for-
mula CeHsOejHaO ; it yields two classes of salts, e.^., sodium saccharone^
C^^O^n, and sodium saccharonafe, C6H807]S"a2, the former of which
is obtained by mixing saccharone solution with the calculated quantity
of sodium carbonate and evaporating, when rhombic crystals are
obtained, sometimes anhydrous, and sometimes containing 1 mol. H2O.
Sodium saccharonate is obtained by boiling an aqueous solution of
saccharone with the calculated quantity of sodium carbonate, and
evaporating. Ammonium saccharo7ie, CeHvOe.NHi, is obtained by
neutralising a cold solution of saccharone with ammonia, and allowing
it to evaporate spontaneously, whilst ammonium saccharonate^
CeHeO,(NH02,
is prepared by boiling saccharone with an excess of ammonia.
Calcium, saccharonate, CeHsOvCa, and silver saccharonate, CeHgOvAga,
have also been prepared, the former ,by boiling saccharone with lime-
water, and the latter by precipitating an alkaline saccharonate with
silver nitrate. Copper compounds are also obtained by boiling a solu-
tion of saccharone with copper carbonate. By the long-continued
boiling (21 hours) of a mixture of saccharone with hydriodic acid and
amorphous phosphorus, an acid, CeHjoOi, is formed, which the
author identifies as a-methylglutaric acid,
COOH.CH2.CH2.CHMe.COOH,
described by Wislicenus and Limpach (Annalen, 192, 134). If the
heating is earned on for a much shorter period, an acid of the formula
CeHgO^ is produced. From the formation of a-methylglutaric acid,
the author assigns to saccharonic acid the constitution
COOH.CH(OH).CH(OH).CMe(OH).COOH,
whilst for saccharone, which is the lactone obtained by the abstrac-
tion of 1 mol. water, two formulas are evidently possible. In the same
ORGANIC CHEMISTRY. . 963
•way hydriodic acid acts on saccharin, yielding a-metliylvalerolactone,
CH3.CH.CH2.CHMe. CO, proving that saccharic acid lias the constitu-
tion, CH2(0H).CH(0H).CH(0H).CMe(0H).C00H.
A. K. M.
Condensation-products of Aldehydes and their Derivatives.
By A. LiEBEN and S. Zeisel (Third Memoir). Constitution of
Butyl Chloral. (Monatsh. Ghem., 4, 531—539). — In a previous
paper (p. 570 of this volume) the authors have endeavoured to explain
the manner in which condensation accompanied by elimination of
water takes place between two molecules of the same or of different
aldehydes ; and in the present communication they examine the con-
densation of an aldehyde with a monohalogenated aldehyde, viz., that
of acetaldehyde with its monochlorinated derivative, which may be
expected to give rise to a monochlorocrotonaldehyde, represented by
one of the following formulae : —
I. CH3.CH : cci.CHO. II. CH2C1.CH : ch.cho.
Either of these compounds would be converted, by addition of chlorine,
into a butyric chloral, C4H5CI3O, isomeric or identical with that already
known.
To obtain such a compound, monochloraldehyde in the form of the
crystallised hydrate, C2H3C10,|H20, was heated in a sealed tube with
an equivalent quantity of aldehyde, a drop of strong hydrochloric
acid being added as condensing agent, and the heating continued for
several days. On distilling the contents with steam, there passed
over, first an oil, then water, and lastly the hydrate of monochlor-
aldehyde, whilst crotonaldehyde and higher-boiling substances
remained in solution. The residue consisted of a black unctuous sub-
stance, which hardened on cooling to a pitch-like mass, surmounted
by a yellow, somewhat turbid liquid, exhibiting a strong green fluo-
rescence. The oil obtained from the distillate, which was somewhat
heavier than water, was dried over calcium chloride and distilled in a
current of carbonic anhydride ; it then passed over between 150" and
160°, but could not be obtained of constant boiling point. It is a
colourless liquid, becoming thicker on keeping, and having an odour like
that of crotonaldehyde, but more pungent. It gave by analysis 37'83
per cent, chlorine, whereas monochlorocrotonaldehyde requires 33*97
per cent. Nevertheless the body in question appears to consist mainly
of chlorocrotonaldehyde, inasmuch as it is capable of uniting with
chlorine, and forming a crystalline hydrate of trichlorobutyraldehyde
or butyric chloral, C4H5CI3O. The crystals of this hydrate are ortho-
rhombic, exhibiting the combination OP . Pcb . P. Axes a : h : c =
0-6486 : 1 : 1-1939.
According to the formulae above cited for monochlorocrotonalde-
hyde, butyric chloral must be represented by one of the two follow-
ing :—
I. CH3.CHCI.CCI2.CHO. II. CH0CI.OHCI.CHCI.CHO,
S t 2
964 ABSTRACTS OP CHEMICAL PAPERS.
both of which differ from the formula hitherto assigned to it, viz.,
CCI3.OH2.CH2.CHO. To decide between the formulas I and II, it
is necessary to ascertain whether butyric chloral contains an entire
methyl-group, and with this view the authors prepared dichloropro-
pylene, O3H4CI2 (b. p. 7T), by boiling the hydrate of butyric chloral
with sodium carbonate, and heating it with chromic acid mixture in
a sealed tube for 48 hours at 100°, and then for 24 hours at 130°. By
this treatment the dichloropropylene was converted into acetic acid,
showing that it contains an entire methyl-group, and must therefore
be represented either by the formula CH3.CH \ CCL, or by
CH3.CCI : CHCl.
Hence also it follows that butyric chloral must be represented by
CH3.CHCI.CCI2.CHO, and this determines also the constitution of the
numerous derivatives of butyric chloral, e.g., trichlorobutyl alcohol,
trichlorobutyric acid, trichlorangelactic acid, &c.
The formation of butyric chloral by the action of chlorine on alde-
hyde or paraldehyde may be explained in two ways : 1. The aldehyde
is converted into crotonaldehyde, then into monochlorocrotonalde-
hyde, which, by the further action of the chlorine, is transformed inte
butj'-ric chloral. 2. The aldehyde is first converted by the chlorine
into monochloraldehyde, which, almost as soon as it is formed, con-
denses with the acetaldehyde, under the influence of the hydrochloric
acid evolved at the same time, into monochlorocrotonaldehyde, and
thereby gives rise to the production of butyric chloral in the manner
above explained. The second view is supported by the consideration
that crotonaldehyde has not yet been found amongst the products
of the action of chlorine on acetaldehyde, and that in presence of
water, chloral is formed from aldehyde, a fact which points to the
previous formation of monochloraldehyde.
The constitution of butyric chloral above established shows that the
monochloraldehyde obtained by condensation must have the formula
CH3.CH I CCl.CHO, and that accordingly, in the process of condensa-
tion, the oxygen of the acetaldehyde must have acted on the hydrogen-
atom of the monochloraldehyde nearest to the chlorine ; and con-
sequently that in this case, as in that of propaldehyde, the methylene-
group is more readily attacked by the aldehydic oxygen than the
methyl-group. . H. W.
ao/-Dichlorocrotonaldehyde, a Condensation-product ot
Monochloraldehyde. — By K. Batterer (Monatsh. Cliem., 4, 539 —
553). — ^When hydrated monochloraldehyde is heated for 15 hours at
lOO"" with a drop of strong sulphuric acid, a heavy dark-coloured oil
passes over, together with a supernatant watery liquid, still containing
chloral dehyde. This layer is removed, and the oily liquid when cold is
washed with water (after which treatment it consists of condensation-
products, and a small quantity of polymerised monochloraldehyde), and
then distilled under reduced pressure, whereupon resinous products
are left behind, and monochloraldehyde collects in the receiver (into
which a little water may be advantageously introduced to dissolve it),
together with tlie more volatile condensation-products formed by dis-
ORGANIC CHEMISTRY. 965
sociation of the polymeride, and a certain quantity of the polymeride
itself.
The oily liquid obtained as above, after renewed washing with
water to remove any attached monochloraldehyde, is dried in a stream
of carbonic anhydride, and then subjected to fractional distillation
in the same gas. In this way a fraction is obtained boiling at 86 —
87°, together with a small quantity of a viscid oil boiling at 130 —
150°.
The liquid boiling at 86 — 87° is mobile, strongly refractive, colour-
less when recently distilled, but soon turns yellow. It becomes
much thicker at — 30° ; solidifies to a vitreous mass at the temperature
of a mixtnre of carbonic anhydride and snow ; has a very pungent
•odour ; is nearly insoluble in water ; and distils, with partial decom-
position, under ordinary pressure. It gives by analysis numbers
agreeing nearly with the formula C4H4CI2O, which is that of
dichlorocrotonaldehyde, formed according to the equation
2C2H3CIO — H2O = C4H4CI3O. All its reactions are in accordance
with the constitutional formula CH2CLCH ! CCl.CHO. Its aldehydic
nature is shown by its power of reducing ammoniacal silver solution ;
by the red coloration and separation of resin consequent on boiling it
-with potash ; by its power of absorbing oxygen, with formation of an
acid ; and of forming a crystalline compound with sodium hydrogen
sulphite.
Dichlorocrotonaldehyde is reduced by acetic acid and iron filings to
normal butyraldehyde, normal butyl alcohol, and crotonaldehyde, the
latter convertible by treatment with bromine and water into butenyl-
glycerol, C4H,(OH)3.
By energetic oxidation with nitric acid, the aldehyde is converted
into hydrochloric, chloracetic, and oxalic acids : CH2CI.CH '. CCl.CHO
+ 2O2 + H2O = HCl + CH2CI.COOH + C2H2O4. The hydrochloric
and nitric acids yield free chlorine, which converts part of the chlor-
acetic acid into chloropicrin.
a7-Dichlorocroton aldehyde forms with acid sodium sulphite the
compound CH2CI.CH ! CCl.CH(0H)(S03Na) + 3 or 4H2O, and on
heating this compound with solution of sodium carbonate, carbonic
anhydride is given off, and a residue is left containing chloride and
sulphate of sodium, and the sodium salt of an aldehyde-sulphonic
acid.
a7-Dichlorocrotonaldehyde unites directly with bromine, forming
a^-dichlor-a^-dibromobutyraldehyde, CH2Cl.CHBr.CCJBr.CHO,
which, when agitated with a strong solution of sodium hydrogen
sulphite, unites therewith, forming a crystalline very slightly soluble
compound. On agitating the bromine addition-compound with an
equal volume of water, it solidifies to a white compact crystalline
mass, which may be purified by trituration with water, draining, and
once recrystal Using from ether, and then consists of the hydrate
C4H4Cl2Br20,H20. This compound is permanent in the air, has a
faint melon-like odour, dissolves sparingly in water, readily in alcohol,
and melts at about 72° to a turbid liquid, the turbidity increasing on
further heating (up to 85°), diminishing again on cooling, and dis-
appearing at about 70°, whilst the clear liquid solidifies after some
966 ABSTRACTS OF CHEMICAL PAPERS.
time at the temperature of the room. This behaviour shows that the
hydrate is resolved into its components even at ordinary tempera-
tures.
When the aqueous solution of the bromine addition-product is
mixed with solution of potash or of sodium carbonate, a heavy oil
smelling like petroleum is immediately deposited, with simultaneous
production of sodium bromide and formate. It Ls highly probable
that the bromine addition-product reacts with aqueous alkalis and
their carbonates in the same manner as chloral or bromal, forming a
bromopropylene or bromallylene, with separation of the CO-group
and of hydrogen bromide.
On slowly passing gaseous hydrogen chloride through a7-dichloro-
crotonaldehyde at 0° for 12 hours, then leaving the liquid to itself for
two days, and expelling the uncombined chlorine with a stream of
carbonic anhydride, a residue is left consisting of trichlorobutyralde-
hyde, isomeric with butyric chloral, and smelling very much like the
latter, but having a more viscid consistence. It solidifies to a vitreous
mass at — 78° ; does not give off HCl on standing ; oxidises but very
slowly on exposure to the air ; is sparingly soluble in water, and does
not form a hydrate. It unites with sodium hydrogen sulphite, and is
very easily converted by fuming nitric acid into the corresponding
trichlorobutyric acid, CH2CI.CHCI.CCI2.COOH, which forms fine
crystals. H. W.
Methyl /3-Butyl Ketone and its Derivatives. By J. Wis-
LTCENUS (Annalen, 219, 307 — 321). — The author has prepared frorn
ethylic ethomethacetoacetate, ethyl /3-butyl ketone, and converted it
into the corresponding secondary alcohol and pinacone. The products
formed by the action of nascent hydrogen, — zinc and acetic acid, — on
the iodide from the secondary alcohol, are also studied.
Methyl ^-hutyl Icetone, Me.CO '. CHMeEt, is formed by the action of
potash on ethvl ethomethacetoacetate: CHa.CO.CMeEtz.COOEt -|-
2K0H = CHa.CO.CHMeEt + K2CO3 + EtOH. It is a light mobile
oil, smelling like peppermint, boiling at 118°, and having a density of
0*8181. This is converted by the action of sodium and water partly
into the corresponding secondary alcohol, and partly into the pinacone.
The former, methyl ^-hutyl carUfiol, CHMe (OH). CHMeEt, is a thick
oil resembling stale peppermint in its odour, boiling at 134°, and
having a density of 0*8307; the latter, methyl ^ -butyl pinacone,
CHMeEt.CMe(OH).CMe(OH)CH.MeEt,
is a colourless pasty mass melting at 248 — 250° ; it yields on heating
with dilute sulphuric acid (1 : 4) probably a mixture of two pina-
colines.
The author calls attention to the difficulty experienced in convert-
ing methyl /3-m.ethyl iodide into /3-hexane ; in this respect the iodide
differs most markedly from the hexyl, heptyl, and octyl iodides already
known. On subjecting to fractional distillation the crude product of
the action of zinc and acetic acid on the iodide, mixtures of methyl-
diethylmethane, a hexylene, and a dihexylene, and methyl diethyl
carbinol, together with subsidiary products, were obtained. The
ORGANIC CHEMISTRY.
967
hexane, methyldietJiylmethane, purified from the define bj repeated
treatment of the mixture of the hydrocarbons with sulphuric or
hydriodic acid, is a liquid having a pleasant odour of peppermint,
boiling at 64°, and of sp. gr. 6765. The product formed by the addi-
tion of hydriodic acid to the hexylene is a tertiary or methyl diethyl
iodide, readily converted by water into methyl ethyl carbinol, boiling
at 122''. From the above it is evident that the first product of the
reaction of zinc and acetic acid on methyl ^S- butyl iodide is methyldi-
ethylmethane,
2(CH3.CHI.CHMeEt) + 2Zn + 2A50H = Znl^ + Zn(0A5), +
2(CH3.0H2.CHMeEt),
together with its derived hexylene or a-methylethylpropylene, thus :
2(CHMeI.CHMeEt) + Zn = Znia + CHMe ! CMeEt + CHMeEtj +
H2. Some portion of the define is polymerised at the moment of its
formation, while another portion combines with the water present to form
diethyl methyl carbinol, thus: CHMe! CMeEt -|- H2O = CMeEto.OH.
The ready conversion of the define into the iodide and the saponifica-
tion of the latter by water, show that it has the constitution of a
tertiary-secondary olefine. Y. H. V.
Specific Volumes of the Alkyl Salts of Fatty Acids. By
E. Elsasser {Annalen, 218, 302 — 338). — The author has made a
number of experiments in continuation of Kopp's work, and repeated
his determinations. Determinations of the boiling points and of the
specific gravities of the pure substances experimented with have also
been made : —
Boiling Points at 760 mm.
Formate.
Acetate.
Propio-
nate.
Butyrate.
Isobuty-
rate.
Valerate.
Methyl .
Ethyl ..
Propyl .
Isobutyl
AmTl . .
32-3°
54-4
81-0
97-9
123-3
57-5°
77 1
100-8
116-3
79-9=
98-3
122-2
136-8
160-2
102 -3°
119-9
142-7
156-9
178-6
92-3°
110 1
133-9
146-6
168-8
116-7°
134-3
155-9
168-7
Specific Gravities at Boiling Points.
Formate.
Acetate.
Propio-
nate.
Butyrate.
Isobuty-
rate.
Valerate.
Methyl .
Ethyl ..
Propyl .
Isobutyl
Amyl . .
0-95196
0-86667
0 -82146
0 -78287
0 -77027
0-88086
0 -82673
0-79439
0 -77080
0 -83680
0 -79868
0-77201
0 -74424
0 -73646
0 -80261
0-76940
0 -74569
0 -71630
0-71148
0 -80397
0 -77725
0-74647
0 -73281
0 -70662
0-77518
0-74764
0 -72740
0 -70549
968
ABSTRACTS OF CHEMICAL PAPERS.
Specific Volumes.
Formate.
Acetate.
Propio-
nate.
Butyrate.
Isobuty-
rate.
Valerate.
Methyl . . .
Ethyl ....
Propyl . . .
Isobutyl . .
Amyl
62-84
85-14
106 -83
129 -95
150 -21
83-77
106-15
128 -06.
150 10
104-86
127 -37
149-87
174 -23
195 -04
126-75
150-37
173 -89
200-53
221 -52
126-54
148-86
173 -71
196 01
223 -04
149-60
173-44
197 -47
223-40
A. K. M.
Monohalogen Derivatives of Crotonic Acids. By R. Fried-
EiCH {Annalen, 219, 322 — 374). — The researches of Fittig and Erlen-
meyer have shown that the products of the decomposition by water of
the mono- and di-halogen derivatives of the acids of the acetic series
vary according to the relative position of the halogen-atoms and the
carboxyl-group. In the case of the a-acids, the halogen element is
replaced by a hydroxyl- or ethoxyl-group ; but the /3-acids are decom-
posed with formation of an acid of the oleic acid series and separation
of the haloid acid. The author has carried on a series of experiments
on the action of alkalis on the monohalogen derivatives of isomeric
and substituted crotonic acids, in order to determine which of the two
above-mentioned reactions takes place. These researches have re-
vealed the existence of a new series of ethoxy-acids, isologous with
ethoxyacetic acid, and have shown that the chlorocrotonic acids
obtained simultaneously from ethyl acetoacetate are probably physical
isomerides. The influence of the concentration of the solution and
the nature of the solvent are also studied. The following acids were
used in the research : iS-chlorisocrotonic acid (m. p. 39-5°), /3-chloro-
crotonic acid (m. p. 94'5°), a-chlorocrotonic acid (m. p. 97"5°), and
a-methyl-^-chlorocrotonic acid.
^-Chlorisocrotonic acid is converted by sodium ethylate or alcoholic
potash into ^-etkoxy crotonic acid, CeHioOa, which crystallises in mono-
clinic prisms melting at 137°, soluble in alcohol and ether, insoluble in
water. Its potassium salt crystallises in long needles, an aqueous
solution of which gives precipitates with solutions of the chloride as of
metals of the iron-group. The ethyl salt crystallises in rhombic tables
melting at 30". Ethoxycrotonic acid is decomposed by dilute sulphu-
ric acid into carbonic anhydride, acetone, and alcohol, thus : CeHioOa
4- H2O = CaHeO -f- CgHeO -j- CO2 (this reaction is perfectly general),
and by concentrated potash into potassium acetate and alcohol,
C6H9O3K H- KOH + H2O = 2(CH3.COOK) + C2H5OH.
Concentrated aqueous solution of potash converts /S-chlorisocro tonic
acid into acetone and carbonic anhydride. A more dilute solution
yields a tetrolic acid melting at 94*6°: as this latter on oxidation
with permanganate solution gives acetic acid, it contains a methyl-
group, and has the composition CMe : C.COOH.
(ii.) When ^-chlorocrotonic acid is treated with concentrated alco-
ORGANIC CHEMISTRY. 969
holic or dilute aqueous solution of potasb., it yields products identical
with those from the iso-acid.
(iii.) a-Chlorocrotonic acid is attacked neither by sodium ethylate
nor by dilute alkali ; by concentrated solutions, it is decomposed into
carbonic anhydride, acetic, and oxalic acids, and a higher carboxylic
acid, probably of the formula C4H6O3.
(iv.) a-Methyl-(3-chlorocrotonic acid is converted by alcoholic potash
into methyl-/3-ethoxycrotonic acid, which crystallises in prisms melt-
ing at 132°. Concentrated aqueous solutions of potash decompose
a.methyl-/3-chlorocrotonic acid into ethyl methyl ketone and carbonic
anhydride ; dilute potash is without action.
The identity of the ethoxycrotonic and tetrolic acid obtained from
y3 normal and isocrotonic acids, proves either that the latter is con-
verted even by very dilute alkali into the former or less stable acid (a
view which the author regards as untenable), or these acids are phy-
sical isomerides. By long-continued heating the author succeeded in
partially converting the ^-chloro-acid (m. p. 94'5°) into its isomeride
melting at 59*5°.
Attention is drawn to the decomposition of the ethoxy-acids by
water according to the equation CMe(OX) ! CY.COOH + HOH =
Me.CO.CYH2 + XOH + CO2, a reaction which is analogous to the
decomposition of that of isocrotyl ether.
The author draws a comparison between the action of alkalis on the
acetoacetates and on the crotonic acids ; with dilute alkalis, the former
yield acids, the latter ketones ; conversely, with concentrated alkalis
the former give ketones, the latter acids. This difference may be
attributed to the presence of a double bond in the crotonic acids.
V. H. V.
Derivatives of the Isomeric Crotonic Acids. By P. Melikofp
(Ber., 16, 1268 — 1271). — By the addition of hypochlorous acid to
isocrotonic acid, and treatment with zinc carbonate, two zinc salts of
chlorhydroxybutyric acids are obtained, one crystalline and the other
gummy. The crystalline salt forms rhombic tables of the formula
(C4H6C103)-2Zn,2H20, sparingly soluble in cold water. The free acid,
C4H7CIO3, from this salt crystallises in long needle-shaped prisms,
melts at 82°, and is readily soluble in water, alcohol, and ether. The
calcium salt, (C4H6C103)2Ca,4H20, consists of granular aggregates
of microscopic crystals, is readily soluble in cold water, and effloresces
slowly in air. By the action of alcoholic potash on the acid, potassium
chloride and hutylglycidic acid are formed: this latter acid is very
unstable, and does not yield any characteristic salts ; it unites with
hydrochloric acid to form the chlorhydroxybutyric acid melting at 82°.
The addition-product of a-crotonic acid and hypochlorous acid has
been already studied by Erlenmeyer and Miiller (Abstr., 1882, 598) ;
the author's results, however, differ somewhat from theirs. The
c7dorhydroxyhuty.ric acid, C4H7CIO3, obtained in this way, crystallises
in stellate groups of needles, is readily soluble in water, deliquesces
in air, and melts at 62 — 63° (Erlenmeyer and Miiller give 53 — 56°).
The zinc salt, (C4H6C103)2Zn, crystallises in groups of tables, and is
very soluble in water; the calcium salt, (C4B[6C103)2Ca, forms an
970 ABSTRACTS OF CHEMICAL PAPERS.
amorplious white powder, readily soluble in water. By the action of
alcoholic potash on this acid, oxypropylenecarhoxylic acid,
o<|
CHMe
I
CH.COOH
isomeric with batylglycidic acid, is obtained. It crystallises in rhom-
bic prisms, melts at 84°, and is readily soluble in water, alcohol, and
ether. The potassium salt, C4H5K03,|H20, crystallises in trans-
parent granules ; the silver salt, CiHsAgOs, is a white crystalline
powder, sparingly soluble in cold water. Hydrochloric acid converts
the acid into a chlorhydroxy butyric acid, C2H2MeCl(OH).COOH,
which crystallises in large prisms or in thin transparent tables, melts
at 85°, and is reconverted into propyleneoxycarboxylic acid by treat-
ment with alcoholic potash. The zinc salt separates from hot aqueous
solution in rhombic prisms containing 2 mols. of water of crystallisa-
tion. "A. J. G.
New Acid of the Series C„H2«_406. By A. Bauer {Monatsh.
Chem., 4, 341 — 344). — Some years ago the author, in conjunction
with Groger, obtained a new acid of this series by the action of potas-
sium cyanide and potassium hydroxide on monochlorosubei*ic acid, and
the present paper is devoted to a further examination of this acid.
It is crystalline, moderately soluble in water, and decomposes when
heated even at 100°, the decomposition apparently consisting in the
reproduction of suberic acid, with separation of carbonic anhydride.
The solution of its ammonium salt gives with barium salts a white pre-
cipitate ; with cupric salts, a bulky mountain-green precipitate ; with
silver nitrate, a white precipitate not much affected by heat or light ;
with magnesium sulphate and with mercuric chloride, white preci-
pitates after some time ; with manganous sulphate, a pale-red pre-
cipitate after a while ; and with ferric chloride at once a very bulky
light-brown precipitate.
The analysis of the acid and of its silver salt led to the formula
CgHuOe or C18H28O12, which has been confirmed by that of the lead salt,
Ci8H23Pb30i2, and of the ferric salt, C,B.nl^e'"Oc. H. W.
Dicarbocaprolactonic Acid. By E. Hjelt (Ber., 16, 1258 —
1259). — Ally lethenyl tricarboxylic acid is dissolved in fuming hydro-
bromic acid and the solution placed over caustic potash, when, after a
time, crystals of an isomeric acid separate. The new acid, dicar-
hoca^rolactonic acid, is bibasic, and crystallises in triclinic forms, wliich,
however, closely resemble the rhombic pyramids of sulphur. It is
soluble in water, sparingly soluble in ether, and melts at 152 — 153°.
The harium salt, CsHgOeBa, is a white amorphous powder, readily
soluble in water ; the silver salt, CsHgOeAgo, is obtained as a pulve-
rulent precipitate on adding a silver salt to a hot ammoniacal solution
of the acid. On boiling the acid with baryta- water, a flocculent pre-
cipitate of the barium salt of the hydroxy-acid is obtained. On fusion,
the lactonic acid is resolved into carbonic anhydride and carbocapro-
ORGANIC CHEMISTRY. 971
lactonic acid (this vol., 656). Dicarbocaprolactonio acid is repre-
C3H5.C(COOH).CH2.COOH
sented by the formula | | , and is the first
O CO
instance of a dibasic lactonic acid. A. J. G.
Alkylsulphamic Acids. By F. Beilstein and E. Wiegand (Ber.,
16, 1264 — 1268). — In the hope of synthesising taurine or isotaurine,
the authors investigated the action of sulphuric anhydride on ethyl-
amine, but obtained instead the isomeric ethylsulphamic acid. Other
bases of the fatty series behave in a similar manner with sulphuric
anhydride, and thus differ entirely from those of the aromatic series.
Ethylsulphamic Acid, NHEt.SOsH. — Sulphuric anhydride and ethyl-
amine, both in the state of vapour, were passed into a cooled flask,
and the product exposed for some time to a moist atmosphere ; then
diluted with water and boiled with barium carbonate, when, on con-
centrating the filtrate, barium ethylsulphamate crystallises. At times,
however, although the working was the same, a thick neutral syrup
was obtained, which contained no barium, and was probably an anhy-
dride, EtH2l^<C | , or amide, S02(NHEt)2 ; boiling vdth baryta-water
^SOa
resolved it into barium ethylsulphonate, and a small amount of ethyl-
amine. The free acid, prepared by the action of hydrogen sulphide on
the lead salt, crystallises in needles, is soluble in water, alcohol, and
ether, and is not decomposed by boiling with water. The calcium
salt, (NHEt.S03)2Ca,2H20, forms moderately large, brilliant prisms,
is soluble in ether, readily soluble in alcohol and water ; the barium
salt, (C2H6NS03)2Ba,^H20, crystallises in lustrous cholesterin-like
plates, and is readily soluble in water ; 1 part of the anhydrous salt
dissolves in 74' 2 parts of alcohol (90 per cent.) at 18°. The lead salt
forms needles readily soluble in water and alcohol.
Diethylamine and sulphuric anhydride unite with great energy;
the product, when treated with water and barium carbonate, yields a
brown syrup, which, on being boiled with baryta-water, is resolved into
diethylamine and barium diethylsulphamate, (NEt2.S03)2Ba,2H20,
readily soluble in water and alcohol, insoluble in ether. The free acid
has already been described by Behrend.
Triethylamine and sulphuric anhydride react with great energy,
yielding a thick viscous mass, from which, on dilution with water,
brilliant crystals separate, and are purified by solution in acetone.
SOa
The Anhydrotriethylsulphamic acidj EtaK^ | , thus obtained forms
^O
colourless tabular crystals, which melt at 91*5°; it is readily soluble
in acetone, alcohol, and hot water, sparingly soluble in cold water and
ether, and reacts neutral. On boiling with water, it is decomposed
into triethylamine and sulphuric acid.
With methylamine and sulphuric anhydride, results are obtained
similar to those with ethylamine. A. J. G.
972 ABSTRACTS OF CHEMICAL PAPERS.
Dialkyldisulphisethionic Acids. By J. Engelcke (Annaleriy
218, 269 — 283). — It has been shown by Laube and by Stengel (see
last Abstract) that the salts of sulphacetic and sulphobenzoic acids
are capable of combining with ethyl sulphate. With a view to ascer-
tain whether the carboxyl-gronp in the above acids plays an essential
part in the reaction, the author has made experiments with isethionic
acid and with benzenesnlphonic acid. Dry sodium isethionate is well
mixed with a slight excess of sulphuric acid, absolute alcohol added,
and the whole digested for several days with frequent shaking ; the
product is then filtered, the excess of alcohol distilled off, and the
syrupy liquid is diluted with water and neutralised with barium car-
bonate in the cold. On evaporating the filtrate at a gentle heat,
crystals are obtained consisting of barium isethionate and the
double salt, (02H4OHSO3)2Ba,SO4Et2, from which the former can be
separated by adding absolute alcohol to the saturated aqueous
solution. A more convenient method is to neutralise with sodium
carbonate instead of barium carbonate, add alcohol to precipitate the
sodium sulphate formed, and then cautiously evaporate the filtrate
on a water-bath to complete dryness. On extracting the residue with
absolute alcohol and recrystallising, the compound is obtained in a
state of purity. Sodium dimethyldisuljphisethionate,
C2H4(OH).S03m,S04Me2,
forms a white silky mass of monoclinic plates ; it is anhydrous, but
rapidly deliquesces on exposure to the air. Attempts to prepare the
free dimethyldisulphoisethionic acid were unsuccessful. On boil-
ing an aqueous solution of the sodium salt, it is decomposed according
to the equation —
C2H4(OH).S03lSra,S04Me2 + 2H2O = C2H4(OH).S03H -f
2MeOH + S04lSraH.
Sodium dietJiyldisuljpliisetMonate^ C2H4(OH).S03K'a,S04Et2, re-
sembles the methyl-derivative in its properties, but is less stable.
The author has also made several experiments with the view of
obtaining a corresponding double compound from benzenesnlphonic
acid, but all his attempts were unsuccessful. A. K. M.
Methylsulphonic Acid. By JSTishack {Annalen, 218, 283 — 288).
— The lithium salt, MeS03Li,H20, obtained on adding lithium sul-
phate to a solution of the barium salt and evaporating the filtrate,
crystallises in hygroscopic prisms, very readily soluble in water ; the
ammonium salt, MeSOsNH^, forms small thin hygroscopic scales of a
mother-of-pearl lustre ; the strontium salt, (MeS03)2Sr,H20, crys-
tallises in concentrically grouped rhombic prisms, which lose their
water at 120° ; the calcium salt, (MeS03)2Ca, is anhydrous, and forms
groups of rhombic prisms ; the magnesium salt, (MeSO3)2Mg,10H2O,
crystallises in clusters of flat rhombic plates, which effloresce in dry
air and dissolve very readily in water. Metlnjlsulplionic chloride,
MeS02Cl, obtained by the action of phosphorus pentachloride on
patassium methylsulphonate, is a colourless liquid having a pene-
trating odour and boiling at 160°.
ORGANIC CHEMISTRY. 973
Attempts to prepare double compounds of methylsulphonates with
methyl and ethyl sulphates proved unsuccessful (see also last Abstr.).
A. K. M.
Constitution of the Double Compounds of the Sulphonates
with Alkyl Sulphates: Constitution and Dimorphism of
Sulphates. By A. Geuther (Annalen, 218, 288 — 302). — From the
results obtained by Laube, Stengel, and Engelcke (p. 972), the author
assigns to the double compounds obtained by them the following con-
stitutional formulae, in which M and R denote respectively metal and
alcohol-radicle : —
C6H4(COOM).SO(OM)<^>SO(OR)2,
Dialkyldisiilphobenzoate.
CH2(0H2.OH).SO(OM)<^>SO(OR)3
Dialkyldisulphoisethionate.
He explains the fact that the sulphonic acids of the hydrocarbons
do not form corresponding compounds, by pointing out that the
stability of these compounds becomes greater the greater the amount
of oxygen present, and vice versa. He regards these compounds as
derivatives of a disulphuric acid^ (OH)2SO<^q>SO(OH)2, the ex-
istence of which would readily explain the constitution of the per-
sulphates S2O8H3M and similar salts, and also the occurrence of
dimorphism and of other variable properties exhibited by many sul-
phates. A. K. M.
Biguanide. By F. Emich (Monatsh. Chem., 4, 408 — 414). —
I. According to Rathke, biguanide, C2H7N'5, is a biacid base, its normal
sulphate having the composition C2H7N5,H2S04 ; but cupric biguanide
is mono-acid, its normal sulphate being represented by the formula
(C2H6^5)2Cu,H2S04 or (C2H6CuISr5)2,H2S04. Emich, however, has
shown (see p. 975) that ethylbiguanide is a monacid base, form-
ing two series of salts, normal and acid. Now as it appeared very
unlikely that the ethyl- derivative should have a saturating power
different from that of biguanide itself, the author was induced to
repeat Rathke's experiments (which were made upon very small
quantities of material), and he finds that biguanide, like its ethyl-
derivative, is a monacid base, its normal and acid sulphates having
respectively the formula? (C2H7N6)2,H2S04 and C2H7N5,H2S04.
II. Biguanide is resolved by prolonged boiling Avith acids or alkalis
into carbonic anhydride and ammonia, according to the equation C2H7N0
+ 4H2O = 2CO2 4- 5NH3, the decomposition being analogous to that
of guanidine : CH5N3 + 2H2O = CO2 + SNHg. The constitution of
these two bases may therefore be represented by analogous formulae,
viz. : —
HN : C(NH2)2 HN : C(NH2).lSrH.C(NH2) : NH
G-uanidine. Biguanide.
n. w.
D74 ABSTRACTS OP CHEMICAL PAPERS.
Methylguanide and its Compounds. By A. F. Reibenschuh
(Mo7iatsh. Chem., 4, 388 — 394). — The copper-derivative of this base
is obtained in the form of sulphate, (C3H8N6)2Cu,H2S04 -}- 2IH2O, by
triturating dicyanodiamide with cupric sulphate, and digesting the
resulting powder with a 20 per cent, solution of methylamine, till the
whole dissolves to a deep blue liquid, which, when left at rest for
several days, deposits the required compound in red needles. A larger
quantity may however be obtained, and in a few hours, by heating the
blue solution in a sealed tube at 100 — 110°. For success in the pre-
paration, however, it is essential that the methylamine solution be of
the strength above mentioned, as weaker solutions are apt to decom-
pose and deposit cupric oxide. By proceeding as above, the copper
sulphate compound is obtained as a network of very slender needles,
having the colour of peach-blossom, and extremely hygroscopic.
The copper-base, (C3H8N5)2Cu, may be prepared in the free state
by repeatedly agitating cupric oxide with methylamine solution during
several days, then shaking up the filtered liquid with pulverised
dicyanodiamide, and heating the resulting solution for several hours
at 100 — 110° ; but a better yield is obtained by mixing a solution of
the sulphate in the smallest possible quantity of dilute sulphuric acid,
with a quantity of soda-lye sufficient to redissolve the resulting pre-
cipitate, then filtering hot, and recrystallising from hot water. The
amaranth- coloured solution on cooling deposits the copper-base in
glittering rose-coloured needles, having the composition
(C3H8N5)2Cu,3iH20,
and giving ofi" their water at 110°.
Methylbiguanide, C3H9N5, is obtained in the free state by decom-
posing its sulphate (infra) with baryta-water, and may be concentrated
in a vacuum over sulphuric acid to a viscid uncrystallisable syrup.
It quickly absorbs carbonic anhydride from the air, and forms both
normal and acid salts, which dissolve readily in water, and crystallise,
with the exception of the extremely deliquescent carbonate, in laminae
or in slender prisms, often aggregated in radio-fibrous hemispherical
groups. The normal sulphate, (C3H9N5)2,H2S04, prepared by decom-
posing the above-described copper sulphate compound with hydrogen
sulphide, crystallises in spherical groups of short rhomboidal prisms,
permanent in the air, not losing weight at 100°, and melting at 110°.
The acid sulphate, 03H9]S'5,H2S04, is a crystalline powder more soluble
than the normal salt. The normal and acid nitrates and hydrochlorides
are obtained by decomposing the corresponding sulphates with nitrate
and chloride of barium. The normal hydrochloride crystallises in
efflorescent laminae, extremely solubler in water, and forming a crys-
talline platinochloride. The chromate and picrate, obtained by direct
combination, crystallise in slender prisms, the former with orange-
yellow, the latter with dark yellow colour. H. W.
Ethylbiguanide and its Compounds. By F. Emich {Monatsh.
Chem., 4, 395 — 408) . — The author prepares this base by the action of
ethylamine on dicyanodiamide, (CN)2(NH2)2 + EtNHj = C2H6EtN5.
rts copper sulphate compound, (C4HioN5)2Cn,H2S04, prepared like the
ORGANIC CHEMISTRY. 975
corresponding methjl-compound (p. 974), by the action of cnpric
snlpliate on dicjanodiamide dissolved in ethylamine, separates in
carmine-red, highly lustrous granules, or in rose-red mostly micro-
scopic needles, containing 1 mol. H2O, accordingly as the reaction
takes place in a hot or cold solution. The crystals of both kinds,
especially the latter, are highly hygroscopic, and to render them anhy-
drous they must be dried for several hours in the exsiccator at 115 —
120°. This salt is nearly insoluble in pure water, but dissolves more
readily in alkaline liquids, with partial separation, however, of the
cupric base. Dilute acids, even aqueous carbonic acid, dissolve it
readily, with formation of the corresponding salts of copper and
ethylbiguanide.
Cupric Ethylbiguanide, (C4B[io]S'5)2Cu, is formed synthetically
by the action of a solution of cupric hydroxide in ethylamine on
dicyanodiamide, but the process is slow, and the compound is more
readily obtained by decomposing the sulphate above described with a
caustic alkali. It dissolves sparingly in cold, more freely in hot
water, forming a pale violet-red strongly alkaline solution, which pre-
cipitates many metallic salts, e.gr.,MgCl2, ZnCl2, HgCL, also potassium
or sodium sulphate, with formation of KOH or NaOH, and the very
slightly soluble copper sulphate compound. The solution absorbs
carbonic acid from the air, and deposits the carbonate of the copper-
base in pale red needles. The copper-base is anhydrous, and bears a
temperature of 125° without alteration, but decomposes at 140° with
evolution of ammoniacal vapours.
Ethylbiguanide, 041111^5 = CgHeEtNg, prepared by decomposing
either of its sulphates with baryta- water, forms a white extremely
delicate crystalline mass, soluble in alcohol, insoluble in ether, and
obtained by concentration of its aqueous solution, as a clear syrup,
which often does not solidify till it has been kept for weeks over sul-
phuric acid. It produces a strong alkaline reaction on moist litmus-
paper, expels ammonia from its salts, and rapidly absorbs carbonic
acid from the air. When heated in a test-tube, it gives off ammonia
and ethylamine with strong effervescence, leaving a yellowish mass
resembling mellone, which sublimes at incipient redness, with evolution
of fumes smelling like prussic acid, leaving scarcely a trace of charcoal.
It forms two series of salts, mono- and bi-acid, most of which are crys-
talline. The carbonate and oxalate are very soluble. H. W.
Nitration of Benzene-derivatives. By P. Spindler (Ber., 16,
1252 — 1257). — The author has worked at this subject in the hope of
obtaining an answer to the following questions : —
1. Can the same result be obtained by nitration with a more dilute
acid continued for a sufficiently long time as with a stronger acia
during a shorter interval ?
2. What is the explanation that the result is only equal within
certain limits in the concentration of the acid ?
3. What degree of concentration of the acid is the most favour-
able?
Benzene, methylbenzene, chlorobenzene, bromobenzene, and ortho-,
meta-, and para-benzonitranilide were nitrated, and all gave similar
976
ABSTRACTS OF CHEMICAL PAPERS,
results ; the experiments with benzene are quoted in the paper in a
series of tables, the main results of which are given below.
Nitration in the Cold.
acid.
Water.
Benzene.
Percentage of NO2 found.
Nitric
acid.
Duration of reaction.
1 day. 10 days.
150 days.
c.c.
c.c.
c.c.
10
1-527
0
5
39-07
39-31
—
10
1-500
0
5
35-79
r 35-49 \
\ 36-13 /
35-88
10
1
5
35-61
36-66
36-94
10
2
5
35-17
35-61
36-41
10
3
5
32-59
35 -21
36 03
10
4
5
28-99
33-09
r36-39
135-97
10
5
5
20-78
28-99
35-37
10
6
5
8-25
18-81
30-78
10
7
5
2-89
13-58
25-56
10
8
5
0-84
4-40
15-94
10
9
5
0 00
1-68
6-73
10
10
5
0-51
r 0-67 "1
I 0-45 /
3 15
10
15
5
—
—
0-79
10
20
5
0-39
—
0-14
Nitration at the Temperature of the Water-hath.
Sp.gr.
of
acid.
Water.
Benzene.
Percentage of NOj found.
Nitric
acid.
Duration of reaction.
10 hours.
30 hours.
120 hours.
c.c.
c.c.
CO.
10
1-500
0
5
35-82
37 -54
—
10
5
5
36-68
—
—
10
10
5
26-33
30-22
—
10
20
5
1-51
5-48
—
10
30
5
— _
1-78
—
10
"
50
5
—
—
0-00
10
»
100
5
""""
~
0-00
The reason of the hindrance to nitration by too great dilution is
still unknown ; itis not due to the decomposing action of water, as after
heating pure nitrobenzene with twice its volume of water for 750 hours
ORGANIC CHEMISTRY. 977
at about 100°, for 25 hours at 125°, or for 6—7 hours at 200°, not the
slightest trace of an acid reaction could be detected in the water.
A. J. G.
Action of Allyl Chloride on Benzene in Presence of
Aluminium Chloride. By P. Wispek and R. Zuber {Amialen, 218,
374 — 382). — Silva showed that diphenylpropane is formed by this
reaction (Absfcr., 1880, 260), but the authors thought it possible that,
by modifying the conditions of the experiment, allylbenzene might be
formed. When the allyl chloride is allowed to react on a mixture
of benzene and aluminium chloride, diphenylpropane is obtained,
together with traces of a substance boiling at 160°. If the benzene
is first warmed with the aluminium chloride in presence of dry
hydrochloric acid, and, after cooling, a mixture of equal volumes of
benzene and allyl chloride is added drop by drop, a different reaction
takes place ; on distilling the product, hydrochloric acid and benzene
first pass over, then between 130° and 200° a slightly coloured fluorescent
liquid, and between 270° and 290° other products, leaving a black
resinous residue in the retort. An examination of the fraction 130 —
200° proves it to consist principally of normal propylbenzene, boiling
at 157-5— 158-5°. A. K. M.
Action of Bromine on Aromatic Hydrocarbons. By J.
Schramm {Annalen, 218, 383 — 396). — It has been shown by Radzis-
zewski that bromethylbenzene is decomposed by distillation into
styrene and hydrobromic acid (Ber., 6, 493), and that bromopropyl-
benzene and bromobutylbenzene also suffer analogous decomposition.
The author has experimented with other aromatic hydrocarbons with
the view of ascertaining if the above reaction is a general one, and has
adopted this method for the preparation of unsaturated hydrocar-
bons. Fentylhenzene, CeHg.CsHn, obtained by the action of sodium on
benzyl bromide and butyl bromide, is a colourless liquid of agreeable
odour, boiling at 200*5 — 201*5° under a pressure of 743 mm. Its sp.
gr. is 0*8602 at 22°. The preparation of iso^entylhenzene (b. p. 193^")
has been described by Fittig and Tollens (Annalen, 129, 369, and 131,
313). Hexylbenzene, 06H5.(CH2)3.CHMe2, is formed by the action of
sodium on a mixture of benzyl bromide and isopentyl bromide ; it
boils at 212—213°, and has a sp. gr. of 0*8568 at 16°. When bro-
mine-vapour is brought into contact with pentylbenzene heated in an
oil-bath at 150 — 155°, it is readily absorbed, with evolution of hydro-
bromic acid ; and on distilling the monobromo-derivative thus formed,
phenylpentylene is obtained, boiling at 210 — 215°. It combines with
bromine to form a dibromide melting at 53 — 54°, crystallising in
needles or'scales, readily soluble in ether and alcohol. In the same way
phenylisojjentylene, C11H14, can be obtained ; it is a colourless liquid,
of sp. gr. 0-878 at 16°, boiling at 200-5—201*5°. The dibromide,
CuHuBra, crystallises from alcohol in white silky needles, readily
soluble in ether, benzene, and toluene, and melting at 128 — 129°.
Hexylbenzene behaves exactly in the same way as the above hydro-
carbons, yielding phenylhexylene and the dibromide Ci2Hi6Br2, the latter
forming star-like groups of needles or scales melting at 79 — 80°.
A. K. M.
VOL. XLIV. 3 U
978
ABSTRACTS OF CHEMICAL PAPERS.
Researches on Periodides. By F. W. Dafert (Monatsh. Chem.,
4, 496 — 511). — I. Periodides of Trialktlphentlium Iodides. —
These compounds are obtained by precipitating the solutions of the
corresponding moniodides in alcohol or water with a solution of
iodine in alcohol or in potassium iodide, as apparently microcrystal-
line or amorphous, easily decomposible bodies, which may be recrys-
tallised from alcohol, and then form well-defined compounds not
much affected by exposure to the air. They may also be prepared
by the action of iodine dissolved in alcohol on solutions of the
hydroxides, as shown by the following equation : —
6(NEt3Ph.OH) + 3I2 = NEtaPhlOa + 5NEt3PhI +'3H20,
the moniodide thus formed uniting with the excess of iodine to form
a periodide. When, however, a solution of iodine in potassium iodide
is used, the iodate formed in the first instance appears to react with
the compound Kljlj in the following manner : —
]SrEt3Ph.I03 + KI,l2 = KIO3 + NEt3PhI,l2 ;
or the reaction may take place as shown by either of the following
equations : —
6(]SrEt3Ph.OH) + 181 f KI = eCN'EtaPhl,!^ + KlOs + SH^O
eCKEtaPh.OH) + 301 + KI = eCNEtaPhl,^) + KIO3 + 3H2O.
These periodides may also be formed from the ammonium iodides
in alcoholic solution by addition of potassium ferricyanide, which is
thereby reduced to ferrocyanide, with separation of iodine.
The periodides of this group hitherto examined are dichroic bodies,
appearing under the microscope as opaque indistinct crystals, some-
times elongated in one or two directions.
The pentiodides are more deeply coloured than the tri-iodides. They
melt with partial decomposition, and give off part of their iodine on
exposure to the air. The law of variation of their melting points
according to the proportion of iodine which they contain, is different
from that which holds good in the corresponding tetralkylium per-
iodides, as shown in the following table : —
Tetralkyl- compounds .
m.p.
NMe3EtI,l2 64°
NMe3EtI,l4 68
NEt4l,l2 142
NEtJjIi —
TrialhylpTienyl-compounds.
NMe3PhI,l2 116°
N]VIe3PhI,l4 87
NEt3PhI,l2 81
NEt3PI,l4 68
The iodine in these compounds, like that of periodides in general,
is easily separated by the action of water, caustic potash, mercury,
sodium- amalgam, &c. The result is usually complicated by secondary
processes, but the primary reaction consists in a separation into free
iodine and the moniodide of the base. Thus when trimethyl-
phenylium tri-iodide is heated with water, iodine is separated, and
several products are formed, amongst which iodoform may be recog-
nised by its smell, colour, crystalline form, and melting point (119°).
ORGANIC CHEMISTRY. 979
As, however, the moniodide of this base likewise yields iodoform
when boiled with water, the occurrence of that substance amongst
the decomposition-products of the periodide may be regarded as due
to a secondary process, the periodide being resolved in the first
instance into NMcgEtl and I2.
Trimethylphenylium tri-iodide, NMcaPhljIa, formed by adding the
weighed quantity of iodine in aqueous or alcoholic solution, crys-
tallises in light-red laminae having a coppery lustre, melting at
116°, easily soluble in alcohol, sparingly in ether. The pentiodide,
NMcaPhljIi, obtained by treating the moniodide with excess of
iodine dissolved in alcohol, crystallises in moss-green glittering
needles, melting at 87°, easily soluble in alcohol, sparingly in ether.
Triethylphenylium tri-iodide, NEt3PhT,l2, is always precipitated from
a solution of the moniodide on addition of alcoholic iodine, even
when the iodine is in excess. It forms glistening laminae, melting
at 81°, easily soluble in alcohol, less soluble in ether than the pre-
ceding periodides. The pentiodide, NEt3PhI,l4, separates from the
mother-liquor of the last compound in large black strongly dichroic
laminae, melting at 68°, easily soluble in alcohol, sparingly in ether.
The higher members of this series also give precipitates with
iodine ; but they have not yet been examined. Bromine throws down
from solutions of the moniodides stable precipitates of perhaloid com-
pounds, containing both bromine and iodine ; from solutions of the
hydroxides, it precipitates unstable compounds containing bromine,
and perhaps consisting of the corresponding perbromides.
II. Peeiodides of the Nitrosodialktlanilines. — These bodies,
nitrosodiethylaniline for example, form with iodine two series of
compounds represented by the formulae —
2NR2C6H4(NO),l3 3NK^CaH4(NO),l2,
a. iS.
'R denoting a radicle of the series 0«H2»+i. The a-formula must
however be doubled, in accordance with the law of even numbers.
These periodides are prepared by treating the nitrosodialkyl-
anilines with the weighed quantity of iodine dissolved in alcohol,
solution of potassium iodide, carbon bisulphide, or chloroform, and may
be purified by washing with ether and crystallisation, which latter
process is however attended with a certain amount of decomposition.
When r eery st alii sed from alcohol, they form well-defined compounds,
which exhibit strong dichroism, and give off a very small portion
of their iodine on exposure to the air. Their melting points rise
as the proportion of iodine diminishes, as may be seen from the fol-
lowing table : —
Melting point. Percentage of iodine.
2I^Me2C6H4(]SrO),l3 115-5° 65-9
2NEt2C6H4(NO),l3 1180 51-7
3NMe306H4(NO),l2 123-5 86-1
3NEt3C6H4(NO),l2 127-0 32-2
All these bodies are decomposed, with separation of iodine, by
water, potash-lye, mercury, sodium-amalgam, and other reagents,
3 u 2
980 ABSTRACTS OF CHEMICAL PAPERS.
secondary decompositions, however, taking place at the same time,
the bases which they contain being much more easily attacked than
those of the trialkylphenylium periodides.
The following are the characters of some of these periodides : —
2NMe2C6H4(N'0),l3. Black crystalline scales having a bluish
shimmer, melting at 115*5°, easily soluble in alcohol and chloroform,
less readily in ether. — 3NMe2C6H4(NO),l2. Brown-red laminae having
a violet shimmer, melting at 123*5°, easily soluble in alcohol, less
easily in ether. — 2NEt2C6H4(NO),l3. Black laminae and needles
having a bluish shimmer, easily soluble in alcohol, sparingly in
ether, crystallising from strong solutions in tufts and in better defined
crystals. — 3NEt2C6H4(NO),l2. Light copper-red laminae having a
golden lustre, and melting at 127°.
III. Peeiodides of Pyridine, CsHsNjHIjIi. — On adding iodine
dissolved in potassium iodide to a solution of pyridine in sulphuric
acid, this compound separates in glittering needles having a splendid
emerald- green colour. It is extremely soluble in alcohol, easily in
benzene, light petroleum, and chloroform, sparingly in ether, and
melts at 89°. Water separates iodine from it. It appears to be
converted into dipyridine by sodium- amalgam.
On adding alcoholic iodine to an alcoholic or aqueous solution of
pyridine, a red precipitate is formed, which is not identical with the
periodide just described. A similar precipitate is formed by a solution
of iodine in potassium iodide or in carbon bisulphide.
IV. Second Periodide of Quinoline. — A solution of iodine in
potassium iodide added to a solution of quinoline in sulphuric acid
forms a precipitate resembling the pyridine compound just described,
and different from the periodide of quinoline described by Glaus and
Istel (Wien. Akad. Ber., 15, 824). This precipitate is crystalline,
has a shimmering aspect, a grass-green colour when moist, dull grey-
green after drying. It dissolves with extreme facility in alcohol,
easily also in benz.ene and light petroleum, sparingly in ether. It
melts at 67°, and is not decomposed by cold water. On heating the
alcoholic solution of this compound with sodium-amalgam rich in
sodium, the liquid becomes decolorised, and ether extracts from it a
crystalline organic substance melting at 110 — 115°. On heating this
body with water, iodine is separated.
The primary bases, such as aniline, toluidine, &c., the secondary
bases, such as diphenylamine, the nitroso- compounds of the latter, the
nitro-derivatives of the tertiary bases, and the homologues of acet-
anilide, treated by either of the methods above described, do not yield
any periodides. The azylines, however, yield addition-products similar
to the periodides of the nitroso-dialkylanilines.
From the facts hitherto observed, it appears that only tertiary bases
and ammonium bases are capable of yielding periodides. Moreover, if
a residue capable of greatly weakening the basic character (e.g., NO2
or C2H3O) be added, or if the base itself is sensibly altered by free
iodine, as is the case with diethylaniline, the formation of a periodide
no longer takes place. H. W.
ORGANIC CHEMISTRY. 981
Derivatives of Triphenylmethane. By B. Renouf (Ber., 16,
1301 — 1307). — I. Paraleucaniline and Leucaniline. — In the prepara-
tion of paraleucaniline from paranitrobenzaldehyde and aniline, another
base is obtained in very small quantity. It separates from benzene in
small crystals containing benzene, is colourless, but turns red on
exposure to air. It is distinguished from paraleucaniline by its
behaviour with oxidising agents ; chloranil oxidises it to a dye of
but little tinctorial power, somewhere between magenta and violet in
shade. The platinochloride is sparingly soluble, and is decomposed
-on boiling its solution.
Faraleucaniline sulphate, prepared by the action of cold concen-
trated sulphuric acid on an alcoholic solution of the leuco-base, crys-
tallises in bundles of needles. A hot solution of the salt oxidises very
readily, with separation of rose-coloured crystals. Paraleucaniline
oxalate forms small, short prisms, readily soluble in water, sparingly
soluble in alcohol and ether. Faraleucaniline platinochloride crystal-
lises in rosettes of thick, yellow needles, sparingly soluble in water,
insoluble in alcohol.
Benzoylparaleucaniline, prepared by heating a solution of paraleuc-
aniline in benzene with excess of benzoic chloride, crystallises in
colourless needles, melts at 149°, is moderately soluble in hot alcohol,
nearly insoluble in ether and benzene. Triacetylparaleiicaniline^
CigHisNaSca,
is obtained by heating the dry leuco-base with excess of acetic anhy-
dride for one hour. It crystallises in pale rose-coloured thin tables,
iand melts at 177°. On oxidising it with chromic acid in glacial acetic
acid solution, and boiling the product with hydrochloric acid, para-
rosaniline is obtained. Triacetyl-leucaniline, CaoHisNa^ica, prepared
in a similar manner from leucaniline, forms tufts of pale rose-
-coloured needles, and melts at 168° : oxidised with chromic acid in
■glacial acetic acid solution, it yields tetracetylrosaniline. Tetracetyl-
.rosaniline, C(C6H4.!N'HZc)2(C6H3Me.NHZc).OXc., prepared by boiling
rosaniline for two hours with acetic anhydride, forms an amorphous
red powder.
II. Condensation of Orthonitrohenz aldehyde with Aniline. — By heat-
ing orthonitrobenzaldehyde and aniline sulphate for ten hours on the
water-bath, in presence of zinc chloride, a nitroleuco-base is ob-
tained as a yellowish-red, indistinctly crystalline mass. This on
reduction with zinc and hydrochloric acid gave the hydrochloride of a
new triamidotQ'iphenylmethane, Ci9Hi9N3,8HCl, crystallising in groups
-of needles, readily soluble in water, sparingly soluble in alcohol,
insoluble in ether. The free base, C19H19N3, forms small pale-brown
•crystals, and melts at 165°. The platinochloride crystallises in yellow
needles, readily soluble in water and alcohol ; the oxalate crystallises
in groups of small brownish needles, readily soluble in water, more
sparingly in alcohol ; the sulphate forms very small quadratic tables,
is readily soluble in water, very sparingly in alcohol. On oxidising
the base with chloranil, only a very faint yellowish-brown colora-
tion is obtained. By heating it with arsenic acid at 150°, a brown dye
is formed ; heated with excess of acetic anhydride, it yields an acetyl-
982 ABSTRACTS OF CHEMICAL PAPERS.
componnd crystalHsirg in needles. As the behaviour of the new
triamidotriphenylmethane on oxidation is so different from that of
the one obtained from orthonitrobenzaldehyde, a comparative exami-
nation of the methiodides of both bodies was made in the expectation
that any difference in structure wonld be manifested by a difference
in these derivatives, but the result showed them to be closely related
substances.
III. Condensation of Salicylaldehyde with Aniline. — Salicylalde-
hyde, aniline sulphate, and zinc chloride heated for 30 — 40 hours at
110 — 120°, yields a compound which, after purification, crystallises
from benzene in groups of pale red-yellow needles of the formula
C19H18N2 + CeHe. The acetyl-compound, obtained by boiling the
base with excess of acetic anhydride, forms reddish-white needles,
A. J. G.
Hydroxyazo-compounds. By R. Meter and H. Keeis {Ber., 16^
1329 — 1333). — Benzeneazoresorcinol is readily purified by solution in
hot aqueous ammonia; on cooling, the ammonium-compound sepa-
rates in nearly black scales or plates of greenish lustre. It loses
ammonia on exposure to air. By treatment with hydrochloric acid,
benzeneazoresorcinol is obtained as a red powder melting at 165°. By
reduction with tin and hydrochloric acid, it yields the amidoresorcinol
of Weselsky, together with aniline.
By the action of orthonitrophenol in alkaline solution on para-
diazobenzenesulphonic acid, the parasulphobenzeneazo - orthonitro-
phenol of Griess is obtained. Paranitrophenol similarly treated
yielded substances which could not be purified, probably belonging
to the class of di-azo-compounds. Parasulphobenzene-azoresorcinol
yielded with both nitrophenols substances which could not be
purified. A. J. G.
Amarine. By A. Claus and K. Elbs (Ber., 16, 1272— 12 ?4).— If
the formula for amarine containing one imide-group only recently
proposed by Claus (Ber., 15, 2333) be correct, a silver salt containing
but 1 atom of silver should be obtained. On mixing silver nitrate with
alcoholic solution of amarine and subsequent addition of concentrated,
aqueous ammonia, a silver derivative, C2iHi7N2Ag, separates in the
course of a few days. The same compound is obtained even when
silver nitrate is employed in large excess. It forms small, brilliant,
nearly colourless crystals, insoluble in water, alcohol, and ether ; con-
centrated ammonia dissolves only traces. On slowly heating it, a
residue of metallic silver is left, whilst pure lophine sublimes in
theoretical amount.
The silver derivative of amarine reacts easily with organic haloids.
Heated with benzyl bromide in sealed vessels at 100° it yields mono-
benzylamarine as a colourless transparent resin, which could not be
obtained in the crystalline state; it dissolves in dilute acids, even
acetic. Addition of platinic chloride to the hydrochloric solution,
gives a fine golden-yellow precipitate of henzylamarine platinochloridey.
[C2iHi7(C7H7)N2]2,H2PtCl6, coutaimng also water of crystallisation,
which is completely driven off" at 120°. On further heating, it softens
ORGANIC CHEMISTRY. 983
at 165 — 167° ; melts to a thick yellow liquid at 236°, and decomposes
into a black mass at 240°.
Monobenzylamarine is distinguished from the bi- derivatives by the
readiness with which its chromate oxidises when boiled in glacial
acetic acid solution. A. J. G.
Silicates of the Phenol By A. Martini and A. Weber (Ber.,
16, 1252). — These compounds are prepared by the action of an excess
of the respective phenols on silicon tetrachloride.
Tetrajphenyl silicate, Si(0Ph)4, forms a colourless syrupy liquid,
which only solidifies after long cooling.
Tetraparacresyl silicate, Si(OC7H7)4, is obtained in fine crystals.
Both compounds distil unchanged at a high temperature.
A. J. G.
Constitution of Benzoyl-carbinol. By J. Plochl and F.
Blumlein {Ber., 16, 1290— 1293).— If the formula of benzoyl car-
binol is really Ph.CO.CH2.OH, — that usually assigned to it, — it will,
on addition of hydrocyanic acid and saponification of the resulting
nitrile, yield atroglyceric acid, CPh(0H)(C00H).CH2.0H; but if,
on the contrary, it has the constitution CHPh(OH).CHO, it will be
converted by such treatment into phenylgly eerie acid,
CHPh(OH) .OH(OH).COOH.
The result of the authors' experiments prove the former supposition
to be correct, the acid formed being identical with atroglyceric acid.
A. J. G.
Hydroxylation by Direct Oxidation. By R. Meyer {Aimalen,
219, 234 — 307). — In this paper an account is given of experiments of
the author and his associates on the hydroxylation by direct oxida-
tion, preliminary notices of which have appeared in the Berichte (see
Abstrs., 1879, 157, 465, 795; 1880, 165 ; 1881, 45, 819, &c.).
In the introduction, a few general remarks are offered on the
subject. Before the author's investigations, it had been observed that
triphenylme thane, CHPhs, is converted by oxidation into triphenyl-
carbinol, C(0H)Ph3 (Hemilian), aniline into quinol, and di- and tri-
nitrobenzene into di- and tri-nitrophenol. In the alizarin manufac-
ture, it had been observed that anthraquinonemonosulphonic acid
when fused with potash yields alizarin, whilst the corresponding
disulphonic acid yields purpurin ; these changes, though effected by
the air, are usually assisted by the manufacturers by the addition of
potassium cljlorate. On reviewing these various reactions it is to be
observed that all the above compounds contain a CH-group, or ter-
tiary hydrogen-atom. The author's investigations have been carried
out with a view of proving that the hydroxylation by oxidation, or
conversion of H into (OH), is a reaction general to all substances
which contain such a tertiary hydrogen- atom. The following are the
principal examples given in the paper : oxidation of isobutyric acid,
CHMes.COOH, into hydroxyisobutyric acid, C(0H)Me2.C00H ;
984 ABSTRACTS OF CHEMICAL PAPERS.
cumic, CHMea.CeHi.COOH, into hydroxypropylbenzoic acid,
C(OH)Me2.C6H4.COOH ; cymene-sulphonic, C6H4(S03H).CHMe2,
into oxypropylbenzenesulphonic acid, C6H4(S03H).C(OH)Me2.
In order to effect these conversions, it is necessary in practice to use
a 4 per cent, strongly alkaline permanganate solution ; the reaction
cannot be effected with an acid substance. V. H. V.
Chloroxy- and Bromoxy-derivatives of Benzene. By R.
Benedikt {Monatsh. Chem., 4, 223 — 236). Third memoir. Compare
this Journal, 36, 717, and 38, 246. — I. Kesorcinol-derivatives. —
TricJilorometadihronioxybenzene, or Tricliloro-resodihromoxyhenzene^
1 3
C6Cl3H(OBr)(OBr).* — To prepare this compound, trichlororesor-
cinol, C6Cl3H(OH)2 (obtained by passing chlorine into a solution of
resorcinol in glacial acetic acid, and melting at 83°), was suspended
in fine powder in a mixture of equal parts of water and hydrochloric
acid, and mixed with excess of bromine-water, and the resulting pre-
cipitate was twice crystallised from chloroform. It forms small
yellowish crystals, decomposing at 130°, with emission of brown
vapours. By heating with sodium hydrogen sulphite or with tin and
hydrochloric acid, it is reconverted into trichlororesorcinol, showing
that both its bromine-atoms are directly attached to oxygen, as repre-
sented by the above formula. Heated to 130 — 140", it decomposes
with evolution of brown vapours containing bromine, but the decom-
position is not very definite,
Chlorodibromo-meta'Chlorobromoxyhe7izene, C6ClBr2H(OCl)(OBr), is
prepared by passing chlorine into a mixture of 500 c.c. water and
600 c.c. hydrochloric acid in which 60 g. tribromoresorcinol is sus-
pended, expelling the excess of chlorine by a stream of air, filtering,
pressing the precipitate, and twice crystallising it from chloroform.
It forms small yellow crystals, melting without decomposition.
Heated to 175° it gives off exactly 1 mol. bromine, but no chlorine,
leaving a residue which crystallises on cooling, and when purified by
washing with ether and recrystallisation from chloroform, gives by
analysis numbers leading to the formula CoBrClaHOa, which when
doubled represents dicliloroxydichlorodihromodiplienoqidnone^
ClO.CeBrClH.O
ClO.CeBrClH.O '
a compound analogous to the product obtained by decomposition of
tribromoresorcinol, viz., dibromoxytetrabromodiphenoquinone,
(BrO.C6Br2H.O)2,
and resembling the latter in all its properties. It begins to turn
brown at 180°, and melts with decomposition at a temperature above
200°. Heated with tin and hydrochloric acid, 'it is converted into a
* Called in the original paper Trichlorresorcinbrom, the other compounds being
similarly named. The method of preparing this compound and also the correspond-
ing orcinol deriyatiye was briefly described by Stenhouse and Groves {Chem. News,
41, p. 287).
ORGANIC CHEMISTRY. 985
white bulky mass, wMch, when crystallised from glacial acetic acid,
has the composition of dichlorodibromotetrahydroxydiphenyl,
(HO),C6BrClH.C6BrCiH(OH)2 ;
it melts without decomposition at 265°. DichloroxydicUorobromo-
diphenoquinone decomposes at 220 — 230° (just like dibromoxytetra-
bromodiphenoquinone), giving off, bowever, not chlorine, as might
be expected, but bromine, and being converted into an amorphous
mass. The decomposition is by no means definite.
Compariso7i of the Behaviour of the four known Pentahalogen-resor-
cinols when Seated.
1. Trichloro-m-dichloroxybenzene, C6Cl3H(OCl)(OCl), volatilises
without decomposition, the chlorine in this compound being much,
more closely united to the oxygen and carbon, than the bromine in the
analogously constituted bromine- and chlorobromine-compounds.
2. Trichloro-m-dibromoxybenzene, C6Cl3H(OBr)(OBr), in like
manner gives off no chlorine, but only bromine, leaving a residue no
longer containing any haloxy-groups, and probably consisting chiefly
of CeClaH '. O2 '. CeClsH. This residue exhibits all the properties of the
bodies Ci2Br6H402 and Ci2Br6H204, obtained respectively by the action
of heat on tribromo-bromoxybenzene and on dibromoxytetrabromo-
diphenoquinone. All these bodies dissolve readily in ether and in
alcohol, and none of them have yet been crystallised.
3. Chlorodibromo-m-chlorobromoxybenzene, C6ClBr2H(OCl) (OBr),
gives up exactly 1 mol. bromine, leaving a crystalline residue insolu-
ble in ether, and having half its chlorine directly united to oxygen, so
that it has not undergone any change of atomic arrangement. Hence
it follows that the compound C6ClBr2H(OCl)(OBr), when heated,
gives up the bromine-atom attached to the oxygen, and another
situated in the benzene-nucleus.
Moreover, since the crystalline residue has been shown to be a
diphenyl-derivative {supra), its formation and constitution must be
represented as follows : —
CaBrlBri01H<Q^i CcBrClH<gCl
o's- = 2Br. + I
CaBrKClH<Qg:i CeBrClH<0^j
4. Tribromo-??i-dibromoxybenzene is decomposed exactly like the
preceding compound.
II. Phenol-derivatives. — Trichloro-chloroxyhenzene, CeClsHa.OCl,
is produced by passing chlorine into a solution of trichlorophenol in
dilute potash-lye : the action is very slow, and requires to be con-
ducted with particular precautions, for which we must refer to the
original paper.
This compound crystallises in shining orthorhombic prisms, having
the axial ratio a : & : c = I : 0-6059 : 0'5073. It melts at 119°, and
distils without decomposition; it may also be crystallised without
decomposition from boiling alcohol. The crystals when drenched
986 ABSTRACTS OP CHEMICAL PAPERS.
with potash-ley assume a fine blue colour without alteration of form.
They are completely decomposed when boiled with the alkaline liquid,
yielding a large quantity of trichlorophenol, together with brown
amorphous bodies. Cold nitric acid does not act upon the compound,
but the boiling acid decomposes it with brisk evolution of gas. On
heating the compound with sulphuric acid, hydrogen chloride is
abundantly evolved, and on pouring the resulting mass into water and
distilling with steam, trichlorophenol passes over and chloranil
remains behind :
SCOeClaH^.OCl) + H2O = 2(C6Cl3H2.0H) + CeCUO^ + 2HC1.
Trichloro-hromoxyhenzene, CeClaHa.OBr, is obtained by mixing a
solution of trichlorophenol in dilute potash-lye with an equal volume
of strong hydrochloric acid, then adding an excess of bromine dis-
solved in the same acid, agitating the liquid repeatedly for some
hours, then filtering and crystallising the product from chloroform.
The resulting crystals are slightly coloured, and melt at 99°. The
compound heated above its melting point gives off bromine, and
leaves an amorphous mass. When fused under sulphuric acid, it is
converted into bromotrichlorophenol, CeHClaBr.OH.
The trichlorophenol used in the preparation of the compounds just
described was obtained by passing chlorine into liquefied phenol
at 80°, till the product solidified at 30°. Now when this pro-
duct is heated with dilute potash-lye, it does not dissolve completely,
but leaves a fused residue which solidifies on cooling, and when crys-
tallised from alcohol yields long needles of consecutive tetrachloro-
benzene [1:2:3:4], melting at 42°. The occurrence of this com-
pound in crude trichlorophenol is in all probability due to a
replacement of the hydroxy I- group of the phenol by chlorine ; and
since the trichlorophenol may also be obtained by chlorination of
ordinary dichlorophenol [OH : CI : CI = 1 : 2 : 4], there remains for
the trichlorophenol only the formula [OH : CI : CI : CI = 1 : 2 : 3 : 4].
There are, however, other considerations which indicate for this com-
pound the formula [1:2:4:6], so that the final decision of the
question must be left for further investigation.
Action of Chlorine on Trihromo^henol. — When chlorine is passed into
tribromophenol suspended in dilute hydrochloric acid, the compound
is gradually converted into a granular mass occupying a much smaller
volume; and, on crystallising the product from chloroform, small
shining crystals are obtained, consisting of two or more isomorphous
substances, separable by fractional crystallisation into portions con-
taining various quantities of chlorine and bromine, and consisting of
tribromo-bromoxybenzene, C6Br3H2.0Br, chlorodibromo-bromoxyben-
zene, CeBrgClHs.OBr, bromodichloro-bromoxybenzene, CeBrCloHa-OBr,
and perhaps other products richer in chlorine. A similar displace-
ment of bromine by chlorine in the benzene nucleus has been already
noticed in the action of chlorine on tribromoresorcinol. In the case
of tribromophenol, part of the displaced bromine appears to act on
hitherto unattacked tribromophenol, converting it into tribromo-
bromoxybenzene. H. W.
ORGANIC CHEMISTRY. 987
Hydroxyquinol, the Third Isomeric Trihydroxybenzene. By
L. Baeth and J. Scheeder {Monatsh. Cliem., 4, 176 — 181). — The-
authors have previously shown {Monatsh., 3, 650) that quinol fused
with sodium hydroxide yields, together with condensation-products,
an unstable difficultly crystallisable body ; and having now obtained
this body in larger quantity, they find that it consists of hydroxy-
quinol, C6H3(OH)3.
To prepare hydroxyquinol, quinol is fused with 8 to 10 parts of
sodium hydroxide, a little water being added at the commencement,
and the heat being quickly raised as soon as this water is evaporated,
till the frothing begins to subside : the temperature is then lowered,
and the operation discontinued as soon as hydrogen ceases to go off.
The cooled mass is then added to dilute sulphuric acid ; the filtered
solution shaken 10 to 15 times with ether ; the ether-solution evapo-
rated ; the residual brownish syrup dissolved in water ; the filtered
solution fractionally precipitated with lead acetate ; the precipitates
decomposed with hydrogen sulphide ; the resulting solutions frac-
tionally shaken up with ether ; and the extracts evaporated, redissolved
in water, fractionally precipitated with lead acetate, and so on, till at
length the lightest-coloured ethereal extracts, after evaporation of the
ether, gradually begin to crystallise. Lastly, the crystalline pulps are
drained, washed with water or amyl alcohol, and dried between paper^
being at the same time protected from light.
Hydroxyquinol softens gradually when heated, and melts com-
pletely at 132 — 133°. It dissolves very readily at ordinary tempera-
tures in water, ether, ethyl acetate, ethyl alcohol, and amyl alcohol,
but is nearly insoluble in light petroleum, chloroform, carbon bisul-
phide, and benzene. The aqueous solution is extremely sensitive ta
light, becoming dark-coloured even in a vacuum over sulphuric acid,
depositing dark-brown flocks, and finally drying up to a black-brown,
somewhat greasy mass. This coloration takes place more quickly in
the open air, still more readily on adding a drop of alkali. The solution
blackens the skin, and gives with dilute aqueous ferric chloride a
brownish -green colour, which quickly becomes paler, and changes to
dark-blue on addition of a little sodium carbonate, wine-red with a
larger quantity. A somewhat large quantity of ferric chloride produces
a dark greenish-brown coloration, which does not become paler but
turns nearly black, on. addition of sodium carbonate. The solution is
not altered by ferrous sulphate, but, on adding a small quantity of
sodium carbonate, a violet colour is produced, changing to deep blue
on addition of a larger quantity. Hydroxyquinol triturated with
bromine forms, with evolution of hydrogen bromide, a brovni substance
which dissolves with dark cherry-red colour in dilute alcohol, and
crystallises therefrom in blue-violet granules. When hydroxyquinol
is subjected to dry distillation in a stream of hydrogen, part of it
goes over unaltered, whilst the rest becomes carbonised, and yields a
distillate of quinol.
Constitution of the Three Trihydroxyhenzenes. — Quinol having the
constitution [OH : OH = 1:4], hydroxyquinol must be the unsymme-
trical trihydroxybenzene [1:2:4]; and, as previous experiments by
the authors have tended to show that phloroglucol has the symme-
*98& ABSTRACTS OF CHEMICAL PAPERS.
trical constitution [1:3:5], they infer that pyrogallol must be the
consecutive modification [1:2:3]. H. W.
Action of Sulphur on Sodium Phenate. By L. Haitingeb
{Monatsh. Chem., 4, 165 — 175). — Kolbe has shown that when sodium
phenate is heated in a stream of carbonic anhydride, a reaction takes
place represented by the equation
2(C6H5.0Na) -f C02 = IiraO.C6H4.COONa -f CsHs.OH,
the products being phenol and disodic salicylate. Sulphur appears to
act upon sodium phenate in a similar manner, not however yielding
immediately the products indicated by the equation
2(C6H5.0N"a) + S = NaO.CeHi.SNa 4- CeHs.OH,
namely, phenol and the disodic derivative of hydroxyphenyl mercaptan,
HO.C6H4.SH, but an oxidation-product of the latter, viz., dihydroxy-
phenyl disulphide, HO.C6H4.S.S.C6H4.OH. To prepare this compound,
2 mols. sodium phenate and 1 of sulphur are mixed in fine powder
and heated in a retort for an hour at 180 — 200°. The mass then
liquefies, and a small quantity of phenol distils over. The cooled melt
is decomposed by dilute sulphuric acid, and the black oil thereby
separated is distilled with steam till the distillate no longer gives a
yellow precipitate with lead salts. There then remains a black viscid
resin, apparently containing a considerable quantity of sulphobenzide,
(CeH,),SOa.
The first portions of the steam distillate contain a heavy oil, con-
sisting mainly of phenol, and the water passing over therewith
quickly becomes turbid on exposure to the air, in consequence of
partial oxidation of the dissolved hydroxyphenyl mercaptan. On neu-
tralising the strongly acid distillate with soda and evaporating to a
syrup, phenol volatilises, the mercaptan is oxidised by the oxygen of
the air, and the liquid deposits, either immediately or after prolonged
exposure in flat dishes, a sulphur-yellow crystalline precipitate, which,
after washing with cold water and recrystallisation from weak spirit,
is found to consist of the primary sodium salt of dihydroxydiphenyl
•disulphide, Ci2H902S2Na -f 6H2O, which gives off the greater part of
its crystal-water at 100°, the rest, with slight decomposition, at 140°.
The primary 'potassium salt, C12H9S2O2K + 6H2O, is somewhat more
soluble than the sodium salt, gives off 3 mols. water at 100°, and
begins to decompose at 120 — 130°. The dimethylic ether, Ci2H8S202Me2,
formed by heating the primary sodium salt with sodium hydroxide
and methyl iodide, crystallises from alcohol in small thick colourless
needles, melting at 119° (corr.).
Free dihydroxyphenyl disulphide, prepared from the sodium salt by
agitation with dilute sulphuric acid and ether, is a thick faintly-
•smelling oil, nearly insoluble in water. Heated above 200°, it begins
to boil briskly, but decomposes completely at the same time, giving off
torrents of hydrogen sulphide, and yielding a small quantity of a
mobile liquid distillate, which after a Avhile deposits a few crystals.
An aqueous solution of the sodium salt of dihydroxyphenyl
disulphide gives a black precipitate with silver nitrate, brown ^dth
ORGANIC CHEMISTRY. 98^
cnpric acetate, white with zinc acetate, egg-yellow with lead acetate,
all insoluble in dilute acetic acid. All the compounds of dihydroxy-
phenyl disulphide, when brought in contact in the dry state with
strong sulphuric acid, produce a very deep bluish-green coloration.
Hydroxyphenyl 7nercapfan, CeHeSO = HO.CeHi.SH, is formed by the
reducing action of sodium-amalgam, zinc-dust, or ferrous oxide and
potash, on the disulphide ; in small quantity also by the action of
alcoholic potash at the boiling heat, or by fusion with potassium
hydroxide. It is best prepared by treating the primary sodium salt of
dihydroxydiphenyl disulphide with sodium-amalgam, as long as a
brisk evolution of hydrogen takes place, care being taken that the
alkaline solution, which rapidly absorbs oxygen, does not remain too
long in contact with the air. The reduction being completed, the
solution, decanted from the mercury, is acidulated with sulphuria
acid, and the precipitated oil is washed, dried, and rectified. The
formation of the disodium- derivative of the mercaptan takes place
according to the equation —
CiaHgSzOaNa + 3NaOH -i- H2 = SH^O 4- 2(NaO.C6H4.SNa).
Hydroxyphenyl mercaptan is a strongly refractive liquid, having an
extremely powerful odour, and cauterising the skin like phenol. It
distils with steam and is moderately soluble in water. Under a
pressure of 750"7 mm. it distils without decomposition at 216 — 217°.
At a very low temperature it solidifies to a shining crystalline mass,
very much like solid phenol, and melting at -f 5° to 6°. Under
certain circumstances, however, it does not crystallise even at the
temperature of a mixture of solid carbonic anhydride and ether. Its
sp. gr. is 1*2373 at 0°; 1'189 at 100°, referred to water at the same
temperature.
Hydroxyphenyl mercaptan is a moderately strong acid, reddening
litmus, and decomposing carbonates. Its aqueous solution, mixed
with a small quantity of ferric chloride, quickly becomes turbid, with
faint and transient violet coloration ; but if a little sodium carbonate
be immediately added, a very deep green colour is produced, which,
on addition of caustic potash, changes to an equally intense red.
Sometimes also blue and violet tints are developed. With lead salts,
hydroxyphenyl mercaptan forms a bulky yellow precipitate, insoluble
in dilute acids (distinction from dihydroxydiphenyl sulphide), be-
coming dense and crystalline on long standing, and then consisting of
CcHiSOPb. This lead salt (not previously dried) gives on dry dis-
tillation a distillate of phenol, together with a small quantity of
diphenylene oxide.
Hydroxyphenyl mercaptan forms with silver nitrate a yellow preci-
pitate, soluble in potash, insoluble in ammonia; it also precipitates
mercury, copper, zinc, and calcium salts. It is slowly oxidised in the
free state by permanganate, chromic acid, &c. ; much more quickly
and completely in alkaline solution, yielding the corresponding salts
of dihydroxydiphenyl disulphide.
Oxidation of the Methylic Ether of Dihydroxylphenyl Disulphide. — A
solution of this compound in acetic acid, mixed with excess of
chromium trioxide dissolved in glacial acetic acid, yields a sulphonic
<)90 ABSTRACTS OF CHEMICAL PAPERS.
acid, the potassium salt of wticli agrees in all its characters with that
of anisoilsulphonic or methyl pheuolsul phonic acid, prepared from
orthophenolsulphonic acid. This salt, fused with a large excess of
potassium hydroxide, yields a considerable quantity of catechol,
whence it may be inferred that hydroxyphenyl mercaptan belongs to
the ortho-series [SH : OH = 1:2]; and this conclusion is confirmed
by the fact that, on triturating the potassium salt of o-methylphenol-
sul phonic acid with phosphorus pentachloride, a product is obtained
which, when treated with water, yields orthomethylphenolsulphonic
chloride in crystals melting at 55°. This sulphochloride, treated in
alcoholic solution with zinc, is converted into the zinc salt of the cor-
responding sulphinic acid ; and on further reducing the latter with
zinc and hydrochloric acid, then adding excess of hydrochloric acid,
and distilling with steam, an oil passes over, very much like that
which is formedfby reduction of the dimethyl- derivative of dihydroxy-
phenyl disulphide. On adding ferric chloride, the aqueous dis-
tillate became turbid, the odour disappeared after some time, and the
oil was converted into a solid mass, which, after exhaustion with
ether and recrystallisation from alcohol, exhibited all the properties of
the previously described dimethylic derivative of the dihydroxy-
phenyl disulphide prepared from sodium phenate and sulphur, espe-
cially in melting at 119°. The reactions by which these products
-are obtained may be represented by the following equations : —
C6H4(OMe).S02Cl -h 6H = C6H4(OMe).SH + 2H2O -f- HCI
2[C6H4(OMe).SH] + Fe.CU = [C6H4(OMe)S]3+ 2HC1 + Fe2Cl4.
As the phenolsulphonic acid employed was the ortho-modification,
^nd the occurrence of intramolecular transposition is very improbable,
it follows that the dimethyl-derivative of the disulphide obtained as
above described belongs to the ortho-series of benzene- derivatives.
H. W.
Similarity of the Boiling Points of the Corresponding
Ketones, Ethereal Salts, and Chloranhydrides. By H. Scheoder
(Ber., 16, 1312 — 1315). — The author draws attention to the fact that
the boiling points of corresponding ketones and ethereal salts are
always very near to one another, whilst with methyl ketones, methyl
salts, and the corresponding chloranhydride, the boiling points are
nearly identical. Taking two examples from those given by the
author : —
B.P.
Ethylmethylketone, CzHj.COMe 79-5-81° (PopofE)
Methyl propionate, CaHjCOOMe 79*9° (Schumann)
Propionyl chloride, C2H5COCI 79-5 (BrUhl).
Phenylmethylketoue, CeHj.COMe 199—200° (Popoff)
Methyl benzoate, CsHs.COOMe 199-2° (BufE)
Benzoyl chloride, CeHs.COCl 198-7 (BufP).
A. J. G.
Aromatic Ketones. By W. Staedel (AnnaZeuj 218, 339—361).
— To prepare tetranitrodijphenylmetliane, Qi^QQ^Oi)ii diphenylme thane
ORGANIC CHEMISTRY. ^91
is gradually introduced into nitric acid (sp. gr. 1'53), kept cool by a
freezing mixture, and the product, after being left at rest for
some time at the ordinary temperature, is gradually heated on a
water-bath to about 70° ; on then precipitating with water and re-
crystallising from glacial acetic acid, a pure product is obtained, melt-
ing at 172° ; it is almost insoluble in benzene, but is moderately
soluble in glacial acetic acid. If the diphenylmethane is added rapidly
to the nitric acid, and the product then poured into water, Doer's
dinitro- derivative is produced, together with a large amount of resin.
Tetranitrohenzophenone, Ci3H60(N02)4, is obtained by the oxidation of
tetranitrodiphenyl methane by means of chromic acid in acetic acid
solution. It is insoluble in benzene, and very sparingly soluble in hot
glacial acetic acid, from which it crystallises in minute plates, melting
at 225°, and decomposing above this temperature. By the action of
tin and hydrochloric acid on tetranitrodiphenylmethane, tetramidodi-
phenylmethane, Ci3ll8(NH2)4, is obtained melting at 161°. It is
sparingly soluble in benzene, readily in hot water and in alcohol ; its
salts are very readily soluble in water. The hydrochloride forms
slender yellow needles ; the acetate a white crystalline powder. The
author previously showed that two dinitro-products are obtained by
the nitration of benzophenone {Annalen, 194, 307), the a-compound
melting at 189—190° and the /3-derivative at 148—149°, whilst by the
nitration of diphenylmethane and subsequent oxidation with chromic
acid, a dinitrobenzophenone is obtained, also melting at 189 — 190°,
and supposed to be identical with the a-compound. An examination
of the corresponding amido- derivative proves however that they are
not identical. By the action of tin and hydrochloric acid on the
dinitrobenzophenone from diphenylmethane, diamidohenzophenone,
Ci3H80(NH2)2, is obtained, crystallising in white needles melting at
172°. It is insoluble in cold water, sparingly soluble in hot water,
and readily in alcohol ; it forms a hydrochloride crystallising in large
thick plates. By the action of zinc-dust and hydrochloric acid, an
intermediate substance is obtained, apparently C13H13N2O2; it crys-
tallises from glacial acetic acid and from aniline in reddish-brown
microscopic needles. By the reduction of the high-melting dinitro;
benzophenone obtained from benzophenone, diamidobenzophenone
is produced, melting at 131°, and crystallising from dilute alcohol
in lustrous plates. It forms an acetate crystallising in plates which
are readily soluble in alcohol, insoluble in water. ^-diamido-
henzhydrol, Ci3H9(OH)(N'H2)2, is obtained by the action of sodium-
amalgam on diamidobenzophenone, and forms lustrous scales melting
at 128 — 129°. The hydrochloride and sulphate crystallise in white
efflorescent needles ; the nitrate forms long silky hygroscopic needles,
and the acetate indistinct crystals, melting at 220°. o(,-Dihydroxyhenzo-
phenone is obtained from a- diamidobenzophenone by means of the
diazo-reaction, and crystallises from hot water in hair-like needles,
melting at 210°. On heating it with an excess of benzoic chloride,
and then decomposing the latter with sodium carbonate, the benzoic
ether of a-dihydroxybenzophenone is formed, crystallising from alcohol
in silky scales melting at 181 — 182°. ^-dihydroxyhenzophenone^ pre-
pared from |S-diamidobenzophenone, is more readily soluble in water
992 ABSTRACTS OF CHE^nCAL PAPERS.
than tlie a-compound, and forms star-like aggregates of crystals
melting at 161—162°; the benzoic ether, B^O.CeHi.CO.CeHi.OBz,
resembles the corresponding a-compound in appearance, but is more
readily soluble in alcohol, and melts at 101 — 102°; the diacetate fonaH
lustrous scales melting at 89 — 90°. By the action of melted potash
on |3-dihydroxybenzophenone, phenol and parahydroxybenzoic acid
are produced as was previously shown for a-dihydroxybenzophenone.
A. K. M.
Cinnamic Acid Derivatives. By E. Erlenmeyer and A.
LiPP (Annalen, 219, 179 — 233). — The authors, in thfe course of their
investigation on the synthesis of tyrosine, prepared and examined
several derivatives of cinnamic and phenyllactic acids.
Phenyl - cc- hydroxypropionitril (phenyl - ethylidene cyanhydrin),
CH2Ph.CH(0H).CN, prepared by the direct addition of hydrocyanic
acid to phenylethaldehyde, crystallises in small needles (m. p. 57°),
easily soluble in alcohol and ether, sparingly soluble in water. It
decomposes at 100° with evolution of hydrocyanic acid.
Phenyl - a, - amidopropionitril, CH2Ph.CH(]SrH2).CN, is obtained
together with the imidonitril by heating the hydroxynitrile vrith
alcoholic ammonia, and is separated from the imido-compound by the
more sparing solubility of the latter in hydrochloric acid. Its hydro-
chloride forms glistening prisms belonging to the rhombic system,
easily soluble in alcohol.
Phenyl-a-imidopropionitril, CH2Ph.CH(CN).NH.CH(CN).CH2Ph,
crystallises in needles of the monoclinic system, sparingly soluble in
cold water, readily soluble in ether. On crystallising out the crude
substance (m. p. 86°) from ether, two crops were obtained, the one
forming six-sided crystals (m. p. 105°), the other rhombic tables
(m. p. 108°). As the authors were unable to convert one modification
into the other, and as the melting and solidifying points were un-
altered even by repeated recrystallisation, they must be regarded not
as physical, but more probably as polymeric isomerides. Similar
modifications have been observed in the case of the imidoisovalero-
and capro-nitrils (Abstr., 1881, 85).
CH2Ph.CH.NH3
Phenyl-a-amidopropionic acid (phenylalanine), | | (?)>
CO o
obtained as a hydrochloride by pouring the crude product of the
action of ammonia on phenylethylidine cyanhydrin into hydrochloric
acid, and boiling the mixture. On dissolving the hydrochloride in
water and saturating the solution with ammonia, the free alanine
crystallises out in glistening prisms, soluble in alcohol and hot water.
When boiled with potash, it evolves no ammonia, thus differing from
the phenylamidopropionic acid of Posen. The phenylalanine forms
crystalline salts both with acids and bases ; the hydrochloride crystal-
lises in white prisms, the platinoohloride in dark golden needles, the
nitrate in hair-like interlaced needles. The copper salt,
(C9HioN02)2Cu,2H20,
forms small blue prisms, the silver salt, white microscopic prisms.
ORGANIC CHEMISTRY. 993
Phenylethylamine, CH2Ph.CH2.N'H2,is obtained, together with, plienyl-
lactimide, by the dry distillation of phenylalanine ; the former passes
over into the receiver, while the great part of the latter remains in the
retort. This componnd is identical, as shown by its melting point
and the solubility of its platinochloride, with the phenylethylamine
obtained by Bernthsen by the action of hydrogen on benzonitrile.
Phenyllactimide, C9H9NO, crystallises in fine silky needles (m. p.
290°), easily electrified ; it is insoluble in cold water and ether,
soluble in acetic acid. The compounds described above differ most
markedly in their chemical and physical properties from Posen's com-
pound obtained from cinnamic acid; the former are a-, whilst the latter
are /3- derivatives.
Parasulphophenylamine, C6H4(S03H).CH2.0H(NH).COOH,. ob-
tained by sulphonating paraphenylalanine, crystallises in small colour-
less prisms, soluble in hot water, insoluble in ether and alcohol ; on
melting with alkali, it yields parahydroxybenzoic acid. The barium
salt of the sulpho-acid crystallises in flat colourless prisms.
Paranitrophenylalanine, C6H4(I^02).CH2.CH(NH2).COOH, pre-
pared by the nitration of paraphenylalanine, crystallises in glistening
prisms melting at 220°, sparingly soluble in water and alcohol. On
oxidation with chromic mixture, it yields paranitrobenzoic acid. It
forms crystalline salts with acids and bases; the hydrochloride,
CgHioTTsOijHCl, crystallises in glistening prisms belonging to the
rhombic system, soluble in water and alcohol ; the copper salt,
(C9H9N204)30u,2H20, forms a sparingly soluble crystalline precipitate.
Paramidophenylalanine, 06H4(NH3).CH2.CH(NH2).COOH, obtained
by reduction of the above compound, crystallises in glistening prisms,
which are decomposed on heating ; when boiled with potash, it does
not evolve ammonia. Its hydrochloride crystallises in glistening prisms,
the platinochloride in light golden needles, and the copper salts in
amethyst-coloured needles. This paramidophenylalanine can also be
obtained by the action of nascent hydrogen on ethylparanitrocin-
namate, CgH4(N02).CH I C(N02).C00Et (Friedlander).
Parahydroxyphemjllactic acid, OH.G6H4.CH2.CH(OH).COOH, is
obtained together with tyrosine, in the preparation of the latter from
amidophenylalanine, and may be separated from the mother-liquors
by the addition of a mineral acid, and taking up the product with
ether. It crystallises in white needles melting at 144°, sparingly
soluble in cold alcohol and ether. Its calcium salt is easily soluble in
water and alcohol.
The nitrate of nitrophenyllactic acid, N02.C6H4.CH2.CH(]S'02).COOH,
obtained by treating phenyllactic acid with excess of nitric acid,
forms a golden pasty mass, easily soluble in ether, sparingly soluble
in water. On oxidation with chromic acid mixture it is converted
first into paranitrobenzaldehyde, and finally into the corresponding
acid.
OHa — OeH^—
Sydroxyhydrocarhostyrily \ yNH, is formed, together with
CH(OH).CO^
paramidophenyllactio acid, by the reduction of the above compound
with tin and hydrochloric acid. It crystallises in white glistening
VOL. XLIV. 3 »
994 ABSTRACTS OF CHEMICAL PAPERS, j
leaflets melting at 198°, sparingly soluble in water and ether, more
soluble in dilute alkalis.
Paramidophenylladic acid, NH2.C6H4.CH2.CH(OH).COOH, crystal-
lises in slender white needles melting at 188°, soluble in water, acids, i
and bases ; the first-named has a strong acid reaction and taste ; it i
does not give Piria's reaction. The authors and others are engaged
in a further study of these derivatives. V. H. Y.
Synthesis of Tyrosine. By E. Erlenmeyer and A. Lipp i
{Annalen, 219, 161 — 178). — At the outset, the authors give a full
historical account of the preparation of tyrosine, C9HX0NO3, and of the
various attempts made to obtain the natural product by an artificial
synthesis. The researches of Barth and Ost have established that
tyrosine, when melted with potash, yields parahydroxybenzoic acid ;
whilst Hiifner has shown that on treatment with hydriodic acid it
yields ammonia only ; and Staedler has demonstrated the presence of
two hydrogen-atoms replaceable by metals. It follows from these facts '
that tyrosine contains a hydroxy phenyl grouping, OeHi.OH (in which
the OH is in the para-position), and that the three remaining carbon- I
atoms are combined in a single side-chain, which must be regarded as :
an alanine less one atom of hydrogen. A comparison of the chemical
properties of the phenylamidopropionic acid (phenylalanine) in which ;
the amido-grouping is in the /5-position, with that of tyrosine and the \
a-amido-acid, renders it probable that tyrosine is an a- and not a ;
/3-derivative. Starting with this knowledge the authors prepared \
paramidophenylalanine, N'H.C2H3(C6H4.NH2).COOH, from phenyl- i
ethaldehyde, ammonia, hydrocyanic and hydrochloric acid (cf. pre-
ceding Abstract) ; and treated the hydrochloride of the latter com-
pound with nitrous acid in order to replace by Griess' reaction the \
amido- by the hydroxyl-group, and thus to convert it into _p-hydroxy- i
phenylalanine, NH2.C2H3(C6H4.0H).COOH. This substance was |
found to be identical in all its chemical and physical properties with j
natural tyrosine ; and in the original paper a full comparison is given j
of the melting point and solubility in hot and cold water of the base, j
of the hydrochlorides, and the metallic salts of the natural and \
artificial products. :
It follows from this synthesis, that tyrosine has the constitution of
an alanine in which one hydrogen-atom of the CHa-grouping is re- ,
placed by the parahydroxyphenyl-residue, ,
J V. H. V. \
Phenylglyceric Acid. By A. Lipp {Ber., 16, 1286— 1290).— In ]
the preparation of phenethylaldehyde from phenylchlorlactic acid, an |
acid was obtained in considerable quantity, and was proved to be ;
identical with the phenylglyceric acid, CHPh(OH).CH(OH).COOH, j
of Anschiitz and Kinnicutt (Abstr., 1879, 644). A. J. G. |
Tannins of Oak-bark. By C. Etti (Monutsli. Chem., 4, 512 — |
530). — The tannin of oak-bark exists in two forms, viz., as a tannic |
I
ORGANIC CHEMISTRY. 995
acid, which, in the free state has a reddish- white colour, and as an
anhydride of that acid, called ^lilohaphene, the colour of which is
brown-red. The distinction between these two bodies is familiar to
tanners, who designate the anhydride simply as " colouring matter,"
and reject barks containing a large proportion of it, as it imparts too
red a colour to leather dyed with such barks.
The question as to the existence of a glucoside in oak-bark is now
decided in the negative, as tannic acid extracted from the bark by
ethyl acetate does not yield any such substance. The reactions which
were supposed to indicate the presence of a glucoside were really due
to la3vulin, which, on treating the bark with dilute sulphuric acid,
was converted into laevulose. ,
The tannic acid obtained by agitating an alcoholic extract of the
bark with ethyl acetate may be contaminated with two substances, a
brownish-green amorphous terpene-resin and phlobaphene. The
former may be separated by its ready solubility in ethyl acetate,
ethyl oxide, and benzene. The phlobaphene is easily recognised by
the brown-red precipitate which it gives with lead acetate.
Quercitannic acid cannot be extracted from the bark in the pure
state by ethyl acetate, inasmuch as it decomposes that compound into
alcohol and acetic acid almost as easily as sulphuric or hydrochloric
acid, and the acetic acid thus set free dehydrates a portion of the
tannic acid, producing phlobaphene. Pure quercitannic acid dissolves
completely in ethyl acetate, and does not give up any foreign bodies
to pure ethyl oxide or to benzene ; its solution in very dilute alcohol
gives with basic lead acetate a precipitate of pure yellow colour.
Phlobaphene is nearly insoluble in water and in ether, but dissolves
readily in alcohol of all strengths. As prepared from the bark, it may
be contaminated with terpene-resin and pectin-substances. The
former of these bodies may be recognised and separated by treatment
with ether or benzene, which dissolve it ; the pectin-substances by
their insolubility in spirit of 90 per cent. The presence of tannic
acid in the phlobaphene may be recognised by the fact that the latter,
after being freed from adhering moisture by drying at 110°, gives off
a further quantity of water at 130 — 140°.
Quercitannic acid is represented by the formula CivHieOg. At
130 — 140°, it gives off water, and is converted into the brown-red
anhydride, C34H30O17 = 2O17H16O9 — H2O, identical with the phlo-
baphene contained in the bark. 1 mol. of this substance boiled with
sulphuric or hydrochloric acid gives up 1 mol. water, and is converted
into a second anhydride, C34H28O16 ; and by boiling the tannic acid
free from anhydrides with either of these anhydrides, a third anhy-
dride, C34H26O15, is obtained. These three anhydrides are soluble in
alcohol and in caustic alkalis.
Lowe (this Journal, 1881, Abstr., 901), by treating quercitannic
acid or phlobaphene with dilute sulphuric acid, or with oxalic acid,
has obtained a fourth anhydride, C34H24O14 = 2Ci7H:609 — 4H3O,
which he designates as oak-red. The same name has been applied to
the first anhydride by Oser, and to the second by Bottinger.
Another oak-bark examined by the author yielded a tannic acid
having the composition C20H20O9, aud agreeing with the former in all
3 a; 2
996 ABSTRACTS OF OHEMTCAL PAPERS.
its properties, excepting in its reaction with ferric chloride, with
which it gives a bluish-green colour, quickly changing to deep green,
and on addition of sodium carbonate, first to blue and then to red,
whereas the quercitannic acid above described, and all its anhydrides^
give with ferric chloride a black-blue precipitate. This tannic acid
begins to lose water at 124°, melts at 140°, resolidifies on further loss
of water, and is converted into a brown-red substance identical in
composition with phlobaphene.
The tannic acid, C20H20O9, also yields four anhydrides agreeing in
character with those obtained from the acid CnHisOg. These anhy-
drides are represented by the formulae C40H38O17, C40H36O16, C40H31O13,
and C40H32O14. The same tannic acid heated in a sealed tube with
hydrochloric acid yielded a gas burning with a green flame, but
smaller in quantity than that obtained from the acid CnHieOg. Heated
in a tube with dilute sulphuric acid, it gave a red liquid and a large
quantity of undissolved anhydrides ; and on agitating this liquid with
ether, a small quantity of crystals was obtained consisting of gallic
acid.
The phlobaphene submitted to dry distillation, yielded pure
catechol, free carbon, and an oil insoluble in potash, smelling like
the terpenes and containing 72"46 per cent. C and 7*11 H. This
oil, oxidised with permanganate, yielded an amorphous resin, whence
the author concludes that it is derived, not from the tannin, but from
the terpenes mixed with the phlobaphene which was submitted to dry
distillation.
For the theoretical considerations relating to the constitution of all
the bodies above described, the original paper must be consulted.
H. W.
Derivatives of Opianic Acid. By R. Wegscheidee (Monafsh.
CJiem., 4, 262 — 271). — Opianic acid heated for six hours at 180 —
190° yields a condensation-product, the formation of which may be
represented by the equation .SC10H10O5 — H2O = CaoH-asOu (not
4O10H10O5 — H2O = CioHsgOig, as stated by Matthiessen and Wright).
The author's analyses give for this product 58*76 per cent, carbon and
4'48 hydrogen, agreeing better with the formula CaoHisOu (which
requires 58-82 0 and 4*58 H), than with C40H38O19 (58*39 C and
4-62 H).
The condensation-product fused with potassium hydroxide and a
little water, yielded a thin jelly, from which, after acidulation, ether
extracted hemipinic acid. The whole was then thrown into dilute
sulphuric acid, whereby a solution was obtained, which, on cooling,
yielded white needles of meconin (m. p. 103°). The formation of
these two bodies is represented by the equation 2C30H28O14 + 2H2O =
3C10H10O4 + SOioHioOe; but as Matthiessen and Foster have shown
that the same two bodies are formed by heating opianic acid with
potash, it appears most probable that the first action of the alkali on
the compound C30H28OU is to reconvert it into opianic acid, which is
then decomposed in the manner just mentioned.
From the preceding results, it follows that the opianic residues in
the" body formed by the action of heat on opianic acid are Hnked
together, not by carbon, but by oxygen. The body is in fact a com-
ORGANIC CHEMISTRY. 997
plex anhydride, analogons to those formed from several of the aromatic
hjdroxy-acids {e.g., the three hydroxybenzoic acids and phloretic
acid), which it moreover resembles in its properties. It may accord-
ingly be designated as Triopianide. Its mode of formation is, however,
somewhat different from that of the anhydrides of the hydroxy-acids,
inasmuch as these latter are formed from n molecules of the corre-
sponding acids by abstraction of n—1 mol. water, whereas triopian-
ide is formed from 3 mols. opianic acid by abstraction of one (that is
to say n—2) molecule of water: C30H28O14 = 3C10H10O5 — H2O. To
account for its composition, we must suppose that the COH-group —
which may be regarded as the anhydride of CH(0H)2 — serves as a
connecting link between the molecules. Of the two possible formulas
thus constructed, viz. : —
C6H2(COOH)(OMe)2.CH[O.CO.C6H2(OMe)2.COH]2,
and C6H2(OMe)2(COH).CO.O.CH(OH)^p j^ mMc^
C6H2(OMe)2(COH).CO.O.CO ^U^aCumeja;
the second can alone be regarded as the true representative of tri-
opianide, inasmuch as this body does not exhibit acid properties, and
therefore cannot contain the group CO OH.
Action of Bromine. — Triopianide triturated with bromine is con-
verted into a viscid brominated resin, which gives up the greater part
of the uncombined bromine on standing, and the rest when pulverised
and heated at 100°. On crystallising the residue from alcohol or
toluene, a mixture of two bodies is obtained, one of which melts at
about 200°, the other at a higher temperature ; the former is more
soluble than the latter in alcohol, less soluble in toluene. A rough
separation of the two having been thus effected, the chief product
is boiled with water, which leaves undissolved small quantities of the
higher-melting secondary product. The more soluble body, purified
by recrystallisation from 'water, forms tufts or arborescent groups of
small white needles melting at 204°. This body is Brom-opianic acid,
CioHgBrOs. It dissolves readily in methyl and ethyl alcohols, glacial
acetic acid, benzene, and xylene ; very sparingly in carbon bisulphide,
scarcely at all in light petroleum ; moderately in hot, very sparingly in
cold water, and separates from all these solutions in anhydrous crystials.
It is a decided acid, uniting with ammonia and the oxides of barium,
silver, copper, mercury, lead, and nickel, forming salts which are
soluble in water, and do not give any characteristic reaction with
ferric chloride or lead acetate. A brom-opianic acid apparently identi-
cal with that above described was obtained, though not pure, by
Prinz (/. 'pr. Chem. [2], 24, 367) by the action of bromine- water on
opianic acid.
The secondary product obtained, as above mentioned, by the action
of bromine on triopianide, appears to be a bromine- derivative of that
iDody. After recrystallisation from xylene, it melts at 250 — 251°,
dissolves very readily in chloroform, easily in ethyl acetate and in
"benzene, with aid of heat also in xylene, glacial ace.tic acid, and amyl
alcohol, sparingly in methyl and ethyl alcohols, very spa,ringly in light
petroleum and boiling water, and is quite insoluble in cold water. It
998 ABSTRACTS OF CHEmCAL PAPERS.
dissolves in boiling potash-lye, and the solution if acidulated after
long boiling yields brom-opianic acid.
Triopianide dissolves without alteration in cold strong nitric acid ;
but on adding it to a lukewarm mixture of strong nitric and sulphuric
acids in equal parts, a nitro-product is obtained melting at 248 — 249°.
"When, however, the experiment was repeated with larger quantities
of material, the action went further, yielding a body which melted afc
248 — 249°, and appeared to consist of nitro-opianic acid. H. W.
Pimelic Acid. By A. Bauer (Monatsh. Chem.., 4, 345 — 348). —
The author in 1878 published, in conjunction with J. Schiiler, some
observations on pimelic acid obtained by a synthetic process from
isopentylene (amylene). The acid thus prepared was crystallised,
and on agitation with ether was obtained in conjunction with another
acid, supposed to be an isomeric pimelic acid. On boiling the normal
ammonium salts of the mixed acids with solution of calcium chloride,
the calcium salt of the crystallised acid separates as a sparingly
soluble precipitate, and the mother-liquor, when decomposed and
shaken up with ether, yields an amorphous acid isomeric with pimelic
acid. The calcium salt of this amorphous acid has the composition
CvHioCaOs, and is more soluble in water than that of crystallised
pimelic acid.
Amorphous pimelic acid has a vitreous aspect ; its reactions with
metallic salts differ for the most part but slightly from those of the
crystallised acid, the only characteristic reaction being that of the
ammonium salt with cupric sulphate, whereby no precipitate is formed,
even in concentrated solutions, either at ordinary temperatures or on
boiling, or after long standing.
By heating pimelic acid in sealed tubes with a quantity of bromine
sufficient to convert it into a dibrominated acid, and decomposing the
product with moist silver oxide, an acid was obtained having nearly
the composition C7H10O5. H. W.
Metazophenylglyoxylic Acid. By 0. M. Thompson (Ber., 16,
1308 — 1311). — Metanitrophenylglyoxylamide is saponified with dilute
potash, and the resulting potassium metanitrophenylgly oxalate re-
duced by means of ferrous sulphate and concentrated potash, the
ferrous sulphate being added from time to time until the colour of the
precipitate has changed to brownish- black ; a large excess of hydro-
chloric acid is then added, and the whole heated to boiling. The
yield of the azo-acid is about 50 per cent, of the nitro-amide
employed.
Metazophenylglyoxylic acid crystallises with 2 mols. H2O in light
orange-yellow needles, loses its water of crystallisation at 100°, but
regains its original weight on a few hours' exposure to air. It is
sparingly soluble in cold water, more readily in hot ; insoluble in dilute
acids, readily soluble in absolute alcohol. It melts at 184*5 — 135°.
The silver salt is an orange-yellow powder, and appears to be slightly
soluble in water. The barium salt is obtained as an orange-yellow
indistinctly crystalline powder insoluble in water. A. J. Gr.
ORGANIC CHEMISTRY. 999
Phthalamidobenzoic Acid. By A. Piutti (Ber., 16, 1319 —
1322). — By the action of aniline on phthalamidobenzoic acid, no
anilide is formed, and the reaction is very complex ; in some opera-
tions, colourless crystallisable bodies of high melting point were
obtained, whilst in other cases, and nnder apparently identical condi-
tions, non- crystalline coloured masses of low melting point were formed.
In all cases large quantities of phthalanil and of the original acid were
formed. As phthalamidobenzoic acid is kuown to decompose into
phthalanil and carbonic anhydride on heating, it was an open question
if the aniline played any other part than that of a solvent during the
reaction, but by employing paratoluidine instead of aniline, tolyl-
phthalamide and amidobenzoic acid were formed, and with ammonia
phthalimide was formed: hence by analogy the aniline must take
part in the reaction. The action of primary monamines on the acid
is represented by the equation —
C6H4(COOH).N<^Q>C6H4 + C„H„,.NH2 =
0«H..N<^^>C6H4 + C6H4(NH0.COOH.
By the action of aniline on amidobenzoic acid, amidobenzanilide is
formed ; it melts at 129° and not at 114° as stated by Engler and Volk-
hauser (this Journal, 1875, p. 643). On heating with aniline at 200°,
it yields a mixture of amidobenzoic anhydrides, of which amidobenzoid,
C6H4<^PQ ^TT^CeHi, crystallises in nodules, melts at 225°, and dis-
solves in alcohol, benzene, chloroform, and ether, and another appa-
rently polymeric compound forms a white amorphous powder,
insoluble in ordinary solvents, soluble in concentrated sulphuric
acid, from which it is precipitated unchanged on addition of water.
By heating amidobenzanilide with phthalic anhydride^ phthalamido'
lenzanilide, C6H4(CO.NHPh).N<^Q>C6H4, is obtained. It crystal-
lises in small prisms, and melts at 207 — 209°. A. J. Gr.
Cymenesulphonic Acids. By E. Patern5 (Ber., 16, 1297).— A
reply to A. Glaus.
Dialkyldisulphobenzoates. By F. Stengel (Annalen, 218,
257 — 269). — These compounds correspond with the diethyldisulpho-
acetates obtained by Laube. To prepare barium diethyldisulpho'
henzoate, CiiHu09S2Ba + SJHgO, sulphuric acid is added to sodium
sulphobenzoate in quantity sufficient to form hydrogen sodium sul-
phate and free sulphobenzoic acid, and the mixture after evaporation
to dryness, is well shaken with absolute ethyl alcohol : after some
days the product is filtered, the excess of alcohol removed by distil-
lation, and the syrupy liqaid obtained is diluted with water and
neutralised with barium carbonate. The product, which must be re-
garded as a compound of harium sulphobenzoate with diethyl sulphate^
C7Hi02(S03)Ba,S04Et2,3JH20, crystallises in groups of long colourless
needles. When its aqueous solution is heated in sealed tubes at
1000 ABSTRACTS OF CHEMICAL PAPERS.
107°, it decomposes, yielding sulphobenzoic acid, barium sulphate,
and alcohol. The sodium salt^ obtained by decomposing the barium
salt with sodium carbonate, is anhydroas, and very readily soluble
in water; the copper salt forms small blue crystalline scales con-
taining 2 J mols. H2O ; the lead salt crystallises with 2^ H2O in small
silky needles.
Barium dimethyldisulphohenzoate, C9Hio09S2Ba,3JH20, is prepared
in the same way as the diethyl-compound, and crystallises in colour-
less monoclinic plates, which lose their water at 100° or when ex-
posed over sulphuric acid. It requires a higher temperature (150°)
for the decomposition of its aqueous solution than in the case of the
corresponding ethyl-compound. The copper salt contains 5H20, and
is readily soluble in water ; the sodium salt is still more readily soluble
and anhydrous ; the lead salt is also anhydrous, and is decomposed
readily at the temperature of the water-bath, with separation of lead
sulphate.
Barium dipropyldisulphohenzoate, Ci3Hi809S2Ba,7H20, crystallises in
long concentrically grouped needles of a vitreous or mother-of-pearl
lustre. When heated with water in sealed tubes, it requires a tem-
perature of 180° for its complete decomposition. It loses its water at
170°, partially decomposing at the same time.
From the mother-liquors of barium diethyl- and dimethyl- disulpho-
benzoates, the author has obtained isomeric salts forming anhydrous
granular crystals. A. K. M.
Sjnatheses with Chloropicrin. By K. Elbs {Ber., 16, 1274 —
1277). — By mixing benzene (4 — 5 mols.) with chloropicrin (1 mol.)
in presence of aluminium chloride, triphenylm ethane and triphenyl-
carbinol are obtained, together with a very small amount of dipbenyl-
m ethane. The nitro-groups are mainly converted into nitrous acid,
only a small amount of nitric oxide being formed.
Phenol (3 mols.) and chloropicrin (1 mol.) do not react readily in
presence of aluminium chloride, the mixture requiring to be heated
for 1 — 2 days on the water-bath. The main product of the reaction
is auiin.
Trinaphthyl carhinol, (CioH7)3C.OH, the main product of the reac-
tion of naphthalene, chloropicrin, and aluminium chloride, forms a
brownish-yellow crystalline powder, softening at 180°, and completely
fusing at 278°. It is readily soluble in chloroform, carbon bisulphide,
benzene, toluene, and nitrobenzene, sparingly soluble in ether and
acetone, and nearly insoluble in alcohol and light petroleum. It
could not be obtained quite pure.
Phenanthrene reacts readily with chloropicrin and aluminium chlo-
ride. The product, which resembles the above naphthalene-derivative,
is under investigation.
Triphenylmethane was brominated according to the method of
Schwarz (Abstr., 1881, p. 913), and a solution of the crude bromide
was treated with ammonia gas, and, after removal of excess of ammonia,
with hydrochloric acid. The hydrochloride of the base obtained in
this way crystallises in colourless needles, melts at 244°, is soluble in
water, very soluble in alcohol. The free base crystallises in colourless
ORGANIC CHEMISTRY. 1001
needles, and melts at 105°. The platinocliloride crystallises in large
orange-yellow needles. The formulas of these compounds are still
under investigation. A. J. Gr.
a-Naphthonitrilsulphonic Acid. By U. K. Dutt (Ber., 16,
1250— 1251).— The barium salt of this acid, (CN.CioH6.S03)2Ba, was
obtained in thin colourless tables by treating with water the product
of the action of chlorosulphonic acid on a solution of a-naphtho-
nitril in carbon bisulphide, and neutralising with barium hydrate.
A. J. G.
Pyrene-derivatives. By G-. Goldschmiedt and R. Wegschneider
(Monatsh. Ghem,, 4, 237 — 261). — Action of Chlorine on Pyrene. — When
a rapid stream of chlorine is passed at ordinary temperatures through
a solution of pyrene in chloroform, hydrogen chloride is abundantly
evolved, the liquid becomes warm, and a yellow crystalline substance
separates, consisting of a mixture of chloropyrenes, some of which
also remain in solution ; they may be separated from one another by
fractional crystallisation from alcohol, chloroform, and xylene, alcohol
being almost exclusively employed to separate the portions boiling
below 200°, xylene for those of highest boiling point, and chloroform
for the intermediate portions. The separation cannot be effected by
sublimation, as partial decomposition takes place at the same time.
By proceeding as above, mono-, di-, tri-, and tetra-chloropyrenes
were isolated, and indications were obtained of a second dichloro-
compound. An easily fusible resin was also separated in very small
quantity. If the passage of the chlorine be continued for three-
quarters of an hour, the chief product obtained is tetrachloropyrene,
small quantities of the lower products being however enclosed within
it, and thereby escaping further chlorination. If the process be con-
tinued for a short time only, a considerable quantity of trichloropyrene
is formed. To obtain a large yield of monochloropyrene, the passage
of the chlorine must not be continued for more than a quarter of an
hour. The two dichloropyrenes are always obtained in subordinate
quantity only.
1. Monochloropyrene, CieHgCl, forms long, thin, flattened, shining
needles, melting at 118 — 119°, very soluble, even in the cold, in ether,
chloroform, carbon bisulphide, benzene, and xylene ; also in ethyl ace-
tate (even at low temperatures) ; in alcohol; also when heated in light
petroleum, amyl alcohol, and glacial acetic acid ; moderately soluble in
cold glacial acetic acid ; soluble also in hot methyl alcohol, insoluble
in water. From all these solutions, it separates on cooling, or on
evaporation, in more or less flattened needles. Strong sulphuric acid
dissolves it on warming, with splendid violet- blue fluorescence. When
boiled with fuming nitric acid, it turns red and dissolves partially,
forming a solution which, on dilution with water, deposits a nitro-
compound.
Chloropyrene -picric acid, Ci6H9Cl,C6H2(N02)30H, formed by mixing
an alcoholic solution of monochloropyrene with excess of picric acid
dissolved in alcohol, crystallises in needles very easily soluble in hot
alcohol, and melts with decomposition at 177 — 178°. It turns yellow
1002 ABSTRACTS OF CHEMICAL PAPERS.
on prolonged exposure to the air, and is readily decomposed by boiling
water. Hot alcohol likewise decomposes it, unless an excess of picric
acid is present.
2. oc-Dichloropyrene, Ci6HyCl2, forms flat, sulphur-yellow, shining
needles, melting at 154 — 156°, easily soluble in carbon bisulphide,
even at ordinary temperatures ; also in ether, chloroform, benzene,
xylene, light petroleum, ethyl acetate, and hot glacial acetic acid ;
moderately soluble in hot, sparingly in cold alcohol, very sparingly in
methyl alcohol, insoluble in water. The alcoholic solutions exhibit
blue, all the others green fluorescence. From solution in alcohol or
glacial acetic acid, the compound crystallises on cooling in needles ; also
from solution in benzene, or ethyl acetate, on spontaneous evaporation.
From ether, it separates on evaporation in slender silky needles, from
chloroform, in felted silky needles, from light petroleum and carbon sul-
phide, in branched groups of needles. Strong sulphuric acid dissolves it,
with aid of heat, forming a solution which exhibits a very deep violet-blue
fluorescence. It is decomposed by ignition with lime, yielding pyrene.
3. /3-I)ichloropyrene (?). — A fraction melting at 194 — 196° gave on
analysis quantities of chlorine indicating a mixture of dichloropyrene
with about 15 per cent, of the trichlorinated compound, and as a
similar mixture of tri- with a-di-chloropyrene would melt at a much
lower temperature, the substance in question was probably a some-
what impure isomeric dichloropyrene.
4. TricMoropyrene, C16H7CI3, forms thin soft felted needles, white
with a tinge of yellow. It dissolves easily, with aid of heat, in ben-
zene and carbon bisulphide (in the latter with almost equal facihty in
the cold), somewhat sparingly in chloroform, amyl alcohol, and light
petroleum, sparingly in ether, glacial acetic acid, and ethyl acetate,
very sparingly in methyl and ethyl alcohols, not at all in water. From
all these solutions it crystallises on cooling, in especial abundance
from amyl alcohol and xylene, also from glacial acetic acid and ben-
zene, but very sparingly from methyl alcohol, ether, or chloroform,
and not at all from carbon bisulphide. Strong sulphuric acid dissolves
it sparingly on slight warming, but if a large quantity of sulphuric
acid be used, a somewhat deep violet-blue fluorescence is produced.
On strong heating, complete solution takes place, but the colour of
the liquid becomes darker and the fluorescence indistinct.
5. Tetrachloropyrene, CieHeCli, forms long slender flexible needles,
having a splendid silky lustre, and a pale yellow colour with a tinge
of green. It dissolves readily in hot xylene, with moderate facility in
hot benzene, somewhat sparingly in hot amyl alcohol, sparingly in
carbon bisulphide, hot ethyl acetate, glacial acetic acid, and chloroform,
and in cold benzene and xylene, very sparingly in light petroleum, hot
methyl or ethyl alcohol, ethyl oxide, cold glacial acetic acid, and
chloroform, and is nearly insoluble in cold methyl, ethyl, or amyl
alcohol, ethyl oxide, and ethyl acetate. By strong sulphuric acid
it is but very slightly attacked, even near boiling heat, a faint rose
colour being produced at the commencement of the action. The solu-
bility of the several chloropyrenes in all the above-mentioned liquids
decreases as the proportion of chlorine becomes greater.
ORGANIC CHEMISTRY. 1003
Tetracliloropyrene melts at a temperature above 330°. By ignition
witli quicklime, it yields a small quantity of pyrene.
Action of Concentrated Sulphuric Acid on Pyrene. — Pyrene-disul-
plionic acid, Ci6H8(S03H)3, is prepared by heating pyrene (10 g.)
on the water-bath with 5 c.c. strong sulphuric acid till it dissolves,
then adding 2J c.c. sulphuric acid, and as soon as a sample is found to
dissolve completely in water, pouring the entire product into water.
The resulting solution, after filtration, is saturated with lead carbo-
nate ; the solution of lead pyrenesulphonate thereby obtained is
decomposed with hydrogen sulphide ; and the liquid filtered from lead
sulphide is evaporated to dryness, whereupon the sulphonic acid
remains in the form of a green uncrystallisable pasty residue, dissolving
readily in water and forming a yellow solution with green fluorescence.
It is insoluble in ether and sparingly soluble in alcohol, the solutions
always leaving on evaporation a small quantity of inorganic matter.
A fraction purified as completely as possible, lost on drying in the
exsiccator, 6' 85 per cent., and at 120°, 9*83 per cent, of its weight.
(Ci6HioS206,2H20, would require 9*05 per cent.) The potassium salt,
obtained by neutralisation, gave on analysis numbers agreeing with
the formula Ci6H8(S03K)2. Its aqueous solution leaves on evaporation
a salt containing 2^ mols. H2O, 2 mols. of which are given off in the
exsiccator or at 100°, the remainder at 120°. The barium salt,
obtained by saturation, remains on evaporating its aqueous solution, in
sulphur-yellow films having the composition Ci6H8S206Ba,3^H30, and
giving off their water at 210°. The calcium salt, Ci6H8(S03)2Ca,2H30,
gives off half its water over sulphuric acid, the rest at 130°.
Potassium pyrenedisulphonate fused with potash does not yield the
corresponding phenol, but, according to the temperature and the pro-
portions used, either pyrene or the monosulphonic acid. The potas-
sium salt of this acid separates from aqueous solution in crystals
having the composition Ci6H9S03K,H20, and gives off half its water
in the exsiccator, the rest at 118°.
Distillation of Potassium Pyrenedisulphonate with Potassium Cyanide
or Ferrocyanide. — The conversion of this salt into cyano-derivatives of
pyrene is best effected by distilling it at a low red heat, in portions of
6 g. each with 8 g. of an intimate mixture of potassium ferrocyanide
and iron filings, whereby an oily distillate is obtained which soon
solidifies to a crystalline mass ; and on treating this mass with water
to remove ammonium salts, and recrystallising it from benzene, alcohol,
and light petroleum, two bodies are obtained, one melting at about
150°, the other above 300°. These are best separated by combining
them with picric acid and repeatedly crystallising the resulting com-
pounds from alcohol, whereby a sparingly soluble fraction was obtained
melting at 222 — 223° and yielding by decomposition with ammonia a
body which melted at 147 — 149°, and exhibited all the properties of
pyrene, — together with an easily soluble fraction which when decom-
posed by ammonia yielded mono-cyanopyrene. This compound,
Ci2H9(CN), is nearly white, usually however with a more or less greenish
tinge. It dissolves very easily at ordinary temperatures in chloroform
and benzene, and at higher temperatures in xylene, easily also in
methyl, ethyl, and amyl alcohols, ethyl oxide, carbon bisulphide,
1004 ABSTRACTS OP CHEMICAL PAPERS.
glacial acetic acid, ethyl acetate, and light petroleum. From the last-
mentioned solvent, and from methyl and ainyl alcohols, it crystallises
in needles.
Gyanopyrene-jpicric acid, 2Ci6H9(CN"),C6H2(OH)(N02)3, is obtained
hy mixing the alcoholic solutions of 1 part cyanopyrene and more than
2 parts picric acid, and distilling till the liquid forms a nearly
saturated solution at boiling heat : it then crystallises on cooling. It
is much more easily decomposible than monochlopyrene-picric acid,
being decomposed by cold alcohol, partially by cold water, completely
loj hot water.
Dicyanopyrene, Ci6H8(CN)3. — The above-mentioned fraction boiling
•above 300° is a yellow granular microcrystalline powder, the solutions
of which exhibit a bright green fluorescence. It appears to decompose
at high temperatures.
Fyrene-carhoxylic Acid. — The monocarboxylic acid, CieHg.COOH,
is obtained, as potassium salt, by fusing monocyanopyrene in a silver
crucible with potassium hydroxide and a little water as long as
ammonia continues to be evolved, dissolving the melt in water, and
decomposing the solution with sulphuric acid. The carboxylic acid
then separates as a very bulky, gelatinous opalescent precipitate,
which may be purified by washing with water, solution in sodium
•carbonate, reprecipitation with sulphuric acid, and recrystallisation
from ether-alcohol, with addition of animal charcoal. It is thus
obtained in yellowish nodules melting at 267°, subliming, when
cautiously heated, in loug needles, which have the same melting point,
but are partly resolved at a slightly higher temperature into pyrene
-and carbonic anhydride. The same decomposition is effected almost
quantitatively by heating with lime. The acid is not quite insoluble
in water, moderately soluble in hot absolute alcohol and in ether.
Its barium salt, (Ci7H902)2Ba,2-|^H20, forms a yellowish crystalline
powder, which gives off its water at 100°. The calcium salty
(Ci7H902)Ca,H20,
is also a microcrystalline powder. The silver salt obtained by pre-
cipitation is yellowish at first, but quickly decomposes and blackens.
When pyrene dicyanide is fused with caustic alkali, the product con-
sists mainly of pyrenemonocarboxylic acid, but a small quantity of the
dicarboxylic acid appears also to be formed.
All the above-mentioned pyrene-derivatives (sulphonic acids,
cyanides, carboxylic acids) agree in the facility with which they take
np hydrogen in exchange for their lateral chains. Thus the disulphonio
acid is converted by fusion with potash chiefly into the monosulphonic
acid, part of it however being reconverted at a higher temperature
into pyrene. The conversion of the monocyanide into the mono-
carboxylic acid is also attended with reproduction of pyrene. A
similar reproduction of a fundamental hydrocarbon has been observed
by Goldschmiedt (Monatsh. Chem.y 1, 234) in the saponification of
idryl cyanide. H. W.
Reichenbach's Picamar. By P. Pastrovich {Monatsh. Chem., 4,
J 82— 187); also by G. Niederist (ibid., 487— 493).— The results
ORGANIC CHEmSTRY. 1005
obtained by these two anthors as to the constitution of Reichenbach's
picamar do not quite agree. Pastrovich assigns to it the formula.
C10H14O3, and regards it as the monomethyl ether of propyl-pyrogallol,
C6H2Pr(OH)2,OMe ; but Niederist, whose experiments were made on
a sample of Reichenbach's original preparation, preserved in the
University Laboratory of Vienna, finds that it gives by analysis
numbers agreeing with the formula CuHisOa, which is that of di-
methylic propyl- pyrogallate, C6H2Pr(OH)(OMe)2 [mean of analyses
67-80 per cent, carbon and 8'27 hydrogen ; calc. 67-35 C and 8*16 H.
Yapour- density by Hofmann's method in aniline- vapour, 6*532 ; calc»
6-78].
Potassium-picamarf C11H15O3K, prepared by boiling picamar with
strong potash-lye, solidifies on cooling to a mass of slender needles,
and when purified by pressure between filter-paper and recrystallisa-
tion from hot alcohol, forms white nacreous laminae which acquire
only a faint brown colour after prolonged exposure to the air.
Acetyl-picamar, OisHisOi = OnHigZcOs, prepared by heating picamar
for several hours in a reflux apparatus with excess of acetic anhy-
dride, is insoluble in water, and crystallises from warm alcohol in
shining prisms melting at 80 — 87°, therein agreeing exactly with tho
acetyl- derivative of Hofmann's dimethylic propylpyrogallate (Niede-
rist).
MonometTiylic Trojpijlpijrogallate, C10H14O3 = C6H2Pr(OH)2,OMe,
which Pastrovich obtained from beech-tar, and from the portion of
birch-bark tar boiling above 270°, is a colourless, oily, strongly
refracting liquid, becoming slightly yellowish on prolonged exposure to
light. It boils at 290° and has a density of 1-10288 at 15°. Vapour-
density 6*41 — 6*53 (exp.) ; 6'32 (calc). By prolonged heating in a
sealed tube at 140° with excess of strong hydrochloric acid, it is con-
verted, with separation of methyl chloride, into the compound C9H12O3,
which after purification crystallises in small colourless prisms melting
at 80°, and agreeing in composition and properties with the compound
which Hofmann obtained in like manner from dimethylic propyl-
pyrogallate (picamar). H. W.
• Coerulignol: Reichenbach's Oxidising Principle. By P.
Pastkovich (Monatsh. Chem., 4, 188—192). — The high-boiling portions
of beech-tar oil are characterised by the splendid blue colour which
they give with chloride of lime, or in alcoholic solution with baryta-
water. The separation of the body to which this colour is due — called
by Reichenbach the " oxidising principle " — from the other constituents
of the tar-oil, is very difficult, but is best effected by boiling the oil for
some time with the weakest acetic acid capable of dissolving it, and
pouring the resulting solution into a large quantity of water, whereby
the oil is separated, while a nitrogenous body remains in solution.
The "blue oil," or Coerulignol, thus purified, distils between 240°
and 241° ; it is nearly colourless, has a not unpleasant creosote-like
odour and burning aromatic taste ; sp. gr. = 1*05645 at 15°. It dis-
solves very sparingly in cold, more readily in hot water, and in almost
any quantity in alcohol, ether, and acetic acid, forming neutral solu-
tions. It is coloured red by strong sulphuric acid, and when mixed
1006 ABSTRACTS OF CHEMICAL PAPERS.
with potasli-lye, becomes dark-coloured on exposure to the air. With
chloride of lime, and in alcoholic solution with baryta- water, it pro-
duces the splendid blue colour already mentioned. Its alcoholic
solution is coloured green by alcoholic ferric chloride; its aqueous
solution gives a fine carmine- colour with aqueous ferric chloride.
Coerulignol gives by analysis numbers leading to the formula C10H14O2,
which is confirmed by the vapour- density (5'69 — 5'84 by V. Meyer's
method; 5" 70 by calculation). By prolonged heating in sealed tubes
at 140° with excess of strong hydrochloric acid, it is resolved into
methyl chloride and a body which when purified by repeated crystal-
lisation from water and finally from benzene, is found to have the com-
position O9H12O2, — its formation, represented by the equation CioHuOa-h
HCl = CH3CI -f C9H12O2, being exactly analogous to that of the
compound CoHisOa from methylic propylpyrogallate (p. 1005). The
solution of this body is coloured green by ferric chloride, and when
mixed with alkalis, gradually acquires a darker colour in contact with
the air.
Acetocoerulignol, C12H16O3 = CioB-iJ^Oz, formed by boiling coerulignol
(3 parts) for two days with 1 part of acetic anhydride, was once obtained
in fan-shaped groups of crystals, but mostly as a viscid nearly colour-
less oil, insoluble in water, freely soluble in alcohol, ether, and acetic
acid, boiling with partial decomposition near 265°.
Nitrocoerulignolj OioHi3(N02)02, formed by treating coerulignol with
nitric acid of sp. gr. 1*2, separates from water or alcohol in honey-
yellow crystals, resembling those of picric acid, and melting at 124°.
The decomposition of coerulignol by hydrochloric acid, and the for-
mation of its acetyl- derivative, show that it contains the groups
OCH3 and OH, and that it may accordingly be regarded as the methyl-
ether of a higher homologue of one of the three dihydroxybenzenes,
the compound C9H12O2 formed from it by the action of hydrochloric
acid being this higher homologue itself, which, together with coeru-
lignol and its acetyl-derivative, may be represented by the formulae —
C9Hio(OH)2 CgHioCOMe) (OH) C9Hio(OMe) (0Z5) .
To determine from which of the three dihydroxybenzenes coerulignol
is derived, a small quantity of each of these compounds was heated at
135° with a drop of nitro-benzene and a drop of strong sulphuric acid,
the melt then dissolved in water, and the solution made slightly
alkaline, — whereupon resorcinol gave a bright red solution with yellow
fluorescence, catechol a blue- violet, and quinol a yellow liquid. Now
coerulignol treated in like manner gave a reaction exactly like that of
catechol, and may therefore perhaps be regarded as a homologue of
guaiacol (methyl- catechol) ; but whether it contains a propyl-group
or some other groups, must for the present remain undecided.
H. W.
Action of Sodium on Camphor. (Preliminary Notice.) By J.
Kachler and F. V. Spitzer (Mojiatsh, Cliem., 4, 494 — 496). — When
sodium acts at ordinary temperatures on camphor dissolved in absolut-e
ether or in partially purified petroleum of low boiling point, the pro-
ducts always consist of compounds containing large proportions of
ORGANIC CHEMISTRY. 1007
sodium and oxygen ; and even when a solvent quite free from oxygen
sucli as light petroleum previously distilled over sodium, is used for
dissolving the camphor, the action being conducted in a stream of
hydrogen, and completed by heating the product in a reflux apparatus,
on the V7ater-bath for several days, a sodium salt is obtained, still
containing a considerable quantity of oxygen. This salt dissolves
readily in water, with separation of a small quantity of camphor (or
borneol?) and the alkaline liquid, when treated with an acid, yields a
flocculent precipitate which ultimately collects into a yellow viscid
mass yielding by dry distillation two substances, viz. : (1.) Shiniug
laminae melting at 141°, insoluble in water, soluble in alcohol and
ether, and having the composition C20H30O2. (2.) Camphoric anhy-
dride, OgoHuOs. The investigation will be continued. H. W.
Mode of Formation of the Isomeric Dibromo camphors.
By J. Kachler and F. Y. Spitzer (Monatsh. Ohem., 4, 480 — 486). —
The results obtained by S warts (p. 214 of this volume) on the forma-
tion of the two dibromocamphors differ from those of the authors
(1882, Abstr,, 864), inasmuch as Swarts never obtained a-dibromo-
camphor melting at 61° by heating monobromocamphor at 100 — 150°
with the requisite quantity of bromine, the product being always the
y3-modification, at whatever temperature the action took place. The
a-modification was however produced when camphor or its mono-
bromo-derivative was heated with bromine in open vessels, and Swarts
supposes that its formation was facilitated by the elimination of the
hydrogen bromide produced in the reaction. For the preparation of
a-dibromocamphor Swarts recommends the process adopted in Schu-
chardt's factory, which consists in heating 1200 g. camphor in, a
reflux apparatus with 640 g. bromine and a little chloroform, adding
another 640 g. bromine after the escape of the resulting hydrogen
bromide, and recrystallising the product from absolute alcohol.
The authors, in following these directions, never obtained a-dibromo-
camphor, the product invariably consisting of monobromocamphor :
in fact, the quantity of bromine employed is not more than sufficient
to convert the whole of the camphor into the monobromo-derivative.
This latter treated in like manner with the requisite quantity of
bromine, yields a good product of a-dibromocamphor ; but camphor
itself similarly treated with the quantity of bromine required to form
dibromocamphor, yields merely a dark-coloured product which crystal-
lises with difficulty or not at all.
The authors now prepare /3- dibromocamphor by heating mono-
bromocamphor for 6 — 10 hours in sealed tubes with li times the
calculated quantity of bromine, mixing the liquid with alcohol, which
throws down the dibromo-compound as a heavy powder, and purify-
ing this product by recrystallisation from boiling alcohol. To obtain
tx-dibromocamphor by a similar process, it is necessary that the capacity
of the sealed tubes should be sufficiently great in proportion to the
volume of the hydrobromic acid formed, to keep the resulting
pressure below that which is required for the formation of the ^-
TQodification. For preparing larger quantities of a-dibromocamphor,
it is advisable to use the process already described, namely to heat
1008 ABSTRACTS OF CHEMICAL PAPERS.
monobromocamphor dissolved in chloroform in a reflux apparatus,
with the theoretical quantity of bromine. H. W.
Reaction of the Two Isomeric Dibromocamphors with
Nitric Acid. By J. Kachler and F. V. Spitzer (Monatsh. Chem., 4,
654 — 569). — a-Dibromocamphor heated with nitric acid yields the
two non-brominated acids formed in like manner from camphor itself,
viz., camphoronic acid, C9H13O5, and hydroxycamphoronic acid,
O9H12O6, together with bromodinitromethane, CHBr(N02)2, and pro-
ducts of more complete decomposition, viz., carbonic anhydride, hydro-
gen bromide, and nitrosyl bromide. H. W.
Hydroxycamphor from j8-Dibromocamphor. By J. Kachlee
and F. V. Spitzer (Monatsh. Ghem., 4, 643 — 651). — This compound is
formed, as already described by the authors (Abstr., 1882, 865), by
the action of sodium- amalgam on ^-dibromocamphor dissolved in
alcohol. It is a faintly yellowish oily liquid, having a turpentine-like
odour and burning taste, easily soluble in alcohol and ether, insoluble
in water. It has at 20° a density equal to that of water at the same
temperature. Boiling point 265° (bar. 758' 5 mm.). It dissolves in
alkalis, yielding corresponding salts. CioHi5Na02 is a white crystal-
line mass; (CioHi502)2Ba,4H20 is a white hard crystalline salt.
Hydroxycamphor heated in a reflux apparatus with excess of acetic
chloride, yields colourless highly deliquescent crystals. Heated with
hydrobromic acid in a sealed tube at 100°, it is converted into a
brown viscid oil. Phosphorus pentachloride acts violently on it,
yielding a liquid apparently consisting of monochloro camphor,
C10H15CIO ; but mixed with condensation-products very difficult to
separate. By the prolonged action of chromic acid mixture, hydroxy-
camphor is completely oxidised to carbonic and acetic acids. Fuming
nitric acid acts violently on it, producing nitrO'hydroxi/campJiorj
CioHu(OH)(N02)0, together with oxalic acid ; with less concentrated
acid, the nitro- com pound is also formed together with Jiydroxycam-
plioronic acid, C9H12O6, and products of more complete oxidation.
Nitro-hydroxy camphor, OioH4(OH)(N02)0, crystalKses fi'om aqueous
alcohol in white woolly needles, or by slow evaporation in monoclinic
prisms, exhibiting the faces ooP^, P<>o, ooPc5o, ooP, ooPob, 2Pob, Pcb.
Axial ratio a : 6 : c = 0-7617 : 1 : 0-4310. Angle ac = 89" 18-5'. It
is insoluble in water, but dissolves readily in boiling alcohol and ether,
also in alkalis, but with separation of nitrous acid. By boiling its
solution in glacial acetic acid with tin, it is reduced to Amidhydroxy'
camphor, CioHu(OH) (NH2)0, the hydrochloride of which,
C,oHi5(NH2)02,HC],
forms colourless laminoe, easily soluble in water and melting at 250°.
The platinochloride, 2CioHi6(NH2)02,H2PtC]6, forms yellow well-defined
crystals or laminsB. H. W.
Addition-products of Quinoline. By A. Glaus and F. Tosse
(Ber., 16, 1277— 128B).— Quinoline Ethyl hromide, C,B.^'N,'EtBT +H2O,
ORGANIC CHEMISTRY. 1009
formed by the direct nnion of its components in tlie cold, crystallises
from water or alcohol in large rhombic tables, melts at 80°, and
becomes anhydrous at 100° ; it is then readily soluble in chloroform,
but insoluble in ether. By the action of silver chloride it is converted
into quinoline ethyl chloride, CgHvNjEtCl + H2O. This also crystal-
lises in large rhombic tables, and melts at 92*5°. The platinochloride,
(09H7N,EtCl)2,PtCl4, is obtained as a bright yellow precipitate,
scarcely soluble in water, and melting at 226° to a dark yellow liquid.
Quinoline ethyl nitrate, C9H7N,EtN'03, prepared from the bromide by
treatment with silver nitrate, forms large colourless rhombic crystals,
melts at 89°, and deliquesces rapidly on exposure to air.
Quinoline amyl bromide, C9H7N,CoHiiBr, is best prepared by heating
a mixture of quinoline and amyl bromide with absolute alcohol in
sealed vessels at a moderate temperature. It crystallises in yellowish
needles, and melts at 87°, but does not resolidify above 67°. The
melting point of the anhydrous compound is 140°. The platino-
chloride, (C9H7N,C5HuCl)2,PtCl4, is obtained as a reddish-yellow crys-
talline precipitate, and melts at 220° to a dark yellow liquid.
Quinoline benzyl chloride is obtained, as already described, in large
tabular crystals containing 3 mols. H2O, and melting at 65°. On
exposure to air these lose 1 mol. H2O, and melt constantly at 129 —
130°. From an alcoholic solution thick rhombic crystals of the
formula C9H7N,C7H7C1 + 2H2O, are obtained, melting at 130°. The
anhydrous salt melts at 170°.
By the action of moist silver oxide or of alkalis on these compounds,
bases are obtained having at once the characters of quaternary
ammonium oxides and of tertiary bases; they are very unstable,
oxidising rapidly on exposure to air to red resins, but when freshly
prepared yield the original salts on neutralisation with acids.
Freshly prepared aqueous solutions have a strongly alkaline reaction,
precipitate all metallic salts, with exception of the alkalis, and expel
ammonia from its salts, even in the cold. Analyses of the amyl and
benzyl compounds dried over potash gave in each case numbers inter-
mediate between that required for the amine (CgHeN.CsHu and
C9H6N.C7H7), and the hydrate (C9H7N,C5H„OH and C9H7N,C7H70H).
The carbonates appear to be only stable in presence of water, a solu-
tion of the base eagerly absorbing carbonic anhydride, but losing it
again on expulsion of the water. A. J. G.
Oxidation of Quinoline Benzyl Chloride. By A. Claus and
F. Gltckherr (Ber., 16, 1283 — 1286). — By oxidation of quinoline
benzyl chloride in aqueous solution with potassium permanganate (best
in such amounts as to give 5 at. oxygen per mol. chloride), benzoic
acid is obtained in small quantity, together with formylbenzylamido-
benzoic acid and some benzylamidobenzoic acid.
Formylbenzylamidobenzoic acid, N(COH)(C7H7).C6H4.COOH, crys-
tallises in slender colourless needles or large tables, melts at 196°
(uncorr.), is sparingly soluble in water, readily in hot alcohol, the
solution showing a fine blue fluorescence. Treatment with alcoholic-
potash decomposes it into benzylamidobenzoic acidj
06H4(NH.C,H7).COOH,
VOL. XLiv. 3 y
1010 ABSTRACTS OF CHEMICAL PAPERS.
crystallising in groups of long thin needles or in thick prisms melting
at 176° (uncorr.). The hydrochloride crystalh'ses in large tables, and
melts at 104 — 106° (uncorr.) ; the platinochloride,
[COOH.C6H,.NH(C7H,)]„H2PtCl6,
crystallises in orange-yellow tables, and melts at 158° (uncorr.).
From these results, it follows that the benzyl-group in benzylquino-
line chloride must be in direct union with the nitrogen -atom, and the
oxidation to formylbenzylamidobenzoic acid is represented by —
CH CH CH CO.OH
/\ /\ /\/
HC C CH HC C
I I I + 50 = I I + CO2 + HCl.
HO C CH HC C COH
\/\/ \/\y
CH N CH N
CI
^C,H,
A. J. G.
a- and /3-Naphthaquinoline. By Z. A. Skeaup and A. Cobenzl
(Monatsh. Chem., 4, 436 — 479). — Skraup has described, under the
name a-naphthaquinoline, a base of the quinoline series, produced by
heating a mixture of a-naphthylamine, a-nitronaphthalene, glycerol,
and sulphuric acid {Monatsh., 2, 139; G. /., 40, 920). This base has
the composition CisHgT^, and may be derived from anthracene or
phenanthrene in the same manner as quinoline from naphthalene or
pyridine from benzene, ^.e., by the introduction of an atom of nitrogen
in place of a CH-group. Its constitution is therefore analogous to that
of phenanthrene, and may be represented by the formula —
As a derivative of naphthalene, it may be expected to yield by oxida-
tion a quinoline-dicarboxylic acid, just as naphthalene yields phthalic
acid, and, on the other hand, in accordance with its phenanthrenic
structure, it should yield by direct oxidation a dicarboxylic acid
analogous to diphenic acid. The first of these changes takes place
when the C-atoms (1) are oxidised to COOH-groups, the second
when the oxidation affects the C-atoms (2). The second of these
transformations is perhaps that which may be expected to occur most
frequently, inasmuch as Skraup has shown ((7. /., 42, 1112) that the
similarly constituted base phenantliroline, which may be regarded as
phenanthrene having two CH-groups replaced by N, is transformed
in a similar manner into an acid analogous to diphenic acid, viz.,
dipyridyl-dicarboxylic acid —
ORGANIC CHEMISTRY. 1011
<z>
N CO2H CO.2K
Dipyridyl-dicarboxylic acid.
The first-mentioned transformation may, however, likewise occur,
inasmuch as a-naphthaquinoline contains two benzene rings, and there-
fore also two groups of atoms susceptible of comparatively easy
oxidation.
To give greater generality to their results, the authors have also
prepared ^-naphthaquinoline from ;8-naphthylamine, and examined the
products of its oxidation.
jS-Naphthaquinoline is best prepared by heating a mixture of
28 g. y3-naphthylamine, 13 g. nitrobenzene, 60 g. glycerol, and
40 strong sulphuric acid in an oil-bath for about five hours, ulti-
mately at 150 — 160°, then adding 3 vols, water and a strong solution
of 20 g. potassium hydroxide; filtering; covering the light brown
filtrate with a layer of ether ; adding caustic potash to alkaline reac-
tion, the liquid being at the same time agitated and kept cool ; drying
the ethereal solution with potassium carbonate ; evaporating off the
ether on the water-bath ; and distilling the residue over an open
flame. The /3-naphthaquinoline then passes over, above the range of
the thermometer, as a nearly colourless easily solidifying oil, which
may be purified by a second distillation, or better by converting it
into the sulphate, which is sparingly soluble in alcohol. As thus
prepared, it is a nearly colourless radio-crystalline substance, very
soluble in ether, alcohol, and benzene, slowly in dilute acids, very
slightly in water. From a boiling aqueous solution, it crystallises on
cooling in snow-white scales, which soon acquire a reddish or yellowish
to light yellow-brown colour. It is nearly scentless when cold, but
smells like a-naphthaquinoline when heated. It melts at 90°, and
readily solidifies to a crystalline mass on cooling. When pure it
distils almost without decomposition. The alcoholic solution is
coloured brown by ferric chloride, and gives a gelatinous precipitate
with silver nitrate. The hydrocliloride, (Ci3H9N)2,2HCl -h HoO, crys-
tallises in long brittle needles ; the chromate^ (Ci3H9N)2Cr207, is a
yellow crystalline precipitate ; the picrate is a light yellow crystalline
precipitate, and crystallises from solution in alcohol or benzene in
slender prisms melting at 251 — 252°. The methiodide, CiaHgNjMel
+ 2H2O, crystallises in pale yellow needles, melting at 200 — 205°,
and giving off their water at 100°. Its aqueous solution has a faint
blue fluorescence.
/3-Naphthaquinoline is very slowly oxidised by chromic acid, but
quickly by a cold dilute solution of potassium permanganate, being
converted thereby into |S-phenylpy ridine - dicarboxylic acid,
C13H9NO4, which is sparingly soluble in cold water, but dissolves
somewhat readily in hot water and in alcohol, and separates from the
aqueous solution in colourless jagged irregular crystals, often white
and opaque ; from alcohol, in short limpid better-shaped prisms. It is
but very slightly soluble in ether and in benzene. The aqueous sola-
3 2/2
1012 ABSTRACTS OP CHEMICAL PAPERS.
tion is coloured orange-red by ferric chloride, and gives a yellowish-
wliite floccuTent precipitate with ferrous sulphate.
The following salts of this acid are described : — Ci3H7K2N04,3H20 ;
white crystalline powder, which gives off its water at 300^, and may
be heated without decomposition to 360°. — Ci3H8KN04,2H20 ; micro-
scopic laminsD, becoming anhydrous at 170°. — Ci3H7CaN04,3H20 ;
shining prisms, very slightly soluble in water even at boiling heat. —
Ci3H7BaN04,4JH20 ; elongated microscopic plates, moderately soluble
in boiling water. — Ci3H8AglN"04,Ci3H9N'04 ; small thick laminae,
sparingly soluble in cold water. — Ci3H7Cu!N'04,4H20 ; light green
crystalline precipitate, insoluble in water, but dissolving readily vnth
blue colour in aqueous cupric acetate. — Ci3H7CuN04,(Ci3H9T^04)2Cu ;
of a light violet colour. — Ci3H9N04,HCl ; small crystalline grains,
sparingly soluble in hydrochloric acid, easily in water, sparingly in
alcohol. — (Ci3H9]S'04)2H2PtCl4 + 24H2O ; separates from hot aqueous
solution in a yellow oil, which slowly crystallises.
The easy conversion of ^-naphthaquinoline into a dicarboxylic acid,
Ci3H9]S'04, shows that the former is analogous in constitution to
phenanthrene, and that the latter may be regarded as a diphenic acid
of the pyridine series.
The connection between /3-naphthylamine, iS-naphthaquinoline, and
/3-phenylpyridine-dicarboxylic acid may be represented by the follow-
ing formulae : —
COjH
jS-Naphthylamine. /S-i^Taplithaquinoline. jS-Phenylpyridiue-
dicarboxjlic aci(i.
^'Fhenylpyridine-monocarhoxijlic acidj
Ci2H9:^ro2 = CuHsisr.cooH,
is formed, with evolution of CO2, when the dicarboxylic acid is heated
at 180 — 185°, and remains as a fused mass which solidifies on cooling
and crystallises from aqueous solution in long brittle prisms, which
may be purified by recrystallisation from alcohol. It separates from
alcohol in soft white crystalline threads, from water in brittle needles,
or sometimes in large short prisms. It dissolves sparingly in cold,
more freely in hot water, still more in alcohol. The aqueous solution
is coloured brownish-yellow by ferric chloride, and gives a light blue
precipitate with cupric acetate. The acid is anhydrous, distils with-
out decomposition, and solidifies to a vitreous mass, but becomes
crystalline on rubbing with a glass rod. The calcium salt,
(Ci2H8N04)2Ca,2H20,
separates from concentrated solutions in long slender needles, which
give off their water at 130°, and begin to turn brown at 250°. The
light blue copper salt, (Ci2H8N04)2Cu, is insoluble in water, appears to
contain water, but remains unaltered at 170°, even in colour.
ORGANIC OHEMISTKY. ' 1013
By oxidation with a very strong solution of chromic acid, this acid
is converted into nicotinic acid, CiHiN.COOH [IST : COOH = 1:3],
a result which indicates that in the decomposition of the phenyl-
dicarboxylic acid by heat, the carboxyl-group which escapes is sepa-
rated from the pyridine residue, and that in the subsequent oxidatioa
of the monocarboxylic acid, the phenyl residue undergoes complete
decomposition, its carboxylic group remaining attached to the pyri-
dine—
COOH I^NcOOH
COOH COOH
jS-Phenylpyridine- j3-Phenylpyridine- Nicotinic acid,
dicarboxylic acid. monocarboxylic acid.
The arrangement [COOH : N = 1 : 3] in nicotinic acid thus deduced
is in accordance with the conclusion previously drawn by Skraup
from the behaviour of the pyridinecarboxylic acid on dry distillation,
a,nd from the behaviour of the three pyridine-monocarboxylic acids.
^-Phenylpyridine, diHylSr = C5H4PhN, is obtained by heating
the calcium salt of ^-phenylpyridine-dicarboxylic acid with quicklime
in very refractory glass tubes, as an oil, which when purified by a
method for which the original paper must be consulted, is nearly
colourless when recently distilled, smells like diphenylamine, boils at
269 — 270° (uncorr. ; bar. 748 — 9 mm.), is heavier than water and in-
soluble therein, but dissolves readily in alcohol, ether, and dilute
mineral acids. Its alcoholic solution forms with picric acid a crystal-
line precipitate, which dissolves with moderate facility in hot alcohol,
and crystallises therefrom on cooling in a pulpy mass of soft light
yellow needles melting at 161 — 163"5°. The platinochloridej
(CuH9N,)2,H2PtCl6,
crystallises in orange-yellow needles, nearly insoluble in water and in
dilute hydrochloric acid, and containing 3 mols. HjO, which they give
off at 100^
The formation of the |S-phenyl pyridine is accompanied by that of
another body which separates from the alcoholic solution in brownish
crystals, apparently consisting of the diketone of iS-phenylpyridine.
yS-Phenylpyridine is converted by oxidation with permanganate
into nicotinic acid, according to the equation C11H9N + O12 =
2H2O + 5CO2 + CeHgNOi, the acid thus obtained being identical with
that which is produced by the oxidation of ^-phenylpyridine-monocar-
boxylic acid, and having the constitution [COOH : N = 1 : 3].
a-NAPHTHAQUiNOLiNE. — This base is best prepared by heating in an
oil-bath a mixture of 28 g. a-naphthylamine, 13 g. nitrobenzene,
^0 g. glycerol, and 40 g. sulphuric acid, the mixture, after the first re-
action is over, being left to itself at 160° for five hours, the resinous
portions of the product removed by partial precipitation with potash-
1014 ABSTRACTS OP CHEMICAL PAPERS.
lye, and nnaltered naphthylamine by converting the bases into sul-
phates, treating the product with water, which leaves the greater part
of the naphthylamine salt undissolved, and adding to the filtrate at
boib'ng heat a solution of potassium dichromate, as long as the blue
oxidation-product of a-naphthylaraine continues to separate. The
filtered liquid treated with ammonia yields an oil which solidifies on
cooling, and after one distillation furnishes pure a-naphthaquinoline.
The chromate of this base, (Ci3H9!N')2H2Cr207, is moderately soluble in
boiling water, and crystallises in long soft yellow needles. The
methiodide, Ci3H9N,MeI,2H20, crystallises in faintly yellow needles,
which suffer partial decomposition at 100°. The crystal-water is
not given off over sulphuric acid, but readily at 100°. Other salts
of this base are described in Skraup's paper, already referred to.
By the action of chromic acid on a-naphthaquinoline, both dissolved
in glacial acetic acid, a quinone, C13H7NO2, is obtained, which dis-
solves somewhat readily in alcohol, benzene, and ether, sparingly in
dilute alcohol, not at all in water ; it dissolves also in dilute mineral
acids, sparingly in acetic acid, and is precipitated by water from its
solution in glacial acetic acid. It may be distilled, with a certain
amount of decomposition, and melts, also with decomposition, at 205 —
207°. Concentrated sulphurous acid converts it into a white substance,
which is coloured deep yellow by ferric chloride, and probably consists
of the quinol of naphthaquinoline. This body crystallises from alcohol
in small indistinct prisms, from dilute alcohol in long needles, from
benzene in thick prisms.
oc-Phenylpyridine-dicarhoxy lie acid, C13H9NO4, is prepared like
the y3-acid by the action of potassium permanganate on a-phenyl-
pyridine. It is much less soluble in water and in alcohol than the
^-acid, more soluble in alcohol than in water, and crystallises from
both solvents in small chalk-white indistinct crystals. The aqueous
solution is coloured faintly reddish by ferric chloride, deep blue by
cupric acetate, and gives with bromine- water a precipitate of crystal-
line flocks. The acid when heated melts, with intumescence, to a
yellowish liquid, quickly changing to dark indigo-blue, and giving off
dark blue vapours which condense on the upper part of the tube ; at
a higher temperature it gives off dark violet vapours, and is in great
part decomposed, with separation of charcoal. In consequence of this
decomposition, the melting point is difficult to determine ; it lies, how-
ever, between 230° and 235°, and brisk effervescence sets in at 236°.
The following salts have been prepared : The normal and acid potas-
sium salts form transparent uncrystallisable varnishes. The calcium
salt J Ci3H7CaN04,2H20,is obtained by neutralisation and evaporation, as
a thick syrup which slowly deposits small crystals. — Ci3H7CuN04,4H20
forms violet crystals. — Ci3H7Ag2N 04,1^1120 is a crystalline precipitate,
quickly turning violet-grey on exposure to light, and decomposing
quietly when heated. — (Ci3H9N04)2,H2PtCl6 + 3H2O, forms orange-
yellow shining laminae, easily soluble in cold, still more in hot water,
and giving off their crystal-water at 100°.
o(,-J)ihr 0 mop henylpyridi7ie-di car boxy lie acid, ClzH.^^r^2N20^y
obtained by direct combination, forms anhydrous crystalline grains,
becomes light sulphur-yellow at 100°, dissolves very sparingly in.
ORGANIC CHEMISTRY. 1015
water, more freely than the non-brominated acid in warm alcohol,
from which it separates on spontaneous evaporation in transparent
crystalline granules. Heated in a capillary tube, it melts at 204 — 205°
to a brownish liquid ; in a test-tnbe over an open flame, it froths up,
becomes partly carbonised, and yields a yellow-brown oily distillate
which readily solidifies to a radio-crystalline mass. The solution of
its ammonium salt gives with cupric salts a light green, with lead
salts a white pulverulent, with silver salts, a white gelatinous pre-
cipitate, becoming crystalline on boiling. The nickel salt is whitish-
green ; the calcium salt crystallises after long standing in small
yellowish-white needles. Ferrous sulphate produces a faint trans-
parent yellow coloration ; ferric "chloride throws down yellowish-red
flocks.
a-Phenylpyridine-dicarboxylic acid when heated gives ofi" water and
carbonic anhydride, and leaves a blue-black substance from which
chloroform extracts a dark-coloured compound, insoluble in water,
very slightly soluble in alcohol, more freely in chloroform and glacial
acetic acid, the solutions having a dark blue colour. Its composition
has not been exactly determined.
The calcium salt of this acid distilled with five times its weight of
quicklime yields a dark brown oil in which crystals soon begin to
separate. The oil consists of a-phenylpyridine, CuHgN, and the crystals
of the ketone of that compound, CuHvNCO, these bodies being formed
according to the following equations :
CiiH7N(COOH)2 = 2CO2 + CuHgN.
CuH7N(COOH)2 = CO2 + H3O + OuHtNCO.
oc-Phenylpyridine, separated from solution in hydrochloric acid
by potash, and dried with potassium carbonate, distils almost com-
pletely between 270° and 275°, leaving a small quantity of the ketone,
which separates out completely after standing for some days. The
oily base thus freed from the ketone boils at 2685 — 270*5° (bar.
749 mm.). It has a faint yellow colour when freshly distilled, but
gradually becomes darker ; it is heavier than water, and insoluble
therein, but soluble in alcohol and ether. It has a pleasant odour, very-
much like that of diphenylamine, and volatilises slowly with steam,
but more quickly than iS-phenylpyridine. Its alcoholic solution gives
with picric acid small yellowish needles, sparingly soluble in cold,
easily in hot alcohol. Heated in a capillary tube, they cake together
at 160° and melt at 161) — 172°. The solution of this base in hydro-
chloric acid crystallises. after long standing in long soft threads which
are extremely soluble in water, but not deliquescent. The platino-
chloride, (CuH9N)2,H2PtCl6, crystallises in hydrated needles which
give off their water at 100 .
oc-Phenylpyridine ketone, Ci2H7N'0, purified by distillation and
repeated crystallisation from alcohol, forms large irregular soft laminae,
having a sulphur-yellow colour. Like a-phenylpyridine it emits, even
at ordinary temperatures, and more strongly when heated, a fruity
odour resembling that of diphenylamine. It is very slightly soluble in
cold, rather more freely in hot water, somewhat abundantly in boiling
1016 ABSTRACTS OF CHEMICAL PAPERS.
alcohol. It boils without decomposition at 315°, and melts in a capil-
lary tube at 140 — 142" to a yellow liquid which solidifies on cooling.
The picrate, when slowly formed in alcoholic solution, separates as
a crystalline precipitate melting at 195 — 199°. The chromate forms
red prisms. The platinochloride, (Ci2H7NO)2,H2PtCl6, closely resembles
that of a-phenylpyridine in colour and solubility. The ketone offers
great resistance to the action of oxidising agents.
a-Phenylpyridine is very slowly oxidised by potassium perman-
ganate, more readily by chromic acid in aqueous solution, yielding
picolinic acid, CsHiN.COOH, identical with that which is prepared
from picoline (m. p. 137'5 to 136°).
The constitution of a-phenylpyridine, of the dicarboxylic acid from
which it is obtained, and of the monocarboxylic acid into which it is
converted when its phenyl-residue is replaced by a carboxyl- group,
may be represented by the following formulae : —
COOH COOH
/ \ / \
\ / \ /
< >-< >
cooH<^ y
N
N
X
a -Plien jlpy ridine-
a-Phenyl-pyridine.
a-Pyridinemono-
dicarboxylic acid.
carboxjlic acid.
a- Pyridine- carboxylic acid, as just observed, is identical with
picolinic acid [1 : 2], and /3-pyridine-carboxylic acid [1 : 3] has been
shown to be identical with nicotinic acid: hence the 7-acid [1:4]
must be identical with cinchomeronic acid. H. W.
Caflfeme and Theobromine. By R. Malt and R. Andeeasch
{^lonatsh. Chem., 4, 369 — 387). I. Action of Dilute Alkalis on Caffeine.
• — The bodies hitherto obtained by the action of alkalis on caffeine arc
products of decomposition due to secondary actions : thus Wurtz by
distilling caffeine with potash obtained methylamine, and Rochleder
obtained the same base by treating caffeine with chlorine. Strecker,
by heating caffeine with baryta- water, obtained a new base, caffeidine,
C7H12N4O, formed according to the equation CsHioN^Oa -f H2O =
CO2 + C7H12N4O. Secondary actions however take place at the same
time, giving rise to methylamine, formic acid, and sarcosine, C3H7NO2,
the formation of these products being represented by the equation —
c,Hi„]sr402 + 6H2O = CsH^isrOa + 2CH5N + CH2O2 + 2CO2 + NH3.
The process, as usually conducted, yields only a small quantity of
caffeidine ; but the authors of the present paper find that by moderat-
ing the action of the alkali, and especially by keeping down the tem-
perature, the formation of secondary products may to a great extent
be avoided. Moreover, they find that caffeidine itself is only a
secondary product, and that caffeine when subjected to the gentle
action of alkalis, simply takes up 1 mol. water, and is converted into
an acid, C8H12N4O3, which is resolved by boiling with water into
carbonic anhydride and caffeidine ; (C8H12N4O3 = CO2 + C7Hi2N^40)
and may therefore be called Caff eidine-carboxylic acid.
ORGANIC CHEMISTRY. 1017
This acid is easily prepared by digesting finely divided caffeine at
30° in a dilute solution of potash and soda, neutralising with acetic
acid, adding a solution of cupric acetate, and decomposing the copper
salt thereby precipitated with hydrogen sulphide ; it may be purified
by solution in chloroform and precipitation with benzene, and is thus
obtained in the form of a thick oil, which on exposure to the air
solidifies to a yellowish-white, slightly crystalline mass, very easily
soluble in water. On boiling its aqueous solution, carbonic anhydride
is evolved, and there remains a reddish oil, which when stirred up with
a small quantity of sulphuric acid and treated with alcohol, solidifies
to a white acicular mass of caffe'idine sulphate. This reaction forms
an easy way of preparing caffeidine : it is merely necessary to decom-
pose the copper salt with hydrogen sulphide, evaporate the filtrate
quickly, and treat it with strong sulphuric acid.
Cupric Caffeidine-carboxylate, (CioHnN403)2Cu, is a pale-blue rather
heavy powder, appearing under the microscope as a mass of crystalline
grains or nodules : it is nearly insoluble in water, quite insoluble in
alcohol. The calcium, barium, zinc, cadmium and magnesium salts
are similarly constituted, and nearly insoluble in water. The silver
salt is very unstable. The lead salt is soluble in water.
A solution of mercuric chloride affords a delicate test for caffeidine-
carboxylic acid, forming with its soluble salts a copious white pre-
cipitate, which is not a simple mercuric salt, but also contains chlorine,
and appears to have the composition (C8HiiN403)2Hg,2HgCl2. When
decomposed by hydrogen sulphide, it yields a filtrate which on evapora-
tion leaves caffeidine hydrochloride.
Action of Alkalis on Theobromine. — The behaviour of this compound
to bases is totally unlike that of caffeine ; in fact it reacts with alkalis
and alkaline earths like an acid, forming definite salts. The sodium
salt, obtained by adding theobromine to soda-lye in such quantity that
a portion remains undissolved after long standing, and evaporating
the filtrate under the air-pump, forms milk-white crusts and rings
destitute of crystalline structure. It is extremely soluble in water ;
has a strong alkaline reaction ; absorbs carbonic anhydride from the
air, and is decomposed thereby. Its aqueous solution forms precipitates
with silver nitrate, lead acetate, and zinc chloride, and after a while with
mercuric chloride. The barium salt, (C7H7N402)2Ba, separates on
adding theobromine to baryta- water, as a mass of microscopic needles,
and on dissolving this in hot water, filtering, and leaving the filtrate
to cool slowly, the compound is obtained in somewhat larger needles ;
forming a snow-white loosely coherent mass having a somewhat silky
lustre. It is but sparingly soluble in cold water, has an alkaline
reaction, and the solution when quickly cooled, solidifies to a stiff jelly
like gelatinous silica. When heated it melts to a liquid which
solidifies by slow cooling to the above-mentioned mass of needles, and
by rapid cooling to the jelly, which latter however gradually passes
into the former. On pouring a little of the hot solution upon a cold
surface, it solidifies and may be pulled off like a membrane.
Oxidation of Caffeidine with Chromic Acid. — The authors have pre-
viously shown that caffeine is converted by oxidation with chromic
acid mixture into cholestrophane, according to the equation —
1018 ABSTRACTS OF CHEMICAL PAPERS.
.N(CH3).C0
CsHioNA + 2H2O + 03= C0< I + CH5N+NH3+2CO,,
^N(CH3).C0
and they now find that caffeidine is converted in like manner into
dimethyloxamide:
NH.(CH3).C0
C,Hi2N40 + 2H2O -1-03= I + CH5N + NH3 + 2CO2.
NH.(CH3).C0
Behaviour of Caffeine in the Animal Organism. — From experiments
in which caffeine was mixed with the food of a dog, the authors infer,
in accordance with the results obtained by other experimenters, that
the greater part, if not the whole, of the caffeine passes unchanged
through the organism, and may be recovered in the urine.
H. W.
Notes on Cinchona Alkaloids. Ry C. H. Wood and E. L.
Barret (Chem. News, 48, 4; comp. Abstr., 1882, 404). — In the
abstract referred to, the authors state that the crystals obtained from an
ethereal extract of cuprea bark were composed of equal quantities of
quinine and quinidine. They have since then investigated this subject
more closely, and publish the results, &c., in the present paper. In
the first case equal quantities of quinine and quinidine sulphates were
dissolved separately in acidulated water, the solution shaken with
ether, excess of soda added, and the whole agitated ; as soon as the
precipitates had dissolved in the ether, the ethereal solutions were
decanted off and mixed. The crystals deposited from this mixed
solution yielded on analysis numbers approximating to the composition
I mol. quinine + 1 mol. quinidine + 2^H20. In another experiment
equal weights of the alkaloids were dissolved together in 50 per cent,
spirit. The crystals obtained from this solution, after 48 hours*
exposure over sulphuric acid, were similar in constitution to those
described above. Whilst in a third experiment equal weights of the
two sulphates were dissolved, &c., as in the first experiment, but the
alkaloids were taken up with warm benzene. This time the crystals,
even after three days' exposure, were found to contain 1 mol. quinine -f-
1 mol. quinidine + 2II2O + CeHe. From these facts the authors infer
that the crystals always contain water, and therefore this compound is
a hydrate of the two alkaloids.
When anhydrous, a mixture of quinine and quinidine has a lower
melting point than either of the constituent alkaloids. Some of the
anhydrous double body dissolved in dry benzene had deposited only a
very few crystals, after remaining corked up ten days, but on removing
the cork and exposing the contents of the flask to the air plenty of
crystals soon formed, and in two days the solution was half filled with
them. Quinine, prepared from the sulphate, when dissolved in warm
benzene, forms rhomboidal crystals of the composition 2 mols. quinine
+ 2OH2 + CsHe. They lose the benzene slowly ; a sample after being
kept for some time bad lost all odour of benzene, but gave evidence
of the presence of the hydrocarbon when treated with an acid. The
PHYSIOLOGICAL CHEMISTRY. 101^
aiitliors remark on the analogy these crystals bear to those of the
quinine and qninidine compound when crystallised from the same
menstruum. When anhydrous quinine is dissolved in dry benzene, it
crystallises out in needles containing a large quantity of benzene,
which is gradually given off until only 1 mol. benzene is retained.
Cinchonidine crystallises from benzene without water, but with
1 mol. benzene, with which it readily parts. The benzene employed
in these experiments was carefully purified. The authors recom-
mended the following test for the purity of quinine : — 0*7 gram of
the quinine sulphate to be tested is dissolved in 20 drops of hydro-
chloric acid and 7 c.c. of water ; 7 c.c. of benzene are added, and the
whole warmed, and then shaken up with 3J c.c. of dilute ammonia.
The benzene layer is separated, the quinine hydrate allowed to crystal-
lise out and filtered off"; the separation of feathery crystals then indicates-
the presence of cinchonidine. These crystals contain a large quantity
of quinine. Less than 1 per cent, of cinchonidine can be recognised
in this way. The crystals must be sought for within the liquid, not
on the surface. The quantities and method of procedure given above
must be strictly followed in order to ensure success. Absolutely pure
benzene is not necessary for this test : the benzene should, however,,
crystallise when placed in a freezing mixture. D. A. L.
Alkophyr, and the True and so-called Biuret Reaction.
By E. Brucker (Monatsh. Chem., 4, 203 — 222). — The author some
years ago (this Journal, 1871, p. 410) described a substance (alkophyr)
obtained from peptones, which gives conspicuously the biuret reaction
of those bodies (purple coloration with cupric oxide and potash) ; and
in the present paper he describes in considerable detail the methods of
obtaining this substance in the pure state. H. W,
Physiological Chemistry
Composition of the Ash of the Entire Animals, and of
certain Separate Parts of some of the Animals used as
Human Food. By J. B. Lawes and J. H. Gilbert {Proc. Roy. Soc.,.
35, 342 — 344). — This is simply an abstract of a paper which itself is-
a supplement to a former communication (Phil. Trans, [ii], 1859). In
the paper referred to, the authors have given the percentage of total
ash of the internal organs and of some other separate parts. Ten
animals were selected, out of 326, for chemical examination, viz., a fat
calf; a half fat and a fat ox ; a fat lamb; a store, a half fat, a fat,
and a very fat sheep ; a store and a fat pig. It was shown that as the
animal matured, the percentage of ash, like the nitrogenous matter,
decreased, both in the entire body and especially in the collective
carcase ; and it is now shown that the fatter the animal the less is the
1020 ABSTRACTS OF CHEMICAL PAPERS.
quantity of every one of the mineral constituents in greater or less
degree in a given live weight. The present paper records the results
of the complete analyses, 40 in number, of the collective carcass parts,
of the collective offal parts, and of a mixture of all parts of each of the
ten animals.
Phosphoric acid, lime, and magnesia comprise more than 80 per
cent, of the ashes. They are present to the largest extent in ash of
oxen, less in that of sheep, and still less in that of the pig. If the
phosphoric acid be calculated as tribasic, ruminants have an excess of
base, whilst pigs have not such excess. From separate analyses of the
ash of the chiefly bony and of the chiefly soft offal parts of the pigs, it
is shown that the ashes of the non-bony portions contain a considerable
excess of acid, especially phosphoric, probably due to the oxidation of
phosphorus during incineration. No such analyses were made with
the other animals ; it has, however, been shown that, although oxen
and sheep have a higher percentage of nitrogenous substance than
pigs, yet the amount of ash from the non-bony parts is less in propor-
tion to that from the bones in the case of the ruminants than in that
of the pigs, because the latter animals have only a relatively small
proportion of bone. Comparing the percentage composition of the
ashes of the entire bodies of the diff'erent animals, the chief points
of distinction are — that the ash of the pig contains more sulphuric acid,
chlorine, potash, and soda than the ash of the other animals ; on the
other hand, the ash from the ruminants contains more lime than
pig ash, whilst in the ash of pigs and oxen there is a higher per-
centage of phosphoric acid than in that of sheep. It is shown that a
given live weight of oxen contains more mineral matter than the
same weight of sheep, but that a given weight of sheep has much more
than the same weight of pigs. The loss of mineral constituents to a
farm by the production and sale of mere fattening increase is estimated
to be very small, greater of course in the case of growing than of only
fattening animals. Approximately it may be stated that the loss of
phosphoric acid per acre would be more in milk, and four or five times
more in wheat or barley grain or in hay, than in the fattening increase
of oxen or sheep. The land would lose about twice as much lime in
the animal's increase as in milk or wheat or barley grain, but only
about one-tenth as much as in hay. Of potash the land would lose
only a fraction of a pound per acre in animal increase, 6 or 8 times
as much in milk, 20 or 30 times as much in wheat or barley grain,
and more than 100 times as much in hay. D. A. L.
Distribution of Poisons in the Human Organism in Cases
of Poisoning. By C. Bischoff (Ber., 16, 1337— 1356).— The sub-
ject of the distribution of poisons amongst the various organs of the
body has hitherto received but little attention. The author in par-
ticular wishes to ascertain which organ or organs is of special
importance in the search for any given poison. The exact estimation
of the amount of poisons is of great importance, when it is remem-
bered that such substances may occur in small quantity in food or
medicine, or may occur normally or otherwise in the human body.
Many of the methods recommended for the estimation of poisons have
PHYSIOLOGICAL CHEMISTRY. 1021
been tried ; those found most satisfactory will alone be quoted. The
present paper deals with cases of poisoning by phenol, potassium
chlorate, oxalic acid, and potassium binoxalate, and by hydrocyanic
acid, potassium cyanide, and essential oil of bitter almonds.
Acute Poisoning hy Carbolic Acid. — For the determination of phenol
from organs and their contents, the author recommends Landolt's
method {Ber., 4, 770), but finds it necessary to continue the distilla-
tion until the distillate gives no further precipitate of tribromophenol
on addition of bromine- water. (To isolate 0*5 gram phenol from
1 kilo, of substance about 2 litres of distillate is required.)
Of four cases of poisoning by phenol investigated, in one only were
the organs examined separately. A man had died 15 minutes after
taking 15 c.c. of ofiBcinal carbolic acid (100 parts phenol + 10 parts
water). The organs were quite fresh.
242 grams contents of stomach and small intestine, gave 0'1711
gram phenol ; 112 grams blood, 0'0259 gram phenol ; 1480 grams liver,
0637 gram phenol ; 322 grams kidney, 0*201 gram phenol ; 508 grams
heart muscle (free from blood), 0'1866 gram phenol; 1445 grams
brain, 0'314 gram phenol ; 420 grams gluteal muscle, traces ; 125
grams urine, 0*0014 gram phenol.
In cases of alleged poisoning by phenol it has to be remembered that
it occurs normally in minute quantity in urine, and that along with its
next homologues it is formed during putrefaction ; 100 grams each of
fresh pancreas and of fresh fibrin having yielded, after six days*
putrefaction, 0*0208 and 0*022 gram of phenol respectively, and that
a liver of 2000 grams in the same time yielded 0*72 gram phenol.
In two cases where putrefaction had set in before the post-mortem,
either traces only or no phenol could be found in the organs.
Poisoning with Potassium Chlorate. — Potassium chlorate is best
estimated by dividing the dialysate from the organs into two parts,
estimating the chlorine of the chlorides directly with silver solution
in one, reducing the other with sulphurous acid, adding not too
dilute nitric acid, and estimating the total silver as silver chloride.
From the difference, the chlorate can be calculated. Direct experi-
ments show that potassium chlorate is very soon reduced by moist
organic substances, and especially by blood, so that chemical evidence
may not be obtainable in undoubted cases of poisoning with potas-
sium chlorate.
Four cases were investigated in which death had occurred in from
twelve hours to six days after the use of considerable quantities of
potassium chlorate for gargling, &c. In two cases not a trace could be
detected ; in one case traces were found ; and in a fourth slight traces
of chlorate could be isolated from the stomach and intestines, and
their contents, but none from the liver, kidneys, or pancreas.
In cases of 'poisoning with oxalic acid or oxalates, quantitative esti-
mation is essential on account of the wide diffusion of oxalic acid in
the vegetable kingdom, and its consequent ingestion in food or medicine.
Salt of sorrel consists more frequently of potassium tetroxalate than
of dioxalate, and the tetroxalate on treatment with absolute alcohol
is completely decomposed into free oxalic acid and insoluble dioxalate.
On finding oxalic acid in an alcoholic extract, therefore, further
1022 ABSTRACTS OF CHEMICAL PAPERS.
experiments are needed to ascertain if the poison was oxalic acid or
salt of sorrel. The organs are best extracted with alcohol (without
addition of acid) to dissolve free oxalic acid and the " half bound "
Acid of tetroxalates, then digested with water to dissolve any alkaline
oxalate, and finally with dilnte hydrochloric acid to dissolve any cal-
cium oxalate, the oxalic acid being estimated in each extract. The
following cases are given : — I. Person 24 years of age, poisoned with
oxalic acid. Death occurred in less than one hour. Analysis com-
menced two days after death. There was obtained from 358 grams
stomach and contents, 0*75 gram oxalic acid, bat little calcium oxalate ;
from 412 grams liver, pancreas, kidneys, and heart, 0'0135 gram cal-
cium oxalate, 0*95 gram oxalic acid as alkaline salt ; from 100 grams
blood, 0*0467 oxalic acid as alkali salt, traces of calcinm oxalate.
II. Case of poisoning with phosphorus and oxalic acid. Analysis two
days after death. From 215 grams stomach and contents 0*446 gram
oxalic acid (total) ; 100 grams intestines and contents, 0"4 gram oxalic
acid (total) ; 400 grams liver and blood, 0*012 gram oxalic acid as Ca
salt. III. Poisoning by oxalic acid. From 2240 grams stomach,
oesophagus, intestines, and contents, 2 '28 grams oxalic acid (mainly
free) ; from 770 grams liver, 0*285 gram combined oxalic acid ; 180
grams blood from heart, 0*0435 gram combined oxalic acid; 350
grams heart, 0*0206 gram combined oxalic acid ; 290 grams kidneys,
0*0145 gram combined oxalic acid ; 40 grams urine, 0*0076 gram com-
bined oxalic acid ; and from 780 grams brain and 590 grams gluteal
muscle no result. IV. Poisoning with salt of sorrel. Investigation
25 days after death. Numerous microscopic crystals of calcium oxalate
on walls of stomach, duodenum, and kidneys. 142 grams of stomach
and contents gave of oxalic acid 0*5555 gram free or f rom tetroxalate,
0*311 gram as alkaline oxalate, 0*3021 gram as calcium salt ; 16 grams
duodenum, traces of calcium oxalate ; 52 grams mixture of liver and
kidney, traces of combined oxalic acid. Y. Attempted poisoning
with potassium tetroxalate. 340 grams stomach and contents and in-
testines gave 0*0275 gram total oxalic acid ; 40 grams urine, 0*0162
gram oxalic acid as Ca salt ; 525 grams mixed blood, liver, kidney,
pancreas, brain, and heart, 0*0595 total oxalic acid.
Poisoning with Hydrocyanic Acid, Cyanides, 8fc. — The best method
for the quantitative estimation of hydrocyanic acid in these cases is to
mix with excess of alcohol, acidulate with tartaric acid, and distil, a
constant stream of air or carbonic anhydride being passed through
the apparatus, and the distillate received into a concentrated solution
of silver nitrate. The results obtained in five cases are tabulated
below. I, II, and III were cases of poisoning with potassium cyanide,
IV with hydrocyanic acid, V with essential oil of bitter almonds,
the investigations being commenced in from 2 — 4 days after death.
PHYSIOLOGICAL CHEMISTRY.
1023
P .2 r^ T3
O 'o
^
O T3
£.2
Ti^
W
III
o "^
^
U§ 2 ^
I I i ^ I I
1,^
88
MM
1 1 I
o o o
"«fl Oi 05
rH CO iH
I 1
is
888 I8§||
|S
lO (M \0 lO .
00 CO tJ* I '^
rH -* I rH
IS
«0 r-l W3 ■*
00 COI> N 2 "^ 2
iH I O rH I Q Pi tH fl
o I 9 9 I o o o o
o o o o o
o nS
• •-* ti r>.
© O rt
fe
^§1
O T3
Mi (M W5 00 (M
OS I (M O I CO I lO
lO I rH O I tH I CO
8
00
00 00 CO 00
(N(Mt>-rHO 0(M ©
OQOOO flO C
99999 09 o
00000 o
n^
o CO 05 eo o
CO T? N (N CO
a $ o p3
s ©
S § s jj © S o « s
2 ^
2 1 ^ -S i
^5 wM^qpLiWopqP
I
I
id
©
©
©
CO
o
43
«*-!
o
*o
o
i
to
CO
1024 ABSTRACTS OP CHEMICAL PAPERS.
Chemistry of Vegetable Physiology and Agriculture.
Constituents of the Beans of the Soja hispida. By E.
Meissl and F. Bockeb (Monatsh. Chem., 4, 349 — 368). — The Soja-
bean, imported from Japan, is a veiy valuable fodder, inasmuch as,
like all leguminous fruits, ifc contains a large amount of proteids, and
is moreover very rich in fatty constituents. The authors have made
an elaborate investigation of these fruits, the results of which are
summarised as follows : —
1. The Soja-bean contains no gluten proteids, and only very small
quantities of amido-compounds.
2. By exhaustion with dilute aqueous potash, or with pure water,
or with a 10 per cent, solution of sodium chloride, it yields a casein
nearly resembling the legumin of ordinary leguminous fruits, and
containing, when freed from ash, 51'24 per cent. C, 6*99 H, 16*38 N,
0-47 S, and 24-92 0.
3. The solution filtered from the casein deposits, on being boiled,
an albuminous substance differing essentially in composition and
properties from ordinary albumin, but closely resembling the albumin
of peas. This albumin is perhaps formed by transformation of the
casein, and contains 52*58 per cent. C, 7*00 H, and 17*27 N.
4. The mother-liquors of the casein and albumin treated with
copper salts yield nitrogenous precipitates, consisting for the most
part of a cupric compound of casein which has escaped precipitation,
contaminated with non-azotised substances.
6. The residue left after exhausting the beans with dilute potash
contains nitrogen belonging to casein which has been rendered in-
soluble. By prolonged keeping, or by roasting of the beans, the
quantity of this insoluble casein is increased, and finally the whole
of the casein is converted into the insoluble modification.
6. Of the nitrogenous constituents of the Soja-beans which are
soluble in dilute potash, more than 90 per cent, consists of casein,
and 1*5 to 2 per cent, of albumin.
7. Combustion with soda-lime cannot be employed for estimating
the nitrogen of the casein, but is well adapted for estimating the
amount of nitrogen in the entire bean.
8. The portion of the Soja-bean soluble in ether consists of 90 —
95 per cent, neutral fat and 5 — 10 per cent, cholesterin, lecithin, wax,
and resin.
9. The other non-azotised constituents of the bean are cellulose, a
small quantity of sugar, about 10 per cent, dextrin, and less than
5 per cent, starch in very small rounded separate grains.
10. The composition of the Soja-bean is, in round numbers, as
follows : —
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
1025
Water lO'C p. c.
Soluble casein 30*0 „
Albumin 0'5 ,,
Insoluble casein .... 7*0 „
Fat 18-0 „
Cholesterin, lecithin,
resin, wax 2*0
Dextrin -10 p. o
Starch (less than) 5 ,,
Cellulose 5 ,,
Ash 5 „
Sugar, amides, &c., small
quantities.
H. W.
Chemistry of Globularia. By Heckel and Schlagdenhauffen
(Ann. Chim. Phys. [3], 28, 67 — 81). — The paper describes tho
analyses of stalks and leaves of Globularia alypum and O. vulgaris,
and the properties of certain of the constituents. In the former
plant, Walz in 1857 found a new glucoside, globularin. The authors
recognise the presence of some substances overlooked by Walz,
and they find that the tannin of the plant is no special modification.
The substances separated and estimated by them are globularin, cin-
namic acid, potassium and sodium cinnamates, tannin, mannite,
glucose, chlorophyll, resins, colouring matters, and fixed salts. The
presence of the volatile compound detected by Walz was confirmed,
but it exists in quantity too small for examination, at least with
the amount of material at the authors' disposal; they think it may
be cinnamic aldehyde, and that it may be the cause of the peculiar
excitement produced by the administration of the extract. The
(johularetin and paraglobularetin of Walz are merely products of de-
composition. R. E,.
Phoma Gentianae: a newly observed Parasitic Fungus.
By J. KiJHN (Landw. Versuchs.-Stat., 28, 455 — 456). — The writer
describes a newly- discovered fungus, having its habitat on the stems,
leaves, and buds of Gentiana ciliata, and takes the opportunity of
denying that plants grown in mountainous districts are freer from
such parasites than those of the lowlands. J. F.
Artificial Digestion of Meadow Hay. By Kern (Landw.
Versuchs.-Stat., 28, 460 — 461). — At the experimental station of Got-
tingen, experiments were made with two sheep, fed for one period on
meadow hay and another on lucerne hay ; and the digestible and
iindigestible protein matter was estimated according to Stutzer's
method, by treatment with acid pepsine. As the excrement contains
nitrogenous matters not directly obtained from the food, it was digested
for half an hour with 1 per cent, hydrochloric acid, extracted with
alcohol and ether and then examined, the unextracted dung being also
examined : it was found that the process of natural and artificial diges-
tion yields very similar results. J. F.
Decomposition of the Diffusion Residues from Beetroot.
By M. MkRCKER (Landw. Versuchs.-Stat., 28, 465 — 467). — It is found
that the residues from the making of beet-sugar by the diffusion pro-
cess, lose considerable portions of their weight when stored in either
pits or barns ; as the substance is considered a valuable food for
cattle, the author undertook the investigation of the cause, and
VOL. XLIV. 3 z
1026
ABSTRACTS OF CHEMICAL PAPERS.
believes it to be due to fermentation, which is greater in warehonses
built of porous materials admitting air, and particularly in pits
thatched with straw ; he recommends that the residues be used for
feeding purposes when fresh, and if that is not possible that they
should be dried in a special apparatus before being stored. J. F.
Culture of Various Descriptions of Sugar-beet. By D. v.
KoBTH (Landw. Versuchs.-Stat.y 28, 451 — 453). — In order to test the
value of different kinds of beet, a large field of limey clay was manured
with 200 kilos, of precipitated phosphate and 150 kilos. Chili salt-
petre, equal to 64 kilos, of phosphoric acid and 23 kilos, of nitrogen,
divided into five parcels, in each of which 77 plants were placed, a
different sort in each plot. When ripe, they were weighed ; the season
being very wet, they showed it in their contents and quality of juice.
The differences between the qualities are considerable. The sugar
contents were estimated in the juice by a saccharometer, a polariscope
not being available, as this instrument would have shown a sugar
result of 20 per cent, too little.
The accompanying table gives the figures : —
Name.
Total
weight.
Percent-
age juice.
Specific
gravity.
Dry sub.
in juice
per cent.
Sugar by
saccharo-
meter.
kilos.
199-5
185
163-5
157
142
kilos.
96 1
96-0
95-8
96-8
96-0
kilos.
1-044
1-041
1040
1043
1-036
kilos.
9-8
10-4
11-2
11-9
7-4
kHos.
10-8
Bes Barres
10 -1
Cylindrical Beets
Griant Mangold
Giant Mammoth
9-9
10-6
8-9
J. F.
Hay and Ensilage from a Poor Quality of Grass. By F.
Sutton (Chem. News, 47, 287). — In the present paper, the author
publishes the comparative composition, &c., of hay and ensilage made
from the same inferior grasses. Grass 1, from which the correspond-
ing hay and ensilage were made, grew in a wood from which the
trees were partially removed, and was very coarse and rank. Grass 2
grew in a rough meadow, was poor and coarse, but somewhat better
than 1.
The two samples of hay were coarse and poor in quality, and desti-
tute of the sweet odour and taste usually found in well-made hay ; the
texture of No. 2 was preferable to No. 1. The hays contained a trace
of ready formed sugar, which was considerably increased by digestion
with acid : distilled with water they yielded no essential oils, nor any
flavour except those of decaying grass.
Both specimens of ensilage were highly odorous from the essential
oils, and had a vinous fragrance accompanied by a slight but pleasant
acidity. When steam distilled, essential oils passed over, but although
powerful in flavour they were too small in quantity to separate. No
ready formed sugar could be detected, but after prolonged digestion
0-73
0-88
1-60
2-12
5-03
7-09
1-41
1-43
7-48
8-87
4-64
7-05
1-29
1-34
0-72
0-89
20-80
19-80
8-28
10-62
33-92
30-27
6-60
9-24
—
—
—
(0-06)
—
—
(0-34)
(0-36)
4-05
3-15
1-78
1-88
4-50
3-70
0-77
0-82
100-00
100-00
100-00
100-00
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 1027
with acid a substance was formed whicli reduced copper solution. The
following are the analytical data (comp. Abstr., 1882, 330) : —
Hay 1. Hay 2. Ensilage 1. Ensilage 2.
Water 22-20 24-90 74-30 65-95
Albumin and albuminoids
soluble in water
Insoluble albuminoids ....
Sugar, gum, and extractive
matter, soluble in water
Oil, wax, chlorophyll, &c. .
Digestible fibre
Indigestible woody fibre . .
Alcohol
Acidity, taken as acetic acid
Soluble inorganic matter . .
Insoluble inorganic matter
The author then points out the manifold benefits derived from the
ensilage in the present case. Firstly, what would have been tasteless,
dry forage is rendered a fragrant appetising and succulent food ; then
comparing the composition of the dry hay and dry ensilage, he draws
attention to the much larger proportion of soluble albuminoids, soluble
extractive matter, and digestible fibre in the latter as compared with
the former, and finally infers that what amounts to a partial digestion
has been effected in the silo. The author, alluding to the composition
of the dried materials, refers to two apparent anomalies ; firstly, the
increase in fatty matter in the ensilage (ibid.) as against the hay,
which he thinks is probably due to some of those substances becoming
insoluble during the drying of the hay ; secondly, the high percentage
of nitrogen in ensilage 1, as compared with the corresponding hay,
which is probably due to the ensilage containing more seed-vessels or
other richer nitrogenous portions of the plant, or perhaps is due to
different periods of growth. D. A. L.
Effect of Water containing Zinc Sulphate and Common
Salt on Soils and Plants. By C. Krauch {Landvj. Versuchs.-Stat.,
28, 468 — 472). — The injurious effect of drainage water from mines
and chemical works on vegetation is well known, and is believed to
be in great measure due to the solvent power of such waters on the
valuable constituents of the soil, as well as their directly poisonous
properties. A series of experiments was undertaken with samples of
earth containing different proportions of common salt and zinc sulphate.
It was found that half a gram of salt added to a litre of water, and
shaken up with a sample of soil, dissolved more potash, phosphoric
acid, and lime, than pure water, and that in a similar experiment with
zinc sulphate the zinc became chemically combined with the soil,
setting free equivalent quantities of lime, magnesia, and potash.
3 z 2
1028 ABSTRACTS OF CHEMICAL PAPERS.
The injurions effects of the common salt were not so evident in
water cnltnre, but when large quantities were used, the plants did not
grow. The results with zinc sulphate were much the same, so that it
would appear that comparatively large quantities are necessary to
produce decidedly injurious effects. Instances of plants which bore
treatment with zinc sulphate without injury were mentioned to the
author, and suggestions that some plants are more sensitive to the
poison than others. J. F.
Analytical Chemistry.
Nitrogen Estimation, a Method of General Application.
By H. Grouyen (Landw. Versuchs.-Stat., 28, 343— 367).— This
method is an adaptation to the purposes of analysis of an arrange-
ment employed by the author on a commercial scale in a factory in
Biirgerhof, for the purpose of obtaining sulphate of ammonia from
peat, the results of which were so satisfactory as to induce him to try
to bring it to a sufficient state of perfection that it might replace the
so largely used soda-lime process, which he thinks yields rather low
results and requires too much care in its execution. The author has
employed his method for three years in more than 3000 estimations
with very satisfactory results. It consists in burning the nitrogenous
matters in contact with steam in a suitable apparatus. The theory
is that superheated steam when forced over glowing carbon gives up
its oxygen ; the nascent hydrogen and nitrogen are brought into inti-
mate molecular contact, and the hydrogen is in such excess that the
whole of the ammonia is obtained. The apparatus cannot be very well
understood without the accompanying illustrations, but may be de-
scribed as consisting of two iron gas-pipes connected by a branch at
one end. One tube acts as a steam generator and superheater ; the
water being fed into it gradually from a burette with which it is con-
nected by an india-rubber tube. This generator is filled with broken
pumice, which receives the drops of water and presents a very large
surface to the heat. The superheated steam passes through the con-
necting branch into the analysing tube and over the substance, which
is contained in a platinum boat : the fore part of this tube is filled
with a substance which the author calls the " contact mass,'' a com-
position of certain earths with peat, highly burned, very light, and
porous. The evolved gases -are thoroughly mixed during their passage
through this substance, and pass thence through an ordinary bulb
arrangement ; the pumice in the generator and the contact mass in the
analyser are seldom changed. The substance to be examined is put
in at the hinder end of the tube, pushed beyond the connecting
branch so that the current of steam will play on it ; the opening is
then closed with an asbestos stopper. These stoppers are a great
ANALYTICAL CHEMISTRY. 1029
feature of the apparatus. They are made of the best American asbestos
millboard, punched out similar to gun- wads, made as thick as neces-
sary, and connected by screw- rivets, trimmed neatly with a file to closely
fit the openings in the tubes. These stoppers last for hundreds of
operations. Tubes of various materials have been tried, but ordinary
gas-tubes protected by cast-iron cases of good quality are found to last
better than any.
A few precautions are recommended. The bulb-tube should be
cooled during the process by a stream of water; the "contact mass,"
although useful for 50 operations, should be cleansed at about every
sixth operation by passing a stream of air through it for about
15 minutes while the tube is at a red heat. The hinder portion of
the analyser tube is cooled before putting in the substance, by placing
a cold iron rod in it and damping the fuel, whilst the portion which
contains the " contact mass " is left glowing. This is to prevent the
too sudden evolution of gas. The substance under examination should
not be previously dried, as the author believes moisture in the sample to
be favourable to the operation, and has employed with success samples
containing as much as 80 per cent, of water. Fresh vegetable matter,
ilesh, blood, and all similar materials can be placed at once in the plati-
num boat without the tedious process of drying and powdering ; grain,
seeds, bread, and air-dried manures should be damped ; fluids of the con-
sistence of milk, such as beer, beet-juice, &c., are concentrated to one-
third of their original bulk with addition of a couple of grams of the
broken " contact mass." The use of gypsum, sulphate of magnesia, and
other substances which yield oxygen to organic matter at a red heat
should be avoided ; the chlorides should not be employed. The sample
should be about 3 grams. The duration of the process is from 20 to 30
minutes, according to the nature of the substance ; in very few cases
40 minutes are required. The end is known by the slowness with
which the gas bubbles pass. The oven employed is one heated by a
fuel composed of 3 parts coke and 1 part wood charcoal ; the author
prefers it to a gas-oven on the score of cheapness and convenience.
Directions are given as to firing and arrangement of the oven : the
heat should be moderate, neither very high nor very low, but a low
heat is less dangerous to the results than if too high ; a coloured and
tarry distillate shows the heat to be too low, and that some ammonia
is being lost. The tube when all goes right appears of a clear red, and
the author estimates the temperature then at about 700 — 800° ; the
gases leave the " contact mass " at about 300 — 350°. The ash of the
substance is perfectly pure, and as well burned as in the best muffle,
so that it can be weighed directly on cooling.
The author is very strongly convinced of the great accuracy of his
process, which always yields a somewhat higher result in ammonia.
Five samples exactly alike, examined one after the other, agreed
within one- tenth c.c, whilst the soda-lime process carefully carried out
with a similar series of five samples showed larger difierences, and
the author mentions that a difference in the latter process leads to
errors fourfold as great as in his, as in his process four times the
quantity of organic matter can be burned.
The author believes that the application of this process to the analysis
1050 ABSTRACTS OF CHEMICAL PAPERS.
of feeding- stnffs has certain advantages — tlie easy separation of the
more valuable protein from the less useful amides, alkaloids, ammo-
nium salts, nitrates, &c. His method consists in cutting the sample
very small, and dividing it into two parts ; the one is introduced im-
mediately into the apparatus for determination of total nitrogen ; the
other is boiled for 10 minutes in distilled water containing 1 c.c. of
acetic acid, filtered on a paper filter, and washed with boiling water ;
the washed filter and substance is then placed wet in the tube, and
the nitrogen determined; this represents the true protein matter,
the difference between it and the total nitrogen, the amides, nitrates,
&c.
The nitrogen in raw and dissolved guano, and in many kinds of
ammonia superphosphate exists in the form of nitric acid to the amount
of J to ^ per cent. ; the author says that the soda-lime process is
quite unsuitable for its determination, even with the precautions
recommended by Ruffle — admixture with charcoal, sulphur, and sul-
phide of soda — yielding unsatisfactory results. Manure merchants
and manufacturers complain of this, but hitherto no remedy has been
found. The author takes 2 grams of the manure in the dry state, mixes
it in the platinum boat by means of a glass rod with 0*5 gram of pure
powdered sugar and 3 grams of acetate of soda, and introduces into
the tube ; the process is finished in about a quarter of an hour. Super-
phosphate manures of this class are poor in organic matter, but con-
tain much acid gypsum, which has a reducing effect, counteracted by
the addition of the sugar and the sodium acetate.
The analysis of sodium nitrate and saltpetre by this method re-
quires a slow and regular evolution of gas, and a considerable excess
of carbon gases in the steam while brought into the " contact mass,'*
wherein the dissociation of the aqueous particles takes place. 500
milligrams of the sample are dissolved in 12 c.c. of wat-er and 7 grams
of pure sugar added, to this solution as much Dinas clay is added as
will make it into a stiff paste. (Dinas clay is rich in magnesia and
liighly plastic.) This paste is rolled on a porcelain plate to a cylinder
20 mm. thick aud 150 mm. long, placed on a thin piece of sheet-iron
and run into the tube previously well cooled. Experience shows that
this produces a slow and regular decomposition. The process is com-
pleted in 30 minutes and the results are very satisfactory. J. F.
Comparative Estimations of Nitrogen in Guano. By J.
KoNiG {Landw. Versuchs.-Stat., 28, 461 — 462). — Raw Peruvian guano
contains a considerable proportion of its nitrogen in the form of nitric
acid, difficult of estimation by common methods of analysis. Manu-
facturers of fertilisers have employed Ruffle's method for its estimation,
but there are objections to it by reason of the numerous weighings
and the retention of a not inconsiderable part of the nitrogen by the
mixture of carbon and sulphur. The author recommends a method
Avhich yields accurate and higher results than the process referred to,
and is preferable for use in commercial analyses. It consists in com-
bustion of the sample with 100 grams finely powdered soda-lime,
12 grams potassium xanthate, and 5 grams tartaric acid ; if saltpetre
has been added to the guano, the results are too low. J. F.
ANALYTICAL CHEMISTRY. 1031
Nitrogen Estimation in Saltpetre by Potassium Xanthate.
By E. A. Grete {Landw. Ver sucks. -Sat, 28, 462— 463).— The author
recommends his process after further trials, as superior to E/uflBe's,
which he looks on as a modification of his own. He recommends the
use of xanthate in quantity about half as much as the sample and
soda-lime together, some xanthate behind the mixture in the tube, and
ordinary soda-lime in the front of the sample. A. Mayer doubts the
wisdom of adopting the process, thinking it would lead to the extensive
mixture of Chili saltpetre with guano. M. Maercker advises its
adoption on the ground that ammonium sulphate is already mixed
with many guanos, and why not saltpetre. J. F.
Phosphoric Acid Determination. By E. A. Grete (Landw.
VersucJis.-Stat., 28, 467 — 469). — The author proposes a new method
for the determination of phosphoric acid in presence of iron and
alumina. The solution is made in the ordinary way, or should the
destruction of organic matter be necessary, 20 grams of the substance
is well moistened with a concentrated solution of soda and potassium
nitrate, gently ignited in a platinum or silver capsule, and the residue
dissolved in hydrochloric or nitric acid; after dilution to 500 c.c, it
is filtered, 50 c.c. of the filtrate nearly neutralised is treated with
50 c.c. of ordinary sodium acetate solution, and the precipitate
collected on a large filter (a slight washing with water is advantageous
but not absolutely necessary), the acetic solution is put aside in a
half -litre flask for later treatment ; the precipitate is washed from the
filter with hot hydrochloric acid by means of a wash-bottle, well
washed, treated with ammonia, then with tartrate or citrate of
ammonia until the iron or aluminium phosphate is dissolved, and the
phosphoric acid in this solution is precipitated by magnesia mixtui'e
in presence of much ammonia ; when freed by frequent washing (by
decantation) the precipitate is dissolved in a small quantity of hydro-
chloric or acetic acid, and added to the reserved filtrate from the first
part of the process, filled to the mark and determined by the uranium
process. The rapidity of the process and its small liability to error from
the large quantity of substance employed, recommend the process
for use. J. F.
Specific Gravity of Minerals and their Mechanical Separa-
tion. By P. GiSEVius (Landiv. Ver sucks. -St at., 28, 369 — 449). —
This paper consists of two divisions, the first being a review of
several previously known methods of ascertaining the sp. gr. of
minerals by immersing them in certain solutions of known density so
that they float midway in the fluid ; the second is occupied with a
description of various precautions taken by the author to avoid errors,
and of an apparatus devised by him to effect the separation of
particles of different sp. gr. contained in the sample under analysis.
He commences by dwelling on the importance to the agriculturalist
of knowing, not only the chemical substances present in his soil, but
also their actual state of combination, and he asserts that the methods
now in use do not afford the required information.
Amongst the methods reviewed are those of — Senf t by washing ;
1032 ABSTRACTS OF OHEMIOAL PAPERS.
Fleuriau de Bellevne and Cordier by differences in sp. gr. ; Schaffgotsch
by means of a solution of mercuric nitrate ; Sonnstadt by a solution of
iodide of potassium and mercury ; Church with the same solution ;
Breon with molten lead and zinc chloride ; but the solution which of
all others seemed most suitable was Klein's (Abstr., 1881, p. 1168),
by which, with certain precautions, particles of densities between
22 and 3*3 sp. gr. can be separated, solutions of any desired density
within these limits being easily made up by dilution or concentration
of the original preparation. As a check upon his own determinations,
he made repeated estimations of the sp. gr. of nine minerals which
were given in Naumann's work edited by Zirkel, employing Joly's
spring balance, the pyknometer, and the hydrostatic balance. In all of
them he found considerable margins of error, and dismisses them as
not being sufficiently accurate : this leads to a description of an instru-
ment of his own invention, which he calls " Volumeometer.'^ With-
out the illustration accompanying the paper it would be difficult to
understand it ; it may be described as a bent tube, one arm much wider
and shorter than the other ; the solution stands at a certain mark in
the wider tube ; the sample is placed in it with the usual precautions,
and the fluid forced to the mark at which it first stood by means of
a caoutchouc ball and a micrometer screw arranged over the aperture
of the larger arm ; this causes the solution to rise in the other arm,
which being very narrow and marked in cubic millimeters, gives at
once the volume of the sample, the reading of the scale being aided
by a microscope provided with cross-wires ; from the volume the
sp. gr. is calculated : of the nine minerals examined the agreement
with Zirkel 's careful determinations was very close.
The second portion of the paper is occupied by a description of
the mechanical separation of mineral particles by means of Klein's
solution. He describes the preparation of the original solution, the
manner of diluting it to the required density, and the various modes
of separating the heavier and lighter particles ; for this purpose he
has devised another instrument, also worked by pressure of air on
one arm of a U-shaped receptacle, the other arm of which forms the
cylinder in which the sample is placed. By varying the pressure, the
fluid is agitated, and when the lighter particles rise to the surface, is
caused to overflow and carry them into a suitable basin; those
particles which are of the same sp. gr. as the fluid can be removed in
a similar manner, and the heavier remain at the bottom.
The remainder of the paper is occupied with instructions for the
preparation of the sample, from which carbonates must be removed
by treatment with dilute acetic acid, but whicb otherwise contains
nothing novel, and with test analyses and estimations, all of which
are intended to show the suitability for the estimation of sp. gr. in
small samples, and the mechanical separation of their particles, but
which scarcely admit of useful abstraction. J. F.
New Method for the Estimation of Minute Quantities of
Carbon in Iron or Steel, and a New Form of Chromometer.
By J. E. Stead (Chem. Neus, 47, 285— 286).— The ordinary colour
method for the estimation of minute quantities of carbon in steel is
ANALYTICAL CHEMISTRY. 1033
not accurate, owing to tlie colour of the iron nitrate interfering with
that due to the carbon. In the course of some investigations, the
author found that this colouring matter is soluble in alkali, and there-
fore by treating the nitric acid solution of the steel with soda it can
be separated from the iron. Moreover the colour is much deeper in
the alkaline than in the acid solution. Upon this discovery the
author has based the following method for the determination of
carbon in iron or steel. The standard solutions required are — nitric
acid, sp. gr. 1*20 ; and sodium hydroxide, sp. gr. 1*27. One gram of
the metal to be tested is dissolved in 12 c.c. of the standard acid,
with the aid of heat (90 — 100°). At the same time some standard
iron containing a known quantity of carbon is treated in a similar
manner, and when both are dissolved 30 c.c. of hot water and 13 c.c.
of soda solution are added to each. They are well shaken, diluted to
60 c.c, well mixed, and after standing ten minutes in a warm place
are filtered through dry filters.
The filtrates are compared by pouring them into two separate
measuring tubes in such quantities that on looking down the tubes
the colours appear equal, and from the difference in height of the
columns the amount of carbon is calculated, the amount of carbon
being inversely proportionate to the bulk of the steel solution under
examination compared with that of the standard. Thus if the steel
to be tested contains half as much carbon as the standard, and 50 mm.
of the standard be used, then 100 mm. of the steel solution will be
required to give the same tint, and then the amount of carbon in the
standard multiplied by 50 and divided by 100, would give the amount
in the steel. Several experiments were made to test the efficacy of
the method. To test the effect of heating, five separate portions of
steel were dissolved in 12 c.c. of the standard acid ; solution was
complete in five minutes : one solution was immediately treated as
above described, the others were heated for different periods, and
then treated in the same way, the results were as follows : —
5 mins. 10 mins. 15 mins. 20 mins. 25 mins.
Carbon per cent.. . 0-098 O'llO O'llO O'llO O'lOS
In another series, the effect of excess of nitric acid was tested with
the following results : —
C.c. of nitric acid used .... 12 16 18 21 25
Carbon per cent 0*41 0'41 0-41 0-402 0-380
whilst excess of soda had the following effect : —
C.c. of soda used .... 13 15 18 21
Carbon per cent O'llO O'llO O'llO 0-115
Less than 13 c.c. of soda precipitate the colour along with the
iron.
Hydrochloric acid affects the quantity but not .the quality of the
colour, showing that chlorides are harmless, but that nitrohydro-
chloric acid even in small quantity prevents the formation of the full
1034 ABSTRACTS OF CHEMICAL PAPERS.
amount of colonr which would be produced by the nitric acid alone.
Several samples of iron have been examined by this method, the
results are very slightly lower than the figures obtained by the com-
bustion process. The colours from low carbon irons are different
in tint from those from higher carbon steels, and therefore a low
carbon iron must be used as a standard for comparison in such cases.
When steel is heated to redness and chilled, the colour from the
chilled steel is less than that from the original steel, but this difference
is not so marked in low carbon steels. The author has detected
two distinct colouring matters in all nitric acid steel solutions, one
yellow like potassium chromate, the other dark brown-red. In some
solutions the yellow preponderates, in others the brown.
Eor these colorimetric carbon determinations, the author suggests a
chromometer, in which a fixed length of liquid column of the carbon
solution under examination is used, and a variable standard column
of the suitable standard solution is employed ; the amount of carbon
is deduced from the length of the latter required to make a
colour column equal in depth to the former, and the percentage is
read off directly from a graduated scale. The apparatus consists of
two parallel tubes of any convenient diameter, one of which is 9 inches
long and is closed at the lower end ; the other tube is contracted at
a point 9 inches from the top and is open at both ends, the lower
end passes through an india-rubber cork to the bottom of a bottle con-
taining the standard solution ; a second tube also passing through the
cork into the bottle is connected with a syringe, used for adjusting
the height of the standard column. Just above the contracted part
of the open tube, and at the bottom of the closed one, a glazed porce-
lain cylinder is placed. When the tubes are placed in a parallel
position the length from the flat surface of the clay to the upper ends
is equal in each. A small looking-glass fixed at an angle of 45" over
the open ends of the tubes facilitates the observations.
D. A. L.
Electrolysis of Bismuth Solutions. By N. W. Thomas and
E. F. Smith (Chem. News, 48, 10).— The authors employ solutions
of the sulphate or citrate of bismuth, the latter either alkaline or
acid. In some experiments, the solutions to be examined were put in
a platinum crucible, which was surrounded by a coil of wire in con-
nection with the negative pole of a battery, the positive electrode
being suspended in the solution ; on the passage of the current,
metallic bismuth is deposited on the interior of the crucible, and can
be washed, dried, and weighed. In other experiments, the platinum
crucible is suspended, from a wire connected with the negative pole,
in the solution in a beaker, the positive electrode being likewise in
the solution ; in this case, the bismuth is deposited on the outside of
the crucible. The authors find that the method works well and accu-
rately. The time required to deposit the bismuth varies according
to the strength of the solution, and is not shortened by application of
heat. D. A L.
New Volumetric Method for the Estimation of Arsenic. By
L. W. McCay {Ghem. News, 48, 7 — 9). — The author has success-
TECHNICAL CHEMISTRY. 103T
the most important ingredients, beyond the silica, are calcium and
magnesium carbonates, which, filling up the interstices between the
particles of sand, form a firm mass ; they amount to 0*52 to 1258 per
cent, of the whole. Alumina varies from 0*32 to 1'77 per cent., and
is either a component of admixed minerals, or else of clay, which is
injurious to the durability of the stone. Iron oxides are contained in
all sandstones, in white stones apparently as silicates, and in red stones
partially at least, as free ferric oxide or hydrate. The colour of the
stone affords no indication of the amount of iron contained ; thus a
white stone from Kenmure contained 2*62 per cent, ferric oxide, another
from Ravenscrag 0*14 per cent., and a red- brown stone from Bothwell
Park only 0'98 per cent. Some stones become disfigured with patches
of ferric oxide ; this arises from the oxidation of pyrites and the
action of calcium carbonate and the air on the sulphate produced.
Calcium sulphate and phosphate exist in small quantities, viz., about
O'l per cemt. The sp. gr. of the air-dried stone varies from 2*048 —
2'318, and the amount of water capable of being absorbed varies from
3 4 to 7" 2 per cent. It may fairly be taken that the durability of a
stone depends on its impermeability to water, its density and the
amount of binding material contained. It is noticeable that building
stones begin first to decay immediately below any flat projecting^
surfaces, which allow the rain to collect and then percolate tliroiigh
them, and thus dissolve or alter the binding materials. All such
horizontal ledges and protections should therefore not be made flat, but
have a steep slope given to them. In order to render the stone im-
pervious, it may be painted, or treated with silicate of soda or a pre-
paration called " Alexinoton," but the stone must first be allowed to
dry as completely as possible. H. B.
Utilisation of Butter-milk in Bread Making. By A. Muller
{Landw. Versuchs.-Stat., 28, 458 — 460). — An examination of an excel-
lent specimen of milk-bread from an official farm near Berlin led to
the present paper. Butter-milk from cows' milk contains 4 to 5 per
cent, of milk-sugar and half per cent, of mineral salts, and after setting
for cheese-making it also contains 1 per cent, of nitrogenous matter,
and nearly as much butter-fat. The value of this article as food has
not been fully investigated ; a very small proportion of the quantity pro-
duced is drunk or used in bakeries, but the greater part is used for pig
and calf feeding, and much of it is allowed to run off into the sewers.
The difficulties in the way of its more extensive use are its large per-
centage of water and its rapid acidification when stored : both diffi-
.culties are removed by concentration; this is practised in the North,
particularly in Norway, where the butter-milk is boiled over a naked
fire in the same way as fruit juices. This process is troublesome and
expensive, and would not find acceptance in Germany. The evapora-
tion in a vacuum apparatus, similar to that employed in sugar-boiling,
would be much more economical, and would yield a cleaner extract, easy
of transport and storage, ready for preparation of milk-sugar, or as food
in many forms. The daily evaporation of 40 hectolitres would reduce
the cost of the operation to about 1 mark per hectolitre. The author
induced a friend to try the new process as applied to bread making,
1038 ABSTRACTS OF CHEMICAL PAPERS.
and for several months bread made with it and wheat and rje was
sold to the public of Berlin, of excellent quality and at moderate
prices. The consumers were pleased with the results, and the bread
was pronounced sweet and tasteful.
The daily process consists in evaporating 300 litres of batter-milk
to one-seventh of its volume, and mixing to a stifE paste with double
its weight of flour. Whole or skimmed milk can be added if butter
fat or albuminous matter is desired in the bread. J. F.
Action of Certain Vegetable Acids on Lead and Tin. By
P. P. Hall {Ghem. News, 47, 290—291; and 300— 302).— Taking into
consideration the large quantities of tinned food which are constantly
being consumed, the author has thought it expedient to study the
action of various organic acids on the materials which are exposed in
the interior of the cans, viz., tin and lead. The present paper con-
tains the results of experiments on this subject, and also investiga-
tions on the quality of tin-plate and tin-foil used as covers for food
products.
The first series of experiments were conducted to determine quanti-
tatively the action of the more common vegetable acids on the metals
in question, all previous quantitative work in this direction having
been made with acetic acid only. First of all, in order to test the
effect of alloying on the corrosion of the metals, the amount of tin
dissolved, when pure, was compared with the amount dissolved under
the same conditions from an alloy exposing the same surface of the
metals in question. This was effected by proportioning the size of the
plates of pure metals according to the composition of the alloy.
Three alloys were made, taking into consideration the specific gravities
of the metals, one with equal parts of each metal, one with excess of
tin, and one with excess of lead. The metals were fused, well mixed
together, cast into thin sheets in iron moulds, rolled into thin strips,
and cut into pieces 1'2 inch wide and 12 inches long, thus exposing
one-fifth of a square foot surface. The tin and lead strips were of the
same width, but varied in length for the reason stated above. The
acetic acid solution employed contained 5 "75 per cent, of acid, the
solutions of tartaric and citric acids were made to an equal degree of
acidity. After an exposure of two weeks to the action of the acids at
25 — 35°, all the metals were found to be tarnished more or less, the
tin more so than the lead ; two of the alloys were sprinkled with
small black crystals of lead ; the smallest pieces of lead in tartaric
acid were covered with transparent crystals of lead tartrate. The
solutions containing tin were yellowish, whilst those with lead were
clear and colourless ; the pieces of tin were covered with a dusty '
powder. The strips of metals were taken out, washed, dried, and
weighed. The solutions were precipitated with hydrogen sulphide.
The lead gave dense black precipitates, finer in the tartaric and citric
acids than in the acetic. The tin came down brown in acetic, and
yellow and flocculent in the tartaric and citric acids. With the alloys,
the precipitates were dark brown in acetic and light-coloured and
flocculent in the other acids. The results are given in the following
table : —
TECHNICAL CHEMISTRY.
1039
"S o
Pure
metals.
^
^
1
1
g-g*
b
b
b
b
1
■— 1 ^ c3
<n
x^
CO
i>
d
|-^5b
1"
s
s
o
H ^
^
o
b
b
o
1
1
\a
00
(N
lO
o
a
00
05
CO
00
00
00
U3
05
o
CO
CO
I— 1
r-i
•^
- 1
©r^
g
s
1>
00
o
s 2
-i
CD
i>.
J>.
Tjt
O
9
o
9
o
o
Ill
OD
00
""ji
Oi
(M
"TJ
1
i?
w
o
rH
1
o
o
9
9
<1
b
b
o
o
x>
i>
00
lO
^
© 'Ti
d
(>i
1^
9
CO
H
fcO «
^ >■ m
&H
o
00
i>
(M
-S'T?'^
Oi
00
4>
00
§ i|
i'-^ a
f^^
1
05
rH
9
?
t*
M
rH
(M
rH
^ a
<n
<N
(M
CO
(M
g-i
<N
■^
!>,
00
^ o
I— 1
CO
"* 9 a
en 1
b
00
b
O
O
'd
lil
1
2
r-l
1
CO
*2
;3
CO
TP
CO
9
03
.2
vi
<1
b
b
b
o
CD
<M
•«ji
->?
o
f3
-*
'"Jl
lO
t*
<«1
© ITS
H
28
^
s
00
1
V^
?
wo
(N
f^^
s
rH
CO
lO
ID
h-:]
rH
f-l
J>
r-i
15§
f^
o> O
, '^'9
CD
1 ^'^
05
H
1 lO O
ceo
48
'28
k
I— 1
1— 1
iH
^ a
1
^
"^•^ 1
O 00
o «
r-l
o
o
h!
8S '
8S '
88 '
CO
I— 1
rH
i-H
s=l »
fl
^ IX)
1 • •
(N (N
CO
iil
H
1 ,H,H
^ Tft
1 1>X>
fH
(N CNJ
iH r-t
CO
-M <n d
■ ■'
^r^
1
::i
CO CO
rH r-4
Hi
•H tH
<NN
1040 ABSTRACTS OF CHEMICAL PAPERS.
Some similar experiments were now conducted in stoppered bottles.
In order to exclude air as much as possible, the bottles were heated^
filled with acid while hot ; boiled ; and at once tightly stoppered.
The results are given in the last line of the above table. Another
series of experiments proved conclusively that galvanic action did not
influence the rapidity of the corrosion, the action generally being
slight at first, and increasing as time went on. Dilute acids, if in
sufficient quantities, cause more corrosion than stronger ones. Some
experiments were next tried on the tins themselves. 200 c.c. of the
acids were put into three empty tins, tied over with paper, and
examined after two weeks. The citric and tartaric acids had removed
the tinning. A white powder was deposited in the citric acid solution,
soluble in hydrochloric acid. The quantities of lead and tin dissolved
were as follows : —
Grams dissolyed by-
Metals. Acetic acid. Tartaric acid. Citric acid.
Lead 0-0117 0-0873 0-1559
Tin 0-4178 1-0430 0-6828
In addition to these metals, there was a good deal of iron dissolved*
The lead was derived from the solder.
The result of the analysis of various samples of tin-plate showed
that the superior class or "Bright plate" was tinned with pure tin,
and that this quality is the one almost universally used for tin- ware ;
the inferior class or " Terne plate," as is nnderstood, contains lead
to the extent of 70 per cent. ; it is considerably duller than bright
plate, and is used almost exclusively for roofing purposes. The
analysis of commercial tin-foil proves it to be of a very mixed cha-
racter, from pure tin to stuff containing 90 per cent, of lead ; the latter
would prove deleterious if used for cheese or like substances.
D. A. L.
1041
General and Physical Chemistry.
Refractive Power of Organic Compounds in Solution. By
J. Kanonnikoff {J. fr. Chem. [2], 27, 362— 364).— The author is re-
investigating the refractive powers of organic substances in order to
confirm the results already obtained, and to settle some questions still
open. In the present communication, he confirms the rule that the
specific refractive power of a substance can be calculated from that of
its solution, provided that the solvent has no action on the dissolved
substance. The specific rotary power of quinic acid shows the
absence of double carbon union. A. J. G.
Cause of the Anomalous Double Refraction of Certain Salts
Crystallising in the Regular System. By R. Brauns (Jahrb. f.
Min., 1883, 2, Mem., 102— 111).— F. Klocke, who described the
double refraction occurring in alum, lead nitrate, and other salts of
the regular system (Jahrb. f. Min., 1880, 1, 53), considered this
phenomenon to be due to the state of tension of the crystals in
question. The author, however, is of opinion that chemically pure
crystals are optically isotropic, and that the anomalous double refrac-
tion occurs only in those crystals with which an isomorphic salt is
mixed. This conclusion was based on the examination of more than
a thousand crystals, including some of Klocke's original crystals. He
found that none of them were chemically pure, but that an appre-
ciable amount of isomorphic material was always present. The
ammonia-alum was always mixed with potash-alum, and the lead
nitrate with nitrate of barium. B. H. B.
Relation between the Composition of Organic Compounds
and their Absorption Spectra. By G. Krijss and S. Oeconomides
(Ber., 16, 2051 — 2056). — One of the authors has already shown that
the absorption spectrum of a mixed solution of two coloured sub-
stances is not equal to the spectrum of each solution taken separately,
but that displacements and concentrations of the bands frequently
occur (Abstr., 1882, 1018). These changes are ascribed to chemical
reactions within the solution, and it would thus be interesting to
decide, if possible, by spectrum analysis the nature of these reactions.
As a preliminary stage to this inquiry the authors have examined the
changes experienced in an absorption spectrum by the alteration in
the composition of a compound, viz., the replacement of a hydrogen-
atom by the groupings Me, Et, NO2, NH2, &c. This subject has been
partially investigated by Dunstan, Soret, and others. The authors
have selected for their experiments indigo and its derivatives, which
give an absorption-band between C and D, a slight absorption in the
red, and a stronger absorption between F and G. The experiments were
conducted with a Kriiss' universal spectrum apparatus (the slit of
which is placed symmetrically to the optical axis), fitted with a micro-
VOL. XLIY. 4 a
1042
ABSTRACTS OF CHEMICAL PAPERS.
meter. Measurements were made of the positions of minimum bright-
ness, whicli for dilute solutions lies between well defined and narrow
limits. Thus, for example, a solution of indigo in chloroform gives
an absorption band from CesD — C90D or Xi = G13-4 and Xj = 596*7;
and the position of minimum brightness can be taken approximately
as the mean of these two numbers, V
The following table contains the authors
\i + A3
Ai + A^
2
results
= 604-8.
for Xj, Xj, and
, for indigo and its various derivatives dissolved either in chlo-
roform or in sulphuric acid
: —
Solution in chloroform.
Solution in sulphuric acid.
K
K
\ + Xa-
2
K
K
2
606-9
628-5
658-1
660-9
614-9
628-5
602-8
610-8
643-4
644-2
597-7
617-5
604-8
619-7
656-8
652-6
606-3
623-0
613-4
595-4
590-0
596-7
582-3
580-2
605-1
588-9
586-1
m-Methyl-indigo ....
w-Oxymethyl-indigo . .
Ethyl- indigo
Mono brom -indigo ....
Dibrom-indigo
Amido-indigo
Dibromoamido-indigo .
The above numbers show that the introduction of the methyl,
oxymethyl, "or ethyl groupings and of bromine displace the position of
minimum brightness to the less refrangible end, while the nitro- and
amido-groupings have a reverse action.
It is remarkable that the introduction of an ethyl in the methyl
group produces the same effect as the replacement of a hydrogen-
atom by oxymethyl : secondly, the introduction of one atom of bro-
mine causes but little change, whilst the effect of the second atom is
equal to that of a methyl-group. This difference is to be ascribed to
the nearness of position of this latter bromine-atom to the imido-group.
A similar phenomenon has been observed by Baeyer and Oeconomides
in the case of mono- and di-bromisatin. V. H. V.
In the abstract referred to above, the word colourless (fourth line in
abstract) is an obvious misprint for coloured. — V. H. V.
Electrolytic Researches. By Hans Jahn (Monafsh. Chem., 4,
679 — 694). — The starting point of all theories of electrolysis is the
well-known law of Faraday, from which, when expressed according
to existing conceptions, we learn that equal quantities of electricity are
capable of setting free equal numbers of combining units or quantivalen,-
cies ; whence also it follows directly that currents of equal intensity
must separate at the electrodes equivalent quantities of the two ions
composing an electrolyte, — and, consequently, that the work done by
GENERAL AND PHYSICAL CHEMISTRY. 1043
the current in decomposing chemically equivalent quantities of the
electrolytes is the same for all electrolytes, and quite independent of
the chemical nature of the ions contained i herein.
If, however, we admit, according to the ordinary assumption, that
the atoms or radicles of an electrolyte are held together by a peculiar
force (affinity) depending only on the chemical nature of those atoms,
the explanation of electrolytic phenomena in the sense of Faraday's
law is attended with considerable difficulty.
Solutions of copper sulphate and zinc sulphate subjected to the
action of currents of equal strength yield equal quantities of oxygen
and sulphuric acid at the anode, and chemically equivalent quantities
of zinc and copper at the cathode. But the quantities of work whicb
must be expended by the current in order to resolve these two salts
into their constituents, viz., metal, oxygen, and sulphuric acid, are
very different^ the zinc salt requiring the expenditure of nearly twice
the amount of work that suffices for the decomposition of the copper
salt ; and in accordance with this fact, it has been shown by Thomsen.
that the formation of zinc sulphate from zinc, oxygen, and sulphuric
acid, is attended with the evolution of nearly twice the amount of
heat that is evolved in the formation of the copper salt, viz. : —
(Zn, 0, SO3, Aq) = 106-01 heat-units.
(Cu, 0, SO3, Aq) = 55-96
Granting, however, the existence of different forces of affinity, it
follows that, in the electrolytic decomposition of a salt, the current
must loosen these forces of affinity by restoring the component atoms
and molecules to their original conditions of movement. But since
the decomposition of zinc sulphate requires the expenditure of an
amount of working force nearly double of that required to decompose
the copper salt, it seems to follow that equal quantities of electricity
will decompose twice as much of the latter salt as of the former, a
result which appears at first sight to be in direct contradiction to
Faraday's law of electrolysis. The author, however, suggests that in
the decomposition of equivalent quantities of the salts under con-
sideration, part of the electric force is expended in the purely chemical
work of neutralising the forces of affinity, and another part in over-
coming the resistance to conduction and other antagonistic forces, — a
view which indeed was suggested by Faraday himself in his classic
researches on electrolysis ; and as the first of those amounts is directly,
and the second inversely proportional to the affinity of the ions, the
sum of the two components must remain constant for all electrolytes,
and consequently the quantities of electricity required for the decom-
position of equivalent quantities of different electrolytes must be the
same in all cases^ — which is Faraday's law.
With the view of throwing further light on this matter, the author
has made a series of experiments on the quantities of heat evolved in
the electrolysis of the sulphates of zinc and copper, using a calori-
meter of peculiar construction, for the description of which we must
refer to the original paper.
The main result of his experiments is that the quantities of elec-
tricity used up, or rather converted into heat, in overcoming the
4 a 2
1044 ABSTRACTS OF CHEMICAL PAPERS.
resistance to conduction and other secondary influences, are inversely
proportional to the forces of aflBnity of the ions of the electrolyte.
Hence it appears that in spite of the different amounts of chemical
work which must be supplied by the current for the decomposition of
the two salts above mentioned, the entire loss of energy in the circuit
is the same in both cases, and therefore that Faraday's law holds
good, even if we admit the existence of a determinate affinity between
the ions to be overcome by the electric current.
The author has also subjected this inference to a further test. If
the quantity of electricity converted into heat by the resistance to con-
duction, the secondary actions, &c., in the circuit, is less as the affinity
between the ions concerned is greater, the amount of heat evolved in
the electrolysis of copper sulphate and zinc sulphate with copper and
zinc electrodes respectively, must be the same for both salts. For it
is clear that if the development or abstraction of heat due to the
solution of the anode, with reproduction of the original salt, increases
in the same ratio as the quantity of heat due to the resistance to con-
duction diminishes, the total amount of heat evolved must be the
same in both cases.
This conclusion is fully borne out by the author's experiments. In
solutions containing respectively CuSOi + 200 M2O and ZnSOi +
2OOH3O, the quantities of heat evolved in the deposition of equivalent
weights of copper and zinc were found to be : for copper, 39497 ; and
for zinc, 39'958 heat-units ; and solutions containing CuSOi 4- lOOHjO
and ZnSOi + IOOH2O gave for copper, 37-95 aaid for zinc 39-39 heat-
units. A solution of silver nitrate containing AgoN20B -r 2OOH2O, gave
for the deposition of an equivalent weight of silver, 34'03 jheat-units.
This somewhat smaller result is regarded by the author as probably
due to the fact observed by Hittorff, that in the electrolysifi -of copper
and zinc solutions equal proportions of the working force are con-
verted into kinetic energy of the ions, whereas in silver -solutions a
larger proportion. of the working force is thus converted, and conse-
quently only a smaller proportion is converted into heat.
In the electrolysis of mixed solutions of zinc and copper ealphates,
the deposit on the cathode consists wholly of copper. H- W.
Relation of the Heat of Combustion of Isomeric Organic
Compounds to their Densities. By Mullee-Erzbach (J?er-, 16,
758 — 761). — From a careful comparison of all the available determi-
nations of teat of combustion ©f various compounds, the author
draws the. conclusion that " of isomeric bodies, that one which has the
lowest (density will show the greatest heat of combustion and the
least heat of formation.'"' He also considers this to be another proof
of the Gorreatnesfi of his law that " the changes brought about by
chemical affinity, acting in accordanoe with the law of "'smallest
space,- force together the active masses, , -causing continued increase in
the meantdensity." L. T. T.
MoleGT]jlar Volume of Iiiquid Substances. By E. Schiff
(Annalen, 220^ 71 — 1 1 2).. — After some remarks on the advance made
ivithin the .last few years in tinacing the interdependence of physical
GENERAL AND PHYSICAL CHEMISTRY.
1045
constants and tlie arrangement of the atoms within the molecule, the
author proceeds to sura up the various results as follows : —
1. In isomeric substances, the boiling point and index of refraction
have a lower value the less continuous the arrangement of the
carbon-atoms within the molecule, and a maximum value when these
atoms are perfectly continuous or normally disposed.
2. The optic constants (atom refraction and molecular polarisation)
and the thermic constants (heat of combustion) are increased by
every so-called double affinity (or bond) between two carbon-atoms.
The author has carried on a series of investigations chiefly with a
view of ascertaining how far this latter generalisation holds good in
the case of molecular volume, as suggested originally by Buff, and
further investigated by Thorpe (this Journal, Trans., 1880), and
Schroder.
As the dilatometer method requires costly apparatus, a number of
observations and measurements at various temperatures, and a series
of calculations, the author has devised another method of measuring
the volume occupied by a known weight of a liquid at its boiling point.
The method is, however, merely a more accurate modification of that
proposed by Ramsay (Trans., 1879, 463), With this apparatus the
author has made more than 200 observations, and the results obtained
agree with those of Kopp, Pierre, and Thorpe.
Great care was used to obtain perfectly pure samples of the liquids
investigated ; fractional distillation was avoided whenever any sub-
stance could be obtained directly by synthesis ; and the degree of
purity was controlled by vapour- density determinations. The results
of the investigation are given in the table below.
Hydrocarbons.
Name.
Molecular
volume—-
Name,
M
D
Secondary pentane, C5II10 ....
Normal hexane, CgHn
Di-isobutyl CgHis
117 17
139 -71
184 -47
231-31
110 01
117-22
211-18
125 -82
95-94
117-97
Xylene, CgHo^
139-74
Ethylbenzene, CgHjo
Styrene, CHPh.CH^
Normal propylbenzene, 1
CeHsPr /
Paraethyl-toluene, CgH^MeEt
Mesitjlene, CgHaMeg
Cymene, C,jH4Me Pr<*
Terpene, CinHie
138 -93
130 -91
Di-idoamyl, CinHoo
161 -82
Caprylene, ChHir
161-94
Diamylene CinH n
162 -41
Diallvl. CftHin
184 -46
Benzene CcHk
182 -83
Toluene O-Ug . . ^
190-32
104(>
ABSTRACTS OF CHEMICAL PAPERS.
Cliloro-derivatives of Hydrocarbons.
Name.
Molecular
volume —
J)-
Name.
M
D'
Cliloroform, CHCI3
84 -50
103 -66
85-24
88-50
102 -77
114-18
Propyl chloride, C3H7CI
Allyl chloride, C3H5CI
Chlorobenzene, CgHjCI
Parachlortoluene, C6H4ClMe.
Benzvlic chloride
Epichlorhydrin, C5H5CCI
91 -43
Tetrachloromethane, CCI4 ....
Ethylene chloride, 1
CtroCl.CH^Cl/
Ethylidene chloride, CHClgMe
Trichlorethane, CHsClCllClo. .
Tctrachlorethylene, CCI2CCI2. .
84-22
114 -27
134-91
133 -47
87-67
Alcohols.
Methyl alcohol, MeOII
42-71
Allyl alcohol, C3H5OH
74 10
Ethyl alcohol, EtOH
62-00
Amyl alcohol, C5H20OH ....
122 -74
Normal propyl alcohol, Pi-^OH
81-28
Dimethyl ethyl carbinol, 1
CMeoEtOH J
121 -26
Isopropyl alcohol, Pr^OU ....
80-75
Normal butyl alcohol, C4H9OH
101 -57
Methyl hexyl carbinol, \
OMeCgHigH.OH f
191 -28
Isobutyl alcohol, CMe^CHaOH
101-63
Ketones, Aldehydes, and their Derivatives,
Acetone, MeoCO
Methyl hexyl ketone, 1
MeCOCeHiaJ
Furfuraldehyde, C5H4O2
77-08
186 -61
95-52
Paraldehyde (C2H40)3
Dimethyl acetal, "I
MeCH(OMe), J
Diethyl acetal, MeCH(0E"t)2
Acids.
Normal butyric acid, C4H8O2
107 -85
Isobutyric acid, C4 ^8^2 • - • •
108 -57
Ethers.
Anisoil PhOMe
125 -18
Phenetoil, PhOEt
148-47
Ethereal Salts.
Methyl formate, HCOOMe. . .
Ethyl formate, HCOOEt. .. .
Butyl formate, HCOOC4H9 . .
Amyl formate, HCOOCsH,! .
Methyl acetate, MeCOOCHa .
Ethyl acetate, MeCOOEt. . .
Ethyl chloracetate, CHsClCOo
Ethyl dichloracetate^ T
CHClaCOOEtJ
Ethyl trichloraeetate, 1
CCl3.C00Et /
62-57
84-57
130 -74
153 -21
83-65
105 -70
123 -09
143 -42
163 -86
Propyl acetate, MeCOOPr . . .
Allyl acetate, MeCOOCaUs. . .
Butyl acetate, MeCOOC4H9. .
Amyl acetate, MeCOOCsHn .
Methyl propionate, EtCOOMe
Ethyl propionate, EtCOOEt .
Propyl propionate, EtCOOPr
.Amylpropionate.EtCOOCsHii
Ethyl butyrate, EtCOOC4H9.
Ethyl i8obutyrate,C4H9COOEt
GENERAL AND PHYSICAL CHEMISTRY.
1047
In conclusion the anthor discusses the magnitude of the errors in
the determination of the boiling point, measurement of the volume of
the liquid, and its weight. If each of the several possible errors were
in the same direction, the total would reach a maximum value of O'lG
unit, a difference which was never observed in two separate determi-
nations of the molecular volume of the same liquid. V. H. V.
Variation of the Constant of Capillarity of the Surfaces,
Water-Ether, and Water-Carbonbisulphide under the Action
of Electromotive Force. By Krouchkoll (Compt. rend, 96,
1725 — 1728). — The author finds that insulating liquids, such as
carbon bisulphide, ether, and turpentine, which are not miscible with
water, acquire a distinct conductivity when placed in contact with it.
He finds that the capillarity constants of the surfaces, water-ether,
and water-carbonbisulphide vary under the action of electromotive
force in the same way as the capillarity constant of the surface, water-
mercury. Lippmann's well-known experiments w^ith mercury can
indeed be repeated with ether or carbon bisulphide. The enormous
resistance of the ether or carbon bisulphide, even when saturated with
metallic salts as in these experiments, exercises considerable effect on
the rapidity of the movements of the meniscus. C. H. B.
Experiments on the Diffusion of some Organic and Inor-
ganic Compounds. By J. D. R. Scheffer (Ber., 16, 1903—1917).
— A continuation of the author's investigations (comp. Abstr., 1882,
1159). The mean results of the author's determinations are collected
in the following table : —
Substance employed.
Hydrochloric acid
>» »
Sodium chloride
>» }>
>> >>
5> 55
,, nitrate
»> '>
Silver nitrate
)> 5>
>» J> • • • .
Sodium thiosulphate. . ,
>> >> • • '
Urea
Tartaric acid ,
Racemic a<id
Sodium sulphobenzoate
Sodium formate
Grams of substance
Tempera-
Diffusion constant,
in 100 c.c. solution.
ture.
k.
4-55
3-5°
1-622
22 "7
jj
2-008
5-45
5-5
0-756
6 1
0-756
12-53
0-727
26-3
0-732
10-35
2-5
0-622
49-09
0-565
4-96
7-5
0-899
35-95
>>
0-774
68-58
0-649
5-6
10-5
0 -630
38-97
•>
0-543
3-3
7-5
0-810
(5 per cent, solution)
5 0
0-374
,,
i)
0 -388
5-16
14-5
0-674
2-47
8 0
0-691
The anthor in conclusion compares his results for hydrochloric acid,
sodium chloride, nitrate, and thiosulphate, and silver nitrate with
1048 . ABSTRACTS OP CHEMICAL PAPERS.
those of Graham and Schulmeisier. For sodium chloride, both
Graham's and the author's results point to a very slight influence of
concentration on the velocity of diffusion; Schulmeister, however,
concludes that with increase of concentration the value for k increases.
In the case of sodium nitrate, and more so for sodium bisulphate and
silver nitrate, the effect of concentration is greater. The author
considers that the variation in the values of Ic for the same substance
in solutions of various degrees of concentration are probably due to a
separation caused by dilution of larger with smaller molecular aggre-
gates. V. H. V.
Affinity, and its Relation to Atomic Volume, Atomic
Weight, and Specific Gravity. By E. Donath and J. Mayrhofeb
{Ber., 16, 1588 — 1696). — After mentioning the views held by Mohr,
Kopp, Gmelin, Wachter, and others, the authors compare the elements
with reference to their specific volumes, i.e.^ the quotient of the atomic
volume divided by the atomic weight, or in other words the reciprocal
of the specific gravity. The order in which the elements are arranged
is such that those in which — has the highest values, and the pro-
perties of which are more opposed, are placed at the two ends of the
list, whilst the elements with lowest specific volumes are placed in
the centre, forming a series which in many respects resembles the
electro-chemical series of elements. A. K. M.
Inorganic Chemistry.
Activity of Oxygen. By F. Hoppe-Seyler {Ber., 16, 1917—
1924). — This paper is an answer to Traube's criticisms on the author's
results (this vol., p. 900). The author has repeated his experiments
(this vol., p. 848), and is satisfied as to their accuracy and the deduc-
tions drawn therefrom. V. H. V.
Lecture Experiments. By A. Ladenbukg {Ber., 16, 1478—
1483). — I. A description of a mercurial trough and apparatus for gas
analysis, which could not be described without the aid of the accom-
panying cuts.
II. Synthesis of Water by Weight. — A modification of the ordinary
apparatus for illustrating the synthesis of water, in which the weight
of hydrogen required to form water by uniting with the oxygen of
the copper oxide is directly determined. Two glass gasholders are
used, one filled with hydrogen the other with water. Each is weighed
before the experiment begins. The hydrogen is driven out of one
gasholder in the usual way by means of water ; this passes through
the apparatus, and the unused hydrogen displaces the water in the
second gasholder. When the experiment is complete, the gasholders
INORGANIC CHEMISTRY. 1019
are again weighed. From the increase in weight, the volume and
weight of hydrogen employed can be calculated. The upper part of
the gasholders must be empty when the weighings are made.
w. c. w.
Unobserved Resemblance between Carbonic Anhydride
and Carbon Bisulphide. By J. Tyndall (Proc Boy. Soc, 35,
129 — 130). — The author has examined the question whether com-
pounds of like chemical constitution possess like vibrating periods of
their constituent molecules. Carbonic anhydride, although the most
transparent of gases, is the most opaque to the radiation from hot
carbonic anhydride produced by the burning of carbonic oxide ; car-
bon bisulphide, whether as liquid or gas, is the most diathermous.
But the author has proved by experiment that carbon bisulphide
absorbs 75 per cent, of the heat radiated from a carbonic oxide flame,
but only 10 per cent, of the heat from a hydrogen flame. Thus carbon
bisulphide transcends as an absorbent of heat from carbonic anhy-
dride many substances which for all other sources of radiation far
transcend it. V. H. V.
Phosphorus Sulphides. By Isambert (Cumpt. rend., 96, 1771 —
1772). — The author admits Lemoine's claim for priority. He points
out, however, that there is a considerable diff'erence between the
liquid sub-sulphide formed by mixing phosphorus and sulphur at 100°,
and that formed by heating the mixture to a temperature higher than
130°, or by mixing phosphorus and phosphorus trisulphide : the latter
is much more stable than the former, a difference due to the fact that
in the first case there is no real chemical combination. When a
mixture of phosphorus with even a large excess of sulphur is distilled
at 100° in a vacuum, all the phosphorus distils over, and a residue of
sulphur is left ; but on distilling a mixture of phosphorus and phos-
phorus trisulphide in the same way, phosphorus distils over and carries
with it some of the trisulphide and a residue of the tiisulphide is
left. The heat developed by the union of Pg with S3, 18*4 cals., is
sufficient to account for the explosion which accompanies combination,
for since the specific heat of the mixture is only about 0*2 and the
combination takes place at about 130°, the temperature of the mass is
suddenly raised to 965°. Solution of iodine in carbon bisulphide
rapidly attacks phosphorus trisulphide, yielding phosphorus tri-iodide,
but has no action on compact red phosphorus, a difference due to
the fact that the formation of phosphorus tri-iodide develops less heat
than the conversion of ordinary phosphorus into red phosphorus.
The phosphorus does not exist in the trisulphide as red phosphorus,
all the latter paving been converted into the ordinary variety at the
moment of combination. C. H. B.
Phosphorus Subsulphide. By H. Schulze (Ber., 16, 2066— 20G8).
— This communication is for tlie most part a polemic directed against
Lemoine, who has recently maintained the existence of phosphorus
subsulphide as a chemical entity. Isambert and the author have,
however, shown that the formation of the subsulphide is not accom-
panied with evolution of heat, and by distillation at 100° in a vacuum
1050 ABSTRACTS OF CHEMICAL PAPERS.
all the phosphorus may be separated from the sulphur. The author
has further shown that the liquid sulphides prepared in accordance
with the assigned formula P4S and P-^S do not solidify as a homo-
geneous mass; from the former, phosphorus, and from the latter,
sulphur separate out. Also the liquids obtained from phosphorus
with excess of sulphur deposit phosphorus on cooling; and by treat-
ment with carbon bisulphide and chloroform can be separated into
their two components. Hence these liquids are solutions of the one
element in the other, and not chemical compounds.
V. H. V.
Preparation of Phosphoric Acid by the Oxidation of Phos-
phorus with Air in Presence of Moisture. By W. T. Wenzell
(Pharm. J. Trans. [3], 14, 24 — 26). — Some years back Moir sugrgested
that phosphoric acid could be prepared by the oxidation of phosphorus
with moist air; and effected it by placing sticks of phosphorus in
glass tubes contracted at one end, and several of these tubes were
placed in a funnel, the end of which dipped into a flask of water.
i-)oebereiner, with the same object in view, filled a flat porcelain dish
to the depth of an inch with powdered glass, which was nearly
covered with water, sticks of phosphorus being laid on the wet glass,
so as not to touch one another, and the whole covered with a bell-
jar. These processes are not only impracticable but dangerous, on
account of there being no arrangement for regulating the air supply.
The author now suggests the use of infusion jars for this purpose ; the
sticks of phosphorus are laid on the diaphragm, and sufficient water
is poured on to leave half the diameter of the sticks exposed. The
lip of the jar is closed with an india-rubber stopper, whilst the top of
the jar, which is ground even and smooth, is covered with a porous
disc of plaster of Paris, which regulates the air supply. The phos-
phorus soon begins to oxidise, and after a week disappears to the sur-
face of the water; the acid liquid is poured off so as to expose more
phosphorus, and the operation is continued until all the phosphorus
is oxidised. For large quantities, the author proposes the use of
shallow glazed pottery trays which can be covered with a plaster of
Paris tile, the phosphorus being arranged on cross bars and the liquid
run out by means of a tube let in the side. Lead does not answer, on
account of lead phosphate being formed.
The products of the oxidation are phospJioric acid in largest propor-
tion, next phosphorous acid, ozone, and hydrogen peroxide in mole-
cular proportions, and besides these, ammonium nitrate and arsenic
acid are present in the final product. The ozone, hydrogen per-
oxide, and ammonium nitrate are the products of the oxidation due, as
the author suggests, to atomic oxygen, which is set free by the break-
ing up of the ordinary oxygen molecule to supply the phosphorus
atoms with the uneven number of oxygen-atoms required to form phos-
phoic and phosphorus anhydrides. The porous cover to the apparatus
not only permits the gradual admission of air, but also dialyses the
ozone from the hydrogen peroxide ; the former diffuses through and
can be recognised by the odour and by test-paper, whilst the latter
remains within the apparatus, forming the white vapour which is pre-
sent during the oxidation. It runs into the liquid and of course takes
INORGANIC CHEMISTRY. 1051
part in the oxidation ; its presence is rendered evident by agitating
some of the liquid with chromic acid and ether, &c.
The arsenic acid is got rid of by heating for a short time at 160°, when
the arsenic is completely precipitated as metal; at IVO'' and above, the
phosphorous acid is decomposed into phosphoric acid and spontaneously
inflammable hydrogen phosphide. The next operation is the conver-
sion of the phosphorous acid into phosphoric ; the acid solution is
heated to about 130°, a small quantity is reserved, the remainder is
treated with nitric acid until no more nitrous fumes are formed, and
the excess of nitric acid is got rid of by adding the reserved portion
of the acid solution. During this operation, nitric oxide is produced
and acts as a carrier of oxygen as it does in the sulphuric acid cham-
bers, and thus economises the nitric acid ; it is therefore advisable to
add the nitric acid gradually so as to avoid the escape of the nitrous
fumes. The process is tedious. D. A. L.
Thionyl Chloride and Pyrosulphuryl Chloride. By K. Heu-
MANN and P. KoECHLiN (Ber., 16, 1625 — 1631). — Thionyl chloride acts
readily on powdered antimony, with formation of antimony trichloride :
3Sb2 + 6SOCI2 = 4SbCl3 + Sb^Sa + 3SO2. On warming mercury-
diphenyl with an excess of thionyl chloride, an energetic reaction
sets in and a yellowish mass is obtained from which, after the addi-
tion of water, crystals of inercury-phenyl chloride, HgPhCl, can be
isolated, melting at 245°. A small quantity of an oily substance con-
taining sulphur is also formed, giving a splendid blue coloration with
concentrated sulphuric acid. A different reaction takes place with
mercury-dinaphthyl, with formation of jS-chloronaphthalene. By the
action of thionyl chloride on butyric, benzoic, and cinnamic acids, the
corresponding chlorides are produced, and from sodium paratoluene-
sulphonate paratoluene-sulphonic chloride can be obtained. On
passing the vapour of thionyl chloride through a red-hot tube, it is
decomposed according to the equation: 4SOCI2 = SzClj + 2SO2 +
6C1. Its vapour-density at 99"" (steam), 154° (bromobenzene vapour)
and at 442° (sulphur vapour), is respectively 3*95, 3*81, and 2 65,
theory requiring 4-11 for SOCI2 and 274 for fSOCla, showing that
the vapour-density is normal up to 154°, whilst at 442° dissociation
takes place according to the above equation.
In reply to Konowalow (Ber., 16, 1127), the authors state that they
have distilled pyrosulphuryl chloride four times over phosphoric anhy-
dride, and that the boiling point remains constant at 147°, whilst sul-
phuric anhydride at once raises the boiling point. This is explained
by the presence of sulphuric acid in the anhydride. The authors are
of opinion that from the mode of preparation adopted by Konowalow,
the differences between his boiling point and vapour-density determi-
nations and their own are due to the presence of sulphuric acid.
A. K. M.
Blue Rock Salt. By B. Wittjen and H. Precht (Ber., 16, 1454
— 1457). — The blue colour of certain pieces of Stassfurt rock salt has
been ascribed to the presence of a sulphur compound by Ochsenius,
to sodium subchloride by Johnson (Gmelin Kraut, 2, 204), and to the
presence of gases by Bischof {8teinsalzwerke hei Stassfurt j P. Bischof).
1052 ABSTRACTS OF CHEMICAL PAPERS.
The authors prove that the salt contains very minute quantities of
hydrogen and marsh-gas. It does not contain sulphur, neither does
it contain any colouring matter soluble in ether or in carbon bisul-
phide. The authors conclude that the colour is not due to the pre-
sence of any blue colouring matter, but is a purely optical phenomenon.
w. c. w.
Silver Hypophosphate. By J. Philip (Ber., 16, 749—752).—
Six grams of silver nitrate are dissolved in 100 c.c. of nitric acid
(sp. gr. 1-2) diluted with 100 c.c. vrater, and heated on the water-bath.
8 — 9 grams of phosphorus are introduced, when at a little below
100° a violent reaction takes place, the phosphorus being oxidised to
phosphorous, phosphoric, and hypophosphoric acids, of which — if the
phosphorus be maintained in excess, and the reaction stopped as soon
as the violent evolution of gas ceases — the hypophosphoric acid forms
the greater part. As the liquid cools, silver hypophosphate crystal-
lises out, the phosphorous and phosphoric acid remaining in solution.
When silver hypophosphate is heated, it decomposes into metallic
silver and silver metaphosphate. L. T. T.
Iodide of Argentammonium. By A. Longi (Gazzetta, 13, 86).
— Kammelsberg (Pogg. Ann., 48, 151) found that dry silver iodide
absorbed gaseous ammonia, with formation of a white easily decom-
posible substance of the formula 2AgI,NH3. The author, by digesting
silver iodide with ammonia solution (sp. gr. 0*960), obtained another
white compound of the formula NHsAgl. It is easily decomposed
when exposed to the air, or when left in contact with water.
C. E. G.
Hydrates of Baryta. By H. Lescceur (Compt. rend., 96, 1578—
1583). — The author has measured the tension of dissociation of
barium oxide in various states of hydration, with a view to determine
how many definite hydrates of baryta actually exist : At 100° two
definite hydrates exist : the hydroxide BaH202 with practically no
tension of dissociation, and the hydrate BaHsOjjHaO with a tension of
dissociation of about 45 mm. : this hydrate is completely converted
into the hydroxide when heated at 100° in a vacuum. At 76'', the
hydroxide, BaH202, has practically no tension of dissociation, and that
of the hydrate, BaHoOzjHjO, is less than 1 mm. A third hydrate,
BaH202,8H20, however, exists at this temperature, and has a ten-
sion of dissociation of 213 mm. Barium oxide therefore forms three
definite compounds : BaO,H20 ; BaO,2H20, and BaO,9H20, and these
are the only definite hydrates which can exist at 75°. C. H. B.
Hydrates of Baryta. By E. J. Maumen^ (Compt rend., 96,
1730 — 1732). — Barium hydroxide fused at a dull red heat has the
percentage composition BaO 87 49, H2O 12'51, corresponding with the
formula BaO(H20)i.2u. If the hydrate crystallised from water is placed
under a small bell-jar over some of the fused hydroxide until it ceases
to lose weight, it yields the hydrate BaO(H20}2.83. The crystallised
hydrate, dried in a similar manner over this second hydrate, has the
INORGANIC CHEMISTRY. 1053
composition BaO,(H20)8.5. The behaviour of baryta is not excep-
tional : tbe crystallised hydrate of sodium oxide obtained by Terreil
has the composition Na20,(H20)3.44, and by fusion in a platinum cru-
cible it yields the hydrate Na20,(H20)|.i4. According to the author,
hydrates containing 1 HgO are very rarely formed. C. H. B.
Platinised Magnesium as a Reducing Agent. By M. Ballo
(Ber., 16, 694). — Pure water is not decomposed by magnesium, but if
a trace of platinum chloride be added, decomposition takes place
freely. The author recommends this as a very useful reducing agent
for organic substances. L. T. T.
Dried Alum. By E. Bailey (Pharm. J. Trans. [3], 13, 838—839).
— There has been some contention with regard to the dried alum
of the B.P. ; some say that it is almost insoluble in water, but
recovers its solubility on boiling, others contend that it is slowly but
completely soluble in water. From several experiments, the author
comes to the following conclusions : — 1. That commercial dried alum
almost always leaves some insoluble residue varying from 65 to 0*5
per cent. 2. That boiling increases the quantity of insoluble matter.
3. That when alum is dried carefully, not exceeding the limit allowed
by the Pharmacopoeia (400° F.), a freely but slowly soluble product
is obtained ; and he therefore asserts that dried alum ought to be
soluble, the insolubility being solely due to carelessness in prepara-
tion.
Judging from his samples, he remarks that it is apparent that
potassium alum has replaced ammonium alum in the preparation in
commerce. D. A. L.
Thorium Sulphate. By E. DEMARgAY (Gompt. rend., 96, 1859 —
1862). — A dilute neutral solution (0'5 per cent.) of thorium sulphate
becomes turbid when heated, and at ] 00° deposits a flocculent basic
salt, the formation of which is prevented by the presence of a very small
quantity of free acid. The composition of this salt has not yet been
determined. A solution of the crystallised sulphate, Th(S04)t,9H20,
in 10 or 15 times its weight of water, is converted at 60^ into a spongy
mass which if heated at 100° for 24 — 48 hours, changes to a pulveru-
lent precipitate, which no longer dissolves on cooling. This precipi-
tate has the composition 3Th(S04)22H20 + Th(S04)0,2H20. The
quantity of thorium remaining in solution is very small, and varies
with the proportion of water present, and with other conditions. The
formation of the basic salt is prevented to some extent by the presence
of 3 — 4 per cent, of free acid. The basic salt when once formed
is almost unaltered by cold water, and is only slowly attacked by acids.
The solubility in water of the hydrate, Th(S04)«,9H20, increases
with the temperature up to 55°, at which point the solution l>ecomes
turbid. The hydrate, Th(S04)2,4HaO, described by Chydenius, and
probably identical with the hydrate, 2Th(S04)2,9H20, of Delafontaine,
is readily obtained by heating the preceding hydrate for some time at
100" in presence of dilute sulphuric acid (5 per cent.). The solubility
of this hydrate diminishes as the temperature increases from 17° to
1054 ABSTRACTS OF CHEMICAL PAPERS.
100°, but above 60° the results are affected by the decomposition of
the salt. It would appear that a solution of the hydrates of
thorium sulphate contains, at a given temperature, a definite quantity
of each hydrate, the relative proportions of the different hydrates
depending on the temperature. C. H. B.
Solubility of Cupric Sulphide in Alkaline Thiomolybdates.
By Debrat (Compt. rend., 96, 1616 — 1617). — Cupric sulphide dis-
solves somewhat easily in solutions of alkaline thiomolybdates, the
maximum solubility corresponding with the formation of a definite
cupric thiomolybdate. On adding hydrochloric acid to the solution,
copper thiomolybdate is precipitated. Prolonged boiling of a solu-
tion of cupric sulphide in ammonium thiomolybdate causes the pre-
cipitation of a crystalline double copper ammonium thiomolybdate,
slightly soluble in water. This double thiomolybdate is green by
reflected, red by transmitted, light. C. H. B.
Colloidal Copper Sulphide. By L. T. Wright (Ber., 16, 1448).
— A question of priority.
Hydrogen Gold Chloride. By J. Thomsen (Ber., 16, 1585—
1587). — According to previous researches of the author, this compound
crystallises with 4 mols. HyO (Ber., 10, 1683) ; whereas, according to
Schottlander (this vol., p. 853), it contains only 3H2O. The author
has repeated his experiments, and finds that hydrogen gold chloride
does crystallise with 4H2O, but that it gradually loses 1 mol. on
exposure to dry air. A. K. M.
Separation of Gallium. By L. de Boisbaudran (Compt. rmd.,
96, 1696—1698, 1838— 1840).— i^rojri lridmm.—(l.) The galliunr is
precipitated by potassium ferrocyanide in presence of a large excess
of hydrochloric acid, the precipitate decomposed by potash, dissolved
in hydrochloric acid, and the precipitation repeated two or three times.
(2.) The gallium is precipitated from a hot solution by cupric hydr-.
oxide, the traces of iridium in the precipitate being removed by repeated
precipitation. (3.) Metallic copper and cuprous oxide may be used
instead of cupric hydroxide. (4.) The chlorides or sulphates of
gallium and iridium are carefully heated to dull redness with a con-
siderable excess of potassium hydrogen sulphate, and the mass dissolved
in boiling water. The cold solution is then nearly neutralised with
potash and allowed to stand, when the greater part of the iridium is
precipitated as iridium potassium sulphate (this vol., p. 905). The
precipitate is washed with a slightly acid solution of potassium sul-
phate, and the filtrate and washings are mixed, almost neutralised
with potash, and boiled for 15 to 30 minutes in contact with the
air. The liquid is then rendered alkaline and the boiling continued
for some time, when iridium oxide is precipitated and gallium remains
in solution. Traces of gallium in the precipitate are removed by
repetition of the process.
From Buthenium. — (1.) The ruthenium is precipitated as sulphide
by passing hydrogen sulphide for some time into the boiling solution
INORGANJC CHEMISTRY. 1055
strongly acidified with hydrochloric acid. The precipitate is washed
with a solution of hydrogen sulphide acidified with hydrochloric acid.
(2.) The solution is mixed with a slight excess of potassium hydroxide
and boiled for some time. The precipitate is dissolved in hydro-
chloric acid, and the precipitation repeated two or three times in order
to remove traces of gallium. The gallium is precipitated from the
filtrate by cupric hydroxide. (3.) The gallium is precipitated as
ferrocyanide in presence of a large excess of hydrochloric acid. If
the ruthenium and gallium exist in an insoluble substance, the latter
is fused at a dull red heat in a gold crucible with a mixture of potas-
sium nitrate and liydroxide, the fused mass treated with water, the
solution acidified with hydrochloric acid and boiled, and the ruthenium
and gallium separated by one of the three methods.
From Osmium. — The osmium is precipitated as sulphide by passing
hydrogen sulphide for some time into the strongly acid solution,
which is gradually heated to boiling. The filtrate, even if colour-
less, may retain traces of osmium, which are removed by evaporating
the liquid to a small bulk (a slow current of hydrogen sulphide being
passed through), then adding a small quantity of solution of hydrogen
sulphide, and filtering off the precipitate. This method is applicable
to both osmic acid and osmic chloride.
From Arsenic. — The arsenic is precipitated as sulphide from the
strongly acid solution, and the precipitate is washed with dilute
hydrochloric acid.
From Selenium. — The selenium, which should be in the state of
selenious acid, is either precipitated as sulphide from a hot strongly
acid solution, or is reduced by passing sulphurous anhydride into the
hot solution acidified with hydrochloric acid. C. H. B.
Oxidation of Titanic Acid. By A. Piccini {Gazzetta, 13, 57 —
G5). — Pure titanic acid prepared from rutile, or from the tetra-
chloride by precipitation with ammonia, is dissolved in sulphuric acid,
and digested in the cold with pure crystallised barium peroxide in
excess, which may be recognised by the solution containing hydrogen
peroxide. The deep-red solution thus obtained is filtered to remove
barium sulphate, and partially precipitated with an alcoholic potash
solution (1 : 10) ; this precipitate, when washed and dried, is of a deep
yellow colour. On adding more potash solution to the filtrate, a pre-
cipitate is thrown down which is more flocculent than the first, and
when dried forms a bright yellow powder, with a slightly greenish
tinge. These both contain water and titanic acid, with excess of
oxygen, which they lose when strongly heated, leaving titanic acid
behind. On boiling them with water, oxygen is evolved, and a white
powder is left. They dissolve in sulphuric acid, yielding solutions of
the colour of potassium dichromate, and with hydrochloric acid they
evolve chlorine. The sulphuric acid solution may be concentrated by
slow evaporation, but at a certain stage oxygen begins to be evolved
and the solution is gradually decolorised, and a white gelatinous mass
is left. With hydrofluoric acid the precipitates give colourless solu-
tions containing hydrogen peroxide. The sulphuric acid solution
gives a white precipitate of normal potassium fluotitanate with potas-
1056 ABSTRACTS OF CHEMICAL PAPERS.
smm flnoride ; a yellowisli precipitate "with disodiam phosphate, pro-
vided the solution be not too acid ; liberates iodine from alkaline
iodides; and decolorises potassium permanganate with liberation of
oxygen.
The proportion of oxygen to titanic acid was determined either by
the amount of permanganate required to decolorise the solution, or
by means of ammonioferrous sulphate, the titanic acid being sub-
sequently precipitated by boiling the dilute solution ; or the estimations
were made directly by heating the substance in a vacuum, measuring
the amount of oxygen evolved, and weighing the residue of titanic
acid. In this way it was found that the first precipitate of a deep
yellow colour contained about 5'Oper cent, oxygen, corresponding with
the ratio 4Ti02 : 0, whilst the second pale yellow precipitate contained
10 per cent., corresponding with 2Ti02 : 0. This applies only to the
freshly-prepared precipitates : if they are dried they lose oxygen, the
deep yellow precipitate ultimately approximating to the ratio 5Ti02 : 0.
The author also obtained another compound, in which the ratio was
3TiO : 0.
When pure hydrogen peroxide solution is added to a solution of
titanic acid, or of either of the two yellow precipitates in sulphuric acid,
until it is in very slight excess (as may be seen by the fugitive bluish
cloud produced on testing it with a drop of potassium dichroraate
solution), a red liquid is obtained, in which the proportions of titanic
acid and oxygen are represented by Ti02 : 0.
If we leave out of consideration the water present in these various
compounds, we have the following series of acids : —
4Ti02,Ti02 = TisOii.
3Ti02,Ti03 = Ti409.
2Ti02,Ti03 = TiaO,.
Ti02,Ti03 = TisOs.
TiOa.
These results establish the existence of coloured unstable com-
pounds in which titanic acid is combined with more or less oxygen,
and the author is inclined to place titanium in the periodic system,
thus:
Ti. y. Cr.
It is known that the vanadates are coloured red by hydrogen per-
oxide, and the study of this reaction may possibly reveal the existence
of a peroxide more stable than that of titanium. C. E. G.
Atomic Weight of Antimony. By J. Bongaril (Ber., 16, 1942
— 1945). — The author at the commencement of his paper reviews the
various methods proposed for the determination of the atomic weight
of antimony, their incidental errors, and their results. The process
adopted by him consists in the oxidation of the sulphide by ammo-
niacal hydrogen peroxide as suggested by Classen (this vol., p. 934),
and precipitation in the form of barium sulphate. Metallic antimony
was first prepared by the electrolysis of a solution of the sulphide in
excess of ammonium sulphide, and purified by fusion with sodium
INORGANIC CHEMISTRY. 1057
carbonate. The regulus was washed with dilate hydrochloric acid,
cleansed with sand, and dried. The metal was dissolved in potassium
sulphide, and the solution precipitated with sulphuric acid. The pre-
cipitated sulphide was then oxidised by hydrogen peroxide, in an
apparatus of the form proposed by Classen, and the solution precipi-
tated by barium chloride. The results of twelve determinations
(Ba = 136-8, S = 31-98, 0 = 15-96) gave a mean of 120-193, the
number varying from a minimum 120*09 to a maximum 120-39.
V. H. V.
Chemistry of the Platinum Metals. By T. Wilm (Ber., 16,
1524 — 1531). — This is a continuation of work previously published by
the author (Abstr., 1880, 854, and 1881, 514). On treating preci-
pitated platinum residues with chlorine and sodium chloride according
to Wohler's method, a black powder is obtained which resists further
action of these reagents. It is readily acted on by fused sodium car-
bonate, and on exhausting the melt with water, filtering, and evapo-
rating, a grey powder is obtained soluble in hydrochloric acid. After
oxidising the solution with nitric acid and adding ammonium chloride,
a crystalline precipitate can be obtained on evaporation, which is pro-
bably a mixture of ruthenium ammonium chloride and iridium ammo-
nium chloride. On treating the insoluble residue from the melt with
hydrochloric acid, a portion is dissolved, yielding a solution from
which a double salt of ammonium chloride can be obtained forming
blackish-violet crystals closely resembling those of iridium ammonium
chloride. The mother-liquor yields, on evaporation in a desiccator,
brownish -yellow crystals, consisting of a double salt of iron with a
platinum- metal (ruthenium ?). The blackish- violet crystals above-
mentioned are, however, distinguished from the iridium salt by their
greater transparency, by their more ready solubility in water, and by
certain reactions, such as that with ammonia. Its properties also
do not agree with those of ruthenium ammonium chloride. The
abnormal reactions are probably due to the presence of a peculiar
compound of rhodium and iron, and perhaps of an unknown metal.
A. K. M.
Violet Iridium Sulphate. By L. de Boisbaudran (Gompt. rend.,
96, 1551 — 1552). — The pale blue colour produced by adding potas-
sium hydroxide to a cold solution of green iridium sulphate (this
vol., p. 905) is due to the formation of a bulky pale blue precipitate
which contracts to a greenish powder, and gradually becomes blue-
violet in colour. This change of colour is due to oxidation. When a
boiling solution of potassium hydroxide is added to a boiling solution
of the green iridium sulphate, only a very faint violet tint is at first
produced, but if the liquid is agitated in contact with air, the blue-
violet colour is gradually developed. The change of colour does not
take place in an atmosphere of hydrogen, and if a current of hydrogen
is passed through the liquid containing the blue-violet oxide, the
latter is decolorised. Sulphurous acid changes the colour of the blue-
violet sulphate to blue, and finally decolorises it. An aqueous solu-
tion of the deep violet sulphate becomes almost colourless on prolonged
VOL. XLIV. 4 b
1058 ABSTRACTS OF CHEMICAL PAPERS.
boiling, but on adding potassium hydroxide tbe colour reappears and
an abundant blue-violet precipitate is formed, soluble in dilute
sulphuric acid. The same changes take place in the cold, although
more slowly.
Hydrochloric acid dissolves the blue-violet oxide, forming a deep
violet liquid, which gradually becomes blue, then green, and finally
orange-yellow, the change being accelerated by heat. If the blue-
violet oxide is dried, or is subjected to prolonged ebullition, it
becomes partly insoluble in dilute sulphuric acid. C. H. B.
Contributions to the Chemistry of the Khodammoninm
Compounds. By S. M. Jorgensen {J.pr. Chem. [2], 27, 433—489).—
I. C hloropurpureorhodiam Salts. — C hloropurpureorhndium chloride^
Cl2(Rh2,lONH3)Cl4, is prepared by evaporating a solution of rhodium
chloride and ammonium. It crystallises best from a solution con-
taining a trace of free hydrochloric acid, when it forms small yellow
rhombic crystals isomorphous with the corresponding cobalt salt
(sp. gr. at 18*4, 2*075). They can be heated for a day at 100°
without losing weight. When heated in dry chlorine, they yield
rhodium chloride ; in dry hydrochloric acid gas metallic rhodium is
produced. Chloropurpureorhodium chloride does not part with all
its chlorine when treated with silver nitrate. When ground with an
excess of freshly precipitated silver oxide, it yields a strongly alkaline
yellow solution, containing chloropurpureorhodium hydroxide and
traces of roseorhodium hydroxide ; the former is a base resembling
potassium hydroxide, and when heated yields a mixture of roseo-
rhodium chloride and roseorhodium hydroxide. Roseorhodium salts
are very readily detected by means of potassium ferrocyanide.
Chloropurpureorhodium nitrate^ Cl2(Rh3,10NH3)4NO3, is prepared by
pouring a hot solution of the chloropurpureo- chloride into well-cooled
concentrated nitric acid. The precipitate so obtained consists of
small octohedral crystals. They are only sparingly soluble in water.
When boiled with soda solution they form the roseo-salt. Chloro-
purpureorhodium- silicofluoride, Cl2(Rh2,10NH3)2SiF6, is obtained when
a hot solution of the chloride (60°) is filtered into an excess of strong
hydrofluosilicic acid. It forms glittering rhomboidal plates of a
straw-yellow colour. It is isomorphous with the corresponding
cobalt and chromium salts. The salt remains unaltered at 100° ; and
when heated to redness it leaves rhodium oxide. Chloropurpureorhodium
platinochloride, Cl2(Rh2lONH3),2PtCl6, is a buff-coloured precipitate
insoluble in cold water. It is isomorphous with the corresponding
cobalt and chromium salts. Chloropurpureorhodium sulphate^ the
acid salt, 2Cl2(Rh2,10NH3)2SO4,3H2SO4, is prepared by grinding the
chlorochloride with concentrated sulphuric acid. On diluting the
mixture and allowing it to cool, glittering yellow prismatic crystals
separate out. They are slightly soluble in cold water. The normal
salt, Cl2(Rh2,10NH3)2SO4,4H2O, is obtained by neutralising the chloro-
purpureo-hydroxide with dilute sulphuric acid. It crystallises in
sulphur-coloured prisms. Chloropurpureorhodium carhonahf
Cl2(Rh2,10NH3)2CO3,2H2O,
TNORGANIC CHEMISTRY. 1059
is prepared by grinding the chlorochloride with silver carbonate
freshly precipitated from an acid solution. It forms a bright yellow
crystalline powder.
II. Bromopurpureorhodium Salts. — Bromopurpureorhodiwn hromide,
Br2(Rh2,10NH3)Br4, can be prepared by heating rhodium zinc with a
solution of bromine in hydrobromic acid, and subsequently proceeding
as in the preparation of the chloro-compound. It is more con-
veniently obtained by treating the basic roseorhodium salt, formed by
heating the chloropurpureo-chloride with soda solution, with hydro-
bromic acid, and then heating the roseorhodium bromide so formed
at 100°, or boiling the aqueous solution. The bromo-bromide forms
yellow rhombic crystals. It is more sparingly soluble in water than
the chloropurpureo-chloride. It only loses traces of hygroscopic
moisture when heated at 100°. It closely resembles the chloro-
purpureo-chloride in all its reactions. Bromopurpureorhodium nitrate,
Br2(Rh2,10NH3)4NO3, is prepared in. a similar manner to the chloro-
purpureo-salt. It crystallises from water in large octohedra. Bromo-
purpureorhodium silicofluoride, Br2(Rh2,10NH3)2SiF6, is prepared in a
similar manner to the chloro-compound. The platino-hromide is
obtained by filtering a solution of the bromo-bromide into sodium
platino-bromide.
III. lodopurpureorhodium Salts. — lodopurpureorhodium iodide,
l2(Rh2,10NH3)l4,
is prepared by treating a solution of roseorhodium hydroxide with
hydriodic acid, and heating the mixture for about two hours on a
water-bath. When pure, it forms small rhombic crystals with a
colour resembling that of potassium dichromate. They are more
soluble in hot water than in cold. When boiled with soda, it is con-
verted into the roseo-salt. On triturating it with moist silver oxide, a
strongly alkaline yellow solution is obtained, which doubtless con-
tains iodopurpureo-hydroxide.
lodopurpureorhodium chloride, l2(Rh2,10NH3)Cl4, is, when dry,
a dark yellow crystalline powder. It is freely soluble in hot water,
but insoluble in hydrochloric acid and in alcohol. lodopur-
pureorhodium nitrate, l2(Rh2,10NH3,)4N"O3, is prepared by filt ring
a solution of the iodochloride into dilute nitric acid. It crystal-
lises from hot water in small octohedra. lodopurpureorhodium silicon
fluoride, l2(Rh2,10NH3)2SiF6, is formed when a warm solution of the
iodochloride is filtered into strong cold hydrofluosilicic acid. It
forms bright glittering yellow plates, which are almost inFolnble in
cold water. lodopurpureorhodium platino-iodide, l2(Rh2,10NH3)2Ptl6,
is prepared by treating the iodochloride with calcium platino-iodide.
It forms a black precipitate consisting of masses of small crystals.
It is quite insoluble in water and in alcohol. lodopurpureorhodium
sulphate.— The hydrated normal salt, l2(Rh2,10NH3)2SO4 + 6H2O, is
obtained by grinding together 3*6 grams of precipitated iodochloride
and 10 grams of concentrated sulphuric acid ; the product is then
dissolved in 40 c.c. of water, and 1 c.c. of alcohol added to the solution.
After 24 hours large orange-yellow crystals separate out. The anhy-
4 6 2
1060 ABSTRACTS OF CHEMICAL PAPERS.
droiis salt is formed wlien a larger quantity of alcohol is present. It
forms orange-yellow quadratic plates.
IV. Ilichlornpyridine Rhodium Salts. — Dichlorotetrapyridine-rhodium
chloride^ CUCRhjjSCsHjNjClg, is prepared by dissolving rhodium-zinc
in aqua regia, and, after removing the nitric acid, heating the aqueous
solution with pyridine ; on cooling, the solution deposits the pyridine
salt in yellow prisms. The salt melts when heated and forms a black
oil, which leaves metallic rhodium on being heated to redness. When
the salt is ground with freshly precipitated moist silver oxide, ii/
yields a yellow strongly alkaline solution containing dichlorotetra-
pyridine-rhodium hydroxide ; this absorbs carbonic anhydride from
the air, and evolves ammonia from solutions of its salts. The dichloro-
nitrate, Cl4(Rho,8C5H5]S')2N03, is obtained by filtering a solution of
the chloride into dilute nitric acid. The dichloro-hroTnide,
Cl4(Rh2,8C5H5N)Br2,
is prepared in a manner similar to the nitrate. The dichloro-sulphate,
Cl4(Rh2,8C5H6N)S04, is precipitated from a saturated aqueous solution
of the chloride on adding dilute sulphuric acid. It can also be pre-
pared in a manner similar to iodopurpureorhodium sulphate. The
platinochloride, Cl4(Rh2,8C5H5N)PtCl6, forms a buff-coloured crystal-
line powder.
V. The Atomic Weight of Rhodium. — Chloropurpureorhodium
chloride and the corresponding bromine compound can be readily
prepared in a state of great purity ; and as the other elements which
they contain, in addition to rhodium, are such as have had their
atomic weights accurately ascertained, the author considered that
they offered an excellent opportunity to determine the atomic weight
of rhodium. The amount of rhodium contained is readily determined
by simply heating in the air, and afterwards in hydrogen and carbonic
anhydride. The mean result of five determinations made by the
author gives 103 04 as the atomic weight of rhodium. J. I. W.
Mineralogical Chemistry.
Application of a Solution of Barium and Mercury Iodide to
Petrographical Purposes. By C. Ron reach (Jahrh. f. Min., 1883,
2, Mem., 186 — 188). — Instead of a solution of mercury iodide with
the alkali iodides, the author employed a solution of barium-mercury
iodide for the preparation of heavy solutions, for which a still higher
sp. gr. than that of Thoulet's solution was to be expected, seeing that
the atomic weight of barium is so much greater than that of potas-
sium. In practice he found that the new solution gave a maximum
sp. gr. of 3-588. B. H. B.
Optical Properties of Nocerine. By E. Bertrand {Jahrh. f.
Min., 1883, 2, Ref., 160). — Nocerine is the name given by Scacchi to
MINER ALOGIOAL CHEMISTRY. 1061
the double fluoride of calcium and magnesium. It occurs in extremely
small hexagonal crystals, which the author observed to be optically
uniaxial and negatively double refracting. B. H. B.
Analyses of Magnetic Pyrites. By C. Bodewig (Jahrh. f. Min.,
1883, 2, Ref., 161). — The author found that freshly distilled carbon
bisulphide dissolved O'Ol to 0*021 gram of sulphur from 10 grams of
the magnetic pyrites from Bodenmais, while the magnetic pyrites
from Schreibershau and crystallised magnetic pyrites from Pallanza
gave up no sulphur. The magnetic pyrites from the three localities
were treated with carbon bisulphide, dried, and very carefully
analysed. The results were as follows : —
1. Magnetic pyrites from Bodenmais contained 38*45 per cent, of
sulphur and 61*53 per cent, of Fe, corresponding to the formula
2. Magnetic pyrites from Schreibershau, in Silesia, gave 38*560 per
cent, sulphur, 61*325 Fe, and 0*290 Co. Then Fe + Co : S =
1*1019 : 1*2057 = FenS,2.
3. Magnetic pyrites from Pallanza gave 38*75 percent. S, 60*59 Fe,
0*63 Co. Then Fe + Co : S = 1*0964 : 1*2117 = FenSi^.
B. H. B.
Tinder Ore from the Harz. By 0. Luedecke (Jahrh. /. Min.,
1883, 2, Mem., 116— 118).— Tinder ore is found at Clausthal and
St. Andreasberg in the Upper Harz, and at Wolfsberg in the Lower
Harz. Hausmann regarded it as a mixture of 82*04 plumosite,
13*46 mispickel, and 4*3 red silver ore. Roesing (Abstr., 1881, p. 24)
regarded it as a lead antimony sulphide, and showed that the analysis
agreed with the formula Pb4Sb6S;7, the lead being partially replaced
by Cu, Fe, Ag, and Zn. He inferred that it was the final product of
the decomposition of an autimonial galena. The author, after a
microscopic examination of the tinder ore from Clausthal, comes to
the conclusion that it is not a mixture, but a distinct mineral, the com-
position of which is expressed by the formula (PbAgFeZnCu)4Sb6Si7.
B. H. B.
Brucite from Cogne. By C. Friedel (Jahrh. f. Min., 1883, 2,
Ref , 161). — The analysis of the brucite from Cogne, in the Aosta
Valley, after the removal of a small amount of silica, gave the
following results : —
MgO.
FeO.
H3O.
Total.
68*53
1-15
30-18
99*81
B. H. B.
Brucite. By A. Weisbach (Jahrh. /. Min., 1883, 2, Mem., 119—
120). — A boiler incrustation from Zwickau gave on analysis the
following results : —
MgO.
Fe^Og.
SOj.
SiOj.
H2O.
Total.
66-09
0*31
3*49
1*31
28*80
100*00
This represents 93*15 per cent, of magnesium hydroxide, so that
brucite is the main constituent.
1062 ABSTRACTS OF CHEMICAL PAPERS.
The feed-water of the boiler contained 0*5306 per cent, of fixed
constitaents, the greater portion of which was magnesium chloride.
B. H. B.
The Inclusions in Sapphire, Ruby, and Spinel. By W.
Prinz {Jalirh. /. Min., 1883, 2, Ref., 156— 157).— The sapphire
contains niimerons inclusions of liquid carbonic anhydride in large
cylindrical cavities, the longitudinal axis of which is perpendicular
to the main axis of the crystal or in the form of the crystal itself. In
the ruby these large fluid inclusions are almost entirely wanting.
Small ones occur only to a slight extent; they also contain liquid
carbonic anhydride. In the inclosed fluids crystal needles, small
opaque hexagonal tablets, and more rarely tetrahedrons are met with.
On the other hand, as Sorby showed, the ruby is very rich in solid
enclosures. Sorby distinguished four varieties, which may, according
to the author, be referred to two kinds : (1) rutile, and (2) doubly
refracting round grains, rhombohedral and columnar crystals, which
are regarded as microscopic rubies and sapphires according to their
colour. The spinel is characterised by frequently enclosing two fluids
which do not mix, a colourless one and a dark orange one. These
fluids frequently contain small cubes, doubly refracting prismatic crys-
tals, and an opaque black substance. The yellow fluid appears to be
viscous, and is regarded as a very concentrated salt solution. The
colourless fluid does not expand like liquid carbonic anhydride. When
heated strongly, the yellow fluid becomes converted into an aggregate
of doubly refracting crystals, while the colourless fluid is enclosed in
drops in the yellow material. . When heated more slowly, the crystals
thus separated out dissolve, and the isolated drops of the colourless
fluid combine again. At a lower temperature, the yellow fluid again
crystallises. B. H. B.
Artificial Production of Barytes, Celestine, and Anhydrite.
By A. GoRGEU (Compt. rend, 96, 1734— 1737).— The artificial pro-
duction of hausmannite (this vol., p. 859) is not impeded by the
presence of iodine or bromine, or of the chlorides of the alkalis or
alkaline earths, and the product retains only very small quantities of
these foreign substances. The sulphates of barium, strontium, and
calcium dissolve quickly in many fused metallic chlorides, and by
gradually cooling the fused mass and extracting the residue with
water, barytes, celestine, and anhydrite are obtained in crystals iden-
tical in form and properties with those of the natural minerals. The
crystals contain no chlorine, and the aqueous solution of the fused
mass is free from more than traces of the alkaline earth.
C. H. B.
Optical Properties of Cobalt Carbonate. By E. Bertrand
(Jahrb.f. Min., 1883, 2, Ref., 161). — The small rhombohedrons of this
mineral are optically uniaxial with negative double refraction, A sec-
tion parallel to c showed distinct pleochroism. B. H. B.
New Locality for Hayesine, and its Novel Occurrence. By
K. H. Harton (Amer. J. Scl, 1882, 23,458—459; Jahrb.f. Min.,
1883, 2, Ref., 161— 162).— Hayesine occurs at Bergen Hill, New
MINER ALOGIOAL CHEMISTRY. 1063
Jersey, with datholite and calcite in cavities in the trap rock. The
analysis gave the following results : —
SiOg. NaaO. MgO.
CaO. B2O3. H2O. ^ , ' Total.
18-39 46-10 35-46 trace 99-95
The sp. gr. was between 1-5 and 1*7. The analysis corresponds to
the formula : CaBjOT + 3H2O. B. H. B.
Two New Minerals, Monetite and Monite, "VTith a Notice
of Pyroclasite. By C. U. Shepard (Amer. J. ScL, 1882, 23,
400 — 405). — The prevailing rock of the islands of Moneta and Mona,
in the West Indies, is a tertiary limestone covered with guano, and
the two minerals were formed by infiltration. The monetite crystal-
lises in the triclinic system. The general form is that of a thin
rhomboid. The fracture is uneven. The mineral is seraitransparent,
has a vitreous lustre, and a pale yellowish-white colour ; H. = 3-5 ;
sp. gr. = 2-75. The chemical analysis corresponds to the formula :
2CaO,H20,P205.
The analysis of monite corresponded to the formula CaaPjOg 4- H2O.
This mineral resembles kaolin in colour and density. Its fracture is
earthy ; hardness below 2, and sp. gr. 2-1. Before the blowpipe it
melts with difficulty to an opaque white enamel.
Two stalactites oi pyroclasite were found in the same caves as monite
and monetite. They strongly resemble the impure stalactites of our
limestone caves. The sp. gr. is 262, H. 3*5 — 4. Before the blowpipe
it decrepitates, emits a decidedly organic odour, and fuses to a white
enamel. The chemical analysis corresponds with the formula :
3(Ca2H2P208) + CaaPaOs + H2O.
Whether this forms a true mineral species, or is only a mechanical
mixture of monetite and monite, must be determined by more extended
examination. B. H. B.
Analysis of a Pyromorphite from Zahringen in Baden. By
0. Baerwald (Jahrb. f. Min., 1883, 2, BeL, 152).— This mineral
occurs in a concentric aggregate covered by a brown layer. It has
been called eusynchite. The analysis g:ave : —
SiOa.
PbO.
ZnO.
V2O3.
PsOfi.
AI2O,.
CaO.
a. Total
3-70
76*39
1*39
305
11*24
1*93
0-21
1-40 99-31
B. H. B.
Analysis of Crocoisite. By C. Baerwald (Jahrh. f. Min.^ 1883,
2, Ref., 152). — The analysis of crocoisite from Berjosowsk gave the
following results : —
PbO. CrsOg. Total.
68-82 31-16 99 98 B. H. B.
Notes on some North Carolina Minerals. By W. E. Hidf.en
{Jahrl. f. Min., 1883, 2, Bef., 148—149; Anier, J. Scl, 1882, 24,
1064 ABSTRACTS OF CHEMICAL PAPERS.
372 — 374). — A remarkable crystal of heryl was found lying loose in
the surface-soil on the land known as Pendergrass land. The large
development of the planes, 3Pf and 4Pf is nnprecedented. Other
planes observed were :— P, 2P, 2P2, OP, ooP and coP2.
The mineral thought to be aeschynite, from Ray's mica mine, Yansey
Co., proves, on analysis, to be columbite.
The sp. gr. of three different specimens of uranite from Mitchell
Co. was found to be 8-968, 9-05, and 9-218.
An analysis was made of the so-called euxenite from Wiseman's
mica mine, with results differing widely from those obtained by J. L.
Smith :—
msOj. SnOa + WOj. ToOg. CegOg. DLOg + la^O^
47-09 0-40 13-46 1-40 4-00
U2O3. FeO. CaO. HgO. Total.
15-15 709 1-53 9-55 9967
The so-called euxenite is probaWy only altered samarekite.
An analysis of the fergusonite from the Brindletown gold placer
gave the following results : —
43-78 4-08
SnOs + WO3.
0-76
Y2O3, &c.
37-21
CejOa.
0-66
DigOg + LasOg.
3-49
UgOj. FeO.
5-81 0-65
H2O.
1-62
Total.
99-87
The form occurring is a very acuste octohedron. The colour is brown-
black, and sp. gr. 5"87.
The author has lately found allanite at two new localities, at the
beryl locality and at Wiseman's mica mine. The mineral occurs in
small well-polished prisms of a light brown colour in the felspar of
the gneiss, and contains 14 per cent. LagOa. B. H. B.
New Sublimates from the Crater of Vesuvius. By A.
ScACCHi (JaJirh.f. Min., 1883, 2, Ret, 157— 160).— Among the subli-
mates from Vesuvius in October, 1880, the author found four new
ones on the same slag. The most important is of a bright blue colour,
and mixed with this is always a white substance of granulai* structure,
the former often covering the latter, A third species spreads over the
slag in the form of a layer 2 to 4 mm. thick, formed of a white crys-
talline mass resembling cork. It appears to be a variety of hornblende.
The fourth species consists of very thin yellowish-brown crystals
firmly fixed to the &lag or mixed with the other minerals. The white
granular substance consists of amorphous, transparent, infusible and
hard grains. At a red heat it loses 0-51 to 0-/2 per cent. HoO ; sp. gr.
= 2-287. All the reactions in the dry way indicate SiOj. The author
does not regard this mineral as opal, but as a special kind of amor-
phous silica. Silica has, up to the present time, rarely been observed
at Vesuvius. It was found only in 1767, 1794. and 1860.
From the examination of another specimen formed in April, 1882,
MINERALOGICAL CHEMISTRY. 1065
the author comes to the conclusion that the mineral is identical with
the variety of silica which is obtained on decomposing silicates with
acids, and for which he suggests the names of granuline.
B. H. B.
Calculation of Analyses of Augites and Amphiboles from Pin-
land. Bj A. Kenngott (Jahrh.f. Min., 1883, 2, Mem., 171—172).—
From the analyses given by Wiik (Abstr., 1883, 560) of augites aud
amphiboles from Finland, the author calculates that they correspond
with the generally accepted formula R0,Si02. B. H. B.
Formation of Bauxite and of Pisolitic Iron Ore. By S. Meu-
NiER {Gompt. rend., 96, 1737 — 1740). — Bauxite and pisolitic iron ore
have probably been formed by the action of marble or limestone on
water holding aluminium and ferric chlorides in solution. This reac-
tion can readily be produced on a small scale. The aluminic and
ferric chlorides are probably formed by the action of superheated water
charged with chlorides on the rocks in the interior of the earth ; this
water would also dissolve from the older rocks the small quantities of
titanium and vanadium usually found in bauxite, and might carry up
with it the granitic sand with which bauxite is frequently associated.
The clay mixed with the bauxite or limonite may have been formed
by the alteration of limestone or by the partial decomposition of
felspathic rocks. C. H. B.
Notes on some Interesting Minerals Occurring near Pike's
Peak, Colorado. By W. Cross and W. F. Hillebrand {Amer. J.
8ci., 1882, 24, 281— 286).— The following minerals have been found
in this region : — Microcline, albite, biotite, quartz, fluorspar, colum-
bite, gothite, haematite, limonite, arfvedsonite, astrophyllite, and
zircon. The authors can now add to this list topaz, phenacite, cryolite,
thomsenolite, and others not yet fully determined.
Three crystals of topaz have been examined, all of them remarkable
for size and clearness. In the most perfect one the prisms ooP and
ooP^ are not developed. The terminations are drusy ; the pyramid
2P has been recognised with certainty, while fp and 2P4 are pro-
bably also present. The sp. gr. is 3*578, and the chemical composition
normal.
The two crystals of phenacite examined were found together. The
forms appearing have been identified as R, — -JR, — B, and f P2. The
crystallographic determination of these crystals as phenacite is con-
firmed by the chemical analysis and physical characteristics. There
is an imperfect cleavage parallel to coP2. The crystals are clear and
colourless ; H. = 8 ; sp. gr. = 2 967.
Zircon was found in a vein of white quartz in gi*anite. The crys-
tals are of a deep reddish-brown colour, occasionally deep emerald-green.
The crystals are perfectly developed and wonderfully transparent.
The observed forms are P, 3P, 3P3, ooP, and ooPoo. The rare face
OP is less frequently developed, and is constantly accompanied by a
pyramid ^|^P. The chemical analysis of the zircon shows it to be very
pure, and the sp. gr. is 4*709. B. H. B.
1066 ABSTRACTS OF CHEMICAL PAPERS.
Mineralogical Notes. By E. Claassen (Amer. J. 8ci., 1882, 23,
67; Jahrh. f. Mm., 1883, 2, Ref., 151).— 1. Analysis of Orthoclase.
— The orthoclase occurs in crystals on haematite at Isapemeng,
Marquette County, Michigan. The forras observed were ooP and
2Pco. The colour is white, reddish, and red. The reddish and red
crystals contain: —
SiOg. AI2O3. FePg. CaO. MgO.
63-712 17-546 1-644 0714 0-172
K2O. NaaO. PsOj- HaO. Total.
13-807 0-233 0-612 0606 99-046
2. Regular Polyhedral Cavities in Hcpmatite. — The author proves by
measurement of the angles that the cavities observed in the mica-
ceous haematite of Lake Superior once contained crystals of pyrites.
Access of air and water effected their disappearance, and not the
smallest particle of pyrites can now be met with. B. H. B.
Chemical Composition of a Green Mica from Syssert in the
Ural Mountains. By A. Damour {Jahrh. f. Min., 1883, 2, Ref., 180
— 181). — The mineral is of an emerald-green colour, and has a
sp. gr. of 2-88. The analysis gave : —
YolatUe
SiOo. AI0O3. CrOg. FeaOg. MgO. X^O. constituents. Total.
46-17 29-71 3-51 2-03 2-28 10-40 5-42 99-52
B. H. B.
Saussurite. By A. Cathrein (Jahrh. f. Min., 1883, 2, Ref., 177—
179). — The author examined microscopically and chemically a namber
of specimens of saussurite from Tyrol. The study of thin sections
showed that numerous crystals of zoisite or, in some cases, epidote,
occur in a colourless ground-mass. In several specimens, a gradual
transition from zoisite to epidote could be observed. At Wildschonau,
the author observed a gradual transition from saussurite to albite. The
result of his researches is that the so-called saussurite is not a mineral
species, but a mixture of plagioclase, more rarely of orthoclase, with
zoisite, chlorite and other minerals occurring as accessory constituents.
The chemical composition of the saussurite resembles mostly that of
the lime-soda felspar, but is poorer in silica and richer in lime ; saus-
,surite also is distinguished from the members of the albite-anorfchite
series corresponding to it in chemical composition by a much higher
sp. gr. The saussurite is a product of the alteration of the felspars
by an interchange of silica and alkalis for lime, iron, and water. The
conversion of the felspars into epidote is also a process of alteration
which is intimately connected with the genesis of the saussurite, and
which is only distinguished by taking up more iron. B. H. B.
Jadeite. By Krenner (Jahrh. f. Min., 1883, 2, Mem., 173—174).
— From the examination of a nephrite-like mineral from Upper Bur-
mah, the author came to the conclusion that it consisted of nephrite.
This conclusion, however, does not agree with Damour's analyses
MINERALOGIOAL CHEMISTRY. 1067
(Ann. Chim. Phys., 1881), which give a percentage of 21 to 24
of alumiiia and 9 to 14 of soda, thus indicating that the mineral is
jadeite. On comparing Damour's analyses with the author's examina-
tion, he concludes that the so-called jadeite is an entirely new mineral,
a soda alumina augite, having the formula NaaAlaSi^Oiz-
B. H. B.
Nepheline in the Oligoclase of D^nise. By Des Cloizeaux and
Jannettaz (Jahrb. f. Min., 1883, 2, 172— 173).— In the basalt of
Denise in Haute-Loire enclosures of decomposed granite occur, contain-
ing cordierite and also glassy masses containing nepheline in large
grains. Analyses of the nepheline (i) and of the accompanying oligo-
clase (ii) are given : —
Loss on
SiOa. AI2O3.
FeA-
CaO.
MgO.
K2O.
NasO.
ignition. Total.
I. 4318 33-50
—
1-50
—
0-90
18-61
0-80 98-49
II. 62-1 20-2
0-5
0-8
0-4
1-0
12-7
1-4 991
B. H. B.
Idocrase from Kedab6k in the Caucasus. By 0. Korn {Jahrh.
f. Min., 1883, 2, Ref., 170 — 171). — This mineral occurs in greenish-
yellow crystals, and in compact masses in limestone. The following
forms were observed : —
P, 2P, 3P, Poo, 2P2, 3P3, ooP, ooPoo, |P, 4P, f P|, -V-P-V"-
The last four are now observed in idocrase crystals for the first
time. 3P3 often predominates. The chemical analysis gave the fol-
lowing results : —
MnO. KgO.
SiOg. Al,03. FeaOa. CaO. MgO. FeO. '^ y ^ HjO. Total.
36 81 15-46 5-42 3557 366 069 traces 206 99-67
Sp. gr. = 3-25. From this analysis is calculated the formula —
8RO,2R203,7Si02 -f- l^HaO. B. H. B.
Discovery of Fluorine in the Idocrase from Vesuvius. By
P. Jannasch {Jahrh. f. Min., 1883, 2, Mem., 123— 135).— The
analysis of idocrase from Vesuvius gave the following results : —
SiOg. AI2O3. FeA- FeO. MnO. CaO. MgO.
36-81 16-42 300 2-07 0-66 3622 2-17
H2O. F. LiaO. Kp. Nap. Total.
1-57 106 008 trace 0-42 100-48
The presence of fluorine is not confined to the Vesuvian idocrase,
for the author found 1-23 per cent, in the idocrase from Christiansand
in Norway, and 0-23 per cent, in the variety from the River Wilui in
Siberia. He was, however, unable to find any in the idocrase from
the Ala valley, recently investigated by Ludwig and Renard.
B. H. B.
Analysis of a Green Pyroxene from the Diamond Mines of
the Cape. By Jannettaz {Jahrh. f. Min., 1883, 2, Ref., 170).— This
1068 ABSTRACTS OF CHEMICAL PAPERS.
mineral resembles diopside in its optical properties. It has a distinct
basal cleavage. H. = 5'5, and sp. gr. = 3'26. It gave on analysis : —
SiOa. CrsOs. Al^O,. PeO. CaO. MgO. HjO. Total.
52-4 2-8 0-6 6-5 20-5 155 1-5 998
The mineral is, therefore, a chromium-diopside. B. H. B.
Chemical Composition of Walujewite. By D. P. Nicolajew
{Jahrh. f. Min., 1883, 2, Ref., 181— 182).— The analysis of this
mineral gave the following results : —
SiOg. AI2O3. Fe.03. FeO. . MgO. CaO. HgO. Total.
16-39 43-40 1-57 0-60 20-38 13'04 4-39 99-77
Sp. gr. = 3-075. B. H. B.
Nephrite. By W. v. Beck and J. W. v. Muschketow (Jahrh. f.
Min., 1883, 2, Ref., 171 — 172). — The authors give microscopic descrip-
tions and analyses of a large number of nephrites from various locali-
ties, and come to the conclusion that all the nephrites from the
province of Irkutsk and from Turkestan must, from their chemical
composition and sp. gr., be regarded as actinolites and not as diop-
sides. The nephrites from the Jarkand valley may be distinguished
from the Siberian varieties by greater homogeneity in the structure,
by a smaller percentage of FeO and absence of chromite, by enclosures
of diopside, and by a cloudy milky appearance. The Siberian
nephrites, on the other hand, are characterised by the presence of
chromate and limonite and enclosures of asbestos. B. H. B.
Chemical Composition of Diallage. By A. Cathrein {Jahrh.
f. Min., 1883, 2, Ref., 180). — The results obtained from the analysis
of three specimens of diallage were as follows : — I and II are from
Wildschonau in Tyrol, III from Ehrsberg in Baden.
Si02.
TiOg.
AI2O3.
CrsOa. FcaOa
FeO.
CaO.
I.
49-25
0-70
5-60
0-20 045
7-15
21-31
II.
50-41
0-88
4-05
0-60 0-11
6-57
21-34
III.
51-34
0-58
5-35
0-43 0-48
Loss on
4-42
2112
MgO.
K,0.
NasO.
ignition.
Total.
Sp.gr.
I.
1441
0-82
1-86
0-30
102-05
3-343
II.
15-33
0-42
1-55
0-37
101-63
3-337
III.
14-08
0-15
0-84
0-70
99-49
3-178
B. H.
B.
Analyses of Hnmite. By A. Kenngott {Jahrh. f. Min., 1883, 2,
Mem., 174 — 176). — In Sjogren's analyses of minerals of the chrondro-
dite groups (Abstr., 1883, 436), the loss is so great as to render the
analyses unsuitable for the calculation of formulae. They are, however,
valuable in confirming the view that all these minei^ls contain more
than 2R to ISi, if they are compared with olivine, and that the per-
MINERALOGICAL CHEMISTRY. 1069
centage of fluorine is variable and is not, as Rammelsberg states,
essential to the group. B. H. B.
Pseudomorph of Nacrite after Fluorspar, By F. E. Geinitz
(Jahrh. f. Min., 1883, 2, Ref., 160 — 161). — In his memoir on mineral
pseudomorphs (Abstr., 1877, 1, 691), the author described a crystal of
fluorspar partially filled with nacrite. At that time he regarded the
nacrite as originally deposited there. Further studies have now led
him to believe that it is an alteration-product of the fluorspar.
B. H. B.
Analysis of the Mansfeld Copper Slate. By Scheerer (Jahrb.
f. Min., 1883, 2, Ref., 197— 198;.— The analysis of a sample of un-
burnt copper slate from the Ernst mine gave —
Si02.
AiA-
CaO.
MgO.
CO2. Fe. Cu. Ag. S. Bitumen.
33-15
12-90
14-39
2-32
10-47 3-31 2-90 0-016 2-15 9-89
B. H. B.
Dioritic Rocks of Klausen in South Tyrol. By F. Teller and
C. V. John {Jahrb. f. Mim., 1883, 2, Ref., 200— 205).— The eruptive
masses in the neighbourhood of Klausen are composed of triclinic fel-
spar, enstatite, hypersthene, diallage, augite, biotite, magnetite, apatite,
and generally free quartz. The plagioclase from a granular norite
rock proved on analysis to be intermediate between labradorite and
andesine. The rocks are partly quartz-mica-diorites, partly norites
and partly norite-porphyrites ; these types being connected by various
intermediate members. An analysis is given of a granular norite from
Oberhofer (1). This rock is composed of diallage, augite, biotite,
hypersthene and a little quartz, passing over into the norite por-
phyrite. (Analysis II.) A quartz norite from the Vildarthal was
also analysed (III.) : from this rock, the quartz-mica-diorites are
developed by the retirement of the pyroxenes. An analysis of a
quartz-mica-diorite, also from the Vildarthal, is given (lY). " The dif-
ference in the eruptive magma is very great, it has an acid dioritic
character in the larger masses and in the central portions, while in
the narrower veins and on the periphery of the principal mass it has
a basic noritic character.
SiOa.
AIA-
FeA-
FeO.
CaO.
I 56-72
16-90
414
6-28
7-25
II. 56-85
16-70
5-92
7-13
5-97
III. 59-97
16-93
2-41
4-83
5-10
IV. 7017
irio
1-92
2-86
Loss on
3-34
MgO.
Na^O.
KsO.
ignition.
Total.
I. 4-62
4-65
0-63
0-75
101-94
II. 3-25
2-78
1-91
0-54
101-05
III. 3-61
3-87
1-32
1-60
99-64
IV. 1-23
3-77
3-23
1-87
99-49
B. H.
B.
1070 ABSTRACTS OF CHEmCAL PAPERS.
Metalliferous Vein Formation at Sulphur Bank. By J.
Le Conte and W. B. Rising (Jahrb. f. Min., 1883, 2, Ref., 195—
197). — The attention of geologists has been called bj J. A. Phillips to
the fact, that metalliferous veins are even now forming at Steamboat
Springs in Nevada, and at Sulphur Bank in California. The mines at
Sulphur Bank, formerly mere open surface excavations, have been
recently developed in a systematic way, thus affording the authors
opportunities of study which were not enjoyed by any previous
observers. The lava stream of Sulphur Bank is 300 yards wide,
600 yards long, and 100 feet thick. The surface consists of pure
silica, the residue from the complete decomposition of the volcanic
rock. Deeper down, the rock consists of decomposed blocks of ande-
site, in every crevice of which sulphur is found in abundance. Still
deeper, the rock assumes its natural square-jointed structure. Cinnabar
now appears mixed with the sulphur. At a greater depth cinnabar is
found without sulphur ; together with this, impregnations of iron
pyrites and bitumen occur. Still deeper, beyond the influence of atmo-
spheric agencies, although still within thQ lava stream, the decompo-
sition is no longer universal, but only in streaks along the waterways ;
the result of decomposition is now tough unctuous blue clay, and finally
the earthy residuum is no longer acid from down-going waters, but
alkaline from up-coming solfataric waters. In this region, irregular
fissures running in all directions are filled with opal, nearly always
clouded witli cinnabar. Here, then, mineral veins are undoubtedly
being formed with quartz vein-stuff and ore. B. H. B.
The Klausenburg Meteorite. By F. v. Hauer, A. Beezina, A.
Koch, G. Tschermak, and E. Doll (Jahrb. f. Min., 1883, 2, Ref., 184
— 188). — At 3.45 P.M. on the 3rd of February, 1882, a meteorite
fell between Gyulatelka and Mocs, 38 km. east of Klausenburg in
Transylvania. The sky was perfectly cloudless at the time.- The
stones spread over an area 2U km. long and 4 km. broad, and the
lustre of the ball of fire was visible throughout Western Tran-
sylvania. When the fiery phenomenon disappeared, the path (N.W. —
S.Ev) was for a long time marked by a greyish- white cloud. Three
minutes after the appearance of the intense light, a series of detona-
tions followed. The heaviest stone fell two miles south of Mocs ; it
weighed 38'534 kg. The smallest stone found weighed only 0*95 grm.
Koch estimates the number of stones fallen at 3,000, and their weight
at 300 kg. The larger ones are described at length.
In order to obtain the average composition, the material for analysis
was taken from six of the larger stones. The results obtained were
as follows : —
Te. Mn. Ni. Co. SiOj. AiPa- FeO. MnO. MgO.
7-93 0-57 1-38 trace 4274 trace 2086 112 15-95
CaO. Na^jO. K^O. LigO. S. P. C. Chromite. Total.
2-78 1-20 0-21 trace 261 041 019 1*56 99*51
52'3 per cent, was soluble in acid. This analysis corresponds with a
MINERALOGICAL CHEMISTRY. 1071
percentage of 9*88 nickel-iron, 6*63 magnetic pyrites (FctSs), and
83-49 silicates. B. H. B.
The Meteorites of Alfianello. By J. Gallia and A. Beezina
(Jahrh.f. Min., 1883, 2, Ref., 188). — A fall of meteoric stones took
place on the 16th of February, 1883, at 2.55 p.m. at Alfianello, near
Brescia, with the usual appearances, bnt without any visible fiery
phenomenon. The stone was 260 kg. in weight and of a conical
shape, ^ m. high, and 75 cm. in basal diameter. It buried itself 1 m.
deep in the earth, singeing the grass in its neighbourhood. Although
the meteorite passed through the air in a S.S.B. direction, it forced
its way into the earth obliquely in the opposite direction. When dug
out, the stone was still warm ; it was covered with a smooth black
crust, and the smell of sulphur was distinctly noticeable.
B. H. B.
Mineral Water at Montrond (Loire). By A. Tereeil (Compt.
rend., 96, 1581 — 1582). — The mineral water at Montrond rises from
a depth of 502 m,, and issues from the bore-hole in the form of a jet,
which rises several meters above the surface of the soil, the water
being driven to this height by the pressure of the carbonic anhydride
with which it is charged. The water has the following composition : —
CO2 CO2
(free). (combined). NasO. KgO. LijO. CaO.
0-9356 2-1994 1-5408 traces traces 0-0336
MgO. AI2O3. FeO. CI. I. SO3.
0-0224 traces 0-0118 00390 traces traces
Non-nitrogenoua
P2O5. AsjOs. Si02. organic matter.
0-0005 0-0003 0-0386 0-0090 = 4-8310.
Arranging the constituents in the usual way, the composition of
the water is —
Free carbonic anhydride 0-9356 gr. = 473 c.c.
Sodium bicarbonate 3-5502
Potassium „ traces
Lithium „ traces
Calcium , 0-0864
Magnesium „ 0*0716
Ferrous „ 0-0262
Alumina • • • traces
Sodium chloride 0-0640
Sodium iodide traces
Sodium sulphate traces
Sodium phosphate O'OOIO
Sodium arsenate 0-0004
Sodium silicate 0*0787
Kon-nitrogenous organic matter . . 0-0090
4-8231
1072 ABSTRACTS OF CHEMICAL PAPERS.
The water is an alkaline carbonated water of unusual purity. It
differs, however, from other waters of the same class by its strongly
chalybeate taste, due to the presence of ferrous carbonate.
C. H. B.
Organic Chemistry.
Hydroxylation by Direct Oxidation. By R. Meter (Annalen,
220, 1 — 71). — The main portion of this paper has already been
abstracted from the Berichte (comp. Abstr., 1881, 45 and 818 ; 1882,
195; this vol., p. 983). At its conclusion, the author offers some
general remarks of interest.
Besides those cases examined or mentioned by the author in his
former memoir, analogous examples have been investigated by other
chemists. For example, the conversion of ethyl-methadetic and iso-
butylformic acids into their corresponding hydroxy-acids, thus:
CHMeEt.COOH + 0 = CMeEt(OH).COOH and CHMe2.CH2.COOH
+ 0 = CMe2(OH).CH2.COOH (Miller), of ethylanthracene dihy-
dride into ethylhydroxanthranile —
CeH.<_CT^!>CeH. + 0 = CeH,<^(O^J^>C.H.
(Liebermann), of hydratropic 'into atrolactic acid, CHMePh.COOH
+ 0 = CMePh(OH).COOH (Ladenburg and Kiigheimer).
The peculiarity of the hydrogen-atom in a CH-group in yielding
generally a hydroxyl-compound can be traced to its isolated position
and to the well-known instability of compounds containing more than
one hydroxyl-group associated with one carbon-atom : for the groups
CH(0H)2 or C(0H)2, which might be formed during oxidation are
immediately converted into the aldehydic CHO or ketonic CO group,
with elimination of a molecule of water.
It might, however, be objected that the transformation of the
primary alcoholic into the aldehydic group, or the formation of
glycollic acid from ethyl alcohol, are examples of hydroxylation by
direct oxidation in substances not containing the so-called tertiary
hydrogen-atom. But the author suggests in answer that both alde-
hyde and glycollic acid are prone to oxidation, and thus can be
considered only as intermediary products.
This hydroxylation by direct oxidation cannot, however, be used as
a final means for determining the existence of a CH-group in the
molecule : for in one case, in ordinary cymene, the normal propyl was
converted into the isopropyl- group, a change analogous to the forma-
tion of isopropyl bromide by the action of bromine and aliiminium
bromide on cymene.
The author remarks that although the basicity of the acid formed
by the oxidation of aromatic compounds determines the number of
ORGANIC CHEMISTRY. 1073
so-called side chains, yet in few cases is any light thrown on the
intimate constitution of these groupings. This arises from the
restricted use of partial oxidation, for generally the substances to be
oxidised are only moderately soluble in the reagent used, nitric or
chromic acid. The reaction thus proceeds slowly, and an intermediate
product is therefore more readily oxidised completely into the COOH-
group,
Hydroxylation by direct oxidation is the first step of a series, and
the substance formed can be converted stage by stage into the final
product of oxidation. As an example, the author adduces the conver-
sion of cumic acid into hydroxypropylbenzoic acid, which further yields
acetylbenzoic and finally terephthalic acid.
This transformation of the CH- into the C(OH)-group is charac-
teristic not only of the side chains of the aromatic derivatives, but
also of the paraffin compounds. V. H. Y.
Caucasian Ozokerite. By F. Beilstein and E. Wiegand (Ber.,
16, 1547 — 1551). — The raw ozokerite occurring on the island Tschele-
ken, in the Caspian Sea, is a brownish-black sticky mass, almost
entirely soluble in boiling benzene. On extracting it with ether, the
oily portion and the colouring matter are dissolved, leaving a hard
residue. The paraffin, named by the authors leken, is obtained from
the latter by boiling with ethyl acetate, and can be obtained pure
and of constant melting point by repeated treatment with animal
charcoal and precipitation from benzene; it forms lustrous crystals,
melting at 79°, sp. gr. 0'93917. It is very readily soluble in benzene,
carbon bisulphide, and chloroform, also in alcohol, ethyl acetate,
light petroleum, aniline, and nitrobenzene. It can be distilled in a
vacuum, but is partially decomposed at the ordinary pressure.
Leken is very stable, dilute nitric acid having very little action on
it after a week's heating on a water-bath. Chromic mixture and
4 per cent, permanganate solution scarcely act on it at 100°, whilst if
sulphuric acid is added, the manganate oxidises the leken to carbonic
anhydride and water ; fuming sulphuric acid decomposes it, with for-
mation of a black carbonaceous mass. On heating a mixture of
leken (6 grams), bromine (3 grams), and water (2 c.c.) at 100°, a
crystalline product is obtained melting at 74'5°, and containing 5' 7 —
6'2 per cent, bromine. A second experiment with double the amount
of bromine and water yielded a compound containing 12'6 per cent,
bromine, half the bromine being evolved as hydrobromic acid.
The oil obtained on extracting ozokerite with ether contained after
distillation in a vacuum 86"13 per cent, carbon and 13'70 per cent,
hydrogen, leken containing 85'1 per cent, carbon and 14'57 per cent,
hydrogen. A. K. M.
Hydrocarbon, CioHis, prepared from Allyl Dipropyl Carbinol.
By S. Reformatsky (/. pr. Ghem. [2], 27, 389— 407).— This hydro-
carbon has already been obtained by Saytzeff and Nikolsky (Abstr.,
1879, 214), by the action of sulphuric acid on allyl dipropyl carbinol.
The author has now investigated it further. Its purification pre-
sented great difficulty, as it readily absorbs oxygen, but was at last
VOL. XLIV. 4 c
1074 ABSTRACTS OF CHEMICAL PAPERS.
effected by digesting the fraction distilling between 160 — 170° with
sodium in sealed tabes at 175° for two days, and subsequently dis-
tilling it in an atmosphere of carbonic anhydride. The pure hydro-
carbon, CioH,8, is a colourless liquid of sp. gr. 07870 at 0°, 07740 at
16°, and 07705 at 21° (water at 0° = 1), boils at about 158°, is in-
soluble in water, readily soluble in alcohol, ether, and benzene. Its
vapour-density is 4*83, and it oxidises rapidly on exposure to air.
When treated with bromine in ethereal solution, it yields a tetra-
bromide, CioHi8Br4, as a thick heavy liquid. On oxidation with
chromic mixture, the hydrocarbon yields butyric and propionic
acids, together with a small quantity of acetic acid. A. J. G.
Hydrocarbon, C12H20, prepared from AUyl Dimethyl Carbinol.
By W. NiKOLSKY and A. Saytzeff {J.pr. Ghem. [2], 27, 880—389).—
A preliminary communication has already appeared (Abstr., 1879,
214) on the hydrocarbons CeHjo and C12H20, obtained by the action of
sulphuric acid on allyl dimethyl carbinol. The compound C12H20 is
best obtained by heating a mixture of 1 vol. allyl dimethyl carbinol
and 2 vols, sulphuric acid (1 part H2SO4 + 1 part water) in sealed
tubes for about three days at 100°. By fractionation, an oil
boiling at 194 — 199° is obtained, still mixed with an oxygen com-
pound ; by treatment with phosphoric anhydride and subsequent
fractionation, the pure hydrocarbon, C12H20, is obtained as a colour-
less mobile liquid, not solidifying in a freezing mixture ; its odour
somewhat resembles that of turpentine. It boils at 196 — 198°, has a
sp. gr. 0-8530 at 0°, and 0-8385 at 21° (water at 0° = 1), vapour-
density, found 5-55, calculated 5-67. It is insoluble in water, readily
soluble in alcohol and ether. An ethereal solution absorbs bromine
readily, but decomposition ensues on attempting to remove the ether
from the liquid. By heating the hydrocarbon with concentrated
hydrochloric acid at 100° for two days, a substance was obtained
whose analysis gave numbers not agreeing very well with the formula
C12H21CI. By oxidation with chromic acid it yields a small quantity
of acetone, acetic and propionic acids, and mainly a non-volatile
acid of the formula doHieOe or CioHuOe. This forms a colourless
syrupy liquid, readily soluble in water, alcohol, and ether. All the
salts yet prepared crystallised badly, and so could not be purified.
A. J. G.
Conversion of Fulminates into Hydroxylamine. , By A.
Steiner {Ber., 16, 1484 — 1486). — When fulminating mercury is dis-
solved in cold strong hydrochloric acid, a mixture of hydroxylamine
hydrochloride and a double chloride of mercury and hydroxylamine is
formed. Pure hydroxylamine hydrochloride may easily be obtained
by expelling the excess of- acid from this solution, and removing the
mercury by means of sulphuretted hydrogen.
This reaction indicates that fulminic acid is an isonitroso-com-
pound, HON : 0 : c : noh. w. c. w.
Preparation of Ammonium Thiocyanate. By J. Schulze
(J. pr. Ghem. [2], 27, 518). — In preparing ammoniam thiocyanate by
ORGANIC CHEMISTRY. 1075
the action of ammonia on carbon bisulphide in alcoholic solution, the
author finds that it is not necessary to use such large quantities of
alcohol and ammonia as Claus recommends. He finds that the best
yield is obtained by employing 600 grams of 95 per cent, alcohol, 800
grams of ammonia (sp. gr. 0*912), and 350 — 400 grams of carbon
bisulphide. J. I. W.
Normal Primary Hexyl Alcohol. By J. Frentzel {Ber., 16,
743 — 746). — The author obtained the alcohol as follows: Ricinoleic
acid, obtained from castor oil, was dry-distilled ; the oenanthaldehyde
thus obtained oxidised to oenanthic acid, which was then converted into
hexylamine by Hofmann's method (Abstr., 1882, pp. 822, 950, and
1052). Hexylammonium chloride was converted into the nitrite by
double decomposition with silver nitrite in aqueous solution, and the
solution thus obtained was subjected to distillation when it yielded
hexyl alcohol as soon as it became concentrated.. Sexyl alcohol boils
at 157-3° (corr.), and solidifies at - 30". Its sp. gr. is 0-813 at 17°.
The yield was 40 — 50 per cent, of theory.
Hexyl formate boils at 146°, has a sp. gr. of 0-8495 at 17°, and an
odour of apples. Sodium hexylate is produced by the action of
sodium on the alcohol, and with benzoic chloride yields hexyl henzoate.
The latter boils at 272° (bar. 770 mm.), has a sp. gr. of 0*99846 at
17°, and a smell of apples. Sexyl chloride boils at about 130°, but
was not obtained in a pure state.
Hexyloimmonlum hexylthiocarhamatey C6Hi3.NH.CS.SH.C6Hj3JN"H2,
was prepared by the action of carbon bisulphide on hexylamine. It
is a white crystalline body, which on being heated yields dihexylthio-
carbamidey CS(NH.C6Hi3)2 ; this crystallises in glistening white plates
melting at 40°. Hexylthiocarbimide, CSiN.CeHia, prepared by decom-
posing copper hexylthiocarbamate with steam, boils at 212° (bar.
578 mm.). Alcoholic ammonia converts the carbimide inta mon-
hexylthiocarhamide, NHg.CS.NH.CeHg, which crystallises in white
plates melting at 83°. L. T. T.
Preparation of Normal Primary Decyl, Dodecyl, Tetradecyl,
Hexdecyl, and Octodecyl Alcohols. By F. Keaffi (Ber^ 16,
1714—1726). — To prepare normal decyl alcohol, C10H22O, the aldehyde
is first obtained by the dry distillation of a mixture of barium caprate
and formate under reduced pressure (8 — 15 mm.). The crude alde-
hyde (b. p. 106° under a pressure of 15 mm.) is dissolved in 10 times
its weight of glacial acetic acid, and 3 to 4 parts of zinc-dust are
gradually added. To complete the reduction, it is necessary to boil
the mixture gently for about a week. The cold acid solution is sepa-
rated from the solid zinc salt, and poured into water ; the oily liquid
is washed with water, dried, and distilled under reduced pressure.
Decyl acetate is a colourless, strongly refractive, mobile liquid, which
boils at 125° under a pressure of 15 mm. The alcohol obtained by
saponifying the acetate with alcoholic potash is a viscous liquid
(b. p. 119° under 15 mm. pressure). It has a sweet smell, and
is powerfully refractive. It crystallises in transparent rectangular
4 c 2
1076 ABSTRACTS OF CHEinCAL P.VPERS.
plates which melt at 7°. Becijl chloride formed by the action of
phosphorus pentachloride on the alcohol is converted into the olefine,
O10H20, which yields normal decane, C10H22, on treatment with hydrio-
dic acid and phosphorus.
By a series of reactions analogous to the preceding, the following
compounds were prepared. (The boiling points are determined under
a pressure of 15 mm. unless otherwise stated.) Dodecyl alcohol melts
at 24° and boils at 143* 5°. The sp. gr. of the alcohol in the liquid
state is 0-8309 at 24° and 0'8201 at 40°. The acetate boils at 151°.
Normal dodecane melts at — 12° and boils at 98°. Tetradecyl acetate
melts at 13° and boils at 176°. The alcohol CuHsoO, melts at 38°,
and boils at 167°. The sp. gr. of the alcohol is 0-8236 at 35° and
0-8153 at 50°. Hexdecyl acetate is sparingly soluble in cold alcohol.
It melts at 22—23° and boils at 200°. The alcohol has been pre-
viously described. Octodecyl alcohol forms silvery plates, sparingly
soluble in alcohol. It melts at 59° and boils at 210-5°. Its sp. gr. is
0-8124 at 59° and 0-7849 at 99-1. The acetate melts at 31° and boils
at 222°.
In conclusion, the author points out that the influence of diminished
pressure on the boiling points of the alcohols increases with the
molecular weight. W. C. W.
Bye-product of the Preparation of Ally! Dimethyl Carbinol.
By W. DiEFF (/. pr. Chem, [2], 27, 364— 380).— This substance,
which appears to be isopropyl allyl dimethyl carhinol, C4H4Me2Pr^.OH,
and is formed by the action of zinc and isopropyl iodide on allyl
dimethyl carbinol, w^as observed several times when impure allyl
iodide containing isopropyl iodide had been employed in the manu-
facture of allyl dimethyl carbinol. The complete purification of the
substance could not be effected ; it boils about 76° ; combines with
2 atoms bromine; is converted into the chloride, C9H17CI (?), by the
action of phosphoric chloride ; and on oxidation gives butyric acid and
other acids not identified. A. J. G.
Oxoctenol. By V. Meter and E. Kageli (Ber., 16, 1622—1624).
— According to Butlerow (Abstr., 1882, 937) the constitution of
CMe2— V
oxoctenol is either \ ;0, or CMeg.CO.CMejCOH). If the
CMe3.C(0H)/
second formula is correct, this substance should yield an isonitroso-
derivative with hydroxylamino, whilst a compound having the first
formula would not be acted on by this reagent. The authors have
experimented under various conditions, but the oxoctenol remained
nnattacked, showing that no CO-group is present, and that the first
formula is the correct one. In order, however, to ascertain whether
the presence of hydroxyl in a ketone interferes with the hydroxyl-
amine reaction, the authors have examined the action of the latter on
benzoyl carbinol, and have obtained isonitrosophenylethyl alcohol,
PhC(N0H).CH2.0H.
ORGANIC CHEMISTRY, 1077
It is insoluble in light petroleum, readily soluble in ether, alcohol,
water, and hot benzene, crystallising from the latter in lustrous scales
melting at 70°. Acids dissolve it on warming, with liberation of
hydroxylamine. A. K. M.
Preparation of Chlorhydrins. By A. Ladenburg (Ber., 16,
1407 — 1408). — Ethylene chlorhydrin is best prepared by passing a
slow current of dry hydrochloric acid gas through glycol heated at
148" in a retort, when water and ethylene chlorhydrin distil over.
The temperature of the glycol is slowly raised to 160°. About 16
hours are required to convert 100 grams of glycol into the chlor-
hydrin. The distillate is mixed with 2 or 3 times its volume of ether,
allowed to stand over potassium carbonate to remove free hydro-
chloric acid, dried over fused potassium carbonate, and then distilled.
The yield is 60 per cent, of the theoreticaL W. C. W.
Effect of Temperature and Concentration of Acid on the
Rate of Inversion of Saccharose. By F. Urech (Ber., 16, 762—
766) . — The author gives a number of equations to obtain the different
coefficients under varying conditions. Of these, the following are
the principal: If Uq = the original quantity of saccharose, u that
remaining after an interval of time t expressed in minutes, and a the
coefficient of rate of inversion :
_ u
" ~ (log 2-7182; . t'
or if Uo be taken as 100 —
log a = log(2 - log u) — (1-63774 + log t).
L. T. T.
Fermentation of Cellulose. By H. Tappeiner (Ber., 16, 1734 —
1740). — Finely divided cotton- wool or paper is introduced into a flask
containing a neutral one per cent, solution of extract of meat. The
vessel is heated at 110°, and when cold a small quantity of the contents
of the pancreas is added. Fermentation begins in a few days ; the gases
evolved consist chiefly of marsh-gas and carbonic anhydride. These
two gases are in the ratio of 1 to 7"2 at the beginning of the process,
but the carbonic acid afterwards diminishes to the ratio of 1 : 3"4.
The actual fio^ures are —
CO2 1
SH, /
Commencement. End.
85-48 76-98
H 0-03 —
CH4 11-86 2301
N 2-73 —
Acetic and isobutyric acids are the chief products of the fermenta-
tion, 5-5 grams of cotton-wool yielding 5-8 grams of volatile acids.
Acetaldehyde is also formed. Cellulose undergoes similar fermenta-
tion in the first stomach of ruminants and in the alimentary canal of
1078 ABSTRACTS OF CHEMICAL PAPERS.
herbivora. When the preceding experiments are varied bj rendering
the meat-extract feebly alkaline, by adding Nageli's solution (potassium
phosphate 0*2 gram, magnesium sulphate 004 gram, and calcium
chloride 0'02 gram), or a solution containing in addition to the above
salts, 0*35 per cent, of ammonium acetate, 0'3 acetamide, or 0'6 aspa-
ragine, the following results were obtained : —
0*5 per cent,
solution of
meat extract. Asparaglne. Acetamide.
CO.,
55-39 86-47 78-14
H 42-71 6-73 13-68
N 1-90 7-80 8-18
No difference could be detected in the bacteria in the two kinds of
fermentation. In addition to aldehyde, isobutyric and acetic acids, a
small quantity of ethyl alcohol appears to be formed by the " hydro-
gen " fermentation of cellulose.
Alcohol, aldehyde and acetic acid are produced during the femien-
tation of hay. The gases evolved contain GO2 51-15, H 44-58, CH4 0*9,
N 4-18 per cent. W. C. W.
Reduction of Saccharin. By C. Liebermann and C. Scheibler
(J5er., 16, 1821 — 1825). — The authors confirm the accuracy of Kiliani's
statement (Annalen, 218, part 3) that the lactone obtained by the
action of hydriodic acid on saccharin is a-methylvalerolactone. Methyl-
propylacetic acid (b. p. 190°) is also produced. W. C. W.
Some Anomalous Reactions. By G. Meyer (Ber., 16, 1439—
1443). — Methyl iodide and Sodium arsenite. — If an alcoholic solution of
methyl iodide is heated in sealed tubes at 75° with an aqueous solu-
tion of sodium arsenite containing a small quantity of free soda, and
the crystalline contents of the tubes are dissolved in warm water and
boiled with calcium chloride, calcium methylarsenite, CaCHsAsOa 4-
H2O, is thrown down as a white crystalline precipitate. On treating
another portion of the aqueous solution with sulphuretted hydrogen,
a mixture of sulphur, methylarsine sulphide and the bisulphide,
CH3ASS2, is precipitated. The precipitate is treated with carbon
bisulphide, and the residue of methylarsine bisulphide is dissolved in
ammonia and reprecipitated by the addition of hydrochloric acid. The
bisulphide is decomposed by heat, yielding methyl sulphide and
arsenious sulphide.
An alcoholic solution of methyl iodide acts at the ordinary tempera-
ture on stannous chloride dissolved in excess of sodium hydroxide.
After the excess of alcohol and methyl iodide have been removed by
boiling, carbonic acid precipitates methylstannic acid, MeSn02H,
from the alkaline solution in the form of a crystalline powder. On
passing sulphuretted hydrogen into the filtrate, a white sulphide is
precipitated. On evaporating the hydrochloric acid solution of methyl
stannic acid or the sulphide, a fuming crystalline mass is produced
which probably consists of MeSnCla. W. C. W.
ORGANIC CHEMISTRY. 1079
Base derived from Crotonaldehyde. By A. Combes (Comjjt.
rend., 96, 1862 — 1863). — A solution of crotonaldehyde in anhydrous
ether is cooled to — 20°, saturated with dry ammonia gas, and exposed
to light in well -closed flasks for two or three days, when the liquid
separates into two layers. When distilled, the lower layer yields
water and an oily liquid which distils with difficulty at 200° in a
vacuum. The same substance is obtained by evaporating the upper
ethereal layer. This oily liquid has the composition CgHigN^O, and
is formed in accordance with the equation, 2C4H6O + 2NH3 =
CsHisNgO + H3O. It has a distinctly alkaline reaction, and combines
with water with development of heat, forming a white crystalline
substance which can also be obtained by adding water to the ethereal
solution. This hydrate is very soluble in water and combines readily
with hydrochloric acid, forming a hydrochloride which crystallises
easily ; the yellow somewhat soluble platinochloride also crystallises
readily. C. H. B.
Acetone- chloroform. By 0. Willgeeodt (Ber., 16, 1585). —
This compound previously described by the author (Abstr., 1882,
492) contains half a molecule of water of crystallisation,
COMe2,CHCl3 + 4H2O,
and melts at 80 — 81°. On treating it with anhydrous solvents, such
as chloroform, light petroleum, benzene and carbon bisulphide, it
loses its water of crystallisation, and then melts at 96°.
A. K. M.
Condensation of Acetone. By A. Pinner (Ber., 16, 1727 —
1734). — Mesityl oxide obtained by the action of hydrochloric acid on
acetone is identical with the mesityl oxide obtained by heating acetone
with lime. The author finds that the reaction which takes place
when cane-sugar is heated with lime is by no means so simple as
Benedikt (Annalen, 162, 303) represents, viz., CgHi^Oe = CsHeO +
2CO2 + CH4 + H2O. Metacetone and phorone are, according to
Benedikt, condensation-products of acetone. The residue in the
retort contains, in addition to calcium carbonate and a small quantity
of caproic acid, an acid of the composition CeHioOj, which forms a
crystalline hygroscopic potassium salt. The calcium salt is precipitated
from an aqueous solution by the addition of alcohol. The white
amorphous silver salt is somewhat soluble in water. It decomposes
even in the dark, and turns brown. The volatile portion of the pro-
ducts of the dry distillation of sugar and lime contains, in addition
to the compounds isolated by previous observers, acetaldehyde, met-
acetone, and several other bodies. W- C. W.
Action of Sodium on Methyl Ethyl Ketone. By X Schramm
(Ber., 16, 1581 — 1582). — The methyl ethyl ketone was dissolved in
benzene, and after the action of the sodium, the latter separated by
distillation and the product fractioned, when the following compounds
were obtained. The fraction 163 — 165° is a liquid of camphoraoeous
odour, insoluble in water, readily soluble in alcohol and in ether, and
combines directly with bromine, forming a heavy dark coloured oil.
1080 ABSTRACTS OF CHEMICAL PAPERS.
In its composition, CgHuO, and properties, it agrees with the homo-
logue of mesityl oxide obtained by Pawlow (Annalerij 188, 138). By
the action of a freezing mixture on the fraction boiling at 200 — 205°, a
white crystalline body is obtained, apparently identical with Lawrino-
wicz's methyl ethyl pinacone, CsHisOj. It melts at 28 — 29°, boils
at 201 — 203" (bar. 745 mm.), and does not again solidify at the ordi-
nary temperature. It has an odour like that of camphor, is moderately
soluble in water, readily in alcohol and in ether. The product boiling
at 248 — 253° is an oily liquid which could not be solidified, and
evidently contains a substance of the formula Ci2n2oO analogous to
phorone. It is thus shown that the above reaction is at least for the
most part analogous to the action of sodium on acetone, the chief pro-
ducts of which are mesityl oxide, pinacone, and phorone.
A. K. M.
Diethyl Ketone. By J. Schramm (5er., 16, 1583— 1584).— Very
different statements occur with regard to the combination of diethyl
ketone with hydrogen sodium sulphite (Annalen, 161, 286 ; 179, 322 ;
and 157, 251 ; Ber., 5, 459). The author finds that the combination
does not take place very readily, but that the temperature rises after
continued shaking, and on cooling a mass of needles is obtained. The
compound C5H10O + NaHSOa is very readily soluble in water, alcohol,
and ether, and decomposes gradually on exposure to the air. In
order to prove that the ketone experimented with was really diethyl
ketone and not methyl propyl ketone, the author converted it into the
corresponding pinacone and obtained a crystalline substance, C10H22O2,
melting at 27 — 28°, almost insoluble in water, readily soluble in
alcohol and in ether. Methyl propyl ketone yields a liquid pinacone
(Jahreshericht, 1869,513). A. K. M.
Ethyl Acetate. By W. I. Clark (Pharm. J. Travis. [3], 13, 777—
783). — The acetic ether of commerce is often impure, and in this
paper the author describes various tests for the impurities, comments
on the present modes of preparation and purification, and on some of
the properties of ethyl acetate ; he finally proposes a new process for
its preparation.
The amount of ethyl acetate present is determined by saponifying
a definite quantity of the ether with a measured volume of a
solution of potassium hydroxide in pure alcohol, of known alkalinity;
the loss of alkalinity represents the total acetic acid combined and
free, the amount of the latter being ascertained by titrating the ethyl
acetate dissolved in spirit with standard alkali, and is deducted from
the total. The alcohol is determined by collecting the distillate from
the saponification, the quantity of ethyl acetate having been deter-
mined, the total alcohol, less the alcohol used and the alcohol pro-
duced in the reaction, gives the quantity of free alcohol present.
Most commercial samples contain large proportions of water, alcohol,
and acetic acid ; for this reason the author has investigated the
methods of preparation. Methods which depend on the production of
ethyl acetate direct from free acetic acid, alcohol, and sulphuric acid,
are quite useless owing to the great quantity of ether, alcohol, and
acetic acid inevitably present in the product. The action of carbonic
ORGANIC CHEMISTRY. . 1081
anhydride on a solution of potassium acetate in absolute alcohol yields
no ethyl acetate after 24 hours, but on adding water a trace of it is
produced.
The British Pharmacopoeia method of distilling a mixture of 8 parts
of dry sodium acetate, 6 parts rectified spirit, and 10 parts of sul-
phuric acid, adding the distillate to half its weight of calcium chlo-
ride, and after 24 hours decanting and rectifying, is unsatisfactory ;
firstly, it is not economical, for the B.P. formula requires a con-
siderable excess both of sulphuric acid and sodium acetate ; secondly,
this great excess of sulphuric acid is deleterious, the ethyl acetate
being decomposed by it into ether, acetic acid, and numerous other
products. The author therefore undertook a series of experiments
with crystalline and dry sodium acetate, with rectified spirits of wine
and absolute alcohol, and with various quantities of sulphuric acid
under various conditions. From these he draws the following conclu-
sions : — 1. Dry sodium acetate should be used. 2. Great excess or
deficiency of sulphuric acid are equally to be avoided ; a slight excess
being advantageous. 3. The advantage gained by the use of absolute
alcohol in place of rectified spirits of wine is not worth the extra
expense. 4. The yield is never more than 91 '2 per ,cent. of the
theoretical. 5. Delay (for example, the previous mixing of the
alcohol with the sulphuric acid and allowing it to stand some time, as
recommended by Frankland and Duppa, so as to favour the formation
of ethyl hydrogen sulphate) lowers the yield. The product obtained
by the authors, whether by the B.P. method or any other, was always
far superior, even before purification, to that occurring in commerce ;
the plea that acetic ether decomposes when moist is inadmissible,
for experiment proves that this decomposition is far too slow to
account for the impurities.
The next point attacked is the removal of impurities ; ether and
secondary products of the action of the sulphuric acid are best
removed by distillation, and acetic acid by agitation with potassium
carbona,te, the ether being slightly moist ; standing over fused calcium
chloride and subsequent distillation from it, as a means of removing
the alcohol, cannot be recommended, as there is always a loss, also
decomposition, which the author points out is due to the alkalinity of
the calcium chloride ; moreover, the distillation is always accompanied
by bumping owing to the deposition of calcium chloride, although the
ethyl acetate dissolves only 0*15 gram per 100 c.c. at 15°. The alcohol
is best removed by a saturated solution of calcium chloride which also
removes some of the water : the author finds that 47 c.c. of calcium
chloride solution (saturated) only dissolve 1 c.c. of ethyl acetate at
15°, and very slightly more at 0°, but this increases directly with the
dilution of the calcium chloride solution, that is, the more alcohol or
alcohol and water present, the greater will be the quantity of acetate
dissolved. Upon this fact he has constructed tables in which are
given the quantities of ethyl acetate remaining undissolved when
stated mixtures of the acetate with alcohol, or with alcohol and water
are agitated with the calcium chloride solution. These tables can be
used in a manner described in the paper to determine approximately
the quantity of ethyl acetate present in such a mixture.
1082 ABSTRACTS OF CHEMICAL PAPERS.
Removal of water : 1 c.c. of ethyl acetate dissolves in 8 e.c. of water
at 0°, and in 9 c.c. at 15° ; it is hence more soluble at 0° than at 15"*.
Water dissolves in ethyl acetate in proportions of 1 c.c. ; 26 c.c. at
0°, and 1 c.c. : 24 c.c. at 15° ; it is hence more soluble at 15° than at
0°. Digestion with potassium carbonate is recommended for the
removal of the water, but distillation from it causes decomposition
and loss. Sodium acetate is also an excellent dehydrant, and the
ethyl acetate may be distilled from it ; the sodium acetate being sub-
sequently used for a fresh preparation of the ether.
The following is the process recommended by the author for the
preparation of ethyl acetate : — 283 c.c. of sulphuric acid are poured
into 283 c.c. of rectified spirit contained in a flask, keeping it cool ; as
soon as the temperature has fallen to about 15° the sodium acetate is
gradually added, agitating constantly, keeping the flask cool, and con-
necting it with a reflux condenser. The contents are then distilled,
digested for three days with 2 oz. of freshly dried potassium carbo-
nate, filtered, and distilled, stopping the distillation at the last ounce.
The excess of sulphuric acid ensures the absence of alcohol in the
distillate, whilst the action of this excess on the acetate itself is
minimised by the above precautions. It is therefore only necessary to
neutralise and free the ether from water as described. From several
observations made on ethyl acetate, as pure as can be procured,
purified both after admixture with alcohol, which would lower the
sp. gr., and with water, which would raise the sp. gr., the author
concludes that the sp. gr. of ethyl acetate is higher than 0*9004 and
lower than 0'9012. It is exceedingly difficult to remove the last traces
of water from the acetate. D. A. L.
Action of Aldehyde-ammonia on Methyl Acetoacetate. By
A. Hantzsch (Ber., 16, 1946 — 1948). — By the action of 2 mols. of
methyl acetoacetate on 1 mol. aldehyde-ammonia, viethyl dihydro-
collidinedicarhoxylate is formed, thus: CHa.CO.CHo.COOMe +
CHMe(0H).NH2 = C5:N'.H2Me3(COOMe)2. This substance resembles
the corresponding ethyl compound as regards its solubility, colour,
and fluorescence, but differs in its melting point, 156°. By boiling with
hydrochloric or nitrous acid, methyl collidinedicarhoxylatey
C6NMe3(COOMe)2
is obtained, which crystallises in white needles (m. p. 82°, b. p. 286°).
This substance, although it has a neutral reaction, combines with
acids to form well-defined salts. The hydrochloride crystallises in
glistening prisms ; the platinochloride in reddish-golden spangles, which
melt at 200° with decomposition : the aurochloride in slender golden
needles, which readily melt into an oil. V. H. V.
Halogen-substituted Ethyl Acetoacetates. By M. Conrad and
M. GuTHZEiT (^67-., 16, 1551 — 1555). — Duisberg showed that bromine
is capable of displacing 5 atoms of hydrogen in ethyl acetoacetate
(Abstr., 1882, 1192). In order to ascertain whether ethyl dichlor-
acetoacetate, which at the ordinary temperature can take up no more
chlorine, undergoes further substitution by bromine, the authors ex-
ORGANIC CHEMISTRY. 1083
posed a mixture of the former (20 grams) with bromine (50 grams)
for some days to direct sunlight. Hydro bromic acid is evolved,
and ethyl dichlorodihromacetoacetate, C6H6Cl2Br203, is formed as a
slightly yellowish liquid insoluble in water, and decomposed on
boiling. With ammonia, it forms a white crystalline compound,
sojuble in ether. On heating ethyl dichlorodihromacetoacetate with
hydrochloric acid, carbonic anhydride is given off with formation of
the compound C3H2Cl2Br20,4H20, which crystallises in six-sided
plates of a vitreous lustre melting at 56° ; it loses its water over
sulphuric acid, and then forms a colourless h'quid (dichlorodibromace-
tone), the vapour of which violently attacks the eyes. In its properties
it agrees with the dichlorodibromacetone obtained by Glaus and Lind-
horst (Abstr., 1880, 862) by the action of bromine on dichlorhydrin,
the constitution of which is CH2Cl.CO.CClBr2. This constitution is,
however, not in accordance with what one would expect, since both
chlorine- atoms in ethyl dichloracetoacetate are united to the same
carbon-atom (Annalen, 186, 232).
By the action of sodium on ethyl chloracetoacetate, the sodium com-
pound is obtained, forming a white crystalline hygroscopic powder.
An attempt to displace the bromine in ethyl bromacetoacetate by
acetyl by boiling it with an alcoholic potassium acetate solution
yielded ethyl succinylsuccinate. Chlorine acts on ethyl diethylaceto-
acetate with evolution of hydrochloric acid. The product distils for
the most part between 245" and 255°, and apparently contains both
mono- and di-chloro-substitution derivatives. A. K. M.
Condensation-products of Ethyl Acetoacetate, By A.
Hantzsch (Ber., 16, 740 — 742). — By the action of strong sulphuric
acid on ethyl acetoacetate, the author has obtained ethyl mesityloxide-
dicarhoxylate, C6H80(COEt)2, ethyl mesityloxideanhydrodicarboxylate,
C6H60<:^ PQ Q PQ ^CeHsO, and a crystalline body of the
empirical formula C2H2O, i.e., isomeric with dehydracetic acid. This
acid is dibasic, and appears to have the molecular formula CuHuO? :
the author proposes for it the preliminary name of metadeliydr acetic
acid. Ammonia forms a peculiar compound with ethyl mesityloxide-
dicarboxylate, having the formula COOEt.C6H80.COO.NH4,NH3, and
giving with mineral acids the acid COOH.CeHgO.COOEt. The three
mesityl-acids give mesiiyloxide-dicarboxylic acid^ C6H80(COOH)2,
when saponified with excess of potash. L. T. T.
Action of Trimethylene Bromide on Ethyl Acetoacetate,
Ethyl Benzoylacetate, and Ethyl Malonate. By W. H. Perkin
(Jun.), Ber., 16, 1787 — 1797). — Acetotetramethijlenecarhoxylic acid,
obtained by the action of trimethylene bromide on ethyl sodacetoace-
tate {Ber., 16, 208) is decomposed by distillation, yielding acetotetra-
methylene, CH3.COC4H8, and carbonic anhydride.
The ethylic salt of benzoyl tetramethylenecarboxylic acid is prepared
by the action of trimethylene bromide (21) on a mixture of ethyl
benzoylacetate (20), and a solution of sodium (2*5) in absolute
alcohol. The sodium bromide which is deposited is removed by fil-
1084 ABSTRACTS OP CHEMICAL PAPERS.
tration and the alcohol distilled off: 2'5 grams of sodium, dissolved
in alcohol, are added to the residue, and the mixture is heated at 100''
until it ceases to exhibit an alkaline reaction. After removing
sodium bromide and alcohol, the mixture is diluted with water and
extracted with ether. From the ethereal solution, the ethyl salt,
PhCO.C(COOEt)<^g2>CH2, is obtained in colourless prisms (m. p.
60"), which dissolve freely in the usual solvents. On saponification
with alcoholic potash, henzoyltetramethyleuecarboxylic acid,
BiC(C3H6).COOH,
is obtained as a crystalline mass, which melts at 143°, decomposing
into carbonic anhydride and benzoyltetramethylene. The acid is
soluble in alcohol, chloroform, benzene, carbon bisulphide, and ether.
Benzoic tetrametliylene,C^i,C0GYi.<^^^y^CH.2i is a colourless oil
boiling at 259°.
By the action of trimethylene bromide on the disodic derivative of
ethyl malonate, ethyl tetraraethylenedicarboxylate,
CH2:(CH2)2:c(COOEt)2,
is obtained as a colourless oil (b. p. 224°), On saponification, it
yields tetramethylenedicarhoxylic acid, CH2 '. (CH2)2* C(C00H)2, which
melts at 155° with decomposition, and is converted into tetramethylene-
■monocarhoxylic acid at a temperature of 210°. The acid dissolves
freely in ether and benzene, but is precipitated from its solution on
the addition of light petroleum. It is also readily soluble in water.
The ammonium salt forms needle-shaped crystals. The silver salt is
sparingly soluble in water.
Tetrametliylenemonocarhoxylic acid, CH2<[ptt'^^CH.C00H, is a
colourless oil boiling at 194°. It is sparingly soluble in water, but
dissolves freely in alcohol and ether. The silver salt is sparingly
soluble in water. The calcium salt forms crystalline needles, which
are very soluble in water.
A comparison of the melting points and boiling points of these com-
pounds with the corresponding allyl derivatives shows that these
bodies contain tetramethylene, and are not allyl derivatives. Their
behaviour with bromine indicates that they differ in constitution from
allyl compounds. W. C. W.
Constitution of Ethyl Succinosuccinate. By F. Herrmann
(JBer., 16, 1411 — 1415). — The substance previously described by the
author as diethyl succinosuccinate {Annalen, 211, 308) has been proved
to be identical with ethyl oxytetrolate obtained by Duisberg (Ber., 16,
133) from ethyl monobromacetate. As the constitution of the body
COOEt.CH.CH2.CO
is represented by Duisberg as | | , the
CO.CH2.CH + COOEt
author suggests that the compound should be called diethylquinone
tetrahydridedicarboxylate. The monethyl salt can be split up into car-
ORGANIC CHEMISTRY. 1085
bonic anhydride and etJiyl quinonetetraJtydridemonocarhoxylate, for-
merly called ethyl succinopropionate. The author also proposes to
substitute the name of diethyl quinonedihydridedicarhoxylate for that
of diethylquinonehydrodicarboxylate for the compound derived from
diethylquinonetetrahydridedicarboxylate by the loss of two atoms of
hydrogen. W. 0. W.
So-called Tetric, Pentic, and Hexic Acids. By R. Fittig
(Ber., 16, 1939 — 1941). — Demar9ay has recently described {Ann.
Chem. Phys. [5], 20, 433) a series of new acids obtained by the action
of bromine and alcoholic potash on the alcoholic derivatives of ethyl
acetoacetate, to which he assigns the composition 3C4H602,H20,
tetric acid ; 3C5H602,H20, pentic acid ; 4C6H802,H'0, hexic acid.
The author, with the assistance of Schultz, has repeated Demar9ay's
work as regards tetric acid, and arrives at the same results as regards
the melting point and other physical properties, but finds that the acid
contains no water, and five not four carbon-atoms, viz., a composition
CsHeOs. It is monobasic, its salts having the formula C5H5O3M. Its
formation from ethylbromomethacetoacetate can be represented by the
equation CiHoBrO.COOEt + H2O = C4H5O.COOH -f HBr + EtOH.
In a postscript the author notices that his results agree with those of
Pawlow, which were published recently and independently.
V. H. y.
Formation of Disodium GlycoUate. By De Forceand (Gompt.
rend., 96, 1728— 1730).— Disodium glycollate, C2H(NaHO)]Sra02 +
2H2O, obtained by adding sodium hydroxide to neutral sodium glycol-
late in the required proportion, forms small deliquescent needles
which lose their water at 180°. Its heat of solution is — 0*36 cal. at
20°. The heat developed on adding a quantity of sulphuric acid suffi-
cient to combine with half the sodium is -|- 15*17 cal. The subsequent
addition of an equal quantity of sulphuric acid causes a further de-
velopment of + 2*19 cal. These results prove that the compound is
really a bi basic glycollate. From these data, it also follows that
2NaH0 solid + C2H4O3 solid = C2H(NaHO)Na02.2H20 solid, de-
velopes + 31*42 cal. The heat of solution of the anhydrous salt is
-f- 9" 18 cal., from which it follows that the formation of the solid
anhydrous salt develops + 24*76 cal. This value is practically the
same as the heat of formation of the normal salt, and consequently
the conversion of the latter into the anhydrous bibasic salt is accom-
panied by practically no thermal disturbance. The heat developed by
the hydration of the bibasic salt (-f 6"62 cal.) is, however, sufficient to
explain its formation. The heat of formation of the anhydrous bi-
basic salt from the normal salt and anhydrous sodium oxide, is
precisely the same as the heat of hydration of the sodium oxide
(4- 17-27 cal.). It follows that C2H4O3 -f NagO = CaHjNaaOs -f H2O
solid, develops + 68-92 cal. 0. H. B.
Basic Potassium Beryllium Oxalate. By J. Philipp (Ber., 16,
752 — 753). — A solution of hydrogen potassium oxalate dissolves
beryllium oxide easily, and from the solution a basic salt,
Be^KeCisOgT + 8H2O,
1086 ABSTRACTS OF CHEMICAL PAPERS.
is obtained, forming large glass-like crystals, which have a high refrac-
tive power. The author considers the constitution of this body to be
Be^CC^OOa + 3K2C2O4 + Be2(HO)6 + SH^O. L. T. T.
Lithium Citrate. By C. Thompson (Pharm. J. Trans. [3], 13,
783 — 786). — In this paper, the author reviews the various modes of
preparing this salt, and describes the processes for making lithium
carbonate from lepidolite. When pure, lithium citrate crystallises
well, and is not deliquescent ; the ordinary salt, however, is generally
impure, containing lithium carbonate (or citric acid), along with salts
of potassium, sodium, and calcium ; the methods for detecting and
estimating those impurities are fully described in the paper.
D. A. L.
Melanuric Acid. By E. Bamberger (Ber., 16, 1703—1704). —
Melanuric acid is sparingly soluble in hot water, not insoluble as
stated by Wohler and Liebig. It is deposited from boiling water in
white microscopic crystals. Dicyanodiamidocarboxylic acid from
dicyanodiamide is identical with melanuric acid. W. C. W.
Action of Sulphuric Acid on Di- and Tri-allylamine. By C.
LiEBERMANN and A. Hagen {Ber., 16, 1641 — 1642). — This is a con-
tinuation of Liebermann and Paal's experiments (this vol., p. 908).
Di- and tri-allylamine were prepared by the action of allyl chloride
on allylamine. The separation of lustrous plates during the fraction-
ing was again observed {loc. cit.), and found to be due to hydrochlo-
rides of the above bases. Concentrated sulphuric acid reacts in the
same way as in the case of the alkylallylamines ; hydroxypropylallyl-
amine and hydroxypropyldiallyl amine being formed in the first phase
of the reaction, but decompose with separation of the elements of
water. A complicated series of bases is produced, the chief fraction
of the product from diallylamine boiling at 130 — 170°, that from tri-
allylamine at 170 — 200°. They are not hydroxy bases, and they have
a penetrating odour resembling that of conine, so that it is probable
they may be derivatives of pyridine and piperidine ; no pure products
have as yet been obtained. The authors prove the presence of pyrro-
line-like substances soluble in dilute sulphuric acid to a red solution.
A. K. M.
New Glyoxalines. By B. Radziszewski (Ber., 16, 747 — 749). —
In a former paper (this vol., 308), the author showed that gloxaline
was the first member of a homologous series of compounds obtainable
by the action of ammonia on a mixture of glyoxal and an aldehyde.
He now describes three new members of the series.
Glyoxalisohutyline, CeHioNj, boils between 240 — 265°, and by further
purification is obtained as a crystalline body melting at 129°, easily
soluble in alcohol, ether, and boiling water. The platinochloride is
crystalline, and easily soluble in water.
Gh/oxalisoamylme, C7H12N2, boiled between 250 — 270°. Further
purified it forms long, slightly bent needles melting at 120 — 121°. It
ORGANIC CHEMISTRY. 1087
is sparingly soluble in boiling water. The platlnocbloride is less
soluble than that of the previous base, and crystallises in needles.
Glyoxaliso-cenanthyline, C9H16N2, is easily soluble in alcohol, spar-
ingly in ether, and insoluble in water. It crystallises in needles and
melts at 84°.
The author is now studying the action of bromine on these bodies
in the hope of throwing new light on their constitution, and so
deciding between the formulaB proposed respectively by Wallack,
Japp, and himself. L. T. T.
Glycocine. By T. Curtius (Ber., 16, 753— 757).— If ethyl acetyl-
amidacetate (m. p. 48° ; b. p. 260°), in hot alcoholic solution, is
treated with hydrochloric acid gas, it splits up into ethyl acetate, and
the hydrochloride of ethyl amidacetate, CH2(NH3Cl).COOEt. This
body is also produced quantitatively by acting on a solution of glyco-
cine in absolute alcohol with hydrochloric acid. It is very soluble in
water and alcohol ; crystallises well, sublimes undecomposed, and
melts at 144''. It forms an easily soluble platinochloride ; and is
decomposed into glycocine and alcohol when boiled with aqueous
alkali. If an aqueous solution of this substance be shaken with exactly
the calculated quantity of silver oxide, the solution extracted with
ether or chloroform, and this extract, after drying, evaporated in a
current of cold dry air, ethyl amidacetate, CH2(NH2).COOEt, is ob-
tained as a colourless oil. This oil is strongly basic and volatile, and
forms dense fumes with hydrochloric acid. With dilute hydrochloric
acid, the original hydrochloride is reproduced, concentrated mineral
acids split off carbonic anhydride, and silver nitrate produces a pre-
cipitate of silver carbonate. It is very unstable, and can only be
preserved in dri/ etheric solution. If any moisture is present, glyco-
cinimide-anhydridej CIl2\ I , is produced, and with acids it yields
a base melting at a high temperature, and showing the biuret reaction.
In aqueous solutions, this base is gradually converted into the imide.
Glycocinimide-anhydride has a neutral reaction, but appears to possess
feebly basic properties, and forms a platinochloride. It is easily
soluble in boiling water and alcohol. When heated quickly it melts,
and sublimes at about 280° to white needles ; if slowly heated, partial
decomposition sets in. It crystallises from its aqueous solution un-
changed, only a small quantity of glycocine being obtained from the
last mother- liquors on continued evaporation.
By the action of acetic chloride on silver amidacetate, the author
obtained an acid analogous to the acid C10H12N3O4, which he formerly
(this vol., p. 337) obtained with benzoic chloride. These acids are,
however, obtained more easily and in a purer state by heating free
glycocine with the ether of acetyl- or benzoyl-glycocine. When using
benzoyl-glycocine, small quantities of another acid- are obtained, having
physically similar properties and the same melting point (172°) as
hippurylamidacetic acid, but having the formula Ci3Hi5N305,H20.
This acid loses its water of crystallisation at 110°, and forms a silver
salt, CiaHuNaOfiAg. The author believes it to be henzoyldiamidoacetyl-
1088 > ABSTRACTS OP CHEMICAL PAPERS.
amidacetic acid, NHBi.CH2.CO.NH.CH2.CO.lSrH.CH2.COOH, standing
in the same relation to hipparamidacetic acid,
NHBi.CH2.CO.NH.CH2.COOH,
as the latter does to hippnric acid, NHBz.CH2.COOH.
Urea and ethyl benzoylamidacetate when heated together at 140 —
150°, yield hippuryl carbamide, NHBz.CHj.CO.NH.CONHj, which
crystallises in silvery scales melting at 216°, and decomposing at the
same time. Boiling with dilute acids splits it np into nrea and hip-
pnric acid.
The best method to prepare acetyl glycocine is to boil a mixture of
acetic chloride, glycocine, and benzene (the latter to prevent the tem-
perature rising too high) : the acid is thus obtained much freer from
secondary products than when the silver salt of glycocine is employed.
All the compounds of this acid are very soluble, and its ether distils
without decomposition. L. T. T.
Preparation of Acetamide and other Amides of the Acetic
Series. By Schulze (/. pr. Ghem. [2], 27, 512— 517).— By heating
20 grams of ammonium acetate with 26 grams of acetic anhydride, 96
per cent, of the theoretical quantity of acetamide can be obtained.
This mode of preparation, however, is costly, owing to the high price
of acetic anhydride. It can be more cheaply prepared by heating
1 molecule of ammonium thiocyanate with 2^ mols. of glacial acetic
acid for three or four days at about the boiling point. The decompo-
sition which takes place is shown by the equation CNS.NH4 + 2ZCHO
= 2ZCNH2 4- COS + H2O. When ammonium thiocyanate is heated
with formic acid, it readily yields formamide. If propionic acid be
employed, propionamide is formed. J. I. W.
Derivatives of Ethyloximide and Ethylsuccinimide. . By A.
Pinner {Ber., 16, 1655 — 1659). — The formation of ethylsuccinimide
hydrochloride, NH ! C(OEt).CH2.CH2.C(OEt) :NH,2HC1, and of suc-
cinamidine hydrochloride, NH \ C(NH2).CH2.CH2.C(NH2) : NH,2HC1,
has been described by the author (this vol., p. 731), and also the con-
version of the latter compound by water into succinimidine hydro-
ch2.c:nh
chloride, | >NH,HC1.* An attempt to obtain oximidine by the
CH2.C : NH
method yielded negative results.
Oxamidine hydrochloride, NH ! C(NH2).C(NH2) ! NH,HC1 + H2O,
can be obtained by the action of alcoholic ammonia on ethyl oximide
hydrochloride. It forms large plates, readily soluble in water,
sparingly in alcohol. It easily decomposes, especially in solution,
but can be recrystallised from water without being converted into
oximidine.
On adding an ammoniacal solution of silver nitrate to an aqueous
solution of succinimidine hydrochloride, a white precipitate of silver
* The errors in the formulse previously given are due to misprints in the original
paper.
ORGANIC CHEMISTRY.
1089
succinimidine, C4H6N'3Ag, is obtained, sparingly soluble in ammonia,
more readily in water, and very readily in nitric acid. Succinimidine
hydrochloride is decomposed by platinic chloride with formation of
succinic acid and precipitation of ammonium platinochloride. By the
action of methylamine on ethyl succinimide hydrochloride, dimethyl-
Clia.C : NMe
succinimidine TiydrocMoride, | "^-NHjHCl, is obtained, and not the
CH2.C:NMe
expected tetramethylsuccinamidine. It gives no precipitate with
ammoniacal solution of silver nitrate, but is decomposed by platinic
chloride in the same way as succinimidine. A. K. M.
Conversion of Nitrils into Imides. By A. Pinner {Ber., 16,
1643 — 1655). — The preparation of ethylformimide hydrochloride has
been previously described by the author (this vol., p. 731) ; also its
reactions with alcohols, with ammonia, and with amines. By means
of the same reaction he has prepared the following compounds : —
Methylformimide hydrochloride, NH ! CH.OMe,HCl, forming short
thick lustrous prisms ; pro^pylformimide hydrochloride, an oil crystal-
lising at low temperatures, moderately soluble in ether ; isohutylformi-
mide hydrochloride, also moderately soluble in ether, and crystallising
on cooling to lustrous scales ; amylformimide hydrochloride, crystal-
lising in scales, sparingly soluble in ether ; and henzylformimide
hydrochloride, forming scales almost insoluble in ether. By the
action of alcohols on these, orthoformates are obtained. In the pre-
paration of mixed orthoformates by the action, e.g., of methyl alcohol
on ethylformamide^ a number of products are formed (^.e., dimethyl
ethyl orthoformate and also the trimethyl and triethyl derivatives),
MO that the author has not succeeded in obtaining them all in a state
of purity. The following list contains the formulae and boiling points
of the orthoformates obtained : —
CH(0Me)3 102°
(MeO)2CH.OEt 116—120
(MeO)2CH.OPr 150—155
(MeO)2CH.OC5HH 234—240
CH(0Et)3 145
(EtO)2CH.OPr 165—170
CH(0Pr)3 192— 19&
(PrO)2CH.OMe 180—182
(PrO),CH.OEt 185—187°
(PrO)2CH.OC5Hn . . . 222—230
(C4H90)oCH.OPr .... 207—208
(C4H90)2CH.OPr .... 212—214
(C4H90)2CH.OC5Hu . 230—235
(C5HnO)2CH.OEt. . . . 253—255
(C5HnO)2CH.OPr . . . 254^-255
CH(OC6H„)3 260-265
Dimethylformamide obtained by the action of an alcoholic solution of
methylamine on ethylformimide yields a platinochloride,
(NMe : CH.NHMe)a,H2PtCl6,
crystallising in short prisms, readily soluble in water. The platino-
chloride of the corresponding ethyl derivative^
(NEfc : CH.NHEt)2,H2PtCl6,
is only sparingly soluble in cold, but readily in hot water, from which
it crystallises in thick red prisms. By the action of dimethylamine
VOL. XLIV. 4 d
1090 ABSTRACTS OF CHEMIOAL PAPERS.
on ethylforraimide hydrochloride, isodi/rnethylformamidme hydrochlo-
ride, NH : CH.NMe2,HCl, is produced, melting at 168—169°. It is
deliquescent, readily soluble in water and in alcohol, and crystallises
in prisms of a vitreous lustre. Different results are obtained by the
action of diethylamine and of methylaniline ; the former yielding a
compound of the formula CioH2iN3,HCl, and the latter methylformani-
lide, CHO.NiyiePh, boiling at 243—244°. By the action of tertiary
amines, ethylformimide is liberated, and salts of the amines pro-
duced. Acetylformimide, NH '. CH.OXc, is obtained by the action of
acetic anhydride on ethylformimide acetate, and forms short thick
white prisms melting at 70°, and readily soluble in the ordinary
solvents.
The author has also prepared the ethyl derivatives of acetimide,
propionimide, capronimide, and benzimide, and from hydrocyanic acid
and glycol he has obtained ethyleneformimide hydrochloride,
(NH:CH.O)2aH4,2HC],
Ethylacetimide hydrochloride, NH ! CMe.OEt,HCl, forms fern-like
groups of lustrous rhombic plates ; ethylacetimide, NH ! CMe.OEt, is
a liquid of peculiar odour boiling at 97°. Ethylpropionimide hydro-
chloride, NH! CEt.OEt.HCl, crystallises in prisms. It is decomposed
by alcoholic ammonia with formation of propionamidine hydrochloride,
NH ! CEt.NH2,HCl, a crystalline deliquescent compound. Ethylcapron-
imide hydrochloride is an oil. Ethylbenzimide hydrochloride,
NH:CPh.OEt,HCl,
forms large transparent prisms decomposing at 118 — 120" before
melting. A. K. M.
Aldehyde- ammonium Bases. By G. Meter {Ber., 16, 1444). —
The author has not succeeded in again obtaining a good yield of
trimethylaldehydeammonium iodide by the method he previously
described (this vol., 568). W. C. W.
Dicyanodiamide. By E. Bamberger (Ber., 16, 1459—1464). —
Guanylthiocarhamide (thiodicyanodiamidine) is best prepared by di-
gesting dicyanodiamide with sulphuretted hydrogen water at 60 — 70°.
The base is precipitated from the solution by the addition of ammo-
nium oxalate and oxalic acid. The precipitate is decomposed by
baryta- water, in order to obtain the free base. If ammonium sul-
phide is substituted for sulphuretted hydrogen, ammonium thio-
cyanate and thiocarbamide are also formed. Guanylthiocarhamide
can also be prepared by heating a salt of guanylcarbamide (dicyan-
diamidine) with sulphuretted hydrogen water.
Ammonia and methylamine are formed when dicyanodiamide is
reduced by zinc and hydrochloric acid, but the presence of guanidine
could not be detected. A sodium salt, CQHsNiNa, is precipitated
when alcoholic solutions of sodium ethylate and dicyanodiamide are
mixed ; it is soluble in water and in dilute alcohol. It is decomposed
by carbonic acid. With hydrochloric acid it yields guanylcarbamide.
ORGANIC CHEMISTRY. 1091
The author considers that the constitution of dicyanodiamide is
best represented by the formula NH! C(NH2).NH.C]S'.
w. c. w.
Thiophene, a Substance contained in Coal-tar Benzene. By
V. Meyer (Ber., 16, 1465 — 1478). — T?je fact that benzene from coal-
tar has the power of yielding a deep blue coloration, due to the for-
mation of indophenine, when shaken with isatin and strong sulphuric
acid (this vol., 315), is owing to the presence of about 05 per cent, of
a sulphur compound, C4H4S, to which the author has given the name
thiophene. Benzene from benzoic acid does not contain this impurity,
and consequently does not yield the indophenine reactions with sul-
phuric acid and isatin.
In order to obtain thiophene in sufficient quantity for investiga-
tion, 250 litres of the purest commercial benzene were shaken with
25 litres of strong sulphuric acid for four hours. The layer of acid
was separated from the benzene, diluted with water, and a lead salt
of thiophenesulphonic acid precipitated. The oily liquid obtained by
distilling the lead salt with ammonium chloride is washed with water
and with potash, to remove mercaptan. It is then dried over calcium,
chloride and distilled. The distillate (b. p. 84°) consists of a mixture
of thiophene (70 per cent.) and benzene (30 per cent.). It does not
solidify when surrounded by a freezing mixture of ice and salt. It
dissolves in strong sulphuric acid at the ordinary temperature, but
the solution soon decomposes, evolving sulphuretted hydrogen and
sulphurous anhydride. IDecomposition does not, however, ensue if
the liquid is diluted with 100 times its volume of light petroleum.
Pure thiophene is obtained by converting this sulphuric acid solution
into lead thiophenesulphonate, and distilling the lead salt with ammo-
nium chloride. Thiophene is a colourless mobile oil boiling at 84°, im-
miscible with water. Its sp. gr. at 23° is 1*062 compared with water
at the same temperature. Thiophene is not attacked by sodium, but
is readily oxidised by nitric acid, and yields two substitution -products
when acted on by bromine. Monohromothiophene (b. p. 150°) is pro-
duced in small quantities in the preparation of the dibromo-cora pound.
It bears a close resemblance to monobrombenzene. The sp. gr. of the
compound is 1"652 at 23°. Dibromothiophene (b. p. 211°) closely
resembles dibromobenzene in its chemical and physical properties.
Like this substance, it does not readily wet glass. The sp. gr. of
dibromothiophene is 2*147 at 23°.
In consequence of the author's discovery that the formation of
indophenine is entirely due to the presence of thiophene in the ben-
zene used, Baeyer has examined his specimen of indophenine, and
found that it contains sulphur. W. C. W.
Tetrethylbenzene and Hexethylbenzene. By K. Galle (Ber.^
16, 1744 — 1748). — To prepare tetrethylbenzene, a mixture of alu-
minium chloride, benzene, and ethyl bromide is heated at 100° in
sealed tubes for nine hours. The tubes are opened three or four
times, and fresh ethyl bromide introduced. The crude product is
purified by treatment with strong sulphuric acid and fractional dis-
tillation. The portion boiling above 255° is again heated for six
4 d 2
1092 ABSTRACTS OF CHEMICAL PAPERS.
hours to convert it into hexethylbenzene. The portion boiling
between 250° and 255° is dissolved in double the volume of faming
sulphuric acid at 60°. By carefully adding one-fourth of the volume
of water to the solution tetrethylhenzenesulphonic acid is obtained as a
silky crystalline mass.
The harium salt, (Ci4H2iS03)2Ba,6H20, crystallises in flat prisms,
which are sparingly soluble. The sodium salt, CuH2iS03Na,5H20,
forms microscopic quadratic plates, which effloresce on exposure to
the air. The copper salt, crystallising in lustrous plates containing
8 mols. H2O, and the cadmium- salt in prisms containing 7 mols. H2O,
are less soluble than the barium sulphonate. The sulphamidCf
CUH21.SO2NH2,
melting at 104 — 105°, crystallises in glistening scales which melt at
104°, and dissolve freely in alcohol and in glacial acetic acid.
Tetrethylhenzene, prepared from the sodium sulphonate, is a colour-
less oil, lighter than water, b. p. 251°. Monohromotetrethylhenzene,
CuHaiBr (b. p. 284°), is a heavy liquid. The (?i6romo-derivative,
Ci4H2oBr2, forms colourless prisms, soluble in alcohol. It melts at
74'5°, and boils at 330°. Dinitrotetrethylhenzene is deposited from an
alcoholic solution in pale lemon -coloured rhombic prisms melting at
115°.
Prolonged boiling with a solution of potassium permanganate
converts tetrethylbenzene into prehnitic acid.
In the preparation of tetrethylbenzene, an isomeride appears to be
formed, which yields a dibromo- derivative crystallising in flat prisms
melting at 110".
Hexethylbenzene, CisHso, is deposited from alcohol in long mono-
clinic prisms, soluble in ether and in hot alcohol. It melts at 126°,
and boils at 305° (corr.). It is identical with the hydrocarbon de-
scribed by Allright, Margan, and Woolworth (Gompt. rend., 86, 887).
Hexethylbenzene dissolves in warm fuming sulphuric acid, and is
deposited unaltered on cooling. Treatment with a mixture of strong
nitric and sulphuric acids converts the hydrocarbon into dinitro-
tetrethylbenzene. Similarly dibromotetrethylbenzene is produced by
the action of bromine on a dry mixture of iodine and hexethyl-
benzene. W. C. W.
Coal-tar Toluene. By V. Meter {Ber., 16, 1624— 1625).— The
author finds that pure toluene does not give Laubenheimer's colour-
reaction with phenanthraquinone {Ber., 8, 224), this property being
destroyed by agitating toluene with concentrated sulphuric acid. It
appears that coal-tar toluene contains a substance analogous to thio-
phene (this vol., p. 1091), which, like the latter, can be removed by
sulphuric acid. A. K. M.
Chlorides of Ortho- and Meta-nitrobenzyl. By M. Abelli
{Gazzetta, 13, 97 — 99). — Chloride of benzyl is allowed to drop
slowly into five times its weight of nitric acid (sp. gr. 1*5), kept cool
by immersion in water ; the product is then precipitated by water, the
solid paranitrobenzyl compound separated by a vacuum filter, and the
ORGANIC CHEMISTRY. 1093
oil, cooled by a frigorific mixture, is again filtered in the same manner
to remove the portion of the para-compound which crystallises out.
The oil could not be distilled per se, even under reduced pressure, but
it passed over in a current of steam as a yellowish oil. On analysis it
j^ave numbers corresponding with the formula C6H4(N02).CH2C1.
When oxidised by potassium permanganate, it yielded a mixture of
para-ortho- and meta-nitrobenzoic acids, showing that the oil is a
mixture of ortho- and meta-nitrobenzyl chlorides holding some of the
para-compound in solution. C. E. Gr.
Trinitrotoluene and Liquid Dinitrotoluene. By A. Glaus
and H. Becker {Ber.^ 16, 1596 — 1598). — From a comparison of the
crystalline form of trinitrotoluene with that of symmetrical trinitro-
benzene, Vriedlander concluded that the former must also have a
symmetrical constitution, C6H2Me(N02)3 [Me : NO2 : N"02 : NO2 =
1:2:4:6], With a view to establish this constitution, the authors
heated trinitrotoluene with concentrated nitric acid in sealed tubes at
180°, and obtained symmetrical trinitrobenzene melting at 121 — 122°.
It is evident from this constitution that the dinitrotoluene obtained by
Staedel and Becker from the trinitro-compound must have the
formula C6H,Me(N02)2 [Me : NO2 : NO2 = 1:2:6], the only other
possible one being the known [1:2:4] dinitrotoluene. From this
solid dinitrotoluene, Staedel and Becker obtained, however, the same
nitrotoluidine which Cunerth {Annalen, 217, 205) and Bernthsen
{Annalen, 172, 223) prepared from liquid dinitrotoluene. From an
examination of the latter, the authors find it to consist of a mixture
of two solid dinitrotoluenes, trinitrotoluene, and orthonitrotoluene, its
liquid condition being due to the presence of the mononitro-deriya-
tive. A. K. M.
Derivatives of Diethyl-toluene.* By W. Dafert {Monatsh. Ckem.,
4, 616— 629).— Diethyl-toluene, CnHie = Celi,.CR(EU), discovered
in 1867 by Lippmann and Louguinine (Annalen^ 145, 106), is pre-
pared by the action of zinc-ethyl mixed with an equal volume of ben-
zene on benzylidene chloride: C6H5.CHCI2 -I- ZnEtj = ZnCl2 -f
C6H5.CHEt2. The process may be conducted either at ordinary
temperatures, or at 40° in a flask filled with carbonic anhydride, the
benzylidene chloride being added by drops, and the mixture cooled if
the escape of vapour becomes violent. The pasty product is added
to water acidulated with hydrochloric acid, and the pale yellow oil
which rises to the surface is washed with aqueous sodium carbonate
and with water, then filtered, dried, and fractionated, the fractions
170—190°, 190—210°, and 210° to beyond the ordinary thermometric
range, being collected separately.
Fraction 1 (170 — 190°) is a turbid mobile yellow liquid, which may
be freed from chlorinated products by heating it in a sealed tube at
100° with lead nitrate, and from benzaldehyde, formed in the treat-
* Called by the author Amyl-hemene ; but this name (or Isopentyl-henzene)
belongs properly to the isomeric hydrocarbon, C6H5.C2H4.CHMe2, obtained by the
action of sodium on a mixture of monobromobenzene and isopentyl or amyl bromide,
CoH^.CHMeijBr.— JI. W.
109 i ABSTRACTS OP CHEMICAL PAPERS.
ment, by agitation with acid Bodinm sulphite. It is then several
times fractionated, the greater part distilling at 178 — 180°. This
portion is die thy 1-tolnene. It is a stronofly refractive, colonrless,
aromatic liquid, having a density of 0*8731 at 21°, very slightly
attacked by reagents, slightly soluble in sulphuric and nitric acids.
It is not attacked by ordinary chromic acid mixture, but is slowly
oxidised by chromic trioxide dissolved in glacial acetic acid, yielding
the monosulphonic acid CuHis.SOsH, the barium salt of which crys-
tallises in large nacreous laminae, having the composition
(C„H,».S03)2Ba + IH2O.
By the action of nitric acid on diethyl- toluene, soluble nitro-products
are obtained, partly oily, partly solid, having a persistent odonr, and
reducible by zinc in acetic acid solution, yielding a base whose hydro-
chloride forms white needles, together with a deep purple dye-stuff.
Fraction II (b. p. 190 — 210°) consists chiefly of benzylidene chlo-
ride, showing that the action of the zinc-ethyl on that compound is
by no means complete.
Fraction III (b. p. 210°) is a thick red oil, which has the odour
of the paraffins, and when gently heated with fuming sulphuric acid
yields a yellow oil, which, after solution in alcohol, precipitation
with water, drying, and distillation, has the composition of bi-
diethyl-tolyl,* C^^Hgo = CHEt2.C6H,— CeHi.CHEts. This com-
pound is a pale yellow oil, having a peculiar odour, miscible with
alcohol and ether in all proportions, but not with water, boiling
above 360°, and not solidifying at 0°. It dissolves, with aid of heat,
in sulphuric and nitric acids, and yields substitution-products with
bromine and iodine, in the latter case only when heated.
On adding bromine (1 mol.) to boiling diethyl-toluene, the latter is
converted, with copious evolution of HBr, but without carbonisation,
into a heavy dark-brown transparent oil ; and on washing this with
aqueous sodium carbonate and with water, then filtering, drying, and
distilling in a vacuum, an oil is obtained, clear and colourless at
first, but turning brown and opaque and decomposing towards the
end. The colourless portion, when distilled, washed, and dried, gave
by analysis numbers agreeing with the formula of bromodi ethyl-toluene
or diethyl-tolyl bromide, CiHisBr = CHaMe.CHPh.CHBrMe.
When this last compound is added by degrees to boiling water, a
fragrant oil is obtained, which floats on the water, and after washing,
drying, and heating with sodium at 170 — 180° for a day or two, is
free from bromine, and distils almost completely at 170 — 180**. The
liquid thus obtained has the composition of a pentenyl-benzene, CnHu
= CsHsrCfiHg), or a polymeride thereof, and is formed from the bromo-
diethyl-toluene by simple abstraction of HBr.
The same compound is formed, together with di-peiitenyl-benzene^
CzzHas, by the action of alcoholic potash on bromodiethyl-toluene. The
two compounds are separated by fractional distillation, the first,
which has not been obtained quite pure, distilling at 173 — 177°, the
second at 208—212°. The former has a density of 08458 at 23°, the
• Called in the original paper, JHamylphenyl.
ORGANIC CHEMISTRY. 1095
latter 0*9601 at the same temperature. Pentenyl-benzene absorbs
bromine, yielding the compound CuHuBrz, in the form of an oil, which
attacks tbe eyes strongly, and gives up its bromine to caustic potash.
Dipentenyl-benzene is not acted on by bromine at ordinary tempera-
tures, but yields sabstitution- products wben beated therewith.
According to its synthesis from the bromide
CHPh. (CHBrMe) .CHoMe,
pentenyl-benzene and dipentenyl-benzene may be represented by the
following formulas : —
CH : CH2 CH2Me.CHPh,CH.CH2
Ph.CH<^ I I .
^CH2.CH3 CHaMe.CHPh.CH.CH2
The polymerisation of pentenyl-benzene is in accordance with
Perkin's view (Chem. News, 1877, 271), that polymerisation takes
place with especial facility in those hydrocarbons which contain the
group — CH : CH2.
Pentenyl- and dipentenyl-benzene are but slowly oxidised by ordi-
nary chromic acid mixture or by aqueous chromic acid ; but chromic
anhydride dissolved in glacial acetic acid acts violently on pentenyl-
benzene, yielding benzoic and acetic acids. Dipentenylbenzene
similarly treated yields products the nature of which has not yet been
determined. H. W.
Mesitylene. By Robtnet and Colson (Gompt. rend., 96, 1863 —
1864). — M.esitylenic glycol, C6H3Me(CH2.0H)2, is obtained by the pro-
longed ebullition of mesitylene dichloride (m. p. 41*5°) with an excess
of lead carbonate suspended in water. It is a colourless viscous liquid,
which boils at 190° under a pressure of 20 mm. and at 280° with par-
tial decomposition under a pressure of 750 mm. ; sp. gr. 1'23 at 25°.
It has a bitter taste, is very soluble in alcohol, dissolves in twice
its weight of anhydrous ether, and in about twenty times its weight of
water. When treated with fuming hydrobromic acid, it yields
mesitylene dibromide melting at 66*4°.
Mesitylene diacetate, C6H3Me(CH2.3[cO)2, is obtained by prolonged
ebullition of a mixture of mesitylene dichloride, acetic acid, and silver
acetate. It is a colourless oily liquid, which boils at 244° under a
pressure of 120 mm. ; sp. gr. at 20° = 1*12. It is almost inodorous,
but has a disagreeable burning taste. When saponiiBed with potas-
sium carbonate it yields the glycol previously described.
C. H. B.
Derivatives of Mesitylene. By P. Wispek {Ber., 16, 1577^
1680). — Mesityl bromide, CeHaMez.CHjBr, forms long white prisms
melting at 37"5 — 38°, and boiling (with slight decomposition) at
229 — 231° under a pressure of 740 mm. It dissolves readily in
alcohol, ether, and chloroform, and crystallises from hot other in
clusters of long needles. Its vapour is very irritating to the eyes.
Mesityl acetate, CgHn.O.^^c, is a colourless liquid of agreeable ethereal
odour boiling at 228—231° (745 mm.) j its sp. gr. is 10903 at 165°.
1096 ABSTRACTS OF CHEMICAL PAPERS.
On saponification with alcoholic potash, a colourless liquid is obtained
boiling at 218 — 221°. It is heavier than water, resembles benzyl
alcohol in odonr, and is doubtless mesityl alcohol, CgHn.OH.
Symmetrical dimethylphenylacetic acid, C6H3Me3.CH2.COOH, dissolves
readily in alcohol and in ether, very sparingly in cold water,
moderately in boiling water ; under hot water, it melts before dissolv-
ing, and crystallises in long prisms resembling phthalic anhydride.
It melts at 100°, boils at 273° (735 mm.), and volatilises veiy slowly
in a current of steam. When warmed with alkaline permanganate
solution, it is readily oxidised, with formation of uvitic acid, whilst
with dilute nitric acid it yields a-nitro-dimethylphenylacetic acid.
Concentrated nitric acid at 0° dissolves it unchanged; at ordinary
temperatures, with formation of two nitro-acids.
The potassium salt, CgHn.COOKjHzO, crystallises in slender silky
needles; the calcium salt, (C9Hii.COO)2Ca,3H20, in hard thick trans-
parent well-formed needles, which are readily soluble in water, and
lose half their water of crystallisation over sulphuric acid ; the barium
salt, (C9Hii.C00)2Ba,4H20, in well-formed characteristic transparent
prisms, which lose their water of crystallisation over sulphuric acid ;
the magnesium salt, (C9Hu.COO)2Mg,5H20, in stellate groups of long
slender silky needles, and the silver salt, CgHn.COOAg, in long thin
needles soluble in boiling water.
OL-NitrodimethyljpTiemjlacetic acid,
C6H2Me2(ISr02).CH2.COOH [CH2.COOH : NO2 : Me : Me = 1 : 2 : 3 : 5 ],
obtained by warming dimethylphenylacetic acid with dilute nitric
acid for 6 — 8 hours, crystallises from hot water in long slender
yellowish-coloured needles melting at 139°, and readily soluble in
alcohol and in ether, sparingly in boiling water, and insoluble in cold
water. The calcium, salt, (C9HioN'02.COO)2Ca,4H20, forms large
thick transparent needles, which lose their water at 100°, and detonate
when strongly heated; the barium salt, (C9HioN'02.COO)2Ba,44H20,
behaves in the same way, and crystallises in slender needles ; the
silver salt, C9HioN02.COOAg, melts on heating and burns, leaving a
residue of spongy silver. On reducing a-nitrodimethylphenylacetic
acid by means of tin and hydrochloric acid, and pouring the product
CH
into cold water, carbomesyl, C6H2Me2<^-jyq^TT^]>CO, is obtained as a
voluminous white precipitate. It is very stable, crystallises from hot
dilute alcohol in white needles, which become brown at about 215° and
sublime ; it melts at 231 — 232°. It is insoluble in cold water, very
sparingly soluble in hot water, readily in hot alcohol or benzene, in-
soluble in ammonia, soluble in warm potash, in hot concentrated
hydrochloric acid, and in cold concentrated sulphuric acid; water
precipitates it unchanged from the two latter solutions.
A. K. M.
Reaction of Aromatic Amines with Lactic Acid. By
O. Wallace and M. Wijsten' (Ber., 16, 2007— 2010).— The authors
have examined the reaction between hydroxyl-acids and aromatic
amines with a view of preparing substances allied to oxindole or
quinoline.
ORGANIC CHEMISTRY. 1097
On heating a mixture of aniline, nitrobenzene, and lactic acid with,
concentrated sulphuric acid, a basic substance boiling at 246"" was
obtained, of the composition C10H9N, or a methylquinoline, which is
probably identical with Dobner's quinaldine. On heating this base
and benzaldehyde in molecular proportions with zinc chloride, a crys-
talline basic substance (m. p. 100°) of formula C17H13N was obtained.
This base combines directly with bromine to form an addition-product.
OivHsNBrs, crystallising in white iridescent leaflets melting at 173°.
This shows that the base CivHialSr is an unsaturated compound, and if
the original base be a methyl quinoline, its composition must be ex-
pressed by the formula (C9H6N)CH ! CHPh, or a representative of a
new series of compounds. The authors also briefly examined ana-
logous substances obtained from metanitrobenzaldehyde and ortho-
and para-hydroxybenzaldehyde. Y. H. V.
Decomposition of Rosaniline by Water. By C. Liebeemann
(J5er., 16, 1927 — 1931). In former experiments, on the decomposition
of rosaniline by water, the author obtained, besides dihydroxybenzo-
phenone, two nitrogenous substances whose separation not only from
hydrobenzophenone, but also from one another, presented several diffi-
culties. The author, working on a larger scale, has succeeded in
separating them by processes described in full in the communication,
and has isolated diamido- and hydroxyamiido-methylbenzophenone. The
former, C6H4(NH2).CO.C6H3Me.NH2, crystallises in needles of a pale
red colour, which melt above 220° and are soluble in hydrochloric
acid, insoluble in alkahs. With benzoic chloride, it gives a dibenzyl-
derivative, C6H4(NHBz).CO.C6H3Me.N"HBz, crystallising in needles
melting at 226°. Hydroxyamidomethylbenzophenone,
C6H4(OH).CO.C6H3Me.NH2,
forms colourless needles, soluble in soda, insoluble in acids and
ammonia ; it gives a dibenzyl-derivative,
C6H4(OBi).CO.C6H3Me.NHBi,
which crystallises in needles melting at 192°.
Judging from the results obtained on the decomposition of rosolic
acid by water, it would appear that in the corresponding decomposi-
tions of rosaniline, besides the three substances, dehydroxydiamido-
methyl- and hydroxyamidomethyl-benzophenone, homologues of them
are also formed. V. H. Y.
The Violet Derivatives of Triphenylmethane. By O. Fischer
and L. German (Ber.^ 16, 706 — 710). — In a paper on methyl-violet
derived from triphenylmethane (Abstr., 1879, 787), E.and 0. Fischer
came to the conclusion that this body was penfamethylpararosaniline.
Several reasons, however, and especially the fact that the sixth amido-
hydrogen-atom could not be replaced by methyl, led the authors of the
present paper to doubt the correctness of that conclusion. They have
therefore subjected methyl-violet to further investigation. It was
prepared as before described; the melting point is 173°, not 163°, as
erroneously given in the former paper. If this substance contained
1098 ABSTRACTS OF CHEMICAL PAPERS.
only five methyl-gronps, the sixth hydrogen-atora shonld be replaceable.
All the authors' endeavours to replace it by continued treatment,
at all temperatures below that at which decomposition sets in, with
acetic anhydride, acetic and benzoic chlorides, proved fruitless.
Neither could the so-called hexmethylparaleucaniline be obtained by
the action of metallic sodium and methyl iodide.
To show that the complexity of the molecule is not the cause of
this difficulty of replacement, the authors have made the acetyl-com-
pound of tetramethylparaleucaniline ; this substance by exhaustive
methylation yields the same end-product as methyl- violet, so that the
two compounds must stand in close relationship.
Aceti/Uetramethylparaleucaniline, C25H29N3O, is easily produced by
boiling the base with excess of acetic anhydride. It crystallises in
needles melting at 108°. It is still a strong base, and its dilute sul-
phuric acid solution, when treated with manganese dioxide, gives
acetyltetrainethylpararosaniline, a fine green colouring-matter. If this
is boiled with concentrated hydrochloric acid, the acetyl-group is split
off, and the same violet is obtained as by the direct oxidation of tetra-
methylparaleucaniline by chloranil. This is in agreement with the
fact pointed out by E. and 0. Fischer that it is the free amido-groups
in the triphenylmethane-derivatives which are the colour-determining
elements. The green colour to which methyl-violet turns on addi-
tion of hydrochloric acid is without doubt due to the acid becoming
added to one of the amido-groups, and thus neutralising it.
From all these facts, the authors believe that methyl-violet is not a
penta-methyl-compound, but is hexmethylpararosaniline, and that the
above-mentioned hexmethylparaleucaniline is really an ethane deri-
vative, and is converted into a methane derivative only during the
oxidation. Finally the authors believe that the colouring-matter
Wichelhaus obtained (Abstr., 1882, 58) by acting on dimethyl aniline
with chloranil is really the lea co-base of methyl- violet, and has not
the formula 01611201^2, which Wichelhaus adopted. His analyses agree
just as well with the formula C25H31N3 as with CieHjoNa.
L. T. T.
Dye-stuff from Dimethylaniline and Chloranil. By H.
Wichelhaus (Ber., 16, 2005 — 2007). — In some former experiments,
the author was unable to prepare in a sufficiently pure state a crys-
talline substance formed by the action of dimethylaniline on chloranil.
By an improvement in the method, this base was successfully
purified, and obtained in the form of small colourless prisms melting
at 190°, having the composition C21II29N3O, insoluble in water and
sparingly soluble in alcohol. As this base and rosaniline have the same
composition, the author has re-examined the latter, and proved that it
is a mixture of two isomeric substances, one of which is identical
with the product from dimethylaniline and chloranil, whilst the other
is a red-brown powder melting at 130°. These two substances can be
separated by frequent solution in sulphuric acid and reprecipitation
by alcohol, and then boiling the precipitate frequently with petroleum,
which leaves the red-brown powder undissolved. When reduced
with tin and hydrochloric acid, the dye-stuffs give isomeric sub-
ORGANIC CHEMISTRY. 1099
stancfi^, the one forming glistening leaflets melting at 173°, which
readily assume a violet colour, the other, steel-grej prismatic crystals
melting at 155°. V. H. V.
Formation of Nitrile Bases from Organic Acids and Amines.
By A. Bernthsen (Ber., 16, 767— 769).— In a former paper (this
vol., p. 580) the author described the formation of a base C19H13N,
by the abstractiori_of water by means of zinc chloride from benzoyl-
diphenylamine, NBzPhj. The author, in conjunction with F. Bender,
has now prepared the same substance directly from benzoic acid and
diphenylamine by heating them with zinc chloride. This reaction
appears to be a general one. Formic acid and diphenylamine (and also
ready-formed formyl diphenylamine) yield a base with an exceed-
ingly burning taste, and having the formula CjsHgN. It forms an
easily soluble hydrochloride and a yellowish-green platinochloride.
Ammonia precipitates the base from a solution of its hydrochloride
in the form of a white crystalline powder. 0. Fischer has recently
(Ber., 16, 74) obtained the analogous base, CuHuN, from diphenyl-
amine and glacial acetic acid. L. T. T.
Action of Acetic Anhydride on the Amidines. By A. Pinner
(Ber., 16,1659 — 1663). — Pinner and Klein showed that dibenzimidine,
NH : CPh.NH.CPh ! NH, is produced by the action of acetic anhy-
dride on benzamidine (J?er., 11, 8). With a view to examine other
amidines in the same direction, the author heated a mixture of acetic
anhydride, formamidine hydrochloride, and sodium acetate, but,
instead of the desired product, he obtained diacetylformamidine,
NZc ! CH.NHXc, crystallising in short thick lustrous prisms
sparingly soluble in cold water, moderately in hot water, and very
sparingly in alcohol. It sublimes at a high temperature without melt-
ing. From propionamidine hydrochloride, sodium acetate, and acetic
anhydride, a compound is obtained of the formula CsHiaNa. Ifc is very
sparingly soluble in cold water, more readily in hot water, and readily
in alcohol and in acids ; it melts at 204° and sublimes in the form of
long white prisms. The platinochloride, CsHiaNajHzPtCle + 3HoO,
crystallises in large red rhombic plates. The formation and constitu-
tion of this substance may probably be explained by the following
equations : —
2NH : CEt.NHg + J^jO = NH : CEt.NH.CEt : NH +
and NH \ CEt.NH.CEt ! NH -f 5B0H = 2H,0 -h
/CEfc : K
N^ ^CMe.
^CEt : W
in which case it must be regarded as ethenyldipropionimidine, or it
may be assumed to be a homologue of cyanethine, thus
Etc N.CMe
I II ;
N : CEt.N
llOO ABSTRACTS OF CHEMICAL PAPERS.
but its high, melting point and the composition of its platinochloride
are opposed to the latter formula. A. K. M.
Azylines. By E. Lippmann and F. Fleissner (Ber., 16, 1421—1434).
— By the cautious addition of potassium nitrite to a solution of di-
raethylanilineazyline in glacial acetic acid, paranitrodimethylaniline is
produced. By a similar reaction, diethylanilineazyline is converted into
jmranitrodiethylaniline, identical with the nitrodiethylaniline obtained
by the oxidation of nitrosodiethylaniline. This substance (m. p. 76°)
crystallises in monoclinic needles [a : 6 : c = 1"0342 : 1 ; 0"8245,
(y = 99° 27']. The crystals are yellow in colour and dissolve freely in*
warm alcohol. The nitro-products form platinochlorides crystallising
in triclinic prisms.
Nitrous acid acts on azylines as an oxidising agent ; the acid being
reduced to nitric oxide ; but as no nitrogen is liberated during the
reaction, the nitro-product must be produced by the direct union of
oxygen with the nitrogen-atoms occupying the para-position.
Diethylanilineazyline is converted into diethylparaphenylenediamine
by treatment with stannous chloride. This base, which can also be
prepared by the reduction of nitrosodiethylaniline, boils at 260 — 262°.
It exhibits the following reactions : — With sodium hypochlorite a
brown coloration, with potassium chromate a violet coloration, with
iodine and copper sulphate a red coloration. Ferric chloride first pro-
duces a red coloration, which is followed by a precipitate. The
platinochloride forms red or yellow triclinic plates. When a mixture
of diethylanilineazyline (1 mol.), ethyl iodide (4 mols.), and a small
quantity of alcohol is heated at 100° in sealed tubes, free iodine,
resinous bye-products, and tetrethylphenylenediamine hydriodide,
C6H4(NEt2)2,2HI, are formed.
Tetretlmjlplienylenediamine prepared by the addition of potash to
this iodide, or from diethylphenylenediamine, melts at 52° and boils at
280°. It forms monoclinic plates which sometimes resemble cubes in
appearance [a : 6 : c = 0*99 : 1 : 1"833, 7 = 90° 30']. The base is very
soluble in ether, chloroform, benzene, and light petroleum. It is best
purified by recrystallisation from a mixture of alcohol and water. The
platinochloride, CeHi (NEt2)2,H2PtCl6, forms pale yellow cubical crys-
tals. The double mercuric chloride, C6H4(NEt.)2,2HCl,2HgCl2,
crystallises in the monoclinic system. The penodide, C6H4(NEt2)2,l6»
forms black prisms sparingly soluble in alcohol. The iodide produced
by the action of methyl iodide on diethylanilineazyline does not yield
a base on the addition of potash, but bases were obtained in this way
from the iodides prepared by the action of ethyl iodide on dimethyl-
anilineazyline and on dipropylanilineazyline, which boil at 275° and
at 295 — 300° respectively. Azylines do not alter on exposure to the
air. When azyline is oxidised by potassium permanganate, ammonia,
and acetic, carbonic, and oxalic acids are formed. The constitution of
these azylines may be represented by the type
NEt2.C6Hi.N : N.C6H,.NEt3 W. C. W.
ORGANIC CHEMISTRY. 1101
Substitution-products of Azobenzeneparasulphonic Acid.
By J. V. Janovsky (Ber., 16, 1486— 1490).— The author has pre-
viously pointed out (Ber., 15, 2576) that in the nitration of azoben-
zeneparasulphonic acid, two nitro-derivatives are formed, viz., a meta-
compound, C6H4(N02)N ! NC6H4.SO3H [NO2 : N. IS : SO3H = 3:1:1:4],
and the isomeric a-acid [NO2 : IST : N : SO3H = 4:1:1:4]. The best
conditions for obtaining the a-acid are to keep the temperature of the
mixture below 100°, and not to use a large excess of nitric acid (1 of
azobenzenesulphonic acid to 5 — 6 parts of nitric acid, sp. gr. 1*4) .
The a-acid crystallises in beautiful needles of a fiery hue. It is depo-
sited from dilute nitric acid in rhombic plates. A warm concentrated
aqueous solution gelatinises on cooling. The salts of this acid crys-
tallise readily; I^02.Ci2E[8N'2-S03K forms orange-coloured rhombic
plates, sparingly soluble in water. 100 c.c. of water at 17° dissolve
0-161 gram of the salt. NOa.CisHgNa.SOsN'a + 2H2O crystallises in
monoclinic plates or needles, which are sparingly soluble in water.
The addition of potash or soda to a moderately-concentrated aqueous
solution of the acid produces a crystalline precipitate of the potassium
or sodium salt respectively. The barium salt, (N02.Ci2H8N2.S03)2Ba,
forms crystalline scales, sparingly soluble in water. On reduction
with tin and hydrochloric acid, the a-nitro-acid is converted into para-
phenylenediamine and sulphanilic acid; but on cautious treatment with
stannous chloride, it yields the hydrazamido-acid, NH2.Ci2H8N^2H2.S03H.
This substance forms microscopic rhombic crystals, which are very
sparingly soluble in water ; 100 parts of water at 97° dissolve
0'39 gram of the acid. The potassium salt forms golden crystals,
sparingly soluble in cold water. The sodium salt is freely soluble.
The barium salt forms flat rhombic prisms, containing 4 mols. H2O.
If, however, an alcoholic solution of the nitro-acid is reduced by
ammonium sulphide, amidazohenzene'parasuljphonic acid is produced :
100 c.c. of water at 22° dissolve 0"0168 gram of the acid. From hot
water, it is deposited in salmon-coloured plates. The potassium salt,
N'Ho.Ci2H8N2.S03K -f H2O, forms golden rhombic plates. The sodium
salt crystallises in needles ; both salts dissolve freely in water. The
barium salt, (NH2.Ci2H8N2.S03)2Ba + 61120, forms brilliant needles,
resembling potassium chlorobromate ; 100 c.c. water at 24° dissolve
0"064 gram of the salt. The calcium salt crystallises in beautiful
efilorescent yellow plates, containing 4 mols. H2O ; 100 c.c. water at
18'5° dissolve 0*2589 gram. The lead salt forms monoclinic plates of
an orange colour ; its solubility is 0*0642 gram per 100 c.c. water at
18-5°. Since this acid yields sulphanilic acid and paraph enylene-
diamine on reduction, its constitution may be represented by the
formula C6H4(NH2).N2.C6H4.S03H [NHa : N : N : SO3H =4:1:1:4];
but this is identical with the formula for the sulphonic acid obtained
by the action of aniline on the compound obtained from sulphanilic
acid by means of the diazo-reaction. A comparison of their salts
shows, however, that the two acids are not identical. W. C. W.
Amidazobenzeneparasulphonic Acid. By J. Y. Janovsky
(Monatsh. Chem., 4, 652 — 659). — The author has already obtained
(p. 324 of this volume) by reduction of paranitrazobenzeneparasul-
1102 ABSTRACTS OF CHEMICAL PAPERS.
phonic acid, a product agreeing nearly in composition, either with
amidazobenzenesulphonic acid, Ci2H8N2(NH)2.S03H, or with amid--
hydrazobenzenesulphonic acid Ci2H8N2H2(NH2).S03H. This acid may
be prepared either with stannous chloride or with ammonium hydro-
sulphide, and its chemical relations show that it is really a hydrazo-
compound, inasmuch as, when treated with potassium nitrite, it
oxidises in the first instance- to an amido-acid, which may then be
converted into a diazo-compound. Whether the action of stannous
chloride gives rise to an azo- or a hydrazo-compound depends on the
duration of the process, but on the whole the hydrazo-acids appeared
to be formed most readily by the action of stannous chloride in acid
solutions.
Amidazohe7izene-ip- sulphonic acid, C6H4(NH2).N ! N.CeHi.SOaH
[4:1 : 1 : 4'], is most readily obtained in the pure state by the action
of ammonium hydrosulphide on the corresponding nitro-acid, the
product obtained with stannous chloride consisting almost wholly of
the hydrazo-acid. The resulting dark brown-red solution boiled with
hydrochloric acid deposits nearly all the amido-acid, together with
sulphur, and the acid may be purified by boiling the filtered solution
with barium carbonate, and decomposing the resulting barium salt,
after crystallisation, with hydrochloric acid. It then separates as a
salmon-coloured precipitate, made up of microscopic crystalline scales,
containing 1 mol. H2O. Its solutions are faintly yellow ; those of its
salts have a deep yellow colour, and crystallise well. The potassium
salt, Ci2H8(NH2)N2.S03K + H2O, crystallises in gold-coloured plates
belonging to the orthorhombic system, and exhibiting the faces
Poo, ooPco, ooPoo. It dissolves very readily in water and is very
hygroscopic. The barium salt, (NH2.Ci2H8N2.S03)2Ba -f 6H2O,
crystallises in fiery-coloured needles, exhibiting very fine colours in
polarised light. The calcium salt, (NH2.Ci2H8N2.S03)2Ca -f 4H2O,
crystallises in nacreous yellow laminae, or from dilute solution in
large rhombic plates, P, ooPob, or in very flat pyramids. The strontium
salt forms very long flexible needles, containing 2 mols. water. The
lead salt crystallises in small laminae, exhibiting in the polarising
microscope a remarkable striation, appearing half light and half
dark. H. W.
Diazo-derivatives. By P. Geiess (Ber., 16, 2028—2036).—
Azohenzenephenylenediaminebenzene, PhN I ]S'.C6H2(NH2)2.N" I NPh,
formed by the action of diazobenzene nitrate on azobenzene-meta-
phenylenediamine (the so-called chrysoidine), crystallises in dull-red
glistening needles melting at 250°, sparingly soluble in most solvents.
Its hydrochloride forms a violet amorphous mass ; the platinochloride
a violet-brown amorphous precipitate.
By the action of diazobenzene nitrate on azoparatoluene-phenylene-
diamine on the one hand, and of diazotoluene nitrate on azobenzene-
phenylenediamine on the other, two identical substances are formed
as subsidiary products, but the chief products are isomeric.
From the former reaction, a-azobenzenephenylenediaminepara-
toluene, PhN ! N.C6H2(NH2)2.N ! NC7H7 is obtained in the form of dark-
red glistening needles m.elting at 192°, insoluble in alcohol, soluble
ORGANIC CHEMISTRY. 1103
in ether; from the latter, azoparatoluenephenylenediaminebenzene,
C7H7N!N.C6H2(]SrH2)2.N:]S'Ph, which crystallises also in red needles
(m. p. 214°). From both the above reactions is obtained /^-azobenzene-
phenylenediamineparatoluene, which forms delicate hairy needles,
melting at 225°.
Azoparatoluenephenylenediamine |8-naphthalene,
CvH,^ : isr.CeH^CNHa)^.^ : nCioHt,
obtained by the action of paradiazotoluene nitrate on jS-azonaphtha-
lenephenylenediamine, forms copper-red glistening leaflets, soluble in
chloroform, insoluble in alcohol. A solution of this substance, although
of a deep colour, possesses no tinctorial properties, but must be con-
verted into the sulphonic acid, the salts of which may be used as
dyes.
Azo-parasulphohenzenepJienylenecUaininehenze7ie, prepared by the
action of paradiazobenzenesulphonic acid on chryosidine hydro-
chloride, forms small microscopic grains; its potassium salt crys-
tallises in red-brown leaflets.
Azophenylenediaminehenzenemetahenzoic acid^ prepared by the action
of metadiazobenzoic acid on chrysoidine, forms a brown-red crystalline
precipitate.
Azodibenzenephenylenediamine, PhT^ ' N.C^Hi.N ! K.C6H3(!N'H2)2, ob-
tained by the action of diazoazobenzene on phenylenediamine, crys-
tallises in brown-red needles melting at 105°, easily soluble in ether and
alcohol ; it dyes silks and wools of a brown-red colour. Its dihydro-
chloride forms a black-brown amorphous mass ; its monohydrochloride,
steel-grey glistening needles ; its platinochloride, brown leaflets.
Azoparasuljjhohenzenephenylenediamine,
C6H4(S03H).N : N.CeH^.N : N.C6H2(NH2)2,
formed by the action of m-diamidobenzene on paradiazoazobenzene-
sulphonic acid, is a dark red amorphous mass; its potassium salt
crystallises in copper-red needles, characterised by their remarkable
solubility in water ; the solution of this substance dyes wools a brown-
red colour.
Azosulphohenzenetoluenediamine, prepared by the action of para-
diazoazobeuzenesulphonic acid on metadiamidotoluene, forms reddish-
brown needles. V. H. V.
Constitution of the Nitrosamines. By E. Erlenmeter (Ber.,
16, 1457 — 1459). — The author is of opinion that nitrosamines contain
the group /^ \ , methylphenylnitrosamine would be represented by
the formula V: ^. Methylphenylhydrazine would consequently
be NHMePh I NH, instead of NMePh.lSTHo. The primary hydrazine
would have the constitution NH2Ph ! NH, and the salts of the
hydrazine NHaR I KH^R'. W. C. W.
1104 ABSTRACTS OF CHEMICAL PAPERS.
Aldoximes. By B. Lach (Ber., 16, 1780— 1787).— Phtbalyl-
hydroxamic acid is produced by the action of hydroxylamine on a
warm concentrated alcoholic solution of phthalic anhydride. Camphoric
anhydride yields' a resinous substance which slowly crystallises when
similarly treated. Lactones are not converted into aldoximes by the
action of hydroxylamine. Unsaturated acids, e.g., oleic and stearolic,
do not combine with hydroxylamine.
Salicylaldoxime, OH.CeHi.CH ! NOH [OH : NOH =1:2], is pre-
pared by adding sodium carbonate to a concenti^ated alcoholic solution
of salicylaldehyde and hydroxylamine hydrochloride. As the reaction
is very energetic, it is best to cool the vessel containing the mixture.
After 24 hours, the solution is rendered feebly acid by hydrochloric
acid ; a portion of the alcohol is removed by evaporation, and the
residue is extracted with ether. From the ethereal solution, the
salicylaldoxime is obtained in white crystals melting at 67°, soluble in
alcohol, ether, and benzene. The base also dissolves easily in hydro-
chloric acid, but decomposition takes place on warming the solution.
The hydrochloride is prepared by passing dry hydrochloric acid gas
into an ethereal solution of the base : it is a hygroscopic body, and
is decomposed by water. The sodium salt, ONa.C6H4.CHNON'a -f
3H2O, is obtained in yellow crystalline scales when salicylaldoxime is
boiled with sodium and absolute alcohol. It decomposes on exposure
to the air. The aqueous solution gives a white precipitate with lead
acetate ; with cobalt and ferric salts brown precipitates ; and with
silver nitrate a white precipitate which changes to black when heated.
The methyl and ethyl salts are aromatic oils. Salicylaldoxime appears
to form an acetic derivative. Paroxyhenzaldoxime forms white needles
which melt at 65''. The sodium salt is more stable than that of the
ortho-compound. Vanillinaldoxime, OH.C6H3(OMe).CH I NOH,
melts at 117°. Resorcylaldehyde and resorcyldialdehyde yield nitro-
genous compounds when they are acted on by hydroxylamine. Thio-
benzaldehyde resembles benzaldehyde in its behaviour with hydroxyl-
amine, yielding benzaldoxime, but thioacetones are not acted on.
w. c. w.
Paranitrobenzaldoxime and Amidobenzaldehyde. By S.
Gabriel and M. Herzbeeg {Ber., 16,2000 — 2004). — The authors have
shown that paranitrobenzaldehyde in an alkaline solution reacts with
hydroxylamine hydrochloride to form paranitrobenzaldoxime. This
latter substance when reduced with ammonium sulphide yields par-
amidohenzaldoxime, CvHsONa, which forms golden crystals melting at
124°, and soluble in alcohol and ether ; when these are dissolved in
acids, the originally clear liquid is converted into a blood-red jelly in
which crystalline needles appear. These crystals, however, could not
be obtained in a state of perfect purity, but they appear to have the
composition of paramidohenzaldehyde, C7H7NO. This compound dis-
solves in acetic anhydride to form paracetamidobenzaldehyde,
NH.ZECeHiiCHO = [4: 1],
which crystallises in long glistening needles ; these melt at 154°, and
iorm paracetamidoheiizaldoxime yivit]ihjdroxjla.riime. V. H. V.
ORGANIC CHEMISTRY. 1105
Metamidobenzaldoxime. By S. Gabriel (Ber., 16, 1997—2000).
— The author in a previous research has shown that orthamidobenz-
aldehyde may be obtained by the oxidation of orthamidobenzaldoxime,
the nature of the reaction being —
C6H4(NH2).CH : KOH + H2O = C6H4(ira2).CHO + NH3O
and 2NH3O 4- Oa = NgO + 3H2O. In the present paper, he examines
the corresponding meta-derivatives ; he was, however, unable to obtain
the metamidoaldehyde. Metamidobenzaldoxime,
(1)NH3.C6H4.CH : N0H(3),
obtained by the reduction of nitrobenzaldoxime, crystallises in snow-
white needles (m. p. 88°), soluble in alcohol and ether; its platino-
chloride crystallises in orange-golden needleis. Y. H. V.
Cinnoline-derivatives. By Y. v. Richter (Bar., 16, 677 — 683).
— The author describes a number of derivatives (obtained from orth-
amidophenylpropiolic acid) of a new base having the formula
CeH4<-^____^>.
This base may be looked upon as quinoline in which one CH-group
has been replaced by N, and the author therefore proposes the name
cinnoline for it.
C(OH) : C.COOH
Hydroxy cinnoUne-carhoxylic acid, CeHi-^^ | . Orth-
amidophenylpropiolic acid (2 grams) is dissolved in hot hydrochloric
acid (6 — 6 parts acid to 15 — 20 of water), and to the crystalline mass
obtained on cooling, a concentrated solution of sodium nitrite (1 gram)
is added. The resulting diazo-cbloride is diluted and heated to about
70°, when hydroxycinnoline-carboxylic acid is gradually deposited in
slightly coloured needles. The yield is from 80 to 85 per cent, of
theory. Purified by crystallisation from 50 per cent, acetic acid, it
forms colourless prisms or slender needles almost insoluble in water,
and but slightly soluble in boiling alcohol and ether. It melts with
evolution of carbonic anhydride at 260 — 265°, being converted into
hydroxycinno line.
Hydroxy cinnoline, C6H4<-jyj^: Ll j^>, is easily soluble in alcohol
and ether, from which solvents it crystallises with difficulty. It
crystallises from water in small scales or prisms, melting at 225° and
subliming to white crystalline flocks. Hydroxycinnoline resembles
a-hydroxyquinoline (carbostyril) in possessing both basic and acid
properties, both in a more marked degree. It dissolves in caustic
alkalis and also in solutions of the carbonates. Warm dilute hydro-
chloric acid dissolves it easily, liydroxycinnoline chloride crystallising
out in colourless needles which effloresce in the air. Hydroxycinnoline
platinochloride crystallises in groups of small prisms.
On reducing hydroxycinnoline by distillation with zinc-dust, an
oil containing small quantities of oxindole is obtained. Dissolved,
VOL. xLiv. 4 e
1106 ABSTRACTS OF CHEMICAL PAPERS.
in dilute hydrochloric acid, and freed from the last traces of ozindole
by washing with ether, it colours pine-shavings an intense orange.
From the hydrochloric solution sodium hydroxide throws down a
white flocculent precipitate having a peculiar smell reminding one at
once of nicotine and quinoline. The author is not at present able to
say whether this is actually the base CgHeNz sought for.
The formation of tbese compounds from orthamidophenylpropiolic
acid is somewhat similar to that of carbostyril discovered by Baeyer
and Bloem (this vol., p. 196).
In the preparation of orthamidophenylpropiolic acid by the reduc-
tion of the nitro-compound with ammonaical ferrous sulphate solution,
the author advises the gradual introduction of the nitro-acid into the
reducing solution as giving a much better yield of the amido-acid than
the reverse operation. L. T. T.
Orthotolylhydantoin. By A. Ehrlich (Ber., 16, 742—743).—
The author has prepared the above body by Swebel's reaction, by
heating together equal weights of orthotolylglycocine and carbamide.
The ingredients were well mixed in a mortar, and then heated at 180° ;
at 170° frothing commenced and continued for about two hours when
the reaction was completed.
Orthotolylhydantoin, CioHioNaOa, crystallises in pale-yellow plates
melting at 176°. It is soluble in alkalis, ammonia, alcohol, boiling
water, and hot hydrochloric acid ; sparingly so in ether and acetic
acid. Boiled with barium hydroxide, it forms a barium compound,
but is thrown down again unchanged on adding a mineral acid ; no
hydantoic acid being produced. Neither could the author obtain
glycollic acid by treatment with alcoholic potash, or monotolyl-
carbamide by boiling with concentrated hydrochloric acid. In both
cases the hydantoin remained unchanged. L. T. T.
Products of the Decomposition of Mixed Aromatic Thiocar-
bamides by Acids. By K. Mainzer (Ber., 16, 2016— 2028).— In a
former research, the author has shown that when mixed aromatic thio-
carbamides are heated with hydrochloric acid, they are decomposed into
two thiocarbamides and two amines (Abstr., 1882, 1212 — 1213). In
the present communication, it is shown that phosphoric acid effects the
same change very completely, the yield of the product of the decom-
position varying from 70 — 100 per cent, of that required by theory.
Diparaphenylethylthiocarhamide, C6H4Et.NH.CS.NH.C6H4Et, from
phenyl ethylamine and carbon bisulphide crystallises in long needles
melting at 144° : it is decomposed by phosphoric acid into phenylethyl-
thiocarbimide and phenylethylamine.
Phenylethylphenylthiocarbamide,l^ILVh.CSJ^H..C6HiEt,iTom.iphe'D.j\-
thiocarbimide and aniline, crystallises in leaflets (m. p. 103°) soluble
in alcohol and ether ; it is decomposed into phenyl- and phenyl-ethyl-
thiocarbamides with aniline and phenylethylamine.
Bhenylethyl - a - riaphthylthiocarbamide, CeH^Et.NH.CS.NH.CioHT,
from phenylethylamine and a-naphthylthiocarbimides crystallises in
needles, decomposed by phosphoric acid into phenylethyl- and a-naph-
thyl-thiocarbimides with phenylethylamine and a-naphthylamine.
ORGANIC CHEMISTRY. 1107
Phenyl-^-naphthylthiocarhamide, from phenyletliylaniine and a-naph-
thylthiocarbamide, crystallises in leaflets melting at 158°, decomposed
by phosphoric acid into plienyl-yS-naphtliyl and /3-naphthylthiocarba-
mides with phenylethylamine and /3-naphthylamine.
Phenisobutylphenylthiocarbamide, C6H4(C4H9).NH.CS.NHPh, from
phenylisobntylamine and phenyl thiocarbamide, crystallises in leaflets
(m. p. 152), decomposed by phosphoric acid into phenyl- and phenyl-
isobutyl-thiocarbamide with aniline and phenylisobntylamine. Phenyl-
isobutylthiocarbimide crystallises in large white needles melting at
266°.
Phenisohutylparatolylthiocarhamide, C6H4(C4H9).NH.CS.NE[.07H7,
from phenylisobntylamine and paratolylthiocarbimide, crystallises in
glistening leaflets melting at 137°, decomposed by phosphoric acid into
paratolyl- and phenylisobutyl-thiocarbimides with paratolnidine and
phenylisobntylamine .
PhenisohutylphenethylthiocarhawMe, CeJii(CiH9).l!fK.CSJ^Ii..CQHiEt,
from phenylisobntylamine and phenylethylthiocarbimide, crystallises
in white glistening prisms melting at 140°, decomposed by phosphoric
acid into phenylisobutyl- and phenylethyl-thiocarbimides with phenyl-
ethyl- and phenyliso-bntylamine.
Phenisobutyl-y3-naphthylthiocarbamide,
C6H4(C4H9).NH.CS.NH.CioH7,
from /3-naphthylthiocarbamide and phenylisobntylamine, forms small
white leaflets melting at 153°, decomposed by phosphoric acid into
phenyl- isobntyl- and y3-naphthyl-thiocarbamide with isobntylamine
and /3-naphthylamine. Y. H. V.
Action of Phenylthiocarbimide on Amido-acids. By 0.
AscHAN (Ber., 16, 1544 — 1545). — When alanine (4 grams) is heated
with phenylthiocarbimide (6'2 grams) nntil no more water is given
off (the temperature being kept below 140°), the following reaction
takes place : —
CH3.CH(NH2).COOH + CSINPh = HoO + C10H10N2OS.
The product melts at 184°, dissolves in alcohol, ether, benzene, glacial
acetic acid, and carbon bisulphide, also in the fixed alkalis, and more
sparingly in ammonia.
Corresponding compounds, C9H8N2OS and CnHisNgOS, have like-
wise been obtained from glycocine and leucine, the former of which is
yellow, dissolves in alkalis to a pink solution, and decomposes without
melting when heated above 200°. The body obtained from leucine
melts at 179°. A. K. M.
Diphenylcarbamide and Triphenylguanidine. By W. Hents-
CHEL (/. pr. Chem. [2], 27, 498— 503).— When ethyl carbanilate is
heated with sodium phenate it yields symmetric diphenylcarbamide,
and the latter, when heated with sodium ethylate, forms triphenyl-
guanidine.
If a mixture of sodium phenate and ethyl carbanilate in equivalent
proportions is distilled, pure phenetol passes over at 220°. When the
4 e 2
1108 ABSTRACTS OF CHEMICAL PAPERS.
distillation is complete, the residue in the retort is boiled several times
with water, whereby sodium carbonate is dissolved and prismatic
crystals of diphenylcarbamide are left. The reactions are expressed
by the following equations : —
(1.) NHPh.COOEt + PhONa = PhOEt + NHPh.COONa.
(2.) 2(NHPh.C00Na) = C0(NHPh)2 + NaaCOs.
The author has prepared large quantities of diphenylcarbamide
according to Hofmann's method, and finds that it is advisable to act
with phosgene gas on aniline suspended in water, instead of in the dry
state. Although Merz and Weith state that diphenylcarbamide is
decomposed by heat into carbonic anhydride, aniline and triphenyl-
guanidine, the author was able to distil it without decomposition
at 260°, or even maintain it at 220° for several hours. When it is
heated with sodium ethylate at 220° in a current of hydrogen, a clear
oily distillate passes over boiling at 180°, and having all the properties
of aniline. The residue in the retort dissolves in hot dilute hydrochloric
acid, and on adding concentrated hydrochloric acid the hydrochloride
of triphenylguanidine crystallises out. The action of sodium ethylate
is shown by the equation 200(NHPh)2 + EtONa = C]SrPh(NHPh),
+ ON'a.COOEt.* In addition to triphenylguanidine, sodium ethyl
carbonate is formed. If sodium phenate be present, sodium salicylate
will be produced.
(1.) C0(NHPh)2 + EtOI^a = CJSrPh(NHPh)2 + NH^Ph
+ COONa.OEt.
(2.) COOKa.OEt 4- CeHs.ONa = ONa.C6H4.COONa + EtOH.
J. I. W.
Phenolic Phosphates. By R. Heim (Ber., 16, 17G3— 1770).—
The neutral phosphates of phenyl, cresyl, and naphthyl are best pre-
pared by the action of phosphorus oxychloride on the phenols in slight
excess, 90 per cent, of the theoretical yield of triphenyl phosphate, and
of triortho- and tripara-cresyl phosphates can be obtained. Triortho-
cresyl phosphate is a brown oil which is partially decomposed by distil-
lation. In preparing a- and ^-trinaphthyl phosphates (CioH7)3P04, the
retort containing the mixture of naphthol and phosphorus oxychloride,
must be heated on a sand-bath or layer of asbestos, so as to cause the
liquid to boil very gently. If the retort is heated too strongly, a slight
explosion may occur. The yield is 60 — 65 per cent, of the theo-
retical. W. C. W.
Chlorophenols obtained by the Action of Alkaline Hypo-
chlorites on Phenol. By T. Chandelon {Ber., 16, 1749—1753).—
If a 3 per cent, solution of phenol in an alkali is mixed with sodium
hypochlorite in molecular proportions, orthomonochlorophenol is pro-
duced. By increasing the quantity of hypochlorite a mixture of
orthoparadichlorophenol, CeHaCl^.OH [OH : 01 : CI = 1 : 2 : 4], b. p.
* The numbers of C, H, and JN'-atoms on the two sides of this equation do not
agree. The error is in the original paper. — [Ed.]
ORGANIC CHEMISTRY. 1109
210°, and orthodichlorophenol [1:2:6], boiling at 218°, is obtained.
A still larger proportion of hypochlorite yields trichlorophenol,
CeHaCla.OH. W. C. W.
Action of Iodine on Sodium Phenate. By C. ScHALL(J5er., 16,
1897 — 1902). — On adding iodine to sodium phenate suspended in
carbon bisulphide, a mixture of mono-, di-, and tri-iodophenols is formed.
In order to separate these constituents, the oil obtained after filtration
of the sodium iodide and evaporation of the carbon bisulphide, is shaken
up with potash and ether, which separates the moniodophenol. The
fraction taken up by potash is acidified and then distilled in a current
of steam ; the distillate separates into a liquid orthiodophenol, and
a solid orthodiiodophenol. The residue left in the distillation flask
consists of triiodophenol.
Action of Chlorine on (3-Sodium Naphthol. — If chlorine gas is passed
into /3- sodium naphthol suspended in carbon bisulphide, and the crude
product after evaporation of the latter is steam-distilled, the distil-
late consists of a monochloronaphthol crystallising in needles, v^hich
melt at 68°.
Action of Nitric Peroxide on Sodium Phenate. — If nitric peroxide be
brought into sodium phenate in carbon bisulphide kept cool, there is
formed orthonitro- and paranitro- phenol, which may be separated by
the usual method of steam distillation. The reaction is as follows : —
2NO2 + CeHs-ONa = NaN02 + C6H4(N02).OH ; the presence of
sodium nitrite was recognised by Liebermann's reaction.
V. H. V.
Diiodophenol. By C. Schall (Ber., 16, 1902— 1903).— Diiodo-
phenol can be conveniently prepared from iodine and sodium phenate,
the sodium iodide being separated by carbon bisulphide. On heating
diiodophenol with acetic chloride, acetyldiiodophenolj C6H3T2.OXC, is
formed; it crystallises in small prisms (m. p, 107°). The benzoyl-
diiodophenol, C6H3I2.OBZ, prepared by a similar process melts at
95*96°. The potassium diiodophenate crystallises in needles.
V. H. V.
Reduction of Monobromorthonitrophenol. By F. Schoff
(Ber.,16, 2069 — 2070). — Pfaff has established that monobromometa-
nitrophenol yields metamidophenol when reduced, and states that the
relative position of the substituting groups can have no effect on the
reaction. On the other hand, the researches of Staedel prove that in
the reduction of bromamido-anisoil and phenetoil the bromine-atom is
not replaced by hydrogen. On account of this discrepancy, the author
has examined the action of tin and hydrochloric acid on parabrom-
orthophenol; the resultant substance was proved by various cha-
racteristic tests to be parabromorthamidophenol. V. H. V.
Amidophenols. By F. A. Kalckhoff (Ber., 16, 1825— -1838). —
Thiocarhamido^henolf C6H4<^ \C.SH, prepared by moistening a
mixture of amidophenol hydrochloride and potassium xanthate, is
1110 . ABSTRACTS OF CHEMICAL PAPERS.
identical with the " oxyphenylthiocarbimide " which Bendix (Abstr.,
1879, 314) obtained by heating orthoxythiocarbamide above its melt-
ing point, and also with the compound which Diinner (Ber., 9, 465)
obtained by the action of carbon bisulphide on orthamidophenol.
AnalidocarbamidojpTienol, CoH4<' ^C.NHPh, formed by boiling a
mixture of aniline and thiocarbamidophenol, crystallises in long needles
melting at 173°, soluble in alcohol, ether, and glacial acetic acid.
Although it dissolves in acids and yields a platinochloride, it can be
extracted from acid solutions by ether. By substituting methyl aniline
in the preceding experiment, methylanilidocarbamidophenolj
CeH/ ^C.KMePh,
is obtained in the form of a blue fluorescent liquid, which boils above
360°. The platinochloride is crystalline. Amidocarhamidophenol has
been described by Bendix under the name of phenylene carbamide.
Acetothivcarhamidophenol, C6H4(NO)CSAc, crystallises in transparent
plates melting at 120°, soluble in alcohol and acetic acid. Benzoic chlo-
ride acts on thiocarbamidophenol, yielding the benzoic-derivative of
orthamidophenol, B^O.CeHi.NH.COPh (m. p. 182°) the "orthobenz-
amidobenzoic phenol " of Morse and Giissefeld (Ber., 15, 370), and
also phenylcarbamidophenol (m. p. 105°). Oxy carbarn idophenolj de-
scribed by Groenvik (Bull. 8oc. Chim., 25, 178), is formed when
oxy phenyl carbamide is heated.
In the preparation of orthhydroxythiocarbanilide, less than the
theoretical quantity of phenylthiocarbimide must be taken, in order
to prevent the formation of thiocarbamidophenol and thiocarbanilide
by a secondary reaction. Hydroxythiocarbanilide, C13H12N2OS, crys-
tallises in white pearly plates melting at 146°, soluble in alcohol. It is
decomposed by heat or by the action of mercuric oxide into anilido-
carbamidophenol and sulphuretted hydrogen.
Derivatives of Paramidojphenol. — Diparahydroxyphenylthiocarba-
mide, CS(NH.C6H4.0H)2, prepared by digesting paramidophenol with
carbon bisulphide, crystallises in plates which melt at 222° with de-
composition. The compound is soluble in alkalis and in alcohol. It
is desulphurised by mercuric oxide, and is apparently converted into
dihydroxyphenylcarbamide.
Acethydroxythiophenylcarhiwide forms white glistening plates melt-
ing at 36°, soluble in alcohol, ether, and glacial acetic acid. It unites
with aniline, yielding paracethydroxythiocarbanilide,
N'HPh.CS.NH.CeHi.OSiH,
(m. p. 137°). This substance dissolves in alcohol, ether, and glacial
acetic acid. By the action of alcoholic ammonia on acethydroxy-
phenylthiocarbimide, parahydroxyphenj'-lthiocarbamide is produced.
Free metamidophenol has not yet been obtained pure.
ORGANIC CHEMISTRY.
Reactions of the Amidophenol Hydrochlorides.
1111
Ortho.
Para.
Meta.
Ferric chloride ....
Violet, changing to
brown
Violet
Brownish-yellow so-
lution.
Potassium dichro-
Brown solution. . . .
Dark precipitate,
Dark brown solu-
mate
brownish-violet
solution
tion.
Bleaching powder .
Yiolet-red-brown
Violet-green-yellow
Bed-brown solution.
solution, dark
solution
precipitate
Ammonia and silver
Dark brown preci-
Grey precipitate,
Gxej precipitate,
nitrate
pitate
violet solution
green solution.
w. c. w.
Reaction of Ethyl Acetoacetate with Orthamidophenol. By
A. Hantzsch (JBer., 16, 1946— 1962).— The formation of pyridine-
derivatives from ethyl acetoacetate and orthamidophenol led the
author to examine a similar reaction in the case of an amidophenol, in
order to form an ethereal salt of a carboxyl-derivative of skatole.
The substance formed by heating orthamidophenol with ethyl aceto-
acetate, has the composition C12H15O3N, and for want of a better name
may be called anhydro-orthamidophenol ethyl aceto-acetate. It crys-
tallises in flat prisms (m. p. 107''), and is readily decomposed into
orthamidophenol and ethyl acetoacetate. It forms a potassium com-
pound of the composition C24H29KO6N2, derived from the original
substance by the replacement of one hydrogen-atom of an amido-group
in 2 mols. by one potassium-atom. This latter reacts with methyl
iodide to form ortho-bromethylphenol ammonium iodide,
CeH^
o
•NMea
,HI.
V. H. Y.
Conversion of Phenols into Nitrils and Acids. By R. Heim
(Ber., 16, 1777 — 1780). — Benzonifcril may be prepared by heating
triphenyl phosphate with dried potassium cyanide or ferrocyanide in a
current of hydrogen or carbonic anhydride. The yield is about 25
per cent, of the theoretical. Tolunitril and a- and /3-naphthonitrils
may be obtained by a similar process from tricresyl and trinaphthyl
phosphates. A small quantity of phenol, cresol, &c., is always
obtained as a bye-product. W. C. W.
Dichloroparacresol and Dichlororthocresol. By A. Claus
and P. RiEMANN {Ber., 16, 1598 — 1603). — These compounds are ob-
tained by the action of chlorine on para- and ortho-cresol heated to
boiling in a large flask provided with an inverted condenser; an
abundant evolution of hydrochloric acid takes place, whilst the liquid
assumes a red colour, changing to dark brown, and finally becoming
nearly black. When the liquid becomes thick, the reaction is stopped,
1112 ABSTRACTS OF CHEMICAL PAPERS.
and the prodact steam-disfcilled. Under these conditions the substitn-
tion takes place in the benzene ring and not in the side chain.
Dichloroparacresol, C7H6CI2O, is readily soluble in alcohol, ether, and
glacial acetic acid, sparingly in hot water, and crystallises in large
prismatic needles. I'rom a hot concentrated solution in light petro-
leum, it crystallises in long transparent needles, melting at 39°, whilst
by the slow evaporation of a dilute solution, large transparent prisms
are formed melting at 42° ; the latter, however, soon become opaque,
fall to pieces, and then melt at 39°. It forms a characteristic com-
pound with ammonia, C7H5CI2.ONH4, crystallising in long colourless
needles, melting at 125° and subliming unchanged. It dissolves very
readily in water. Dichloroparacresol is oxidised by nitric acid, with
formation of oxalic acid, whilst a solution of chromic acid in glacial
acetic acid oxidises it to dichlorojparahydroxyhenzoic acid, crystallising
in long white needles melting at 156°. The sodium salt forms small
lustrous needles readily soluble in water and in alcohol ; the silver
salt, obtained by precipitation from the latter, has the formula
CTHsClgOsAg. Dichlororthocresolj C7H6CI2O (m. p. 55°) forms silky
needles, readily soluble in alcohol, ether, benzene, chloroform, and
light petroleum, sparingly in hot water. It is distinguished from the
para-compound by forming no compound with ammonia. Nitric acid
oxidises it to oxalic acid, whilst with chromic acid it yields trichloro-
toluquinone, C7H3O2CI3, crystallising in gold-coloured scales, readily
soluble in ether and in hot alcohol. Trichlorotoluhydroquinoney
obtained on heating the latter compound with sulphurous acid, forms
white feathery crystals melting at 211 — 212°. A. K. M.
Thymol-derivatives. By A. K. Richter (/. pr. Chem. [2], 27,
503— 511).— Hentschel (J. pr. Chem. [2], 27, 42) has found that
ethyl phenyl carbonate and dipheuyl carbonate, when treated with
alkaline oxides of alcohol radicals are readily converted into salicylic
acid. The author finds that ethyl thymyl carbonate and dithymyl
carbonate when treated in a similar manner do not yield thymolic
acid, but salicylic acid.
Ethyl thymyl carbonate is prepared by gradually adding an excess of
ethyl chlorocarbonate to sodium thymol, the oil which separates being
fractionally distilled. The carbonate boils at 259 — 262°.
Dithymyl carbonate is prepared by passing carbonyl chloride into
an aqueous solution of sodium thymol, washing the oil which is
formed with dilute soda solution, and finally distilling it ; a clear
liquid passes over above 270°, and solidifies on cooling to a striated
crystalline mass. It has a faint odour, and melts at 48°. It dissolves
in hot alcohol, ether, and chloroform, and crystallises from all of them
iu long needles or prisms. The author finds that if the liquid boiling
above 270° be allowed to solidify slowly, a certain quantity of liquid
of an unpleasant odonr can be abstracted from the crystalline
mass ; it consists of ethyl thymyl carbonyl chloride. The same body
has been previously observed by Kemp, but he was unable to obtain it
sufficiently pure for analysis. He did not convert it into the amido-
derivative, as he did the corresponding phenol and cresol bodies. The
author has done so by passing dry ammonia gas into an ethereal solut
ORGANIC CHEMISTRY. 1113
tion of the substance. After filtering off the ammonium chloride and
evaporating, the filtrate deposits slender needles of ethyl thymyl car-
bamic acid, C11H13O2CI. J. I. W.
Preparation of Phenetoil. By H. Kolbe (/. ^r. Chem. [2], 27,
424 — 425). — Crude sodium ethyl sulphate is mixed with a thick solu-
tion of sodium phenol and heated in an autoclave under seven atmo-
spheres' pressure for some hours at 150°. On opening the vessel, the
phenetol is found floating on the semi-solid saline mass, and can be
purified by washing with water and rectifying. A. J. Gr.
Molecular Transformations. By W. Bottcher (Ber., 16, 1933
— 1939). — The authorjia*? rtreviously observed that orthonitrobenzo-
phenol, C6H4(N02).OBz, undergoes a molecular transformation when
reduced, yielding orthobenzamidophenol, C6H4(OH).NHBz, a change
which is attributed to the intermediate formation of benzamidophenol,
CeHZ >CPh.
In order to see whether the reaction is general and the interpretation
is correct, the behaviour of analogous substances under similar con-
ditions is examined.
Orthonitroacetophenol, C6Hi(N02).OZc, formed by the action of
acetic chloride on sodium orthonitrophenate, forms asymmetrical
crystals which melt at 40°, and boil at 255° with partial decomposition.
It was not found possible to effect a molecular transformation with
this substance.
a,-Nitro-(3-benzonaj)hthol, CioH6(N02).OBz, prepared from the sodium
salt of a-nitro-^-naphthol and benzoic chloride, crystallises in colour-
less needles melting at 142°, sparingly soluble in ether, easily soluble
in boiling alcohol. When reduced with zinc-dust and acetic acid, it
yields by molecular transformation benzoyl-cx,-amido-^-na])htholy
CioHe(NHB^).OH,
which crystallises in colourless leaflets (m. p. 245°).
Besides the latter substance, the intermediate compound, henzenyU
amidonaphthol, CioHex "^CPh, was formed, which confirms the
author's interpretation of his results. A better yield of material is
obtained by the sublimation of benzoylamidonaphthol ; it crystallises
in long colourless needles (m. p. 136°), soluble in ether and benzene,
insoluble in water. The platinochloride forms golden needles.
a-Nitro-^-acetonaphthol, CioH6(N03).OAc, from acetic chloride and
the sodium salt of nitronaphthol, crystallises in long colourless
needles, melting at 61°, soluble in alcohol and ether, insoluble in
water. On reduction with zinc-dust and acetic acid, it is converted
by a transformation analogous to that of the benzoyl-compound into
acetyl a.amido-/3-naphthol, CioH6(NHZ5).OH [NHAc = a, OH = (5)].
1114 ABSTRACTS OF CHEMICAL PAPERS.
This latter substance crystallises in leaflets melting at 225° ; by subli-
.... yK
mation, it is converted into ethenylamidonajphthol, CwHe^ "^CMe.
V. H. V.
Nitroresorcinolsnlphonic Acid. By K. Hazuka (Monatsh.
Chem., 4, 610 — 615). — Mononitroresorcinol heated at 80 — 90° with
strong sulphuric acid, dissolves, with red- brown colour, and, on pour-
ing the product into water, a small quantity of crystalline dinitro-
resorcinol separates out, while mononitroresorcinolsulphonic acid
remains in solution.
Dinitrodiresorcinol, Ci2H4(]S['02)2(OH)4, is slightly soluble in water
and in alcohol, easily soluble in ammonia, and is precipitated from
the ammoniacal solution by acetic acid. It turns brown at 170°, and
carbonises, without melting, at a higher temperature. It is formed
by oxidation of the mononitroresorcinol, according to the equation
2C6H3(]S"02)(OH)2 + O = H2O + C:2H4(N02)o.(OH)4.
Nitroresorcinolsulplionic acid, C6H2(]S'02)(OH)2.S03H, is obtained
by evaporating the filtrate to a syrup, and leaving it to cool, where-
npon the whole solidifies to a thickish pulp, which may be freed from
excess of sulphuric acid by draining on earthenware plates, then dis-
solved in the smallest possible quantity of water, and crystallised
under the air-pump. As thus obtained, it contains 1\ mol. H2O ;
crystallises in white scales unctuous to the touch, dissolves very
readily in water and in alcohol, but is insoluble in benzene and in
chloroform. It melts at 124 — 125°. It forms three barium salts,
viz.: a. [CeH2(N02)(OH)2.S03]>Ba + ^H^O, obtained by adding
caustic baryta to a strong solution of the acid as long as the ciystal-
line precipitate exhibits a sulphur-yellow, and not a lemon-yellow
colour. It dissolves readily in water, and crystallises from boiling
SO
water in large sulphur-yellow needles. — |S. C6H2(]S'02)(OH)< Q^>Ba
-t- 2H2O, obtained by adding a large quantity of baryta to the sulphur-
yellow solution, is slightly soluble in cold, easily in hot water, and
crystallises in lemon-yellow scales. — 7. (C6H2N02)2(S03)2Ba.(02Ba)2
+ IOH3O, is obtained by adding an excess of baryta- water to a hot
solution of the lemon-yellow salt in boiling water, and crystallises in
blood-red needles. — These three salts differ remarkably in their
behaviour when heated, the first carbonising at 125°, the second sus-
taining a temperature of 145°, while the third may be heated without
decomposition to 180°. The potassium, copper, cobalt, and nickel
salts are soluble in water, and may be obtained by decomposing the
first barium salt with the corresponding soluble sulphates. The
copper, cobalt, and nickel salts crystallise in long needles. By decom-
posing the potassium salt thus formed with potassium hydroxide, two
potassium salts may be obtained analogous to the y3 and 7 barium salts.
When nitroresorcinolsnlphonic acid is treated with bromine it is
converted, not into a brominated sulphonic acid, but into dibromo-
nitroresorcinol, melting at 147°.
Amidoresorcinolsul'phonic acid, C6H2(]S^H2)(OH)2.S03H, is obtained
by heating the nitro-acid with tin and hydrochloric acid, the greater
ORGANIC CHEMISTRY. 1115
part separating from the liquid while still hot, the remainder on
cooling. It crystallises in reddish-white, anhydrous, dimetric prisms,
exhibiting the faces OP, coFco, ooP. It is nearly insoluble in cold,
and but slightly soluble in hot water, but dissolves readily in aqueous
potash, forming a solution colourless at first, but quickly turning
blue, green, and finally black. With ferric chloride, it gives a brown
precipitate, which acquires a violet tinge on addition of sodium car-
bonate ; with basic lead acetate a white precipitate becoming violet-
blue on exposure to the air.
On passing hydrogen sulphide into the mother-liquor of amido-
resorcinolsulphonic acid, filtering from tin sulphide, and concentrating
the filtrate in a stream of carbonic anhydride, needle-shaped crystals
were obtained, soluble in water, exhibiting with potash the same
colour-reactions as amidoresorcinolsulphonic acid, and giving with
basic lead acetate a violet-blue solution, which after some time de-
posited a blue precipitate, gradually turning black. These crystals
gave by analysis numbers agreeing approximately with the formula of
diamidoresorcinol hydrochloride, Ci2H4(N'H2)2(OH)4. By prolonged
treatment with tin and hydrochloric acid, amidoresorcinolsulphonic
acid is converted into a non-sulphuretted body, which however differs
in its reactions with potash, from the last-mentioned compound.
Further experiments on these two bodies are promised. H. W.
Sulphonic Acids of Quinol. By A. Setda (Ber., 16, 687—694).
— For the preparation of quinol, the following modification of Nietzki's
process was found to give the best results. 1 part of aniline is
dissolved in 8 parts sulphuric acid previously diluted with 10 parts
water, and when the mixture is cold, 3^ parts of potassium di-
chromate dissolved in 20 of water is gradually added, the whole
being left at rest for 12 hours, and the quinone extracted
with ether. After distilling off the ether, 2 parts of boiling water
are added, and sulphurous anhydride passed into the mixture until
all the quinone is dissolved. After decoloration with animal char-
coal the quinol is extracted with ether. The yield is about 60 per
cent.
Quinol dissolves in mixed sulphuric acid very slowly in the cold,
easily on heating, easily and with evolution of heat in fuming sulphu-
ric acid ; in both cases, however, mixtures of the mono- and di-sul-
phonic acids are produced, the complete separation of which is almost
impossible. The author has therefore sought to find conditions more
favourable for obtaining each acid alone.
Quinol-mo7iosulphomc Acid. — 1 part of quinol is heated with
8 parts mixed sulphuric acid at 50° for three hours with constant
stirring, allowed to stand for 24 hours, and diluted. The liquid is
then heated to boiling, and barium carbonate added to saturation ; the
filtered solution on being concentrated out of contact with the air,
and allowed to cool, yields the barium salt in a crystalline state.
Barium quinolsidphonate, [C6H3(OH)2.S03]2Ba, is easily soluble in
hot water and dilute alcohol. In the cold ferric chloride produces a
deep blue coloration, which gradually disappears on standing. It
reduces mercury and silver salts. Its reaction is neutral, and it is
1116 ABSTRACTS OF CHEMTOAL PAPERS.
decomposed at 110°. The zinc salt, [C6H3(OH)2,S03]2Zn + 4H2O, is
obtained from the barium salt by double decomposition with zinc
sulphate, and is easily soluble in water and alcohol. It gives the
same reactions as the barium salt. It eflBoresces over sulphuric acid,
but does not lose all its water of crystallisation below 135° : it decom-
poses at 140°. The potassium, salty C6H3(OH)2.S03K, crystallises well,
and is the best means of purifying the acid; the barium salt is
decomposed with potassium carbonate, and the concentrated filtrate is
mixed with double its volume of alcohol, whereby a brown flocculent pre-
cipitate is produced, which is filtered ofF, and the alcohol removed by
distillation out of contact with the air, when the concentrated aqueous
solution deposits large, anhydrous, monoclinic crystals on cooling,
the axis-ratios of these crystals are a : b : c = 0*960028 : 1 : 2*225665
and Z /3 = 107° 23' 91". This salt has a bitter taste, and is easily
soluble in cold water. It is not decomposed at 170°. The sodium salt
crystallises in minute octohedra; the lead salt is amorphous. Quinol-
sidjphonic acid, obtained from the lead salt, solidifies over sulphuric
acid to a crystalline mass, which deliquesces in the air, and gives an
evanescent blue coloration with ferric chloride.
QuinoldisuljpTionic acid is best obtained by heating 1 part quinol
with 5 parts fuming sulphuric acid for an hour at 100 — 110°. Water
is added to the cold crystalline magma, the whole saturated with
barium carbonate, the filtrate concentrated on the water- bath, and
allowed to cool, when the barium salt of the disulphonic acid crystal-
lises out.
Barium quinoldisulphonate, C6H2(OBr)2(S03)2Ba -|- 3JH2O, is spar-
i-ngly soluble in cold water, easily in hot, and is precipitated even
from dilute aqueous solutions by alcohol (difference from the mono-
sulphate). It crystallises in long needles or prisms belonging to the
monoclinic system. Ferric chloride gives a deep blue colour, which is
permanent in the cold. Silver and mercury salts are reduced by it on
boiling. It eflfloresces slowly over sulphuric acid, but only becomes
anhydrous at 160°. The zinc salt crystallises with 6H2O in white
concentrically grouped needles. It is soluble in hot water, insoluble
in alcohol. The potassium salt crystallises in prisms containing 4H2O,
which they lose over sulphuric acid, or at 130°. It is not decomposed
at 165°. The sodium, salt is amorphous, soluble in water, insoluble
in alcohol. The lead salt appears to have the formula
C6H2(OH)2(S03)2Pb + 3Pb(OH)2.
QvAnoldisulphonic acid prepared from the barium salt crystallises over
sulphuric acid in long needles, of astringent taste, which deliquesce in
the air.
From a comparison of his results with those already obtained, the
author concludes that his (8) disulphonic acid is identical with that
obtained by Graebe from potassium thiocronate ; isomeric with the
(a) acid obtained by Hesse from quinic acid ; and that the third (7)
acid is at present unknown.
The author also endeavoured to replace the sulphonic groups by
hydroxyl or the amido-group, but without success. Aqueous potash
has no action, fusing potash re-forms quinol from both acids. Heating
ORGANIC CHEmSTRY. 1117
in closed tubes at 180° with aqueous or alcoliolic ammonia also repro-
duces quinol. The potassium monosulphonate when heated with
alcoholic potassium cyanide at 160° gives small quantities of a crys-
talline acid, soluble in alkalis, with a dark blue colour. L. T. T.
Chlorine and Bromine-derivatives of Quinone. By S. Levy
{Ber., 16, 1444 — 1448). — Metadichloroquinone prepared by Weselsky's
method (Ber., 3, 646) may be best purified by recrystallisation from
benzene or light petroleum. It is deposited from these solvents in
yellow rhombic crystals. Dichlorquinol yields a diacetic derivative,
C6H2Cl3(OAc)2, crystallising in slender needles melting at 66*5°, and
a dibenzoic- derivative, which crystallises in colourless opaque needles
melting at 105°. Metadichloroquinone is formed by the oxidation of
metadichloroparaphenylenediamine with sulphuric acid and potas-
sium chromate.
Metadichlorometadibromoquinoney CeOzClzBrj, is easily prepared by
boiling metadichloroquinone dissolved in acetic acid with bromine;
when the liquid cools, the dichlorodibromoquinone is deposited, and
by recrystallisation from benzene is obtained in reddish-yellow mono-
clinic plates isomorphous with tetrachloroquinone,
a:h:c= 1*1445 : 1 : 3-0286. ^ = 74° 31'.
On reduction with stannous chloride solution, the metadichlorometa-
dibromoquinol described by Krause {Ber., 12, 56) is formed. This sub-
stance is deposited from alcoholic chloroform in transparent monoclinic
crystals isomorphous with tetrachlorhydroquinone,
a : & : c = 2-976 : 1 : 2-7813. ^ = 77° 22'.
ChloTobromanilic acid from metadichlorometabromoquinone is iden-
tical with that obtained by Krause. W. C. W.
Action of Amines on Quinones. By T. Zincke {Ber., 16,
1555 — 1562). — By the action of dry ammonia on dry quinone, a black
apparently crystalline substance is formed, together with quinhydrone
and hydroquinone ; its composition agrees with the formula C12H9NO4.
If the action takes place in anhydrous ether or in chloroform, a brown
amorphous substance is obtained resembling the above in its properties,
but of different composition, C6H3(NH2)02. The nature of these
compounds is not understood. Dianilidoquinone, C6H202(NHPh)2,
obtained by the action of aniline on quinone, is nearly insoluble in
hot alcohol, but can be crystallised from hot glacial acetic acid or
from aniline, forming small bluish- violet scales. Nitrous acid does
not act on it in suspension in alcohol except in the presence of acetic
acid, when a reddish-yellow substance is formed almost insoluble in
the ordinary solvents ; it melts at about 245°. The numbers obtained
on analysis indicate the formula C6H02(NO) (NH.CeBU.NOs),. It dis-
solves in ammonia, sodium carbonate, and sodium hydroxide solutions
with decomposition and formation of ortho- and para-nitraniline.
Dinitranilides are readily obtained by the action of nitraniline on
quinone, and from the orthonitraniline compound a dinitranilido-
dinitroquinone can be formed by means of nitric acid. It resembles
1118 ABSTRACTS OF CHEMICAL PAPERS.
the above-mentioned compound obtained from dianilidoqulnone.
From ortbo- and para-toluidine, compounds of the formula
are obtained analogous to the aniline- derivative. From toluquinone and
aniline in alcoholic solution, dianilidotoluquinone, C6HMe02(NHPh)2,
is obtained melting at 232 — 233°, and crystallising from hot alcohol in
brownish-yellow needles. A small quantity of the monoanilide is
simultaneously formed. Aiiilidohydroxy toluquinone ^
C6HMe02(OH)(NHPh),
obtained by boiling dianilidotoluquinone with alcoholic sulphuric acid
(20 per cent.), crystallises in deep blue lustrous needles decomposing
at 250°; it forms soluble potassium and sodium derivatives and in-
soluble barium, copper, and silver compounds. Dianilidotoluquinone-
a7iiUde, C6HMeO(NPh)(NHPh)2, is formed by the action of aniline
on toluquinone in alcoholic acetic acid solution. It crystallises in
dark-brown broad leaflets melting at 167°, and forms well characterised
salts. The hydriodide forms hard, brown lustrous crystals, the hydro-
hromide dark-green needles of metallic lustre, the platinochloride,
(C26H2iN30)2,H2PtCl6, Small dark prisms of metallic lustre. Anilido-
ethoxytoluquinoneanilide, C6HMeO(lsrPh)(NHPh).OEt, is obtained by
the action of alcoholic sulphuric acid on the trianilide, forming red
silky needles readily soluble in alcohol, and melting at 115 — 116°.
The hydriodide crystallises from alcohol in dark- blue coloured leaflets,
sparingly soluble in water; the nitrate forms similar crystals also
sparingly soluble ; the hydrochloride and sulphate are readily soluble ;
the jpicrate forms blue-coloured needles ; the platinochloride,
(C2lH2oN202)2)B[2PtCl6,
separates from alcohol in blue granular crystals. The meihoxy-
derivative, C6HMeO(NPh)(NHPh).OMe, and the isohutoxy-derivative,
C6HMeO(N'Ph)(]S'HPh).OBu, have also been prepared, the former
crystallising in long delicate brownish-red needles melting at 131°,
and the latter in small red needles melting at 117°. Anilidohydroxy-
toluquinoneanilide, C6HMeO(]S'Ph)(N'HPh).OH, crystallises from hot
dilute acetic acid in brownish needles, which decompose without
melting when heated. It forms metallic derivatives, which are
mostly insoluble or sparingly soluble. When it is treated with dilute
potash solution dihydroxy toluquinone, C6HMe02(OH)2, is formed,
crystallising in broad brownish-yellow lustrous leaflets melting at 177°.
It yields easily soluble salts with the alkalis ; the calcium salt forms
small dark-coloured crystals. A. K. M.
Halogen Derivatives. By R. Benedikt and M. v. Schmidt
(Monatsh, Chem., 4, 604 — 615). — 1. Displacement of Bromine by
Chlorine. — It is known that when tribromoresorcinol or tribromo-
phenol suspended in water is treated with chlorine gas, part of the
bromine is replaced by chlorine; and the authors find that when
chlorine is passed into a solution of tribromophenol in glacial acetic
acid at the boiling heat, the whole of the bromine is expelled, the
ORGANIC CHEMISTRY. 1119
liquid on cooling depositing a small quantity of cUoranil, and the
mother-liqnor as it cools, yielding crystals of trichlorophenol.
2. Action of Potassium Iodide on Tribromophloroglucol. — Iodine-
derivatives of the fatty series have repeatedly been obtained by
heating the corresponding chlorine- or bromine -derivatives with
potassium iodide ; and the same reaction takes place with aromatic
compounds, like benzyl chloride, in which the substituting element
is situated in a side-chain. The following experiments were made
with the view of ascertaining whether a similar result can be obtained
with aromatic derivatives having the substituting element in the
nucleus : —
Tribromophenol undergoes no alteration, and tribromoresorcinol
very little, when boiled with aqueous potassium iodide. Tribromo-
phloroglucol, on the contrary, is somewhat strongly attacked by potas-
sium iodide, the course of the reaction depending on the proportions
used. When 1 part of tribromophloroglucol (1 mol.) is boiled with
15 parts water and 0*8 — 1 part KI (2 — 2J mols.), considerable quan-
tities of iodine are evolved, and a heavy precipitate is formed, con-
sisting of bromodiiodophloroglucol, C6Brl2(OH)3, which crystallises in
brown needles and decomposes, when heated, with evolution of
iodine. The same body, and not tri-iodophloroglucol, is formed, in
smaller quantity, when tribromophloroglucol is boiled with 3 or 4 mols.
potassium iodide ; indeed, as the proportion of potassium iodide is
increased, larger quantities of a soluble body are formed ; and finally
with 7 mols. KI this latter body is the sole product of the reaction,
the whole remaining dissolved on cooling. By acidulating with sul-
phuric acid, agitating with ether, and leaving the ether to evaporate,
a residue is obtained which, when washed with carbon bisulphide to
remove adhering iodine, and then recrystallised from water, yields
crystals of pure phloroglucol, probably formed according to the equa-
tion :— 206Br3H303 + 7KI + 6H2O = 2C6H6O3 + 6KBr -\- KIO3 + 31s,
+ 3H2O.
3. Action of Chlorine on Pentachlorophenol. — When chlorine is
passed for several days into pentachlorophenol suspended in hydro-
chloric acid, the pentachlorophenol is mbstly converted into a tear-
exciting oil, which does not solidify. In one experiment, however, a
solid body was obtained, which, when crystallised from boiling ben-
zene, was found to consist of pentachlorophenol, while the mother-
liquor yielded large yellow crystals having the composition CeCleO,
and melting at 46°. This substance, heated with tin and hydrochloric
acid, is converted into pentachlorophenol, and may therefore be
regarded as chloroxy-pentachloro-henzene, CeClsO.OCl, but its melt-
ing point is considerably below those of the corresponding com-
pounds, C6H2Br3.0Br, C6HBr4.0Br, CeBrj.OBr, and CeHgCla-OCl,
which range from 118° to 128°. Langer, by passing chlorine into
a solution of aniline in glacial acetic acid, obtained a body CeCleO,
melting at 106°, approaching, therefore, more nearly in this respect
to the compounds just mentioned. The author, however, in repeating
Langer's experiment, obtained, not CeCleO, but CeClsO, probably
hexchlorophenol chloride^ C6Cl60,Cl2. This compound forms large well-
defined shining colourless to wine-yellow prisms, melting at 102°,
1120 ABSTRACTS OF CHEMICAL PAPERS.
distilling nndecomposed when slowly heated, and reduced by tin and
hydrochloric acid to pentachlorophenol. On agitating* the mother-
liqnors of this body with water and light petroleum and distilling ofE
the latter, there remained a small residue, which, when recrystallised,
yielded a body containing 70"03 per cent, chlorine, and, melting at
about 100°, probably therefore identical with Langer's hexchloro-
phenol. H. W.
Paranitrobenzaldehyde and Acetone. By A. Babteb and P.
Becker (Ber., 16, 1968 — 1971).— Claisen has observed that benz-
aldehyde reacts with acetone to form methyl cinnamyl ketone with
elimination of a molecule of water ; whereas under similar conditions
Baeyer and Drewsen obtained from orthonitrobenzaldehyde an aldol,
or the methyl ketone of orthonitro-|S-phenyl lactic acid, without elimi-
nation of water. Baeyer and Drewsen consider that in both these
changes an aldol is formed, but that in the latter case the presence of
the nitro-group adds to its stability. The author has investigated a
similar change in the para-derivatives, in order to examine the cor-
rectness of the above hypothesis. By the action of nitrobenzaldehyde
on acetone, paranitro-^-phenyllactyl-m ethyl ketone is formed thus :
C6H4(N02).CHO + CHs.COMe = C6H4(N02).CH(OH).CH2.COMe;
this substance forms colourless crystals melting at 58°, soluble in
ether and alcohol, insoluble in petroleum. When boiled with acids or
water, it gives off a molecule of water, and yields paranitro-cinnamy I
methyl ketone, thus :
C6H4(lsr02).CH(OH).CH2.COMe-OH2 = CeHiCNOO-CHICKCOMe,
which melts at 110°. If the aqueous solution of the lactyl ketone be
mixed directly with potash or soda, paranitrodicinnamylJcetone is formed,
whicb crystallises in golden glistening needles melting at 254°),
sparingly soluble in alcohol, soluble in acetic acid. As this substance
yields paranitrobenzoic acid on oxidation, it follows that the nitro-
group remains intact ; in this respect, the para- differs most markedly
from the corresponding ortho- derivative, which under similar con-
ditions yields the characteristic indigo-grouping. V. H. Y.
Benzil. By H. Goldschmidt and V. Meter (Ber., 16, 1616 —
1617). — Wittenberg and Meyer (this vol., p. 804) showed that benzil
differs from glyoxal in its reaction with hydroxylamine, only one
oxygen-atom of the former becoming replaced by the group NOH, whilst
in the case of glyoxal both oxygen-atoms become substituted with
formation of glyoxime. This led them to doubt the correctness of the
formula PhCO.COPh. The authors find, however, that when pow-
dered hydroxylamine hydrochloride and a drop of hydrochloric acid
are added to a solution of Wittenberg and Meyer's compound,
PhC(NOH).COPh, in wood spirit and the mixture heated to boiling,
it yields diphenylglyoxime, CUH12N2O2. This forms white lustrous
scales melting at 237°, sparingly soluble in cold wood-spirit, alcohol,
and ether. It dissolves in strong soda solution, and is precipitated by
the addition of an acid. Ammonia dissolves it sparingly, the solution
giving a yellowish precipitate with silver nitrate. A. K. M.
ORGANIC CHEMISTRY. 1121
Derivatives of Orthotoluic Acid. By O. Jacobsen and F.
WiERSS (Ber., 16, 1956 — 1962). — Bromorthotoluic acid,
C6H3BrMe,COOH [Me : COOH : Br == 1 : 2 : 3],
prepared by the direct action of bromine on ortbotoluic acid, crys-
tallises in long needles melting at 167", soluble in alcohol and ether,
sparingly soluble in water; its salts do not crystallise readily. Nitro-
orthotoluic acid, formed by nitrating toluic acid, although it has a
well-defined melting point, 146°, is a mixture of two isomerides, which
can be separated only by frequent fractional crystallisation from alcohol.
OL-Nitro - orthotoluic acid, CsHaCNOoJMe.COOH [NO2 : Me : COOH
= 1:2:3], forms small needles melting at 179°, soluble in hot water
and alcohol ; its barium, calcium, and potassium salts crystallise in
needles. ^-Nitro-orthotoluic acid, [NO2 : Me : COOH = 1:4:5],
also forms needles melting at 145°, more soluble in dilute alcohol than
its isomeride. a-AmidortJiotoluic acid crystallises in flat prisms,
melting at 196° ; the |8-acid in glistening needles. Both a- and
)3-nitro-orthotoluic acid give the same dinitro-acid,
C6H3Me(N02)2.COOH [NO2 : NO2 : Me : COOH =1:3:4:5],
which forms long needles, melting at 206°.
Sulpho-orthotoluic acid, C6H3Me(HS03).COOH, prepared by the
action of ordinary sulphuric acid on orthotoluic acid, forms a crystalline
mass ; the disulphonic acid fine microscopic needles. On melting the
latter substance with potash, a dihydroxyorthotoluic or cresorsellinic
acid, C6H2Me(OH)2.COOH, is obtained, which crystallises in hard
glistening needles melting at 245°. A solution of the acid, heated
with concentrated sulphuric acid, forms a beautiful magenta-red
colour ; on dilution with a further quantity of acid, the red solution
gives two strong absorption-bands in the green part of the spectrum.
This reaction with sulphuric acid resembles that of its homologue
dihydroxybenzoic acid. The ammonium salt of cresorsellinic acid
crystallises in thick transparent prisms, which at 155° are dissociated
completely into ammonia and the free acid ; the barium- salt forms
microscopic needles. Cresorsellinic acid is not identical with any of
the known bromodihydroxybenzoic acids. Experiments made with a
view of determining its constitution were unsuccessful.
V. H. V.
Benzyl Derivatives. By S. Gabriel and 0. BoRGMANN(Ber., 16,
2064 — 2066). — The authors have prepared the third or metanitro-
phenylacetic acid, taking as their starting point the metanitrobenzyl
alcohol, prepared by the action of sodium hydroxide on metanitro-
benzaldehyde. The crude alcohol was converted into the chloride,
C6H4(N02).CH2C1 [NO2 : CH2CI = 1:3], which crystallises in long
golden needles melting at 45 — 47°, soluble in alcohol and ether. The
nitrophenylacetic acid, C6H4(N02).CH2.COOH, prepared from the
chloride through the medium of the cyanide, forms colourless needles
melting at 117"' ; its silver salt forms colourless silky crystals. Meta-
midophenylacetic acid, C6Ht(NH2).CH3.COOH, obtained by the reduc-
tion of the nitro-derivative, forms pale golden tabular crystals melting
at 148°.
VOL. XLIV. 4 /
1122 ABSTRACTS OP CHEMICAL PAPERS.
The authors suggest, as a convenient material for the preparation
of the corresponding ortho-compounds, the oil obtained from the crude
metanitrobenzaldehjde by pressure. V. H. V.
Pormation of Phenylamidopropionic Acid by the Action
of Stannous Chloride on Albuminoids. By E. Scuulze and
J. Barbieri (Ber., 16, 1711— 1714).— By boiling 2 kilos, of the
albuminous matter contained in beans with stannous chloride and
hydrochloric acid, the authors have obtained an acid which is identical
with the phenylamidopropionic acid they have previously extracted
from germinating lupins. W. C. W.
Phenylamidopropionic Acid, Phenylamido valeric Acid, and
other Nitrogenous Constituents of Lupine Shoots. By E.
ScHULZE and J. Barbieri (/. pr. Chem. [2], 27, 337— 362).— The
authors have already described the phenylamidopropionic acid from
this source (Abstr., 1882, 189), they regard it as identical with phenyl-
alanine. The yellow residue left on melting the acid consists of
phenyllactimide (?), CgHyNO ; it is soluble in boiling alcohol, and
crystallises in thin needles, melts at 280°, and sublimes if strongly
heated. The mother-liquor from the copper salt of phenylamido-
propionic acid contains an amidovaleric acid, CsHnNOa. This crystal-
lises in transparent brilliant plates, resembling leucine in appearance,
'moderately soluble in water, sparingly in strong alcohol, readily in hot
dilute alcohol ; when heated, it volatilises completely, yielding a white
woolly sublimate. It is readily distinguished from leucine by its
yielding a soluble copper salt. The hydrochloride,- C5HuN02,'HC1,
crystallises in small prisms, and is readily soluble in alcohol and
water. The authors have also found lecithine and peptones in the
shoots, and have confirmed the presence of xanthine, hypoxanthine,
leucine, tyrosine, and asparagine. A. J. G.
Perkin's Reaction. By R. Fittig (Ber., 16, 1436— 1438) .—A
reaction takes place at the ordinary temperature, when benzaldehyde,
sodium malonate, and acetic anhydride are mixed together, giving rise
to the formation of cinnamic and carbonic acids. If sodium isosuc-
cinate is substituted for malonate, phenylcrotonic acid is produced.
If glacial acetic acid is substituted for acetic anhydride in the preced-
ing reactions, the acid, CHPh ! C(C00H)2, described by Claisen and
Crismer (Annalen, 218, 129), is obtained in the former case, and
phenylcrotonic acid, as well as a small quantity of cinnamic acid in
the latter case, if the reaction takes place at about 180".
When a mixture of benzaldehyde, acetic anhydride, and sodium
butyrate is heated at 100° for 60 hours, phenylangelic acid is pro-
duced, but no cinnamic acid could be detected. Another acid is also
formed, probably an acetic derivative of phenyloxy valeric acid, which
-is much more soluble than phenylangelic acid. The formation of
cinnamic acid observed by Perkin, is due to a secondary reaction.
At 150° a mixture of cinnamic and phenylangelic acids is obtained.
Valeraldehyde and oenanthal also have the power of acting od the
sodium salts of the acetic series, but as the action does not take place
ORGANIC CHEMISTRY. 1123
below 180°, a large portion of aldehyde polymerises, and consequently
a poor yield is obtained. By the action of acetic acid and sodium
acetate on valeraldehyde, the acid,
CHMe2.CH2.CH : CH.COOH,
is formed, and in the same way the acid, C7H14 ! CH.COOH, is obtained
from cenanthol. Both acids are colourless liquids, sparingly soluble in
water, and volatile in a current of steam. W. C. W.
Derivatives of Cinnamic and Hydrocinnamic Acids. By
S. Gabriel and M. Herzberg {Ber., 16, 2026— 204^3).— Orthochloro-
cinnamic acid^ C6H4CI.C2H2.COOH, prepared by the action of hydro-
chloric acid on orthodiazocinnamic acid, forms golden crystals, melt-
ing at 200°, soluble in alcohol and ether, insoluble in water ; ortho-
chlorhydrocinnamic acid, C6H4Cl.C2H4.COOH, crystallises' in needles
melting at 96*5°. The corresponding iodocinnamic acid is a crystal-
line solid melting at 212 — 214°, the iodohydrocinnamic acid forms
leaflets melting at 102° ; it is slowly converted into hydrocinnamic
acid by nascent hydrogen.
Metachlorocinn amic acid forms golden needles melting at 167°,
soluble in hot alcohol and ether ; inetacJdorhydrocinnamic acid crys-
tallises in leaflets. The corresponding iodocirmamic and iodohydro-
cinnamic acids melt at 181° and 65° respectively.
ParacMorocinnamic acid does not crystallise in a well-defined form ;
it melts at 241°, is sparingly soluble in cold water, readily in alcohol ;
parachlorhydrocinnamic acid melts at 124°; and the corresponding
iodocinnamic and iodohydrocinnamic acids at 255° and 140° respec-
tively.
Paracetamidocinnamic acid, NHSc.C6H4.C2H2.COOH, crystallises
in long colourless needles melting at 259°, soluble in hot alcohol, inso-
luble in ether. Dinitroacetamidostyrole, NHXc.C6H2(N02)2-C2H3,
obtained by the action of nitric acid on the above compound, crys-
tallises in needles melting at 211°. If the nitration be effected in
. the cold, an impure nitropararaidocinnaniic acid is formed, which on
boiling with sodium hydroxide yields sodium mononitroparamido-
cinnamate. By the action of hydrochloric acid, the corresponding acid,
is obtained in red needles melting at 224 — 5°, and soluble in hot
alcohol, less soluble in water ; as this substance yields metanitrocin-
namic acid when boiled with ethyl nitrate, the nitro-group is in the
meta-position to the C2H2.COOH-gronp. Metaparadiamidocinnamlc
acid, obtained by the reduction of the above nitro-acid, crystallises in
golden needles melting at 167°, soluble iu water and alcohol, insoluble
in ether and benzene.
Bromacetamidostyrole, [4]NH^.C6H3Br.C2H3[l], formed by the
action of bromine on paramidocinnamic acid, crystallises in needles
melting at 182*5°, insoluble in ammonia, soluble in alcohol and ether.
V. H. V. .
4/2
1124 ABSTRACTS OF CHEMICAL PAPERS.
Hydroxytoluic and Hydroxyphthalic Acid. By O. Jacobsek
(Ber.,16, 1962 — 1968). — ^-metahydroxytoluic acid,
C6H3Me(OH).COOH [Me : COOH : OH = 1 : 2 : 5],
obtained from the corresponding bromo-, nitro-, or sulpho-toluic acids,
crystallises in long glistening prisms melting at 168° ; its solation
gives a blue-violet colour with ferric chloride.
^-Orthohydroxytoluic acid, C6H3Me(OH).COOH [OH:Me : COOH =
1 : 2 : 3], crystallises in long glistening needles melting at 183^ ; its
aqueous solution gives a bright brown precipitate with ferric chloride.
This acid, when heated with lime, yields a cresol* convertible into
salicylic acid. Its methyl-derivative, C2H3Me(OMe)3.COOH, crystal-
lises in small needles. On oxidation with potassium permanganate,
this acid is converted into |3- methoxyphthalic acid,
C6H3(OMe)(COOH)2 [OMe : COOH : COOH = 1:2:3],
which forms small prisms melting at 160° with partial decomposition
into the anhydride and water. The former sublimes in needles melt-
ing at 87°. This methoxyphthalic acid gives precipitates with solutions
of silver, lead, and barium salts.
^-Hydroxy ortkophthalic acid,
C6H3(OH)(COOH)2 [OH : COOH : COOH = 1:2:3],
obtained from the methoxy-derivative by fusion with potash, crystal-
lises in hard compact prisms, which melt at 200° when heat-ed up
quickly, but decompose at 150° into water and the anhydride when
lieated slowly. The anhydride melts at 145". This hydroxyphthalic
acid gives a cherry-red coloration with ferric chloride, thus differing
from the a-acid. The salts of this acid are not readily obtained in a
crvstalline state ; their solutions give precipitates with salts of lead
and silver. Y. H. V.
Laevorotatory Mandelic Acid. By J. Lewkowitsch {Ber., 16,
1565 — 1568). — The mandelic acid was prepared from amygdalin by
Wohler's method (Annal&n, 66, 238), and melted at 1.32-8^ the
melting point of the acid prepared from benzaldehyde being 118°. The
acid obtained from amygdalin is laevorotatory, the specific rotatory
power of an aqueous solution at 20° being — [a]© = 212'52 — 0*57779,
and of a solution in glacial acetic acid — [a]© = 209*95 — 0*27139.
A. K. M.
Separation of Inactive Mandelic Acid into Two Optically
Active Isomerides. By J. Lewkowitsch (Ber., 16, 1568 — 1577). —
The author previously showed that dextrorotatory mandelic acid could
be obtained from the inactive acid by the action of certain organisms
(Abstr., 1882, 1076). He has now succeeded in separating both dextro-
and IsBvo-rotatory acids from the inactive substance, and in reproduc-
ing the latter from equal parts of the two active isomerides. The
dextrorotatory acid obtained by the action of Penicillium glaucum on
inactive mandelic acid has the same specific rotatory power as the
laevorotatory acid (see last Abstr.) ; both melt at 132*8°, show the
ORGANIC CHEMISTRT. 1125
same degree of solubility, and in fact agree in all their properties
except in the direction in which they polarise a ray of light. The
lesvorotatory acid is obtained from the inactive mandelic acid by means
of Saccharomyces elUpso'ideus and of a schizomycetes (?) vibrio. When
equal molecular weights of inactive mandelic acid and pure crystallised
cinchonine are dissolved in boiling water, and a crystal of the cin-
chonine salt of the dextrorotatory acid added, an abundant separation
of the latter salt takes place, forming rosette-like groups of anhydrous
needles, from which the pure dextrorotatory acid can be obtained,
melting at 133°. When the mother-liquor is concentrated, a deep
yellow solution is obtained, which, after being exposed for some weeks
in a vacuum, deposits crystals of the cinchonine salt of Isevorotatory
mandelic acid. It is much more readily soluble than the dextrorota-
tory salt ; both are anhydrous and crystallise alike. The inactive
mandelic acid obtained by the union of the two active varieties agrees
in melting point (118°) and in its other properties with the inactive
acid (paramandelic acid) prepared from oil of bitter almonds. From
the close analogy thus exhiblited between mandelic and tartaric acids,
the author assumes the possibility of converting leevomandelic acid
into paramandelic and dextromandelic acids, and he has already
succeeded in obtaining a partial conversion into an inactive variety.
A. K. M.
Dry Distillation of Sodium Dibromanisate. By L. Balbiajjo
(Gazzetta,13, 65 — 72). — When a mixture of sodium dibromanisate with
an equal weight of lime is cautiously heated in a retort, a violent reac-
tion takes place, the mass becomes incandescent, and a small quantity
of a yellowish liquid distils over, which on cooling becomes crystalline
in great part. The yield is about 10 to 12 per cent, of the dibrom-
anisate employed. The product dissolved in ether is washed by
agitation with dilute soda solution, the ether distilled off, and the
residue crystallised two or three times from alcohol. It forms small
white lustrous needles melting at 1)1 "5 — 92°, and insoluble in water.
When saponified with alcoholic potash, it yields dibromanisic acid ;
this fact and the results of the analyses prove the substance to be
methyl dibromanisate, C6H2Br2(OMe).COOMe.
The carbonaceous residue in the retort is exhausted with boiling
water, the solution concentrated, acidified with hydrochloric acid, and
{igitated with ether. On evaporating the ethereal solution and crys-
tallising the residue from alcohol, a dibromhydroxybenzoic acid is
obtained in colourless needles, melting at 266 — 268° with decomposition,
but subliming at a lower temperature. It is almost insoluble in water.
When this acid is carefully treated with sodium amalgam so as to
replace the bromine by hydrogen, it yields parahydroxy benzoic acid
melting at 211°, and having all the properties ascribed to it by Hlasi-
wetz and Barth. The calcium salt of dibromoparahydroxybenzoic
acid is very soluble in water, and crystallises in small tables with
3 mols. H2O.
In the mother-liquors from the crystallisation of the crude dibromo-
parahydroxybenzoic acid, there is a very small quantity of another acid
which crystallises from ether in small needles melting]with decomposi-
1126 ABSTRACTS OP CHEMICAL PAPERS.
tion at 269°. Its alcoholic solution gives no coloration with ferric
chloride.
From these results, it will be seen that the reaction by which the
methyl dibromanisate and dibromoparahydroxybenzoic acid are pro-
duced is —
2[C6H2Br2(OMe).COONa] = C6H2Br2(OMe).COOMe +
C6H2Br2(ONa).COONa;
moreover, there is no intramolecular change, the dibromanisic acid
obtained by the saponification of the methyl salt being identical with
that originally employed. C. E. G.
Derivatives of ParacresolglycoUic Acid. By M. Napolitano
(Gazzetta, 13, 73 — 77). — The cresolgly colic acid is prepared by adding
sodium hydroxide solution, sp. gr. 1"3 (400), to a mixture of paracresol
(98) with monochloracetic acid (84) ; when cold, the sodium salt of
the new acid is crystallised from water and decomposed by hydro-
chloric acid. Sodium paracresolgly collate, CgHgOgNa, obtained as above,
is sparingly soluble in cold, moderately in hot water, and forms thin
plates or long slender prisms, the former containing one, the latter
0"5 mol. of water of crystallisation. The barium salt, prepared by
neutralising the pure acid with barium hydroxide solution, crystallises
in plates or prisms containing 2 mols. H2O. The lead salt was pre-
pared by decomposing the barium salt with sulphuric acid, and then
neutralising with pure lead carbonate. It forms plates containing
1 mol. H2O ; it is moderately soluble in water, but does not crystallise
readily. C. E. G.
Action of Phthalic Anhydride on Amido-acids. By E. Drech-
SEL (J. pr. Cham. [2], 27, 418 — 422). — By fusing phthalic anhydride
with glycocine, phthaluric add (phthalylglycocine),
CeHi : (C0)3 : N.CH2.C00H,
is obtained. It crystallises in very long thin needles, is sparingly
soluble in cold water and ether, readily in hot water, soluble in alco-
hol; it melts at 191 — 192°, and on further heating yields an oily sub-
limate crystallising on cooling. It is resolved into phthalic acid and
glycocine when boiled with hydrochloric acid. The sodium salt crys-
tallises in large flat prisms ; the calcium salt, (CioH6N04)2Ca -|- 2H2O,
forms very thin flat prisms ; the platodiammonium salt,
Pt[N2H6(CioHeNO,)]2
crystallises in large prisms or small needles, the copper salt,
(CioHeNOOaCu+SHaO,
forms light blue rhombic tables. A. J. G. .
Azophthalic Acid. By A. Claus and G. Hemmann (Ber., 16,
1759 — 1762). — Benzidinetetracarboa'i/Uc anhydride is formed by the
action of a concentrated solution of stannous chloride on azophthalic
ORGANIC OHEMISTRY. 1127
acid. It is a pale yellow powder insoluble iu water, alcohol, ether, and
in dilute acids. It dissolves in hot solutions of alkaline carbonates,
yielding the acid potassium or sodium salt of benzidinetetracarboxylic
acid. The potassium salt, containing 5 mols. HjO, crystallises in prisms
which effloresce at the ordinary temperature. The anhydrous salt is
hygroscopic. The sodium salt, NaaCieHgNaOi, forms microscopic
needles which dissolve in water yielding a brown solution. The silver
salts, AgaCieHgNaOT, and AgiCisHeNaOs, are easily decomposed by
light. They are pale yellow powders insoluble in water. An ammo-
nium salt of the composition CieHgNaOejNHi.OH, crystallises in yellow
prisms.
When the anhydride is heated at 360°, water and carbonic anhy-
dride are evolved, and a pale yellow sublimate of the auhydrimide,
CO/^ I I yCO, is deposited in needle-shaped crystals. The
OsHs — CeHa
anhydrimide (m. p. 283°) is soluble in alcohol and ether. It also dis-
solves in alkalis, forming a dark yellow liquid which grows darker on
exposure to the air. On the addition of an acid a brown powder is
obtained soluble in water and alcohol, and sparingly soluble in ether.
It melts with decomposition at 235°. W. C. W.
Constitution of Phthalylacetic Acid. By S. Gabriel (J5er., 16,
1992— 1997).— According as the complex grouping ! CH.COOH in
phthalylacetic acid is associated with one or two carbon-atoms, so the
acids benzoylacetocarboxylic and acetyl phenonecarboxy lie acid can
be expressed by either of the formulaB written below ; —
I.
Phthalylacetic C«H4<^q>CH.C00H (a).
+ X±2^ ^ ^ pQ pTX POOH
Benzoylacetocarboxylic... ^«-^*>^r^OOH^ ^^'
— CO2 = COMe
Acetophenonecarboxylic . . ^«^*"^POOH ^^^*
II.
C6H4<^Q>0 = CH2.COOH {a).
p ^ ^C(OH) : CH.COOH ...
^«^*^COOH ^^>'*
n H ^^(^H) • ^^« (A
C6il4<(.QQJJ {c}.
Pormer researches of the author have established for acetophenone-
carboxylic acid the formula 1(c); the pi*esent paper not only confirms
this view, but the formula l{h) for benzoylacetocarboxylic acid. V.
Meyer's hydro xylamine reaction was used to recognise the presence
of a CO grouping associated directly with the carbon atoms.
From the crude product of the action of hydroxylamine hydrochlo-
i^ide on benzoylacetocarboxylic acid in presence of soda, hydrochloric
1128 ABSTRACTS OF CHEMICAL PAPERS.
acid precipitates a crystalline substance of composition CioH704N,
whose formation can be expressed by the equation CioHsOs -f NH^ —
2H2O = CioH704N. This compound is probably an anhydride of
^-isonitrosopropiono-o-benzoic acid derived from an oximide com-
pound COOH.C6H4.C(N.OH).CH2.COOH, by the abstraction of 1 mol.
of water thus :
COoH.C6H4.CN(OH)CH,C02H - H,0 = C.u/ >CH,.COOH.
This substance is a monobasic acid forming salts of the composition,
C10H6NO4N. On melting, it is converted into an anhydride of phenyl
methyl acetoxime-orthocarhoxylia acid, a compound best obtained by
the direct action of hydroxylamine hydrochloride on ethyl aceto-
phenone carboxylate in presence of soda. This change may be repre-
sented thus : —
(I.) C6H4<(^QQ^^ + NH3O = H3O + C^^Kqq'q^^ ^'
/C(N.OH)Me yCMe^
(11.) CeHZ - EtOH = CeH/ >N.
^COOEt ^COO'
This substance crystallises in colourless needles melting at 157**,
sparingly soluble in water ; by the action of bromine it is converted
into a dibromo-derivative, C9H6Br2N02, which crystallises in needles
melting at 223°.
As the above reactions are best explained on assuming the formulaj
I(fe) and I (c) for benzoylacetocarboxylic and acetophenonecarboxylic
acids, then the formula la for phthalylacetic acid becomes the more
probable. Y. H. Y.
Anilpyruvic Acid. By C. Bottinger (Ber., 16, 1926—1927).—
In former experiments the author obtained anilpyruvic acid and
its aniline salt by the action of aniline on pyruvic acid ; both these
substances decompose on long keeping into a blackish powder, from
which hydrochloric acid extracts the hydrochloride of aniluvitonic
acid.
By the action of bromine on anilpyruvic acid in chloroform solution,
a pentabromo-derivative is obtained, which crystallises in needles,
always associated with impurities. This substance is insoluble in
water, readily soluble in alcohol ; it gives white precipitates with solu-
tions of salts of lead and silver. Its solution in alcohol decomposes,
with evolution of heat, into tribromaniline, dibromaldehyde, and car-
bonic anhydride. This decomposition points to the formula,
COOH.(CHBr)C I ^.C^HsBrs,
for the bromoanilpyruvic acid.
It is, however, noticeable that whereas tribromaniline is neutral,
the above mentioned acid combines with hydrobromic acid to form a
true salt. Y. H. Y.
ORGANIC CHKMISTRY. 1120
Derivatives of Anhydro-amidotolyloxamic Acid. Bj 0. Hins-
BKEG {Ber.^ 16, 1531 — 1534). — This acid was obtained by the author
on reducing nitrotolyloxamic acid (this vol., p. 323), and can also be
prepared by heating the oxalic acid derivative of diamidotoluene,
CsHaMeCNHaO.CO.COOH)^ + H2O, to 160°, or by boiling it with
glacial acetic acid. The silver salt is rather unstable ; its formula
is C6H3MeN2C20.Ag2.
By the action of phosphorus pentachloride on the dry acid, the
n:cci
chloride CeHaMe^^^ | is formed, melting at 114 — 115°. It crys-
^n:cci
tallises in white needles insoluble in water, soluble in alcohol, ether,
and chloroform ; it can be boiled with water, dilute soda solution, or
with ammonia without decomposition ; silver nitrate and oxide are
also without action on its boiling alcoholic solution. By the action of
alcoholic potash, a substance still containing chlorine is obtained melt-
ing at 40°, long continued boiling with concentrated alkali being
required for the displacement of the whole of the chlorine and repro-
dnction of the original acid. By the reduction of the chloride by
means of zinc and glacial acetic or hydrochloric acid, or of hydriodic
acid and glacial acetic acid, dark blue solutions are obtained, whilst
a part of the product is precipitated in black flocks dissolving in ace-
tone to a blue solution. The colouring matter is unstable, and
instantly decomposed by water. Sodium acts on the alcoholic solution
of the chloride with formation of a solid neutral compound.
A. K. M.
Cymenesulphonic Acids. By A. Claus (5<?r.,16, 1603).— A reply
to Paterno {Ber., 16, 12y7).
Isonitroso-acids. By A. Muller {Ber., 16, 1617— 1622).— In con-
tinuation of Meyer and Miiller's experiments with nitrosomalonic acid
(this vol., p. 790), the author has examined the action of hydroxy 1-
amine on two other ketonic acids. From levulic acid,
CH3.CO.CH2.CH2.COOH,
he obtains ^i-isonitrosovaleric acid, CH3.C(NOH).CH2.CH2.COOH,
melting at 95 — 96°. It is very readily soluble in water, less so iu
ether and in alcohol. The barium salt, (C5H80aN)2Ba,2H20, decom-
poses when gently heated ; the silver salt, CsHgOaNAg, is obtained as
a white precipitate, which blackens on exposure to light ; the ethyl deri-
vative, CsHftOsNEt, is a liquid of an agreeable odour, which is decom-
posed by distillation. By the action of tin and hydrochloric acid ou
7-isonitrosovalerianic acid, levulic acid is formed ; sodium amalgam
has no action ; on boiling it with hydrochloric acid, it is converted
into levulic acid and hydroxylamine. By the action of hydroxyl-
amine on phenylglyoxylic acid, isonitrosophenylacetic acid^
PhC(NOH).COOH,
is obtained, melting at 127 — 128°. It is moderately soluble in ether,
alcohol, and water, and has a slight, aromatic odour. It is decom-
1130 ABSTRACTS OF CHEMICAL PAPERS.
posed when heated with hydrochloric acid, hydroxylamine being
liberated. The barium salt, [PhC(NOH).COO]2Ba,liH20, crystal-
lises in needles of silky lustre, and decomposes when gently heated ;
the potassium salt, PhC(N0H).C00K,H20, is crystalline, and very
readily soluble in water ; the silver salt obtained by precipitation has
the formula PhC(NOH).COOAg. By the action of tin and hydro-
chloric acid on isonitrosophenylacetic acid, phenylaviidoacetic acid^
GHPh(NH2).C00H (m. p. 255—256°), is produced, together with
ammonia and benzoic acid. Benzoic cyanide and hydroxylamine
yield pure dibenzhydroxamic acid melting at 153°. A. K. M..
Isatin. By H. Kolbe (/. pr. Chem. [2], 27, 490— 497).— The
author considers isatin to be a compound of formyl with benzoyl, the
latter having one of its hydrogen-atoms replaced by an atom of
monovalent nitrogen. It is therefore nitrogenbenzoyl-formyl,
(C6|^*|C0).C0H.
He considers that when isatic acid loses water and forms isatin, the
two hydrogen-atoms of the amido-group combine with the oxygen-
atom of the hydroxyl-group, and that the carboxyl is converted into
formyl according to the equation : — •
Ce I g*-^ j CO.COOH = Ce I ^* I CO.COH + H^O.
Amidobenzojlcarboxylic acid Nitrogenbenzoyl-formyl
(Isatic acid). (Isatin).
When isatin is treated with phosphorus pentachloride, he considers
that the trivalent-group CCl is formed, the formula of the chloride
being (Ce l^'\ C0.CC1)".(C6 1 S I CO.CCiy. On replacing the
chlorine with hydrogen, the compound nitrogen-benzoyl-methine or
indigo-blue is formed.
The author considers isatin, dioxindole, and indole to be analogously
constituted formyl compounds, and represents their composition by
corresponding formulae. He considers indole to be a compound of
nitrogen- benzoyl with the univalent radical (CH)', its formula being
(C.{^.}cH.y.(CH)'. jj^
Oxindole and Isatoxime. By A. Baeyer and W, Comstock
{Ber., 16, 1704 — 1711). — Oxindole is more soluble in alkalis than in
water, but it can be extracted from the alkaline solutions by ether.
It is converted into barium orthamidophenylacetate by the action of
baryta- water at 150°. The ethyl derivative of oxindole, CgHeEt^N'O,
prepared by heating alcoholic solutions of oxindole and sodium with
ethyl iodide, is a colourless oil at the ordinary temperature, sparingly
soluble in water. It is not decomposed by baryta at 200°, and it is
only slowly attacked by strong hydrochloric acid at 150°, but oxindole
ORGANIC CHEMISTRY. 1131
is not fonnd amongst the products of decomposition. As isonitroso-
indole and isaxotime have been shown to be identical, and as the
ethyl derivatives are easily converted into isatine, this compound
must be regarded as a derivative of isatine. The name ^^ isaxotime''
will therefore be retained, and '^ isonitrosoindole " discarded. Silver
isatoxime is thrown down when dilute ammonia is added to an alco-
holic solution of silver nitrate and isatoxime. By the action of ethyl
iodide on this salt, monethylisatoxime, CsHgEtNoOo, is produced. It is
deposited from an alcoholic . solution in yellow needles (m. p. 138°).
Ethylisatoxime is soluble in alkalis, but is reprecipitated from the
solution by carbonic acid. It dissolves in hot solutions of alkaline
carbonates, but is deposited on cooling. It is easily converted into
isatine by reducing it with zinc-dust and acetic acid, and oxidising
the product with ferric chloride.
By a similar process, ethylisatoethyloxime can be prepared from the
silver salt of isatoethyloxirae. It is an unstable compound, and has
not been obtained in a state of purity. It is converted into isato-
ethyloxime by boiling sodium hydroxide. The unstability of this
compound, and the stability of the monethyl-derivative testify in
C(NOEt)
favour of the formula CeHi/^ \C.OH for isatoethyloxime, and
\ N^
C(]S'OEt)
CfiHi/ \C.OEt for ethylisatoethyloxime.
\- — N^
Dihromisatoxime, CgHiBraNzOa, prepared by the action of sodium
carbonate on an alcoholic solution of dibromisatine and hydroxyl-
amine hydrochloride, forms pale yellow needle-shaped crystals,
sparingly soluble in alcohol. It chars at 255° without melting.
Dihromisatoxime is reprecipitated from its solution in an alkali by
carbonic acid. Dibromisatoethyloxime, CioH8Br2N202, forms yellow
needles which melt at 252°. Uihromethylisatoethyloxime is deposited
from acetone in long silky needles (m. p. 115°). It is a stable com-
pound, and is converted into dibromisatine by reduction and oxida-
tion. The presence of the oxime-group appears to increase the
resistance which the isatine nucleus offers to the action of alkalis.
w. c. w.
Nitrosoxindole and Nitrosindoxyl. By A. Baeyer (Ber., 16,
769 — 770). — In reference to Gabriel's synthesis of nitrosoxindole
froji isatin and hydroxylamine, the author points out that he made
that synthesis some time ago, and is now (in conjunction with Com-
stock and Sapper and with Victor Meyer's permission) investigating
the constitution of nitrosoxindole and nitrosindoxyl with the help
of that reaction. He finds that on the reduction and subsequent
oxidation of the ether of nitrosoxindole isatin is obtained, whereas
with diethylated nitrosindoxyl a new body, isomeric with isatin, is
CO
produced, the formula of which is probably C6H4<^jg^p. ^-CO.
L. T. T. .
1132 ABSTRACTS OF CHEMICAL PAPERS.
New Synthesis of Skatole. By O. Fischer and L. German
(Ber.j 16, 710 — 712). — 100 grams of aniline were carefully mixed with
70 — 80' grams of zinc chloride to form the double salt : 100 grams of
glycerol were then added and heated for some time at 160 — 170°,
finally for two hours at 240° ; the product was then acidified with
very dilute sulphuric acid and steam-distilled. The distillate con-
tained a mixture of various substances of which only skatole has yet
been isolated. It fused at 93°, and showed all the reactions of skatole,
but could not be obtained free from smell. The authors believe they
have also identified methylketole in the mixture, and ascribe the odour
of the skatole to traces of adhering methylketole. L. T. T.
Synthesis of Unsymmetrical Tetraphenylethane. By R.
Anschutz and F. Eltzbacher (Ber., 16, 1435 — 1436). — Anthracene is
produced by the action of aluminium chloride and benzene on sym-
metrical tetrabromethane. By a similar reaction tetraphenylethane
can be obtained from unsymmetrical tetrabromethane.
w. c. w.
Ethylhydrocarbazostyril. By E. Fischer and H. Kuzel (Ber.,
16, 1449 — 1454). — NitrosoetTvylamidohydrocinnamic acid,
C6H4(NEtN^O).aH4.COOH,
is prepared by treating an alkaline solution of ethylamidocinnamic
acid with sodium-amalgam. When acetic acid ceases to produce a
yellow coloration with a few drops of the mixture, the solution is
acidified with dilute sulphuric acid and treated with sodium nitrite.
By recrystallisation from benzene and from dilute sulphuric acid,
nitrosoethylamidohydrocinnamic acid is obtained in colourless
oblong plates which are freely soluble in alcohol, ether, benzene, and
alkalis, bat are less soluble in hot water.
The crystals melt at 78° and decompose at 150°. An alcoholic
solution of this substance is converted into ethylhydrazinhydrocinnamic
acid by reduction with zinc-dust and acetic acid. The operation is
complete when a drop of the solution no longer exhibits Liebermann's
reaction with phenol and sulphuric acid. The solution decomposes on
evaporation; the crystalline residue consists of a mixture of ethyl-
hydrocarbazostyril and zinc acetate. The zinc salt is dissolved out by
water ; the residue is treated with ether to remove small quantities of
ethylhydrocarbostyril, and the crude product on recrystallisation iroTD.
hot water yields the pure substance in white needles (m. p. 165'5°)
freely soluble in alcohol. This compound closely resembles hydrocar-
bostyril, but is dis*^iuguished from it by its behaviour with hot hydro-
chloric acid. Hydrocarbostyril remains unchanged, and ethylhydro-
carbazostyril unites with water, forming ethylhydrazinhydrocinnamic
acid. A solution of ethylhydrocarbazostyril in strong cold hydrochloric
acid is precipitated unaltered if water is at once added, but if the
solution is left at rest for some hours a soluble crystalline hydro-
chloride is formed which melts at 146° and decomposes at 150° into
water, hydrochloric acid, and hydrocarbazostyril.
Hydrocarbostyril yields a sulphonic acid, C18N2H16O2S2O6H2, when
ORGANIC CHEMISTRY.
1133
it is treated with strong sulphuric acid at 100°. The barium salt of
this acid is soluble in water and almost insoluble in alcohol and ether.
w. c. w.
Formation of Nitril Bases from Organic Acids and Amines.
Synthesis of Acridines. By A. Bernthsen and F. Bender (J5er.,
16, 1802— 1819).— The authors find that the base they obtained by
the action of zinc chloride on a mixture of formic acid and diphenyl-
amine (p. 1099) is identical with the acridine which Graebe and
Caro (Annalen, 158, 266; Ber., 13, 09) extracted from the high-
boiling portion of coal-tar. Tbe authors are of opinion that the
composition of acridine should be expressed by the formula C13H9N,
instead of C12H9N. The base, CuHnN", which Bernthsen and Fischer
prepared from diphenylamine and glacial acetic acid {Ber., 16, 68), is
methylacridme, and the base C19H13N, obtained from diphenylamine
and benzoic acid {Ber., 15, 3011), is phenylacridine.
The close resemblance in the properties of these three compounds
is shown by the following table : —
Pure base
Solubility in water . . .
Salts
Fluorescence of salts . .
Dissociation
Nitrate
Precipitates with
KsCrA.KI.orHgCl.,
Distilled with sodium
hydroxide
Strong HNO.-,
Acridine.
Colourless
Slight
Yellow
Blue-green
0
Long needles, spar
ingly soluble
YeUow
Undecomposed . .
0
Methylacridine.
Colourless .
Very shght
YeUow. . . .
Blue-green
0
Yellow. . . .
0
Phenylacridine.
Colourless.
0.
Yellow.
Green.
Partial.
Long needles, spar-
ingly soluble.
Yellow.
Undecomposed.
0.
Phenylacridine melts at 181° and boils above 360° without decom-
position. It is not attacked by acetic anhydride or by benzoic chlo-
ride, but it unites with methyl iodide, forming brilliant dark crystals
of the ammonium iodide, Ci9Hi3N,MeI. The crystals are soluble in
alcohol and in hot water. The addition of silver oxide or of caustic
soda to the aqneous solution precipitates methylphenylacridium hy^
droxide, Ci9Hi3NMe,OH. This substance is deposited from its alcoholic
solution in prisms melting at 108°, soluble in ether. The chloride crys-
tallises in needles which dissolve freely in water, and the nitrate forms
sparingly soluble needles of a yellow colour. Dilute solutions of the
salts, with the exception of the iodide, exhibit a dark-green flno-
rescence. The reactions with potassium chromate, mercuric chloride,
potassium chloride, and potassium iodoiodide, are similar to those
exhibited by phenylacridine. The platinoehloride is converted at 60*
into phenylacridine platinoehloride.
The yellow solution of phenylacridine hydrochloride is decolorised
by zinc-dust, and all organic matter is removed from the solution.
1134 ABSTRACTS OF CHEMICAL PAPERS.
By extracting the zinc-dust with boiling alcohol, kydrophenylacrtdinej
CigHisN, is obtained in colourless needles. This substance has no
basic properties. When boiled, it readily loses hydrogen, forming
phenylacridine. Hydromethylacridine, CuHuN, resembles the pre-
ceding compound.
When hydro phenylacridine is heated at 130° with methyl iodide,
it yields methylhydrophenylacridine, CigHuMeN. This substance is
deposited from an alcoholic solution in needles or prisms (m.p. 104°).
Acetylhydrophenylanridine, CipHuXcN (m. p. 128°), dissolves freely
in alcohol, ether, benzene, chloroform, and acetone. Methylhydro-
phenylacridine is converted into methylphenylacridinium hydroxide
by oxidation with hydrochloric acid and sodium nitrite. Conversely th6
hydrochloride of methylphenylacridinium hydroxide is converted into
methylhydrophenylacridine by reduction with zinc and hydrochloric
acid.
Acridine resembles anthracene in constitution. It may be regarded
as anthracene in which nitrogen replaces a CH-group.
CPh
Acridine.
Phenylacridine.
C6H4<-^jj ^CeHi
c.HK^sri>ce]
Hydrophenylacridine.
Methylphenylaeridine.
Bases were also obtained by the action of diphenylamine on phthalic
acid, ethylaniline on benzoic acid, and by methylaniline on acetic
acid. W. C. W.
Acridine. By 0. Fischer (Ber., 16, 1820— 1821).— The base,
C14H11N, obtained by the action of glacial acetic acid and zinc chloride
on diphenylamine (Ber., 16, 68) bears such a close resemblance in its
properties to acridine, recently described by Riedel (ibid., 16, 1612),
that the author considers it may be regarded as methylacridine. The
formation of methylacridine from acetyldiphenylamine is easily
explained by means of Riedel's formula for acridine.
Acridine. Acetyldiphenjlamine. Methylacridine.
w. c. w.
Acridine. By A, Bernthsen and F. Bender (Ber., 16, 1971—1974).
— The authors' researches has shown that the composition of acridine
is represented by the formula C13H9N, and not C12H9N', and its con-
CH
stitntion thus : CeHX | yC^Ki. Accordingly, hydroacridine, ob-
ORGANIC CHEMISTRY. 1 135
tained by the action of reducing agents on acridine, -will possess a
constitution, C6H4<[t^tt ^CeH^.
The authors point out that the same soluble hydrophenylacridine is
formed whether phenylacridiiie is reduced by sodium amalgam or by
zinc and hydrochloric acid. Further, hydroacridine in alcoholic solution
is decomposed by silver nitrate in accordance with the equation —
/CH, CH
CeHZ >C6H4 + 2AgN03 = CeHZ | >C6H4,HN03 + 2HNO3
+ Ag2.
Insoluble hydroacridine has the consitution, | ,
CeSLi<^QTT '^CeS-i
which the authors propose to prove by the silver nitrate reaction.
The relation of acridine to quinoline and pyridine is also discnssed.
V. H. V.
Methylnaphthalene. By P. Boessneck (Ber., 16, 1546 — 1547). —
By the action of sodium on a mixture of a-bromonaphthalene and
methyl iodide, Fittig and Remsen (Annalen, 155, 112) obtained a
small quantity of a-methylnaphthalene boiling at 231 — 232°, the
chief product being naphthalene. The author finds that a much
better yield is obtained by the distillation of a mixture of a-naphthyl-
acetic acid with lime, 10 grams a-naphthylacetic acid yielding nearly
5 grams of hydrocarbon. A. K. M.
Phenylhydrazine-derivatives of the Quinones. (Preliminary
Notice.) By T. Zincke (Ber., 16, 1563— 1564).— When an aqueous
solution of phenyl hydrazine hydrochloride is added to /3-naphtha-
quinone in alcohol or glacial acetic acid, a dark red solution is
obtained, yielding red needles which, after re crystallisation from
alcohol, melt at 138°. ^-Naphthaquinone}Jienylhjdrazine, C16H12N2O,
dissolves with moderate ease in hot alcohol and acetic acid, but is in-
soluble in water; it dissolves sparingly in dilute alkalis and acids,
but does not form salts; concentrated sulphuric acid dissolves it,
forming a violet-red solution from which water precipitates it un-
changed. Tt forms a pale red acetyl- derivative melting at 120°. A
second substance is obtained in the above reaction, which dissolves
more readily and crystallises in white needles, the composition of which
is unknown. Phenanthraqidnonehydrazine, C20H14N2O, is obtained by
an analogous reaction, and forms bright red broad lustrous needles or
scales melting at 165°, sparingly soluble in hot alcohol, more readily
in hot acetic acid. It dissolves in concentrated sulphuric acid with a
violet colour, and is precipitated unchanged on dilution with water.
Acetic anhydride has no action on it. A. K. M.
^-Napthylaminesulphonic Acid. By L. Landshoff {Ber., 16,
1931 — 1933). — Although phenol, even at a high temperature, is un-
1136 ABSTRACTS OF CHEMICAL PAPERS.
affected by atnmonia, yet ;3-naphthol can be converted into ^-naphthyl-
amine by the action of this gas ; the reaction is however far from
complete. In the present paper the author points out that the
sulphonic derivatives of /3-naphthol can be converted readily into the
corresponding /3-naphthylaminesulphonic acid. In order to effect
this change ammonia gas is slowly passed through the alkaline salts
of the 8-naphtholsulphonic acids heated at 250*^. Dye-stufFs obtained
from the /3-naphthylaminemono-, di-, and tri-sulphonic acids are briefly
noticed. V. H. V.
Naphtholtrisulphonic Acid. By L. Limpach {Ber., 16, 726). —
Levinstein (Ber., 16, 462) called in question the correctness of the
author's description of his method of preparation of y3-naphtholtri-
sul phonic acid. The author now quotes the words of his German
patent to show that his description was correct. He also says that,
contrary to Levinstein's statement, only one trisulphonic acid is
produced by his method. L. T. T.
/3-Naphthacoumarin. By Gr. Kauffmann (^er.,16, 683—686).—
y3-Naphthoxylaldehyde, already described by the author (Abstr., 1882,
1068), was mixed with anhydrous sodium acetate and acetic anhy-
dride, and boiled for some time in a flask provided with a condensing
tube. On treatment with water, a brown oil was obtained, which
quickly solidified to a crystalline mass. Purified by repeated crystal-
lisation from alcohol, this substance forms colourless plates, which
melt at 124°. This substance was not the coumarin anticpiated, but
the triacetyl compound of the aldehyde, CioH6(OXc).CH(OZc)2. It is
insoluble in water, easily soluble in alcohol and acetic acid. It gives
a dark brown coloration with ferric chloride. On boiling with sodium
hydroxide, it is decomposed into the original aldehyde and acetic acid.
On distilling the acetyl compound, acetic acid passes over, and a small
quantity of the coumarin is obtained. The author then repeated his
experiment, but heating in a sealed tube at 180° for 2| hours. When
cold the contents solidified to a brown crystalline mass, which on
purification yielded fine, silky, and almost colourless needles of
najyhthacoumarin.
PIT * PIT
Naphthacoumarin, CioE[6<C A ^CO, is soluble in acetic acid,
alcohol, ether, and chloroform, slightly so in boiling water, and the
aqueous solution has a bluish fluorescence. Its melting point is 118°.
When boiled with dilute potash, the naphthacoumarin is dissolved with
a yellow coloration, but is reprecipitated unchanged on adding an acid.
Heated to a higher temperature with very concentrated potash, a
nophthacoumaric acid is produced. Naphthacoumarin thus shows the
same reaction with alkalis as ordinary coumarin, and the author there-
fore concludes that in the dilute alkaline solution a salt of an isomeric
naphthacoumaric acid exists corresponding to a-coumaric acid.
^ - Naphtha coumaric acid is soluble in alcohol, from which it separates
as a pale yellow crystalline powder, melting at 170°.
The formation of ^-naphthacoumarin proves that the side groups in
/3-naphthoxyl aldehyde are in the ortho-position to one another. Ita
ORGANIC CHEMISTRY. 1137
formation from tlie acetyl-compoaiid by direct distillation is also of
interest as showing that the presence of a sodium salt is not essential
to the CO umarin- condensation. L. T. T.
New Method of Forming Anthracene. By 0. Henzold {J. pr.
Ghein. [2j, 27, 518—520). — When benzyl ethyl ether is heated with
phosphoric anhydride, a violent reaction takes place. On distilling
the product, a semi-solid mass is obtained, which, when re-crystallised
from glacial acetic acid, forms glittering monoclinic plates of anthra-
cene, melting at 208°. When treated with chromic acid, they yield
anthraquinone. They are probably formed by the oxidation of stilbene,
aH,Ph2 -f 0 = H2O + CK.XCeU,),. J. I. W.
Reduction in the Anthracene Series. By H. Roemer (Ber., 16,
1631— 1635).— The author showed (Abstr., 1882,974) that metamido-
anthraquinone is reduced when heated with hydriodic acid and amor-
phous phosphorus with formation of anthracylamine. Orthamido-
anthraquinone (this vol., p. 72) is much less readily acted upon, and
amidomethylanthraquinone with still greater difficulty. On boiling the
latter for 1—2 hours with hydriodic acid of sp. gr. 1'96, amidomethyl-
anthranol is obtained, whilst if the reduction is effected in sealed tubes
at a temperature of 150°, the hydriodide of amidomdhylanthrifc.ene-
dikydride, CuHioMe.NHo, is formed. The hydrochloride forms lustrous
needles melting at 245°, and the free base bright yellow lustrous scales,
melting at 78 — 79°, and subliming at 130—140° with slight decom-
position. It is almost insoluble in water, but dissolves very readily in
alcohol and in ether, forming a yellow slightly fluorescent liquid, and
also in chloroform, carbon bisulphide, benzene, xylene, and glacial
acetic acid. With dilute nitric and sulphuric acids, it forms colourless
solutions, from which the respective salts crystallise in white needles.
It dissolves in concentrated sulphuric acid to a yellow solution, which
however soon becomes green with evolution of sulphurous anhydride
and formation of a sulphonic acid. Its solution in nitric acid is at
first green, then yellow. On adding potassium nitrite to a solution of
the hydrochloride, a green solution is obtained, from which ammonia
throws down a red precipitate. It is insoluble in potash, and gives no
coloured solution on boiliiig with zinc-dust and potash (distinctions
from amidomethylanthranol) . AcetylamidonnethylanthraceMedihydride,
CuHioMe.NHAc, forms white lustrous needles (m. p. 198°), readily
soluble in alcohol and in ether, with faint blue fluorescence. It is
insoluble in hydrochloric acid, and is not decomposed if boiled with
the latter or with potash, whilst at 150° hydrochloric acid converts it
into the hydrochloride. When amidomethylanthracenedihydride is
heated to 230° it remains unaltered in composition, its colour becomes
somewhat darker, and its solution in ether more strongly flurrescent.
With chromic acid, it yields a body insoluble in h3^drochloric acid.
A. K. M.
Amidomethylanthranol. By H. Roemer and W. Link {Ber.,
16, 703— 706).— Roemer formerly (Abstr., 1882, 974) described the
reduction of amidoanthtaquinone (by hydriodic acid and amoiphous
phosphorus) to anthracylamine. Tlie authors have now investigated
VOL. XLIV. 4i g
1138 ABSTRACTS OF CHEMICAL PAPERS.
the same subject with the amidometliylanthraquinone described in the
uext abstract. Using hydriodic acid of sp. gr. 1*7, an unstable
compound, easily soluble in alcohol, hydrochloric acid, and alkalis
is produced, which they have not further investigated. Using acid of
sp. gr. l'&6, a precipitate insoluble in water was obtained. This dissolves
in hot dilute hydrochloric acid, and its hydrochloride crystallises cat
on cooling in long needles. Washed with water, these needles lose
hydrochloric acid, and leave the free base ; this crystallises from alcohol
in almost colourless needles, which darken on exposure to the air. It
dissolves in alkalis, and the fluorescent solution deposits re-formed
amidomethylanthraquinone. Its formula is CiaHnlSrO, and it yields a
diacetyl-derivative, showing that a hydroxyl-group must be present
as well as the amido-group. These properties leave no doubt that it
is an amidomethylanthranolj C6H4<^_ Jstt _^CJi2^e.'NH2, but the
position of the CH3 and NHj groups, and whether they are in the same
nucleus or not, is at present unknown. It melts at 183°, and at a
slightly higher temperature sublimes with partial decomposition, in
red needles. It is easily soluble in- alcohol, ether, benzene, chloro-
form, and glacial acetic acid, very sparingly in water. Ferric chloride
gives a green coloration in alkaline solution. Strong sulphuric acid
produces a yellow solution, turning purple when heated ; strong nitric
acid (sp. gr. 1'48), a violet colour, slowly changing to orange. Its
hydrochloride crystallises in glistening white needles containing 4H2O,
which they lose at 80°. Diacetylamidomethylanthranol crystallises in
white needles, melting at 170°. It is very unstable, is easily soluble
in alcohol with a blue fluorescence, but its solution decomposes
readily.
Traces of another body were also produced which remained behind
with the phosphorus, after the extraction of the anthranol. It distils
in steam, melts at 100", and appears to be a dihydride of methyl-
anthracene. L. T: T.
Nitro-, Amido-, and Hydroxy-methylanthraquinone. By H.
ROEMER and W. Link {Ber., 16, 695 — 703). — In crude anthracene,
there is often present a methylanthracene which is very stable, and
interferes with the preparation of alizarin. A mixture of methyl-
anthraquinone and anthraquinone is formed, and the methyl-group is
not eliminated by the subsequent processes, but contaminates the
alizarin and damages its shade considerably. Messrs. Bronner have
patented a process for getting rid of the methyl-compound by digesting
the mixed quinones with benzene: raethylanthraquinone is easily
soluble; anthraquinone but very sparingly so. The authors have
investigated the methylanthraquinone extracted by Messrs. Bronner,
and prepared some derivatives. The crude extract was freed from
resinous matter by washing with a very little benzene, crystallised
from benzene, and finally from alcohol (in which anthraquinone is
only very slightly soluble). Methylanthraquinone crystallises in pale
yellow needles, soluble in acetic acid and benzene, sparingly in ether.
Concentrated sulphuric acid dissolves it with blood-red coloration,
which changes to violet on heating. It melts at 177^ and sublimes in
ORGANIC CHEMISTRY. 1139
wliite needles. Ifc appears to be identical with the methylanthra-
quinone of Wachendorf and Zincke (Ber., 10, 1485), and with that
obtained from the same source by Bornstein (this vol., p. 70), but is
isomeric with that of 0. Fischer.
Nitromethyl-anthraquinone was obtained by treating the quinone
with sulphuric acid and potassium nitrate; it melts at 269 — 270°
when pure. It is sparingly soluble in alcohol, ether, benzene,
chloroform, and acetic acid; easily in xylene, nitrobenzene, and
aniline. It crystallises in pale yellow needles, which sublime in white
needles. It dissolves in strong sulphuric acid with a yellow colour,
which becomes yellowish- red, and finally brown on heating, sulphurous
acid being produced at the same time. If the acid solution be poured
into water, a purple colouring-matter is precipitated, which dissolves
in alkalis to a fine violet-blue solution. Amidomethylanthraquinone
was obtained by the reduction of the nitro-compound with alkaline
stannous oxide solution. It crystallises from alcohol in red needles,
fusing at 202°. It sublimes to long dark-red crystals. It is insoluble
in water, soluble with a yellow coloration in ether, alcohol, benzene,
acetic acid, and chloroform. Hot hydrochloric acid gives an almost
colourless solution, from which the hydrochloride crystallises out on
cooling in white scales, which are decomposed by water. Acetyl-
amidomethylanthraquinone forms small bright red needles, meltino" at
176—177°.
HydroxymetJiylanthraqninone was obtained from the amido-body by
means of the diazo-reaotion. It is sparingly soluble in alcohol and
crystallises in orange needles, melting at 177 — 178°. It sublimes
almost without charring, in long yellow needles. Acetijlhydroxy-
viethylanthraquinone crystallises from alcohol in orange-yellow scales,
melting at 177°. L. T. T.
Derivatives of Anthramine. By A. Bot.lert {Ber., 16, 1635 —
1640). — When anthramine is boiled with glacial acetic acid, the solu-
tion obtained at once deposits small lustrous scales of very sparing
solubility in the ordinary solvents. On boiling the precipitate with
alcohol to separate acetylanthramine, pure dianthraminej {CuHq}.^!!,
is obtained, closely resembling anthramine in appearance. It does
not melt at 320°; it yields a blue-green solution with concentrated
sulphuric acid, and on heating it with amyl nitrite, a red-coloured
nitroso-derivative is produced. Trimethylanthrammoninm iodide^
CuHgMesNI, is readily obtained by the action of an excess of methyl
iodide on anthramine at 100°. It is sparingly soluble in cold water,
more readily in hot water, and almost insoluble in alcohol; a very
dilute solution shows a faint blue fluorescence. It melts at 215" with
decomposition. On treating its aqueous solution with freshly-pre-
cipitated silver oxide, a strongly alkaline liquid is obtained containing
t rimethylanthrammonium hydroxide, CuHgMeaN.OH. The latter yields
crystalline salts; the hydrochloride forms small lustrous crystals, readily
soluble in cold water; the platinochloride, (CuH9Me;,NCI).,PtCl4, is
obtained as a yellowish crystalline precipitate. When a solution of
the ammonium base is evaporated on a water-bath f nd the residue
heated at 120 — 130°, dimethylanthraminej CuHgNMca, is produced,
4^2
1140 ABSTRACTS OF CHEMICAL PAPERS.
and on boiling the product with water and crystallising the residue
from boiling alcohol, thin scales are obtained, melting at 155°.
CuHgMeaN.OH = CuHgNMe^ 4- MeOH. This base is moderately
soluble in hot alcohol, the solution showing a green fluorescence. It
is much more readily soluble in hot dilute hydrochloric acid than
anthramine, and from this solution the hydrochloride crystallises in
colourless, lustrous scales. On boiling an alcoholic solution of
anthramine with amyl nitrite, or on adding a very dilute solution of
nitrous, acid to a cold alcoholic solution of anthramine, a red crys-
talline precipitate, C-eHziON., (m. p. 250°), is obtained, sparingly
soluble in alcohol, ether, and glacial acetic acid, more readily in am}'!
alcohol and carbon bisulphide. It is not acted on by potash or dilute
acids, whilst concentrated sulphuric acid yields a blue solution. It is
easily reduced by stannous chloride, with formation of anthramine.
An attempt to prepare the isonitril of anthramine by the action of
chloroform on its solution in alcoholic potash yielded a product which
is probably methenyldianthramineaifnidine^ C14H9.N '. CH.NH.ChH9.
It is readily soluble in hot alcohol, from which it separates on cooling
r.s a brownish-yellow amorphous substance. ForTnanthramine,
CuHaNH.CHO, is obtained as a yellow crystalline precipitate, by
heating anthramine with an excess of concentrated formic acid (sp. gr.
1'22) at 100°. It melts at 242°, dissolves sparingly in hot alcohol,
the solution showing a blue fluorescence. A. K. M.
Addition-products of some Terpenes. By P. Meissen (Gazzetta,
13, 99 — 102). — From the results of Tonnies' experiments (Abstr.,
]879, 35) it would seem that unsaturated hydrocarbons are capable of
forming addition-products with nitrous anhydride. Nitrosyl chloride,
as Tilden has shown, also has the property of uniting in a similar
manner with most of the terpenes, and the author has succeeded
in forming addition-products which, besides the terpene-group, contain
a molecule of nitrosyl chloride, and one of nitric acid. The terpenes
which yield these interesting compounds are those obtained from the
essential oils of carroway (carvene), lemons, and orange. The puri-
fied terpene (50 grams) is saturated with dry hydrogen chloride, mixed
with glacial a(3etic acid (30), and to this is added a mixture of amyl
nitrite (70) with nitric acid (35), of sp. gr. 1'40, taking care to keep
the whole well cooled. In this way a homogeneous greenish-blue
liquid is obtained, which after some time deposits a white crystalline
substance, the temperature rising somewhat at the same time. The
crystals are insoluble in alcohol, but very soluble in chloroform, so
that they may be purified by precipitating the chloroform solution
with alcohol. The carvene compound, which forms small hard crystals,
melts at 114 — 115° with decomposition and evolution of nitrous
vapours. Analyses are given of the compounds formed with the
three terpenes, and in all cases they agree with the formula
C,oHi6(HNO;O.NOCl.
When submitted to the action of different reagents, all three of the
coni pounds decompose with the greatest ease, yielding dark-coloured
resinous products. C. E. G.
ORGANIC CHEMISTRY. 1141
Aldehydic Nature of Oxidation-products of Terebene. By
H. ScHiFF (Ber., 16, 2010— 2013).— The oxygen compound, formed
on exposing turpentine-oil to the air, has attracted the attention of
many chemists, but no satisfactory results have been obtained with. it.
The author shows that turpentine-oil, if not exposed for too long a time
to the air in presence of diffuse sunlight, gives many of the reactions of
an aldehyde, viz., a reduction of ammoniacal solutions of silver, a
violet coloration with rosaniline sulphite, and an evolution of heat on
addition of sodium hydrogen sulphite. After the oil is heated to its
boiling point, the two former reactions can be observed, but not the
latter, owing probably to a more intimate oxidation of the oil. The
author endeavoured to separate the product of oxidation, and obtained
a small quantity of a thick golden oil, which is altered readily by the
air. It combines with ammonia and aniline, forming a crystalline
compound with the latter. When oxidised by nitric acid, the oil gives
a white solid acid melting at 50 — 60°, which appears to be neither
camphoric nor abiotic acid. When citron oil is exposed to sunlight, a
similar violet coloration is produced by the addition of rosaniline
sulphite. V. H. Y.
Bitter Principle of Hymenodictyon Excelsum. By W. A. H.
Naylor (Pharm. J. Trans. [3], 13, 817— 818).— The barks of two
species of Hymenodictyon, H. excelsum, and H. ohovatum, are bitter,
and are used in India as tonics. Previous investigation of the bitter
principle of the bark resulted in its being attributed to the presence
of assculin. The author has studied the behaviour of the bitter sub-
stance, and pronounces it to be an alkaloid allied to paricine. The
bitter substance may be extracted from a mixture of the bark with lime
by percolation with alcohol ; it is not crystalline, melts at 120°, is
deliquescent, has an alkaline reaction, and a persistent bitter taste.
It dissolves in and nearly neutralises acids. The hydrochloric acid
solution gives amorphous precipitates of various colours with the
following reagents, — phosphomolybdic, picric, and tannic acids; the
double iodides of potassium with bismuth, mercury, and cadmium ;
mercuric chloride ; potassium ferro- and ferri-cyanide ; sodium piios-
phate, chloride, and nitrate ; and ammonium chloride. The sulphate
is precipitated by nitric acid. The platinochloride contained 20'08
per cent, platinum ; a combustion yielded results 7-5'82 carbon,
9 8 hydrogen (paricine requires C 75'59, H 7*08). The alcoholic
solution is optically inactive. The author intends to continue this
investigation. D. A. L.
Solubility of the Colouring-matter of Wine in the various
Constituents of Grape-juice. By F. Gantter {Ber., 16, 1701 —
1703). — The colouring-matter in the skin of the grape is soluble in a
solution of tartaric acid or cream of tartar; the Folubility increases
with the temperature. It is only sparingly soluble in alcohol or in an
aqueous solution of sugar. W. C. W.
Active Principle of the Root of Apocynum Cannabinum.
By 0. ScHMiEDEBERG {Pilar m. J. Trans. [3], 13, 942). — This vegetable
1142 ABSTRACTS OF CHEMICAL PAPERS.
root contains two snbstances, one aporynin, an amorphous resinons
substance, soluble in alcohol and in ether, almost insoluble in water ;
a very small quantity causes systolic pause in the heart of a frof^. It
does not seem to be a glucoside, although when boiled with moderately
strong hydrochloric acid it pi"oduces a liquid which reduces alkaline
cupric oxide, and itself becomes inert as regards the heart, &c. The
second substance is apocyne'in, which is a glucoside, and in its proper-
ties agrees essentially with nerein or digitale'in, but, like apocynin,
does not give any remarkable reaction with sulphuric acid and
bromine. D. A. L.
Action of Nascent Hydrogen on Pyrroline. By G-. L. Ciamician
and M. Dennstedt (Ber., 16, 1536 — 1544). — The pyrroline is heated
with zinc-dust and acetic acid for 24 hours, and the product distilled
on a water-bath under diminished pressure to expel the acetic acid
and the unaltered pyrroline ; on treating the residue with water, a
green solution is obtained, leaving an insoluble residue of zinc-dust
mixed with a resinous substance insoluble in alcohol. The solution is
freed from zinc by means of hydrogen sulphide, acidulated with
hydrochloric acid, evaporated, and the residue steam-distilled with an
excess of potash, when a quantity of ammonia is given off. The dis-
tillate is acidulated with hydrochloric acid, evaporated, and the residue
dissolved in a small quantity of water, and again distilled with potash.
The purified oil boils at 90 — 91° ; it is extremely soluble in water, and
absorbs carbonic anhydride from the air, forming a solid deliquescent
compound. It forms a hi/drochloride, dH^'N^liiCl, melting at 173 —
174°, readily soluble in boiling alcohol, from which it crystallises in
prisms. From the formula of the hydrochloride, it is evident that the
free hydropyrroline has the formula €4117]^^. The platinochloride^
(C4H7N)o,H2Pt'Cl6, is sparingly soluble in cold water, readily in boiling
water ; it crystallises in the triclinic system,
a'.h'.c = 1-65801 : 1 : 1-58370.
Methyl iodide acts very violently on hydropyrroline, with formation
of the compound C4H6MeN,MeI ; this crystallises from boiling alcohol
in nacreous scales, melting at 286° with decomposition; it dissolves
very readily in water, and its solution is not decomposed by potash.
By the action of freshly precipitated silver chloride, the corresponding
chloride is obtained. The pi afinochloride, (G6Hi2N)2,HoPtCl6, crystal-
lises in orange-coloured needles, with variable amounts of water. By
the action of silver oxide on a solution of the methiodide, a strongly
akaline liquid is obtained, which can be evaporated nearly to dry-
ness without decomposition ; on distilling the residue it decomposes,
yielding a nearly colourless distillate, sparingly soluble in water, and
having a penetrating odour resembling that of the isonitriles.
Nitrosohydropyrrolwe, C4H6N.NO, can be prepared by the action of
potassium nitrite on a solution of the base in dilute sulphuric acid. It
crystallises from light petroleum in needles melting at 37 — 38° ; it
dissolves very readily in water, alcohol, and ether, and gives the
characteristic nitrosamine reaction with phenol and sulphuric acid.
ORGANIC CHEMISTRY. 1143
The reactions with methyl iodide and nitrous acid show that hydro-
pyrroline is a secondary base of the formula C4H6 '. NH.
A. K. M.
Tetrahydroquinoline. By L. Hoffmann and W. KoNros (Ber.,
16, 727 — 740). — After a brief survey of the evidence now existing
of the probability that the alkaloids are hydrogenised pyrldine-
derivatives, the authors proceed to the careful investigation of tetra-
hydroquinoline and its derivatives as likely to throw some light on
the quinine-alkaloids.
Two secondary bases are formed by the reduction of quinoline, the
one containing 4, the other 2 more atoms of hydrogen than quinoline.
The latter melts at 161°, and does not distil, and is probably produced
by the union of two molecules of quinoline. The present paper refers
to the volatile hydride with four additional hydrogen-atoms. It was
prepared by Wischnegrad sky's method by reduction with tin and
hydrochloric acid. Tetrahydroquinoline is liquid at ordinary tempera-
tures, but solidifies, when pure, at very low temperatures to* colourless
needles. It boils at 244—246" (bar. 724 mm.), or 15° higher than
quinoline. The hydrochloride crystallises in thin prisms melting at
180 — 181°, and is soluble in water and alcohol. The platinochloride
forms reddish-yellow crystals melting at 200°. The acid sulphate
crystallises from alcohol in prisms, from water (in which it is very
soluble) in large monoclinic plates. The tartrate and oxalate are
easily soluble ; the picrate forms yellow sparingly soluble needles
which melt when heated under water. Tetrahydroquinoline forms an
easily soluble double salt with zinc chloride, and with mercuric chloride,
a similar sparingly soluble compound : both compounds crystallise in
white needles. Gold chloride produces in solutions of the hydro-
chloride, a yellow precipitate which is quickly reduced ; silver is also
reduced from an alcoholic solution of silver nitrate. Ferric chloride,
or potassium dichromate and sulphuric acid, produce deep coloration
in dilute, and an amorphous precipitate in concentrated solutions.
The addition of sodium nitrite to a slightly acid solution of tetra-
hydroquinoline precipitates nitrosotetrahydroquinoline as a yellowish
oil showing Liebermann's reaction. On standing with excess of
nitrous acid, or more quickly by shaking with nitric acid (1 vol. acid
of sp. gr. 1*4 and 2 vols, water), it is converted into nitronitrosotetra-
hydroquinoline, C9H9N(N02)NO, crystallising from alcohol in yellow
needles melting at 187—138°.
Teirahydroqninolinehydrazine, C9H9N.NH2, is obtained by the reduc-
tion of the nitroso-body in alcoholic solution with zinc-dust and glacial
acetic acid. It separates From light petroleum in white crystals melt-
ing at 55 — 56°. It boils, with partial decomposition, at 255°. The
neutral snlphate is sparingly soluble in water, and crystallises with
2 mols. HoO. The hydrochloride is easily soluble in water, sparinglv
so in concentrated hydrochloric acid. The hydrazine reduces gold and
platinum salts in the cold, Fehling's solution on boiling. Nitrous acid
reconverts it into the nitroso-compound.
Tetrahydroquinolinetetrazone, C9H9N.N2.]SrC9H9, is produced by shak-
ing a cold etheric solution of the hydrazine with mercuric oxide. It
resembles E. Fischer's aromatic tetrazones in possessing scarcely any
1144 ABSTRACTS OF CHEMICAL PAPERS.
basic properties. It is insoluble in water, sparingly soluble in alcohol
and mineral acids, freely in chloroform, ether, carbon bisulphide, and
benzene. It crystallises in needles melting at 160°. By lonor boiling
with dilate hydrochloric or sulphuric acids, it is decomposed into
quinoLine and hydroquinoline, gas being at the same time evolved.
Acetic acid produces this decomposition more readily, owing to its
greater solvent power for the tetrazone.
MethyUetra/iydroquinoline, C9H10N.CH3, is obtained by the action of
methyl iodide on tetrahydroquinoline. It is an oil which boils at 242
— 244° (bar. 720° mm.). The platinochloride forms red crystals
melting, with evolution of gas, at 177°. The simple salts are mostly
deliquescent, and scarcely crystallisable. The acid sulphate is obtained
by the slow evaporation of its solution in absolute alcohol in crystals
which deliquesce in the air. With sodium nitrite, an acid solution of
methyltetraquinoline becomes of an intense orange colour, from the
formation of a nitroso- compound ; this body is precipitated as an oil
by the addition of an alkali, but does not seem to be attacked by boil-
ing therewith. The nitroso-compound is soluble in ether to a green
solution, from which nitric acid precipitates a yellow solid, which is
scarcely basic in properties, and is probably nitroinethyltetraqninolinc.
Simultaneously with methyltetrahydroquinoline, the quaternaru
ammonmvi iodide, CgHioNMe.Mel, is formed, and remains in the
alkaline solution. It was isolated by E. Fischer's method (Abstr.,
1878, 407). The chloride thus obtained forms short white prisms.
Tetrahydroquinoline-carhamide, CgHioN.CO.NHo, is easily formed by
mixing equivalent proportions of tetrahydroquinoline hydrochloride
and potassium cyanate in aqueous solution. Tne liquid soon becomes
filled with white needles which, when recrystallised from water, melfc
at 146*5°. This substance is sparingly soluble in cold water, almost
insoluble in alcohol. Dilute acids have no action on it, boiling with
alkalis regenerates tetrahydroquinoline. Carbon bisulphide which
acts violently on piperidine, is without action on tetiahydroquinoline.
Benzoyl- and Acetyl-tetrahydrnquinoline have both been already cur-
sorily described by Wischnegradsky. The former crystallises from
alcohol in plates belonging to the monosymmetric system, melting at
75°, and boiling undecomposed. The latter boils at 295°. Both
have but very feeble basic properties, and are easily saponified by
boiling with concentrated hydrochloric acid. By oxidation in the
cold with a 4 per cent, solution of potassium permanganate, oxalyl-
anthranilic acid was produced, together with acetic acid. The forma-
tion of this substance probably takes place in a manner similar to its
formation from carbostyril already observed by Friedlander and
Ostermaier (Abstr., 1882, 732).
Oxidation of Tetrahydroquinoline. — All attempts to obtain oxalyl-
anthranilic acid by the direct oxidation of tetrahydroquinoline proved
futile ; the products formed were oxalic acid, quinoline, traces
of anthranilic aoid, and an amorphous feebly basic bod}' resembling in
properties the amorphous reduction-product obtained from quinoline.
This amorphous body was always the principal product.
Some time ago Konig showed that by the action of sulphuric acid
on piperidine, pyridine was produced, together with some sul^Dhonic
ORGANIC CHEMISTRV. 1145
acids not fclien investigated. The authors have now isolated barium
pyridinedisulphonafe, C5H3(S03)2Ba. It crystallises in white needles
containing water of crystallisation. Part of the water goes off at 110°,
but the last -J mol. requires a temperature of 200°. Sulphuric acid
acts on tetrahydroquinoline in a similar manner, but more readily,
quinoline and quinoline-sulphonic acids being produced. Dilute nitric
acid (1 : 6) does not attack tetrahydroquinoline ; stronger acid (1:2)
forms first nitroso- and nitronitroso-compounds, but after continued
heating, the addition of water precipitates quinolic acid,
C9H4K(N02)(OH)2.
Action of Bromine on Tetrahydroquinoline. — Excess of bromine yields
tribromoquinoline already described by Lubavin. By using less
bromine, the authors have obtained mono- and di-bromo-substitution
products of the hydro-base. The two are separated by boiling with
dilute hydrobromic acid ; the monobromo-derivative being still
strongly basic goes into solution, whilst the di-derivative is left behind
as an oil. Monobromotetrahydroquinoline hydrobromide,
CgHioBrlSrjHBr,
crystallises from the above solution in white silky needles melting at
about 192° with decomposition. Dibromotetrahydroquinoline hyJrO'
chloride, 09H9Br2N,HCl, is obtained by boiling the above oil with
moderately strong hydrochloric acid (1:2): it melts at 162°, and is at
the same time decomposed. With platinum chloride, it gives a crys-
talline platinochloride. The hydrochloride is decomposed by water,
and is therefore different from the hydrochloride of the dibromohydro-
quinoline obtained by Glaus and Istel by the reduction of tetrabromo-
quinoline, which may be crystallised from water, and melts at 74
—75°.
Both the mono- and di-bromo-compounds form nitroso-bodies,
showing Liebermann's reaction : they are both volatile in a current of
steam ; and are decomposed when heated, yielding hydrobromic acid,
quinoline, and other products not investigated. The bromine there-
fore appears, to be attached to a carbon-atom in the pyridine-ring.
The free monobromo-body forms a crystalline mass melting below the
temperature of the hand, and yields crystalline sulphates and chlo-
rides. The dibromo-derivative is a thick oil, which solidifies in a
freezing mixture. By passing tetrahydroquinoline over red hot
pumice, quinoline and indole are obtained. An attempt to obtain
skatole from methyl-tetrahydroquinoline was unsuccessful.
Physiological Action of Hydroyenised Pyridine Derivatives. — Pro-
fessor Filehne has investigated this subject. Ethylpiperidine hydro-
chloride, CsHioNEtjHCl, is similar in its action to conine. Tetra-
hydroquinoline chloride is more energetic than quinoline, but causes
injurious local action. Dimethyltetrahydroquinolium chloride,
C9lI,oNMe,MeCl,
is similar in its action to curare. For the action of " kairine " and
" kairoline " see this vol., p. 1147. From Filehne's researches it
appears probable that those derivatives of hydroquinoline (perhaps of
1146 ABSTRACTS OF CHEMICAL PAPERS.
hydrogenised diquinoline) will be of most medical value, in which the
imido-hjdrogen is replaced bj an alcohol radical, and render it pro-
bable that this is the case in quinine. L. T. T.
Derivatives of Hydroxyquinoline. By O. Fischer (Ber., 16,
712 — 721). — The author has continued his work on the hydroxyquino-
lines derived from the quinolinesulphonic acids. Both the a- and /i-
hydroxyquinolines are identical with those described by Skraup (this
vol., 92), and in the present paper the author only gives those deriva-
tives of the a-body which have not yet been described. The author
upholds the correctness of the melting point (75 — 76°) of a-hydroxy-
quinoline given in his previous paper, against the lower one (73 — 74°)
given by Skraup.
a^-Hydroxyquinolinetetraliydride has been already described. The
tin double salt is easily soluble in water, sparingly in hydrochloric
acid. It crystallises in iridescent scales or yellowish prisms. The
zinc double salt forms hexagonal plates, sparingly soluble in strong
hydrochloric acid. Potassium ferrocyanide produces a white crystal-
line precipitate in acid solutions of the tetrahydride. The latter body
gives an intense red coloration when boiled with acetic anhydride.
a-Hydroxyquinolinetetrahydride can be converted into a tertiary base
by methylating, ethylating, or benzylating.
a-HijdroxymethylhydroquinoUne, C10H13NO, is obtained by treating
the tetrahydride with methyl iodide (bromide or chloride). It is a
strong base ; dissolves easily in caustic alkalis, benzene, hot alcohol,
and ether, and sparingly in water. The colourless rhombic crystals
obtained from the alcoholic solution had the axis ratio : a : h : c =
0'6o09 : 1 : 1*5383, and melted at 114°. A solution in dilute sulphuric
acid gives an orange colour with sodium nitrite. Ferric chloride pro-
duces a deep brown colour in alcoholic solutions, a dark-brown
flocculent precipitate being gradually deposited. The hydrochloride
(hairine) is easily soluble in water, and gives, over sulphuric acid,
monoclinic crystals containing 1 mol. HoO, which they lose at 110°.
The measurements of the crystals gave a : 6 : c = 0*7 180 : 1 : 0"3858
and /3 = 80° 17'. The sulphate forms easily soluble flat prisms. The
picrate crystallises from dilute alcohol (20 — 30 per cent.) in small
yellowish-green plates sparingly soluble in water.
a-Hydroxyhydroethylquinolirie is prepared in a manner similar to the
methyl compound. It is easily soluble in benzene, alcohol, wood
spirit, and ether, sparingly in water and light petroleum. The hydro-
chloride {hairine A) crystallises in white anhydrous prisms, easily
soluble in water. Boiling with platinic chloride oxidises the solution.
Ethoxyquinoline, CiHuNO, was obtained by heating 1 mol. hy-
droxyquinoline in alcoholic solution with 1 mol. potassium hydroxide
and 1 mol. ethyl bromide for an hour. It distils at 285 — 287° (bar.
718 mm.) as a thick oil which solidifies to a crystalline mass in the
winter. Nitrous acid produces a yellow colour in dilute solutions.
Ethoxyhydroquinoline is obtained from the preceding by reduction
with tin and hydrochloric acid. It distils at 275 — 276"", and remains
liquid. The nzYroso-derivative was obtained by adding it to a dilute
sulphuric solution of sodium nitrite; the liquid becomes red, and.
ORGANIC CHEMISTRY. 1147
after a few seconds, deposits small jellow crystals ; purified by solu-
tion in hot alcohol, the substance was obtained in pale yellow prisms.
It shows Liebermann's reaction well. Concentrated hydrochloric acid
dissolves the nitroso-body with deep-red coloration.
ac.Ethoxyhydromethylquinoline was obtained from ethoxyhydroquino-
line by treating it with methyl iodide. It forms a pale yellow oil,
boiling at 269 — 270° (bar. 716 mm.). Its salts are easily soluble
crystalline substances which are mostly deliquescent.
When 2 mols. of a-hydroxyhydroquinoline are heated in a sealed
tube at 100 — 110'' for an hour with 1 mol. monochloracetic acid, a
body of the formula CuHnNOo, which the author names hairocoll,
crystallises out on cooling, whilst a-hydroxyhydroquinoline chloride
remains in solution. The reaction takes place according to the
equation : —
2C9HnNO + C2H3CIO2 = CnHnNO^ + C9HuN0,HCl + H^O.
The author calls attention to this formation of an anhydride in the
presence of water. Kairocoll is sparingly soluble in water, freely in
alcohol, ether, and light petroleum, and crystallises from the latter in
long thin white needles fusing at Q&^.
The hydroxy-derivatives obtained from coal-tar quinoline and
synthetic quinoline are identical, thus affording another proof of the
identity of these two quinolines.
Physiological Effects of Hydroxy quinoline Derivatives. — Professor
FileKne has investigated the physiological action of many of the
foregoing substances, cc- Hydroxy quinoline and ac-7nethoxyquinoline and
their salts possess poisonous properties. The chlorides of oc-hydroxy-
hydroquinoiiue and oc-methoxyhydroqtiinoline approach quinone in their
action, but cause unpleasant secondary action, such as local decom-
position of albumin, &c. Hydroxymethylhydroquinoline hydrochloride
has exceedingly strong febrifuge properties unattended by any
unpleasant secondary effects, and is now much used under the name
of hairine. Methyltetrahydroquinoline, (3-hydroxyhydroquinoline^ and
01- ethoxy methyl hydroqninoline, all show similar action, varying, however,
in the duration of the effect. The action of the sulphate of the last
named is of longest duration, lasting about 15 — 16 hours.
L. T. T.
iS-Hydroxyqmnoline. By C. Eiemerschmied (Ber., 16, 721 —
726). — /3-Hydroxyquinoline was prepared as described by O. Fischer
(this vol. 91). With Nordhausen acid below 200°, the a-sulphonic
acid predominates, but if the heating is carried to 270° or a larger
proportion of sulphuric anhydride used in the sulphuric acid,- a much
better yield of the yS-acid is obtained. /3-Hydroxyquinoline differs
from the a-body in its non-volatility with steam, and its solubility in
solution of sodium carbonate, from which it can be extracted by ether.
/5-Hydroxyquinoline is undoubtedly identical with that obtained by
Skraup (this vol., 92) from metanitro- and metamido-phenol, but the
author was not able to obtain Skraup's melting point (235 — 288°),
his preparations always melting between 224 — 228°. An acid solu-
tion of potassium dichromate gives red needles of the chromate of
this base. The platinochloride crystallises in orange-yellow plates
1148 ABSTRACTS OF CHEMICAL PAPERS.
with 4H2O whicli it loses at 110°. Skraup gives orange-yellow needles
with 2H2O.
fS-Hydroxyhydrogvinoline, C9H11NO, is obtained similarly to the
a-body (see preceding Abstr.) by reduction with tin and hydrochloric
acid. It is easily soluble in alcohol, ether, wood-spirit, water, <fec.,
sparingly in light petroleum and cold benzene. It crystallises in
stellate groups of needles and melts at 116 — ll?'*. It sublimes with
scarcely any decomposition. Ferric chloride in aqueous solution gives
a very deep-red coloration. The nitroso-der'iysitive is almost insoluble
in water and weak acids, easily soluble in alcohol or wood-spirit. It
crystallises in almost colourless plates, and gives Liebermann's
reaction.
^- Hydroxy ethylhydroquinoUne forms striated crystals, melting at
73°. It is easily soluble in alcohol, ether, benzene, and wood-spirit,
sparingly in water and light petroleum. Ifs hydrochloride contain.s
1 mol. H2O, which it loses at 110°. It has a burning taste and bitter
after-taste, and is, according to Filehne, similar in its physiological
effects to kairine (see p. 1147). A white crystalline precipitate is
produced by potassium ferrocyanide. An alkaline solution gives a
dark brownish-red colour with ferric chloride : sodium nitrite gives
an intense yellow.
^-Hydroxyquinolinesulphonic acid, CgHeNO.SOsHjHaO, is produced
by treating /3-hydroxyquinoline at low temperatures, with 8 times its
weight of fuming sulphuric acid and allowing it to stand 48 hours.
It is easily soluble in boiling water, crystallises with 1 mol. H2O, and
melts at 270°. It gives a dark- green coloration with ferric chloride.
Its salts are yellow in colour : the potassium and sodium salts are
easily soluble in water, the barium salt rather sparingly so. Fused
with sodium hydroxide, it gives a brown mass from which ether
extracts a new body, probably a dihydroxyquinoline.
3-Amidoquinoline, CgHsNo, is obtained by heating 1 part y3-hydroxy-
quinoline with 8 parts ammonium zinc chloride. The mass softens at
160°, becomes liquid at 220°, but very little amide is formed, unless the
mixture is heated for some hours at 300°. yS-Amidohydroxyquinoline
melts at 109 — 110°, and decomposes at a slightly higher temperature.
If heated quickly, however, it sublimes, almost without decomposi-
tion. It is easily soluble in alcohol, ether, wood-spirit, and boiling
water, sparingly so in cold water, light petroleum, and benzene. The.
picrate crystallises from alcohol in long red needles, insoluble in ether.
Chloroform and caustic potash give the carbamine reaction. The
diazo-salts of iS-amidohydroxyquinoline produce, with phenols and
tertiary bases, intense azo-dyes, as, for example, with y3-sodium naph-
tholate a red, with dimethylaniline a yellowish-brown. L. T. T.
Preparation of Substituted Quinolines. By P. Friedlander
and C. F. Gohking {Ber., 16, 1833— 1839). — a-Methylquinoline
(quinaldine) can be prepared by the direct union of orthamidobenz-
aldehyde and acetone in the presence of an alkali. a-Phenylquinoline,
formed on gently warming a solution of orthamidobenzaldehyde and
excess of acetophenone in dilute alcohol with a few drops of soda solu-
tion, is identical with the 7-phenylquinoline of Grimaux (Cornpt.
ORGANIC CHExMISTRY. 1149
rend., 1883, 584), and the a-phenylquinoline of Dobner and v. Miller
(^Ber., 16, 1664). The formula for this compound is —
^CH : CH
CeH/ I
^NZZCPh.
Phenylacetaldeliyde unites with orthamidobenzaldehyde, forming
CH : CPh
^-phenylquinoline, C6H4<^ | , which crystallises in needles melt-
^-n: CH
ing at 93°. With an alkaline solution of ethyl ace toacetate, amido-
benzaldehyde combines, producing the ethyl salt of OL-methylquhioliae
CH : C.COOEt
^-carloxylic acid, C6H4<^ | . This ethereal salt is de-
^-N : CMe
posited from an alcoholic solution in white needles (m. p. 71°), which
are insoluble in water. It forms a crystalline platinochloride,
(Ci3H,3N02)2,H2PtCl6 + 2H2O. On saponification with alcoholic soda
or hydrochloric acid, it yields a-lepidinecarboxylic acid (m. p. 234°).
If ethyl acetoacetate and amidobenzaldehyde are heated at 160°
(without a solvent), hydroxijquinolinemethylhetoney
/CH : C.COMe
CeH4<( I
^-N : c.OH
is obtained as a crystalline mass (m. p. 232°), soluble in hot water.
The compound is precipitated by carbonic acid from its solution in
alkalis. Amidobenzaldehyde acts on ethyl benzoylacetate, forming the
CH : C.COMe
compound, CgH/ | . It melts above 270°, and is less
^-N : C.OH
soluble than the preceding substance, which it closely resembles in
other respects. "W. C. W.
a-Methylquinoline. By Y. B. Djiewsen (7?er., 16, 1955—1956).
— Orthonitrobenzylidene- acetone is best prepared by the direct nitra-
tion of benzylidene-acetone ; on. reduction with stannous chloride in
acid solution it is converted into methylqninoline, CgHgNMe, a heavy
golden-yellow oil (b. p. 240^^), combining with acids to form well
characterised salts. Its platinochloride crystallises in golden needles.
On oxidation with potassium permanganate, it yields a substance
identical in its physical and chemical properties with the acetyl
anthranilic acid, obtained by the oxidation of quinaldine under the
same conditions. When lepidine is oxidised with potassium perman-
ganate, it yields an acid of the composition, C9H9NO3 crystallising in
needles melting at 179°, soluble in alcohol and ether, sparingly soluble
in cold water. V. H. V.
Phenylquinoline. By 0. Doebner and W. v. Meller {Ber., 16,
1664 — 166 ). — The formation of quinaldine from a mixture of aniline,
nitrobenzene, sulphuric acid, and aldehyde or glycol (Abstr., 1882,
1150 ABSTRACTS OF OHKMICAL PAPERS.
868), was assumed by the authors to be dne to the formation in the
first case of crotonaldehyde. Experiments made with mixtures of
aeetaldehyde with higher homologues, e.g., butyraldehyde and
valeraldehyde, show that aeetaldehyde alone yields this reaction.
Cinnamic aldehyde should, however, yield phenylquinolinef
--N : cPh
CeH/ I ,
^CH : CH
-N : CMe
corresponding to quinaldine, CsHi^^ | . On warming a mix-
^CH : CH
ture of aniline and cinnamic aldehyde the compound CgHg ! NCeHs is
formed, crystallising in yellow scales melting at 109°. It is sparingly
soluble in water, readily in ether and hot alcohol. Its hydrochloride
crystallises in long yellow needles. Phenijlquinoline is prepared by
heating a mixture of 30 parts cinnamic acid, 20 parts aniline, and
20 parts hydrochloric acid, for two hours at 200 — 220' ; the brown
product is boiled with dilute hydrochloric acid, the cold filtered
solution supersaturated with soda, and the phenylquinoline extracted
with ether. It crystallises from dilute alcohol in long silky needles,
melting at 83°, and it boils above 300° without decomposition. It
dissolves sparingly in water, readily in ether and in boiling alcohol.
The hydrochloride, rdtrate, ?ind sulphate are readily soluble in water ;
the plat inochloride, (Ci5HuN)2,Il2PtCl6, forms yellow needles, sparingly
soluble in water ; the chroniate, Ci5HnN,Cr207H2, is a characteristic
salt crystallising in gold-coloured scales. A. K. M,
Methylenediquinoil Hydrochloride. By A. Rhoussopoulos
(JBer., 16, 2004 — 2005). — By gently heating methylenediquinoYl
hydroxide and freshly precipitated silver chloride on a water- bath, a
solution of methylenediquinoil hydrochloride is obtained. On evapora-
tion, this substance separates in white glistening tables melting at
160°, easily soluble in water, insoluble in ether. Itis decomposed into
quinoline and methylene chloride when boiled with potash. Its pla-
t inochloride, CH2(C9ll6N)2,il2PtCl6, crystallises both in prismatic
needles and octohedra, sparingly soluble in water, insoluble in alcohol.
V. H. V.
Colouring-matters from Coal-tar Quinoline. By W. Spalte-
HOLZ (Ber., 16, 1847 — 1852). — After referring to the researches of
Skraup {Monatsh. Chem.j 1881, 214) HoogewerfP and v. Dorp {Bee.
Trav. Chim., 2, 28), and Jacobsen and Beimer {Ber., 16, 1(82), on
the identity of quinoline from different sources, the author points out
that the colouring-matter which Williams obtained {Boy. Soc. Edin.
Trans. ^ 31, 377) by the action of alkalis on quinoline ethiodide,
cannot be obtained if pure quinoline or pure quinaldine ethiodide is
employed. It is best prepared by warming an aqueous solution of
quinaldine ethiodide (1 part) and quinoline ethiodide (2 parts) with
excess of potassium hydroxide. After the product has been digested
in ether to remove resinous matter, the colouring matter remains in
ORGANIC OHEMISTRT. 1151
green crystals, which have the coraposition, CosH-psNal -f- iH^O, and
are identical with those obtained from crude quinoline.
w. c. w.
Syntheses in the Pyridine Series. By A. Ladenburg {Ber., 16,
1410 — 1411). — When pyridinethyl iodide is heated at the melting
point of lead, a black mass is formed which, on distillation with excess
of soda, yields water and an alkaline oil, insoluble in water. The oil
(dried over potash) has not a constant boiling point, but distils between
130° and 170°. It appears to consist of a mixture of aromatic hydro-
carbons (b. p. 80 — 140 ), pyridine, and ethylpyridine.
w. c. w.
Introduction of Hydrocarbon Radicles into the Pyridine-
group. By R. Schiff and J. Puliti {Ber., 16, 1607—1608).—
Hantzsch obtained diethylic hydrocoUidinedicarboxylate by the action
of aldehydammonia on ethyl acetoacetate (this vol., p. 82). A similar
reaction takes place when benzaldehyde (1 mol.) is mixed with
ethyl acetoacetate (2 mols.), alcoholic ammonia added, and the mixture
gently warmed. On crystallising the product from dilute alcohol
diethy I hydrojihemjllutidiiiedicarboxylatef
CMe
^ \
COOEt.C CH.COOEt
I I
MeC CHPh
N
is obtained, melting at 156 — 157°. In the same way furfuraldehyde
yields diethylic hydrofurfuryllutidinedicarhoxylate melting at 164° :
2C6Hxo03 + C4H3O.COH + NH3 = 3H2O + CnHsiNOe.
By the action of nitrous acid on these products, the ethyl-deriva-
tives of phenyl- and furfuryl-lutidinedicarboxylic acids are obtained.
Diethylic phenyllutidinedicarhoxi/late, C19II21NO4, melts at 66 — 67°. On
distilling salts of these acids, substituted lutidines are formed.
A. K. M.
Synthesis of Ethylpyridine. By A. Ladenburg (Ber., 16, 2059
— 2063). — The author in a former paper has noticed the formation of
ethyl-7-pyridine, when ethyl pyridium iodide is heated, a change which
involves an isomeric transtbrmation thus: C5H5N',Etl = CsHiEtN,!!!.
In the present paper, this reaction is more fully investigated, and
7-ethylpyridine is described. When etliylpyridium iodide is heated in
sealed tubes at 290°, there is formed, besides 7-ethylpyridine and
traces of ammonia, ethylbenzene, which may be separated from the
base by distillation after addition of hydrochloric acid to the crude
product of the reaction. r^-Ethylpyriditie is a colourless liquid (m. p.
152°, sp. gr. = 0*9553), sparingly soluble in water; its odour resembles
that of pyridine. Its platinoc/d or ide crystallises in small six or cght-
sided orange-coloured tables ; its aurochloride in crystalline leaflets
1152 ABSTRACTS OF CHEMICAL PAPERS.
(m. p. 120°). By oxidation with potassium permanganate, 7-etliyl-
pyridine is converted into 7-pyridinecarboxylic or isonicotic acid of
Skraup and Weidel.
In conclusion, it is remarked that the formation* of ethylbenzene
from pyridine points to a somewhat similar arrangement of the atoms
in pyridine and benzene. V. H. V.
Quinoline- and Pyridine-carboxylic Acids. By C. Riedel
(^Ber., 16, 1609 — 1616). — Hoogewerff' and van Dorp showed that when
lepidine is oxidised by permanganate, the benzene ring is first at-
tacked, with formation of methylpyridinedicarboxylic acid (Ber., 13,
1639). The author finds that by the oxidation of y3-ethylquinoline
(Abstr., 1880, 407), the ethyl-group is first oxidised, with formation of
|S-quinolinecarboxylic acid, and that by further oxidation the benzene
ring is destroyed and pyridinetricarboxylic acid produced. This differ-
ence of behaviour beWeen /9-ethylquinoline and lepidine is explained
by the presence of the ethyl-group in the former, yS-methylquinoline
behaving in the same way as lepidine. The above /3-quinolinecar-
boxylic acid is identical with the acid which Graebe and Caro obtained
by the action of heat on acridinic acid; but if their formula for
acridine (Abstr., 1880, 398) were correct, this should be 7-quinoline-
carboxylic acid. The author is of opinion that acridine is related
to anthracene, and that its formula is C13H9N, and not C12H9N, as
found by Graebe and Caro. Its constitution would then be
CeH<| \CeH4,
CH.C.COOH
acridinic acid being C^H/ I II ' ^^^ /3-qainolinecarboxylic
^N— C.COOH
CH.C.COOH
acid, CgH/ I II . For quinoline and pyridine he likewise
^N— CH
suggests the formulae : —
CH
CH.CH HC
C6H4<^ I II and
CH
II
CH
N . CH HC
\/
N
/3-Quinolinecarboxylic acid is sparingly soluble in cold wa^er, more
readily in hot water and in hot alcohol; it melts at 271 — 272° with
partial decomposition. It forms readily soluble salts with the
mineinl acids; the hydrochloride crystallising in long colourless
needles. With picric acid, it forms a compound sparingly soluble in
cold alcohol, and crystallising in long slender needles melting at 216°
with decomposition. The allcali-salts are readily soluble in water,
those of the alkaline- earths less so. The copper and silver salts are
ORGANIC CHEMISTRY. 1153-
almost insoluble in cold water, the latter being, however, somewhat?
soluble in hot water. The platinochloride, (CioH7N'02)i,H2PtCl6, crys-
tallises in yellow concentrically- grouped needles, readily soluble in
water. Pyridinetricarboxylic acid, [1, 2, 3, StN^l], obtained by
the oxidation of /3-quinolinecarboxylic acid, appears to be different
from all three known acids. It is readily soluble in water and in
alcohol ; its solution is coloured reddish-yellow by ferrous sulphate.
When heated, it softens at 145 — 150^ with evolution of carbonic
anhydride, then solidifies, and does not again melt even at 275°; the
product (7-pyridinecarboxylic acid [N : COOH = 1 : 3 or 1 : 2]), is
sparingly soluble in cold water, moderately in hot. A. K. M.
Triacetonalkamine. By B. Fischer (Ber., 16, 1604—1607). —
The author previously showed (this vol., p. 790) that this compound
obtained by the reduction of triacetoneamine, is a hydroxytetra-
raethylpiperidine. On heating it with concentrated sulphuric acid at
100° (160° as previously stated is too high), it loses water, with forma-
tion of the base CgHnN" (triacetonine), closely resembling piperidine ;
the reaction probably takes place thus :
CH.OH
CH
/\
H,c "bn
H2O CH,
1 1
- H2O' =
1 1
Me^C CMea
Me^C CMe»:
\/
\/
NH
NH
similar to the formation of tropidiae from tropine..
Triacetonine is readily volatile in steam, forming a crystalline
hydrate, from which the free base is obtained by digestion with solid
potash. It is a colourless, mobile liquid, having an odour resembling
that of piperidine. The hydrochloride, C9Hi7N,HCl, is readily soluble
in water and in alcohol, almost insoluble in ether ; the hydrobromide
forms characteristic white prisms, readily soluble in hot water,
sparingly in cold water. Triacetonine is a secondary base, yielding a
nitrosamine with nitrous acid. Triacetonemeth^lalkar)iineyCjlisNOMej
is readily obtained by heating triacetonealkaraine (1 part), with
methyl iodide (2 parts), and methyl alcohol (3 parts), for 8 hours at
100°. It melts at 74°, dissolves readily in luke-warm water, and
shows a strongly alkaline reaction. The hydrochloride and sulphate
are readily soluble in water ;. the aurochlorlde crystallises from hot
water in splendid yellow needles. Triacetonemethylalkamine forms a
compound with mandelic acid which has a mydriatic action on the
eye. A. K. M.
Compounds of the Creatinine-group. By E.. Duvillier (Compt.
rend. J 96, 1583 — 1585). — Methylamido-oc-caprocyamidine, CsHisNgO,
is obtained by mixing cold concentrated solutions of methylamido-
a-caproic acid and cyanamide in equivalent proportions, adding a few
drops of ammonia, and allowing the liquid to stand. After some
weeks the liquid becomes converted into a mass of white crystals, and
VOL. XLIV. 4 h
1154 ABSTRACTS OF CHEMICAL PAPERS.
these are purified by crystallisation from water. This caproic creati-
nine forms an unctuous powder, only slightly soluble in cold water,
but more soluble in hot water, and very soluble in hot or cold alcohol.
Ethylamido-ix.caprocyamidine is obtained by the action of cyanamide
on ethylamido-a-caproic acid. It crystallises in long needles, which
are somewhat soluble in cold water, much more soluble in hot water,
and very soluble in alcohol.
As in the case of methylamido-a-butyric and methylamidoisovaleric
acids (this vol., p. 220) the action of cyanamide on methylamido-a-
caproic and ethylamido-«- caproic acids yields creatinines without any
intermediate formation of creatines.
a-Oxyhutyrocyamine hydrochloride, C5HnN302,HCl, obtained by dis-
solving a-oxybutyrocyamine in hydrochloric acid, forms an uncrystal-
lisable syrup, soluble in all proportions in absolute alcohol. The
sulphate, (C5HuN302)2,H2S04 + H2O, forms crystals resembling those
of potassium sulphate. They are somewhat soluble in water, and
slightly soluble in alcohol. Mercuric chloride and mercuric nitrate
give no precipitate with solutions of a-oxybutyrocyamine, but a white
precipitate is formed on adding a drop of potassium hydroxide solu-
tion. C. H. B.
Action of Methyl Alcohol on Piperidine Hydrochloride. By
A. Ladenbueg (Ber., 16, 2057 — 2059). — If piperidine hydrochloride is
heated at 200° with methyl alcohol, the hydrochlorides of methyl- and
dimethyl-piperidine are formed together with methyl ether. These
changes may be represented by the following equations : —
(II) ...V...
and (III) 2MeOH
The author offers some remarks on the constitution of the piperidine
derivatives. Dimethjlpiperidine hydrochloride, CsHgNMejHCl, which
behaves generally as a substituted ammonium chloride, forms methyl-
piperidine when distilled, but dimethylpiperidine if heated with
potash. Hofmann explains this change by supposing a transformation
of a methyl-group from a nitrogen to a carbon-atom, similar to that
which takes place in the conversion of methylaniline into toluidine.
The author objects to this explanation, and points oat that dimethyl-
piperidine by the action of hydrochloric acid is converted into methyl
chloride and methylpiperidine ; a change which is without parallel in
the benzene derivatives. The author puts forwai'd another view, in
supposing that in the formation of dimethylpiperidine an affinity
between the carbon- and nitrogen-atoms is broken up, and then the
second methyl group attaches itself to the nitrogen-atom. Dimethyl-
piperidine will then have the constitution
CH3: CH.CHa.CHz.CHa^TTMez,
and on treatment with hydrochloric acid will yield a base isomeric
with piperidine, CH2iCILCH2.CII2.CII2.NMe2, which is converted
into methylpiperidine. Several other observations agree with this
explanation ; first, the fonnation of trimethylamine and not trimethyl-
ORGANIC CHEMISTRY. 1155
piperidine, by the action of methyl iodide on dimethylpiperidine ;
secondly, the fact that piperylene takes up four and not two atoms of
bromine ; thirdly, the decomposition of the base obtained from di-
methylpiperidine by the action of methyl iodide and silver oxide into
piperylene and trimethylamine, thus : —
CH2 : CH.(CH2)3.NMe2,MeOH = CH^ : CH.CH2.CH2 I CH2 +
NMe, + H2O. V. H. V.
Hydrotropidine. By A. Ladenburg (Ber., 16, 1408—1410).—
The sparingly soluble compound which is produced by the action of
amorphous phosphorus and fuming hydriodic acid on tropiue (jBer.,
14, 227) is tropine iodide, C8H15NI2.
Hydrotropidine, CgHisN, is formed when tropidine iodide is sub-
jected to the action of zinc-dust and hydrochloric acid. The crude
product is distilled with excess of soda, dried over sticks of potash, and
redistilled. Hydrotropidine is only slightly soluble in water, and is
less soluble in warm than in cold water, so that dilute solutions are
rendered turbid by the heat of the hand. It is a powerful base, form-
ing crystalline salts. The base boils at 167 — 169°, and has the
sp. gr. 0-9366 at 0° and 0-9259 at 15°. The hydrochloride, CsHijNjHCl,
forms white deliquescent crystals. The platinochloride,
(C8Hx5N)2,H2PtCl6,
crystallises in orange- coloured plates, which are moderately soluble in
water. The aurochloride forms yellow crystals, soluble in warm
water. The picrate is deposited from a hot aqueous solution in
slender needles.
The author regards hydrotropidine as a methyl derivative of tetra-
hydroethylpyridine, and assigns it the formula CsHvNMeEt.
w. c. w.
New Alkaloid in Cannabis Indica or Indian Hemp. By
M. Hay (Pharm. J. Trans. [3], 13, 998— 999).— The alkaloid is
obtained in the following manner : — The aqueous extract of powdered
Cannabis indica is treated with lead subacetate, filtered, and the
filtrate precipitated with ammonia. The filtered ammoniacal solution
is acidified with sulphuric acid, and the alkaloids precipitated from it
by phosphotungstic acid. The precipitate is washed, treated with
barium hydroxide, and filtered. After the removal of the excess of
barium by means of a current of carbonic anhydride, the filtrate is
evaporated almost to dryness, acidified with sulphuric acid, and
treated with absolute alcohol, in which the sulphate of the alkaloid is
soluble. The sulphate in solution is converted into chloride by first
adding barium hydroxide, and subsequently treating it with hydro-
chloric acid. The chloride is evaporated, taken up with absolute alcohol,
and the alcoholic solution treated with sodium carbonate, and ex-
tracted with ether ; the alkaloid is deposited from the ethereal extract
in colourless needles, which are readily soluble in water and alcohol,
and moderately so in ether and chloroform. The aqueous solution is
precipitated by the various precipitants of alkaloids. It does not give
a violet colour with sulphuric acid and potassium dichromate, but like
4 ;i 2
1156 ABSTRACTS OF CHEMICAL PAPERS.
stiyclinine canses tetanus in frogs. The author proposes the name
tetano-cannahine for this alkaloid. The quantity of alkaloid obtained
from 1 kilo, was insufficient for an analysis. D. A. L.
Existence of a Basic Substance in Maize. By 0. Luxardo
{Gazzetta, 13, 94 — 97). — Maize flour was extracted with dilute sul-
phuric acid, the extract treated with basic lead acetate, filtered, and
slowly evaporated; the residue was then exhausted with absolute
alcohol, and the alcohol removed by distillation ; the substance thus
obtained was examined for alkaloids by the methods detailed in the
paper. From the results, the author infers that in sound maize seeds
there may be nitrogenous substances analogous to alkaloids and
ptomaines in their behaviour with reagents. He notices, however,
that the methods of DragendorfF and Stas and Otto, based as they are
on the treatment of the substance with dilute acids, may give rise to
basic substances by the action of the acids on the albuminoid sub-
stances present in the seeds, especially if warmed with them, and
therefore they do not afford certain evidence that the basic substances
were originally present as such. C. E. G.
Ptomaines. By J. Gcjareschi and A. Mosso (J.pr. Chem. [2], 27,
425 — 432). — 140 kilos, of well washed fibrin from ox-blood was
placed in two glazed earthenware vessels, covered with a large zinc
bell, whose edges dipped about 15 cm. deep into water, and allowed
to stand for five months. The fibrin had at the end of that time
been converted into a thick dark-red homogeneous liquid. This was
acidulated with sulphuric acid, evaporated at 60° to a thick paste,
baryta-water added to alkaline reaction, filtered after 24 hours, and
the filtrate and wash- waters shaken for a long time with chloroform.
(The extraction with chloroform was repeated 12 times ; all the
extracts contained the same ptomaine.) The chloroform extract was
evaporated, and the resulting dark golden-yellow oily residue mixed
with tartaric acid ; a resin that then separated was removed by
shaking with ether, and the now colourless liquid mixed with excess
of 50 per cent, potash, and the liberated oil extracted with ether.
On evaporating the ethereal solution, a strongly alkaline brown oil of
faint pyridine or conine-like odour was obtained. It is sparingly
soluble in water, and resinifies very readily. The hydrochloride crys-
tallises in somewhat deliquescent, colourless, cholesterin-like plates.
The platinochloride, CioHisNjHgPtCle, forms a light flesh-coloured
crystalline precipitate, insoluble in water, alcohol, and ether ; it is
not decomposed at 100°. (The platinochloride from each chloroform
extract was analysed, and showed that only the one ptomaine was
present.) The hydrochloride gave a crystalline yellow precipitate
with auric chloride ; white precipitates with Mayer's reagent, mer-
curic chloride, or tannin ; a yellow precipitate with phosphomolybdic
acid, sparingly soluble in ammonia without blue coloration ; and a
whitish-yellow precipitate with phosphotungstic acid. The physio-
logical action of the ptomaine is similar to that of curare, but it is
much less active than the latter. A. J. G.
ORGANIC CHEMISTRY. 1157
Putrefaction Alkaloids. By A. Poehl (Ber., 16, 1975—1981).—
Epidemics caused by nnsound bread have long been recognised, and it
has been observed that they are preceded by long-continued rains and
floods, which cause an abundance of ergot {Glaviceps purpurea) in the
following harvests. These epidemics take two forms, viz., Ergotismus
convnlsivus, more common in France, Switzerland, and this country,
and Ergotismus gangrcenosus, which prevails in Russia, Germany, and
Sweden. In Russia there were two remarkable outbreaks of the
latter in the years 1832 and 1837, which caused a mortality among
children attacked of 1 : 1*75 to 1 : 4, and of the former in 1824. In
the course of the rainy summer of 1881 Russia was threatened with
another outbreak of ergotismus ; accordingly the Minister of the
Interior instituted a Commission, of which the author was a member,
to investigate this phenomenon of ergot.
Eichwald, in his history of ergotismus epidemics, has shown
(1) that the appearance of the epidemic stands in no direct relation
to the proportion of blight in the grain ; (2) that animals cannot be
80 inoculated as to produce in them similar symptoms ; (3) that the
putrefaction of the corn is a necessary condition of the ergotismus ;
(4) that the poisonous results are produced only in certain stages of
the decomposition ; (5) that the various forms of ergotismus cannot
be explained by the quantity of ergot introduced within the system or
its time of action.
In the present paper, the author elucidates the following conditions
of the putrefaction alkaloids in blighted rye meal : (1) the conver-
sion of the starch into glucose ; (2) fermentation of the glucose with
formation of lactic acid ; (3) peptonisation of the albumins by the
peptic action of the mycelium of Claviceps purpurea ; (4) conversion
of the peptone into ptomopeptone, and its decomposition with forma-
tion of putrefaction alkaloids.
Firstly. In the year 1873, the author recognised that damp caused
in the meal a large proportion of glucose, by the action of a ferment
contained in the endocarp and perisperm of the grain. The experi-
ments of Hammarsten have also proved that the starches of maize,
rye, and oats are more easily converted into glucose by diastatic
action than the starches of potatoes, pease, and wheat (comp. Bell's
recent researches, this vol., p. 1160). In this connection it may be
mentioned that the inhabitants of Lombardy suffer from an epidemic
caused by maize. A form of mildew has been observed on maize,
and this has the power of peptonising albumins, with formation of
putrefaction alkaloids.
Secondlij. In presence of a ferment the glucose would further decom-
pose into butyric and lactic acids.
The author further observed that rye grain, even if not attacked
by the claviceps, yet when merely exposed to damp, evolved trimethyl-
amine when heated with alkalis, and it is well known that albumins
at the moment of putrefaction evolve ammonia or amines under the
action of alkalis.
Thirdly. One of the most important phenomena of the change of
the albumin of meal is the formation of peptones; it has also been
noticed that lactic acid is a better test for peptonisation than other
1158
ABSTRACTS OP CHEMICAL PAPERS.
acids, as phosphoric, acetic, oxalic, or tartaric. The author has
frequently observed the formation of peptone from the albumin of
meal, caused by the action of Penicillium glaucum and the fungus of
Claviceps purpurea, the latter of which produces the most marked
effects.
Fourthly. The author exposed pure and tainted rye meal to a damp
atmosphere, and found that the latter more readily entered into
decomposition, with formation of the putrefaction alkaloids or
ptomaines. Further large quantities of pure and tainted meal were
allowed to rot, and the putrefying mass examined from time to time
by Stas-Otto's process. From alkaline and from acid ethereal
extracts of the mass, substances were obtained of various degrees of
consistence and of various odours. These products gave all the
general reactions for alkaloids, and differed from one another towards
precipitants and colour reagents according as they had been obtained
at various stages of the decomposition. By shaking the alkali solu-
tion with chloroform, benzene, and amyl alcohol, an alkaloid was
obtained, which gave precipitates with potassio-mercuric iodide, phos-
phomolybdic and tungstic acids, potassio-bismuth and -cadmium
iodides, platinum and gold chlorides, &c. It also gave a beautiful
violet coloration with Frohde's reagent (sulphuric acid and sodium
molybdate), resembling that produced by morphine; the absorption-
spectra, however, of the two alkaloids differ most markedly. The
author was only able to observe the formation of the above alkaloid
during summer time.
Starting from the view that peptones on further putrefaction are
converted into ptomopeptones which yield nitrogen when heated with
sodium hypobromite, then the quantity of nitrogen so evolved may be
taken as a measure of this conversion. Accordingly the author made
comparative experiments with samples of damp rye-meal and meal
mixed with peptic ferment, with 5 per cent, ergot, and with . blight.
The results are given in the table below.
Percentage of nitrogen given off from
Time of action.
Pure meal.
Meal with
bHght.
Meal with
ergot.
Meal with
peptic ferment.
3 days
4 „
8 „
13 „
20 „
0 -1316
0 -1527
0-1989
0 -2196
0 -5259
0 -1671
0 -2592
0 -2842
0 -3415
0-1933
0 -2909
0 -3157
0 -4269
0-5662
0 -3762
0-3940
0 -4210
From these results it follows — (1) that ergot and mould have a
peptonising action on the albumins and favour their decomposition ;
(2) the degree of putrefaction of the albumins is directly proportional
to their peptonisation ; (3) in the first stages of putrefaction, the de-
composition of the albumins is greater in ergot meal than in mouldy
ORGANIC CHEMISTRY. 1159
or pure meal, but in the more advanced stages these differences are
not so marked. Further researches on the decomposition of albumins
by the Claviceps purpurea^ and the part played by various genera of
fungi are promised. V. II. V.
Putrefaction Alkaloids. By L. Beieger (Ber., 16, 1405—1407).—
The gelatinous product which the author obtained (this vol., p. 924) by
treating the hydrochloride C5IIUN2H2CI2 of the base contained in
putrefying flesh with moist silver oxide, is the free base, and not an
oxidation product, as the author formerly believed. The salts do not
possess the characteristic, disgusting smell of the free base ; this has
not yet been obtained in a crystalline state. It is sparingly soluble
in amyl alcohol, freely soluble in water, insoluble in ether and in abso-
lute alcohol. It gives white precipitates with mercuric chloride and
lead acetate, a yellow precipitate with potassium cadmium iodide, and
a red precipitate with potassium bismuth iodide. It does not exhibit
any reaction with the other reagents for alkaloids.
The poisonous base CaHnN, formed by the putrefaction of flesh, is
precipitated by mercuric chloride and by basic lead acetate. It is
readily soluble in ether and alcohol. A subcutaneous injection of this
poison causes increased activity of the heart, rapid respiration, and a
copious secretion of saliva exhibiting an alkaline reaction. Under the
influence of this alkaloid, cats perspire freely at the paws, and their
sweat has an alkaline reaction. W. C. W.
Putrefaction Alkaloids. By E. and H. Salkowski (Ber., 16,
1798— 1802).— Reply to L. Brieger.
Colouring Matter of Bile of Invertebrates and Vertebrates
and Unusual Urine Pigments. By C. A. McMunn {Proc. Roy.
80c. J 35, 132 — 134). — The author has observed the existence of
chlorophyll colouring matter in the bile and various extracts of the
livers of Mollusca and Anthropoda, and of the pyloric or radial caeca
of the Echinodermata : for this the name enterochlorophyll is proposed.
The slight differences observable in various cases are shown to be
due to the probable greater or less amount of chlorophyll con-
stituents, viz., blue and yellow chlorophyll, chlorofucine, xanthophyll,
and luteine. The bile of the crayfish and pulmonate mollusca con-
tains hsemochromogen associated with enterochlorophyll. The so-
called liver of the invertebrates is not only a digestive, but a pig-
ment producing and storing organ.
The identity of stercobilin and hydrobilin produced by the action of
nascent hydrogen on bilirubin is established, and a difference between
them and fibrils urobilin is shown to exist. V. H. V.
1160 ABSTRACTS OP CHEMICAL PAPERS.
Physiological Chemistry
Chemistry of Food. By J. Bell (Proc. Emj. Soc, 35, 161—162).
— The author has carried out a series of researches on butter, cheese,
milk, the cereal foods, bread, and lentil flour.
Butter.-;— It is indicated that the soluble and insoluble fatty acids in
butter fat do not exist as simple, but as complex glycerides, palmitic
and oleic acids being combined in the same molecule with butyric
acid.
Cheese. — The ratio of soluble to insoluble fatty acids in the fat ex-
tracted from cheese is the same as that in milk fat. This result is at
variance with the view maintained by some chemists that albuminoids
are slowly converted into fat.
Milk. — The changes occurring in sour milk have been investigated,
and the diminution in the propoition of fats not solid has been deter-
mined.
Oereals. — The author suggests that the saccharine matter appears to
Ihave been developed or determined only in aqueous extract, without
regard to the transformations effected by the soluble albuminoids on
the saccharoses and carbohydrates. These albuminoids are shown
to possess a varying diastatic action on starch, that of rye being the
most, that of rice the least active. Y. H. Y.
Physiology of Carbohydrates in the Animal System. By
F. W. Pavt {FroG. Boy. Soc, 35, 145— 147).— The most complex
members of the carbohydrates and saccharose groups are transformed
generally by ferments, chemical reagents, or heat into less complex
substances ; for example, starch into the dextrins and finally into
maltose, cane-sugar into dextrose. In this note, the author shows that
there exists in the alimentary canal, the circulatory system, and the
liver, a ferment which effects a reverse transformation, converting
both glucose and cane-sugar into maltose, but starch either into
maltose or a dextrin of low cupric oxide reducing power.
Y. H. Y.
Filtration of Albumin Solutions through Animal Mem-
branes. By J. W. RuNBBERG (Zeitschr. Physiol. Chem., 6, 508—527).
— The author's earlier experiments on the filtration of solutions of
albumin through animal membranes have already been described
{Arch. /. Heilkunde, 18). He has there shown that the permeability
of a membrane towards albuminous fluids and emulsions diminishes
under the influence of increasing pressure, and vice versa, whereby
the proportion of albumin in the resulting filtrate is less under
high pressures than under low ones. His results, carefully con-
trolled and repeated, were constant and unambiguous. It may be,
however, that the behaviour of membranes other than those then
employed may be different. In these instances, sheep intestine pre-
served in alcohol, was commonly used, only exceptionally the fresh
intestine of sheep and rabbit. Last year, Gottwald, of Moscow,
PHYSIOLOGICAL CHEMISTRY. 1161
described the results of an investigation carried on in Hoppe-Seyler's
laboratory at Strassburg, wherein he used the human ureter, as freshly
obtained as possible, for the filter membrane, and from which he con-
cludes that the influence of pressure is diametrically opposite to that
stated by the author, who has accordinglj instituted a fresh series of
experiments, with a view of determining the source of this dis-
crepancy.
He gives details of seven experiments in which the filter membranes
were in two, human ureters; in one, fresh intestine of a sheep ; and in
the remaining four surface membranes, the membrane from a condonia
being employed in three of these, and fresh costal pleura from an ox
in the seventh. The albuminous fluids employed in these experi-
ments were various pleuritic effusions, containing 2*88 per cent.,
3*40 per cent., 5"34 per cent., and 6*44i per cent, of albumin; ascitic
fluids removed from patients suffering from peritoneal cancer, and
containing respectively 2*70 per cent, and 3*72 per cent, of albumin ;
and lastly, a solution of dried serum albumin with a percentage of
2 "46. The apparatus used by the author is fully described in the
earlier publication alluded to, and the present paper is accompanied
by a sketch of its arrangement during experiments. The experi-
ments, for the sake of simplicity, were made under two conditions of
pressure, a higher pressure of 100 cm. and a lower one of 40 cm.
The results of the experiments wherein the human ureter was
employed show that the permeability of this form of membrane also
increases with diminished pressure and vice versa, so that for each
degree of pressure a pretty constant ratio is observed.
The experiments with surface membranes yielded precisely similar
results. The author consequently assumes it to be proved that on
filtration of albuminous fluids through compound animal membranes
outside the organism, their permeability is inversely proportional
to the pressure exerted. It cannot be at once concluded from
this that the same relation exists within the living organism — a
problem requiring pathological and physiological investigation. But
the author has made certain observations and experiments in regard to
the question of transudation of albumin from the kidneys in cases of
albuminuria, which go to establish the identity of the process with
that which is known to take place outside the body. And it may
with a high degree of probability be assumed that those forms of
albuminuria, which are so frequently met with unaccompanied by
any inflammatory or degenerative process in the kidneys, find an ex-
planation in an exalted permeability of the filtering membrane,
brought about by changed conditions of pressure in the glomeruli.
Acetonuria. By K,. v. Jaksch (Zeitschr. Physiol. Chem., 6, 541 — 556).
— Little is yet known of the occurrence and elimination of acetone in
the human body. Kaulich has established its presence in the case of
diabetic urine, and has concluded on insufficient grounds, however
(from the odour of the distillate), that it makes its appearance in the
urine in the course of certain acute diseases.
The discovery by the author in an instance of diabetic coma when
sugar was absent from the urine that the ferric chloride reaction first
1162 ABSTRACTS OF CHEMICAL PAPERS.
described by Gerhardt was obtained, caused him to similarly test the
urine in a large number of cases. Further investigation has shown
that urine giving a distinct ferric chloride reaction will likewise
yield a distillate which shows Lieben's iodoform reaction (iodoform
produced with iodine, potassium iodide, and soda solution). But he
also obtained the same result with the distillates of urine which gave
no reaction with ferric chloride, and especially with the urine of
fever patients. Deichmiiller has confirmed these results in the instance
of scarlet fever.
Since a number of volatile substances furnish the iodoform reaction,
the problem was to determine the particular volatile constituents of
fever urine upon which it depended, especially whether upon acetone.
With this object the urine of fever patients was subjected to examina-
tion with positive results. The quantitative estimation of the small
quantities of acetone occurring in urine was made by a photometric
method, for details of which, as also those relating to the examination
of urine, the reader is referred to the author's paper. He also showed
that putrefaction does not interfere with the presence of acetone,
and urine containing a known amount of it was found to yield the
same amount unchanged three weeks after spontaneous fermentation
had occurred. Acetone was found in the urine of healthy individuals,
in quantities varying from a mere undeterminable trace up to 0"01
gram in the excretion for the 24 hours. Hence the author concludes
that there is a condition of physiological acetonuria, acetone being a
normal and constant product of tissue change, becoming under certain
pathological conditions excessively produced and eliminated. The
pathological states in which this excess is exceptionally well shown
are in high continued fever, when the quantity amounts as a rule to
several decigrams, keeping approximately parallel to the height of the
fever. The kind of fever and the presence of complications are
without influence. In diseases unaccompanied by fever, the elimina-
tion of acetone is, as a rule, not augmented ; but there are exceptions
met with, and which the author has noted in some cases of cancer, in
the so-called acetonuria, and in certain cases of diabetes mellitus.
In diabetes, the quantity of acetone may be increased or remain
normal without any clinical indications of this difference. In some
rare cases of diabetes, the urine yields much acetone on distillation,
and gives at the same time Grerhardt's ferric chloride reaction. This
reaction the author refers to the presence of acetoacetic acid in the
urine, and as this affords acetone on distillation, the richness of
such urine in acetone is simply explained. This augmented ace-
tonuria and the ferric chloride reaction are not alone found coincident
with certain cases of diabetes, but in other diseases, as measles, scar-
latina, and pneumonia, although rarely. Both may stand in a certain
interdependence, but increased acetonuria and the occurrence of aceto-
acetic acid in the urine are certainly not identical. On the contrary,
the association of the two is exceptional. D. P.
Hemialbumosuria. By Ter-Grigoriantz (Zeitschr. Physiol. Chem.,
6, 537 — 540). — Hemialbumose was first found by Bence Jones in the
urine of a patient suffering from osteomalacia. Kiihne also found it
PHYSIOLOGICAL CHEMISTRY. 1163
in a similar case, and as a product of the peptic and tryptic diges-
tion of albuminates. Albumin peptone is changed into hemialbumose
when heated to 140°. In a case described by the author, and
forming the subject of this paper, the hemialbumose disappeared from
the urine, and was replaced by peptone, hemialbumosuria thus be-
coming peptonuria.
The patient, a man of 24 years of age, was admitted to hospital
with syphilitic ulcer, and there underwent treatment by inunction
with mercurial ointment. In three weeks an acute generally diffused
eruption spread over his whole body, at first resembling that of
measles, but becoming confluent, and running the course of an
intense dermatitis accompanied by fever. At the end of 14 days, it
terminated with profuse lamellar desquamation of the entire epider-
mis. The urine of this subject on examination gave the recognised
reaction of hemialbumose as described by H. Huppert, and later
those of peptone. This transformation also was observed to occur
simultaneously in urine which had been kept for three days.
D. P.
Further Contributions to the Distribution and Elimination
of Lead. By V. Lehmann (Zeitschr. Physiol. Chem., 6, 528—536).—
In regard to the modes whereby lead is extracted from the body,
most diverse statements are met with as to its presence in the urine,
which of all media has been the most frequently examined ; whilst its
excretion by the bile, milk and saliva has been established by various
authors. So far as Lehmann is aware, the faeces have hitherto
escaped examination.
In this new series of experiments he employed rabbits, in which
plumbic nitrate was injected in quantities varying from 16 mgr. to
0'5 gram. The separation and quantitative determination of the lead
were effected by electrolysis and the colorimetric method, using
hydrogen sulphide in presence of alkali (this vol., p. 687).
The results show that the liver, an organ which in cases of metallic
poisoning almost always holds the first place in order of examination,
contains relatively to the weight very little lead. The bile, on the
other hand, contains a large proportion, confirming the previous ob-
servations of Annaschat, and the bones likewise show a high propor-
tion, a result which is in harmony also with the statements of Gus-
serow and Heubel.
As much lead was found to be excreted in the faeces as iu the urine :
the lead thus got rid of must have been eliminated in the bile, and not
reabsorbed by the intestines, a circumstance which serves to explain
the lesser proportion found in the liver, from which elimination by
the bile would naturally occur.
The author investigated the changes which are brought about in
the elimination of lead in the urine under the action of various thera-
peutic agents, especially potassium iodide, a salt which has long been
given in cases of metallic poisoning, particularly in chronic mercury
and lead poisoning, for the purpose of promoting elimination from the
system.
He found that the action of this salt is to promote the elimination
of lead, exciting it when this has ceased to take place naturally by
1164 ABSTRACTS OF CHEMICAL PAPERS.
bringing again into circulation that which so far as his investigations
tend to show, had become deposited in the bones. He farther found
that potassium bromide, and probably also potassium chloride, have
analogous effects in promoting elimination, a result of some thera-
peutic importance, for potassium iodide cannot always be administered
with safety, and these salts may in such cases serve as substitutes.
Sodium chloride did not appear to exert any influence on the pro-
cess. D. P.
Chemistry of Vegetable Physiology and Agriculture.
Submersion of Vineyards. By P. De Gasparin (Compt. rend.,
96, 1552 — 1555). — One of the best methods of preventing the
ravages of the phylloxera is to keep the soil of the vineyard con-
tinually moist, and in the south-east of France this is effected by
submerging the vineyard during winter. The soils which are thus
treated are compact argillo-calcareous soils which, wdth one or two
exceptions, contain more than 30 per cent, of impalpable constituents,
and more than 30 per cent, of calcium carbonate. Soils of this cha-
racter are sufficiently pervious to allow the water to diffuse through
them by capillary action, and yet are sufficiently impervious to pre-
vent the water passing through them rapidly. In those cases where
the surface soil is sandy, the subsoil is found to be compact, calcareous,
and argillaceous. The same method of treatment is, however, applied
successfully to the dunes of Aigues Mortes and to other sandy soils.
C. H. B.
"Sap. By J. Attfield (Pharm. J. Trans. [3], 13, 819— 820).— The
present paper contains an accouat of observations made on sap exud-
ing from a woanded silver birch tree. A branch had been lopped off
a birch tree 39 feet high, and 7 inches in diameter about 10 feet from
the ground, before the leaves had expanded, leaving a wound about an
inch in diameter, from which sap dropped. A bottle was suspended
so as to catch the sap, and from observations taken, it was found that
the flow was apparently faster in sunshine than in the shade, and by
day than by night ; and altogether amounted to about 4 litres a day,
this had been running for 15 days, but how long it would continue is
uncertain. The sap was clear and bright, sp. gr. 1*005, had a faintly
sweet taste and a slightly aromatic odour. After 12 hours it deposited
a trace of a sediment which, when examined microscopically, was found
to consist of parenchymatous cells and a few so-called sphere- crystals.
The liquid contained 99 per cent, water and 1 per cent, solid matter,
which was composed mainly of sugar 91 per cent., the other consti-
tuents being ammonium salts ; albuminoids ; nitrates ; phosphates,
and organic salts of calcium and magnesium ; mucilage, and traces of
nitrites and potassium salts. It had calcium and magnesium salts in
solution equal to 25 degrees of total permanent hardness. It con-
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
1165
tained a ferment capable of converting starch into sugar, and when
exposed to the air, it soon teemed with bacteria, the sngar being
changed into alcohol. D. A. L.
Effect of Altitude on the Alkaloids of the Bark of Cinchona
Succirubra. By J. E. Howard (Pharm. J. Trans., 13, 1013—1015).
— After some remarks on the growth and cultivation of cinchonas in
general, in which the author makes special reference to the physical
relationship existing between quinine and cinchonidine (both Isevo-
gyrate), and between quinidine and cinchonine (both dextrogyrate) ;
attention is drawn to the results of the analyses of two specimens of
red bark (G. succirubra) from two trees of common origin ; they were
also of the same age, 19 years old, and had grown up under fairly
similar conditions, climatic excepted, — the one. A, being cultivated at
Hakgala, 5,500 feet elevation, being the larger of the two trees, yield-
ing 25 lbs. of dry bark, with a " brown coat;" the other, B, yielding
7 lbs. of dry bark " with a grey coat," was cultivated at Peradeniya,
1,500 feet elevation.
Total
Quinine.
Cinchonidine.
Cinchonine.
Quinidine.
Amorphous.
alkaloids.
A. 2-06
3-47
0-61
trace
0-66
6-80
B. 0-47
0-05
1-67
0-30
1-06
3-55
From these results it would seem that altitude has a beneficial in-
fluence, not only on the quantity but also on the quality of the alka-
loids. The quantity from the tree grown at the greater elevation is
nearly double, whilst the quality is also much superior to that of the
tree grown in the low-lying district. Quinine and cinchonidine in
the former seem to have replaced the quinidine and cinchonine of
the latter. D. A. L.
Cinchona Bark grown in Jamaica. By B. H. Paul (Pharm. J.
Trans. [3], 13, 897). — The author has examined samples of the bark
produced for sale in Jamaica ; the results are tabulated below : —
Variety of plant.
a
£
1
Quinine.
6
•3
(y
6
c
1
-6
o
<
Total alka-
loid.
Cinchona officinalis. . .
Trunk
3-74
0-04
1-77
0-23
0-30
6 08
Twig
1-08
trace
0-37
0-60
0-20
2-25
Root
2-90
1-01
0-67
4-60
0-58
9-76
„ succirubra . .
Trunk
2 04
0 13
2-58
2-45
0-50
7-70
Twig
0-78
—
0-47
0-23
0-29
1-77
Root
1-76
0-34
1-39
4-40
0-90
8-79
„ calimya . . .
Trunk
0-34
0-23
0-82
0-82
1-80
4 01
Twig
Root
trace
4-07
0-45
1-80
0-65
1-30
6 97
„ micrantha . .
Trunk
113
0-30
0-67
3-24
0-68
6-02
Twig
0-43
"~~
0-28
0-60
0-50
1-81
1166 ABSTRACTS OF CHEMICAL PAPERS.
The large proportion of quinidine in the root-bark of the Calisaya
plant is exceptional, and coupled with the small quantity of quinine,
may be evidence of unhealthy growth, or perhaps the plants sent to
Jamaica were not Calisaya, but really Cinchona micrantha. The amount
of quinine in the succirubra sample shows that there is a good type of
this cinchona being cultivated in Jamaica. Comparing these results
with analyses made some few years back, it is inferred that in most
cases the quality of the bark has improved. The reverse, however, is
the case with the " calisaya " plants ; perhaps for the reason given
above. D. A. L.
Seeds of Camellia oleifera. By H. McCallum (Pharm. J. Trans.
[3], 14, 21). — The Camellia oleifera grows abundantly in China, where
the seeds are gathered and the oil pressed out and used for hair dress-
ing and illuminating. The residue is made into cakes or powdered,
the powder being used for washing purposes, especially for extracting
grease spots ; an infusion of it is also made for killing worms, grubs,
&c., and even fish. The cakes are used with water as a hair wash. The
seeds contain a glucoside, saponin, as well as the oil. 44 per cent, of
oil may be extracted by means of ether, using a Soxhlet's tube, and
10 per cent, of saponin from the residue by treatment with 84 per cent,
alcohol ; even after this treatment it is soapy.
The oil is viscid, yellowish, scentless, with an unpleasant after
taste, and is not soluble in 84 per cent, alcohol. The saponin is not
quite pure, as it leaves 0*9 per cent. ash. It is a friable amorphous
white powder, which irritates the nostrils ; when dry it is almost
odourless, but its aqueous solution has a disagreeable odour. Its taste
is at first sweetish, then bitter and disagreeable, causing a biting sen-
sation in the throat. It is hygroscopic, very soluble in water, freely
in 84 per cent, alcohol, sparingly in absolute alcohol, and insoluble in
ether. An aqueous solution is precipitated by barium hydroxide, by
Eehling's solution, by basic lead acetate in the cold, and by normal
lead acetate and dilute hydrochloric acid when warmed ; in the last
case a glucose remains in solution. When the aqueous solution is
boiled with Fehling's solution, a slight reduction takes place. It
forms emulsions with oils and chloroform ; and when it is shaken
with mercury, the metal is reduced to a fine grey powder.
D. A. L.
Occurrence of Nuclein in Moulds and in Yeast. By A. Stutzek
(Zeitschr. Physiol. Chem., 6, 572 — 574). — The author placed a solu-
tion containing a percentage of 1*05 potassium chloride, I'O calcium
nitrate, 0'25 magnesium sulphate, 0*5 potassium phosphate, and 5'0
tartaric acid in open saucers in a locality tolerably free from dust.
Moulds were soon developed which, after forming in sufficient quan-
tity, were washed with distilled water, pressed between filter-paper,
and dried over sulphuric acid.
The dried mean contained 3*776 per cent of nitrogen.
As protein IS" 3'026
As nuclein N 1*539.
100 parts of nitrogen consisted of —
ANALTTICAL CHEMISTRY. 1167
19*86 N as amides, peptones, &c.
39-39 albumin N.
40-75 nuclei Q N.
The moulds are consequently able to form, besides albumin, a tolerably
large amount of nuclein. Hoppe-Seyler had already observed that
yeast likewise contains nuclein.
In these experiments, fresh beer yeast was left for some days with
alcohol of 95 per cent., then pressed between filter-paper, several
times extracted with alcohol in the cold, and finally dried over sul-
phuric acid.
Two sets of analyses yielded like results : —
Total nitrogen .... 8-648 per cent.
Protein N 7773
Nuclein N 2-257
It contained in 100 parts nitrogen —
lO'll N as amides and peptones, &c.
63-80 N as albumin.
26-09 lyJ" as nuclein. D. P.
Analytical Chemistry.
L
Experiments on the Small Scale in Sealed Tubes. By E.
Drechsel (/. pr. Ghem. [2], 27, 422—423). — Preliminary experiments
on reactions in sealed tubes can be readily effected with the use of only
a few milligrams of substance by employing tubes (made of ordinary
tubing) 5 — 6 cm. long and 3—4 mm. wide, sealed at one end and
drawn out at the other to a thick- walled capillary tube of 10 — 15 cm,
long. This tube is then fixed by means of a split cork in a test tube
containing a liquid boiling at the temperature required.
A. J. G.
Alkalimetric Indicators. By J. Wieland {Ber.y 16, 1989 —
1991). — The author has examined the relative sensitiveness of various
Hzo dye-stuffs proposed as indicators for alkalimetry. Of substances
not affected by carbonic acid, ethyl-orange is the most delicate;
2 drops of a 0-05 per cent, solution is sufficient for 50 cc to obtain a
sharp change of colour. The analytical results are compared in the
original memoir in a tabular form. V. H. V.
Separation of Chlorine, Bromine, and Iodine. By J. B.
Barnes, Junr. (PJuirm. J. Trans. [3], 13, 940— 942).— The author has
tried a few experiments on the efficiency of Vortraann's process,
already described (this vol., 119), for qualitative purposes. He
remarks that practically iodine is wholly expelled from a solution of
an iodide by evaporating almost to dryness four times with either lead
1168 ABSTRACTS OF CHEMICAL PAPERS.
or manganese dioxide and 3 per cent, acetic acid ; on the other hand,
bromine is only expelled from bromides when strong acid (33 per
cent, or above) is used ; whilst chlorides treated in a similar manner
are but very slightly decomposed, or not at all. In this manner also
the iodine and bromine are readily expelled from a mixed solution of
iodides and bromides ; provided the lead oxide is added little by little,
while the acidified solutions are in a state of ebullition, thus prevent-
ing the formation of iodic acid (ibid). In a mixture of chlorides,
bromides, and iodides, chlorine alone could be detected after the
fourth evaporatoin with 33 per cent, acetic acid and lead dioxide.
Another experiment proved that iodine could be removed from a
similar mixture by treatment with manganese dioxide, whilst the
bromine could be separated from the chlorine by subsequent treat-
ment with lead oxide. The last experiment can be utilised to ad-
vantage for testing for these substances ; — The mass to be tested is
put into a dish, and ordinary acetic acid and manganic oxide are added
to it; the appearance of a brown colour indicates iodine, if it is
present, the whole is boiled vigorously until the vapour ceases to
"blue" starch-paste, showing that the iodine is removed. Now test
for bromine (or in case there is no iodine, test at once previous to
boiling), and if it is present boil with acetic acid and lead oxide until
the vapour does not turn starch-paste and potassium iodide blue,
showing the total expulsion of bromine. The residue is filtered and
tested for chlorine. An objection to the use of manganic oxide is, that
solutions containing it are very liable to spurt during evaporation.
D. A. L.
Detection of Free Sulphuric Acid in Presence of Aluminium
Sulphate. By 0. Miller (Ber., 16, 1991— 1992).— In the paper
manufactory the detection and estimation of sulphuric acid is of great
practical importance. The experiments of the author prove that of
the indicators hitherto proposed, methyl-orange is the most delicate
for the detection of free sulphuric acid in presence of aluminium sul-
phate. The degree of dissociation on boiling an aqueous solution of
this salt can be determined by the use of methyl-orange. For the
quantitative estimation of the free acid in aluminium sulphate, its
solution is precipitated by alcohol, and the filtrate evaporated over a
small flame, and then titrated. Experiments are quoted to prove the
accuracy of the process. Ethyl-orange, although the most sensitive
indicator towards free acid, yet is coloured a rose tint by neutral
aluminium sulphate, which prevents the observation of the neutral
point. Y. H. V.
Estimation of Iron by means of Permanganate Solution.
By J. Krutwig and A. Cocheteux (Ber., 16, 1534- 1536).— The
authors find that the inaccuracy due to the presence of hydrochloric
acid may be avoided if the following conditions are observed : — The
ore should be dissolved in the smallest possible quantity of hydro-
chloric acid, reduced by means of zinc, sulphuric acid added in
quantity double that of the hydrochloric acid, the solution diluted to
300 c.c. and titrated with a dilute solution of potassium perman-
ganpte. A. K. M.
ANALYTICAL CHEMISTRY. 1169
Precipitation of Iron by Hydrogen Sulphide. By L. Storch
(Ber., 16,2014 — 2015). — If hydrogen sulphide be passed into a solution
of tin chloride or ammonium tin chloride mixed with an excess of
an iron salt, a dirty yellow or greyish-green precipitate is formed,
containing tin and iron in the proportion of 100 to 4. This pre-
cipitate is soluble in hydrochloric acid, and hydrogen sulphide pre-
cipitates from the solution tin sulphide only ; warm potash, ammonia,
or sodium hydrosulphide dissolves the tin precipitate, and the solu-
tions, when allowed to stand, deposit the iron as hydroxide or sul-
phide. Ammonium sulphide dissolves the tin, leaving the iron
sulphide. V. H. Y.
Solubility of Metallic Sulphides in Thio-acids. By L.
Storch {Ber., 16, 2015 — 2016). — The precipitation of copper as sul-
phide is prevented in a most marked way, not only by thio-molybdates,
(Debray), -arsenates, and -stannates (Berzelius), but also by thio-
tnngstates and -vanadates. This phenomenon is also more noticeable
with cuprous than cupric salts. Similarly the precipitation of iron,
mercury, and cadmium sulphides is prevented by the above-named
acids, especially thiostannates. The resultant solution is either clear
or contains the thio-salt of the precipitable metal in the colloidal
state. Thus, for example, on adding ammonium sulphide to ferric
chloride, in presence of ammonium molybdate, a green solution is
obtained, which after a time deposits the iron thiomolybdate of
Berzelius. Y. H. Y.
Detection of Mercury in Animal Tissues. By H. Paschkts
{ZeitsrJir. Fhijsiol. Ghem., 6, 495 — 503). — Until a few years ago, elec-
trolysis was almost exclusively employed in the examination of animal
tissues for mercury. Schneider's method left little to be desired in
point of delicacy and accuracy, but was tedious in detail, and the
apparatus somewhat complicated. E. Ludwig's method for the
separation of mercury from the tissues is, however, easier of applica-
tion, and needs much less time, whilst equal in other respects to the
former. By it the mercury is separated from the largely diluted
solution by means of finely divided zinc or copper, from which, by
simple heating, the metal is obtained directly. Originally Ludwig
distilled the mercury from the washed and dried zinc-dust in a slow
current of air, passing it over a layer of red-hot oxide of copper, to
complete the combustion of other products of distillation, and con-
densing mercury and water in a quill-sized capillary tube. Subse-
quently he has so far modified the process as to dispense with the air-
stream, heating the zinc amalgam in a tube closed at one end, and
getting rid of the aqueous vapour by passing the products over a
layer of ignited zinc- dust before their entrance into the capillary
tube.
Fiirbringer has proposed a modification of Ludwig's process, in so
far that he substitutes the so-called brass-wool for the zinc, which
after removal from the mercurial solution is washed in water, alcohol,
and ether, dried and heated in a tube drawn out at both ends in which
the mercury becomes condensed {Berlin. Klin. Wochenschr., 1878,
YOL. XLIY. 4 i
1170 ABSTRACTS OF CHEMICAL PAPERS.
p. 332). Recently V. Lehmann has adversely criticised Ludwig's
method, and concludes that it is neither accurate nor simple and
expeditious. This opinion is quite contrary to the experience of the
author of this paper as well as of Giintz, O. Hassenstein, and Ober-
lander, whose results are likewise confirmatory of the accuracy of
Ludwig's process.
The fact that Lehmann's criticism called in question the validity of
certain investigations made by the author conjointly with L. v. Vajda,
induced him to repeat a series of experiments with this process and
its* modifications.
1. Ludwig^s Method. — About 400 c.c. of normal urine, containing
a known amount of mercuric chloride, were warmed to 60 — 70°,
acidified with hydrochloric acid, about 3 grams of zinc-dust added,
and after agitation for some time the clear solution poured off, and
the resulting amalgam washed several times, first with pure water
and then with water to which a few drops of potash solution had
been added. After drying upon the water-bath, this amalgam was
introduced into a tube of hard glass of about 8 mm. diameter, closed
at one end with successive layers of asbestos, coarse cupric oxide, and
zinc-dust in front : the tube being then drawn out to a capillary bore
of the thickness of an ordinary straw, was placed in a small combus-
tion furnace, the cupric oxide first raised to a low red heat, the zinc-
dust moderately heated, and at last the amalgam is strongly ignited.
In 10 — 15 minutes the mercury is found in the capillary portion of
the tube, which is then cut off", a small fragment of iodine inserted in
the widest part, and gently heated. In five such experiments, in
which the quantities of mercuric chloride used were respectively O'OOo,
0002, 0-001, 0-0005, and 0-0002 gram, distinct iodide sublimates were
obtained. In a sixth experiment, in which 0*0002 gram of mercuric
chloride was added to 400 c.c. of urine, also containing albumin, the
result was equally decided.
2. Furhrincfer s Method. — 400 c.c. of the same urine, as prepared
for the above experiments, was similarly treated, brass- wool being
substituted for the zinc-diist. The wool, after washing with hot
water, alcohol, and ether, was introduced into a tube of 8 mm.
diameter, drawn out in capillary fashion at both ends, heated over a
Bunsen lamp, and a fragment of iodine introduced into the still warm
tube. In three experiments in which O'OOl, 0*0005, and 0*0002 gram
of mercuric chloride were employed, a distinct reaction was obtained
in both of the capillary extremities of the tube. In a fourth instance,
the reaction was also distinctly given by 50 c.c. of urine taken from
the body of a man who had poisoned himself with corrosive sub-
limate.
3. Modification of Ludwig^s Method. — The advantage shown in wash-
ing the zinc-amalgam with a weak alkaline solution, whereby organic
matters, especially uric acid, are removed, and empyreumatic products
avoided in the subsequent distillation, induced the author to dispense
with the layers of cupric oxide and zinc-dust in the combustion tube.
The latter containing only the zinc-amalgam, was heated over a Bunsen
lamp, as already described, and distinct reactions were yielded by
similar quantities of mercuric chloride.
ANALYTICAL CHEMISTRY. 1171
4. Experiments with Leaf-gold. — The process was the same as in
the previous experiments, the leaf-gold washed with ether, dried on a
watch-glass in the water-bath, and after kneading into a pellet intro-
duced into a thick glass tube of 3^ mm. diameter, closed at one end
and drawn out at the other. The sublimate of mercury obtained upon
heating in the capillary portion, gave a distinct reaction with iodine
in each of the four experiments in which the quantities of mercuric
chloride employed were respectively 0-002, O'OOl, 0*0005, and 0'0002
gram. The author concludes that Ludwig's process, in skilful
hands, is neither complicated nor tedious, whilst in point of delicacy
it is at least equal to its several modifications. Fiirbringer's process
is undoubtedly somewhat quicker and more simple in its details, but
it must be borne in mind that the same intimate contact of solution
and metal attainable in the case of zinc-dust, is hardly to be expected
when brass- wool is employed. The process is most simplified by the
substitution of leaf-gold. The destruction of the urine by potassium
chlorate and hydrochloric acid, as proposed by Lehmann (this vol.,
p. 687), is in no case necessary. Lastly, an objection lately urged
against Ludwig's method by Schuster, that the simultaneous distil-
lation of the zinc itself may conceal the mercurial sublimate, is
possible only when excessive ignition has been resorted to. That
the iodides of arsenic or bismuth should be mistaken for mercuric
iodide is, as already shown by Ludwig, only conceivable in inexperi-
enced hands. D. P.
Determination of Organic Matter in Potable Water. By J. W.
Mallet (Chem. News, 47, 218—220 and 232— 233).— Apparatus is
described, whereby the water to be examined may be evaporated under
greatly reduced pressure and at a correspondingly low temperature,
out of contact with the air. Under such conditions the organic
matter is altered much less than in the apparatus generally made use
of. As test materials, leucine and tyrosine were selected, as repre-
senting the more stable products of putrefaction liable to occur in
natural water, and for which the combustion process in its usual form
had been found to give results far from satisfactory. Sixteen experi-
ments were made; from leucine 95" 77 per cent, of the total carbon
was obtained (97'24 to 91*40), and 93'32 per cent, of the total nitrogen
(95"C4 to 88*27) ; whilst from tyrosine 97*04 per cent, of the carbon
(98*13—92*65), and 9572 per cent, of the nitrogen (97-29 to 90*45)
were obtained. These numbers show a marked improvement on results
previously obtained, and the error in the determination of the two
elements is in one direction, viz., a partial loss. It has been proposed
to remove nitrogen existing as ammoniacal salts, by treatment with
magnesia, before estimating the organic nitrogen, but it is found that
at 40° to 45°, urea in a very short time begins to evolve ammonia ; still
in waters containing relatively very large quantities of ammoniacal
salts the error due to the decomposition of urea, &c., would be per-
haps less than that attributable to the dissociation of these salts
during the evaporation, to an extent not accurately determinable. It
has been proposed to remove nitrates and nitrites by the reducing
action of phosphorous or hypophosphorous acid ; solutions of tyrosine
1172
ABSTRACTS OF CHEmCAL PAPERS.
and potassium nitrate were evaporated with addition of phospliorons
acid, the residue just neutralised with magnesia, and then brought
to a suitable condition by the addition of pure silica and drying
in the previously described vacuum apparatus. On combustion,
results were obtained for the carbon and nitrogen of the tyrosine
as good as those obtained from solntions of this substance in pure
water. A series of experiments under different conditions showed
that on distilling a very dilute solution of ammonia a not incon-
siderable amount is lost ; thus under ordinary conditions it araounis
to about 14 per cent, of the whole. In this case the temperature
of the distillate was about 28^, but by reducing this to 6*, the
average loss became only 2 per cent. If a cuiTent of air be drawn
through or over a dilute solution of ammonia — 0*5 mgrm. in 500 cc.
— the ammonia is very slowly removed, but at a temperature of 50 —
60°, the whole of the ammonia may be removed in about 16 honrs. A
solution of urea when boiled or kept at a high temperature is decom-
posed gradually with evolution of ammonia, but at lower tempera-
tures, i.e., 50 — 60°, this decomposition is much less rapid. A few
experiments were also made to test the modification of the permanga-
nate process proposed by Tidy, viz., the maintenance of an approxi-
mately constant excess of permanganate ; the modification seems to
be an improvement, but further experiments are required.
H. B.
Coefficients of Solubility of some Silver Salts, and Systematic
Method of Testing for Hydrocyanic, Hydrochloric, Hydrobro-
mic, Hydriodic, Chloric, Bromic, Iodic, Hydroferrocyanic, and
Hydroferricyanic Acids. By A. Longi (Gazzetta, 13, 87 — 89). —
The author has carefully determined the coefficients of solubility of
certain silver salts in various solvents, as in the subjoined table, and
Solvent.
Temp.
Silver Salt.
A.
B.
' 12°
Cvanide
433 17
431 -73
}>
Chloride
430-20
428 -64
Ammonia, 5 p. c. j sp. gr. 0998 ■
25°
Bromide
Iodide
8805-55
00
8779 -37
QD
j>
Bromate
28-49
28-14
jj
lodate
42 73
43 -39
r
18°
Cyanide
192 -52
184 -59
1
J,
Chloride
13-46
12 76
1
Ammonia, 10 p. c. ; sp. gr. 0'96 -{
12°
Bromide
Iodide
300 -33
27,420 -35
288-46
26,327 -54
1
25°
Bromate
2 -254
2 162
I
yy
lodate
2 -3^3
2-202
Water ■
>)
Bromate
597 -73
595 -31
»
lodate
27,821-88
27,728-94
Nitric acid, 35 p. c. ; sp. gr. 1'21 •
Bromate
lodate
262 -83
859 -81
320-36
1044 -32
A is the number of cubic centimeters of the solvent required to dissolve 1 gram
of the salt.
B is the number of grams of solvent required to dissolve 1 gram of the salt.
ANALYTICAL CHEMISTRY. 1173
on the results has based a method for testing for the acids mentioned
above.
In order to test the substance, if insoluble in water, it is boiled
with sodium carbonate, and the filtrate acidified with acetic acid ; if
soluble, the aqueous solution is rendered acid in the same way ; the
solution is then precipitated with silver nitrate in slight excess and a
little nitric acid is added ; but if hydrogen sulphide is present it must
first be heated until the gas is entirely dispelled.
The solution may contain chlorate and some bromate of silver and
also mercuric cyanide : it is treated with zinc and a little sulphuric
acid ; this precipitates the mercury and silver, and reduces the chloric
and hromic to hydrochloric and hydrobromic acids. When the reduc»
tion is complete, the liquid is divided into three parts ; in one hydro-
cyanic acid is tested for by a f errosoferric salt ; another is tested for
bromine indicating bromic acid ; and the third for chlorine by pre-
cipitating with silver nitrate and digesting with ammonia (0*998) ; if
a white precipitate insoluble in boiling nitric acid is formed on adding
nitric acid to the filtrate, it indicates that a chlorate was present.
The original precipitate, which may contain cyanide, bromide, iodide,
bromate, iodate, ferrocyanide, and ferricyanide of silver, is carefully
washed and digested with ammonia (0*998).* This leaves undissolved
the silver bromide, iodide, and ferrocyanide, which is carefully
washed and treated with hydrogen sulphide solution and a little
hydrochloric acid : after removal of the excess of hydrogen sulphide
the solution is tested for hydroferrocyanic acid in the usual way with
a ferrosoferric salt, and the filtrate from the prussian blue precipitate
is then examined for iodine and bromine with carbon bisulphide, &c.
Into the ammoniacal solution containing the cyanide, chloride, bro-
mate, iodate, and ferricyanide, an excess of sulphurous acid solution is
poured; this precipitates the silver cyanide and chloride, and reduces
the other acids, precipitating them as bromide, iodide, and ferro-
cyanide of silver. On treating the washed precipitate with ammonia
(0*998) the three last are left undissolved and are tested in the
manner described above, showing the presence in the original solution
of bromic, iodic, and hydroferricyanic acids. The silver chloride and
cyanide dissolved by the ammonia are reprecipitated by nitric acid,
and the precipitate divided into two parts; one is treated with a little
dilate hydrochloric acid and the solution tested for hydrocyanic acid,
whilst the presence of chloride in the other is indicated by its leaving
an insoluble residue when boiled with nitric acid. C. E. G.
Method of Determining Hydrochloric, Hydrocyanic, and
Thiocyanic Acids when Simultaneously Present. By W.
BoRCHERS (Ofieni. News, 47, 218). — A portion of the solution is
titrated with silver solution. The quantii)' of silver thus found,
required to combine with the three acids is added to another portion
of the solution and the precipitate filtered quickly ; it need not be
washed unless sulphates are also present. The precipitate is washed
* The quantity of ammonia required is relatively large, and the treatment of th<i
precipitate must be continued until nothing appreciable passea into solution.
4 i 2
1174 ABSTRACTS OF CHEMICAL PAPERS.
into a flask with nitric acid of 1'37 sp. gr., and boiled until complete
oxidation has taken place. There then remains silver chloride, which
separated and weighed gives the chlorine present; the solution con-
tains silver nitrate corresponding with the silver cyanide, and also
silver sulphate corresponding with the silver thiocyanide. The sul-
phuric acid is determined by precipitation with barium nitrate, and
in the partially neutralised filtrate, the silver is determined by titra-
tion. If a ferrocyanide is also present, it is precipitated by an acid
ferric salt free from chlorine, and in the filtrate the three acids are
determined as before. If the titration with silver is made before
removing the ferrocyanide, an excess of silver must be added before
the addition of the ferric salt used as indicator. H. B.
Estimation of Hydrocyanic Acid. By R. A. Cripps (Pharm. J.
Trans. [3], 13, 917 — 918). — In the directions for the estimation of
hydrocyanic acid in the United States Pharmacopoeia, it is stated that
i3"5 grams of dilute hydrocyanic acid mixed with magnesia, when
titrated, using potassium chromate as indicator, should require 50 c.c.
standard silver nitrate, representing 2 per cent, absolute hydrocyanic
acid. The author points out that this quantity would be correct pro-
vided a double cyanide of magnesium and silver were formed and the
completion of the formation indicated by the chrorcate. It happens
that a magnesium silver cyanide, MgCy2,2AgCy, does exist, and can
be obtained in crystals by dissolving silver cyanide in magnesium
cyanide, but potassium chromate cannot be used as an indicator of
the completion of its formation. The author is of opinion therefore
that 100° of standard silver nitrate would be required instead of
50 c.c, and that the British Pharmacopoeia process is preferable to
that recommended in the United States Pharmacopoeia.
D. A. L.
Milk. By H. Struve (J. pr. Chem [21, 27, 249— 256).— In oppo-
sition to the results of Biedent and Badenhausen as to the nature and
condition of the casein of both cow's and human milk, it is contended
that theie is no difference in the quality of the albuminoids contained
in both kinds of milk, but that human milk contains a smaller pro-
portion of nitrogenous matters, and specially of casein than cow's
milk does. All dissolved albuminoids are separable from the in-
soluble casein and fat by means of dialysis into an aqueous solution
of chloroform ; most of the insoluble casein forming the coverings
of the fat-globules separating together with the casein. By agitat-
ing milk with ether, the fat-globules become much distended, the
coverings burst, and the fat passes into solution. Only very few fat-
globules are in a free condition. O. H.
Ether Test for Quinine. By A. J. Cownlet (Pharm J". Trans.
[3], 13, 917) ; (compare ihid., 7, (553, and this vol., 1018). — The author
remarks on the inefticiency of the testfor the detection of cinchonidine,
even when Byassin's improvement ot adding ammonia and using small
quantities of ether is resorted to: as much as 10 per cent, cinchonidine
may be overlooked in a sample of quinine sulphate. D. A. L.
ANALYTICAL CHEMISTRY. 1175
Use of Bromine in Testing for Alkaloids. By C. L. Bloxam
(Ghem. News, 47, 215). — If the alkaloid be dissolved in dilute hydro-
chloric acid, and bromine- water added drop by drop, the following
reactions are obtained : — Brucine gives a violet colour, strychnine the
same on boiling, narcotine a rose-pink, and the same with quinine.
With excess of bromine, strychnine, brucine, and narcotine readily give
yellow precipitates, whilst quinine, morphine, and cinchonine are only
precipitated with difficulty or from strong solutions. If ammonia be
added to the quinine and bromine solution, the characteristic green
colour is produced. If the morphine solution containing excess of
bromine-water be boiled, zinc added and again boiled, cooled and
dilute ammonia added, a pink colour is produced. H. B.
Bromine as a Test for Strychnine. By H. Jackson (Ghem..
News, 48, 11). — The author finds that acidifying with a few drops of
concentrated sulphuric acid greatly intensifies and hastens the pro-
duction of the violet coloration with bromine in solutions of strych-
nine. A distinct rose-pink coloration is produced in a solution con-
taining ao'oo o^ ^ grain of strychnine. The author suggests a
plan for the estimation of strychnine, using a standard solution of
strychnine and then comparing colours in a manner similar to the
N^esslerising method. D. A. L.
Analysis of Nux Vomica. Ey W. R. Dcnstan and F. W. Short
(Pharm. J. Trans. [3], 13, 1053— 1055).— The authors have analysed
samples of nux vomica beans from different localities. The process
employed is substantially that described at p. 689 of this volume, the
percolate, however, is acidified with 5 per cent, sulphuric acid, and
10 c.c. of it only are taken for the second agitation ; the liquid having
been rendered alkaline with ammonia, the extraction is effected by
two successive treatments with 15 c.c. of chloroform. The beans
varied in size and appearance ; all the cotyledons were seven- veined ;
the analytical results were as follow : —
Percentage of Strychnine and Brucine.
Bombay Bombay
Variety. Madras. Cochin. ordinary. fine.
Collected 1877 .... 274 3-04 3*14 3-46
1883 .... 315 3-60 390
When the nux vomica seeds are exposed to a temperature above 100°
decomposition takes place, and then the chloT-oform alcoholic percolate
is discoloured. If the colour is deep or brown, it is advisable to
remove it; this can be readily effected by shaking the percolate with
a 5 per cent, solution of sodium carbonate.
The authors have made several experiments to test the efficiency of
various precipitants for ascertaining the parity of alkaloidal residues.
They now test by dissolving the residue in dilute sulphuric acid,
exactly neutralising with ammonia, and precipitating with ammonium
tannate solution ; the precipitate is dissolved in a saturated solution of
1176 ABSTRACTS OF CHEMICAL PAPERS.
sodium carbonate, the alkaloid extracted with chloroform, and the
chloroform evaporated. D. A. L.
Picric Acid as a Test for Albumin and Sugar in Urine. By G.
Johnson (Fharm J. Trans. [3], 13, 1015— 1019).— To test for albumin,
add to the urine either a small quantity of solid picric acid, or an
equal volume of a saturated solution of picric acid, or pour some of
the solution on the urine so as to form a layer ; in all cases the presence
of albumin is indicated by the immediate appearance of a coagulum ;
in the last case, the coagulum forms a horizontal ring at the junction
of the liquids. This coagulum is soluble in alkalis ; if therefore the
urine is very alkaline it must be acidified before testing ; this precau-
tion is seldom necessary, as the picric acid is sufficient to effect the
required neutralisation. This test is more delicate than the old nitric
acid one. Any turbidity of the urine must be got rid of previously
to testing with picric acid.
To test for, and determine the amount of glucose in a saccharine
solution or urine, the author makes use of the reduction of picric to
picramic acid by glucose in the presence of potash. This change, as
is well known, is accompanied by a change of colour from yellow to
deep red ; now the author has found by experiment that the depth of
the red colour produced depends entirely on the amount of glucose
present, and is, moreover, invariably proportionate to the dilution of
the solution. Thus, if one solution contained a certain quantity of
sugar, and another solution contained four times as much, then the
colour produced by the latter, diluted to four times its own bulk, would
be of the same depth as the colour produced by the former. Therefore
a certain colour-strength is settled upon as a standard, and all solu-
ti»'ns are very carefully and accurately diluted down to this standard ;
the dilution is conveniently conducted in a graduated vessel alongside
of which the tube containing the standard is attached ; then the
quantity of glucose in the standard, multiplied into the degree of
dilution, will give the quantity of glucose in the solution under
examination. The author's standard colour is that produced by a
quarter-grain of sugar to the fluid ounce, and is thus obtained : — A
fluid drachm of a solution of sugar containing 1 grain to the ounce, is
mixed with half a drachm of potash solution (B.P.) and 10 minims
of a saturated solution of picric acid, and made up to 4 drachms
with distilled water. This mixture is now boiled for one minute,
cooled, and, if necessary, made up to 4 drachms. The picramic colour
is very fugitive, therefore the 4-grain colour is imitated by the follow-
ing mixture : all solutions are B.P. preparations, strong ferric chloride
solution (1 drachm), ammonium acetate solution (4 drachms), glacial
acetic (4 drachms), distilled water (2| ozs.), which produces a much
more stable colour. All quantitative experiments with saccharine
solutions or urine, are conducted in the same way as the standard is
produced. It is not necessary to alter the quantity of potash, the
amount of picric acid must however vary with the quantity of sugar
present; it is always better to have a slight excess, as the yellow
colour does not interfere with the red. The colour is not affected by
pure albumin ; the colouring-matter, however, of egg-albumin has a
TECHNICAL CHEMISTRY. 1177
redncinq" action on picric acid : this colonring-niatter is easily removed
by filtration through animal charcoal. Results obtained by this process
compared with those by Pavy's ammonio - cupric method, show
rather lower figures ; this the author attributes to something not
saccharine reducing the copper solution, but not the picric acid ; and
he finds that normal urine contains two cupric-oxide-reducing sub-
stances : — 1. Those not destroyed by potash, such as uric acid, &c.
2. Those destroyed by potash. Those of class 1 do not reduce picric
acid, hence it happens that if the cnpric oxide reduction obtained
from a urine which has been boiled for some time with dilute potash
be deducted from the cupric oxide reduction effected by the original
urine, the reduction thus obtained is equal to that given by the picric
acid with the original urine. This reducing substance only differs
from glucose in not being fermentable by yeast ; there are some
sugars which behave in a similar manner, namely, sorbite and eucalin ;
it is therefore very probable that this saccharo'id ingredient of normal
human urine may be a true sugar, although its identity with glucose
is incomplete. D. A. L.
Dialysis of Putrescible Substances. By H. Strove {J. pr.
Chem. [2], 27, 231 — 24i)). — The author recommends suspending a
bladder filled vrith the fluid to be dialysed in a saturated solution of
chloroform in water, or in pure ether, and details the results thus
obtained in the case of white of egg, and of milk both cows' and human.
He finds that the whole of the albumin and soluble casein, as well as
all crystalline constituents, pass through the bladder, leaving behind
the cell-walls and the fat. He contends that these results show the
distinction between colloids and crystalloids to be without foundation.
O. H.
Use of Phosphoric Acid in Pettenkofer's Reaction for Bile
Acids. By E. Drechsel (J", pr. Ghem. [2], 27, 424).— The failure in
obtaining Pettenkofer's reaction when phosphoric acid is used in
place of sulphuric acid is due to the employment of too large a quan-
tity or too concentrated an acid. A few drops of a mixture of 5 vols,
of commercial syrupy phosphoric acid with 1 vol. of water, should be
used. A. J. G.
Technical Chemistry.
Marsh-gas Fermentation in the Mud of Ditches, Swamps,
and Sewers. By H. Tappeiner {Ber., 16, 1740— 1744).— The fer-
mentation produced by the addition of mud to a sterilised 1 per cent,
solution of meat extract containing cotton wool and Nageli's salts,
yields a gaseous mixture containing 48*05 per cent. CO2 and SHo and
51*68 per cent, of H. The gases evolved by the action of mud on the
meat extract solution and cotton wool consist of COj and SH2 81'81,
1178 ABSTRACTS OF CHEMICAL PAPERS.
CH4 13*07, and H 489 per cent. Butyric and acetic acids were pro-
duced in each case. The relative amounts of CO2 and CH4, produced
by the action of mud on meat extract alone, are in the ratio of
1 : 31 — 36. Similar results are obtained if vegetable albumin or
peptone is substituted for meat extract. Small quantities of these
bodies give rise to an evolution of gas which lasts for weeks.
w. c. w.
New Properties of Ferric Sulphate. By Rohart (Compt. rpMd.,
96, 1705 — 1708). — Ferric sulphate, as neutral as possible and free
from any appreciable quantity of ferrous sulphate or ferric chloride,
combines with animal and vegetable substances, precipitating them
from solution, and forming definite and highly stable compounds,
which undergo no alteration when exposed to air. A solution of
ferric sulphate of 50° B. containing 26 per cent, of ferric oxide, added
to urine in the proportion of 2 per cent., instantly precipitates urea,
mucus, and urinary phosphates, and the urine thus treated undergoes
no change on exposure to air. Similar results are obtained with
sewage. Different parts of animals, and entire tish and small animals,
when suspended for a few days in a solution containing 1 per cent, of
ferric sulphate, are rendered non-putrescible, and may be dried with-
out undergoing change. There is actual combination between the
ferric sulphate and the organic matter, the former appearing to take
the place of some of the water contained in the latter. An adder
weighing 59 grams was dried completely : it weighed 19 grams. It
was then immersed for six days in the ferric sulphate solution, and
again dried ; it now weighed 25 grams, or an increase of 32 per cent,
on its weight in the dry state. The ferric sulphate which thus com-
bines with the organic matter cannot be dissolved out by hydrochloric
acid, and is not decomposed by boiling with barium chloride solution.
Meat treated with this reagent retains its red colour, but becomes so
hard that it can scarcely be scratched with the nail. Experiments
with eggs show that the ferric sulphate solution penetrates into the
organisms by endosmosis. C. H. B.
Employment of Boric Acid for Preserving Food. By J.
FoRSTER (J?er., 16, 1754 — 1759). — The author considers the use of
boric acid for preserving articles of food to be a questionable practice.
Boric acid increases the secretion of bile and the amount of albu-
minous matters excreted. W. C. W.
Manufacture of Tartaric Acid. By L. H. Friedburg {Pharm.
J. Trans. [3], 13, 992— 1000).— In the process described, the finely
powdered argol, sablons, or lees, is added gradually to milk of lime
and boiled with constant stirring for two hours ; in this way potassium
hydroxide and calcium tartrate are formed, and the nitrogenous
organic matter decomposed, ammonia going off with the steam.
When the boiling is complete, the mass is diluted, and the potash
neutralised with hydrochloric or sulphuric acid, more cold water is
now added, and the whole well stirred for some considerable time (all
night). The liquor containing potassium salts, &c., is filtered off,
concentrated, and otherwise made marketable. The impure calcium
TECHNICAL CHEMISTRY. 1179
tartrate, which is very prone to putrefaction, is speedily decomposed
witli sulphuric acid in the cold, methyl- violet paper being used to in-
dicate when the required quantity of sulphuric acid has been added.
From this brown solution, the tartaric acid is carefully reprecipitated
as calcium tartrate, lime being used at first, but chalk towards the
end, using litmus as indicator of the complete neutralisation. The
precipitate is filtered and slightly washed ; the calcium tartrate forms
light greenish -yellow crystals, which may be kept for any length of
time without decomposing. This is also decomposed by sulphuric
acid in the cold, again using methyl-violet paper. The precipitated
gypsum is filtered off and well washed, and the tartaric acid solution
evaporated at 80° until the gypsum in solution is deposited ; it is
then run into crystallising boxes. The brown crystals thus obtained
are dissolved to a liquor density of 25° B., treated with animal charcoal
(which has been washed with hydrochloric acid), filtered, evaporated
to 39° to 40° B., and either run into lead boxes to crystallise slowly,
or delivered into a tank fitted with a stirrer, where it is stirred for
several hours, and a crop of small crystals formed directly. The
crystals are washed and dried in centrifugals, steam being used for
washing. The liquid from the first crystallisation deposits another crop
of white crystals ; it then becomes brown mother-liquor, from which
crops of crystals are obtained until the predomination of sulphuric
acid and other impurities does not allow further crystallisation. They
are then diluted, the greater part of sulphuric acid removed by lime ;
and iron and aluminium phosphates got rid of by further treatment
with lime, when acid calcium tartrate is left in solution ; this is filtered
hot, and decomposed by sulphuric acid, when it yields a very pure
solution of tartaric acid.
For the preparation of potassium hydrogen tartrate, the acid solu-
tion is divided into two equal parts, the one is neutralised with potas-
sium carbonate, the two are then mixed, and the potassium hydrogen
tartrate is precipitated. D. A. L.
Chemistry of Fish. By W. 0. Atwater (Ber., 16, 1839—1846).
— The author gives the results of the analyses of the flesh of 64
kinds of fresh and preserved fish, which are used for food.
w. c. w.
Fermentation of Bread. By Moussette (Compt. rend.^ 96,
1865). — The liquid obtained by condensing the vapours from a bread
oven contained 1*6 per cent, by volume of alcohol, and 0*06 per cent.
by weight of acetic acid, together with a small quantity of ferric ace-
tate (from the walls of the oven), and a very small quantity of ammo-
nia. This experiment, which was made in 1854, proves that alcohol is
one of the products of the fermentation of bread (see next Abstract).
C. H. B.
Fermentation of Bread. By G. Chicandard (Compt. rend.^ 96,
1585 — 1588). — It is generally supposed that in the fermentation of
flour paste the starch is converted into maltose under the influence of
diastases existing in the flour, the maltose being eventually converted
into glucoses, which undergo alcoholic fermentation. But the dias-
1180 ABSTRACTS OF CHEMICAL PAFERS.
tases existing in flour act only on starch altered by heat, and have no
action on unaltered starch ; moreover, the presence of alcohol in the
paste has never been proved. The author has analysed filtered in-
fusions of flour, paste with leaven, paste with yeast, and bread, and
he finds that there is no soluble starch in flour, or in the two pastes,
but that a considerable quantity exists in bread. The four substances
contain equivalent quantities of glucose, from which it follows that the
glucose originally existing in the flour is not decomposed. Flour con-
tains albumin which is coagulated by heat and is precipitated by nitric
acid and by potassium ferrocyanide and acetic acid. The two pastes
contain no albumin coagulable by heat, but they contain albuminoids
precipitable by nitric acid and by potassium ferrocyanide and acetic
acid, together with peptones not precipitated by these reagents, but
precipitated by tannin. Bread contains no albuminoids, but it contains
peptones precipitated by tannin, corrosive sublimate, &c. Microscopic
examination shows that the paste with leaven contains no saccharo-
oiiycesjaiid that the cells of saccharomyces cerevisice introduced into the
paste with yeast gradually diminish in number. Both pastes con-
tain a number of moving microbes, of very varying length, which
appear to be bacteria. These bacteria develop very rapidly in paste
with yeast, and they can be cultivated in water holding yeast in sus-
pension, from which it would appear that yeast is favourable to their
development. The gas evolved during fermentation is a mixture of
carbonic anhydride, hydrogen, and nitrogen, and is analogous in com-
position to the gas evolved in the putrefaction of albuminoids.
The author concludes that the fermentation of bread is not due to a
saccharomyces, and that it consists, not in hydration of the starch fol-
lowed by alcoholic fermentation, but consists in the conversion of a
portion of the insoluble albuminoids of the gluten into soluble albumi-
noids, and eventually into peptones. The starch is modified by the heat
only, a considerable quantity of soluble starch and a small quantity of
dextrin being formed. The agent of fermentation is a bacterium
which develops normally in paste, the development being accelerated
by the presence of yeast.
These remarks do not apply to the English process, in which fer-
mentation is produced by a mixture of yeast with potato-starch altered
by heat. C. H. B.
Italian Petroleums. By B. Porro (Gazzetta, 13, 77 — 85).— The
author has examined four specimens of petroleum found in Italy at
Petralio Montanaro near Piacenza, at Rivanazzuno near Voghera, at
Tocco Casanria, and at San Giovanni Incarico.
The first had a sp. gr. of 0*7849 at 15°, and when distilled gave
4i4!'7 per cent, light petroleum ; 19*8 distilling between 127" and 150* :
22 between 150" and 203° ; 14-4 above 203°, and left 6-9 per cent!
residue.
The second of sp. gr. 0-9132, gave 22 distilling below 230^ ; 33
between 230° and 270'' ; 37 above 270°, and 7'7 residue.
The third and fourth of sp. gr. 0*951 and 0"974, gave respectively
635 and 696 per cent, oilj 32*2 and 28*3 of pitch, and about 12 and
20 of gas. C. E. G.
^
INDEX OF AUTHOES' NAMES.
ABSTRACTS. 1883.
A.
Abeles, M., secretion of the kidney fed
witli defibrinated blood, 875.
Abelli, M., chlorides of ortho- and
meta-nitrobenzyl, 1092.
Abney, W. de W., and E, Fes ting,
atmospheric absorption of the infra-
red of the solar spectrum, 837.
Abraham, K., the currents of the gases
in sulphuric acid chambers, 129.
Agrestini, A., derivatives of naphtha-
lene hexhydrides, 345.
Albrecht. See Will.
Alen, J. C, nitronaphthalene-disul-
phonic acids, 596.
Alexejeff, W., mutual solution of
liquids, 11.
Allen, A. H., action of water on lead,
128.
Allen, C. L., composition of two speci-
mens of jade, 163.
Allihn, F., reducing power of grape-
sugar for alkaline copper solutions,
244.
Allihn. See also Degener.
Am a gat, E. H., compressibility of
nitrogen, 150.
Amthor, C, glycerol in beer, 385.
studies on ripe grapes, 881.
An acker, poisoning of cattle by earth-
nut-cake, 818.
A n d r e, G-., ammonio-bromides and oxy-
bromides of zinc, 713.
— — double chlorides of lead and am-
monium and oiy chlorides of lead,
717.
double salts of lead, 903.
Andreasch, R., oxidation of the bases
obtained by the action of halogen
compounds on thiocarbamide, 664.
potassium ethylene-disulphonate,
912.
Andreasch. See also Maly.
Anschiitz, R., action of aluminium
bromide on symmetrical dibrom-
ethylene and benzene, 807.
VOL. XL IV.
Anschiitz, E., and F. Eltzbacher,
new synthesis of anthracene, 809.
synthesis of unsymmetrical
tetraphenylethane, 1132.
Ansdell, G-., critical point of mixed
gases, 277.
Arbos, J., pyrolein, 519.
Archbold, G-., a new method of manu-
facturing paper pulp, 759.
Arne'l, K. E., a-chlornaphthyl-sul-
phonic acid, 595.
Arnold, C, estimation of organic
nitrogen, 378.
new colour reactions of the alka-
loids, 386.
poisonous principles contained in
certain lupines, 740.
Arnold, H., bromine amalgamation
process, 399.
Aronstein, L., transformation of
propyl bromide into isopropyl bromide,
under the influence of heat, 172.
Arzruni, A., artificial and natural gay-
lussite, 430.
dietrichite, 433.
jadeite axe from Rabbes, Hanover,
437.
Arzruni. See also Cossa.
Aschan, O., action of phenylthiocar-
bimide on amido-acids, 1107.
Aschenbrandt, H., paradiethylben-
zene, 318.
Attfield, J., sap, 1164.
At water, W. O., chemistry of fish,
1179.
Aubin. See Miintz.
Austin, P. T., preparation of stannic
oxide from sodium stannate, 425.
Austin, P. T., and G. B. Hurff, re-
duction of ferric salts, 511.
B.
Bachmann, A., aldehydethyl chloride
and behaviour of acetals to alcohols r.t
a high temperature, 726.
4 k
1182
INDEX OF AUTHORS.
Bachnieyer,W., test for organic acids
in phenol, 385.
test for sodium carbonate in milk,
385.
Baerwald, C, analysis of a pyromor-
phite from Ziihringen in Baden, 1063.
analysis of croeoisite, 1063.
thenardite from Aguas Blancas, 434.
Baeyer, A,, benzoylacetic acid, 336.
nitroso-oxindole and nitroso-in-
doxyl, 1131.
Baeyer, A., and P. Becker, para-
nitrobenzaldehyde and acetone, 1120.
Baeyer, A., and F. Bloem, orthamido-
phenylpropiolic acid and its deriva-
tives, 196.
Baeyer, A., and "W. Comstock,
oxindole and isatoxime, 1130.
Baeyer, A., and V. Drewsen, pre-
paration of indigo-blue from ortho-
nitrobenzaldeliyde, 341.
Baeyer, A., and S. (Economides,
isatin, 201.
Babrmann, B., amarine and fur-
furine, 799.
Bailey, E., dried alum, 1053.
Balbiano, L., dry distillation of sodium
dibromanisate, 1125. ,
Ballo, M., ear! onic hydrate, 574.
platii:iised magnesium as a reduc-
ing agent, 1053.
Balsohn. See Friedel.
Bamberger, E., Bechi's so-called
picranalcime from Monte Catini mine,
Monte Caporciano, 438.
dicyanodiamide, 907, 1090.
formation of phenylxanthamide,
185.
melanuric acid, 1086.
Barbie r. P., liquid terebenthene hydro-
chlorides, 809.
Barbieri. See Schulze.
Baret, chlorophyllite from Loquidy,
near Nantes, 443.
Barf f, and others, preservation of milk,
&c., 253.
B arker, G. P., secondary batteries, 765.
Barlow, W. H., mechanical properties
of aluminium, 424.
Barner, F., crystallographic examina-
tion of a-^-dinitroparaxylene and of
diiiitroparaxylene (m. p. 93°), 179.
Barnes, J. h., separation of chlorine,
bromine, aiid iodine, llb7.
Barret. See Wood.
Barth, L., and J. Schreder, action of
melting potassium hydroxide on ben-
zoic acid, 468.
fusion of orcinol and gallic
acid with soda, 59.
hydroxyquinol, the third
isomeric trihydroxybenzene, 987.
Barth, See also Nessler.
Bartheleray, A,, respiration of
aquatic and submerged aero-aquatic
plants, 747.
Bartoli, A., constitution of electro-
lytes, 540.
Bartoli, A., and G. Papasogli, elec-
trolysis of hydrofluoric acid and of
potassium antimonate with carbon
electrodes, 590.
electrolysis of water and of
solutions of boric acid, 540.
electrolysis with carbon elec-
trodes of solutions of binary com-
pounds and of various acids and salts,
592.
Basaroff, A., oxidation of sulphur in
the air, 551.
Bastelaer, A. v., analysis of butter,
246.
Baubigny, transformation of amides
into amines, 175.
Baubigny, H., action of ammonium
sulphide on stannous sulphide, 22.
action of heat on an acid solution
of nickel sulphate in pre^ence of
hydrogen sulphide, 25.
action of hydrogen sulphide on
nickel sulphate in acetic acid solu-
tion, 25.
action of hydrogen sulphide on
solutions of normal nickel sulphate,
24.
Baudet, prevention of boiler incrusta-
tion, 408.
Baudrowski, E., acetylenedicarboiy lie
acid, 313.
propargylic acid. 314.
Bauer, A., new acids of the series
C„H2»-406, 970
piinelic acid, 998.
Bauer, A. H., pi*eservation of beer,
136.
Bauer, E., influence of invertin on the
fermentation of cane-sugar, 101.
nature and formation of dextran,
105.
Bauer, M., dioptase from the Corde-
rillas of Chili, 446.
Bauer. See also Classen.
Baumann, E., detection and estima-
tion of phenols and oxy-acids in the
urine, 885.
Baumert, G., action of dehydrating
agents on lupinine, 100.
preparation of lupinine hydro-
chloride from lupinine residues, 224.
Baumhauer, H., the trapezohedral
hemihedry of strychnine sulphate,
485.
Baur, C, radiation of rock-salt at vari-
ous temperatures, 702.
INDEX OF AUTHORS.
Ilb3
Baur, H. v., and W. Staedel, di-
methylxylidines, dimethylmetachlor-
aniline, and dimethylmetamido-
plieneto'il, 579.
Be cell i, E., prehnite and laumontite
from Monte Catini, 442.
Becchi. See also Cor si.
Bechamp, A., action of hydrogen per-
oxide on the red colouring-matter of
the blood and on hsematosin, 103.
decomposition of hydrogen per-
oxide by certain organised bodies, 103.
evolution of oxygen from hydrogen
peroxide by fibrin, 225.
micro zy mas, the cause of the de-
composition of hydrogen peroxide by
animal tissiies, 103.
spontaneous fermentation of
animal matter, 226!
zymase of human milk, 926.
Beck, W. v., and J. W. v. Muschke-
tow, nephrite, 1068;
Be eke, F., euclase from the Alps, 34.
hornblende and anthrophyllite after
olivine, 444.
Becker. See Baeyer and Claus.
Beckmann, E., barium aluminates,
289, 649.
basic halogen salts of barium,
649.
Becker, R, metanitrodiphenylmethane,
202.
Becquerel, H., observations of infra-
red spectra by means of phospho-
rescence, 761.
Beer, A., itamalic, paraconic, andaconic
acids, 457.
Behr. See Soxhlet.
Beilstein, F., and E. Wiegand,
alkylsulphamic acid, 971.
Caucasian ozokerite, 1073.
some ethereal oils, 346.
Bell, J., chemistry of food, 1160.
Bellati, H., and R. Romanese,
specific heat and heat of transforma-
tion of silver iodide and its alloys
with cuprous and lead iodides, 274.
Bemmelen, J. M. v., glucinum hy-
drated oxides, 291.
Bender. See Bernthsen.
Benedikt, K,., chloroxy- and bromoxy-
derivatives of benzene, 984.
nitro-derivatives of resorcinol, 803.
test for resorcinol dyes, H89.
Benedikt, R., and M. v. Schmidt,
halogen-derivatives, 1118.
Benz, *Jt., primary and secondary
naphthylamines, 594.
Berger. See Honig.
Bernthsen, A., methylene-blue, 916.
formation of nitril bases from
organic acids and amines, 1099.
Bernthsen, A., nitrotoluidines from
liquid nitrotoluene, 579.
preparation of the base C19H13N"
from benzoyldiphenylamine, 580.
Be rnthsen, A., and F. Bender, acri-
dine, 1134.
derivatives of styrolene, 70,
synthesis of acridines, 1133.
Berthelot, alkaline thiosulphates, 707.
alkaline metasulphites, 704.
alkaline sulphites, 704.
Berthollet's laws and the combina-
tions of mercuric oxide with acids, 10.
chromates, 707.
decomposition of cyanogen, 303.
direct combination of hydrogen
with ethylene, 565.
ethyl peroxide, 305.
ethylene oxide, 174, 275.
heat of formation of chromic acid,
642.
— ^ lead iodidfes, 275.
natural formation of manganese
dioxide, and' some reactions of per-
oxides, 425.
perchloric acid, 8.
properties of chlorinated organic
gases and vapours, 394.
reactions between sulphur, sulphur
oxides, carbon, and carbon oxides, 551.
reciprocal displacements of the
halogens, 8.
some relations between tempera-
tures of combustion, specific heats,
dissociation, and pressure of explosive
mixtures, 771.
the light emitted by comets, 261.
Berthelot and Ilosvay, double salts
formed by fusion, 11.
Berthelot and J. Ogier, researches on
the hyponitrites, 422.
specific heat of gaseous acetic
acid, 6.
Berthelot and Vieille, nitrogen se-
lenide, 707.
wave of explosion, 777.
Bertrand, E., optical properties of
cobalt carbonate, 1062.
optical properties of nocerine,
1060.
waltherite from Joachimsthal, 36.
Bertrand, E., and Damour, zmc alu-
minate, a new mineral species, 413.
Beseler, manuring sugar-beet with
acids, 238.
Besthorn, E., and O. Fischer, a new
class of colouring matters, 600.
Bichat, E., and R. Blondlot, oscilla-
tions of t' e plane of polarisation by
electric discharge, 4.
Bid well, J., electric resistance of car-
bon contacts, 811.
4^2
1184
INDEX OF AUTHORS.
Billitz, 0-., and K. Heumann, new
modes of formation of pyrosulphuric
chloride and of chlorosulphonic acid,
710.
B 11 Iwi Her, E,, influence of fallen snow
on the temperature of the air, 500.
Binder. See Prudhomme.
B inz, C, behaviour of ozone with blood,
486.
Bischoff, C, distribution of poisons in
the human organism in cases of
poisoning, 1020.
Bischoff, C. A., action of the alkyl-
derivatires of the halogen substituted
fatty acids on aniline, 919.
ethereal salts of propenyltricar-
boxylic acid, 45.
ethyl ethenyltricarboxylate, 45.
ethyl isallylenetetracarboxylate,
46.
ethyl monochlorethenyltricarboxy-
late, 45.
synthesis of ketonlc acids, 912.
Bischoff. See also Conrad.
Blake, J., relative toxic power of me-
tallic salts, 745.
Blarez, deplastering of wines, 252.
Bias and Mi est, extraction of the
precious metals from all kinds of ores
by electrolysis, 134.
Blaserna, P., and S. Cannizzaro,
report on a memoir by E. Schiff " On
the molecular volumes of liquids,"
279.
Blendermann, H., formation and de-
composition of tyrosine in the body,
818, 876.
Bloem. SeeBaeyer.
Blomstrand, C. W., oxy-acids of
chlorine, 645.
Blondlot. SeeBichat.
Bloxam, C. L., reconversion of nitro-
glycerol into glycerol, 788.
use of bromine in testing for
alkaloids, 1036, 1175.
Blumlein. See Plochl.
Bockorny. See Loew.
Bode wig, C, analyses of magnetic
pyrites, 1061.
Bocker. SeeMeissl.
Bockmann, F., manufacture of sorgho-
and imphy-sugar in the United
States, 633."
Bohm, J., formation of starch from
sugar, 820.
Bohmer, C, albuminoVd and non-albu-
minoid nitrogen compounds of certain
vegetables, 236.
estimation of nitric oxide and nitric
acid, 508.
Bornstein, E., methylanthraquinone
and some of its derivatives, 70.
Boessneck, P., derivatives of a-naph-
thoic acid, 807.
methylnaphthalene, 1135.
o-naphthoic cyanide, 595.
Bottcher, W., anhydro-compounds,
800.
molecular transformations, 1113.
Bohn, R., and K. Henmann, par-
azophenol, 583.
Boisbaudran, L. de, iridium potas-
sium sulphate, 905.
reactions of iridium, 905.
separation of gallium, 21, 153, 156,
293,715, 1054.
violet iridium sulphate, 1057.
Bollert, A., derivatives of anthramine,
1139.
Bolton, H. C, application of organic
acids to the examination of minerals,
857.
atomic weight of anti-
Bongartz, J.,
mony, 1056.
Borchers, W.
hydrochloric,
method of determining
hydrocyanic, and thio-
eyanic acids when simultaneously pre-
sent, 1173.
Borgmann, photoelectric battery, 625.
Borgmann, E., presence of formic and
acetic acids in plants, 611.
relation between the glycerol and
alcohol in wine, 518.
sulphuric acid in sherry, 829.
Borgmann. See also Fresenius
and Grabriel.
Borntrager, H., preparation of sele-
nium on a large scale, 852.
Bosshard. See Schulze.
Bottinger, C, anilpyruvic acid, 1128.
Bouchart. SeeNoelting.
Bourgeois, L., artificial production of
witherite, strontianite, and calcite, 31.
artificial production of wollastonite
and meionite, 560.
Boussingault, bronze implement used
by the miners of Peru, 691.
cultivation of the cacao-tree, 933.
deposits of manganese on the sur-
faces of rocks, 170.
mineral combustibles, 941.
Braithwaite. See Naylor.
Brame, C, certain properties of hydro-
gen cyanide, 129.
Brandl, J., chemical composition of
minei-als of the cryolite group, 29.
B ran I ey, E., estimation of hsemoglobin
in blood by optical means, 394.
Brard, currents produced by fused
nitrates in contact with incandescent
carbon, 273.
fuel to produce electricity, 626.
Braun, F., electrical energy and chemi-
cal action, 413.
INDEX OF AUTHORS.
1185
Braun, F., electromotive force of cer-
tain galvanic combinations, 764.
Braun, J., unipolar conductivity of
solid bodies, 769.
Brauner, B., didymium, 18.
Braun 8, E., cause of the anomalous
double refraction of certain salts crys-
tallising in the regular system, 1041.
Brauns. See also Zincke.
Bredt, J., action of nitric acid on fatty
acids containing the isopropyl group,
176.
Brezina. See G^allia.
Brieger, L., putrefaction alkaloids,
924, 1159.
Britton, B., normal solutions for the
volumetric estimation of iron, 241.
Brockhaus, experiments on the poi-
sonous action of potato-brandy, 362.
Brogger, W. C, the siluriau rocks of
Christiania, 723.
Broockmann, K., estimation of phos-
phoric acid and of magnesia, 380.
Broun, P. H., ethoxymetatoluic acid,
471.
Briicker, E., alkophyr, and the true
and so-called biuret reaction, 1019.
Brugelmann, Q-., experiments on
crystallisation, exemplifying Berthe-
lot's law of affinity, 148.
observations on crystallisation,
147.
Brun, A., galena with octohedral
cleavage, 428.
mineralogical notes, 31.
Brunck, H., and C. Grraebe, soluble
alizarin-blue, 74.
Brunton, T. L., and T. Cash, action
of calcium, barium, and potassium
salts on muscle, 875.
Brush, Q-. J., and E. S. Dana, spo-
dumene and the products of its altera-
tion, 438.
Biirow, F., new process for preparing
press cake from maize, Ac, 695.
Buri, E., hydropiperic and piperhy-
dronic acids, 485.
Busse, preservation of milk, 254.
Butlerow, A., notice on the atomic
weights, 846.
c.
Calm, A., paradichlorazobenzene-mono-
sulphonic acid, 341.
Cannizzaro, 8., and Gt. Carnelutti,
santonous and isosantonous acids, 77.
Cannizzaro. See also Blaserna.
Canzoneri, F., dibromonaphthalene
from /3-naphthol, 67.
Canzoneri, F., and P. Spica, bro-
minated derivative of toluquinone,
330.
Carnelutti. See Cannizzaro.
Carri^res, E. A., and others, phyl-
loxera, and means for its destruction.
680.
Casamajor, P., asbestos filters, 506.
detection of anhydrous glucose
mixed with refined caue-sugar, 884.
Cash. See Brunton.
Cathrein, A., chemical composition of
diallage, 1068.
saussurite, 1066.
Caul, B. H., liquid extract of cinchona,
693.
Cazeneuve, P., a new monochloro-
camphor, 214.
chloronitrocamphor, 667.
physical isomerism of monochloro-
camphor, 598.
Ceresole, M., acetoacetic acids, 41.
violuric acid, 913.
Ceresole. See also V". Meyer.
Chancel, G-., alkyl nitrous acids,
914.
Chandelon, T.,, chlorophenols ob-
tained by the action of alkaline hypo-
chlorites on plienol, 1108.
volumetric estimation of phenol,
124.
Chanlaroffy M., action of thiacetic
acid on ethyl thiocyanate, 39.
Ckapoteaut, P., essence of sandal-
wood, 76.
the gastric juice, 103.
Chappuis, P., evolution of heat in the
absorption of gases by solids and
liquids, 702.
de Chardonnet, reflection of actinic
rays : influence of the reflecting sur-
face, 138.
Chat in, M., hygienic action of maize
as fodder, 488.
Chicandard, A., fermentation of
bread, 1179.
Chittenden, R. H., and J. S. Ely,
alkalinity and diastatic action of
human saliva, 488.
Ciamician, Q-. L., and M. Denn-
stedt, action of cyanogen chloride
on potassium-pyrroline, 599.
action of nascent hydrogen
on pyrroline, 82, 1142.
compounds of the pyrroline
series, 350.
■ derivatives of citraconic acid,
312.
Claassen, E., mineralogical noti^s,
1066.
Clark, W. 1., ethyl acetate, lOSO.
Classen, A., and O. Bauer, use of
1186
INDEX OF AUTHORS.
hydrogen peroxide in analytical
chemistry, 934.
Classen, E., analysis of a variety of
siderite, 559.
Claus, A., amarine, 203.
cymenesulphonic acids, 1129.
dibromosuccinic acid and diamido-
suecinic acid, 43.
occurrence and estimation of free
tartaric acid in wine, 935.
sulphonic acids of paracymene, 918.
Claus, A., and H. Becker, trinitro-
toluene and liquid dinitrotoluene,
1093.
Claus, A., and K. Ell^s, amarine, 982.
Claus, A., and F. GUyckherr, oxida-
tion of quinoline benzyl chloride,
1009.
Claus, A., «.nd Or. Henamann, azo-
phthalic adld, 1 126.
Claus, A., and H. Lippe, oxidation of
pentachloronaphthalene, 921.
Claus, A., and P. Rieniann, dichloro-
paracresol and dichlororthocresol,
nil.
Claus, A., and T. Tosse, addition-
products of quinoline, 1008.
Clausius, E., the units of electricity
and magnetism, 764.
Clausnitzer. See A. Mayer.
Clermont, A., preparation of ethers of
trichloracetic acid, 729.
Cleve, P. T., atomic weight of didy-
mium, 852.
atomic wei^t of lanthanum, 553.
atomic weight of yttrium, 292.
didymium, 18.
Cobenzl. See Skraup.
Cocheteux. See Krutwig.
Cochin, D., action of air on yeast, 746.
Coleman, A. P., melaphyres of Lower
Silesia, 563.
Collan. SeeHjelt.
Collier, P., a remarkable platinum
nugget, 426.
Col son, A., an aromatic tribromhydrin,
734.
combination of tetratomic ele-
ments, 15.
Colson. See also Schiitzenberger.
Combes, A., base derived from croton-
aldehyde, 1079.
Combes, on the supposed compound
NH2, 14.
Comstock. See Baeyei%
Coninck, O. de, bases of the pyridine
and quinoline series, 738.
hydrates of pyridic bases derived
, from cinchonine, 220.
isomerism in the pyridine series,
740.
quinoline from cinchonine, 88.
de Coninck. See also Marcus.
Conrad, M., halogen substitution com-
pounds of ethyl acetoacetate, 177.
Conrad, M., and C. A. Bischoff,
tetrethyl acetylenetetracarboxylate,
46.
Conrad, M., and M. G-uthzeit, action
of chloroform on sodium ethylmalo-
nate, 311.
derivatives of barbituric acid,
314.
ethyl methenyltricarboxylate
and ethyl acetomalonate, 44.
halogen substituted ethyl
acetoacetates, 1082.
tetrethyl dicarbontetracar-
boxylate, 46.
•Constam. See V, Meyer,
Cook, E. H., carbonic anhydride in the
atmosphere, 284.
Coppola, F., genesis of ptomaines, 522,
624.
Corenwinder,B., biological researches
on the beet-root, 613.
Corsi, A., and E. Becchi, prehnite
from Tuscany, 441.
Cossa, A., chemical and microscopical
researches on Italian rocks and mine-
rals, 446.
hieratite, a newmineral species, 955.
Cossa, A., and A. Arzruni, chromic
tourmalin and the deposit* of chrome
iron ore in the Urals, 444.
Courtonne, H., solidification of dif-
ferent mixtures of naphthalene and
Stearic acid, 176.
Cownley, A. J., ether test for quinine,
1174.
Crafts, J. M., comparison of mercurini
thermometers with the hydrogen
thermometer, 144.
density of chlorine at high tempe-
ratures, 710.
thermometric measurements, 842.
Craig, Gr. E., estimation of sulphur in
iron and steel, 121, 512.
Cramer, T., vegetarianism from a
physiological standpoint, 928.
Criper, W. R., analyses of Indian
wood, 107.
Cripps, R. A., estimation of hydro-
cyanic acid, 1174.
Croft, H. H., rattlesnake poison, 104.
Cronquest, A. W., analysis of a
spring water from Bindo near Stock-
holm, 449.
■ the lake deposits of Kolsnaren,
Viren, and Hogsjon, Sweden, 448.
Cros, C, and A., Vergerand, a new
photographic paper, 752.
Cross, C., and A. Higgin, decomposi-
tion of wat«r by metalloids, 900.
INDEX OF AUTHORS.
1187
I
Cross, C. F., rehydration of ferric
oxide, 853.
technical aspects of lignification,
694.
Cross, W., and W. F. Hillebrand,
minerals, mainly zeolites, occurring
in the basalt of Table Mountain near
G-olden, Colorado, 164, 956.
notes on some interesting
minerals occurring near Pike's Peak,
Colorado, 1065.
Crova, A., a new condensation hygro-
meter, 118.
Cuisinier, L,, and H. Kiliani, sac-
charin and lactic acid from sugars,
42.
Curtius, T., glycocine, 1087.
synthesis of some acids analogous
in constitution to hippuric acid, 337.
Czimatis, L., mixed aromatic tertiary
pliosphines, 57.
Czimatis. See also Michael is.
D.
Dabaele. See Pellet.
d'Achiardi, A., minerals found near
Massa in the Apuanian Alps, 428.
Daf ert, F. W., amylbenzene, 659.
derivatives of diethyltoluene,
1093.
researches on periodides, 978.
Dam our. A,, aluminium borate from
Siberia, 719.
chemical composition of a green
mica from Syssert, 1066.
rhodizite, 956.
Damour. See also Bertrand and
Des Cloizeaux.
Dana, J. D., metamorphism of massive
crystalline rocks, 562.
Dana. See also Brush.
Danger, L., and others, parasitic
diseases of plants, and their preven-
tion, 110.
Darton, N". H., new locality for hayes-
ine, 162.
Daubree, A., meteorite of Louan,
449.
David, J., estimation of glycerol in
fatty matters, 123.
Davy, E. W., determination of ni-
trites, 515.
Deb ray, solubility of cupric sulphide
in alkaline thiomolybdates, 1054.
Deb ray, H., artificial production of
iridosmin, 298.
preparation of cerium oxide, 713.
Debray. See also Dev ille.
gun-
Debus, II., chemical theory of
powder, 258.
De Foreran d, compounds of hydro-
gen sulphide with ethers, 961.
formation of disodium glycollate,
1085.
heat of formation of glycollates,
708.
heat of formation of solid glycol-
lates, 644.
neutralisation of glycoUic acid by
bases, 774.
salts of glycollic acid, 775.
Degener, P., influence of chlorides of
the alkalis and alkaline earths on the
precipitation of lime saccharate, 692.
Degener, P., and F. AUihn, estima-
tion of sugar by alkaline copper solu-
tions, 519.
Deherain, P. P., influence of the
electric light on the development of
plants, 105.
loss and gain of nitrogen in arable
land, 373, 749.
Deherain, P. P., and L. Maquenne,
butyric ferment in arable soils, 610.
reduction of nitrates in
arable soil, 229.
reduction of nitrates in the
soil, 229, 503.
Deherain, P. P., and Meyer, develop-
ment of wheat, 493.
Delacharlonny, P. M., aluminium
sulphate, 714.
— ^ transformation of blood into a
solid inodorous manure, 239.
Delafond, steel from pig-iron contain-
ing phosphorus, 403.
Delattre, treatment of the washings
from wool, 940.
DemarQay, E., thorium sulphate, 1053.
Demarchi, L., and O. Fodera, pro-
duction of pozzolana, 529.
Demel, W., dopplerite from Aussee,
160.
Denaro. See Scichilone.
Dennstedt. See Ciamician.
Denuce, D., preservation of wine by
salicylic acid, 535.
Derby, O. A., Brazilian specimens of
martite, 559.
Desains, distribution of heat in the
ultra-red region of the solar spectrum,
143.
Des Cloizeaux and Damour, chal-
comenite, a new mineral species (sele-
nite of copper), 31.
Des Cloizeaux and Jannetta/,
nepheline in the oUgoclase of Denise,
1067.
Desprax, P., method of estimating the
alkalinity of limed beet-syrup, 689.
1188
INDEX OF AUTHORS.
Defcmer, W., action of various gases,
especially nitrous oxide, on plant cells,
105.
contributions to the dissociation-
hypothesis, 489.
influence of foreign matter in the
conyersion of starch by diastase, 631.
Deville, H. Sainte-Claire, and H.
Deb ray, explosive alloys of zinc with
certain platinum metals, 19.
Dewar, J., and A. Scott, atomic
■weight of manganese, 856.
Dewar. See also Liveing.
Dieff, W., bye-product of the pre-
paration of allyl dimethyl carbinol,
1076.
Diehl, W., volumetric estimation of
peroxides, 242.
Dietzell, B., preservation of milk,
254.
Dieulafait, lithium, strontium, and
boric acid in the mineral waters of
Contrexeville and Schinznach, 301.
manganese in sea water and in
certain marine deposits, 725.
Dircks, V., occurrence of myronic acid
and estimation of mustard oil in the
seeds of cruciferce, and in oil-cakes,
245.
Ditte, A., brom-apatites and bromo-
wagnerites, 783.
compound of tin disulphide and
diselenide, 156.
crystallisation of chlorine hydrate,
550.
crystallised stannates, 716.
decomposition of salts by fused
substances, 11.
formation of crystallised uranates
in the dry way, 296.
iodo-apatites, 784.
production of brom-apatites and
bromo-wagnerites, 648.
production of crystallised vana-
dates in the dry way, 784.
stannous oxide and some of its
compounds, 294.
Divers, E., the Leclanche cell and the
reactions of manganese oxide with
ammonium chloride, 272.
Dixon, H. B., influence of aqueous
vapour on the explosion of carbonic
oxide and oxygen, 12.
velocity of explosion of a mixture
of carbonic oxide and oxygen with
varying quantities of aqueous vapour,
12,
Dixon, W. A., inorganic constituents
of some epiphytic ferns, 108.
Doebner, A., compounds of benzotri-
chloride with phenols and jshenyl-
amines, 861.
Doebner, C, and W. v. Miller,
phenylquinoline, 1149.
quinaldine, 602.
Dohn, W., and F. Nob be, cultivation
and feeding value of some varieties of
vetches, 612.
D o 1 te r, C, crystalline form of idocrase,
441.
the volcanic rocks of the Cape
Verde Islands, 720.
Donath, E., and J. Mayrhofer,
affinity and its relations to atomic
volume, atomic weight, and specific
gravity, 1048.
V. Dorp. See Hoogewerff.
Dossekel. See Rinicker.
Drechsel, E., action of phthalic anhy-
dride on amido-acids, 1126.
ammonioplatinum-diammonium
compounds, 28.
■ experiments on the small scale in
sealed tubes, 1167.
use of phosphoric acid in Petten-
kofer's reaction for bUe acids, 1176.
Drechsler, specific gravity of cereal
grains. 111.
Drews en, V. B., methylquinoline,
1149.
Drewsen. See also Baeyer.
Drown, T. M., sidphur in coal, 383.
Dufet, H., variations of the indices of
refraction of water and quartz with
the temperature, 762.
Dugast, M., composition of different
varieties of fodder-cabbage, 373.
Duisberg, C, addition of bromine to
ethyl acetoacetate, 656.
Dumas, L., retentive capacity for plant
food possessed by soils, 681.
Dumreicher, O. v., action of alu-
minium chloride on the monohalogen
derivatives of benzene, 53.
Duustan, W. R., and F. Ransom,
action of chlorine on solution of
carbonate, 647.
constitution of liquor sodos
chloratcB, 647.
Dunstan, W. R., and F. W. Short,
analysis of nux vomica, 689, 1175.
Dupetit, G-., poisonous principle of
edible mushrooms, 611.
Dupetit. See also Gayon.
Durin, E., hydrocarbons from peat,
652.
Dutt, U. K., o-naphthonitrilsulphonic
acid, 1001.
Duvillier, E., compounds of the creati-
nine-group, 220, 1153.
Dvorak, v., researches in statical elec-
tricity, 763.
INDEX OF AUTHORS.
1189
Ebert, Or., coumarin, 471.
Ebert. See also Eittig.
E dinger, L., reaction of the living
mucous lining of the stomach, 815.
Edler, manuring potatoes with potas-
sium nitrate, 117.
Edlund, E., researches on the heat
changes at the poles of a voltameter,
767.
Egleston, T., tellurium in copper, 531.
Eg or off, absorption-spectrum of the
earth's atmosphere, 137.
Ehrlich, A., glycocines, glycocine
ethers, and oxethylenecarbamides of
the tolyl and xylyl series, 593.
metatoluidine, 54.
orthotolylhydantoin, 1106.
Elbs, K., synthesis with chloropicrin,
1000.
Elbs. See also CI au 8.
Ellenberger, results of the suppres-
sion of perspiration of animals, 817.
Ellenberger and Hofmeister, the
digestive fluids and digestion of the
horse, 487.
Elsasser, E., specific volumes of the
ethereal salts of fatty acids, 967.
Elsbach, L., a-naphthaquinone-ethyl-
anilide, 70.
Elster, J., and H. Q-eitel, electricity
of flame, 141, 412.
Eltekoff, A., some oxides of the
ethylene series and their action on
water, 566.
Eltzbacher. SeeAnschiitz.
Ely. See Chittenden.
Emich, F., biguanide, 973.
ethylbiguanide and its compounds,
974.
Emich. See also Mai y.
Emmerich, R., estimation of milk fat,
246.
Emmert, A., and R. Friedrich, y-di-
ethylbutyroiactone, 39.
En gel, R., analogy between the allo-
tropic modification of phosphorus and
arsenic, 901.
Engelcke, J., dialkyldisulphoisethionic
acids, 972.
Engelmann, T. W., assimilation by
hsematococcus, 611.
colour and assimilation, 819.
elimination of oxygen from plant -
cells, 105.
Enklaar, J. E., osmosis of salts, 420.
Ensel, R., allotropic arsenic, 554.
Erdmann, E., action of sulphuric acid
on cinnamic acid, 474.
-— change of colour in felspar under
the influence of light, 438.
Erdmann, E., and Gr. Schultz,
haematoxylin and haematoin, 349.
Erdmann. See also Fittig.
Erlenmeyer, milking of cows twice
and thrice daily, 227.
Erlenmeyer, E., constitution of the
nitrosamines, 1103.
derivatives of cinnamic acid, 196.
Erlenmeyer, E,, and A. Lipp, cinna-
mic acid derivatives, 992.
synthesis of tyrosine, 994.
Erman, adipocere, 818.
!^tard, A., benzyleneorthotolylamine
aud methylphenanthridine, 179.
transformations of cuprosocupric
^ sulphites, 20.
Etard, A., and L. Oliver, reduction
of sulphates by living organisms, 229.
Etard, A., and C. Richet,estimaHonof .
the reducing power of urine and of
the extractive matter which it con-
, tains, 751.
Etard, A., and others, reduction of sul-
phates by algae, 680.
;fitard. See also G-autier.
Etti, C, compounds of vanillin with
pyrogallol and with phloroglucinol,
61.
tannic acids of oak-bark, 994.
Eykman, J. F., poisonous principle of
Andromeda Japonica, 215, 348.
Fahlberg, C, preparation from baux-
ite of aluminium sulphate free from
iron, 130.
Fankhauser, comparative meteorologi-
cal observations in forests, 614.
Far sky, chlorine as a plant food, 497.
Fauconnier, A., second anhydride of
mannitol, 305.
Feemster, J. H., average amount of
caffeine in the guarana of commerce
compared with that in the seeds,
232.
Fehrmann, A., preparation of lead
dioxide, 157.
Festing. See Abney.
F^vre, A., mononitroresorcinol, 733.
Filhol, E., and Sendereus, action of
svdphur on alkaline phosphates, 783.
action of sulphur on oxides, 710.
neutral phosphates of the alkalis,
151.
Findeisen, feeding horses with flesh-
meal, 102.
Fischer, E., caffeine, theobromine,
xanthine, and guanine, 354.
1190
INDEX OF AUTHORS.
Fischer, E., triacetonealkamine, 1153.
triacton amine, 790.
Fischer, E., and H. Koch, ethyl
phthalylacetoacetate, 806.
Fischer, E., and H. Kuzel, ethyl
orthonitrocinnamylacetoacetate, 587,
588.
ethylhydrocarbazostyril,
1132.
' quinazole-compounds, 812.
Fischer, F., application of electricity
in metallurgy, 398.
contribution to a knowledge of
sewer gases, 88H.
flameless combustion, 626.
investigation on boiler fires, 942.
practical application of thermo-
electricity, 625.
Fischer, H., tin ores, aventurine glass,
and green aventurine quartz from
Asia, and krokydolite quartz from
Greenland, 435.
Fischer, O., acridine, 1134.
derivatives of hydroxy quinoline,
1146.
hydroxyquinolines, 91.
Fischer, O., and L. German, new
synthesis of skatole, 1132.
the violet derivatives of tri-
phenylmethane, 1097.
Fischer, O., and C. Riemerschmid,
pyridinemonosulphonic acid, 923.
Fischer. See also Besthorn and
Penzoldt.
Fittbogen, J., and others, cultivation
of various crops, 235.
Fit tig, R., action of water on lactones,
730.
conversion of unsaturated acids
into the isomeric lactones, 730.
non-satiirated acids, 454.
Perkin's reaction, 1122.
so-called tetric, pentic, and heiic
acids, 1085.
Fittig, R., and Q-. Ebert, coumsrilic
acid, 474.
Fittig, R., and H. Erdmann, synthe-
sis of a-naphtliol, 595.
Fittig, R., and H. W. Jayne, phenyl-
hydroxypivalic acid, 471.
Fittig, R.,andF. Roeder, anon-satu-
rated acid isomeric with itaconic acid,
730.
Fleichtinger, cause of the acid reac-
tion exhibited by some kinds of paper,
696.
Fleischer, M., and R. Kissling,
application of insoluble phosphates to
soils, 822.
Fleischmann,W., preserved milk, &c.,
254.
Fleischmann, W., and A. Morgen,
Scherff's preserved milk, 757.
Fleischmann, W., and R. Sach-
tleben, Becker's creaming process,
253.
Jacobsen's testing chum,
253.
Fleissner. See Lippmann.
Fleming, H., glycerolphosphoric acid,
682.
Fletcher, T., flameless combustion,
523.
Flight, W., examination of certain
meteorites, 169.
Fliickiger, F. A., potassium carbonate,
902.
Fliickiger, F. A., and W. t. Miller,
American storax, 407.
Fodera. SeeDemarchi.
Fohr, K. F., sources of error in esti-
mating iron in ores by the stannous
chloride method, 242.
Fontaine, W. F., notes on the occur-
rence of certain minerals in Amelia
Co., Virginia, 959.
Forster, J., employment of boric acid
for preserving food, 1178.
Fort, J. A., physiological action of
CO flee, 745.
Fouque, F., and A. Michel-L6vy,
artificial formation of various rocks,
448.
Foussereau, G-., influence of temper
on the electrical resistauce of glass,
701.
Franchimont, A. P. N., action of
anhydrides on aldehydes, ketones, and
oxides, 452.
paraldehyde, 453.
Fran eke, G., estimation of starch in
grain, 624.
Frank, A. B., hypochlorin and it*
formation, 483.
Frankland, E., chemistry of storage
batteries, 839.
Freih, O., reduction of tungsten com-
pounds, 785.
Frentzel, J., normal primary hexyl
alcohol, 1075.
Fresenius, R., and E. Borgmann,
analyses of pure wines, 518.
Freydl, J., dry distillation of tartaric
and citric acids with excess of lime,
658.
Friedburg, L. H., carbon bisulphide,
535.
manufacture of tartaric acid, 1178.
Fried el, C, brucite from Cogne, 1061.
Friedel, C, and M. Balsohn, arti-
ficial production of mellite, 427.
Friedel, C, and J. Curie, pyroelec-
tricity of quartz, 897.
INDEX OF AUTHORS.
1191
Friedel, C, and E. Sara sin, artificial
production of phosgenite, 431.
Trie del, C, and others, composition of
dawsonite, 430.
Friedlander, P., orthamidobenzalde-
hvde, 331.
substitution derivatives of quino-
line, 351.
Friedlander,?., and C. F. G-ohring,
preparation of substituted quinolines,
1148.
Friedlander, P., and R. Henrique s,
reduction of orthonitrobenzaldehyde,
187.
Friedlander P., and J. Mahly, iso-
indole, 918.
Friedlander, P., and A. Weinberg,
constitution of corbostyril and hjdro-
carbostyril, 204.
Friedrich, R., monohalogen deriva-
tives of crotonic acids, 968.
Friedrich. See also Em me rt.
From me, C, electric researches, 697,
766.
Friihling, J., y -hydroxy butyric acid,
42.
Q-abriel, S., aromatic nitroso- com-
pounds, 919.
■ constitution of phthalylacetic acid,
1127.
hydrocinnamic and einnamic acids,
195.
metamidobenzaldoxime, 1105.
nitrobenzaldoxime, 916.
orthamidobenzaldehyde, 62,
phenylacetic acid, 64.
so-called nitrosomethylbenzene
compounds, 581.
Gabriel, S., and O. Borgmann,
benzyl derivatives, 1121.
Gabriel, S., and M. Herzberg, deri-
vatives of einnamic and hydrocinnamic
acids, 1123.
paranitrobenzaldoxime and
amidobenzaldehyde, 1104.
Gab el, D., margarimeter of Lenne and
Harbulet, 247.
on creaming, 253.
Gal, H., action of zinc- ethyl on amines
and phosphines, 653.
metallic derivatives of amides :
method of distinguishing between
monamides and diamides, 913.
passage of alcoholic liquids through
membranes, 549.
passage of alcoholic liquids through
porous vessels, 279.
Galle, K., tetrethylbenzene and hex-
ethylbenzene, 1091.
Gallia, J., and A. Brezina, the
meteorites of Alfianello, 1071.
Galloway, R., estimation of coke and
volatile products in coal, 517.
Galloway, W., influence of coal-dust
in colliery explosions, 127.
Gantter, F., colouring matter of wine,
1141.
Garnier, L., albumin from urine
coagulated by nitric acid and soluble
in alcohol, 247.
Garrod, A. B., formation of uric acid
in the animal economy, 876.
Gasparin, P. de, estimation of phos-
phoric acid in arable soils, 619.
submersion of vineyards, 1164.
Gattermann, L., symmetrical tri-
bromaniline, 796.
Gautier, A., formation of alkaloids
from normal human fluids, 101.
Gautier, A., and A. Etard, bases
formed by putrefaction, 100.
putrid fermentation and the
alkaloids produced by it, 224.
Gawalovski, A., estimation of tannin,
391.
Gay on, U., and G. Dupetit, fermen-
tation of nitrates, 230.
reduction of nitrates and
nitrites, 609.
Gay on and others, a denitrifying fer-
ment in soils, 679.
de Geer, G., a manganese mineral from
Upsala, 429.
Geibel, P., and others, removal of the
leaves of roots, 613.
Geibel. See also S chopper.
Geinitz, F. E., phyllitefrom Rimogens,
in the Ardennes, 447.
pseudomorph of nacrite after fluor-
spar, 1069.
Geitel. SeeElster.
Gelis, A. and T., sulphocarbometer,
386.
Geppert, J., improvements in gas
analysis apparatus, 378.
Gerdes, B., electrolysis of ammonium
carbamate and carbonate, 27.
Gerichten, E. v., and H. Schrotter,
morphine, 221.
German. See Fischer.
Gernez, D., velocity of solidification
of bodies in a state of superfusiou,
546.
Geuther, A., affinity value of carbon,
779.
constitution of the compounds of
the sulphonates with alkyl sul-
phates : constitution and dimorphism
of sulphates, 973.
1192
INDEX OF AUTHORS.
Q-evekoht, H., preparation of the
three isomeric nitracetophenones,
191.
Gibbons, W., uranium oleate, 692.
Gilbert. SeeLawes.
Gintl, W., and F, Reinitzer, consti-
tuents of the leaves of Fraxinus excel-
sior, 216.
Girard, C, and A. Pabst, azo-deriva-
tives, 583.
Gisevius, P., specific gravity of
minerals and their mechanical separa-
tion, 1031.
Gissmann, R., oxidation of durene by
chromic acid ; dinitrodurj'lic acid,
333.
Gladding, T. S., estimation of phos-
phoric acid as magnesium pyrophos-
phate, 240.
Gleichmann. See Michaelis.
Glyckherr. See Glaus.
Godlewski, E., respiration of plants,
498.
Gohring. See Friedlander.
Goldschmidt, G., products of the
distillation of calcium parahydroxy-
benzoate, 664.
products of the distillation of
salicylic anhydride, 664.
pyrenequinone, 869.
Goldschmiedt, G., and R. Weg-
schneider, pyrene-derivatives, 1001.
Goldschmidt, H., strychnine, 99.
Goldschmidt, H., and Y. Meyer,
benzil, 1120.
Goldschmidt, Y., application of a
solution of potassium and mercury
iodides to mineralogical and petro-
graphical researches, 159.
Goldstein, E., electric discharge in
rarefied gases, 266.
Gonnard, F., existence of apatite in
the pegmatites of Lyons, 432.
gedrite in the gneiss of Beaunan,
near Lyons, 444.
the granite on the banks of the
Sa6ne, 36.
Goodwin, W. L., nature of solution,
550.
Goossens, B. J., the metallic galvanic
circuit of Ayrton and Perry, 141.
Gorgeu, A., artificial hausmannite,
859.
— — artificial production of barytes,
celestine, and anhydrite, 1062.
double sulphates of manganese and
the alkalis, 718.
manganese sulphite, 558.
Go tt stein, L., two new caprolactones,
454.
Gouy, distortion of polarised elec-
trodes, 897.
Graebe. See Brunck.
Gratzel, A., creosote from beech wood
tar, 393.
Grandeau, H., decomposition of phos-
phates by potassium sulphate at high
temperatures, 151.
Gregoire, T., cultivation of gombo,
613.
Grete, E. A., nitrogen estimation in
saltpetre by potassium xanthate,
1031.
phosphoric acid determination,
1031.
Griess, P., constitution of the azimido-
compounds, 56.
creatine-oompounds of the aromatic
group, 669.
diazo-derivatives, 180, 1102.
Griessmayer, Y., loss of sugar by
long steaming of the " mash," 136.
the ferment of chica beer, 535.
Griffiths, A. B., an ammonia-phos-
phatic deposit in the vicinity of Cape
Town, 859.
analysis of a new guano from
Australia, 375,
analyses of some minerals, 858.
growth of plants under special
conditions, 496.
Grigoreff, P., analyses of some
Moscow waters, 622.
new mineral manure deposits,
529.
Grimaldi. See Macaluso.
Grimaux, E., phenol quinoline, 668.
some derivatives of morphine,
358.
Groddeck, A. v., sericite rocks occur-
ing in ore deposits, 168.
Grodzki, M., test for acetal, 790.
Groth, P., natural barium nitrate,
431.
Grouven, H., nitrogen estimation, a
method of general apphcation, 1028.
Gr lining, W., chemistry of ihe Nym-
phcBacecB, 369.
Gruner, relative oxidisabihty of cast
and malleable iron and steel, 755.
Guareschi, J., and A. Mosso, pto-
maines, 1156.
Guckelberger, G., ultramarine, 714.
Gum b el, C. W., the so-called andesites
of South and Central America, 448.
Guillaume, L., chemical manures and
farmyard manure, 501.
mineral phosphates in arable soil,
118.
Gundermann, purification of mo-
lasses, 835.
Gustavson, G., action of aluminium
chloride and bromide on hydrocar-
bons, 577.
INDEX OF AUTHORS.
1193
G-ustavson, Or., conrersion of the
propyl into the isopropyl-group, 565.
Q-uthzeit, M., diethyl aeetylenetetra-
carboxylate, 46.
G-uthzeit. See also Conrad.
Gutzkoff's process for the separation
of gold in California, 251.
Q-uyot, P., analysis of the coal of the
Muaraze, 299.
calcination of alunite, 397.
industrial value of crude alunite,
250.
Q-uyot-Dannecy, analysis of potas-
sium thiocarbonate. 241.
Habermann, J., and H. Honig, action
of cupric hydroxide on sugars, 38.
Haerling, cause of the acid reaction
exhibited by some kinds of paper,
260, 759.
Ha^a, II., amalgamation currents, 412.
Hagemann, W., preservation of but-
ter, 254.
Hagen. See Liebermann.
Ha gen bach, E., Stokes's law of fluo-
rescence, 537.
Hager, H., detection of arsenic micro-
scopically, 381.
Haines, E., helvite from Yirginia,
437.
Haitinger, L., action of sulphur on
sodium phenate, 9^8.
occurrence of organic bases in com-
mercial amyl alcohol, 127.
Haitinger. See also Lieben.
Halberstadt, W., separation of vana-
dio acid from metals, 513.
Hall, F. P., action of certain vegetable
acids on lead and tin, 1038.
Hallberg, C. S., ergot, 640.
Hal lock, E. D., analysis of columbite,
434.
Hamburger. See Mulder.
Ham man ten, O., metalbumin and
paralbumin, 874.
Hampe, desilvering of lead, 134.
Hank el, W. G-., actino-electric and
piezo-electric properties of quartz and
their relation to the pyro- electric,
412.
observations on thermo- and
actino- electricity of quartz, 950.
thermoelectric properties of mine-
rals, 546.
Hannay, J. B., limitof the liquid state,
-145.
Han riot, strychnine derivatives, 6^9.
Hanriot and Blarez, solubility of
strychnine in acids, 924.
Hantzsch, A., action of aldehyde-am-
monia on methyl acetoacetate, 1082.
condensation products of ethyl
acetoacetate, 1083.
reaction of ethyl acetoacetate with
orthamidophenol, 1111.
synthesis of pyridine-derivatives
from ethyl acetoacetate and aldehyd-
ammonia, 82.
Harada, T., the Lugano district, 167.
Har court, A. V., an instrument for
correcting gaseous volume, 378.
Harmuth, and others, lupine sickness
in sheep, 228.
Harnack, E., Carlsbad salts, 396.
Harrington, B. J., diorites of Mont-
real, 561.
H a r 1 1 e y, W. N"., researches on spectrum
photography, 263.
reversal of metallic lines in over-
exposed photographs of spectra, 263.
Har ton, N. H., new locality for hayes-
ine and its novel occurrence, 1062.
Harvey, J. W. C, a modified process
for the estimation of chlorine in
bleaching powder, 507.
volumetric estimation of chromic
acid in chromates and dichromates,
686.
volumetric estimation of man-
ganese dioxide, 513.
Has e brock, X., coagulation of the
blood, 608.
Has lam, A. B., detection of albumin
in urine, 885.
Hauer, F. v., and others, the Klausen-
burg meteorite, 1070.
Hautefeuille, P., and J. Margottet,
combination of phosphoric acid with
silica, 782.
crystalline phosphates, 711.
phosphates, 782.
silica and lithium silicates,
559.
Hay, M., new alkaloid in Cannabis
indica, or Indian hemp, 1155.
Hay duck, M., influence of alcohol on
the development of yeast, 104.
Hazura, K., nitroresorcinolsulphonic
acid, 1114.
Hazara. See Weidel.
Heberand, A., compounds of benzo-
and tolu-quinol with amines, and of
quinone with nitranilines, 61.
Heckel, E., ice-plant (Mesembj-ian-
tkemum crystallintim), 680.
Heckel and Schlagdenhauffen,
chemistry of globularia, 1025.
Heddle, M. F., new face on stilbite,
441.
im
INDEX OF AUTHORS.
Heim, R., conversion of phenols into
nitrils and acids, 1111.
phenolic phosphates, 1108.
Heinr'ich, R., influence of the per-
centage of moisture in peaty soils on
vegetation, 681.
Hell, C, and F. TJrech, carbon thio-
bromides, 907.
formation of a new colouring
matter by the action of heat on car-
botrithiohexbromide, 907.
Hellmann, H., difference of positive
and negative discharge, 949.
Hellon. See Tcherniac.
Henninger, a new alcohol in wine,
631.
Ilenriques, R., new nitro-derivatives
of phenol, 327.
Ilenriques. See also Friedlander.
Henry, L., a-monochlorallylic alcohol,
and its derivatives, 173.
phenol derivatives, 802.
" reaction aptitudes " of the halo-
gens in mixed haloid ethers, 787.
Hen sen, V., fertility of a soil as de-
pendent on the action of worms,
237.
Hentschel, W., conversion of phenyl
ethers of carbonic acid into salicylic
acid, 588.
diphenylcarbamide and triphenyl-
guanidine, 1107.
Henzhold, O., new method of form-
ing anthracene, 1137.
Hepp, P., addition-products of nitro-
derivatives with hydrocarbons, 317.
trinitro-derivatives of benzene and
toluene, 315.
Hermann, F., constitution of ethyl
succinosuccinate, 1084.
Herz, H., electric discharges, 700.
■ researches on the glow discharge,
949.
Herzberg. See Gabriel.
Herzfeld, A., maltose and isomeric
gluconic acids, 652.
Herzig, J., action of nitrous acid on
guaiacol, 464.
guaiaconic and guaiaretic acids,
470.
Hesse, O., anhydrous grape-sugar from
aqueous solution, 175.
cuprea-bark, 601.
hydrocinchonidine, 97.
■ by drocon quinine and conquinine,
602.
Heumann, K., and P.Kochlin, action
of heat on sulphuric monochloride
and dichloride, 781.
pyrosulphuric chloride, 710.
thioiiyl chloride and pyrosul-
phurylic chloride, 1051.
Heumann. See also Billitz, Bohn,
Claup, and Pierson.
Hidden, W. E., anatase and xenotime
from Burke Co., N. Carolina, 435.
notes on some N. Carolina mine-
rals, 163, 1063.
Hiepe. See Schmitt.
Higgin. See Cross.
Hill, H. B., constitution of the substi-
tuted acrylic and propionic acids, 310.
substituted pyromucic acids, 912.
Hill, H. B., and C. F. Mabery, tetra-
substituted propionic acids, 309.
Hill, H. B., and C. R. Sanger, action
of potassium nitrite on mucobromic
acid, 47.
Hill, S. A., the constituent of the
atmosphere which absorbs radiant
heat, 7.
Hiliebrand. See Cross.
Hinsberg, O., derivatives of anhydro-
aniidofolyloxamic acid, 1129.
oxalic acid derivatives of meta-
nitroparatoluidine and 3-4 diamido-
toluene, 323.
Hintze, C, pseudomorphic senamon-
tite crystals, 430.
Hitchcock, R., examination of water
and air for sanitary purposes, 514.
Hittorf, W., luminosity of flame, 697.
Hjelt, E., allylsuccinic and carbo-
caprolactonic acids, 656.
dicarbocaprolactonic acid, 970.
lactones from allylmalonic, diallyl-
malonic, and dially acetic acirls, 456.
Hjelt, E., and U. Collan, ledum cam-
phor, 346.
Ho ad ley, J. C, platinum water pyro-
meter, 769.
Hodgkinson. See Matthews.
Holzer, A., sources of error in polaris-
ing, 3.
Honig, M., and F. Berger, action of
chloroform on naphthalene in presence
of aluminium chloride, 68.
Honig. See Habermann.
Honigsberg, P., digestibility of flesh,
815.
Hoffmann, M., digestibility of casein
from heated milk, 487, 815.
Hoffmann, L.. and W. Konigs,
tetrahydroquinoline, 1143.
Hofmann, A. W., action of bromine
on amines in alkaline solution, 789.
conliydrine, 220.
crystalline cumidine, 324.
lecture experiments, 279.
piperidine and pyridine, 813.
Hofmeister, F., distribution of pep-
tone in the animal body, 675.
the proportion of peptone in the
gastric mucous membrane, 675.
I>rt)EX OF AUTHORS.
1195
Hofineister. See also Ellenberger.
Holm, .T,, fluorene derivatives, 921,
Holzer, A., compound of phenol witli
sulphurous anhydride, 585.
Hoogewerf f, S., and W. A. v. Dorp,
the quinoline of coal-tar and of the
cinchona alkaloids, and its oxidation
by potassium permanganate, 89.
Hoppe-Seyler, F., action of oxygen
on fermentation, 489.
activity of oxygen, 1048.
activity of oxygen in presence of
nascent hydrogen, 848.
fermentation of cellulose, 821.
metahaemaglobin, 814.
HorbaczevFski, J., behaviour of elas-
tin in peptic digestion, 927.
synthesis of uric acid, 179.
Hornberger, K., and E. v. Raumer,
researches on the growth of the maize
plant, 491.
Houzeau, A., variation of the amount
of ammonia in rain-water, 753.
Howard, J. E., effect of altitude on the
alkaloids of the bark of Cinchona
succiruhra, 1165.
Hiifner, G., on the oxygen pressure
under which, at a temperature of 35°,
the oxy haemoglobin of the dog begins
to give up its oxygen, 678.
Huntington, A. K., reactions of the
Mexican amalgamation process, 134.
Hiippe, F., behaviour of unorganised
ferments at high temperatures, 101.
Hurff. See also Austin.
Hussak, E., serpentine from the Alps,
562.
I.
lies, M. W., occurrence of smaltite in
Colorado, 559.
vanadium in the Leadville ores,
562.
Ilosvay, physical properties of carbon
oxysulphide, 43.
Ilosvay. See also Berthelot.
Is amber t, F., ammonium hydrogen
sulphide, 548.
ammonium hydrosulphide and cya-
nide, 775.
dissociation of phosphino hydro-
bromide, 646.
phospliorus sulphides, 901, 1049.
vapour of carbamide, 645.
vapour-tensions of ethylamine and
diethylamine hydrosulphides, 727.
Ivan, A., bauxite, 397.
Jackson, C. L., and A. E. Menke,
certain substances obtained from tur-
meric, 480.
turmeric oil : turmerol, 482.
Jackson, E., a new test for titanium
and the formation of a new oxide of
the metal, 828.
Jackson, H., bromine as a test for
strychnine, 1175.
Jacobs en, O., hydroxytoluic and hy-
droxy phthalic acids, 1124.
isodurene, isodurylic acids, and the
third trimethylbenzene 52.
phosphorescence of sulphur, 710.
Jacobsen, 0., and H. Ledderboge,
amidometaxylenesulphonic acid, 593.
Jacobsen, O., and H. Meyer, sul-
phamic and hydroxy-acids from
pseudocumene, 589.
Jacobsen, E., and C. L. Reimer,
action of phthalic anhydride on quino-
line, 812.
coal-tar quinoline, 922.
Jacobsen, 0., and F. Wierss, deri-
vatives of orthotoluic acid, 1121.
Jacquelain, preparation and purifica-
tion of carbon for electric lighting,
752.
Jahn, H., electrolytic researches, 1042.
new method for preparing carbonic
oxide, 655.
Jaksch, R. v., acetonuria, 1161.
J am in, J., critical point of gases,
898.
Jamin, and G-. Maneuvrier, the re-
action current of the electric arc, 4.
Jandous, A., composition of ivy ber-
ries, 499.
Jannasch, P., discovery of fluorine in
the idocase from Vesuvius, 1067.
epistilbite and heulandite, 442.
Jannettaz, E., a phosphide of nickel,
651.
analysis of a green pyroxene from
the diamond mines of the Cape, 1067.
study of " longrain," and measure
of tlie ibliation in scliistose rocks by
means of their thermic properties,
800.
Jannettaz, E., and L. Michel,
nephrite or jade of Siberia, 436.
— — relation between the chemical
composition and optical characters in
the group of pyromorphites and
mimetesites, 433.
Janny, A., acetoximes, 580, 581.
J a n o V s k y, H., substitution-products of
azobenzene, 324.
Janovsky, J. v., amidazobenzenepara-
sulphonic acid, 1101.
1196
IXDEX OF AUTHORS.
Janovslcy, J. Y., nitro- and ainido-
derivatives of azobenzene, 867.
■ substitution-products of azoben-
zeneparasulphonic acid, 1101.
Jan 8 8 en, J., telluric rays and the
spectrum of water- vapour, 261.
Japp, F. R., addition of acetone under
the influence of caustic alkalis, 596.
Jarolimek, A., relation between pres-
sure and temperature in the saturated
vapour of water and carbonic anhy-
dride, 417.
■ relation between the tension and
temperature of saturated vapours,
951.
Ja y n e, H. W., phenylbutyrolactone and
phenylparaconic acid, 472.
Jayne. See also Fittig.
Jensen, J. L., cure for potato disease,
233.
Jorgensen, S. M., chemistry of the
chromammonium compounds, 554.
contributions to the chemistry of
the rhodammonium compounds, 1058.
Joffre, J., new method of detecting
dyes on yarns or tissues, 523.
V. John. See Teller.
Johnson, G-., picric acid as a test for
albumin and sugar in urine, 1176.
Johnson, G-. S., action of potash on
albumin, 674.
Joly, N., glairin or baregin, 302.
Joubert, J., method of determining
the Ohm, 4.
Joulie. See Kuhn.
J our dan, F., decomposition of benzil
by potassium cyanide, 805.
Jordan, W. H., action of manures on
the quantity and quality of a wheat
crop, 681.
Jiiptner, H. v., Haswell's method for
the volumetric estimation of mercury,
242.
K.
Kachler, J., and F. V. Spitzer, action
of nitric acid on hydroxycamphor
from /3-dibromocamphor, 215.
action of sodium on camphor,
1006.
bromodinitro-methane, 961.
hydroxycamphor from /3-di-
bromocamphor, 1008.
mode of formation of the
isomeric dibromocamphors, 1007.
reaction of the two isomeric
dibromocamphors with nitric acid,
1008.
Kalckhoff, F. A., amidophenols, 734,
1109.
Kanonnikoff, J,, refractive power of
organic compounds in solution, 1041.
Kappel, S., formation of ozone and
hydrogen peroxide, 282,
nitrification in presence of copper
and other metals, 286.
Kauffmann, G., /3-naphthacoumarin,
1136.
Kelbe, W., action of acid amides on
aromatic amides, 915.
barium paratoluenesulphonate.
807.
displacement of the sulphonic
group by chlorine, 80G.
oxidising action of dilute nitric
acid on metaisobutyltoluene, 796.
Kelbe, W., and J. Lwoff, occurrence
of methyl alcohol in the products
of the dry distillation of colophony,
738.
Ke liner, O., researches on the digesti-
bility of purified lupine seeds by the
horse, and observations on the working
power of the horse when fed with
lupines and oats, 102,
Kenngott, A., analysis of humite,
1068.
calculation of analyses of augites
and amphibolea from Finland, 1C^5.
Kern, artificial digestion of meadow-
hay, 1025.
Kern, E., a new milk ferment, 229.
Kern, S., Russian basic steel, 1036.
Kessler, L., hardening of soft calca-
reous rocks by means of fluosilicates
of soluble bases, 940.
Kienlen, P., extraction of selenium
from a waste product, 16. ■
Kietz, A., researches on digestion in
the stomach, 815.
Kiliani, H., saccharin and saccharic
acid, 565.
saccharone and saccharin, 962.
Kiliani. See also Cuisinier.
Kinch, E., soja bean, 235.
Kissling. See Fleischer.
Kiticsan, S., distillation of wine, 934.
Kit tier, E., electromotive force of a
Daniell's element, 409,
Kjedahl, M. J., invertin, 225.
Klein, C., cryolite, pachnolite, and
thomsenolite, 427.
Klein, D., borotungstates, 23, 786.
modification of the usual state-
ment of the law of isomorphism, 147.
Klepl, A., compound of phenol with
carbonic anhydride, 584.
hydroxybenzoic acid, 664.
preparation of methyl chlorocar-
bonate, 311.
Klinger, H., basic double-salts, 904.
isobenzil, 920.
INDEX OF AUTHORS.
1197
Klinkenberg, W., proportion of
nitrogen in the form of amides, albu-
min, and nucle'in in different feeding
stuffs, 748.
Klingenberg, W., and A. Stutzer,
nuclein, 814.
Klingenberg. See also Stutzer.
Knop, W., analysis of silicates, 379.
percentage of ash in the sugar-
cane, 110.
Knorre, G. v., tungsten compounds,
650.
Knublauch, O., determination of sul-
phur in coal-gas, 382.
Knyrim. See Zimmermann.
Kcch, R,, disinfectants, 249.
Koch, S., wuKenite, 435.
Koch. See also Fischer.
Kochlin, H., fixation of artificial
colouring matters by means of metal-
lic mordants, 256.
gallo-cyanins, 796.
indophenol, 695.
Koechlin. See also He um an n.
Kohne and others, employment of
dried potatoes, 614.
Kohnlein, B., preparation of paraffins,
787.
Konig, A., substitution of hydrogen
peroxide for nitric acid in galvanic
batteries, 765.
Konig, A., and others, researches on
the behaviour of insoluble phosphates
in peaty soils and in dilute solvents,
681.
Konig, G-. A., alaskaite, a new bismuth
mineral, 429.
Konig, J., comparative estimation of
nitrogen in guano, 1030.
cultivation of lupines, 114.
nutritive value of skim milk, 102.
purification of contaminated
vt^aters, 691.
Konigs. See Hoffmann.
Koerner, Q-., caffeic acid from cuprea
bark, 66.
paradipropylbenzene, 321.
Koeth, D. v., culture of various de-
scriptions of sugar beet, 1026.
Kohlrausch, W., electrical conduc-
tivity of silver haloid salts, 769.
specific conductivity of sulphuric
and pyrosulphuric acids, and the
specific gravity of concentrated sul-
phuric acid, 413.
Kolbe, C, brom-addition derivatives
of the crotonic acids and of metb-
aerylic acid, 573.
Kolbe, H., antiseptic properties of
carbonic anhydride, 395.
isatin, 1130.
preparation of pheneto'il, 1113.
VOL. XLIV.
Konowaloff, D., pyrosulphuric chlo-
ride, 553, 782, 900.
Korn, 0., idocrase from Kedabek in
the Caucasus, 1067.
Korschelt, O., Japanese soils — a natu-
ral cement, 131.
Kosmann, minerals from Upper Sile-
sia, 955.
roasting of zinc-blende, 399.
Kossel, A., xanthine and hypoxan-
thine, 924.
Kottman, G-., application of stron-
tium chloride in purifying syrups,
252.
Kraaz. See Tiemann.
Krafft, F., preparation of normal
primary decyl, dodecyl, tetradecyl,
hexdecyl, and octodecyl alcohols,
1075.
Kratschmerand Sztankovanszky,
volumetric estimation of phosphoric
acid, 380.
Krauch, C, effect of water containing
zinc sulphate and common salt on
soils and plants, 1027.
Otto's method for the estimation
of fusel oil in brandy, 123.
poisoning of plants, 612.
Kraut, K., chloride of lime and chlo-
ride of lithia, 17.
Magnesia alba, 153.
Kreis. See R. Meyer.
Krenner, jadeite, 1066.
Kretschy, M., oxidation of kynurine
and kynurenic acid, 674.
Kretzschmar, L., the test for life,
489.
Krouchkoll, variation of the constant
of capillarity of the surfaces, water-
ether, and water-carbon bisulphide,
under the action of electromotive
force, 1047.
Kriiss, G^., and S. OEconomides, re-
lation between the composition of
organic compoimds and their absorp-
tion spectra, 1041.
Krutwig, J., and A. Cocheteux,
estimation of iron by means of per-
manganate, 1168.
Kuckein, F., tissue- waste in the fowl
during starvation, 603.
Kiihn, Or., and others, digestibility of
meadow hay and wheat bran treated
with hot and cold water, 816.
Kiihn, J., examination of ophites from
the Pyrenees, 448.
Pkoma gentiancB, a newly observed
parasitic fungus, 1025.
Kiihn, J., and H. Joulie, diseases of
sugar-beet. 111.
Kiistel, roasting of gold telluride, 691.
Kutscheroff, M. G., action of hydro.
4 I
1198
INDEX OF AUTHORS.
carbons of the acetylene series on
mercuric salts, 172.
Kutzleb, v., researches on the causes
of clover sickness, 233.
Kuzel. See Fischer.
Laar, C, use of diphenylaniine and
aniline in qualitative analysis, 239.
Laatsch, H., ethyiidene oxy chloride,
788.
Lach, B., aldoximes, 1104.
Lachowicz, B., action of the chlorides
of phosphorus on phenanthraqui-
none, 666.
La Coste, "W., bromoquinoline-sulpho-
nic acids, 96.
nitro- and amido-bromoquinoline,
90.
nitroquinolines, 811.
Lacroix, A., melanite from Lantigne
(Eh6ne), 438.
Ladenburg, A., action of methyl
alcohol on piperidine hydrochloride,
1154.
benzene formulae, 51.
constitution of atropine, 670.
hydrotropidine, 1155.
imines, 910.
lecture experiments, 1048.
preparation of chlorhydrins, 1077.
synthesis in the pyridine series,
1151.
synthesis of y- ethyl pyridine, 1151.
Ladureau, A., cultivation of the
sugar-beet, 114.
Lafitte, P. de, and others, on phyl-
loxera, 233.
Lagarde, H., photometric intensity of
the lines of the Jjydrogen spectrum,
537.
Lagarde. See also Thoulet.
Landolf, F., decomposition of a-fluo-
boracetone by water, 655.
Landrin, E., action of different varie-
ties of silica on lime-vrater, 712.
action of water on the lime of
Theil ; existence of a new compound,
" Pouzzo-Portland," 830.
analysis of puzzuolanas, and esti-
mation of their comparative value,
628.
hydraulic silica and its functions
in hydraulic cements, 754.
Landsberg, M., imides of bibasic acids,
475.
Landshoff, L., naphthylaminesul-
phonic acid, 1135.
Langer, C, and V. Meyer, dissocia-
- tion of chlorine and bromine, 546.
Langer, T., amount of carbonic anhy-
dride in beer, 535.
Langsdorff, K. v., fattening calves,
815.
Langley, observations on the solar
spectrum, 137.
Langley, J. N., decomposition of di-
gestive ferments, 815.
Lauberand A. Steinheil, use of soap
in dyeing, 894.
Lawes, J. B., and J. H. Gilbert,
composition of the ash of the entire
animals and of certain separate parts
of some of the animals used as
human food, 1019.
Lebedeff, A., nutrition by fat, 740.
Le Bel, J. A., formation of amyl alco-
hol in alcoholic fermentation, 908.
geometrical formulae of maleic and
fumaric acids, 44.
Le Ch atelier, H., hardening of ce-
ments, 831.
hydraulic silica, 755.
the setting of plaster of Paris,
712.
Le Chatelier. See also Malard.
Le Conte, J., and W. B. Rising,
metalliferous vein formation at Sul-
phur Bank, 1070.
Lecouteaux, E., composition of pig-
dung, 117.
Ledderboge. SeeJacobsen.
Ledebuhr, A., a colour-method for
the estimation of .manganese, 242.
estimation of oxygen and carbon
in iron, 121.
Leeds, A. R., acrolein-ureide and con-
densed ureides, 664.
cryptidine, 669.
insoluble residue from the distil-
lation of castor oil, 655.
oenanthalaniline, oenanthalxylidine,
and cenanthalnaphthylaraine, 659.
Legler, E., a new product of the slow
combustion of ether, 860.
Legler, L., estimation of methaldehyde,
1035.
Legros. See Spring.
Lehniann, V., further contributions
to the distribution and elimination of
lead, 1163.
methods of detecting lead, silver,
and mercury in the body in cases of
poisoning, 687.
Lellmann, E., a case of physical iso-
merism. 343.
cyanic acid derivatives of the three
isomeric phenylenediamines, 798.
derivatives of diphenyl, 343.
nitro- and amido-derivatives of
benzenesulphonanilide and benzene-
sulphonparatoluide, 800.
INDEX OF AUTHORS.
1199
Lellmann, E., phenylenethiocarba-
mides, 185.
the three isomeric phenylene-
diamines, 334.
Lenne, A., employment of peat as
litter, 238.
Lenz, W., examination of bismuth sub-
nitrate, 382.
Leplay, H., chemistry of the maize
plant, 366, 747.
chemistry of white Silesian beet-
root, 235, 368.
Lescoeur, hydrates of baryta, 1052.
Levy, S., chlorine and bromine deriva-
tives of quinone, 1117.
Le win stein, I., /3-naphtholtrisul-
phonic acid, 737.
Lewis, H. C, substance resembling
dopplerite from a peat bog near
Scranton, 427.
Lewkowitsch, J., Isevorotatory man-
deHc acid, 1124.
separation of inactive mandelic
acid into two optically active iso-
merides, 1124.
Lextreit, strychnine sulphate, 223.
Leydhecker, A., and others, potato-
culture, 114.
Li doff, A., analyses of petroleum-
coke, 408.
Lidoff, A., and W. Tichomiroff,
action of the galvanic current on
chlorates, 149.
Lieben, A., and L. Haitinger, cheli-
donic acid, 870.
Lieben, A., and S. Zeisel, condensa-
tion-products of aldehydes and their
derivatives, 570, 963.
Liebenberg, A. v., part played by
lime in the germination of seeds, 490.
Lieber, K., application of aluminium
palmitate, 405.
Liebermann, C, action of concen-
trated sulphuric acid on dinitro-
anthraquinone, 597.
decomposition of rosaniline by
water, 1097.
Liebermann, C, and ^. Hagen,
action of concentrated sulphuric acid
on dinitroanthraquinone, 72.
action of sulphuric acid on
di- and tri-allylamine, 1086.
derivatives of anthrol salts,
73.
Liebermann, C, and C. Paal, allyl-
amine derivatives, 908.
Liebermann, C, and C. Scheibler,
reduction of saccharin, 1078.
Liebermann, L., detection of sulphur-
ous acid in w4ne, 384.
Liebniann, A., isobutyl- and amyl-
phenols, 59.
Limpach, L., naphtholtrisulphonic
acid, 1136.
Lindgren, W., arsenates from Laang-
ban, 434.
Link. See Roemer.
Lipp, A., phenylglyceric acid, 994.
Lipp. See also Erlenmeyer.
Lippe. SeeClaus.
Lippmann, E., addition of bromine to
ethyl acetoacetate, 177.
diamidocumic acid, 194.
Lippmann, E., and F. Fleissner,
azylines, 55, 184, 868, 1100.
Lippmann, E. O. v., occurrence of
a new acid in beet- juice, 913.
occurrence of conifem in the
woody structure of the beet-root,
611.
Livache, A., action of certain metals
on oils, 756.
Liveing, G. D., and J. Dewar, an
arrangement of the electric arc for the
study of radiation of vapours, 262.
disappearance of some spec-
tral lines and the variation of metallic
spectra due to mixed vapours, 2.
note on the absorption of
ultra-violet rays by various sub-
stances, 837.
order of reversibility of
lithium lines, 839.
origin of the hydrocarbon
flame spectrum, 641.
reversal of hydrogen lines,
838.
spectra of carbon and
compounds, 1, 261.
spectrum of carbon, 1.
spectrum of water, 140.
the ultra-violet spectra
elements, 262.
Ljubavin, N., action of ammonium
cyanate on glyoxal, 178.
Loew, 0., chemical character of living
protoplasm, 819.
Loew, O., and T. Bokorny, employ-
ment of magenta with sulphurous
anhydride as a microchemical test for
aldehyde, 829.
Loew, O., and others, changes occur-
ring in preserved milk, 634.
Loewe, J., adulteration of cochineal,
408.
storage of oxygen in zinc gas-
holders, 619.
Loges, Gt., estimation of humus in soils,
247, 830.
Lommel, E., fluorescence of iodine
vapoiu*, 763.
Longi, A., iodide of argentamnionium,
1052.
testing for hydrocyanic, hydro-
4 i 2
its
of
1200
INDEX OP AUTHORS.
chloric, hydrobromic, hydriodic,
chloric, bromic, iodic, hydroferro-
cyanic and hydroferricyanic acids,
1172.
Lorenzen, J., minerals in the sodalite
syenite of S. Greenland, 960,
Losanitsch, S. M., action of iodine on
mono- and di-nitrodiphenylthiocar-
bamide, 582.
formation of dibromodinitro-
methane and of Villiers's tetranitro-
ethylene bromide, 564t.
Los sen, W., specific volumes of liquids,
13.
Louise, E., action of anhydrous alumi-
nium chloride on acetone, 176.
a new hydrocarbon, 323.
benzoylmesitylene, 577.
Lubisch, T., toughened glass, 399.
Ludwig, E., chemical composition of
epidote, 443.
danburite from the Siopi in Gran-
biindten, 437.
Ludiwg. See also Tiemann.
Luedecke, O., tinder ore from the
Harz, 1061.
Lunge, G-., determination of caustic
alkalis in presence of the carbonates,
828.
recent progress in the soda indus-
try, 524.
Lunge, G., and P. Naef, bleaching
powder and analogous compounds,
953.
Lunge, G., and R. Schoch, calcium
hypoiodite, 17.
Lustgarten, L., detection of iodoform,
naphthol, and chloroform, 243.
Luxardo, O., existence of basic sub-
stances in maize, 1156.
Lwoff. See Kelbe.
M.
Mabery. See Hill.
Macaluso, D., and G. Grimaldi,
influence of hygroscopic condensation
in glass vessels on the determination
of the density of aqueous vapour,
507.
Macarthur, R., determination of zinc
as sulphide, 828.
McCallum, H., Camellia oleifera
seeds, 1166.
McCay, L. W., new volumetric method
for the estimation of arsenic, 1034.
water analysis, 829.
Mach, E., and C. Portele, amount of
extract in Tyrolese wines, 245.
McMunn, C. A., colouring-matter of
bile of invertebratcB and vertebrates,
and unusual urine pigments, 1159.
Macpherson, J., occurrence of aere-
nite, 562.
Mahly. See Friedlander.
Marcker, M., decomposition of dif-
fusion residues from beet-root, 1025.
manuring Alpine meadows, 238.
manuring with sulphuric acid, 681.
Magnanimi. See Scichilone.
Mainzer, K., products of the flecom-
position of mixed aromatic thiocar-
bamides by acids, 1106.
Malenfant, alteration of syrup of
tolu, 407.
Mallard and Le Chatelier, combus-
tion of gaseous mixtures, 844.
momentary pressures pro-
duced during the combustion
gaseous mixtures, 542.
nature of the vibratory move-
ments which accompany the propaga-
tion of flame in mixtures of combusti-
ble gases, 148.
Mallet, J. W., crystalline form of
sipyUte, 435.
determination of organic matter in
potable water, 1171.
properties of pure aluminium, 151.
Maly, R., and R. Andreasch, caffeine
and theobromine, 1016.
Maly, R., and F. Emich, behaviour of
the bile acids with albumin and
peptones : antiseptic action of the bile
acids, 673.
Maneuvrier. See Jamin.
Mangon, H., the ice plant {M. crystal-
linum), 499.
Mann, P., rutile as a product of the
decomposition of titanite, 33.
Maquenne, L., action of carbonic
oxide on steam, 860.
action of ozone on hydrocarbons,
37.
ammonio-cobalt compounds, 557.
decomposition of formic acid by
the silent discharge, 457.
Maquenne. See also Deherain.
Marachetti, C, picrates of a- and /3-
naphthol, 344.
Marcano, V., direct fermentation of
starch, 365.
Marcus and O. de Co nine k, physio-
logical action of /S-coUidine, 104.
Mareck, G., diffusion of sugar in beet,
124.
Margottet. See Hautef euille.
Marie-Davy, nitrification in the soil,
116.
Markownikoff, W., and W. Oglo-
blin, chlorination of hydrocarbons
from Caucasian petroleum, 564.
INDEX OF AUTHORS.
1201
Marpmann, Q-., progress in the know-
ledge of bacteria, 364.
schizomycetic fermentation, 363.
Marsh, C. W., ammonia process for
water analysis, 514.
Martini, A., and A. Weber, silicates
of the phenols, 983.
Mas si e, F. A., colourless mimetite
from the Richmond mine, 163.
Masure, F., evaporation of water from
the soil, 615.
Matthews, A. E., and W. R. Hodg-
kin son, ethyl acetoacetate, 311.
Maumene, E., chlorine hydrates,
780.
Maumene, E. J., hydrates of baryta,
1052.
oenocyanin, 215.
Mayer, A., action of invertin, 486.
antiseptics, 249.
Mayer, A., and F. Clausnitzer,
analysis of gas-lime, 506.
Mayer, A., and others, the temperature
most favourable to the action of in-
vertin, 101.
Mayer, L., and E. v. Schmid, estima-
of phosphoric acid, 241.
Mayer, L., and O. Wagner, analysis
of bauxite, 888.
Mayrhofer. SeeDonath.
Mazzara, G-., isopropyl-, diisopropyl-,
and dipropyl-metacresols, 463.
Meissen, P., addition-products of some
terpenes, 1140.
Meissl, E., detection of benzoic and
boric acids in milk, 385.
Meissl, E., and F. Bocker, con-
situents of the beans of Sqja hispida,
1024.
Meldola, R., action of dibromonaph-
thol on amines, 536.
rosaniHne colouring matters, 807.
Melikoff, P., addition of hypochlor-
ous acid to j3-crotonic acid, 311.
derivatives of the isomeric crotonic
acids, 969.
Melville, W. H., crystalline form of
tribromacrylic acid, 310.
Menke. SeeJackson.
Menu el, E., meconic acid and some of
its derivatives, 656.
Menschutkin, N., decomposition of
acetanihde by water, 326.
decomposition of tertiary amyl
acetate by heat, 178, 309.
mutual displacement of bases of
neutral salts in homogeneous systems,
550, 708.
V. Mering, does potato-sugar contaLa
any deleterious matter ? 136.
Merz, v., conversion of phenols into
nitrils and carboxylic acids, 802.
Merz, Y., and W. We it h, nitro-deriva-
tives of naphthalene, 343.
Meschtchersky, I., barium com-
pounds of bismuth peroxide, 158.
Mennier, J., action of potassium car-
bonate on benzyl and benzylene chlo-
ride, 59.
Meunier, S., formation of bauxite and
of pisolitic iron-ore, 1065.
lithological determination of the
meteorite of EstherviUe, Emmet Co.,
Iowa, 37.
Meyer, A., gentianosis, 810.
nature of Pringsheim's hypochlorin
crystals, 483.
Meyer, E. v., cyanethine and bases de-
rived from it, 352.
cyanmethine, 653.
Meyer, Gr., aldehydeammoniinn bases,
568, 1090.
some anomalous reactions, 1078.
Meyer, H., electric resistance of psilo-
melane, 701.
— — quantitative estimation of cinchona
alkaloids, 388.
Meyer, H. See also Jacob sen.
Meyer, L., air-baths, 900.
basis of thermochemistry, 773.
formation and decomposition of
acetanilide, 56.
recognition of suint in suet and
other fats, 750.
Meyer, R., benzene formulae, 51.
hydroxylation by direct oxidation,
983, 1072.
microscopic investigation of dyed
cotton fabrics, 751.
Meyer, R., and E. Miiller, synthesis
of cumic acid, 63.
Meyer, R., and H. Kreis, hydroxy-
azo-compounds, 982.
Meyer, V., benzene from various
sources, 315.
coal-tar toluene, 1092.
hydroxylamine hydrochloride, 646*
isonitroso-compounds, 569.
thiophene, a substance contained in
coal-tar benzene, 1091.
— — vapour-density determination,
618.
Meyer, Y., and M. Ceresole, consti-
tution of nitroso-compounds, 572.
Meyer, Y., and E. J. Constam, az-
aurolic acid, 40.
Meyer, Y., and A. Miiller, constitu-
tion of nitrosomalonic acid, 790.
Meyer, Y., and E. Nageli, oxoctenol,
1076.
Y. Meyer. See also G-oldschmidt,
Langer, Treadwell, and Witten-
berg.
Meyer. See also D^herain.
1202
INDEX OP AUTHORS.
Michael, A., synthesis of salicin and of
anhydrosalicylic glucoside, 77.
Michaelis, W., Portland cement and
its adulteration, 530.
Michaelis, A., and L. Czimatis, tri-
methylphosphorbenzobetaine, 55.
Michaelis, A., and L. Q-leichmann,
aromatic isophosphines, 185.
Michaelis, A., and A. Eeese, aroma-
tic arsenic and antimony compounds,
327.
Michaelis, A., and C. Schulte, ar-
senobenzene, arsenonaphthalene, and
phenylcacodyl, 187.
Michel. See Jannettaz,
Michel-Levy, A., micaceous porphy-
rite of Morvan, 447.
Michel-Levy. See also Fou que.
Miller, O., detection of free sulphuric
acid in presence of alxuninium sul-
phate, 1168.
Miller. See also Fluckiger.
V. Miller, W. See Doebner.
Mil lot. A., electrolytic estimation of
zinc, 122.
oxidation products obtained from
carbon by electrolysis, 65.
Mixter, W. G-., Sauer's method of esti-
mating sulphur, 239.
Mohlau, R., acetophenoneanilide, 332.
action of bromacetophenone on
phenol, 332.
azo-colouring substances from di-
phenyldiisoindole, 342.
bromacetophenone, 332.
diphenyldusoindole, 342.
Moissan, H., chromous sulphate, 22.
Moltchanoff sky, N., Klinger's
method of preparing azoxybenzene,
180.
Monckhoven, D. v., influence of tem-
perature on the spectra of non-metals,
140.
widening of the lines in the hydro-
gen spectrum, 139.
Morgen, A., feeding value of fresh and
dried diffusion residue, 680.
Morgen. See also Fleischmann.
Mori, A., the first product of plant-
assimilation, 365.
Moritz, J., freezing of wine, 135.
Mosso. See G-uareschi.
Moulton. See Spottiswoode.
Mousette, fermentation of bread,
1179.
Muel, M. E., manuring forest trees,
617.
Mil Her, A., cleaning of glass labora-
tory vessels, 395.
isonitroso-acids, 1129.
utilisation of butter-milk in bread
making, 1037.
Mil Her, H., contribution to the know-
ledge of the interchange of material
in amylaceous plant organs, 497.
Miiller. See also E. Meyer and V.
Meyer.
Miiller- Erzbach, W., relation of the
heat of combustion of isomeric or-
ganic compounds to their densities,
1044.
specific gravity and chemical affini-
ties of elements in various allotropic
modifications, 779.
Mulder, E., a reaction of the com-
pounds of normal cyanuric acid and
cyanetholine, 305.
■ properties of normal cyanic acid,
304.
synthesis of optically active carbon
compounds, 457.
Mulder, E., and G. Hamburger,
action of sodium ethylate on the
sodium salt of symmetric dibromo-
succinic acid, 312.
estimation of the halogens in
carbon compounds, 379.
Mulder, E., and H. G-. L. van der
Meulen, ozone in presence of pla-
tinum-black, 284.
Munier, J., butter testing, 247.
Miintz, A., estimation of carbon bisul-
phide in thiocarbonates, 935.
Miintz, A., andE. Aubin, atmospheric
nitrification, 233.
estimation of carbonic anliy-
dride in the atmosphere, 121.
Muschketow. See Beck.
Musgrave, R. N., analysis of beauti-
fully crystallised albite, from Ameha
Co., 34.
nitrites in human saliva, 227.
N.
Nachbauer, K., embryos of ungermi-
nated rye, 107.
Naef. See Lunge.
Nageli, E., the hydroxylamine reaction,
728.
Nageli. See also V. Meyer.
Napolitano, M., derivatives of para-
cresolgly collie acid, 1126.
Nasini, R., atomic refraction of sul-
phur, 264.
Natterer, K., ay-dichlorocrotonalde-
hyde, a condensation-product of mono-
chloraldehyde, 964.
Naudin, L., essence of angelica root,
809.
N a w r a t i 1, A., examination of Gralician
petroleum, 533.
i
INDEX OF AUTHORS.
1203
Baylor, W. A. H., bitter principle of
Hymenodictyon excelsum, 1141.
JS"aylor, W. A. H., and J. O. Braith-
waite, test for arsenic, 513.
Nee 8 en, F., specific beat of water,
541.
Nencki, M., and N. Sieber, urorosem,
101.
Nessler, J., and M. Barth, examina-
tion of alcoholic liquors, 518.
Nicol, W. W. J., coefficient of expan-
sion of sodium sulphate solutions, 17.
JNicolajew, D. P., chemical composi-
tion of walujewite, 1068.
Niederist, Q-., trimet by lene glycol and
trimethylene bases, 450.
Niederstadt, meat extract from South.
America, 406.
Nies, F., and A. Winkelmann,
volume change of metals on fusion,
545.
Niessing, C, and others, diseases of
plants and their prevention, 612.
Is iefczki, R., colouring matters of the
safranine series, 731.
' quinones and quinols, 465.
Nikolsky, W., and A. Saytzeff,
hydrocarbon, C12H20, prepared from
allyl dimethyl carbinol, 1074.
JNilson, L. F., crystalline form, specific
heat, and atomicity of thorium, 553.
determination of the equivalent
of thorium, 152.
metallic thorium, 152.
■ specific heat and valency of thorium,
649.
' the thorite of Arendal, 299.
Nishack, methylsulphonic acid, 972.
Noack, E., new method for preparing
carbonic oxide, 574.
phenyl salts of phosphorous acids,
735.
Nobbe. See Dohn.
Noellner, A., some artificial products
from cryolite, 30.
JN^oelting, E., dissociation of trichloro-
methyl sulphochloride, 38.
rosaniline derivatives, 54.
Noelting, E., and R. Bourchart,
action of siilphuric acid on proto-
catechuic acid, 65.
N oelting, E., and E. v. Sails, nitro-
derivatives of the cresols, 59.
Nordstrom, T., silver amalgam from
the Sala mines, 426.
the pyrolusite mines of Bolet, 31.
Norton. See Tcherniac.
Noyes, W. A., oxidation of the nitro-
toluenes by potassium ferricyanide,
577.
Obach, E., purification of carbon bisul-
phide, 43.
Oberbeck, A., electrodynamic inter-
ference of alternating currents, 897.
Obernetter, J. B., silver bromide gela-
tin-emulsion, 395.
CEconomides. See Baeyer and
Kriiss.
Ogier, J., pyrosulphuric chloride, 423,
646.
sulphuric monochloride, 642.
Ogier. See also Berth elot.
Oglobin. See Markownikoff.
Ohlmiiller, W., decrease in weight of
individual organs in children dying
from atrophy, 606.
Oliveri. See :^tard.
Ollech, H. v., estimation of "half-
soluble " phosphoric acid, 508.
Olszewski. See Wroblewski.
Orth, A., mechanical and chemical
analysis of soils, 621.
Ost, H., derivatives of meconic acid
containing nitrogen, and their conver-
sion into pyridine, 791.
Ostwald, W., action of acids on acet-
amide, 575.
manufacture and correction of
burettes, 619.
Oudemans, A. C, laws of the varia-
tion of the specific rotatory power of
alkaloids under the influence of acids,
81.
specific rotatory power of apocin-
chonine and hydrochlorapocinchonine
under the influence of acids, 359.
Paal, C, action of acetic chloride on
benzaldehyde in presence of zinc-dust,
62, 805.
Paal. See also Liebermann.
Pabst, M. A., indophenol, 69.
Pabst. See also Girard.
Page, W. T., metallic iron accompany-
ing native gold in Montgomery Co.,
Virginia, 29.
new sulphide received as tetra-
hedrite, from Great Eastern mine,
Colorado, 161.
Pampe, F., contribution to the pro-
blem of frothy fermentation, 892.
Papasogli. SeeBartoli.
Par men tier, F., a hydrate of molybdic
acid, 158.
Pascher, C, argentine, 405.
1204
INDEX OF AUTHORS.
Paschikis, H., detection of mercury in
animal tissues, 1169.
Pastrovitch, P., coerulignol: Reichen-
bach's oxidising principle, 1005.
Reichenbach's picamar, 1004.
Paternd, E., cymenesulphonic acids,
999.
lapachic acid, 210.
Patrouillard, C, use of oxalic acid as
a test for arsenates in alkaline salts,
243.
Paul, B. H., cinchona bark grown in
Jamaica, 1165.
Paul, G-. A., feeding calves with skim
milk, 615.
Pavel, O., nitrososulphides and nitroso-
cyanides, 297.
Pavy, F. W., physiology of carbo-
hydrates in the animal system, 1160.
Pawlewski, P., determination of
vapour- density, 951.
critical temperature of ethereal
salts, 276.
stability of trimethylcarbinol,
565.
Paw low, W., tetric acid, 730.
Pebal, L., mechanical separation of
minerals, 158.
Pechmann, H. v., synthesis of dihydro-
naphthoic acid, 808.
Pellet, H.,and A. Dabaele, manufac-
ture of sugar without bone-charcoal
or sulphurous anhydride, 835.
Pellet. See also Robinet.
Pellizzari. SeeTommasi.
Pemberton, H., potash alum from
felspar, 424.
working of sulphuric acid chambers,
887.
Penfield, S. L., occurrence and com-
position of some American varieties
of monazite, 162.
" phenylhomoparaconic acid, 473.
Penzoldt, F., and E. Fischer, new
test for aldehydes, 829.
Perkin, Jun., W. H., action of trime-
thylene bromide on ethyl acetoacetate,
benzoylacetate, and malonate, 1083.
Petermann, A., analysis of materials
used in the preparation of composts,
504.
composition of fodders, 111.
manurial value of" dissolved wool,"
500.
Petraczek, J., aldoximes, 569.
Pfaff, F., a new homologue of resor-
cinol, 918.
reduction of substituted phenols,
802.
Pfaundler, L,, explosion of a tube
containing liquid carbonic anhydiide,
422.
Pfaundler, L., explosion of a zinc
gasometer containing oxygen, 524.
Pfeiff er, E., milk analysis, 521.
Pfeiffer, T., artificial and natural
digestion of nitrogenous matter, 227.
Pfeiffer, T., and others, formula of
starch, 307.
Pfordten, O. v. d., estimation of phos-
phoric acid, 121.
reduction of molybdenum com-
pounds, 122.
reduction of tungsten compounds,.
554.
Philip, J., silver hypophosphate^
1052.
Philipp, J., basic potassium berylliumi
oxalate, 1085.
Philipp s, F. C, absorption of metallic-
oxides by plants, 231.
Phillips, S. J., conversion of maltose-
into glucose, 38.
P hip son, T. L., colouring matter
(ruberine) and alkaloid (agarythrine)
in Agaricus ruber, 100.
Piccini, A., oxidation of titanic acid,
1055.
P i c h a r d, P., plastering of wines ; rapid
estimation of cream of tartar, 755.
Pickering, S. U., basic sulphate of
copper, 853,
supersaturation, 645.
testing for barium or sulphuric
acid, 240.
Pieper, R., four metameric benzanis-
ethyl-hydroxylamines, 460.
Pierson, A., and K. Heumann, action
of ethyldichloramine on aromatic-
amines, and on hydrazobenzene, 915.
Piest. See Tiemann.
Pillitz, W., argentous oxide, 288.
Pinard, &., on a bed of coal discovered
in Algiers, and on the layers of white
sand accompanying the same, 160,
Pinner, A., action of acetic anhydride
on the amidines, 1099,
action of hydrocyanic acid and
ethylene cyanide on hydrochloric acid
and alcohol, 731,
condensation of acetone, 1079,
conversion of nitrils into imides,.
731, 1089,
■ ■ derivatives of ethyloiimide and
ethylsuccinimide, 1088,
Piutti, A., phthalj>midobenzoic acid,
999.
Plauchud, reduction of sulphates by
*' sulfuraires " and formation of natu-
ral mineral sulphides, 610.
Plochl, J., constitution of the halogen
cinnamic acids, 194.
Plochl, J., and F. Bliimlein, con-
stitution of benzoylcarbinol, 983,
INDEX OF AUTHORS.
1205
Plosz, p., new crystalline colouring
matter in urine, 814.
Precht. SeeWittjen.
Preece, W. H., effects of temperature
on the electromotive force and resist-
ance of batteries, 840.
Preis, K., and B. Raym an, compounds
of tin with bromine, 424.
Pressler. See Schmidt.
Prinz, W., the inclusions in sapphire,
ruby, and spinel, 1062.
Probert, J., and R. W. Soward,
effect of the absorbed gases on the
electrical conductivity of carbon, 769.
Prop per, M., action of nitric acid on
ethyl acetoacetate and chloracetate,
573.
Prudhomme, M., and F. Binder,
cliromic acid and chromates, 22.
Puliti. See Schiff.
Puscher, E., process for rendering
cement and lime less subject to atmo-
spheric influences, 398, 530.
Poehl, A., formation of peptone and
its conversion into albuminoid sub-
stances, 603.
peptone, 926.
putrefaction alkaloids, 1157.
Poetsch, W., action of carbonic oxide
on a mixture of sodium acetate and
sodium isopentylate, 729.
Poleck, T., analysis of a mineral spring
at Salzbrunn, 563.
Porro, B., Italian petroleums, 1180.
Portele. SeeMach.
Potilitzin, A., analysis of waters
accompanying petroleum and of those
ejected by mud-volcanoes, 171.
Poll diet, A. Gr., sugar from the lungs
of phthisical patients, 929.
Power, J. B., excretion of nitrogen
from the skin, 227.
Q.
Quincke, G., electric researches, 945.
Raabe, F. W., direct determination of
the heat of combination of certain
gases, 274.
Radziszewski, B., glyoxaline and its
homologues, 308.
new gloxalines, 1086.
synthesis of oxaline bases, 728.
theory of phosphorescence, 763.
Rammelsberg, C, double chloride of
potassium and thallium, 424.
potassium sesquicarbonate, 646.
thallium and lithium phosphates,
424.
Ransom, F., detection of strontium,.
509.
Ransom. See also Dunstan.
Raoult, F. M., law of freezing of
aqueous solutions of carbon com-
pounds, 7, 952.
law of freezing of solvents, 278.
Ra sin ski, F., biuret dicyanamide,,
658.
Rath, G-. v., iron glance and augite
from Ascension, 436.
Raumer. See Hornberger.
Raydt, W., liquid carbonic anhydride
as a fire extinguisher, 408.
Rayman. See Preis.
Reboul, E., action of triethylamine on.
symmetrical trichlorhydrin, and on
the two dichloropropylenes, 307.
Reese. See Michaelis.
Reformatsky, S., hydrocarbon, CioHjg,
prepared from allyl dipropyl carbinol,
1073.
Reibenschuh, A. F., methylbiguanide
and its compounds, 974.
Reimer. SeeJacobsen.
Reinders, Or., manuring experiments^
in Holland, 617.
Reinhardt, H., and W. Staedel,
methylation and ethylation of aniline
and toluidine, 578.
Reinitzer. See Gintl.
Reinke, J., autoxidation in plant ceUs,.
819.
easily oxidisable constituents of
plants, 880.
Reisenegger, H., compounds of the-
hydrazines with the ketones, 798.
Reiset, J., blue milk, 742.
exhalation of nitrogen gas during
the respiration of animals, 675.
Remont, A., estimation of salicylic
acid in milk and butter, 522.
rapid method of estimating salicylic
acid in wines, 245.
Reychler, A., silver nitrate and am-
monia, 902.
Renard, A., garnet and amphibole
rocks of the Bastogne region, 958.
monazite and zircon from the-
quarries of Nil-St. Vincent, 561.
products of the distillation of colo-
phony, 699.
Renouard, A., cotton cake. 111.
Renouf, E., derivatives of triphenyl-
methane, 981.
Renter, A., action of zinc chloride on
camphor, 810.
1206
INDEX OF AUTHORS.
Reynier, E., observations on TrouTe's
paper on the bichromate battery,
700.
Reynolds, J. E., comparative effect of
two raetameric bodies on the growth
of Nicotiana longijiora^ 495.
Rhoussopoulos, O., action of chlo-
roform and iodoform on quinoline, 600.
methylenediquinoil hydrochloride,
1150.
quinoline derivatives, 96.
Riban, J., conversion of tricalcium
phosphate into chlorine compounds
of phosphorus, 287.
Ricciardi, L., composition of the ban-
ana at different stages of maturity, 231.
composition of various layers of a
lava current from Etna, 36.
Richet. SeeEtard.
Richter, A. R., thymol derivatives,
1112.
Richter, V. v., cinnoline-derivatives,
1105.
Riedel, C, quinoline- and pyridine-
carboxylic acids, 1152.
Riemann. See Glaus.
Riemerschmied, C, /8-hydroxyquino-
line, 1147.
Riemerschmied. See also Fischer.
Riess, P., electric shadows, 416.
Riffard, E., artificial manuring of
sugar-canes, 506.
Rinicker and Dossekel, hailstorms,
and their origin, 234.
Rimpau, W., and others, sugar-beet
culture, 114.
Rinman, L., composition of fir-wood
charcoal, 533.
Rising. See Le Conte.
Ritthausen, H., albuminoids in peach-
kernels and sesame-cake, 360.
behaviour of conglutin from lu-
pines towards saline solutions, 360.
legumin, 675.
skim milk as food, 102.
Riviere, C, law of cooling, 144.
Robinet, C, derivatives of mesitylene,
577.
Robinet and Colson, mesitylene,
1095.
Robinet, E.,and H. Pellet, antiseptic
action of salicyUc acid, 128.
Rocholl, H., estimation of sulphur in
pig-iron, 512.
Rodatz, P., brominated azobonzenedi-
sulphonic acids, 478.
' constitution of some azobenzene-
disulphonic acids, 477.
Roeder. See Fittig.
Rohrmann, F., observations on a dog
with biliary fistula, 818.
E-oemer, H., dinitroanthraquinone and
diorthamidoanthraquinone ; a new
method of preparing anthrarufin,
737.
Boemer, H., new nitro- and amido-
anthraquinone, 71.
reduction in the anthracene series,
1137.
Roemer, H., and W. Link, amido-
methylanthranol, 1137.
nitro-, amido-, and hydroxy-
methylanthraquinones, 1138.
Roessler's method for the separation
of gold, silver, lead, and copper from
sulphides by air-blast, 400.
Rohart, new properties of ferric sul-
phate, 1178.
Rohrbach, C, appUcation of a solu-
tion of barium mercury iodide to
petrological purposes, 1060.
Romanese. See Bellati.
Romanis, N., water of Rangoon, 128.
analysis of tobacco ash, 372.
Romburgh, P. v., action of benzoic
anhydride on epichlorhydrin, 62.
action of benzoic anhydride on
monochloracetone and on pyruvyl
benzoate, 63.
conversion of organic chloridet*
into iodides by means of calcium
iodide, 303.
isomeric monochlorallyl iodides,
449.
Roser, W., xeronic and pyrocinchonic
acids, 98.
R other, R., ferrous citrate and its
double and secondary salts, 458.
Rumpf, J., analysis of miargyrite
from Pribram, 428.
RunebergjJ. W., filtration of albumin
solutions through animal membranes,
1160.
Russo. See Weidel.
Ruttgenbach, separation of minerals
af;coi*ding to the degree of cohesion,
858.
s.
Sabatier, P., compounds of silicon
with sulphur, 15.
Sachtleben. See Fleischmann.
Sadtler, B., minerals from Fritz
Island, Pennsylvania, 441.
St. Martin, L. Q-. de, special form of
gasometer, 847.
S a if eld, A., comparative manuring
experiments, 116.
V. Salis. SeeNoelting.
Salkowski, E. and H., putrefaction
alkaloids, 925, 1159.
INDEX OF AUTHORS.
1207
Salomon, F., estimation of rice starch,
124.
Salomon, G^., paraxanthine, a new
constituent of human urine, 601.
Salzer, L., purification of alcohol pre-
pared from molasses or beet-root, 630.
Samonoff, N., azoxylene, 180.
Sandberger, F., rutile in phlogopite,
34.
Sanger. See Hill.
Sarasin. See Friedel and Soret.
Saytzeff. See Nikolsky.
Scacchi, A., new sublimates from the
crater of Vesuvius, 1064.
Schaal, E., injurious action of a cu-
priferous oil used in Turkey-red dye-
ing, 256.
Schaeppi, H., recovery of sulphur by
Mond's process, 129.
Schall, C, action of iodine on sodium
phenate, 1109.
■ diiodophenol, 1109.
Seharitzer, R., idrialite, 427.
Schatz, F., oiling and the operations
connected therewith in Turkey-red
dyeing, 635.
Scheffer, J. D. R., diffusion of some
organic and inorganic compounds,
1047.
Scheerer, analysis of the Mansfeld
copper slate, 1069.
Scheibe, E., separation of morphia in
chemico-legal investigations, 1036.
Scheibler, C, recovery of sugar from
molasses by means of strontium hy-
droxide, 252, 536.
Scheibler. See also Liebermann.
Schepper, H. Y. de, and A. Q-eibel,
examination of fat, 125.
Schertel, A., volume- weight of sul-
phuric acid, 288.
Scheurer-Kestner, A,, formation of
nitrous acid in the evaporation of
water, 850.
note on the soda industry, 887.
Schiff, H., aldehydic nature of oxida-
tion-products of terebene, 1141.
glucosides, 347.
methylarbutin, 60.
protocatechutannic acid and anhy-
drides of aromatic hydroxycarboxylic
acids, 335.
Schiff, R., constant of capillarity of
liquids at their boiling points, 549.
■ molecular volume of Hquid sub-
stances, 1044.
Schiff, R., and J. Puliti, introduc-
tion of hydrocarbon radicles into the
pyridene group, 1151.
Schlagdenhauffen, M., origin of
arsenic and lithium in waters contain-
ing calcium sulphate, 302.
Schlagdenhauffen, M., presence of
arsenic in the waters of Bareges,
302.
Schlagdenhauffen. See also Hec-
kel.
Schmid, H., application of Baeyer's
artificial indigo, 257.
Schmid. See also L. May er.
Schmidt, A., pseudobrookite, 435.
Schmidt, E., action of hydrochloric
acid on caffeine, 873.
action of hydrochloric acid on
xanthine, 871.
occurrence of caffeine, 873.
Schmidt, E., and H. Pressler, theo-
bromine, 872.
Schmidt. See also Benedikt.
Schmiedeberg, O., active principle
of the root of Apocynum cannabinuniy
1141.
decomposition and synthesis in the
animal organism, 361.
oxidations and syntheses in the
animal organism, 361.
Schmitt, C., and C. Hiepe, estima-
tion of fixed organic acids in wine,
384.
Schmitt, E., adulteration of butter,
521.
Schober, J, B., examination of the
ores from Amberger, and of the ac-
companying phosphates, 432.
Schoch. See Lunge.
Schoff, F., reduction of monobrom-
orthonitrophenol, 1109.
Schorlemmer,C.,and T. E. Thorpe,
normal paraffins, 651.
Schott and others, purification of
sugar-beet juice, 136.
Schott en, C., conine, 220.
oxidation of piperidine, 813.
Schottlander, P., gold compounds,
853.
Schramm, C, acetoximie acids, 590.
isonitroso-ketones, 573.
Schramm, J., action of bromine on
aromatic hydrocarbons, 977.
action of sodium on methyl ethyl
ketone, 1079.
diethyl ketone, 1080.
position of thallium in the che-
mical system, and its presence in
sylvin, 954.
Schrauf, A., the so-called liebigite
from Joachimsthal, 955.
Schrauf, A., and others, danburite
from Switzerland, 956.
Schrodt, M., and others, on milk,
254.
Schroder, H., boiling points of the
corresponding ketones, ethereal salts>
and chloranhydrides, 990.
1208
INDEX OF AUTHORS.
Schroder, H., constitution of liquid
compounds, 422.
dependence of molecular refraction
of liquid carbon compounds on their
chemical constitution, 538.
Schroder. See also Barth.
Schrotter. See v. Gerichten.
Schubert, B., occurrence of minerals
at Jordansmuhl, in Silesia, 35.
Schubert, S., diisobutylquinol, 60.
S c h ii 1 e r, G-., dihydroxyanthracene
from a-anthraquinonesulphonic acid
(flavol), 74.
Schiitzenberger, P^ and A. Colson,
sihcon, 15.
Schuller, A,, distillation in a vacuum,
545.
Schulte. See Michaelis.
Schulten, A. de, artificial analcime,
34.
artificial production of a crystal-
lised hydrated silicate, 33.
barium potassium phosphate and
barium sodium phosphate, 711.
Schultz. SeeErdmann.
Schulze, B., estimation of sulphuric
acid in presence of alkaline chlorides,
240.
Schulze, E., appendix to the paper on
cholesterin, 586.
extraction of asparagine from
Hquids, 315.
Schulze, E., and J. Barbieri, forma-
tion of phenylamidopropionic acid by
the action of stannous chloride on
albuminoids, 1122.
phenylamidopropionic and
phenylamidovaleric acid from lupine
shoots, 1122.
Schulze, E., and E. Bosshard, glu-
tamine, 658.
Schulze, F., and others, cultivation of
potatoes, 680.
Schulze, H., antimonious sulphide in
aqueous solution, 784.
arsenious sulphide in aqueous solu-
tion, 295.
phosphorus subsulphide, 1049.
Schulze, J., preparation of acetamide
and other amides of the acetic series,
1088.
preparation of ammonium thio-
cyanate, 1074.
Schulze. See also Wallach.
Schutte, C, phenylarsine sulphides,
186.
Schwarz, H., lecture experiment illus-
trating the combination of zinc with
sulphur, 292.
modification of v. Meyer's vapour-
density apparatus, 899.
a-, /3-, and y-pyrocresoles, 204.
S eh web el, P., specific rotatory power
of salts of nicotine, 354.
Scichilone, S., allyloxybenzoic acids,
335.
Scichilone, S., and A. Denaro, man-
nitine, a new alkaloid from mannitol,
50.
Scichilone, S., and v. Magnanimi,
distillation of strychnine with zinc-
dust, 99.
Scott. SeeDewar.
Scrivanow's chloride of silver ele-
ment, 840.
Seamon, W. H., alloys of gold, silver,
kc, found in grains along with the
native platinum of Columbia, 160.
analysis of a mineral allied ta
orthite, 164.
analysis of a niobate which haa
been improperly called euxenite, from
Mitchell Co., N. Carohna, 32.
fergusonite from Brindletown,
Burke Co., N. Carolina, 32.
native palladium-gold from Ta-
guaril, Brazil, 160.
supposed meteorite found in Au-
gusta Co., Yirginia, 37.
See gen, J., peptone the source of sugar
in the liver, 818.
S e g e r, H., analysis of clay from Lothain,
627.
Sell, W. T., series of salts containing
chromium and urea, 178.
Semmola, E., new experiment in elec-
trolysis, 540.
Senderens. See Filhol.
Sestini, F., preparation of . thiocar-
bonates for the destruction of phyl-
loxera, 405.
Seyda, A., sulphonic acids of quinol,
1115.
Shenstone, W. A., Jafferabad aloes,
480.
Shepherd, H. H. B., determination of
nitrogen in mixtures containing nitro-
genous organic matter, ammoniacal
salts, and nitrates, 685.
Shepard, C. U., two new minerals,
monetite and monite, with a notice of
pyroclasite, 1063.
Short. SeeDunstan.
Sidersky, D., separation of strontium
and calcium, 508.
Sieber. SeeNencki.
Siemens, W., luminosity of flame,
539.
Siewert, M., oxalic acid in potatoes
and in malt, 232.
Silberstein, H., diazo-derivatives of
symmetrical tribromaniline, 660.
Silliman, B., martite of the Cerro de
Mercado, or Iron Mountain of Du-
INDEX OF AUTHORS.
1209
rango, Mexico, and iron ores of
Sinaloa, 162.
Silliman, B., turquoise of New Mexico,
431.
Simand, F., estimation of tannin,
391.
Sipocz,
440.
Sjogren
L., analyses of scapolite,
H., composition of minerals
of the chrondrodite group, 436.
Skraup, Z. H., synthetic researches in
the quinoline series, 92.
Skraup, Z. H,, and A. Cobenzl, a-
and /3-naphthoquinoline, 1010,
Skraup, Z. H,, and G-. Vortmann,
dipyridyl-derivatives, 85.
Smith, J. L,, and others, hiddenite, an
emerald-green variety of spodumene,
440.
Solthien, separation of silver from
alloys, 243.
Sommerlad, H., basalt rocks contain-
ing hornblende, 169.
Sonden, K., analysis of petalite from
Uto, 440.
modification of Scheibler's azo-
tometer, 508.
Soret, J. L., and E, Sarasin, circular
polarisation of quartz, 140.
Soward. See Probert.
Soxhlet, F., and A. Behr, manufac-
ture of starch-sugar, 39.
Spalteholz, W., colouring-matter
from coal-tar quinoline, 1150.
Spezia, G-., beryl from Craveggia, Pied-
mont, 958.
the gneiss of Beura, 960.
Spica, P., a metacymene and a new
isomeride of thymol, 459.
camphor-cymene and the so-called
second sulphonic acid of paracymene,
320.
Spica, Gl-., psoromie acid, a new acid
extracted from Psoroma crassum, 80.
Spica. See also Canzoneri.
Spiegel, A., euxanthic acid, 219.
Spindle r. P., nitration of benzene-
derivatives, 975.
Spitzer, See Kachler.
Spottiswoode, W., and J. F.Moul-
ton, movement of gas in vacuum dis-
charges, 5.
Spring, W., coUo'idal copper sulphide,
904.
expansion of isomorphous salts,
146.
formation of arsenides by pressure,
650.
formation of sulphides by pressure,
904.
Spring, W., and E. Legros, alkyl-
thiosulphuric acids, 47.
Spring, W., and C. Winssinger, ac-
tion of chlorine on sulpho-derivatives
of organic oxysulpliides, 659.
Staedel, W., action of nitric acid on
phenols, 861.
aromatic ketones, 990.
bromacetophenone and acetophe-
none derivatives, 586.
bromonitro- and bromamido-ani-
soils and phenetoils, 662.
ethyl amidocresols, 866.
hydrobromides and hydriodides of
aromatic bases, 578.
nitrocresols, 662.
nitrophenols and nitrocresols, 864.
relation between boiling points
and specific volumes, 302.
substitution-products of ethereal
derivatives of phenols, 662.
the history of the metanitriles,
323.
Staedel, W., and others, new ethereal
derivatives of phenols, 585.
Staedel. Seealsov. Baur and Rein-
hardt. *
Stanford, E. C. C, new substance ob-
tained from some of the commoner
species of marine algae, 943.
Stapleton, J., preparation of alkaline
potassium permanganate solution for
water analysis, 516.
Starkl, Q-., bole from Steinkirchen, near
Budweis, in Bohemia, 444.
polyhydrite from St. Cristoph
Mine, Breitenbrunn, in Saxony, 444.
Stead, J. E., chemistry of the Bessemer
converter, 832.
new method of estimating carbon
in iron and steel : a new form of
chromometer, 1032.
Stein, Q-. E., the metaphyres of the
Little Carpathians, 447.
Steiner, A., conversion of fulminates
into hydroxylamine, 1074.
Steinheil. See Lauber.
Stellway, A., rise of temperature in-
duced in soils by the condensation of
liquid and gaseous water, and of gases,
615.
Stelzner, A., melilite and melilite
basalts, 719.
Stengel, F., dialkyldisulphobenzoates,
999.
Step h an, C, fluidity and galvanic
conductivity, 769.
Stephan. See also Tiemann.
Steudemann, H., metanitrophenyl-
thiocarbimide, 801.
Stoddard, J. T., flashing point of
petroleum, 383, 517.
Stoltler, L., crystals in cementation
steel, 629.
1210
INDEX OF AUTHORS.
S torch, L., precipitation of iron by
hydrogen sulphide, 1169.
solubility of metallic sulphides in
thio-acids, 1169.
Strebel and others, cultivation of
cereals, 612.
Sfcrecker, K., specific heat of gaseous
compounds of chlorine, bromine, and
iodine with one another, and with
hydrogen, 417.
Streintz, F., galvanic polarisation,
410.
Struve, H., dialysis of putrescible sub-
stances, 1176.
milk, 1174.
Stumpf, alteration in the secretion of
milk under the influence of drugs,
818.
amount of gluten in starch, 236.
Stutzer, A., occurrence of nuclein in
moulds and in yeast, 1166.
Stutzer, A., and W. Klingenberg,
decomposition of nitrogenous animal
manures, 615.
Stutzer. See also Klingenberg.
Siissenguth, H., monobromopseudo-
cumic acid and dibromomesitylenic
acid, 469.
Sutton, F., hay and ensilage from a
poor quahty of grass, 1026.
Szabd, J., garnet and cordierite in the
trachytes of Hungary, 166.
Sztankovanszky. SeeKratsohmer.
S warts, T., contributions to the history
of the isomerism of the dibromo-
camphors, 214.
T.
Tamm, A., analysis of iron, 510.
Tan ret, caffeine, 97.
Tappeiner, H., comparative investiga-
tion of intestinal gases, 928.
fermentation of cellulose, 1077.
marsh-gas fermentation in the mud
of ditches, swamps, and sewers, 1177.
Taquet, C, chromic selenite, 717.
Tauber, E., estimation of phosphorus
by the molybdate method, 750.
Taylor, J., preparation of hydrogen
sulphide from coal-gas, 824.
Taylor, I., Rupert's drops, 422.
Tcherniac, J., and R. Hellon, thio-
cyanacetone, 654.
Tcherniac, J., and T. H. Norton,
thiocyanopropimine, 568.
Tcherniac, J., and others, manufac-
ture of thiocyanates, 639.
Tecklenburg, the clay -iron stone of
Rheinhesse, 448.
Teller, F., and C. v. John, dioritic
rocks of Klausen, in the Tyrol, 1069.
Ter-Grigoriantz, hemialbumosuria,
1162.
Terrell, A., mineral water at Mont-
rond (Loire), 1071.
Teuchert, irrigation of meadows by
waste water from beet-sugar factories,
500.
Thalen, T., spectral researches on
scandium, ytterbium, erbium, and
thuhum, 954.
Than, C. v., examination of illumi-
nating gas, 629.
Thenard, P., black phosphorus, 150.
Thomas, C, examination of wine
coloured by aromatic sulphonic deri-
vatives, 625.
Thomas, N. W., and E. F. Smith,
electrolysis of bismuth solutions, 1034.
Thompson, C, hthium citrate, 1086.
Thompson, C. M., metazophenyl-
glyoxylic acid, 998.
Thomsen, J., heat of formation of
carbon tetrachloride and ethylene per-
chloride, 544.
heat of formation of the chlorides
and oxides of antimony and bismuth,
544.
heat of formation of the chlorides
of phosphorus and arsenic, 544.
hydrogen gold chloride, 1054.
method of estimating the heat of
formation of difficultly combustible
volatile carbon-compounds, .543.
thermochemical investigation of
the chlorides of iodine, 543. .
thermochemical investigation on
the chlorides of sulphxir, selenium,
and tellurium, 543.
Thomson, R. T., litmus, methyl-
orange, phenacetolin, and phenol-
phthale'm as indicators, 682, 824.
use of rosoHc acid as indicator ;
additional notes on phenolpbthalem
and methyl-orange, 827.
Thoulet and Lagarde, specific heats
of small quantities of substances, 6.
Thresh, J. C, the Orchard alum spring,
171.
T hum en, F. v., and others, vine dis-
eases, 110.
Tichborne, C. R. C, new form of
apparatus for estimating ammonia in
potable waters, 382.
preparation of a volumetric solu-
tion for determining the hardness of
water, 516.
Tichomiroff. See Lidoff.
Tiemann, F., a-phenamidoisobutyric
acid and its amide and nitril, 199.
triphenyl orthoformate, 340.
INDEX OF AUTHORS.
1211
Tiemann, F., and R. Kraaz, constitu-
tion of eugenol, 200.
derivatives of homoferulic
acid, 198.
Tiemann, F., and R. Ludwig, iso-
metric nitrobenzaldehydes, 586.
metahydroxybenzaldehyde
and some of its derivatives, 188.
Tiemann, F., and K. Piest, phenyl-
phenamidoacetic acid, and its amide
and nitril, 198.
Tiemann, F., and R. Stephan,
nitrils of a-phenamido-, a-paraiolu-
amido-, and a-orthotoluamido- pro-
pionic acids, and their amides and
nitrils, 199.
Tiemann, F., and W. Will, constitu-
tion of aesculetin, 199.
Tilden, W. A., hydrocarbons of the
formula (C5H8)„, 75.
Timiriazeff, C, chlorophyll and the
distribution of energy in the solar
spectrum, 697.
Tobias, Gr., behaviour of alkaline phos-
phates to various indicators, 380.
formanilide and its homologues,
325.
formation of anilides, 325.
To bin, T. W., explosive and dangerous
dusts, 836.
Tobisch, influence exerted by the
weight of potato sets, 236.
Tornebohm, A. E., occurrence of iron-
ores at Taberg, in Smaaland, 429.
To liens, B., ammoniacal silver solu-
tion as reagent for f ormaldeliyde, 125.
Tommasi, D., action of aluminium on
cupric chloride, 19.
action of light on silver bromide,
3.
electrolysis of hydrochloric acid,
142.
ferric hydrates, 24.
heat of combination of glycoUates,
775.
heat of formation of glycollates,
708.
laws of thermal constants of sub-
stitution, 143.
nascent hydrogen, 7.
stability of cupric hydroxide 19.
zinc-carbon couples in electrolysis,
4.
Tommasi, D., and G-. Pellizzari,
change which ferric hydrate under-
goes after a time, 24.
Topsoe, H., estimation of chlorides,
bromides, and iodides in presence of
sulphuretted hydrogen, 508.
Tosse. See Claiis.
Traub, M. C, action of phthalic anhy-
dride on quinoline, 667.
Traube, J., action of cyanogen chloride
on amido-acids, 192.
contributions to the knowledge of
meta-uramidobenzoic acid and carba.
midodibenzoic acid, 194.
Traube, M., a correction, 709.
action of nascent hydrogen on
oxygen gas, 900.
action of platinum and palladium
on carbonic oxide and hydrogen, 422^
activity of oxygen, 282.
oxidation of carbonic oxide by
palladium hydride and oxygen, 150,
Tread well, F. P., and V. Meyer,.
molecular weight of isoindole, 665.
Treadwell, F. P., and B. Westen-
berger, nitrosoketones, 572.
Trechmann, C. O., epistilbite, 442.
Treves, prevention of boiler explosions,.
250, 835.
Troost, L., boiling point of selenium^
17.
Trouve, modification of the bichromate
battery, 700.
reply to the observations of Reynier
on bichromate batteries, 765.
Trzcinski, W., action of dibrorao-
barbituric acid on thiocarbamide and
thiocyanates, 913.
Tsehirch, A., microchemical reaction
methods, 376.
Tschuschke, A., manuring sugar-
beet, 823.
Tyndall, J., unobserved resemblance
between carbonic anhydride and
carbon bisulphide, 1049.
Typke, P. Gr. W., nitro-derivatives of
resorcinol, 917.
u.
Ullik, F., nitrogenous constituents of
malt, wort, beer, and bread, 821.
Ungern Sternberg, T. v., the Rapa-
kiwi granite from Finland, 447.
Urech, F., influence of mass and time
on the inversion of sugar, 306-
effect of temperature and concen-
tration of acid on the rate of inversion
of saccharose, 1077.
rapidity of separation of cuprous
oxide by the action of invert-sugar on
Fehling's solution, 385.
strobometric determination of the
rate of inversion of cane-sugar, and
transition of the birotation of milk-
sugar to its normal rotation, 174.
Urech. See also Hell.
1212
INDEX OF AUTHORS.
Tan der Meulen. See Mulder.
Venator, E., strontianite in West-
phalia, 431.
Vergeraud. See Cros.
Verneuil, nitrogen selenide, 423.
Vie ill e, measurement of pressures
developed in closed vessels by the ex-
plosion of gaseous mixtures, 542.
specific heats of gases at high tem-
peratures, 771, 898.
Vieille. See also Berthelot.
Vieth, P., and others, cheese, oleomar-
gin-cheese, &c., 256.
Violle, J., apparatus for the deter-
mination of specific heats by cooling,
6.
radiation from silver at the soli-
difying point, 771.
Vogel, A., estimation of the fertility of
a soil, 517.
Vogel, H. W., Lockyer's dissociation
theory, 762.
modification of silver bromide and
chloride, 936.
Vogler, C. A., variations of the amount
of oxygen in the atmosphere, 284,
551.
Vortmann, Or., cobalt sulphate, 25.
cobaltamine compounds, 25.
• direct estimation of chlorine in
presence of bromine and iodine, 119.
separation of nickel from cobalt,
621.
Vortmann. See also Skraup.
Voswinckel, H., new derivatives of
salicylaldehyde, 189.
Tries, H. de, function of resins in
plants, 365.
w.
Waage, A., action of ammonia on pro-
paldehyde, 39.
Wachtel, &., utilisation of the nitrogen
compounds from the manufacture of
sulphuric acid, 130.
Wachter, H., analysis of Markgrafler
of difierent districts and vintages,
631.
Wachter, F., particles of matter in the
electric spark, 415.
Wagener, Q-., glass enamels, porcelain,
and refractory clays, 397.
Wagner, A., oxygen prepared from
potassium chlorate, 281.
Wagner, F., influence of organic
manures on the temperatxire of the
soil, 821.
Wagner, P., influence of the state of
division of manures on their action,
117.
Wagner. See also L. Mayer.
W alb roth, K. A., action of micro-
cosmic salt on various oxides, 850.
Walder, H., ^S-dinaphthol, 208.
a-/3-hydroxynaphthobenzoic acid,
666.
Wallace, W., decay of building stones,
1036.
insensibility arising from a defi-
ciency of oxygen in the air, 819.
Wallach, O., action of phosphorus
pentachloride on acid amides, 48.
conversion of tolyldiamine into an
amidocresol and y-orcinol, 329.
new azo- and diazo-compounds,
584.
metanitrUes, 577.
oxaline and gloxalines, 910.
Wallach, O., and E. Schulze, azo-
and diazo-derivatives of phenylenedi-
amine, 583.
Wallach, O.andM. Wiisten, reaction
of aromatic amines with lactic acid,
1096.
Walther, F., experiments on the value
of various fodders for cows, 820.
Waltz, G., ethylic propyl- and isopro-
pylethenyltricarboxylates, 46.
Warden, C. J. H., ash of Pistia
straUotes or "pana salt," 822.
Warington, E.., nitrif action of soils,
115.
Wart ha, V., estimation of sulphurous
acid in wine, 621.
Wassilieff, N, P., influence of calomel
on fermentation and the life of micro-
organisms, 743.
Wasum, A., influence of sulphur and
copper on steel, 404.
Weber, A., calcium chloride, 151.
Weber. See also Martini.
Weddige, A., tribasic nitrophenyl
orthoformate, 340.
Wegscheider, B.., derivatives of
opianic acid, 996.
isovamUin, 190.
Wegscheider. See also Q-old-
schmidt.
Wehmer, J., preparation of pressed
yeast, 692.
Weidel, H., and K. Hazara, cin-
chonine, 222.
Weidel, H., andM. Russo, researches
on pyi'idine, 483.
Weidmann, M., composition and
ripening of Emmenthal cheese, 692.
Weil's method for the determination
of copper, iron, and antimony, 509.
Weinberg. See Friedlander.
INDEX OF AUTHORS.
1213
We is bach, A., brucite, 1061.
mineralogical notes, 432.
Weiske, H., occurrence of crystals of
ammonium magnesium phosphate in
wine, 609.
Weiske, H., and others, composition
and feeding value of Symphytum
asperrimum, 613.
effect of food on sheep of
different breeds, 226.
Weith. See Merz.
Wei don, W., manufacture of sodium
sulphide, 627.
We Her, A., a higher oxide of titanium,
295.
detection and estimation of tita-
nium, 381.
ethylnitraniline, 579.
phenacylethylanilide, 582.
Wengell, W. T., preparation of phos-
phoric acid by the oxidation of phos-
phorus with air in presence of mois-
ture, 1050.
Werner, H., the thiocyanate reaction
for iron, 510.
We sen do nek, K., spectra of carbon
compounds, 761.
Westenberger. See Treadwell.
Weyl, T., influence of chemical agents
on the assimilative capacity of green
plants, 611.
Wichelhaus, H., dyestuffs from di-
methylaniline and chloranil, 1098.
Widmann, O., a- and t-dichloro-
naphthalenes, 208.
synthesis of indole from cuminol,
329.
"Wiedemann, E., constitution of hy-
drated salts, 780.
dissociation-heat of the water-mole-
cule and the electric luminosity of
gases, 547.
molecular refraction, 762.
thermochemical researches, 704.
Wiegand, E., estimation of titanic
acid in presence of iron, 381.
Wiegand. See also Beilstein.
Wieland, J., alkalimetric indicators,
1167.
Wierss. SeeJacobsen.
Wiesner, uranyl potassium chromate,
425.
Wiik, F. J., emerald from Paavo in
Finland, 561.
relation between the optical pro-
perties and chemical composition of
pyroxene and amphibole, 560.
the so-called ersbyite from Pargas,
561.
Wiley, H. W., estimation of dextrose,
maltose, and dextrin, in starch-sugar,
123.
VOL. XLIV.
Will, H., effect of steeping and drying
on the germination of seeds, 490.
Will, W., and K. Albrecht, diabase
from Weilburg, 959.
Will. See alse Tiemann.
Willgerodt, C, acetone-chloroform,
1079.
bye-products in the preparation of
acetone-chloroform, 177-
conversion of acetone-chloroform
into hydroxyisobutyric acid, 177.
Williams, G-. H., the eruptive rocks
near Try berg in the Black Forest,
723.
Willm, T., chemistry of the platinum
metals, 1057.
magnetic property of platinum ore,
859.
preliminary notice on a substance
obtained from native platinum, 954.
Wilson, W. P., elimination of carbonic
anhydride by plants in absence of
oxygen, 105.
Winkelmann. See Nies.
Winssinger. See Spring.
Win t her. A., process for preparing
orcinol, 893.
Wislicenus, J., methyl-jS-butyl ketone
and its derivatives, 966.
Wispek, P., derivatives of mesitylene,
1095.
Wispek, P., and R. Zuber, action of
allyl chloride on benzene in presence
of aluminium chloride, 977.
Witkowski, A., theory of galvanic
circuits, 948.
Wittenberg, M., and V. Meyer,
benzil, 803.
Wittjen, B., and H. Precht, blue
rock-salt, 1051.
Wittmack, detection of adulteration of
flour with rye-meal, 392.
Wolde, W., rice and earth-nut meal as
food for milch cows, 820.
Wolff, C. H., detection of rosaniline
hydrochloride in wine by means of
stearin, 384.
examination of molasses for dextrin
syrup, 624.
Wolff, L., lactones of normal caproic
acid, 455.
Wo liny, E., effect on the fertihty of
the soil produced by covering it witli
farmyard manure, 237.
influence of climate and weather
on the amount of carbonic anhydride
in air, 614.
influence of the state of aggrega-
tion on the temperature of and moit -
ture in a soil, 500.
Wood, C. H., and E. L. Barret, notes
on cinchona alkaloids, 1018.
4 m
1214
INDEX OF AUTHORS.
Worm-M tiller, estimation of sugar in
urine, 829.
Worm-Muller, and J. Otto, Scliwarz's
process for preparing pure grape-
sugar, 565.
"Worms, R,, constitution of nitro-
naphthols, 69.
Wortmann, J., diastatic ferment of
bacteria, 930.
Wortschach, G., the granite hills of
Konigshein'inOberlausitz, with special
regard to the minerals found therein,
446.
Wright, L. T., colloidal copper sul-
phide, 1054.
Wro blew ski, S,, absorption of gases
by liquids under high pressures, 418.
Wroblewsky, S., and K. Olszewski,
liquefaction of nitrogen and of car-
bonic oxide, 781, 952.
Wusten. See Wallach.
Wurtz, A., quarternary base derived
from hydroxylamine, 923.
Young, S., hegto- and octo-lactones,
445.
peculiar decomposition of the
ethereal salts of substituted aceto-
acetic acids, 456.
Zander, A., specific volumes of aUyl
and propyl compounds, 13.
Zatzek, E., beeswax, 39.
Zecchini, M., compact magnetic iron-
ore from Cogne, Valley of Aosta,
429.
Zeis el, S., colchicine and colchiceme,^
672.
Zeisel. See also Lieben.
Zimmermann, J,, and M. Knyrim,
action of ethyl chloracetate on
primary diamines, 797.
Zincke, T., action of amines on
quinones, 1117.
phenylhydrazine derivatives of the-
quinones, 1135.
Zincke, T., and F. Brauns, action of
amines on quinones, 209.
Zuber. See Wispek,
Zulkowsky, K., analysis of fats, 936,
1036.
Zweif el. P., behaviour of blood when
deprived of oxygen, 818.
scientific basis of antiseptics, and
origin of septic poison, 937.
i
INDEX OF SUBJECTS.
ABSTRACTS. 188 3.
Aerenite, occurrence of, 562.
Absorption, atmospheric, in the infra-
red of the solar spectrum, 837.
Absorption-spectra, relation between
the composition of organic com-
pounds and their, 1041.
Absorption-spectrum of the earth's at-
mosphere, 137.
Acecaffeine, 356.
Acetal, test for, 790.
Acetals, behaviour of, with alcohols at a
high temperature, 726.
Acetamide, action of acids on, 575.
and other amides of the acetic
series, preparation of, 1088.
Acetanilide, decomposition of, by water,
56, 325, 326.
Acethydroxythiophenylcarbimide, 1110.
Acetic acid, presence of, in plants, 611.
specific heat of, in the gase-
ous state, 6.
trichlor-, preparation of
ethers of, 729.
Acetoacetic acid and its deriratives,
41.
Acetoacetic acids, substituted, peculiar
decomposition of the ethereal salts of,
456.
Acetobarbituric acid ? 314.
y-Acetobutyric acid, 455.
Acetocoerulignol, 1006.
Acetometacoumaric acid, 189.
Acetonaloxyisobutyric acid, 177.
Acetonapbthalide, 916.
(8-Acetonaphthol, a-nitro-, molecular
transformation of, 1113.
Acetone, action of anhydrous aluminium
chloride on, 176.
action of paranitrobenzaldehyde
on, 1120.
addition of, under the influence of
caustic alkalis, 596.
• condensation of, 1079.
dichlorodibrom-, 1083.
hexbrom-, 464.
• monochlor-, action of benzoic an-
hydride on, 63.
Acetone, nitroso-, action of benzyl Jchlo-
ride on the sodium salt of, 572.
mono- and di-hydrofluoride, 655.
Acetone-chloroform, 1079.
bye-products in the preparation of,
177.
conversion of, into hydroxyisobu-
tyric acid, 177.
Acetonephenanthraquinone, 596.
Acetonephenylhydrazine, 798.
Acetonuria, 1161.
Acetonylquinoline, 588.
Acetophenol, orthonitro-, 1113.
Acetophenone, brom-, and its action on
phenol, 332.
derivatives, 586.
brom-, 586.
formation of, from ethylic benzoyl-
acetoacetate, 587.
orthamido-, and its acetyl-deriva-
tive, 197, 198.
Acetophenone-anilide and its derivatives,
332.
Acetophenone-carboxylic acid, formula
of, 1127.
Acetophenone-dimethylhydrazine, 798.
Acetophenone-paranitrophenyl ether,
332.
Acetophenone-phenyl ether and its
nitro- derivative, 332.
Acetophenone-phenylhydrazine, 798,
Acetophenones, nitro-, preparation of
the three isomeric, 191.
Acetotetramethylenecarboxylic acid,.
1083.
Acetothiocarbamidophenol, 1110.
Acetotoluide, ortho- and para-, 916.
Acetoxime, formula of, 569.
hydrochloride, 581.
Acetoximes, 580, 581.
Acetoximic acids, 572, 690.
Acetoxylide, 916.
Acetylacecaffeine, 356,
Acetylanthranilic acid, 188, 602.
Acetyldiiodophenol, 1109.
Acetyl-dimethylnaphthol, 79.
Acetylenedicarboxylic acid and its di-
methyl-derivative, 313.
Acetylflavenol, 600.
4 m 2
1216
INDEX OF SUBJECTS.
Acetylformimide, 1090.
Acetylfurfurine, 799.
Acetylglycocine, preparation of, 1088.
Acetyl-picamar, 1005.
Acetyltetrahydroquinoline, 1144.
Acetyltetramethylparaleukaniline, 1098.
Acetyltetramethylpararosaniline, 1098.
Acid, non-saturated, isomeric witli ita-
conic acid, 730.
Acid amides, action of phosphorus pen-
tachloride on, 48.
Acids analogous in constitution to hip-
puric acid, synthesis o£ some, 337.
unsaturated, 454.
conversion of, into the iso-
meric lactones, 730.
vegetable, certain, action of, on
lead and tin, 1038.
Aconic acid, 457.
Acralxylidine, dry distillation of, 669.
Acridine, 1134.
Acridines, synthesis of, 1133.
Acroleinureide and condensed ureides,
664.
Acrylic acid, tribrom-, crystalline form
of, 310.
Acrylic acids, substituted, constitution
of, 310.
Actinic rays, reflection of: influence of
the reflecting surface, 138.
Actinoelectricity, 412.
Adipocere, 818.
Aerorthometer, 378.
Aeschynite from N. Carolina, 1064.
supposed, from Ray's mine,
Yancey Co., 163.
-^sculetin, constitution of, 199.
Affinity and its relation to atomic
volume, atomic weight, and specific
gravity, 1048.
Agarieus ruber, colouring matter (rube-
rine) and alkaloid (agarythrine) in,
100.
Agarythrine in Agarieus ruber, 100.
Air at Cape Horn, carbonic anhydride
in, 121.
examination of, for sanitary pur-
poses, with remarks on disinfection,
514.
influence of climate and weather
on the amount of carbonic anhydride
in, 614.
variation in the amount of oxygen
in, 284, 551.
Air-baths, improvements in, 900.
Alanine, action of cyanogen chloride on,
192.
Alaskaite, a new bismuth mineral, 429.
Albite after spodumene, 439.
beautifully crystallised, from Ame-
lia Co., analysis of, 34.
Albumin, action of potash on, 674.
Albumin, behaviour of bile acids with,
673.
detection of, in urine, 885.
from urine, coagulated by nitric
acid and soluble in alcohol, 247.
in urine, picric acid as a test for,
1176.
solutions, filtration of, through
animal membranes, 1160.
Albuminoids in peach kernels and
sesame cake, 360.
Alcohol prepared from molasses or beet-
root, purification of, 630.
solidification of, 781.
AlcohoUc Hquors, estimation of, 518.
Alcohols, behaviour of acetals with, at
a high temperature, 726.
Aldehyde, use of magenta with sulphu-
rous anhydride as a microchemical
test for, 829.
ammonium bases, 568, 1090.
Aldehydes, action of anhydrides on,
452.
new test for, 829.
and their derivatives, condensation -
products of, 570,
Aldehydethyl chloride, 726.
Aldoximes and their derivatives, 569,
1104.
AHzarin-blue, 635.
soluble, 74.
AlkaUne phosphates, behaviour of, to
various indicators, 380.
sulphites, thermochemical re-
searches on, 704.
thiosulphates, 707.
Alkalis, improvements in the prepara-
tion of, 528.
Alkaloid, new, in Cannabis indica or
Indian hemp, 1155.
Alkaloids, action of zinc ethvl on,
653.
cinchona, quantitative estitnatioiii
of, 388.
formation of, from normal human
fluids, 101.
from putrid animal matter, 100^
224, 924, 925.
in mushrooms, 612.
laws of vfiriation of the specific
rotatory power of, under the influence
of acids, 81.
new colour reactions of, 386.
of the bark of Cinchona svccirubray
eflect of altitude on, 1165.
use of bromine in testing for,
1175.
Alkophyr, and the true and so-called
biuret reaction, 1019.
Alkyl-derivatives of the halogen-substi-
tuted fatty acids, action of, on anihne,
919.
INDEX OF SUBJECTS.
1217
Alkyl salts, critical temperature of,
276.
. of the fatty acids, specific
volumes, boiling points of, and sp. gr.
at boiling points, 967.
sulphates, constitution of the
double compounds of the sulphonates
with, 973.
Alkyl-nitrous acids, 914.
Alkylsulphamic acids, 971.
Alkylthiosulphuric acids, 47.
Allanite from Alexander Co., and
Mitchell Co., 163.
from N. Carolina, 1064.
Allocaffeine, 355.
Alloys, explosiye, of zinc with certain
platinum metals, 19.
of gold, silver, &c., found in grains
along with the native platinum of
Columbia, 160.
separation of silver from, 243.
Allyl alcohol, a- and /3-chlor-, 450.
a-monochlor-, and its deriva-
tives, 173.
compounds, specific volumes of,
13.
dimethyl carbinol, bye -product of
the preparation of, 1076.
■ dipropyl carbinol, hydrocarbon pre-
pared by the action of sulphuric acid
on, 1073, 1074.
iodides, monochlor-, isomeric,
449.
AUylacetoxime, 728.
Allylamine derivatives, 908.
platinochloride, 909.
Allylene, 172.
Allyiethenyltricarboxylic acid and its
ether, 656.
Allyloxybenzoic acids, 335.
Allylpyrroline, 350.
Allylsalicylic acid, 336.
AUylsuccinic acid, 656.
Allyltriethylammonium chloride, a- and
/3-chlor-, 307.
Algin, 943.
Aloes, JafPerabad, 480.
Aloms, 480.
Alpine meadows, manuring, 238.
Alum, dried, of the B.P., 1053.
from felspar, 424.
Aluminium, action of, on cupric chloride,
19.
behaviour of, in chromic and nitric
acids, 699, 700.
borate, from Siberia, 719.
mechanical properties of, 424.
metaphosphate, 711.
oxychloride, 19.
palmitate, application of, 405.
pure, properties of, 151.
sulphate, 714.
Aluminium sulphate free from iron, pre-
paration from bauxite of, 130.
natural, of Kio Saldana,
composition of, 714.
thiocyanate, preparation of, 256.
Alunite, calcination of, 397.
crude, industrial value of, 250.
Amalgamation currents, 412.
process, Mexican, reactions of,
134.
Amarine, and its derivatives, 203, 799,
982.
acetyl chloride, 799.
benzoyl chloride, 799.
Amidacetic acid, and the action of ben-
zoic chloride on, 337, 338.
Amides, acid, action of, on aromatic
amines, 915.
metaUic derivatives of, and a
method of distinguishing mon- and
di-amides, 913.
of oxalic acid, action of phosphorus
pentachloride on, 49.
transformation of, into amines,
175.
Amidines, action of acetic anhydride on,
1099.
Amido-acids, action of cyanogen chloride
on, 192.
Amidophenols, 734.
Amines, action of bromine on, in alka-
line solutions, 789.
action of dibromonaphthol on,
536.
action of zinc-ethyl on, 653.
aromatic, action of acid amides on,
915.
action of ethyldichloramine
on, 915.
reaction of, with lactic acid,
1096.
transformation of amides into, 175.
Ammonchelidonic acid, 871.
Ammonia, extraction of, from coal,
888.
in potable waters, new form of
apparatus for estimating, 382.
in rain-water, variation of the
amount of, 753.
sp. gr. of solutions of, 849.
volumetric analysis of, a lecture
experiment, 281.
volumetric relation of, to the nitro-
gen it contains, a lecture experiment,
281.
Ammonia-process for water analysis,
514.
Ammoniocobalt compounds, 557.
Ammonia-phosphatic deposit in the
vicinity of Cape Town, 859.
Ammonioplatinum diammonium com-
pounds, 28.
1218
INDEX OP SUBJECTS.
Ammoniostannic bromide, 425.
Ammonium carbamate and carbonate,
electrolysis of, 27.
carbonate, sp. gr. of solutions of,
849.
cyanide, vapour of, 775.
hydrogen sulphide, examination of
the vapour of, 548, 775.
magnesium phosphate, occurrence
of crystals of, in urine, 609.
thiocyanate, preparation of, 1074.
Ammonium and lead, double chlorides
of, 717.
Amphibole and pyroxene, relation be-
tween the optical properties and
chemical composition of, 560.
Amphibole rocks of the Bastogne region,
958.
Amphiboles from Finland, calculation of
analyses of, 1065.
Amphinitrile, 919.
Amyl acetate, tertiary, decomposition of,
by heat, 178, 309.
alcohol, commercial, occurrence of
organic bases in, 127.
formation of, in alcoholic fer-
mentation, 908.
— ■ — bisulphide, 48.
triehloracetate, 729.
Amylbenzene, 659.
derivatives of, 1093.
Amylene oxide, 566.
Amylformimide hydrochloride, 1089.
Amylnaphthalene, 212.
Amylphenol, 59.
Amylphenyl ethyl oxide, 59.
Analcime, 957.
artificial, 34.
Analcite from Colorado, 165.
Anatase from Burke Co., JS". Carolina,
435.
^' Ancella-Schicht," 529.
Andesites, so-called, of South and Cen-
tral America, 448.
Andromeda japonica, poisonous con-
stituents of, 215, 348.
Andromedatoxin, 349.
Angelica root, essence of, 809.
Anhvdrite, artificial production of,
1?62.
Anhydro-amidotolyloxamic acid, deriva-
tives of, 1129.
Anhydro-compounds, 800.
Anhydrolupinine, 100.
Anhydro-orthamidophenol ethyl aceto-
acetate, 1111.
Anhydrosalicylic glucoside, synthesis of,
76.
Anhydrotriethylsulphamic acid, 971.
Anilic acid, nitro-, and its salts, 465.
Anilides, formation of, 325, 915.
AniUdocarbamidophenol, 1110.
Anilidoethoxytoluquinoneanilide and its
derivatives, 1118.
Aniline, action of the alkyl-derivatives
of the halogen-substituted fatty acids
on, 919.
di- and tri-chlor-, 915.
hydrobromide, meta-, and para-
nitro-, 578.
parabrom-, and parachlor-,
578.
methylation and ethylation of,
578.
tribrom-, symmetrical, and its hy-
drobromide and chloride, 797.
symmetrical, diazo-derivatives
of, 660.
use of, in qualitative analysis, 239.
Anilpyruvic acid, and its bromine-de-
rivative, 1128.
Animal body, detection of iodoform,
naphthol, and chloroform in the fluids
and organs of, 243.
Animal matters, spontaneous fermenta-
tion of, 226.
Animal organism, decomposition in,
361.
oxidations and synthesis in,
361.
Animals, entire, composition of the ash
of, and of certain separate parts of
some of the animals used as human
food, 1019.
exhalation of nitrogen-gas during
the respiration of, 675.
results of the suppression of per-
spiration of, 817.
Anisethylbenzhydroxylamine,. 462.
Anisidine, dibrom-, ortho-, and para-,
663.
monobromortho-, and para-, and
their salts, 663.
Anisoil, metamido-, 802.
Anisoils, bromonitro- and bromamido-,
662.
Anisoilsulphonic acid, 990.
Anomalous reactions, some, 1078.
Anoxygenheemia, 939.
Anthophyllite after olivine, 444.
Anthracene, new method of forming,
1137.
new source of, 534.
new synthesis of, 809.
series, reduction in, 1137.
Anthracite from Cliili, New Granada,
and Brazil, analysis of, 941.
Anthramine, derivatives of, 1139.
Anthranil, 188.
constitution of, 332.
Anthranilic acid, 188.
Anthraquinone, dinitro-, 737.
action of concentrated sul-
phuric acid on, 72, 597.
i
INDEX OF SUBJECTS.
1219
Antliraquinone, diorthamido-, 737.
Anthraquinones, new nitro- and amido-,
71.
Antlirarufin, new method of preparing,
737.
Anthrol salts, derivatives of, 73.
Antimonious sulphide in aqueous solu-
tion, 784.
Antimonite, pseudomorph of, 430.
Antimony, atomic weight of, 1056.
chlorides and oxides, heat of for-
mation of, 544,
Weil's method for the estimation
of, 509.
Antimony-compounds, aromatic, 327.
Antisepsis, scientific basis of, 937.
Antiseptics, 249.
Apatite, 432.
brom-, production of, 648, 783,
784.
• existence of, in the pegmatite of
Lyons, 432.
iodo-, 783, 784.
Aphrosiderite, from Konigshain, Ober-
lausitz, 446.
Apocaffeine, 355.
Apocinchonine, specific rotatory power
of, under the influence of acids, 359.
hydrochlor-, specific rotatory
power of, under the influence of acids,
359.
Apocolchiceine, 673.
Apocynein, 1142.
Apocynin, 1142.
Apocynum cannahinum, active principle
of the root of, 1141.
Apoethyl theobromine, 357.
ApophyUite, 441, 957.
from Colorado, 165.
Apparatus for gas analysis, 1048.
for the determination of specific
heats by cooling, 6.
Aqueous vapour, influence of hygro-
scopic condensation in glass vessels on
the determination of the density of,
507.
Arable land, loss and gain of nitrogen
in, 749. ^
loss and gain of nitrogen in,
under the influence of different
systems of cultivation, 373.
mineral phosphates on, 118.
Arbutin, 347.
Argentammonium iodide, 1052.
Argentine, 405.
Argentous oxide, 288.
Aromatic arsenic and antimony-com-
pounds, 327.
bases, hydrobromides and hydrio-
dides of, 578.
Arsenates from Laangban, 434.
Arsenic, allotropic, 554.
Arsenic chlorides, heat of formation of,
544.
detection of, microscopically, 381.
new volumetric method for the
estimation of, 1034.
test for, 513.
and phosphorus, analogy between
the allotropic modifications of, 901.
Arsenic-compounds, aromatic, 327.
Arsenides, formation of, by pressure,
650.
Arsenious sulphide in aqueous solution,
295.
solubility of, in water, 900.
Arsenites in alkaline salts, use of oxalic
acid as a test for, 243.
Arsenobenzene, 187.
Arsenonaphthalene, 187.
Asbestos-filters, preparation of, 506.
Asebotoxin, 215, 349.
Ash of Pistia stratiotes : " Pana salt,"
822.
of the entire animals, and of cer-
tain separate parts of some of the
animals used as human food, 1019.
Asparagine, extraction of, from Hquids,
315.
Asphalt, Egyptian, analysis of, 941.
Assimilation by Haematococcus, 611.
and colour, 819.
Assimilative capacity of green plants,
influence of chemical agents on, 611.
Atmosphere, carbonic anhydride in,
121, 284, 614.
earth's, absorption - spectrum of,
137-
variations of the amount of oxygen
in, 284, 551.
constituent of, which absorbs
radiant heat, 7.
Atomic weights, notice on, 846.
Atrolactic tropeine, and some ot its
salts, 671.
Atrophy, decrease in weight of indivi-
dual organs in children dying from,
606.
Atropine, constitution of, 670.
Atropyltropeine, 672.
Augite, from Ascension, 436.
Augites from Finland, calculation of
analysis of, 1065.
Augitite, from S. Vicente, analysis of,
723.
Aurin, synthesis of, 1000.
Auryl nitrate, 855.
sulphate, 855.
Autoxidation in plant cells, 819.
" Autoxydabel," 709.
" Autoxydators, 819."
Aventurine glass from Asia, 435.
Aventurine quartz, green, from Asia,
435.
1220
INDEX OF SUBJECTS.
Axe, jadeite, from Eabber, Hanover,
437.
Azaurolic acids, 40.
Azimidobenzene, 184.
Azimidobenzoic acid, 57.
Azimido-compounds, constitution of,
56.
Azimido-uramidobenzoic acid, 57.
Azoamidobenzenesulphonic acid, 181.
Azoamidobenzenedisulphonic acid, and
its barium salt, 181.
Azo-a- and /3-amidonaphthalenepara-
benzenesulphonic acids, 182, 183.
Azo - a - amidosidphonaphthalene - para-
benzenesulphonic acid, 183.
Azobenzene disulphochloride, tetra-
brom-, 479.
hexbrom-, 480.
nitro- and amide- deriTatives of,
867.
substitution-products of, 324.
Azobenzenediazine sulphite, 181.
Azobenzenedisulphamide, hexbrom-,
480.
tetrabrom-, 479.
Azobenzenedisulphonic acid, 182.
Azobenzenedisulphonic acids, bromi-
nated, and their derivatives, 478.
some, constitution of, 477.
Azobenzenemonosulphonic acid, para-
dichlor-, salts of, 341.
Azobenzeneparasulphonic acid, amido-,
and its salts, 1101.
paranitro- and paramido-,
and their salts, 867.
substitution - products of,
1101.
Azobenzenephenylenediaminebenzene,
1102.
a- and j3-azobenzenephenylenediamine-
paratoluene, 1102, 1103.
Azobenzenesulphonic acid, amido-, 181.
Azobenzenesulphonic acids and their
salts, and nitro-compounds, 324.
Azo-colouring matters, 871, 1148.
from diphenyldiisoindole,
342.
Azo-derivatives, 583, 584.
Azodibenzenephenylenediamine, 1103.
Azocarboxyhc acid, 792.
Azoparasulphobenzene-5-diamidobenzoic
acid, 184.
Azoparasulphobenzenephenylenedi-
amine, 1103.
Azoparasulphobenzenephenylenedi-
aminebenzene, 1103.
Azoparatoluenephenylenediamineben-
zene, 1103. "
Azoparatoluenephenylenediamine /S-
naphthalene, 1103.
Azophenylenediaminebenzenemetaben-
zoic acid, 1103.
Azophthalic acid, action of stannous'
chloride on, 1126.
Azosulphobenzenetoluenediamine, 1103.
Azotometer, Scheibler's modification of,
508.
Az otr ibromobenzene, dimethy lam ido- , .
661.
-- — methylphenylamido-, 662.
Azoxybenzene, KUnger's method of
preparing, 180.
Azoxylene, 180.
Azoxylenedisulphonic acid, and its salts,.
593.
Azoxypropylbenzoic acid, 330.
AzyUnes, 55, 184, 868, 1100.
B.
Bacteria, action of, on starch, 931.
diastatic ferment of, 930,
progress in the knowledge of,.
364.
Baeyer's artificial indigo, application of,
257.
Banana, composition of, at diiferent
stages of maturity, 231.
Barbituric acid, derivatives of, 314.
dibromo-, action of, on thio-
carbamide and thiocyanates, 913.
Baregin or glairin, 302.
Barium aluminates, 649.
and basic haloid salts of,
289.
basic halogen salts of, 649.
hydroxide, crystallised, 649.
and haloid salts, notes on,
289.
mercury iodide, application of a
solution of to petrographical pur-
poses, 1060.
nitrate, natural, 431.
paratoluenesidphonate, 807.
potassium phosphate, 711.
sodium phosphate, 711.
testing for, 240.
Barley, estimation of the value of, for
brewing purposes, 632.
influence of, on the fermentation
process, 756.
Baryta, hydrates of, 1052.
Barytes, artificial production of, 1062.
Basalt from S. Thiago, analysis of,
722.
Basalt rocks containing hornblende^
169.
Basanites, 721.
Base, C9H13N, 39.
C14H11N, 600, 1099.
INDEX OF SUBJECTS.
1221
C19H13N, 1099.
(obtained from benzenyliso-
diphenylamidine), preparation of,
from benzoyldiphenylamine, 580.
derived from crotonaWehyde, 1079.
Bases formed by putrefaction, 100, 224,
924, 925.
mutual displacements of, in homo-
geneous systems, 550.
obtained by the action of halogen
compounds on thiocarbamide, oxida-
tion of, 664.
of neutral salts, mutual displace-
ment of, in homogeneous systems,
708.
of the pyridine and quinoline
series, 738.
Bastonite, analysis of, 959.
Batteries, chromic and nitric acid, varia-
tion of the electromotive force in,
766.
effects of temperature on the elec-
tromotive force and resistance of,
840.
secondary, 765.
Battery residues, utilisation of, 896.
Bauxite, 397.
analyses of, 888.
formation of, 1065.
preparation from, of aluminium
sulphate free from iron, 130.
Beans of the Soja hispida, constituents
of, 1024.
Becker's creaming process, 253.
Beech-tar oil, 1005.
Beer, amount of carbonic acid in,
535.
Chica, the ferment of, 535.
glycerol in, 385.
nitrogenous constituents of, 821.
preservation of, 136.
Beer-grains, estimation of wort removed
from and starch left in, 136.
Bees' wax, 39.
Beet, biological researches on, 613.
culture of various descriptions of,
114, 1026.
decomposition of the diffusion resi-
dues from, 1025.
diseases of. 111.
distribution of sugar in, 124.
manuring, 238, 823.
white, Silesian, chemical studies
on, 235, 368.
Beet-juice, defecation of, with strontium
saccharate, 756.
occurrence of a new acid in,
913.
purification of, 136.
Beet-red, 881.
Beet-syrup, limed, ready method of
estimating the alkalinity of, 689.
Benzaldehyde, action of acetic chloride-
on, in presence of zinc-dust, 62, 805.
orthamido-, 62, 331.
orthonitro-, condensation of, with
aniline, 981.
reduction of, 187.
para- and meta-mido-, 1104, 1105.
paranitro-, action of, on acetone,,
1121 >.
Benzaldehydes, nitro-, isomeric, 586.
Benzaldoxime, nitro-, compounds of,.
preparation of, 916.
paracetamido-, 1104.
paranitro-, 1104.
Benzamidophenol, 800.
BenzaniUde, amido-, and the action of
aniline on, 999.
Benzanisethyl - hydroxy lamines, four
metameric, 460.
Benzene, action of allyl chloride on,,
in presence of aluminium chloride,
977.
action of aluminium chloride on,
the monohalogen derivatives of, 53.
chloroxy- and bromoxy-derivatives
of, 984.
chloroxypentachloro-, 1119.
derivatives, nitration of, 975.
— — dinitro- and trinitro-, compounds
of, with hydrocarbons, 317, 318.
formulae, 51.
from various sources, 315.
new source of, 53 i.
tribromiodo-, 661.
tribromochloro-, 661.
trinitro-derivatives of, 315.
trinitro-iodo-, 316.
Benzene, and symmetrical dibromethy-
lene, action of aluminium bromide on^.
807.
Benzene- aniline, trinitro-, 316.
Benzene-azoresorcinol, and purification*
of, 982.
Benzene-diazophenol, 583.
Benzene-dhnethylaniline, trinitro-, 316.
Benzenes, trinitro-, 315.
Benzenesulphanilide, 48.
Benzenesulphodiphenylamine, 48.
Benzenesulphonanilide, nitro- and
amido-derivatives of, 800.
Benzenesulplionic acids, amido-, 325.
Benzenesulphonparatoluide, nitro- and
amido-derivatives of, 800.
Benzenylamidonaphthol, 1113.
Benzenyl-a-amido-jS- naplithol, 69.
Benzenyl-/3-amido-a-naphthol, 69.
B en z eneor thamidopheny Imercaptan,
198.
Benzethylanishydroxylamine, 462.
Benzethylbenzhvdroxylamine, 461.
Benzhydrol, jS-diamido-, and its com-
pounds, 991.
1222
INDEX OF SUBJECTS.
Benzidinetetracarboxylic auhydride, and
salts of the acid, 1126.
Benzil, 921, 1120.
action of lead oxide and of hy-
droxylamine on, 803, 804.
' decomposition of, by potassium
cyanide, 805.
Benzoic acid, action of melting potassium
hydroxide on, 467.
detection of, in milk, 385.
^-diamido-, action of para-
diazobenzenesulphonic acid on, 184.
metaeyanamido-, 192.
y-monocliloro-, 339.
triamido-, new, 184.
Benzoid, amido-, 999.
Benzoin, action of lead oxide, and of
hydroxylamine on, 804.
/3-Benzoisosuccinic acid, 912,
/3-Benzonaphthol, a-nitro-, moleciilar
transformation of, 1113.
.Benzonitril, preparation of, 1111.
metanitro-, 916.
Benzophenone, diamido-, and its, cdin-
pounds, 991.
metanitro-, 203.
tetranitro-, 991.
Benzoquinol, compounds of, with amines,
60.
Benzotrichloride, compounds of, with
phenols and plienylamines, 861.
Benzotropeine, 671.
Benzoylacetic acid, 336. ^
Benzoylacetocarboxylic acid, action of
hydroxylamine hydrochloride on,
1127.
formula of, 1127.
Benzoyl-a-amido-j3-naphthol, 1113.
Benzoyl-carbinol, constitution of, 983.
Benzoyldi amidoacetylamidacetic acid,
1087.
Benzoyldiiodopheuol, 1109.
Benzoylethoxyfurf urine, 800.
Benzoylmesitylene, 577.
Benzoylparaleucaniline, 981.
Benzoyltetrahydroquinoline, 1144.
Benzoyltetramethylene, 1084.
Benzoyltetramethylenecarboxylic acid,
1084.
Benzyl acetoacetate, action of sulphuric
acid, 808.
chlorides, action of potassium car-
bonate on, 58.
cresyl ether, 585, 586.
cyanide, acetamidobromonitro-, 64.
derivatives, 1121.
a- and j3-naphthyl ether, 586.
• nitrate, paranitro-, 866.
nitro-, chlorides of ortho- and
meta-, 1092.
phenol ether, 585.
Benzylacetoacetic acid, 41.
Benzylacetone, nitroso-, 41.
Benzylaeetoxime and its hydrochloride,
581.
Benzylaldoxime, 569.
ortho- and meta-nitro-, preparation
of, 581.
Benzylamarine, and its platinochloride,
982.
Benzylamidobenzoic acid, 1009.
Benzylbarbituric acid, 314.
Benzyl-dinitro-orthocresol, mononitro-,
864.
Benzyl-dinitro-phenol, mononitro-, 864.
Benzylene chlorides, action of potassium
carbonate on, 58.
Benzyleneorthotolylamine, 179.
Benzylformiinide hydrochloride, 1089.
Beazylglyoxaline, 911.
Benzylhydroxylamine, formula of, 569.
Benzyl-mesitylene, 323.
Benzylnitrosoaeetone, an isomeride of,
572.
Benzyl- ortho-, and -para-cresol, nitro-
derivatives of, 863.
Benylphenol, nitro-derivatives of, 863.
Benzylpurpuric acid, 315.
Berthollet's laws and the combination
of mercuric oxide with acids, 10.
Beryl from N. CaroUna, 1064. *
from Craveggia in Piedmont,
958.
Beryllium hydroxides, 291.
Berzeliite, doubly-refracting, 434.
Bessemer converter, chemistry of, 832.
Bibasic acids, imides of, 475.
Bichromate batteries, reply to the ob-
servations of Reynier on, 765.
battery, modification of, and ob-
servation on, 700.
Bidiethyltolyl, 1094.
Biguanide, and its constitution, 973.
Bile of invertebrates and vertebrates,
colouriug-matter of, 1159.
Bile acids, behaviour of, with albumin
and peptones, and antiseptic action of,
673.
use of phosphoric acid in
Pettenkofer's reaction for, 1177.
Biliary fistula, observations on a dog
with, 818.
Bismuth carbonate, from Q-uanajuato,
Mexico, 432.
chlorides and oxides, heat of for-
mation of, 544.
peroxide, barium compounds of,
158.
solutions, electrolysis of, 1034.
subnitrate, examination of, 382.
Bitumen, analysis of, 941.
Biuret dicyauamide, and its salts, 658.
reaction, the true and so-called,
1019.
INDEX OF SUBJECTS.
1223
Blast-furnace practice with coke and
with charcoal, 531.
Bleach ing-powder and analogous com-
pounds, 953.
modified process for the
estimation of chlorine in, 507.
Blood, action of hydrogen peroxide on
the red colouring-matter of, 103.
behaviour of ozone with, 486.
behaviour of, when deprived of
oxygen, 818.
coagulation of, 608.
transformation of, into a solid and
inodorous manure by means of a new-
ferric sulphate, 239.
•*' Blooming " of black Russian earth,
679.
Boiler explosions, 129.
prevention of, 835.
Boiler fires, investigation of, 942.
Boiler incrustation, prevention of, 408.
Boilers, effect of the presence of sheet
zinc in, and a method for preventing
explosions, 250.
Boiling points, errors in the determina-
tion of, 844.
of the corresponding ketones,
ethereal salts, and chloranhydrides,
similarity of, 990.
and specific volume, relation
between, 302.
Bole from Steinkirchen, in Bohemia,
444.
Boric acid, detection of, in milk, 385.
electrolysis of solutions of,
540.
use of, for preserving food,
1178.
Boroquatuordecitungstates, 23.
Borotungstates, new, 23, 786.
Bouruonite, a variety of, 162.
•" Bradoxydabel," 709.
Brandy, Otto's method for the estima-
tion of fusel oil in, 123.
Bread, fermentation of, 1179.
nitrogenous constituents of, 821.
Bread-making, utilisation of butter-milk
in, 1037.
Bromanilic acid, chloro-, from meta-
dichlorometabromoquinone, 1117.
Bromic acid, systematic method of
testing for, 1172.
Bromides, estimation of, in presence of
sulphuretted hydrogen, 508.
Bromine amalgamation process, 399.
displacement of, by chlorine in
organic compounds, 1118.
dissociation of, 546.
estimation of, in presence of iodine,
119.
separation of, from chlorine and
iodine, 1167.
Bromine, use of, in testing for alkaloids,
1175.
Bronze implements used by the miners
of Peru, 691.
Bronzite, 432.
Brucite, 1061.
from Cogne, 1061.
Buckwheat flour, detection of rice-meal
in, 885.
Building stones, decay of, 1036.
Burettes, manufacture and correction of,
619.
Butenylbenzene, 471.
Butter, adulteration of, 521.
analysis of, 246, 247, 750.
chemistry of, 1160.
estimation of salicylic acid in,
522.
preservation of, 254.
Butter-milk, utilisation of, in bread-
making, 1037.
Butyl bisulphide, 48.
chloral, constitution of, 963.
Butylenedicarboxylic acid, and its amide,
353.
Butylglycidic acid, 311, 969.
Butylmethylethylene, 652.
Butyl-nitrous acid, and some of its salts,
915.
Butyraldehyde, a-y-dichloro- a - ^ - di-
bromo-, 965.
' trichloro-, 966.
Butyric ferment in arable soils, 610.
a-Butyric-creatinine, 220.
Cacao tree, cultivation of, 933.
Cadmium nitrate, basic, 904.
Caffeic acid from cuprea bark, 66.
Caffeidine, 1016.
oxidation of, with chromic acid,
1017.
Caffeidine-carboiylic acid, and its salts,
1016.
Caffeine, action of dilute alkalis on,
1016.
action of hydrochloric acid on,
873.
amount of, in guarana, 232,
and its derivatives, constitution of,
357.
artificial, salts of, 873.
behaviour of, in the animal
organism, 1018.
derivatives of, 354.
occurrence of, in cacao, 873.
salts of, 97.
Caff'oline, 356.
Caff uric acid, 356.
1224
INDEX OF SUBJECTS.
Calcite, 957.
artificial production of, 31.
from Colorado, 165.
Calcium chloride, 151.
hydroxide, estimation of, in pre-
sence of calcium carbonate, 828.
hypochlorite, 17.
hypoiodite, 17.
parahydroxybenzoate, products of
the distillation of, 664.
and strontium, separation of, 509.
Calico-printing, novelties in, 895.
Calomel, influence of, on fermentation
and the life of micro-organisms,
743.
Calves, fattening of, 815.
feeding, with skim-milk, 675.
Camellia oleifera seeds, 1166.
Camphor, action of sodium on, 1006.
action of zinc chloride on, 810.
chloronitro-, 667.
a- and /3-dibromo-, preparation of,
1007.
monochlorO", a new, 214.
physical isomerism of, 598.
nitroxy-, 215.
tribromo-, constitution of, 215.
Camphor-cymene and its sulphonic
acids, 320.
Camphorethylimidethylimidine, 49.
Camphoric anhydride, 1007.
Camphoronic acid, 1008.
Camphoroxime, 728.
Camphors, dibromo-, isomerism of,
214.
isomeric dibromo-, 1007, 1008.
Cane-sugar, action of lime on, 1079.
influence of invertin on the fer-
mentation of, 101.
strobometric estimation of the rate
of inversion of, 174.
Cannabis indica, new alkaloid in, 1155.
Capillarity of liquids, 549.
Capillarity of the surfaces water-ether
and water-carbonbisulphide under the
action of electromotive force, varia-
tions of the constant of, 1047.
Caproic acid, normal, ^-lactone of, 455.
Caprolactones, two new, 454.
Carbamide, vapour of, 645.
Carbamidoacetosulphonic acid, 664.
Carbamido-dibenzoic acid, 194.
Carbamido phenol, amido-, 1110.
Carbocaprolactonic acid, 656, 971.
Carbohydrates, physiology of, in the
animal system, 1160.
Carbolic acid, poisoning with, 1021.
Carbomesyl, 1096.
Carbon, affinity values of, 779.
and its compounds, spectra of,
261.
bisulphide, 535.
Carbon bisulphide, estimation of, in-
thiocarbonates, 935.
purification of, 43.
solidification of, 781.
and carbonic anhydride, un-
observed resemblance between, 1049.
contacts, electric resistance of, 841.
effect of absorbed gases on the
electrical conductivity of, 769.
for electric lighting, preparation
and purification of, 752.
new method for the estimation ol
minute quantities of, in iron or steel,
1032.
oxidation -products of, obtained by
electrolysis, 65.
oxides, sulphur, and sulphur
oxides, reaction between, 551.
oxysulphide, physical properties of,
43.
spectrum of, 1.
tetrachloride, heat of formation of,
544.
thiobromides, 907.
Carbon-compounds, law of freezing of
aqueous solutions of, 7.
liquid, dependence of molecular
refraction of, on their chemical con-
stitution, 538.
optically active, synthesis of, 457.
spectra of, 761.
volatile, method of estimating the
heat of formation of, 543.
Carbonic anhydride, antiseptic proper-
ties of, 395.
in terrestrial air, influence of
climate and weather on the amount
of, 614.
in the air at Cape Horn, 121.
in the atmosphere, 284.
liqvdd, as a tire extinguisher,
408.
explosion of a tube con-
taining, 422.
relation between pres-
sure and temperature in the saturated
vapour of, 417.
and carbon bisulphide, un-
observed resemblance between, 1049.
Carbonic hydroxide, 574.
Carbonic oxide, action of, on steam, 860.
action of platinum and palla-
dium on, 422.
heat of formation of, 544.
liquefaction of, 781, 952.
new method for preparing,.
574, 655.
oxidation of, by palladium
hydride and oxygen, 150.
and oxygen, influence of
aqueous vapour on the explosion of,
12.
INDEX OF SUBJECTS.
1225
Carbonyldiphenyl oxide, 664.
Carbosilicide, a, 15.
Carbosilicon compounds, 15.
Carbostyril, y-bromo-, 351.
^-chloro-, 351.
constitution of, 204.
V-halogen-derivatives of, 196.
Carbotrithiohexbromide, and. forma-
tion of a new colouring matter by the
action of heat on, 907.
Carbovalerolactonic acid, 456.
Carboxylic acids, conversion of phenols
into, 802.
Carlsbad salts, 396.
Casein from heated milk, digestibility
of, 487, 815.
Caseo-glutin, 693.
Castor-oil, insoluble residue from the
distillation of, 655.
Catechol, fusion of, with soda, 60.
Cattle, feeding of, with dry fodder,
816.
poisoning of, by earth-nut cake,
818.
Caustic alkalis, estimation of, in pre-
sence of alkaline carbonates, 828.
■Celestine, artificial production of, 1062.
Cellulose, brown and white, preparation
of, 253.
fermentation of, 821, 1077.
Cement, a natural, 131.
and its appHcation, 131.
English, analyses of, 530.
hardening of, 831.
preparation and testing of, 753.
Cement and lime, process for rendering
them less subject to atmospheric in-
fluences, 398, 530.
■Cementation steel, crystals in, 629.
Cereal grains, specific gravity of. 111.
Cereals, chemistry of, 1160.
cultivation of, 612.
Cerium oxide, preparation of, 713.
Cerotic acid, 39.
•Ohabazite, 441, 957.
from Colorado, 164.
Chalcomenite, a new mineral species
(selenite of copper) , 31.
Charcoal, firwood, composition of, 533.
influence of, on the amount of
phosphorus in pig-iron, 403.
Cheese, chemistry of, 1160.
composition of, 256.
Emmenthal, composition and
ripening of, 692.
Chelidonic acid, and its derivatives,
870.
Chemical action and electrical energy,
413.
affinities of elements in various
allotropic modifications, 779.
vCliica beer, 365, 535.
Children dying from atrophy, decrease
in weight of individual organs in,
606.
ChioUte, chemical composition of, 29.
Chloracetoacetate of ethyl, action of
nitric acid on, 573.
Chloral hydrate, action of hydroxyl-
amine on, 728.
Chlorates, action of the galvanic current
on, 149.
Chlorhydrins, preparation of, 1077.
Chloric acid, systematic method of test-
ing for, 1172.
" Chloride of lime," 17.
" Chloride of lithia," 17.
Chlorides, action of the galvanic current
on, 149.
estimation of, in presence of sul-
phuretted hydrogen, 508.
Chlorine as a plant-food, 497.
density of, at high temperatures,
710.
dissociation of, 546.
estimation of, in presence of bro-
mine and iodine, 119.
hydrate, crystallisation of, 550.
hydrates, 780.
oxyacids of, constitution of, 645.
separation of, from bromine and
iodine, 1167.
' solubility of, in water, 550.
Chloroform, detection of, in tlie fluids
and organs of the animal body,
243.
Chlorophyll and the distribution of
energy in the solar spectrum, 697.
Chlorophyllite from Loquidy, near
Nantes, 443.
Chloropicrin, syntheses with, 1000.
Chlorosulphonic acid, new mode of for-
mation of, 710.
Cholesterin, appendix to the paper on,
586.
Chondrodite, composition of, 436.
minerals, composition of, 436.
Chromammonium compounds, chemistry
of, 554.
Chromates, action of acids on, 707.
and chromic acid, 22.
Chrome-iron, deposits of, in the Urals,
444.
Chrome-orange for calico-printing, pre-
paration of, 896.
Chromic acid and some of its salts, heat
of formation of, 642.
volumetric estimation of, in
chromates and dichromates, 686.
and chromates, 22.
Chromic selenite, 717.
tourmalin in the Urals, 444.
Chromium and urea, series of salts con-
taining, 178.
1226
INDEX OF SUBJECTS.
Chromometer, a new form of, 1032.
Chromophyll, 820.
Chromous sulphate, 22.
Cinchomeronic acid, 739.
Cinchona, liquid extract of, 693.
Cinchona alkaloids, notes on, 1018.
quantitative estimation of,
388.
Cinchona bark grown in Jamaica, 1165.
Cinchonidine, detection of, in quinine,
1019.
Cinchonine, oxidation-products of, 222.
Cinnamic acid, action of sulphuric acid
on, 474.
195.
derivatires of, 195, 196, 992,
1123.
paradiazo-, decomposition of,
196.
Cinnamic acids, hromo-, 195.
■ halogen, 196.
halogen, constitution of, 194.
Cinnamyl methyl ketone, orthonitro-,
341, 587.
paranitro-, 1120.
Cinnamylacetone, orthonitro-, 587, 588.
Cinnamylformic acid, orthonitro-, 341.
Cinnamyltrope'ine, 671.
Cinnoline-derivatives, 1105.
Citraconic acid, derivatives of, 312.
Citraconimide, 313.
Citric acid, action of, on minerals,
857.
dry distillation of, with ex-
cess of lime, 658.
Clay from Lothain, analysis of, 627.
Clay ironstone of Eheinhesse, 448.
Clays, best American, composition of,
888.
refractory, 397.
Clinohumite, composition of, 436.
Clover sickness, caitses of, 233.
Coal, a bed of, discovered in Algiers and
the layers of white sand accompany-
ing the same, 160.
estimation of coke and volatile
products in, 517.
from Canoas, analysis of, 941.
of the Muaraze, analysis of, 299.
spontaneous combustion of, 892.
■ sulphur in, 383.
Coal-dust, influence of, in colliery explo-
sions, 127.
Coal-gas, estimation of sulphur in, 382.
Coal-tar, new compounds from, 204.
Coal-tar colours, various, 636.
Cobalt carbonate, optical properties of,
1062.
separation of nickel from, 621.
sulphate, 25.
Cobaltamine compounds (Part III),
25.
Cochineal, adulteration of, 408.
Codeine and monobromo-, non-nitro-
genous bodies from, 221.
Codeines, 358.
Codethyline, 358.
non-nitrogenous substance from^
221.
Codomethyline, 358.
Ccerulignol, 393.
nitro-, 1006.
Reichenbach's oxidising principle,
1005.
Coffee, physiological action of, 745.
Colchiceine, 672.
Colchicine, 672.
^-CoUidine, 83, 739.
hydrate of, 220.
physiological action of, 104.
Collidinedicarboxylic acid, 83.
oxidation-products of, 84.
Colophony, occurrence of methyl alco-
hol in the products of the dry distil-
lation of, 738.
products of the distillation of,
599.
Colour and assimilation, 819.
Colouring-matter, new crystalline, in
urine, 814.
new, formation of, by the
action of heat on carbotrithiohexabro-
mide, 907.
of bile of invertebrates and
vertebrates and unusual urine pig-
ments, 1159.
Colouring-matters, a new class of, 600.
artificial, mordants used for
fixing, 256, 894.
from coal-tar quinoline, 1150.
of the safranine series, 731.
Columbite, analysis of, 434.
Comenamic acid, 792.
Comenic acid, bromoxybromo-, 657.
Comets, light emitted by, 261.
Composts, analysis of materials used in
the preparation of, 504.
Concusconidine, 602.
Concusconine, 602.
Conduct-pipes, luting for, 536.
Congelation of aqueous solutions of or-
ganic bodies, 952.
Conglutin from lupines, behaviour of,
towards saline solutions, 360.
Conhydrine, action of dehydrating
agents on, 220.
Coniferin, occurrence of, in the woody
structures of beetroot, 611.
Conine, action of bromine on, in alkaline
solution, 789.
and its derivatives, 220.
Coninic acid, 813.
Conquinine, separation of, from hydro-
eonquinine, 602.
INDEX OF SUBJECTS.
122T
Conylurethane, action of nitric acid on,
8i3.
and derivatives of, 220.
Copper, influence of, on the working of
steel, 404.
modification of the Hunt-Douglas
process for the extraction of, 400.
selenite (chalcomenite, a new
mineral species), 31.
separation of, from lead, by refin-
ing in Freiberg, 400.
separation of, from sulphides by
air-blast, 400.
sulphate, quantity of heat evolved
in the electrolysis of, 1043.
sulphates, basic, 853.
sulphide, colloidal, 904, 1054.
tellurium in, 531.
Weil's method for the estimation
of, 509.
Copper-ammonium thiomolybdate, 1054.
Copper ore from Nova Scotia, analysis
of, 859.
Copper slate, Mansfeld, analysis of,
1069.
Cordierite in the trachytes of Hungary,
166.
Correction, a, 709.
potassium ethylenedisulphonate,
912.
Cotton cake, 111.
Cotton fabrics, dyed, microscopic investi-
gation of, 751.
Coumarilic acid, and its derivatives,
474.
Coumarin, 471.
Coumarone, 474.
Cows, milch, rice and earth-nut meal as
food for, 820.
milking of, twice or thrice daily,
227.
• value of various fodders for,
8'iO.
Cream of tartar, rapid estimation of,
755.
Creaming, 253.
Creaming process, Becker's, 253.
Creasote from beechwood tar, 393.
Creatine-compounds of the aromatic
group, 669.
Creatinine-group, compounds of, 220,
1153.
Cresol, amido-, from tolylenediamine,
329.
ortho-, and para-, dichloro-, and
their derivatives, 1111.
ortho-, meta-, and para-, nitro-
derivalives of, 861.
Cresols, ethylamido-, 866.
nitro-, 59, 662, 864.
Cresorsellinic acid, and its salts, 1121.
Critical point of mixed gases, 277.
Critical temperatures of alkvl salts,.
276.
Crocoisite, analysis of, 1063.
Crocin- scarlet, process for preparing,
635.
Crocin-yellow, process for preparing,
635.
Crops, various, cultivation of, 235.
Crotonaldehyde, action of dry ammonia
on,' 1079.
chloro-, 963.
ay-dichloro-, a condensation-pro-
duct of monochloraldehyde, 964.
jS-Crotonic acid, addition of hypochlor-
ous acid to, 311.
Crotonic acid, a- and |8-cliloro-, action of
potash, on, 968.
Crotonic acids, brom-addition-deriva-
tives of, 573.
isomeric, derivatives of, 969.
monohalogen derivatives of,
action of alkalis on, 968.
CryoHte, 427.
cliemical composition of, 29.
some artificial products from, 30.
Cryptidine, 669.
Crystallisation, experiments in, exem-
plifying Berthollet's laws of affinity,.
148.
observations on, 147.
Cumic acid, diamido-, and its hydro-
chloride, 194.
synthesis of, 63.
Cumidine, crystalline, and its methyl-
derivatives, 324.
Cuprea bark, 601.
Cupric chloride, action of aluminium on,.
19.
hydroxide, stability of, 19.
sulphide, solubility of, in alkaline
thiomolybdates, 1054.
Cuproso-cupric sulphites, transforma-
tions of, 20.
Curcumin, tetrabromo-, 481.
dibromide, pentabromo-, 481.
dihydride, and an anhydride of,
481.
tetrabromide, 481.
Currents, alternating, electro- dynamic
interference of, 897.
produced by fused nitrates in con-
tact with incandescent carbon, 273.
Cyanconiine and its derivatives, 352.
Cyanethine, action of bromine on, 353.
action of nitrous acid on, 352.
and bases derived from it, 352.
Cyanetholine, 304.
a reaction of the compounds of
normal cyanuric acid and, 305.
Cyanic acid, normal, properties of, 304.
Cyanmethine and its derivatives, 653.
Cyanogen, decomposition of, 303.
1228
INDEX OF SUBJECTS.
a-Cyanonaphthalene, 807.
•Cyanopyrene, 1003.
Cyanopyrene-picric acid, 1004.
Cyanoquinolines, ortho- and meta-,'92.
Cyanuric acid, normal, a reaction of the
compounds of, and cyanetlioline
(corps de M. Cloez), 305.
Cymatolite, from spodumene, 439.
Cymene, tetrachloro-, 806.
Cymenesulphonic acid, trichloro-, and
its sodium salt, 806.
Cymenesulplionic acids, 999, 1129.
Danburite, from Switzerland, 956.
from the Scopi, in Graubundten,
437.
Daniell's element, electromotive force of,
409.
Dawsonite, composition of, 430.
Decyl alcohol, normal primary, prepara-
tion of, and its derivatives, 1075.
Dehydrodipyridine, foot-note, 483.
Dehydropiperylurethane, nitro-, and its
bromhydroxy-derivative, 814.
Dehydroxy-caproic acid, 571.
Density of aqueous vapour, influence of
hydroscopic condensation in glass
vessels in the determination of, 507.
Dextran, nature and formation of, 105.
Dextrin, formula of, 307.
Dextrin syrup, examination of molasses
for, 624.
Diabase from St. Vicente, Cape Verde
Islands, analysis of, 720.
. from Weilburg, 959.
Diacetonephenanthraquinone, 597.
Diacetylamarine, 799.
Diacetylflavol, 74.
Diacetylformamidine, 1099.
Diacetylphenylenediamine, 916.
Diacetylpyromecazonic acid, 791.
Diacetylresorcinol, 917.
Diacetylsafranine hydrochloride, 732.
D iacety Itoluy lene di amine, 916.
Dialkylanilines, nitroso-, periodides of,
979.
Dialkyldisulphisethionic acids, 972.
Dialkyldisulphobenzoates, 999.
Diallage, chemical composition of,
1068.
Diallylamine, action of sulphuric acid
on, 1086.
Diamidobenzenes, isomeric, action of
paradiazobenzenesulphonic acids on,
183.
Diamines, primary, action of ethyl chlor-
acetate on, 797.
Diamylanilineazyline, 55, 185.
Dianhydrolupinine, 100.
Dianilidoquinone and its deriratives,
1117.
Dianilidotoluquinone, and derivatives
of, 1118.
Dianthramine, 1139.
Diaspore, 35.
Diazoamidobenzene, tri- and hexa-
bromo-, 661.
Diazoazobenzenedisulphonic acid, 182,
Diazoazobenzenesulphonic acid, 181.
Diazobenzene, tribromo-, nitrate and
other salts of, 660.
Diazobenzenimide, tribromo-, 661.
Diazo-derivatives, 180, 584, 1102.
of "symmetrical" tribrom-
aniline, 660.
Diazophenol, dibromo-, 660.
Diazoresorufin, 733.
Dibenzhydroxamic acid, 1130.
Dibenzyl, 807.
Dibenzylamarine and its iodides, 203.
Dibenzylbenzene, metadinitro-, 203.
Dibutyianilineazyline, 55, 185.
Dicarbocaprolactonic acid and its de-
rivatives, 970.
Dichromates, process for preparing, 890.
Dicinnamyl ketone, paranitro-, 1120.
Dicodethine, 359.
Dicyanodiamide, 907, 1090.
Dicyandiamidocarboxylic acid and it-
salts, 907.
from dicryanodiamide, 1086.
Dicyanopyrene, 1004.
Di-diphenyl, 469.
Didymium, a new element accompany-
ing, 18.
atomic weight of, 852.
Dielectric constants of insulating liquids,
945.
Diethoxydinitrodiphenylamine, 466.
Diethoxyhydroxycaffeine, 355.
Diethoxyhydroxyethyltheobromine, 357.
Diethyl acetylenetetracarboxylate, 46.
amarinedicarboxylate, 799.
furf urinedicarboxylatc, 800.
hydrocollidinedicarboxylate, 82.
hydi'ofurfuryllutidinedicarboxy-
late,"ll51.
hydrophenyllutidinedicarboxylat^,
1151.
ketone, combination of, with hy-
drogen sodium sulphite, 1080.
monomethylpropenyltricarboxy*
late, 45.
phenyUutidinedicarboxylate, 1 151.
quinone tetrahydridedicarboxylate,
1084.
Diethyl allylamine and its platino- and
platini- chloride, 909.
Diethylamine hydrosulphide, vapour-
tension of, 727.
IXDEX OF SUBJECTS.
122i)
Diethylaniline, action of benzotrichloride
on, 861.
and its platinochloride, preparation
of, 578.
nitro-, 868.
paranitro-, 1100.
Diethylanilineazyline, 55, 185.
Diethylbarbituric acid, 315.
Diethylbenzoylaniline, 861.
y-Diethylbutyrolactone, 39.
Diethyldisulphisethionic acid, sodium
salt of, 972.
Diethyldisulphobenzoic acid, salts of,
999.
Diethylformamide, platinochloride of,
1089.
Diethylorthotoluidine and its platino-
chloride, preparation of, 578.
Diethylparaphenylenediamine, 869,
1100
Dietbylquinol, nitro - derivatives of,
466.
DieMiylsafranines, two, 732.
Diethylsulphamic acid and its barium
salt, 971.
Diethyltoluene and its derivatives, 1093.
Diethyltolyl bromide, 1094.
Diethylxylylphosphine, 58.
Dietrichite, 433.
Diformylmetaphenylenediamine ? 326.
Diffusion of some organic and inorganic
compounds, experiments on, 1047.
Diffusion residue, feeding value of fresh
and dried, 680.
from beet- 811 gar manufacture,
preservation of. 695.
DifPusioscope, 630.
Diffusometer, 629.
Digestion, artificial and natural, of ni-
trogenous matter, 227.
in the stomach, researches on, 815.
influence of calomel on, 743.
Digestive ferments, decomposition of,
815.
Dihexylthiocarbamide, 1075.
Dihydrocollidine and its salts, 84.
Dihydrohydroxypyridinecarboxylicacid,
aldehyde of, 793.
Dihydronaphthoic acid, synthesis of, 808.
Dihydro-oxindole, 919.
Dihydroxyanthracene from a-anthra-
quinonedisulphonic acid (flavol), 74.
Dihydroxybenzene, tetranitro-, 327, 329.
a- and /S-Dihydroxybenzophenone and
its compounds, 991.
Dihydroxy butyric acid, 574.
Dihydroxycoumarin, 200.
Dihydroxyphenyl disulphide and its
compounds, 988.
oxidation of the methylic
ether of, 989.
Dihydroxytoluquinone, 1118.
VOL. XLTV.
Dihydroxy-xylene, 918.
Di-isobutylquinol and its chloro-,
bromo-, and nitro-derivatives, 60.
Di-isopropylmetacresol and its deriva-
tives, 463.
Dilituric acid, 913.
Dimethoxyumbellic acid, 200.
Dimethoxybenzoid, 335.
Dimethyl acetylenedicarboxylate, 313.
Dimethylacetoacetic acid, 41.
Dimethylacetoxime, 580, 581.
Dimethylsesculetin, 199.
Dimethylamarine, formula of, 204.
Dimethylamidoazotribromobenzene, 661 .
DimethylamidoquinoHne, 811.
Dimethylaniline and its platinochloride,
preparation of, 578.
paranitro-, 1100.
Dimethylanilineazyline, 55, 185.
Dimethylanthramine, 1139.
Dimethylbarbituric acid, 315.
Dimethylcumidine, 324.
Dimethyldisulphisethionic acid, sodium
salt of, 972.
Dimethyldisulphobenzoic acid, salts of,
1000.
Dimethylethylene oxide, symmetrical,
567.
Dimethylformamide, platinochloride of,
1089.
Dimethylformamidine, and its hydro-
chloride, 731.
Dimethylmetachloraniline and its salts,
579.
Dimethylmetamidopheneto'il, 579.
Dimethylnaphthalene, 79.
Dimethylnaphthol, 79.
Dimethylorthotoluidine and its platino-
chloride, preparation of, 578.
Dimethyloxamide, 1018.
Dimethylparatoluidine and its platino-
chloride, preparation of, 578.
Diraethylphenylacetic acid, a-nitro-, and
its salts, 1096.
symmetrical, and its salts,
1096.
Dimethylpiperidine, and its constitu-
tion, 1154.
Dimethylsuccinimidine hydrochloride,
1089.
Dimethyltropine, decomposition of, by
heat, 672.
Dimethylxylidines, 579.
Dimethylxylylphosphine, 58.
a-Dinaphthadiquinone ? 70.
/3-Dinaphthalene oxide, 209.
j8-Dinaphthol, and its derivatives, 208.
picrute, 209.
a-Dinaphthyl, 209.
Dinaphthylamine, a-, j3-, and a-^-, 594.
Dinaphthylenamide and its derivatives,
209.
1230
INDEX OF SUBJECTS.
Dinaphthylenepbenylamine, 209.
Dioptase from the Corderillas of Chili,
446.
Diorite, analysis of, 720.
Diorites of Montreal, 561.
Dioritic rocks of Klausen in the Tyrol,
1069.
Dioxalethyline, 50.
])ioxymethylditolyl, quinone of, 467.
Diparahydroxyphenylthiocarbamide,
1110.
Diparaphenylethylthiocarbamide, 1106.
Dipentenyl-benzene, 1094.
Diphenoquinone, dichloroxydichlorodi-
bromo-, 984.
Diphenyl, derivatives of, 343.
mononitrodibromo-, 343.
trinitrodibromo-, 343.
carbonate, conversion of, into sali-
cylic acid, 589.
Diphenylacetoxime, 580.
Dipbenylamine, use of, in qualitative
analysis, 239.
Diplienylarsine trichloride, 187.
Diphenylcarbamide, 1107.
metadinitro-, 583.
w-Diphenylcarboxylic acid and its salts,
468.
^-Diphenylcarboxylic acid, 468.
Diphenyldiisoindolazobenzenesulphonic
acid, 343.
Diphenyldiisoindolazodibromophenol,
342.
Diphenyldiisoindolazotribromobenzene
hydrochloride, 342.
Diphenyldiisoindole, and its salts, 342.
azo-colouring substances from,
342.
Diphenyldiisoindolesulphanilic acid, 343.
Diphenyleneketone, dibromo-, 921.
Diphenylformamidine, 49, 731.
Diplienylglyoxime, 1120.
Diphenylmethane, metanitro-, and me-
tamido-, 202, 203.
tetramido-, and its compounds,
991.
tetranitro-, preparation of, 990.
Diphenyloxide ketone, 664.
Diphenylpararosaniline, 807.
Diphenylphosphoryl chloride, 735.
Diphenylpropane, 977.
Diphenyltaurocarbamic anhydride, 664.
Diphenylthiocarbimide, meta-, nitro-,
and dinitro-, 801.
Diphenylthiocarbamide, mono- and di-
nitro-, action of iodine on, 582.
Dipropylallylamine, and its platinochlo-
ride,'909.
Dipropylaniline, 185.
Dipropylanilineazyline, 55, 185.
Dipropyldisulphobenzoic acid, barium
suit of, 1000.
Dipropylmetacresol, 463.
Dipropylsulphone, 659.
Diprotocatechuic acid, 335.
Dipyridine, 483.
Dipyridyl, 88.
y-Dipyridyl and its derivatives, 483.
Dipyridyl-carboxyUc acids and their
salts, 87.
Dipyridyl derivatives, 85.
Dipyridyl-dicarboxylic acid, 1010.
Dipyromeconic acid, nitroso-, 793.
Diquinidine and its platinochlo ride, 601.
Diresorcinol, dinitro-, 1114.
Disinfectants, 249.
Disodium glycollate, formation of,
1085.
phenylsulpharsenate, 187.
salicylate, action of acetochlorhy-
drose on, 76.
Dissociation heat of the water molecule
and the electric luminosity of gases,
547.
hypothesis, contributions to, 489.
Lockyer's, 762.
" Dissolved wool," manurial value of,
500.
Distillation in a vacuum, 545.
Distyrene, 474.
Distyrenic acid, 474.
Dithymyl carbonate, 1112.
Dodecyl alcohol, normal primary, pre-
paration of, 1075.
Dog, oxygen-pressure under which, at a
temperature of 35°, the oxyheemoglo-
bin of, begins to give up its oxygen,
678.
with biliary fistula, observations
on, 818.
Dolomite from Teruel in Spain, 31.
Domeykite, from Zurickau, 433.
Dopplerite, substance resembUng, from
a peat bog near Scranton, Pa., 427.
from Aussee, 160.
Double chlorides of lead and ammonium,
717.
Double refraction, anomalous, of certain
salts crystallising in the regular
system, 1041.
Double salts, basic, 904.
formed by fusion, 11.
Double sulphites of manganese and the
alkalis, 718.
Driving-bands, dressing for, 640.
Dulong and Petit's law, demonstration
of : a lecture experiment, 281.
Durene, oxidation of, by chromic acid,
333.
monobromo-, 334.
Dr.rylic acid, and its dinitro-derivative,
333.
Dusts, explosive and dangerous, 836.
Dyeing novelties in, 895.
INDEX OF SUBJECTS.
1231
Dyes from dimethylaniline and chlo-
ranil, 1098.
• blue and violet, preparation of,
759.
green, 861.
new, 406.
new method of detecting, in yarns
or tissues, 523.
obtained by the action of phthalic
anhydride on coal-tar quinoline, 922.
preparation of, 636.^
resorcinol, tests for, 689.
" Dysoxydabel," 709.
E.
Earthenware goods, 888, 890.
Earth-nut cake, poisoning of cattle by,
818.
■ meal as food for milch cows, 820.
Edmondsite, 169.
Elastin, behaviour of, in peptic diges-
tion, 927.
Elastin peptone, 927.
Electric a,ro, an arrangement of, for the
study of radiation of vapours, 262.
reaction current of, 4.
Electric discharge in rarefied gases, 266.
positive and negative, dif-
ference of, 949.
in air and other gases. 700.
Electric double refraction of insulating
liquids, 946.
Electric liquid condenser for examining
the phenomenon of double refraction,
947.
Electric researches, 697, 766, 945.
Electric resistance of carbon contacts,
841.
Electric shadows, 416.
Electric spark, particles of matter in,
415.
Electrical conductivity of silver haloid
salts, 769.
Electrical energy and chemical action,
413.
Electricity, application of, in metal-
lurgy, 398.
fuel to produce, 626.
of flame, 141.
statical, researches on, 763.
units of, 764.
Electrodes, polarised, distortion of, 897.
Electro- dynamic interference of alter-
nating currents, 897.
Electrolysis of the sulphates of zinc and
copper, quantities of heat evolved in,
1043.
new experiment in, 540.
with carbon electrodes, of solu-
tions of binary compounds and of
various acids and salts, 592.
Electrolysis, zinc-carbon couples in, 4.
Electrolytes, constitution of, 540.
Electrolytic researches, 1042.
Electromotive force of certain galvanic
combinations, 764.
Element, new, accompany ingdidymium,
18.
Elements in various allotropic modifica-
tions, sp. gr. and chemical affinities
of, 779.
ultra-violet spectra of, 262.
Embryos of ungerminated rye, analvsis
of, 107.
Emerald from Paavo, in Finland, 561.
Enamels, porcelain, composition of, 397.
Encysted fluids, contribution to the
chemistry of, 874.
Ensilage and hay from a poor quality of
grass, 1026.
Enterochlorophyll, 1159.
Epichlorhydrin, action of benzoic anhy-
dride on, 62.
Epidemics caused by unsound bread,
1157.
Epidote, chemical composition of, 443.
Epistilbite, analysis of, 442.
Erbium, spectral researclies on, 954.
Ergot, and pharmaceutical preparations
of, 640.
Ersbyite, so-called, from Pargas, 561.
Eruptive rocks near Try berg, in the
Black Forest, 723.
Erythrochromium salts, normal and
basic, 554, 556.
Erythroxyanthraquinone, new method
of preparing, 71 .
Essence of angelica root, 809.
sandal wood, 76.
Ethaldehyde, action of acetic chloride
on, in presence of zinc-dust, 62.
Ethane, heat of formation of, 515.
Ethenylamidonaphthol, 1114.
Ethenjldipropioniniidine, 1099.
Ethenyltricarboxylic acid, 45.
Ether, a new product of the slow com-
bustion of, 860.
Ethereal oils, some, 3 16.
Ethers, compounds of hydrogen sulphide
and selenide with, 961.
Ethoxycaffeine, 355.
/3-Ethoxycrotonic acid and its salts,
9o8.
Ethoxyethenyltricarboxylio acid, 45.
Etboxyethyltheobromine, 357.
a-Ethoxyhydromethylquinoline, 1147.
Ethoxyhydroquinoline, 1146.
Ethoxymetatoluic acid, 471.
Ethoxyquinoline, 1146.
tetrahydride, preparation of
methyl- and ethyl-derivatives of, 87i.
4 n 2
1232
INDEX OF SUBJECTS.
Kthyl acetate, commercial, and prepa-
ration of, 1080.
acetoacetate, action of nitric acid
on, 573.
action of trimethylene bro-
mide on, 1083.
. addition of bromine to, 177,
656.
■ and its mono-derivatives,
action of nitric acid on, 914,
« condensation-products of,
1083.
— — dibromide, 177.
halogen substitution-com-
pounds of, 177.
preparation of, from mono-
chloracetone, 311.
acetoacetates, halogen-substituted,
1082.
acetomalonate, 44.
acetopropylacetate, 915.
aeetyldithiocarbamate, 40.
acetylenetetracarboxylate, 912.
amidacetate, and its hydrochloride,
1087.
anishydroxamate, 462.
benzanishydroxamate, a- and i3-,
and decomposition of, by heat, 1461.
. benzhydroxamate, 462.
/3-benzoiso8uccinate, 912.
benzomalonate, 912.
• benzoyl acetate, action of trimethy-
lene bromide on, 1083.
benzoylsantonite, 77.
butonhexacarboxylate, 912.
^-butyl ketone, 966.
chloracetate, action of, on primary
diamines, 797.
coUidinedicarboxylate, and its de-
rivatives, 83.
coUidinemonocarboxylate, 84.
dibromhydrocoUidinedicarboxylate
dibromide, 82.
dibromocollidinedicarboxylate
dibromide, 82.
dihydrocollidinemonocarboxylate,
84.
dinitrocinnamate, reduction of,
918.
■" ethenyltricarboxylate, 45.
' /3-ethylacetosuccinate, decomposi-
tion of, 456.
"■ ethylsantonite, 78.
hippuramidacetate, 339.
isallylenetetracarboxylate, 46.
• isopropylethenyltricarboxylate, 46.
■ malonate, action of trimethylene
bromide on, 1083.
" meconates, 656.
- raesityloxideanhydrodicarboxylate,
1083.
- ' ■ me8ityloxidedicarboxyl{:te, 1083.
Ethyl methenyltricarboxylate, 44.
monochlorethenyltricarboxylate,
45.
mononitroanthrolate, nitro80-an-
throne of, 73.
mucobromate, action of potassium
nitrite on, 47.
nitro-orthocresolate, 662.
nitroparacresolate, 662.
orthocresyl ether, preparation of,
585.
orthonitrobenzomalonate, 912.
orthonitrocinnamylacetoacetate,
587, 588.
orthonitrophenvlisonitrosoacetate,
920.
orthonitrophenylnitrosoacetate,
920.
peroxide, 305.
phenylcarbonate, conversion of,
into salicylic acid, 588, 589.
phenylisonitrosoacetate, 920.
phthalylacetoacetate, 806.
propenyltricarboxylate, 45.
propylethenyltricarboxylate, 46.
quinonetetrahydridemonocarboxv-
late, 1085.
succinosuccinate, constitution of,
1084.
tetramethylenedicarboxylate, 1084.
thiocyanate, action of thiacetic
acid on, 39.
thymol carbonate, 1112.
Ethy lace timid e, and its hydrochloride,
1090.
Ethylacetonitranibde, 579.
Kthylaldoxime, 569.
Ethylallylamine and its platino- and
platini-chloride, 909.
Ethylamido-a-caprocyamidine, 1154.
Ethyl-am ido-cresols, 866.
Ethylamiue hydrosulphide, vapour-ten-
sion of, 727.'
Ethylaniline and its acetyl-derivative,
preparation of, 578.
Ethylazaurolic acid and its derivatives,
40.
Ethylbarbituric acid, 314.
Ethylbenzene, brom-, from styrolene, 70.
parabrom-, 320.
Etliylbenzimide hydrochloride, 1090.
Ethylbenzoyltetramethylenecarboxylic
acid, 1083.
Ethylbiguanide and its compounds, 974.
Ethylbromisatoid, 201.
Ethylcapronimide hydrochloride, 1090.
Ethylcarbostyril, 204.
Etlivlcoumaric acid, 472.
Ethylcoumaric acid and its salts, 471.
Ethylcurcumin dihydride, mono- aJid
di-, 481.
Ethylcyanethine, 353.
INDEX OF SUBJECTS.
1233
Ethyldibromosuccinic acid and its salts,
44.
Ethyldichloramine, action of, on aro-
matic amines, and on hydrazoben-
zene, 915.
Ethylene bromide, tetranitro-, Villier's,
formation of, 564.
ehlorhydrin, preparation of,
1077.
c;yanide, action of, on hydrochloric
acid and alcohol, 730.
dibrom-, symmetrical and benzene,
action of aluminium bromide on,
807.
direct combination of hydrogen
with, 565.
orthocresyl ether, preparation of,
585.
oxide, thermal constants of, 275.
thermochemical study of,
174.
perchloride, heat of formation of,
514.
phenylethyl oxide, 803.
series, some oxides of, and their
action on water, 566.
Ethylene-dimorphine, 359.
Ethylenedisulphonic acid,
salt of, 912.
Ethyleneimidothiocarbamate
mide, 665.
Ethylformimide, and its derivatives,
731.
Ethylglyoxaline, and its derivatives,
910, 911.
Eth ylhydrazinhydrocinnamic
li32.
Ethylhydrocarbazostyril, 1132.
Ethylhydrocarbostyril, 204.
Ethylidene acetocliloride, 452.
diacetate, 453.
oxyalcoholates, 783.
oxychloride, constitution of, 788.
Ethylideneoxyethyl alcobolate, 788.
Ethylidenimide silver nitrate, 903.
Ethyl-leucazone and its derivatives, 40.
Ethylmalic acid, monobrom-, sodium
salt of, 312.
Ethylmalonic acid, action of chloroform
on the sodium salt of, 312.
action of ethylene bromide
on the sodium salt of, 730.
Ethylmetatoluylglycocine, 54.
Ethyl-a-metaxylylglycocine, 594.
Ethylmethylacetoxime, 580.
Ethylmethylacetoximic acid, 573.
a-Ethyl-/3-methylvalerolaetone, 456.
Ethylmorphine, 358.
Ethylnitraniline, 579.
Ethylnitrolic acid, preparation of, 40.
Ethyl-nitrous acid, potassium salt of,
914.
potassium
hydrobro-
acid.
Ethylorthotoluidine and its acetyl-deri-
vative, preparation of, 578.
Ethylorthotolylglycocine, 594.
Ethyloximide, derivatives of, 1088.
Ethylphenolammonium iodide, ortho-
brom-, 1111.
Ethylphthalimide, 476.
Ethylpropionimide hydrochloride, 1090.
y-Ethylpyridine, synthesis of, 3 151.
Ethylquinazolcarboxylic acid, 812.
Ethylquinazole, and its salts, 812.
Ethylsantonous acid, 78.
Ethylsuccinimide, 477.
derivatives of, 1088.
hydrochloride, 731.
Ethylsulphamic acid, 971.
Ethylsulphonic acid and its salts, 971.
Ethyltheobromine, brom-, and its deri-
vatives, 357.
Ethyltoluylenediglycocine, 797.
Ethyltrinitro-a- and |8-naphthol, 863.
ot-Ethylvaierolactone, 455.
Euclase from the Alps, 34.
Eucryptite, 439.
Eugenol, constitution of, 200.
Eulytine, 433.
Eurite, Dumont's, 958.
Eusynchite, analysis of, 1063.
Euxanthic acid, derivatives of, 219.
Euxanthone, 219.
Euxenite from N. Carolina, 1064.
from Wiseman's mica mine, 163.
Explosion of a mixture of carbonic
oxide and oxygen with varying quan-
tities of aqueous vapour, velocity of,
12.
of a tube containing liquid car-
bonic anhydride, 422.
wave of, 777.
Explosive alloys of zinc with certain
platinum metals, 19.
Explosive mixtures, some relations be-
tween temperatures of combustion,
specific heats, dissociation, and pres-
sure of, 771.
F.
Fat, examination of, 125, 936.
nutrition by, 740.
transformation of, in the alimen-
tary canal, 744.
Fats, analysis of, 1036.
recognition of suint in, 750.
Fatty acids containing the isopropyl-
group, action of nitric acid on, 176.
from peat, 652.
Fatty matters, estimation of glycerol in,
123.
1234
INDEX OP SUBJECTS.
I'eeding stuffs, different, proportion of
nitrogen in the form of imides, albu-
min, and nuclein in, 748.
Fehling's solution, rapidity of separa-
tion of cuprous oxide by the action of
invert-sugar on, 385.
Felspar, change of colour in, under the
influence of light, 438.
Fergusonite from Brindletown, Burke
Co., N. Carolina, 32, 163, 1064.
Fermentation, alcoholic, formation of
amyl alcohol in, 908.
frothy, contribution to the problem
of, 892.
influence of barley on, 756.
influence of calomel on, 743.
influence of oxygen on, 489.
schizomycetic, 363.
Ferments, digestive, decomposition of,
815.
unorganised, behaviour of, at high
temperatures, 101.
Ferns, some epiphytic, inorganic con-
stituents of, 108.
Ferric hydrate, change which it under-
goes after a time, 24.
hydrates, 24.
oxide, rehydration of, 853.
salts, reduction of, 512.
sulphate, new properties of, 1178.
Ferromanganese ore from Portugal,
analysis of, 858.
Ferronitrosulphuric acid, salts of, 297.
Ferrous citrate and its double and se-
condary salts, 458.
Fibrin, cause of the evolution of oxygen
from hydrogen peroxide by, and the
influence of hydrocyanic acid in pre-
venting the activity of, 227.
Fibrous coal from Antioquia, analysis of,
941.
Filters, asbestos, preparation of, 506.
Fire extinguisher, liquid carbonic anhy-
dride as, 408.
Firwood charcoal, composition of,
533.
Fish, chemistry of, 1179.
Fish oil, new process for the extraction
of, 692.
Flame, electricity of, 141, 412.
luminosity of, 539, 697.
nature of the vibratory movements
which accompany the propagation of,
in mixtures of combustible gases,
148.
velocity of propagation of, 845.
Flameless combustion, 523, 626.
Plashing point of petroleum, determina-
tion of, 517.
Flavaniline, 600.
Flavanthracenedisulphonic acid and its
salts, 74.
Flavenol, 600.
Flavol and some of its derivatives, 74.
Flavoline, 600.
Flour, detection of adulteration of, with
rye-meal, 392.
Fluidity and galvanic conductivity,
769.
a-Fluoboracetone, decomposition of, by
water, 655.
Fluorene, trichloro-, 922.
derivatives, oxidation of, 921.
Fluorescence, 763.
Stokes's law of, 537.
Fluorine, discovery of, in the idocra^e
from Vesuvius, i067.
Fluosilicates of insoluble bases, harden-
ing of soft calcareous rocks by means
of, 940.
Fodder, dry, feeding of cattle with,
816.
Fodder-cabbage, composition of different
varieties of, 373.
Fodders, composition of. 111.
various, for cows, value of, 820.
Foliation, study of "longrain," and
measure of, in schistose rocks by
means of their thermic properties,
300.
Food, chemistry of, 1160.
effect of, on sheep of different
breeds, 226.
use of boric acid for preserving,
1178.
Forest trees, manuring of, 617.
Forests, comparative meteorological ob-
servations in, 614. £
Formaldehyde, ammoniacal alkaline sQ- I
ver solution as a test for, 125. i
Formamide, preparation of, 1088. ^
Formamidine hydrochloride, 731.
Formanilide and its homologues,
325.
Formanthramine, 1140.
Formic acid, decomposition of, by the
silent discharge, 457.
presence of, in plants, 611.
Formoparatoluide, 326.
Formorthotoluide, 326.
Formylbenzylamidobenzoic acid, 1009.
Fossil resin, analysis of, 941.
Fowl, tissue-waste in, during starvation,
603.
Fozaite from S. Vicente, Cape Verde
Islands, analysis of, 720.
Fraxinus excelsior, constituents of the
leaves of, 216.
Fraxitannic acid and its derivatives,
216.
Freezing of aqueous solutions of carbon
compounds, law of, 7.
Frigidite, 428.
Fuel to produce electricity, 626.
INDEX OF SL/B.TECTS.
1235
Fulminates, coiiTersion of, into hy-
(Iroxylamine, 1074.
Fumaric acid, geometrical formula of,
deduced from its products of oxida-
tion, 44.
bromo-, 313.
chloro-, and its salts, 313.
iodo-, and some of its salts,
313.
Fungus, parasitic, a newly observed
{Phoma gentiancB) , 1025.
Furfurane, tetrabromo-, 912.
dibromo-, tetrabromide of, 912.
Furfurine, derivatives of, 799.
Furil, action of potassium cyanide on,
805.
Furnace gases, absorption and utilisa-
tion of sulphurous anhydride con-
tained in, 248.
Fusaiu, analysis of, 941.
Fusel oil in brandy. Otto's method for
the estimation of, 123.
. G.
Gralena with octohedral cleavage, 428.
Gallamide, 335.
Gallanilide, 335.
Gallic acid, fusion of, with soda, 59.
Gallium, separation of, 21, 153, 156,
293, 715, 1054.
separation of, from rhodium, 715.
Gallocyanins, 70, 796.
Galvanic batteries, substitution of hy-
drogen peroxide for nitric acid in,
765.
Galvanic circuit, metallic, of Ayrton
and Perry, 141.
Galvanic combinations, electromotive
force of, 764.
Galvanic conductivity, fluidity and,
769.
Galvanic current, action of, on chlorides
and chlorates, 149.
Galvanic currents, theory of, 948.
Galvanic polarisation, 410.
Garnet, chromium, 35.
in the trachytes of Hungary,
166.
white, 35.
Garnet rock, 35.
Garnet rocks of the Bastogne region,
958.
Gas, illuminating, examination of, 629.
in " vacuum discharges," move-
ment of, 5.
Gas analysis, apparatus for, 1048.
apparatus, improvements of,
378.
Gas-carbon, behaviour of, in chromic
acid, 699.
Gaseous mixtures, combustion of, 844.
Gaseous volume, an instrument for cor-
recting, 378.
Gases, absorbed, effect of, on the elec-
trical conductivity of carbon, 769.
absorption of, by liquids under
high pressures, 418.
certain, direct estimation of the
heat of combination of, 274.
combustible, nature of the vibra- '
tory movements which accompany tht^
propagation of flame in mixtures of,
148.
critical point of, 277, 898.
dissociation heat of the water
molecule and the electric luminosity
of, 547.
from a boiler furnace, examination
of, 942.
mixed, critical point of, 277.
non-luminosity of, at high tem-
peratures, 697.
rarefied, electric discharge in,
266.
specific heats of, at high tempera-
tures, 771, 898.
Gasiiolders, zinc, storage of oxygen in,
619.
Gas-lime, analysis of, 506.
Gasometer, special form of, 847.
zinc, containing oxygen, explosion
of, 524.
Gastric juice, a pepsin in, 103.
Gay-lussite, artificial and natural,
430.
Gedrite in the gneiss of fieaunan, near
Lyons, 444.
Gentianose, 810.
Gi rman standard silver coins, presence
of gold in, 629.
Germination of seeds, part played by
lime in, 490.
Glairin or baregin, 302.
Glass, 397.
influence of temper on the electri-
cal resistance of, 701.
toughened, 399.
Glass laboratory vessels, cleansing of,
395.
Glass stoppers, fixed, removal of, 524.
Glazes, experiments on, 890.
Globularetin, 1025.
Globularia, chemistry of, 1025.
Glow discharge, researches on, 949.
Gluconic acids, isomeric, 652.
Glucosalicyl-carbamide, 347.
Glucosalicyl-thiocarbamide, 348.
Glucosalicyl-t-olylenediamine, 348.
Glucose, anhydrous, mixed with refined
cane-sugar, detection of, 8S4.
1236
INDEX OF SUBJECTS.
Glucose, conrersion of maltose into, 38.
GHucosides, 347.
Glutamine, 658.
Gluten, amount of, in wheat, 236.
Glutonic acid, 312.
Glycerol, estimation of , in fatty matters,
i23.
in beer, 385.
nitro-, reconversion of, into gly-
cerol, 788.
Glycerylphosphoric acid, 682.
Glj'cocine, action of hydrochloric acid
on, 1087.
pure, preparation of, 337.
Glycocine ethers, 593.
Glycocineiniide-anhydride, 1087.
Glycocines, 593.
Gly collates, solid, heat of formation of,
644.
Glycollic acid, heat of formation of its
salts, 774, 775,
Glycuronic anhydride, 219.
Glyoxal, action of ammonium cyanate
on, 178.
action of hydroxylamine on, 804.
Glyoxalethyline, synthesis of, 72S.
Glyoxaline and its homologues, 308.
Glyoxalines, 910.
Glyoxahsoamyline, 1086.
Gly oxalisobuty line, 1086.
Glyoxahso-oenanthyline, 1087.
Glyoxalpropyline, synthesis of, 729.
Glyoxime, 8U4.
" Glyoximes," 805.
Gneiss of Beura, 960.
Gold, behaviour of, in chromic and
nitric acids, 699, 700.
Gutzkoff's process for the separa-
tion of, in California, 251.
oxides, hydrated, 855.
salts, 853.
■ separation of, from sulphides by
air-blast, 400.
tellurides, roasting of, 691.
Gombo, cultivation of, 613.
Goose fat, 741.
Grain, estimation of starch in, 624.
and potatoes, simultaneous use of,
in spirit factories, 630.
Granite, Kapikiwi, from Finland, 447.
vein, near Tryberg in the Black
Forest, 724.
hills of Konigshain, in Oberlausitz,
with especial regard to the minerals
found therein, 446.
Granites on the banks of the S^adne, 36.
Granitite from " Tryberg," 723.
Granuline, 1065.
Grape- juice, solubility of the colouring-
matter of wine in the various con-
stituents of, 1141.
Grapes, ripe, studies on, 881.
Grape-sugar, anhydrous, from aqueous
solution, 175.
pure, Schwarz's process for
preparing, 565.
reducing power of, for alka-
line copper solutions, 244.
Graphite from Kaison, analysis of,
941.
Graphitic acid, 593.
Guaiacol, action of nitrous acid on, 464.
dinitro-, diamido-, and diimido-,
464.
Guaiaconic acid, 470.
Guaiaretic acid, 470.
Guanidine, constitution of, 973.
Guano, a new, from Australia, analysis
of, 375.
comparative estimations of nitro-
gen in, 1030.
Guanylthiocarbamide, 1090.
Guarana, amount of caffeine in, as
compared with that in the seeds, &c.,
232.
Gunpowder, chemical theory of, 258.
H.
Hsematein, 349.
Haematite, regular polyhedral cavities
in, 1066.
Hsematococcus, assimilation by, 611 .
llsematosin, action of hydrogen peroxide
on, 103.
Hsematoxylin, 349.
Haemoglobin, estimation of, in blood by
optical means, 394.
Hailstorms and their origin, 234.
Halogen acids, estimation of, in presence
of hydrogen sulphide, 934.
Halogens, estimation of, in carbon-com-
pounds, 379.
in mixed haloid ethers, " reaction
aptitudes " of, 787.
reciprocal displacement of, 8.
Hamathionic acid, 219.
Hausmannite, artificial, 859, 1062.
Hay, meadow, artificial digestion of,
1025.
Hay and ensilage from a poor quality of
grass, 1026.
Hayesine, new locality for, 162, 1062.
Heat changes at the poles of a volta-
meter, 767.
distribution of, in the idtra-red
region of the solar spectrum, 143.
evolution and absorption of : a lec-
ture experiment, 454.
evolution of, in the absorption of
gases by solids and liquids, 702.
INDEX OF SUBJECTS.
1237
gases,
Heat of combination of certain
direct estimation of, 274.
of combustion of isomeric organic
compounds, relation of, to their den-
sities, 1044.
formation of carbon tetrachloride
and ethylene perchloride, 544.
— of double salts of lead and
potassium iodides, 275.
of silver iodide, and its alloys
with cuprous and lead iodides, 274.
of solid glycoUates, 644.
of the chlorides and oxides of
antimony and bismuth, 544.
of the chlorides of phosphorus
and arsenic, 544.
of volatile carbon compounds,
543.
' of glycoUates, 708.
■ of potassium salts containing
sulphur, 706.
of the salts of glycollic acid,
774, 775.
Helicin, constitution of, 347.
Helvite from Virginia, 437.
Hemellithene and its derivatives, 53.
Hemmellithenesulphonic acid, 53.
Hemialbumosuria, 1162.
Hemielastin, 927.
Hemillactine, 927.
Hemipinic acid, 996.
Heptane of Finns sahiniana, and deri-
vatives of, 651.
Hepto-lactones, 455.
Heptylene from Pinus sabiniana, 652.
Hei landite, analysis of, 442.
j8-Hexane, conversion of methyl-/3-
methyl iodide into, 966.
Hexdecyl alcohol, normal primary, pre-
paration of, 1075.
Hexenylglycerol, 570.
Hexethylbenzene, 1091.
Hexhydropicolinic acid, 794.
Hexic acid, so-called, 1085.
Hexyl alcohol, normal primary, and its
derivatives, 1075.
Hexylammonium hexylthiocarbamate,
1075.
Hexyl benzoate, 1075.
caproate, 570.
chloride, 1075.
formate, 1075.
methyl ketone, 729.
Hexylbenzene, 977.
Hexylene oxide, 567.
Hexylthiocarbauiide, 1075.
Hexylthiocarbimide, 1075.
Hiddenite, an emerald-green variety of
spodumene, 440.
Hieratite, a new mineral species, 955.
High temperatures, determination of,
274.
Hippuramidacetic acid and its salts,
339.
Hippuric acid, 337. *
Hippuryl carbamide, 1088,
glycollamide, and its hydrochloride,
339.
Homatropin, salts of, 671.
Homoferulic acid, 201.
derivatives of, 198.
Homonieotianic acid, 739.
Hornblende after olivine, 444.
Horse, digestive fluids and digestion of,
487.
observations on the working power
of, when fed with lupines and oats,
102.
Horses, feeding of, with flesh-meal, 102.
Human saliva, alkalinity and diastatie
action of, 488.
nitrites in, 227.
urine, paraxanthine, a new consti-
tuent of, 601.
Humite, composition of, 436, 1068.
Humus, in soils, estimation of, 247,
830.
Hunt-Douglas process for the extraction
of copper, modification of, 400.
Hydrated salts, constitution of, 780.
Hydraulic silica and its functions in
hydraulic cements, 754, 755.
Hyrazines, compounds of, with the
ketones, 798.
Hydrazobenzene, action of ethyldichlor-
amine on, 915.
Hydrazobenzenedisulphonic acid, 479.
Hydriodic acid, systematic method of
testing for, 1172.
Hydroacridine, 1134.
Hydrobenzoin diacetate, 806.
Hydrobilin and stercobilin, identity of,
1159.
Hydrobromic acid, systematic method
of testing for, 1172.
Hydrocatfuric acid, 356.
Hydrocarbon, (CsHii)^, 39.
CioUig, prepared from
allyl
allyl
di-
di-
propyl carbinol, 1073
t!i2H2o, prepared from
methyl carbinol, 1074.
flame spectrum, origin of, 641.
Hydrocarbons, action of aluminium
chloride and bromide on, 577.
action of ozone on, 37.
addition-products of tlie nitro-de-
rivatives with, 317.
aromatic, action of bromine on,
977.
from Caucasian petroleum, chlo-
rination of, 564.
from peat, 652.
of the acetylene series, action of,
on mercuric salts, 172.
i2a«
INDEX OF SUBJECTS.
its
Hydrocarbons of the formula (CgHg),,,
75.
Ilydrocarbostyril, 1132.
constitution of, 204.
Hydrochloric acid, electrolysis of, 142.
a lecture experiment,
280.
systematic method of testing
for, 1172.
hydrocyanic, and thiocyanic
acids, method of estimating when
8imultaneou?ly present, 1173.
Hydrocinchonidine, and its salts, 97.
Hydrocinnamic acid and some of
derivatives, 195, 1123.
bromacetoparamido-, 195.
bromamido-, 195.
diamido-, 195.
diazoamidobrom-, 195.
metabrom-, 195.
nitrosoethylamido-, 1132.
Hydroeonquinine, separation of c<
quinone from, 602.
sulphate, 602.
Hydrocoumarilic acid, and its
474.
Hydrocyanic acid, action of, on hydro-
chloric acid and alcohol, 730.
certain properties of, 129.
cyanides, «fec., poisoning with,
1022.
estimation of, 1174.
systematic method of testing
for, 1172.
hydrochloric and thiocyanic acids,
method of estimating when simul-
taneously present, 1173.
Hydrodimethylamarine methvl chloride,
203.
Hydroferricyanic acid, systematic method
of testing for, 1172.
Hydroferrocyanic acid, systematic
method of testing for, 1172.
Hydrofluoric acid, electrolysis of solu-
tions of, with carbon electrodes,
590.
Hydrogen, action of platinum and palla-
dium on, 422.
nascent, 7.
cyanide, certain properties of,
129.
gold chloride, 853, 1054.
T peroxide, action of, on the red
colouring matter of the blood, and on
hsematoxin, 103.
cause of the evolution of
oxygen from, by fibrin,- 227.
> decomposition of, by certain
organised bodies, 103.
formation of, 282.
use of, in analytical chemistry,
934.
Hydrogen lines, reversal of, 838.
spectrum, photometric intensity of
the lines of, 537.
widening of the lines in, 139.
sulphide, estimation of, 934.
preparation of, from coal-gas,
824.
and selenide compounds of,
with ethers, 961.
Hydrogen thermometer, comparison of
mercurial thermometer with, 144.
Hydrohomoferulic acid and its methoxy-
derivative, 198.
Hydro-hydroxyqmnoline, 93, 94, 96.
Hydromellic acid, 593.
Hydrometacoumaric acid, 189.
Hydromethylacridine, 1134.
Hydromethylbenzylamarine, 203.
Hydrophenylaci'idine, and it-s deriva-
tives, 1134, 1135.
Hydropiperic acid, 485.
Hydropyromellic acid, 593.
Hjdropyrroline, and its salts, 1142.
Hydrotoluquinone, and methyl-ethers
of, and their condensation-products,
467.
Hydrotrimethylamarine, 203.
Hydrotropidine, and its salts, 1155.
iodide, 672.
Hydroxy-acids, detection and estimation
of, in urine, 885.
derived from pseudocumol, 589.
Hydroxyanthraqvunone salts, reactions
of, 73.
Hydroxyazo-compounds, 982.
Hydroxybenzoic acid, action of baryta
on, 664.
and its dibromo-derivative,
1125.
dichloropara-, 1112.
Hydroxybenzotropeine, and its salts,
671.
y-Hydroxybutyric acid, 42.
Hydroxybutyric acid, brom-, 574.
ehlor-, and some of their
salts, 969.
Hydroxycaffeine, and its salts, 355.
Hydroxycainphor from /3-dibron)ocam-
phor, 1008.
nitro- and amido-, 1008.
Hydroxycamphorouic acid, 1008.
Hydroxycarboftyril, 197, 351.
j3-Hydroxycarbostyril, 351.
y-Hydroxycarbostyril, 351.
Hydroxycarbostyrilsulphonic acid, 197.
Hydroxycarboxylic acids, aromatic,
anhydrides of, 335.
Hydroxycinnoline, and its derivatives,
1105.
Hydroxycinnoline-carboxylic acid, 1105.
Hydroxycitric acid, 913.
Hydroxycomenamic acid, 792.
INDEX OF SUBJECTS.
1239
Hydroxy comenic acid, brom-, 792.
Hydroxycyanconiine and its derivatives,
352.
behaviour of, -with bromine and
potassium hydroxide, 354.
Hydroxydicarbocaprolactomc acid, ba-
rium salt of, 970.
j3-Hydroxyethylhydroquinoline, 1148.
Hydroxyethylhydroxyquinoline, and
some of its salts, 923.
Hydroxyethyltheobromine, 357.
Hydroxyheptylic acid, salts of, 455.
Hydroxyhydrocarbostyril, 993.
a-Hydroxyhodroethylquinoline, 1146.
jS-Hydroxyhydroquinoline, 1148.
Hydroxyisobutyi'ic acid, brom-, 573.
conversion of acetone-chloro-
form into, 177.
a- and j3-Hydroxyisophthalaldehyde,
190.
Hydroxyisophthalic acid, 190.
Hydroxylactone, 456.
Hydroxylamine hydrochloride, prepara-
tion of, 646.
reaction, 728.
Hydroxylation by direct oxidation, 983,
1072.
Hydroxymethylanthraquinone and its
acetyl- derivative, 1139.
a-Hydroxymethylhydroquinohne and its
salts, 1146.
Hydroxynaphthaquinone, trichlor-,
921.
a- and /3-Hydroxynaphthobenzoic acid,
and its derivatives, 666.
Hydroxynaphthatoluic acid, 666.
Hydroxyoctylic acid, salts of, 456.
Hydroxyphenyl mercaptan, 989.
^-Hydroxyphenylalanine, 994. ,
Hydroxyphthalic acid, 1124.
a-Hydroxypicolinic acid, and its salts,
795.
dichloro-, 795.
^-Hydroxypicolinic acid, and mono-
chloro-, 795.
Hydroxypicolinic acid, mono- and di-
chlor-, 794.
Hydroxypropylamine, 909.
Hydroxypropylamylamine, 910.
Hydroxypropylbenzoic acid and its deri-
vatives, 330.
Hydroxypropyldiethylamine platino-
chloride, 910.
Hydroxypropyldipropylamine and its
platinochloride, 910.
Hydroxypropylethylamine and its pla-
tinochloride, 910.
Hydroxyphenanthroline, 811.
Hydroxy propylmalonic acid, salts of,
456.
Hydro xypropylpropylamine platinochlo-
ride, 910.
Hydroxypyridine, and its dibromo-deri-
vative, 871.
Hydroxyquinol, the third isomeric tri-
hydroxybenzene, 987.
Hydroxyquinoline, 91, 92, 93
j3-amido-, and the action of the
diazo-salts of, on phenols and tertiary
bases, 1148.
derivatives of, 1146.
derivatives, physiological effects of,
1147.
Hydroxyquinoline methyl ketone, 1149.
nitro-, 223.
quartemary base derived from,
923.
j3-Hydroxyquinoline, and its derivatives,
1147.
]8-Hydroxyquinolinesulphonic acid and
its salts, 1148.
tetrahydride, preparation of me thy 1-
and ethyl-derivatives of, 871.
Hydroxyquinophenol, 351.
Hydroxythiocarbanilide, 1110.
Hydroxytoluic acids, 1124.
Hydroxytrimellic acid and its salts,
590.
Hydroxyxylidic acid, 590.
Hygrometer, a new condensation, 118.
Hymenodictyon excelsum, bitter prin-
ciple of, 1141.
Hypocaffeine and its salts, 356.
Hypochiorin and its formation, 483.
crystals, Pringeheim's, nature of,
483.
Hypoethyltheobromine, 357.
Hyponitrites, researches on, 422.
Hyponitrous acid, heat of formation of,
423.
Hypoxanthine, 924.
Tee plant {^^ Mesembrianthemum crys-
tallinum")y 499, 680.
Ictrogen, 228.
Idocrase from Kedebek in the Caucasus,
1067.
from Vesuvius, discovery of fluo-
rine in, 1067.
(Vesuvian), crystalline form of,
441.
Idrialite, 427.
Illuminating gas, examination of, 629.
Imides, conversion of nitriles into, 730.
of bibasic acids, 475.
Imines, 910.
Implements, bronze, used by the miners
of Peru, 6i)l.
Incandescent lamps, Swan's, spectrum
of, 1.
1240
INDlfiX OF SUBJECTS.
Inclusions in sapphire, ruby, and spinel,
1062.
Indian hemp, new alkaloid in, 1155.
Indian wood, analyses of, 107.
Indicators, alkalimetric, 1167.
litmus, methyl-orange, phenaceto-
lin and phenol-phthalein as, 824.
Indices of refraction of water and quartz,
variation of, with the temperature, 762.
Indigo, Baeyer's artificial, appHcation
of, 257.
Indigo-blue, preparation of, from ortho-
nitrobenzaldehyde, 341.
Indole, 1130.
synthesis of, from cuminol, 329.
Indophenine, formation of, 1091.
Indophenol, 69, 695.
preparation of, 759.
Indoxyl, nitroso-, 1131.
Infra-red of the solar speculum, atmo-
spheric absorption in, 837.
• spectra, observations of, by means
of phosphorescence, 761.
Insensibility arising from a deficiency of
oxygen in the air, 819.
Instrument for correcting gaseous
volume, 378.
Insulating liquids, dielectric constants
of, 945.
Intestinal gases, comparative investiga-
tions of, 928.
Inulin, formula of, 307.
Invertin, 225.
action of, 486.
' influence of, on the fermentation
of cane-sugar, 101.
the temperature most favourable
to the action of, 101.
Invert-sugar, rapidity of separation of
cuprous oxide by the action of, on
Fehling's solution, 385.
Iodic acid, systematic method of testing
for, 1172.
Iodides, estimation of, in presence of
sulphuretted hydrogen, 508.
Iodine chlorides, thermochemical in-
vestigation on, 543.
estimation of, in presence of chlo-
rine and bromine, 120.
separation of, from chlorine and
bromine, 1167.
vapour, fluorescence of, 763.
Iodoform, detection of, in the fluids and
organs of the animal body, 243.
Iridium, detection of, 907.
reactions of, 905.*
potassium sulphate, 905.
• sulphate, violet, 1057.
Iridosmin, artificial production of, 298.
Iron, analysis of, 510.
cast and malleable, relative oxidi-
sability of, 755.
Iron, estinmtion of, by means of per-
manganate solution, 1168.
estimation of manganese in, 883.
estimation of oxygen and carbon
in, 121.
estimation of silicon and sulphur
in, 883.
estimation of sulphur in, 121, 512.
estimation of total carbon in, 882.
galvanising and nickeling of, in
Cleveland, Ohio, 404.
improvements in the manufacture
of, 402.
in ores, sources of error in esti-
mating, by the stannous chloride
method, 242.
■ new method for the estimation of
minute quantities of carbon in,
1032.
normal solutions for the volumetric
estimation of, 241.
precipitation of, by hydrogen sul-
phide, 1169.
thiocyanate reaction for, 510.
Weil's method for the estimation
of, 509.
Iron glance from Ascension, 436.
Iron industry, 132, 402.
novelties in, 531.
Iron ores, certain, of Sinaloa, 162.
occurrence of, at Taberg in
Smaaland (Sweden), 429.
Irrigation of meadows by waste water
from beet-sugar factories, 500.
Isallylenetetracarboxylic and its sal's,
46.
Isallylenetricarboxylic acid, 46.
Isatic acid, dibrom-, 202.
Isatin, 1130.
action of potassium cyanide on,
805.
acetylbrom-, 201.
brom-, ethers of, 201.
dibrom-, ethers of, 202.
ethers of, 201.
Isatoethylozime and its derivatives,
1131.
Isatoxime, and its derivatives, 1130.
Isoamylallylamine, 909.
Isobenzyl, preparation of, 920.
Isobenzylphenylphosphine, 185.
Jsobutyl turmerylate, 482.
Isobutylaldoxime, 569.
Isobutylbromisatoid, 202.
Isobutylene oxide, 567.
Isobutylformimide hydrochloride, 1089.
Isobutylketone, nitroso-, 572.
Isobutylphenol, 59.
Isobutylphenyl ethyl oxide, 59.
Isobutyric acid, dibrom-, 573.
Isocholesterin, 586.
Isocholine and its salts, 568.
INDEX OF SUBJECTS.
1241
Isocrotonic acid, /3-chlor-, action of
potash on, 968.
Isodirnethylformamidine hydrochloride,
1090.
Isodurene and its derivatives, 52.
Isodurylic acids, 52.
Isoeugenol, 201.
Isoindole, 918.
molecular weight of, 665.
Isomerism, physical, a case of, 343.
Isomorphism, modification of the usual
statement of the law of, 147.
Isomorphous salts, expansion of, 146.
Isonicotine, 484.
Isonicotinic acid, 484.
Isonitroso-acids, 1129.
Isonitroso-compounds, 569.
Isonitrosoketones, 573.
Isopentylacetic acid, 729.
Isopentylbenzene, 977.
Isophenylcrotonic acid and its deriva-
tives, 472.
Isophosphines, aromatic, 185.
Isoprene, 75.
Isopropane, dinitro-, 176.
Isopropyl allyl dimethyl carbinol, 1076.
bromide, transformation of propyl
bromide into, under the influence of
heat, 172.
ethylene oxide, 566.
gi'oup, conversion of the propyl
into, 565.
Isopropylmetacresol, and its derivatives,
463.
Isopropylsuccinic acid, 46.
Isosantonous acid, and its derivatives,
77.
Isotolylbenzylphosphine, 186.
Isovaleric acid, action of nitric acid on,
176.
/9-nitro-, and /3-amido-, 176.
Isovaleric creatinine, 221.
Isovanillin, 190.
Itaconic acid, a non-saturated acid iso-
meric with, 730.
Itamalic acid and its salts, 457.
Ivy berries, composition of, 499.
Jade, composition of two specimens of,
163.
or nephrite of Siberia, 436.
Jadeite, 1066.
Jadeite axe from Kabber, Hanover, 437.
Jafferabad aloes, 480.
Jakobsen's testing-chum, 253.
Japanese soils : a natural cement, 131.
Jeremerewite, 719.
Kairine, 1146, 1147.
Kairocoll, 1147.
Karyinite, 434.
Katellagic acid, 835.
Kephir, 229.
Keramonalite, 432.
Ketolactonic acid and its snlts, 457.
Ketones, action of anhydrides on, 452.
aromatic, 990.
compounds of the hydrazines with,
798.
ethereal salts, and chloranhydrides,
similarity of the boiling points of the
corresponding, 990.
nitroso-, and isonitroso-, 572, 573.
Ketonic acids, synthesis of, 912.
Kidney fed with defibrinated blood,
secretion by, 875.
KiUinite, 440.
Klausenburg meteorite, 1070.
Koumiss, 365.
Krokydolite quartz, from Greenland,
435.
Kynurenic acid, oxidation of, 674.
Kynuric acid, 674.
Kynurine, oxidation of, 674.
Lactam, 202.
Lactic acid, formation of, from sugars,
42.
Lactim, 202.
^-Lactone of normal caproic acid, 455.
Lactones, action of water on, 730.
from allylmalonic, diallylmalonic,
and diallylacetic acids, 456.
hepto- and octo-, 455.
isomeric, conversion of unsaturated
acids into the, 730.
Lake deposits of Kolsnaren, Viren, and
Hogsjon, Sodermanland, Sweden,
4i8.
Lanthanum, atomic weight of, 553.
Lapachic acid, acetyl-derivatives, 211.
action of concentrated acids
on, 212.
action of reducing agents on,
212.
and its derivatives, 210.
constitution of, 214.
monobromo-, 211.
Lapacone, 213.
Laumontite, 957.
from Monte Catini, 442.
Lautite from Lauta, Saxony, 432.
Laut's violet, 916.
1242
INDEX OF SUBJECTS.
Lava current from Etna, chemical com-
position of various layers of, 36.
Law of cooling, 144.
freezing of solvents, 278.
isomorphism, modification of the
usual statement of, 147.
thermal constants of substitution,
143.
Lead, action of certain vegetable acids
on, 1038.
action of water on, 128.
calcium salt, basic, 904.
desilvering of, 134.
dioxide, preparation of, 157.
distribution and elimination of,
1163.
double salts of, 903.
extraction of, from ores occurring
in the Upper Hartz, 891.
method of detecting, in the body
in cases of poisoning, 687.
oxybromide, 903.
oxychlorides, 717, 903.
separation of copper from, by re-
fining, in Freiberg, 400.
■ separation of, from sulphides by
air-blast, 400.
and ammonium, double chlorides
of, 717.
and potassium iodides, heat of for-
mation of double salts of, 275.
Leaves of roots, removal of, 613.
Leclanohe cell, and the reactions of
manganese oxides with ammonium
chloride, 272.
Lecture experiment : the evolution and
absorption of heat, 454.
Lecture experiments, 279, 281, 292,
454, 1048.
Ledum camphor, 346.
Legumin, 675.
Leidenfrost's experiment reversed : a
lecture experiment, 281.
Leken, the paraffin from ozokerite,
1073.
o-Lepidinecarboxylic acid, 1149.
Leucaniline, 981.
Leucite, analysis of, 721.
Leuco-indophenol, preparation of, 759.
Leyden batteries, electric discharge of,
763.
Liebigite, so-called, from Joachimsthal,
955.
Life, test for, 489.
Light, action of, on silver bromide, 3.
emitted by comets, 261.
Lignification, technical aspects of, 694.
Limburgite, analysis of, 722.
Lime of Theil, action of water on,
830.
— -— sacchara^e, influence of chlorides
of the alkalis and alkaline earths on
the precipitation of, from warm solu-
tions, 692.
Lime-water, action of different rarieties
of silica on, 712.
Lime and cement, process for rendering,
less subject to atmospheric influencen,
530.
Liquid compounds, constitution of, 422.
Liquid state, limit of, 145.
Liquids, alcoholic, passage of, througli
membranes, 549.
passage of, through porous
vessels, 279.
constant of capillarity of, 549.
molecular volumes of, 279, 1044.
mutual solution of, 11.
specific volumes of, 13.
** Liquor sodse chloratae," constitution
of, 647.
Litliarge, process for preparing, 891.
Lithium carbonate, preparation of,
from lepidolite, 1086.
citrate, 1086.
hypochlorite, 17.
lines, order of reversibility of,
839.
phosphates, 424.
silicates, 559.
Litmus as an indicator, 682, 824.
Liver, peptone the source of sugar in,
818.
Lockyer's dissociation theory, 762.
"Longrain" and measure of the folia-
tion in schistose rocks by means of
their thermic properties, study of,
300.
Lugano eruptive district, 167.
Lupine seeds, purified, researches on the
di'jjestibilty of, by the horse, and ob-
servations on the working power of
the horse when fed with lupines and
oats, 102.
sickness in sheep, 228.
shoots, constituents of, 1122.
Lupines, behaviour of conglutin from,
towards saline solutions, 360.
poisonous principles contained
in, 740.
cultivation of, 114.
Lupinine, action of dehydrating agents
on, 100.
hydrochloride from lupinine resi-
dues, preparation of, 224.
Lutidine, 85.
^-Lutidine, 739.
y-Lutidine, 99.
^-Lutidine, hydrate of, 220.
Lutidines, isomeric, separation of, 740.
Lutidinetricarboxylic acid and its salt«,
85.
Luting for conduct-pipes, 536.
INDEX OF SUBJECTS.
1243
M.
Madder colours, 598.
Magenta, use of, with sulphurous anhy-
dride as a micro-chemical test for
aldehyde, 829.
Magnesia alba, 153.
Magnesium, action of alkaline carbonates
and bicarbonates on, 574.
platinised, as a reducing agent.
1053.
spectrum of, under various condi-
tions, 2.
Magnetic iron ore, compact, from Cogne,
Valley of Aosta, 429.
Magnetic pyrites, analysis of, 1061.
Magnetism, units of, 764.
Maize, existence of basic substance in,
1156.
hygienic action of, as fodder, 488.
plant, chemistry of, 366, 747.
growth of, 491.
Maleic acid, geometrical formula of,
deduced from its products of oxida-
tion, 44.
Malonic acid, nitroso-, constitution of,
790.
Malt, 631.
from 1877 barley, composition of,
111.
■ nitrogenous constituents of, 821.
oxalic acid in, 232.
Maltic acid, 42.
Maltosaccharin, 42.
Maltose, 652.
conversion of, into glucose, 38.
Mandelic acid, inactive, separation of,
into two optically active isomerides,
1124.
Isevorotatory, 1124.
Manganese, a colour-method for the
estimation of, 242.
atomic weight of, 856.
deposits on the surfaces of rocks,
170.
dioxide, natural formation of, 425.
volumetric estimation of, 513.
estimation of, 380.
estimation of, in iron, 883.
in sea- water, and in certain marine
deposits, 725.
mineral from TJpsala, 429.
oxides, reactions of, with ammo-
nium chloride, 272.
sulphite, 558.
and the alkalis, double sulphites of,
718.
Manganese-ochre, 429.
Manganese-ore, 36.
Mannitine, a new alkaloid obtained fi'om
mannitol, 50.
Mannitol, second anhydride of, 805.
Mansfeld copper slate, analysis of,
1069.
Manure, farmyard, and chemical
manures, comparison of, 501.
solid and inodorous, transforma-
tion of blood into, by means of a new
ferric sulphate, 239.
deposits, new mineral, 529.
Manures, action of, on the quantity and
quality of a wheat crop, 681.
chemical, and farmyard manure,
comparison of, 501.
estimation of phosphoric acid in,
620.
influence of the state of division of,
on their action, 117.
nitrogenous animal, decomposi-
tion of, 615.
organic, influence of, on the tem-
perature of the soil, 821.
Manuring experiments, comparative,
116.
in Holland, 617.
of forest trees, 617.
with sulphuric acid, 681,
Margarimeter of Leune and Harbulot,
247.
Marine algse, new substance obtained
from some of the commoner species
of, 943.
Markgrafler of different districts and
vintages, analysis of, 631.
Marsh-gas fermentation in the mud of
ditches, swamps, and sewers, 1177.
Martite, Brazilian specimens of, 559.
of the Cerro de Mercado, or Iron
Mountain of Durango, Mexico, and
certain iron ores of Sinaloa, 162.
Mash, loss of sugar by long steaming of,
136.
Meadow hay, artificial digestion of,
1025.
treated with hot and co'd
water, digestibility of, 816.
Meadows, irrigation of, by waste water
from beet-sugar factories, 500.
Meat, digestibility of, 815.
Meat extract from South America, 406.
Meconamic acid and its ammonium
salt, 657.
Meconic acid and some of its deriva-
tives, 656.
derivatives of, containing
nitrogen, and their conversion int •
pyridine, 791.
Meconin, 996.
Mecylene, perchloro-, 796.
Meionite, artificial production of, 561.
Melanite from Lantigne (Rh6ne), 438.
Melanuric acid, 1086.
Melaphyres of Lower Silesia, 563.
of the Little Carpathians, 447.
1244
INDEX OF SUBJECTS.
Melilite, 719.
Melilite basalts, 719.
Mellic acid, 593.
Mellite, artificial production of, 427.
Mellogen, analyses of, 592.
Melting points, errors in determination
of, 844.
Mercurial thermometers, comparison of,
with the hydrogen thermometer, 144.
Mercurial trough, 1048.
Mercuric oxide, combinations of, with
acids, and Berthollet's laws, 10.
Mercuric salts, action of hydrocarbons
of the acetylene series on, 172.
Mercury calcium chloride, basic, 904.
detection of, in animal tissues, 1109.
Haswell's method for the volu-
metric estimation of, 242.
method of detecting, in the body in
cases of poisoning, 687.
Mesembrianthemum crystallinum (ice
plant), 499, 680.
Mesityl acetate, 1095.
bromide, 1095.
Mesitylene acetate, 577.
action of bromine on, 734.
derivatives of, 577, 1095.
dibromo-, from coal-tar oil, 469.
• dinitro-monobromo-, 470.
diacetate, 1095.
Mesitylenic acid, bromo-, preparation of,
from bromomesitylene, 469.
dibromo-, and its salts, 470.
Mesitylenic glycol, 1095.
Mesityloxidedicarboxylic acid, 1083.
Mesityloxime, 728.
Mesolite, 165, 441, 957-
from Colorado, 165.
Metacoumaric acid, and some of its deri-
vatives, 189.
Metacymene, 459.
Metadehydracetic acid, 1083.
Metahsemoglobin, 814.
Metahydroxybenzaldehyde, and some of
its derivatives, 188.
a-, /3-, and 7-nitro-, 586.
nitro- derivatives of, and their con-
stitution, 189.
Metahydroxyquinoline, and its deriva-
tives, 91, 95.
Metaisobutyltoluene, oxidising action of
dilute nitric acid on, 796.
Metaisocymenesulphonic acid, action of
chlorine on, 806.
Metalbumin and paralbumin; a contri-
bution to the chemistry of encysted
fluids, 874.
Metallic iron, accompanjdng native gold
in Montgomery Co., Virginia, and in
Burke Co., N. Carolina, 29.
Metallic lines in over-exposed photo-
graphs of spectra, reversal of, 263.
Metallic salts, relative toxic power of,
745.
Metallic spectra, variations of, due to
mixed vapours, 2.
Metallic sulphides, solubility of, in thio-
acids, 1169.
Metalliferous vein formation at Sulphur
Bank, 1070.
Metallurgy, application of electricity in,
398.
Metals, certain, action of, on oils, 756.
precious, extraction of, from all
kinds of ores by electrolysis, 134.
scale of hardness of, 890.
volume-change of, on fusion, 545.
Metameric bodies, comparative effect of,
on the growth of Nicotiana longijlora,
495.
MetamethoxyquinoHne, 91.
Metamorphism of massive crystalline
rocks, 562.
Metanitrils, 577.
history of, 323.
Metaphosphates, crystallised, 711.
Metasulphites, 704, 705.
Metatoluic acid, 459.
Metatoluidine, and preparation of, 54.
trinitro-, 59.
Metatolylglycocine and its derivatives,
54.
Metatropine, 672.
Meta-uramidobenzoic acid, 193, 194.
Metaxylenesulphonic acid, amido-, and
its salts, 593.
a-Metaxylylglycocine and its ether, 59 1.
Metazophenylglyoxylic acid, and its
salts, 998.
Meteorite, Klausenburg, 1070.
of Estherville, Emmet Co., Iowa
(10th May, 1879), lithological deter-
mination of, 37.
of Louans (Indre-et-Loire) , 449.
supposed, found in Augusta Co.,
Virginia, 37.
Meteorites, certain, examination of, 169.
of Alfianello, 1071.
Methacrylic acid, brom-addition-deri-
vatives of, 573.
Methaldehyde, estimation of, 1035.
Methane, bromodinitro-, 961.
dibromodinitro-, formation of,
564.
heat of formation of, 544.
iVfethanetriquinoil hydriodide, 600.
Methenyldianthramineamidine, 1140.
Methenyldiphenyldiamine, 326.
Methocodeine, 359.
Methoxyquinoline tetrahydride, prepara-
tion of methyl- and ethyl-derivatives
of, 871.
Methyl acetoacetat«, action of aldehyde-
ammonia on, 1082.
INDEX OF SUBJECTS.
1245
of,
its
Methyl alcohol, occurrence of, in the pro-
ducts of the dry distillation of colo-
phony, 738.
^-butyl carbinol, 966.
ketone and its derivatives,
966.
pinacone, 966.
chlorocarbonate, preparation
311.
collidinedicarboxylate, and
salts, 1082.
dibromanisate, 1125.
diliydrocollidinedicarboxylate,
1082.
dimethoxyumbellate, 200.
dimethylnaphtholate, 79.
ethyl ketone, action of sodium
on, 1079.
pinacone, 1080.
iodide, action of sodium arsenite,
and of stannous choloride on, 1078.
isopropyl ketone, 566.
a- and j8-naphthol ether, 585.
propyl ketone, 570, 571.
propylpyrogallate, 1005.
sulphochloride, trichloro-, disso-
ciation of, 38.
trimethoxysesculeate, 200.
Methylacetone, nitroso-, 41.
Methylacridine, 1133, 1134.
Methylamido-a-butyrocyamidine, 220.
Methylamido-a-caprocyamidine, 1153.
Methylamidoisovalerocyamidine, 221 .
Methylanilidocarbamidophenol, 1110.
Methylaniline and its acetyl-derivative,
preparation of, 578.
Methylanthracene, dihydride of, 1138.
amido-, and its derivatives,
1137.
Methylanthranol, amido-, and its acetyl-
derivative, 1137.
JVIethylanthraquinone and its nitro- and
amido-derivatives, 1138.
and some of its derivatives, 70.
Methylarbutin, 60, 347.
Methylazaurolic acid, 41.
Methylbenzene compounds, nitroso-, so-
called, 581.
Methylbenzophenone, diamido-, and
hydroxy amido-, 1097.
Methylbenzylacetoximic acid, 590.
Methylbiguanide and its compounds, 974.
Methylbromisatoid, 201.
a-Metliyl-j3-chlorocrotonic acid, action of
potash on, 969.
Methylcyanethine, 352.
Methyldibromosuccinic acid and its
salts, 44.
Methyldiethylmethane, 967.
Methyldiethylphosphonium platino-
chloride, 58.
Methylene-blue and allied dyes, 916.
VOL. XLIV.
Methylenediquinoil hydrochloride, 1150.
Methylene-white, 916.
Methylenitan, 37.
Methyl -j3-ethoxycro tonic acid, 969.
Metliylethylacrolein and its derivatives,
570.
a-Methyl-i8-ethylacrolem and its oxida-
tion, 570.
Methylethylacrylic acid and its salts,
571.
Methylethylethylene oxide, 566.
a-Methylethyl propylene, 967-
Methylethyl pyridine (jS-collidine), 739.
Methylformanilide, 1090.
Methylformimide hydrochloride, 1089.
a-Methylglutaric acid, 962.
Methylglyoxaline, 50.
a-tribromo-, 911.
Methylguanide and its compoundB,
974.
Methylhydrometacoumaric acid, 189.
a-Methyl-y-hydroxyvaleric acid, 455.
Methylisatoid, 201.
Methyl malic acid, 176.
Methylmetacoumaric acid, 189.
Methylmetahydroxybenzaldehyde, 189.
nitro-derivatives of, and their con-
stitution, 189.
Methylmetanitrobenzene, nitroso-, 919.
Methylnaphthalene, 1135.
Methylnitrobenzene, isonitroso-, com-
pounds of, preparation of, 916.
Methyl-orange as an indicator, 682, 824,
827.
Methylorthonitrobenzene, nitroso-, pre-
paration of, 581.
Methylortliotoluidine and its acetyl-
derivative, pi'eparation of, 578,
Methylplienantliridine, 179.
Metliylphenolsulphonic acid, 990.
Methylphenylacetoxime, 580.
Methylphenylacridium hydroxide,
1133.
Methylphenylamidoazotribromobenzen^
662.
Methylphenylhydrazine, constitution of,
1103.
Methvlphenylnitrosamine, constitation
of, 1103.
Methylpiperidine, 1154.
Methylpropylacetic acid, 670.
Methylpropyhxcetoximic acid, 590.
Methylpro])ylethylene oxide, 567.
Metliylpscudobutylacetoxime, 580.
Methylpyridine, dibromo-, 672.
Methylquinoline, 588, 1097.
tt -Methylquinoline, preparation of, 11 i3,
1149.
a - Methylquinoline - ti - earboxylic acid,
ethyl salt of, 1149.
Methylsahcylaldehyde, 190.
nitro-, 190.
4 o
1246
INDEX OF SUBJECTS.
Methylsulplionic acid, salts of, 972.
MethyltetrahTclroquinoline and its de-
rivatives, 114-4.
Methyltrinitro-a- and /3-naphthol, 863.
Methyltropine, decomposition of, by
potash, 672.
a- and j8-Methylvalerolactone, 454.
Methyl-violet, 1098.
Mexican amalgamation process, reac-
tions of, 134.
Miargyrite from Pribram, 428.
Mica, green, from Syssert in the Ural
Mountains, chemical composition of,
1066.
Mica diorite near Tryberg, in the Black
Forest, 724.
Mica syenite porphyry, near Tryberg, in
the Black Forest, 724.
Microchemical reaction methods, 376.
Microcline, from Konigshain, Oberlau-
sitz, 446.
from spodumene, 439.
Microcosmic salt, action of, on various
oxides, 850.
Micro-organisms, influence of calomel on
the life of, 743.
Microphone, superiority of carbon over
metals in, 842.
Mierozymas the cause of the decomposi-
tion of hydrogen peroxide by animal
tissues, 103.
Milk, 254, 1174.
alteration in the secretion of, under
the influence of drugs, 818.
blue, 742.
chemistry of, 1160.
condensed, preparation of, 759.
detection of benzoic and boric acids
in, 385.
estimation of salicylic acid in,
522.
formation of a blue mould on,
742.
heated, digestibility of casein
from, 815.
human, zymase of, 926.
investigations on, 757.
preservation of, 253, 254, 758.
preserved, changes occurring in,
634.
ScherfF's, 757.
test for sodium carbonate in, 385.
Milk analysis, 521.
Milk fat, estimation of, 246.
Milk ferment, a new, 229.
Milk-sugar, transition of the birotation
of, into its normal rotation, 174.
Mimetite, colourless, from the Eichmond
Mine, Nevada, 163.
Mimetites, bromo-, 783.
Mineral allied to orthite, analysis of,
164.
Mineral combustibles, 941.
Mineral spring at Salzbrunn, analvsis
of, 563.
Mineral sulphides, natural, formation
of, 610.
Mineral water at Montrond (Loire),
1071.
Mineral waters of Contrexeville and
Schinznach (.Switzerland), lithium,
strontium, and boric acid in, 300.
Minerals, application of citric acid t(y
the examination of, 857.
in Amelia Co., Virginia, notes on
the occurrence of, 959.
from Fritz Island, Pennsylvania,
441.
from Upper Silesia, 955.
found in the granite hills of
Konigshain in Oberlausitz, 446.
found near Massa, in the Apuanian
Alps, 428.
in the sodalite syenite of South
Greenland, 960.
Italian, chemical and microscopical
researches on, 446.
mainly zeolites, occurring in the
basalt of Table Mountain, near
Golden, Colorado, 164, 956.
meclianical separation of, 158,
159, 858.
N. Carolina, notes on some, 163,
1063.
occurring near Pike's Peak, Colo-
rado, notes on some interesting,
1065.
of the cryolite group, chemical
composition of, 29.
of the Miage Glacier, M. Blanc,
31.
separation of, according to the
degree of cohesion, 858.
sp. gr. of, and their mechanical
separation, 1031.
thermoelectric properties of, 540.
two new, monetite and monite,
1063.
Molasses, purification of, 835.
strontia process for the separation
of sugar from, 536, 252.
testing for dextrin syrup, 624.
Molecular heat of solids, estimation of,
for their solution in wat^r and other
liquids, 704.
Molecular refraction, 762.
of liquid carbon compounds,
dependence of, on their chemical con-
stitution, 538.
Molecular transformations, 1113.
Molecular voliune of liquid substances,
279, 1044.
Molvbdenum compounds, reduction of,.
122.
INDEX OF SUBJECTS.
1247
Molybdic acid, a hydrate of, 158.
volumetric estimation of,
123.
Monacetometaphenylenediamine hydro-
chloride, 583.
Monazite from the quarries of Nil-St.
Vincent, 561.
occurrence and composition of
some American varieties of, 162.
Monetite, 1063.
Monite, 1063.
Monomethylacetoacetic acid, 41.
Monomethylsesculetin, 199.
Monomethylcumidine, 324.
Mordants used for fixing artificial
colouring-matters, 894.
Morphine, 221.
separation of, in chemieo-legal in-
vestigations, 1036.
some derivatives of, 358.
MorphineglycoUic acid, 359.
Moscow waters, analyses of, 622.
Moulds, occurrence of nuclein in,
1166.
Mucobromic acid, action of potassium
nitrite on, 47.
Mucus-lining of the stomach, reaction
of, 815.
Mud from the mouth of the Eider,
analysis of, 117.
Muscle, action of calcium, barium, and
potassium salts on, 875.
Mushrooms, edible, poisonous principle
of, 611.
Mustard oil, occurrence of mjronic acid
and estimation of the corresponding,
in the seeds of Cruciferse and in oil-
cakes, 245.
Myronic acid, occurrence of, and esti-
mation of the corresponding mvistard
oil in the seeds of Cruciferse and in
oil-cakes, 245.
N.
Nacrite, pseudomorph of, after fluorspar,
1069.
j8-Naphthacoumaric acid, 1136.
' /S-Naphthacoumarin, 1136.
Naphthalene, action of chloroform on,
in presence of aluminium chloride,
68.
diamido-, 183.
• dibromo-, from /3-naphthol, 67.
a- and t-dichloro-, 208.
/S-dichloro-, 596.
dihydride, monobromo-, 346.
heptacliloro-, 921.
hexhydride, derivatives of, 345.
Naphthalene, ^-monobromo-, 67.
new source of, 534.
nitro-derivatives of, 343.
nitrodibromo-, a new (?), 67.
pentachloro-, preparation and oxi-
dation of, 921.
trinitro-, 863.
Naphthalene and stearic acid, solidifica-
tion of different mixtures of, 176.
Naphthalenedisulphonic acids, nitro-,
and chlorides of, 596.
Naphthalenehexydrosulphonic acids
and their potassium salts, 345.
Naphthalenesulphonic acid, a-bromo-,
constitution of, 596.
a- and ^S-naphthaquinoline and their
derivatives, 1010, 1013.
Naphthaquinone, tetrachloro-, and its
derivatives, 921.
a-Naphthaquinone-ethylanilide, 70.
/3-Naphthaquinou ephenylhy drazine ,
1135.
/3-Naphthaquinonetoluide, action of
nitrous acid on, 210.
and ethers of, 209.
ct-Naphthoic acid, derivatives of, 807.
a-Naphthoic cyanide and its derivatives,
51)5.,
Naphthol, detection of, in the fluids and
organs of the animal body, 243.
dibromo-, action of, on amines,
536.
monochloro-, 1109.
picrates of, 344.
preparation of the homologues of,
253.
tetranitro-, and its salts, 344.
a-Naphthol, synthesis of, 595.
/3-Naphthol, bromo-, acetyl- and nitroso-
derivative of, 68.
Naphthols, nitro-, constitution of, 69.
Naphtholtrisulphonic acid, 737, 1136.
a-Naphthonitrilsulphonic acid, barium
salt of, 1001.
a-Naphthylacetamide, 808.
a-Naphthylacetic acid, 808.
a-Naphthylacetonitril, 808.
a- and /3-Naphthylamine, action of para-
diazobenzenesulphonic acid on, 182.
tetranitro-, 344.
Naphthylamine, trinitro-, 863.
Naphthylamines, primary and secondary,
594.
)8-NaphthyIaminesulphonic acid, and
dye-stuffs from, 1135.
/3-Naphthylbenzoglycocyamine, and its
hydrochloride, 669.
a-Naphthylethenyldiphenyldiamine,
808.
a- and /3-Naphthylformamide, 326.
a-Naphthylglyco!lic acid, 808.
a-Naphthylglyoxylaniide, 595.
4 0 t>
1248
INDEX OF SUBJECTS.
o-Naphfchylglyoxylic acid, 595, 808.
a-Naphthylmethenyldiphenyldiamine,
808.
-Naphthylphenylamine, action of
oxalic acid on, 807.
«- and /3-Naphthylphenylamine, tetra-
nitro-, 314.
Naphthylsulphonic acid, a-cliloro-, 595.
Nascent hydrogen, 7.
Natrolite, 35.
Nepheline in the oligoclase of Denise,
1067.
Nepheline basalt from S. Anta6, analysis
of, 722.
near Tryberg, in the Black
Forest, 725.
Nephelinite from the Island of S. Anta6,
analysis of, 722.
Nephrite, 1068.
or jade of Siberia, 436.
New acid of the series C„H2«-406, 970.
NHs, supposed compound, 14.
Nickel, a phosphide of, 651.
separation of, from cobalt, 621.
— — sulphate, normal, action of hydro-
gen sulphide on solutions of, 24.
Nicotiana longifiora, comparative effect
of two metamerie bodies on the growth
of, 495.
Nicotianic acid, 739.
Nicotic acid, 90.
Nicotine, specific rotatory power of salts
of, 354.
Nicotinic acid, 1013.
Niobate, which has been improperly
called euxenite, from Mitchell Co.,
N. Carolina, analysis of, 32.
Nitracetophenones, preparation of the
three isomeric, 191.
Nitrates, fermentation of, 230.
in the soil, reduction of, 229,
503.
reduction of, to nitrites, 609.
Nitric acid, estimation of, 508.
Nitric oxide, estimation of, 508.
Nitrification, atmospheric, 233.
in presence of copper and other
metals, 286.
Nitril bases, formation of, from organic
acids and amines, 1099.
Nitril s, conversion of, into imides, 730,
1089.
conversion of phenols into, 802.
of «-phenamido-, a-paratoluamido-,
and a-orthotoluamido-propionic acids
and the corresponding amides and
nitriles, 199.
Nitrilotriphenylmethane, 580.
Nitrites, estimation of, 515.
in human saliva, 227.
Nitro-derivatives, addition-products of,
with hydrocarbons, 317.
Nitrogen, comparable estimation of, in
guano, 1030.
compressibility of, 150.
estimation in saltpetre by potas-
sium xanthate, 1031.
of, in mixtures containing
nitrogenous organic matter, ammo-
niacal salts, and nitrates, 685.
estimation, a method of general ap-
plication, 1028.
excretion of, from the skin, 227.
exhalation of, during the respira-
tion of animals, 675.
in arable land, loss and gain of,
373, 749.
liquefaction of, 781, 952.
organic, estimation of, as recom-
mended by Ruflle and Tamm-G-uvard,
378.
proportion of, in the form of
amides, albumin, and nuclein in dif-
ferent feeding stuffs, 748.
selenide, 423.
heat of explosion of, 707.
Nitrogen-compounds, from the manu-
facture of sulphuric acid, utilisation
of, 130.
Nitrogenous constituents of malt, wort,
beer, and bread, 821.
matter, artificial and natural
digestion of, 227.
Nitrosamines, constitution of, 1103.
Nitroso-compounds, aromatic, 919.
constitution of, 572.
Nitrosocyanides, 297.
Nitrosoketones, 572.
Nitrososulphides, 297.
Nitrous acid, formation of, ini the evapo-
ration of water, 850.
Nocerine, optical properties of, 1060.
Non-metals, influence of temperature
on the spectra of, 140.
Nonodilactone, 456.
Norite, gi-anular and quartz, analysis of,
1069.
Nuclein, 814.
■ ■ occurrence of, in moulds and in
yeast, 1166.
Nuphariiie, 370.
Niix vomica, analysis of, 1175.
assay of, 689.
Nymphsea, chemistry of, 369.
Oak-red, 995.
Octodecyl alcohol, normal primary, pre-
paration of, 1075.
Octolactones, 455.
INDEX OF SUBJECTS.
1249
Octometoxybenzoid, 335.
CEnanthal-aniline, 659.
CEnanthal-naphthylamine, 659.
CEnanthal-xylidine, 659.
CEnocyanin, 215.
Ohm, method of determining, 4.
Oil, cupriferous, used in Turkey-red
dyeing, injurious action of, 256.
Oil of cedar, 76.
erecthidis, 346.
Erigeron canadense, 346.
marjoram, 346.
Oil, volatile, of ash-leaves, 219.
Oil-cakes, examination of, 751.
Oil-cakes and the seeds of Cruciferse,
occurrence of myronic acid and esti-
mation of the corresponding mustard
oil in, 245.
Oils, action of certain metals on, 756.
fixed, distillation of, with glycerol,
519.
Oleomargarin cheese, composition of,
256.
Oligoclase of Denise, analysis of, 1067.
Opal, 36.
Ophites from the Pyrenees, examination
of, 448.
Opianic acid, derivatives of, 996.
Orchard alum spring, 171.
-y-Orcinol from tolylenediamine, 329.
Orcinol, fusion of, with soda, 59.
process for preparing, 893.
Ores from Am berg, examination of,
and of the accompanying phosphates,
432.
Organic acids in phenols, test for, 385.
chlorides, conversion of, into
iodides by means of calcium iodide,
303.
compounds, congelation of aqueous
solutions of, 952.
in solution, refractive power
of, 1041.
isomeric, relation of the heat
of combustion of, to their densities,
1044.
relation between the com-
position of, aud their absorption-
spectra, 1041.
gases and vapours, chlorinated,
properties of, 394.
matter, estimation of, in potable
water, 1171.
nitrogen, estimation of, as recom-
mended by Eulfle and Tamm-Guyard,
378.
oxysulphides, action of chlorine,
659.
Orthoclase, analysis of, 1066.
a- and /3-Orthocoumaric acids, oxidation
of, 200.
Orthhydroxyphenylcarbamido, 734.
Orthhydroxyquinoline and its deriva-
tives, 92.
Orthomethoxymandelic acid, 190.
Orthomethoxyphenylphenamidoacetic
acid, nitrile of, 190.
Orthophenylenethiocarbamide, 324.
a-Orthotoluamidopropionic acid and its
amide and nitrile, 199.
Orthotoluic acid, derivatives of, 1121.
Orthotoluidine hydrobromide and hy-
driodide, 578.
Orthotoluylhydantom, 1106.
Orthotolylacetamidine, 48.
Orthotolylglycocinetoluidide, 593.
Osmose of salts, 420.
Ottrelite from Liemeux, analysis of,
959.
Oxacetylcodeine, 359.
Oxalamyline, chlor-, 50.
Oxalethylethyline, synthesis of, 729.
Oxalethyline, properties of, 910.
chlor-, and its derivatives, 49.
Oxalethylpropyline, synthesis of, 729.
Oxalic acid derivatives of metanitro-
paratoluidine and metaparadiamido-
toluene, 323.
in potatoes and in malt, 232.
use of, as a test for arsenites
in alkahne salts, 243.
or oxalates, poisoning with,
1021.
OxaUne, 910.
Oxaline bases, synthesis of, 728.
Oxalraethylethyline, synthesis of, 728.
Oxalmethylpropyline, synthesis of, 729.
Oxalpropylethyline, synthesis of, 729.
Oxalpropyline, 911.
/3-Oxalpropylpropyline, synthesis of,
729.
Oxalylanthranilic acid, 1144.
Oxalylnitrotoluidide, 323.
Oxethylenecarbamides of the tolyl and
xylyl series, 593.
Oxidations in the animal organism, 361.
Oxides, action of sulphur on, 710.
organic, action of anhydrides on,
452.
Oximidine hydrochloride, 1088.
Oxindole and its derivatives, 1130.
nitroso-, 920, 1131.
Oxoctenol, 1076.
Oxyacids of cliloriuo, constitution of,
645.
Oxyanthraquinone ethylate, nitro- and
amido-, 73.
Oxybutyric acid, chlor-, 311.
a-Oxybutyrocyamine hydrochloride,
1154.
Oxycamphor from /3-dibromocamphor,
action of nitric acid on, 215.
Oxycarbamidophenol, 1110.
Oxyethenylamylacetic acid, 729, 730.
1250
INDEX OF SUBJECTS.
Oxygen, action of nascent hydrogen on,
900.
activity of, 282, 1048.
in presence of nascent hydro-
gen, 848.
combustion of, in hydrogen : A
lecture experiment, 280.
estimation of, from plant cells,
105.
influence of, on fermentation, 489.
liquefaction of, 781.
prepared from potassium chlorate,
281.
storage of, in zinc gasholders, 619.
variations of the amount of, in the
atmosphere, 284.
Oxygen and carbonic oxide, influence of
aqueous vapour on the explosion of,
12.
Oxyhsemoglobin of the dog, oxygen-
pressure under which, at a tempera-
ture of 35°, it begins to give up its
oxygen, 678.
Oxyhydroparacumaric acid, 818.
Oxylupinine, 100.
Oxyphenyletbylene, 803.
OxypropylenecarboxyHc acid, and some
of its salts, 970.
Ozokerite, Caucasian, 1073.
Ozone, behaviour of, with blood, 486.
formation of, 282.
in presence of platinum -black,
284.
Pachnolite, 427.
chemical composition of, 29.
Paint, waterproof, for stones, &c., 760.
Palladium, behaviour of, in chromic
and nitric acids, 699, 700.
electric properties of, when con-
taining hydrogen, 766.
Palladium-gold, native, from Taguaril,
Brazil, 160.
** Pan& salt," preparation and analysis
of, 822.
Paper, cause of the acid reaction ex-
hibited by some kinds of, 260, 696,
759.
Paper-pulp, new method of manufac-
turing, 759.
Paracetylhydroxy thiocarbanilide, 1 110.
Paraconic acid, 457.
Paracresol, dinitro-, constitution of,
865.
Paracresolglycollic acid, derivatives of,
1126.
Paracymene, sulphonic acids of, 320,
918.
Paradiazobenzenesulphonic acid, action
of, on isomeric toluidines, 182.
action of, on primary amido-
compounds, 181.
Paradiethylbenzene and its derivatives,
318.
Paradiethylbenzenesulphonic acid and
its salts, 318.
Paradiethyltolylphosphine, 58.
Paradimethyltolylphosphine and its de-
rivatives, 57.
Paradipropylbenzene, 321.
dibromo-, 322.
dinitro-, 321.
Paradipropylbenzene sulphonic acid and
its salts, 321.
Paraethylbenzoic acid and its salts, 319.
nitro-, and its salts, 320.
Paraffins, normal, 651.
preparation of, 787.
Paragiobularetin, 1025.
Parahydroxyphenylcarbamide, 735.
Parahydroxyphenyllactic acid, 993.
Parahydroxyphenylthiocarbamide, 735.
Parahydroxyquinoline and its deriva-
tives, 93.
Parahydroxystyrolene, 70.
Parahydroxythiocarbanilide, 735.
Paralbumin and metalbumin ; a contri-
bution to the chemistry of encysted
fluids, 874.
Paraldehyde, 453.
ParaleucaniUne and its compounds, 981.
Paranitriles, 342.
Para-oxalmethyline, 50.
Parapropylbenzoic acid and its salts,
322.
nitro-, and some of its salts,
322.
Parasitic diseases of plants, and their
prevention, 110.
Parasulphobenzeue-azorthonitrophenol,
G-riess's, 982.
Parasulphophenylamine, 993.
a-Paratoluamidopropionic acid and its
amide and nitrile, 199.
Paratoluidine, dinitro-, constitution of,
865.
metanitro-, oxalic acid, derivatives
of, 323.
hydrobromide and hydriodide, 578.
Parauramidophenylacetic acid, 193.
Paraxanthine, a new constituent of
human urine, 601.
Paraxylenes, dinitro-, crystallograpliic
examination of, 179.
Paraaophenol and its sulphonic add,
583.
Parazotoluene, 915.
Paroxalmethyline, 308.
synthesis of, 728.
Paroxybenzaldoxime, 1104.
INDEX OF SUBJECTS.
1251
Peach kernels, albuminoids in, 360.
Peafc, hydrocarbons and fatty acids
from, 652.
Peat, use of, as litter, 238.
Pegmatite, existence of apatite in, 432.
Pentametliyl-aniline, 324.
Pentamethylenediamine and some of its
salts, 910.
Pentamethylpararosaniline, 1097.
Pentenyl-benzene, 1094.
Pentic acid, so-called, 1085.
Pentylbenzene, 977.
Peptone, 926.
distribution of, in the animal body,
675.
formation of, and its conversion
into albuminoid substances, 603.
proportion of, in the gastric mu-
cous membrane, 677.
the source of sugar in the liver,
818.
Peptones, behaviour of bile acids with,
673.
Perchloric acid, thermo-chemical in-
vestigation of, 8.
Periodides, researches on, 978.
Perkin's reaction, 1122.
Peroxides, some reactions of, 425.
volumetric estimation of, 242.
Perspiration of animals, results of the
suppression of, 817.
Petalite from Uto, analysis of, 440.
Petrographical purposes, application of
a solution of barium-mercury iodide
to, 1060.
Petroleum, determination of the flash-
ing point of, 383, 517.
G-alician, examination of, 533.
Petroleum-coke, analysis of, 408.
Petroleums, Itahan, 1180.
Phenacetolin as an indicator, 682, 824.
Phenacite from Colorado, 1065.
Phenacyl bromide, 582.
Phenacylethylanilide, 582.
<3t-Phenamidoi8obutyric acid, and its
amide and nitrile, 199.
•a-Phenamidopropionic acid and its
amide and nitrile, 199.
Phenanthradichloroketone, 667.
Phenanthraquinone, action of lead oxide
on, 804.
action of the chlorides of phos-
phorus on, 666.
Phenanthraquinonehydrazine, 1135.
Phenanthrene, action of chloropicrin on,
in presence of aluminium chloride,
1000.
Phenanthroline, 86, 811, 1010.
• and its derivatives, 86.
Phenanthrolini(5 acid and its salts, 87.
Phenetidine, dibrom-ortho-, and para-,
663.
Phenetidine, monobrom-ortho-, and
para-, and their salts, 663.
Phenetoil hydrobromide, metamido-, 578.
Pheneto'ils, bromonitro-, and brom-
amido-, 662.
Phenetol, 1107.
preparation of, 1113.
Phenisobutyl-jy-naphthylthiocarbamide,
1107.
Phenisobutylparatolylthiocarbamide,
1107.
Phenisobutylphenethylthiocarbamide,
1107.
Phenisobutylphenylthiocarbaraide, 1107.
Phenol benzoate, orthamido-, 800.
bromotrichloro-, 986.
chloride, hexchloro-, 1119.
compound of, with carbonic
anhydride, 584.
compound of, with sulphurous
anhydride, 585.
y-dinitro-, constitution of, 327.
j8-dinitroamido-, 328.
hydrochlorides, amido-, reactions
of, nil.
monobrometanitro-, and its potas-
sium and sodium salts, 802.
mouobromorthonitro-, reduction of,
1109.
new nitro-derivatives of, 327.
orthamido-, reaction of ethylaceto-
acetate with, 1111.
paranitro-, 1109.
pentachloro-, action of chlorine on,
1119.
phosphates, 1108.
poisoning with, 1021.
preparation of the homologues of,
253.
test for organic acids in, 385.
tribromo-, action of chlorine on,
986.
iS- and y-trinitro-, 327, 328.
volumetrical estimation of, 124.
Plienolazoacetometamidobenzene, 583.
Phenolazoamidobenzene livdmcliloride,
583.
Phenolazobenzeneparasulphonic acid,
181.
Phenol-derivatives, 802, 985.
Phenol-phthalein as an indicator, 682,
824, 827.
Phenolquinoline, and some of its salts,
668.
Phenols, action of nitric acid on, 861.
— . — amido-, 734.
derivatives of, 1109.
chloro-, obtained by the action of
alkaline hypochlorites on phenol,
1108.
-■ compounds of benzotrichloride
with, 861.
1252
INDEX OF SUBJECTS.
Phenols, conversion of, into nitrils and
carboxylic acids, 802, 1111,
detection and estimation of, in
urine, 885.
ethereal derivatives of, 585.
iodo-, 1109.
nitro-, 864.
silicates of, 983.
substituted, reduction of, 802.
substitution-products of ethereal
derivatives of, 662.
Phenosafranine and its derivatives, 731.
Phenyl, dibenzoyldiamidodibromo, 343.
ethers of carbonic acid, conversion
of, into salicylic acid, 588.
itamalates, 473.
Phenyl monobromallyl oxide, 803.
Phenyl monochlorothyl oxide, 802,
orthoformatc, tribasic nitro-, 340,
salts of phosphorous acid, 735.
Phenylacetic acid, derivatives of, 64.
amidobromonitro-, 6i.
isonitroso-, and its salts,
1129.
metanitro-, and its amido-
compound, 1121.
paracyanamido-, 193.
Phenylacetotropeine, 671.
Phenylacridine, 1133.
Phenylalanine, and its derivatives, 992,
993, 994.
Phenylamidoisethionic acid and its salts,
665.
Phenyl- a-amidopropionic acid, and its
salts, 992.
Pbenylamidopropionic acid, formation
of, by the action of stannous chloride
on albuminoids, 1122.
Phenyl-a-amidopropionitril, 992.
Phenylamidovaleric acid, and other con-
stituents of lupine shoots, 1122.
Phenylamines, compounds of benzotri-
chloride with, 861.
Phenylamphinitrile, paraniido-, and its
salts, 919.
Phenylarsine sulphides, 186.
Phenylbenzocreatine, 193.
Phenylbenzoglycocyamine, and amide-,
and their hydrochlorides, 669.
Phenylbenzoic acid, dibromo-, 922.
Phenylbromobutyric acid, 472.
Phenylbromolactic acid, 196. .
Phenylbutyric acid, 473.
Phenylbutyrolactone, 472.
Phenylcacodyl, 187.
Phenylchlorobromc'propionic acid, 196.
Phenyldichloropropionic acid, 196.
Phenyldiethylarsine, 186.
Phenylenediamine, action of ethyl chlor-
acetate on, 797.
azo- and diazo-derivatives of,
583.
Phenylenediamines, three isomeric, and
some of their derivatives, 324.
three isomeric, cyanic derivative*
of, 798.
Phenylenedicarbamides, three isomeric,.
798.
Phenylenediglycocine, hydrochloride of^
797.
Phenylenedithiocarbamide, meta- and
para-, 324.
Phenyl enethiocarbam ides, 185.
Phenylethyl alcohol, isonitroso-, 1076.
Phenylethylamine, 993.
Phenylethylidene cyanhydrin, 992.
Phenylethyl-a-naphthvlthiocarbamide,
1106.
Pheny lethylph enylthiocarbamide, 1 1 06.
Phenylethylurethane, and nitro-, 802.
Phenylglyceric acid, 994.
Phenylgly colic tropeine, salts of, 671.
Phenylhalogenacrylic acids, 196.
Phenylhexylene and its dibromide, 977.
Phenylhomoitamahc acid, calcium salt
of, 473.
Phenylhomoparaconic acid and its salts,
473.
Phenylhydrazine-derivatives of the
quinones, 1135.
Phenylhydroxybutyric acid, 473.
Pheny IhydroxylpivaUc acid, 471.
Phenyl-a-hydroxypropionitril, 992.
Phenyl-o-imidopropionitril, 992.
Phenyhsopentylene and its dibromide,.
977.
Phenyllactic acid, nitro-, nitrate of, 993.
paramido-, 994.
/3-Phenyllactic acid, orthouitro-, alcohol
of, 341.
Phenyllactimide, 993.
-Phenyllactyl methyl ketone, ort'jo-
nitro-, paraniiro-, 341, 1120.
Phenylmethylacetoxime, metanitro-^
582.
Phenylmethylacetoximeorthocarboxylic
acid, anhydride of, 1128.
Phenylmethylurethane, 802.
Phenylmonothiourethane, nitro-, 582.
Phenyl -^-naphthylthiocarbamide, 1107-
Pheny Iparaconic acid and its salts, 472.
Phenylpentylene and its dibromide, 977.
Pheny Iphenamidoacetic acid and its^
amide and nitrile, 198.
Phenylphosphorous acid, mono- and di-,
736, 737.
Phenvlphosphoryl chlorides, mono- and
di-* 735.
Phenylpropargyl oxide, 803.
Phenylpropiolic acid, orfchamido-, andl
its derivatives, 196.
o-Phenylpyridiue, 1015.
/3-Phenylpyridine, and its diketone^
1013.
INDEX OF SUBJECTS.
125a
a-Phenylpyridine-dicarboxylic acid and
its salts, 1014.
jtJ-Plienylpjiidine-dicarboxylic acid and
its saltsj 1011.
Phenylpyridine-dicarboxylic acid, a-
dibromo-, and its salts, 1014.
a-Plienylpyridine ketone, and its salts,
1015.
/3-Phenylpyridine-monocarboxylic acid
and its salts, 1012.
a- and /S-Phenylquinoline, preparation
of, 1148, 1149.
Plienylrosaniline, dinitro- ? 54.
Phenylsulphoplienyl benzamidine, 48.
Plienyitaurine and its salts, 664.
Plienylthiocarbimide, action of, on
amido-acids, 1107.
metanitro-, 801, 802.
Phenylxanthamide, formation of, 185.
Phlobaphene, 995.
Phlogopite, I'utile in, 34.
Phloroglucinolvanillein, 62.
Pliloroglucol, tribromo-, action of potas-
sium iodide on, 1119.
Phoma gentiancB ; a newly observed
parasitic fungus, 1025.
Plionolite, analysis of, 721.
Phonolite-pumiee from S. Antao, analy-
sis of, 723.
Phoronoxirae, 728.
Phosgenite, artificial production of, 431.
Phosphate of sodium or potassium,
method for the valuation of, 827.
Phospliates, 782.
alkaline, action of sulphur on,
783.
behaviour of, to various indi-
cators, 380.
crystallised, 711.
decomposition of, by potassium
sulphate at high temperatures, 151.
insoluble, application of, to soils,
822.
behaviour of, in peaty soils
and in dilute solvents, 681.
mineral, on arable soil, 118.
of dyad, ti'iad, and tetrad metals,
double, 850.
of the alkalis, neuti'al, 151.
Phosphide of nickel, a, 651.
Phosphine hydrobromide, dissociation
of, 646.
Phosphines, action of zinc-ethyl on,
653.
tertiary, action of carbon bisul-
phide on, 58.
Phosphorescence, theory of, 763.
Phosphoric acid, combination of, with
sihoa, 782.
estimation of, 121, 240, 241,
380, 508, 619, 620, 1031.
in arable soils, 619.
Phosphoric acid, estimation of, in
manures, 620.
half soluble, estimation of,
508.
or the sodium or potassium.
salt of, method for the valuation of,
827.
preparation of, by the oxida-
tion of phosphorus with air in
presence of moisture, 1050.
Phosphorus, black, 150.
chlorides, conversion of tricalcium
phosphate into, 287.
heat of formation of, 544.
estimation of, by the molybdate
method, 750.
in pig-iron, influence of charcoal
on the amount of, 403.
poisoning in man and in the dog,
878, 879.
sulphides, 901, 1049.
trichloride, preparation of, from
phosphorus oxy chloride, 288.
and arsenic, analogy between the
allotropic modifications of, 901.
Photo-electric battery, 625.
Photographic paper, a new, 752.
Photographs of spectra, over-exposed,.
reversal of metallic lines in, 263.
Phthalimidobenzanihde, 999.
Phthalamidobenzoic acid, action of ani-
line and paratoluidine on, 999.
Phthalic acid, action of, on amido-acids^
1126.
amido-, salts of, 476.
Phthalic acids, two dinitro-, 344.
Phthalimide and its derivatives, 475.
Phthaluric acid and its salts, 1126.
Phthalylacetic acid, constitution of,.
1127.
Phthalylglycocine and its salts, 1126.
Phthalyltropeine, 672.
Phthisical patients, sugar from the lungs-
and saliva of, 929.
Phyllite from Bimogens, in the
Ardennes, 447.
Phylloxera, 233.
and means for its destruction,
680.
preparation of thiocarbonates for
the destruction of, 405.
Phytocollite, 427.
Picamar, Eeicheubach's, and its deriva-
tives, 1004.
Picoline, 85.
chloriodo-, 793.
a-Picoline, mono-, penta-, and hexa-
chloro-, 793.
PicoUnetetracarboxylic acid and it»-
salts, 85.
Picolinetricarboxylic acid, 600.
Picolmic acid, 794, 3015.
1254
INDEX OF SUBJECTS.
Picolinic acid, mono-, dichloro-, and
their salts, 794.
tetrahydromonochloro-, 794.
Picramide, derivatives of, 316.
Picranalcime, Bechi's so-called, 438.
Picric acid as a test for albumin and
sugar in urine, 1176.
Piezoelectricity, 412, 413.
Pig-dung, composition of, 117.
Pig-iron, analyses of, 133.
influence of charcoal on the amount
of phosphorus in, 403.
Pimelic acid, and the action of bromine
on, 998.
Pinacone, 568.
Piperhydronic acid, 485.
Piperidine, action of bromine on, in
alkaline solution, 789.
hydrochloride, action of metliyl
alcohol on, 1154.
isomeride of, 910.
oxidation of, 813.
pi-eparation of pyridine from, 813.
Piperidinic acid, and some of its salts,
813.
Piperylethylurethane, action of bromine
on, 814.
and its nitrodehydro-derivative,
814.
Pisolitic iron ore, formation of, 1065.
Plant assimilation, first product of,
365.
Plant cells, action of various gases,
especially nitrous oxide, on, 105.
autoxidation in, 819.
elimination of oxygen from,
105.
Plant-food, retentive capacity for, pos-
sessed by soils, 681.
Plant-organs, amylaceous, interchange
of material in, 497.
Plants, absorption of metallic oxides bv,
231.
aquatic and submerged aero-
aquatic, respiration of, 747.
diseases of, and their prevention,
612.
easily oxidisuble constituents of,
880.
effect of water containing zinc-
sulphate and common salt on, 1027.
elimination of carbonic anhydride
by, in absence of oxyc^en, 105.
function of resins in, 365.
green, influence of chemical agents
on the assimilative capacity of, 611.
growth of, under special conditions,
496.
influence of the electric light on
the development of, 105.
■ parasitic diseases of, and their pre-
vention, 110.
Plants, poisoning of, 612.
presence of formic and acetic acid
in, 611.-
respiration of, 498.
Plaster of Paris, setting of, 712.
Platinum, behaviour of, in chromic and
nitric acids, 608, 699.
electric properties of, when con-
taining hydrogen, 766.
metals, chemistry of, 1057.
native, new substance in, 954.
nugget, a remarkable, 426.
ore, magnetic property of, 859.
residues, a black powder obtained
from, 1057.
Platinum- water pyrometer, 769.
Platodiammonium carbonate, 28.
nitrate, 28.
Platosammonium carbonate, 28.
Poisoning, methods of detecting lead,
silver, and mercury in the body ia
cases of, 687.
Poisons, distribution of, in the human
organism in cases of poisoning, 1020.
Polarisation, oscillations of the plane of,
by electric discharges, 4.
Polarising, sources of error in, 3.
Polychrome varnish for white metal,
896.
Polyhydrite from St. Christoph mine,
in Saxony, 444.
Porcelain, 397.
Porphyrite, micaceous, of Morvan, 447.
Porphyry, from the Lugano district,
167.
tuff near Tryberg in the Black
Forest, 725.
Portland cement and its adiilteration,
530.
testing of, 753.
Potable water, estimation of oi^nic
matter in, 1171.
Potash alum from felspar, 424.
Potassium anhydrosulphite, 705.
antimonate, electrolysis of solutions
of, with carbon electrodes, 590.
beryllium oxalate, basic, 1085.
carbonate, 902.
chloi-ate, poisoning with, 1021.
gold bromide, 854.
picamar, 1005.
pyrosulnhite, and hvdrates of, 705,
706.
pyrroline, action of cyanogen
chloride on, 599.
salts containing sidphur, heats of
formation of, 706.
sesquicarbonate, Gid.
thiocarbonafe, analysis of, 241.
thiosulp hates, 707.
and lead iodides, heat of forma-
tion of double salts of, 275.
INDEX OF SUBJECTS.
1255
Potassium and thallium, double chlo-
ride of, 424.
Potato brandy, poisonous action of, 362.
disease, cure for, 233.
■ " sets," influence exerted by the
weight of, 286.
Potato-sugar, does it contain any dele-
terious matter ? 136.
Potatoes, conversion of starch into
sugar in, 497.
cultivation of, 114, 680.
dried, use of, 614.
influence of manuring on the com-
position of, 882.
• manuring, with potassium nitrate,
117.
oxalic acid in, 232.
and grain, simultaneous use of, in
spirit factories, 630.
^' Pouzzo-Portland," existence of anew
compound, 830.
Pozzolana, production of, 529.
Prehnite, 35.
from Monte Catini, 442.
from Tuscany, &c., 441.
Press-cake, new process for preparing,
from maize, &c., 695.
Pressures developed in closed vessels by
the explosion of gaseous mixtures,
measurement of, 542.
momentary, produced during the
combustion of gaseous mixtures, 542.
Primary diamines, action of ethyl chlor-
acetate on, 797.
Printing ink, process for preparing,
896.
Propaldehyde, action of ammonia on,
39.
Propane, tri- and tetra-chloro-, 659.
Propargyl-phenol, 803.
Propiargylic acid, 314.
Propenylbenzoic acid and its salts, 330.
Propenyltricarboxylic Eujid, and ethereal
salts of, 45.
Propiohomoferulic acid, 200.
Propionamide, preparation of, 1088.
Propionamidine hydrochloride, 1090.
Propionic acid, substituted, constitution
of, 310.
tetra-substituted, and their
salts, 309.
Propyl bisulphide, normal and iso-, 48.
bromide, transformation of, into
isopropyl bromide under the influence
of heat, 172.
compounds, specific volumes of,
13.
group, conversion of, into the
isopropyl group, 565.
oxvsulphide, action of chlorine on,
659. "
trichloracetate, 729.
Propylaldoxime, 569.
Propylallylamine and its platinochlo-
ride, 909.
Propylazaurolic acid, 41.
Propylenes, two dichloro-, action of
triethylamine on, 307.
Propylethenyltricarboxylic acid and its
salts, 46.
Propylformimide hydrochloride, 1089.
Propyl glyoxaline, para-, 911.
Propylidenepropaldeliyde, 570.
Propyl -nitrous acid, potassium salt of,
915.
Propyls uccinic acid, 46.
Pro pylsul phonic acid, action of chlorine
on, 659.
chloro-, 659.
Prosopite, chemical composition of, 30.
Protocatechuic acid, action of sulphuric
acid on, 65.
Protocatechutannic acid and its deri-
vatives, 335.
Protoplasm, living, chemical character
of, 819.
Prussic acid, cyanides, &c., poisoning
with, 1022.
Pseudobrookite, 435.
Pseudocumene, monobromo-, prepara-
tion of, 469.
sulphamic acids and hydroxy-
acids derived from, 589.
Pseudocumic acid, monobromo-, and its
salts, 469.
Pseudomorph of nacrite after fluorspar,
1069.
Pseudomucin, 874.
Pseudopurpurin, 598.
Psilomelane, electric resistance of, 701.
Psoromic acid, a new acid extracted
from Psoroma crassum, 80.
Psoromic anhydride, 81.
Ptomaines, 224, 1156, 1157, 1159.
genesis of, 522, 624.
Pfcomopeptone, 926.
Purpureorhodium compounds, chloro-,
bromo-, and iodo-, 1058.
Purpurin, commercial, 598.
Purree, source of, 219.
Putrescible substances, dialysis of, 1177.
Putrid fermentation, and the alkaloids
produced by it, 224.
Puzzuolanas, analysis of, and estimation
of their comparative values, 628.
Pyrene, action of chlorine on, 1001.
Pyrene-carboxylic acid, and its salts,
1004.
Pyrene -derivatives, 1001.
Pyrene-disulphonic acid and its salts,
1003.
distillation of the potassium
salt of, with potassium cyanide or
ferrocvanide, 1003.
1256
INDEX OF SUBJECTS.
Pyrene-picric acid, chloro-, 1001.
Pyrenequinol and its diacetyl-deriva-
tive, 870.
Pyrenequinone and its derivatives, 869.
Pyridic bases derived from cinchonine,
hydrates of, 220.
Pyridine, 85, 739.
bases, 738.
derivatives, hydrogenised, physi-
ological action of, 1145.
• synthesis of, from ethyl
acetoacetate and aldehyde-ammonia,
82.
monobromo-, 813.
periodides of, 980.
preparation of, from piperidine,
813.
researches on, 483.
rliodium salts, dicliloro-, 1060.
j8-Pyridine dibromide, 923.
Pyridine series, isomerism in, 740.
syntheses in, 1151.
Pyridine- group, introduction of hydro-
carbon radicles into, 1151.
Pyridinemonocarboxylic acid, 484.
Pyridinemonosulphonic acid and its
salts, 923.
Pyridinepentacarboxylic acid and its
salts, 85.
Pyridine thyl iodide, action of heat on,
1151.
Pyridinetricarboxylic acid, 1152.
Pyrocinchonic acid, 98.
Pyroclasite, stalactites of, 1063.
Pyrocomenamic acid, 792.
Pyrocresole dioxide, 208.
oxides, and oxynitro-products of,
206.
bromo-, 207.
Pyrocresoles, a-, j3-, and y-, 204.
Pyrocresolesulphonic compounds, 208.
Pyroelectricity, 412.
Pyrogallovanille'in, 61.
Pyrolein, 519.
Pyrolusite mines of Bolet in Sveeden, 31.
Pyromecazone and its nitro-derivative,
791.
Pyromecazonic acid and its derivatives,
791.
Pyromellic acid, 593.
Pyrometer, platinum-water, 769.
Pyromorphite from Zahringen in Baden,
analysis of, 1063.
Pyromorphites and Mimetesites, relation
between the chemical composition
and optical characters in the group of,
433.
Pyromucic acids, substituted, 912.
Pyrosulphites, 705.
Pyrosulphuric acid, specific conduc-
tivity of, 413.
chloride, 553, 782, 900, 1051.
Pyrosulphuric chloride, converBion of,
into sulphuric monochloride, 642.
new mode of formation, 710.
vapour-density of, 423, 646,
710.
Pyroxene, green, from the diamond
mines of the Cape, analysis of, 1067.
Pyroxene and amphibole, relation be-
tween the optical properties and che-
mical composition of, 560.
Pyroxenite from S. Vicente, Cape de
Verde Islands, 722.
Pyrroline, action of nascent hydrogen
on, 82, 1142.
tetriodo-, 350.
Pyrroline-series, compounds of, 350.
Pyruvyl benzoate, and the action of
benzoic anhydride on, 63.
Quartz, actinoelectric and piezoelectric-
properties of, and their relation to the
pyroelectric, 412, 950.
circular polarisation of, 140.
observations on thermo- and actino-
electricity of, 950,
pyroelectricity of, 897.
Quartz and water, variation of the-
indices of refraction of, with the
temperature, 762.
Quartz-mica-diorites, analysis of, 1069.
Quartz -porphyrv near Try berg in the-
Black Forest,' 724.
Quartz-rock, 36.
Quartzite, Dumont's, 958.
Q.uercitannic acid, 995.
Quinaldine and its salts, 602.
Quinanisoil, or methoxvquinoline, 93,
94.
Quinazole-compounds, 812.
Quinidine, 1018.
Quinine, 1018.
ether test for, 1174.
test for the purity of, 1019.
Q.uinol, fusion of, with soda, 60.
nitro-derivatives of, 465.
preparation of, 1115.
sulphonic acids of, and their salts,.
1115.
Quinoleic acid, and its salts, 89.
Quinolic acid, 1145.
Quinoline, 739.
acetamidobromo-, 91.
action of chloroform and iodoform^
on, 600.
ethyl monochloracetate on,
96.
phthalic anhvdride on, 667r
812.
INDEX OF SUBJECTS.
1257
^uinoline, addition-products of, 1008.
/3-amido-, 1148.
amidobromo-, 90.
amyl bromide, 1009.
benzyl chloride, and oxidation of,
1009. .
coal-tar, colouring- matters from,
1150.
dyes obtained by the action
of phthalic anhydride on, 922.
and of the cinchona alka-
loids, and its oxidation by potassium
permanganate, 89.
a-/3- dichloro-, 197.
ethyl bromide, chloride, and ni-
trate, 1008, 1009.
from cinchonine, 88.
nitrobromo-, 90.
paranitro-, and its derivatives,
811.
second periodide of, 980.
substitution-derivatives of, 351.
Quinoline-betaine, 96.
j8-Quinolinecarboxylic acid, and its salts,
1152.
Quinolinecarboxylic acid, nitro-, 602.
Quinoline-derivatives, 92, 96, 738.
Quinolines, nitro-, 811.
substituted, preparation of, 1148.
Quinolinesulphonic acids, bromo-, and
their salts, 96.
Quinols, 465.
Quinone, C13H7NO2, 1014.
chlorine and bromine-derivatiA^es
of, 1] 17.
combinations of, with phenols,
465.
compounds of, with nitranilines,
60.
nitro-derivatives of, 465.
Quinonedinitranilides, 61.
Quinones, 465.
action of amines on, 209, 1117.
phenylhydrazine - derivatives of,
1135.
Quinophthalone, 668.
B.
Radiant heat, constituent of the atmo -
sphere which absorbs, 7.
Eadiation from silver at the solidifying
point, 771.
of rock-salt at various tempera-
tures, 702.
Radiation-spectra, 762.
Rain-waters, variation of the amount of
ammonia in, 753.
Ralstonite, chemical composition of, 29.
Rapakiwi granite from Finland, 447.
Rattlesnake poison, antidote for, 104.
" Reaction aptitudes " of the halogens
.in mixed haloid ethers, 787.
Red lead, process for preparing, 891.
Refraction of water and quartz, varia-
tion of the indices of, with the tem-
perature, 762.
Refractive index of liquids, change of,
by electric forces, 948.
Refractive power of organic compounds
in solution, 1041.
Refractory clays, 397.
Reichenbach's oxidising principle, 1005.
Resins in plants, function of, 365.
Resodibromoxybenzene, trichloro-, 984.
Resorcinol, amido-, 733.
-derivatives, 984.
diamido-, hydrochloride, 917.
dibromonitro-, 733.
diimido-, 918.
dinitro-, 733, 917.
dinitromonobromo-, 733.
dyes, tests for, 689.
monobromo-dinitro-, 917.
mononitro-, and its salts, 733.
nitro-, action of, on aniline acetate,
734.
new homologue of, 918.
nitro-derivatives of, 803, 917.
preparation of the homologues of,
253.
trinitro-, constitution of, 329.
Resoreinols, pentahalogen, comparison
of the behaviour of the four known,
when heated, 985.
Resorcinolsulphonic acid, nitro-, and its
derivatives, 1114
Respiration of aquatic and submerged
aero-aquatic plants, 747.
Rhodammonium compounds, chemistry
of, 1058.
Rhodium, atomic weight of, 1060.
-black, action of, on hydrogen per-
oxide, 849. .
some reactions of the salts of, 715.
Rhodizite, 956.
Rhodogen from sugar-beet, and its
oxidation-product, 881
Rice-meal as food for milch cows, 820.
detection of, in buckwheat flour,
885.
Rice-starch, estimation of, 124.
Rock-salt, blue, 1051.
radiation of, at various tempera-
tures, 702.
Rocks, Italian, chemical and micro-
scopical researches on, 446.
massive crystalline, metamor-
phism of, 562.
Silurian, of Christiana, 723.
soft calcareous, hardening of, by
1258
INDEX OF SUBJECTS.
means of fluosilicates of insoluble
bases, 940.
Rock-salts, various, artificial formation
of, 448.
Koessler's method for the separation of
gold, silver, lead, and copper from
sulphides by air-blast, 400.
Boots, removal of the leaves of, 613.
Rosaniline, decomposition of, by water,
1097.
colouring-matters, 807.
-derivatives, 54.
hydrochloride, detection of, in
wine by means of stearin, 384.
Koseo-salts, basic, 557.
Kosolic acid, use of, as an indicator,
827.
Ruberine in Agaricus ruber, 100.
Euby, inclusions in, 1062.
Rufiopine, 65.
Rupert's drops, 422.
Russian basic steel, 1036.
Rutile, as a product of the decomposi-
tion of titanite, 33.
in phlogopite, 34.
Rye, ungerminated, and the embryos of,
analyses of, 107.
Rye-meal, detection of, in flour, 392.
s.
Saccharic acid, and some of its salts,
565.
constitution of, 963.
Saccharin, 962.
formation of, from sugars, 42.
new acid obtained by the action of
nitric acid on, 566.
preparation of, 565.
reduction of, 1078.
Saccharone and its salts, 962.
Saccharonic acid and its salts, 962.
Saccharose, effect of temperature and
concentration of acid on the rate of
inversion of, 1077.
Safranine colouring matters, 731.
Salicin, synthesis of, 76.
Salicvlaldehvde, condensation of, with
aniHne, 982.
cyanhydrin, 190.
new derivatives of, 189.
Salicylaldoxime, 1104.
Sahcylic acid, antiseptic action of, 128.
conversion of phenyl ethers
of carbonic acid into, 588.
estimation of, in milk and
butter, 522.
rapid method of estimating,
in wines, &c., 245.
Salicylic anhydride, products of the dis-
tillation of, 664.
Salicylic trope'ine, 671.
Saliva, human, alkalinity and diastatie
action of, 488.
Saltpetre, nitrogen estimation in, by
potassiuin xanthate, 1031.
Salts containing chromium and urea,.
series of, 178.
' decompositions of, by fused sub-
stances, 11.
galvanic conductivity of solutions
of, in mixtures of alcohol and water,
769.
hyd rated, constitution of, 780.
metallic, relative toxic power of,
745.
osmose of, 420.
Sandal wood, essence of, 76.
Santonin, distillation of, with zinc-
powder, 80.
Santonous acid and its derivatives, 77.
Sap from a silver birch tree, 1164.
Saponin, 1166.
Sapphire, inclusions in, 1062.
Sarcosine anhydride, 192.
Saussurite, 1066.
Scandium, spectral researches on, 954.
Scapolite, analysis of, 440.
Scherff's preserved milk, 757.
Schizomycetic fermentation, 363.
Sclerocrystallin, 640.
Sea-water, manganese in, and in certain
marine deposits, 725.
Sealed tubes, experiments on the small
scale in, 1167.
Secondary batteries, 765.
Seeds, part played by Kme in thegenni-
nation of, 490.
value of sprouted grain for, 490.
effect of steeping and drying ou
the germination of, 490.
Seleniothiostannic acid, salts of, 156.
Selenium, boiling point of, 17.
extraction of, from a waste pro-
duct, 16.
preparation of, on a large scale.
852.
thermochemical investigation on
the chlorides of, 543.
Senarmontite crystals, pseudomorphic,
430.
Septic poison, origin of, 937.
Sericite rocks occurring in ore deposits,
168.
Serpentine, 36.
from the Alps, 562.
Sesame cake, albuminoids in, 360.
Sesquiterpene hydrate, 346.
Sewer gases, contributions to the know-
ledge of, 886.
Sheep, lupine sickness in, 228.
INDEX OF SUBJECTS.
1259'
Sheep of different breeds, effect of food
on, 226.
Sherry, snlphviric acid in, 829.
Siderite, analysis of a variety of, 559.
SiHca, action of different varieties of, on
lime-water, 712.
combination of phosphoric acid
with, 782.
hydraulic, and its functions in
hydraulic cements, 754, 755.
Silicate, a crystallised hydrated, artificial
production of, 33.
Silicates, analysis of, 379.
of phenols, 983.
Silicon, 15.
estimation of, in iron and steel,
883.
sulphides, 15.
Silurian rocks of Christiana, 723.
Silver amalgam from the Sala mines,
426.
ammonium nitrate, 902.
bromide, action of light on, 3.
and chloride, modifications
of, 936.
gelatin-emiilsion, 395.
chloride element, Scrivanow's, 840.
coins, German standard, presence
of gold in, 629.
haloid salts, electrical conductivity
of, 769.
hyponitrite, heat of formation of,
423.
hypophosphate, 1052.
iodide, and its alloys with cuprous
and lead iodides, specific heat and
heat of transformation of, 274.
method of detecting, in the body
in cases of poisoning, 687.
nitrate, action of certain metallic
compounds on, 288.
testing of, 381.
and ammonia, 902.
salts, some, coefiicients of solu-
bility of, 1172.
separation of, from alloys, 243.
separation of, from sulphides by
air-blast, 400.
Sinidor, 396.
Sipylite, crystalline form of, 435.
Skatole, new synthesis of, 1132.
Skim-milk, feeding calves with, 675.
nutritive value of, 102.
Skin, excretion of nitrogen from, 227.
fcl basic, obtained in the dephospho-
rising process, utilisation of, for agri-
cultural pvirposes, 133.
from the basic dephosphorising
process, utilisation of, in agriculture,
375.
Smaltite, occurrence of, in Colorado,
559.
Snow, fallen, influence of, on the tem-
perature of the air, 500.
Soap, use of, in djeing, 894.
Soaps, adulterated, 893.
Soda industry, notes on, 887.
recent progress in, 524.
Soda-lyes, crude, presence of vanadium,
fluorine, and phosphorus in, 887.
Sodalite syenite of South Greenland,
minerals in, 960.
Sodioferrous citrate, 458.
hydroxycitrate, 458.
Sodium, loss of, in caustification, 888.
in the Le Blanc process, 887.
acetate and sodium isopentylate,
action of carbonic oxide on a mixture-
of, 729.
arsenate, reduction of, with oxalie
acid, 513.
carbonate, action of chlorine on
solutions of, 647.
test for, in milk, 385.
dibromanisate, dry distillation of,.
1125.
■ ethylraalonate, action of chloro-
form on, 311.
isopentylate and sodium acetate,
action of carbonic oxide on a mixture
of, 729.
plienate, action of iodine and of
nitric peroxide on, 1109.
action of sulphur on, 988.
sulphate solutions, coefficient of
expansion of, 17.
sulphide, manufacture of, 627.
sulpliite, neutral, thermochemical
researches on, 705.
tungritates, 651.
Soil, effect on the fertility of, produced
by covering it with farmyard manure,.
237.
estimation of the fertility of, 517.
evaporation of water from, 615.
fertility of, as dependent on the
action of worms, 237.
influence of organic manures on
the temperature of, 821.
the state of aggregation on
the temperature of, and moisture in,
500.
reduction of nitrates in, 229, 503.
Soils, application of insoluble phos-
phates to, 822.
arable, butyric ferment in, 610.
estimation of phosphoric acid,.
619.
a denitrifying ferment in, 679.
effect of water containing zinc sul-
phate and common salt on, 1027.
estimation of humus in, 247, 830.
mechanical and chemical analysis-
of, 621.
1260
INDEX OP SUBJECTS.
Soils, nitrification in, 115, 116.
peaty, influence of the percentage
of moisture in, on vegetation, 681.
retentive capacity for plant food
possessed by, 681.
rise of temperature induced in, by
the condensation of liquid and gaseous
water and of gases, 615.
Soja bean, analysis of, and tables of the
composition of various Japanese foods
made from, 235.
constituents of, 1024.
Solar spectrum, atmospheric absorption
in the infra-red of, 837.
chlorophyll and the distribu-
tion of energy in, 697.
distribution of heat in the
ultra-red region of, 143.
observations on, 137.
Solid bodies, unipolar conductivity of,
769.
Solidification of bodies in a state of
superfusion, velocity of, 546.
Solids, estimation of the molecular heat
of, for the solution in water and other
liquids, 704.
Solution, nature of, 550.
Solvents, law of freezing of, 278.
Sorgho juice, analysis of, 634.
Specific gravity of elements in various
allotropic modifications, 779.
Specific heat of gaseous acetic acid, 6.
of gaseous compounds of
chlorine, bi'omine, and iodine with one
another and with hydrogen, 417.
of silver iodide, and its alloys
with cuprous and lead iodides, 274.
Specific heats, apparatus for the deter-
mination of, by cooling, 6.
law of variation of, 845.
of gases at high temperatures,
771, 898.
of small quantities of sub-
stances, 6.
Specific volume and boiling point, rela-
tion between, 302.
Specific volumes of allyl and propyl
compounds, 13.
of liquids, 13.
of the alkyl salts of fatty
acids, 967.
Spectra, infra-red. observations of, by
means of phosphorescence, 761.
metallic, variations of, due to mixed
vapours, 2.
of carbon and its compounds, 261.
of non-metals, influence of tempe-
ra tiire on, 140.
Spectral lines, some, disappearance of, 2.
Spectrum of Swan's incandescent lamps,
1.
of water, 140.
Spectrum of water- vapour, 261.
Spectrum photography, 263.
Spinel, inclusions in, 1062.
Spirit, manufacture of, from wlieat,
630.
/3-Spodumene, 439.
Spodumene and the products of its
alteration, 438.
Spring-water from Rindo near Stock-
holm, analysis of, 449.
Sprouted grain, value of, for seed, 490.
Sprudelsalz, preparation of, 396.
Stannates, crystallised, 716.
Stannic acid, bromo-, 425.
oxide, preparation of, ' from
sodium stannate, 425.
Stannous oxide and some of its com-
pounds, 294.
sulphide, action of ammonium sul-
phide on, 22.
Starch, action of bacteria on, 931.
direct fermentation of, 365.
estimation of, in grain, 624.
formula of, 307.
formation of, from sugar, 820.
influence of foreign matter on the
conversion of, by diastase, 631.
Starch-sugar, estimation of dextrose,
maltose, and dextrin in, 123.
manufacture of, 39.
Steam, action of carbonic oxide on, 860.
Stearic acid and naphthalene, solidifica-
tions of different mixtures of, 176.
Steel, cast and malleable, relative oii-
disabihty of, 755.
cementation, crystals in, 629.
estimation of silicon and sulphur
in, 883.
estimation of sulphur in, 121, 512.
estimation of total carbon in, 882.
from pig-iron containing phospho-
rus, at Creusot, 403.
hardness of, 883.
influence of sulphur and copper
on the working of, 404.
new method for the estimation of
minute quantities of carbon in, 1032.
Russian basic, 1036.
Steel ingots, rolling of, with their own
initial heat without the use of fuel,
532.
Steel-rails, chemical composition and
testing of, 531.
Steenstrupine, analysis of, 960.
Steeping of barley, influence of different
kinds of water in, 631.
Stercobilin and hvdrobilirubin, identity
of, 1159.
Stibiographic acid, 592.
Stibiomellogen, 591.
Stilbite, 957.
(Desmin), new face on, 441.
INDEX OF SUB.JECTS.
1261
Stomach, reaction of the living mucous-
lining of, 815.
Stones, building, decay of, 1036.
&c., waterproof paint for, 760.
Stoneware, 397.
Storage batteries, chemistry of, 839.
Storax, American, 407.
Strontianite, artificial production of,
31.
in Westphalia, 431.
Strontium chloride, application of, in
purifying syrups, 252.
detection of, 509.
Strontium and calcium, separation of,
509.
Strychnine, bromine as a test for,
1175.
-derivatives, 669.
diamido-, 670.
dinitro-, and its salts, 669.
distillation of, with zinc, 99.
indole from, 99.
solubility of, in acids, 924.
sulphate, 223.
trapezohedral hemihedry of,
485.
Styphnic acid, constitution of, 329.
Stypticite from Chili, 31.
Styrole, dinitro- and brom-acetamido-,
1123.
Styrolene, derivatives of, 70.
paramido-, 70.
Suberic acid, monochloro-, action of
potassium cyanide and potassium hy-
droxide on, 970.
Suberoxime, 728.
Succinamidine hydrochloride, 731.
Succinic acid, diamido-, 43.
dibromo-, 43.
— — symmetric, action of so-
dium ethylate on the sodium salt of,
312.
Succinimide and its derivatives, 476.
Succinimidine hydrochloride, 731, 1088.
Suet and other fats, recognition of suint
in, 750.
Sugar, distribution of, in beet, 124.
estimation of, by alkaline copper
solutions, 519.
estimation of, in urine, 829.
■ from the lungs and saliva of
phthisical patients, 929.
in urine, picric acid as a test for,
1176.
influence of mass and time on the
inversion of, 306.
manufacture of, without the aid of
bone-charcoal, sand, or sulphurous
anhydride, 835.
manufacture, preservation of dif-
fusion residues from, 695.
recovery of, from molasses by
VOL. XLIV.
means of strontium hydroxide, 252,
536.
Sugar, sorgho- and imphy-, manufacture
of, in the United States, 633.
Sugar-cane, percentage of ash in, 110.
Sugar-canes, artificial manuring of, 506.
Sugars, action of cupric hydroxide on,
38.
Suint, recognition of, in suet and other
fats, 750.
" Sulfuraires," reduction of sulphates
by, 610.
Sulphamic acids derived from pseudo-
cumene, 589.
Sulphaminisodurylic acids, 53.
Sulphates, constitution and dimorphism
of, 973.
reduction of, by algae, 229, 680.
reduction of, by *' sulfuraires,"
610.
Sulphide, new, received as tetrahedrite
from Q-reat Eastern Mine, Colorado,
161.
Sulphides, estimation of, 934.
formation of, by pressure, 904.
metallic, solubiUty of, in thio-acids,
1169.
Sulphocarbometer, 386.
Sulpho-derivatives, action of chlorine on,
659.
Sulphonamidotrimellic acid, salts of,
590.
Sulphonamidoiylidic acid, 589.
Sulphonamidoxylylic acid, 589.
Sulphonates, constitution of the double
compoimds of, with alkyl sulphates,
973.
Sulphonic group, displacement of, by
chlorine, 806.
Sulphotrimellic acid, salts of, 690.
Sulphur, action of, on oxides, 710.
atomic refraction of, 264.
decomposition of water by, 900.
estimation of, in coal-gas, 382.
estimation of, in iron and steel,
121, 512, 883.
in coal, 383.
influence of, on the working of
steel, 404.
oxidation of, in the air, 551.
phosphorescence of, 710.
recovery of, by Mond's process, 129.
Sauer's method of estimating, and.
some modifications of it, 239.
sulphur oxides, carbon, and carbon
oxides, reactions between, 551.
thermochemical investigation on
the chlorides of, 543.
Sulphuric acid, concentrated, specific
gravity of, 413.
estimation of, in presence of
alkaline chlorides, 240.
4 p
1262
INDEX OF SUBJECTS.
Sulphuric acid, free, detection of, in
presence of aluminium sulphate, 1168.
quantitative production of : a
lecture experiment, 281.
— sp. gr. of, 851.
specific conductivity of, 413.
testing for, 240.
utilisation of the nitrogen-
compounds from the manufacture of,
130.
volume- weight of, 288,
Sulphuric acid chambers, the ciurents of
the gases in, 129.
working of, 887.
Sulphuric mono- and di-cMoride, action
of heat on, 781.
Sulphuric monochloride, conversion of
pyrosulphuric chloride into, 642,
thermal constants of, 642.
— — vapour-density of, 781,
Sulphurous acid and its salts, estimation
of, 934.
detection of, in wine, 384.
estimation of, in wine, 621.
— — contained in furnace gases,
absorption and utilisation of , 248.
Supersaturation, 645.
Syenite, Dresden, analysis of, 859.
Sylvin, presence of thallium in, 954.
Symphytum asperrimum^ comparative
feeding value of, 613.
Syntheses in the animal organism, 361.
with chloropicrin, 1000.
Syrup of tolu, alteration of, 407.
Syrups, application of strontium chlo-
ride in purifying, 252.
T.
Tannin, estimation of, 391.
Tannins of oak-bark, 994.
Tartaric acid, dry distillation of, with
excess of lime, 658.
free, occurrence and estima-
tion of, in wine, 935.
manufacture of, 1178.
Taurocholic acid, behavioxir of, with
albumin and peptones, 673.
Telluric rays, 261.
Tellurium in copper, 531.
' thermochemical investigation on
the chlorides of, 543.
Temper, influence of, on the electrical
resistance of glass, 701.
Temperature, effects of, on the electro-
motive force and resistance of bat-
teries, 840.
Tephrites, 721.
/3-Terebangelene, 810.
Terebene, aldehydic nature of oxidation-
product of, 1141.
Terebenthene hydrochlorides, liquid,
809.
Terpenes, some, addition-products of,
1140.
Terra cotta lumber, preparation of, 896.
Tertiary phosphines, mixed aromatic, 57.
Testing-churn, Jakobsen's, 253.
Tetano-cannabine, 1156.
Tetracetylrosanihne, 981.
Tetradecyl alcohol, normal primary,
preparation of, 1075.
Tetrahydrodicollidine and its derivatives,
84.
Tetraliydroquinoline, action of bromine
on, 1145.
and its derivatives, 1143.
from crude quinoline, 739.
oxidation of, 1144.
Tetrahydroxydiphenyl, dichlorodi-
bromo-, 985.
Tetrahydroxydiphenylmethane ? 59.
Tetramethylenedi- and mono- car boxylio
acid and their salts, 1084.
Tetramethylethylene oxide, 567.
Tetraparacresyl silicate, 983.
Tetraparaoxybenzoid, 335.
Tetraphenyl sihcate, 983.
Tetraphenylethane, unsymmetrical, syn-
thesis of, 1132.
Tetraprotocatechutannic acid, 335.
Tetratomic elements, combination of, 15.
Tetrethylic acetylenetetracarboxylate,
46.
dicarbontetracarboxylate and its
salts, 46.
Tetrethylbenzene and its derivatives,
1091.
Tetrethylphenylenediamine and its de-
rivatives, 869, 1100.
Tetrethylsafranine, 732.
Tetric acid, so-called, 730, 1085.
Tetrolcarbamide, 350.
Tetrolurethane, 350.
Tetroxy-ditolyl, anhydride of, 467.
Thallium, position of, in the chemical
system, and its presence in sylvin,
954.
phosphates, 424.
and potassium, double chloride of,
424.
Thenardite from Aguas Blancas, 434.
Theobromine, action of alkalis on, 1017.
derivatives of, 356.
and its salts, 872, 1017.
Thermal constants of substitution, law
of, 143.
Therochemical researches, 704.
Thermo-chemistry, basis of, 773.
Thermo-electricitv, practical application
of, 625.
INDEX OF SURJECTS.
1263
Thermometers, mercurial and hydrogen,
comparison of, 144.
Thermometric measurements, 842.
Thiacetic acid, action of, on ethyl thio-
cyanate, 39.
Thiocarbamide, action of dibromobarbi-
turic acid on, 913.
oxidation of the bases obtained by
the action of halogen compounds on,
664.
Thiocarbamides, mixed aromatic, pro-
ducts of the decomposition of by
acids, 1106.
Thiocarbamidophenol and deriyatives of,
1109, 1110.
Thiocarbonates, estimation of carbon
bisulphide in, 935.
preparation of, for the destruction
of phylloxera, 405.
Thiocyanacetone, preparation and pro-
perties of, 654.
Thiocyanates, action of dibromobarbi-
turic acid on, 913.
manufacture of, 639.
Thiocyanic, hydrocyanic, and hydro-
chloric acids, method of estimating
when simuttaneously present, 1173.
Thiocvanobarbituris acid, some salts of,
914.
Thiocyanopropimine and its derivatives,
568.
thiocyanate, 654.
Thiodialuric acid, 914.
Thiodicyanodiamidine, 1090.
Thionyl chloride and its action on
organic compounds, 1051.
Thiophene : a substance contained in
coal-tar benzene, 1091.
Thiopseudouric acid, 914.
Thiostannic acid, salts of, 156.
Thiouramidobenzoic acid, 193.
Thomas-Gilchrist process, 832.
Thomsenolite, 427.
chemical composition of, 29.
Thomsonite, 957, 958.
from Colorado, 164.
Thorite of Arendal, 299.
Thorium, crystalline form, specific heat,
and atomicity of, 553.
determination of the equivalent of,
152.
metallic, preparation of, 152.
specific heat and yalency of, 649.
sulphate, 1053.
Thulium, spectral researches on, 954.
Thymol, new isomeride of, 459.
Thymol-derivatives, 1112.
Tin, action of certain vegetable acids on,
1038.
compounds of, with bromine, 424.
disulphide and diselenide, com-
pounds of, 156.
Tin-ores from Asia, 435.
oxybromide, 425.
tetrabromide and its hydrate, 424,
425.
Tinder ore from the Harz, 1061.
Tissue- waste in the fowl during starva-
tion, 603.
Titanic acid, estimation of, in presence
of iron, 381.
oxidationi of, 1055.
Titanic acids, 1056-
Titanite, rutile, as a product of the
decomposition, of, 33^
Titanium, a higher oxide of, 295.
a new oxide of, 828.
a new test for, 828.
detection and. estimation of, 381.
Tobacco ash, analyses of, 372.
Toluene from coal-tar, 1092.
dinitro-, liquid, 1093.
constitution of, 865.
and trinitro-, compounds of,
with hydrocarbons^ 318.
metaparadiamido-, oxalic acid de-
rivatives of, 323.
symmetric dinitro-, preparation of,
864, 865.
trinitro-, 1093.
trinitro-derivatiyes of, 315.
Toluene-aniline, a-trinitro-, 317.
Toluenes, nitro-, oxidation of, by po-
tassium ferricyanide, 577.
trinitro-, 317.
Toluidine, methylation and ethylation
of, 578.
j3 and y-dinitro-, 317.
nitro-, symmetric, 865.
Toluidines, isomeric, action of paradi-
azobenzenesulphonic acid on, 182.
nitro-, from liquid dinitrotoluene,
579.
Toluquinol, compounds of, with amines,
60.
tribromo-, 331.
trichloro-, 1112.
Toluquinone, brominated derivatives of,
330.
compound of, with orthonitrani-
line, 61.
trichloro-, 1112.
Toluylenediamine, action of ethyl chlor-
acetate on, 797.
conversion of, into an amidocresol
and y-orcinol, 329.
symmetric, 865.
Tolyloxamic acid, nitro-, and its deriva-
tives, 323.
Tohlphenylamine, y-dinitro-, 317.
Tolylsulphophenylbenzamidine, 48.
Topaz occurring near Pike's Peak, Colo-
rado, 1065.
Toughened glass, 399.
1264
INDEX OF SUBJECTS.
Tourmalin, chromic, in the Urals, 444.
Triacetonamine, action of phosphorus
pentachloride and oxychloride on,
790.
Triacetonealkamine, 1153.
Triacetonemethylalkamine and its salts,
1153.
Triacetonine and its salts, 1153.
Triacetyl-leucaniline, 981.
Triacetylparaleucaniline, 981.
Trialkylphenylium iodides, periodides
of, 978.
Triallylamine, action of sulphuiic acid
on, 1086.
Tribenzoicin, 63.
Tribromhydrin, an aromatic, 734.
Tricalcium phosphate, conversion of,
into chlorine compounds of phos-
phorus, 287.
Trichlorhydrin, symmetrical, action of
triethylamine on, 307.
Triethylamine, action of, on symmetrical
trichlorhydrin and on the two dichlo-
ropropylenes, 307.
Triethylphenylium tri- and pent-iodide,
979.
Trihydroxybenzene, third isomeric (hy-
droxyquinol), 987.
Trihydroxy benzenes, three, constitution
of, 987.
Trihydroxylactone, 456.
Trimethylanthrammonium compounds,
1139.
Trimethylbenzene, third, 52.
Trimethylcarbinol, stability of, 565.
Trimethylene bases, 450.
bromhydrin, 42.
bromide, action of ammonia on,
450.
glycol, 450.
Trimethylethylene oxide, 566.
Trimethylphenvlium tri- and pent-
iodide, 979. *
Trimethylphosphobenzobetaine, and its
salts, 55.
8-Trimethylpyridine, 83.
Trimethyltolylphosphonium periodide,
57.
Trinaphthyl carbinol, synthesis of,
1000.
a- and |S-Trinaphthyl phosphate, 1108.
Tri-^-naphthylpararosaniline, 807.
Triopianide, and the action of bromine
and of nitric acid on, 997, 998.
Triorthocresyl phosphate, 1108.
Triphenyl carbinol, synthesis of, 1030.
orthoformate, 340.
phosphite, 735.
Triphenylarsine and the corresponding
antimony-compound, preparation of,
327.
Triphenylguanidine. 1107.
Triphenylguanidine, metanitro-, 583.
trinitro-, and its hydriodide, 582,
583.
Triphenylmethane, brominated, action
of ammonia on, 1000.
derivatives of, 981.
synthesis of, 1000.
triamido-, and its derivatives, 981.
violet derivatives of, 1097.
Trimethylphosphoryl dibromide, 736.
Tropeines, 671.
Tropidine, action of bromine on, 672.
and its derivatives, 672.
Tropiledene, 672.
Tropilene, and its oxidation, 672.
Tropine iodide, 1155.
Tufas from the Lugano district, 168.
Tungsten bronzes, 650.
compounds, 650.
reduction of, 554, 785.
steel, 533.
■ trioxide, estimation of, 785.
Tungstic acid, sodium salts of, 651.
Turkey-red dyeing, injurious action of
a cupriferous oil used in, 256.
oiling and the operations con-
nected therewith, 635.
Turmeric, certain substances obtained
from, 480.
Turmeric oil, and its oxidation, 482,
483.
Turmerol and its oxidation, 482, 483.
Turmeryl chloride, 482.
Turquoise of New Mexico, 431.
Tyrosine, administration of, in the food,
879.
detection of, in urine, 879.-
formation and decomposition of,
818.
in the body, 876.
synthesis of, 994.
hydantoin, 818.
Ultramarine, and analyses of, 714.
-green, 715.
Ultra-violet rays, absorption of, by
various substances, 837.
spectra of elements, 262.
Unipolar conductivity of sohd bodies,
769.
Units of electricity and magnetism, 764.
Uramidobenzoic acids, ^- and ^-nitro-,
action of potash on, 57.
Uranates, crystallised, formation of, in
the dry way, 296.
Uranite from Mitchell Co., N. Carolina,
163, 1064.
INDEX OF SUBJECTS.
1265
Uranium oclire, from Johanngeorgen-
stadt, 433.
oleate, 692.
Uranothallite, 956.
Uranothorite, 299.
Uranyl potassium chromate, 425.
Urea, detection of, in. an aqueous solu-
tion, 1036.
Urea and chromium, series of salts con-
taining, 178.
Ureides, condensed, 664.
Uric acid and its more important salts,
solubility of, at the temperature of
the healthy human body, 876.
decomposition of, by hippu-
rates and benzoates, 876.
formation of, in the animal
economy, 876.
synthesis of, 179.
Urine, albumin from, coagulated by
nitric acid and soluble in alcohol,
247.
detection and estimation of phe-
nols and hydroxy-acids in, 885.
albumin in, 885.
tyrosine in, 879.
estimation of sugar in, 829.
the reducing power of, and of
the extractive matter which it con-
tains, 751.
new crystalline colouring-matter
in, 814.
occurrence of crystals of ammo-
nium magnesium phosphate in, 609.
of fever patients, 1162.
Urine-pigments, unusual, colouring-
. matter of, 1159.
Urorosein, 101.
Vacuum discharges, movement of gas in,
5.
Valeric acid, y-isonitroso-, and its salts,
1129.
Vanadates, crystallised, production of,
in the dry way, 784.
Vanadic acid, separation of, from metals,
513.
Vanadinites, bromo-, 783.
Vanadium in the Leadville ores, 562.
Vanillin, compounds of, with pyrogallol
and with phloroglucol, 61.
Vanillinaldoxime, 1104.
Vapour-density, determination of, 618,
951.
■ apparatus, V. Meyer's, modifica-
tion of, 899.
Vapour-tensions of ethylamine and di-
ethylamine hydrosulpliides, 727.
Vapours, an arrangement of the electric
arc for the study of radiation of, 262.
saturated, relation between the
tension and temperature of, 951.
Varnish, polychrome, for white metal,
896.
Vegetables, albuminoid and non-albumi-
noYd nitrogen-compounds of certain,
236.
Vegetarianism from a physiological
standpoint, 928.
Vegetation, influence of the percentage
of moisture in peaty soils on, 681.
Vesuvian, 35.
Vesuvius, new sublimate from the crater
of, 1064.
Vetches, cultivation and feeding value
of some varieties of, 612.
Vine disease, use of sulphur for, 551.
Vine diseases and remedies, 110.
Vineyards, submersion of, 1164.
Violuric acid, 913.
Volcanic fragmental rocks, 723.
Volcanic rocks of the Cape Verde
Islands, 720.
Voltameter, heat- changes at the poles
of, 767.
Volumeometer, an instrument for taking
the specific gravity of minerals, 1032.
w.
Wagnerites, bromarsenio-manganese,
784.
bromo-, 648.
Wall paintings, weatherproof, process
for preparing, 942.
Waltherite from Joachimsthal, 36.
Walujewite, chemical composition of,
1068.
Water, alternate decomposition and re-
production of : a lecture experiment,
280.
action of, on lead, 128.
decomposition of, by metalloids,
900.
by sodium : a lecture experi-
ment, 280.
drinking, estimation and investiga-
tion of, 382, 883.
electrolysis of, 540.
evaporation of, from the soil, 615.
examination of, for sanitary pur-
poses, with remarks on disinfection,
514.
maximum density of : a lecture ex-
periment, 280.
of Rangoon, 128.
preparation of a volumetric solu-
tion for estimating the hardness of, 516.
1266
INDEX OF SUBJECTS.
Water, relation between pressure and
temperature in the saturated vapour
of, 417.
relative volumes of, in the liquid
and gaseous state : a lecture experi-
ment, 280.
specific heat of, 541.
spectrum of, 140.
spring, from Rindo, near Stock-
holm, analysis of, 449.
synthesis of, by weight : a lecture
experiment, 1('48.
Water and quartz, variation of the in-
dices of refraction of, with the tempe-
rature, 762.
Water-analysis, ammonia-process for,
514.
preparation of permanganate solu-
tion for, 516.
Tidy's permanganate method, 829.
Water-carbon bisulphide, under the
action of electromotive force, varia-
tion of the constant of capillarity of
the surfaces, 1047.
Water-ether under the action of electro-
motive force, variation of the con-
stant of capillaritv of the surfaces,
1047.
Water-molecule, dissociation-heat of,
and the electric luminosity of gases,
547.
Water- vapour, spectrum of, 261.
Waterproof paint for stones, &c., 760.
Waters accompanying petroleum and
those ejected by mud volcanoes, 171.
containing calcium sulphate, origin
of arsenic and lithium in, 302.
contaminated, purification of, 691.
of Moscow, analysis of, 622.
of Bareges, presence of arsenic in,
302.
potable, new form of apparatus for
estimating ammonia in, 382.
Weatherproof wall paintings, process for
preparing, 942.
Weil's method for the estimation of
copper, iron, and antimony, 509.
Wheat, amount of gluten in, 236.
development of, 493.
manufacture of spirit from, 630.
Wheat-bran treated with hot and cold
water, digestibility of, 816.
Wheat-crop, action of manures on the
quantity and quality of, 681.
White metal, polychrome varnish for,
896.
Wine, a new alcohol in, 631.
coloured by aromatic sulphonic
derivatives, examination of, 625.
detection of rosaniline hydro-
chloride in, by means of stearin,
384.
Wine, detection of sulphurous acid in,
384.
distillation of, 934.
estimation of fixed organic acids
in, 384.
estimation of sulphurous acid in,
621.
freezing of, 135.
occurrence and estimation of free
tartaric acid in, 935.
preservation of, by salicylic acid,
535.
relation between the glycerol and
alcohol in, 518.
solubility of the colouring-matter
of, in the various constituents of
grape -juice, 1141.
Wines, deplastering of, 252.
&c., rapid method of estimating
salicyhc acid in, 245.
Italian red, analyses of, 892.
plastering of, 755.
pure, analyses of, 518.
(Tyrolese), amount of extract in,
245.
Winklerite from Almeria, South
Spain, 433.
Witherite, artificial production of, 31.
Wollastonite, artificial production of,
560.
" Wool, dissolved," manurial value of,
500.
treatment of the washings from,
940.
Wort, nitrogenous constituents of, 821.
Wulfenite, 435.
Xanthine, 924.
action of hydrochloric acid and of
barium hydroxide on, 871.
and its derivatives, 357.
Xenotime from Burke Co., N. Carolina,
435.
Xeronic acid, 98.
Xylenol, amido-, and its hydrochloride,
918.
mononitro", derivatives of, 918.
nitro-, 802.
Xylidine hydrobromides, 578.
Xyloquinol, 467.
Xyloquinone, 467.
Xylorcinol, 918.
Xylylglycocinexylidide, 594.
Yeast, action of air on, 746.
INDEX OF SUBJECTS.
12(^7
Yeast, influence of alcohol on the deve-
lopment of, 104.
occurrence of nuclein in, 1166.
pressed, preparation of, 692.
Ytterbium, spectral researches on, 954.
Yttrium, atomic weight of, 292.
z.
Zinc, electrolytic estimation of, 122.
estimation of, as sulphide, 828.
explosive alloys of, with certain
platinum metals, 19.
lecture experiments illustrating the
combination of, with sulphur, 292.
Zinc, alumiuite, a new mineral species,
443.
ammoniobromides, 713.
blende, roasting of, and neutralisa-
tion of the evolved gases with cal-
cium sulphide solution, 399.
diiimmonium chloride, 272.
ethyl, action of, on amides, 913.
oxy bromides, 713.
sulphate, quantity of heat evolved
in the electrolysis of, 1043.
Zinc-carbon couples in electrolysis, 4.
Zircon from Colorado, 1U65.
from the quarries of Nil-St. Vin-
cent, 561.
Zymase of human milk, 926.
ERRATA IN VOL. XLIV.
Page
Line
100
21 from top
for insoluble read soluble.
for rose-red read bright blue.
for bright blue read rose-red.
—
22
» »
116
24
„ bottom .....
for The analyses of drainage of fallows at a depth
of 27 inches show a loss of, read The analyses
of fallows show that the uppermost 27 inches
contain.
116
10
„ bottom
for sand and flint, read sand and gravel, such as
form the soil of the plain of GenneviUiers.
432
4
tOD
for Amberger read Amberg.
for Lutherite read Witherite.
541
20
„ bottom
589
24
„ bottom
for pseudocumol read pseudocumene.
693
7
„ bottom
for Caul read Paul.
769
2
,, top
/or J. Probert and A. W. Poward, read I. Probert
and A. W. Soward.
814
815
4 and 8 from bottom. .
1 at top
■for Klingenberg read Klinkenberg.
917
13 from top
for acetamide read acetanilide.
—
12
„ bottom
for melting at 2125°, read which explode on heat-
943
11 and 12 from bottom
ing.
for Laminaria Fucus
vesiculosus. stenophylla.
read
Laminaria Fucus
stenophylla. vesiculosus.
1159
3 from bottom
for hydrobilin read hydrobilirubin.
L£
18
for fibrile read febrile.
for Badenhausen read Eadenhausen.
1174
from bottom c
BABBISUN AND SONS, PBINTEUS IN OEDINABI TO Vi&W UAJSaTT, ST. UARTTM ii LAM:.
QD
Chemical Society, London
1
Journal
C6
^.UU
cop, 3
Physical &
Applied 3^
Serial
PLEASE DO NOT REMOVE
CARDS OR SLIPS FROM THIS POCKET
UNIVERSITY OF TORONTO LIBRARY
STORAGE
Live Music Archive
Librivox Free Audio
Metropolitan Museum
Cleveland Museum of Art
Internet Arcade
Console Living Room
Books to Borrow
Open Library
TV News
Understanding 9/11