Full text of "Journal"
JOURNAL
OF
THE CHEMICAL SOCIETY
Committee of ^ublixation:
H. E. Aemsteoxg, Ph.D., F.R.S.
W. Ceookes, F.R.S.
A. DiTPEE, Ph.D., F.R.S.
E. Feankland, D.C.L., F.R.S.
C. Geaham, D.Sc.
C. W. Heaton, F.C.S.
Httgo MiJLLEE, Ph.D., F.R.S.
W. H. Peekin, F.R.S.
H. E. RoscoE, LL.D., F.R.S.
W. J. RrssELL, Ph.D., F.R.S.
C. R. A. Weight, D.Sc.
Cbitor ;
Henry Watts, B.A., F.R.S.
Snb-6bitor:
C. E. Groves, F.C.S.
Abstractors
Gt. T. Atkinson.
P. P. Bedson, D.Sc.
Chichestee a. Bell, M.B.
D. Bendix.
C. H. BoT HAMLET.
F. D. Beown.
C. A. Btjeghaedt, Ph.D.
T. Caenellet, D.Sc.
Frank Clowes, D.Sc.
A. J. Cownlet.
C. F. Ceoss.
J. K. Ceow, D.Sc.
Joseph Fletcheb.
A. J. Geeenawat.
W. R. HODGKINSON, D.Sc.
M. M. Pattison MriE.
J. M. H. MuNEO, D.Sc.
W. Nosth.
E. W. Peetost, Ph.D.
John Robinson.
R. ROTJTLEDGE, B.Sc.
L. T. O'Shea.
J. Tatloe.
F. L. Teed.
W. Thomson.
C. W. Watts.
John Watts, D.Sc.
W. C. Williams.
Vol. XXXVIII.
1880. ABSTRACTS.
LONDON:
J. VAN VOORST, 1, PATERNOSTER ROW.
1880.
LONDON :
HABKISON AND SONS, PRINTERS IN OKUINARY TO HEB MAJESTY, ST. MARTIN's LANE.
^^60
\
CONTENTS.
ABSTRACTS OF PAPERS PUBLISHED IN OTHER JOURNALS:—
General and Physical Chemistry.
PAGE
FiscHEK (F.). Apparatus for Measuring the Heat of Combustion . . 1
Beethelot. Chemical Coufetitution of Amalgams of the Alkali-metals . 1
Bemmelex (J. M. tan). Condition of Alkaline Phosphates in Aqueous
Solutions. ............ 2
Peirce (B. O.). Emission Spectra of Haloid Mercury Compounds . . 81
Peoctob (B. S.). Smoke of an Electric Lamp 81
TnoMSEN (J.). Thermochemical Investigation of the Oxides and Acids of
Nitrogen ............ 81
Thomsen (J.). Thermochemical Research on the Carbonates . . . 82
Venables (F. p.). Mutual Relations of Potassium and Sodium Alums in
Aqueous Solution .......... 83
WiLLOTTE (H.) . Law of Dulong and Petit applied to Perfect Gases . . 83
Jolly (P. v.) . Variation in the Composition of the Air .... 85
Schmidt (G.)- Relative Space occupied by Ga^^es 87
WiEBE (H. F.). Absolute Expansion of Liquid and Solid Bodies . . 88
HiNTEEEGGEE (F.). Diffusion Experiments with Acid Solutions of Mixtures
of Salts 89
NiAUDET (A.). New Galvanic Couple 149
Meyee (V.) and H. Zublin. Determination of the Density of Vapours
which attack Porcelain at a Red Heat ....... 149
ViOLLE (J.). Specific Heats and Melting Points of the Refractory Metals . 149
Beethelot. Decomposition of Hydrogen Selenide by Mercury . . . 150
Ogiee (J.). Combinations of Phosphine with the Haloid Acids . . . 150
Cheoustchoff (P.). Thermic Study of Succinic Acid .... 151
Deapee (J. C.) . Dark Lines in the Solar Spectrum on the less Refrangible
Side of G 201
CoENU (A.) . Ultra-violet Limit of the Spectrum at Various Heights . . 20]
Haetley (W. N.) and A. E. Huntington. Examination of Essential Oils 201
SoEET (J. L.) and A. A. Rilliet. Ultra-violet Absorption-spectra of Ethe-
real Salts of Nitric and Nitrous Acids 202
De la Rue (W.) and H. Mullee. Electric Discharge of the Chloride of
Silver Battery 203
Wiedemann (E.). Phos^phorescence produced by Electrical Discharges . 204
Volta (A.). Action of Ozone on some Noble Metals 205
Debeun (E.). An Electro-Capillary Thermometer 205
Caenelley (T.). Mendeiejeff's Periodic Law on the Magnetic Properties of
the Elements 206
RossETTi (F.). Thermal Absorption and Emission of Flames, and the Tem-
perature of the Electric Arc . . . . . . . . . 206
Hammeel (H.). Specific Heat of Concentrated Solutions of Hydi-ochloric
Acid 207
Beethelot. Heat of Formation of Ammonia 207
Beethelot. Relation between the Heat Developed on Solution and that
Developed on Dilution with Complex Solvents ..... 208
Beethelot. Thermo-chemistry of Cuprous Chloride 208
St. Claiee-Detille (H). The Temperature of Decomposition of Vapours . 209
Hannay (J. B.) and J. Hogaeth. Solubility of Solids in Gases . . . 210
a 2
iv CONTENTS.
PARF
Pauchox (E.). Tension of the Yapoiirs of Saline Solutions . . . . 211
Vaeenne (L.)- Passive State of Iron 211
SOUTHWORTH (R. J.)- Relation of the Volumes of Solutions of Hjdrated
Salts to their Composition 212
Than (C v.). Six Leeture Experiments 212
Deville (St. Claire). Motion produced by the Diifusion of Gases and
Liquids ......••••••• 293
WuETZ (A.). Temperature of the Decomposition of Vapours . . . 293
Beethelot. Heat of Formation of Chloral Hydrate 293
WuETZ (A.)- Heat of Formation of Chloral Hydrate 293
Beuhl (J. \V.). Relations between the Physical Properties of Organic
Bodies and their Chemical Constitution 293
Beuhl (J. W.). Chemical Constitution of Organic Compounds iu Relation
to their Refractive Power and Density 295
Ciamician (G. L.). Spectroscopic Researclies ...... 3fil
Eder (J. M.). A New Chemical Photometer 361
Thomsen (•!.). Heat of Formation of Cuprous Chloride .... 361
Thomsen (J.). Heat of Formation of Cyanogen 361
Thomsen (J.). On the Carbonates ........ 361
Thomsen (J.). Thermo-chemical Researches 363
ScHLEiEEMACHEE (A.). Condensation of a Liquid at the Wet Surface of a
SoUd 363
Steean (J.). Diffusion of Liquids 364
Janovsky (J. v.). Some Chemical Constants ...... 365
PoTiLiTZiN (A.). Limits and Velocities of Chemical Reactions . . . 365
PoTiLiTZiN (A.). Mutual Replacement of the Halogens .... 365
ScHULZE (H.). Lecture Experiment ........ 366
Abney (Captain). Photograph of the Ultra-red Portion of the Solar
Spectrum ............ 429
LocKYEE (J. N.). Existence of Carbon iu the Coronal Atmosphere of the
Sun . . . . . .429
Abney (Captain). Acceleration of Oxidation caused by the less Refrangible
End of the Spectrum 429
ScHUST^E (A.). Spectra of Metalloids ; Spectrum of Oxygen . . . 430
Haetley (W. N.) and A. K. Huntington. Absorption of the Ultra-violet
Rays by the Spectra of Organic Substances ...... 430
GOEE (G.). Thermo-electric Properties of Liquids ..... 431
Crafts (J. M.). Density of Chlorine at High Temperatures . . . 431
Meyee (V.) and H. Zijblin. Behaviour of Ciilorine at High Temperatures 432
Meyee (V.) and H. Zublin. Density of Bromine at High Temperatures . 432
Meyer (V.). Behaviour of Iodine at High Temperatures .... 433
Ceafts (J. M.) and F. Meiee. Density of lodme at High Temperatures . 433
Meyee (V.). Observations on VajTour-densities ...... 433
Meyer (V.). Vapour-densities of the Alkali-metals 434
Meyer (V.). Calorimetrical Temperatui'e-deteruiinations .... 434
Ceafts (J. M.). Density of some Gases at a High Temperature . . . 434
Beethelot. Heat of Formation of Gaseous Chloral Hydrate . . . 434
Wuetz (A.). Reply to Berthelot on the Heat of Formation of Chloral
Hydrate 435
Hammerl (H.). Action of Water on Silicon and Boron Fluorides: Solu-
tion of Cyanogen in Water ......... 435
MoNDESiE (P. de). Comparison of the Curves of the Tensions of Saturated
Vapours .............. 435
Hammerl (H.). Specific Heat of Solutions of Potash and Soda . . . 435
ScHULZE (II.). Oxidation of Haloid Salts ....... 436
Beethelot. Chemical Stability of Matter in Sonorous Vibration . . 437
Mills (E. J.) and T. W. Walton. Researches on Chemical Equivalence.
Part I. Sodium and Potassium Sulphates ...... 437
Mills (E. J.) and J. Hogaeth. Researches on Chemical Equivalence.
Part II. Hydrogen Chloride and Sulphate ...... 438
CONTEXTS. V
PAGE
Pawlewski (B.). The Speed of Reactions 4??8
ToMLiNSOK (C). Supersaturated Saline Solutions ..... 438
Galloway (W.). Influence of Coal-dust in Colliery Explosions . . . 439
Frankland (E.). Dry Fog " 439
Blunt (T. P.). Effect of Light on Chemical Compounds .... 521
D'Arsoxtal. a New Voltaic Condenser 521
Deville (H. St. Claire) and L. Tboost. Determination of High Tem-
peratures ............ 521
Berth elot. Heat of Formation of the Oxides of Nitrogen . . . . 522'
Sabatier (P.). Thermochemical Study of Sulphides of the Earth-metals . 523
Raoult (F. M.). Freezing Point of Alcoholic Liquids .... 523
ViNCEST (C.) and Delachaxal. Some Properties of Mixtures of Methyl
Cyanide with Ethyl and Metliyl Alcohols 524
Naumanx (a.). Relation between Molecular Weight and Density of Gases 525
Naccari (A.) and S. Pagliaxi. Absorption of Gases by Liquids . . 525
Deville (H. St. Claire) and L. Troost. Determination of High Tem-
peratures ............ 526
JoTJLix (L.). Researches on Diffusion ........ 526
YoGEL (H. W.). New Hydrogen Lines and the Dissociation of Calcium . 597
Lommel (E.). Dichroic Fluorescence of Magnesium Platino-cyanide . . 598
Sturtz (B.). Phosphorescence ......... 598
Kerr (T.). Electro-optic Observat'ons on Various Liquids .... 599
Baumgartxer. Specific Heat of Water 601
DiTTE (A.). Freezing Mixtures of an Acid and a Hydrated Salt . . . G02
Berthelot. Compounds of Hydrogen Peroxide ...... 602
Thomsex (J.). Heat of Formation of Ammonia, of the Oxides of Nitrogen,
and of the Nitrates 603
WrRiz (A.). Heat of Formation of Chloral Hydrate 604
LorGUiNiNE (W.). Heats of Combustion of Glycerol and of Ethvlenic
Glycol I . 604
Meter' (V.) and H. Zublin. Volatile Metallic Chlorides .... 604
Cailletet (L.). Compression of Gaseous Mixtures ..... 604
Mondesir (P. de). Variation in the Tension of Vapour emitted Above and
Below the Point of Fusion ......... 60.5
Reiset (J.) . Proportion of Carbonic Anhydride in the Air .... 605
Hermann (F.). The Problem of Estimating the Number of Isomeric
Paraffins of the Formida C„H.2„+2 ........ 605
Meyer (h.). History of Periodic Atomicity 605
Smith (R. A.). Measurement of the Actinism of the Sun's Rays and of
Dayhght ' . . 685
Capron (.T. R.). Relative Intensity of the Spectral Lines of Gases . . 685
TiiAL^N (R.). Bright-line Spectrum of Scandium ..... 685
BfiiJHL (J. W.). Relations between the Physical Projjerties of Bodies and
their Chemical Constitution ......... 685
Wright (C. R. A.) and E. H. Rennie. Determination of Chemical AfSnity
in terms of Electromotive Force ........ 686-
Regnier (E.). Constant and Powerful Voltaic Pile 686-
Lodge (O. J.). Determination of the Specific Electrical Resistance of cer-
tain Copper-tin Alloys .......... 687
Roberts (W. C). .Analogy between the Conductivity for Heat and the
Induction Balance EH'ect of Copper-tin Alloys ..... 687
Berthelot. Freezing Mixtures formed by an Acid and a Hydrated Salt . 687
Berthelot. Some Relations between the Chemical Mass of the Elements
and the Heat of Formation of their Compounds ..... 688
Thojisen (J.). Thermo-chemistry of the Oxides of Nitrogen . . . 689
Sabatier (P.). Thermo-chemical Study of the Alkaline Polysulphides . 689
Sabatier (P.). Thermo-chemical Study of Ammonium Polysulphides and
Hydrogen Persulphide .......... 690
Clausifs (R.). Behaviour of Carbonic Anhydride in Relation to Pressure,
Volume, and Temperature ......... 691
VI CONTENTS.
PAGK
RiJCKEE (A.W.). Suggestion as to the Constitution of Chlorine offered by
the Dynamical Theory of Grases 692
WiNKELMANX (A.). Relations between the Pressures, Temperatures, and
Densities of Saturated Vapours ........ 692
Bekthelot. Heat of Vaporisation of Sulphuric Anhydride . . . 693
Hannay (J. B.) and J. Hogaeth. Solubility of Solids in Grases . . . 693
RiEMSDiJK (A. D. v.). "Flashing" in Assays of Gold . . . .693
Mills (E. J.). Chemical Repulsion 693
Schroder (H.)- Molecular Volumes of Solid Carbon Compounds . . 694
Beijhl (J. W.). Chemical Constitution of Organic Compounds in relation
to their Refractive Power and Density. Part II . . . . . 781
Mascaet. Atmospheric Electricity ........ 783
JouBEET (J.). Alternating Currents and the Electromotive Force of the
Electric Arc . 783
WiTZ (A.). A New Air Thermometer 783
WiEBE (H. F.). Specific Heat and Expansion of the Solid Elements . . 783
WiEBE (H. F.). Expansion and Molecular Volumes of Liquid Organic
Compounds ............ 784
DiTTE (A.). Refrigerating Mixtures -with Two Crystallised Salts . . . 784
'J'homsen (J.). Heat of Combustion of Sulpliur .... . 785
Thomsen (J.). Thermochemical Investigation of the Theory of the Carbon
Compounds ........... 785
Beeihelot. Heat of Combustion of the Principal Gaseous Hydrocarbons . 786
Lotjguinine (W.). Heat disengaged in the Combustion of some Isomeric
Alcohols 7S7
Beethelot. Thermochemistry of Ethylamine and of Trimethylamine. . 787
Leeds (A. R.). New Methods in Actino-Chcmistry . . . . . 837
VoGEL (H. W.). Photochemical Behaviour of Silver Bromide in Presence of
Gelatin • 837
Siemens (W.). Electric Conductivity of Carbon as affected by Tem-
perature ............ 837
Beetz (W.). Galvanic Polarisation 837
Haxkel (W.). Direct Transformation of Radiant Heat into Electricity . 838
WoHLER (F.). An Aluminium Battery ....... 838
NiLSON (L. F.) and O. Petteesson. Molecular Heats and Molecular
Volumes of the Rare Earths and their Salts ...... 838
Beethelot. Heat of Formation of Hydrocyanic Acid and Cyanides . . 839
Thomsen (J.). Thermo-ehemical Research on Cyanogen and Hvdrocyanic
Acid .' . . 840
Thomsen (J.). Constitution of Isomeric Hydrocarbons .... 840
Ceafts (J. M.). Variations in the Coefficient of Expansion of Glass . . 841
Petteesson (O.) and G. Ecksteand. Meyer's Method of Determining
Vapovir-densities . . . ' . . . . . . . . 841
Dbwae (J.). Critical Point of Mixed Vapours 8^2
Dewar (J.). Lowering of the Freezing Point of Water by Pressure . . 845
Babo (L. v.). Oven for Heating Sealed Tubes 846
Rosenfeld (M.). Lecture Experiments 846
f
Inorganic Chemistry.
Lionet (A.). Purification of Hydrogen ....... 2
Tommasi (D.). Non-existence of Nascent Hydrogen ..... 2
Hoppe-Setler (F.). Active Condition of Oxygen induced by Nascent
Hydrogen ............ 3
Kingzett (C. T.). Is Ozone produced during the Atmospheric Oxidation of
Phosphorus ?............ 3
ZoEN (W.). New Method of forming Hyponitrites and Hydroxylamine . 4
LocKTEE (N.). Experiments tending to show the Non-elementary Character
of Phosphorus ............ 4
CONTEXTS.
vii
Matimen^ (E. J.). Compounds of Hjdracids with Ammonia
Maumene (E. J.). OsYgen-acids of Sulphur ....
KoLBE (H.). Basicity of Dithionic Acid .....
BiEXBATJM (K.) and M. Mahu. Behaviour of Calcium Oxide to Carbonic
Anhydride . . . . . .
Bother (R.). Calcium Phosphite ......
Patkull (S. R.). Zirconium Derivatives .....
BoisBAUDEAN (L. de). Researches on Erbia ....
Cleve (P. T.). Two New Elements in Erbia . .
SoEET (J. L.). Spectra of the Earths of the Yttria-group
Cleve (P. T.)- Scandium
G-AT (J.). Absorption of Nitrogen Dioxide by Ferrous Salts
RosEKBEEG (J. O.). Nitrosotliioferrates .....
Hensgen (C). Potassium and Ammonium Ferric Chromates
JoEGEXSEN (S. M.). Contributions to the Chemistry of the Chromammonium
Compounds ...........
Stock (W. F. K.). Behaviour of Copper-ammonium Chloride with Ferrou;
Sulphide ............
DiTTE (A.). Action of the Hydracids on the Sulphates of Mercury
BiEXBAUM (K.). A New Salt of an Iridiamraonium ....
Thomsen (J.) . Allotropic Modifications of Hydrogen ....
Bbuylants (G-.). a New Method for Preparing Hydriodic Acid and Hydro
bromic Acid ...........
Leeds (A. R.). Influence of Volume and Temperature in the Preparation of
Ozone : a New Ozoniser .......
MoELEY (E. W.). Possible cause of Yariation of the Proportion of Oxygen
in the Air . . . . . .
Wolfeam (C) . Preparation of Perbromic Acid ....
Lunge (C). Researches on Nitrous Acid and Nitrogen Tetroxide
Dahll (T.). Norwegium
CoNEAD (P.). Constitution of Antimonic Acid ....
Seidel (O.) . Salts of Plumbic Acid
Seelheim (F.). Yolatility of Platinum in Chlorine
ScHiJTZENBERGER (P.). Silicon Nitride .....
Ditte (A.). Action of Metallic titrates on Nitric Acid
DiTTE (A.). Action of Metallic Nitrates on Nitric Acid
Contributions to our Knowledge of Clays and Earthenware Goods
Knapp. Ultramarine .........
Cleve (P. T.). Erbium
Philipp (J.) and P. Schwebel. Tungsten Bronze
Speing (\V.). New Basic Salts of Mercuric Sulphide .
Beethelot. Oxidation of Gold by Galvanic Action .
Leeds (A. R.). Non-production of Ozone in the Crystallisation of Iodic
Acid ...........
Leeds (A. R.). Solubility of Ozone in Water ....
Meyee (Y. and C.) . Behaviour of Chlorine at High Temperatures
Philipp (J.) Sohdifying Point of Bromine ....
Speing (W.). Non-existence of Pentathionic Acid
Roberts (W. B.). Action of Lime on Silica in Mortar
Salkowski (H.). Arsenates of Zinc and Cadmium
Deuel (W.). Arsenates of Zinc and Cadmium ....
Heujiann (R.). Ultramarine Compounds . . . . .
Pawel (O.). Roussm's Salt . .
Pawel (O.). Roussin's Salt .......
Demel (W.). Roussin's Salt .......
Post (J.). Composition of the Weldon "Manganese Mud" and
similar Compounds ........
Schneider (R.). Behaviour of Bismuth containing Arsenic towards Nitric
Acid, and the Preparation of Basic Bismuth Nitrate free from Arsenic
Caenelley (T.). Yapour-density of Stannous Chloride
some
VIU
CONTENTS.
PAGE
PiUTTi (A.). Action of Phosphorus Pentachloride on Molybdic Anhydride
Bertom (G.). Preparation of Hydroxylamine
Bertoni (G.). Conversion of Hydroxylamine into Nitrous and Nitric Acids
Leeds (A. R.) . Reduction of Carbonic Anhydride by Phosphorus at ordi
nary Temperatures .......
Ogier (J.). A New Hydride of Silicon ....
MtJLLER-ERZBAcn (W.)'. Luminosity of Phosphorus .
Kessler (F.). Pentathionic Acid
Mijller-Erzbach (W.). Reduction of Metallic Oxides by Ilydr
Berthelot. Copper Hydride
Copper Hydride
Copper Hydride : a Reply to Wurtz
Copper Hydride ......
Atomic Weight of Antimony
Atomic Weight of Antimony
ogen ,
Wurtz (A.).
Berthelot.
Wurtz (A.).
Kessler (F.).
Cooke (J. P.).
Drechsel (E.). Galvnnic Experiments (Platinum Bases)
Spring (W.). Non-existence of Pentathionic Acid
Horn (W. F.). Phosphoric Acid ....
BoTMOND. Sodium Hypophosphite ....
Heumann (K.). Ultramarine Compounds .
Post (J.). Spontaneous Oxidation of Manganese Oxides with reference to
the Manganese Recovery Process
Post (J.). Composition of " Weldon Mud" and similar Compounds .
Lunge (G-.). Researches on Nitrous Anhydride and Nitrogen Tetroxide
Berthelot. Action of Hydrogen Peroxide on Silver Oxide and Metallic
Silver
Berthelot.
Simpson (M.)
MiLLOT (A.).
Rod WELL (G.
Silver Sesquioxide
Compound of Calcium Iodide with Silver Iodide .
Dicalcium Phosphate .......
F.) and H. M. Elder. Effect of Heat on Mercury Dioxide
PoLis (A.). Cubic Alum and Chrome Alum .....
Preis (K.) and B. Rayman. Certain Bichromates
Berthelot. Decomposition of Potassium Permanganate by Hydroger
Peroxide ...........
Meter (V.) and H. Zijblin. Platinic Bromide
MoissAN (H.). Sulphides and Selenides of Chromium .
Hautefeuille (P.). A New Property of Vanadates ....
Lunge (G.). Composition and Analysis of the Binoxide of Manganese re
covered in the Weldon Process . . . . .
Meier (F.) and J. M. Crafts. Vapour-density of Iodine ...
SCHONE (E.). Action of Potassium Iodide on Hydrogen Peroxide
SCHONE (E.). Decomposition of Hydrogen Peroxide in Presence of Alkalis
and Alkaline Earths . . .
BiRNBAUM (K.) and C. Wittich. Action of Sulphurous Anhydride on thi
Oxides of the Alkaline Earth-metals ......
Berthelot. Persulphuric Acid ........
Michaelis (A.) and B. Landmann. Constitution of Selenious Acid .
Friedel (C.) and A. Ladenburg. Silicon-ethyl Series
Reinitzer (B.) and H. Goldschmidt. Action of certain Metals and Non
metals on Phosphorus Oxychloride ......
Schone (E.). Composition of Hydrated Barium Dioxide .
BoussiNGAULT. Dissociation of Barium Dioxide . . .
Des Cloizeaux. CryetaUine Form of Magnesium ....
Delafontaine (M.). The New Metals of Gadolinite and of Samarskite
Rammelsberg (C). Vesbium and Norwegium
Post (J.) and G. Lunge. Composition of Weldon-mud
Klein (D.). Borotungstates ........
Teclu (N.). Red Antimony
KoHLER (H.)- Action of Antimony Pentachloride on Phosphorus Trichlo
ride
CONTEXTS.
IX
Tkoost (L.). Density of Iodine Vapour .......
Meyer (V.). Density of Iodine Vapour .......
Navmanx (A.). Dissociation of Iodine Vapour ......
Ansdell (Gt-). Physical Constants of Liquid Ilydrochloric Acid .
Macagno (H.). Analyses of Air .........
Jolly (P. v.) and E. W. Morley. Variations in the Composition of the
Atmosphere . ...........
Hasselbarth (P.) and J. Fittbogen. Variations in the Carbonic Anhydride
of the Atmosphere ...........
Leeds (A. R.) Formation of Hydrogen Peroxide; and Ozone by the Action
of Moist Phosphorus on Air .........
Gross (T.). An Experiment with Sulphur .......
Levallois (A.) and S. Meunier. Crystallised Calcium Oxide
NiVET. Reactions between Calcium Carbonate and Ammoniacal Salts .
Brugelmann (Gr.). Characteristics of the Alkaline Earths and of Zinc Oxide
Mallet (J. W.). Revision of the Atomic Weights and Quantivalence of
Aluminium ...........
Love (E. G.). Edible Earth from Japan
Meyer (C. F.). Retrogradation of Superphosphates containing Iron and
Aluminium ...........
NiLSON (L. F.). Atomic Weiaht and Characteristic Salts of Ytterbium
Parker (R. H.). Action of Potassium Chlorate on Ferrous Iodide
LxTNGE (H.). Comijosition and Analysis of Weldon Mud
CooKE (J. P.). Atomic Weight of Antimony .....
CoxECHY (Gr. AI.) . Volatilising Point of Metallic Arsenic .
Thresh (J. C). Preparation of Potassium Bismuth Iodide .
ToiiMASi (D.). Reduction of Gold Chloride by Hydrogen in presence of
Platinum ...........
Scheurer-Kestner. Action of Sulphuric A^id on Platinum
Pitkin (L.). Compound Platinates and a New Platino-potassium Salt
Debray (H.). Action of Acids on Alloys of Rhodium wiih Lead and Zinc
Meyer (V.), Vapour-density of Iodine ......
Crafts (J. M.). Vapour-density of Iodine . . . . . ' .
Da^TT (M.). Proportion of Carbonic Anhydride in the Air .
Kessler (M.). Crystallised HydrofluosiHcic Acid ....
Pfeiffer (E.). Pentahydrated Calcium Carbonate ....
LrxGE (G.) and H. Schappi. Formation and Constitution of Bleaching
Powder ............
Baeth (M.). Compound of Alumina with Carbonic Anhydride and Ammo
nia .............
Margferite (P.). Xew Aluminium Sulphate
NiLSON (L. F.) and O. Pettersson. Specific Heat and Atomic Weight of
Glucinum .... ......
Magnmer DE La SoFRCE (L.). Colloidal Ferric Hydrate
Moissan (H.). Action of Clilorine on Chromium Sesquioxide
Ditte (A.). Combinations of Uranium Oxyfluo-compounds with Fluorides
of the Alkali Metals
Berthelot. Vapour-density of Iodine, &c
Hautefeuille (P.) and J. Chappfis. Ozone
Leeds (A. R.). Formation of Hydrogen Peroxide and Ozone
Deville fll. St. Claire) and Troost. Vapour-densities of Selenium and
Tellurium ...........
L:6ty (A.). Ammonia in Air and Water ......
Bemmelen (J. M. V.) Chemical Composition of Certain Ilydrated Oxides
ToMMASi (D.). Isomeric Modification of Aluminium Hydrate
Prescott (A. B.). Potassium and Sodium Aluminates
NiLSON (L. F.) and O. Petterssox. Atomic Weight of Glucinum
NiLsov (L. F.). Atomic Weight and Characteristic Salts of Scandium
CosSA (A.) and M. Zecchini. Cerium Tungstate ....
Peescott (A. B.). Zinc Oxide in Alkaline Solutions ....
PAGE
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788
788
788
789
789
789
791
792
792
792
793
794
846
847
847
847
848
849
849
849
850
850
851
852
CONTENTS.
Pkescott (A. B.). Silver Ammonium Oxide
RosENFELD (M.). Two New Basic Copper Chromates
DiTTE (A.). Fluorine Compounds of Uranium
WiLM (T.). Chemistry of the Platinum Metals .
PAGE
852
853
853
854
Mlneralogical Chemistry.
Groth (P.)- Cobalt-glance
Groth (P.). Cobalt-speis
Weisbach (A.). Sulphide of Silver
Sjogren (H.). Bismuth Minerals from Norberg's Mine, Wermland
Strijver (J.). Poljsynthetical Twin -crystals of Oriental Spiuelle
Groth (P.)- Manganite .........
Sjogren (A.). Occurrence of Manganese in Nordmark's ^ine, Wermland
Nordstrom (T.). Vanadite
Blomstrand (C. W.). Titanites from Smaland .
Rath (G. tom). Pseudomorphs of Calcite after Aragonite
HiRSCHWALD (J.)- Crystal-system of Leucite
RiEss (E. R.). Composition of Kclogite
LiNDSTRoM (G.). Thaumasitc .....
GiJMBEL (C. W.). Manganese Nodules from the Bed of the Pacific Ocean
Dieulafait (L.). Occurrence of Lithium in Rocks, Sea Water, Mineral
Waters, and Saline Deposits .
Tripke (P.). Note on the Silesian Basalts and their Mineral Constituents
HU!?SAK (E.). Basaltic Lavas of the Eifel
Prenhel (R.). The Meteorite of Vavilovka .
TsCHERMAK (G.). Tlic Meteorite of Grosnaja
AlmjSn (.a.). Chalybeate Springs of Carlstad
Fletcher (J.). Water of the River Vartry
Sloan (B. E.). Rock Salt from Saltville
Venables (F. p.). Livingstonite
Smith (E. C). Magnetite ....
Sella (Q.). Crystalline form of Sardinian Anglesite .
Penfield (S. L.). Composition of Amblygonite .
Genth (F. a.). Uranium Minerals from North Carolina
Pellegrini (N.). Analyses of Chrysocolla from Chiii
Santos (J. R.). Volcanic Ash from Cotopaxi
Delesse. Explosion in a Coal Mine due to Carbonic Anhydride .
CoMSTOCK (W. J.). Analysis of Terahcdrite from Huallanca, Peru
Christy (S. B.). Genesis of Cinnabar Deposits .....
Daw (F. R. W.). Emplectite
St. Claire- Deville (H.) and H. Debrat. Artificial Laurite and Platinife
rous Iron ...........
Coppola (M.). Artificial Production of Oligist .....
Rammelsberg (C). The Mica Group .......
JuLiEN (A. A.). Composition of Cyraatolite from Goshen (Mass.)
GouNARD (F.). Associated Minerals contained in certain Trachytes from the
Ravine of Riveau Grande
Speciale (S.). The Lavas of the Volcanoes of Ernici, in the Valle del
Sacco (Rome) .....
Datjbr^e. a Meteorite which Fell on January 31, 1879, at La Becasse, Com
mune of Dun-le-Pceher (Indre) .......
PoLECK (T.). Water of the Oberbrunnen, Flinsberg, Silesia
Streng (A.). Mlneralogical Notes on the Ores of Clianarcillo, North Cliili
Gintl (W. F.). Water of Ferdinand's Brunnquelle at Marienbad, Bohemia
Maissen (P.). The Meteorite of Albarello .
Janovskt (J. v.). Niobiie from the Isergebirge
Scacchi (A.). Examination of the Yellow Incrustation on the Vesuvian
Lava of 1631 : Vesbium ..........
445
CONTENTS.
XI
DoMETKO. Phospliates and Boropliosphates of Magnesia and Lime in the
Guano Deposit of Mcjillones
Meuxier (S.). Artificial Production of Spinel and Corundum
GrORCEiX. Martite from Brazil ........
HAUTEFEriLLE (P.). New Silicates of Aluminium and Lithium.
FocQri (F.) and A. M. Levy. Artificial Production of Leucitophvr iden
lieal with the Crystalline Lavas of Vesuvius and Somma
ForQr^ (F.) and A. M. L£vt. Artificial Production of Felspars containing
Barium, Strontium, and Lead .......
HAUTETEriLLE (P). Production of Amphigene .....
Hazard (J.). Formation of Soils b_v Weathering ....
J)ArBREE Examination of the Volcanic Dust which fell at Dominica,
January 4, 18S0, and of the Water which ac-orapanied it
TitvY (L.). Sketch of the Origin of the Mineral Waters of Savoy
WiLLM (E.) Composition of the Waters of Cransac (Avevrou)
WiLLM (E.). Mineral Waters of Bussang (Vosges) ....
RiCHE (A.). Waters of Bourboule .......
ScHARFF (F.). Step-like and Skeleton Growth of some regular Crystals
Klocke (F.). Sensitiveness of Alum-crystals to Variations in the Strength
of tlieir Mother-liquors .........
CoMSTOCK (W. J.). Chemical Composition of the Pitchblende from Branch
ville, Conn., U.S.
Ibbt. Crystallography of Calcite ........
Pexfield (S. L.). chemical Composition of Amblygonite .
CoMSTOCK (W. J.). Analysis of some American Tautalates .
UAriEFEUiLLE (P.). Two Ncw Silicotitanatcs of Soaium
HAUTEFEriLLE (P.). Simultaneous Reproduction of Quartz and Ortho
clase ............
TscHERMAK (G.) . The Micas
Rath (G. v.). Crystal System of Cyanite ......
Bi'CKiNG (H.). Crystal Forms of Epidote
Peckham (S. F.) and C. W. Hall. Lintonite and other Forms of Thom
sonite ............
Daxa (J. D.). Some Points in Lithology. II. Composition of the Capillary
Volcanic Glass of Kilauea, Hawaii .......
Lasaulx (A. v.). The Eruptive Rocks in the Saar and MoseUe Districts
Sadebeck (A.). Crystal-tectonic of Silver ......
Verxecil and Bocbgeois. Artificial Production of Scorodite .
Klels (C). Felspar in the Basalt from the Hohen Hagen, near Gottingen
Rammelsbekg (C). The Mica Group
Baier (M.). Crystallisation of Cyanite ......
Frenzel (A.). Caucasian Minerals .......
Koch (A.V New ^Minerals from tlie Andesite of Mount Arany .
WiLLM (E.). Ferruginous and Nitrated Mineral Waters
Flight (W.). Analyses of Two New Amalgams and of a Specimen of
Native Gold ...........
Artificial Formation of the Diamond
Condition in which Sulpliur exists in Coal .
Existence of Zinc in all Primary Rocks, and in Sea Waters
Haxxat (J. B.).
Wallace (AV.).
DlErLAFilT (L.)
of all Ages
Tacchisi. Presence of Iron in the Dust Showers of Sicily and Italy
Plaxc'HUD (E.). Formation of Sulphuretted Mineral Waters
Martix (K.). Hemihedry of the Diamond .....
Sadebeck (A.). Two Regular Intergrowths of Different Minerals
Klocke (F.). Microscopical Observations of the Growth and Re-solution of
the Alums in Solution of Isomorphous Substances
Schbatjf (A.). Feuerblende from Chanarcillo
Heddle. Manganese Garnet ....
Lasavlx (A. T.;. Desmine ....
HiLGEE (A.). Analyses of Minerals and Rocks .
PAGE
446
447
447
447
448
449
449
449
453
453
454
455
455
529
529
530
530
530
531
531
532
532
534
534
535
536
537
613
613
614
614
614
615
616
617
707
707
708
708
709
709
854
855
855
856
856
856
856
xu
CONTEXTS.
CnrRCH (J. A.). Heat of the Comstock Lode . . . . .
NoRDENSKioLD (A. E.). Two Keiimrkable Meteors observed in Sweden
PAGE
858
859
Organic Chemistry.
ScHHODEE (H.). Specific Gravities of Solid Organic Compounds .
Dewar (J.). Formation of Hvdrocjanic Acid in the Electric Arc
Renard (A.). Oxidation of Alcohols by Electrolysis
Landolph (F.). Two New Hydrofluoboric Acids and Ethylene-fluoboric
Acid ............
Claesson (P.). Sulphates of Mono- and Poly-hydric Alcohols and Carbo
hydrates ...........
Carl (F.). Changes of Ammonium Isethionate at High Temperatures .
Breslatier (M.). Epichlorhydrin Derivatives .....
Lippmann (E. O.). Sugar from Populin ......
Demole (E.). Partial Synthesis of Milk-sugar and a Contribution to the
Synthesis of Cane-sugar ......
Klein. Beaction of Tiingstates in presence of Mannitol
FiLETi (M.) and A. Riccini. Decomposition of Ethylamine Hydrochloride
by Heat ..........
Meter (E. v.). Cyanethine
IjOIR: a Double Function of Monobasic Acids
Ingenhoes (P. H. B.). Existence of Double Salts in Solution
Cazeneuti: (P.). Transformation of Acetic Acid into GlycoUic Acid by
Cupric Oxide ..........
RiCHTER (V. V.) . Action of Nitric Acid on Epichlorhydrin .
Forcrand. Ethyl Nitracetate
Lewkowitsch (J.) . Prejmration of Nitro-fatty Acids .
Gabriel (S.). Derivatives of Thiacetic Acid ....
Krafft (F.). Laurie Acid and its Conversion into Undecoic Acid
Krafft (F.). Tridecoic, Pentadecoic, and Margaric Acids .
Miller (W. y.). Hydroxethylmethylacetic Acid ....
Miller (W.v). Hydroxyisobutylformic Acid ....
HoFFERlCHTER (P.). Synthesis of Ketonic Acids .
Tanatar (S.). Maleic Acid from Dichloracetic Acid
Lippmann (E. O. v.). Occurrence of Tricarballyhc and Aconitic Acids in
Beet Juice ......
Stein (G.). The Acid oi Drosera intermedia
CoNEN (J.). Derivatives of Triethyl Citrate .
De la Motte (H ). Action of Phosphorus Pentachloride and Hydriodic
Acid on Saccharic Acid .......
Klein (J.). Constitution of Deoxalic Acid ....
Richter (V. v.). Synthesis of the Closed Benzene Ring
Bielefeldt (M.). Derivatives of Isodurene
Jacobsen (O.). Behaviour of Cymene in the Animal Organism
CiAMiciAN (G. L.). Products of the Distillation of Gum-ammoniac with
Zinc-dust
Fischer (O.).
Bases
Fischer (O.).
Gbeiff (P.).
Gabriel (S.).
WlCHELHAUS (H.)
Erlenmeyee (E.).
Condensation-products of Aldehydes with Primary Aromatic
Condensation-products of Tertiary Aromatic Bases
Some New Colouring Matters. ....
Action of Hydrocyanic Acid on Diazo-compounds
Formula of Quinhydrone ....
Constitution of Phenyl-halogen-propionic Acids
Barisch (F.). Monobromocinnamic Acids and Plienylfumaric Acid
OsT (H.) . Formation of Pai-ahydroxybenzoic Acid from Sodium Phenate
ScHiFF (H.). Constitution of Ellagic Acid
Thoener (W.). New Organic Acid in Agaricus integer
Kketschy (M.). Kynuric Acid
CONTENTS.
XI 11
Feueebeix (C). Aromatic Thiocarbamidi's ......
LiEBEKMANN (C.) and A. Lange. Formulae of ThiohydantoViis .
Baeyee (A.). Action of Potassium Pyrosulphate on Indigo-white
Kade (R.). Action of Chlorine on Dibenzyl . .....
Cleve (P. T.). Derivatives of v-Dichlorouaphthalene and Nitronaphthaleue
sulphonic Acid ..........
WiDMAN (O.). Action of Chlorine onChlorouaphthalene, — Nitro-derivatives
of a- and ^-Dichloron:iphtlialene .......
Thoenee (VV.). On the Quinone occun-ing in Aqaricus atrotomentosus
ZlxcKE (T.). Action of Ammonia and Amines on Quinones.
Peugee (H. R. v.). Amidauthraquinone from Anthraquinone-sulphonic
Acid ............
Liebeemann (C.) and J. Dehnst. Decomposition of Oxyanthraquinone
Ballo (M.). Constitution of Camphor-compounds ....
Beuylants. Essences of Marjoram .......
Brftlaxts. Essence of Lavender and Spike .....
KiNGZETT (C. T.). Atmospheric Oxidation of Turpentine .
Smoeawski (S.). Fusion of Rharanetin with Potash ....
Hoppe-Seylee (F). Chlorophyll
Phipsox (T. L.) . Characin
Letts (E. A.). Phthalein of Haematoxylin
WiscHNEGEADSKY. Collidine from Aldehyde
Hjobtdahl (T.). Piperidine Salts, Quinine Sulphate, and Selenate
Feaude (Gr.). Aspidospermine . ......
Tappeixee (H.). Oxidation of Cholic Acid
Latschinoff (P.) . Oxidation-products of Cholic Acid ....
Anschutz (R). Tetrabroniethanes
WtESTEE (C.) and L. Rosee. Ferro- and Ferri-cyanides of certain Tertiary
Bases ............
PiNNEE (A.). AUyl Cyanide and the Products of its Saponification
Gkimaux (E.) and P. Adam. Action of Bromine on Dichlorhydrin .
Dbagexdoeff. Mannitol as a Bye-product in the Formation of Lactic Acid
from Cane Sugar ..........
Sugar from the Date Palm ......
Neutral and Inverted Sugar ......
Triacetonamine Chromates ......
Products of the Oxidation of Triacetonamine
Action of Potassium Cyanide on Ammoiuacal
Deon (P. H.).
Deon (P. H.).
Heixtz (W.).
Heixtz (W.).
and
ScHiFF (R.) and S. Speciale
Derivatives of Chloral
Ueech (F.). Action of Potassium Carbonate on Isobutaldeliyde .
TJbech (F.). Action of certain Reagents on Paraisobutaldehyde .
Ueech (F.). Polymerides of Isobutaldeliyde .....
Fbaxchimont (A. P. N.). Preparation of Ethereal Acetates
Sestini (F.). Some Neutral Ammonium Salts : Citrate, Phosphate,
Photosantonate ..........
Heintz (W.). Urea Platinochloride
Geimaux (E.). New Derivative of the Parabanic Series
Panebianxo (R). Crystalline Form of some Aromatic Compounds
WuESTEE (C.) and A. Beean. Action of Nitric Acid on Tribromobonzene
Patebno (E.) and P. Spica. Cymene from Cumic Alcohol .
AtTSTiN (A.). Diamylbeiizene ........
Wuestee (C.) and A. Scheibe. Bromodimethylaniline
WUESTEE (C.) and A. Beean. Parabromodimethylaniline . .
MiCHLEB (W.) and K. Metee. Action of Sulphonic Chlorides on Amines
MiCHLEE (W.) and F. Salath^. Action of Sulphonic Chlorides on Amines
WrESTEE (C.) and C. RiEDEl. Dimethylmetatoluidnie Derivatives
XocH (A.). Colouring Matter containing Sulphur from Paraphenylenedi
amine ............
Witestee (C.) and E. Sendtnee. Dimethylparaphenylenediamine Deriva
fives ............
PAGE
44
44
46
46
47
47
47
48
49
49
50
50
50
51
53
53
53
54
54
54
54
55
56
98
98
99
99
100
100
100
101
101
102
103
103
104
104
104
104
105
105
106
106
107
107
108
108
108
109
110
110
XIV
CONTENTS.
WuESTER (C.) and H. F. Morlet. TetraTnetliylmetapheiiylencdiamine
WURSTER (G.) and E. Schobig. Action of Oxidizing Agents on Tetraniethyl
paraphenylenediamine .........
WuRSTKR (C). Colouring Matters obtained by the Oxidation of Di- and
Tetra-raethylparaphenylenediamine ......
MoRLEY (H. F.). Action of Nitrous Acid on Mono- and Di-etbylenediphenyl
diamine ....•••.....
JAhns (E.). Ethereal Oil of Origanum hirtum
Merz (V.) and G-. Zetter. Resorcinol and Orcinol Derivatives .
ZiNCKE (T.). Compounds of the Hydrobenzo'in and Stilbene Series
Breuer (A.) and T. Zincke. Compoxmds obtained from Hydro- and Isohy
dro-benzoin by the Action of Dilute Sulpliuric Acid
Zincke (T.). Physical Isomerism, with Special Reference to Hydro- and
Isoliydro-benzoin ..........
Rhalis (M.). Ortliobromobenzoic Acid
Maxwell (T.). Paranitrophenylacetic Acid .....
FiTTiG (R.). Polymerised Non-saturated Acids . .
ScHiFf (H.) and F. Masino. The Isomeric Nitrosalicylic Acids .
Freda (P.) . Artificial Tannin ........
Zander (O.). Amidobenzenedisulphonic Acids . . . . .
Smith (W.). Synthesis of Phenylnaplithalene
Armstrong (H. E.). Action of Iodine on Oil of Turpentine
Dragendokff. Formation of Resin, and Chemistry of Ethereal Oils .
CiAMiciAN (Gr. L.). Action of Zinc-dust on Resins ....
SCHIFF (H.). Formation of Complex Glucosides . ....
DoTTO-ScRiBANi (F.) . Economical Process for Preparing Bibasic Quinine
Citrate
AlkaloTds of Alsionia constricta
Roster {Gr.).
Baswitz (M.).
Franchimont.
Franchimont.
ScHiFF (R.). Piperidine
Oberlin and Schlagdenhauffen
Spica (P.). Satureja Juliana ....
Peckolt (J.). Carica Papai/a and Papayatin
Litliofellic Acid and some Lithofellates
Diastase . . .......
Schorlemmer (C). Normal Paraffins
Demole(E). Constitution of Dibrom -ethylene .....
Grlucose .........
CeUulose
DXTVILLIER (E.) and A. Btiisine. Commercial Trimethylamine .
KoHLER (H.). Etliylamine .........
Danesi (L.). Action of Potassium Dichromate on Acetic Acid .
Melikoff (P.). Action of Hypochlorous Acid on Acrylic Acid .
Bandrowski (E.). Acetylenedicarboxylic Acid .....
Drechsel (E.). Carbamido-palladious Chloride .....
Jackson (C. L.). Relative DisplaceabiUty of Bromine in the Monobromo
benzyl Bromides . . ... . . .
Mazzara (G.). Tolylphenol
Meldola (R.)- Action of Nitrosodimethylaniline on Phenols which do not
contain the Methj'l Grroup ........
Rudolph (C). Action of Ferric Chloride on Orthodiamidobenzene
NiETZKi (R.). Tolylenediamines . . . .
Geaebe (C). Occurrence of Paraleucanihne in the Manufactm-e
Rosaniline . . . . . . .
Zimmermann (J.). Phenylbeta'ine or Dimethylphenylglycocine .
Mazzara (G.). Hydroxyazobenzene and Paramethylhydroxyazobenzene
Paterno (E.) and P. Spica. Cymenecarboxylic Acid ....
Mazzara (G.). Metamidocinnamic Acid ......
Oglialoro (A.). Synthesis of Phenylcoumarin .....
HoFMANN (A. W.). Pittical and Eupittuiiic Acid
Meter (R.) and A. Bafr. Hydrosyiation by direct Oxidation .
Spica (P.). Cumenesulphouic Acids and a New Cumol
of
pagk
111
111
111
112
112
113
114
116
118
118
119
120
121
122
122
125
125
125
126
126
126
127
127
128
128
131
132
158
158
158
159
159
159
160
160
160
161
161
161
162
162
162
162
162
163
163
163
164
164
165
166
CONTENTS.
XV
Chloride
Nencki (M.). Empirical Formula of Skatole
WiDMANN (O.). Action of Chlorine on Naphthalene-o-sulphonic
y-Trichloronaplithalcne ......
WiDMANN (O.). ])ic)iloronap]ithalene-a-sulphonie Acid
Graebe (C.) and W. Knecht. Phenvlna])htlivlcarbazol
HiBSCH (B.). Balsamum antarthriticum Indicum
Kennedy (G. W.). Coca
Lloyd (J. U.). Berberine Salts ....
Bullock (C). Veratrum viride ....
Hammarsten (O.). Casein, and the Action of Rennet
Hammarsten (O.). Fibrinogen ....
Greene (W. H.) and A. J. Parker. IVote on Hyraceum
Denzel (J.). Halogen Derivatives of Ethane and Ethylene
Brauner (B.). Action of Silver Cyanate on Isobutyl Iodide
Beauner (B.), Constitutional Changes in the Molecule of the Isobutyl
Group .........
EiCHLER (E.). Octyl Derivatives ....
CouNCLER (C). Fluoborethylene ....
BuTLEROW (A.). Isotnbutylene .....
TuGOLESSOFF. The Hydrocarbon, CjoHig, from Diamylene
EiSENBERG (L. J.). Action of Ferro- and Ferri-cyanic Acids on Amines
Henry (L.). On the Addition of Oxygen to Unsaturated Compounds .
Belohoubek (A.). Preparation of Propylene Glycol from Glycerol
Peligot (E.). Some Properties of Glucose ......
Berthelot. Remarks on the Saccharoses ......
Franchimont. Tunicin .........
Vincent (C). Calcination of Beet-root Molasses ....
Tatarinoff (P.). Action of Cyanamide on Dimethylamine Hydrochloride
KoiiLBR (H.). Chloro-deriva'ives of Amines .....
MiXTER (W. G.). Ethylidenaniine Silver Sulphate ....
ScHEOTTi R (H.). Bases from Fusel Oil ......
Fischer (E.). Hydrazines of tlie Fatty Series
Kbestownikoff. /3-Chloropropaldchyde ......
Karexnikoff. j3-Chlorobutyraldehyde
Tawildaroff. Some reactions of Acrolein and Glycerol
Cazeneuve (P.). Oxidation of Formic Acid and Oxahc Acid by Ammoniacal
Cupric Oxide ...........
Henry (L.). Dry Distillation of Sodium Trichloracetate
Winogeadoff (W.). Action of Aluminium Chloride on Acetic Chloride
Andseasch (R.). Characteristic Reaction of Thioglycollic Acid .
Andeeasch (R.). Decomposition of Thiohydantoi'n by Barium Hydrate
Henry (L.). Spontaneous Oxidation of Nitrolaetic Acid
Leeds (A. R.). Reduction of Carbonic Anhydride by Phosphorus at
Ordinary Temperature .........
Leeds (A. R,). Oxidation of Carbonic Oxide by Moist Air in Presence of
Phosphorus at the Urdinary Temperature .....
BoTTiNGER (C). Decomposition of Mesoxalic Acid by Sulphuretted Hydro
gen . • . • • •
Maekownikoff and Keestownikoff. Homoitaconic Acid
B6ttingie(C.). New Method of Preparing Tliiochlactic Acid
Post (J.^. Influence of Nitro- and Amido-groups on a Sulphonic Group
entering the Benzene Molecule
Doebnee (O.). Compounds of Benzotrichloride with Phenols and Tertiary
Aromatic Bases ..........
Wroblewsky. Separation of Orthoxylene from its Isomerides
Maitschewsky. Aniline Dithionate .......
Spica (P.). Amines Corresponding with a-Toluic Alcohol .
Fischer (E.) and W. Ehehard. Ethyl Derivatives of Phenylhydrazine
Erlenmeyer (E.). Synthesis of Substituted Guanidinei
Beegee (F.). Orthotoliudine-guanidines and their Cyanogen-derivatives
th
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■ 228
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231
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232
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233
233
233
233
234.
234
234
234,
235
235
235
236
236
236
236
237
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237
237
238
238
238
239
240
240
241
242
243
244
x\a
COxVTEXTS.
Deri
CosACK (J.) . Carhamkles derived from the Isomeric Toluidines
StriDA (W.) . Action of Oxalic Acid on Carbazol .
Uenedikt (R.). Bromoxyl-denTatives of Benzene
Pateeno (E.) and F. Canzoneei. Products of the Oxidation of the
Ethers of Thymol
NiETZKi (R.). Formula of Qiuuhydrone
Hesse (O.). Amidomethylenepyrocatechols . .
Meyer (R.)- Behaviour of Hsematoxylin on Destructive Distillation
HoFMANN (A. W.). Methylpyrogallol and the Formation of Pittacal
Magatti (G.)- Ethylene Ether of Pyrogallol ....
LiPPMANN (E.) and W. Steeckee. Nitrocuminaldehyde and its
vatives ............
Bode WIG (C). Fittica's Nitrobenzoic Acids . .
Adoe (E.) and F. Meiee. Xylic Acid ; its Preparation and Derivatives
Salkowski (H.). ParahyHroxyphenylacetic Acid ....
Oglialoko (A.). Paraniethosyphenylcinuanuc Acid and Methoxystilbeue
Claiskn (L.) and C. M. Thompson. Metamidophenylglyoxylic Acid .
Batjmann (E.). Formation of Hvdroparacoumaric Acid from Tyrosine
Hesse (O.). Californian OrcellaWml
MiLLEE (O.). Products of the Dry Distillation of Calcium Phthalate .
Claesson (P.) and K. Wallix. Tolueneinonospulphonic Acid .
Hall (L. B.) and I. Kemsen. Oxidation-products of CynuMiesulphonamide
Kemsen (I.) and R. D. Coale. Anhydrosulphonamidoisophthalic Acid
Beciii (Gr. v.). Solubilities of some Constituents of Coal-tar.
Beiegee (L.). Skatole .
Liebermaxn (C.) and J. Homeyeb. Peculiar Formation of Tolane Tetra
chloride ............
Silva (R. D.). Synthesis of Diphenylpropane ; New Method of forming
Dibenzyl
Meldola (R.).
Maechetti (C).
of
Di- and Tri-derivatives of Naphthalene
Some Naphthol-derivatives .....
Ecksteand (a. Gr.). Nitronaphthoic Acids
Smith (W.). Synthesis of Phenylnaphthalene .....
Jacksox (C. L.) and J. F. White. Synthesis of Anthracene
Geaebe (C.). Constitution of Alizarin-blue ......
BouECAET (R.). Action of Ammonia on Anthraquinonesulphonic Acids
AbLEE (A.). Products from Brown Coal-tar and some Derivatives
Chrysene ...........
Flawitzky (F.) . Hydration of Terpenes
Emmebling (O.). Abietic Acid
Will (H.) and A. Laubenheimeb. The Glucoside from White Mustard
Seed ...........
Gatjtier (A.) Chlorophyll
Negei (A. and G. de). Colouring Matter of Anguria and Colycynth
Paterno (E.). Lapachic Acid .......
Weidel (H.). Compounds from Animal Tar ....
Wischnegeadskt (A.). Some Derivatives of Cinchonine
Skraup (Z. H.). Homocinchonidine
Hesse (O.). Quinamine . . . . . .
Roster (G.). Lithobihc Acid
Bleunard (A.). Constitution of Stag's Horn .....
Greene (W. H.). Dioxymethylene — Preparation of Methylene Chloride
Battdrimont (E.) . Action of Potassium Permanganate on Potassium Cya
nide ............
Deechsel (E.). Cyanamiile ........
Behrend (P.)- Action of Sulphonic Monochloride on Alcohols .
Simon (S. E.). Combinations of Lithium and Magnesium Chlorides with
Alcohols
Letelliee (A.).
Cupric Oxide
Oxidation of Alcohol by an Ammoniacal Solution of
PAGE
245
245
246
CONTENTS.
xvu
Hkezfield (A.)'. Action of Diastase on Starch-paste ....
TscHNEENiAK (J.)'. Spontaneous Decomposition of Dicliloretliylamine
Btk (S.). Desulphuration of GrUanidine Thiocvanate ....
SCHEEINEE (L.) . Action of Ethyl Chlorocarbonate on Amines
Schmidt (H.). Preparation of Glyceryl Triacetate ....
Feeytag (B.). Some Derivativ.es of Propionic Acid ....
Passat ANT (S. C). Nitrites from Hydrocyanic Acid and Aldehydeamrao
nia ............
JouEDAN (F.). .Synthesis of Normal Nonoic Acid and of an Isomeride of
Palmitic Acid ............
MiLLEE (W. v.). Hydroxy valeric Acids and Angelic Acid .
Bredt (J.) and R. Fittig. Pyroterebic Acid
G-RiESS (P.). Action of Methyl' Iodide on Asparagine ....
Greene (W. H.). Preparation of Bromobenzene and lodobenzenes
Geiess (P.). Action of Cyanogen Compounds on Diazobenzene .
Weddige (A.). Ethylene Derivatives of Phenol and Salicylic Acid
Hesse (G.). Quinic Acid, Quinone and Alhed Compounds .
Baebiee (P.). Action of Acetic Anhydride on Phenol Aldehydes
Geeene (W. H.) . Synthesis of Saligenol
Feitzsche (P.). Phenoxyacetic Acid
Degenee (P.). Action of Fused Alkalis on Aromatic Sulphonic Acids
Laae (C). Sulphanilic Acid
Geiess (P.). Trimethylparamidobenzenesulphonic Acid
PosEN (E.). Phenyllactimide
Peckmann (H. v.). Constitutioji of Anthraquinone . . .
Bouchaedat (G.). Action of Haloid Acids on Isoprene. Formation of
Caoutchouc . .
Kachlek (J.) and F. V. Spitzee. Relations of the Camphenes obtained
from Borneol and from Camphor . .
Phipson (T. L.). Palmellin and Characin extracted from Algse by Water
JoBST (J.) and O. Hesse. Coto-barks and their Chara^jteristic Ingredients
Hesse (O.). Cinchona Barks . ...
Jahn (H.). Action of Phosphonium Iodide on Carbon Bisulphide
GtJSTATsoN (G.). Reactions due to the Presence of Aluminium Bromide and
Chloride ........
SOEOKIN (W.). Constitution of Diallyl
Peatoeius-Seidlee (G.). Cyanaraide .
FiTZ CA.). Normal Propyl Alcoholfrom Glycerol
Semlianizin. AUylmethylpropyl Carbinol .
RJABININ. Methyl and Ethyl Ethers of Diallyl; Carbinol .
Edee (J. M.) . Composition of Pyroxylin
Meez (V.) and J. T1BIE19A. Synthetical Formation of Formic Acid .
Tanater (S.). Maleic and Malic Acids from n-Dibromopropionic Acid
Mexschptkin (N.). Etherification of Unsaturated Monobasic Acids .
FiTTiG (R.) and others. Unsaturated Monobasic Acids with Six Atoms
Carbon ............
Engelhoen (F.). MethacryUc Acid
Thomson (G. C). Decomposition of the Substitution-products of the Lower
Fatty Acids by Water .........
Menschutkin (N.). Structure of Sorbic and Hydrosorbic Acids .
Schieokoff. /3-Dipropyl- and /3-Diethylene-lactic Acid ; Oxidation of Allyl
dimethylcarbinol and Dialiylcarbinol . . . . .
Coppola (M.). Stereocaulon Vesurianum ......
Prei^aration of Pure Dioxyfumaric Acid
Formation of |3-Methyloxyglutaric Acid from Diallylmethyl
Tanatee (S.).
soeoein (w.).
Carbinol .
Leuckart (R.).
LlEBMANN (A.).
La Valle (G.).
Landolph (F.).
Ethyl-carbamide-and'some of its Derivatives
Synthesis of Cumene. ......
Crystallographic Constants of some Benzene-derivatives
Anethol-derivatives .......
of
PAGB
310
311
311
311
312
312
313
313
314
315
315
316
316
316
317
318
318
318
320
320
322
322
323
323
324
325
325
328
370
370
370
370
372
372
372
372
374
374
375
375
378
379
382
382
382
383
383
383
384
384
384
VOL. XXXVIII.
xvm
CONTEXTS.
KosiCKi (J.). Eesorcinol-isosuccinei'n
Sarauw. Broniine-derivatiTes of Quinone
HoFMANN (A. W.). Action of Sulphur on Phenylbenzamide
KiEDEL (C). Constitution of Nitrosodimethylmetatoluidine
Staats (G.). Ortbo- and Para-toluidine-deriTatives ....
Smith (E. F.)- ^ New Base
HoFMANN (A, W.). A Series of Aromatic Bases, Isomerides of the Thioear
bimides ............
Stebbins (F.). Some Azo-derivatives ,
Fischer (E. and O.). Dye-stuifs of the Rosaniliue Group .
BiNDSCHEDLER (R.). Safranine . .
ScHiFF (H.). Colouring Matters from Furfuraldehyde
Smith (E. F.) and Or. K. Peiece. Nitration of Metachlorosalicylic Acid
Saarbach (L.). Action of Phenols on Halogen-substituted Fatty Acids
OsER (J.) and F. BoCSER. Condensation-products of Gallic Acid
Post (.J.) and E. Hardtung. Sulphonic Acids from Isomeric Nitramido-
and Diamido-benzenes .........
Baeter (A.) and G. E. Jackson. Synthesis of Methylketole, an Isomeride of
Skatole .
Michaelis (A.) and P. Becker. Monophenylboron Chloride
La Coste (W.) and A. MigHaelis. Arom^itic Arsenic-compounds
Gr^be (C.) and H. Cimo. Acridine
Eeverdin (F.) and E. NoETIng. The a- and j3-Positions in Naphthalene
Goes (B.). Diphenyldiiniidonapbthol .......
LiEBERMANN (U.) and A. BisciiOF. The Third Anthraeenecarboxylic Acid
FiTTiG (R.) and H. Liepma^n. Fluoranthene, a New Hydrocarbon from
Coal-tar ............
Flawitzky (F.). Changes produced by Hydration and Dehydration in th
Lsevorotary Terpene from French Turpentine Oil ....
Weidel (H.) and G. L. Ciamician. Compounds in Animal Tar .
KcENiGS (W.). Conversion of Piperidine into Pyridine
Hoogewerff (S.) and W. A. v. Dorp. Pyridinecarboxvlic Acids
HooGEWEEFF (S.) and W. A. V. Doep. Pyridinetricarboxyhc Acid from
Cinchona Alkaloids . . . .
Baeter (A.) and O. R. jTackson. Synthesis of the Homologues of Hydro
carbostyril and Quinoline ........
PoLSTORFF (K.). Action of Benzoic Chloride on Morphine .
PoLSTORFF (K.). Action of Potiissium Ferricyanide on Morphine
Broockmann {K.) and K. Polstorff. Schiitzenberger's Oxyniorjihine
Beoockmann (K.) and K. Polstorff. Methylmorphine Hydroxide .
Polstorff (K.). Action of Potassium Ferricyanide on Methylmorphine
Iodide ............
Skraup (Z. H.). Constitution of Cinchonme and Cinchonidine .
Kraut (K.). Belladonnine .........
Ladenbueg (A.). Artificial Alkaloids
SnuLL (D. F.). Erythroxylon Coca .......
Greene (F. V.). Baptisia tinctoria .......
Claessen (T. E.). Phytolaccin ........
Ehrhard (A. C). Phiitolacca deeandra . . . .
Whitnev (H. C). Apiol . .
BiscHOFF (H.). Colouring Matter of the Caryophyllaceae
Salkowski (E. and H.). Putrefaction-products of Albumin
LossEN (F.). Guanidine. an Oxidation-product of Albumin .
Simpson (M.). Direct Formation of the Clilorobromides of the defines and
other Unsaturated Compounds .......
JuNGFLEiscH. Preparation of Acetylene ......
Regnault (J.) and E. Haedt. Action of Bleaching Powder on Pi-opyl
Butyl, and Amyl Ah-ohols ........
Grimaux (E.) and P. Adam. Action of Bromine on Epichlorhydrin .
Haneiot. Action of Sodium on Epichlorhydrin .....
PAGE
385
385
386
386
386
387
387
389
390
391
391
392
392
394
394
395
395
396
398
399
399
399
400
402
403
4G4
405
406
406
407
408
408
408
409
409
410
410
411
411
412
412
412
413
413
413
456
456
456
457
457
COXTENTS.
XIX
High
and
Haneiot. Constitution of Epiclilorhydrin ...
Gaton (U.). Inactive Glucose or Neutral Sugar.
HoESiN-D^ON. Inactive and Inverted Sugar
Engel (K.) and De Gieabd. Method of Producing Acetal .
Mills (E. J.) and J. Hogarth. Kesearches on Lactin .
Simpson (M.). Action of Acetic Chloride on Taleraldehvde
Vangel (B.). Action of Dehydrating Substances on Organic Acids
Geuther (a.). Action of Carbonic Oxide on Alkaline Hydrates at
Temperatures ..........
LoEW (O.). Synthesis of Formic Acid . ......
Beetkand (A.). Action of Titanium Tetrachloride, Stannic Chloride
Antimony Pentachloride on Acetic Acid and Acetic Anhydride
Masino (F.). Compounds of the Myristic Series .....
Waxkltx (J. A.) and W. J. Cooper. Products of the Oxidation of Wool
Cyanopropionic Acid .........
Balbiano (L.). Amides and Anilides of /3-Hydroxybutyric Acid
BouEGOiN (E.). Electrolysis of Malonic Acid
Beemer (G. J. W.). Inactive Malic Acid ......
FuxARO (A.) and L. Daxesi. Succinin ......
Balsohx (M.). Synthesis of Ethylbenzene from Ether and Benzene .
Ratmax (B.) and K. Peeis. Action of Iodine on Aromatic Compounds with
Long Side-chains ..........
Natanson (S.). Fittica's Fourth Nitrophenol
Foster (M.). Ethyl Derivatives of Orthamidophenetol and Orthamido
phenol ............
Andreae (H.). Nitro-orth- and Nitropar-azophenetols
ScHEiBLEE (C). Occurrence of VaniUin in certain kinds of Raw Beetroot
Sugar ............
Etaed (A.). Synthesis of Aromatic Aldehydes : Cuminaldeliyde .
Babbiee (P.) . Action of Acetic Anhydride on some Aromatic Aldehydes
Rudolph (C). Action of Nascent Hydrogen on Orthonitrobenzaldehyde
OssiKOTszKT (J.). Formation of Cinnamic Aldehyde during Fibrin-pancreas
Digestion ...........
Feiedel (C.) and M. Balsohx. Limited Oxidation of Ethylbenzene .
Feiedel (C.) and M. Balsohx. Conversion of Bromostyrolene into Methyl
phenylketone . ..........
Adoe (E.). Isophthalophenone ........
BuEGOi'x (E.). Solubility of Benzoic and Salicylic Acids ...
Beilsteix (F.) and A. KrEBATO\.v. Dinitrobenzoic Acid
Eblexmetee (E.). Phenyl-lactic Acids
Eblexmeyeb (E.). Phenylbromolactic Acid
Ladexburg (A.) and L. RiJGHEiiiER. Artificial Formation of Tropic Acid
TiEMANN (F.) and L. Friedlaxdeb. Aromatic Amido-acids
Remsex (I.). Oxidation of Sulphaminemetatoluic Acid
OssiKOVSZKT (J.). Constitution of Tyrosin and Skatole ...
Geeichtex (E. v.) Constitution of P'hthalie Chloride ....
FisCHEB (E.). A New Series of Dye-stuiTs
Bafmajs'x (E.) and F. Tiemaxx. Potassium Hydrindigotin-sulphate and
Potassium Indoxyl-sulphate .......
Gabbiel (S.) and A. Deutsch. Sulphur Derivatives of Diphenyl
Beilsteix (F.) and A. Kuebatow. Dinitronaphthalene
Lehxe (A.). Condensation of Benzhydrol and Naphthalene .
Fischer (E.). Phenanfhrenedisulphonic Acid and its Derivatives
Rexaed (A.). Electrolysis of Terebenthene .
GuAEESCHi (I.). Podophyllin.
RiCHABD (A.). Bases of the Pyridine Series
Taneet (C). Alkaloids of the Pomegranate
Schmidt (E.). Daturine ....
Ladexbueg (A.) and G. Meter. Daturine .
MiLLOT (A.). Synthesis of Ubnic Substances
b 2
PAGE
457
458
458
458
458
459
459
459
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400
460
460
461
462
462
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463
463
463
463
466
467
467
468
469
469
469
469
470
471
471
471
472
472
473
473
473
473
474
475
476
477
478
478
479
479
480
481
481
482
482
XX
CONTENTS.
Wetl (T.) and Bischoff. Gluten
Bleunakd. Products of the Decomposition of Prote'ids . . . .
Vines (S. H.). Chemical Composition of Aleurone Grains . . . .
TJkech (F.)- Action of Potassium Carbonate on Isobutaldehyde .
HtJBNER (H.) and E. Lellmann. Diiodoproj);! Alcohol and Moniodoallyl
Alcohol .............
Sestini (F.). Ulmic Compounds formed from Sixgaf bv the Action of
Acids .............
Peligot (E.). Comijound of Levulose with Lime
Hell (C). Kate ot Substitution of Bromine in the Acetic Acid Series
Cahours (A.) and E. DEiiARfAY. The Acids which are formed by the
Distillation of the Crude Fatty Acids in a Current of Superheated Steam
Pabst (J. A.). Preparation of Ethyl Acetate ......
Aeonstein (L.) and J. M. A. Kramps. Action of Ethjl Iodide on Ethjl
lodoacetate ...........
Balbiaxo (L.). Some DeriTatives of (S-Chlorobutyric Acid .
Hell (C.) and O. Mxjlhausee. Action of finely-divided Silver on Ethyl
Monobromobutyrate .........
Hell (C.) and O. iiiiJLHAUSEK. Acids of the Formula C8H14O4 derived from
Bromobutyric Acid
DuviLLiER (K.). Amido-acids from a-Bromocaproic Acid .
ViLLiERS (A.). CrystaUised Oxalic Acid
Eder (J. M.). Reducing Properties of Potassium Ferrous Oxalate
Ehlenmeyeb (E.). Oxypropionie Acid (Oxacryhc Acid)
Ueech (F.). Reaction of Acetone with Potassium Cyanide, Thiocyanate,
and Aqueous Hydrochloric Acid
Htjtilliee (E.) and A. Buisine. Formation of Teti-amethylammonium
Nitrate
RuDNEFF (W.). Amines containing Tertiaiy Radicles .
Wallach (O.) and G. Steickee. Oxalethyline and Chloroxalallyline
"Wal.lach (O.) and E. Schulze. Bases of the Oxalic Acid Series
Wallach (O.) and J. Kamenski. Formation of Bases from Acid Amides
Wallach (O.). Remarks on the Preceding Papers . . . •
Rfdneff (W.)- Thiocarbamides with Tertiary Radicles
Panebianco (R.)- Crystalhne Form of Nitrosothymol, Lapachic Acid, and
Cuniic Acid ...........
HiJBNEE (H.) and A. Steometee. Nitration of Paranitrobenzoic Acid
Heine (K.). y-Sidphoisophthalic Acid and the Correspondiug y-Hydroxyiso
phtlialic Acid ..........
Geeene (W. H.). Aceto-Benzoic Anhydride
Schiff (H.). Digallic Acid
Pateeno (E.). Chemical Constituents of Stereocaulon Vesuvianum
ScHWAEZ (H.). Homofluorescein, a New Colouring Matter from Orcinol
NjETZEi (R.). Xylene Derivatives . . .' .
RosENSTiEHL (A.). Constitution of Rosanilinc Salts ....
Wallach (O.) and L. Belli. Conversion of Azoxybenzene into Oxyazo
benzene ............
Mensching (C). Nitration of Salicylanilide ......
Wallach (O.). Thiamides .........
Scheeib (H.). Orthochlorobenzparatoluide and its Derivatives .
Wallach (O.) and A. Liebmanx. Action of Alcohols and Phenols on
Acid Imide Chlorides
Kohler (H.). Synthesis of Phosphenyl Sulphochloride
Friedel (C.) and M. Balsohn. Action of Bromine on Diphenylmethane
Miller (W. v.). A New Colouring M'atter
Flavitzkt (F.) . Lffivorotary Terebenthene from French Turpentine Oil
Kachlee (J.). Adipic Acid from Camphor .....
Teereil (A.) and A. Wolff. Resin from Rosewood ....
Peingsheim. Chlorophyll
Rogalski. Analyses of Chlorophyll
PAGB
482
482
483
538
538
538
539
539
540
541
541
541
542
543
543
514
5^4
544
545
545
545
546
547
547
548
548
548
549
549
550
651
551
551
552
553
556
556
556
557
557
558
558
559
559
559
559
560
561
CONTEXTS.
XXI
LADENBUEa (A.) . Alkaloids of Belladonna, Datura, Jusquiame-, and Du
boisia ............
ZxJLKOWSKi (C ) and G-. Eenxee. Composition of Diastase and Beet Mucilage
Kjeldahl (J.). Diastase .........
Latschinoff (P.). Oxidation of Cliolic Acid
Ksop (W.). Albuminoids .........
8TAEDEL (W.). Vapour Tension of the Halogen Derivatives of Ethane
Demaecay (E.). Preparation of Acetonitril .....
GrAUTiEE (A.). Pure Methyl Cyanide .
Wteouboff (Gr.). Note on Platinum Thiocyanate ....
Andrews (L. W.). Ethylene lodopicrate
DiECE (E.) and B. Tollens. Carbohydrates from the Tubers of Jei'usalem
Artichoke ..........
Heezfeld (A.). Acetylisation of some Carbohydrates
Peligot (E.). Saccharin .........
Ueech (F.). Vapour-density of tlie Viscous Polymerid« of Isobutaldehyde
Lipp (A.). Derivatives of Isobutaldehyde .....
BoTTiXGEE (C.) . G^lyoxylic Acid
Geuthee (a.), O. Fbohlich, and A. Looss. JS'ew Synthesis of Carbon
Acids ............
Beeteaxd (A.). Compound of Titanium Tetrachloride with Acetic Chlo
ride , .
DmLLiEE (E.). New Mode of Forming Dimethacrylic Acid
DEMAE9AT (E.). Tetrolic and OsytetroUe Acids and their Homologues
Melikoff (P.). Hyuroxyacry lie Acid ......
Emmerling (A.). Carbouyl Bromide ,
CoNEAD (M.) and C. A. Bischoff. Syntheses by means of Ethyl Malonate
Schneider (G-. H.). Inversion of Ordinary Malic Acid
Gecthee (A.). Behaviour of Monochlorotetracrylic Acid on Fusion
Maly (R.) and R. Andreasch. NitrosothioglycoUic Acid .
Bell (C. A.). Action of Zinc on Succinimide ....
Keamps (.1. M. A.). Contribution to a Knowledge of the Ureides
Claus (A.) and H. Hansen. Orthocymeue
Claus (A.) and T. Stl'ssee. Metacymene .....
Claus (A.) and C. Ceatz. Paracymene and Sulphuric Acid
Claus (A.) and C. WiiriiEL. Oxidation of Dibromocymene
Klein (O.). Compounds of Organic Bases with the Haloid Salts of Mercury
Dennstedt (M.). Derivatives of Parabromaniline ....
Widman (O.). Metatoluidine
Beilstein (F.). Dinitroparatoluidine
FiscHEE (O.) . Condensition Products of Tertiary Aromatic Bases
GrEiEss (P.). A New Class of Ammonium Compounds. Part I .
GrEiESS (P.). A New Class of Ammonium Compounds. Part II .
Bebnthsen (A.) and F. Sztman-ski. Formation of Diamines
Staedel (W.) and O. Sikpeemann. New Synthesis of Organic Bases con
taining Oxygen ..........
Fischer (O.) and P. Gbeiff. Synthesis of Leucanihne
Zieglee (J.). Some Compounds of the Leuco-base from Cuminol and
Dimethylaniline .........
Miller (W. v.). Supplementary Notice on New Colouring Matters
MicHAELis (A.) and C. Panek. Homologues of Phosphenyl Cliloride
Staedel (W.) and G. Daum. Bromonitro- and Bronaamido-anisod
MiJLHAUSEE (O.). Orthanisidine .
Post (J.) and L. Holst. Benzamidophenolsulphonic Acids
WiLLGEEODT (C). a-Dinitrophenyl Ether
ilAGATTi (C). Oxidation of Substituted Plienols
DoEBNEE (O.). Compounds of Benzotrichloride with Phenols and Tertiary
Aromatic Bases ..........
Eeymann (S.). a Product obtained by the Action of Aqua Regia
Orcinol ............
PAGE
on
XXll
CONTENTS.
Beeuee (A.) and T. Zincke. Oxidation of Benzoic and Acetic Carbinols
Thoener (W.) and T. Zincke. Pinacones and Pinacolins .
Dennstedt (M.)- Crystalline Form of Benzyl Orthothioformate .
LiPPMANN (E. O. y.). Occurrence of Vanillin in Eaw Sugars
Staedel (W.) and E. Sauee. Dioxybenzophenone
Claxjs (A.). Nitrobenzoic Acids .......
Clatjs (A.) and W. Halbeestadt. Metaparadinitrobenzoic Acid by Niti-a
tiou of Paranitrobenzoic Acid ......
FiSCHEE (E.). Ovtbohydrazinbenzoic Acid .....
GrEEiFF (P.). Anthranilic Acid from Ortbonitrotoluene
Baumann (E.). Aromatic Products of the Animal Body
Bernthsen (A.). History of Phenylacetamide ....
BoTTiNGEE (C.). Pblobapbene .......
Baetee (A.). Compounds of Phthalic Acid with Phenols .
LiEBEEMANN (C.) and M. VoELTZKOW. PhenTltliiocarbimide-glycollide
Staedel ^W.) and F. Kleinschmidt. Isoindole ....
Graebe (C). Carbazol
Geaebe (C.) and B. v. Adleeskeon. Some Deriyatives of Carbazol
Knecht (W.). Chloro-deriyatives of Carbazol ....
FiscHEE (O.) and L. Rosee. Amidotriphenylmethane
FiscHEE (O.). Diamidotriphenylmethane .....
FiscHEE (O.) and J. Zieglee. A New Triami'lotriphenylmethane
Atteebeeg (A.). Probable Occurrence of Furfurane (Tetrapbenol) and a
Homologous Compound in the Products of the Dry Distillation of Pine
Wood
Geaebe (C.) and W. Knecht. Plienylnaplithylcarbazol
Hemilian (V.). Synthesis of Naphthyldiphenylmethane
NiETZKi (E.). Colouring Matters obtained by the Action of Naphthol on
Diazoazobenzene ..........
Miller (W. v.). Rouge Fran^ais
LiEBEEMANN (C). Fluoresccnce in the Anthracene Series .
Beeuee (A.) and T. Zincke. Derivatives of the Quinone from the Hydro
carbon CigHjo . . . . . . ' .
Bevan (E. J.) and C. F. Ceoss. Chemistry of Bast Fibres .
Kachleb (J.) and F. V. Spitzes. Hydrocamphene ....
Letts (E. A.). Action of Sodium on Turpentine Hydrochloride .
Hjelt (E.). Action of Ammonia on Ethyl Camphoronates .
Stillman (J. M.). Ethereal Oil from the Californian Bay Tree .
Eelbe (W.). Abietic Acid
Hjelt (E.). Caryophyllin
Hesse (O.). Caroba Leaves . ........
Habeemann (J.). Glycyrrhizin
Peingsheim. Hypochlorin and its Origin
KoENiGS (W.). Synthesis of Quinoline
Cahoues (A.) and A. Etaed. Nicotiue Derivatives ....
Deechsel (E.). Formation of Hpyoxanthine from Albuminoids .
Hesse (O.). Morphine Hydrocldoride
KoENiGS (W.). Action of Phosphorus Pentachloride and Oxychloride on
Cinchonine Hydrochloride .......
Ladenbueg (A.). Hyoscyamine . . . . i . .
Ladenbueg (A.). Hyoscyamine and Atropine ....
Ladenbueg (A.). Duboisine .......
Ladenbueg (A.). Tropidine .......
Hesse (O.). Pereiro Bark
Stutzee (A.). Protein Compounds
Ritthausen (H.). Albuminoids of Various Oily Seeds
BoucHAEDAT (G.). Transformation of Amyleneand Valerylene into Cymene
and Hydrocarbons of the Benzene Series ....
Villiees (A.). Etherification of the Haloid Acids
YuLiEES (A.). Etherification of Hydriodic and Hydrochloric Acids
PAGE
645
646
646
646
646
647
647
647
648
648
650
650
650
659
659
660
660
660
661
661
662
663
663
664
664
664
665
665
666
669
669
669
670
670
670
671
671
671
672
672
672
673
673
674
674
675
675
675
676
676
710
711
711
CONTEXTS. XXlll
PAGE
Desteem (A.). Compounds of Alcohols with Baryta and Lime, and the
Products of their Decomposition ........ 711
GuTKXECHT (H.). a-Xitrosopropionic Acid ....... 712
Saytzeff (A.). Constitution of tlie Reduction-product of Succinic Chloride 712
Erlenjietek (E.). Amidolactic Acids . 713
Beknthsex (A.). Action of Phosphorus Pentachloride and of Zinc-dust on
Succiuimide ............ 713
CosACK (J.). DeriratiTCS of the Toluidines . ...... 713
Ladenbueg (A.). Tropeines '. . 714
Stebbixgs (J. H.). Xew Azo-colours 715
G-rACOSA (P.). Saliretone 716
Weyl (T.) and B. v. Axeep. Formation of Hippuric ajid Benzoic Acids in
the Animal Organism during Fe^er ....... 716
ViGNoy (L.) and J. B. Boasson. Two New Dje-stuffs .... 717
Spitzee (F. v.). Camphor Chlorides 717
Stevexsox (A. F.). Eesins contained in Jalap 717
Blanchet (C.). Thapsia Garganica 718
Geeenish (H. Gr.). Nigella Satcva 718
PoDWTSzoTZKT. Emetine 720
Phipsox (T. L.). Preservation of Solutions of PalmelKne .... 720
Barnes (J. B.). Taraxacum Root 720
Lloyd (J. U.). Yerba Mausa . . . 721
Pakodi (D.). Tayuja .721
Latschixoff (P.). Cholecamphoric Acid and its Relation to Cholanic
Acid 722
ZoLLEE (P.) . Globulin-substances in Potatoes 723
HoHBACZEWSKi (J.). Products of the Action of Hydrochloric Acid on Albu-
minoids 723
DuTiLLiEE (E.) and A. BrisiXE. Action of Ethyl Chloride on Elhyl-
amine ............. 79 1
Jahn (H.). Decomposition of Simple Organic Compounds by Zinc-dust . 791
ViNCEXT (C.) and Delachanal. Combination of Allyl Alcohol with
Baryta 794
Griesshammee (0.). Action of Bromine on Cane-sugar .... 795
Leyallois (A.). Presence in the Soja hispida of a Substance transformable
into Glucose ............ 796
Otto (R.). Beha\-iour of Mercury and Lead Ethylmercaptides at High
Temperatures ............ 796
ViLLiEES (A.). Etherifi cation of Sulphuric Acid 796
Villiees (A.). Preparation of Neutral Ethyl Sulphate .... 797
HoFiiAXN (A. W.). Transformation of Methyl Thiocyanate at High Tem-
peratures ....... 797
Fischer (E.). Furfuraldehyde 798
FiTTiG (R.). New Lactones' 799
FiTZ (A.). Double Salts of the Lower Members of the Acetic Acid Series . 799 •
Wallace (O.). Dichloracrylic Acid 799
Melikoff (P.). Constitution of Liquid Chlorolactic Acid and of Oxyacrvlic
Acid ' , ' . 800
Melikoff (P.). j3-Bromolactic Acid 800
Melikoff (P.). Amidolactic Acid bOO
Heixtz (W.). Diethyl idenelactamidic Acid . . 801
BiEXBAUM (K.) and J. Gaiee. Action of Iodine on the Silver Salts of
Dibasic Acids 801
BorRGOix (E.). Preparation of Malonic Acid 801
Grimaux (E.) and P. Adam. Synthesis of Citric Acid .... 801
Eexard (A.). Electrolysis of Benzene 802
Kramer (G.) and M. Geodzky. Influence of Constituents of Wood Spirit
on the Production of Dimethylaniline ....... 802
Beegee (F.). Aromatic Guanidine-compounds ...... 802
Geiess (P.). Creatine-compounds of the Ai'omatic Group .... 803
XXIV
CONTENTS.
PAGE
Otto (E.).
Otto (E.).
Otto (E.).
DoEBNER (0.). Aromatic Amidolie-tones .....
Mahrenhoitz and GtIlbeet. An Azobenzenesulphonic Acid
Reiche (H. v.). Two AzobenzenedisLdf)honic Acids
Neale (A. T.). Two Azotoluenesulplionic Acids ....
Brunnemann (C). An Azoxybenzenesulphonic Acid .
Jordan (O.). Dibrom- and Tetrabrom-liydrazobenzenesulpbonic Acids
Balentine (W.) . Diazo-compound of Hydrazobenzenesulphonic Acid
Action of Sulpburic Acid on Aromatic Sulphydrates .
Beckurts' Toluenemetasuiphonic Acid ....
Constitution of tbe Stdphinic Acids .....
Otto (E.) and E. Ludees. Benzyl Derivatives containing Sulphur
Otto (E.). Synthesis of Ethereal Salts of Thiosulpbonates .
Losanitch (S. M.). Constitution of Tetranitrodiphenylcarbaraide
Geaebe (C.) and C. Menschino. Diphenic Anhydride
BoTTlNGER (C). Diamidotriphenylmethane .....
Mebz (V.) and W. Weith. Substitution in the Phenyl Gi'oup .
Hantzsch (A.). Conversion of rt-Naphthylamine into a-N'aphthyl Methy
Ether
Miller (W. v.) . Biebrich Scarlet
ScHULTz (Gi-.). Constitution of Phenanthrene .....
Cahofrs (A.) and A. Etard. A Bromo-derivative of Nicotine .
Ladenbtjrg (A.). Homatropine ........
B^cuAMP (A.) Non-identity of the Soluble Albuminoids of Crystallin with
those of White of Egg and Serum ......
LoEW (O.). Lecithin and Nuclein in Yeast .....
Weyl (T.) and B. v. Aneep. Hsemoglobin Carbonic Oxide
Gladstone (J. H.) and A. Tribe. Aluminium Iodine Eeaction .
Claus (A.) and E. Lindhorst. Action of Bromine on Dichlorhydrin and
Propylphycite .........
Bouteoux (L.). Fermentation of Glucose
Maumene. Fermentation of Glucose
Chemistry of Sugar . . .
Reichardt (E.) and others. Decomposition-products of Sugar .
Sestini (F.). Saculmic Acid and Saculmin
Zttlkowski (K.). Action of Glycerol on Starch ....
Seegen (J.) and F. Keatschmee. Nature of the Sugar in the Liver
Herzfeld (A.). Malto-dextrin . . . • .
Keafft (F.). Preparation of Laurie, Myristic, Palmitic, and Steiric
Aldehydes ..........
EiiMEELiNG (A.) and E. Wagner. Monobromacetone and the Alcohol of
Acetone ...........
Eppinger (O.). Action of Ethylamine and Diethylamine on Acetone .
Petteesson (O.) and G. Eksteand. Vapovir-densities of Anhydrous and
Hydrated Formic and Acetic Acids . . * . . " .
Campani (G.) and D. Bizzaeei. Butyl and Isobutyl Hippiu-ates
Testa (A.). Action of Potash on Ethyl Isochlorobutyrate .
Balbiano (L.) and A. Testa. Dibutyllaetic Acid and a Polymeride cf Met!
acrylic Acid ...........
Guthzeit (M.) . Octylic Aceto-acetate and its Derivatives .
Booking (E.). Two New Syntheses of Methyl-ethyl-hydroxyaeetic Acid
Gantter (F.). and C. Hell. Suberic Acid produced by Oxidation
Tanatar (S.). Trioxymaleic Acid
Anschutz (E.) and "A. Pictet. Preparation of the Ethereal Salts
Tartaric and Eacemic Acids
Andeeoni (G.). Citric Acid
MoELEY (H. G.). Propylneurine
Andeeasch (E.). Synthesis of Thiohydantoin
Andeeasch (E.). Carbamideacetosulphonic Acid ....
ZiEGLEE (A.) and W. Kelbe. Synthesis of Meta-isopropyltoluene
Kelbe (W.) a New Cymene from Light Eesin Oil . " .
of
CONTEXTS. XXV
PAGE
Jacksox (C. L). and A. W. Field. Action df Bromine on Toluene and its
Derivatives ............ 878
Jacksox (C. L.) and J. White. Parachlorobenzyl-compounds . . . 878
Jackson (C. L.) and J. F. White. Orthobromobenzvl-compounds . . 879
Mazzara (Gr.). Tetrabroniodibcnzvleneparadimethylphenjlamine . . 879
Stebbixs (J. H.). Action of Benzotrichloride on Primary Amines . . 880
Calm (A.) and K. Hetmanx. Substituted Azobenzenes . . . : 880
Stebbins (J. II.). Colouring Matters produced by the Action of Diazo-
compounds on Phenols .......... 880
Meldola (R.). Colouring Matters from Phenols . ..... 881
Claus (A.) and K. Elbs. Amariae ........ 881
Mazzaba (G.). Paraethylmetliyl Phenol • 882
Spica (P.). Cumophenols 882
FiLETi (M.). A New Cumoplienol 883
Pater>'6 (E.) and F. Caxzoneri. Derivatives of Natural and Synthetical
Thymol ............. 883
HoFMAXX (A. W.). Amidophenyl Mercaptans or Thiohydranilines . . 884
Levy (S.) and G-. Schtjltz. Chlorinated Quinones ..... 888
Spica (P.). Thymolglycollic Acids ........ 888
Classex (P.) and H. Berg. Constitution of a-Toluenedisulphonic
Acid 889
Spica (P.). Cymenesulphonic Acids . 890
Gabriel (S.) and A. K. Dambebgis. Nitro-derivatives of Diphenyl-mono-
and di-sulphonic Acids .......... 890
AxscHiJTz (Pi.) and I. v. Siemexski. Phenanthrene-derivatires . . . 891
SCHIFF (R.). Bromo-, Nitro-, and Amido-camphor 891
ScHiFF (R.). Constitution of Bromo-camphor ...... 892
ScHiFF (R.). Action of Zinc Cliloride on Bromo-camphor .... 892
KiCHLER (J.) and F. Y. Spitzer. Camphocarboxylic Acid .... 892
Maissex (P.). Preparation of Camphoric Acid and Camphoric Anhydride . 893
Rexard (A.) . Products of the Distillation of Colophony .... 893
ScHUXCK (E.). ChloroTphyHtrova Eucali/pius fflobulus . .... 894
Hoppe-Setler. Crystallised Chlorophyll ....... 894
HooGEWERFF CS.) and W. A. r. Doep. Behaviour of the Cinchona Alka-
loids ^vith Potassium Permanganate ....... 895
Laiblix" (R.). Bromo-dcrivatives of Nicotine ...... 897
DcrviLLiER (E.). Compounds belonging to the Creatine and Creatinine
Groups ............. 897
Salomox (G.) . Hypoxanthine from Albuminoid Bodies .... 897
Vrij (J. E. de). The Form in which the Cinchona Alkaloids occur in the
Bark 898
Selmi (F.). Alkaloids from the Decomposition of Albumin . . . 898
Hamack (E.) and H. Meyer. Researches on the Alkaloids of Jaborandi
Leires ............. 898
Berkhardt (W.). Alkaloid in Aethusa Cynapium ..... 899
Ajiato (D.) and A. Capparelli. Chemistry of the Yew .... 899
Mezzo (G.) and C. Mexozzi. Milk Albumin and Curd Formation . . 900
Pekelhabixg (C. a.). Peptone . 901
PJiysiological CJiemistrij.
DiJXKELBEHG. Feeding Horses with Fleshmeal ...... 57
ScHULTiz (H. C. E.), E. Wildt, and others. Poisoning of Sheep by Lupines 57
Wolff (E. v.) and other?. Assimilation of ordinary Horse Fodder . . 173
Wolff (E. t.). Fattening Animals . 173
LoEW (O.). Source of Hippuric Acid in the Urine of Herbivora . . 173
Peters (P.) and K. Mijlleh. Analysis of a Calculus from a Horse . . 174
ScHiiiTZ (A.). Physiological Influence of Adulterated Wine . . . 174
XXVI
CONTEXTS.
PAGE
BiNZ (C.) and H. Schulz. Chemical Cause of the Toxieological Action of
Arsenic ............. 174
Bechamp (J.) . Presence of Alcohol in Animal Tissues during Life and after
Death 174
Seegen (J.) and J. Nowak. Gaseous Nitrogen, a Product of the Decom-
position of Albuminoids in the Body . . . . . . . 272
ScHiscHKOFF (L.). Chemical Composition of Milk 273
Jolly (L.). Combinations of Phosphoric Acid in the Nervous Substance . 274
Jolly (L.). Disti-ibution of Phospliates in the Muscles and Tendons . . 275
GriUNTi (M.). Distribution of Copper in the Animal Kingdom . . . 275
Wolff (E. t.) and Others. Nutritive Value of Grass at Various Stages of
Growth 329
Weiske (H.) and Others. Nutritive Value of Asparagine .... 330
Weiske (H.). Digestive Power of Geese for Fibrin ..... 330
Defresne (T.). PtyaUn and Diastase 330
Stintzing (R.) . Carbonic Anhydride from Muscle ..... 330
Fleischmann (W.) and P. Vieth. Milk Secretion 330
Maechand (C). Abnormal Composition of Human Milk .... 332
Dehiiel (B.). Occurrence of a Reducing Substance in the Urine of Her-
bivorous Animals ........... 332
Thoms (G.) . Analysis of Concretions taken from an Abscess on the Jaw-
bone of a Horse ........... 333
Heubel (E.). Action of Dehvdrating Agents on the Crystalline Lens of the
Eye . . . .' 333
Wolff (E. v.) and others. Digestion of Food by the Horse when at Work . 414
Absorption of Food ........... 414
Wolff (E. v.), W. v. Funke, and G. Dittmann. Feeding Experiments
with Pigs 415
Eelenmeyee (E.) and A. v. Planta-Reichb>'ati. Activity of Bees . . 415
Cyon (E. de) and G. le Box. Pliysiological Action of Borax . . . 415
Rosenthal (I.). Specific Heat of Animal Tissues ..... 483
Maecet (VV.). Function of Respiration at Different Altitudes . . . 483
Schmidt (A.). Digestion of Albuminoids 484
Wolff (E. v.) and others. Digestion in Slieep ...... 484
Weiske (H.) and others. Nutritive Value of Asparagine .... 485
Pavy (F. W.). Physiology of Sugar in Relation to tlie Blood . . . 486
Kellnee (O.). Muscular Activity and Waste of Tissue .... 486
Fleischmann (W.) and P. Vieth. Observations on the Milk of a Large
Herd of Cows 487
KiECHNEE (W. J.) and P. Dtr Roi. Influence of Ground Nuts on the Pro-
duction of Milk 487
Weiske (H.). Lifluence of Shearing on Yield of Milk .... 487
Emmeeich (R.). Influence of Impure Water on Health . . . . 488
Gautuiee (A.). Presence of Copper in Food ...... 490
Weigelt. Injury to Fishes by Waste Liquids ...... 490
Pedler (A.) and others. Cobra Poison ....... 490
Weiske (H.) and others. Digestibility and Nutrient Power of Caroba
Beans .............. 563
Kellnee (O.) Quantitative Estimation of Digested Protein . . . 563
Rubnee (M.)- Absorption of Various Alimentary Materials in the Human
Intestinal Canal ........... 563
Adamkiewicz (A.). Interchange of Material in the Animal Organism . 565
Bizio (G.). Distribution of Copper in the Animal Kingdom . . . 565
BiMMEEMANN (E. H.). Changes which Starch undergoes in the Animal
Organism ............ 677
Wolff (E. v.) and others. Feeding Experiments on Swine . . . . 724
Weiske (H.). Assimilation in Sheep of Various Ages . .... 724
Peel (L.). Absorption of Lime Salts ........ 725
Hengefeld (G. I.). Effect of Feeding-cakes on Milk Production . . 725
Eelenmeyee (E.) and Planta-Reichenatj. Activity of Bees . . . 725
CONTEXTS.
XX VU
PAGE
Demaxt (B.). Extractires from Muscle 726
TscHiRWiNSKT (N.). Influence of Glycerol on the Decomposition of Pro-
teids in the Animal Body ......... 817
Lewix (L.). Influence of Grlycerol on Proteid Tissue Change . . . 817
Oppenheim (H.). Influence of the Supply of Water, the Secretion of
Sweat, and Muscular Labour on the Elimination of Nitrogenous Decom-
position Products ........... 818
Setschexow (J.). Respiration under Reduced Pressure .... 903
Beown (H. T.) and J. Heron. Hydrolytie Ferments of the Pancreas and
Small Intestines 003
RuBNER (M.). Nutritive Value of Fluid Meat 904
Bowie (H. C). The Proteid required by the Average Workman . . 905
SiEDAMGROTZKY and V. HoFMEiSTER. Influence of Lactic Acid in Fodder . 905
Seegen (J.) and F. Kratschmeb. Formation of Sugar in the Liver . . 905
ScHiAPPARELLi (C.) and Gr. Peroni. Some Ingredients of Normal Urine . 907
GrEUBER (M.). Influence of Borax on the Decomposition of Albumin in the
Organism ............ 907
Fleischmanx (W.). Influence of Fodder on the Secretion of Milk . . 907
GiES (C). Influence of Arsenic on Animals . ...... 907
Chemistry of Vegetable Physiology and Agriculture.
Keatjs (C.) . Influence of Light on the Growth of Plants
Leeds (A. R.). Action of Ozone on the Colouring-matter of Plants
Borodin (J.). Distribution and Functions of Asparagine in the Vegetable
Kingdom ...........
Rojen (A. E. V.) and Keelage. Mineral Constituents of Hyacinths .
Lamek (.J.) and C. Portele. Experiments with Various Sorts of Beet
HiJNEFELD, E. Reichardt, and Hertz. Formation of Nitric Acid in the
Soil
Storer (F. H.) and S. Lewis. Calcium Carbonate in Water filtered through
Dry SoU
Friedburg. MiU- waste for Manure
KoNiG (J.). Analyses of Marl
Wagner (P.). Influence of the Physical Condition of Superphosphate on
its Value. ...........
Storer (F. H.) and J. A. Henshaw. The Shells of Crabs, Oysters
Mussels, &c., as Manure .........
MlQTTEL (P.). Fermentation accompanied by Formation of Hydrogen Sul
phide ............
MlQUEL (P.).
ROTONDI (E.)
MOSER (J.).
Bacillus Urece ........
and A. Ghizzoni. Researches on the Bleeding of Vines
Composition of the Kernels and Husks of the Seed of Gledit
schia rjlahra ...........
RoTONDi (E.). Ash of Different Parts of the Vine ....
KlNCH (E.). Agricultural Chemistry in Japan .....
Ibled (D.). Method of Selecting Beet for Seeding ....
Haberlandt (G.). Relation of the Colour of Clover Seed to its Value
Ammon (G.). Absorptive Power of Soil-constituents for Gases
Wagner (P.) and W. Rohn. Experiments on the Manuring of Barley
Jenssen (C.) . Manuring Experiments with Oats ....
ViBRANS (O.). Manuring of Beetroot
BoDENBENDEE (H.). Manuring of Beetroot
Keauch (C). Unorganised Ferments in Plants .....
Nencki (M.) and F. ."^chaffee. Chemical Composition of Bacteria .
Peteemann (A.). Germinating Power of Beetroot Seeds
Canto (E. da). Influence of Smoke on the Development of Blossoms .
Godlewski (E.). Causes of the Change in the Form of Etiolated Plants
HowAED (D.). Notes on Cinchona Bark ......
57
58
58
58
59
59
59
60
60
60
60
132
133
133
133
133
133
134
134
134
135
136
137
137
175
176
177
177
177
177
XXVIU
COXTENTS.
ipkin
Hanamann (J.). Helation of Yield of Beefc to Eain and Sunshine
PoKTELE (C). Eesearclies on the Eipening of Grapes and Fruits
Latjenstein. Depreciation of Barley by Overgrowth .
Wagner (P.) and W. Rohn. On the Quantities of Acid and Sugar in
Grapes cut at various Stages of their G-rowth
TsCHAPLOWiTZ (F.) . Eipening of Apples after Gathering .
Schulze (E.) and J. Bakbieki. Decomposition of Albuminoids in Pi
Sprouts ...........
Haberlandt (F.) . The Most Advantageous Method of Sowing Corn
Schenk-Bauhof. Proper Thickness and Depth to Sow Corn
WoLFFHiJGEL (G-.). Amount of Carbonic' Anhydride in Shingle .
ScHWARZ (A. v.). Peaty Soils . .......
Grandeau (L.) . Composition of Ma/ize . .
Deininger (J.). New Plant for Fodder .....
WiTTELSHOFER (P.). Analysis of Materials used for Fodder
MosER (J.). Feeding Value of some Manufacturers' Waste.
Haez (C. O.). Certain Sorts of Pumpkin ....
Weiske (H.), M. Schrodt, and B. Dehmel. Influence of Fodder on the
Quantity and Quality of Milk Fat .....
VoELCKER (A.). Four-yearly Eotation of Crops ....
Carsten (H. J.). Manuring of Oats on Fen Lands
Pasqualini (A.). Effect of G-ypsum on the Quantity and Quality of Clover
Crops
MosER (J.). Manuring of Sugar Beet .....
Beiem (H.). Manuring of Beet ..... . .
Jamieson (T.). Influence of Soluble and Insoluble ' Phosphates as Manure
for Turnips ...........
Paulsen (VV.). Action of Difi'erent Manures on the Yield of Potatoes.
Cochin (D.). Aleohohc Fermentation .......
Beethelot. Eemarks on Cochin's Note relating to Alcoholic Fermentation
Cochin (D.). Alcoholic Feimientation : Eeply to Berthelot .
Gunning (J. W.). Vital Power of Schizomycetes in Absence of Oxygen
SCHLOESING (V.) and A. Muntz. Nitrification . . . . ' .
Davy (E. W.). Nitrification
Kellner (O.). Albumin and Amido-compounds in Plants .
GiGLiOLi (I.). Eesistance of Seeds to the Prolonged Action of Chemical
Agents ...........
Moritz (J.). Mode of Action of Sulphur as a Eemedy against Vine Disease
Weber (E.). Analysis of SoUs from the Variegated Sandstone Formation
Tieohem (P. T.). The Butyric Ferment in the Carboniferous Period .
WuRM (E.). Formation of Vinegar by Bacteria .....
Baranetzky (J.) . Starch-altering Ferments in Plants
Cienkowski (L.) . Organisms in Beet Sap
Marie-Datt. Carbonic Acid in the Air
Freyberg (E.). Eespirative Power of Marsh and Water Plants .
BuRGERSTEiN (A.). Influence of Nutritive Material on the Transpiration of
Plants
Heckel (E.). Influence of Salicylic Acid and other Bodies on Germina
tion
Detmer (W.). Passage of Plant-material in Seedlings .
Schroder (J.). Coui-se of the Nitrogen and Mineral Constituents in the
Development of the Early Shoots .
Deheeain (P.) and Nantier. Development of Oats
Corenwinder (B.) and G. Contamine. Influence of the Leaves on the
Production of Sugar in the Beet ....
PoRTELE (C). Eipening of Grapes ....
Faesky (F.). Growth of Plants in Artificial Solutions .
Nageli (C. v.) and 0. Loew
Emmerling (A.). Formation of Vegetable Albumin .
Schulze (E.) and J. Barbieri. Leucine and Tyrosine in Potatoes
Formation of Fat in the Growth of Fungi
COXTEXTS.
XXIX
Amount of Oil in Grass Seeds and its Relation to tlieir
Beeiholz (H.).
Germination .........
CoRENWixuER (B.) and G. Contamine. Analysis of Parsnips
HiLGER (A.). Mineral Constituents of the Riesling Grape
Schroder (J.). Mineral Constituents of Fir and Bireli
Thoms (G.). Ash Analyses .......
Thoms (G.). Analyses of Feeding Stuffs ....
Kei.lxer rO.). S])ent Hops as Fodder ....
Sivers (M. v.). Xitrogeii in Turf .....
MosER (J.). On various Manures .....
BlLCK (F.). Manuring Experiments .....
Petermann (A.). Composition of Fowls' Dung .
VoLCKER (A.). Bat-guano from various Soui-ces .
ScHCLZ (H. C.). A\kii\oid oi Lupinns Iitteus
Increase of Dry Matter in Several Agricultural Plants during Growth
MoissAN (H.). Absorption of Oxygen and Expiration of Carbonic- Anhydride
by Plants
Schroder (J.)
ROTONDI (E.)
Tines
Reinke (J.) and G. Berthold. Dry and Wet Rot in Potatoes
Harz (C. O.). Comparative Investigation of Hops
Supposed Presence of Catechol in Plants
Influence of Manures on the Combustibility of Tobacco
Combustibility of and Amount of Chlorine in Manured
. Constitution of Frozen Beech-leaves .
and A. Galimberti. Composition of Leaves of Dis
eased
Plants
which grow on
Preusse (C).
Cantoni (G.).
Mafee (A.).
Tobacco ............
UiiiK (F.). Application of Natural Products as Manures .
Koth (D. v.). Determination of the Chemical Peculiarities of Soils and
Manures requisite for them ; and on the Action of Soluble and Reduced
Pliosphates . .......
Goessmaxx (C. a.). Manuring of Sugar-beet in America
Blaxkeshorx (A.). Raising Tines from Seed
Muller-Thurgau (H.). Locality of Albumin Secretion in
ScHULZE (E.). Decomposition of Albuminoids in Plants
Desbaeres (L.). Passage of Nutritive Materials in Plants
Hampel (L.) . Amount of Dew on Plants
RiMPAr (\V.). Fertilisation of Rye ....
WoLLNT (E.). Result of Drying Seeds
DiEULAFAiT. Normal Presence of Copper ui the Plants
Primordial Rocks ......
Pagnoul (A.). Formation of Nitrates in Sugar Beets
Baeral (J. A.). Nitrates in Sugar Beets
Wagnee (P.). Beetroot
Batjdeimoxt (A.). Researches on Beetroot .
Bodenbendee (H.) and Ihl£e. Composition of Ash of two Kinds of Beet
Seed
Hasenclevee (R). Effect of Acid Gases on Tegetation
ScHEODEB (J.). Injury to Tegetation caused by Acid Gases
EoNiG (J.). Injurious Effect of Industrial Effluent Water and of Gases on
Soils and Plants ..........
WOLLNT (E.). Grass Mowing
Speee. Relation of the Grasses of Meadows and Pastures . .
Keefslee (U.) and others. Digestibility of Steamed Hay .
GoDEFEOY (J.) and others. Pei'manent Pasture ; a Substitute for Clover
Weiske (H.) and others. Composition of Red Clover and Maize .
HoFFMEiSTEE (W.). 'Nutritive Yulue oi the Slodea ca/iadetisis .
RiTTEE. Cotton-seed Cake as Fodder .......
RoDiczKY (E. v.). Culture of the Lentil Tetch
Ulbricht (R.). Seeds of the Corn-cockle as Fodder and Distilling Material
Weisee (H.) and others. Digestibility and Nutritive Talue of the Sojabean
page
342
3i2
343
343
343
343
344
344
344
345
345
345
416
416
416
416
416
416
417
417
417
417
417
418
418
418
492
493
493
493
493
493
494
494
495
495
495
496
496
496
497
498
498
498
499
499
500
500
500
501
501
XXX
CONTENTS.
Fehiatt. Flesh-meal as Fodder for Milch Cows .....
Maercker (M.) and E. Wein. Spent Hops as Fodder for Cattle
Weiske (H.) and others. Spent Hops as Fodder .....
Samee. Caeao-rind as Fodder for Calves ......
Influence of the Potato Blossom on the Amount of Produce .
Behrend (P.) and A. Morgen. Growth of Beets ....
Hanamann (J.). Planting of Sugar Beets
ScHNORRENPFEiL (F.). Eesults with Stall-feeding of Sheep
Lemberg (J.). Decomposition of Silicates ......
Moller (J.). Free Carbonic Anhydride in Soils .....
Emmerlino (A.) and E. Wagner. Clover Sickness ....
Lattche. Manures for Cabbages and Fruit Trees .....
Schroder (.J.). Amount of ifitrogen in Forest Trees and in the Under
Litter of Leaves ..........
Nerlinger (T.). Employment of Peat as Manure ....
NiEDERSTADT (B. C. ). Guano from the Island of Ichaboe .
Hanamann (J.). Natural Phosphates and their Value in Agriculture .
BuLOW (v.). Experiments with Artificial Manures ....
Drechsler (G.). Chili Potash Saltpetre
ScHWERiN-PuTZAE. Manuring Experiments with Superphosphate and Chil
Saltpetre ...........
Selmi (A.) and others. Lupine Seeds as a Manure ....
RoTONDi (E.) and A. Galimberti. Action of Various Manures on tht
Composition of the Must ........
Thaer (A.). Manuring Experiments on Wheat and Eye ...
Bkenning. Manuring of Oats ........
Hanamamn (J.). Manuring of Beetroot ......
Hess and L. Hampel. Effect of Manures on Growth of Larches and
Pines .............
Gurnand (M.). Light, Shade, and Soil, studied in their Influence on the
Growth of Forest Trees .........
Pott (E,). Growth of Legumes ........
FuNARO (A.). Formation of Fatty Matter and Eipening of the Olive .
HoLDEFLEiss (F.). Amount of Albuminoids in Potatoes
Pelet (H.). Existence of Ammonia in Vegetables ....
Eaumer (E. v.) and C. Kelleemakn. Lime in Plant Life .
Pellet (H.). Eolation between the Sugar and the Mineral and Nitrogenous
Matters in Normal Beetroot and in Beetroot run to Seed
EiDOLFi (L.). Manuring of Field Beans
Leclerc (M.) and M. Moeeau. Experiments with Manures
JouLiE (H.) and others. Eeduction of Superphosphates, and the Be
haviour of Phosphoric Acid in Soils ......
Petermann (A.) and others'. Agricidtural Value of Eeduced and Insoluble
Phosphates . . . . ' .
ZoEBL (A.). Sulphurous Acid as a Eemedy for Bunt in Wheat .
VoELCKER (A.). Comparative Value of Soluble and Insoluble Phosphates
VoELCKER (A.). Analyses of Manures and of Cattle Food? .
CoHN (F.) and B. Mendelshon. Influence of the Galvanic Current on
Bacteria . . . . . . . ... . . ' .
Wernich. Effect of Putrefactive Changes on Bacteria
Miflet. Bacteria in the Atmosphere .......
Miguel (P.). Atmos])heric Bacteria . . . . .
BoBCHUT. Digestive Ferment of the Juice of the Fig Tree .
Delbruck (M.) and others. Chemical Changes in Nitrogenous Substances
during Fermentation .........
Haberlandt (G.). Seed-production of Eed Clover ....
PuTTE (P.). Germination of Beet Seeds ......
Kellner (O.). Quantities of Amides and Albuminoids in Green Plants
Decomposition of Nitric Acid and Ammonia in Plants .
Macagno (H.). Tannin of Sumach Leaves
COXTENTS.
XXXI
Mdllek (A.). Oxalic Acid in Beet Leaves ......
Pellet (H.). Distribution of Potassium Nitrate in the Beet
Flijckiger. Effect of Cold on Cherry Laurel
KoxiG (J.). Nutritive Value of Fruits ......
HoHNBERGER. Influence of Steaming on the Digestibility of Hay
Pellet (H.) and Ch. de Levandiek. Beet Residues as Fodder .
Makck (G.). Damage to t'eed Peas by Weevil
WiLDT (E.) and others. Si/mphi/fum asperrimum as a Fodder
Flicke (P.) and L. Graxdeau. Chemical Examination of Ligneous Papilio
nacecB ............
LADrHEAr (A.). Cultivation of Sugar Beet
Weix (E.). Cultivation of the Yellow Lupine .....
"WoLLNY (E.). Fallowing
Hatexstein (G.). Behaviour of Natural Soils and of Plants growing in
them towards Water .........
Orth. Absorption of Ammonia by the Soil ......
Fautrat (M.). Influence of Forests on the Eainfall ....
Matthief (A.). Comparative Eainfall on Woods and Fields
Kleix. Injurious Efl'ect of Peat Water on Meadows ....
Pagel (A.) and H. Meyer. Manure Experiments with Eye, Wheat, and
Oats
Meyer. Bone-meal as a Manure for Potatoes .....
Petekmanx. Eeport on the Agricidtural Value of the so-called " Eetro
grade Phosphoric Acid" .........
Heidex (E.). Nitrogen Manure for Oats ......
PLrcHET. Chili Saltpetre for Beets
Marcker pL). Manuring Beets with Sodium Nitrat«
Stecher. Thirty-eighth Year of a Farm witbout Stable Manure .
Wqlff (E. t.). Beet-sugar Befuse as Manure .....
Hansex (E. C.). Influence of Air on Fermentation ....
FiTZ (A.). Schizomycetic Fermentation. Part VI ... .
Behrexd (P.) and A. Morgex. Influence of Fermentation on the Nit
genous Constituents of Potato-mash ......
Herzex (A.). Influence of Boric Acid in Aijetous Fermentation .
Kegel (E.). Nutrition of the Drosera ......
Davy (il.) and others. Loss of Dried Substance in Plants during Eipen
CzuBATA (H.). Chemical Clianges in Frozen and Eotten Potatoes
Weiske (H.) and others. Digestibility and Nutritive Value of Acorns
WiLDT (E.). Methods Proposed for Cleansing Lupines
ViLMOHix (L.). Cultivation of Beetroot
Rexk (F.). Permeability of Soil for Air
WoLLXY (E.). Influence of Shade on the Amount of Carbonic Anhydride
in the Air of the Soil
Difference between Loam and Clay .......
Riegler (W.). Permeation of Vegetable Matter by Water .
Marcker (M.). Tlie Best Mode of Applying Artificial Manure to Pota
toes ............
^Iayer (A.). Influence of Oxygen on Fermentation ....
Uaxsex (E. C). Lower Organisms in the Air .....
Leeds (A. R.). Action of Light and Darkness on Tannin Solutions
TlEGHEir (P. Y.). Gelatinous Matter in Beets
Storer (J. H.). Fermentation Theorj' of Nitrification ...
Naudin (C). Influence of Atmospheric Electricity on the Growth of
Plants
Weber (C. A.). Energy of Assimilation in Plants ....
Ff.AHAULT (C). Formation of Chlorophyll in the Dark
Stohr (A.). Chlorophyll in the Epidermis of Foliage of Phanerogams .
HoFFMAXN (H.). Influence of Annual Temperature on Change of Colour in
Leaves .............
ro-
PAGK
733
733
733
733
734
734
734
735
735
736
736
736
737
737
737
737
738
738
739
739
741
741
741
741
742
819
819
819
819
820
820
820
820
820
821
821
823
823
823
824
908
908
908
908
909
909
910
910
910
910
XXXll
CONTENTS.
Jamieson (J.). Ereathing of Plants and Animals ....
WoRTMANN (J.). Intramolecular Respiration of Plants
ScHTTBELER. Influence of Continuous Sunlight on Plants
BoHM (J.). Functions of Vegetable Duets
Vesque (J.). Influence of Salts on the Absorption of Water by Eoots
Geleznow (N.). Quantity and Distribution of Water in Trees .
Nordlinger. Sap of Trees and Specific (Iravity of their Wood .
Pellet (H.) . Relation between the Starch, Phosphoi'ic Acid, and Mineral
Constituents of the Potato ........
Yan der Ploeg (B. J.). Calcium Oxalate in Plants ....
G-tttzeit. Presence of Alcohols and Paraffins in Plants
RicciARDi (L.). Composition of the Ashes of the Trunk, Leaves, and Fruit
of the Orange and Mandarin Orange ......
Edzardi (C). Analyses of the Ash of Certain Spice Seed's .
Endemann (H.) and Gr. A. Prochazka. Sweet Potatoes
Maecker (M.). Influence of the Manure on Potato Disease, and the Starch
in Potatoes ...........
Rabuteaf (C). Influence of Ethyl Iodide on Germination
DiRCKS (W.). Analyses of Norwegian Hay ......
Wolff (E.) and others. Digestibility of Oat-straw, Hay, and Pea-haulms
Keocker (F.). Disease in Sheep caused by Lupines ....
KiJHN (J.). Disease in Sheep caused by Lxipines .....
Janecek (G.). Composition of Two Varieties of Turnips
Czubata (H.). Value of Acorns as Fodder ......
Ladttreau (A.). Cultivation of Svigar-beets . .....
Wagner (P.) and W. Rohn. Potato Culture
WoLLNT (E.) and others. Damage to Pea and Bean Seeds by Weevil .
MiJLLER (K.). Cultivation of Beet Seeds
Pellet (H.) and M. Liebschutz. Analysis of Beet Seed .
Reichardt (E.). Investigation of the Composition of Soil from a Grave
yard ............
Fleischer (M.). Influence of the Soil on the Tannin of Oak -bark
Pellet (H.). Ash of Beet
EoGEN (A. E. v.). Experiments on the Growth of Hyacinths
Paetow. Sowing Broadcast or in Drills ......
Wagner (P.) and G. Drechsler. Manuring Experiments .
Genat (P.). Manuring Experiments with Wheat ....
AValdner and Staubesand. Manuring Experiments on Moorland
Maeckes (M.). Manuring Experiments with Sugar-beet
Analytical Chemistry.
Siebold (L.). Specific Gravity of liiquids ......
Landolph (F.). Analysis of Organic Compounds containing Fluorine and
Boron ............
Beilstein (F.) and L. Jawein. Direct Separation of Manganese from Iron
Pellet (H.) . Estimation of Organic Nitrogen in Natural Waters
Phipson (T. L.). Notes on some Analyses of Waiters- ....
Casamajor (P.). Rapid Estimation of Pure Sugar in Raw and Refined Com
mercial Sugars
SOXHLET (F.)
Solution
SCHIFF (H).
Claisen (L.).
Fletcher (F
Bell (J. C
and others. The Behaviour of Various Sugars with Fehling'
Estimation of Acetyl by means of Magnesia .
Test for Phenylglyoxylic Acid
W.). Citrate of Iron and Quinine .
Iodic Acid as a Test for Morpliine .
Tatlock (R. R.). Nitric Nitrogen in Guano
FeaUDE (G.). Perchloric Acid as a Test for Alkolo'ids .
Wignee (G. W.) . Koettstorfer's Process fur Butter Analysis
CONTENTS.
XXX 111
with
WiGNEB (G. W.). Coefficient of Expansion of Butter, Lard, Fats, &c.
Haoee (H.)- Specific Gravities of Fats, Eesins, &c.
SiEBOLD (L.). Testing Drugs
SCHULTZE (W.). Testing Malt
Fischer (F.)- Apparatus for Estimating Oxygen in the Atmosphere
TiESiAXX (F.) and C. Pbecsse. Quantitative Estimation of Oxygen dis
solved in Water .........
Mi;LLEB (A.). Water Analysis .......
CoLsox (A.). Estimation of Sulphur in Natui-al Sulphides .
PiCClXl (A.). Testing for Nitric Acid in Presence of Nitrous Acid
Wein (E.), L. Rosch, and J. LEHiiAxy. Analysis of Superphosphates
Wein (E.). Superphosphates from Pure Tricaleium Phosphate .
YOLHAKD (J.). Estimation and Separation of Manganese .
WiCHELHAFS (H.), K. EissFELD, and K. Stammeb. Experiments
Scheibler's Method of Analysing Raw Sugar ....
BiTTMAN (C). Estimation of Sugar in Beet Juice
Keeuslee (M.). Method for the Continuous Measurement of the Intensity
of Daylight and of its Apphcation to Physiologico-botanical Investiga
tions . . . . . . . . . .
WiLLM (T.). Estimation of Chromium
ZiMMERMANX (C). Separation of the Heavy Metals of the Ammonium
Sulphide Group .........
Adamec (J.) and E. Klose. New Method of Estimating the Air Space in
Seeds and Fruits ..........
HAifAiiAxy (T.). Composition of Bohemian Beer-wort determined by
Chemico-optical Processes .......
Salomon (F.). Determination of the Acid in Sugar of Lead and in Lead
Tinegar ...........
Analysis of Cinchona Barks ........
Sestisi (F.). Estimation of Albuminoids in Fodders .
BoucHrT (E.). Enumeration of Fat Globules in Milk as a Test .
Nesslke (J.). Foreign Colouring Matters in Eed Wine
Lepel (F.). Adulteration of Wine ......
Peescott (A. B.). Morphiometric Processes for Opium
Prescott (A. B.). Valuation of Tincture of Opium ,
AiLEX (A. H.). Analytical Examination of Tinctures .
LcCKOw (C). Application of the Galvanic Current to Analytical Chemistry
NoLTE (R.). Estimation of Chlorine in Grain and in Forage
DoNATH (E.). Method for the Detection and Estimation of Iodine in pre
sence of Chlorine and Bromine .......
Allaey (E.). Uitration of Iodine by Stable Standard Solutions .
Deeome (P.). Separation of Phosphoric Acid from Iron and Alumina.
CoBENWixDER (B.) and G. Contamine. New Process of Analysing Com
mercial Potash ..........
Papasogli (G.) . Detection of Cobalt and Nickel in presence of each other
DiEVELL (P.). New Method of separating Nickel from Cobalt
DoNATH (E.). Estimation of Cobalt and Nickel
ScHOFFEL (R.). Estimation of Chromium and Tungsten in Steel and in their
Alloys with Iron .........
Jewett (J.). Influence of Acetic Acid on the Separation of Iron as Basic
Acetate from Manganese, Zinc, Cobalt, and Nickel ....
Beilsteix and Jaweix. New Method of separating Manganese and Iron
Keex (S.). Estimation of Carbon in Cast Steel .....
Dewey (F. P.). Clarke's Method for the Separation of Tin from Arsenic
and Antimony. ..........
TiEiiAXX (F.) and C. Preusse. Methods for Indicating the presence
Organic Matter in Water ........
Nickels (B.). Use of the Polariscope in testing Crude Anthraquinone for
Anthracene ..........
AiiATO (D.) and P. Figueea. Gasometric Methods .
of
PAGB
70
70
71
71
137
137
139
139
139
140
141
141
144
144
188
188
188
189
189
189
190
190
191
191
191
191
193
194
282
285
285
285
286
286
286
287
287
288
289
289
289
289
290
292
345
VOL. XXXVIII.
XXXIV
CONTENTS.
PAGE
Trachsel (E.). Extension of Dietrich's Table for the Calculation of Nitro
gen
WiGNEE {Or. W.). Determination of Carbonic Acid in Carbonates
RossLEE (C). Volumetric Estimation of Manganese and Cobalt .
DoNATH (E.). Decomposition of Arsenic and Antimony Compounds .
Spica (P.). Process for Simultaneously Detecting Nitrogen, Sulphur, and
Chlorine in Organic Compounds . .
Peehn (A.) and E. Hoenbergee. Examination of the Will and Varrentrap
Methods of Nitrogen Determination
Krefsler (W.)- Estimation of Nitrogen in Albuminoids .
TsCHAPLOWiTZ (F.). Determination of Dry Substances by the Use of
Alcohol . . . . • . • • • • • _ •
Weigeet (L.). Detection of Salicylic Acid in Wine and in Fruit-juices
Schmidt (F.) and others. Determination of tlie Fat in Milk by the Lacto
butyrometer ...........
Schulze (H.), E. Feuhling, and J. Schulz. Quality of Milk .
Dehmel (B.). Estimation of Albuminoids in Vegetable Substances
PoLLACCi (E.). New Method of Ascertaining the Eipeness of Grapes .
Alien (A. H.). Examination of Coffee ......
PooLEY (T. A.). Analysis and Composition of English Beers
Keockee. Adidteration of Bone-meal ......
Lepel (F. v.). Behaviour of Fruit-juices with Eeagents
TscHELZAFF. Determination of Nitrogen in Explosive Ethereal Nitrates
SoMMEEKORN (H.) . Determination of the Specifi'- Gravity of Liquids .
Eos TEE (G.) New Method of Determining the Fusing Points of Organic
Substances , . . . . . . . • ...
Kapusstin (M.). Estimation of Carbonic Acid in the Air .
EtTDORFF (F.). Estimation of Aqueous Vapour in the Atmosphere
KoNiG (J.). Estimation of Oxygen dissolved in Water
Natlor (W. A. H.). Volumetric Estimation of Arsenic Acid
HouDART and T. Petit. Valuation of Wine
Eeinecee and G. Meter. Estimation of the Decolorising Power of Animal
Charcoal. ...........
Fischer (F.) . Adulteration and Examination of Food and Drink
Musso (G.) and F. Schmidt. Presence of Sulphuric Aoid in Milk
Orookes (W. G.) and others. Butter Adulteration ....
Petit (A.) Testing of Pepsin .
ScHUNCK (E.) and H. Eoemee. Detection of Ahzarin, Iso- and Flavo
purpurins ; and the Estimation of Alizarin .....
Crafts (J. M.) and F. Meier. Method of Measuring High Temperatures
VoRTMANN (G.). Detection and Estimation of Clilorine in Presence i
Iodine and Bromine .........
TJlbricht (E.). Parkes's Method of Estimating Copper
Lefort (J.). Use of Smithson's Pile for the Detection of Mercury
Mineral Waters ..........
Breon (E.). Separation of Minerals of Greater Density than Quartz,
Means of Fused Mixtures of Lead and Zinc Chloride
Sestini (F.) . Physico-chemical Analysis of Clay Soils
Pellegrini (N.). Physico-Chemical Analysis of Clay Soils
Eeynaud (H.). Estimation of Glycerol in Wine
Battandier. Estimation of Glucose .......
Paty (F. W.). Volumetric Estimation of Sugar by an Ammoniacal Copper
Test, giving Eeduction without Precipitation .....
Siewert. Estimation of Starch in Potatoes ......
Behrend (P.) and others. Estimation of Starch in Potatoes
Fauconnier (A.) . Estimation of Urea ......
Jay. Estimation of Urea in Urine . . .
Cazeneute (P.). Lactic Fermentation
Kellneb (O). Estimation of Non-albuminous Nitr:;gen Compoimds
Plants
346
346
347
348
348
348
350
351
352
352
352
352
352
353
353
354
354
354
419
419
420
420
421
421
421
422
422
423
423
424
424
509
509
510
in
by
510
511
511
511
512
512
512
512
513
513
513
513
513
CONTENTS. XXXV
PAGE
Janke (L.) . Analysis of Milk . . 514
Pbunieb. Adulteration of Coffee with Chicory 514
Nessleb. Determination of Wine Extract 515
Bltth (A. W.) . Determination of Specific Gravity 572
Kbaut (K.). Filter Paper and Filtering 573
Gawalotski (A.). Estimation of Carbonic Anhydride in Gasea . . . 573
Wagnee (A.). Reduction of Carbonic Anhydride to Carbonic Oxide by
Eed-hot Stannous Oxide .......... 574
Wagnee (A.). Formation of Nitric Oxide by Ignition of Nitre . . . 574
Metee (C. F.). Contribution to the Knowledge of Reduced Phosphoric
Acid 574
MoHR (C.) . Tolunietric Determination of Phosphoric Acid by Means of
Uranium in the Presence of Iron ........ 575
BErNNEE. Analysis of ilineral Superphosphates and of " Phosphate Prgci-
pite" 576
Peecht (H.). Volumetric Estimation of Sulphates 576
Peecht (H.). Estimation of Potassium as Platinochloride .... 577
Hasselt (A. v.). Direct Determination of Soda in Potashes . . . 580
Muck (F.). Removal of Large Quantities of Sodium Chloride in Mineral
Analyses ............ 580
KoNiNCK (L.). Action of Fused Alkaline Carbonates on Platinum . . 581
Meeling (G.). Lithium Phosphates 581
Eder (J. M.). Estimation of Ferrous Oxide in Presence of Organic Acids
or Sugar ............ 583
HouzEATJ (A.). Valuation of Pyrites by the Gravivolumetric Method . . 583
Ohl (W.) . Electrolytic Estimation of Cobalt, Nickel, and Copper . . 583
Ltte(F. M.). Blowpipe Assay of Silver-Lead 585
Lux (F.). Volumetric Analysis of Red Lead ...... 585
Baetlett (H. C). Presence of Arsenic in the Atmosphere . . . 585
Haswell (A. E.). Volhard's Permanganate Method of Titrating Manganese 585
Ulbeicht (R.). Must and Wine Analysis 586
ScHULZE (F.). Estimation of Sugar-Beet and the Amount of Sugar the
Roots contain. ........... 586
ScHEiBLER (C.) and others. Scheibler's New Process for the Determination
of Sugar in Beet ........... 587
WOLLF (J.). Separation of Fats from Soaps ...... 587
Medicus (L.) and S. Scherer. Testing of Butter 587
Keauch (C.). Woody Fibre Estimation and its Defects .... 588
ScHULZE (E.). Estimation of Non-Albuminoid Nitrogen in Fodder . . 588
Wagner (R.). Estimation of Protei'ds in Fodder 588
Bbenken (O.). Examination of Mineral Oils 589
Muck (F.). Determination of Ash in Coal 590
Knecht (W.). Vapour-density Determinations in the Vapour of Phos-
phorus Pentasulphide 679
Ludwig (E.). Modification of Zulkowsky's Apparatus for the Volumetric
Estimation of Nitrogen . . . . . . . . . . 679
ScHiFF (H.). Determination of Nitrogen 679
Keaus (F.). Determination of Gold and Silver by Quartation with Cad-
mium ............. 679
Mann (C). Detection of Water in Alcohol and Ether 679
Waetha (V.) . Analysis of Wine 680
Mehu (C). Estimation of Urea by Sodium Hypobromite . . . . 681
Pflijger (E.). Quantitative Estimation of Urea . ..... 681
KiENiEN (P.). Commercial Valuation of Bituminous Rocks and Limestones 682
Remont (A.). Analysis of Heavy Mineral, Resin, and Fatty Oils, and of
Resin in Commercial Oils. Part I . , . . . . . . 683
KoNiGS (E.). Detection of Coal Gas in Earth 684
PiccAED (J.). Modification of V. Meyer's Vapour-density Apparatus . . 743
DuNNiNGTON (F. P.). New Form of Instrument for the Determination of
Specific Gravity . . . . . , . - . . . 743
XXXvi CONTENTS.
PAGE
SoMMEEKOEN (H.). New Metbod of taking the Specific Gravity of
Liquids 743
Wiley (H. W.). Detection of Hydrochloric Acid by Sulphuric Acid and
Potassium Bichromate .......... 744
Beeteand (M. a.). Determination of Actire Oxygen in Barium or Hydrogen
Peroxide 744
Detjtecom (B.). Estimation of Sulphur in Pyrites ..... 744
Geossmann (J.). Alkalimetric Determination of Sulphates .... 744
BocHOLL (H.). Separation of Silicic Anhydi-ide in the Analysis of Lime-
stones, Iron Ores, and other Minerals ....... 745
Macteae (J.) . Estimation of Nitrous Compounds in the Manufacture of Sul-
phuric Acid . 745
Davis (G. E.). Direct Method of Testing Vitriol Exits for Nitrogen Com-
pounds ............. 746
Eoss (W. A.). New Blowpipe Test for Phosphoric Acid .... 746
Dellfs (H.), Behaviour of Sulphuretted Hydrogen with Salts of the Heavy
Metals 746
ScHiCHT (L.). Electrolytic Determination of Metals ..... 747
Feesenius (H.) and F. Beegmann. Electrolytic Estimation of Silver . . 747
Balling (C). Estimation of Silver in Galena ...... 748
Alexandeowicz (W.). Actual State of tlie Determination of Zinc . . 748
Hutchinson (C. C.). Estimation of Cadmium in Presence of Zinc : Sepa-
ration of Zinc, Cadmium, and Copper ....... 748
Stolba (F.). Volumetric Determination of Cerium ..... 7.49
Paekee (R. H.). Estimation of Ferrous Iodide 749
Allen (A. H.). Presence of Nitrogen in Iron and Steel .... 749
JuTSUM (S. C). Estimation of Total Carbon in Iron and Steel . . . 751
Westmoreland (J. W.) . Estimation of Carbon in Steel .... 751
Feesenius (H.) and F. Beegmann. Electrolytic Estimation of Nickel and
Cobalt 751
Diehl (W.). Volumetric Estimation of Lead 752
Boeke (T. D.). Detection and Estimation of Arsenic ..... 752
Theesh (J. C). Detection of Bismuth 752
Ktihaea (M.). Method for Estimating Bismuth Volumetrically . . . 753
ZuLKOWSKY (K.). Modification of Dumas' Method for Estimating Ni-
trogen ... 753
Paesons (H. B.). Proximate Analyses of Plants 754
Nickels (B.). Use of the Spectroscope in Discriminating Anthracenes . 757
Lenz (W.). Estimation of Glycerol 757
Casamajoe (P.). Detection of Starch-sugar mechanically mixed with Re-
fined Cane-sugar ........... 758
Casamajoe (P.). Action of Bone-black on Sugar Solutions . . . . 758
SoxHLET (F.). Behaviourof Various Sugars with Alkaline, Copper, and Mer-
cury Solutions ........... 758
Cupric Test Pellets for Sugars ......... 761
Keattch (C). Report on the Methods of Estimating Cellulose, and on their
Defects 761
ViETH (P.). Estimation of Fat in Milk .761
Becke (von deb). Saponification of Fats . . ' . . . . . 762
Wagnee (P.). Estimation of Fat in Fodder 762
HiESCHSOHN (E.). Detection of Wax . 763
Tatteesall (T.) Tests for Alkaloids 763
Theesh (J. C). Determination of the Alkaloids 763
Keen. Estimation of Amido-compounds ....... 764
ScHTJLZE (E.). Estimation of Albuminoids and Non-albuminoidal Nitrogen-
compoimds in various kinds of Fodder ....... 764
ZoLLEE (P.). Xanthic Acid as a Precipitant for Albumin .... 765
Meyeb (L.). Meyer's Vapour-density Determinations ..... 824
Schlickum (O.). New Alkalimetrical Method for Estimating Phosphoric
Acid . . . . . .824
CONTENTS.
XXXVll
PAGE
Geupe (A.) and B. ToLLENS. Action of Ammonium Citrate on Phos-
phates 825
Beilstein (F.) and L. Jaweijt. Valuation of Zinc and Ziiic-dust . . 826
MuLLEE (A.). Valuation of Copper for Roofing ...... 826
Kramer (Gr.). Quantitative Determination of Acetone in Methyl Alcohol . 826
Fkicklinger (H.). Estimation of Starch in Sausages . .... 826
Masixg (E.). Comparative Examination of the Most Important Kinds of
Commercial Gum Arabic ......... 827
Oh5I (B.). Observations on Milk 828
Werkowitsch (C.) and v. Klexze. Taking Samples of Milk . . . 828
Marchaxd (E.). Analvsis of Milk 828
VOGEL (H.). Analysis of Milk . . . . . .' . . .828
Meissl (E.). Analysis of Butter . ........ 828
Armsbt H. p.). Estimation of Albumin ....... 829
VuLPius. Detection of Paralbumin ........ 829
G-AWALOWSKi (A.). Determination of Sap in Beet ..... 829
Mylius (E.). Opium Testing 829
Waetha (V.). Method for Determining the Temporary Hardness of Water 923
KoNiG (A.). Estimation of Retrograde Phosphoric Acid by Ammonium
Citrate 924
.ExDEMAXy (H.) and G. A. Peochazka. Standard Soda Solution . . 924
E>'DEMA>">' (H.) and G. A. Peochazka. Detection of Copper . . . 924
A Lecture Experiment ........... 924
NiCKELLS (B.). Detection of Cotton-seed Oil in OUve OU .... 925
Du Eoi (P.) and Kibchxee. Stall Sampling in Milk Analysis . . . 925
Beheend and others. Milk Analysis ........ 925
Weix (E.). Condensed Milk 926
ViTALi (D.). On Blood Stains 926
Andeee (A.). Colouring Matter of Grapes and Bilberries, and the Artificial
Colouring of Red Wines . 927
Gbete (E. A.). Determination of Wine-extract ...... 928
Lipps (J. S.). Malt Examination . 929
HiMLT (C). Detection of Oiled Wheat 929
Technical Chemistry.
Abnet (W. W.). Production of Photographs exhibiting Natural Colours . 72
Than (C. t.). Action of Phenol Vapour on Organic Matter at High Tem-
peratures ............ 72
Siebee (N.). Antiseptic Action of Acids 72
Bovet (V.). Antiseptic Action of Pyrogallol 73
Post (J.). Spontaneous Oxidation of Manganous Oxide with reference to
the Manganese Recovery Process ........ 73
Keen (S.). Some Analyses of Iron 73
Blaie (T.). Separation of Phosphorus from Iron . ..... 74
Leeds (A. R.). Bleaching Sugar Syrups by Ozone ..... 74
KiBCHXEE (VV.) and others. Experiments on Creaming .... 75
WiNKEL. Experiments on Churning ........ 75
HASSEXXAiiP (H.). A New Method of preparing Methyl-violet ... 75
Wolff (J.). Transferring Lightfoot Black from one Fibre to Another . 75
Wolff (J.). Aniline-blacks 76
Haetdegen (A.). Production of the Red Colour in Salting Meat . . 80
FiscHEE (F.). Burning of Fuel in House Stoves 145
FuNAEO (A.). Salts obtained from the Mother-liquors of the Volterra
Brine Springs ..... ...... 146
Feexch (A.). Lead Fume, and a New Process of Fume Condensing . . 146
Klebs (E.). Preservation of Milk 148
Maekl (A.). Composition of " Grains " from Malt 148
Wetzig (B.). Recent Improvements in the Iodine Industry . . . 195
c 2
XXXVlll
CONTENTS.
es of
LiEBiG (M.). Introduction o£ Nitric Acid into the Sulphuric Acid Chambers
along with the Steam ........
Clermont (P. de) and J. Frommel. Observations on Sulphur-baths
KossLER (C). Use of Copper Phosphide in the Kefining of Copper
Peteemann (A.). On Belgian Phosphorites ....
On Cement ...........
BiRNBATTM (K.). Pecviliar Changes of Gas-pipcs . . . .
Eeichardt (E.). Action of Water on Lead Piping
Yenables (F. P.). Tungsten-Manganese Bronze .
Horler (H.). Petroleum
Negri (A. de). Improvement of Italian Tobacco by permeating the Leaves
■nith the Juice of Exotic Tobacco ......
Blaneenhorn (A.) and Othei-s. Preparation of Wine
Singer (M.). Bleaching of Jute
Krieger-Delft (J.). Application of Potatoes and Undried Malt in the
Preparation of Yeast ........
Ney (O.). Influence of Light on Beer . .....
KoNiG (J.). Adulteration of Rje Bran with Eice Husks
Young (W. C). Oxidation of Sulphur in Gas on Combustion
Petermann (A.). Norwegian Phosphoi-ite . . . .
VoRSTER (F.). Preparation of Phosphorite
Personne (M.). Constitiition and Properties of Dialysed Iron
Kern (S.) . Bessemer Steel Plates
WiisT. Comparison of Various Milk Coolers ....
EuGLiNG and Others. Machines for Milk Churning
WiGNER (G. W.) and A. Church. Analysis of two Ancient Sampl
Butter
Manom-y's Method of Desugarising Molasses . ....
Behrend (P.) and A. Morgan. Changes Effected by Fermentation in the
Nitrogenous Constituents of Sweet Mash ....
Weigelt (C). Influence of Varying Pressures on Grape Must and Wine
Use of Thiocyanates in Calico Printing
New Coal-tar Colours .........
New Azo-colours ..........
Thresh (J. C). Soluble Essence of Ginger
Hehner (O.). Mineral Constituents of Cinnamon and Cassia
Post (J.). Action of Sulphuric Acid on Phosphates, especially Calcium
Phosphate, in connection with the Manufacture of Superphosphates
HeSz (J. J.). Electro-brass Plating
RoTONDi (E.) and E. Galimbeeti. Composition of Must at different Stages
of Ripeness of the Grape ........
Maumen:^, Cail, and Co. Patent Process for Preparing Inverted Sugar
Bretet (H.). Extracts of Narcotic Plants
Bindschedler. Manufacture of Resorcinol and Colouring-matters derived
from it . . . . ...
Reichl (C). New Class of Phenol Colours
Engel (G.). Action of Infusorial Eaith on Colouring-matters
Heinzerling (C). Mineral Tanning
MoELLER (J.). Linaloes-wood ........
Cech (C. O.). Wild Croatian Hops
MoRAWSKi (T.). Glycerina Cement ......
SoYKA (I.). Rapidity of Germ Diffusion in the Air
Schultz (A.). Antiseptic Action of Salicylic Acid
Wachtel (A. v.). Adulteration of Bone-meal with Phosphorite .
Donath (E.) . Chemical Technological Notes ....
XuHLMANN (F.). Explosion of a Platinum Still used for Concentrating
Sulphuric Acid .........
Weigelt (C). Picking of Grapes
Weigelt (C.) and O. Saare. Time of First Drawing of Wine .
Weigelt (C.) and O. Saare. Cleai-ing Action of Spanish Earth .
PAGE
196
196
197
198
198
198
198
199
199
200
200
200
200
200
200
355
356
356
356
356
357
357
357
357
357
358
358
358
359
359
360
425
425
425
425
425
426
426
427
427
428
428
428
515
515
516
516
517
517
517
517
CONTEXTS.
XXXIX
Mahcker (M.). Density of the Mash
Hammer. Apparatus for Quick Fermentation .....
Marqcaedt (F. W.). Malt Combings a Source of Yeast
Bauer (E.) . On Frothy Fermentation
Delbruck (M.) and others. Surface Fermentation of Potato Mash
Souring of Yeast ..........
MiLLOT (A.) and MAQrESNE. Fermentations Produced in Preparing
Syrups from Beet Juice by Diffusion ......
Fkltz (E.) and H. Briem. Proportion of Sugar to the Weight of Beet
roots ............
MosER (J.) and others. Analyses of Sugar ......
RiCHE (A.) and A. Eemoxt. Bassia Jongifolia .....
Stammer (K.). Valuation of Raw Sugar ......
ScHULZE (E.) and J Baebieri. Suint
KoiBE (H.). Destructive Action of Wood on Salicylic Acid
Moser (J.) and F. Soxhlet. Analyses of Milk
Eder (J.M.). Potassium-ferrous Oxalate and its Use for Dereloping Photo
graphic Bromide of Silver Plates .......
LiEBEN (A.). Analysis of Four Waters for Turin ....
Caxnizzabo (S.). Analysis of Four Waters for Turin
Wallace (W.). A Peculiar Water
Fischer (F.). Evolution of Carbonic Oxide from Ecd-hot Iron Stoves
Mode of Desulphui'ising the Crude Soda-lyes obtained in the Le Blanc Pro
cess ............
GuTZKOW (F.). Preparation of Soda from the Sulphate by Means of Lime
and Sulphur ...........
Wagner (R. v.). Dephosphorisation of Pig-iron ....
Preparation of Nickel ..........
SorxHBT (E. R.). Examination of the Effect of Hard and Soft Water on
the Brewing of Beer .........
GoESSMAXN (C. A.). Amount of Sugar in Sorghum, Maize, and Melons
Kellner (C). Formation of Fat in Ripening Cheese
WoLLXT (E.). Estimation of the Value of Grain ....
Wigner (G. W.). Analysis of Various Tinned Foods
New Coal-tar Colouring Matters ........
HoLDEFLEiss (F.). Some Analyses of Starchmakers' Residizes
NiEDEESTADT (B. C). On Explosivcs for Blasting, especially Nitro
glycerin ............
Xessler (J.). Liquid for the Preservation of Botanical Specimens
MOELLEE (J.). Primavera-wood ........
Eder (J. M.). Rapid Developer for Wet Plate Photographs
Industrial Utilisation of Solar Heat ....
Heating Powers of Coal-gas of Different Qualities
Examination of some County Dubhn Waters
Action of Water an Zinc and Lead ....
Report on the Treatment of Sewage ....
Endemaxn (H.). Boric Acid as a Preservative .....
RiCKMAN and Thompson. Ammonia from the Nitrogen of the Atmosphere
and the Hydrogen of Water ........
Dtckeehoff (R.). On Cement
Redwood (T.). Diffusive Properties of some Preparations of Iron
Tamm (A.). Grases from the Bessemer Converters ....
Keen (S.). Some Remarks on Siemens-Martin Steel ....
"^onath (E.). Contributions to the Metallurgy and Docimacy of Nickel
Priwoznik (E.). Lead Analyses . .......
Braga (J. F.). Analyses of some Hair Dyes .....
Rlemsdijk (A. D. T.). Influence of Superfusion on the MoiecxUar Arrange
ment of Cupelled Gold .........
Cohn6 (S.) and A. H. Allen. Alcohol Tables
Halenke. SpeyerBeer . . .......
mouchot (a.).
Wallace (W.).
Fletcher (J.).
ROCQUES (X.).
Smith (R. A.).
page
517
518
518
518
518
519
519
519
519
520
520
520
520
590
591
591
591
592
592
592
593
593
593
594
594
594
594
595
595
595
596
596
765
765
766
766
766
767
767
767
767
768
769
769
770
772
772
773
773
773
xl
CONTENTS.
PAGE
Langer (T.) and W. Schultze. Carbonic Anhydride in Beer
Mach (E.) and others. Tartar and Tartaric Acid in Must and Wine .
Nesslee (J.) and H. Wachteb. Free Tartaric Acid in Wine
Macagno (I ). Tannin in Wine ........
Scheuree-Kestnee. Digestive Femient produced dui'ing Panification
ScHULZE (W.). Malt Extract and Maltose in Beer-mash
SCHULZE (W.). Moisture in Malting Barley
E.ICHTEE (W.). Adulteration of Malt -combings .
Improvements in the Treatment of Yeast
Delbeijck (M.). Eye as a Material for Pressed Yeast.
Fischer (F.). Investigation of Lubricating Oils .
VoELCKEE (A.). Composition of Skim Milk and Cream from De Laval's
Cream Separator .......
Cellidoid
Saeratj and Vieilie. Eesearches on the Decomposition of
sives .........
Reichardt (E.). Purification of Eefuse Water .
Kehlstadt (A.). Occurrence of Free Sulphur in the Dry Distillation of
Tar
the Eipening of
BlscHOP (K.). Magnesium and Calcivim Compounds as Eefi-actory and De
phosphorising Materials . . . .
Bersch (W.). Enamelled Cast-iron Vessels .
Alcohol from Potatoes ......
Analyses of Tokay Wines .....
Niedeestadt. Analyses of Beer ....
Extraction of Malt ... . .
EiEBE (A.). Experiments on Various Kinds of Yeast
Heixzelmann. Estimation of the Value of the Eaw Material in the Prepa
ration of Yeast .......
Etjgling (W.). Inversion of Beet-sugar for Wine
Collier (P.). Sugar from the Stems of Maize and Sorgho
Desoe (F.). Action of Lime on Solutions of Sugar
Wachtel (A. Y.). Grypsum in the Manufacture of Sugar
Pellet (H.). Certain Properties of Bone Charcoal
Stumpf (M.). Influence of Steaming on Starch .
Notes on Milking ........
Experiments with Milk Cooling Apparatus .
SiEBER (N.). Supposed Conversion of Albumin into Fat in
Eoquefort Cheese .......
Mayer (A.). Examination of Dog Biscuit .
GrEEEAED (A. W.). Tonga
Nichols (W. E.). Deterioration of Library Bindings .
Sloctim (F. L.). Fruit oi Adansonia diffitaia
Schnauss (T.). Silver Bromide Gelatin Emidsion
Vatjtelet (E.). Disinfection and Preservation of Animal Matters, svich as
Blood, for Agi'icultviral Purposes .
Knatjee (VV.) and others. Purification of Water from Sug;
G-ARNIER (J.). Malleable Nickel .
LiNDO (D.). Mercuric Oxide in Grey Powder
Dwight (G. S.). Strong's Water-gas System
Werner (H.). Vaseline ....
Berlien (J. E.). Purification of Spirit
Fiedler (M.). Fermentation of Molasses .
MiLLOT (A.) and Maquenne. Fermentation
Diffusion ......
EoTONDi (E.). Aeration of Must .
Pault (M.). Direct Decomposition of Sugar-lime
Geiesmetee (V.). New Clarifier for Beer
Sachs (F.). Sap-quotient of Beet
LowiG (K.). Preparation of Sugar from Sap of Beetroot
of
Beetroot
certain Explo
ar Works
Sap obtained by
CONTEXTS.
xli
Wachtel (A. v.). Sorghum saccharalum .
Haas. Sugar in Raisins .....
KoHB. Production of Sugar from Starch
Bay (H.). Preservation of Butter
ScHRODT (M.) and P. Dp Ror. 'Wliole Milk Butter compared with Cream
Butter
Engstkom (X.). Experiments with Laval's Separator .
Mater (A.) and F. Clausnitzer. A New Skimming Process
ScHRODT (M.) and C. Du Roi. Experiments with Skimming by the Schwartz
and Holstein Systems ......
RuBNEB (M.). Composition of Curds .
Stohch (V.). Examination of Danisli Export Cheese
Cleansing Lupines
Weighting of Silk ....
" Mogdad " Coffee
Kellxeh (O.).
KoxiGs (E.).
MOELLER (J.).
Eeichabdt (E.). "Wild and Cultivated Raspberries
PAGE
932
932
932
932
932
933
933
934
934
934
935
935
936
936
J OUENAL
OF
THE CHEMICAL SOCIETY.
ABSTEACTS OF CHEMICAL PAPERS PUBLISHED HS
BRITISH AND FOREIGN JOURNALS.
General and Physical Chemistry.
Apparatus for Measuring the Heat of Combustion. Bj
P. FiscHEE {Ber.* 12, 1694—1696).
Chemical Constitution of Amalgams of the Alkali-Metals.
By Berthelot (Compt. rend., 89, 465). — The solution of the potas-
sium-amalgam Hgi4K, in four times its weight of mercury, absorbs
— 8'0 kilogram-degrees of beat, and in twenty times its weight,
— 9'0 kil.-degs. The solution of the sodium-amalgam NaHgi2, in
3 parts of mercury, absorbs — 2"8 kil.-degs., and in 18 parts, — 2'9.
It may thus be concluded that the solution of definite amalgams in
different quantities of mercury, like the solution of salts in water,
absorbs a constant amount of heat. Only one amalgam of potassium
and one of sodium is known in the crystallised form, but from experi-
ments on the varying quantities of heat evolved by the addition of
potassium or of sodium to these amalgams, the author concludes that
there are two more of each.
The progressive addition of potassium to the amalgam Hgj^K,
evolves nearly constant quantities of heat, until an amalgam, 8" 7Hg +
K, is obtained; the heat evolved then varies from 87 to 57, and
remains constant from 5"7 to 2"9. There exist, therefore, two more
amalgams of potassium, the first having the composition HggK, and
evolving in its formation -|- 29'3 kil.-degs. (Hg liquid), or + 27'1
(Hg solid), the last figure being identical with that for Hgo4K. The
formula of the other amalgam, that richest in potassium, cannot be
calculated with any degree of accuracy. The progressive addition of
sodium to the amalgam Hgi2Na, evolves constant quantities of heat
up to 81 Na, and is also constant from 8'1 to 3'5 Na. It is probable,
* The " Berichte der deutscheii chemisclien Gesellschaft " will in f utui-e be ab-
bi-eviated to " Ber."
VOL. XXXVIII. h
2 ABSTRACTS OF CHEMICAL PAPERS.
therefore, that two sodium-amalgams, HgglSra, and Hg7T^a2, may-
exist, c. w. w.
Condition of Alkaline Phosphates in Aqueous Solution.
By J. M. VAN Bremmelen (Ber., 12, 1675 — 1678). — When a solution
of trisodic phosphate is suhjected to dialysis, the soda diffuses rapidly,
and a small quantity of disodio-hydric phosphate is formed in the
dialyser. This experiment shows that trisodic phosphate undergoes
partial dissociation when dissolved in water. Disodio-hydric phos-
phate, dihydro-sodic phosphate, and microcosraic salt do not dissociate
under these circumstances. W. C. W.
Inorganic Chemistry.
Purification of Hydrogen. By A. Lionet {Compt. rend., 89,
440). — Metallic copper removes all the impurities from hydrogen,
except hydrogen phosphide, hydrogen silicide, and hydrocarbons.
Cuprous oxide removes all but hydrogen silicide and the hydrocarbons.
Cupric oxide removes all but the hydrocarbons. The best form of
cupric oxide is that precipitated by potash from a solution of cupric
sulphate, and dried at 100°. C. W. W.
Non-existence of Nascent Hydrogen. By D. Tommasi (Cliem.
Neius, 40, 171). — Reduction of Potassium Perchlorate. — It was found
that when chemically pure potassium perchlorate was submitted to the
action of various reducing agents, giving nascent hydrogen, it did
not undergo reduction, although it is easily transformed into chloride
by the action of a compound which does not set hydrogen free, viz.,
sodium-hydrogen sulphite. The author asks, how can it be explained
that this same perchlorate which undergoes no reduction by means of
nascent hydrogen, as shown by sixteen different reactions, can be
reduced by the hydrogen disengaged by the action of zinc on sodium-
hydrogen sulphite. Although Wurtz declares himself to be in favour
of the nascent state of bodies, it appears to the author unlikely that
when hydrogen is set free by a reaction, it can be in the state of iso-
lated atoms. It is known that copper, even when finely divided, is but
very slightly attacked by hydrochloric acid at the ordinary tempera-
ture, although copper hydride is decomposed very energetically.
" How can this fact be explained," justly remarks Wurtz, in his Atomic
Theory, " if to the affinity of. chlorine for copper be not added the
affinity of the two atoms of hydrogen to form a molecule ?" This
reasoning may be said to apply equally to all the reactions producing
hydrogen ; for example, we know that by the action of hydrochloric
acid on zinc, there neither is nor can be any hydrogen in the state of
isolated atoms, as Wurtz thinks, and the special properties of nascent
hydrogen can be attributed only to the heat which accompanies
hydrogen while it is being set free. It is therefore impossible to con-
clude that hydrogen can be active only in the molecular state, as hun-
IXORGAXIC CHEMISTRY. 3
dreds of examples prove to us fchat in many- cases- it is not tlie mole-
cule of hydrogen that acts, but its atom.
In conclusion it is mentioned that the recent results of Gladstone
and Tribe coincide entirely Avith the above hypothesis. These chemists,
as is known, consider the different allotropic states of hydrogen as
ordinary hych-ogen in different physical conditions. D. B.
Active Condition of Oxygen induced by Nascent Hydrogen.
By F. Hoppe-Setler (Ber., 12, 1551 — 1555). — Every attempt to
explain the vital processes of animals and plants necessarily implies
the assumption of a cause whereby the oxygen is rendered active.
Hydrogen is evolved in the free state only when oxygen is not present ;
and most curiously, in presence of oxygen, nascent hydrogen leads to
energetic oxidation of any oxidisable substance which may happen to
be present. This is specially the case with ferments. The author has
proved the fact by two very striking examples. The alloy of palla-
dium with hydrogen discovered by Gi'aham, when placed in oxygeu,
gives rise to water, owing to combination of the hydrogen of the alloy
with the oxygen. This, of course, is well known, but it is not so well
known that if indigo be present it is decolorised, and then destroyed ;•
that a mixture of starch with potassium iodide is first turned blue, and
that the starch is then completely oxidised ; that ammonia is oxidised
to ammonium nitrite : that benzene is oxidised to phenol; and that
toluene yields benzoic acid. Perhaps a still more remarkable instance
is the oxidation of rock-oil by metallic sodium in presence of the small
quantity of aqueous vapour which comes in contact with it. The pro-
ducts appear to be acetic and caproic acid, and perhaps butyric acid;
and the hard crust which forms round sodium, when it is kept under
rock-oil, is really a product of oxidation of the oil, and in fact may be
made to yield a number of the higher members of the fatty acid series,
It thus appears to be the case that when nascent hydrogen acts on
oxygen, it renders the latter gas also nascent, or at least active.
W. R.
Is Ozone produced during the Atmospheric Oxidation of
Phosphorus? By C. T. Kingzett (Chem. Neivs, 40, 9G). — It is
genei'ally believed that ozone is produced during the atmospheric
oxidation of phosphorns, but the author considers it to be improbable
tliat ozone is formed by the aerial oxidation of phosphorus, considering
the constitution of ozone. Moreover, as peroxide of hydrogen is the
only known agent which resembles ozone in its general properties,
and it is known that hydrogen peroxide is produced in various pro-
cesses of slow oxidation, it would seem likely that it is this substance
which is produced in connection with the oxidation of phosphorus. In
addition to various objections which the author has pointed out to
viewing the active agent produced in the atmospheric oxidation of tur-
pentine as ozone, there are many considerations which lead to the con-
clusion that the active agent is peroxide of hydrogen.
There is no known process of slow oxidation which has been esta-
blished to produce ozone. In various writings on this subject
observers have always relied on properties which are common to ozone
and hydrogen peroxide, and have never instituted volumetric inves-
h 2
4 ABSTRACTS OF CHEMICAL PAPERS.
tio-ations, wliicli are alone sufficient to decide tlie question. On tlie
other hand, several processes of slow oxidation are known, in which
peroxide of hydrogen is formed, as for instance, those relating to ether
and the terpenes ; and it is thonght that as hj-drogen peroxide is formed
in each of these cases as a secondary product, due to the action of water
on a peroxide, so also the oxidation of phosphorus by air gives rise to
an oxide which generates peroxide of hydrogen hy contact with water.
In conclusion, the author mentions ^hat iintil it has been proved
that the active agent produced in the aerial oxidation of phosphorus
'has the volumetric relations of ozone, such very decided statements as
are to be found in chemical text-books should not be made. D. B.
New Method of forming Hyponitrites and Hydroxylamine.
By W. ZOKN (Ber., 12, 1509 — loll). — This consists in the electrolysis
of a nitrite, using mercuiy electrodes. Thorpe describes an experiment
in which he passed a current from platinum electrodes through a solu-
tion of potassium nitrite, and at the negative pole only hydrogen was
evolved. On using mercury electrodes, however, if the current is
stopped as soon as ammonia begins to be evolved, the liquid, after
neutralisation and addition of silver nitrate, gives a copious precipitate
of silver hvponitrite. In this reduction, hydroxylamine is also formed,
and it is necessary to remove it from the solution by precipitation
with mercuric oxide, before adding silver nitrate to precipitate the
hyponitrous acid. Four Bunsen's elements ai'e sufficient for this reac-
tion ; it is recommended as an advantageous method of preparing
hyponitrites. W. R.
Experiments tending to show the Non-elementary Charac-
ter of Phosphorus. By IST, Locktee (Gompt. rend., 89, 51-1). —
Phosphorus heated in a tube with copper gives a gas exhibiting the
spectrum of hydrogen ; heated alone, phosphorus gives no gas. Phos-
phorus at the negative pole of a battery in a tube-apparatus (of which
a drawing is given), gives a large quantity of gas which shows the
specti'um of hydrogen, and is not phosphoretted hydrogen.
c. w. w.
Compounds of Hydracids with Ammonia. By E. J. Mau-
MEXE {Compt. rend., 89, 506). — In the preparation of ammonium
sulphide, the hydrogen sulphide which passes through the first bottle
carries ammonia with it, and colourless crystals are deposited in the
connecting tube. These crystals have the composition NII3.HS. When
they are added to strong aqueous ammonia at 0'^, colourless crystals
are deposited in a few hours having the composition (NH3)3HS.
The author imagines the existence of two series of ammonium-
compounds containing respectively excess of ammonia and excess of
hydrogen sulphide, 1 mol. of one of the constituents being united
with ('!,, — 1) molecules of the other. Members of one series may
unite -with membei'S of the other series, producing compounds like
HS(NH3),5.2[(HS)7XH3] = (HS)i5(lS'H3)n, w^hich might be mistaken
for (NH3)HS.
The compounds of ammonia with hydrochloric acid present analogies
with the above compounds. C. W. W.
INORGANIC CHEMISTEY. 5
Oxygen-acids of Sulphur. By E. J. Maumen^ {Compt. rem!.,
89, 422). — The action of iodine on barium thiosulphate gives rise to
tetratliionic acid, as observed by Fordos and Gelis, bnt seven other
acids shoukl be produced, according to the proportions of iodine and
thiosulphate employed. The acids, H0S2O1 and HoSgOg, have been
obtained. The latter is prepai-ed by mixing 3 mols. of barium thio-
sulphate and 2 atoms of iodine. The mixture becomes colourless in
three or four days. It is then filtered through cotton-wool, and the
crystals remaining behind ax'C washed with alcohol. They are then
pure and have the composition BaSsOg ; with silver nitrate, this salt
gives a white precipitate, turning black, and the liquid at the same
time becomes acid. The sodium salt crystallises in large, colourless,
very soluble crystals, containing a large quantity of water.
C. W. W.
Basicity of Dithionic Acid. By H. Kolbe (J. pr. Chem. [2],
19, 485 — 487). — As the author has been unable to obtain an acid salt
of this acid or a neutral salt containing two bases, he doubts the cor-
rectness of the usually accepted view of the bibasicity of this acid,
and is now inclined tiD the original supposition of Berzelius that it is
a monobasic acid, and is represented by the formula SO^OH. In fact,
that it contains the radicle SO2, but united with only one atom of
hydroxyl, that is, joined with only one atom of hydrogen by one atom
of oxygen. On this supposition sulphur must exist in this acid as a
pentad.
That the radicle sulphoxyl (SO2) may exist as a dyad in sulphuric
acid, and as a monad in dithionic acid, appears to the author to be not
more improbable than the tetrad and dyad atomicities of tin in stannic
and stannous compounds. A. J. C.
Behaviour of Calcium Oxide with Carbonic Anhydride. By
K. Ih.MBAUM and M. Mahu {B'u\, 12, l-j47 — loGl). — The object of the
experiments described in this paper was to ascertain at what tempera-
ture calcium oxide begins to absorb carbonic anhydride, and at what
temperature calcium carbonate begins to dissociate. It was found
that the lowest temperature at which absorption takes place is the
melting point of zinc, 415'3°, and that the carbonate dissociates par-
tially at that temperature, although dissociation begins at a much
lower one. The amount of anliydride absorbed by the oxide is about
half an equivalent. W. R.
Calcium Phosphite. By R. Rother (Pharm. J. Trans. [3], 10,
286). — By adding sugar to a solution of calcium hypophosphite, the
latter is precipitated, a circumstance which is generally unknown, and
hence it is highly probable that a dense syrup of the mixed hypophos-
phites contains little if any calcium salt. In the presence of iron, a
precipitate is also formed ; the proportion of sugar, however, has no
share in this change. Ferric hypophosphite, when contained in such
a sugar, is said to revert easily to the ferrous form, and it was found
that the ferrous salt readily oxidises even in the presence of sugar,
forming the dark green and very soluble ferroso-ferric hypophosphite.
Ferric hypophosphite occurs in several modifications, of which the cry.s-
6 ABSTRACTS OF CHEMICAL PAPERS.
talline variety is almost insoluble in hypophosphorous acid, and hence
it is this compound which deposits from the syrup. It was attempted
to regenerate this sediment by reducing it to the ferrous condition by
the interyention of sulphurous acid. However, the latter was de-
composed into sulphuric acid, sulphur, and oxygen, which reacted
with the hypophosphoi'ous acid of the sediment, and converted it
into phosphorous acid. When solutions of calcium hypophosphite and
sodium sulphite are mixed, calcium sulphite is precipitated, which is
redissolved by hydrochloric acid, no further reaction setting in until
both the hypophosphorous and sulphurous acids are entirely freed by
the addition of enough hydrochloric acid. The solution, after filtering
off the sulphur, yields, on the addition of ammonia, a crystalline pre-
cipitate of calcium phosphite. The latter, however, contains less than
half of the phosphorous acid generated, owing to the fact that hypo-
phosphorous acid is monobasic, whilst phosphorous acid is dibasic, and
also that a small loss of calcium is incurred as sulphate. By treating
the liquid filtered from the sulphur with calcium carbonate, a much
larger amount of phosphite is thrown down than with ammonia. The
addition of a solution of calcium chloride to the filtrate causes a further
precipitation of phosphite, which becomes more distinctly crystalline,
and siibsides moi'e rapidly when a very little ammonia has been added
to the precipitate.
Calcium phosphite is a white crystalline powder, which when heated
in a test-tube evolves spontaneously inflammable hydrogen phosphide
accompanied by slight detonations. At a certain temperature, it sud-
denly becomes incandescent, and leaves a residue of calcium phos-
phate. D. B.
Zirconium Derivatives. By S. R. PATKiJLL (Ber., 12, 1719). —
The moist bydrated oxide, ZrO(OH)2, absorbs carbonic anhydride
from the atmosphere. By treating zirconium sulphate with the
hydrate, one amorphous and two crystalline basic salts were obtained,
VIZ., ZrOo.SOa + a^Aq, 3ZrOo.4S03 + 15H.jO, and 6ZrO,.7S03 + 19H20.
The sulphate forms with potassium sulphate basic double salts, e.g.,
Ko02SOo + 2(ZrO.O.>.S02) + 14HoO. W. C. W.
Researches on Erbia. By Lecoq db Boisbaudran (Compt. rend.,
89, 51Gj. — The author examined the spectrum of erbia from various
sources, and with one exception the spectra thus obtained exhibited
identical lines of the same intensity. The exception was the erbia
derived from samarskite. The principal differences were that with
samarskite-erbia, the ray in the gi'een, X — 536"3, is much more in-
tense that the ray \ = 540"9, whilst in the other erbias the difference
is but slight ; and the line in the red, \ = 6404, is as strong, or
stronger, than X = 653"4 ; whereas in the other erbias, the line
X := 653'4 is much stronger than X, = 640'4.
Two specimens of erbia were taken, one nearly pure, giving the
normal spectrum, the other from samarskite, and containing a large
quantity of yttria. On fractionation by means of ammonia and sub-
sequently by potassium or sodium sulphate, a portion was obtained
from the first which gave a spectrum resembling that of the second,
INORGANIC CHEJUSTRY. 7
and a portion was obtained from the second giving a spectram like
that of the first.
The author is contiuuintj this research. C. W. W.
Two New Elements in Erbia. By P. T. Cleve (Gompi. rend.,
89, 4:7b). — In attempting to obtain pure erbia, the author was led to
suspect the existence of two other earths in the erbia obtained. The
mixture was therefore fractionated, and the different fractions ex-
amined spectroscopically. It was found that, in addition to bands
common to all, one band \ ^ G840 was strong in the residues rich in
ytterbia, and wanting in those containing yttria and erbia, whilst two
others, X = 6400 and 5360, were strong in the yttria and ytterbia
residues.
The colour of the fraction treated for ytterbia was a violet-rose,
whilst the yttria fraction had an orange tint.
The metal characterised by the first baud, X, = 6840, the author pro-
poses to name thulium ; it would have an atomic weight of about 113
(the oxide being TmO). Pure erbia, to which must be attributed the
common bands, has probably an atomic weight of 110 — 111. Its oxide
has a clear rose colour. The third metal, holmium, is characterised by
the bands X = 641)0 and 5360 ; it should have an atomic weight less
than lU8 ; its oxide seems to be yellow. C. W. W.
Spectra of the Earths of the Yttria-group. By J. L. Soret
(Compt. rend., 89, 521). — The author considers that the new earth,
holinia, discovered by Cleve, is identical with an earth discovered by
Delafontaine and Marignac, whose absorption-siDCctrum was described
by himself (Compt. rend., April 29, 1878), and to which Delafontaine
gave the name pldlippia. Cieve's holmium is chai'acterised by two
bands \ = 640 and \ = 536, and these two belong likewise to philip-
pium, which is characterised by several other bands.
Cieve's second earth, thulia, is characterised by a red ray X. = 684.
The author claims to have indicated the existence of this element also
[Arch. Sci, 63, 99). Marignac also showed the probable existence of
this earth in the products rich in philippia and having a low equiva-
lent. C. W. W.
Scandium. By P. T. Cleve (Compt. rend., 89, 419).— This metal
occurs only in gadolinite (0'002 to 0*003 per cent.) and yttrotitanite
(0'005 percent.). Scandium forms but one oxide, scandia, ScvO^ ; the
composition of which is proved by that of potassium scandium oxalate,
and of the double sulphates of scandium with the sulphates of potas-
sium and with ammonium. 8 to 10 grams of scandium oxide, having
a molecular weight of 106, agreeing with the number obtained by
Nilson, yielded, by i-epeated decompositions of its nitrate, about 1 gram
of a white oxide. This was converted into sulphate, and 1*451 grams
of this sulphate yielded 0"5293 gram of scandium oxide.
The atomic weight of the metal is therefore 44'91, and the mole-
cular weight of the oxide, considered as ScO, is 45-94 (? 60'91 =
44'91 + 16), differing greatly from the lowest number found by
Nilson, viz., 105'83. The author considers that this is due to a large
8
ABSTRACTS OF CHEMICAL PAPERS.
admixture of ytterbia in Nilson's scandia. The atomic weight, as
determined by the decomposition of the nitrate, is 45*12. The atomic
weight of scandium may therefore be taken as 45.
Scandium oxide or Scandia, SC2O3, is a light, white, infusible powder
of sp. gr. 3'8, resembling magnesia ; it is scarcely soluble even in
strong acids, but more so than alumina. Sulphuric acid converts it
into a bulky white mass of sulphate ; hydrochloric acid dissolves the
oxide more easily than nitric acid.
Scavdium hydrate is a bulky white precipitate, drying up to semi-
transparent fragments. It does not absorb carbonic acid from the
air, is insoluble in ammonia or in potash, and does not decompose
ammonium salts when heated with them.
Scandium salts are colourless or white, and have an acid, astringent
taste, very different from the sweet taste of the salts of the yttrium
metals. The sulphate does not form distinct crystals ; the nitrate,
oxalate, acetate, and formate, are crystallisable. The chloride ex-
hibits the following reactions : — It gives no spectrum when heated in
a gas flame. Potash and ammonia produce bulky white precipitates,
insoluble in excess ; tartaric acid prevents the precipitation by
ammonia in the cold, but on heating an abundant precipitate falls.
Sodium carbonate gives a precipitate, soluble in excess. Sulphuretted
hydrogen produces no change ; ammonium sulphide precipitates the
hydrate. Sodium orthophosphate gives a gelatinous precipitate. Oxalic
acid gives a curdy precipitate, quickl}' becoming crystalline ; this preci-
pitate dissolves in strong acids, and cannot be completely reprecipitated.
Although it appears more soluble than the oxalates of the other
yttrium metals, it is found in the first precipitates in the fractional
precipitation of a mixture of scandium and ytterbium by oxalic acid.
Acid potassium oxalate precipitates a crystalline double salt. Sodium
hyposulphite precipitates a boiling solution easily'-, but incompletely.
Sodium acetate behaves similarly. The sulphates of potassium and
sodium precipitate crystalline double salts, soluble in a saturated
solution of the precipitant.
The author describes in a previous paper (Bull. 80c. Gliim., 31, 486)
the chloride, nitrate, and sulphate of scandium ; the double sulphates,
Sc,(S04).,.2K,S04, Sc2(S04)3.3Na,S04.12H,0, Sc.,(S04)3.(NH4),S04 ;
the double oxalate, Sc2(C..04)3.K2C204.3H.>.0 ; the acetate, the formate,
and selenite, 3Sc2O3.lOSe62.4H26.
The existence of scandium was predicted by Mendelejeff, audits pro-
perties described under the name of eJcabor {Annalen,, Sup., 8, 133).
The following table shows a comparison of "the observed properties of
scandium with those predicted of ekabor.
Siif posed diameters of Wcahor.
Atomic Weight = 44.
Ekabor should have but one
stable oxide, EboOs, a stronger
base than alumina, which it
should resemble in many i^espects.
It should be less basic than mag-
nesia.
Observed Characters of Scandium.
Atomic Weight = 45.
Scandium forms only one oxide,
SC2O?, more energetic than alu-
mina, and less so than magnesia.
INORGANIC CHEMISTRY.
9
Ekabor oxide should resemble
yttria, although less basic. The se-
paration of these two earths will be
difficult, depending on differences
of solubility or of basicity.
Oxide of ekabor is insoluble in
alkalis ; it will probably not de-
compose ammonium salts.
The salts should be colourless,
and srive gelatinous precipitates
with kHO, Na,C03, and HNaSO,.
The sulphate should form a
double salt with KoSOi, having
the composition of alum, but not
isomorphous with it.
But few ekabor salts should
crystallise well.
The anhydrous chloride should
be decomposed by water, giving
off hydrochloric acid.
The oxide is infusible and so-
luble with difficulty in acids after
ignition.
The density of the oxide would
be about 3" 5.
Scandia is less basic than yttria,
and their separation depends on
differences of solubility between
their nitrates.
Scandium hydrate is insoluble
in alkalis ; it does not decompose
ammonium chloride.
The salts are colourless, and
give gelatinous precipitates with
KHO, NaaCOs, and HNaSOo.
Potassium - scandium sulphate
is anhydrous, but otherwise cor-
responds in coiaposition with
alum.
Scandium sulphate does not
form distinct crystals, but the
nitrate, acetate, and formate crys-
tallise well.
The crystallised chloride is de-
composecl by heat, giving off
hvdrochloric acid.
The oxide is an infusible
powder, nearly insoluble in acids
after ignition.
The density of the oxide = 3'8.
c. w. w.
Absorption of Nitrogen Dioxide by Ferrous Salts. By
J. Gay (Compt. rent]., 89, 41u). — Peligot assigned the formula
4FeS04.N202 to the compound of nitrogen dioxide with ferrous sul-
phate. The author finds that the composition of this body depends on
the temperature and on the pressure of the residual niti-ogen dioxide.
At temperatures up to 8° and at the ordinary pressure, the com-
pound formed has the formula 8FeS04.]S'202 ; from 8° to 2-5°, at the
atmospheric pressure, it Las the formula 4FeS04-.N202 ; at tempera-
tures above 2-5^ nitrogen dioxide is rapidly given off, and the com-
pound oFeS04.jS'202 is produced.
All these compounds exhibit very marked tensions of dissociation,
a fact which explains their decomposition in a vacuum ; they are also
decomposed by a current of hydrogen.
Reducing agents, such as ferrous oxide, rediace the nitrogen dioxide,
a mixture of monoxide and free nitrogen being evolved, while the
temperature rises sensibly. C. W. W.
Nitrosothioferrates. By J. O. Rosenberg (Ber. 12, 1715 — 1717).
— By the action of potassium nitrite and ammonium sulphide on a
ferrous salt, Roussin (Ann. Ghim. Phys. [3], 52, 285) obtained a black
substance, which was afterwards examined bv Porczinsky (Annalen,
125, 302), Demel (Ber., 12, 461), and Pawel (ibid., 12, 1407). This
is named by the author ammnnnim nitrosoferrothioferrate.
10 ABSTRACTS OF CHEMICAL PAPERS.
On the addition of an alkali ferrous oxide is precipitated, and
potassium nitrosotliioferrate is obtained. The free acid wliich is
liberated when this salt is treated with hydrochloric acid, combines
with alkaline suljjhides to form a red salt, to which the name nitroso-
ferrous potassium sulpJdcle is given.
Salts corresponding wdth each of the two first-mentioned acids have
been prepared. They are all converted into nitroprussides by the action
of potassium cyanide. W. C. W.
Potassium and Ammonium Ferric Chromates. By C.
Hensgen (Ber., 12, 1656 — 1658). — These salts sejDarate out in dark-7*ed
plates containiug 4 mols. HoO [K or NH4], when a solution containing
ferric chloride and ammonium or potassium dichromate, is slowly
evaporated. They have the formula KoCr04.Fe2(Cr04)3.4H20. The
ammonium salt is decomposed by cold water and also by the action of
heat. W. C. W.
Contributions to the Chemistry of the Chromaramonium-
compounds. By S. M. Jokgensen (/. pr. Chem. [2], 20, 105—145.
— I. Chloroparpureo-chrommm Salts. — The starting point for these
salts is the chloride, Cl2(Cr2lONH3)Cl4. This is prepared by reducing
violet chromic chloride in a stream of pure dry hydrogen, at a red
heat, and adding it to a solution of ammonium chloride in strong
ammonia (25 grams CroCle reduced to Cr2Cl4, 90 grams NHiCl,
0"5 litre ammonia). Air is then passed through the blue liquid until
oxidation is complete. Two litres of crude hydrochloric acid are
added, and the mixture is boiled for some minutes, daring which
chloropurpureo-chromium chloride separates as a carmine- coloured
powder. The crude chloride is washed with a mixture of equal volumes
of hydrochloric acid and water, dissolved in very weak sulphuric
acid, and filtered into a great excess of strong cold hydrochloric acid.
The resulting precipitate is boiled with hydrochloric acid, and washed
first with a mixture of acid and water, then with alcohol, and
finally dried in the air at the ordinary temperature. This chloride is
also a bye-product in preparing Cleve's tetramine chloride by the
following process: — Ammonium dichromate is reduced by boiling with
hydrochloric acid and alcohol, and after addition of ammonium
chloride the liquid is evaporated to dryness. The dry residue is then
dissolved in strong ammonia ; strong hydrochloric acid is added, and
the crystals which are deposited on standing are washed first with a
mixture of equal parts of hydi'ochloric acid and water until free from
ammonium chloride, then with water, and finally dried. It consists
of a mixture of chromium-tetramine chloride and chloropurpureo
chloride. This mixture must be protected from the actiou of light
during the remaining operations. It is dissolved in cold water, and
shaken with a solution of one part of ammonium sulphate in five parts
of water. The tetramine chlorosulphate precipitates in crystals ;
the filtrate containing the purpureochloride is mixed with hydrosilico-
fluoric acid, and gives a precipitate of chloropurpureo-chromium silico-
fluoride. After being washed, it is treated with dilute hydi-ochloric
INORGANIC CHEMISTRY. 11
acid, to reconvert it into chloride ; after reprecipitatiou with strong
acid and washing, first witli dilute acid and then with alcohol, it is
quite pure. The two salts may also be separated by taking advantage
of the insolubility of the compound Cl2(Cr2l0NH3)(Hg3Cl8)2, produced
by adding mercuric chloride to the mixture. The mercury-compound
after washing is easily reconverted into the chloride by treatment
with hydrochloric acid.
Chloropurpureo-chromium chloride is a red crystalline powder, of a
purer red colour than the corresponding cobalt-compound. It appears
to crystallise in octohedra of sp. gr. 1"687. It dissolves in 154 parts
of water at 16°, and forms a violet-red solution, which, on exposure to
light, deposits chromium hydrate. "When it is kept, even in the dark,
or boiled, roseochromium chloride is produced. It gives the follow-
ing reactions : — With sodium hypochlorite, nitrogen is evolved, and
the chromium is oxidised to chromic acid. Its solution gives a preci-
pitate with strong hydrochloric acid, owing to the insolubility of the
chloride in acid. With hydrobromic acid, it gives a crystalline preci-
pitate of the bromide, and with solid potassium iodide one of the
iodide. When boiled with potassium cyanide, it turns yellow. Strong
nitric acid precipitates the chloro-nitrate. Hydrosilicofiuoric acid
throws down the red crystalline chlorosilicofluoride. Platinic chloride
precipitates, even from a very dilute solution, the chloropurpureo-
chromium plat ino chloride. Sodium platino-bromide gives an ana-
logous precipitate. Mercuric chloride gives red needles of the double
salt. Precipitates are also produced by potassium mercuribromide
and iodide, by sodium dithionate, potassium chromate, and dichromate,
ammonium molybdate, and phosphomolybdate, and by picric and oxalic
acids. In these respects this salt closely resembles the analogous
cobalt salt. On treatment with silver nitrate only four atoms of
chlorine are removed, and the chloro-nitrate is formed. By rubbing
the solid chloride with silver oxide and w^ater, roseochromium hy-
drate is formed. It is a deep red alkaline liquid, which gives a
yellowish-red precipitate of roseochromium bromide with strong
liydrobromic acid ; this, when boiled with hydrobromic acid, changes
to bromopurpureo-chromium bromide. In the chloro-chloride, the
radicle chlorine is so firmly combined that hot strong sulphuric acid
does not expel it ; the product is acid chloro-sulphate.
Towards reducing agents, however, the chromium series differ in
behaviour from the cobalt series, for the chromium is not so easily re-
duced. With sulphuretted hydrogen, or with ammonium sulphide,
the purpureo-cobalt-compounds give cobalt sulphide, but thepurpureo-
chromium compounds suffer no change, except the formation of a
crystalline purpureopolysulphide, if the ammonium sulphide contains
much free sulphur. The cobalt salts are also reduced by potassium
ferrocyanide, whereas the chromium salts give a precipitate of ferro-
cyanide of chloropurpureo-chromium.
The latter part of this paper is occupied with detailed descriptions
and analyses of numerous salts of chloi'opurpureo-chromium chloride,
prepared by double decomposition. They have all a red or orange-red
colour, and closely resemble the corresponding salts of chloropurpureo-
cobalt. W. R.
12 ABSTRACTS OF CHEJIICAL PAPERS.
Behaviour of Copper-Ammonium Chloride with Ferrous
Sulphide. By W. F. K. Stock {Chem. News, 40, 159).— In the
course of recent experiments on the accurate determination of carbon
in iron and steel containing much sulphur, it appeared desirable to
ascertain definitely in what manner the reagent used for the carbon
separation acted on the iron sulphur compound, but as the composition
of that compound is unknown, it was thought best to experiment with
a sulphide of known quality. The process used for the carbon separa-
tion was McCreath's method based on treating a weighed quantity of
iron or steel with a hot concentrated solution of copper ammonium
chloride.
From, the results, it was evident that the actions of the double cop-
per ammonium salt upon iron cai'bide and upon iron sulphide were pre-
cisely analogous, and that the method held out no hope of separation.
It only remained to find to wliat extent the decomposition had pro-
ceeded during the exposure, which was for half an hour at nearly
boilino' heat. It is shown that allowing for oxidation dui'ino- washino-
&c., it may safely be assumed that 80 per cent, of the original sul-
phide was decomposed by the double copper salt with liberation of the
corresponding amount of free sulphur.
A second experiment was made with native ferric sulphide, which
was very finely powdered and exposed at boiling heat for over an hour
to the copper solution, but although some free sulphur was obtained,
the decomposition was far from complete. D. B.
Action of the Haloid Acids on the Sulphates of Mercury.
By A. DiTTE (Ann. Cltim. PJujs. [5], 17, 120— 128).— It has been stated
that dry hydrochloric acid gas decomposes mercuric sulphate, foi'ming
mercuric chloride and free sulphuric acid, and that since the chloride
is more volatile than the acid, the former can be separated by sublima-
tion at a suitable temperature ; and further, that hydriodicand hydro-
cyanic acids act in a similar manner. The author shows that these
statements are wholly incorrect.
NVhen dry hydrochloric acid is passed over mercuric sulphate at
ordinary temperatures, no reaction ensues : on warming the sulphate,
absorption takes place, with .disengagement of heat and without forma-
tion of water ; on heating more strongly, the product sublimes, but
the crystals have no resemblance whatever to sublimed mercuric chlo-
ride. An analysis of the crystals showed that their composition
exactly corresponded with the formula HgS04.2HCl ; they are very
hygrometric, dissolving in water apparently without decomposition.
When volatilised they do not disengage hydrochloric acid.
Hydrobromic acid gas acts in a precisely similar manner, forming
the compound HgS04.2HBr.
The body HgS04.2HCl is likewise formed with great facility by
gently heating a mixture of sulphuric acid and mercuric chloride, in
molecular proportions ; or by dissolving the neutral sulphate in hydro-
chloric acid, and evaporating until crystals are obtained.
The action of hydriodic acid is different ; sulphuric acid decom-
poses mercuric iodide on heaticg, no compound of the formula
HgS04.2HI being formed. In the same mannei', solution of hydriodic
MINERALOGICAL CHEMISTRY. 13
acid in excess, partly or wholly decomposes mercuric sulphate, but no
definite combination takes place.
Hydrofluoric and hydrocyanic acids are without action on mercuric
sulphate.
Basic mercuric sulphate, turpeth mineral, acts with regard to hydro-
cbloric acid in a manner analogous to mercuric sulphate, but it ab-
sorbs 6 molecules of HCl for every molecule of sulphate, forming the
compound HgSO4.2HgO.6HCl ; the latter on being heated strongly,
breaks up into the mercuric compound and mercuric chloride,
thus : —
Hg3S06.6HCl = HgS0,.2HCl + 2HgCl2 + ^H^O.
A precisely similar compound is formed by the action of either
gaseous or liquid hydrobromic acid on turpeth mineral. J. W.
A New Salt of an Iridammonium. By K. Birnbaum {Ber.,
12, 1544 1547). — By boiling the double salt of iridic sulphite and
sodium sulphite with hydrochloric acid, an acid salt is formed pre-
sumably of the formula Ir2(S03)3.3NaHS03. When its solution is
saturated with gaseous ammonia, a compound crystallises out in red
crusts, having the formula lr2lS'a3(SO3)6(NH3)9.10HoO. The author
assigns to it the constitutional formula—
SO3 : Ir(NH3)3 NH4
S03<| +3 >S03.0H,0,
SO3 : Ir(NH3)3 Na^
and supposes the SO3 group to be in combination with an irid-
ammonium of the formula (NH3)6lr2. W. R.
Mineralogical Chemistry.
Cobalt-glance. By P. Geoth {Jahrl. f. Min., 1878, 864—865).
— In addition to the forms already known to occur on cobalt-glance,
the author has observed two dyakisdodecahedrons, two trapezohedrons,
and one triakisoctohedron. On cobalt-glance from Tunaberg, Sweden,
he observed the following combinations, viz. : —
(1.) 22O2 . 0 . ooOoo . ^ (2.) ^ . 0. fO| . fOf
00O2 ^ 20f 00O2 ^ 20|
y"^-) 2 2 ■ 2 ■ ■ 2 ■
Crystals from Skutterud, near Modum, in ISTorway, exhibited the
following forms in combination, viz. : — - — • O . 20. CAB
Cobalt-speis. By P. Groth (Jahrl. f. Min., 1878, 865).— Hitherto
it has been considered doubtful whether the crystals of this mineral
were holohedral or hemihedral, but the author has succeeded in prov-
14 ABSTRACTS OF CHEMICAL PAPERS.
in^ the occurrence of pentagon dodecahedrons, and consequently the
isomorphism of cobalt-speis and iron pyrites. On one crystal of cobalt-
speis from Wolkenstein '^ '^ and ?^-- — were observed. A large
crystal from Schneeberg exhibited the following forms in combina-
tion, viz. : coOco . 0 . ooO . 202 . — — ^ and a dyakisdodecahedron,
which could not be more nearly determined. C. A. B,
Sulphide of Silver (Silber-kies). By A. 'Wiiisbach {Jafirh. f.
Mil}., 1878,866). — Argyropvrites (AgaFevSn) occupy an intermediate
position, chemically speaking, between sternbergite (AgsFceSg) and
aro-entopyrites (AggFcgSio), and the same fact is observed in regard to
its physical properties.
Argentopy rites crystallises in the rhombic system, the crystals from
Marienberg being but small, whilst those from Freiberg attained a
leno-th of 3 mm. The prisms were terminated either by the basal
terminal plane, which was macrodiagonally striated, or else by an
obtuse pyramid, the Freiberg crystals being characterised also by a
very distinct basal cleavage.
The crvstals exhibiting the obtuse pyramids in combination were
probably " penetration trillings." C. A. B.
Bismuth Minerals from Norberg's Mine, Wermland. By H.
SjoGREM (Ber., 12, 1723).— Bismuth occurs in Wermland : 1st, native,
mixed with galena and pyrites ; 2nd, as bjelkite, 2PbS.Bi2.S3 ; and
3rd, as the new mineral galenohismutliite, PbS.BijSa. W.. C. W.
Polysynthetical Twin-crystals of Oriental Spinelle. By J.
StrOver (Jajirh. f. Miti., 1878, 865 — 866). — This paper can only
be thoroughly understood by reference to the drawings given. The
author concludes that there are three groups of polysynthetical
spinelle crystals, viz. : (1.) Those with one twin-axis in common.
(2.) Those in which, the twin-axes are not parallel to each other,
but in which the " twin-face" is common to all, for instance, a form
composed of three individuals having a face of ooO in common, as
twin-plane, and two of their twin- axes parallel to that face. Trillings
were also observed resembling a tetrahedron, owing to the predomi-
nation of an individual having a tetrahedral development. Some-
times groups composed of four individuals were observed, having all
the twin-axes parallel with the twin-planes (ooO). (3.) Those in
which there is no parallelism in the twin-axes, nor a twin-plane com-
mon to all the forms. C. A. B.
Manganite. By P. Groth (Jahrh.f. Min., 1878, 863— 861).— The
finest crystals of this mineral are found at llfeld, and are characterised
by the great number of forms occurring in combination. According
to Haidinger, the hemihedry of this mineral is peculiar to tlie pyramid
^ P2, a fact which appears all the more singular when the great
number of pyramids observed on manganite is taken into considera-
5IIXERAL0G1CAL CHEMISTRY. 15
tioTi, and also that, in the case of the isomorplious mineral goethite,
no such occurrence is observed. The author, on the contrary, did not
observe a single instance of hemihodrr, or even twins according- to the
law " the twin-plane coPco," altliougli he examined one of the finest
collections of Ilfeld manganite crystals. The results of his investiga-
tion are briefly as follows : — 1. Manganite must be considered as a
holohcdral mineral, hemihedral combinations being very rare. 2. Man-
ganite crystals can be divided into four types, the first two being
characterised by an almost entire absence of twins, according to the law
" the twin-plane a face of Pco " and tlie occurrence of intermediate
forms, whilst the last two types are characterised by the crystals
occurring nearly always as twins according to the above-mentioned
law, and a more sharply-defined distinction of the types fi'om each
other.
The following table will show this more clearly : —
r Type I. Prisms, and basal terminal plane pre-
. -J- . ,. ) dominating.
ong prisma ic<. fp^pg jj Prisms, with macropyramids as termi-
L nals.
"Type III. Twins, with somewhat numerous
forms in combination, the basal terminal
-p. 5j, . , . ■ plane and obtuse macrodomes predominating.
P j Type IV. Twins, with very numerous forms
I in combination, macropyramids predominat-
^ ing.
From the above table it seems probable that an intimate connection
exists between the twin formation and the number of forms occurring
in combination. The third and fourth types are the rarest.
C. A. B.
Occurrence of Manganese in Nordmark's Mine, Wermland.
By A. Sjogren (Ber., 12, 1723). — In this locality manganese is found
as manganosite, MnO ; pyrochroite, MnOH20 ; hausmannite and
manganese-spar, together with brucite, heavy spar, hornblende, and
garnet. W. C. W.
Vanadinite. By T. ISTordstrom (Ber., 12, 1723). — Yandanite has
been found in the Undenas manganese dioxide mine in West Goth-
land. A mineral has also been discovered at Fahlun, containing 5 per
cent, of selenium. W. C. W.
Titanates from Smaland, By C. W. Blomstraxp (Ber., 12, 1721
— 1723). — The following minerals were found at Slattakra, Alsheda,
occurring in coarse granite: — 1. Pohjcro.se. 2. Titaniferous iron ore,
remarkable on account of the water it contained ; and 3. A new mineral
alshedite, which appears to occupy an intermediate position as regards
composition between yttrotitanite and groothite. In this compound
titanium dioxide plays the part of a base. W. C. W.
Pseudomorphs of Calcite after Aragonite. By G. voii Eath
(Jahrh. f. Min., 1878, 863). — -The crystals in question came from
Schemnitz, and were from 10 to 20 cm. in length and from 4 to 6 cm.
IT) ABSTRACTS OF CHEMICAL PAPERS.
in breadtli : they wei'e terminated apparently by a bracliydome, the
space originally filled by aragonite being taken up by calcite. One
specimeu, 7 cm. long, 4 cm. broad, and from 2 to 3 cm. thick, con-
sisted of the outer shell of an aragonite crystal, which was built up
out of an aggregate of small, well- developed calcite crystals, exhibiting
the following forms in combination,, viz. : R^. — -lE/.coR, the crystals
not occupying any regular position with regard to the original arago-
nite crystal. C. A, B.
Crystal- system of Leucite. By J. Hirschwald (Jahrb. f. Mm.,
1878, 867). — Hirschwald stated in a former paper that leucite might
be considereri as a mineral ciystallising in the regular system, with a
polysymmetrical development in the sense of the quadratic system.
From further investigations he arrives at the conclusion that a dif-
ference in opinion about the practical relationships of leucite is possible
in the two following cases only, viz. : — 1. Is the polysynthetical twin-
formation a complete dodecahedral one, or does it only represent the
faces of the pyramid ? 2. Have the imbedded crystals the interfacial
angles (winkelwerthern) of 202, or have the apparently regular forms,
without exception, the angles of the acuter lateral edge of the eight-
sided pyramid ? Hirschwald considers that he has found a complete
answer to these questions in the results of his investigations, and states
that the imbedded leucite crystals have undoubtedly the interfacial
angles of 202, whilst the optical properties prove a complete dodeca-
hedral twin-formation. C. A. B.
Composition of Eclogite. By E. E. Riess (Jahrh.f. Min., 1878,
877).^ — Eclogite is a non-felspathic crystalline rock which, in its
simplest forms, consists of omphazite and garnet, whilst the varieties
of this rock are produced by the occurrence of quartz, hornblende,
cyanite, zoisite, or mica. The accessory minerals are zircon, apatite,
titanite, epidote, iron-pyrites, magnetic iron-pyrites, and magnetite.
Omphazite occurs as an augite in short, thin prisms of a grass-green
colour ; the rai'e smaragdite as a green hornblendic mineral. The
garnet often contains numerous enclosures of zircon, quartz, &c., and
is occasionally decomposed. Zircon occurs enclosed in large amount
(in reddish-brown grains or greyish-yellow prisms, exhibiting P with
ooP and coPoo, also twins, parallel to a face of Poo) in the garnet and
omphazite. The true eclogite is found imbedded in the strata of the
crystalline slates, and is often intimately associated with hornblendic
plagioclase o-arnet-i-ocks, but not with those containing omphazite.
C. A. B.
Thaumasite. By G. Lindstrom (Ber., 12, 1723). — This new
mineral, having the composition CaOSi02 + CaC03+ CaSO^ -j- 14HaO,
is found in the Areskutan mountains in Jutland. W. C. W.
Manganese-nodules from the Bed of the Pacific Ocean.
By C. W. GiJMBEL (Jahrh. f. Min., 1878, 869— 870).— These nodules
were collected at a depth of 2740 fathoms, between Japan and the
Sandwich Islands, by the " Challenger" Expedition. They were either
round or long in shape, with a dull, dirty-brown coloured surface, and
MIXERALOGICAL CHEMISTRY. 17
enclosed fragments of pumice-stone, and more rarely teeth of sharks
or fragments of mussels. A microscopical examination showed that
organic life had nothing to do with their formation, which was due to
a mechanical concretion of inorganic matter ; a kind of oolitic forma-
tion on a large scale. The pumice-stone was most probably the result of
submarine eruptions ; it was trachytic in cliaracter, and there was
evidence to show that it had lain for a considerable space of time in
muddy water, which penetrated it eventually, and left behind a depo-
sition of manganese oxide. The author believes that the nodules in
question derived some of their constituents from submarine springs,
whilst their form can be accounted for by the action of the waves. An
analysis gave the followiiig results : —
FeoO:).
MnOo.
H2O.
SiOj.
A1.0,.
Na.,0.
27-460
23-600
17-819
16-030
10-210
2-358
CI.
CaO.
TiO..
SO3.
K2O.
MgO.
0-941
0-920
0-660
0-484
0-396
0-181
COo.
P.O..
CuO.
NiOCoO.
BaO.
0-047
0-023
0023
0012
0-009 =
101-173
The minute quantity of carbonic acid is striking, and it would
appear from the above analysis that an energetic oxidation takes place
at great depths. The occurrence of these manganese-nodules at the
bottom of the sea is of great geological interest, as similar manganese-
nodules are common in various sedimentary formations.
C. A. B.
Occurrence of Lithium in Rocks, Sea Water, Mineral
Waters, and Saline Deposits. By L. Dieulafait {Auu. Chim.
Fhj/s. [5], 16, 377 — 391). — Primary Bocks {Granite, Syenite, Gneiss).
— The author has examined one hundred and thirty-nine specimens
from different localities in Europe and Africa, and detected lithium in
all of them, although in very different proportions.
Mother Waters of Salt-marshes. — The author found these to be so
rich in lithia, that by simply dipping a platinum wire into the water
and holding it in the flame, the lithium spectrum obtained was as
intense as that of sodium. Lithium could always be detected in the
waters of from 15 — 25° B., as at that concentration almost all the
gypsum is deposited; the crystals of gypsum themselves, however,
contained only excessively minute traces of lithium. The sedimentary
deposits forming the bottom of the basins invariably contained it.
Lithium was found also in all sedimentary deposits left by the
spontaneous evaporation of sea water.
Sea Water. — Bunsen succeeded in detecting lithium in 40 c.c. of sea
water, but the author found that on evaporating 1 c.c. of the water of
the Mediteri-anean to dryness, treating the residue with alcohol, and
evaporating the alcoholic solution, the second residue gave a very dis-
tinct lithium spectrum. As lithium was shown to be a constituent of
all the primitive rocks, it appeared highlv probable that it would be
found in all sea waters. The author has detected it in the waters of
VOL. XXXVIII. c
]8 ABSTRACTS OF CHEMICAL PAPERS.
the Red Sea, the Indian Ocean, the Chinese Sea, the Atlantic Ocean,
the Antarctic Ocean, and the Northern Ocean. Neither Forchhammer
nor Credner, in his Traite de Geologie, jnentions lithium as a constituent
of sea water.
The author applies the results of his experiments to test his theory,
that deposits of gypsum of all ao^es have a purely sedimentary origin.
This theory has been opposed by geologists, especially as applied to
gypsums of the tertiary formation.
Giifsum of the Tertiary Period. — Paris. — Samples of the pure crys-
tals from the quarries of Montmartre and Pantin were found to be
qaite free from lithium, although in every case the yellow calcareous
deposit adhering to the crystals or embedded in their cavities con-
tained it in such quantity, that •0002 gram was amply sufficient to
give the characteristic spectrum.
A'ix and Provence. — In these localities the gypsum occurs in beds,
separated by thin layers of marl. In certain spots, large honey-yellow
crystals of gypsum occur, imbedded in a yellowish deposit. In all
cases the pure gypsum was free from lithium, whilst the yellow marl
contained it in considerable quantity. Similar results were obtained
on examining the gypsum from Camoins and Dauphin, near Mar-
seilles, from Vaucluse, and from different parts of Italy. The waters
from the Suffioui were found to contain lithium in considerable
quantity.
Gyi>snm of the Secondarn Formation. — Forty-eight samples from the
Alpine district, eleven from Languedoc, seven from the Pyrenees,
three from Lori"aine, and four from Wurtemberg, all belonging to the
triassic formation, were examined, with results similar to those ob-
tained with the gypsums of the tertiary periods. The samples of pure
gypsum were free from lithium, or contained only traces ; whilst the
associated earthy deposits were invariably rich in this element.
These investigations show a complete analosry between the triassic
gypsum deposits, those of the tertiary formation, and those from the
salt marshes of the modern period : whence the conclusion that the
former two classes of deposits were formed under the same conditions
as those we now see causing the formation of gypsum in the salt
marshes.
Mineral Waters of the Primanj Formation. — A characteristic group
of these waters is found in France in the Pyrenees district. The fol-
lowing were examined, and in every case lithium was found to be a
constituent : — Luchon, Cauterets, Bareges, Saint-Sauveur, Labassere,
Visos, Bonnes, Ax, Amelie.
Saline Waters. — Those of AUevard, Balaruc, Bourbonne, Capvern,
Contrexeville, Digne, Grreoulx, Miers, Montbrun, Montmirail, Pougues,
Saint Gervais, Salies, Salins, Uriage, Vittel, Haurmem Meskoutin
(Algiers), La Reine (near Oran), Baden (Switzerland), Birmenstooff
(Switzerland), Loeche (Switzerland), Wildegg (Switzerland), Pullna,
Flombourg, Kissingen, Kreusnach, Naucheim, and Soultzmatt, were
examined, and lithium found in all ; in some cases in such quantity
that it could be detected in the evaporation residue of a single drop of
the water. This fact, taken in conjunction with the previous expe-
rime7\ts, strengthens the author's theory that saline waters are mine-
MTXERALOGICAL CHEMISTRY. 19
ralised at the expense of saliferous deposits left by the evaporation of
ancient seas. J. M. H. M.
Note on the Silesian Basalts and their Mineral Consti-
tuents. By P. Trii'ke {Jahrh. f. Min.,. 1878, 876— 877).— Of these
basalts from Upper and Lower Silesia, fifteen were plagioclase basalts,
two were nepheline basalts, and one from Wickenstein, near Querbach,
was nephelinite. The microscopical characteristics of these basalts
were briefly as follows, viz. : — A colourless glass-zone (which was
itself surrounded by a glassy wreath of felt-like augite-microlites)
surrounded the quartz inclosures, this observation agreeing with that
of Lehniann on the inclosures of the basalts of the Lower Rhine.
Some of the interfused quartz-fragments were converted into tridymite.
The orthoclase was nofc surrounded by glass substance or augite.
Lamellar enstatite occurs alternately with lamellar diallagite in the
olivine nodules of the Groditzberg, the lamella? being parallel to the
macropinaco'fd of the enstatite. The acicular and tabular inclosures
in these minerals the author considers to be negative forms of enstatite
and diallagite, filled with opal. The phillipsite from Sirgwitz was
monosymmetrical, and exhibited a complicated polysynthetical twin-
formation. The basalt of Steuberwitz contains simple augite crystals,
and those with a polysynthetical twin-formation. The olivine from
Thomasdorf was changed into magnesium carbonate, whilst the
nephelinite from Wickenstein contains augites having a zonal struc-
ture. C. A. B.
Basaltic Lavas of the Eifel. By E. Hussak {Jahrh. f. Min.,
1878, 871). — The author made a thorough examination of the above-
mentioned basalts, and arrived at the following conclusions, viz. : —
(1.) There are no felspathic basaltic lavas in the Upper Eifel, but
only nepheline or lencite-basaltic lavas, which differ considerably from
the non-melted, mound-forming basalts. (2.) The olivine from the
Eifel lava is always fresh ; it is not ]n*esent, however, in the lava from
Dockweiler. (3.) The lava from the Eifel contains biotite, in contra-
distinction to the basalt of the Eifel. (4.) Melilite occurs in con-
siderable quantity in some of the lavas, especially in that from Bongs-
berg, where it can be microscopically detected. (5.) Hauyn is only
present in the lava from Scharteberg. (6.) Perowskite occurs as a
characteristic of the lava from Scharteberg, but it is also present in
lavas of the Laacher See district (the three last-named minerals do not
occur in the basalts of the Eifel). (7.) The chemical analyses of the
lavas agree very well with the results of the microscopical examina-
tions. (8.) The tufa of the Kolenberg, near Anel, was found to be
true palagonite-tufa, containing, however, leucite and mtignetite.
(9.) The microscopical examination of this tufa fully confirms Rosen-
busch's theory of the formation of the palagonite-tufa. (10.) Mits-
cherlich's analysis of this palagonite-tufa agrees fully with its micro-
scopical analysis. (11.) The so-called basalt-rock from Luxenberg,
near Weierhof, in the Eifel, proves to be a true garnetiferous picrite,
the first which has been observed on the left bank of the Rhine.
(12.) The garnets in this picrite exhibited a zonal structure, were par-
c 2
20 ABSTRACTS OF CHEMICAL PAPERS.
tially double-refracting, and v^ry probably were the variety called
uielanite. C. A. B.
The Meteorite of Vavilovka. By B. Prendel (Jahrh. f. Min.,
1878, 868). — N'umerous meteorites fell on the 7th of June, 1876, near
the village of Vavilovka, in Cherson, Russia, accompanied by a sound
resembling thunder. A specimen examined by the author exhibited
the characteristic black rind, which was 0'6 — 1 mm. in thickness, also
irregular stripes here and there. A polished surface shtjwed the mass
of the meteorite to consist of nnmerons angular whitish specks. The
Tnetallic constituents were particles of nickel-iron disseminated
throughout the whole mass, and grains of magnetic-pyrites not, how-
ever, magnetic. Sp. gr. = 3'51. Chemical composition as follows,
viz. : —
SiO.n. MgO. AI2O3. CaO.
53-81 ■18-54 8-75 2-07
Alkalis. FcjOj. Magnetic pyrites. Mekel.
1-14 9-41 5-26 0-70 = 99-68
The meteorite belonsrs to the chondrites. C. A. B.
O"
The Meteorite of Grosnaja. By Gr. Tschermak {Jahrh. f. Min.,
1878, 868— 8G9).— Two .specimens which fell on the 28th of June,
1861, at the above locality on the Terek, Caucasus, were examined by
the author. They were encrusted with a moderately thick fused sur-
face (schmelz-rinde), and were black-grey in colour. The ground
mass was massive, black, and opaque, and enclosed numerous light-
coloured particles consisting of olivine, enstatite, bronzite, and magnetic
iron-pyrites. The bronzite, olivine, and a mineral resembling augite
were found together forming nodules in the ground mass, whilst specks
of the magnetic iron-pyrites were observed in the inclosures and also
in the groiand mass. The bronzite-nodules exhibited an incrustation
or rind, and the magnetic iron-pyrites occurred zonaliy on the enclo.sed
minerals. An analysis of the meteorite furnished the following
results : —
SiOo. AI0O3. • FeO. CaO. MgO.
33-7'8 3-44 28-66 3-22 23-55
Magnetic
KjO. Hi&^O. C. H. iron pyrites.
0-30 0-63 0-68 0-17 5-37 = 100-00
8p. gr. = 3-55. The Grosnaja meteorite is a chondrite one, poor in
carbon. C. A. B.
Chalybeate Springs of Carlstad. By A. Almen {Ber., 12, 1724
— 1725). — These springs are exceptionally rich in ferrous carbonate.
Total solids. FeCOj.
Ko. 1 contains in 10,000 parts 1-348 0-593
„ 2 „ „ .... 1-653 0-669
w. c. w.
ORGANIC CHEMISTRY, 21
Water of the River Vartry. By J. Flrtoher {Ghent. News, 40,
171). — This water sliows on analysis very little chlorine, 0001155 per
litre or 0"8025 grain per gallon. It is of great softness, the hardness
being only 3^ on Clark's scale, and yielding a total solid residue vary-
ing, as the result of many e.x:periments, from 4 to 6 grains per gallon.
The results of the author's experiments show that the watsr is of
great purity, chemically considered, bub strongly impregnated with
peat, having a very decided action on lead when flowing through pipes
of that material, although without action on it when at rest, but rather
leaving an organic deposit. D. B.
Organic Chemistry.
Specific Gravities of Solid Organic Compounds. By H.
Schroder (Ber., 12, 1611 — 1618). — The author has determined the
specific gravity and molecular volumes of the following compounds : —
Sp. gr. Volume.
Malic acid 1-559 85-9
Dimethyloxamide 1-281 90-5
r»- fi, 1 -A r 1-164 123-7
JJietnyloxamide I 1 -1 7'^ 1 99-8
o T T ., r 1-485 92-9
baiicylic acid < -■ ,.q^ q.^.,
Metahydroxy benzoic acid 1-473 93-7
-r, 1 -, , ' 'J f 1-476 93-5
Ir'arahydroxybenzoic acid ...... < -..^ q ..r
Phthalic anhydride . < i .-qa op. '7
rl-247 181-3
Benzoic anhydride J 1-234 183-2
I 1-231 183-6
T, , , , . ., f 1-542 99-9—100-0
r'rotocatechuic acid < -, ~ .-i
I l-o41
^ IT ., [1-703 99-8
^^"'^^^'"^ •• 1 1-685 100-9
Mandelic acid } -, op 7 111 -9
Phenylacetic acid i -, .^'^ 111-"
r 1-385 109-8
Methylparahydroxybenzoic acid < 1-376 110-5
1 1-364 111-5
^. . .. r 1-249 118-6
Cmnamic acid | -^.^^g ^^^g.g
r. . ., r 1-169 140-3
Cumic acid ^ ^.-^.g j^^,,
'li ABSTRACTS OF CHEMICAL PAPERS.
Sp. gr. Volume.
^ . , f 1-296 109-7
T3 .. / 1-344 90-0
Benzamide j^.ggg ^^.^^
A -1 u • -A /1-51-5 90-5
Amidobeuzoic acid. < , .k^.. q-, .^^
Orthonitrobenzoic acid i l •"74. lOR-1
Metanitrolaenzoic acid s , . .Xf, 119 0
A ^ -n / 1-216 111-0
Acetamlide < -, .^^^ -^^2-0
-p ...-, r 1-321 149-2
Benzamlide j^.g^^ ^^^.^
rn,. 1 .,•, /1-33 171-5
Imocarbanilide s -|.q-|-| T-^S-Q
r 1-227 10-5-6
Aniline liydrocliloride < 1-216 106-5
L 1-201 107-8
. .,. ., , / 1-360 114-8
Aniline nitrate • S t o-/? n k a
(.l-3o6 115-0
Aniline sulphate 1*377 206-3
Js^aphthaleue 1-145 111-9
Nitronaphthalene < -■ .o.,-. -■ .-,-. ,^
a-^^aphthol 1-224 117-8
/3-I^aphtbol 1-217 118-2
, . , ^ 11-264 110-0
Ammonium, benzoate < -■ .^^^ -. ^ ^-...^
^ 1 . , , / 1-457 230-6
Ualcium benzoate < -i .iqi; 9^4,-l
Tlie molecular volumes of the majority of the above compounds are
multiples of 5-91, which in a former communication {Ber., 12, 566)
was shown to be true for some benzene derivatives.
In the case of some isomerides, the " stere " appears to vary a little
from 5-91, as shown by the following : —
Volume. " Stere."
J r Quinol 82-6— 831 6^
' I Pyrocatechol 81-6—82-1 5-8
r Parahydroxybenzoic acid 93-5 — 94-5 5-91
2.'s Metahydrosybenzoic acid 93-7 5-9 — 5-8
L Orthohydroxybenzoic acid 92-9 — 93*1 5-8
g r Orthonitrophenol 95-8—96-3 6h)— 6mj5
■ I Paranitrophenol 94-5—94-7 6^1
^ fMandelic acid 111-2—112-2 5^
■ 1 Anisic acid 109-8 — 110-5 5^
_. r Isonaphthol 118-2
' ■ I a-Naphthol 117-8
ORGA.VIC CHEMISTRY. 23
The members of the followinor six groups are isosteric : (1.) Malic
and tartaric acids. (2.) Benzoic and paraoxybenzoic acids. (3.) Re-
sorcinol and pvrogallol. (4.) Phenylacetic and anisic acids. (5.)
Protocatechuic and gallic acids. (6.) Benzamide and benzamic acids.
In former communications, the author has shown that the elements
carbon, hydrogen, oxygen, and nitrogen occupy in the solid state the
space of one " stere."'
The determinations given above offer further support of this state-
ment, thus : oxamide, dimethyloxamide, and diethyloxamide have
molecular volumes differing by CaH^, or 6 steres. In naphthalene and
isonaphthol we have difference of 0} = 1 stere, and in benzoic and
orthonitrobenzoic acids we have the difference NjO^ — HJ = 2 steres.
Some other examples are given.
From this rule, it follows that the benzene nucleus possesses one
stere more than the sum of those of the elementary atoms contained
in it. Thus: benzoic acid, CgHs.COOH = 16 x 6^1. Paranitro-
phenol, C6H5.NO,0 = 16 X 5-91, phthalic anhydride, CsHX>3 = 16 x
&0d. Orthonitrobenzoic acid, C6H5.NO,.C02 = 18 X ry[n. Phenyl-
acetic acid = 19 X 58. Naphthalene, CeHi.CiHi = 19 x 5-91. Iso-
naphthol^Hi.CiHiO = 20 x ly^. Cinnamic acid, CbHs.C.Ho.COOH
= 20 x 5^. P. P. B.
Formation of Hydrocyanic Acid in the Electric Arc. By J.
Dewar {Chem. News, 39, 282). — From the statements made by Plucker,
Angstrom, and Thalon, that the so-called carbon lines are invariably
associated with the formation of acetylene, the author made experi-
ments with a view to extract this substance from the electric arc,
which shows this spectrum at the positive pole when the electric cur-
rent is powerful and occasionally intermittent. The carbons were
used in the form of tubes so that air could be drawn through them,
and so that any gas might be passed up one tube and drawn down
the other and then examined.
A Siemens and a De Meritens magneto-machine were employed.
In the first experiment a current of air was drawn down the nega-
tive pole and passed through solutions of potash and potassium
iodide and starch. No nitrates were indicated, but the potash solution
contained sulphides.
In the second experiment in which hydrogen was led in by the posi-
tive pole and withdrawn by the negative, acetylene was found by the
ammoniacal sub-chloride of copper-test, whilst water through which the
gases were passed gave distinct evidence of hydrocyanic acid. The
hydrogen Hame burning alone gave no evidence of these substances.
Air drawn through the negative pole gave considerable quantities
of hydrocyanic acid, but when drawn through the positive pole a
larger proportion was found, whilst the same carbons used with De
Meritens' magneto-machine gave no result.
If the carbons are not puritied, hydrogen sulphide is always found
along with the other compound.
The author concludes that the high temperature of the positive pole
is required to produce the hydrocyanic acid, which is in all probability
24 ABSTRACTS OF CHEMICAI> PAPERS.
formed by the free Bitrogen reacting on the acetylene thus : C3H.J +
2]Sr =: 2HC]Sr, and that the hydrogen to form the acetylene is obtained
from the decomposition of aqueous vapour and from the combined
hydrogen in the carbons. W. T.
Oxidation of Alcohols by Electrolysis. By A. Renard (An7i.
Ghliu. I'hys. [5], 16, 289 — o37). — I. Electrolysis of Alcohols in presenae
of Water Acidulated by Sidpliuric Acid. Methyl Alcohol. — The purest
methyl alcohol of commerce, after being carefully freed from traces of
acetone and methyl ethers, was acidified with about 5 per cent, of
dilute sulphuric acid (1 : 4), placed in a flask holding from 100 — 200
(\c., and submitted to the action of a current from 4 Bunsen cells of
about a litre and a half capacity. Hydrogen was evolved at the nega-
tive pole, and at the positive pole a gas was very slowly given off
(at the rate of 25 — 80 c.c. in 24 hours) : it contained CO2, 23-9 ; CO,
50'0 ; 0, 26"1. At the end of 48 hours the yellowish liquid was dis-
tilled. The distillate was found to contain methyl formate and methylal.
Methyl aldehyde was never found as a product of the electrolysis,
being no doubt oxidised to formic acid as soon as formed, or reacting
with the methyl alcohol to form methylal. The methylal is one of the
chief products of the reaction, and may be prepared quite easily by
this method. The residue of the distillation of the electrolysed liquid
contained hydrogen methyl sulphate. To show that this was pro-
duced by the electroly.sis, a mixture of the alcohol with dilute sul-
phuric acid was prepared and divided into two parts, one being
allowed to rest, and the other submitted to electrolysis. The latter
was found to contain hydrogen methyl sulphate, whilst the former was
quite free from it.
Ethyl Alcohol. — The electrolysis of ethyl alcohol has already been
attempted by various chemists, amongst others by tiiche, D'Almeida
and Bontan, and Jaillard. The only products hitherto recognised,
besides chloracetic acid and compound ammonias resulting from the
hydrochloric and nitric acids employed for acidification, are aldehyde
and acetic acid.
The author's experiments were conducted in the same manner as
those with methyl alcohol-. An abundant evolution of hydrogen
occurred at the negative pole ; but at the positive pole no gas was
disengaged, all the oxygen being absorbed by the oxidation of the
alcohol. The process was arrested at the end of 48 hours, and the
liquid on being distilled yielded (besides alcohol) ethyl formate, a little
aldehyde, and a large proportion of ethyl acetate ; small quantities of
acetal were likewise obtained, and a new substance which the author
considers to be ethylidene vionethylate, CH3.CH(HO).EtO, i.e., acetal,
in which C2H5 is replaced by H. This substance when separated,
and purified by fractional distillation, boiled at 88 — 90° C, and on
analysis gave numbers corresponding with the formula C4H10O2. The
residue from the distillation of the electrolysed mixture contained
hydrogen ethyl sulphate, the forination of Avhich was proved, as in the
])revious case, to be really due to the electrolysis. Under certain con-
ditions, more than 60 per cent, of the sulphuric acid employed for
acidification is transformed into the sulphate.
ORGANIC CHEMISTRY. 25
If the electrolysis of methyl or ethyl alcohol be continued for several
days, a point is retiched at which the liquid appears to contain nothing
but formic or acetic acid ; on still prolonging the operation, almost
pure oxygen is disengaged at the positive pole, in volume almost
exactly half that of the hydrogen, and the liquid is found still to
contain a little hydrogen methyl or ethyl sulphate, the decompasition
of which is very slow.
Electrolysis of Hydrogen Methyl Sulphate. — 100 c.c. of a solution
containing 20 grams of this ethereal salt, prepared by decomposing
barium methyl sulphate with sulphuric acid,, was submitted to the
action of the current from 4 Bunsen cells. Hydrogen was disengaged
at the negative pole, aud oxygen containing 5 or 6 per cent, of the
oxides of carbon at the positive pole, about 23 volumes of oxygen
being evolved for every 100 volumes hydrogen. After 48 hours the
liquid way distilled, and the distillate was found to contain fui'mic
acid and a solid polymeride of methaldehyde, trioxy methylene, CsHeOs,
which was obtained as a white, amorpho-as, insoluble residue by
evaporation of the solution over sulphuric acid in a bell-jar. Similar
results were obtained by the electrolysis of a more dilute (5 per cent.)
solution of hydrogen methyl sulphate, and also of a similar solution
containing a little free sulphuric acid. From this, it would seem that
methaldehyde is first produced, a part being at once transformed into
the polymeric modification, whilst the other is oxidised to formic acid.
Ko trioxymethylene is produced by electrolysis of methyl alcohol,
because the methaldehyde as fast as it is formed, reacts on the methyl
alcohol to produce methyl al.
Electrolysis of Hydrogen Ethyl Suljyhate. — This compound was sub-
mitted to electrolysis in a manner similar to the corresponding methyl
compound, and gave acetic acid and a little formic acid. No aldehyde
was found in the distillate, but the odour of aldehyde was perceptible
during the progress of the electrolysis.
Electrolysis of Glycerol. — Glycerol diluted with two-thirds of its
volume of water, acidulated with one-tenth of sulphuric acid, was sub-
mitted to the action of the current from 5 Bunsen cells. Hydroo-en was
disengaged at the negative- pole, and at the positive pole a gaseous mix-
ture containing COo, 29 ; CO, 32-8 ;. O, 64-3. volumes. After 48 hours
the process was arrested, the liquid saturated with calcium carbonate,
filtered, and submitted to distillation without boiliug at a low pressure
in an atmosphere of carbonic anhydride. On spontaneous evaporation
over sulphuric acid, the dLstillate left a white amorphous residue,
which gave on analysis numbers agreeing with the formula CxH2j:0j,
and which proved to be identical with trioxymethylene, CsHgOs, The
yield of this substance is very small, 130 c.c. of the . distillate giving
about half a gram of the dry substance. Submitted to electrolysis,
trioxymethylene gives rise to formic acid, and a gaseous mixture con-
Ixiining, in 100 volumes, CO2, 5 ; CO, lo ; and O, 8U. By treating a .solu-
tion of trioxymethylene with sulphuretted hydrogen., a white precipitate
is obtained, of the formula (CsHsSaOjoHoC). It differs therefore from
the body CsHgSs, which Hoffmann obtained by acting on trioxy-
methylene with a mixture of hydrochloric and hydrosulphuric acids.
The oxysulphide obtained by the author melts at 80 — 82^, and solidifies
26 ABSTRACTS OF CHEMICAL PAPERS.
on cooling to a hard, white, opaque mass, like wax. It is soluble in
hot water, insoluble in alcohol and ether, and boils at 180 — 185° C.
By treating the trioxymethylene with ammonia, the author obtained
tbe hexamethylen amine of Bntlerow, C6Hi2l*r4, but was unable to obtain
from it the hydrochloride CeHuNiCl, described by that chemist.
Tlie residue from the distillation of theelectrolysed glycerol contained
calcium formate, acetate, and g-lycerate. Besides these substances there
is formed by electrolysis of glycerol a small quantity of a glucose isomeric
with ordinary glucose, and which is probably a polymeride of trioxy-
methylene. It is found in the alcohol used to precipitate the lime
salts from the distillation residue of the electrolysed liquid. This alco-
holic solution also contains the lime salt of a new acid, identical with
that formed in the electrolysis of mannitol. The pure glucose is
obtained in the form of a yellow-brown syrup, which may be dried at
G0° in a current of hydrogen. At 80 — 100° it blackens, loses water,
and gives out the odour of caramel. Its alcoholic solution yields a
precipitate with barium hydrate, the composition of which agrees with
the formula (C6Hi206)4(BaO)3. The glucose reduces silver nitrate,
with formation of a mirror, and precipitates cuprous oxide from
Fehling's solution on heating. It is oxidised to oxalic acid when heated
with dilute nitric acid. Slightly heated with soda its solution darkens
strongly. It is very soluble in water and alcohol, is not precipitated
by lead subacetate, but forms an abundant precipitate with ammoniacal
lead acetate. It appears to be incapable of fermentation by beer yeast.
When the electrolysis of glycerol is prolonged for several days, tbe
trioxymethylene and glucose disappear, the liquid becomes strongly
charged with oxalic acid, and this, as well as the formic and acetic
acids, is finally resolved into carbonic anhydride and carbonic oxide,
so that the solution at last contains nothing but sulphuric acid.
Electrolysis of Glycol. — Hydrogen was evolved at the negative pole,
and at the positive pole a gaseotis mixture containing C0>, 5 '00 ;
CO, 57"15; O, 37'85. The current was interrupted at the end of
36 hours. The liquid, saturated with calcium carbonate and distilled,
gave a distillate containing trioxymethylene, whilst the residtie in the
retort contained calcium formate and calcium glycoUate, some unaltered
glycol, and a glucose identical with that obtained by the electrolysis
of glycerol.
Electrulysls of Mannitol. — Hydrogen was evolved at the negative pole,
and at the positive pole a gaseous mixture containing OO2, 22 1 ;
CO, 55"0 ; O, 22'9. The liquid treated as in the glycol experiment, gave
trioxymethylene, calcium formate, and the calcium salt of a new acid.
This calcium salt, when separated from the accompanying calcium
formate, purified, and analysed, gave numbers corresponding with the
formula CeHgCaOg + ^H..O. It is very soluble in water, and it
is not precipitated either by lime water, or by lead acetate or sub-
acetate. It reduces silver nitrate almost instantaneously, without
heating, and in the dark ; if the mixture be heated slightly a metallic
mirror is obtained. At 120° C, the calcium salt loses 6 — 7 per cent.
cf water, and at 160° it swells up, and begins to decompose. Tlie
acid, obtained from the calcium salt by decomposition with oxalic acid,
is a syrupy product, forming very soluble, gummy salts, with barium,
ORGANIC CHEMISTRY. 27
lead, and magnesium. The author assigns the formula CgHsOh to
this acid, and suggests that it may be an aldehyde of saccharic acid,
CeHioOs, bearing the same relation to the latter that glyoxylic (or gly-
oxalic) acid, CoHoOs, does to glycollic acid, C^HjOa. A glucose iden-
tical with that obtained from glycerol, and probably also with tlie
mannitose of Gornp-Besanez, was also formed during the electrolysis,
together with a considerable quantity of oxalic acid, but no saccharic
acid or mannitic acid could be detected.
Electrolysis of Glucose. — Hydrogen was evolved at the negative pole,
and at the positive pole a gaseous mixture containing COo, 228 ;
CO, 18"2 ; O, o9'0. The electrolysed liquid contained trioxymethylene,
formic acid, and saccharic acid.
Electrolysis of Alcohols when the Electrodes are separated ly a Porous
Partition. — In these experiments, the liquids to be electrolysed were
contained in a porous cell, into which the positive electrode was intro-
duced, the porous cell being surrounded with acidulated water, into
which the negative electrode was plunged. The alcohols experimented
with were methyl alcohol, ethyl alcohol, and glycerol. The products
were the same as in the experiment in which no porous partition was
employed.
Electrolysis of Acetic Acid. — 25 c.c. of glacial acetic acid was mixed
with 40 c.c. of water, acidulated with one-tenth of sulphuric acid, and
submitted to the action of the current from 4 Bunsen cells. At the
end of three hours the gaseous mixture evolved at the positive pole
contained CO,, 413; CO, 11-4; 0, 47-3. After 24 hours the gas
evolved consisted of COj, 45"4 ; CO, 9'2 ; O, 45'4. The proportion of
carbonic anhydride was still greater at the end of 86 hours. After
48 hours the liquid was examined, and found to contain formic acid,
but no oxalic acid.
Electrolysis of Oxalic Acid. — The sole products in this case were car-
bonic anhydride and carbonic oxide. The gaseous mixture evolved at
the positive pole contained about 50 per cent. CO2, and 10 percent. CO,
the rest being oxygen. At the end of 48 hours all the oxalic acid had
disappeared.
Electrolysis of Formic Acid. — The sole products were carbonic anhy-
dride and carbonic oxide. If concentrated formic acid is used, car-
bonic anhydride is the only product.
Electrolysis of Alcohols in presence of Phosphoric Acid. — Experiments
were made with solutions of methyl alcohol, ethyl alcohol, glycerol,
and glycol, acidulated with pho.sphoric instea.d of snlphuric acid. A
larger proportion of phosphoric acid than of sulphuric acid was found
necessary, in order to secure the decomposition of the alcohols, but the
products were exactly the same, and in about the same proportions as
when sulphuric acid was used, except that in the case of methyl and
ethyl alcohols no hydrogen methyl or ethyl phosphate was formed.
Action of Or^one on the Alcohols. — The action of ozonised oxygen on
the alcohols is very slow ; for example, when a stream of this gas is
passed through solutions of glycerol, glucose, or mannitol, the escaping
gas is still strongly odoi'ous, and the liquid contains only very small
quantities of acetic or formic acid, even after many days' action.
Carbon dioxide and carbon monoxide are also formed. Contrary to
28 ABSTRACTS OF CHEMICAL PAPERS.
expectation, ozone was found to act much more quickly on tlie alcohols
of low atomicity, such as methyl and ethyl alcohols, than on the poly-
atomic alcohols, glycol, glycerol, mannitol, and glucose. The action of
electrolytic oxygen is similar to that of ozone in this respect.
Action of Hijclrogen Peroxide on the Alcohols. — Hydrogen peroxide
appears to have no action on the alcohols, whether in acid, neutral, or
alkaline solutions, dilute or concentrated, even after the lapse of
several days.
The aathor concludes that the products obtained in the electrolytic
experiments above described are not due to direct electrolysis of the
alcohols, but are simply due to the action on the alcohols of the oxygen,
resulting from the electrolysis of the acidulated water. He suggests
the electrolytic method as a convenient one for effecting the oxidation
of organic "bodies at a low temperature, and in a manner permitting
the examination of intermediate products. J. M. H. M.
Two New Hydrofluoboric Acids and Ethylene Fluoboric
Acid. By F. Landolph {Ber., 12, 1583— 1086).— When boric fluoride
acts on araylene, the latter is polymerised, and a fluoboric acid,
B02O7H43HFI, is obtained. It is a clear yellow liquid boiling at 160°,
is easily decomposed by water, forming boric acid. A second fluoboric
acid, BoiOgHi'iHFl, is obtained when boric flaoride acts on anethol at
high temperatures. It is a heavy, transparent liquid, boiling at 130°.
Like the above it fumes in contact with air, and is decomposed by
water.
Ethylene fliiohoric acid^ CaHiHFl.BoO,, is formed by the action of
boric flaoride on ethylene at 25 — 30" in sunlight. It is a clear, mobile,
fuming liquid (b. p.. 124 — 125''),. of sp. gr. 10478 at 23°. It burns
with a green flame. Water decomposes this compound, forming boric
acid, and a volatile compound (b. p. 10 — 15°), which does not burn
with a yreen flame, and is supposed to be ethyl fluoride.
^ ^ P. P. B.
Sulphates of Mono- and Poly-hydric Alcohols and Carbo-
hydrates. By P. Claesson (Ber., 12, 1719— 1721).— Me'hyl saljjhate
is best prepared by the decomposition at 130 — 140° of hydrogen
methyl sulphate obtained by the action of sulphuric monochloride
on methyl alcohol.
Ethyl sulpliate is an oily liquid insoluble in water (b. p. 208°).
The polvhydi'ic alcohols when treated with sulphuric monochloride
yield the corresponding hydrogen sulphates.
Dextrose, dextrin, starch, and cellulose, form with sulphuric mono-
chloride dextrosechloride-tetrasuljjhonic acz'c?, C4H5(S020H)4.CHC1.CH0,
which crystallises in large prisms. Corresponding compounds could
not be obtained with levulose and galactose. W. C. W.
Changes of Ammonium Isethionate at High Temperatures.
By F. Carl {Ber., 12, 1GU4- — 1607).- — Ammonium isethionate heated
at 210 — 220° loses 12 per cent, of its weight, forming a body w^hich
crystallises from alcohol in leaflets, having a pearly lustre (m. p.
3^96 — 198). — Seyberth (Ber., 7, 391) has observed the same change,
but gives 190 — 193° as the melting point of the compound ftroduced,
ORGANIC CHEMISTRY. 29
which he describes as an amide of the formula C0H7NSO3. The
author finds this compound has the formula CiHioS-iKoO-, and explains
Sejberth's results by the supposition that his product contained small
quantities of another substance, which is formed simultaneously. By
boiling with baryta-water, this compound does not form barium ise-
thionate as it would if it were an amide, but a barium salt is formed
crystallising in prismatic tables united to globular masses, having the
composition CiHsSoBaOv + H3O. This salt differs from barium ise-
thionate in its action on polarised light, as also in its solubility in
alcohol. The author regards the new product as ammonium di-
isethionate, ]SrH4S03.(CH,),.0.(CHo).,S03NH,.
Besides ammonium di-isethionate another body is produced, which is
more soluble in alcohol, and has the composition C^HisSoNOt. It
owes its existence to the evolution of ammonia observed when
ammonium isethionate is heated. That it is not an acid salt is shown
by the fact that when treated with alcoholic ammonia, and the solution
evaporated on the water-bath, the solution has still an acid reaction.
For this reason the author attributes to this compound the formula
NH,S03.(CH2)2.S03.(CHo),.OH. P. P. B.
Epichlorhydrin-Derivatives. By M. Breslauer (J. pr. Chem.
[2], 20, 188— 193).— Yon Richter (Ber., 10, 677) observed that dry
sodium acetate has no action on epichlorhydrin, but that in presence
of absolute alcohol, ethyl acetate and epihj^drin alcohol (glvcide) are
formed. The author confirms von Gegerfelt's statement {Bull. 80c.
Chim., 23, IGO), that epihydrin acetate, C3H5OAC, is produced by the
action of potassium acetate on epichlorhydrin. The best mode of
preparing this acetate is to heat equivalent proportions of epichlor-
hydrin and potassium acetate in a flask provided with an upright
condenser at 110 — 115° for several hours, and then raise the tem-
perature slowly to 150°. By extracting the product with ether,
epihydrin acefate (b. p. 164 — 168°) is obtained, and also a liquid boiling
at 258 — 261°, which Gegerfelt regarded as glycerol- triacetin, but
which is really a polymeride of epihydrin acetate.
Epihydrin acetate is a mobile liquid (sp. gr. 1T29 at 20°), soluble in
alcohol and ether. It precipitates metallic silver from an ammoniacal
solution of silver nitrate. By the action of potash on epihydrin acetate
diluted with ethyl acetate, glycerol is pi'oduced, but if soda is used
instead of potash epihydrin alcohol, C3H3O.OH, is obtained. The
alcohol boils at 160°, and is soluble in water, alcohol, and ether.
When heated with water glycerol is formed.
Diglycid, (C3H50.0H)2, results from the saponification of the poly-
meric modification of epihydrin acetate. W. C. W.
Sugar from Populin. By E. O. v. Lippmann (Ber., 12, 1648—
1649). When the glucoside populin, CjoHj.Og + 2H2O, is decom-
posed by dilute acids, it splits up into benzoic acid, saliretin, CuHuOa,
and rjrcqoe sugar. W. C. W.
Partial Synthesis of Milk-sugar, and a Contribution to the
Synthesis of Cane-sugar. By E. Demole (Compt. rend., 89, 481).
30 ABSTRACTS OF CHEMICAL PAPERS.
■ — Schiitzenbero'er (Ann. Chim. Phys., 21, 235), by tbe action of acetic
anhydride on glucose, obtained an acetyl-derivative of a body formed
by the union of 2 mols. of glucose with elimination of water, for which
the author proposes the name of diglucose. Schiitzcnberger considered
this body identical with octacetyl-saccharose. The solubilities cf these
two ethers in alcohol are, however, different ; and octacetyl-saccharose
has a specific rotatory power [a]D == 3836, whilst that of octacetyl-
diglucose is [a]D = 64"G2 ; moreover, the saccharose-derivative yields
snceharose by saponification, whereas the diglucose-compound yields
diglucose.
When milk-sugar is heated with a dilute acid, it is converted by
assimilation of water into galactose and lactoglucose. When the
mixture of these bodies, obtained in the above manner, is dried and
heated with acetic anhydride, it is converted into a pitch-like ether,
having all the properties of octacteyl-lactose, and giving milk-sugar by
treatment with alkalis.
When 2 mols. of glucose, like or unlike, are in presence of a dehy-
drating agent, they are converted into their anhydrides ; and by the
action of these anhydrides on acetic anhydride, an ether of a diglucose
is formed, just as ethylene oxide takes up acetic anhydride to form an
ether of diglycol. C. W. W.
Reaction of Tungstates in presence of Mannitol. By Klein
(Gompt. reinl., 89, 484). — The action of tungstates on mannitol
resembles that of borax. A solution of 12 grams mannitol and
4 grams sodium tungstate, made up to 100 c.c, gives a deviation of
+ 40'. The solution has an alkaline reaction ; boiling effects no
change.
A solution of 10 gleams of mannitol and 4 grams of sodium paratung-
state, 5]!>ra20.12W03.25H20, made up to 100 c.c,, has no rotatory j^ower
in the cold, but after boiling produces a deviation of + 36'. The
solution, wliich is originally neutral, becomes strongly acid on
boilins'.
Barium metatungstate, BaW40i5.9H20, added to a solution of
mannitol, produces no deviation, even after boiling. The barium salt
is not decomposed by the solution of mannitol, although it is by water
alone.
If baryta-water be added to the above solution when boiling, the
liquid, after filtering, has a rotatory power of + 25' ; this effect is not
produced in the cold. C. W. W.
Decomposition of Ethylamine Hydrochloride by Heat. By
M. FiLF.Ti and A. RicciNi (LVr., 12, 1508).— When this salt is heated
to a temperature somewhat lower than that at which lead melts, a
mixture of ammonia and mono- and di-ethylamine (separated in neutral
solution by means of potassium nitrite), ethyl chloride and ethylene is
evolved, whilst the residue consists of ammonium chloride, diethyl-
amine hydrochloride, and some uudecomposed ethylamine hydrochlo-
I'ide. The reaction is thus analqgous to the decomposition of phenyl-
ethylamine by heat, except that a further decomposition into ammonia
and ethyl chloride takes place. W. R.
ORGxVXIC CHEMISTRY. 31
Cyanethine. By E. v. Meter {J. pr. Chem. [2], 19, 484—485).—
Cyanetliiiic ap]iears to be a tertiaiy base. When heated witli mode-
rately diluk' sulpliui-ic or liydroeliloric acid afc 180 — 200°, it is trans-
formed into a crystalline base, C9H14N2O, Avhicli forms easily soluble
and finely crystallising salts.
The investisjation is beinfj continued. A. J. C.
A Double Function of the Monobasic Acids. By Loir (Ann.
Chilli, rin/.-i. [5], 18, 125 — 138). — In reference to Gerhardt's paper on
the anhydrides (ilnl. [3], 37, 333), the author considers that if the
anhydrides are classed as ethers, that under certain circumstances the
acids may act as alcohols, and if such be the case they must also have
the properties of aldehydes. This becomes evident on examination of
the formula for acetic acid, which may be written thus : OH.CH2.COH.
Considered as an alcohol it, is C-.HbO(HO), the CoH.jO containino^ an
aldehyde grouping CHo.COH. The following experiments are adduced
in support of this view.
By the action of reducing agents on aldehydes, alcohols are obtained,
and when acids are treated with hydriodic acid, Berthelot has shown
that the hydrides of the alcohol radicles are formed.
Butyric acid (b. p. 155 — 160°) when heated with a concentrated
solution of sodium hydrogen sulphite at 0°, yields long transparent
needles ; these melt at 20" without the evolution of sulphurous anhy-
dride, whilst butyric acid floats on the top of the solution. On col-
lecting the crystals, dissolving in water, and distilling with sulphuric
acid, sulphurous anhydride is evolved, and butyric acid distils over.
Bntyric acid decolorises potassium permanganate, and reduces ammo-
niated silver solutions. Valeric acid has similar properties.
That acetic anh^-dride possesses the functions of an aldehyde as well
as an ether has been shown by the author (this Journal, Abst., 1879,
621). The same holds good for butyric anhydride.
Acetobenzoic anhydride, however, exists in two isomeric modifica-
tions, according as it is prepared from sodium benzoate and acetic
chloride, in which case the author calls it acetijl henzoic anJiijdride, or
from sodium acetate, and benzoic chloride, when it is called benzoijl-
acefic anhydnde. The two bodies have the same chemical properties,
except in their reaction with hydrochloric acid.
Benzoyl- acetic anhydride vf hen heated in hydrochloric acid gas boils at
130°, and acetic chloride comes over, leaving benzoic acid as a crystal-
line residue.
Acetyl -henzoic anhydride when treated in a similar manner boils at
160°, and benzoic chloride distils over.
With chlorine similar results are obtained, the residue in the first
case beinof chlorohenzoic acid, and in the second chloracetic acid.
These two isomeric bodies may be considered as ethereal salts;
benzoyl acetic anhydride being the acetic salt of benzoic acid which
acts as an alcohol, whilst acetyl benzoic anhydride is the benzoic salt
of acetic acid acting as an alcohol.
Benzoic chloride at 0^ forms a crystalline compound with sodium
hydrogen sulphite.
Since glyoxal and glyoxylic acid are obtained from alcohol by the
32 ABSTRACTS OF CHEMICAL PAPERS.
action of nitric acid, they may be considered as derivatives of aldehyde
and acetic acid. As glyoxal, COH.COH, contains the aldehyde-group
twice, its mode of formation depends on the previous formation of an
alcohol aldehyde ; and as we have acetic acid (alcohol), OH.CHo.COH,
yielding glyoxylic acid, OH. CO. COH, containing the acid and aldehyde
groups, it requires the same conditions.
A table showing the relations of the derivatives of alcohol and acetic
acids is given. L. T. O'S.
Existence of Double Salts in Solution. By P. H. B. Ing ex-
hoes {Ber., 12, 1678—1684).~Barmmform{on{trate, Ba.NO3.CHO3 +
2H0O, is prepared by dissolving barium nitrate in an almost satu-
rated warm solution of barium formate. Crystals of barium nitrate
are first deposited, and then the double salt separates out. Solutions
of barium formio-nitrate and aceto-nitrate and calcium acetochloride
when dialysed, diffuse like mixtures of simple salts ; this shows that
these salts dissociate in dilute solutions. W. C. W.
Oxidising Action of Cupric Oxide ; Transformation of Acetic
Acid into Glycollic Acid. By P. Casexeuve (Compt. rend., 89,
525). — It is known that formic acid is oxidised by cupric oxide to
carbonic acid, and similarly, if carbonic acid be regarded as the acid
of methylene glycol, it might be expected that acetic acid, the homo-
logue of formic acid, v/ould be oxidised to glycollic acid.
Cupric acetate was heated in a sealed tube with water at 200° for
an hour. The tube contained crystallised cuprous oxide, and a liquid
which deposited crystals of glycollate of copper. A small quantity
of carbonic anhydride was also foi'med. The reaction is probably
expressed by the equation, 2Cu(C2H302)o + 2HaO = C2Hi03 -f-
CuoO + SCoHiOo.
The carbonic anhydride is due to a secondary reaction by which
propionic acid is also formed : 2Cu(C2H302)2 + H2O = COo +
C3H6O2 + CuoO + 2C2H4O2 : this reaction takes place to a very limited
and variable extent. C. W. W.
Action of Nitric Acid on Epichlorhydrin. By Y. v. Rtchter
(J. pr. Chem. [2], 20, 193 — 196). — When epichlorhydrin is treated
with 3 or 4 parts of warm nitric acid (sp. gr. 1"38) an energetic reac-
tion takes place. On pouring the acid liquid into water and extracting
with ether, monochloroladic acid is obtained. To remove the chloro-
nitrohydrin and oxalic acid with which it is mixed, it is dissolved in
water, again extracted with ether and converted into the calcium salt.
The acid crystallises in flat prisms (m. p. 77°), which are deliquescent
and dissolve readily in alcohol, ether, and water. W. C. W.
Ethyl Nitracetate. ByFoRCRAND (J. pr. Ghem. [2], 19, 487—488).
— This is obtained by the action of silver nitrite on ethyl bromacetate.
The product is distilled, and the portion which passes over at 150°
(with slight decomposition) is essentially etliijl nitracetate, a liquid of
sp. gr. 1'133 atO° (b. p. 151 — 152°). By the action of zinc and hydro-
ORGANIC CHEMISTRY. 33
cliloric acid it was converted into amido-acetic hydroclilorido, whence
the silver salt was obtained in iridescent crystals which blacken on
exposure to the light. A. J. C.
Preparation of Nitrated Fatty Acids. By J. Lewkowitsch (/. pr.
Chem. [2], 20, L59 — l~o). — Xitro-products could not be obtained by
the action of the strongest nitric acid (sp. gr. 1'55) or of a mixture of
nitric and sulphuric acids on caproic and stearic acids.
Ethyl nitroacetate, CH2(N02).COOEt, is formed by digesting ethyl
iodacetate with silver nitrite at 100° ; towards the end of the process
the mixture is heated up to 130"^. On treating the product with abso-
lute ether, a pale-yellow liquid, insoluble in water, is obtained, which
boils between 150° and 160° with decomposition.
Ethyl 7iitropropionate, prepared by the action of silver nitrite on
ethyl ^-iodopropionate (which is most readily obtained by heating an
alcoholic solution of (J-iodoprojiionic acid with a small quantitv of sul-
phuric acid), is a colourless mobile liquid (b. p. IGl — 165''). The
ethyl salt dissolves in a dilute solution of potash ; by acidifying the
liquid with sulphuric acid and extracting with ether, crystals of nitro-
propionic acid were in one instance obtained, but the operation gene-
rally yields a thick liquid which dries up to a hard gla.ssy mass when
exposed over sulphuric acid.
fi-Nitrojjrcqnoiiic acid is easily obtained by adding about 2 equivalent.s
of silver nitrite to 1 of /3-iodopropionic acid dissolved in water. (The
best results are gained by working with not more than 5 gi'ams of
iodopropionic acid for each operation.) The solution of silver nitro-
propionate which is formed is decomposed by hydrochloric acid and
extracted with ether. After evaporating the ethereal solution, a thick
liquid remains which solidifies forming a white deliquescent crystalline
mass. By recrystallisation from chloroform, the nitro-acid is obtained
in pearly-white scales which melt at 66° and decompose at 160°. The
acid is soluble in water, alcohol, and ether; its salts are also soluble in
water, but undergo decomposition. By reduction with tin and hydro-
chloric acid, /3-nitropropionic acid is converted into (3-alanine hydro-
chloride, W. C. W.
Derivatives of Thiacetic Acid. By S. Gabeiel {Ber., 12, 1639 —
1641). — Fhemjlene-dithiaGetic acid, C6H4(S.CH2.COOH)o, is prepared
by the action of chloracetic acid (2 mols.) on a warm alkaline solution
of thioresorcinol (1 mol.). On acidifying the mixture with hydro-
chloric acid, the acid separates out as an oily liquid, which soon
solidifies to a crystalline mass. The crj'stals melt at 127°, forming a
turbid liquid which becomes clear at 150°.
Toluene-dithiacetic acid, C6H3Me(S.CH2.COOH)2, obtained by a
similar reaction, crystallises in needles (m. p. 151"5°), soluble in hot
water.
Phenylene-dioxyacetic acid, C6H4(O.CH3.COOH)o,. produced by the
action of chloracetic acid on an alkaline solution of resorcinol, forms
pale-yellow crystals (m. p. 193°). Dihromopjhenylene-dioxyacetic acid,
separates out as a white powder when bromine vapour is passed into
the aqueous solution of this acid. It is deposited from a hot alcoholic
VOL. XXXVIII. d
.34 ABSTRACTS OF CHEMICAL PAPERS.
solution in white, silky needles (m.^i"). 250°). Benzyl-tliiaceiic acid,
CeHs.CH.-S.CHo.COOH, crystallises in -flat plates (m. p. 59°). The
amide, CGHg.CHa.S.CHo.CONH-.., is obtained in rectangular plates
(m. p. 97°), by the action of ammonia at 100° on ethvl benzyl-thi-
acetate(b.p. 275— 290°). W. C. W.
Laurie Acid and its Conversion into Undecylic Acid. By F.
Kkafft {Ber., 12, 16G4 — 16GS).— Laurie acid is best prepared from
commercial bay oil (01. lanrin nngninos). For this purpose the oil is
saponified by boiling with a solution of potash for several hours ; the
potash soap is decomposed by Wcxrm hydrochloric acid, and the niixture
of acids thus set fi'ee is distilled under greatly diminished pressure.
The first poi'tion of the distillate subjected to repeated redistillation
under diminished pressure yields pure lauric acid (m. p. 43"5°, b. p.
222'5° under 100 mm. pressure).
The l-etone, C13H26O, obtained by the dry distillation of a mixture
of baiium laurate and acetate under diminished pressure, melts at 28°
and boils at 263°. On oxidation with chromic mixture this substance
yields acetic acid and an oily liquid consisting of a mixture of unde-
cylic acid and unaltered ketone. The undecylic acid is converted into
its barium salt, which is treated with ether to remove the ketone.
This acid crystallises in scales, which melt at 28" 5° and boil at 213°
under 100 mm. pressui'e. 'W. C. W.
Tridecylic, Pentadecoic, and Margaric Acids. By F. Krafft
{Ber., 12, 16G8 — 1675). — ]\Iyristicacid, prepai'ed by the saponification
of Muscata butter and purified by distillation under diminished pres-
sure, melts at 5o"5° and boils at 248° under 100 mm. pressure.
The ketone, C15H13O, obtained by the dry distillation under dimi-
nished pressure of a mixture of barium acetate and myristate, melts
at 39°, boils at 294°, and on oxidation yields acetic and tridecoic
acids.
The latter acid, purified by redistillation and conversion into its
barium salt, melts at 40"5° and boils at 236° under 100 mm. pressure.
By a similar process pentadecoic acid, C15H30O2, can be obtained
from palmitic acid (m.p. 62° and b. p. 268"5° under 100 mm. pressure).
The ketone melts at 48° and boils at 320°. Pentadecoic acid melts
at 51°, and boils at 257° under 100 mm. pressure.
Margaric acid, prepared synthetically from stearic acid (b. p. 287°
under 100 mm. pressure), is identical with the margaric acid obtained
hy Heintz (Fogg. Ann., 102, 257) by the saponification of cetyl
cyanide. The acid melts at 59'8° (uncorr.), and boils at 277° under
,100 mm. pressure.
The discovery of tridecoic and pentadecoic acids makes the list of
fatty acids complete as far as stearic acid. W. C. W.
Hydroxethylmethylacetic Acid. By W. v. Miller (Ber., 12,
1544). — To show that JSTeubauer's angelic acid resulted from ethyl-
methylaeetic acid, which, together with isobutylformie acid, is a product
of the oxidation of amyl alcohol obtained by fermentation, the author
ORGAXIC CHEMISTRY. 35
prepared ethj Imethylacetic acid by Sauer's process, and oxidised it
with potassium permanganate. The product was 'a-hydroxethyl-
methyhxcetic acid. CKt:\Ie(OH).COOH (m. p. 68°). On distilling this
acid with sulphuric acid no methylcrotonic acid was formed.
W. R.
Hydroxisobutylformic Acid. By W. v. Mfller (Her, 12, 1.542
— 154;3). — From a careful comparison of the copper salts, the author
concludes tluit the dimethacrylic acid, prepared by him by oxidising
/3-hydroxisobutylformic acid, CMe.>(OH).CH...COOJEI, is identical
with an acid obtained by A. and M. Saytzeff, by oxidising syntheti-
cally prepared allyl dimethyl carbinol. The /3-hydroxisobutylformic
acid, of which the formula is given above, is an intermediate product
between isobutylformic acid and its ultimate product of oxidation
with potassium permanganate, viz., dimethacrylic acid. W. R.
Synthesis of Ketonic Acids. By P. Hofferichter (J. ])r. Chem.
[2], 20, 195 — 200). — Trichloro.ceiic cyanide, prepared by the action of
silver cyanide on trichloracetic bromide, is a colourless liquid (b. p.
117 — 119°), soluble in ether. It refracts light powerfully, and has a
sp. gr. 1'559 at 15°. It is decomposed by water with formation of
hydrocyanic and trichloracetic acids. On exposure to moist air, a
deliquescent white crystalline substance is formed. A solid poly-
meride, which is produced in small quantities in the preparation of the
liquid trichloracetic cyanide, crystallises in rhombic plates (m. p. 140°),
soluble in alcohol and in ether. It is decomposed on boiling with
water.
TricMoracetylcarboxylic acid is formed when the liquid cyanide is
treated with, dilute hydrochloric acid (sp. gr. 1"1G) at 50°. It is
separated from trichloracetic acid by recrystallisation of the sodium,
salts. Sodium trichloracetylcarboxylate crystallises in prisms contain-
ing 2 mols. HjO, which are less soluble than the tabular crystals of
sodium trichloracetate. The acid forms small prisms (m. p. 89°),
soluble in water. By the action of fuming hydrochloric acid on tri-
chloracetic cyanide, a white crystalline amide is produced, which
appears to have the composition CgCleOsHsN.j. W. C. W.
Maleic Acid from Dichloracetic Acid. By S. Tanatab (Ber.,
12, 1563 — 1566). — Ethyl dichloracetate dissolved in alcohol is not
acted on by molecular silver at the boiling point of alcohol ; if, how-
ever, ethyl dichloracetate is heated with molecular .silver at 210° in
sealed tubes, silver chloride is formed, and a small quantity of an
ethereal salt boiling about 210°, which on saponification with baryta-
water yields barium maleate.
Sodium acts energetically on dry ethyl dichloracetate ; if the reaction
is modified by use of anhydrous ether, thcT'e is found amongst the pro-
ducts of decomposition, an ethereal salt distilling between 100 — 120°,
which is more soluble in water than the ethyl dichloracetate ; it is
soluble in warm baryta- water. On standing, this solution decomposes
with formation of barium carbonate. The nature of this product is
as yet unexplained. P. P. B.
d 2
3G ABSTRACTS OF CHEMICAL PAPERS.
Occurrence of Tricarballylic and Aconitic Acids in Beet-
Juice. By E. 0. VON. LiPPMANN (Ber., 12, 1649 — 1651). — Tricarbally-
lic acid is not found in fresh beeti^oot, but the author confirms his
previous observation (Ber., 11, 707, this Journal, 1878, Abst., 662) as to
the occurrence of the calcium salt of this acid in the vacuum pans of
the beet-sugar manufactoiy. Aconitic acid, detected by Behr in the
juice of the sugar-cane (Ber., .10, 351, this Journal, 1877, 2, 182) is
also present in beet-juice. W, C. W.
The Acid of Drosera Intermedia. By G. Stein (Ber., 12,
160o). — According to Lucas and Trommsdorf (Annalen, 8, 237) the
acid contained in this plant is malic, whilst Reess and Will (Centrul-
II aft f. ArjriculfyyrcJtevne, 10, 230) siippose it to contain formic, pro-
pionic, and butyric acids, and finally Hager asserts that it contains
citric and malic acids. The author has extracted some of this acid,
and from the chai'acters of its salts concludes that it is citric acid.
The acid has also been obtained ci-ystallising in rhombic prisms, and
the analysis of its lead salt shows it to be citric acid. P. P. B.
Derivatives of Triethyl citrate. By J. Conen (Ber., 12, 1653 —
1655). — Triethyl citrate, C3H40H(COOEt)3, prepared by the action of
hydrochloric acid on a mixture of citric acid and alcoliol, is a thick
colourless liquid, sp. gr. 1*1369 at 20° compared with water at 4°,
b. p. 261° under 300 mm. pressure.
Tetrethyl citrate, C3H40Et(COOEt)3, is formed when tbe j^roduct of
the action of sodium, on triethyl citi-ate (diluted with dry ether) is
heated wnth ethyl iodide at 100°. This citrate is a pale-yellow oil,
sp. gr. 1-1022 at 20°, boiling at 290° with decomposition.
A liquid having the composition C3H3(COOEt)3, and of sp. gr.
1"1064, is produced by heating a mixture of phosphoroiTS chloride and
ethyl citrate at 100°. This substance decomposes on distillation.
w. c. w.
Action of Phosphorus Pentachloride and Hydriodic Acid on
Saccharic Acid. By H. dk la Motte (Ber., 12, 1571 — 1573).— The
results published by C. J. Bell (this Journal, Abst., 1879, 917) are
the same as those published by the author in his Dissertation (Halle,
1878). The author also points out that chloromucic acid obtained
from saccharic or mncic acid always crystallises with 2 mols. of water
of crystallisation, CcH,CL042H20.
Saccharic acid when heated with hydriodic acid and amoi'phoixs
phosphorus in sealed tubes at 140 — 150", yields a small quantity of an
acid, m. p. 148 — 149°, the analysis of which, and its properties, as also
those of its salts, show it to be adipic acid. P. P. B.
Constitution of Deoxalic Acid. By J. Klein (J. pr. Ghem. [2],
20, 146 — 159).^ — By acting on ethyl oxalate with sodium-amalgam,
Lowig, in 1861, obtained a substance of the formula ChHikOs, which
he regarded as the triethyl salt of deoxalic acid, CoHoOg, and by heat-
ing this with dilute sulphuric acid, he converted it into ethyl racemate,
with evolution of carbonic anhydride. Brunner, in 1870, contended
ORGAXIC CnEMISTRY. 37
that the original reduction-product of ethyl oxalate has the formula
CviHooOg, and is the triethyl salt of an acid of the formula CftHcOg,
which, however, he could not isolate, owing to its decomposition into
racemic and glyoxylic acids. The author has confirmed Lowig's results
in the following manner: — Ethyl deoxalate prepared by the action of
sodium-amalgam on ethyl oxalate melts at 8-5'', and has all the pro-
perties attributed to it by Lowig. The barium salt was prepared by
titrating the ethyl salt with standard baryta-water. Both^he titra-
tion and the analysis of the barium salt point to the correctness of
Lowig's formula. The calcium salt has the formula (C5H308)-Ca3.
The free acid, prepared from the barium salt by means of sulphuric
acid, forms very deliquescent crystals, and from several analyses
appears to have the formula CsHeOy.HaO.
Treated with acetic or with benzoic chloride, it forms nionacetyl-
and benzoyl-deoxalic acid, and with acetic anhydride, or with benzoic
chloride, at a higher temperature, a diacetyl or dibenzoyl acid. It
appears therefore to contain two alcoholic hj'droxyls. Tlie amount of
carbonic anhydride evolved on boiling the acid with dilute sulphuric
acid was estimated, and agreed with the equation CoHsOs.Et^ =
C4H306.Et3 + COo, ethyl racemate being formed at the same time.
The ethyl racemate gave an acid agreeing with tlie ordinary racemio
acid in all its properties.
On heating deoxalic acid with hydriodic acid no reduction took
place, but it was converted into racemic acid, and at a still higher
temperature, succinic acid was produced. The tricarboxylic acid,
of which deoxalic acid is a hydroxylic derivative, was not isolated in
this reaction. W.. R.
Synthesis of the Closed Benzene Ring. By V. v.. Richter
{J.yr. Chein. [2], 19,205 — 208. — In order to accomplish the synthesis
of benzene by means of diethylenc-diketone the author subjected the
succinates of potassium, sodium, magnesium, calcium, and lead to dry
distillation. The distillate contained quinol, and benzene was obtained
by the action of zinc dust on the distillate, but diethylene-diketone has
not yet been isolated.
No benzene derivatives were formed by distJilling ethylene succinate
with zinc dust. W. C. W.
Derivatives of Isodurene. By M. Bielefeldt [{Amialeiv, 198,
380 — 388). — The isodurene used in these experiments was prepared by
the method described by Jannasch {Bur., 8, 355), viz., by the action
of sodium on a mixture of monobromomesitylene and methyl iodide
diluted with a small quantity of benzene. Isodurene boils at 195 —
197°. Isodurenesuljjhonic acid obtained by treating the hydrocarbon
with fuming sulphuric acid crystallises in plates which melt
in their water of crystallisation at lOO"".. Lead isodiirenesulpltate,
(C6lIMe4S03)..Pb + 3H,iO, forms needle-shaped .cijstals, so also do
the salts of barium (anhydrous), calcimn ,(3H20), and jjotassium
(IHoO). The cop^per salt crystallises in pale bluish-gi*een needles,
which are anhydrous. The silver salt forms transparent rhombic
plates; the strordiuni salt is deposited in lustrous plates containing
38 ABSTRACTS OF CHEMICAL PAPERS.
9 mols. HoO. The sodium salt crystallises in shining rhombic plates
containing ^ mol. HoO. The coiaJt salt crystallises- in pale red four-
sided plates which contain 7^ mols. HoO.
When isodurene is boiled with dilute nitric acid (1 : 4), for two days,
a mixture of a- and (S-isoduric acids (C10H12O2) is formed, together
with a polybasic acid, which does not. melt at 300", and also several
nitro-prodncts. The a- and /3-acids can be separated by recrystallisa-
tion fromf* hot water, or by fractional crystallisation of their calcium
salts.
a-Isodttric acid melts at 215° and at a higher temperature sublimes,
forming long glistening needles. It is very sparingly soluble in
water, but dissolves in alcohol, ether, and hot benzene. From a dilute
ethereal solution, the acid is deposited in clear monoclinic crystals
which refract light powerfully. The a-acid can be distilled in a
current of steam. Its salts are crystalline and are soluble in water.
(Ci„H„02)2Ca + 5H20, (CioHu02)2Sr+ 5H2O, and (CioH„02)2Ba + 4H20
form needle-shaped crystals.
(3-Isodi(rio acid is much more soluble in water, ether, chloroform,
benzene, alcohol, a^ud light petroleum than the a-acid. It crystallises
in needles which melt at 120 — 123°, The calcium salt forms ghsten-
ing needle-shaped crystals containing 2 mols. HoO.
Monobromisodurene boils at 252 — 254°,. and crystallises in nacreous
plates. W. C. W.
Behaviour of Cymene in the Animal Organism. By Jacobsen
(Ber., 12, 1512 — 1518). — As cymene has been prepared from normal
propyl iodide and parabromotoluene, and as the author has shown that
the hydrocarbon produced from parabromocumene and methyl iodide i.s
not cymene, but an isomeride, no doubt would remain regarding the
constitution of cymene were it not for two reactions. The first of these,
noticed b}^ Kraut and confirmed by the author, is that cymene is pro-
duced by the action of zinc dust on cymyl alcohol, and the second is
the oxidation of cymene in the organism to cuminic acid, observed by
Nencki and Ziegler. Both of these results are unfavourable to the
theory that cymene contains a normal propyl group. In the present
paper, the author gives an account of a repetition of Nencki and
Ziegler's experiments.
The cymene was administered to a dog, and its ui'ine, after evapo-
ration, was acidified and shak-en with ether. After distillating off the
ether, the residue gave a copious precipitate with hydrochloi'ic acid,
which was found to consist for the most part of cuminuric acid,
C10H15NO3. The filtrate from this precipitate gave a distillate contain-
ing a little paraxylylic acid, showdng that the cymene administered to
the dog had contained a little pseudocumene.
Cuminuric acid melts at 168°, and volatilises without decomposi-
tion. It is almost insoluble in cold, but comparatively easily soluble
in warm water ; it dissolves with the greatest readiness in alcohol ;
ether, however, dissolves it with difficulty. From water it crystal-
lises— (1), on addition of an acid, in nacreous scales; and (2), on
slow evaporation, in large iridescent rhombic plates, without water of
ctystallisation -, and from alcohol, on evaporation, in radiated crystals.
ORGANIC CHEMISTRY. 39
The barium salt, (C..HuN03)..H,0, dissolveswith some difficulty,
aud crystallises from its hot solution in long right-angled plates or
in flat needles, arranged in a fan-shaped form. The calcium salt,
(Ci..H..iN0,)..3H,0, crystallises in thin needles, and is also soluble
witii difficulty. The ajnmonium^ and potassium salts are very easily
soluble, and crystallise in needles. The two latter salts give pre-
cipitates with salts of zinc, manganese, cadmium, magnesmm, ferrous
and ferric salts, copper, lead, and silver ; with mercuric chloride, it
gives no precipitate, and with mercuric nitrate, a flocculent insoluble
precipitate. , ■, . , r-. i
This cuminuric acid probably differsfrom that which Cahours pre-
pared from cuminic chloride and glycolyl silver.
In order further to confirm the relations of this acid, it was decom-
posed by heating with hydrochloric acid ; it split up into glycocme and
cuminic acid, melting at 116—117°, and agreeingin all its properties
with that described by others. It thus appears that cuminic acid is
really a product of oxidation of cymene in the animal organism, but
to remove all doubt, and further to connect cuminic and cu mi nunc
acids, the latter acid was svnthetically prepared from cymyl alcolioi
and glycocol silver. The product was identical in all respects with
that separated from the urine. .
If then, there is conclusive proof that cumene contains normal
nrop'yl and that cuminic acid contains isopropyl, then the preparation
of cumene from cymyl alcohol with zinc dust involves the trans-
tbrmatioiL of isopropyl into normal propyl, and, on the other hand, the
formation of cuminic acid from cymene implies the opposite change
In conclusion, the author draws attention. to the fact tnat m bis
experiments, the chief product was cuminuric acid, whilst m those of
Xencki and Ziegler, cuminic acid was formed. He also found the
latter acid, but in very small amount. ^^ • ^■
Products of Distillation of Gum-ammoniac Resin with
Zinc-dust. By G. L. Ciamician (IJcr., 12, 1008— 1604).— Tlie oily
liquid which is obtained by the distillation of gum-ammoniac resm
with zinc-dust consists of a mixture of para- and metaxylenes (b. p.
136— 1380, meta-ethyltoluene (b. p. 160°), methyl ortho-ethylphenate
(I p 180 200"), and a hvdrocarbon having the composition CiatLooU,
which yields on oxidation benzoic, acetic, and perhaps propionic acids.
No naphthalene derivatives are formed. Ortho-ethylphenol obtained
by the saponification of the methyl ether is a thick, colourless oil
(b p 2'>00 which remains liquid when cooled down m a freezing
mixture. On fusion with potash, it is decomposed with P^duction of
salicylic acid.
Condensation-products of Aldehydes with Primary Aromatic
Bases. By O. Fischek {Ber., 12, 16'Jo—16'J-l).— Although the author
was unable to obtain diamlJotrijjheuylmethane by decomposing tetra-
methyldiamidotriphenylmethane with concentrated hydrochloric acid,
he has succeeded in preparing it by the action of zmc chloride on a
mixture of aniline and benzaldehyde. This base is a crystalline sub-
stance and is soluble in light petroleum. By the action of methyl
40 ABSTRACTS OF CHEMICAL PAPERS.
iodide, at 130°, on the solution of the base in methyl alcohol, tetra-
methyldiamidotriphenylmethane methiodide is produced.
w. c. w.
Condensation-products of Tertiary Aromatic Bases. By
0. Fischer (Ber., 12, 1685 — 1693).— A good mode of preparing
tetrametltyldiamidotriphenylnietliane consists in digesting on a water-
bath a mixture of beuzaldehyde (1 mol.) and dimethylaniline (2 mols.)
-vvith a quantity of solid zinc chloride, equal in weight to the dimethyl-
aniline taken, until scarcely any dimethylaniline separates out on the
addition of an alkali to a small quantity of the product. If the mass
grows very thick during the operation, sufficient water should be
added to reduce it to a pasty consistency. The solution obtained by
treating the crude product with boiling water deposits the base in a
state of comparative purity. The Jiydroehloride, C23H26l^22HCl, crys-
tallises out in colourless hygroscopic needles, when ether is added to a
solution of the base dissolved in strong hydrochloric acid mixed with
alcohol. The methiodide, C2.3H26N22MeI, is deposited from concentrated
aqueous solutions in plates, and from dilute solutions in needles,
which melt at 218 — 222° with decomposition into methiodide and
the original base.
TetrametliyldiamidotripJienylcaTbinol, C23H2iN2.H20, the base con-
tained in benzaldehyde green, is obtained in colourless needles by
recrystallising from light petroleum the precipitate formed by the
action of an alkali on the salts pi'oduced by the oxidation of the leuco-
base.
The crystals melt at 120°, and form ethers when recrystallised
from alcohol. The ethyl ether., best prepared by heating the carbinol
with alcohol at 110"", melts at 162°.
The zincocMoride, C23H24N^2 + ZnCl^ + H2O, crystallises in dark-
green glistening needles or scales freely soluble in water. The
sulphate, ■C23H24N3 -h H2SO4, forms beetle-g^reen needles, containing
1 mol. of water. The methiodide, C23H2oOCH3]Sr2(MeI)2 + 2H2O, crys-
tallises in colourless needles, which begin to decompose at 100°.
The constitution of benzaldehyde gi-een (Ber., 12, 796 ; and this
Journal, 1879, Abst., 787) is represented by one of the following
f 04"mula3 1-^^
ri XT
Ph(C6Hi.NMe2)C<p'Tj^>NMe, or Ph(C6H,.NMe2)C<f {
^^' ^NMe : CHo.
Tetramethyldiamidopj-ojyyltrijjhenylmefJiane, obtained from cumic alde-
hyde and dimethylaniline, crystallises in long colourless needles (m. p.
118°). It bears close resemblance to the leuco-base of benzaldehyde
green, yielding on oxidation a bluish-green colouring matter.
Dimethylaniline and methylal yield tetramethyldiamidodiphenyl-
methane (m. p. 91°), which has been previously described by Han-
hart (Bevc, 12, 681 ; this Journal, 1879, Ahst., 714. Doebner (Ber.,
12, 810), and by Michler and Moro (ibid., 12, 1170). The compound
Vshich Pauly (A)t7talen, 187, 198) obtained by the action of benzo-
ORGAXIC CttEMISTRY. 41
phenone cliloride on dimethylaniline has the composition C21H21N, and
not CoiHigN as given by the discoverer.
Dimethylanilinc-phthalein, C24H>ilSr,Oo, is prepared by the action of
zinc chloride on a mixture of phthalic chloride and dimethylaniline.
The excess of dimethylaniline is removed from the resulting product
by treatment with hot water, and the residue is dissolved in dihite
acetic acid. The precipitate which is thrown down on the addition
of an alkali to this acid liquid is dried and dissolved in a small quantity
of benzene. When light petroleum is poured into this solution, the
impurities separate oat, together with a portion of the phthale'in. On
evaporating the filtrate, the phthalein slowly crystallises out, and is
purified by recrystallisation from benzene. The pure substance forms
colourless rhombohedrons, which melt at 188°. A green colouring
matter is produced as a bye-product in the preparation of dimethyl-
anilinc-phthalein ; its formation increases with the temperature at
which the process is conducted. W. C. W.
Some New Colouring Matters. By P. Greiff (Ber., 12,
1610 — ItJll). — By the action of chloranil on dimethylaniline, a deep
bluish-violet colouring matter is obtained : it is insoluble in water, but
dissolves in alcohol and acetic acid. Methyldiphenylamine gives a
folouring matter of a deeper blue. These reactions take place at the
ordinary temperature, and give good yi.elds. C^uinone gives similar
products. Chloranilic acid and the sulpho-acids of chloranil react
differently. Phenanthraquinone gives under similar circumstances
bluish- violet bodies, having strongly marked dichroism. The addition
of zinc chloride in all these reactions is advantageous. P. P. B.
*o^
Action of Hydrocyanic Acid on Diazo-compounds. By
S. Gabriel {Bur., 12, 1087 — lGo9). — A substance, having the com-
position CfeHeNj, separates out in orange-coloured crystals when a cold
aqueous solution of diazobenzenesulphate or nitrate is allowed to drop
slowly into a well-cooled solution of potassium cyanide. The crystals
are dissolved in a small quantity of warm alcohol, and warm water is
added to the solution. When the mixture cools, large prisms (m. p.
69°) are deposited, which decompose, forming a brown resin, if left in
contact with the mother-liquor for several hours. The compound is
also decomposed by boiling in water, hydrocyanic acid being evolved,
and a resinous body formed.
By the action of potassium cyanide on bromodiazobenzene nitrate
(from bromaniline, m. p. 61) an unstable crystalline product (m. p.
127*5") is obtained, which appears to have the composition CsHsBrNi.
By a similar reaction, the compound CoHsXi may be prepared from
toluene. It is deposited from an alcoholic solution in reddish-yellow
plates or needles, which melt at 77"5°, but decompose if heated at 60°
for some time. W. C. W.
Formula of Quinhydrone. By H. Wichelhaus (Ber., 12, 1500 —
loOo). — The question considered in this paper is Avhich one of the fol-
lowing formulae for quinhydrone is the correct one : —
HO.CsHi.O.O.CeH^.OH = CrHi,A
42 ABSTRACTS OF CHEMICAL PAPERS.
proposed by Graebe, or H0.C6H,0.0CGH,0.0CeH,.0H = CoHjoOe,
suggested by the author.
Nietzki's argument in favour of the former formula is, that as
quinone is reduced to quino] in theoretical proportion by sulphurous
acid, quinhydrone should also be acted on in the same manner. In
support of this view, he has adduced a series of experiments, in which
quinhydrone was reduced by such a quantity of sulj^hurous acid as to
lead to the formula CioHi()04.
The author has repeated these experiments, and has found that they
are untrustworthy,. owing to the fugitive blue colour produced by iodine
in presence of quinhydrone during titration., of excess of sulphurous
acid.
He next brings foi'ward in support of liis own views, the fact
that metUylquinhydrone, prepared by melting at 100° a mixture of
methylquiuol with, quinone, gives numbers which, though differing
but slightly from those required for Graebe's formula, still agree
better with the formula proposed by him ; also, that during the re-
action between methylquinol and quinone, hydrogen is set free, which
reduces the latter, giving rise to a considerable formation of quinol ;
and, lastly, that on decomposing methylquinhydrone with sulphurous
acid, the resulting quinol bears to the methylquinol the proportion of
1 : 2"5. This agrees closely with the proportion calculated for
CooHiaOfi, viz., 1 : 2-26, but not with that for C13H10O4, viz., 1 : 1-13.
In further suppoi't of his 'views, the author calls attention to the
fact that dimethyl- and diethyl-quinone have no action on quinol, for
liydroxyl is not present in their molecules. When substituted quinols
act on quinone, unsubstituted quinhydrone is invariably formed, whilst
a reduction takes place owing to the liberated hydrogen.
In a similar manner the formation of chloroquinol by. treatment of
quinone with hydrochloric acid is explicable by the following
equations : —
CcH^O^ + 2HC1 = CgHoOo -f Clo ; and CI2 + CeHeOs =
CeH^ClOo +; HCl.
An analogous reaction takes place with hydrobromic acid. The
resulting monobromoquinol has the formula^ C6H5Br02 ; it may be
sublimed in small quantities, melts at 110 — 112°, and is soluble in
chloroform, benzene, and hot water; During its purification by crys-
tallisation from light petroleum, a product, agreeing fairly with the
formula C6H4BroO, is obtained less soluble than the former ; it crys-
tallises in white needles grouped in stars, and melts at 185 — 186°.
W. R.
Constitution of Phenylhalogenpropionic Acids, By E. Erlen-
MEYKK (Ber., 12, 1G07 — 1610). The author criticises the views held
by Glaser (A^malen, 154, 167) and Fittig (ibid., 195, 170) on the
constitution of the phenylhalogenpropionic acids and phenyllactic
acids prepared by them, and concludes that these acids have the fol-
lowing constitutions : —
CeHs.CHX.CH-.COOH ; CcH5.CH(OH).CH2.COOH, and
aH5.CH(0H).CHX.C00H. P. P. B.
ORGANIC CHEMISTRY. 43
Monobromocinnamic Acids and Phenylfumaric Acid. By
V. Bakisch (/. pr. Chem. [2], 20, 173— 188).— By the action of
alcoholic potash on dibromohydrocinnamic acid, Glaser (Anualea, 143,
330) obtained two isomeric monobromocinnamic acids, which were
separated by recrystallising their ammonium salts. yS-Bromostyrene,
PhCBr '. CHj (b. p. 117°), is formeil as a bye-product in this opera-
tion from the decomposition of a portion of the monobromocinnamic
acid (m. p. 131°), PhCBr : CH.COOH.
Glaser prefixes a to the acid crystallising in needles (m. p. 131°),
and calls the isomeride which forms crystalline plates (m. p. 120°)
the /3-acid. The author proposes to reverse this nomenclature, since
a-dferivatives have a lower melting point, and enter more readily into
reactions than /3-compounds. Both a- and /3-mouobromocinnamic acid
when treated with alcoholic potash yield the same pheuylpropionic acid,
PhC : C.COOH. When hydrochloric acid is passed through their
alcoholic solutions, they both yield the same ethyl /3-bromocinnaraate
(b. p. 290°). The a-acid during the act of etherification is transformed
into the /3-acid.
Fhenylfumaric acid, CI0H8O4, or COOH.CPh '. CH.COOH, is ob-
tained by heating at 150° a mixture of potassium cvanide, alcohol, and
ethyl-/3-bromocinnamate, and boiling the product with alcoholic
potash. On the addition of hydrochloric acid, a resinous substance
separates out, the supernatant liqiiid is concentrated by evaporation
and extracted with ether, when the new acid is obtained in white
crystals (m. p. 161°),- freely soluble in alcohol, ether, and hot water.
The potassium, sodium, ammonium, calcium, and barium salts of this
acid dissolve readily in water. W. C. W.
Formation of Para-hydroxybenzoic Acid from Sodium Phe-
nate. By H. Osr (/. pr. Chem. [2] 20, 208)-.— Very small quantities
of para-hydroxybenzoic acid and ti-aces of a-phenol-dicarboxylic acid
are formed by the action of carbonic anhydride on sodium phenate.
The presence of these acids can be detected in the filtrate after the
precipitation of the salicylic acid. W. C. W.
Constitution of EUagic Acid. By H. Schiff (Ber., 12, 1533—
1537). — Gallic acid, when boiled with arsenic anhydride, forms digallic
acid by union of two molecules. If the mass is dried and heated to
160°, the arsenic acid is reduced and ellagic acid is formed : —
2CuH„A + AS.O5 = 2CuH60, + 4H,0 -f- As.Os.
The question is, are the two benzene-groups in ellagic acid united
directly, or by means of oxygen ? The ease with which that acid is
formed from gallic a-cid seems to point to a negative answer ; but, on
the other hand, no attempt to convert ellagic into gallic acid has been
successful. Assuming: that direct union subsi.sts, the author sugofests
the following formula) : —
2C6H2(OH)3.COOH = C6H(OH),(COOH).C6H(OH)3.COOH.
2 mols. of ellagic acid. Ellagic acid dried in air.
Ellagic anhydride cannot be etherified, does not combine with hydro-
o-en, and cannot be reconverted into g'allic or tannic acids ; it forms a
44 ABSTRACTS OF CHEMICAL PAPERS.
tetracetyl derivative. The author supposes it to have one of the follow-
ing formulae : —
CO— C6H(OH)2 0^ >C6H(0H),
/0\| °" 10-^1
CO— C6H;0H)., CO- CeHCOH)^.
The two molecules of water are not expelled at the sam-e temperature,
but it has recently been shown that the temperature at which the
second is expelled is much lower than was formerly supposed. These
formulae sufficiently represent the neutral and basic salts formed by
ellaffic acid. W. R.
"o'
New Organic Acid occurring in Agaricus Integer. By W.
Teornek {Ber., 12, 1635 — 1637). — From 19 to 20 per cent, of mannitol
can be extracted from Agaricus integer by treatment with boiling
alcohol. An acid having the composition CisHsoOo is contained in the
alcoholic mother-liquors. In order to isolate it, the alcoholic solution
is evaporated to dryness on a water-bath, the residue is exhausted first
with water to remove any mannitol which may be present, and then
with hydrochloric acid. It is finally dissolved in a solution of soda to
which one-third of its volume of alcohol has been added. After eva-
porating- off" the alcohol, the acid is precipita^ted by boiling with dilute
hydi-ochloric acid. The pure acid is deposited from an alcoholic solu-
tion in white needles (m. p. 70°) soluble in ether, benzene, toluene,
carbon bisulphide, chloroform, boiling alcohol, and boiling glacial acetic
acid. The potassium, sodium, and ammonium salts are sparingly soluble
in cold water, but dissolve in warm dilate alcohol. Ba( 015112902)2 and
Pb(Ci5H2902)2, and also the calcium, magnesium, and silver salts are
white insoluble compounds. The lead salt melts at 114°.
w. c. w.
Kynuric Acid. By M. Kretschy '{Ber., 12, 1673—1675).—
Kynuric acid is completely resolved into its elements by fusion with
potash. Chinoline is formed when this acid is heated at 240° with
strong h3'drochloric acid, and also when it is distilled with zinc-dust.
W. C. w.
Aromatic Thiocarbamides. By C. FEUERLEm {Ber. ,11, 1602 —
1603). — The preparation of phenylcyanamide from monopheuyl thio-
carbamide has been described in a former communication (this Journal,
Abst., 1879, 804). From analysis, its formula is (IS"!! \ C '. NPh)2_ +
3H3O ; when placed over sulphuric acid, it forms a syrupy mass, which
on standing becomes crystalline, forming phenylcyanamide. The
platinum, (NH '. C '. NPhHCl)2PtCl4, and the silver compounds,
(NH : C ; N(Ph))2Ag, have been obtained. Monophenyl thiocarb-
amide is converted into monophenylguauidine, NH2.C(NH)2Ph, by the
action of alcoholic ammonia. This compound when heated burns with-
out previously melting, and is decomposed by exposure to the air or
over sulphuric acid into phenylcyanamide. P. P. B.
Formulae of Thiohydantoins. By C. Liebermann and A. Laxge
{Ber., 12, 1388 — 1595). — One of the authors has already described
ORGANIC CHEMISTRY. 45
the prepai-ation of diphenylthioliydanto'in. (this Journal, Abst., 1879,
651), which when decomposed with alcoholic potash Avas supposed to
yield diphenyl thiocarbamide, potassium sulphide, and potassium gly-
collate. Further investigation has shown that this decomposition
yields thioglycollic acid, a reaction also observed by Andreasch (Ber.,
12, 1885). This decomposition is expressed thus : CuHioN-.SO +
KOH + H,0 = CisHi^NoO + C0H3KSO,. Diphenyl-thiohydantoin
is similarly decomposed by alcoholic ammonia at 150", forming aniline
and thioglycollic acid, thus: C„H,,N.,SO + 3NH3 + 4H.0 =
2aH,N + C0H3SO2NH, 4- CO,(NH0>.
The supposition that thioglycollic acid owes its formation to a
secondary reaction, is found to be untenable, since glycollic acid cannot
be converted into this thio-acid either by boiling with potassium hydi'O-
gen sulphide or with diphenylthiocarbamide and alcoholic potash.
Further, the product C9H7NSO2 obtained from diphenylthiocarbamide
(Joe. cit.) is also resolved by alcoholic potash and baryta-water into
carbanilide, carbonic anhydride, and thioglycollic acid. These i-esults
NPh— CH,
show that the formula, CS\ | , attributed to diphenylthio-
^I^Ph-CO
hydanto'in is incorrect. Rather must it be regarded as analogous to
Jager's phenylcarbodiimido-thiacetic acid,
COOH.CH.S.CCNHPh) : NH
(/. pr. Chem. [2], 16, 17), and therefore its formula is
/ S.H.,C
PhN:C< I .
^NPh.CO
Its formation may then be explained as follows : —
(1.) CS(XHPh), + CiaHoO, = ClC(NHPh),.S.CH,.COOH.
(2.) ClC(XHPh)oS.CH.,COOH - HCl - H,d =
^ S.H2C
PhN : C< I .
^XPh.CO
This view of the constitution of the thiohydanto'in is supported by
the investigations of Wallaeh (this Journal, 36, 312), Wallach and
Bleibtreu (Ber., 12,1061;, Bemthsen (A7male», 197, 341), and the
investigation on thiocarbamide of Clans (Ber., 7, 236 and 841).
In this light thiohydantoin will have the formula —
and the product obtained by Lange from diphenylthiohydantoi'n (loc.
cit.) is a derivative of monothiocarbanilic acid, having the formula
0 : CS<^pj^>CO. This is analogous to Volhard's CaH.XSOa
(J.pr. Chem., 9, 8), which may be written 0 '. CS<^.^'>CO. In
46 ABSTRACTS OF CHE.MICAL PAPERS.
an analogous manner Nencki's compounds (/. pr. Ghem. [2], 16, 1) has
PIT
the constitution S '. CS<-j^tj->CO, and to the carbaminethiacetic
acid of the same author, the formula 0 '. C(]SrHo)S.CH.,COOH may
be attributed.
These new formulfe also explain why it is so difficult to remove the
sulphur from thiohydantoins, a fact which has been pointed out by
Volhard (Annalen, 166, 384), Mulder (Ber., 8, \264^),M?i\j (Annalen,
168, 133), and noticed by the authors in the case of diphenylthiohy-
dantoin. P- P- B.
Action of Potassium Pyrosulphate on Indigo-white. By
A. Baeter (Ber., 12, 1600 — 1602). — According to Baumann, the indi-
can contained in urine is not a glucoside, but the potassium salt of a
sulphonic acid of indoxyl (Zeit. f. Physiol. Chem., 1, 60 ; Die Syntlie-
lischen Processe in ThierJcorper, Berlin, 1878, 6 ; E. Baumann and L.
Brieger, Zeit. f. Physiol. Ghem., 3, 254; and Baumann and Tiemann,
this Journal, Abst., 1879, 936). A body possessing the same proper-
ties as the above-mentioned indican is obtained by heating 1 part of
indigo, 1 of ferrous sulphate, 2 of potash, 2 of water, and 3—4 of potas-
sium pyrosulphate in sealed tubes for 12 lioui^s at 60°. "From tliis, the
author concludes that the indican from ui'ine is potassium liydrin-
digotin-sulphonate, Ci6HioN"2(O.S03K)2. Baumann's analyses contirm
this observation. P. P. B.
Action of Chlorine on Dibenzyl. Bv R. Kade (/. pv. Ghem. [2],
19, 4:^1— 4.^7).— ParadicUorodihenzyl, CeHiCl.CHo.CHo.CeHiCl (m. p.
112°), is formed by passing chlorine over the crystalline product
obtained by melting together iodine and dibenzyl, and continuing the
action until hydi"ochloric acid begins to be evolved. The resulting
thick cherry-coloured oil is distilled, and the crystals of paradichloro-
dibenzyl deposited from the oily distillate are purifiedby crystallisation
from alcohol. It forms rhin fine lamince, closely resembling naph-
thalene, and is easily soluble in alcohol, ether, and chloroform.
It can be sublimed, giving an odour of bitter almonds when heated,
and be distilled without decomposition. It yields parachlorobenzoic
acid by oxidation with chromic mixture.
The oily body which is formed at the same time is probably mono-
chlorodibenzyl.
Quite a different reaction takes place when chlorine is passed into a
mixture of pidverised dibenzyl with, iodine. In this case toluylene
with unaltered dibenzyl is produced. Toluylene is also formed to some
extent by the action of chlorine on the vapour of dibenzyl, and by
passing chlorine into melted dibenzyl until it begins to turn brown,
and then distilling, the whole is transformed into toluylene. Con-
tinning the action until hydrochloi'ic acid is again given off, dichloro-
toluylene, CuHmClo (m. p. 170") is obtained. It crystallises in silky
white needles or laminae, and easily dissolves in alcohol and ether.
Toluylene is also formed from dibenzyl by the action of potassium
chlorate and hydrochloric acid. It can be distilled and sublimed like
ORGANIC CHEMISTRY. 47
benzoic acid. Its alcoholic solution gives a red coloration with ferric
chloride. A. J. C.
Derivatives of j;-Dichloronaphthalene, r-Nitronaphthalene-
sulphonic Acid. Ey P. T. Cleve {Ber., 12, 1714).— e-Trichloro-
naplithaleue (m. p. 65°) was prepared by the action of phosphorus
pentachloride on »;-dichloroiiaphthalene (m. p. 48'^). The salts of
r-nitronaphthalenesulphonic acid are crj^stalline. The chloride of this
acid melts at 169°, the amide at 210'^, and the ethyl salt at 108'^.
W. C. W.
Action of Chlorine on Chloronaphthalene : Nitro-derivatives
of a- and /:i-Dichloronaphtlialene. By O. Widmaxx {Bar., 12,
1714 — 1715). — K-Monochloronaplithalene combines with chlorine to
form CoHsCl, (m. p. Q7°), and CoH^Cl.Cli (m. p. 131-5°), whilst
/i-monoohloi'onaphthalone forms a liquid trichloronaphthalene, and a
tetrachloride, C10H7CI.CU (m. p. 81°), which when treated with potash
gives a trichloronaphthalene, melting at 140°. By the action of chlo-
rine on an acetic acid solution of a-monochloronaphthalene, an aceto-
chloride, CloHgClo.ClsOAc (m. p. 195°) is produced. a-Dichloronaph-
thalene yields only one nitro-derivative, viz., the trinitro (m. p. 178°),
but the S-compound forms a mono- and a dinitro-derivative, which melt
at 92° and 158° respectively. W. C. W.
On the Quinone occurring in Agaricus Atrotomentosus.
By W. Thorner (iV., 12, IGoU — 1635). — The spectrum of the red
alcoholic solution of the quinone extracted from Agaricus atrotomen-
tosus by means of ether is characterised by a deep red band between
B and D.
A crystalline ammonium salt separates out as a dirty green-coloured
powder, when strong ammonia is added to a hot alcoholic solution of
the quinone. It dissolves in dilute alcohol and in water, forming a
violet solution, which produces coloured pi-ecipitates with many
metallic salts, viz., a flesh-coloured crystalline precipitate with barium
chloride:; dirty pink flocculent precipitate with calcium chloride ;
brownish-green with lead acetate ; black with ferric chloi'ide ; dark
green with mercuric chloride ; brownish-black with alum ; reddish-
brown with copper sulphate ; brown with platinum chloride ; dirty
green with silver nitrate ; and a beautiful green crystalline precipitate
with magnesium sulphate.
The compound obtained by the action of benzoic anhydride on the
quinone forms yellow needle-shaped crystals, which melt at 285° with
decomposition. By heating the quinone with dilute nitric acid, oxalic
and nitric acids and also a nitro-product are formed. The latter body
is a yellow powder (m. p. 255 — 260°) soluble in alcohol and chloro-
form.
By the reduction of the quinone with hydriodic acid, or by zinc and
hydrochloric acid, two bodies are produced, viz., a yellow powder,
insoluble in the usual solvents, but easily converted into quinone by
alkalis, and a white crystalline compound (m. p. 162 — 164'), soluble
in alcohol and ether.
48 ABSTRACTS OF CHEMICAL PAPERS.
When heated with zinc-dust, a large volume of gas is evolved, hut
no solid hydrocarbons were formed in appreciable quantity. From
these results, the author concludes that this substance is methyldihy-
droxynaphthoquinone, CioH3Me(02) (0H)2.
The mother-liquor from the quinone contains an acid (m. p. 54°),
which dissolves in benzene, toluene, ether, chloroform, carbon bisul-
phide, gla,cial acetic acid, and petroleum ether. Its barium, calcium,
lead, and silver salts are insoluble in water. W. C. W,
Action of Ammonia and Amines on Quinones. By T. Zincke
Ber., 12, 1641 — 1647). — Phenanthrenequinonimide, CuHgO.NH (m. p.
159°) is obtained in yellow, needle-shaped crystals, by passing gaseous
ammonia into a warm alcoholic solution of tlie quinone, or by dissolv-
ing the quinone in warm concentrated alcoholic ammonia, CuHhOj +
NHg = CuHg.O.NH + HoO. The imide is decomposed by boiling
with alcohol, the quinone being regenerated. It combines with acids
to produce red-coloured compounds, which are destroyed by water,
with production of the quinone. When heated with acetic or benzoic
anhydride, the imide loses a molecule of water, giving rise to a crystal-
line compound (m. p. 24'/°) which is sparingly soluble in hot benzene.
By the prolonged action of alcoholic ammonia on phenanthrenequinone,
the imide which is first formed disappears, and a mixture of a basic
substance soluble in acetic acid, and a neutral compound insoluble in
acetic acid, is produced. The latter compound sublimes in lustrous
yellow needles, wliich have the composition CosHieNo. A second basic
substance, very soluble in alcohol, is also formed. It is probably iden-
tical with von Sommaruga's base (Ber., 12, 982). A yellow crystalline
compound, probably CuHg.O.NMe, separates out, when phenanthrene
quinone is treated with an alcoholic solution of methylamine. The
crystals are insoluble in alcohol, but dissolve in hot benzene. They
foi^m a blue compound with strong hydrochloric acid.
The mother-liquor from the yellow compound contains a strong
base, CieHuN'', which appears to be formed according to the following-
equation : CuH.Oa + 2MeNH2 = C,4H«(KMe)3 + 2H.,0. This sub-
stance crystallises in colourless prisms (m. p. 186°), and forms
well crystallised salts, viz., the hydrochloride CieHuNoIICl, colour-
less prisms, soluble in water, insoluble in alcohol ; the nitrate, fine
needles, sparingly soluble in water and in alcohol ; the sulphate, needles
sparingly soluble in alcohol ; the oxalate, transparent prisms, soluble
in hot dilute alcohol. Najjhthoqninone iorms with ammonia a brown
amorphous product, but with primary amines it yields crystalline
derivatives, according to the equation : —
2CwH60., + NH,R' = Cu)H6(0).,NR' + C,oHe(OH),.
Naphtlio- Amiaie. New compouud. Naphthoquinol.
quinone.
The compound doHe.Oa.NPh is obtained by adding an excess of
aniline to a hot alcoholic solution of naphthoquinone. The precipitate
which is thrown down on the addition of water to the mixture is
treated with acetic acid to remove excess of aniline, and is then
recrystallised from alcohol, when the pure substance separates out in
ORGANIC CHEMISTRY. 49
lustrous red needles, -wliich melt at 191°, and sublime at a higher tem-
perature. The crystals dissolve in hot benzene, alcohol, and ether;
they yield with sulphuric acid a red solution, and with alcoholic potash
a purple colour.
By the action of zinc and hydrochloric acid, or of sulphurous acid,
the compound is split up into naphthoquiuol and aniline.
AVith paratoluidine, naphthoquinone forms a beautiful red compound,
crystallising in needles (m. p. 200°). The methylamine compound
crystallises in bright red needles, which melt at 225°, and the ethyl-
amine compound forms orange-coloured needles (m. p. 140°).
A crystalline substance is also produced by the action of diphenyl-
amine on naphthoquinone, in presence of hydrochloric acid.
Benzoquinone differs from naphthoquinone in its behaviour to
amines, e.q., tC.^.O^ + 2Ph.NH., = CsH^O-CNHPh), + CU.^OB.).^.
W. C. W.
Amid oanthraquin one from Anthraquinone-monosulphonic
Acid. By H. R. v. Pekger (Ucr., 12. i5(3G — 1571). — Anthiaquinone-
raonosulphonic acid, or its ammonium salt, when heated with ammonia
in sealed tubes at 190°, yields a red crystalline product, which is soluble
in concentrated hydrochloric acid, and on addition of water is thrown
down again as an orange or red flocculent precipitate. By repeated
sublimation in a current of carbonic anhydride, and crystallisation
from alcohol and benzene, this compound is obtained pure. Analysis
shows it to be monamidoanthraquinone, CUH7O2.XH2 (m. p. 302°) ; and
its formation may be expressed thus : CuH702S03iSrH4 + (NH,), =
CuH^Oo.NHj + (XHOoSOa. Bourcart (Ber., 12, 1418) describes a
compound obtained in the same way, which melts at o01°, and to which
he attributes the formula CuH6O2.NH2.OH; such an amidoanthraquinol
should be soluble in alkalis, which is not the case with this compound.
The views of the author are further supported by the behaviour of this
compound with nitrous acid ; first a yellow crystalline body is obtained
(m. p. 238°), which on boiling with alcohol yields authraquinone ; and
on boiling with water, a-monoxyanthraquinone is obtained.
Heated with acetic anhydride amidoanthraquinone yields the yellow
acetoxy-derivative, CuHvOoNHAc ; it is soluble in alcohol and ether.
It melts at 257°, the melting-point of Bourcart's (loc.cit.) acetoxy-
derivative, to which he attributes the formula CuHoOaNAca.
In conclusion, the author states that attempts made to prepare mono-
nitroanthraquinone according to Bottger and Petersen's method
{Annale7i, 166, 147) have given negative results. P. P. B.
Decomposition of Hydroxyanthraquinone by Potash. By C.
LiEBEKMANN and J. Dehnst (Ber., 12, 1597). — Amongst the products
obtained by the fusion of anthraquinonemonosulphonic acid with potash,
the authors found small quantities of paraoxybenzoic acid. This
owes its existence to the decomposition of monhydroxyanthra,quinone,
which may, therefore, have the constitutional formula —
Z'^— CO— /\0H.
-CO—, y p_ p_ B_
VOL. XXXVIII. e
50 ABSTRACTS OF CHEMICAL PAPERS.
Constitution of Camphor-compounds. By M. Ballo (Ber., 12,
1597 — 160U). — -In anotlier communication {Annalen, 197, .321) tlie
author has given his reasons for reg-arding camphor as a tertiary alco-
HC: C(CH3)-CH.,
hoi, having the constitution | | . This view is sup-
(0H)C:C(C3H,)— CH^
ported by the fact that when camphor is oxidised by boiling chromic
mixture, acetic, carbonic, and adipic acids are formed, thus:
CioHieO + lOO = 2CO2 + CoH.O, + CeHioOi + HoO ;
the central nucleus of the camphor forming adipic acid,
(CH04(COOH)o,
the methyl group, carbonic acid, whilst the propyl group forms carbonic
acid and acetic acid.
The author regards camphrene, CgHuO, as a homologue of camphor,
since it also yields adipic acid when oxidised (Kachler, Annalen, 164,
90), and has the properties of an alcohol. P. P. B.
Essence of Marjoram. By Brutlants (,/. Pharm. [4], 30, 33 —
35). — Essence of marjoram, obtained by distilling the flowery tops of
Orignnum Marjorana in a current of steam, is a yellowish liquid, when
freshly prepared (sp. gr. 0"9ll at 15°), but becomes brown on stand-
ing. It has a pungent smell, and a hot, peppery, and slightly bitter
taste. It is dextrorotatory, and has an acid reaction. When distilled,
it begins to boil at 185°, but the temperature rapidly rises to 200°, and
remains constant between 215 to 220°, a resinous mass being left in
the retort.
By repeatedly fractioning the oil which passes over at 185 — 190°, a
portion is obtained, boiling between 160 — 162°, consisting principally
of a terpene.
The fraction boiling at 215 — 220° yields no portion having a constant
boiling point, nor does it deposit crystals when cooled to — 25°. Its
vapour- density and analysis correspond with either laurel camphor or
borneol. When distilled with phosphoric anhydride, it yields a mix-
ture of cymene and a terpene (b. p. 160 — 170°). When treated with
acetic anhydride, it forms a compound (b. p. 230 — 235°), which with
alcoholic potash yields- terpene and potassic acetate. Chromic
mixture oxidises it with the formation of acetic and formic acids, and
laurel camphor.
Essence of marjoram is therefore composed of a dextrorotary hydro-
carbon, 5 per cent. ; a mixture of dextrorotatory camphor and borneol,
85 per cent. ; resin, 10 per cent. L. T. O'S.
Essences of Lavender and Spike. By Bruylants (J. Fliarm.
[4], 30, 139 — 141). — Essence of lavender when freshly prepared
is a colourless liquid, which becomes yellow on standing; it smells
of lavender, and its taste is hot, camphorous, and slightly bitter.
It is Igevorotatory, has an acid reaction, and sp. gr. 0'875 at 15°. It
begins to boil at 185°, the temperature quickly rises to 190°, and the
greater portion distils over between 195^ — 215°. The first portion of
the distillate consists of a mixture of acetic and formic acids, but con-
tains no valeric acid. By repeated fractionation, a l^vorotatory ter-
ORGANIC CHEMISTRY. 51
jierene (b. p. 162°) is separated, capable of forming a crystalline
liydrochloride. The essence also contains a mixture of camphor and
borneol : this mixture forms an acetate (b. p. 230°), which is decom-
posed by potash, yielding a terpene and potassium acetate. When it is
distilled with phosphoric anhydride, a hydrocarbon is obtained, con-
sisting for the most part of terpene, and. containing also some cymene.
Essence of lavender consists of terpene, 25 ; borneol (f ), and cam-
phor (\), 65 ; resin, 10 per cent.
Essence of Sijike. — 1'his essence obtained from Lavandula aspica'
Jatifolia is a colourless liquid, which in time thickens and darkens in
colour. It has an acid reaction, and sp. gr. 0"9081 at 15^. Its
odour resembles that of lavender. Its composition is almost identical
with that of essence of lavender, but as it contains more hydrocarbon,
it begins to boil at 1 70 — 1 75°. It is laevorotatory. Its composition is
as follows : — Terpene, 35 ; borneol and camphor, 55 ; resin, 10 per
cent. L. T. O'S.
Limited Oxidation of the Essential Oils. Part V. The
Atmospheric Oxidation of Turpentine. By C. T. Kiugzett
(Chem.- Neics, 39, 270). — The author has shown in his previous papers
that when so-called essential oils are exposed to the atmosphere, per-
oxide of hydrogen is indirectly produced. In turpentine oil, it appears
as if a camphoric peroxide, Cii,Hi404, i.s first formed, and that in con-
tact with water this is decomposed, yielding hydrogen peroxide and
camphoric acid, thus : CwHuOi + 2H2O = CioHieOi + H2O2.
Similarly,- terpene, Ci„H,6, and menthene, CmHig, give rise to per-
oxide of hydrogen, whilst hydrocarbons of the formula CiaHn, do not.
As all terpenes and menthene yield cymene, CioHu, and as cj-raene
itself yields hydrogen peroxide, the author believes that there is some
relation between the formation of this body and that of hydrogen pei'-
oxide, and this opinion is strengthened by the fact that the hydro-
carbon fi-om oil of cloves, C15H24, yields neither cymene nor hydrogen
peroxide.
The product of oxidation which is formed by exposing turpentine
to the action of the air, and which in contact with water forms hydro-
gen peroxide, may be produced in such quantities that when the tur-
pentine oil containing it is heated a little above the boiling point,
decomposition occurs A\ith almost explosive violence. The atmo--
spheric oxidation of turpentine is now carried out, on the large scale, in
the manufacture of the disinfectant called " sanitas."
Different essential oils and varieties of turpentine absorb oxygen
with different degrees of rapidity, and when oxidation has once com-
menced, the oil absorbs oxygen with increasing rapidity in jiroportion
as the oxidation increases, up to a certain point. As to the differences
in this respect in different oils, the author gives the following results
deduced from, experiment by exposing the various oils under similar
conditions to light and air. Assuming that the amount of oxygen
absorbed by Russian oil of turpentine (which absorbs the largest
amount) be represented by 100, then Swedish oil of turpentine absorbs
100.
52 ABSTRACTS OF CHEMICAL PAPERS.
An oil obtained from Switzerland 89'4
American oil of turpentine 789
Oil of eucalyptus 7^-0
Adulterated Swedish turpentine 52 "6
" Scotch distilled American turpentine " 42"1
The two last-mentioned oils were presumed to be adulterated with so-
called pine-oil of commerce. When these oils are placed in cylinders,
the mouths of which are covered with papers saturated with a mix-
ture of jjotassic iodide and starch, the papers become coloured in the
order given above, owing to the formation of different quantities of
hydrogen peroxide in the vicinity of each.
When the aqueous solution obtained by blowing air through a mix-
ture of turpentine and water (" sanitas "), is evaporated to dryness
on a steam-bath, the hydrogen peroxide contained in it is decomposed,
the acetic acid is expelled, and there remains a dark coloured matter,
which when hot is viscid, and has a sugar-like odour, but on cooling
sets to an adhesive but firm mass ; when treated with sulphuric
acid it gives a colour reaction somewhat resembling that bearing
Pettenkofer's name. This adhesive mass, which was slightly volatile
at 100°, after drying gave numbers corresponding with the formula
CioHigOa. It has remarkable antiseptic properties, to which the
similar properties of " sanitas " are largely due.
About 95 per cent, of this adhesive matter is soluble in water,
forming a yellowish-brown solution, from which charcoal failed to
remove the colour, although it absorbed a considerable proportion of
the substance itself. This solution on evaporation to dryness left a
transparent varnish-like substance, semi-fluid when hot, and volatile at
100°. From analysis, the formula CioHigOa was calculated.
The 5 per cent, of the original adhesive substance which was in-
soluble in water did not give the vivid reaction with sulphuric acid
which the soluble portion did ; this insoluble matter is soluble in
presence of an oily substance which the original aqueous solution
contained, and which was expelled on evaporation.
On submitting the soluble portion to distillation, it melted, boiled,
and a small quantity of an almost colourless oil passed over, which on
cooling became a colourless, soft crystalline mass ; this was followed
by a permanent oil, which became darker as the distillation pro-
ceeded ; towards the end, the vapour in the retort had a green colour,
and a pitch was left. None of these products have as yet been further
examined.
On acidulating the solution of the soluble portion, CioHigOs, with
dilute sulphuric acid, it becomes milky, and on standing, a slightly
coloured oily body separates in considerable quantity. The author
hopes that a study of this substance will throw light not only on the
constitution of the soluble substance, but also on that of the terpenes
as a class.
The aqueous solution (" sanitas ") obtained by oxidising Russian
turpentine, when neutralised with soda, darkens very much in colour,
and on evaporation of the mixture at 100°, a dark soft resin-like residue
is left. On treating this with dilute sulphuric acid, it yields a dark
ORGAXIC CHEMISTRY. 53
oily mass : the clear acid solution is filtered and subjected to distilla-
tion ; as it becomes hot more oil separates out, and an acid distillate
passes over, together with 20 or 30 c.c. of a slightly yellow oil with an
odour resembling that of mixed cymene and eucalyptus. At the end
of the distillation a quantity of tarry-looking matter remains in the
retort floating on the acid solution. The acidity of the distillate was
found to be due to acetic acid, which amounted to about 0'25 gram
per litre of the aqueous solution ("sanitas"), and no other volatile
acid could be detected. The author anticipates that the further study
of those compounds will be attended with very important and interest-
ing results, inasmuch as they have the advantage of having been
produced by the mildest possible oxidation. W. T.
Fusion of Rhamnetin with Potash. By L. Smorawski (Ber.,
12, loUo — loOGj. — According to Stein (Zeit. f. Ghein. [2], 5, 183, 568),
rhamnetin when fused with potash yields phloroglucinol and quercetic
acid. The author finds that by fusion with potash or soda, rham-
netin is decomposed into phloroglucinol and protocatechuic acid ; at
the sam-e time, small quantities of a substance are formed which, like
quercetic acid, gives a deep red coloration with alkalis. This last-
named body could not, however, be obtained in quantities sufficient for
analj-sis. P. P. B.
Chlorophyll. By F. Hoppe-Setleb {Bar., 12, 1555—1556). —
When grass-blades, after treatment with ether to remove was, are
cohobated with alcohol, two crystalline calouring matters :ire dissolved,
one of which, named erythrophyll by Bougarel, crystallises out first in
greenish-white quadratic tables, whilst the other is more soluble in
hot alcohol, and may be purified by crystallisation from ether, from
which it is deposited in microscopic needles and scales, dai'k green by
reflected, and brown by transmitted light. The crystals of the latter
bodv are of the consistence of soft wax ; it dissolves with difficnltv in
cold alcohol, easily in hot alcohol, and readily in ether and chloroform.
The ethereal and alcoholic solutions of this substance have the known
red fluorescence of chlorophyll, and absorb the light between B and C
of the spectrum with such intensity, that 1 milligram dissolved in a
litre of water gives distinct absorption-bands in a thickness of 3"5
cm., with a Browning's spectroscope. Several analyses show it to
have the composition: C, 734; H, 97; N, 562; 0,9-57; P, 137;
Mg, 0"34 p.c. The presence of phosphorus and magnesium may be due
to impurities, and the author proposes to investigate this more closely.
He has named this substance chlorophyll an, and remarks in conclusion,
that it is now possible to estimate the amount of chlorophyll in plants
approximately by means of its power of absorbing light. W. R.
Characin. By T. L. Phipsox (Chem. News, 40, 86). — Amongst the
organic substances present in fresh water ts a new and interesting pro-
duct, to which algae in general owe their peculiar odour, and commu-
nicate this odour to the water in which they abound. The author has
obtained this substance in minute quantities only at present from
Palmella cruenta, Vaucheria terrestris, and from several Oscillariae. It
54 ABSTRACTS OF CHEMICAL PAPERS.
is apparently moi-e developed in the genus Chara, and C. foetida will
probably yield it in larger quantity than the plants already mentioned.
Characin is a kind of camphor, which is extracted from the aboye
plants in the following manner.
The Palmella or Oscillaria -which is to be treated must be previously
dried by exposure to tl\e air, at a temperature not exceeding summer
heat, for about 24 hours ; it is then covered with cold water in a
capsule, which must itself be covered with a sheet of glass, and in the
course of about o'o hours more (with Palmella criienfd) thin films of
characin will be observed floating on the water. The latter is then
decanted off into a long tube, together with the films, and shaken up
with ether. On evaporation a product is obtained which is quite white,
devoid of crystallisation, and more or less unctuous in appearance.
Up to the pi'eseut time, the author has not obtained this substance
in sufficient quantity to ascertain more of its properties. D. B.
Phthalein of Hsematoxylin. By E. A. Letts (Ber., 12, 1651 —
1653). — Hcemaio-xnjlin-phthalein, C40H30OU, is prepared by heating
hsematoxylin with rather more than half its eqiiivalent of phthalic
anhydride at 150 — 170° for five hours. The alcoholic solution of the
crude product is poured into water, when a brown tiocculent precipi-
tate separates out, which is filtered, washed, and dried in a vacuum.
The phthalein could not be obtained in the crystalline state ; when the
alcoholic solution is evaporated, it leaves a gummy residue insoluble
in water, but soluble in ammonia and soda, with a purple colour.
Hsematoxylin forms white crystalline potassium, sodium, and barium
compounds. W. C. W.
Collidine from Aldehyde. By A. Wischxegradsky {Ber., 12,
1506 — 15U8). — The object of this research was to ascertain by oxida-
tion whether collidine, CgHnN, is trimethyl-pyridine, CsUi^Mes,
ethyl-methyl-pyridine, CoHjjSTMeEt, or propyl-pyridine, C5H4NC3H7.
The collidine was oxidised with chromic acid in presence of sulphuric
acid, and yielded an acid crystallising in white slender prisms, soluble
with difficulty in cold, but easily soluble in hot water. Its formula
was C8H7]N'04, and as it yielded picoline on distillation with lime, it is
probably methyl-dicarbopyridenic acid. From this research, the
author believes that collidine may be viewed as trimethyl-pyridine.
W. R.
Piperidine Salts : Quinine Sulphate, and Selenate. By T.
Hjortdahl {Ber., 12, 1730 — 1731). — The hydrochlorides and gold
double salts of piperidine and methylpiperidine are isomorphous.
Quinine sulphate and selenate are also isomorphous ; the relation
between the axes of the latter snb.stance is a : & :c = 0'9804 : 1 : O'ollO.
w. c. w.
Aspidospermine. By G. Fraude {Ber., 12, 1560 — 1562). — Some
account of this alkaloid has already been given by the author (this
Journal, 1879, Abst., 470). The bark containing it is that of Aspido-
sperma querhracho hlanco (Schlectendahl). Further analyses show
aspidospermine to have the composition 022^301^^202. Concerning its
ORGANIC CHEMISTRY. 55
preparation, the author finds that the liquors obtained after a precipi-
tation of the alkaloid bj means of sodium carbonate yield a further
quantity by treatment -with phosphotunijfstic acid. This precipitate is
treated with bai-yta- water, and the solution thus obtained with car-
bonic acid to precipitate the Ijarium ; the alkaloid is then extracted by
means of alcohol from the residue left on evaporation. One part of
aspidospermine is soluble in GOOD parts of water at 14° ; this solution
has a bitter taste. It is also soluble in 48 parts of alcohol (99 per
cent.) at 14°, and in 106 parts of pure ether at the same tempera-
ture.
A small quantity of aspidospermine treated with a few drops of
concentrated sulphuric acid, and then with a little lead peroxide, gives
a cherry-red coloration, which has a violet shade if the alkaloid is not
quite pure.
Iodic anhydride and sulphuric acid produce the same reaction,
whilst potassium dichromate and sulphuric acid give a brown zone
slowly changing to an olive-green. Chlorine reacts on aspidospermine
suspended in water, producing a white flocculent mass, which is not
dissolved by hydrochloric acid ; this compound begins to decompose at
145°. Bromine acts similarly.
Aspidospermine sulphate, (C22H3o]Sr202)2H4S04, is obtained by
evaporation and drying at 120" as a hard, transparent, resinous mass.
The hydrochloride, ^(C-i-Jiii^iOo -f 4HC1, has similar properties to the
sulphate. By treating solutions of the base with potassium chromate
the chromate is obtained as a yellow precipitate, which on exposure
to the air becomes green. The perchlorate is obtained by adding
aqueous perchloric acid to a not too dilute solution of the base.
Hydrochloric acid solutions of the base are precipitated by potassium
mei"curic iodide in yellow flocks ; by potassium sulphocyanide, as a
white flocculent precipitate ; by iodine dissolved in potassium iodide, as
brown flocks; by picric acid, as a yellcw precipitate; and by tannin,
as a white precipitate. Further, these solutions reduce Fehling's
solution when boiled with it.
According to Penzoldt {Berl. Klin. Wochenschrift, 1879, 14), the
bark of Aspidosperma querbracho bianco has important medicinal pro-
perties. P. P. B.
Oxidation of Cholic Acid. By H. Tappeixer (Ber., 12, 1627—
1629). — The author obtained stearic acid as an oxidation-product of
cholic acid {Ber., 11, 2258), but Latschinofl^ denies that this acid is
formed (Ber., 10, 2U59, and 12, 1022). The discrepancy between these
results is explained by the fact that the author employed a mixture of
potassium dichromate and sulphuric acid as the oxidising agent, whilst
Latschinoif used potassium permanganate.
A weak solution of the oxidising mixture must be used when it is
desired to isolate the fatty acids obtained by the oxidation of a small
quantity of cholic acid.
A crystalline barium salt, (Ci2Hi3C7)2Ba3 + 6II-;0, is formed by
heating a saturated solution of cholic acid in baryta-water in sealed
tubes at 120°. It crystallises in long white prisms, which are very
sparingly soluble in water.
56 ABSTRACTS OF CHEMICAL PAPERS.
To prepare pyrocholesteric acid on the large scale, a solution of
cliolesteric acid in glycerol is heated at 198° for a week ; the glycerate
is then saponified, and after removing the volatile products by distilla-
tion, the pyrocholesteric acid is extracted from the residue by means
of ether. W. C. W.
Oxidation-products of Cholic Acid. By P. Latschinoff (Ber.,
12, 151S — 1528). — By oxidation of cholic acid, the author did not
obtain cholesteric acid, nor fatty acids, as Tappeiner did^ but an acid
termed choloidic acid, to which Redtenbacher gave the formula
C16H24O7. This acid, which he prepared by oxidising cholic acid with
nitric acid of sp. gr. 1"37, evaporating the oxidised product to dryness,
and separating the acid first \vith alcohol, and then as soluble barium
salt, after repeated crystallisation from alcohol, gave numbers agree-
ing with the formula C10H16O4 ; it is thus isomeric with camphoric
acid, and the author has therefore named it cliolecam/plioric acid.
The properties of cholecamphoric acid are as follows : — It is soluble
in water and in ether with difficulty; easily in alcohol, more easily
when aqueous, also in acetone, and in acetic acid. From a boiling
aqueous solution, it is deposited in such a thick mass of interlaced
hair-like crystals, that it presents the appearance of a jelly. It has a
bitter, acid, somewhat astringent taste. When heated,, it loses water,
varying in quantity, but approximating to ^H20. It does not melt,
but begins to blacken at 27U°. Its solution is dextrorotatory. It is a
dibasic acid, forming soluble salts with metals of the alkalis and
alkaline earths, and insoluble salts with the heavy metals. The author
adduces numerous analyses of the salts to confirm the formula of the
acid, and indicates the acid potassium salt, C10HJ5KO4, as a proof of its
dibasic character.
Cholecamphoric acid may be regarded as a product of hydration of
cholic acid, thus : CooH.bOb + 2H,0 = 2CioH,604.
Such bodies, and many resembling them, for example cholesterin
and cholic acid, may be regarded as compounds of condensed valery-
lenes, and may be connected with the terpenes. Thus cholesterin may
pi'ovisionally be given the formula {C;jY{f)^nO-, and cholic acid
(C5H8)505.-|^H20. This view is supported by the oxidation of cholic
acid into cholecamphoric acid, and also by the results of oxidising
cholesterin, the product being trioxycholesterin, analogous to betu-
lin. W. R.
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 57
Physiological Chemistry.
Feeding Horses with Fleshmeal. By Duxrelberg (Bied.
Centr., Ib7'.>, :U2 — o-iA).— At Diinkelberg-'s suggestion, Voigts-Rhetz
introduced fleshmeal into the food of the horses of his regiment. The
results were very satisfactory, the condition and appetite of the horses
becoming much improved. Diinkelberg states that to every kilogram of
dried fleshmeal must be added 5"25 grams chloride of potassium,
279 grams phosphate of potassium, and 29 grams phosphate of mag-
nesium, in order that the whole of the albumin may be assimilated.
J. K. C.
Poisoning of Sheep by Lupines. By H. C. E. Schulz, E. Wildt,
and others {Bied. Gentr., 1879, o4-t — 3-")0). — The disease arises from
blood poisoning, caused by paralysis of the urinary and gall-bladder
muscles, Avhereby the constituents of the urine and bile pass into the
blood. Schulz has investigated the alkaloids of the lupine, and from
experiments on three of them, he finds that they difier very much in
their physiological action. No gi'eat difference can be observed in the
ash of wholesome and injurious lupines, but in some cases the latter
contain more alkaloid than the former. There is less alkaloid present
in the lupines when in bloom than when fully ripe.
"Wildt finds two alkaloids in lupines, of which one is a white crys-
talline solid, and the other a yellow oily liquid ; the latter, according
to Schulz, consLsting of two different bodies. The crystallised alkaloid
appeared quite harmless, but the other had a very poi-sonous action,
producing trembling, violent cramp, diarrhoea, and finally death ; but
in no case could the same appearances be observed after death as in
the case when it has been caused by feeding on lupines. Reports from
various sheep farmers go to show that lupines act differently on
different sheep, and that when injui'ious,. they have generally been
grown on a poor damp soil, or on one which, has been sown with
lupines for several years previously. J. K. C.
Chemistry of Vegetable Physiology and Agriculture.
Influence of Light on the Growth of Plants, By C. Kraus
(Bitd. Centr., 1879, obi). — The alterations of growth produced in
plants by absence of light are of two kinds, one part of an organ or
plant exhibiting an excessive, whilst another exhibits a diminished
growth. This is easily verified in the case of dicotyledonous plants,
where the internodes are subject to an increased and the leaves
to a diminished growth when the plant is placed in the dark. Similar
phenomena are observed in the case of monocotyledons and cryp-
togam.s. Methyl alcohol when applied to the roots of plants causes
them to die off", and has the same effect as light in promoting the
formation of chlorophyll in the cells. Under the influence of
methyl alcohol, young plants live longer in the dark, and their weight
58 ABSTRACTS OF CHEMICAL PAPERS.
wheu dried is o-reater than iu the case of plants which have not been
phiced under the same influence. J. K. C.
Action of Ozone on the Colouring Matters of Plants. By
A. R. Lekds (CJtem. News, 40, 86). — In the first trial, in which many-
varieties of flowers wei'e exposed during nineteen hours to the action
of a current of 152 litres of air, containing in all 228 mgrms. of ozone,
the bleaching effected was extremely imperfect. When 1,200 litres of
air were passed over various flowers (total ozone 1"8 grams), they
were partly or wholly bleached at the end of five days. A piece of
calico with a pattern in bright green and black was completely
bleached during the same interval, the green having disappeared
completely, and the stain of the mordant only remaining where the
black had been.
From these and other results, it is concluded that the colouring
matters of both leaves and flowers of the species (Lantana, Fuchsia,
Petunia, Rosa, Verbena, Pelargonium, Bouvardia, Euphorhia, &c.) ex-
perimented with wei'e partly or wholly destroyed by ozone ; but a
considerable percentage of ozone is required to produce this result,
or if such small amounts as are obtained in the customary methods of
ozonising air by phosphorus are employed (1 to 3 mgrms. per litre), a
large volume of ozonised air must be used, and a considerable interval
elapse before bleaching is effected. D. B,
Distribution and Functions of Asparagine in the Vegetable
Kingdom. By J. Borodin (Pied. Gentr., 1879, 857— 360). — Aspara-
gine, according to Pfeft'er, occurs only in a few plants, and in these
only at the time of germination. The author finds, however, that
asparagine is present at the time of budding in most plants, and also
when they are in bloom. It appears to be a decomposition-product of
albumin, and is formed when there is a lack of carbohydrates in the
plant. When these, however, reappear, the asparagine is reconverted
by their agency into albumin. From his researclaes, the author con-
cludes that iu the early processes of growth there is a lack of these
carbohydrates, and therefore asparagine is formed at these periods,
being afterwards converted into albumin. J. K. C.
Mineral Constituents in Hyacinths. By A. E. Rojen and
Krelage {Pied. (Jentr., 1879, 360 — 366). — The hyacinths were planted
according to size, at the rate of 42, 90, and 196 plants to the square
metre. The results of the examination of their mineral constituents
may be seen from the following table.
Mineral constituents in grams iu each plant.
196 to sq. metre. 90 to sq. metre. 42 to sq. metre.
Blossoms 0-042 0-230 0-303
Stem 0-027 0-036 0-106
Leaves 0-082 0-245 0-632
Bulb 0-146 0-355 1-380
Roots 0-022 0-022 0-31J
Total 0-319 0-888 2-732
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 59
From this table, it is at once evident that the mineral constituents
increase very rapidly with the size of the plant, and also that the
quantity extracted from the soil is by no means small. From one
hectare alone, when planted with 42 hyacinths to the square meter,
would be extracted in one season 1,147 kilos, of mineral substance.
The following table shows the difference in quantity of mineral
matter in the bulbs when taken out of the ground just after the
blossoming period and at the end of summer : —
196 to sq. metre. 90 to sq. metre. 42 to sq. metre.
Bulbs dug out just after
blossoming 0"146
At the end of summer. . 0"o57
0-355
1-380
0-987
2-314
J. K. C
Experiments -with Various Sorts of Beet. By J. Lamek and
C. PoKTELE (Bied. Ctntr., 1879, oGB— 370).— The authors bring for-
ward an account of the results obtained by growing various kinds of
beet. They find that the " mammoth " variety yielded the largest crop,
whilst the " imperial" contained the largest percentage (10-7) of sugar.
J. K. C.
Formation of Nitric Acid in the Soil. By Hunefeld, E.
Height RDT, and Hertz (Bled. Centr., 1879, 327). — According to a
former paper of Hiinefeld's, nitric acid is produced when the higher
oxides of manganese are brought into contact with air, water, and
magnesium carbonate. To confirm this statement, Reichardt and
Hertz performed the following experiments. Hydrated oxide of
manganese, together with various oxides and earths, such as magne-
sium and calcium carbonates, alumina, and oxide of iron, were placed
with a little water in a large flask, which was then closed and
shaken at intervals, care being taken to ascertain that no nitric acid
was present at the beginning of the ex,periments. No nitric or nitrous
acid was obtained when the manganese was used in conjunction with
calcium carbonate or oxide of iron and alumina, but when mixed with
magnesia or alkaline carbonates, nitric acid was recognised in the pro-
duct. Pyiolusite gave the strongest reactions, and it was found that
50 grams put in a litre flask with 500 c.c. of water after standing for
eight days and frequent agitation yielded 0-055 gram of nitric acid.
J. K. C.
Calcium Carbonate in Water filtered through Dry Soil.
By F. H. Stoker and S. Lewis (Bied. Centr., 1879, 328— 331).— The
authors find that a soil which has been ignited at a temperature just
sufficient to destroy the organic matter yields calcium carbonate when
treated with pure water, even after it has just cooled. They have
arrived, therefore, at the conclusion that when ignited at a low tem-
perature, a soil has the power of still retaining carbonic acid. When
a dried soil is treated with water containing carbonic acid, part of the
latter is retained by the soil. This, according to Storer, is merely a
mechanical result, and is due to the adhesion of the gas to the solid
particles of the soil. J. K. C.
GO ABSTRACTS OF CHEJMICAL PAPERS.
Mill Waste for Manure. By Friedburg (Bied. Centr., 1879,
386). — This waste, consisting clnetiy of dust and cliaff from rye, was
found on analysis to contain the following percentages of consti-
tuents: — Phosphoric acid, 0-96; nitrogen, I'SO ; water, 5-80; organic
substance, 62-84; ash, 31-36. J. K. C.
Analyses of Marl. By J. Konig (Bied. Centr., 1879, 385).— The
following are the results of the analysis of 85 samples from West-
phalia : — The calcium carbonate varied from 1-36 to 94-83 per cent. ;
magnesium carbonate was pi-esent in 21 samples, and in quantity from
Q-38 to 27'39 per cent. Phosphoric acid varying in amount from
0-029 to 1'55 per cent, was found in 23 samples. Lastly potassium
was estimated in 28 samples, and varied from 0-08 to 2-43 per cent.
J. K. C.
Influence of the Physical Condition of Superphosphate on
its Value. By P. Wagni^r (Bled. Centr., 1879, 336— 389).— The
soluble phosphoric acid in superphosphate on coming into contact
with the lime of the soil is converted into an insoluble form, and
consequently does not penetrate into the soil ; this is especially the
case with a soil which contains much limestone, the author finding in one
experiment that 93 per cent, of the soluble phosphoric acid had, after
three hours' contact with a calcareous soil, become insoluble ; the
more quickly this conversion takes place, the less is the penetrating
power of the phosphoric aeid, and the more necessary it becomes to
have the superphosphate in as tine a state of division as possible, and
well mixed with the soil. J. K. C.
The Shells of Crabs, Oysters, Mussels, Sec, as Manure. By
F. H. Storer and J. A. Henshaw (Bied. Centr., 1879, 331—336).
— The authors have made several analyses of the shells of these
animals, with a view to ascertain their value as manure. They find
that the shells of oysters and mussels are composed almost entirely of
carbonate of lime, and contain very little available phosphorus, nitro-
gen, or potash, with the single exception of the common small mussel
(Mytilus horealis), 1000 kilos, of which contain 2-8 kilos, of nitrogen.
On the other hand the shells of crabs and crawfish are tolerably rich in
fertilising materials, the king-crab (Limulus americanus) containing
as much as 12*5 per cent, of nitrogen, the agricultural value of which
being, however, probably less than that of the nitrogen in guano. On
the whole, the shells of oysters and mussels may be used with advan-
tage as a lime manure, especially after burning, whereby the small
pei'centases of phosphorus and potash are increased, and in those
countries where they are cheaper than calcined limestone.
J. K. C.
ANALYTICS^ CHEMISTRY. HI
Analytical Chemistry.
Specific Gravity of Liquids. By L. Siebold (Analyst, 1879,
189). — From expurimeiits carried out by the author, it is cleai'ly
shown that hydrometers affoixi reliable indications of the speoitic
gravity of liquids, no matter whether their gravity is due to substance
dissolved or in suspension. L. T. O'S.
Analyses of Organic Compounds containing Fluorine and
Boron. ByF. Landolph (Ber., 12, 1580 — 1588). — In the determina-
tion of carbon and hydrog-en in such compounds, the author recom-
mends the use of fused lead chromate, which is placed before the
copper oxide and only heated gently, as otherwise the boric acid is
volatilised. To determine the fluorine and boron, the compound is
decomposed by a solution of calcium chloride. The fluorine is thus
separated as calcium fluoride, and the boric acid remaining in solution
is determined as magnesium borate. P. P. B.
o
Direct Separation of Manganese from Iron. By P. Beilstein
and L. Jawein (Ber., 12, 1528 — 1531). — The author describes two
processes, both of which are preferable to the ordinary method of
separating the iron as basic acetate. The first depends on the fact
that all the manganese is precipitated as peroxide or sesquioxide from
a solution of manganocyanide of potassium, on addition of iodine,
whereas no precipitate is produced in potassium ferrocyanide by
iodine. The details are as follows : The solution of ferric and mau-
ganous salt is poured into excess of concentrated solution of potassium
cyanide. A minute insoluble residue always remains, which contains
only iron ; it is removed by filtration. Iodine is then added until all
the cyanide has been decomposed, and the slight excess is removed by
addition of a few drops of soda. The precipitated oxide of manganese
is filtered off, washed, and dissolved in hydrochloric acid, and esti-
mated as sulphide. The only disadvantage of the process is the large
amount of iodine required (about 30 grams), but as it can be nearly
all recovered by addition of crude nitric acid to the filtrate from
the manganese precijutate, this inconvenience is removed.
The second process depends on the conversion of salts of manganese
into peroxide by boiling with strong nitric acid and potassium
chlorate. The salts are dissolved in nitric acid, sp. gr. 1".35, aud after
the solution has been heated to boiling, potassium chlorate is added
until all manganese is precipitated. The liquor is then diluted and
filtered. The precipitate contains iron, but by dissolving it in hydro-
chloric acid and repeating the process, it contains only an infinitesimal
trace of iron. Both of these processes are applicable to the estimation
of maneanese in cast-iron and steel.* W. 11.
*te^
* The second of these processes has heen suggested by Hannay (this Journal,
1878, Trans., 269).— W. R.
G2 ABSTRxVCTS OF CHEMICAL PAPERS.
Estimation of Organic Nitrogen in Natural Waters. By F.
Pellet (Co)upt. rend., 89, 523). — The ammonia is estimated by
BoLissinCTauH's process; the nitric acid, in three litres of water, by
Schloesing's method ; and the total nitrogen by evaporating three
litres of water to dryness, with addition of a small quantity of magne-
sia, mixing with a small quantity of starch, and heating with soda-
lime in the ordinary way. The starch converts the nitric acid into
ammonia, if the nitric acid does not exceed 0'25 gram of potassium
nitrate. C. W. W.
Notes on Some Analyses of Waters. By T. L. Phipson (CJwm.
Netvs, 40, 1). — The author considers that a very long experience is
necessary for a chemist to decide whether a water is fit for drinking
purposes or not; other questions such as- its effect in attacking and
dissolving lead, or eori'oding iron pipes or boiler plates have often to
be decided by the chemist.
For deciding the questions as to the arlaptability of water for drink-
ing pui'poses, much stress has been laid tipon the proportion of organic
matter, but this is a mistake, because some waters containing as much
as 6 or 8 grains per gallon may be drunk with impunity, whilst others
containing much less are known to be exceedingly injurious, if not
fatal.
Four or five grains of crenate of ammonia per gallon is not at all
hurtful, whilst putrid organic matter, numerous Bacteria and Micro-
coccus and minute wliite fungoid growths are sources of imminent
danger.
He gives the following as examples of water which he has ana-
lysed : —
(1.) Well near Sleaford (Lincnhishire). — Water not quite clear,
slightly alkaline with decided saline taste, and well aerated with air
and carbonic acid ; contains some minute green algge ; total residue,
169 grains per gallon, which is composed of: —
Organic
matter.
NaCl.
NaoCOg.
Na.S04.
K.SO4.
MgCL.
SiO,.
Fe-03.
CaCOs.
2-0
76-0
44-0
85-0
2-0
1-5
1-0
0-5
7-0
Total, 169 grains. There were traces of phosphoric acid and of
bromine.
(2.) St. Anne's Well, Buxton (Berhyshire), contains mineral
matter 18 grains, organic matter 2'0 ; total, 20 grains per gallon.
The mineral matter is composed chiefly of calcium carbonate and
sodium chloride, with a little calcium sulphate and traces of iron,
silica, caesium, and strontium, but no lithium or rubidium. The
water is beaiitifuUy clear and tasteless, and is said to have a constant
temperature of 80° to 82° F., sp. gr. at 60° 1-003. The fact that
this water cures gout is owing probably to its great purity, and to its
being drnnk warm and in large quantities.
(3.) Well on Wimhledon Common {Stirrey), contains mineral
matter 26 grains, organic matter and niti'ic acid 6 grains ; total, 32
ANALYTICAL CHEMISTRY. (53
grains per gallon. The mineral matter is composed principally of
calcium carbonate and sulphate, with a small proportion of alkaline
salts. It is well aerated, and contains no phosphoric acid. A single drop
of a very dilute solution of potassium permanganate gave a rose tint
to 200 c.c. of the water, which persisted for several hours. This is an
example of a good well water.
(4.) Well ill the Loicer Bagshot Sand, near Esher (Surrey). — The
well is 40 feet deep, and is situated about 40 feet from a small ceme-
tery. The water is beautifully bright, clear, and odourless. It
attacks and dissolves lead easily, and shows decided indications of
nitrates and lunch chlorides. It contains nitric acid and organic
matter 7"0 grains, sodium chloride 14"0, sulphates, carbonates, &c., 37'8 ;
total, o8"8 grains per gallon. A very deceitful water; certainly im-
pregnated and likely to get worse, sp. gr. 1'0032. A spring much
farther from the little cemetery gave nitric acid and organic matter
3 grains, mineral matter 21 grains ; total, 24 grains per gallon. This
water dissolves lead easily.
(5.) A Yellmo Water (South of England), supposed to be ferrugi-
nous, remains clear even on boiling, but gives off a strong marshy
odour. Total residue, 2'1 grains per gallon, consists principally of
the ulmates of lime and ammonia, a little cai'bonate of lime, and traces
of chloriiles, &c.
(6.) Wi'll at indland Banli, Birmingham, contains mineral matter
(after calcination) oS"?! grains; total residue, 8r62 grains per gallon.
This water contains a very large amount of nitrates and ammonia. It
is a bad water for household use, and it is said to corrode metals.
(7.) Well in an Artificial Manure Mamifactori/ near Soitthampton. —
The water contains free sulphuric acid 1500 grains, pho.sphate.s, cal-
cium sulphate, alkaline salts, &c., 1820 grains.
(8.) Well at Alh'iny Barrach':, London. — Organic matter and nitric
acid 3 grains, mineral matter 72 grains per gallon. Supposed to have
caused an outbreak of typhoid.
(P.) Wdl near Huntingdon contained calcium sulphate 36'89 grains,
calcium carbonate lo'37, sodium chloride 1600, organic matter and
nitric acid S'OO, silica, magnesia, oxide of iron, &c., 8" 74.
(10.) Water from a Sctdlery Pumjp in Bolton Street, Piccadilly. —
Total residue, 1024 grains per gallon. It contained abundance of
phosphates, resembled dilute urine, and was said to have caused sickness
and diarrhoea.
(11.) Wells at Putney, S.W. — The total resid^ie varies from 38 to
120 grains, and some containing from 38 to 48 grains, of which 7 or 8
grains are composed of organic matter and nitric acid, have been used
for many years for drinking purposes without having produced any
bad effects. Others that yield 60 grains of total residue, of which 10
grains are composed of organic matter and nitric acid, have been pro-
scribed by the medical authorities. Evidence is quoted from an
analysis made bv the late Dr. D. Thomson to show that although
these waters are highly contaminated, they have not changed in com-
position for 25 years.
The author generalises as follows : —
64 ABSTRACTS OF CHEMICAL PAPERS.
(1.) The depth of a well has no iufluence on the quantity of solid
residue which a water contains.
(2.) The purer a water, the more easily does it dissolve lead.
(3.) Boiler deposits from all parts of the world with a few ex-
ceptions, consist almost entirely (over 90 per cent.) of calcium car-
bonate.
(4.) The presence of phosphoric acid is always a had indication.
W. T.
Rapid Estimation of Pure Sugar in Raw and Refined Com-
mercial Sugars. By P. CASAMAJOii (Chevi. News, 40, 74 — 76; 97 —
98 ; 107 and lol). — In Payen's process, two alcoholic solutions satu-
rated with sugar are used, and finally absolute alcohol, to wash out tlie
last traces of tlie sugar-saturated solutions. The first solution is
obtained by taking alcohol of 85 per cent, and adding to this 5 per
cent, of strong acetic acid ; this mixture is saturated with sugar. This
addition of acetic acid was made in order to decompose the sucrates,
which were a great nuisance to chemists in former days, but in addi-
tion, it seems to make the mixture better able to remove the impurities
of gummy sugar. This first of Payen's solutions was the one adopted
by Dumas in a process published several years ago, which, however,
has never been studied by sugar analysts : the author's process is
based on this. Dumas proposed to agitate 100 c.c. of the first Payen
solution with 50 grams of sugar, filter, and observe the alcohoraetric
degree corresponding to 15°. For ever)^ per cent, of sugar less than
100 the solution is said to indicate 1 per cent, less than 74. For sugars
having 87 per cent, or more pure sugar, the results agree very closely
with those of the saccharometer, even within 0"1 per cent., but for
sugars of lower grade the results obtained are not satisfactory.
As nearly one-half of the raw sugars which occur in commerce
stand below 87 per cent., there seemed to be little use in a process
which was declared to be inapplicable to sugars of low grade. The
author found, however, after trying the process sevei-al times, that,
although the results obtained were mostly unfavourable, it was im-
possible to dismiss it entirely ; for, upon reflecting upon the results,
it was found that many questions arose which required to be solved,
and on their solution the author based the hope of modifying this
process so as to apply it to the analysis of cane-sugars of all grades.
By employing methyl instead of ethyl alcohol, the author suc-
ceeded in obtaining, with an alcohometer, results that agree veiy
closely with those of the optical saccharometer, and that with cane-
sugars of all classes from the highest to the lowest. After making a
gi'eat number of trials, it was found that methyl alcohol of 83'5^ of
the alcohometer (or 87 per cent.), when saturated with sugar, stands
at 77'1°. This solution is the one that has given the most accurate
results. It is easily obtained by taking methyl alcohol, standing
at 83-^° by the alcohometer, and saturating it with sugar by the pro-
cess which Numa Grav suggested to Payen. Since the solution is
liable to alteration from loss of alcohol, it is best to test it before
using it. When the degree is lower than required, it may be raised
by adding more alcohol. If a certain volume V of alcohol and water,
whose alcohometric degree is t^ is to be raised to D, with strong
ANALYTICAL CHEiHSTRY. 65
aleoliol of degree A, if the volume of the latter to be added is called x,
we shall have Yd + .cA = (V + .c)D, whence x = ZjGIzL^. Thus
A — D
to raise 1000 c.c. of alcohol at 81 to 83"5 with alcohol of 92 per cent.
where cZ = 81, D = SS^o, V = 1000, and A = 92, the volume of alcohol
of 92 to be added is, x = — — =ll = 2941 c.c. If the addition
of alcohol has been too great, the degree may be diminished by add-
ing water very gradually and stirring up the mixture with an excess
of sugar. To ascertain the quantity of water the above formula may
be used, but it must be noted that A = 0, and as both numerator and
denominator have become negative quantities, the signs may be
changed when x = — — ^- i.
Next in importance is the weight of commercial sugar to be taken
for 100 c.c. ruethyl alcohol solution saturated with sugar. At first an
arbitrary quantity may be taken and the result noted, which may be
coi-rected by the following consideration. The lowering of the alco-
honietric degree depends on the water and the soluble impurities con-
tained in the sugar. If a certain weight of sugar is taken, say
45 grams, the result by the alcohol ])rocess may be 91'5 per cent, of
sugar. If the same sugar is tested by the optical saccharometer and
yields 93 per cent, of sugar, it shows that the alcohol process has
given too low a result, and this because the solution was too dense.
The first result shows in the sugar 100 — 91'5 = 8'5 of impurities
and water, whilst it ought to be 100 — 93 = 7. To obtain 93 therefore
45a; 7
a weight must be taken equal to \ =^ 37"05 grams.
o'5
After trying many experiments with solutions of different strengths,
it was found that each solution required a different weight. For the
saturated solution of 77'1° of the alcohometer, which is the standard
solution employed by the author, the weight is 39'6 grams for 100 c.c.
of the solution. Instead of usinc^ 100 c.c. the author for a Ions' time
1 - ..."
used only 50 c.c. To be able to use a cylinder in which this volume
would give indications, alcohometers had to be employed of small
diameter. For 50 c.c. of standard solution the proper weight is
19'8 grams, i.e., half of the one for 100 c.c. This weight was obtained
by calculation. Using this weight ^vith. 50 c.c. of standard solu-
tion, 15 consecutive tests of raw and refined sugars were made, the
results obtained showing that the difference between the percentage
of pure sugar by the saccharometer and that by methyl alcohol was
very slight, the greatest deviation being 0'7. If the operations are
made at temperatures different from 15'^ C. or 60° F. the corrections
can be made by using either of the tables of Gay-Lussac or those for
the instrument of Tralles. Another correction for the variation of
temperature relative to the volume of standard solution to be taken
for a weight of sugar equal to 19' 8 grams is given in the table —
At 15° C. 20^ 25°. SO''. 35°. 40°.
19-8 grams 197 19-6 19-5 19-4 193
VOL. XXXVIIl. /
66 ABSTRACTS OF CHEMICAL PAPERS.
The following table contains corresponding corrections for methyl
alcohol of various strengths saturated with sugar: —
)egrees of the
alcohometer
Degrees of
Degree of the
before
saturation
saecharometer
Grams of sugar
saturation.
with sugar.
(Ventzke).
in 100 c.c.
92-5
91-8
17
0-44
83-5
77-1
13-2
3-43
827
76'5
81-5
75-0
Method of procedure in testing. — The sugar to be tested shoiild not
be weighed until everything is ready. The cylinder is filled with the
standard solution to a line indicating 50 c.c, and 19*8 grams of sugar
are weighed out. This is transferred to a mortar and the standard
solution poured in; the whole is then ground until all lumps and
large crystals are broken up. The contents of the mortar are now
filtered into the cylinder and washed out with the filtered solution.
The filtered solution is then tested with an alcohometer and a ther-
mometer in succession. To the alcohoraetric degree, corrected for
temperature, is added the difference between 100 and the alcohometric
degree of the standard solution. This sum represents the percentage
of sugrar. D. B.
n
Behaviour of Various Sugars with Fehling's Solution. By
Y. SoxHLET and others (Bied. Cevtr., 1879, 370). — Soxhiet questions
the accuracy of the prevailing opinion, that under all circumstances
5 mols. of copper are reduced in alkaline solution by one of sugar, and
states that the quantity of copper reduced varies with the dilution of the
Fehling's reagent and the amount of the latter present in excess. In
the early part of the titration a large excess is present, as is also the
case when the oxide of copper formed is weighed, the liquid still
remaining blue. Soxhiet, in common with the rest, finds it the best
plan to keep two solutions, one of Rochelle salt and soda, and the other
of copper sulphate, a sufficient quantity of each being measured out
and mixed before each experiment. When a ^ per cent, solution of
dextrose was used it was found that from undiluted Fehling's solution
5"0.5 mols. of cuprous oxide, and from diluted only 4"85 mols., are pre-
cipitated by 1 mol. of sugar in titration. Similar differences are seen
when the gravimetric method is used, 5'5 mols. and 4'85 mols. being
reduced according as the Fehling's solution was in large excess or only
just so. As the amount of sugar is an unknown quantity, the same
conditions cannot be exactly preserved during each experiment, and
Soxhiet is therefore of the opinion that an accurate analysis by the
gravimetric method is impossible. On the other hand, Marcker,
Behrend, and Morgen hold that if certain conditions are maintained
throughout, the analysis gives accurate results. They recommend
using the same quantity of Fehling's solution and the same volume of
liquid in every experiment and calculating the result by means of an
empirical table. Their method is as follows : — 25 c.c. of each part of
the Fehling's solution is mixed with a certain quantity of sugar solu-
ANALYTICAL CHEMISTRY. 67
fion containing not more than 012 gram dextrose, and the whole made
up with water to 100 c.c. and heated on a water-bath for 20 minutes.
The cuprous oxide is then filtered off, washed with 300 c.c. of hot
water, and reduced in hydrogen and weighed.
From the various numbers obtained, the authors have compiled the
following table, bj means of which the amount of sagar may be calcu-
lated : —
Reduced Cu.
Dextrose.
Reduced Cu.
Dextrose
ingrms.
mgnn?.
ingrms.
mgrms.
196
111-1
152-5
80
194-7
110
144-4
75
188-5
105
135-8
70
182-0
100
127-0
65
175-1
95
117-8
60
167-9
90
108-2
55
160-4
85
98-3
50
or the amount may be calculated by the formula- —
a = -19-26 + 2-689 & -0-006764 &^
where a is the copper and b the dextrose.
The authors consider that by the use of the above table the process
gives very satisfactory results.
Soxhlet has also found that the quantities of cuprous oxide obtained
by reduction with milk-sugar vary in the same manner as with dex-
trose, according to the strength of Fehling's solution employed, from
7-4 to 7'Q7 mols. of copper to 1 of milk-sugar. Rodewald and ToUens
maintain, however, that accurate results are obtainable when certain
precautions are taken, the experiments being all carried out under the
same conditions of volume, strength, &c. ; under the conditions which
they emplov, 1 mol. of milk-sugar reduces 7-47 mols. of copper sulphate.
J. K. C.
Estimation of Acetyl by Means of Magnesia. By H. Schiff
(Ber., 12, 1581 — 1538). — This process has an advantage over the use of
soda, inasmuch as magnesia seldom has a decomposing inflaence on the
products of the reaction. The magnesia is prepared by precipitating the
sulphate or chloride with caustic soda, excess being avoided. 5 grams
of the paste are boiled with 1 to 1-5 grams of the acetyl-derivative
and 80 — 100 c.c. of water for four to six hours in a flask with inverted
condenser. After the reaction i& over, the liquid is evaporated to one-
third of its volume and filtered, the magnesia is then estimated in the
filtrate by the usual process, and from its amount that of the acetyl can
be deduced. W. R.
Test for Phenylglyoxylic Acid. By L Claisen (Ber., 12, 1505).
— Concentrated sulphuric acid, added to a solution of phenylglyoxylic
acid in benzene, gives a deep red coloration, changing to intense blue -
violet. On addition of water, the colouring matter remains dissolved
in the benzene and may be obtained by evaporation. The amides and
ethers of this acid, as well as benzoyl cyanide, give the same reaction.
/2
08 ABSTRACTS OF CHEMICAL PAPERS.
Metanitrophenylglyoxjlic acid produces a carmine, and orthonitroben-
zoyl cyanide a bluish-green colour, analogous to that produced by treat-
ing isatin with benzene and sulphuric acid. W. R.
Citrate of Iron and Quinine. By F. W. Fletcher {Analyst,
1879 191 — 193). — The author has applied the following modification
of Paul's method for testing quinine to the determination of the
quantity and purity of the alkaloid in citrate of iron and quinine.
20 grams of citrate of iron and quinine are dissolved in 50 c.c. of
water, and shaken with excess of strong ammonia. The mixture is
treated with 25 c.c. of ether, and shaken until the alkaloid is dissolved ;
the two liquids are separated, and the aqueous solution shaken with
ether a second and third time. The ethereal washings are mixed
together and evaporated to the consistency of a paste at the ordinary
temperature, and finally dried at 120°. It is then weighed ; the
weio-ht multiplied by 5 gives the percentage of alkaloid present. The
alkaloid is converted into basic sulphate by adding the requisite
quantity of acid. The weight of alkaloid multiplied by 30'86 gives the
number of c.c. of decinormal H2SO4 required. The liquid is heated
until all the substance is dissolved, the solution allowed to cool spon-
taneously, and the crystalline mass filtered through calico. The
volume of the filtrate is taken, and to it 20 c.c. of ether and excess of
ammonia are added, and the mixture well shaken. It is then allowed
to stand for six hours, when, at the junction of the two liquids, crys-
tals of cinchonine and quinidine will be found. These are collected on
a weighed filter, dried at 120", and weighed.
The crystalline residue is dried at 100° and weighed, and the weight
multiplied by 1"18 gives its value as crystallised sulphate of quinine.
L. T. O'S.
Iodic Acid as a Test for Morphine. By J. C. Bell (AnaJyd,
1879, 181).- — Iodic acid is shown by the author to be most unsatisfac-
tory as a distinguishing test for morphine. Other organic bodies, such
as ipecacuanha and guaiacum, reduce iodic acid with separation of
iodine. And, moreover, the statement that the colour is not destroyed
by ammonia in the case of morphine is incorrect. L. T. O'S.
Nitric Nitrogen in Guano. By R. R. Tatlock (Ghem. Neivs, 39,
268 — 270). — The author was led by experiments made some years ago
to believe that a large proportion, and in some cases nearly the whole
of the nitrogen present in guano as nitrates was converted by the
soda-lime combustion process into ammonia, and estimated as such,
and the extent of this change he has since found to depend on the
relative proportion of the organic matter to the nitrates present.
He was suri^ised to find that it was the practice of chemists of
large experience in such analyses to determine the ammonia as if tlie
nitrates present were not decomposed ; thus a much lai'ger percentage
of that substance would be represented than what really existed.
When nitrates are heated with soda-lime, no ammonia is produced,
but when heated with soda-lime in presence of organic matter am-
monia is produced, and its quantity depends on the nature and propor-
tion of the organic matter employed. The author experimented with
ANALYTICAL CHEinSTRY. lo9
potassium nitrate in presence of different quantities of starcli, sugar,
camphor, albumin, and wood charcoal, and the following are some of
the results obtained : —
20 of starch to 1 of nitrate gave 50'74 per cent, of the nitric
nitrogen as ammonia.
3 of camphor to 1 of nitrate gave 26" 38 per cent.
1| of wood charcoal to 1 of nitrate gave. . ll'o6 ,,
6 of albumin „• „ ,. 49'94 „
6 of sugar ,, „ .. 63"35 „
30 of sugar „■ ,,- .. 97"40 „
They vary somewhat, however, even with the same proportions of
the same oi'ganic materials.
The author criticises the various processes for estimating the nitric
nitrogen in guanos, and concludes that Crum's (Proc. Olasgoio
Phil. Soc, 1848, 162) is the best, the nitric acid being determined in
the nitrometer as nitric oxide. It sometimes happens, however, that
a little free nitrogen is evolved at the same time, by the action of
the strong sulphuric acid on nitrogenous organic matters. This can
be determined by introducing a warm solution of ferrous sulphate into
the nitrometer, which absorbs only the nitric oxide present. The
author has not yet arrived at a satisfactory solution of the question.
Tatlock's results (Chem. Xeus, 39, 281) are criticised by B. J.
Grosjean. He says that he published (ihid., 25, 20o) some results on
this subject, in which he drew attention to the conversion of nitric
nitrogen into ammonia by the soda-lime process, but this fact is stated
both in Fresenius's "Quantitative Analysis" and in Church's
" Laboratory Guide." The author described encouraging results for
the conversion of all the nitric nitrogen into ammonia by the combus-
tion of nitre with sugrar and iron filinjjs. His best results were
obtained by mixing the nitre with a caustic alkaline solution m a re-
tort, adding iron filings, and distilling the mixture to a pasty mass,
which was allowed to cool, powdered, mixed with soda-lime, and a
combustion made to determine the residue of the organic nitrocren.
W. T.
Perchloric Acid as a Test for Alkaloids. By G. Fraude
(Per., 12, 1558 — 1560). — Perchloric acid of sp. gr. 1-13 — 1"14 has no
action on quinine, quinidine, cinchonine, cinchonidine, morphine,
codeine, papaverine, veratrine, caffeine, atropine, nicotine, nor conine.
When boiled with brucine, it gives a dark sherry colour, with strych-
nine a reddish-yellow, and with aspidospermine an intense red. Iodic
anhydride and snlphuric acid give with brucine an intense orange-
yellow ; morphine, deep violet, then orange brown ; and curarine,
pink. These reactions are suitable as lecture experiments.
W. R.
Koettstorfer's Process for Butter Analysis. By G. TV. Wigxer
{Analyst, 1870, ISo). — The author points out that for the analysis of
samples of genuine butter this process may be used, but in cases of
doubt, a complete analysis should be made. . L. T. O'S.
70 ABSTRACTS OF CHEMICAL PAPERS.
Coefficients of Expansion of Butter, Lard, Fats, &c. By
G. W. WiGNEK (Analyst, 1879, "183 — 185). — By comparing the sp. gr.
of butter and lard fat, &c., at different temperatures, the coefficients of
expansion have been determined.
Butter fat between 100° and 212° F., has the coefficient 0-0434 per
degree F. Between 150'^ and 190° the coefficient is slightly greater
than this number, but remains the same for all other temperatures.
Lard Fat and Butterine. — The coefficients of expansion of these two
bodies are almost identical, that of lard fat being 0*0420 per degree F.
L. T. O'S.
Specific Gravities of Fats, Resins, &c. By H. Hager (Pharm.
J. Trans. [3], 10, 287). — The fat is melted, dropped into a flat vessel
containing alcohol, in such a manner that the point from which the
drops are allowed to fall is not more than three centimeters distant from
the surface of the alcohol, and that each drop is allowed to fall on a
different spot. The fat globules thus deposited are then removed to a
liquid, consisting of either alcohol, water, or glycerol, or mixtures of
these, until after careful stirring and reduction or increase of the
density, by the addition of one or another of the above liquids, the fat
globules are held in equilibrium in any part of the liquid. The sp.
gr. of the latter is then determined, and this of course at the same
time represents the sp. gr. of the fat. Many of the following sp. gr.'s
may be used as criteria for distinguishing the various bodies investi-
gated : —
Sp.gr. at 15— 16° C.
Butter fat, clarified by settling 0-938— 0-940
„ several months old 0-936—0-937
Artificial butter 0-924-0-930
Hog's lard, fresh 0-931-0-932
old 0-940—0-942
Beef tallow 0-925—0-929
Sheep's tallow 0-937— 0-940
Beef and sheep's tallow, mixed 1:1 0-936—0-938
Butter of cacao, fresh 0-950—0-952
very old 0-945—0-946
Butter and beef tallow, 1:1 0-938—0-939
Expressed oil of nutmegs 1-016 — 1-018
Ditto, extracted with CS. 1-014— 1-015
Ditto, crystalline 0-965 — 0-966
Stearic acid, melted, and in drops 0-964
crystalline 0-967—0-969
Wax, yellow 0-959—0 932
„ African 0-960
„ yellow and resin, 1:1 0-973-0-976
„ „ and paraffin, 1:1 0-916—0-919
„ „ and yellow ceresin, 2:1 . . 0-942-0-943
Ceresin, yellow 0-925-0-928
Wax, Japan 0-977—0-978
„ very old 0-968—0-970
„ white, very old and true 0963 — 0-964
„ „ new 0-916-0-925
ANALYTICAL CHEMISTRY. 71
Sp. gr. at 15—16° C.
Wax, Japan, new, and stearic acid, 1:1.. 0945
"Wax, sp. gr. 0"P63, and stearic acid,
sp. gr. 0-903, mixed, 1:1 0-975
Ceresin, very white, pure 0-905 — 0-908
white 0-923—0-924
Araucai'ia wax 0-990
Resin (fir. pine), yellow, transparent . . 1"083 — 1-084
„ whitish, opaque 1-044 — 1-047
Shellac, light-coloured 1-113—1-114
,, darker 1123
Dammar, old 1075
Copal, East and West Indian 1063—1-800
Benzoin, Siam l-2o5
„ Penang 1-145 — 1-155
„ Borneo 1-165—1-170
Guaiac resin, pure 1-236 — 1-237
Amber 1-074—1-094
Sandarac 1-038—1-044
Mastic 1056-1060
Balsam of tolu, old brittle 1-231—1-232
D. B.
Testing Drugs. By L. Siebold (Analyst, 1879, 190— 191).— The
method for the detection of mineral adultei^ation in flour by means of
chloroform (C. Himly, Year Book of Fharmacy, 1877) may be ap-
plied for the same purpose to drugs. The powdered drug is shaken
with chloroform when the mineral matter sinks to the bottom, and in
the cases of acacia, tragacanth, starches, myrrh, Barbadoes aloes,
jalap, saffron, cinchonas, nux vomica, mustard, white pepper, capsi-
cum, and guarana, the drugs float on the top. By pouring the chloro-
form off, the lower stratum of mineral matter may be collected and
weighed.
In some cases, however, such as gamboge, scammony, opium, Socotrine
aloes, liquorice root, ginger, colocj-nth, coussa, ipecacuanha, cinnamon,
and cardamoms, a portion of the drug sinks vv'ith the mineral matter.
The test may, however, be applied qualitatively, since adulteration
may be detected by a careful inspection of the sediment.
L. T. O'S.
Testing Malt. By W. Schultze (^^'erl Centr., 1879, 375—377).
— Malt is usually mashed at from 70° to 75° C : the author finds,
however, that the yield obtained at this temperature is always smaller
than when the mashing takes place at 60°, 65°, or 70°. The extract is,
however, much more quickly produced at the former temperature,
only 20 niiuutes being required at 70° as against 18-5 hours at 60*^.
Ko more extract is obtained after the starch has been converted into
maltose and dextrin, and it is therefore unnecessary to continue the
mashing longer. J. K. C.
72 ABSTRACTS OF CHEMICAL PAPERS.
Technical Chemistry.
Production of Photographs exhibiting Natural Colours. By
W. W. Abney {CJiem. Neivs, 39, 282). — The author suggests that
the natural colours in the photographs exhibited by Becquerel last
year are produced by the oxidation of the silver compounds em-
ployed, and are not due to interference.
He has photographed the solar spectrum on silver plates, and on
compounds of silver held in sihc by collodion, in both of which, the
spectrum has imprinted itself approximately in its natural colours.
In the former, the image is the brighter, but in the latter the spectrum
can be seen both bv transmitted and reflected lio-ht. The colourins:
matter seems to be due to a mixture of two different sizes of molecules
of the same chemical composition, one of which absorbs at the blue
and the other at the red end of the spectrum. The author believes it
will be possible to preserve the colours unchanged when exposed to
ordinary daylight. \y. T.
Action of Phenol Vapour on Organic Matter at High Tem-
peratures. By C. V. Than (Annalen, 198, 273— 289).— As the
result of a series of experiments on a process for disinfection used in
the Hungarian Custom House, it is shown that although exposure to a
temperature of 137" for three hours retards the development of
organic germs, it is incapable of destroying them. If, however, the
germs are subjected to the action of the vapour of phenol at 137",
they are completely destroyed. The articles to be disinfected are
placed in a leaden chamber (containing phenol), which is provided
with an outer jacket. The apparatus' is heated over a fire, and by
means of an ingenious arrangement, the pyrometer which I'egisters the
temperatures rings an electric bell when the temperature exceeds
137°. By opening dampers in the outer jacket, the temperature can
be rapidlv cooled down to 137°, when the bell will cease rinsrinsr.
vv ritten and printed matter, linen, cotton, quilting, lace, white and
coloured silk and woollen materials, raw wool, and plain and lacquered
leather, were exposed to this treatment without any deleterious effects,
excepting the white wool, which acquired a yellowi.sh tint.
Cluimois leather is rendered friable by exposure to phenol vapour.
^Y. c. w.
Antiseptic Action of Acids. By IN". Stebeb (./. pr. CJiem. [2],
19, 433 — 444). — The presence of so small a proportion as 0"5 per cent,
of hydrochloric, sulphuric, phosphoric, acetic, or even of butyric acid
is suflicient for antiseptic purposes. Phenol is somewhat less active,
whilst lactic and boric acids are much less active, 4 p.c. of boric acid
being insuflScient to prevent putrefaction.
The experiments were made simultaneously with meat and with the
pancreas of the ox, in both cases suspended in water, and without ex-
ception decomposition occurred sooner in the case of the pancreas.
TECHXICAL CHEMSTRT. 73
There was fungoid growth but no Bacteria, when using 0*5 p.c. sul-
phuric acid, 1*0 p.c. phosphoric, 2 and even with 4 p.c. lactic acid.
The author discusses the question whether the acidity of the gastric
juice is of itself sufficient to maintain the healthy action of the
stomach, and he inclines to the aflBi'mative opinion, as he found that
0 25 p.c. of hydrochloric acid, about the normal quantity in the
stomach, was sufficient to prevent putrefaction for 24 hours in the
tissues of meat and ox-pancreas, and when putrefaction did occur, the
solution was no longer acid, but neutral.
As antiseptics, dilute solutions of acid salts would be no doubt as
active as the acids, for Gr. Glaser has lately shown that in this respect
alnminic acetate is equal to acetic acid. A. J. C.
Antiseptic Action of Pyrogallol. By V. Bovet (./. pr. Chem. [2],
19, 44-5 — 401). — From a number of experiments it has been found that
an aqueous solution containing 1 — 1|- p.c. of pyrogallol, will pre.serve
meat for a month free from micro-organisms and bad smell, and that
a 2 — 2^ p.c. solution will arrest decomposition in putrefying sub-
stances, and prevent alcoholic fermentation of grape-sugar. In this
latter respect H. Kolbe and E. v. Meyer state in a note that they have
alreadv shown that it is far less active than salicylic acid (./. pr. Chem.
[2], 32, 151).
It also arrests the movements of Bocillus suhtilis and the formation
of mildew. For many antiseptic purposes, such as wound dres.sings,
pyrogallol, it is suggested, may be substituted with advantage for
phenol.
It is a question whether the antiseptic action of pyrogallol is due to
its power of absorbing oxygen or to some other property which may
be common to all the aromatic phenols. A. J. C.
Spontaneous Oxidation of Manganous Oxides with refer-
ence to the Manganese-recovery Process. By .]. Post (Be,:, 12,
1537 — 1542). — The author's experiments were made on a small scale in
ordinary evaporating basins, and relate to the influence of " whipping,"
addition of soap, and to the use of soda or lime in the recovery of
manganese. The only noteworthy result he obtained is, that a slight
excess of caustic alkali gives a larger yield of manganic oxide than a
slight excess of lime, and that a large excess of alkali, whether lime or
soda, has no corresponding influence on the proportion of manganese
oxidised. W. R.
Some Analyses of Iron. By S. Kerx (Chem. Xeic.?, 39, 281).—
The author states that in many cases the analysis of iron or steel is
not a criterion of the quality of the metal ; thus a sample of boiler
plate which he analysed and found to contain silicon O-OlO per cent.,
manganese 0"120, sulphur absent, phosphorus a trace, copper 0'028,
was found to be of inferior quality by the mechanical tests. This
the author attributes to the rolling of the metal having been badly
conducted. W. T.
74 ABSTRACTS OF CHEMICAL PAPERS.
Separation of Phosphorus and Iron especially with reference
to the Manufacture of Steel. By T. Blair {Chem. News, 40,
150 — 152, and 160 — 163). — The first part of the paper contains a
review of the various processes which have hitherto been proposed
with this object, and which are well known. With regard to Krupp's
or Marje's process for dephosphorising pig-iron by means of the oxides
of iron and manganese, some data are given, from which it is pi'obable,
although it has not jet been proved experimentally, that mangani-
ferous iron will work more favourably still than pig-iron. Another
point which has not yet been settled is whether it will be possible by
addition of a siliceous pig to fit the refined metal for the Bessemer
process, for which, as at present constituted, it is not suitable, since
the dephosphorising process also eliminates the silicon.
In discussing the Thomas and Gilchrist process, the author mentions
that, although it must be admitted that all the initial difficulties have
not been entirely surmounted, it is obvious that the great problem as
to the dephosphorisation of iron is solved, and that nothing more is
wanting than the rapid and effectual removal of the minor difficulties.
Briefly the process consists of the following points: — 1. A durable
basic lining. 2. The addition of basic materials. 3. Removal of
phosphorus by blowing after the carbon has been eliminated. As a
set-off against the objections as to the cost of the new process may be
considered the utilisation of the large deposits of phosphoretic ores in
this and other countries, which may be so much more cheaply woi'ked
and dedivered to the works than haematite ores from distant countries,
and the prolongation of the lease of life of inland iron-producing
districts in all countries, which have their own coal and ironstone.
D. B.
Bleaching-Sugar Syrups by Ozone. By A. R. Leeds (Chem.
News, 40, 86). — The first specimen operated on was of syrup, which
had undergone but one filtration, and was of a brownish-yellow
colour. At the close of the bleaching with ozone, the syrup was of a
faint straw colour, and of slightly acid reaction. A second trial was
made with a syrup which had beeu twice filtered, but still retained a
strong yellow tint. 20 c.c. of the syrup was introduced into a
Geisler absorption apparatus, and a slow current of oxygen, ozonised
to the extent of 24 mgrms. ozone per litre, passed through it for
several hours. When about 100 mgrms. ozone had been brought into
contact with the syrup, it had become almost colourless and almost
neuti-al in reaction.
As determined by Behr, the filtered syrup when it came from the
refinery contained, in 1<)0 parts, 50 parts of dry substance and
40 parts of dry sugar. The alteration in the course of bleaching is
seen in the following table : —
Effect of Ozone upon Filtered Syrup,
Dry substance contains : — Unbleached. Bleached.
Cane sugar (by polariscope). . 79' 7 per cent. 80"0 per cent.
Inverted sugar 12' 7 ,, 12' 7 ,,
D. B.
TECHNICAL CHEMISTRY. 75
Experiments on Creaming. By W. Kikchner and others {Bled.
Cent)-., 187',', '677 — o81). — As the result of numerous experiments,
Kirchner comes to the conclusion that pans made of tin are better
than wooden pans for the cream to rise in. The other authors have
experimented on the cooling of the milk by various processes before
churning, and tind that a larger yield of butter is usually obtained
■when the milk has been cooled by ice. J. K. C.
Experiments on Churning. By Winkel {Bied. Centr., 1879,
382). — The author sums up the results of his investigations as
follows : — The more carefully the cream is skimmed off, that is, the less
milk it contains, the lower the temperature of churning required, the
number and swiftness of the turnings remaining the same ; or in
other words, so much the more quickly will the butter separate at the
same temperature and quickness of churning. J. K. C.
A New Method of Preparing Methyl-violet. By H. HAs.sE^^-
CAMP (JJeut. C'hein. Ges. Ber., 12, l-J.7o — i"27G). — When a mixture of
one part of benzenesulphonic chloride and two of dimethylaniline is
heated on a water-bath, a blue coloration is produced, which gradually
becomes more intense, and after some hours the wdiole is converted
into a viscous dark-coloured mass. The colouring properties of this show
it to be methyl-violet. Further, when the product is boiled with water,
the presence of an oily liquid was observed, which had the characteristic
odour of phenyl sulphide. The reaction, therefore, takes pla.ce as
follows:— CfiHs.SO.CI -f SCeHsNMe. = (Me.,N.C6H4)2C^ { + HCl +
\NMe
2H2O + CeHj-SH. Benzenesulphonic chloride and methyldiphenyl-
amine appear to yield diphenylamine blue. P. P. B.
Transferring Lightfoot-black from one Fibre to Another.
By J. Wolff (Ckem. Ne%cs, 40, 59). — Lightfoot-black dissolves in a
strong aqueous solution of aniline hydrochloride, but incompletely, and
with a deep greenish-black coloration. The solution obtained in this
way mixes with hot watei', producing a black-violet liquid, which dyes
cotton, wool, and silk of a grey tint. Even the Lightfoot-black on the
fibre dissolves in a strong solution of aniline hydrochloride. Some
time ago the author dyed a large quantity of China grass yarn with
Lightfoot-black, by soaking the yarn thoroughly in a strong solution
of aniline hydrochloride and potassium chloride. A small quantity of
that yarn treated lately with a strong solution of aniline hydrochloride
produced a dark greenish-blaek solution, whilst the remaining fibi'e,
after washing and drying, showed a dark greenish-grey colour. The
greenish-black solution mixed with water dyed cotton a beautiful
bluish-grey, and wool and silk a blackish-gi-ey, showing that this
colouring-matter itself has a very great affinity for the fibres, without
being produced on the fibre as in the Lightfoot process. The shades
thus produced on wool and silk are not bright, proving that the
Lightfoot-black process is unable to produce fine black shades at all
on these animal fibres. The solutions obtained in the above manner
76 ABSTRACTS OF CHEMICAL PAPERS.
contain too mucli acid and comparatively small quantities of colonring-
matter, so that it is very difficult to dye a deep black with them.
As far as the author knows, this is the first case of transferring
Lightfoot-black from one fibre to another.
If the solution of Lightfoot-black in aniline salt solution is neu-
tralised with caustic soda and boiled until all aniline is driven off, a
greyish-black powder remains in a light bi'own-coloured slightly
alkaline liquid. The powder filtered from the liquid and washed on
the filter with boiling water, consists of two different colouring
matters ; the one dissolving with a bright red colour in boiling water
acidulated with hydrochloric acid, and dyeing cotton and wool of a
dull-red shade, which by washing with clear water turns reddish-
brown, and by soaping, clear brown ; the other consisting of a dark
blue-black powder, insolnble in neutral and acidulated water. This
is another proof that Lightfoot-black consists of two colouring matters
— one dark blue, the other brown. D. B.
Aniline Blacks. By J. Wolff (Chem. Neios, 39, 270—273 ; and
40, 3 — 6). — The author divides aniline blacks into two series, those
which are produced in or on the fibi'e, and those which are first manu-
factured and afterwards applied to the fibre by the usual process of
dyeing.
The first was invented by J. Lightfoot, of Accrington, in 1866, and
are extremely well adapted for prirdinf/ black on vegetable tissues, but
all attempts to use this process for dyeing have proved more or less
unsatisfactory, owing mainly to the difficulty of evenly distributing
the colour, and for silk and wool dyeing this difficulty becomes still
greater. The basis of the method usually employed to dye by this
process is to soak the yarn or woven fabric in aniline hydrochloride,
with or without free aniline, and potassium chlorate, with or without
tlie addition of other, especially metallic compounds, and afterwards
to expose the goods to the air in a warm room until they are changed
to a dark gi'een colour. They are then passed through a warm bath of
soda, which develops the black in a short time, or they are passed
through a bath of chrome and hydrochloric acid, which produces a
much deeper and finer black, which does not turn green.
The Lightfoot blacks can be divided into (1) those which turn
green and (2) those which remain black on exposure to the air. The
first are the common and the second the oxidised Lightfoot blacks.
The shades of these series of blacks run from blue of ditl'erent shades
of grey, and of brown- black to black- brown. The fii^st link of these
series is the blue invented by the late F. Crace-Calvert, and obtained
by the action on aniline hydrochloi-ide of a smaller quantity of potas-
sium chlorate than that required for the black with use of ferrous
sulphate to moderate the oxidation.
The aniline blacks are mixtures of at least two distinct colouring
matters, the one a very deep blue, the other browns of different
shades. The less toluidine the aniline contains, the bluer will be the
black produced by this process ; hence it would appear that the brown
colouring matter is derived from the toluidines. Again, from their
ability to inci'ease the strength of the oxidation, copper, cerium, vana-
TECHXICAL CHE-MISTRY. 77
dinm, and other metallic compounds, even in very minnte quantities,
have the property of deepening tlie dark blxie-black to a very fine blue-
black. Little is known respecting the chemical constitution of the
Lightfoot black; Eeinbeck says it is a powerful violet-black base
forming with acids green-coloured compounds. Muller gives to the
black the formula C12H14N2O11, but on account of the large proportions
of hydrogen and oxygen the author considers it an improbable one.
A more trustworthy elementary analysis by Goppelsroeder leads to the
formula C.i4Ho„Ni for the common Lightfoot black, which he interprets
as = 4(C6H5)N. The chemical constitution of the oxidised black he
represents as (C6H5N)40, and of the reduced common black as
HX(C6H5).X(CeH5).N(C«Ha).(C6H5)NH. With ])otassium-hydrogen
sulphate he produces naphthalene pink from this black, thus, 5Co4HcniS'4)
+ I6HKSO4 = 8X -f I6H.2O + 8SO2 + 4 of naphthalene pink,
C3.,H;iX3.
Another chemist, by treatment of Lightfoot's black ^svith aniline, has
obtained a fine aniline pink of the formula C36H33N5.
All these formula3 of aniline blacks show that they are the products
of powerful oxidation taking place simultaneously with considerable
condensation. Another interpretation of these results may be o-iven,
supported by the production of naphthalene pink above mentioned,
and by the property the black has of forming substitution-products
with aniline, such as aniline pink. (C6H4).,(XH)4(C6H4),. The oxidised
Lightfootblack(CeH4.NH),0(C6H4.NH),. The reduced Lightfoot black.
In the aniline blacks which are manufactured first, and then applied
to the cloth or yam, there are two, known by the commercial names
" indulin " and ''nigrosin." The latter name was given to a product
invented by the author in 1862. He also discovered the first link of
the indulin series in 1865, by treating the bases of magenta refuse with
aniline and acetic acid. The spirit-soluble indulin thus produced was
converted by sulphuric acid into water-soluble indulin, fraudulently
called bv some firms " niofrosin."
Indulin may be manufactured by several methods.
(1.) From magenta refuse, which is treated with boilino- water
acidulated with hydrochloric acid, to extract completely the salts of
mauvaniline, rosaniline, and chrysaniline, and to leave the violaniline
salt undissolved, which is then decomposed Avith impure caustic soda.
10 parts of the impure violaniline thus left are treated with 6 parts of
commercial acetic acid (of the equivalent 120), and 20 parts of " aniline
for blue," and heated to between 140° and 160", as long as ammonia
is given off and until the mass dissolves and gives the desired shade,
in alcohol acidulated with acetic acid. Caustic soda is then added in
sufiicient quantity to neutralise the 6 parts of acetic acid, and the
liberated aniline is driven off by steam. The indulin base thus ob-
tained may then be separated from the soda acetate solution and
dried. To convert it into the water-soluble form, 1 part of the base
is introduced slowly into 3 or 4 parts of sulphuric acid of 66° B., heated
to 100°, and kept agitated ; the acid solution is then heated at 120 —
140° for about five hours until a sample when taken out, washed with
water, and treated with ammonia at 60° or 70° dissolves quickly and
78 ABSTRACTS OF CHEMICAL PAPERS.
completely. When the process is finished, the whole is washed with
water, filtered, and boiled with sufficient soda solution to dissolve and
form a neutral salt with it. The solution is then evaporated, and the
residue, which is the water-soliable indulin, is dried at a temperature
not exceeding 70°. Ammonia is sometimes used instead of soda.
Another way of preparing indulin is by heating 10 parts of pure
aniline with 20 of syrupy arsenic acid at 185° or 190°, until it forms
on cooling a dull, yellowish, bronze-coloured, brittle substance, which
is composed principally of violanilin. Caustic soda is added to the
fused mass, to combine with the arsenious and arsenic acids, the free
aniline driven off by steam, and the base after being powdered and
dried is converted by aniline and acetic acid into indulin in the man-
ner described.
It may also be prepared by a number of different methods based on
the action of suitable oxidising or debydrogenating agents, such as
cblorine, nitric acid and its compounds, on pui'e aniline or suitable
aniline salts at a temperature of 185° to 190°. The author gives equa-
tions in explanation of these reactions.
In the most soluble indulin blues, the triphenyl-violaniline predo-
minates in quantity, but in many, the mono- and di-phenyl-violaniline
and mauvanilines accompany it. Thus indulin may be principally
triphenyl-violaniline hydrochloride.
By treating these bases with sulphuric acid, they are converted into
the corresponding coniugated acids, from which salts may be obtained,
by neutralisation. Thus there may be formed sodium triphenyl-
violaniline monosulphonate ; and the di-, tri, and tetra-sulphonates
may also be obtained. The monosulphonates are insoluble in water,
the disulphonatcs are sparingly, and the tri- and tetra-sulphonates
easily soluble. The alkaline salts of all are easily soluble.
These, together with the phenylated mauvanilines, form the prin-
cipal constituents of water-soluble indalins ; they sometimes, how-
ever, contain nigrosin-sulphonic acids and their salts.
Spirit-soluble indulin dyes wool, silk, and cotton of different shades
of grey. In dyeing", the acidulated alcoholic solution is added to an
acidulated cold bath, the goods to be dyed are immersed, and the
whole heated to the boiling point and kept there until the desired,
shade is obtained.
Spirit-soluble indulin dissolves at 115° in 2 to 3 parts of its weight
of glycerine acidulated with 5 per cent, of hydrochloric acid, but
dveing with these products is not satisfactory, owing to the liability
of their separating from solution and rendering the dyed shades un-
even.
The w^ater-soluble indulins dye fabrics of good light and dark shades
of grey, even approaching black, but the blacks are not satisfactory
either in colour or " fastness."
The third scries of aniline blacks is the one of which nisrrosin is a
link ; they are used for dyeing blacks and greys on wool, silk, and
leather. They resist well the action of light and air, and their alco-
holic solutions are employed with varnish producing oils and resins
for making black varnish.
Nigrosin was first manufactured by heating a mixture of 44! parts
TECHNICAL CHEMISTRY. 79
of anilixie, 20 of stannous chloride, and 11 of nitrobenzene durino-
four hours at 190°, and afterwards at 220° or 230° for five to eight
hours more, until a sample poured into water gives to the latter a pale
yellow coloration. At this point, the unaltered aniline in the "melt"
■was driven off by a current of steam. The " melt " separates from
the condensed steam, and when powdered and dried constitutes the
nigrosin of commerce. The author soon found that the presence of
stannous chloride was unnecessary, and assuming that the nitroben-
zene acted simply as an oxidising agent, he made experiments, and
found that by the action of arsenic acid on a mixture of aniline and
aniline salt, a fine nigrosin could be produced. In trying to make the
water-soluble nigrosin from a product produced from aniline contain-
ing toluidine, a brown-yellow extract was obtained by boiling with
water acidulated with hydi'ochloric acid, and no nigrosin was dis-
solved, but when boiled with fresh quantities of acidulated water the
brown-yellow substance was ultimately removed, and then the nigrosin
became soluble.
In the first stage of the process in the production of nigrosin, viol-
aniline is produced, and at this stage a mixture of violaniline and
aniline salts remains. When these are heated at 220'' or 230°, the
colour of the melted mass changes gradually from violet-blue to dark
blue, and later on to greenish-black, whilst ammonia is formed. Tri-
phenylviolaniline (the base of spirit-soluble indulin) when heated with
aniline salts as above described, yields also nigrosin in both the
soluble and insoluble form, but without the formation of ammonia.
Pure nigrosin is prepared by heating 22 parts of pure aniline hydro-
chloride with 10 parts of pure syrupy arsenic acid, (containing 70 per
cent, of dry acid) for four or five hours at 190° in glass or enamelled
iron vessels, the liquid being agitated from time to time, and after-
wards heated at 220° to 230° until a sample when drawn off dissolves
with a faint yellow colour in boiling water. The unaltered aniline is
liberated with soda, and it, in company with diphenylamine, is re-
moved with a current of steam ; the remaining nigrosin base is
washed with boiling water, then dissolved in boiling water acidulated
with excess of hydrochloric acid, and precipitated with soda. The
precipitated nigrosin is collected on a filter, washed, and again dis-
solved in acidulated boiling water, and when cold is precipitated by
adding common salt. It is further purified by dissolving it in boiling
water, filtering, and allowing it to cool, when the nigrosin separates,
the process being repeated several times. Nigrosin has a blue colour
if pure aniline is used, but if toluidine is present even in small quan-
tities, the black shades of nigrosin are obtained. The author found
the formula for the pure nigrosin base to be C36H27N3, and for
nigro.sin itself, CssHovN^ClH, but this is also the formula for triphenyl-
violaniline, the conversion of the one into the other beinar brouo-ht
about by intramolecular change.
By dry distillation, nigrosin yields substances belonging to the de-
rivatives of di- and tri-phenyl-diamine, whilst triphenylviolaniline
yields diphenylamine and aniline, and from this the author infers the
difference in the molecular constitution of these two bodies.
Pure blue nigrosin dissolves in water, producing a dull blue solu-
80 ABSTRACTS OF CHEMICAL PAPERS.
tion, becoming brigliter and greener on the addition of hjdrocliloric
ficid. It possesses a remarkable blood-red fluorescence, and all the
blue and black nigrosins have this property more or less, and some
so strongly that when so little is disscjlved in water that no colour can
be seen by transmitted light, the solution has the appearance by re-
flected light as if particles of bright metallic copper were moving
about in it. The nigrosins dye yarns and goods slowly and evenly of
blue, or blue-black colours, which when deep enough will stand light,
air, and soap well, but not the fulling process.
The following mixtures treated in the manner above described, in
which aniline salts and arsenic acid are made to react on each other,
produce the different shades of blue and black nigrosins.
60 parts of pure aniline hydi'ochloride, and lU parts of pure nitro-
benzene, yield a dark blae dyeing nigrosin, whilst the same mixture
with 1 part of cuprous or cupric chloride added to it yields a fine
blue-black.
60 parts of aniline hydrochloride (prepared from aniline containing
2 per cent, of toluidine) and 10 parts of nitrobenzene (made from ben-
zene containing 2 per cent, of toluene) yields a blue-black dyeing
colouring matter, which by addition of certain metallic compounds
(such as cupric chloride) is much deepened.
In the manufacture of nigrosins, the careful regulation of the tem-
perature is of great importance, otherwise a considerable quantity of
bye-products would be formed.
The nigrosins are slightly soluble in weak boiling alkaline solutions,
easily soluble in benzene, petroleum, and certain oils, especially when
alkaline, with a bright purple colour, and when acid, with a fine green-
blue shade. Oxidising agents convert nigrosins on the fibre into dull
and reddish-grey violets, whilst reducing agents render them colour-
less, forming leuco-nigrosins. I^itric acid, even of 1"5 sp. gr., has
very little action on these colouring matters. The author gives
formulae showing the typical relations which he assumes to exist
between nigrosin and Lightfoot black.
Nigrosin is specially well adapted for dj^eing silk a fine black
colour without injuring the gloss of the fibre or increasing its weight
more than a few per cent. W. T.
Production of the Red Colour in Salting Meat. By A. Haet-
DEGEN (JBied. Ceutr., 1879, 478). — Salt added in large quantities pre-
vents the appearance of the red colour, but if it is applied a little at a
time, and the meat is afterwards smoked, a better red is obtained.
J. K. C.
81
General and Physical Chemistry.
Emission Spectra of Haloid Mercury Compounds. Bj B. 0.
Pkikce (Ann. Fliys. C'hevi. [2], 6, 597 — 599). — The emission spectra
were obtained bj passing the electric current through a Geissler tube
containing a small quantity of the salt ; when the salt is warmed with
a Bunsen burner, the mercury spectrum is seen, and as the heat is
increased bands appear which dili'er according to the salt employed.
The measurements were made with a Steinheim spectroscope, the
scale of which carresponded as follows with the lines of the spectrum :
Si + 81, Na - 100, Hg7 - l02-9 and 103-8, Baa - 111, Hga - 114,
Sr3 - 157, Hg/3 - 176, Hgc - 138, Hge - 207.
When mercuric chloride was used, a band appeared at 108^^ — 100^^.
The edge of this band was sharply defined on the less refi'angible side ;
but when the salt was strongly heated, a continuous spectrum was
observed, stretching for some distance on the more refrangible side.
Mercurous chloride gives the same band, whence it is argued that
mercurous chloride is dissociated.
Mercuric bromide gives a band between 131 and 135 ; mercuric
iodide a band between 168 and 172. It is remarked that the bromide
band is exactly half way between that of the chloride and that of
the iodide. F. D. B.
Smoke of an Electric Lamp. By B. S. Proctor (Chem. Neu-s,
39, 2'S3j. — At the Newcastle-upon-Tjne Chemical Society Mr. J. W.
Swan exhibited an electric lamp on the incandescent principle, in
which the current had to pass through and heat a cylinder of carbon
placed between two platinum conductors ; this arrangement was
placed in a vacuum in a glass vessel, and as the current was too strong
the carbon cylinder broke down.
The author examined the glass which enclosed it, and found the
inside covered with a sooty deposit which, under a j-inch micro-
scopic objective, appeared nebulous, with some bright specks of plati-
num here and there. The platinum supports were also covered with the
black deposit, which burned off easily on being heated to dull redness.
A piece of the glass was treated with aqu-a regia, and platinum and
iron were found in the solution. It is possible tha.t the platinum
particles were scattered about by the disruptive discharge, which fol-
lowed the breaking down of the carbon cylinder. W. T.
Thermochemical Investigation of the Oxides and Acids of
Nitrogen. By J. Thomsex {Her., 12, 2062 — 2u65).— In order to
calculate the heat of formation of the oxides of nitrogen, the following-
values were determined by experiment : —
VOL. XXXVIII.
82
ABSTRACTS OF CHEMICAL PAPERS.
Reaction. Heat of formation.
K, + Hi + 0, = NFiT^O, 64950 uuits
NoOo + 02 = N.Oi 39140 „
N.,04 + Aq 15510 „
N, + O , -18320 „
Oxidation of an aqueous solution of IST.Oi. ISTjOiAq + O = + 18320.
From these data, the following- results were obtained, which differ
considerably from Berthelot's determinations {Ami. Phys. Chem. [5],
6, 178) :—
Berthelot.
No + 0 —
No + 0.> -86600 units
No + 03 + Aq -51800 „
N2+O, —
No + O4 -f Aq —
No + 05 + Aq -14800 „
Thomsen.
- 18320 units
- 72790
- 36460
- 33650
- 18140
+ 180
The following table
shows in columns I and II the heat of forma-
tion of the anhj-drous nitrates ; in I by the direct union of their
elements, and in II according to the equation M'o + Oj + N2O4.
Column III shows the heat of solution of these salts : —
Nitrates of I.
Potassium 104660
Sodium 96430
Lithium .... 96800
Thallium .... 43330
Silver 13920
Barium 196100
Strontium . . . 190210
Calcium 173590
Lead 75860
Sr + Oo + N0O4 + 4H20
Ca + Oo + N2O, + 4H,0
Cd + Oo + N0O4 + 4HoO
Mg+Oo + NA + 6H0O
Zn + Oo + N0O4 + 6H0.O
Ni + O2 + N0O4 + 6H0O
Co + O2 + N0O4 + 6H,0
Cu+ Oo + N0O4 + 6H3O
II.
III.
242960
- 17040
226500
- 10060
227240
+ 600
120300
- 19940
61480
- 10880
22^>750
- 9400
223860
- 4620
207240
+ 3950
109510
- 7610
231540
- 12300
218440
- 7250
124870
- 5040
214530
- 4220
142180
- 5840
124720
- 7470
123330
- 4960
96950
- 10710
w. c. w
Thermochemical Research on the Carbonates. By J.
Thomsen (Ber., 12, 2031— 2032).— The heat evolved in the formation
of the following anhydrous carbonates by the combination of carbonic
oxide, oxygen and the metal, is given in column I ; the heat evolved
by the combination of carbonic acid with the metallic oxide is shown
in column III. For the sake of comparison the heat of formation
of the corresponding anhydrous sulphates from metal, oxygen and
sulphurous anhydride is giveu in column II.
GENERAL AXD PHYSICAL CHEMISTRY.
83
Carbonates and
sulphates. L II. III.
K. 250940 273560 —
Na.. 242490 257510 —
Ba 252770 266490 55580
Sr 251020 259820 53230
Ca 240660 248970 42490
:Mn 180690 178790 —
Cd 151360 150210 —
Pb 139690 145130 22580
Ago 92770 96200 20060
w. c. w.
Mutual Relations of Potassium and Sodium Alum in Aqueous
Solution. By F. P. Yexables (Chem. News, 40, 198— 199).— Two
forms of isomorphism between these two salts may be conceived :
the formation of a double alkaline alum, KNaS04.Al2(S04)3.24H20 ;
and the isomorphous admixture of the two alums in the various crys-
tals. All attempts to prepare the double alkaline alum failed, the
isomorphous displacement always beingr of the second kind, the potas-
sium salt predominating, owing to its being less soluble in water than
tlie sodium salt. Experiments were also made on the solubility of
potassium alum in a solution of sodium alum of different strengths
and at different temperatures, the results being that 100 grams water
containing —
Grams sodium alum 4-8 lO'O 12-1 15-4 21-1 337 55-6 767
Will dissolve potas- 1 -.g g.-^ ^.^ ^.3 ^.^ 3.3 ^7 17
Slum alum J
L. T. O'S.
Law of Dulong and Petit applied to Perfect Gases. By H.
WiLLOTTE {Compt. rend., 89, 54u— 543). — The product AC of the mole-
cular weight A into the specific heat at constant volume C is very nearly
the same for all gases. In order therefore that any two gases maybe at
the same temperature, it is necessary and sufficient that the mean total
energy of any molecule whatever shall have the same value in both
gases, that is to say, that AB^ = A'B'-; A and A' being the molecular
AB^ A'B'*
weights of the gases under consideration, and , , the means
of the total energies of the molecules of each gas. Two or more gases
are at the same temperature, if, when placed in contact with each other
they nevertheless preserve their total respective energies unchanged.
It may be shown (1) by making use of the theory of Carnot, or (2) by
the homogeneity as far as velocity is concerned of the equations rela-
ting to the theory of percussion, that if the rule AB^ = A'B'- holds
good for any one temperature, it does so for all other temperatures ;
the question is how far this can be explained from a purely mechanical
point of view. It cannot be due to the mutual collisions of the mole-
cules, for Clausius has shown that inter-molecular shocks exert only a
disturbing influence in the theory of gases ; the author therefore
prefers to explain it by molecular collisions against the atoms of a
material ether, a gas of exceedingly low density, having its constituent
g 2
84 ABSTRACTS OF CHEMICAL PAPERS.
particles situated at distances very small in relation to the dimensions
of the molecules of ordinary gases ; a supposition which serves as a
basis tor several theories.
If A represents the weiocht of any molecule endued with a rapidity
of translation 5,, the arithmetical mean of the quantities of move-
ment representinfj the forces of percussion due to the displacement of
the molecule A, can be represented by X'EAh'liU, the sum 2 being taken
during any moment of which dt is the element, \ being a constant
independent of the nature of the molecule under consideration. The
sum of the terms calculated for unity of time is approximately
'S,AJ>{dt =r ABi, where Wi is a quantity equal to the mean of &i.
If in any vessel there are n molecules whose mass is equal to A, and
%'wliose mass is equal to A', the arithmetical law of the forces of per-
cussion acting in unity of time on the mass of ether in question will
be X(nAB'l + w'A'B'i). Again, if while n + v' = const., the sum just
mentioned does not vary when the composition of the mixture is
altered, the systems formed by the forces of percussion will not vary
either ; and again the sum will remain invariable whatever be the
ratio ~ if ABi = A'B'?.
n'
With a mass of molecules whose centres of gravity are fixed, but of
which the various parts are endowed with reciprocal movements, it
niay be found by similar reasoning that in the case of equilibrium of
temperature, the energies corresponding to these movements satisfy
the relation AB'o = A'B'!, whence by addition —
AB; + AB^ = A'B'l + A'B'i or AB* = AB'^
AB^ j^'B'2
■, representing the total mean energies of the molecules.
KW
It is thus seen why the ratio -— — i is the same for all gases at any deter-
j AB^ ^ ^
minate temperatures ; further by making use of the principle of homo-
geneity bet'ore mentioned, it may be easily demonstrated that if
AB^ .
the ratio — — i is the same for all gases at any temperature arbitrarily
chosen, it will hold good, or very nearly so, for all other temperatures,
the value of the ratio varying very slowly with the tempei'ature.
(Ibid., 8Q, 568 — -570). In determining the conditions of equilibrium of
temperature in the case of a solid body surrounded by its own vapour,
two principal facts have to be established : (1) the influence of the colli-
sions between the molecules of the solid and those of the gas ; (2) the
influence of the ether. In the first case, on account of the equality of
the masses of these molecules, these collisions, far from having a
disturbing effect as in the case of a mixture of two gases, are, on the
contrary, sufficient of theiriselves to maintain an equilibrium, if all the
molecules have the same mean energy, that is to say, if the B'^ of the
molecules of the solid is the same as the B* of the molecules of the
"" , . . AB'^
gas. (B" is a quantity such that represents the total mean
energy of a molecule whose weight is A.)
GENERAL AND PHYSICAL CHEMISTRY. 85
As far as the ether is concerned, it is obvious that the molecules of the
solid ai'e in the same conditions as the molecules of the gas ; if B'' has
the same value in both, the total mean energy being then the same, the
conditions of equilibrium are determined. As an illustration, if we
consider two volatile solids wholly immersed in their own vapour, the
two atmospheres being separated from each other by a piston moving*
in a horizontal cylinder, when the temperature of the system is in
equilibrium, the gases on each side of the piston satisfy the equation
AB* — ■ A'B'-, and this equality holds good equally for the solids A and
A', since they have the same B'^ as their respective vapours. But
the equality AB* = A'B"^ is affected by the collisions of the molecules
of the gases against the walls of the cylinder and piston; this disturb-
ing influence obviously diminishes with the degree of expansion of the
gases, so that, at the extreme limit, when a vacuum exists on both sides
of the piston, the cause of error will disappear, and, since the piston
has then become useless, it may be removed. The law may, therefore,
be stated as follows : — Given two simple solid bodies in a vacuum but
not in contact, whose atomic weights are repi-esented by AA', the
actual energy of each of these bodies when their temperature is in
equilibrium should be such as to satisfy the equation AB'^ =; A'B'"'.
From the preceding it follows that the product of the atomic weight
of a body by its absolute calorific capacily (Hiru), is constant for all
.simple bodies. For compound bodies, an analogous law may be de-
AC
duced. The product is the same for every substance; A being
n
a quantity proportional to the weight of the chemical molecule under
consideration ; C the absolute calorific capacity of the latter ; and ic
th.e number of atoms entering into the composition of the molecule.
J. ^Y.
Variation in the Composition of the Air. By P. v. Jolly
(Aiin.PIujs. Chem. [2], 6, 52U — 544). — The analyses of air which have
from time to time been m^ade exhibit slight variations in the percentage
of oxygen. These differences might be attributed to unavoidable errors
in the olaservations ; it appeared, however, that air collected in the same
place at different times had not always the 8arae density, and conse-
quently not the same composition ; experiments were therefore under-
taken to clear up any uncertainty in the matter.
The composition of the air was determined by two separate methods:
firstly, by observing its density ; secondly, by eudiometric analysis.
In the first method, the air was weighed in a glass globe holding
about a litre, and the amount of oxygen which it contained calculated
by means of the equation —
xWo + (1 - a')W, = W,
where x = vol. of O at 0^ and 760 mm. in the unit of volume of air.
Wo — weight of contents of the globe when filled with pure oxygen
at 0° and 76U mm. ; W„ = weight of contents of the globe when tilled
Avith pure nitrogen at 0''' and 760 mm. ; and W = weight of contents
of the globe when filled with the air at 0^ and 760 mm.
It was necessary in the first place to determine the values of Wo and
^^'„. The oxygen used in these determinations was obtained by the
86
ABSTRACTS OF CHEMICAL PAPERS.
decomposition of water by electrolysis; the nitrogen bypassing air
over lieated copper ganze, which had previously been reduced by
hydrogen. It was found that the copper thus reduced retained a con-
siderable amount of hydrogen, which could only be removed by heat-
ing it to a red heat in a vacuum. The weighings were conducted with
all possible precautions against error, full details of which are given in
the paper.
Tlae mean value of Wo obtained fi'om seven experiments was
1'442545 gram, the probable error being + '000013, that of W„ ob-
tained from the same number of observations was 1"269455 gram, the
probable error being + "000024. The larger probable error in the casi'
of nitrogen must be attributed to the greater difficulty experienced in
obtaining the gas in a pure state.
The samples of air, the composition of which was to be determined,
were always collected at the same place, about 2 kilometers from the
city of Munich. The following table gives the date of collection, the
direction of the wind, and the corresponding value of W. (The experi-
ments were made in 1875-76) : —
Jan. 3 . . .
Jan. 25 .
Feb. 9 . . .
¥eh. 16 .
March 7 .
]\rarch 18
May 9 . . .
May 18 .
s.w.
1 -305035
jS'.E.
1 305754
N.W.
1-305281
W.
1 • 305099
X.W.
1 -305157
s.
1 -305014
E.
1 -305200
E.
1 -305131
June 7 W.
June 29 W.
July 15 N.W.
July 22 I N.
Aug. 2 i ISr.E.
Aug. 29 I N.E.
Sept. 11 W.
Sept. 17 I S. (?)
1 -305046
1 -305397
305239
305594
30529b
305469
305075
1 -304931
The greatest weight, 1-305754, was observed du.ring a north-east
wind ; the least, 1-304931, during a south wind; in both cases the wind
had blown for a considerable time in the same direction. The first
value of W corresponds to 20"965 per cent, of oxvgen ; the second to
20-477.
Before passing to the second method, and to the experiments made
by its means, the weights of a litre of oxygen and of nitrogen respec-
tively were obtained from the values of Wo and W„ given above. To
do this it was only necessary to find the weight of distilled water at
4° which the glass globe would contain. This weight was found to
be 1009-412 giams, the weight of a liter of oxygen in the latitude of
Munich (48"^ 8') and at an altitude of 515 meters above the sea level,
is therefore 1-429094 gram : that of a liter of nitrogen in the same
locality 1-257614 gram. Reducing these values to the latitude and
altitude of Paris, we find that in that city 1 liter of oxygen weighs
l-429o884 gram ; 1 liter of nitrogen weighs 1-2578731 gr:im. The
numbers found by Regnault were 1-4293802 and 1-256167 respectively ;
the differences may be due to the differences in the weights used, or to
the impurity of the gases used by Regnault.
The composition of the air was determined eudiometrically by first
observing the pressure of a given volume of the air at 0° in the eudi-
ometer, then absorbing the oxygen by means of a red-hot copper spiral.
GENERAL AXD PHYSICAL CHEMISTRY.
87
licated by an electric current, and finally observing the pressure of the
remaining nitrogen, occupying the same volume at 0°. Determined
in this manner the percentage of oxygen is not liable to an error
exceeding U-U2 per cent.
The following table o-ives the results of experiments thus made : —
Date.
Oxygen
per cent.
Bar.
Wind.
June 13
„ 18
20-53
20-95
20-73
20-65
20-69
20 -66
20-64
20-56
20-75
20-78
20 -86
20-83
20-75
20-^
20-84
21-01
20-85
20:91
20-56
20-67
20-65
7 14 03
717-7
716-8
718-7
718-1
716-9
713-1
713-9
719-9
715-7
720-9
719-3
723-3
723 0
710-6
721-5
714-2
724-1
718-2
707-0
708-9
W.
,, 24
„ 27
?s-.E.
N.E.
„ 31
July 3
„ 17
N.E.
E.
S.
„ 19
97
October 12
s.w.
N.E.
E.
14
15 .. .•
N.W.
E.
16
21
23
27
E.
E.
IS'.W.
jS.
„ 31
W.
NoTember 2
N.E.
10
13
20
S.E.
W.
x.w.
These experiments, which were made in 1877, show that the per-
centage of oxygen varied from 21"01, when the north wind blew, to
2U'53 during the west wind.
The density of the air is therefore not a constant number.
F. D. B.
Relative Space occupied by Gases. By G. Schmidt (Aim.
Fh>is. Chem. [2], 6, 612 — (il.j). — If the molecular weight of hydrogen
= 2, and the density of the air = 1, the molecular volume of a per-
manent gas is ordinarily set down as —
Y = 28-8725,
it is contended that this number should be 28-8.384, on the supposi-
tion that the air contains 20-96 per cent, in volume of oxygen, and a
table is given of the densities d of the various gases and vapours, calcu-
lated by means of the formula s = , where m =: the molecular
weiarht.*
r. D. B.
* It is clearly shown in the preceding abstract of the paper by P. v. Jolly, that
the density of the air is a variable quantity ; the value of Y must therefore also be
variable, and the densities of gases cannot be expressed in terms of the density
of the air.— F. D. B.
88
ABSTRACTS OF CHEMICAL PAPERS.
Absolute Expansion of Liquid and Solid Bodies. By H.
F. WiEBE (Ber., 12, 1761 — 1764). — The force of cohesion which binds
together the molecular groups in liquids and solids, is measured by the
expansion whicli these bodies undergo under the influence of heat.
The absolute expansion of an atom, i.e., the coefficient of expansion of
the atomic volume, bears a relation to the number of atoms which
have combined together to foi'm a liquid or solid, group of molecules.
Since all bodies have the same cohesion at their boiling and also at
their melting points, if the absolute expansion is multiplied by the
temperature of these fixed points (calculated from the absolute zero),
multiples of the coefficients of expansion, 0 00365, are obtained, as is
shown in the ioWowina; table : —
I.
Absolute
expansion
for 1°.
II.
B. p. calcu-
lated from
absolute zero.
Product of
I X II.
Coefficient
of expansion, m.
s
0 -003015
0 -001872
0 000795
0 -001188
0 -003013
0 -001872
U 000795
0 -001188
772
975
1315
1135
m. p.
388-6
492 - 0
687 0
590 -0
2-17683
1 -82520
1 -045425
1 -348380
1 -171620
0 -921024
0-546165
0-700920
0-003628 X 600
8e
0-00365 X 500
Zn
Ccl
s
0- 003485 X 300
0 -003371 X 400
0 -003905 X 300
Se
0-003607 X 2.50
Zn
Cd....
0-003641 X 150
0 003505 X 200
When (7 equals the atomic weight, d the density, a the mean coeffi-
cient of expansion between the melting and boiling points, T the tem-
perature of the boiling or melting point (above the absolute zero), and
/3 the coefficient of expansion in the gaseous state ; then - - T = (^.m.
Cv
In this equation m bears a relation to the number of atoms in the liquid
or solid molecule.
The author has investigated homologous series of organic compounds,
and obtained the following results : —
I.
II.
III.
lY.
IVIean absolute
expansion (between
B p. calcu-
lated from
Product
of I X II.
b.p. and m.p.) for 1°.
absolute O''.
Formic acid
0 04326
375 0
15-6
5-2x3
Acetic acid
0 -06828
392 -3
26-2
5-2x5
Eutvric acid
0 10235
421-0
46-8
5-2x9
^letliTl alcoliol
0 05000
341 -3
17-06
8-5 X 2
Ethyl alcohol
0- 07143
353-3
25-26
8-5 X 3
Amyl alcohol
0-12500
406-8
50-8
8 5x6
For the acids, the product of the mean absolute expansion for l'^
INORGANIC CHEMISTRY. 89
by the boiling point is equal to the constant 5"2 mnltiplied by the
number of hydrogen atoms coutiiined in the gaseous molecule, + 1.
For the alcohols the constant 8"5 is multiplied by half the number of
hydrogen atoms in th.e molecule. ^V. C W.
Diffusion Experiments with Acid Solutions of Mixtures of
Salts. By F. HiNTEEEiiGEii (i>er., 12, 1619 — 1626).— Experiments
-witli mixtures of sulphuric acid and potassium-hydrogen sulphate, and
of the latter and potassium sulphate, which were diffused into water,
show that the acid diffuses more quickly than the acid salt, and the
latter more quickly than the neutral salt. The same was found to be
the case with oxalic acid and putassium and sodium oxalates; after a
time, however, this relationship is reversed. Mouosodic and disodic
phosphates gave a result similar to that exhibited by oxalic acid. At
first the monosodic phosphate diffuses more quickly, and after some
time the disodic phosphate diHuses more rapidly. Hippuric acid
diffuses more slowly than sodium hippurate, which is accounted for
by the fact that the latter is more soluble than the former.
P. P. B.
Inorganic Chemistry.
Allotropic Modifications of Hydrogen. By J. Thomsen (Ber.,
12, 2u3o'). — The author points out that Tommasis statement (Acad.
Milan'), that " the heat of formation of potassium chlorate is 9,760,
and that of potassium chloride 104,476 units, and consequently
104,476 — 9,760, i.e., 94,716 heat-units, are absorbed in the conversion
of potassium chlorate into chloi'ide, cont;iins no less than three errors.
The heat of formation of potassium chlorate is 95,840, and not 9,760,
the latter number representing the heat evolved in the conversion of
jiotassium chlorate into chloride in the dry way. Instead of 94,716
heat- units being absorbed in the reduction of the chlorate to the chlo-
ride, a liberation of 15,370 heat-units takes place. It is obvious that
the theoretical speculations based on these incorrect data ai^e valueless.
w. c. w.
A New Method for Preparing Hydriodic and Hydrcbromic
Acids. By G. Beltlants {Ber., 12, 2059 — 2062).— Hvdriodic acid
can be easily prepared by heating a solution of iodine (20 grams) in
copaiba oil (6U grams) in a retort connected with an upright condenser.
The gas is purihed by passing it through a drying tube. When the
evolution of gas slackens, fresh iodine is brought into the retort, and
the process is continued until about loO grams of iodine have been
used.
In the preparation of hydrobromic acid by this method, the bromine
must be slowly dropped into the retort containing the oil, and the gas
should be puritied by passing through three drying towers.
AV. C. W.
90 ABSTRACTS OF CHEMICAL PAPERS.
Influence of Volume and Temperature in the Preparation
of Ozone. A New Ozoniser. — By A. R .Lkeds {AnnaUn, 198, 30 —
42). — A solution of potassium dichromate (not necessarily saturated)
mixed with sulphuric acid is placed in a suitable vessel, within which a
bell-jar can be placed, and pieces of phosphorus are partly immersed in
the liquid. It is better, however, to connect three such jars and draw
the air through them by means of an aspirator. For this purpose, the
necks of the jars are cemented into brass caps, which are screwed to a
bar capable of being raised and lowered as in a g'alvanic battery ; the
stoppers are replaced by corks covered with paraffin, through each of
which pass three glass tubes, one ending just below the stopper,
another just above the liquid, and the third bent into a horizontal ring
at the end. The fir.st two tubes are connected so as to allow a current
of air to be drawn through the apparatus ; the third is for lowering or
raising the phosphorus. The pieces of phosphorus are melted in
watch-glasses to give them a more convenient sliape, and are placed
on glass plates in glass cells in the liquid. A flexible tube for con-
veying the ozone from the generators was made of " cerite" ("kerite-"
schlauch), and found to answer very well.
A temperature of 24° gives the best results. The maximum amount
of ozone obtained was a little over 2"5 mgrms. per litre of air ; but as
the generator may be connected with the aspirator and allowed to
work for any length of time, the supply is unlimited. G. T. A.
A Possible Cause of Variation of the Proportion of Oxygen
in the Air. By E. W. Morley {Ghem. News, 40, 184—186, and
Iy9 — 201). — Loomis has proposed the theory that certain great and
sodden depressions in the temperature of the atmosphere are caused
by the vertical descent of currents of air from cold elevated regions.
If such is the case, then the air at the surface of the earth during such
depressions may contain a smaller amount of oxygen than the average.
Jolly concludes from his experiments that the air at the equator is
poorer in oxygen than that at the polar regions, owing to the amount
of oxygen consumed in oxidation being greater than that liberated by
reduction. Facts, however, do not confirm these conclusions, no dif-
ference in the composition of the atmosphere of the two regions having
hitherto been detected.
According to the author's views, based on Loomis' theory, air col-
lected at the centre of an ai-ea covered by a descending current would,
at a given moment, be a sample fresh from the upper atmosphere ;
whilst a sample collected on one side of this centre w.oald consist of a
mixture of surface and upper air, but still containing a deficiency of
oxygen. Although the author has not jei succeeded in making these
experiments, he has, while laying plans for the work, conducted expe-
riments on ordinary air, to ascertain what light can be thrown on the
changes in composition of the atmosphere. The apparatus used was
constructed on McLood's modification of Frankland and Ward's appa-
ratus, with important modifications, so as to reduce all causes of error
to a minimum.
The samples were collected in the open country, in glass vessels, and
preserved over mercury freed from carbonic anhydride, and exploded
IXORGANIC CHEMISTRY. 91
with pure hydrogen. Some samples were collected in stoppered and
capped bottles, which were inverted, and the caps filled with water.
Analyses of air were made daily from 28th December, 1878, to 6th
April, 1879, during which period some very marked and sudden de-
pressions of teniperature occurred, which were accompanied by a
decrease in the quantity of oxygen. The deficiency, however, as might
have been expected, was not proj)ortioual to the decrease in tempe-
rature (see also p. 85 of this volume). L. T. O'S.
Preparation of Perbromic Acid. Bv G. Wolfram (Annalen,
198, 115— 98).— Kiimmerer (./. pr. Chem., 90, 190) has described a
method according to which perbromic acid may be obtained by the
action of dry bromine on dry perchloric acid, the latter being prepared
at the time by the decomposition of potassium perchlorate by sulphuric
acid. Tlie author has repeated this experiment, and finds that the
acid thus obtained, corresponding in all respects with that described
by Kammerer, is nothing more than a mixture of perchloric and
sulphuric acids. The apparent absorption of the bromine by the
perchloric acid is explained by the fact that perchloric acid, when
heated with an excess of sulphuric acid, is decomposed into oxygen
and chlorine, and it is this latter which takes up the bromine in the
above experiment, forming bromide of chlorine : this is volatilised,
together with the excess of bromine, during the subsequent concen-
tration of the liquid. T. C.
Researches on Nitrous Acid and Nitrogen Tetroxide. By G.
Lunge {Bimjl. polyt. J., 233, 155 — 165 ; comp. this Journal, Abst.,
1879, 770). — Second Part. — On the Relations of the Acids of Nitrogen to
Sulphuric Acid. — Our knowledge of this relation is not by any means
complete. It is well known that nitrous acid, either in the liquid or
gaseous form, or produced nascent from the union of nitrogen dioxide
with oxygen, is dissolved by sulphuric acid of about Iv sp. gr. ; but
the behaviour of nitrogen tetroxide towards sulphuric acid is not accu-
i-ately known. The author has shown that it is dissolved by sulphuric
acid, forming nitrosulphuric and nitric acids ; but according to Weber
and Winkler, niti ogen tetroxide is dissolved as such by sulphuric acid
of Q'o' B., producing a reddish-yellow solution, which, when heated,
gives ofi^ nitrogen tetroxide with violent ebullition, and leaves a liquid
having the properties of nitrosulphuric acid. Winkler stated that
28 072 grams of sulphuric acid at 60° B. absorbed 7"397 grams of
nitrogen tetroxide, but that on heating gently, the latter was entirely
expelled. Weber describes the effects of nitrogen tetroxide on
sulphuric acid of different specific gravities, but only qualitatively :
thus, sulphui-ic acid at a sp. gr. of 17 absorbs nitrogen tetroxide
without becoming coloured: hence it was assumed that the latter
Avas decomposed; at a sp. gr. of 1-55 the sulphuric acid becomes
yellow, and hence it was supposed that the greater part of the
nitrogen tetroxide was simply dissolved. Acid of 1-49 sp. gr. takes a
greenish-yellow colour; acid of 1*41 sp. gr. takes an intense green
colour; acid of l^Sl sp. gr. becomes blue and liberates nitrogen dioxide,
which escapes with violent ebullition on gently heating. The green
92 ABiSTRACTS OF CHEMICAL PAPERS.
and blue colours were supposed to be due to the formation of nitrons
acid, the nitrogen tetroxide having been decomposed into that sub-
stance and nitrogen dioxide. As these results are very important to
vitriol mauufacturei's, the author studied them more accurately, and,
as far as possible, quantitatively. The nitrogen tetroxide, prepared
from dry fused lead nitrate, was measured off from a bui*ette, and
mixed with pure sulphuric acid, which had been diluted to diti'erent
strengths with water, and the effects of heat upon these mixtures
were also noted.
The following are given as examples of the method employed and of
the results obtained by the author in carrying out the experiments : —
TOO c.c. sulphuric acid of 1"84 sp. gr., to which was added 2 c.c.
== 3 grams liquid nitrogen tetroxide, gave a colourless solution with
a verv feeble odour, recoiling that of ozone. The amount of
nitrogen dioxide evolved from 1 c.c. of this solution in the nitro-
meter was determined, and also the amount required to decolorise
10 c.c. seminormal potassium permanganate solution. From the
results, the author calculates that his nitrogen tetroxide contained of
pure nitrogen tetroxide 93 percent., and of nitric acid 7 percent. ; but
he argues, as in I'cality the nitrogen tetroxide does not exist as such in
the sulphuric acid, but has undergone a decomposition, one part of
tlie tetroxide having been converted into nitric acid at the expense of
the oxygen of the otlier part, whilst the part which has been robbed
of its oxygen remains as nitrous acid in combination with the sul-
phuric acid ; then assuming that this lower oxide takes the oxygen
from, and decolorises the potassium permanganate, this would give
46"5 per cent, as nitrous acid, and -53'5 per cent, as nitric acid. The
other calculations are made on this supposition, that is, it is first
assumed that all the nitrogen tetroxide remains as such, and the defi-
ciency in the theoretical amount of oxygen required is calculated as
nitric acid ; but if, on the contrai'y, the amount of oxygen required
be less than that found by the permanganate process, then he assumes
that no nitric acid is present, but that nitrous acid must have been
originally present as an impurity.
(I.) The acid was heated to 280°, and kept at that temperature for one
hour ; any free nitrogen tetroxide, if it were present, must have been
thus expelled. When the temperature rose to 200°, a little red vapour
Avas evolved, and the liquid acquired a golden-yellow colour ; but on
cooling, it again became colourless.
On analysis the author calculated that 77"9 per cent, of the nitrogen
present existed as N2O3, and 21'1 per cent, as HNO3; there is, con-
sequently, he says, a large amount of the nitric acid driven olf and
another part changed into nitrous acid.
(II.) On continuing to heat for one hour longer, a further change
took place of the same kind, and 94'5 per cent, of the nitrogen re-
maining existed as N0O3, in combination with the sulphuric acid
forming nitrosulphuric acid ; whilst 5'.5 per cent, remained as HNO3,
and 18 per cent, of the nitrogen originally present having been ex-
pelled by the heating.
(III.) Another experiment was made by adding pure nitric to pure
rSORGAXIC CHEMISTRY. 93
sulplini'ic acid, and analysing the resulting mixture, but no eliange was
found to have taken place.
(IV.) On boiling the mixture for half-an-hour, however, red fumes
were given olT, and the whole of the nitrogen present was converted
into nitrous acid, which was found in combination with, the sulphuric
acid.
That nitric acid is thus broken up has also been demonstrated in
another way by Winkler, who collected the oxygen which was evolved
from the decomposition.
The author did not find the same result as Winkler with sulphuric
acid of 66" B. above mentioned, and he explains this by assuming that
W^inkler employed so much nitrogen tetroxide that it left a large
excess beyond that which could combine with the sulphuric acid as
nitrous acid : hence the sudden and violent ebullition and liberation of
nitrogfen tetroxide on heating- the mixture.
2 c.c. nitrogen tetroxide added to sulphuric acid of 1"805 sp. gr. was
broken up into practically the same proportions of nitrous and nitric
acids as in the first experiment, with acid of 1'84 sp. gr.
Other experiments are described in which sulphuric acid of
1*75 sp. gr. was mixed with nitrogen tetroxide and then heated («), so
that the vapour evolved might at once escape, and (6) where a long
tube was attached to the flask in which the mixture was heated, so
that the vapour might condense and flow back again to the acid in
the flask. In (a) nitrous acid, but no nitric acid was found, whilst in (b)
nitric acid was present but no nitrous acid ; this is explained by the fact
that it requires concentrated sulphuric acid to combine with and
retain the nitrous acid ; and in (n) the acid became concentrated by
evaporation, whilst in (h) it remained of about the same strength, and
was unable to retain the nitrous acid.
Again, when the mixture was heated on a water-bath at about 96°,
no such changes occurred.
As Winkler found, that on heating his mixture of acid of 60° B.
with nitrogen tetroxide, the latter was evolved, he presumed that it
existed as a mechanical mixture with the acid. This the author denies,
stating that had Winkler examined the acid after boiling, he would
have found that it contained nitric acid, and that the nitrogen
tetroxide had really undergone decomposition; and further, that he
must have heated it considerably above the temperature of boiling
water, otlierwi.se no change would have resulted, and no red fumes
would have been liberated.
When the amount of nitrogen tetroxide added is in excess of that
required to form nitrosulphuric acid, the author is uncertain from
analysis whether it exists in the acid in the form of nitrous acid or
of nitrogen tetroxide. W. T.
Norwegium. r>j T. Dahll (Ber., 12, 1731— 1732).— The prepara-
tion of this metal from the ore has already been described (this
Journal, Abs., 1875-', 890). It melts at 2o4', and its atomic weight is
14.5-i'52 (RO), or 218-928 (R-Os). It can be separated from bismuth,
which it closely resembles, by the solubility of its oxide in alkalis and
alkaline carbonates. W. C. W.
94 ABSTRACTS OF CHEMICAL PAPERS.
Constitution of Antimonic Acid. By P. Conrad (Chem. Nev:i?,
40, 197 — 198). — With a view to decide the constitution of antimonic
acid, specimens of it wei^e prepared from the pure metal by seven
different methods, and carefully analysed.
The antimony was determined as sulphide, with the usual precau-
tions, whilst the water was determined, first by exposure over sulphu-
ric acid, and Ihen by heating- in a slow stream of nitrog-en, and
collecting tlie water in a weighed calcium chloride tube. The sub-
stance was weighed after heating, and any discrepancy between the
loss of weight by the substance and the Avater expelled, was regarded
as due to the reduction of the oxide. The loss of water takes place
very gradually.
The acid dried over sulpluTric acid at the ordinary temperature has
the constitution Sb205.3H20, whereas the acid dried in a current of
dry air at the ordinary temperature is represented by SbaOp.T^HoO.
At 100°, this loses 3 mols. HoO, Sb^Oo.HaO being formed ; and between
100° and 200" one moi-e mol. H,0 is expelled, leaving Sb.O5.H2O.
Contrary to the statement of Daubrawa {AnnfUen, 186, 110), the
anhydrous pentoxide is not formed at 275°, and even at 300° the pro-
duct still contains i a mol. H2O. This is driven off only at a red heat
when the oxide begins to decompose.
There seems to be reason to believe in the existence of three anti-
monic acids, corresponding with three acids of phosphorus —
Orthoantimonic acid, HsSbOi = 3H20.Sb..05.
Pyroantimonic acid (metantimonic acid, Freniy) H4Sb207 =
2H20.Sb205.
Meta-antimonic acid (antimonic acid, Fremy) HSbOs =
H20.Sb205.
The gradual formation by heat of the second and third acids from
the first is similar to the formation of the corresponding acids of phos-
phorus. L. T. O'S.
Salts of Plumbic Acid. By O. Seidel (J. pr. Chem. [2] 20,
2(H3 — 205). — The author has repeated Fremy's research on plumbic
acid (Ann. Phiis. Chem. [3], 12, 490), partly confirming his results.
Potassium plumhate, KjPbOa -|- 3H2O, crystallises in quadratic pyra-
mids ; a : c = 1 : 1 221G. The crystals are efflorescent and are not
isomorphous with potassium stannate. The sodium salt has not been
obtained in a state of purity. Potassium plumbate does not produce
a precipitate in alkaline solutions of tin and aluminium, but impure
plum bates are thrown down on boiling a solution of the potassium salt
with lime, baryta, and magnesia.
The precipitate which separates out when an alkaline solution of
lead oxide is added to potassium plumbate is the hydrated sesquioxide,
and not PbaOi, as stated by Fremy. The precipitate is completely
soluble in hydrochloric acid ; when treated with nitric or acetic acid,
or with a hot solution of potash, lead di-oxide remains undissolved.
W. C. W.
Volatility of Platinum in Chlorine. By F. Seelhetm {Ber., 12,
200G — 2008). — When a piece of platinum is heated to redness in a
MIXERALOGICAL CHEMISTRY. 95
•rlass or porcelain tube, through which a current of chlorine is passed,
crystals of the metal are deposited on the sides of the tube. A subli-
mate of platinum is also obtained, by exposing a porcelain flask con-
tainins: platinous chloride to a bright red heat. The author discusses
the bearing of these experiments on the abnormal density of chlorine
at high temperatures observed by V. and C. Meyer (Ber., 12, 142tj).
W. C. W.
Note. — In a recent comrannication (Be7-., 12, 2202), V. Meyer
states that, under the conditions in Avhich his experiments were con-
ducted, platinum does not volatilise. He also points out that Seel-
heim's explanation cannot account for the abnormal vapour-density of
iodine, since in these determinations iodine and not platinum iodide
was employed. W. C. W.
Mineralogical Chemistry.
Rock Salt from Saltville. By B. E. Sloan {Chem. News, 40,
187). — Some specimens of dark brownish-red rock salt obtained from
the salt wells at Saltville, Washington Co., Virginia, gave the follow-
ing.results on analysis : —
XaCl. KCl. CaS04.2H20
89-21 trace 4-86
).
FeA-
SiOj.
0-84
4-53
or
lithium
could not
be de-
L. T.
O'S.
The presence of strontium, barium,
tected.
Livingstonite. ByF. P.Yemables (Chem.Neivs, 40, 186 — 187). —
Owing to doubts as to the purity of the samples of this mineral
analysed by Barcena, and consequently as to the accuracy of the formnla
assigned to it by him, the author has at his request examined purer
specimens, and the numbers obtained give the formula Ho-S.2Sb2S3
instead of 4Sb2S3 + HgS + FeSj. Calcium sulphate was pi-esent in
considerable quantities, but as it occurs only as a matrix, it may be
eliminated from the results of analysis. This is the most stron<i-ly
acid sulphantimonite yet known. L. T. O'S.
Magnetite. By E. C. Smith (Chem. News, 40, 189).— This
mineral occurs in Henry Co., Virginia, in loose crystals coated with
ferric oxide, which can easily be washed off, when they present the
ordinary black colour and general appearance of magnetic iron ore.
Hardness = 6 ; sp. gr. 4'98. The "crystals are strongly mao-netic,
and are curiously distorted on the surface by step-like projections
and depressions, giving them the appearance of rhombic octohedrons,
but with irregularly varying inclinations of the general surfaces. The
analysis of the cleansed crystals show them to consist of pure map--
netite. • L. T. OS.'^
r»r» ABSTRACTS OF CHEMICAL PAPERS.
Crystalline Form of Sardinian Anglesite. By Q. Selt,.\
(Gazzetta, 9, 344 — 353). — Anglesite, whicli is foand so frequently and.
in such fiue crystals iu the mines of Monteponi and elsewhere in the
island of Sardinia, formed the subject of a monograph by Lang, and
since then this mineral has been studied by other crystallographers,
especially Hessenbarg, Zepharowich, and Kreuner. Although the
number of forms already described is considerable, a table of no less
than 44 being givfen in the paper, a careful examination of numerous
line crystals has enabled the author to increase it greatly. Details ot'
the ineasurements of 38 specimens are given, but many of these
symbols cannot be considered as deKnitely established until they
have been carefully compared with the results of former workers in
this field. In the second part of the memoir the author proposes to
discuss the relation between the different forms and the size of the
crystals, as -well as to give descriptions of other forms of anglesite.
C. E. G.
Compcsition of Amblygonite. By S. L. Penfielp (Chem.
News, 40, 208— 209).— Brush and Dana (Ain. Jour. Sci. [3], 16, 42)
have shown that triploidite, (Mn,Fc):iP208 + (Mn,Fe)(0H)2, is isomor-
phnus with wagnerite, MgsP.Oa + MgPo, and similar in composition
to triplite, (Mn,Fe)3Po08 + (MD,Fe)F2, and consequently argue that the
OH-group plays the same part in triploidite as fluorine does in the
other two minerals. In amblygonite the author shows that hydroxyl
and fluorine are also isomnrphous. The results of the analyses give
the ratios of P : Al : (Li,Na) : (OH,F) =r 1:1:1:1, cori-esponding
with the formula ALP^Os +2(Li,Na)(0H,F), or—
SAl-P-^Op I , f AU(OH,F)«
3(Li,m)3P04 j "^ ) 2(Li,Na)(0H,F)
Owing to a dilference in the optical properties of some specimens,
Des Cloizeaux separates the mineral into two varieties, but the varia-
tion is so slight as hardly to afford sufficient ground for the dis-
tinction.
Details of the method of analysis are given. L. T. O'S.
Uranium Minerals from North Carolina. By P. A. Genth
(Chem.. Netvs, 40, 210— 212).— These minerals, found in the Flat
Rock Mine, Mitchell Co., North Carolina, are as follows : —
Uranotll occurs as a pale yellow coating on gummite, and is amor-
phous, massive, and compact. Hardness = 2"5 ; sp. gr. 3'84 ; lustre
dull. In colour it varies from a straw-yellow to lemon-yellow ; its
streak is of a pale straw yellow, it is opaque, and has an uneven fracture.
The analysis agrees with the formula Ca3(02)6Si602i.l8H20, rather
than Ca3(02)6SiisOi8.15H20 given by Rammelsberg.
Gummite. — This orange-coloured mineral occurs in compact, amor-
phous, nodular masses. Hardness 3 ; sp. gr. 484 ; lustre resinous ;
and streak oi-ange-yellow. It is opaque, and has a subconchoidal
fracture. It is soluble in acetic acid. Various opinions have
been held concerning the constitution of this mineral, and the
author, with Patera, maintains that it is principally lead uranate.
Gummite is the result of the alteration of uraninite, and that from
5)
55-
5?
)i
MINERALOGICAL CHEMISTRY. «)7
North Carolina is a mechanical mixture, since uranotil penetrates the
mass throughout. From the author's analyses it is found to consist
of—
Uranium hvdrate, H.,('U02)0o + H,0 40-10 per cent.
Uranotil, Ca3(U0,)HSiG0,i + ISH^O .... 33-38
Lead uranate, Pb(U02)j03 + GhJo 22-66
Barium uranate, Ba(U02)203 + 6HoO 4-26
Gummite from Joliann Georgenstadt has probably the following
composition calculated from Kerstcn's analyses : —
Uranium hydrate, H.(UOo)0., + H.O 6-32 per cent.
Uranotil, Ca3(UO,),Si60,i + 18H.,0 .... 30-54
Phosphuranylite, (UO,)3P208 + 6HoO 8-/3
Calcium uranate, CasCUO-OoOs + 6H3O . . 52-99
PhospJncranylite exhibits under the microscope rectangular pearl v
scales, having a deep brown colour. The analysis shows that it may
be expressed by a formula similar to that of troegerite.
Phospburanvlite = (U0.2)3PoOs + 6H0O
Troegerite \. .. = (UO^jsAs.Os + 12H.,0
The analyses of pittinito andeliasite admit of no calculation, as they
appear to contain too many foreign substances. A, sample supposed
to be ui'anite was found to contain lime and not a trace of copper, and
therefore consists of autunite. L. T. 0"S.
Analyses of Chrysocolla from Chili. By N. Pellegrini (Ga=-
zetta* 9, 293). — This specimen of chrysocolla, from Cerro Blanco in
Chili, was bright green on the outside, farther in it was a beautiful
deep green, and in the centre a dark greenish-blue approaching to
brown. These were mechanically separated and analysed : —
Outside. Second lajer. Centre.
HoO. 7-296. 24-007 26-148
Sib.. 16-621 26-685 25-938
Cud 65-306 39-891 31-913
AI3O3I 4.9.^ f 1-4991 .
FesOsJ ^^""^ l-fO-415/ -^^"^
FeO — 1-824 —
CaO 3081 2-307 8-992
Loss 2-739 0-372 2-782
100-000 100-000 100-000
C. E. G.
Volcanic Ash from Cotopaxi. By J. R. Santos (CJiem. News,
40, 186). — This ash, which fell during a recent eruption at Bahia de
Caraguez, a distance of 120 miles from Cotopaxi, consisted of a fine
brown powder containing glassy granules mixed with ferric oxide.
Its specific gravity = 2^743 and its analysis gave —
* The Gazzetta cMmica italiana will iu future be abbreviated to Gazzetta.
t This is perhaps 3-415.— C. E. G.
VOL. XXXVIII. h
98 ABSTRACTS OF CHEMICAL PAPERS.
SiO.,.
AI2O3.
FeoOa.
PbO. CaO.
MgO.
56-6t5l
19-398
7-523
0-575 6-229
trace
Na.20.
KoO.
H2O.
6-123
2-425
0-8G2
Discarding the iron and water, the above numbers lead to the for-
mula (K2Na2CaPb)Al2SioOi4. The qnantitj of lead contained in this
ash is interestinj^, as is also its state of combination, nanielj, silicate.
L. T. O'S.
Organic Chemistry.
Tetrabromethanss. Bj R. Anschutz (Ber., 12, 2073—2076).—
Acetylene tefcrabromide, prepared by the direct union of bromine and
acetylene, distils without decomposition at 137° under 36 mm. pres-
sure. It is a colourless liquid, which, refracts light powerfully, and
does not solidify at — 24°. It is converted into symmetrical ethylene
dibromide (b. p. 110°) by the action of zinc-dusfc. The dibromide
combines with 2 atoms of bromine to form a tetrabromethane, which
is identical with acetylene tetrabromide. Unsymmetrical ethylene
dibi'omide boils at 93°, and readily passes into polymeric modifications.
In the latter respect it diifers from the symmetrical isomeride.
The tetrabromethane obtained by .Bourgoin (Atiii. Ghim. Phijs.,
1873 [4], 29, 378, and 1874 [5], 2, 227) by'the action of bromine on
dibromosuccinic acid, is considered by the author to be probably
ethylene perbromide. W. C. W.
Ferro- and Ferri-cyanides of certain Tertiary Bases. By
C. WuRSTER and L. Roskr {Ber., 12, 1822— 1827).— The following
ferro- and ferri-cyanides are precipitated on the addition of potassium
ferro- and ferri-cyanides to a concentrated solution of the corresponding
sulphates.
Nitrosodimethylanilineferi-ocyanide, (NMe2.C6H4NO)2H4FeCy6 + H2O,
reddisb-brown needles, blue ' by reflected light ; ferricycuiiJe
(NMe2.CGH4NO)2HeFeCy,.2 -f 6H2O, silky yellow needles. Nitroso-
dimethijlmetatohtklme ferroajanide, Tiolet:-brown needles, containing
5 mols. H2O ; the ferricyanide, yellow needles, containing 4 mols. HjO.
Bromodhnethylamline ferrocyanide, silver-white plates, contain-
ing 2 mols. H2O ; the ferricyanide, yellow crystals, containing SHgO.
Bromodintethylmetatoluidine ferrocyiiiiide, white crystals with 4II2O ;
the ferricycmide, yellow crystals with 9II2O.
Dimethylurthotohiidine ferrocyanide, white anhydrous needles ; ferri-
cyanide, yellow unstable crystals, containing 9 mols. HoO.
Dimet]iylnieta.toluidine ferrocyanide, white needles, containing 2HoO ;
ferricyanide, yellow needles with 3H2O.
Diniefhylparatoluidine ferrocyanide, white powdei', containing 1 mol.
H2O ; ferricyanide, yellow needles with SHjO.
ORGANIC CHEMISTRY. 99
TeframefJn/lrnetajfTienylenediamineferror.yanide, pearly scales, contain-
ing I raol. HoO.
Tetramethijlparaphenylenediamine ferrocyamde, anhydrous white
scales.
The ferricyanides are, as a rale, more soluble thau theferrocyanides.
Nitrosodimethylaniline is deposited from an ethereal solution in
emei*ald-green tri clinic crystals, and from a solution in benzene in
dark-green triclinic prisms, containing a molecule of benzene of crys-
tallisation, which is lust on exposure to tlie air, the crystal losing its
transparency. W. 0. W.
Allyl Cyanide and the Products of its Saponification. By
A. PixxER (/'e/-., 12, liijoo — 2u5'-^;. — When a mixture of equal volumes
of allyl chloride, alcohol, and water is treated with potassium cyanide
for several weeks at the ordinary temperature, potassium chloride
separates out, and on distilling the supernatant liquid, trial! ylamine
(C3H5)3X (b. p. 150°) passes over. The residue in the retort forms
two lavers ; the lighter liquid on fractionation yields propylene cyanide
(b. p." 252-254°) and ethoxybutyronitril CH3.CH(0Et).CH,.CX
(b. p. 178"), described by Rinne (Ber., 6, 389). Pyrotai^taric acid is
obtained by adding hydrochloric acid to the heavier liquid and
extracting with ether.
Potassium cyanide acts very slowly on allyl chloride at the ordinary
temperature when alcohol is not present. The sole products of the
reaction are allyl cyanide and a small quantity of pyrotartaric acid.
Allyl cyanide dis.solves freely in fuming hydrochloric acid ; if the
solution is left at rest for 12 hours and then neutralised with sodium
carbonate, an oily liquid and crystals of crotonamide (m. p. 159°) are
formed. When the hydrochloric acid solution of allyl cyanide is ex-
posed to a temperature of 50 — 60° for two hours, ammonium chloride
is deposited, and /3-monochlorobutyric acid, CHMeCl.CHo.COOH, is
produced. This acid is very unstable; it boils with evolution of
hydrochloric acid at 200°.
The formation of crotonic acid from allyl cyanide may be repre-
sented by the following equations : —
CH, : CH.CHo.CN + 2HoO + HCl = CHj.CHCl.CHo.COOH + NH3 ;
CHMeCLCHo.COOH = CHMe : CH.COOH + HCl.
An attempt to isolate /3-oxybutyric acid by saponifying allyl cyanide
with aqueous potash was unsuccessful ; crotonic acid was obtained.
On saponification with cold hydrochloric acid, ethoxybutyroni,.."!,
CHMe.Cn(EtO).CH2.C:N', yields the amide of ethoxyhutyric udd
(m. p. 71°), and on treatment with warm hydrochloric acid it splits
ixp into ammonium chloride and ethoxyhutyric acid (b. p. 213 — 220°).
By the action of alcoholic potash on the nitril, a mixture of ethoxy-
and hydroxy-butyric acids appears to be formed. W. C. W.
Action of Bromine on Dichlorhydrin. By E. Grimaux and
P. Adam {Bull. Sue. Clam. [2], 32, lb— 19).— This paper is devoted
to an account of a repetition of Carius' experiments, in which his
h 2
100 ABSTRACTS OF CHEMICAL PAPERS.
results are confii'mcd. By the action of bromine on dichlorliydrin in
molecular proportions, a ketone of the formula CBr3Cl.CO.CH2Cl is
formed, wliicli on exposure to moist air forms a hydrate containing
4HoO. W. R.
Mannitol as Bye-product in the formation of Lactic Acid
from Cane-sugar. By Draoendorff (Arch. Pharm. [ 3], 15, 47 — 49).
— 3 kilograms of cane-sugar which had been heated for three hours
with 15 grams tartaric acid and 13 litres of water, when allowed to
stand for 10 days after being mixed with 1|- kilograms levigated
chalk, 120 grains cheese, and 3, GOO grams milk, yielded besides lacth",
acid, 150 grams perfectly pure mannitol, identical with that obtained
from manna. Attempts were made on other occasions to obtain a
like yield under similar conditions, but they were unsuccessful.
E. W. P.
Sugar from the Date-palm. By P. H. DifioN (Bull. Soc. Chim.
[2], 32, 125 — 126). — This sugar has the following composition: —
Saccharose 87'97
Glucose 1"5.3
Levulose 0"18
Gum 4-88
Water and volatile matter 1"88
Ash 0-50
Mannitol, fatty matter, and loss . . 3'06
100-00
The sample analysed was undergoing mannitic fermentation, a.nd
contained a filiform and a globular ferment, both much smaller than
that of beer. The rotatory power of the gum was found to be
[a]D = 193'32°. A greenish fat was separable from the sugar by treat-
ment with ether. W. R.
Neutral and Inverted Sugar. By H. P. D£on (Bull. Soc Glvim..
[2], 32, 121 — 125). — The nature of sugar which does not afPect polar-
ised light has not been as yet satisfactorily explained ; the author has
made it the object of some experiments. When diffused through parch-
ment paper it acquires a Ijevorotatory power, sensibly equal to that of
ordinary inverted sugar, retaining the same reducing action on cupric
salts. Now pure sugar, when boiled with alcohol and hydrochloric
acid in presence of water just sufficient to hydrate it, becomes inverted,
and the solution has no action on polai'ised light. When this solution
is evaporated in a vacuum, the resulting colourless solid is neutral to
light when dissolved in water ; but when it is evaporated slowly in
contact with moist air, a semicrystalline mass consisting of a mixture
of glucose and levulose remains, which acts on polarised light like
inverted sugar. When ordinai-y inverted sugar is dissolved in strong
alcohol and precipitated with ether, the precipitate, although it re-
duces Fehling's solution when dissolved in water, has no action on
polarised light, but may be converted into the active modification by
slow evaporation. The author explains these facts as follows : — Soon
ORGANIC CHEM4STRY. 101
after glucose has been dissolved in water, it lias the rotatory power
[ajo = + 53"2o^, Avhich slowly decreases after lapse of time. Its
alcoholic solution has also [ajp = 4- 5323°, but this does not decrease,
whilst the rotatory power of levulose is [a]d = — y437°. When cane-
sugar is inverted by boiliug with water, a process which demands a
lengthened time, its la^vorotatory power is zero at first, but gradually
increases to — 21"52°. Saccharose is therefore inverted to neutral su(jar,
which if dissolved in alcohol remains neutral, but if brought in con-
tact with water slowly becomes hydrated, and acquires the power of
influencing polarised light. In this manner, the author accounts for
the neutral sugar noticed by Mitscherlich, as existing in crude sugar
and molasses, and which reduces Fehliug's solution without affecting-
polarised light. W. R.
Triacetonamine Chromates. By W. Heixtz (Annalen, 198,
87 — 9U). — When triacetonamine sulphate and potassium dichromate
are dissolved in hot water, crystals of dichromate of triacetonamine
separate out on cooling, but it may be moi^e readily obtained by mixing
4 parts of chromic acid with 7 parts of crystallised ti'iaeetonamine.
The crystals are extremely brittle, of a tabular form, and not well
formed at the ends. When heated they decompose into triacetonamine,
and a brownisli-red alkaline liquid, which, when treated with platinum
chloride, yields acicular crystals of the triacetonamine platinochloride.
Triacetonamine dichromate is soluble in alcohol, but not in ether.
It gives off traces of water at lOC^, but is decomposed at a higher
temperature, leaving pure chromic oxide. Analysis shows that it
consists of (C9H,s,NO)2Cro07.
The normal chroniate is obtained by mixing solutions of 1 part of
chromic acid with 4 parts of crystalli.sed triacetonamine. It crystal-
lises in small yellow prisms readily soluble in water. From a hot
solution of this salt orange-red crystals of the dichromate are deposited.
The normal chromate exhibits the same deportment as the acid salt
when heated, but it dissolves more readily in water. Its formula is
(C9H,8NO)2Cr04. G. T. A.
Products of Oxidation of Di- and Tri-acetonamine, particu-
larly Amidodimethylacetic, Amidodimetliylpropionic, and
Imidodimethylaceto-dimethylpropionic Acids. By W. Heintz
{Ann<dt'ii, 198, 42 — 87). — By uxidation with potassium dichromate
and sulphuric acid, diacetonamine yields an amidovaleric acid (amido-
dimethylacetic acid), and an amidobutyric acid (amidodimethylpro-
]iionic acid), the amount of the former being relatively greater. Formic
and acetic acids are also formed.
When the aqueous solution of the amidovaleric acid is heated with
silver oxide, ad-cer amidodimethijlpro-piouate is formed, but if silver
nitrate is first added to the concentrated aqueous solution of the acid,
and then a few drops of ammonia, a crystalline body is obtained which
consists of a compound of 2 mols. of silver amidodimethylpropionate
with 1 mol. of silver nitrate and 1 mol. of water, which is expelled at
100°. A compound acid can also be obtained by- the action of alcohol
and hydrochloric acid on amidodimethylpropionic acid, which crystal-
102 ABSTRACTS OF CHEMICAL PAPERS.
lises in silky needles, and consists of C5H12NO2CI. A similar body is
formed with nitric acid. Platinum tetrachloride combines with the
compound of hydrochloric and amidodiinethylpropionic acids to form
a platinochloride, (C5Hii]S'Oo.HCl)o.PtCl4, which crystallises in the
triclinic system.
Schneider's amidobutyric acid, obtained from monobutyric acid
(Porj'j. Ann., 114, 627), is quite iiifferent from the amidodimethyl-
acetic acid described above, although the two are isomeric. It is
possibly amido-ethylacetic acid.
The amidovaleric acid obtained by Gorup-Besanez from the pancreas,
and that prepared by Clark and Fittig from monobromovaleric acid,
are also quite different from the author's a midodime thy Ipropionic acid.
The points of difference between these compounds are given in
tabular form in the paper.
The chief product obtained on oxidation of triacetonamine is imido-
dimethylaceto-dimethylpropionic acid, a small quantity of amidodi-
methy Ipropionic acid being formed at the same time.
Iinidodiinethylaceto-dimetliylpropiotnc acid,
COOH,C(CH3)..NH.C(CH3)2.CH,.COOH,
forms small colourless crystals which have an acid reaction and a sour
taste, and are sohible in hot water, but nearly insoluble in alcohol.
The aqueous solution gives no precipitate with lead acetate, mercurous
nitrate, picric acid, mercuric chloride, or platinum tetrachloride. The
acid volatilises without melting, leaving a small amount of carbona-
ceous residue. It is anliydrous and dibasic, and forms compounds
with acids. A copper, silver, ammonium, barium, and two zinc salts
have been prepared. It also forms a double salt with silver nitrate,
CaH.fiAgNOi + AgNOs + H.O.
Compounds of the acid with hydrochloric acid, nitric acid, and sul-
phuric acid have also been prepared, but a platinum double salt does
not seem to exist.
From the foregoing experiments the author concludes that the struc-
ture of triacetonamine is expressed by the formula —
(CH3).C<^-^g-^>C(CH:02. (. T A.
Action of Potassium Cyanide on Ammoniacal Derivatives
of Chloral. By R. Schiff and S. Speciale (Gaszetia, 9, 336—344).
— When an alcoholic solution of chloralammonia and potassium
cyanide is digested for a short time on the water-bath, a violent reac-
tion sets in, and the liquid enters into ebullition, evolving torrents of
hydrogen cyanide. On evaporation it leaves a crystalline mass of
dichloracetamide, CCloH.CONH,, the yield being so abundant that it
is certainly the most convenient method for preparing this substance.
The authors consider the reaction to take place in three stages : —
CCl3.CH(0H).NHo = CCl2:C(0H)NHo + HCl,
CC1,:C(0H)NH. + H.OH = CCUH.C(OH)oNH2,
CCLH : C(0H)oNH2 = CCI3H.CONH2 + H,6.
It was thought possible that if compounds of chloral with the sub-
ORGANIC CHEMISTRY. 103
stituted ammonias were treated in the same manner, substances mig-lit
be obtained which woukl throw some light on the coustitutiou of
acetylchloralammonia, wliich SchifB considex-s to be
CC!3.CH(0H)NHAc;
whilst Pinner contenjls that its formula should be represented by the
formula CCls.CH(0Ac)XH2. The results obtained, however, are com-
])licated, although it seems probable that compounds analogous to
dichloracetamide are first found.
Chloral combines directly with dichloracetamide, and the product,
when recry stall ised from boiling water, forms large lustrous prisms
(tn. p. 105^) exceedingly soluble in alcohol or ether. If this sub-
stance, CCI3.CH(0H).XH.C0.CC1,H, is treated with potassium cyanide
in alcoholic solution as above described, it yields nothing but dichlor-
acetamide and potassium dichlaracetate.
With chloracetamide, however, prepared directly from chloral and
acetamidcj potassium cyanide gives potassium chloride and acetate,
and a substance which may be extracted by treating the crude product
with ether. This forms colourless crystals (ra. p. 120°) which are mode-
i-ately soluble in etber^ alcohol, and hot water, but only very sparingly
in cold water. The results of the analysis agree with the formula.
C)4Hi,hC1^N405, The authors consider it possible that the x^ompound
may be formed as follows :—2CCloH.C0NHAc + 2CCLH.CONH2 +
C.HeO = 2H2O -f 2CCl,H.C(NHAc) ! N.CO.CCloH + aH^O =
CuHisNjClsOs, but uotvrithstanding this substance gives Lieben's
iodoform reaction, indicating the presence of alcoliol, the formula
given cannot be regarded as definitely established.
Chloralbenzamide, CCl3.CH(0H).XHBz, when treated with potas-
sium cyanide in a similar manner, gives rise to a white crystalline sub-
stance (m. p. 131°), very soluble in dilute alcohol. The analyses lead
to the formula CMHuChXiO, but further investigation is necessary to
decide the constitution of this compound. C. E. G.
Action of Potassium Carbonate on Isobutaldehyde. By F.
Ukech (Ber., 12, 1711—1747). — The thick liquid which the author
obtained by treating isobutaldehyde with potassium carbonate (Ber.,
12, 193, this Journal, 1879, Abst., 520) is a polymeride of isobutalde-
hyde, and has the sp. gr. 0'969 at 24°, whilst the sp. gr. of ordinary
isobutaldehyde is 0'795 at 20°. On distillation it yields isobutalde-
hyde and condensation-products which appear to form an acid,
C«Hu02, on oxidation. W. C. W.
Action of certain Reagents on Parisobutaldehyde. By F.
Ueech {Ber., 12, 1717 — 1719). — Parisobutaldehyde is deposited in
crystalline needles, when a mixture of crude isobutaldehyde (contain-
ing isobutyl alcohol and acetone) with Youth its volume of sulphuric
acid, is left at rest for several days. A further yield may be obtained
Vjy heating the mother-liquor on a water-bath to expel acetone and
unaltered isobutaklehyde, and distilling the residue in a current of
steam, when the parisobutaldehyde will crystallise out of the distillate.
This compound is also formed when isobutaldehyde is distilled with
104 ABSTRACTS OF CHEMICAL PAPERS.
small qaantities of calcium cliloride. PaT-isobutaldelijde is not attacked
by a solution of soda ; chromic acid mixture scarcely acts on the body
at 100°, but at 130" isobutyric acid is formed. By the action of potas-
sium permanganate at 130°, parisobutaldehyde is converted into
acetonic acid, and a second acid less soluble in water, which forms
crystals melting at 125°. W. C. W.
Polymerides of Isobutaldehyde. By F. XJeech (i?er., 12, 1749
— 1751). — Parisobutaldehyde resembles paracetaldehyde in its proper-
ties, and the viscous polymeric modification resembles aldol in many
respects, but differs from it in so far that on distillation it not only
splits up into water and higher molecular compounds, but at the same
time yields isobutaldehyde. The author considers it probable that this
substance is a mixture of two polymerides.
CHMe,.CH(0;H).CMe3.C0H CHMe2.CH|(0H).HiCH.CHMe.C0H
I. II.
W. C. W.
Preparation of Ethereal Acetates. By A. P. N. Franchimont
(Ber., 12, 2059). — The acetic derivatives of the carbohydrates and of
mannitol are easily prepared by heating the alcohols with four times
their weight of acetic anhydride and a small piece of fused zinc
chloride. W.. C. Yf.
Some Neutral Amnionium Salts : Citrate, Phosphate, and
Photosantonate. By F. Sestini {Gazzdta, 9, 298— 304).— These
salts were prepared by dissolving the acids in a large excess of con-
centrated aqueous ammonia, and exposing the solutions over quick-lime
under a large bell- jar rendered air-tight by means of mercury. In
this way the solution is concentrated in an atmosphere of ammonia,
and deposits the neutral salt in crystals which were collected and
analysed.
Triammonimn Citrate. — The crystals are deliquescent, and have an
ammoniacal odour, decomposing on exposure to the air. When heated,
they rapidly lose water and ammonia, and leave triammonium citrate.
Their composition is represented by the formula €611507(^114)4. H,,0.
Triammonium Phosphate, P04(iSrH4)3.5H20. — The crystals were not
sharp enough for goniometric observation. They evolve ammonia on
exposure to the air.
Diammonium Photosantonate, Ci5His04(NIl4)2. 711^0, is deposited in
crystalline crusts on evaporating a solution of the acid in excess of
ammonia as above described. Like the salts previously mentioned, it
has an odour of ammonia. C. E. G.
Urea Platino-chloride. By ^Y. Heintz {Annalen, 198, 91—94).
When concentrated solutions of urea and platinum tetrachloride are
juixed in such proportions that one atom of j^latinum is present for
each two molecules of uvea, and the solution is concentrated in a vacuum
over sulphuric acid, a crystalline crust is formed on the surface of the
liquid. If this crust is constantly disturbed so as to expose fresh sur-
ORG.VNIG CHEMISTRY. • 105
faces of the liquid, the crystals settle down to the bottom of the vessel.
Tboy are of a yellow coloui', and often have the appearance of rectau-
-ular plates, although they are really rhombic prisms.
They are extremely deliquescent, and effloresce in dry air. They
are soluble in alcohol but not in ether. They contain two molecules
of water, and have the formula, (CH.N.O.HCl), + PtCl. + ^H^O.
When heated, they do not. change colour, but evolve much water
and carbonic anhydride, whilst ammonium platinochloride is formed,
probably together with cyanic and cyanuric acids, and possibly a
platinum compound of guanidine. G. T. A.
New Derivative of the Parabanic Series. By E. Grimaux (BnU.
Soc. Chim. [2], 32, 120 — 122). — When an intimate mixture of urea
and oxalylurea (parabanic acid) is heated at 125 — 130'^, the following-
reaction takes place ; the amide of oxalyl-biuretic acid being
formed —
CO.NH. .XH.CO.NH3
I >C0 + C0(NH..)2 = C0<
CO.XH^ XH.CO.CG.NH,.
The new body is very sparingly soluble in water, and is destroyed
by prolonged ebullition. It dissolves in strong sulphuric acid, and is
precipitated by water as a jelly.
It gives a violet-pink colour with copper sulphate. When boiled
with ammonia, it yields oxalate and urea, along with a trace of
biuret. W. R.
Crystalline Form of some Aromatic Compounds. By R.
PA^ElilA'SCo{<Jac;ttta,Q, '.jo-i: — 3G-1). — Tribroiitobeii^tnt[liv : Br: XO^iBr
= 1:3:4: 6]. — Monoclinic svstem, a : b : c = 06518-i5 : 1 : 0'369545 ;
,/ = + X : + Z = 99-46=. FoVms observed, (010), (001), (110), (Oil),
(101), (121). -Cleavage parallel to (101), perfect. Twin planes
jjarallel to (lUl). The ano-le of the optical axes for ordinary light in
oil is about 60°; {p<^v) tor the i-ed. The crystals are sensibly di-
chroic.
Tribromodinitrohenzene (m. p. 135'5°). — The crystals are sulphur
vellow, and belong to the triclinic s^-stem, a : b_: c =^ 0'4.5560 :1:0'45717.
Forms observed, (010), (001), (Il0;,(il0), (111), (III), (041). Cleav-
age parallel to (OOl) perfect. The angle of the optical axes in oil is
about 74:^. Dichroism is very distinct on the face (010), the tints being-
deep lemon-yellow, and almost colourless. The dichroism on (110)
and (llO) is sensibly the same._
Bromacetaniiide, CeHiBr.NHAc. — Colourless crystals belonging to
the monoclinic system, a: b :c = 1"53838 : 1 : 1 •43539 -7 = +X : +Z =
117-12°._ Observed forms, (100), (OlO), (001), (110), (210), (101),
(i02), (101), (012). Cleavage parallel to (101) perfect, but inter-
rupted parallel to (100). There is a plane of maximum extinction,
making an angle of about 52^ with the plane of symmetry (ordinary
lightj.
Xitrotoliddine [CH,: NO2 : NH> =1:2: 4]. — Monoclinic sj'stem
a:b:c = 1-35781 : 1 : 1-75472 ; ,/ = + X : + Z = 125" 10'. Observed
106 ABSTRACTS OF CHEMICAL PAPERS.
forms, (110), (001), (Oil), (112), ("772). Cleavage perfect parallel
to (001) ; laminjB flexible. Twin plane observed parallel to (001).
The plane of the optical axes is parallel to the plane of symmetry, and
the angle of the axes in oil is about 11'^ for red light. Dichroism is
only sensible in thin laminae or in very small crystals.
Nitroiodohe7izey}e. — The crystals are colourless and belong to the
monoclinio system, a : /) : c~2"2961 : 1 : 1-1297; i/= +X : +Z='l04° 28'.
Observed combination, (100), (uOl), (110), (101). Cleavage per-
fect parallel to (100). Twin plane observed parallel to (100).
Potassium nltrophenolsulphnte [OH : KSO, : KO, =1:2: 4].— The
crystals examined were beautifully perfect, and of a straw-yellow colour.
The7 belong to the monoclinic system, a -.h : c= 1-70451 : 1 : 1-52466 ;
y=+X: + Z = 117° 58' 45". Combinations observed, (100), (110),
(101), (101), (111). The cleavage parallel to (101) is perfect. The
plane of the optical axes makes an angle of about 4" with the axis c
with ordinary light. Eotatory dispersion {f><Cv). 2Ha = 66'' 10'
for red light. The dichroism is distinct, normal to the faces of the
vertical prism and of the pinacoid lUO: the tints are bright yellow and
almost colourless.
MdlnjhmiheUic acid, CcH3(0H)(0Me).CH.,.CHo.C00H.— The crys-
tals belong to the monoclinic system, a:h:e =^ 1-7131:1:3-5017;
7,= +X:+Z = 93° 58'. Forms observed, (100), (OOl), (010), (HO),
(115), (115), (015). There is a perfect cleavage parallel to (507).
The plane of the optical axes is normal to the plane of symmetry. In
a lamina obtained by cleavage, the angle of the optical axes in air was
106° 20' for red, and 107° for violet light (^<v).
An account of the two 1 : 4 acetoluides has already been published
in this Journal (Abst., 1879,626). C. E. G.
Action of Nitric Acid on Tribromobenzene. By C. Wurstkb
and A. Bf.ran {]Jer., 12, 1821 — 1822). — When tribromobenzene is
treated with nitric acid (sp. gr. 1-534) at 100°, monondtrotribromo-
benzene (m. p. 142-5°) is formed, and on nitrating this substance with
a mixture of nitric and sulpluiric acids, dinitrotribromobenzene is ob-
tained in glistening needles (m. p. 192°). Attempts to prepare tri-
nitrotribromobenzene by this method were unsuccessful.
These results are in dii^ect contradiction to those of Kovjier (Gazzettn,
1874, 422), w^ho states that when nitric acid acts on tribromobenzene
no mononitro-derivative is produced, but that a mixture of di- and
tri-nitrotribromobenzenes is obtained. W. C. W.
Cymene from Cumic Alcohol. By E. Paterno and P. Spica
(Gazzetta, 9, 397 — 400). — The synthesis of paramethylcumene or isocy-
mene recently effected by Jacobsen (Ber., 12, 429), and the marked
difference in properties between it and the known cymene, has con-
firmed the authors in their opinion that the cumic compounds contain
isopropyl, whilst cymene contains normal propyl, and has also removed
all doubt as to the identity of the cymene obtained from camphor, from
essence of cumin, and from cymyl alcohol by the action of zinc chloride,
although in the last-named reaction there must have been a transfor-
mation of the isopropyl group into normal propyl. In ox^der further
ORGANIC CHEMISTRY. 107
to elncidate this question, the authors endeavoured to convert cumic
alcoliol into the paraisopropylmeth^-lbenzene or isocymene of Jacobsen
by a ditferent method of treatment. For this purpose, pure cumic
alcohol was transformed into cuntyl chhride, C6H4(C3H7).ClioCl, by
saturating it with dry hydrochloric acid gas, separating the oily layer
from the aqueous solution of hydrochloric acid, drying it, and rectify-
ing. The pure chloride was thus obtained as a colourless liquid
(1). p. 230°), which yitdded cumic acid and a little terephthalic acid
on oxidation, showing that the isopropyl group had not undergone
molecular change.
In order to convert the chloride, C6H4(C3H7).CH-jCl, into isocymene,
C6H4(C3H7).CH3, it was dissolved in alcohol and treated Avith hydro-
chloric acid and zinc. The product submitted to fractional distillation
yielded a hydrocarbon boiling at 175 — l/S*^, which when converted
into the sulphonic acid gave a barium salt having all the properties of
that prepared from ordinary cymene. The sulphonamide also, pre-
pared from the cymt-nesulphonic chloride, melted at 114 — 115^, the
melting point of cymenesulphonamide, whilst the corresponding deri-
vative of isocymene melts at 97 — 98°. It is evident, therefore, that
in the reduction of the chloride, not only is the chlorine in the CHoCl
group displaced by chlorine, but at the same time the isopropyl
group CH^CHa^o is converted into normal propyl, CH0.CH0.CH3.
C. E. G.
Diamylbenzene. By A. Austin (Bull, Soc. Chim. [2], 32, 12—13).
This hydrocarbon was prepared by heating 750 c.c. of benzene with
oO grams of anhydrous alumininui chloride for some days at 85°,
gradually adding 2o0 c.c. of optically active amyl alcohol.
The product of this reaction, consisting chiefly of amylbenzene, was
mixed with a tenth of its weight of aluminium chloride, and boiled
with an equal volume of amyl chloride. The product boiled between
260"" and 270°, and on anah'sis gave numbers corresponding with the
formula CeHifCoHn)^- It is a colourless aromatic liquid, with a taste
resembling that of turpentine. It is very mobile. It does not .solidify
at — 20°. Its sp. gr. at 0° is 0"8868. Its vapour-density was found
equal to 8'09 : theory, 755. It probably belongs to the meta series.
W. R.
Bromodimethylaniline. By C. Wuester and A. Scheibe {Ber.,
12. I'SU; — l>^ll'). — According to the authors, the monobromodimethyl-
aniline (m. p. 55^) which Weber (Ber., 10, 764) obtained by the action
of bromine on a solution of dimethylaniline in acetic acid, is not a
meta but a para compound, since on treatment with sodium nitrite it
does not yield a nitroso-derivative, but paranitrodimethylaniliue (m. p.
161") and monobromomonomethylaniline nitrosamine. The latter
suKstance crystallises in white needles (m. p. 74°), and is reduced by
tin and hydrochloric acid to monobromomethylaniline. This base boils
at 260°, and decomposes at a higher temperature, forming a substance
which dissolves in alcohol, with intense red coloration, and which
appears to be dimethylrosaniline.
Metabromodimethi/laniline. — By the action of methyl iodide and
soda on metabromaniline, the compound of this base with methyl
108 ABSTRACTS OF CHEMICAL PAPERS.
iodide is obtained in crystalline scales (m. p. 201). On distillation in a
vacuum, it splits up into methyl iodide and metabromodimethylaniline
(m. p. 11^, b. p. 250^). This compound appears to yield a nitroso-
derivative (m. p. 148°J, and is totally different from Weber's mono-
bromodimethylaniline. W. C. \Y.
Parabromodimethylaniline. By C. Wurstee and A. Beran
(Ber., 12, 1820). — By the action of methyl iodide and a solution of
soda on pure parabromaniline, a compound of methyl iodide and para-
bromodimethylaniline is obtained in white crystals, which melt with
decomposition at 185°. By treating this substance with oxide of
silver, parabromodimethylaniline (m. p. 55") is formed. It is iden-
tical in every respect with Weber's (Ber., 10; 763) so-called metabro-
modimethylaniline. . W. C. W.
Action of Sulphonic Chlorides on Amines. By W. Michler
and K. Meter (Ber., 12, 1701 — 1703;. — A mixture of ietra-
metJDjUiamdclndiphenylmethane and cliplnniyldimebliijlamidosulplio^ie.,
PhSO..C(iH4NMe2, is formed by the action of dimetliylaniline on ben-
zenesulphonic chloride. Hassencamp (Ber., 12, 1275) observed the
formation of methyl violet in this reaction, but the chief products,
A'iz., the base and sulphoue, appear to have escaped his notice. To
obtain the sulphone, the tetramethyldiamidodi[)lienylmethaiie, with
which it is mixed, is removed by treatment with hydrochloric acid.
On recrystallising the residue from alcohol, it is deposited in white
needles (m. p. 82""), which are soluble in alcohol, benzene, and ether.
The sulphone is decomposed by strong nitric acid, forming three nitro-
benzenesul phonic acids and pentanitro-dimethylauiline (m.. p. 127°).
^y the acticm of paratoluenesulphonic chloride on dimethylaniline,
tolyldimelhylamidophenylsulphoue, C7H7.SO.;C6HiNMe2, a blue colour-
ing matter and a base ai-e formed. The sulphone melts at 05°, is
soluble in alcohol and ether, and yields a trinitro- derivative on nitra-
ti.m. W. C. W.
Action of Sulphonic Chlorides on Amines. By W. Michler
and ¥. Salathe (jb'er., 12, 1780 — 1001). — By the action of a-naphtha-
lenesulphonic chloride (1 mol.) on dimethylaniline (2 mols.), a blue
mass is obtained, which, after saturation with ammonia and distilla-
tion in a current of steam, to remove free dimethylaniline, leaves a
mixture of fetrametJi.yldknKidodipJifmi/lvietJtane and cc-^iaphtJujldiiaethyl-
aiiilddphenylsaljihuue, CioH7.SO,;.C,;H4NMe>. By treating the mixture
with dilute hydrochloric acid, the former compound is dissolved ; it
may be obtained in white plates by precipitation with ammonia and
lecrystallisation from alcohol. The residue insoluble in hydrochloric
acid dissolves in alcohol, and on slow evaporation yields crystals of the
sulphone (m. p. 01°), soluble in alcohol and ether, bub insoluble in
water. This compound is decomposed by fuming hydrochloric acid at
180°, forming aniline, naphthalene, methyl chloride, and sulphuric
acid. By the action of strong nitric acid, it is converted into penta-
nitrodimethylaniline, CfifNO.JsNMea (m. p. 127°), and /3-uitronaph-
thalencsulphonic acid. /S-naphthalenesuljDhonic chloride and dimethyl-
ORGANIC CHEMISTUT. 109
aniline yield totramctliykliamidocliplienylmetbane, and fS-naphtliyl-
dimethyldiamidophenylsulpboue. "Jlio latter compound is decomposed
by strons: nitric acid into psntauitrodimethylaniline, and /3-uitronapli-
thalenesulphonic acid. W. C. W.
Dimetliylmetatoluidine Derivatives, By C. Wurster and C.
RiEDSL {JJer., 12, irut) — 1802). — Nitrosodimeth[/lmet(doluiditi,e Injdro-
i-Jdoride is deposited on adding a saturated solution of sodium.
nitrite to a solution of dimethylmetatolaidine iu dilute hydrochloric
acid. It is sparingly soluble in cold, but dissolves in hot water in
presence of hydrochloric acid, and crystallises on cooling in yellow
needles.
The free base obtained by decomposing the hydrochloride v/ith
sodium carbonate crystallises from ether in green plates or needles
(m. p. 92°), soluble in benzene, chloroform, and water. It resembles
nitrosodimethylaniline in its reactions.
Nit wane resol is formed, together with dimethylamine when nitro-
sodimethylmetatolaidine is boiled with soda, and is precipitated on
acidifying the alkaline liquid with sulphuric acid. Nitrosoci^esol crys-
tallis.s in white needles (m. p. 14-5 — 150"), soluble in alcohol, benzene,
chloroform, and glacial acetic acid, and sparingly soluble in boilino-
water and in ether. The acetyl-derivative forms prismatic crystals
(m. p. 92°), soluble in alcohol.
Trinitrocresol is produced by the action of nitric acid on an acetic
acid solution of nitrosocrcsoL
Nitrodimethyhnetatoluidnie is formed when potassium permano-anate
is added to an aqueous solution of nitrosodimethylmetatoluidine hydro-
chloride, and may be extracted from the liquid with ether. It crys-
tallises in long yellow needles (m. p. 84°). The corresponding dinitro-
derivative is obtained in yellow needle-shaped crystals (m. p. 107°),
by adding nitric acid to a solution of " dimetliylmetatoluidine in glacial
acetic acid. If the nitration is carried on with dilute niti'ic acid, or
if the ipixture of sulphuric and nitric acids is kept pei'f ectly cold, three
nitro-derivatives are obtained, viz., the mono-nitro (m. p. 84''), and
two dinitros melting at 107° and 168° respectively. The latter is less
soluble in alcohol than the dinitro-compound, melting at 107"'.
B romodimefhylmetatoluidine melts at 98^ and boils at 276*^. It is
soluble in benzene, aniline, alcohol, and peti'oleum spirit. On treat-
ment with sodium nitrite, the hydrochloric acid solution yields the nitro-
samine in the form of an oily liquid.
Dimet]ii/]t()]i/leiipdiami)ie, obtained liy the reduction of nitrosodimethyl-
metatoluidine with tin and hydrochloric acid, crystallises in white
prisms (m. p 28""), soluble in water, alcohol, ether, and chloroform.
The acetyl-derivative melts at 155°.
Tetramethyltolylenediamine, pi'epared by the action of hydrochloric
acid and methyl alcohol on the preceding base at 180°, is an oilv
liquid (b. p. 260°). It combines with methyl iodide to form the
compound C6H3Me(N'Me2)2.(MeI), which crystallises in needles
(m. p. 160°). On distillation, it splits up into methyl iodide and the
free base.
Ferric chloride produces an intense blue coloration in an aqueous
110 iVBSTRACTS OF CHEMICAL PAPERS.
solution of tetrametliyltolylenediamine. Sodium nitrite gives a similar
reaction with an acetic acid solution of tlie base.
To estimate the metatoluidine in crude toluidine, the liquid toluidine
is first freed from paratoluidine by Bindscliedler's process (Ber., 6,
448), converted into hydrochloride, and the orthotoluidine hydro-
chloride removed by filtration ; the filtrate is then evaporated to
dryness, converted into dimethyltoluidine, and precipitated as nitroso-
dimethylmetatoluidine hydrochloride. W. C. W.
A Colouring Matter containing Sulphur from Parapheny-
lenediamine. By A. Koch (Ber., 12, 2069—2071). — By treating an
acid solution of paraphenylenediamine hydrochloride successively with
sulphuretted hydrogen and ferric chloride, a beetle-green crystalline
mass is obtained, which has the composition C24H2nN6S2.2HCl + 4H2O.
This compound is soluble in water and alcohol, forming a violet colo-
ration, which is destroyed by reducing agents and restored by exposure
to the air.
The free base, CajHinNf.So, is deposited in dark-brown scales, on the
addition of ammonia to the hydrochloride. The base is less soluble
than the hydrochloride. The snlpltate, 0041120X682.112804 + HoO, and
the oxalate, C24H2nN6S2.H2C204 + 4H2O, form dark-green needles. The
nitrate, C2iB.2o^S2-''2.}i.'^0:i + 4H2O, crystallises in brown needles. The
hydrochloride forms double salts with the chlorides of zinc and mer-
curv, viz., a4Ho,N6S.,.2HCl.ZnCl., -f H2O and C.,4H2oN6S2.2HClHgClo.
w. c. w.
Dimethylparaphenylenedi amine Derivatives. By C. Wcrster
and R. Senutner (Ber., 12, 1(S03 — 1807). — Action of Bromine. — When
a 10 per cent, solution of bromine in glacial acetic acid is added to a
somewhat more dilute solution of dimethylparaphenylenediamine in
the same solvent, a green substance is precipitated, which has the com-
position CsHuISrjBr. The precipitate must be thoroughly washed with
glacial acetic acid and with anhydrous ether, and it may be rapidly
recrystallised from hot alcohol. From this solvent it is deposited in
green scales (m. p. 146'^), having a metallic lustre. The aqueous and
alcoholic solutions of this substance exhibit an intense red colour,
which is destroyed by exposure to the air or by the addition of sul-
phurous acid.
Action of Nitrons Acid on Dimethylparaphenylenediamine Eth-
oxamate. — On the addition of sodium nitrite to a solution of dimethyl-
paraphenylenediamine ethoxamate in dilute hydrochloric acid, a
yellowish-red nitro-product, NMe2.C6H,(N02).NH'CO.COOEt, collects
on the surface. By recrystallisation from acetic acid, it is obtained in
red needles (m. p. 152°), freely soluble in benzene, but less soluble in
ether and boiling water. On reduction with tin and hydrochloric acid, it
yields oxalic acid and dimethyltriariiidohenzene [NMe2 : NH3 : NHj =
1:3: 4].
This base crystallises in colourless prisms (m. p. 42 — 44°, b. p. 298°),
soluble in water and petroleum ether. It forms a monoacetyl-deriva-
tive, which is deposited from an aqueous solution in transparent prisms
or plates, containing 1 mol. H3O, which begin to melt at 82°. The
anhydrous crystals melt at 153'^.
ORGANIC CHEMISTRY. Ill
Dimethvltrianiidobcnzcne is also formed by the rednction ofMertca's
dmitrometUylauiliue (m. p. 87 ), (Jier., 10, 763 and 995).
w. c. w,
Tetramethylmetaphenylenediamine. By C. Wurstek and H. F.
MuiiLEV (ij</-., 12, 1814 — iSlij. — On the udditiou of soda to tlie pro-
duct of the action of methyl alcohol and hydrochloric acid at 180^ on
phenylenediamine, tetramethylmetapheiiijlenediamiiie separates out as an
uucrystallisahle oil (b. p. 250"^ corr.), having- a peculiar odour. The
hydrochloride forms hygroscopic crystals. The free base unites with
methyl iodide to form the compound C6H4('NMe2)2.MeI + H-.O, which
dissolves freely in water, but is less soluble in alcohol. It melts at
192° with decomposition into its constituents. Tetramethylmeta-
phenylenediamiue forms a liquid dibromo-compound, and is converted
by the action of nitric acid on its acetic acid solution into trinitrotri-
methylmetaphenylenediamine, a yellow crystalline body (ra. p. 132°),
.soluble in alcoliol and in benzene. W. C. W.
Action of Oxidising Agents on Tetramethylparaphenylene-
diamine. By C. WuHsiTii and E. Scnutiiu {JJer., 12, lbO*7— l8l;3).—
The unstable blue compound, which is formed by the action of bromine
on an acetic acid solution of tetramethylparaphenylenediamine, can be
obtained in the form of a microscopic crystalline precipitate by adding
ether to the mixture. Its solution in water and in alcohol has a;i
intense blue colour, which is destroyed by sulphurous acid. The sub-
stance can also be obtained as ferrocyauide, by adding- potassiiTui ferri-
cyanide to tetramethylphenylenediamine sulphate, CioHigN^ +
H«Fe,Cy.,. = CmHuN^.H.FeCye + H^FeCyg.
The ferrocyanide forms blue needle-shaped crystals, having a metal-
lic lustre.
By the action of sodium nitrite on tetramethylparaphenylene-
diamine, trimethylphenylenediaminenitrosanune is obtained, and a blue
colouring matter is produced, which, however, could not be isolated.
The nitrosamine crystallises in greenish-yellow plates (m. p. 98°),
.soluble in benzene, chloroform, ether, and hot water. On reduction
with tin and hydrochloric acid, it yields trimethylparaphenylene-
diamine, IS'^Me..CfiH4.NHMe, an oily liquid (b. p. 2G5°), sparingly
soluble in water. The acetyl-derivative crystallises in pi-isms containing
water (m. p. 78''). The anhydrous crystals melt at 95°.
When an excess of sodium nitrite is added to an acid solution of
tetramethylparaphenylenediamine, ')ntr(drimethylparcq)heni/lenc(lia7riine-
nitrosamine, NMe2.C6H3(NMe.NO)(N02), separates otit in orange-
coloured needles (m. p. 87"^), soluble in benzene and chloroform, but
insoluble in w-ater. On reduction with tin and hydrochloric acid, this
compound yields trimethyUriamidobenzene, NMe2.C6H3(NHMe).NH2,
which crystallises in white needles (m. p. 90°, b. p. 294°), soluble in
water. Its diacetyl-derivative crystallises in white plates (m. p. 184°).
w. c. w.
Colouring Matters obtained by the Oxidation of Di- and
Tetra-methylparaphenylenediamine. By C. Wurster (JJer., 12,
2071 — 2072). — The author proposes to represent the formation of the
red and blue colouring matters obtained by the action of oxidising
1 12 ABSTRACTS OF CHEMICAL PAPERS.
agents on di- and tetra-methylparaplienylenediamine respectively (Ber.,
12, 1803 and 1807), by the following equations: —
H2N.C6H4.NMe3 + Bro = HBr + MeN<*g^*>NH3Br.
Dimethjlparaplienylenectiamine
MezN.CoHi.NMeo + Br,
TctramethvlphenTlenediamine.
Me2JS'.CBH4.NMe3 + Br., = MeN<^''^'>NMe.,Br + HBr.
W. C. W.
Action of Nitrous Acid on Mono- and Diethylenediphenyl-
diamine. By H. F. Morley (Ber., 12, 1793— 1796).— The ethylene-
diphenyldiamine used in these experiments was pre]5ared by -warming
a mixture of ethylene bromide (1 mol.) with aniline (4 mols.) in a
large flask provided with an upright condenser. An active reaction
takes place, and on cooling, the contents of the flask solidify. Aniline
hydro bromide is dissolved out on heating the product with water,
leaving the diamine, which may be obtained in glistening scales
(m. p. 63"), by recrystallisation from dilute alcohol.
EtJajlenediphenylriivltrosamme separates out as a yellowish-green pre-
cipitate on the addition of sodium nitrite to a solution of ethylene-
(liphenyldiamine in dilute hydrochloric acid. On recrystallisation
from acetic acid, it is obtained in scales (m. p. 157°), insoluble in
water, ether, and cold alcohol.
Binitrosodiethylevedi'phenyldiamine, obtained as a yellowish -green
precipitate, yields, on reduction with tin and hydrochloric acid, dietJiy-
Jened'iphe7iylenetetramine, XHo.CgHiN ! (CsHi), I N.CfiHi.NH,. This
base crystallises in glistening scales (m. p. 221°), sparingly soluble in
ether, alcohol, and benzene. Fei^ric chloride produces a violet colora-
tion in solutions of its salts. W. C W.
Ethereal Oil of Origanum Hirtum and Cretan Oil of Mar-
joram. By E. Jahxs (ArcJi.Fharui. [3], 15.1 — 19). — The essential oil
of Origanum hirturahns an aromatic thyme-like odour, neutral reaction,
and a sp. gr. of 0"951 at 15° ; it is feebly lasvorotatory (100 mm. pro-
ducing a rotation of — 0"40"). When treated with a 15 per cent, solu-
tion of sodium carbonate, it dissolves, and on diluting the clear brown
solution with warm water, the greater portion of the hydi^ocarbon sepa-
rates, leaving a phenol in solution. This phenol, CmHuO, which
amounts to half the oil, was proved to be carvacrol, as on chlorina-
tion it yielded a chlorcymene, CH3 : CI : C3H7 = [1:2:4], which on
oxidation yielded chlorparatoluic acid. The sodium, potassium, barium,
calcium, magnesium, and silver salts of carvacrol sulphonic acid are
described ; the barium salt crystallises with SHoO, and appears to be
different from that described by Pott, which has the composition
(CioHi30.S03)2Ba. The sulphonic acid, when distilled with manganese
dioxide and sulphuric acid, yields thymoquinone. The melting point
of the carvacrol, I'o — 2°, does not appear quite to agree with those
obtained by other investigators. It yields ordinary cymene when
treated with phosphorus trisulphide. In the acid solution, from which
the carvacrol was separated, there appeared to be a small quantity of
ORGANIC CHEMISTRY. 113
a volatile acid, which reduced silver solution (t^rmic acid?). That
portion of the oil which was separated by the addition of water to the
soda solution appeared to be a mixture of terpenes. Submitted to dis-
tillation, a third passed over at ] 70 — 180° ; another third at 180 —
190^ ; the remainder at 250^. Finally, the portion 172 — 176° (a quarter
of the whole), which had an odour of oil of lemons, yielded, when
treated with sulphuric acid, a very small quantity of cymenesulphonic
acid. The results of the investigation are, that oil of Origanum hirtuni
consists of 50 — 60 per cent, of carvacrol, the rest being a mixture of
terpenes. There also appears to be a small quantity of a phenol which
gives a reddish-violet colour with ferric chloride. This oil is the only
natural source of carvacrol, except the oil of Thymus serpyllrtm, where
it is present to the amount of 3 per cent. Oil of Origatium Greticum
obtained from various sources, which had a deeper and more red-brown
colour than that of Oritjammi hirtiim, was also remarkable for the large
amount of carvacrol which it contained. All the specimens contained
the phenol (1 — 2 per cent.) which is coloured violet by ferric chloride.
An oil prepared in France, having the name 01. origani Gall., contains
no carvacrol ; it should therefore be distinguished from Cretan oil of
marjoram, this name being applied only to that from Greece and Asia
Minor. Tests for identification which can be applied are : mixing
with 90 per cent, alcohol in all proportions ; production of a green or
violet colour by ferric chloride ; violent reaction with phosphorus penta-
chloride, accompanied by evolution of hydrochloric acid gas, followed
by the production of a bluish-red coloration. Those oils which
contain 50 per cent, or more of carvacrol will produce a clear mixture
with half their volume of a 15 per cent, soda solution.
E. W. P.
Resorcinol and Oreinol Derivatives. By Y. Mkez and G.
Zetter (Brr., 12, 2035 — 2049). — The best yield of trinitroresorcinol
or styphnic acid is obtained by nitrating resorciuoldisulphonic acid.
For this purpose finely powdered resorcinol is added in small portions
at a time, to five times its weight of strong sulphuric acid at 40° ; the
clear red solution is heated at 100°, when it crystallises, forming a
thick paste. The acid mixture is poured into cold water, and nitric
acid diluted with 10 percent, of water is slowly added, care being taken
to avoid any rise of temperature. Towards the end of the operation
fuming nitric acid is employed ; at least twice the theoretical amount
of nitric acid must be used for nitration. The product of the reaction
is left at rest for 12 hours, and then poured into twice its volume of
cold water, when trinitroresorciuol separates out as a granular crystal-
line mass (m. p. 174"5°).
Trinitro-orcinol can be prepared by a similar method, but the yield
is not so good as in the case of trinitroresorciuol, only about 60 per
cent, of the theoretical yield being obtained. The mixture of oreinol
and sulphuric acid is heated on a water-bath, but in order to complete
the reaction, the temperature must be raised to 150". In the process
of nitration, it is necessary to use rather dilute nitric acid, and to cool
the mixture with ice. Trinitro-orcinol crystallises in long yellow
needles (m. p. 163'5°).
VOL. xxxviii. i
114 ABSTRACTS OF CHEMICAL PAPERS.
Trihydroxi/henzoqtcinone is formed by the action of dilnte hydrochloric
acid (8 — 10 per cent, solution) at 140 — 150° on the hydrochloride
of amidodi-imidoresorcinol, prepared by the addition of ferric chloride
to a solution of triamidoresorcinol hydrochloride (Schreder, Armalen,
158, 244). The ci-ude product may be purified by solution in soda,
and reprecipitation by hydrochloric acid. Trihydroxybenzoquinone
exists as a dark, almost black, amorphous powder, and also in the form
of dark crystalline scales, which are sparingly soluble in the usual
solvents. The ammoniacal solution of this substance produces dark
coloured precipitates Avith salts of the heavy metals and alkaline earth-
metals, _e.</., (C6H02)2(Ba02)3 ;_ CoH03(Ag6)3. _
Acetic chloride attacks trihydroxybenzoquinone at the ordinary
temperature, forming triacetoxyqtdnone, C6H02(OAc)3, which is de-
posited from a solution in hot acetic acid in smajl crystalline scales.
The corresponding tribenzoyl compound, C6H02(OBz)3 has not yet been
obtained in a crystalline state. Bromotnhydroxyqtiinone, C6Br02(OH)3,
prepared by warming a solution of trihydroxybenzoquinone in acetic
acid with bromine, is a brown uncrystallisable powder, sparingly
soluble in alcohol. It forms insoluble compounds with the heavy
metals, e.g., Pb3(C6Br02.03)2. Trihydroxytoluquirwne, C6Me02(OH)3,
is deposited in dark-coloured crystals when amidodiimido-orcinol hydro-
chloi-ide is heated with a 10 per cent, solution of hydrochloric acid at
140 — 150°. The crude prodiict is purified by conversion into the tri-
acetyl derivative, CBMe02(OAc)3, a yellow lustrous crystalline powder,
soluble in hot alcohol. When treated with a solution of soda, this
yields a brown liquid, from which pure trihydroxytoluquinone is pre-
cipitated on the addition of an acid.
This toluqninone dissolves in hot alcohol, forming a dark cherry-
coloured solution. It foi'ms with calcium, barium, and silver dark-
coloured precipitates, which are insoluble in water.
Trinitroresorcinol dissolves in fuming sulphuric acid, but is not repre-
cipitated on dilution with water. When air containing bromine vapour
is passed through an aqueous solution of monosodium trinitroresor-
cinol, C6H(N02):,ONa.OH, a mixture of bromopicrin and nitrodibrom-
ethylene, CBrj '. CH.NO2, is formed. The latter on recrystallisation
from chloroform is deposited in transparent, six-sided T-hombic prisms
(m. p. 112°), soluble in alcohol, ether, carbon bisulphide, and benzene.
The solution stains the skin red. The addition of alkalis to the alco-
holic solution pa'oduces a tTansient red coloration ; nitrate of silver and
lead acetate throw down from the red liquid a red precipitate, which
rapidly changes to the corresponding metalhc bromide
w. c. w.
Compounds of the Hydrobenzoins and Stilbene. Series II.
By T. ZiNCKE {Annalen, 198, 115 — 141). — This is an important paper
on a probable case of true physical isomerism. It has been previously
shown (Annalen, 182, 241 ; Chem. Soc. J., 1875, 453), that the two
diatomic alcohols obtained from stilbene, CeHs.CH ! CH.CeHs, by
the addition of bromine, and conversion of the bromide into the acetate
or benzoate, and subsequent saponification, are respectively identical
with the hydro- and isohydro-benzo'in obtained from benzaldehyde by
ORGANIC CHEMISTRT. 115
the action of lijclrogfenising agents. Althougli any two of the follow-
iug formulie: I. CHPh(OH).CHPh(OH) ; II. CH,Ph.C(OH)..Ph ;
III. CHPh(0H).CcH4.CH,(0H), for these two alcohols would explain
their isomerism, and sinnUtaneous formation from stilbene or benzalde-
liyde, vet such formula? would not agree with other reactions of tho
alcohols. So far, it has not been possible to prove the existence of two
isomeric dibromides in crude stilbene bromide.
On oxidation with chromic mixture, both alcohols behave exactly
alike, and give first benzaldehyde and then benzoic acid, together with
small quantities of benzophenone, the formation of the latter being
due to a secondary reaction. These facts show that the third of the
above formulae is inadmissible for either alcohol.
By oxidation with nitric acid, hydi*obenzoin gives first benzoin,
Ph.CO.CHPh(OH), and then benzil PhCO.COPh, from which io
follows that it has the constitution represented by formula I. Ammann
and Fittig (Annahn, 168. 75) found that isohydrobenzoin on oxida-
tion with nitric acid, gave only resinous products ; the author, how-
ever, finds that this oxidation gives first a substance which crystallises
in monoclinic crystals (m. p. 98°), and then a body crystallising in
yellow needles (m. p. 78 — 81)°. Both these compounds are still under
investigation. From the above-mentioned results obtained by oxida-
tion, it follows that the only possible formula; for hydro- and isohydro-
benzoin are I and II respectively, and the latter on oxidation with
nitric acid would give, first, CPh(OH).,.COPh, or PhCO.CH.Ph, and
then benzil. Tie author, however, considers that the oxidation pro-
duct (m. p. 98°) is a physical isomeride of benzoin, and the product
(m. p. 78 — 81"^) the corresponding physical isomeride of benzil : for in
several subsequent experiments on the oxidation of isohydrobenzoin
with nitric acid, these two bodies (m. p. 98° and 78 — 81°) were not
obtained, but only ordinary henzdin and benzil, the only difference
between hydro- and isohydro-benzoin in this respect being that with
the latter, the crude products were always resinous.
On treatment with phosphorus pentabromide, both hydro- and iso-
hydro-benzoin give exactly the same dibromide (m. p. 237°), which,
with silver acetate or benzoate, gives in both cases the hydro- and
isohydro-benzoate, and these on saponification yield again hydro- and
isohydro-benzoin respectively, exactly as stilbene bromide does.
By the action of phosphorus, pentachloride hydrobenzoin gives two
isomeric dichlorides, C11H12CI2 (m. p. 192° and 94)°), whilst isohydro-
benzoin gives only one (m. p. 192°) which ia identical with the former
of the two just mentioned.
ix-Hydrobenzom dicldoride, CuHiaCU, already described by Ammann
and Fittig (Jjoe. cit.), crystallises Ln needles or prisms (m.. p. 192^),
which are sparingly soluble in alcohol, but easily soluble in toluene,
ether, and chloroform, and sublime in plates.
i3- Hydrobenzoin (or isohydrubenzoin) dicldoride, C14H12CI2, differs gi'eatly
from the preceding compound in physical, but has exactly the same
chemical properties. It dissolves easily in most solvents, and crystal-
lises in four- or six-sided plates (m. p. 94°), and sublimes without
decomposition. When heated, both, the a- and ^-chlorides undergo a
■most remarkable change as regards melting point, in such a way that
i 2
llg ABSTRACTS OF CHEMICAL PAPERS.
they both apparently give a third dichloride (in. p. 160°), which is
more stable than the other two. Tlie investigation of the anhydrides
of hydro- and isohydro-benzom has also proved the existence o± a third
dichloride (m. p. 153°). The dichloride (m. p. 160°) is however
probably a mixture of the a- and /3-chlorides, since on crystallisation it
may be separated into the a- and ^-dichlorides.
Both hydro- and isohydro-benzom, when treated with phosphorus
trichloride, give only one dichloride, viz., that melting at 192°. By
conversion into the acetate, and subsequent saponification and crystal-
lisation from hot water, a-hvdrobenzoin chloride (m. p. 192 ) is eon-
verted almost wholly into isohydrobenzoin, together with small quan-
tities of hydrobenzom. Under similar circumstances, ^-hydrobenzom
(or isohydrobenzoin) dichloride (m. p. 94°) gives the same results. If,
however, for the conversion of these chlorides into the alcohols, silver
1 enzoate is used in place of the acetate, then both a- and ,5-chlori.le
give chiefly hydrobenzoin, together with small quantities of isohydro-
benzom. ^ • A \.
The author considers that the above facts cannot be explamed by a
different grouping of the atoms, and that hydro- and isohydro-benzom
must have identically the same chemical molecule,
CoH5.CH(OH).CH(OH).C6H5.
In other words they ai-e true physical isomerides. T. C.
Compounds obtained from Hydro- and Isohydro-benzoin
by the Action of Dilute Sulphuric Acid. By A. Breuer and
T. ZiNCKE {Annalen, 198, 141— 190).— This is a continuation^ of
Zincke's investigation with regard to the isomerism of hydro- and iso-
hydro-benzoin (see preceding Abstract). The authors advance the fol-
lowing general rule :— " On abstraction of water, which can be effected
by various reagents, all diatomic alcohols, containing the OH-groups
attached to two neighbouring carbon atoms, give first oxides (anhy-
drides or ethers) without any intramolecular changes, and then by
further action of the reagent, ketones, or aldehydes, or both." Both
hydro- and isohydro-benzoin must be considered as aldehyde- pinacones,
thus:— C6H5.CH(OH).CH(OH).aH5. By the action of dilute sul-
phuric acid, zinc chloride, or hydrochloric acid both give two com-
pounds, the one crystalhne and the other liquid. With hydrobenzoin
the yield is 20 to 25 per cent, of the former, and 50 to 60 per cent, of
the latter, whereas with isohydrobenzoin the reverse is the case. The
former compoands are anhydrides —
CeHs.CH CeHs.CH.O.CH.CeHs
1 >0, or more probably | |
CsH^.CH^ CeH^.CH.O.CH.CeH,
and although chemically identical, they are physically (in melting point
and crystalline form) different. The liquid compounds appear to be
identical both chemically and physically; they are aUIehydes,
CHPho.COH, and their formation therefore can only be explained by
intramolecular transference of the CoHj-group. By the continued
ORGANIC CHEMISTRY. 117
action of the reagent, the above crystalline compounds are also con-
verted into this aldehyde, and by oxidation both give the same pro-
duct, C&Ho.Os.
Convenient methods of preparing hydro- and isohydro-benzo'in are
described. Benzoin by the action of sodium amalgam in dilute alco-
holic solution gives not only hydrobenzoi'n (33 per cent.) but also
small quantities of isohydrobenzoin (1 per cent.).
Hydrobenzom amhydride, Cuili2.0, forms monoclinic crystals (m. p.
132^), which are easily soluble in hot alcohol, benzene, chloi-oform,
and glacial acetic acid, and but sparingly soluble in light petroleum.
It is not volatile in steam.
Isoh tjdrobenzom anhydride, CnH-nO, ^orvas brilliant monoclinic crys-
tals (m. p. 102''), very similar in form to gypsum ; these become dull
on keeping. It is more soluble in alcohol than the hydrobenzo'in-
compound, but behaves in a similar manner towards other solvents.
Neither anhydride is attacked by sodium amalgam; both give stil-
bene bromide on treatment with bromine, and both when heated in
Staled tubes at 260° yield benzaldehyde and stilbene, 2CuHi20 =
2C7H6O + CuHi2. Heated with benzoic acid at 240°, the hydroben-
zo'in anhydride gives very small quantities of hydrobenzom benzoate
(m. p. 242°), whilst the iso-compound gives only traces of isohydro-
benzo'in. Treated with acetic anhydride in sealed tubes, both com-
pounds yield small quantities of hydro- and isohydro-benzo'in. Heated
with acetic acid at 165°, the hydrobenzo'in anhydride is converted
into hydrobenzo'in acetate, whilst the iso-couLpound is but slightly
attacked even at 2o0°, and besides benzaldehyde and stilbene gives
only small quantities of isohydrobenzoin.
On treating hydrobenzoiu anhydride with phosphorus pentachloride
at 130°, the same chloride, CUH12CI2 (m. p. 192°), is obtained as from
hydrobenzoiu itself, together with but a small quantity of resin, and
none of the chloride of melting point ^4°. Isohydrobenzoin anhydride
under similar circumstances gives, besides the chloride (m. p. 192°),
also a resinous body (CosHaiOCU, m. p. 87° ?), which was far more
abundant than in the case of the hydrobenzo'in compound. On saponi-
fication, this resin gave hydro- and isohydro-benzoin ; by recrystallisa-
tion, it was converted into the compound C28H2:jOCI (m. p. 1.53°),
which is more soluble in alcohol than the dichloride (m. p. 192°).
Both anhydrides on oxidation give a compound, C2t,H2203, together
with small quantities of benzoic acid and other products, amongst
which there is one crystallising in needles or jjlates (m. p. 144°),.
which appears to be a reduction-product of the compound C28H32O3.
This latter substance is easily soluble in benzene and chloroform, and
but sparingly soluble in light petroleum ; it is also difficultly soluble
in cold, but more easily soluble in hot alcohol, and crystallises in
needles or plates (m. p. 155°). The formation of this body by the
oxidation of hydro- and isohydro-benzoin anhydrides seems to show
that the formula of these latter is more probably C28H21O2 than
CiiHiaO. On oxidation with chromic and acetic acids, it gives neither
benzoic acid nor benzophenone, but a new compound (C08H29O1 or
C28H20O3?), which crystallises in plates (m. p. 98°). On reduction with
phosphorus and hydriodic acid, the compound CogH^sOa gives dibenzyl
118 ABSTRACTS OF CHEMICAL PAPERS.
(m. p. 52"^), and a substance, C15H10O2, crystallising in needles (m. p.
144°), sparing'lj soluble in water, but easily soluble in alcohol, ether,
and benzene, and which on further oxidation give chiefly benzophenone.
By reduction with phosphorus and hydriodic acid, hydro- and iso-
hydro-benzoin anhydrides both yield dibenzyl, together with a small
quantity of an oil, thus showing that they are both, derivatives of the
same hydrocarbon ; the oil on oxidation gave benzophenone. Diphenyl-
aldehyde is obtained on heating either anhydride with dilute sulphuric
acid at 210° : hydrobenzo'in chloride (m. p. 182°), together with
diphenylaldehyde, is obtained by heating the anhydrides with strong
hydrochloric acid at 170°. Benzoic chloride converts both anhydrides
into hydrobenzo'in chlorides (m. p. 192°). All the above reactions
show that the two anhydrides are almost completely identical, and
that the difference between them is probabl}^ of the same kind as that
between the corresponding alcohols. These results also on the whole
point to the formula, C-,)8H:402, for the anhydrides, rather than to the
simpler formula, C14H12O.
It has not yet been possible to decide finally Avhether the aldehydes
obtained from hydro- and isohydro-bpnzo'in, by the action of dilute
sulphuric acid, are absolutely identical both physically and chemically,
but it is very probable that they are.
Both these aldehydes give benzophenone on oxidation, and not di-
phenylacetic acid, and only by treatment with alcoholic potash was it
possible to convert them into the latter compound ; even then, the
chief products were benzhydrol and diphenylmethane. These alde-
hydes which the authors consider on the whole to be identical, have
the composition of a diphenyl-aldelnjde, C14H12O ; the product is a
colourless oil, heavier than water, and insoluble therein, but easily
soluble in ether, alcohol, benzene, and chloroform. It boils at 315^
with slight decomposition. On keeping for many weeks it yields
formic acid and benzophenone, and gradually becomes crystalline. The
crystals from the hydrobenzo'in aldehyde melt at 213°, and those
from the iso-compound at 167°. In a second experiment, however,
the hydrobenzo'in aldehyde also gave crystals melting at 167°, and not
at 213^ ; the change which here takes place is probably as follows : —
2(C6H5),Cn.COH -F O2 = (C6H5)oC \ CfCeH,), -f 2CH0O2, and
(C6H5)2CH.COH + O2 = (C6Ha)2.CO + CH2O2. Both the crystalline
bodies on oxidation give benzophenones, and by treating the one
melting at 167° with acetic chloride, a crystalline body (m. p. 125 —
130°) is obtained. T. C.
Physical Isomerism, with Special Reference to Hydro- and
Isohydro-benzoin. By T. Zincke (Annalen, 198, 191— 203).— In
this paper the theories which have been proposed by Lanbeuhcimer
(Ber., 9, 766), Lehmann (Zeits.f. KnjstaJlorjrajyhie, 1, 110), and Van't
Hotf, to account for physical isomerism, are severally discussed, and
the author arrives at the conclusion that the physical isomerism in the
case of the hydrobenzo'ins cannot be satisfactorily explained by means
of any of them. T. C.
Orthobrombenzoic Acid. By M. Rhalis {Anialev, 198, 99 —
ORGANIC CHEMISTRY. 119
11-1-). — This acid is best prepared by oxidising liquid bromotoluene
with potassium permanganate. It crystallises from hot water in
colourless silky needles (m. p. = 150° ; 148°, Zincke, Ber., 7, 1502 ;
138°, Bichter, Her., 4, 459), which are sparingly soluble in cold water,
but far more soluble than either the meta- or para-derivatives, from,
which it is still further distinguished by being little or not at all vola-
tile in steam. It is easily soluble in alcohol, ether, and chloroform.
"When fused with potash it yields parahydroxybenzoic acid (?), and
but a trace of .salicylic acid. The salts of the alkalis and alkaline
earths are easily soluble in water, and those of the heavy metals but
shghtly soluble. The following salts were prepared and examined: —
The iMtassium salt, C7H4BrO^K.2H.,0 (m. p. 245) ; sodium salt,
CTHiBrO.Na ; harium salt, Ba(C7H4Br02)..2aH60 (from alcohol) ;
calcium salt, (C7H4Br02)3Ca.3H20 ; zinc salt, (C7H4Br02)2Zn ; neutral
copper salt, (C7H4Br02).Cu.H20 (m. p. = 257° with decomposition)
are crystalline, whilst the basic copper salt, C7HtBrO,.Cu.OH, silver
salt and lead salt, (C7H4Br02)2Pb.C2H60 (m. p. = 176—180"), are
amorphous precipitates.
Methyl orthohrornohenzoate, C7H4Br02.Me, is obtained as a colourless
liquid (b. p. = 246°) by the action of methyl iodide on the silver
salts.
Ethyl orthohromobenzoate, C7H4BrO'>, is a colourless liquid (b. p. =
254°).
Nitro-orthobromobenzoic acid, C6H3Br(N02).COOH, is obtained by
dissolving the bromobenzoic acid in cold fuming nitric acid, and is
identical with the acid previously prepared by Burghardt (]3er., 8,
560). It crystallises from hot water in brilliant needles (m. p. =
180'^), which are sparingly soluble in cold, but more easily in hot
water, and very easily in alcohol, ether, and chloroform. The barium
salt [C7H3Br(N02)02]2Ba.5^H20, crystallising in needles or prisms,
and the silver salt were prepared. Ethyl nitro-orthobroniobenzoate^
CcIl3Br(N02).COOEt, crystallises in needles (m. p. = 66°), which
are insoluble in water, but easily soluble in alcohol and in ether.
That nitro-orthobromobenzoic acid has the constitution —
[COOH : Br : NO2 =1:2:5],
was proved by converting it (by treatment wnth aqueous ammonia)
into nitro-amidobenzoic acid (m. p. 270°), which is identical with that
obtained by Waltenberg (Ber., 8, 1217) from ethyl paranitro.salicylate.
Now KJruse has shown that the nitro-group of this acid must be in
the meta-position in reference to the cai-boxyl-group, and hence the
acid must have one of the two following constitutions : —
[COOH : NH2 : XO2 = 1 : 2 : 3, or 1 : 2 : 5],
but the fact that nitro-orthobromobenzoic acid gives paranitraniline
(m. p. 148°) on treatment with alcoholic ammonia proves that the
latter of these is the true one. T. C.
Paranitrophenylacetic Acid. By T. Maxwell (Ber., 12, 1764
— 1768). — The nitrophenylacetic acid (m. p. 114°) which Radziszewski
120 ABSTRACTS OF CHEMICAL P.iPERS.
(Ber., 2, 209 and 3, 648) obtained by nitrating phenylacetic acid is not
a definite compound, but a mixture of para- and ortho-nitrophenjlacetic
acids, which cannot be separated by recrystallisation from alcohol.
The mixed acids (m. p. 114") were converted into methyl salrs and
dissolved in boiling light petroleum, when pure methyl paranitro-
phenylacetate was deposited in long glistening needles (m. p. 54°),
leaving a mixture of methyl ortho- and para-nitrophenylacetates in
the mother-liquor.
The paranitro acid crystallises in silky needles (m. p, 152°) soluble
in alcohol, ether, and benzene. On oxidation, it yields paranitroben-
zoic acid (m. p. 238°), and on reduction with tin and hydrochloric
acid, amidophenylacetic acid.
Barium paravitroplienylacetate crystallises in yellow anhydrous
needles, freely soluble in water.
The zinc salt forms needles containing one mol. HoO, the silver salt
also forms colourless needles, which are sparingly soluble in cold water.
The salts of the alkalis are very soluble. Methyl paniintrophenylacetate
melts at 54°, and is soluble in alcohol, benzene, and ether. The addi-
tion of a few drops of alcoholic potash produces a beautiful violet
coloration in the alcoholic solution of this substance.
The etltyl salt crystallises in thin plates (m. p. 65*5'') soluble in
alcohol and ether. W. C. W.
Polymerised Non-saturated Acids. By R. Fittig (Ber., 12,
1739 — 1744).^ — When methacrylic acid is heated at 130° in sealed
tubes, it is converted into a polymeric modification in the form of a
white hard mass resembling porcelain in appearance. This substance
does not dissolve in water, but slowly unites with it, forming a clear
transparent liquid, from which the polymeride can be separated as a
colourless gelatinous mass, by filtration. Attempts to ascertain the
constitution of this compound have been unsuccessful, since it is either
not acted on by treatment with oxidising agents, or else completely
destroyed.
Isatroj'ic acid obtained by heating atropic acid at a temperature
above its melting point, is converted into anthraquinone and ortho-
benzoylbenzoic acid, Ph.CO.C6H4.COOH (b. p. 127°) when chromic
acid is added in small portions at a time, to an acetic acid solution of
the acid.
By the action of sulphuric acid on isatropic acid at a temperature
not exceeding 50°, carbonic oxide and a monobasic acid, CjvHuOo, are
produced. The acid is deposited from an alcoholic solution in colour-
less plates which melt at 156°, and decompose on distillation into
carbonic anhydride and a liquid hydrocarbon, CieHu (b. p. 320°). If
the mixture of sulphuric and isatropic acids is heated at 100°, a sul-
phonic acid, CieHisSOs or CisHjoSOa is formed. This compound,
which can also be prepared by the action of sulphuric acid on the new
acid, CnHuOo, is insoluble in water. It dissolves in acetic acid and
crystallises from this solution in transparent prisms, which melt with
decomposition at 258°.
The solution of the sulphonic acid in water containing sodium car-
bonate may be preserved in the dark without undergoing any altera-
ORGANIC CHEMISTRY. 121
tion, but on exposure to the light, the liquid rapidly becomes turbid,
and deposits a yellow precipitate (m. p. lOS""), solulile in alcohol.
Isatropic acid is decomposed by distillation, yielding: (1) a hydro-
carbon, CjeHu (b. p. 3-2(f) ; (2) a monobasic acid, d-HuOo, crystal-
lising in prisms (m. p. 16S^), which is not identical with the pre-
viously described acid of the same composition ; (3) a soluble acid,
probalDly CnHieOo, not yet obtained in the crystalline state. From
the preceding observations, the author concludes that the conversion
of atropic into isatropic acid, may be best represented thus : —
cCoaCPh ; cS: C0OH.CPh< CH..CH,>cH.COOH
2 mols. atropic acid. Isatropic acid.
In the preparation of isatropic acid by the long-continued boiling
of atropic acid with water, a second polymeride is formed. On re-
crystallising the product from acetic acid, the new acid is found in
the mother-liquor, from which it can be obtained in plates (m.p. 205°).
It is converted into isatropic acid (m. p. 237°) by exposure to a tem-
perature of 220° for some time.
Cirinamic acAd can easily be polymerised, but the dibasic acid,
CisHigOi, corresponding to isatropic acid, has not yet been isolated.
The monobasic acid, CnHisOj, is formed by boiling a .solution of cin-
namic acid in 5 parts of glacial acetic acid with \ its volume of
sulphuric acid, or by treating cinnamic acid with sulphuric acid
diluted with 1^ times its volume of water. In the latter method, the
hydrocarbon, CjeHie (b. p. 310 — 312°), described by Erlenmeyer as
distijrene, and also investigated by Krateau (Ber., 11, 1260), is ob-
tained as a bye-product. The acid, CnHieOo, is a colourless amor-
phous substance, insoluble in water, but dissolved by ether, alcohol,
and acetic acid. Its calcium salt is insoluble in hot water.
W. C. W.
The Isomeric Nitrosalicylic Acids, By H. Schiff and
F. Masixo {Gazzetta, 9, 31y — o27j. — In the first part of the paper the
authors give an account of the various researches which have been
made on the nitrosalicylic acid obtained by the action of dilute nitric
acid on indigo, hitherto supposed to be homojjeneous, and the nitro-
salicylic acid from salicin or salicylic acid, which has been shown to
be a mixture of two isomerides, melting at 125° (144° when anhydi-ous)
and at 228° respectively. The authors find, however, that the nitro-
salicylic acid from indigo may also be separated into two portions, one
melting at 125° and the other at 228°. This is effected by first con-
verting the crude acid into ammonium salt, and after separating the
resin, boiling the solution with excess of baryta-water. The barium
salts thus obtained are then separated by fractional crystallisation,
the one containing the acid of melting point 228" being least soluble.
According to the authors,^ the acid which forms anhydrous crystals
(m. p. 228°) has the constitution [COOH : OH : NOo = 1:2: 5], whilst
the acid crystallising with one HnO (m. p. 125°) has the constitution
[1:2:3]. From these results, it is evident that the acid obtained
from indigo, like that from salicin or salicylic acid, is a mixture of two
isomerides. C. E. G.
122 ABSTRACTS OF CHEMICAL PAPERS.
Artificial Tannin. By P. Freda. (Gazzetta, 9, 327— 332).— The
author has repeated the experiments described by Schiif (Gazzetta, 8,
363, and this Journal, Abst., 1879, 646), but obtains totally different
results, all tending to confirm the conclusion at which he had arrived,
that the supposed digallic acid or artificial tannin of Schiff, obtained
by the action of arsenic acid on gallic acid, is merely an arsenical
compound of gallic acid. He has analysed the precipitate formed in
qainine solution, and finds that it contains as much as 7 — 8 per cent, of
arsenic in different specimens ; when the arsenic is removed, none of
the tannin reactions could be observed. The author's experiments
show that arsenic acid, whether in aqueous or alcohol solution, does not
transform gallic acid into digallic acid, but into an arsenical compound,
^vhich has some properiies in common with tannin, and that when
this compound is freed from arsenic by hydrogen sulphide, gallic acid
is regenerated. The author has observed also that the melting point
of gallic acid is much lower (210°) when it is gradually heated than
when it is rapidly heated (240 — 252°), probably owing to incipient
decomposition. C. E. Gr.
Amidobenzenedisulphonic Acids. By 0. Zaxder (Amialen,
198, 1 — 29). — (1.) Panimidohenzenedisul'plwnic or disulphanilic acid,
C6H3NH,(S03H)2.2H30 [SO3H : SO3H : NH,. = 1 : 3 : 4], is obtained
by the action of faming sulphuric acid on paramidobenzenesulphonic
acid (sulphanilic acid), and is also found in the mother-liquor left in
the preparation of sulphanilic acid. It crystallises in small reddish
needles, which dissolve readily in water and alcohol, but not in ether.
Bromine throws down tribromaniline from an aqueous sokition of the
acid. It forms normal and acid salts, the former of which dissolve
easily in water, the latter less readily, whilst both are insoluble in
alcohol. Normal ammonium paramidobenzenedisulphonate,
CeH3(NH,)(SO3NH02.H,O,
forms small transpai-ent yellowish hexagonal prisms. The acid salt,
C6H3(NH.,)(S03H).S03NH4.2HoO, crystallises in large white needles,
which become reddish when exposed to the air.
The normal potassium salt, C6H3NHo(S03K)2.H20, forms very hard
yellowish nodules, and the acid salt white silky needles.
The salts of calciujn, barium, lead, and silver, resemble those
described, except that the acid calcium salt and both the silver salts
are anhydrous.
Din.zoparal)enzenedisulplwniG acid, C6H3(S03H) '. N2SO3 may be ob-
tained by the action of nitrous acid on an alcoholic solution of the
amidodisulphonic acid, but a better method of preparing it is by
nitration of an acid salt.
The diazoparabenzenedisulphonates dissolve in cold water, and are
precipitated by alcohol from the aqueous solution. They do not
explode by percussion. Heated on platinum foil they buim brightly,
leaving a carbonaceous residue. When heated with alcohol, or boiled
with water or with hydrobromic acid, they yield benzenedisulphonates,
phenoldisulphonates, and bromobenzenedisulphonates.
Ammonium diazoparahenzenedibulpJionate, C6H3(NH4S03) '. N2SO3,
ORGAXIC CHEmSTRV. 123
prepared by passing nitrous acid into an ice-cold concentrated solnt'on
of hydrogen-ammoninm paramidobenzenedisulphonate, forms white
needles. The potassium salt obtained in a similar manner is also
iinhvdrous. The barium and calcium salts contain 2, the lead salt
3 mols. of water of crystallisation.
Mttahenzenedisnlphoiric acid[SO:,ll : SO3H = 1 : 3]. — When calcinm
diazoparabenzenedisnlphonate is heated with alcohol under pressure,
nitrogen is evolved, and the free benzenedisulphonic acid is found in
the solution (this Journal, 1878, Abst., 409).
Bromobenzenedisnlphonic acid [SO3H : SO3H : Br =1:3: 4], is
obtained by heating the salts of the diazodisulphonic acid with hydro-
bromic acid, converting the potassium salt into the chloride, and
heating the latter with water at 150^. It crystallises in slender
transparent, deliquescent needles, and seems to be identical with
Heinzelman's /5-bromobenzenedisulphonic acid and Nolting's bromo-
benzenedisulphonic acid (see this Journal, 1878, Abst., 410, and vol.
13, 895, 1195, and Ber., 7, 1311). The normal salts dissolve readily
in water; acid salts could not be obtained.
Potassium, hromohemeiiedisulplionate, C6H3Br(S03K)2.HoO, obtained
by decomposing the potassium diazo-salt with concentrated hydro-
bromic acid, crystallises in small white nodular masses.
The barium, salt contains 4 mols. H^O. The silver salt is anhydrous.
Bromobenzenp.disidphonic chloride, C6H3Br(SO.iCl)o, is formed by the
action of phosphorus pentachloride on the potassium salt. It melts at
103—105°.
Bromobetizenedisulphonamide, C6H3Br(SOo.NHo)2, obtained by warm-
ing the chloride with strong ammonia, forms slender white needles
(m. p. 238°), sparingly soluble in cold, but readily in hot water.
Action of Bromine on Paramidobenzenedisulph'mic Acid. — The pro-
ducts are tribromaniline, dibromamidobenzenesulphonic and paramido-
bromobenzenedisulphonic acids.
JParamidobromobenzenedisulphonic acid, [SO3H : SOsH : NHo : Br
= 1:3:4: 5], consists of masses of slender microscopical needles,
which have sometimes a silky lustre. It dissolves readily in water,
and forms normal and acid salts, of which the former are the more
.soluble.
The ammoniura salt, C6Ho.Br(XH,)(S03XH4),.2H,0, crystallises in
transparent, bright yellow hexagonal pHsms, which are decomposed
w4th explosive violence by concentrated nitric acid.
The potassium salt resembles the ammonium salt ; the normal salt
of barium has 3, the acid 1, and the acid lead salt 5 mols. of H.,0.
The diazobromobeitzenedisulphonic acid, C6H2Br(S03H)N..S03.2Il30,
is obtained by the action of nitrous acid on bromoparamidobenzene-
disulphonie acid in white tabular crystals, which are not explosive.
They evolve nitrogen when their aqueous solution is heated. The
potassium salt forms pointed microscopical prisms, and contains
3 mols. H.,0.
Dibromamidobenzenedisulphonic acid [SO3 : Br : NH2 : Br =
1:3:4:5], crystallises in pale reddish crusts, formed of prisms con-
taining 2II2O, which effloresce when exposed to the air. It is easily
soluble in water, sparingly in spirit.
124 ABSTRACTS OF CHEMICAL PAPERS.
The harium salt with oHnO forms white crystals, which acquire a red
tint on exposure to air ; they are slightly soluble, and are decomposed
at 180°.
The diazo-com])ouncl of this acid yields a dihromohenzenesulfho'nic acid,
[SO3H : Br : Br = 1 : 3 : 5],. and also a tribromo-acid [SO3 : Br : Br : Br
= 1:3:4:5].
(2.) Orthamidohenzenedisidplionic acid is obtained from orthamido-
benzenesulphoiiic acid by the action of fuming sulphuric acid at
170 — 180", and is identical with disulphanilic acid. It crystallises in
slender red microscopical needles, soluble in water, and forms normal
and acid salts. Bromine precipitates tribromaniline (m. p. IIS'O^)
from dilute aqueous solutions of theacid.
TAxQ jpiitasKium, harium, and lead salts have been prepared.
The barium diazoienzenedisidphonate is obtained by the action of
nitrous acid on a cold concentrated solution of the barium salt of the
amido-acid.
(3.) MetamidobenzenedisnlphoniG acid, ■C6H3(]SrHo)(S03H)o.4H20, is
formed from metamidobenzenesul phonic acid by heating it with
fuming sulphuric acid at 180°. It forms rhombic octohedrons, easily
soluble in water and in alcohol ; it slowly absorbs moisture on exposure
to the air, and quickly effloresces over sulphuric acid. When heated, it
melts in its watei- of crystallisation and decomposes, leaving an easily
combustible carbonaceous residue. Concentrated nitric acid causes it
to deflngrate. It forms normal and acid salts, of which the latter are
less soluble than the former. The salts of ammonium, potassiuin, barium,
and lead have been prepared, and resemble in general characters the
salts previously described. The acid potassium salt is anhydrous.
When metamidobenzenedisulphonic acid is acted on by nitrous acid
a diazo-acid is formed, which yields salts with potassium, &c. When
the potassium salt, C6ll3(KS03) '. N2SO3, is heated with alcohol under
pressure, a new body is formed containing an acid, which the author
names oxethylbenzenedisulphonic acid, C6H3(EtO)(S03H)2. The ])otas-
simn salt of this acid crystallises in slender, yellow transparent
needles, soluble in water, and precipitated by alcohol from the aqueous
solution as a white powder, redissolving in water with a yellow colour.
The bariutyb salt crystallises with 2H2O, when the solution is rapidly
evaporated, otherwise with 3H2O.
The cldoride, G6H3(EtO)(SOvCl)2, obtained from the acid by
treatment with phosphorus pentachloride, forms white hexagonal
plates (m. p. 106 — lOS""'), soluble in benzene, apparently forming a
compound with it. Strong ammonia converts the chloride into the
amide, which crystallises in nodular groups of needles (m. p. 233°).
This behaviour of the diazo-compound with alcohol is similar to
that of ortliamidotoluene-parasulphonic acid described by Hayduch
{Annalen, 172, 215).
The bromobenzenedisulphonic acid, C6H3Br(SO:iH)2, is formed when
hydrobromic acid acts on the diazobenzenedisulphonates (obtained
from the acid metamidobenzenedisulphonates). It consists of slender,
white deliquescent needles, and forms sparingly soluble normal salts,
resembliug in general characters those previously described.
Bromobenzeiiedisulphomc chloride, C6H3Br(S02Cl)o melts at 104°.
ORGANIC CHEMSTRY. 125
Bromohenzenedisulphonamide, C6H3Br(S02.NH2)2, formed by the
action of ammonia on the chloride, forms slender silky needles
(m.p. 210^). G. T. A.
Synthesis of Phenylnaphthalene. By W. Smith (Ber., 12,
2<)49 — 2053). — The "author has recently shown that when a mixture
of broraobenzene and naphthalene is passed throuo^h a red-hot tube
containing pumice stone, phenylnaphthalene, Ci„H7Ph, dinaplithyl,
and diphenyl are formed. An increased yield of phenylnaphthalene is
effected by distillinc the crude product, and again passing the first
portion of the distillate mixed with a fresh portion of naphthalene
througli the red-hot tnbe.
The new hydrocarbon crystallises in colourless transparent scales
(m. p. 95° corr.), and probably has the constitution
Action of Iodine on Oil of Turpentine. By H. E. Armstrong
B'jr., 12, 175l> — 1759). — When turpentine oil is heated in a retort
with one-fourth its weight of iodine, no apparent chano-e takes place
nntil half the liquid has distilled over : at this stage hydriodic acid and
iodine vapours are given off. The distillate is now poured back into
the retort, and the distillation continued. These operations are
repeated until iodine vapours are evolved as soon as the distillation is
commenced ; the product is then distilled in a current of steam. The
residue consists of colophene ; the chief portion of the distillate boils
between 155 — 100°, 175 — 180°, and at 170"; it contains cymene and a
mixture of two hydrocarbons of the composition CmHoo, one of which
boils at about 160°, and the other at about 170°. Cymene is the only
hydrocarbon of the benzene series which is produced by this reaction.
w. c. w.
Formation of Resin, and Chemistry of Ethereal Oils. By
iJKAGtXDOKFF (Arch. Pharm. [3], 15, 5U — 54). — Of the two theories
that have been proposed for the formation of resins, the author con-
siders that the oxidation theory is the correct one. It was found that
the oil of Pinus pumilio, when kept for a year in a flask, deposited a
crystalline resin having the composition CjoHaoOs ; it is hence inferred
that all resins are produced by the oxidation of hydrocarbons. The
presence of water does not appear to aid the formation of the resin.
Certain oils after they have been kept for some time will no longer
mix to a clear solution with excess of alcohol, although a small quan-
tity of alcohol produces no turbidity. This turbidity is due to the
precipitation of the resin which was dissolved in the oil.
This theory is opposed to experiments made by Godeffroy and Lie-
bermaun (Zeits. Oest. Apot., 15, 583), in which they foimd that oil
freshly prepared from green juniper berries, became turbid on addition
of alcohol. The author, however, found that oil of unripe juniper
berries, prepared by himself, did not become turbid ; he can, therefore,
account for the results of Godeffroy only by the supposition that the
oil from green junipers oxidises more rapidly than that prepared from
the ripe berries. E. W. P.
126 ABSTRACTS OF CHEMICAL PAPERS.
Action of Zinc-dust on Resins. By G. L. Ciamician (Gazzetfa,
9, 304 — 318). — The first two sections of this paper describing the
products obtained from abietic acid and from elemi-resin, have already
appeared in this Journal (Abst., 1878, 438, and 1879, 69). The third
ti-eats of the action of zinc-dust on gum ammoniac. The resin after
being separated from the gum by means of alcohol is distilled with
zinc-dust in a current of hydrogen, when it yields about 45 per cent,
of an oily liquid. By distilling this in a current of steam, and by
repeated fractional distillation, it may be separated into four por-
tions— one boiling at 136 — 138°, which, gives isophthalic and tere-
phthalic acids on oxidation, and is a mixture of meta- and para-
xylenes, CsHjo ; the second (b. p. 160°) is metametJiylethylbenzene,
CgHio ; the third, boiling at 190 — 192"", the methyl ether of orthoethyl-
pheiwl, CgHg.MeO, which when heated with hydriodic acid yields
methyl iodide and orthoethylphenol, CsHjoO. The phenol is oxidised
to salicylic acid by fusion with potash, and does not appear to be
identical with any of the known ethylphenols (comp. Annalen, 102,
166; 156, 211 and 251 ; 170, 345). The fourth fraction (b. p. 235)
is a homologue of benzene of the formula C13H20, and on oxidation
with chromic mixture yields acetic and propionic acids and a small
quantity of benzoic acid. C. E. G.
Formation of Complex Glucosides. By H. Schifb^ (J5er., 12,
2032 — 2U35). — Metamidobenzoic acid dissolves in a warm aqueous
solution of heliciu. On evaporating the liquid, a transparent, fluo-
rescent, glass-like substance remains, which can be obtained in colour-
less plates (m. p. 142°) by recrystallisation from alcohol. This com-
pound has the composition CijHigOv.CvHtNOo, or
CHO.(CH.OH),CH2.0.C6H4.CH(OH).NH.C6H4.COOH.
By boiling with acids it is decomposed into glucose, an amido-acid, and
an aldehydeijhenol. Similar crystalline compounds are formed when
the hydrochlorides of amidocinnamic and amidosalicylic (1:2:3 and
1:2:5) acids are added to a solution of helicin in dilute soda. They
are purified by recrystallisation from alcohol, and have the composition
C13H16O7.C1UH13NO0 and Ci^H.bOt.CHvNOs respectively.
Unstable substances having the general formula
CHO.(CH.OH)i.CH...O.C6H4(OH).S02.0.NH,.C.H,«.COaH,
are obtained by dissolving helicin in an aqueous solution of amido-
benzoic acid, glycocine, leucine, &c., saturating with sulphurous oxide,
and evaporating the liquid over sulphuric acid.
These compounds slowly lose a portion of their sulphui'ous oxide
at the ordinary temperature; they resemble the compounds of the
aldehydes with acid potassium sulphite in their behaviour with dilute
acids. W. C, W.
Economical Process for Preparing Bibasic Quinine Citrate.
By F. DoTTO-SCKlBANi (Guzzettu, 9, 2to — 285). — Two processes are
ORGAxVIC CHEMISTRY. 127
at present employed for the preparation of quinine citrate, either by
dissolving quinine in boiling water by the aid of citric acid, or by
adding the requisite quantity of sodium citrate solution to quinine
sulphate dissolved in 40 parts of boiling water. On cooling, quinine
citrate crystallises out. The author finds it much more economical
first to prepare calcium citrate by neutralising boiling lemon-juice with
lime, washing the precipitate with boiling water, and, after drying,
decomposing it with quinine sulphate. For this purpose 100 grams
of quinine sulphate are dissolved in 3 litres of boiHng water previously
acidified with 3'669 grams sulphuric acid, 32"685 grafcis of the dry
calcium citrate are added, and the whole boiled for half an hour. On
cooling, the clear solution deposits quinine citrate in tufts of needles,
which may be purified by recrystallisation. The mother-liquors yield
a further quantity of the citrate on evaporation. C. E. G.
Piperidine. By R. Schiff (Gazzetta, 9, 333—335). — Considering
the supposition that piperidine is a methylcrotonylamine as the most
simple, the author determined to make attempts to reduce it, in hopes
of obtaining normal methylbutylamine, but not succeeding, he then
tried the reduction of a bromine derivative. He found that acetyl-
piperidine in chloroform solution absorbed a molecule of bromine with
avidity, but no crystalline compound could be obtained from it, neither
did the action of reducing agents lead to any satisfactory result. He
then j>ve^?ivedi phthahjJpq')eride, C6H4(CO.NC5Hio)2, by the evaporation
of an alcoholic solution of piperidine (2mols.) and phthalic anhydride
(1 mol.). It forms large transparent crystals which readily unite with
bromine, producing the compound C6H4(CO.NC5Hio)2Br4 ; this crys-
tallises in long colourless needles, very soluble in water or alcohol, but
insoluble in ether. When treated with potash, it does not yield mono-
bromopiperidine as might be expected, but all the bromine is removed,
and the original compound is regenerated : silver oxide acts in a
similar manner. From this it would seem improbable that the double
bond in piperidine exists between two cai'bon atoms, but rather that it
is between a carbon atom and a nitrojjen atom. C. E. G.
o
Alkaloids of " Alstonia Constricta." By Oberlin and Schlag-
DENHAUKFEN (Fharm. J. Trans. [3], 10, lOoO— 1060). — The bark was
exhausted successively with ether, alcohol, and water, which took up
1'038, 27"740, and 1"375 per cent, respectively, but no examination
was made of the alcoholic or aqueous extract. The orange-coloured
residue left on evaporation of the ethereal extract was taken up with
dilute hydrochloric acid (1 : 200), treated with animal charcoal, and
precipitated with ammonia. The dried precipitate was then exhausted
with ether, evaporated, taken up with dilute acid, and reprecipitated,
repeating these operations until all colouring matter was removed.
It was finally obtained in silky tufts of lustrous needles by recrystalli-
sation from ether. It is .soluble in ether, alcohol, chloroform, benzene,
acetone, and light petroleum, moderately soluble in boiling water, but
insoluble in the cold. It dissolves readily in dilute acids, and is pre-
cipitated by the same reagents as the other alkaloids. It is easily
soluble in concentrated sulphuric, nitric, or hydrochloric acids, without
128 ABSTRACTS OF CHEMICAL PAPERS.
any perceptible coloration, but on diluting these solubions with, water,
a beautiful blue fluorescence is produced. Concentrated sulphuric
acid and potassium dichromate colour the crystals of an intense blue-
green, passing to violet and then to purple ; on adding water a crimson
solution is obtained.
The ethereal mother-liquors from which the alstonine had crystal-
lised left an amorphous alkaloid on evaporation, which the authors
propose to call alstonicine. It resembles alstonine in many points, but
is only sparingly soluble in boiling water. It dissolves in concentrated
sulphuric and* hydrochloric acids with a greenish-brown tint; whilst
with nitric acid it gives a splendid crimson-red. The acid solutions of
the amorphous alkaloid do not exhibit fluorescence. The authors are
of opinion that alstonine and alstonicine may possibly be related in
the same way that quinine and quinicine are. C, E. G.
Satureja Juliana. By P. Spica (Gazzetta, 9, 285— 289).— This
plant, called " erva de ibh'isi " in the Sicilian dialect, is used by the
])easantry to prepare a decoction which is taken in cases of intermit-
tent fever : it is an herbaceous plant of the labiate order, having an
aromatic odour, and somewhat pungent taste. In order to ascertain
to what the active properties of the plant were due, the residue left
on evaporating the alcoholic extract of the plant was washed with cold
alcohol to free it as much as possible from chlorophyll, then dissolved
in boiling alcohol, pi*ecipitated with an alcoholic solution of lead
acetate, and filtered boiling. After separating the excess of lead by
adding ammonia carbonate to the clear liquid, it was concentrated
and precipitated with water. The substance was further purified by
treating its alcoholic solution with animal charcoal and again pre-
cipitating with water. The white gelatinous product was separated
by means of ether into two compounds, one of which, moderately
soluble in ether (m. p. 204 — 205°), gave numbers agreeing with the
formula C34H5SO4, or, with less probability, CgHigO. The other sub-
stance, which is much less soluble in ether, especially in the cold,
does not melt even at 250°, and above that temperature it is decom-
posed ; the results of the analysis agree with the formula C35H56O4.
The more soluble substance acquires a greenish-yellow tinge when
boiled with dilute sulphuric acid, but otherwise remains unchanged :
a minute quantity dissolves, but the solution does not reduce Fehling's
test, although when evaporated at 100° it blackens and emits an odour
between that of wax and caramel. This is only a preliminary notice,
the author intending to examine the plant more carefully as soon as
he can obtain a sufticient quantity. C. E. G.
Carica Papaya and Papayatin. By J. Peckolt (Pharm. J.
Trans. [3], 10, 343—346, and 383— 386).— The author gives a detailed
description of the Carica papaya, or papaw tree, its growth and cul-
tivation. The trees are dioecious and hermaphrodite ; the herma-
phrodite variety is called Mamao macho (male mamao), the fruit
bearing variety Mamao femea (female mamao) , and a cultivated variety
of the latter Mainoo melao (papaw-beariug mamao).
Fruit. — The fruit is gathered in the full-grown but unripe condi-
ORGANIC CHEMISTRY. 129'
tion, when it contains a considerable quantity of a milky juice, which
disappears almost entirely on ripening, and in the " mamao macho"^ is
found a caoutchouc-liko substance; in the "mamao femoa," a soft
yellow resin; and in the "mamao melao," a dark reddish-yellow
fatty oU ; these substances doubtless originated from the milky juice.
The ripe fruit contained no free acid. The analyses of the fresh fruit
of the three varieties freed from acid gave the following numbers : —
Mamao Mamao Mamao
feniea. melao. macho.
Caoutchouc-like substance — — 0"04G
Soft yellow resin 0165 — —
Reddisb-vellow fat — 0020 —
Albuminoids I'O/O O'oOO 0-73.>
Sugar :1288 3-580 4-333.
Pectinous matter 1-315"^
Tartaric acidi , • ^ -.i 0075 I
Citric acid I combined with ^.^,^^ ^^ ^,^^ 2-332
Malic acid J ^^^^^ 0-083 |
Dextrin, &c 5-503J
Water 85-351 92-500 89-445
Cellulose 3180 2-920 5-091
The fresh fruit of the " mamao femea" gave 1-239 per cent, of ash,
and the dried fruit, 8-457 per cent. It contains a large amount of
soda, potash, and phosphoric acid.
Seeds. — The examination of the seeds is not yet completed, but a de-
tailed account of the method of analysis is given. They are found to
contain: — An oil,. Pupmja oil; Garicin, an oil- like substance, with a
disagreeable taste and smell, soluble in ether and alcohol ; an acid
similar to palmitic acid, Carica fat acid;, a crystalline acid, P(//:>a?//c
acid, insoluble in cold water, but soluble in hot water and alcohol ; a
resin acid having an irritating and bitter taste, insoluble in water and
ether, soluble in alcohol and alkalis ; and a soft resin similar to that
found in the fruit flesh of the " mamao femea."
Mill-;/ Juice. — This juice occurs in all parts of the plant, but in quan-
tity only in the unripe fruit. It is extracted with difficulty, the method
beinof to make longitudinal incisions through the skin of the srowina"
fruit, and as soon as one wound ceases to yield any juice, another is
made ; the gathered fruit yields only a few drops of juice. The milk
resembles sheep's milk, has a strongly acid reaction, and gelatinises
when mixed with three times its volume of water; it is without smell,
and its taste is astringent and bitter: its sp. gr. = 1-023 at 20°.
Analyses of the milk were made in various ways.
(I.) The milk was repeatedly shaken with ether until nothing more
was extracted. The ethereal solution, on evaporation, left a residue of
wax, Mamao icax. The residue, insoluble in ether, was treated with
alcohol, which extracted a resin, and the insoluble portion was treated
with water and filtered; a caoutchouc-like substance remained on the
filter ; the filtrate was treated with absolute alcohol, when a white pre-
cipitate of paioayotin was thrown down, which, when dried over cal-
VOL. xxxvin. k
130 ABSTRACTS OF CHEMICAL PAPERS.
cium chloride, formed an amorplious powder. The aleoliolic filtrate
contained a small quantity of extractive matter ; 7"845 per cent, of
papayotin was obtained liy this method.
(II.) A quantity of the milk was evaporated to dryness, and the
mass exhausted successively with ether, alcohol, and rectified spirit ; the
insoluble residue was dissolved in water, and alcohol added to the
solution, when a light-brown precipitate separated out oi para2:)apayotvii
(5'3o8 per cent.), a substance formed by the decomposition of papayotin
by heat.
(III.) The milk was mixed with four times its volume of water, fil-
tered from insohible matter, and the filtrate treated with absolute
alcohol. The precipitate was dried over calcium chloride, and con-
sisted of snow-white papayotin to the amoimt of 3"762 per cent.
(IV.) The milk was exhausted repeatedly with warm water ; the
aqueous extracts concentrated, filtered, and precipitated with absolute
alcohol ; 4'304 per cent, of papayotin of a greyish colour was obtained.
(V.) The aqueous extracts of the milk were treated with lead
acetate, the precipitates decomposed with sulphuretted hydrogen, and
the filtered solution treated with absolute alcohol, in one case without
and in another after concentration. A diflFerence in the colour of the
two products was all that was noticed.
MilJc frnm the Stem. — The stem yields but a small quantity of milk,
which had more the consistency of cream than that from the fruit. It
contains o'OOl per cent, of snow-white papayotin.
Green Leaves. — The leaves yield 33 per cent, of a green juice, which
is treated with absolute alcohol and filtered ; the residue washed free
from chlorophyll, and exhausted with water ; the solution which con-
tains impure papayotin is pi*ecipitated with basic lead acetate, and
the precipitate treated as in No. V. A yield of '117 per cent, is
obtaiDcd.
In the preparation of papayotin, strong heat should be avoided, to
obtain an active product of a white colour. The best papayotin is
obtained by method I or III, or from the stem ; the most advan-
tageous source, however, is the leaves, notwithstanding the small
yield, since they can be obtained in large quantities. Papayotin is an
amorphous, snow-white, non-hygroscopic powder, without smell, but
with a slightly sw^eet, saline, astringent taste. It is insoluble in ether,
alcohol, chloroform, aud petroleum spirit, but soluble in glycerol and
in water, nitric acid, and hydrochloric acid. Sulphuric acid colours
it yellow ; potash and soda colour it brown, and ammonia, yellow.
An aqueous solution gave the followin<j reactions : — White precipitates
with alcohol, lead acetate, mercuric chloride, tannic acid, and sodium
carbonate ; with silver nitrate, a white turbidity, which, on standing,
forms a deep yellow precipitate and a brown solution ; iodine solu-
tion, a light-brown precipitate ; ferric chloride, slight yellow preci-
pitate ; with phosphoric acid, on standing, a white precipitate; Avith
Trommer's sugar-test, a beautiful violet-blue, which, after boiling,
became red-violet.
Papayotin readily dissolves roasted meat ; "28 gram dissolved
•2 gi-am meat in 10 minutes. Parapayotin has no action on cooked
meat, even when heat is applied. Papayotin coagulates milk very
ORGANIC CnEmSTRY. 131
rapidly, as do tliose milk-juices of other Brazilian plants which have
au acid reaction.
The fruit of the Curica papaya is used as a food, and the syrup
formed by boiling the juice of the ripe fruit with sugar as a sedative
and expectorant. The milky juice taken internally causes intestinal
inflammation, but in small doses is given as a vermifuge, as are also
the seeds. It is also used as a wash for the skin.
The.se results confirm those of Wittraack and Roy.
L. T. O'S.
Lithofellic Acid a,nd some Lithofellates. By G. Roster
(^Gazzetla, 9, oG-4 — o'Jo). — The hnely-powdered oriental bezoar is ex-
tracted with boiling alcohol, and the filtered solution allowed to eva-
porate spontaneously, when it deposits the impure lithofellic acid in
crystalline crusts. This, after recrystallisation, is converted into the
sodium salt by neutralising the alcoliolic solution with sodium carbo-
nate, evaporating to dryness, and extracting the sodiuna lithofellate
from the residue by treatment with boiling absolute alcohol. The
sodium salt is converted into the corresponding barium .«;alt by decom-
posing it in aqueous solution, with a slight excess of barium chloride,
and may then be purified by recrystallisation.
Barium lithofellate, C4oH7oBa0^.10HoO, may be obtained from its
aqueous solution in very perfect prismatic crystals, as much as 4 cm.
long ; they have many lateral faces, and are terminated by rhnm-
bohedral summits. The measurements show that they do not differ
much from the rhombohedric system. The crystals (ra. p. 185°) con-
tain 10 mols. of water of crystallisation, of which they readily lose 4
in a dry atmosphere, and the remainder at 150^. The salt is very
soluble in boiling water and in alcohol. Its rotatoi-y power in aqeuous
solution, as determined with a Wild's polaristrobometer, is [ajo =
+ 19'68°, at a temperature of 15°.
Lithofellic acid, Ca,H3604.H20, is easily prepared from the barium
salt by precipitating it in dilute solution with hydi^ochloric acid, and
washing the precipitate with boiling water until the washings no
longer give a precipitate with silver nitrate. Prepared in this way, it
is a white crystalline powder (m. p. 205°, corr.), which may be obtained
in distinct crystals from its alcoholic solution. The general appearance
of these crystals is that of a hexagonal prism ; but accurate measure-
ments show that they are more complicated, and that they do not
belong to the rhombohedric system, as stated by Hoppe-Seyler, but to
the clinorhombic. The specific rotatory power of the acid in alcoholic
solution is [a]D = + 13'76^, as determined with a "Wild's polaristro-
bometer.
Sodium lithofellate, obtained by neutralising pure lithofellic acid
with sodium carbonate and evaporating the aqueous solution, forms a
gummy transparent mass, of pale yellow colour. It is exceedingly
soluble both in water and in alcohol ; its solutions have a very bitter
taste. Its concentrated alcoholic solution, on cooling, deposits the
sodium salt in microscopic crystals, consisting of stellate sfi'oups of
slender needles. Its rotatory power at a temperature of 14"5° is [a]D=
-I- 18T6°.
In recrystallising the crude precipitated barium lithofellate, a I'esi-
k 2
132 ABSTRACTS OF CHEMICAL PAPERS.
noicl substance remains behind, apparently the bai'ium salt of a new
acid, but whicb the author has not as yet investigated.
The author considers that although lithofellic acid differs from the
bile acids, and especially from cholalic acid in its crystalline form, in
its behaviour with acids and with alkalis, and in its action on polarised
lio-ht, it shouhl yet be classed with them, considering the ratio of the
carbon and hydi'ogen, its dextroratory action, and its behaviour with
Pettenkofer's reagent. C. E. G.
Diastase. By U. Baswitz (Ber., 12, 1827— 1831).— The author
previously stated (Ber., 11, 1443, aiad this Journal, 1878, Abst. 903)
that the presence of carbonic acid is favoui-able to the conversion of
starch into sugar by diastase. He now finds that diastase acts on
some specimens of commercial starch equally well in the absence of
carbonic acid.
Potato-paste, rye meal, and barley extract contain a body which
enables the diastase to convert the starch into sugar without the pre-
sence of carbonic acid.
The action of diastase on starch is not affected by increased or
diminished pressure. The most favourable temperature is about 50° :
above 60°, very little sugar is formed, the ferment being destroyed ;
whilst below 45° the formation of sugar takes place but slowly, although
the maximum amount will be formed if the experiment is carried on
for a sufficient length of time.
The quantity of sugar formed increases when the amount of diastase
used is increased, but the increase is not. proportional to the addi-
tional diastase. W. C. W.
Chemistry of Vegetable Physiology and Agriculture.
Fermentation accompanied by formation of Hydrogen
Sulphide. By P. Miquel {BhU. Soc. Chi,u. [2], 32, 127— lo8).—
A peculiar organism, existing in sewage watei*, has the power of con-
verting not only combined, but even free sulphur into hydrogen sul-
phide. When placed in water containing solid albumin, this ferment
causes the sulphur to be evolved in combination with hydrogen, until
the amount of gas has increased to 60 — 7o c.c. per litre of liquid. The
organism then dies. But if the solution be made alkaline with ammo-
nia, soda, potash, or lime, about twice as much hydrogen sulphide is
produced, before the ferment ceases to act. The sulphur contained in
india-rubber is also evolved by this organism, and if the hydrogen sul-
phide be prevented from accumulating in the liquid, which can be
accomplished by passing a current of carbonic anhydride through it,
the evolution goes on as long as sulphur is present. A litre of water,
to which had been added sulpliur, 4 per cent, of normal urine, and a
trace of the ferment, evolved 0'236 gram of sulphur combined with
hydrogen in two days. To the naked eye, solutions undergoing this
fermentation are almost limpid ; the ferment, seen under the microscope,
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 133
forms elonfjated or circular cells of less tlian a thousandth of a milli-
meter in thickness. It is capable of existing in media free from
oxygen. W. R.
Bacillus Urese. By P. Miquel (Bull. Soc. Chim. [2], 32, 126—127).
— This ferment, which exists in sewage, belongs to the class named
Aiuvruhies by Pasteur; it resists expo.sure for some hours to a tempera-
ture of 95 — 96°, and causes urea to disappear from urine. It also
removes urea rapidly from a solution of pure urea to which a little
gelatin has been added. "W. R.
Researches on the Bleeding of Vines. By E. Rotondi and
A. GnizzoM {Bled. Centr., Ib79, 527 — 53U). — After giving the results
of his analyses of the sap of vines cut in April and Maj^, the fir.st
named author remarks that on the average a litre of vine-sap contains
0"147 gram of solids, and 0"052 gram of ash, the red sorts yield-
ing, however, more solids than the white ; the time of cutting does not
seem to have any influence on the quantity of phosphoric acid and
potash contained in the sap. Ghizzoni's investigations lead him to the
additional conclusion that sap taken from a lower part of the plant
contains more mineral and less organic matter than that taken from
upper parts. J. K. C.
Composition of the Kernels and Husks of the Seed of
" Gleditschia Glabra." By J. Moser {BieA. Cent,:, 1879, 388).—
The author obtained the following results : —
Non-
nitrogenous
Water. Protein. Pat. extract. Fibre. Ash. Sand.
Kernels.. 10-90 20-94 2-96 51-68 10-66 2-77 009
Husks .. 1-24 4-54 3-67 60-70 19-80 300 0-05
After boiling with dilute sulphuric acid, it was found that 41-4 per
cent, of the kernels had been converted into dextrose.
Tannic acid was found to be present in the husks to the extent of
'J-'? per cent. J. K. C.
Ash of Different Parts of the Vine. By E. Rotoxoi {Bled.
Centr., 1879, 530 — 532). — The following briefly noticed investigations
of the mineral constituents of the must, branches, and leaves of the
vine relate to the products of two vine hills in the neighbourhood of
Asti, on each of which were planted three kinds. The author gives the
results of his analyses in tabular form, and infers from them that the
composition of the ash varies with the locality rather than with the
sort of vine ; potash is found in greatest quantity in the ash of the
must (60 to 70 per cent.), and in the least (6 per cent.) in that of the
leaves, the latter also being poorest in phosphoric acid, and very rich
in lime and silica. Soda is absent in all the samples analysed.
J. K. C.
Agricultural Chemistry in Japan. By E. Kixch (Chem. Neios,
40, 195, lV6). — This is a short account of the collection of soils,
134 ABSTRACTS OF CHEMICAL PAPERS.
manures, and agricultural products, shown by the Imperial College of
Agriculture, Japan, at the International Exhibition, at Sydney.
Accompanjing the collection is a report containing analyses of the
greater number of the products, from which Mr. R. Warington has
selected those of the principal foods, such as rice, soy beans, sweet
potato, large radish, sea-weeds, tea, and saki. The last, a fermented
liquor prepared from rice (tliis Journal, 1879, Abst., 413), contains from
ll'3o to 15'0 per cent, of alcohol, and the free acid, reckoned as acetic
acid, amounts to 0'20 to 0'27 per cent. Besides these, the report
contains analyses of manures, including lime, wood-ashes, nitre, waste
vegetable substances, and residue from various manufactures, fish
manure, bone superphosphates, excrement of birds, and hair. There
is also a summary of the principal dye-stuffs and their methods of pre-
paration, and the analyses of the most important. The different oils
and waxes form the concluding section of the catalogue.
L. T. O'S.
Method of Selecting Beet for Seeding. By D. Ibled {Bied.
Centr., 1679, 5o5 — 5oG). — This is usually done by taking the specific
gravity of the whole root ; but on account of the difficulties connected
with this plan, the author suggests that pieces be cut out of the root,
about one third from the top ; these do not differ greatly in specific
gravity from the rest of the root, and should be placed in a bath of
salt of 105'^, only those roots the cuttings from which sink being used
for seed. J. K. C.
Relation of the Colour of Clover Seed to its Value. By
G. Haberlandt (Bled. Ceidr., 1879, 532 — 534). — The autiior divides
clover seed into two groups, the one comprising the yellow and violet
being more valuable and less altered by keeping than the other group,
in which he includes the brown and gray seeds. J. K. C
Absorptive Power of Soil-constituents for Gases. By G.
Ammon {Bled. Centr., 1879, 511 — 515). — The substances used in these
experiments were sand, aluminium silicate, calcium carbonate, hy-
drated oxide of iron, gypsum, clay, and humus, all powdered to various
degrees of fineness. The author tried the effect of aqueous vapour
and ammonia on these substances at various temperatures ; his experi-
ments showing that the most favourable temperature for absorption
lay between 0° and 10", and that the quantity absorbed varied directly
with the fineness to which the substance had been powdered. The
following are the numbers obtained, 100 c.c. of each substance being
used, and the water being calculated by volume in the state of gas : —
Cubic centimetres of water-vripoiir condenser! bv
J
Hvclrateil
Calcium
\
At
Humus.
ii-ou oxide.
Quartz.
carbonate.
Kaolin.
10" C-
12717
12973
2026
208
5378
0
14206
47332
2198
4258
5375
10
36504
99712
1185
4775
6447
20
26789
98990
277
962
1541
30
16497
54753
99
233
1335
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 135
Of ammonia gas at 0° C. the following quantities were absorbed : —
By bytlrated Bv carbonate
By hiiraus. iron oxide. By quartz. of lime. By taolin.
29517 38992 938 1552 '2447
Part of the ammonia was converted into nitric acid by tlie oxide of
iron. Carbonic anhydride was absorbed in very small quantity, except
in the case of hvdrated oxide of iron, from which the o^as could not
be expelled by air, as was the case ia the other materials employed.
By treating the soil-constituents with marsh-gas, einpyreumatic
substances were formed which prevented the experiments in this direc-
tion being completed. The condensation was greatest in the case of
hydrated oxide of iron. Treatment with sulphuretted hydrogen was
fi;llowed by a separation of sulphur in the case of all the substances
employed: the greatest increase in weight was observed, in gypsum.
Oxygen was not absorbed by quartz^ carbonate of lime, or kaolin :
humus even lost in weight by exposure to the gas; 100 c.c. of gypsum
absorbed 1189, and lOO c.c. hydrated oxide of iron absorbed t)t35 c.c.
of oxygen. The condensation power for nitrogen was greater, as is
shown by the following numbers : —
100 c.c. of
' ' ^
Hydrated Carbonate
Humus, iron oxide. Sand. of linie. Kaolin. Gypsum.
,. . \ 126 23986 24 3303 813 10253
ot nitroiren j
Absorbed c.c.
o
In this case also nitric acid was found in the aqueous extract from
the hydrated oxide of iron.
To show the influence of oxide of iron on the absorption of nitrogen
by the soil, the author made the following determinations, in which
ferruginous sand and clay, and the same substances freed from iron by
hydrochloric acid, are compared in their absorptive power for nitro-
gen :-
100 c.c. of sand 100 c.c. of kaolin
Containing iron. Pure. Containing iron. Pure.
Absorbed.. 217 101 1687 816 c.c. of nitrogen.
J. K. C.
Experiments on the Manuring of Barley. By P.. Wagner and
AV. RuHN (i>/'j'/. L'e////-., 1879, 515—519). — The soil in which the.se
experiments were carried out was a sand containing 1^ per cent, of
liumus, the phosphate being applied in the following exiperiments one
dav before, and tlie nitrogen (in the form of Chili saltpetre) the day
after sowing. The following table shows the quantities of manure
applied per hectare and the yield obtained : —
Corn. Straw.
Kilos. Kilos.
(1.) Unmanured 4120 3770
(2.) 20 kilos, nitrogen 5280 4890
(3.) 50 kilos, soluble phosphoric acid 4570 4490
136 ABSTRACTS OP CHEMICAL PAPERS.
Corn. Straw.
Kilos. Kilos.
(4.) 50 kilos, soluble ])liosplioric acid with
20 kilos. Bitroc^en 5320 4920
(5.) 60 kilos, pliosplioric acid in the form
of freshly pi-ecipitated calcium phos-
phate, and 20 kilos, nitrogen 5600 5110
(G.) 50 kilos, soluble, with 43 kilos, insoluble
phosphoric acid in form of phospho-
rite, with 20 kilos, nitrogen 5970 5370
(7.) 35 kilos, soluble, and 30 kilos, insoluble
phosphoric acid as above, with 20
kilos, of nitrogen . , . . 56G0 5350
(8.) 50 kilos, soluble phosphoric acid in the
form of phosphate of potash, with
20 kilos, nitrogen , . . . 6170 6500
It is 'evident from the above that although the soluble phosphoric
acid yielded poor results, the use of saltpetre proved very advantageous.
The reason of this may be looked for in the fact that the soil was so
very poor i)i lime as not to be able to arrest the phosphoric acid during
its percolation through the soil after rains, thus only a small quantity
of it came into actual contact with the roots of the barley. This was
of course different in the cases of experiments (5), (6), and (7), where
part at least of the phosphoric acid was applied in the insoluble form,
and larger yields were the result. With regard to experiment (8),
the authoi-s do not explain whethei-'the remarkable yield obtained was
the result of the way in which the phosphoric acid "was combined, or
of the presence of potash. J. K. C.
Manuring Experiments with Oats. By C. Jenssen (Bled.
Centr., 1879, 519 — 523). — A field was marked off into eleven plots of
975 square metres each ; of these two were not manured, the remain-
ing nine being treated with quantities of manure of various sorts
equal in value commercially. The table following shows the various
naanures used and the resulting produce :■ —
•Quantity Yield in
Chili saltpetre . ■• . ■. . ...... .
Unmanui'ed .
Bone meal
Bone meal superphosphate . .
Ammoniacal superphosphate
Peru guano
Unman\ii-ed
Bone guano superphosphate
Animal manure
Stable dung
Mejillon guano superphosphate
a.pplied
per hectare.
Grain.
Straw.
CliafT.
Kilos.
Kilos.
Kilos.
Kilos.
19
201
268
29
151
190
18
25
181
227
21
25
178
216
21
177
199
20
16
181
209
17
—
168
194
16
31
194
242
17
17-5
172
213
18
1100
194
233
23
: 29-5
170
200
14
AXALYTICy:, CHEMISTRY. 137
The above tables show that Chili saltpetre, and next to it stable
dung and bone guano superphosphate, produced the best yields. Fur-
ther researches are necessary to establish any conclusions from the
above results. J. K. C
Manuring of Beetroot. By 0. Vibrans (Bled. Centr., 1879,
520 j. — The object of these investigations was to ascertain the value of
the potash contained in molasses lees and charcoal residues as a
manure. The action of several other well-known manures was tried,
with results not differing much from the ordinary. From his experi-
ments the author draws the conclusion that the potash of the charcoal
residues is in a form which can be more readily absorbed by the beet
than the potash of the lees. J. K. C.
Manuring of Beetroot. By H. Bodenbender (Bled. Centr., 1879,
623 — •52-i). — Samples of the sugar-beet taken from plots of land to
wliich various manures had been applied, were tested for sugar at
different periods of their growth. The seeds were sown on the 9th
of May, and from the 1st of August to the 14th of September the
plants were subjected to quantitative investigation. On the results
of his researches the author makes the following remarks : — Nitrogen
when applied as manure in the form of Chili saltpetre, delays the
ripening of the root to a considerable extent, and lessens the per-
centage of sugar, although the yield by weight of the root is much
increased. Phosphoric acid and guano give very favourable results
as regards the percentage of sugar in the yield. J. K. C.
Analytical Chemistry,
Apparatus for Estimating Oxygen in the Atmosphere. By
F. Fischer {Ber., 12, 1696 — 1698). — The oxygen in the atmosphere
is determined by measuring the diminution in volume which takes
place when a copper spiral is heated to redness, by means of a galvanic
current in a known volume of air. A description of the apparatus
and full details of the process employed are given in the orisjfinal
paper. ' ^y. C. W.
Quantitative Estimation of Oxygen dissolved in Water. By
F. TiE.MAXX and C. Pei'lsse (Ber., 12, 176« — 1789). — The authors
have examined three methods of determinincc the amount of oxvffen
dissolved m water, viz. : —
1. Mohr's volumetric process {^Tohr's titrirmetlwde) in which soda
and a standard solution of ferrous sulphate are added to 500 c.c. of the
water, which must be heated to 40° ; after an interval of half an hour
the precipitated ferrous hydroxide is dissolved in sulphuric acid, and
the unoxidised ferrous salt determined by titration with potassium per-
138 ABSTRACTS OF CHEMICAL PAPERS.
raanganate. From the amount of ferrous sulphate oxidised by the
water, the quantity of oxyG^en is easily calculated. The results obtained
by this method are invariably too low.
2. Gasomefric Method. — In order to expel the dissolved ^ases from
the water, a slightly modified form of Reichardt's apparatus (Zeits.
Anal. Chem., 11, 271, and this Journal, 26, 412) is employed. In pre-
sence of combustible gases, e.g., marsh-gas, the oxygen is determined
by absorption with potassium pyrogallol, but when the mixture con-
tains only oxygen, nitrogen, and carbonic anhydride, the latter is
removed by a solution of soda, and the oxygen estimated by explosion
with hydrogen. This method yields excellent results, but requires
complicated apparatus. In certain cnses when the water is boiled to
expel the goses, there is a risk of a part of the oxygen not being
evolved, owing to its having oxidised some of the constituents of the
water.
3. The process of Schiitzenberger and Risler (Bull. Soe. CJtlm., 19,
153, and 20, 145) is very accurate, and seems to be the best adapted
for general use. In this method, the oxygen is determined by the
amount of iudio-o-white it converts into indigo-blue. Standard solu-
tions of ammoniacal copper sulphate, sodium hyposulphite, NaoSOo,
and indigo-carmine are required.
The standard copper solution is prepared by dissolving 4*469 grams
of CUSO4 + 6H2O in water, adding excess of ammonia, and diluting
to a litre with water free from air; 10 c.e. of this solution are equiva-
lent to 0'0014336 gi'am, or 1 c.e. oxygen at 0° and 760° mm. The
hyposulphite solution is prepared by treating with ainc-dust for
five minutes a solution of commercial sodium hydrogen sulphite,
which has been diluted to sp. gr. 1"25. The liquid is now mixed with
ten times its volume of boiled water, separated from the zinc-dust by
decantation, and ti-ansfei-red to stoppered bottles, milk of lime being
added until a slightly alkaline reaction is produced. The precipitated
zinc oxide is allowed to settle, and the supernatant liquid is rapidly
filtered. To standardise the hyposulphite, 10 or 25 c.e. of the standard
ammoniacal copper solution are brought into a Woulf's flask, from
which the air is displaced by a current of pui-e hydrogen. The hypo-
sulphite is added from a burette, the point of which passes through a
cork in the tubulus of the Woulf's bottle. The exact point when the
blue copper solution is completely decolorised by the hyposulphite is
easily observed. After this experiment, the h\-posu]phite is diluted
with water free from air until 5 c.e. are required to reduce 10 c.e. of
the copper solution.
The indigo solution is prepared by dissolving 100 grams of com-
mercial indigo carmine paste or commercial indigotin (sodium indigo
sulphate) in 2 litres of water. Its strength, which should equal that
of the ammoniacal copper solution, is determined by titration with
hyposulphite.
The apparatus required for the determination consists of a three-
necked Woulf's bottle, of J I litres capacity, which stands in an evapo-
rating basin, containing warm water. Each tubulus is provided with
a double-bored cork ; through the first pass a thermometer and a glass
tube, connected with an apjjaratus for generating pure hydrogen. The
axalytic^Mj chemistry. 139
second contains two drawn out pioces of glass tubinof, wliicli are
attached bv means of a caoutchouc tubing to the burettes containing
the standard hyposulphite and indigo solutions. The upper end of
the hyposulphite burette is provided with a tube containing pumice
stone soaked in potassium pyrogallate. A funnel fitted with a stop-
cock, and a glass tube bent twice at right angles, and dipping into
water, pass through the cork in the third tubulus.
About 250 c.c. of warm water free from air, and 30 — 40 c.c. of the
indigo solution, are brought into the flask, from which the air is
expelled by a current of hydrogen. The contents of the flask must be
kept at a temperature of 4-5° during the experiment. Standard hypo-
sulphite is added until the indigo is bleached. 250 c.c. of the water
to be examined are now brought into the flask through the tap funnel,
care being taken to prevent the admission of air. The mixture is well
.shaken, and hyposniphite added until the blue colour is destroyed.
From the c.c. of hyposulphite used, the quantity of oxygen may at once
be calculated, e.g., 4"2 c.c. hyposulphite are equivalent to 10 c.c. of the
standard copper solution =: 00014336 gram, or 1 c.c. oxygen.
2H-8
250 c.c. water required 7"2 c.c. hyposulphite, or 28'8 per litre, "—— =■
G'85 c.c. of oxygen at 0° and 7(50 mm. Three oxygen determinations
in succession may be made without changing the apparatus ; but since
the hyposulphite changes rapidly, its streng-th must be determined by
titration with ammoniacal copper solution every time the burette is
filled. W. C. ^Y.
Water Analysis. By A. Muller {ArcJi. Flmrm. [3], 15, 25 — 27).
— The residue obtained by evaporating the water is usually heated to
120 — 140'^. This temperature is insufficient to remove the crystal-
line water of magnesium and calcium sulphates, therefore the solid
matter is always reported too high. It is advisable therefore always
to add a known weight of sodium carbonate, and svibsequently to
neutralise after separation of the earths according to the process
described in Ber., 1870. E. W. P.
Estimation of Sulphur in Natural Sulphides. By A. Colsox
(Bull. »b'r/c. Chilli. [2j, 32, 115 — llGj. — The method described is par-
ticularly applicable to estimation of sulphur in pyrites. The sample
is placed in a platinum boat near the sealed end of a piece of combu.stion
tube, the other end of which is clo.sed wdth a double-bored india-rubber
cork. Through one of the holes a tube passes to the end of the com-
bnstion tube, and conveys oxygen to the sulphide, whilst the resulting
sulphurous anhydride escapes through the other tube into soda. The
sulphurous acid may be estimated by the io<line process, and the sul-
phuric acid by baryta, or if a standard solution of soda be used, the
portion remaining unneutralised may be estimated with standard
acid, and the total sulphur deduced by calculation. W. R.
Testing for Nitric Acid in Presence of Nitrous Acid. By A.
Piccixi (GazzMa, 9, o'Jo — o'Jt>). — This method is useful for detecting
140 ABSTEACTS OF CHEMICAL PAPERS.
minute quantities of nitrates in the presence of large quantities of
nitrites, and is founded on tlie property urea has of decomposing the
latter in acid solution. Urea is added to the solution containing the
nitrate, and it is then gradually added to another solution of urea in
dilate sulphuric acid. As soon as the evolution of nitrogen due to the
decomposition of the nitrites has ceased, some iodised starch is added,
and then a fragment of zinc, when a blue coloration is produced if any
nitrate is present. C. E. G.
Analysis of Superphosphates. By B. Wein, L. Rosch, and J.
LcHMAJiN (AmiuIen,lQ8, 'IVO — o07). — As advei'se criticisms have been
made against the process which was adopted at the Magdeburg Con-
ference in 1872 for the extraction of soluble phosphoric acid from
superphosphates, the authors have investigated the different points
objected to, and some of the methods which have been proposed to be
substituted for it. In their opinion the differences which frequently
arise in the analysis of superphosphates are to be attributed entirely
to a want of uniformity in preparing the aqueous solution, and not to
the method that may be employed for the determination of the
soluble phosphoric acid. The points investigated were as follows : —
a. Tlie time necessary for Digestion. — In the opinion of Abesser, Jani,
and Miircker {Zeits. Anal. Chem. 12, 231:'), a digestion of the super-
phosphate in water for a few minutes is sufficient, as by digestion for
a longer time more soluble phosphoric acid may be obtained than was
originally present as such, probably owing to the action of free sul-
phuric acid on the phosphate.
On the other hand, too low results are possible either from a trans-
formation of soluble monocalcium phosphate into insoluble dicalcium
]ihosphate, or, in the presence of oxides of iron and alumina from the
formation of insoluble phosphates of these bases.
With these statements the authors entirely disagree. Their experi-
ments prove that altho;igh in some cases a shorter time may suffice,
yet with all kinds of superphosphates, whether containing much or
little iron oxide and alumina, a digestion in cold water for two hours
gives the most accurate results.
h. The Extraction of the Soluhle Phosphoric Acid by Washing the
Superj)hosphate on a Filter tvhich is connected with a Bunsen^s Pump. —
This method has been recommended by Fresenius, Luck, and Neubauer
{Zeits. Anal. Chem., 7, 304) ; and by Miircker, who states that the re-
duction of the soluble phosphoric acid is thereby avoided. The
authors, however, obtained results from nine different kinds of super-
phosphates which were from "06 to ■825 p. c. too low, arising no doubt,
as explained by Erlenmeyer, from the decomposition on the filter of
the monocalcium phosphate owing to the absence of free phosphoric
acid. In the })resence of excess of free phosphoric acid, tliis process
was accurate, and this is believed to explain Fresenins's results,
Avhich were obtained with a superphosphate containing 5'85 p. c. free
phosphoric acid.
c. The quantity of Water which is necessary for Gomplete Extraction.
— With the exception of a slight increase in the amount of soluble
phosphoric acid from superphosphates containing much oxide of iron
AXALYTICAL CHEmSTRY. 141
and ahiniina, no advantage is gained by increasing the quantity of
water above that used in the Magdel)iirg process.
The authors' results, therefore, confirm the accuracy of the Magde-
burg metliod, which consists in digesting 20 grams of the superphos-
phate in a litre of cold water for two hours. A. J. C.
Superphosphates from Pure Tricalcium Phosphate. By E.
"Wkix (Annalcit, 198, oU7 — 318). — In order to ascertain the cause of
the ditJerence in the results obtained by the methods described in the
previous paper, similar experiments were made with calcium super-
phosphates which had been prepared by the action of sulphuric acid on
pure tricalcium phosphate in such a manner as to obtain superphos-
phates of three kinds, a, b, c.
The soluble phosphoric acid was in all cases determined by the
paolybdic acid method. The results are as follows : —
a. Suptrjjliosjjhatea wliich contain much Free Phosphoric Acid
(ir35 p. c). — A very short period of digestion in water is sufficient
to extract the whole of the soluble phosphoric acid. An increase in
the quantity of water (1000 c.c. for 20 grams) is unnecessary. Correct
results are obtained by washing the superphosphate on a filter-pump,
but the quantity of wash water required before the filtrate is free
from acid, that is, before the extraction is completed, is considerably
greater than 125 c.c. for five grams, as stated by Miircker.
b. Superphosphates containing only a Small Quantity of Free Phos-
phoric Acid ('05 p. c). — It is necessary to continue the digestion in
water for two hours to be certain that the extraction is completed.
Washing on a filter-pump gives results which are considerably too low
for the reasons stated in the previous paper.
c. Superphosphates %cith no Free Phosphoric Acid. — Digestion in water
for two hours is also necessary in this case : the filter-pump method
is wholly inapplicable.
If superphosphates, which contain mono- and di-calciura phosphates
but no free acid, are ti-eated with more than the usual quantity of
water, e.g., with 5 : 1000, then more soluble phosphoric acid is obtained
than when the same superphosphate is digested for two hours in the wav
recommended, that is 20 : lUOO. This result is due to the solubilitvof
the dicalcium phosphate. The opposite results obtained by Watten-
berg {J. fur Landiuirthst, 1879, 27 — 52) on this point are stated to be
due in all probalnlity to the presence of free phosphoric acid which
the author found could oidy be removed with great difficulty from a
mixture of mono- and di-calcium phosphates.
The decomposition of monocalcium phosphate which occurs accord-
ing to Erlenmeyer (Per., 9, 1839j when it is treated with a small
quantity of water is too trifling to affi^ct the results.
The conclusions therefore arrived at in the previous paper are con-
firmed. A. J. C.
Estimation and Separation of Manganese. By J. Volhard
(Annalen, 198, '616 — oGi). — The volumetric method proposed by
Guyard {Bull. Sac. Chim. [2], 1, 88) for the determination of mano-a-
nese in a manganous salt by titrating the neutral and very dilute
solution with a standard solution of potassium permanganate, has not
142 ABSTRACTS OF CIIE:i]ICAL PAPERS.
been found to give exact results on account of the precipitate which is
caused by the permanganate being always of an uncertain and variable
composition, and because of the extreme difficulty in ascertaining the
end of the reaction. Guyard stated that the whole of the manganese
was precipitated as Mn03.Mn207.
The author shows that if a salt of calcium, magnesium, barium or
zinc, be added to a solution of manganous salt, the whole of the man-
cranese is precipitated by potassium permanganate as dioxide ;* more-
over, the end of the reaction can be very readily observed, as the preci pi-
tate settles ra]:>idly and the supernatant liquid becomes quite clear. The
reaction occurs according to the equation, 3MnO + MuoOv = 5Mn02.
The salts of all strongly basic metallic oxides which are not sus-
ceptible of oxidation, have a similar action. Alkaline salts to a great
extent obscure the end of the reaction.
Prefatory to describing the modified process, the author's opinions
are expressed on several points moi-e or less connected with it.
Titration of the Solution uf rotossinm Pennmiganate. — Objections are
made against most of the usually adopted methods for standai'dising
this solution. The use of the double salt of iron and ammonium is
specially objected to on account of the difficulty of obtaining it free
from ferric salt.
Methods are described by Avhich it can be standardised by deter-
mininp' the manganese in it, either as sulphate or as oxide, Mn304.
In either case the permanganate is reduced by sulphurous or hydro-
chloric acid, and the manganese after precipitation by ammonium
carbonate is converted into sulphate, or into oxide by igniting the
chloride with mercuric oxide.
The mercuric oxide used for this purpose is prepared by precipita-
tion (with pure sodium hydrate) from the chloride which has been
sublimed from a mixture of the chloride with one-tenth its weight of
oxide; thus prepared, it can be similarly employed with great ad-
vantage for the conversion of most metallic chlorides into oxides ;
and to precipitate ferric or aluminic oxide, w^hen in solution as chlo-
ride, free from alkalis, but not from alkaline earths ; also to separate
ferric oxide completely from manganese.
To any of the methods above mentioned, the author prefers to stan-
dardise the permanganate solution by means of a solution of potassium
iodide in presence of hydrochloric acid, determining the liberated
iodine in the usual way with standard sodium thiosulphate and calcu-
lating the manganese from 80 mgrms. 0=3 X 55 := 165 mgrms. Mn.
The solution of permanganate must be free from chlorates, and the
water used in the process from nitrites. The solutions required are
potassium permanganate containing 3*833 grams per litre, 1 c.c. =
2 mgrms. Mn; sodium thiosulphate prepared by dissolving 30061 grams
wdth addition of 3 grams of ammonium carbonate in 1 litre of water,
1 c.c. = 2 mgrms. Mn, and a solution of potassium iodide approxi-
mately equivalent to 55 grams free hydriodic acid per litre.
* Kessler has previously vised zinc cliloride for the same purpose in precipitating
a manganous salt with bromine {Zeits. Anal. Chem., 1879, 1 — 14, and tliis Journal,
1879, 341, Abst.). Pat.tinson subsequently found that ferric cliloride had a similar
action (this Journal, 1879, 3G5, Trans.). — A. J. C.
ANALYTICAL CHE:\IISTRY. 143
Sej^aration of Iron from Man^janese. — Iron is the only metal wliicli,
if present in large quantity, hinders the determination of manganese
by this method. In preference to any other method, the author sepa-
rates the iron from manganese by precipitation with zinc oxide, which
can be prepared for this purpose by igniting ordinary zinc white and
levigfatino' it with water.
In the absence of iron or in the presence of a small quantity of it,
the process is as follows : —
The solution of manganous salt is mixed with about 1 gram of zinc
sulphate and diluted so that lUO c.c. does not contain more tlian
0'25 gram Mn, and if the solution is neutral 2 to 3 di'ops of nitric
acid (1"2 sp. gr.) are added; if acid, it is neutralised witli sodium
carbonate (free from sulphite) and nitric acid then added as before.
The solution is heated to boiUng, and the solution of permanganate
added nntil the colour remains permanent. Properly performed, the
titration occupies from twelve to fifteen minutes. A blank experi-
ment must be made with the solution of zinc sulphate.
Metallic alloys, wrought iron, and steel, are dissolved in a mixture
of 3 vols, of sulphuric acid (I'lo sp. gr.) and 1 vol. of nitric acid
(1'4 sp. gr.). Substances dissolved in hydrochloric acid are evaporated
to dryness with sulphuric acid, and then taken up with water. Spiegel-
eisen or ferromangauese is dissolved in nitric acid, the solution then
evaporated to dryness, and the residue heated until the nitrate is
decomposed and carbcmaceous matter is burnt off. The residue is
dissolved in hydrochloric acid, and this acid expelled with sulphuric
acid as before described. In all cases, the greater part of the acid is
neutralised with sodium carbonate or sodium hydrate (free from man-
ganese), then zinc oxide is added until the supei'natant liquid is milky,
showing that the whole of the iron has been pi^ecipitated.
The oxide of ii^on precipitate generally settles so rapidly that it is
unnecessaiy to filter, and a portion of the liquid can be taken oil with
a pipette and the manganese determined as befoi'e.
Separation of Manganese from other Metals in a Stronghj Acid Sola-
Hon. — Manganese is usually separated from other metals by precipita-
tion in a slightly acid or neutral solution by means of lead dioxide,
chlorine, or bromine. It has been found possible to do this in a
strongly nitric acid solution, with lead oxide as a precipitant, in a
manner which is described by the author ; but the method is not
recommended, and the following is considered preferable : — The solu-
tion of manganous compound is heated to boiling with strong nitric
acid and pure mercuric oxide. Chlorine or bromine water is adde'd
until the oxidation is completed, which is shown either by the solution
being red or becoming quite clear. In this manner, from a solution
containing 0"o gram pure manganous sulphate and lo — 20 c.c. nitric
acid (1'2 sp. gr.), and about 1 gram mercuric oxide, the manga.nese is
completely precipitated in 15 — 20 minutes. The precipitate is then
heated to redness to expel mercuric oxide, and can be weighed
either as oxide or as sulphate. If cobalt, nickel, zinc, calcium,
magnesium or potassium are present, the precipitate should be dis-
solved and repreeipitated.
Frecfjjitatiuit of Manganese hy Oxidising Agents. — The author dis-
144 ABSTRACTS OF CHEMICAL PAPERS.
cusses the formation of tlie precipitate which is produced when nn
oxidisinw' asrent is added to a solution of mancranous salt, and he
expresses the opinion that permanganic acid is most probably the
first result of the oxidation, and this combines with the mang-anous
oxide, so that the whole of the manganese is precipitated as dioxide
(" hyperoxide ").* In furtherance of this view, it is shown that either
permanganic acid or dioxide can be obtained as the result of the
oxidation ; in fact, Crum's test for manganese depends on producing
the one, viz., permanganic acid, in presence of nitric acid, leaving no
manganous oxide in solution, in which case the solution retains the
colour of permanganic acid.
Crum's test is best performed by heating almost to boiling 10 c.c.
of a solution made from equal parts of nitric acid (sp. gr. 1"2) and
water containing a little plumbic dioxide, then adding the dilute solu-
tion of manganese compound ; the coloration occurs immediately even
in presence of chlorides. It has been proposed to use Crum's test
for the quantitative determination of manganese, but it cannot be
used when the amount of manganese in solution exceeds 100 mgrms.,
as this appears to be the maximum that can be oxidised to permanganic
acid without precipitation of oxide.
Titration with potassium permanganate as above described is con-
sidered to be quite as delicate tor the detection of minute quantities
of manganese. A. J. C.
Experiments with Scheibler's Method of Analysing Raw
Sugar. By H. Wichelhaus, K. Eissfeld, and K. SiAjniER {Bied.
Cenir., 1879, 542). — Scheibler's method consists in boiling the raw
sugar with a saturated alcoholic solution of sugar, and weighing the
residue. After numerous experiments with various kinds of raw
suo-ai*, it was found that on the average Scheibler's method gave
fairly good results, no variation being greater than one and a half per
cent. J. K. C.
Estimation of Sugar in Beet Juice. By C. Bittman (Arch.
Phann. [3], 15, 63 — 69). — In the manufacture of sugar from sugar-
beet, there always appears to be a loss of sugar during the filtering
and concentration of the juice. This loss is, however, only apparent,
as the amount of sugar is estimated by the polariscope, and is con-
sequently affected by the presence in the raw juice of dextrin, arable
acid, and asparagin ; these being dextrorotatory cause the amount of
sugar to appear greater than it really is. The total amount of sugar
in the roots is sometimes deduced from the amount of sugar in the juice
as follows : — If the sugar in the juice amounts to say 12 per cent, and
the mark 5 per cent, of the roots, then the percentage of juice is 95
per cent., and the ])ercentag-e of sugar in the roots is 12 X 0'95 = 11"4.
This calculation takes for granted that the amount of sugar in the
whole of the juice coincides Avith that found in the sample, that is, that
the cells of the root contain a homogeneous liquid. This hypothesis the
* Wi'iglit and Luff (this Journal, 1878, 513) have shown that the precipitate
produced on adding bromine to maugauous chloride containing excess of caustic
soda, consists of dioxide mixed with a certain amount of lower oxide. — A. J. C.
TECHNICAL CHEmSTRY. 145
author combats, and quotes in corroboration Yicinskj, Heintz, and
Sclieibler, who state that every portion of the juice in the root must
not be considered as holding equal quantities of sugar in solution
that in the root there is water containing no sugar, and which must
be considered as water of organisation. The conclusion drawn is, that
the present method of determining the amount of sugar in sugar-beet
is very unsatisfactory. E. W. P.
Technical Chemistry.
Burning of Fuel in House Stoves. By F. Fischek (Dingl.
]''fili/t. J., 233, ioo — I'SiJ).- — During the 18 months previous to
January, 1879, 56 patents for house stoves were taken out in Germany.
AVhat is required of the house stove is that it should raise and keep
the temperature of a room about 15° to 20°, and that as cheaply a,nd
conveniently as possible.
The usual plan of putting coal into house stoves is to do so after the
fire has burned down, the result being that much combustible gas is
distilled off, which thus produces waste of heat-giving material, besides
using up part of the heat from another portion of the fuel for the
distillation ; and again when the heat rises sufficiently high to ignite
these gases, a proper supply of air is frequently not allowed to enter
the fire, so that much waste is caused by incomplete combustion,
accompanied by the formation of soot and carbonic oxide.
The stove acts best when the fuel Imrns from above downwards, as
the hydrocarbons which are distilled from the fresh coal at the bottom
burn when they reach the top of the fire. Too much atmospheric
air should, however, not be admitted.
The coal should be separated from the sides of the stove by a layer
of fire-clay, to prevent loss of heat, and so to avoid the resulting loss
of fuel from imperfect combustion. The habit of wetting the coal is a
very objectionable one.
Tlie author endeavoured to determine the loss of heat consequent
on the above-mentioned conditions, employing different kinds of
stoves, and different sorts of fuel. He analysed from time to time the
gases wliich passed up the flue during the combustion, and noted the
temperature in the flues and in the room, and the force of the current
in the chimney. He embodies his results in a number of tables ; as
examples, the following are given.
In one experiment, calculating from the amount of air required to
burn the fuel, the heat produced by the combustion, and that carried
off" by the flue gases, the author arrived at the conclusion that 40 per
cent, of the total fuel value of the coal was carried off with the smoke
gases, even when the fire was carefully managed.
In a second experiment, when the same coal and stove were employed,
but in which the current of air in the flue was much increased, it was
found that 80 per cent, of the heat was carried off" by the smoke gases.
VOL. XXXVIII. I
146 ABSTRACTS OF CHEMICAL PAPERS.
The tliird experiment was made with an iron stove, 0*5 meter high,
lined with iire-proof stone, the smoke gases rising by one side of a
partitioned pipe or trunk, nearly to the roof of the room, descending
to the level of the stove by the other side, and again rising to the roof
and raaking their escape into the chimney. All the joints about the
stove were closed by a mixture of soluble glass, asbestos, and clay.
la this experiment, Piesberg anthracite was used as fuel, and the
loss of heat, calculated as above mentioned, was 15 per cent, of the
total fuel value of the coal. The temperature of the smoke at the fire-
hole and at the exit into the chimney at the roof were measured by
pyrometers, and the loss of heat which was given to the air of the room
between those two points was very great.
The influence which the opening of the doors of the stove have
OR the loss of heat is great, as shown by the results obtained from
burning coke in the iron stove. When the door of the ash-hole was
partly opened, the loss amounted to 17 per cent., and when closed, to
6 per cent., but when the ash-hole door was completely opened, and
the fire-place door partly opened, the combustion became very vigorous,
the temperature of the gases in the flue rose rapidly, so that the ther-
mometer had to be removed, whilst in propoi-tion to the increased
draught the amount of carbonic anhydride diminished, and the loss in
heat corresponded to about 40 per cent, of the fuel value. The draught
ranged between 2'5 and 4'4 mm. W. T.
Salts obtained from the Mother-liquors of the Brine-springs
of Volterra. By A. Fdnaro (Gaz;:etta, 9, 289— 293).— In a note on
these brine-springs (Gazzetta, 8, 71, and this Journal, Abst., 1878, 652)
the author suggested that they might be utilised for the extraction of
potash salts. Experiments have been made with this object, and
analyses are given : —
1. Of the residue left on evaporating the mother-liquors. .
2. Of the salt obtained by the evaporation of the mother-liquor to
two-thirds of its volume.
3. Of the salt left on evaporating the mother-liquors from 2.
4. Of the salt obtained by lixiviating the residual salt with fresh
mother-liquors, evaporating, again lixiviating the residue, and so on,
by which means the proportion of sodium chloride is greatly diminished.
In this way it is easy to obtain a salt containing 17 — 18 per cent,
potassium sulphate, and consequently but little inferior to the
" Kalisalz " of Stassfurt. C. E. G.
Lead Fume, and a New Process of Fume Condensing.
By A. French (Chem. Neirs, 40, 1G3 — 160). — This paper describes a
series of experiments made by the author and Messrs. H. J. and
J. Wycliffe Wilson with a view to discover a good process for conden-
sing fumes of lead, silver, and other metals, which volatilise in the
smelting and refining operations. Not only does the loss of lead by
sublimation amount to hundreds of tons in a year at many works,
but the injury which is done to health and vegetation is very great.
The various methods of condensing fumes which have been tried in
this and other countries may be classed as follows : —
TECHNICAL CHEMISTRY. 147
1. Deposition of the fume by its own gravity in long flues with or
without the addition of a sei'ies of settling chambers, placed either
near to or at some distance from the furnace.
2. Filtering through flues, towers, or chambers containing brush-
wood, coke, coarsely woven fabric, or similar porous material, using
water either in a constant or intermittent stream to keep the filters
from becoming choked.
3. The use of water, either in the form of steam or in showers of
drops or jets, projected with some considerable degree of force into
and across the current of smoke.
4. Processes based on the inverse of the preceding principle, viz.,
passing the smoke under and through a depth of water, either in
great volumes, as in the old Stagg's condenser, or in a more or less
comminuted condition.
As to the physical nature of the lead fumes and their deportment
under varying conditions of temperature and friction, experiments
have proved that as the vaporised lead cools, it assumes the condition
of a vast number of minute isolated particles. Lead fume appears to
have no definite composition, as the proportions of its constituents
vary in every specimen. The lead varies from 35 — 65 per cent.
Lead fume, besides silver, invariably contains a little gold ; usually
from ^ to 1 per cent, of the quantity of silver. Platinum and
iridium have also been found in the fumes on several occasions.
The greatest deposition of lead fume takes place, as might be ex-
pected, near the furnace, and the fume is most abundant whenever
the gases have suffered the greatest friction and fall in temperature.
The author, in the next place, discusses the various methods of
condensing fumes as classified in the above manner, and points out
the objections they are subject to. He then describes a new apparatus
for condensing these fumes. Copper-Avire gauze, having about
15 meshes to a lineal inch, is used in the apparatus, the meshes being
about one-twentieth of an inch wide. A number of gauze diaphragms
are arranged one above the other in horizontal planes, and at small
distances apart. The whole apparatus is submerged in water, the
smoke being equally distributed under the diaphragms by means of a
horizontal series of perforated pipes. The gauze diaphragms do not
add much to the resistance which the smoke current has to overcome
in its passage through the apparatus : three of the size mentioned above
add about half an inch of water pressure. The depth of water usually
employed is 7 inches above the perforated pipes, and with this depth
the water-gauge indicates a resistance of about 10 inches, one half
inch only of which is due to the gauze, the remainder being due to the
depth to which the smoke depresses the water at the inlet passages.
The ascending gases set up an upward current of water through the
gauzes, and to promote a steady circulation of this, a return passage is
provided. Each square foot of area of the diaphragm space is capable
of passing about 40 cubic feet of smoke per minute, and when a
blast furnace is employed for smelting lead-ore about 1 foot of area
will be required for each ton of ore smelted in 24 hours.
During the past six months, almost daily assays have been made of
the smoke before it entered and after it left the condensers at the
148 ABSTRACTS OF CHEMICAL PAPERS.
Sheffield Smelting Company's works. With a few exceptions these
have exceeded 95 per cent, of fume caught. In a few cases as
much as 90'5 per cent, of the metallic contents of the smoke has been
caught. After the lead has been removed from the smoke, the large
quantity of sulphurous acid which is usually contained in it may be
recovered in a very simple manner. The gases can be mixed with a
little air, if enough of oxygen is not ali-eady present, and then propelled
by means of a steam jet through a heating apparatus similar to the
hot blast heaters used in iron smelting works, and the hot sulphurous
acid, steam, and air passed through common salt, according to
Hargreave's process. By this means lead or copper smoke will be
rendered not more pernicious than that from ordinary chimneys.
Any arsenic or zinc which reaches the condenser is dissolved in the
water, and thus separated from the lead fume, which subsides to the
bottom. The apparatus was tried with hydrochloric acid vapour, and
condensed 97"75 per cent. ; of common salt vapour, it condensed 93 per
cent.
A Root's blower is used with iron revolvers for forcing the smoke
through the apparatus ; from 2^ to 3-horse power is amply sufficient
to work a condenser large enough for a furnace to smelt 15 tons of
lead-ore per 24 hours. The weight of a condenser for that size of
furnace is 18 cwts. The smoke should be cooled to about 120 — 130° F.
by passing it through iron pipes, or any other kind of flue. This is
necessary to prevent rapid evaporation of the water with which the
condenser is supplied. It is also very important to cool the smoke as
far as possible, so as to have a smaller volume to pass, and thereby save
both power and cost of a larger apparatus. D. B.
Preservation of Milk. By E. Klebs (Bied. Cenfr., 1879, 541).—
The author heats the milk to a temperature of 65 — 70°, whereby the
fresh taste is preserved. J. K. C.
Composition of "Grains" from Malt. By A. Markl (Bied.
Centr., 1879, 388).' — Malt, weakly dried, gives " grains " richer in starch
than when it has been more strongly dried. 100 parts of grains
obtained by the infusion process contained : —
Fresh.
Strongly
Fr
om gently.
Stronger.
ch'iecl malt.
Water . . .
79-3
4-1
791
4-7
78-6
Albumin .
5-4
Fat
0-4
0-3
0-4
Fibre . . . .
6-2
7-8
9-4
Starch . .
9-5
&-7
5-3
Ash
11
1-3
1-2
J. K
c.
U9
General and Physical Chemistry.
New Galvanic Couple. By A. Niacdet (Compt. rmd., 89, 703
— 7u8). — This couple consists of a plate of zinc for a positive, and a
plate of carbon, surrounded with pieces of carbon, for a negative
electrode : the former is immersed in a solution of common salt, and
the latter in a solution of chloride of lime in a porous cell. The
chloride of lime acts as a depolariser, the hydrogen decomposing the
hypochlorous acid, forming water and hydi'ochlorie acid, which, unites
with the zinc or lime, forming salts which are very soluble and good
conductors. As zinc is not attacked by chloride of lime, the action
takes place only when the circuit is closed ; so that with a broken
circuit, a couple may be kept for any length of time.
When sodium chloride is used, the electromotive force is greater
than with any other solution, being 1'6 volts, and l"o after standing for
some months. The depolai'ising action of chloride of lime is not com-
plete, as is the case with copper sulphate, and with a slight external
resistance the electromotive force slightly diminishes if the current con-
tinues ; but it regains its former sti'ength on standing. The internal
resistance is reduced to a minimum by bringing the plates as close
together as possible. To prevent the smell of the bleaching powder
being disagreeable, the porous cell is closed with a cork.
L. T. O.'S.
Determination of the Density of Vapours which Attack
Porcelain at a Red Heat. By V. Mever and H. Zublix (Ber., 12,
2204 — 2205). — The apparatus used for determining the vapour-density
of those bodies which attack porcelain, consists of a platinum cylinder
245 mm. in length and 26 mm. diameter, to which is soldered, by
means of the oxyhydrogen blowpipe, a platinum tube 400 mm. long
and 7 mm. in diameter. To protect the cylinder from the action of
the furnace-gases, which would permeate the platinum walls, it must
be surrounded by a Berlin porcelain tube, glazed inside and out,
60 cm. long. W. C. W.
Specific Heats and Melting Points of the Refractory Metals.
By J. YiOLLE {Coiiqjt. i-tiiJ., 89, r"»2 — 703j. — The specific heat of
iridium, which has been determined up to a temperature of 1400°, is
found to increase regularly with the temperature according to the
formula C'o = 0-037 + 0-000006 t. The melting point determined by
the calorimetric method (this Journal, Abst., 1879, 294) is found to
be 1950°.
The specific heat of gold remains nearly constant between 0' and
60U°, but increases constantly between 600° and its melting point ;
according to Regnault, the specific heat of gold = 0-0324 between 0°
and 100°. and is nearly the same at 600°, but according to the author
it is a little less at 100°, namely, 0-0316. At 900^ it is 0-0345, and
0-0352 at 1020°.
VOL. XXXYIII. VI
150 ABSTRACTS OF CHEMICAL PAPERS.
The melting points of the different metals determined by the author
are —
Silver 954°
Gold 1035
Copper 1054
Palladium 1500
Platinnra 1775
Iridium 1950 L. T. O'S.
Decomposition of Seleniuretted Hydrogen by Mercury. By
Berthelot {Conipt. rend., 89, 684). — Seleniuretted hydrogen, when
kept in contact with mercury for some time at the ordinary tempera-
ture, is decomposed, with formation of mercuric selenide ; under
similar circumstances, sulphuretted hydrogen has no appreciable action
on mercury, it being only at 550° that decomposition takes place.
This difference may be due to the difference in the heat of formation
of the two hydrides.
Ho + S solid = HoS disengages + 4*6 cal.
Hs + Se solid = H0S2 absorbs — 5'4 ,,
A similar case is met with when hydrobromic and hydrochloric acids
are treated with mercury ; the latter acid is decomposed only at high
temperatures ; the former slowly at the ordinary temperature, the
heats of formation from the elements in the gaseous state beiug HBr =:
+ 13-5, HCl = + 22.
In all such cases, the decomposed bodies being analogous and com-
parable with one another, their decomposition is easier the less heat
disengaged in their initial formation. L. T. O'S.
Combinations of Phosphine with the Haloid Acids. By J.
Ogier (Oompt. rend., 89, 705 — 708). — PJwsjpliine hydrochloride (phos-
phonium chloride), PH4CI, is obtained by mixing equal volumes of
phosphine and hydrochloric acid, at a temperature of 14°, and submit-
ting them to a pressure of 20 atmospheres, when small crystals similar
to those of the bromide deposit on the sides of the vessel. At 20° a
liquid is obtained which, on cooling, deposits crystals. A mixture of
equal volumes of the two gases under the ordinary pressure, deposits
crystals when cooled to — 30° to — 35°.
Fhos'phhie hydrohromide (phosphonium bromide), PHiBr. The heat
of formation of this body is measured by decomposing it with water,
when PHsHBr + water = PH3 gas + HBr dissolved, absorbs
— 3'03 cal. By deducting from this number, representing the thermal
action of water on 1 equiv. of PHiBr, the heat of solution of hydro-
bromic acid in water (H-20'0), and changing the signs, the heat dis-
engaged by the union of the two gaseous bodies is obtained.
PH3 gas + HBr gas =: PHiBr solid disengages + 23'03 cal.
Phosphine hydriodide (phosphonium iodide), PH4I. The heat of
formation of this body is determined like that of the hydrohromide,
PH3HI + water = PH3 + HI dissolved, absorbs —4-77 cal. By
deducting the heat of solution of HI in water and changing the sign,
GEXERAL AXD PHYSICAL CHEMISTRY. 151
•we get PH3 gas + HI gas = PHJ solid disengages + 24' 17 ca1. By
directly measuring the heat evolved by the union of the two gases,
+ 24!'2 oal. was obtained.
The author corrects an error made in the calculation of the heat
developed in the formation of phosphinc (ibid., 87, 210, and this
Journal, Abst., 5, 1879) due to the heat of formation of rjaseous water
instead of solid water being used. The corrected calculation stands
thus : —
1st Seiies.
P + H3 disengages a--
5(H + 0) „ A = + 172-5 cal.
PH3 + 81Br „ B = + 254-6 „
2nd Series.
P + O5 = PO3 disengages C = + 202-7 (Thomsen)
1(H + Br) disengages ^'D — + 236-0 (Berthelot).
From which a- = (C + D) — (A + B) = + 11-6 cal., therefore
p -|- H:; = PH3 gas disengages + 11-6 cal.
Similarly, P2 + H = PoH solid disengages 17-7 cal.
As + H3 = AsHs gas absorbs d6'7 „
The heat of formation of phosphine is less than that of ammonia.
By comparing the heats of formation of ammonia and phosphine com-
pounds we find —
HCl gas + NH3 gas = ISTHjCl disengages 42-5 cal.
HBr „ + NH, „ = NH^Br „' 45'6 „
HI „ + NH3 „ = NHJ „ 44-2 „
PH3 + HBr = PH.Br „ 23-0 „
PH3 + HI = PH.Br „ 24-1 „
Starting from the elements themselves, we get — ■
N + H, + CI = XH4CI disengages 91-2 cal.
Is" - H4 + Br (liq.) = NH.Br „ 81-7
N + H4 + I (sol.) = Xnj „ 65-1
P (sol.) + H4 + Br (liq.) = PH^Br „ 44-1
P (sol.) + H, + I (.sol.) = PHJ „ 29-5
The heat developed by the formation of ammonium cyanide and
ammonium sul[)hide are —
HCN + NH3 = NH.CN disengages 20-5 cal.
H,S + NH3 = NH^HSi 23-0 „
As a reducing agent, phosphine hydriodide is not as effectual in
some cases as hydriodic acid, on account of the loss of energy which
takes place in its formation. L. T. O'S.
Thermic Study of Succinic Acid. By P. Cheoustchoff (Gompt.
rend., 89, 579 — 582). — The following numbers repi^esent the heat
evolved by various salts of succinic acid when dissolved in 400 cc. of
water : —
m 2
152 ABSTRACTS OF CHEMICAL PAPERS.
C4H,0,Na. = 8-4 C,H,Na,0,.6H,0 = - H'O
C H.O,K,' = 0-2 C,H,O.K..H,0 = - 3-4
C4H.0,HK = - 7-6 C,H,0,H.NH, = - 4-9
From these may be calculated the heat evolved by the combination
of the solid salt with water. In the case of the soda salt, it becomes
10-8 • with the potash salt, 2-2 iinits. Succinic acid dried at iiU
gives by solution in 500 c.c. at 11° an absorption of heat equal to
6"4 units. , .,, ... . • •
The heat of neutralisation by alkalis made with a solution contaimiis-
i of an equivalent of acid gave as follows, everything being dissolved,
and remaining dissolved: —
With soda 26-4; with potash 26-4-, with ammonia 22-9.
Bv increasing the relative proportions of succinic acid to alkali the
numbers were slightly altered: thus with 2 mols. of acid to 2 mols. o
i.otash 27-25 units were obtained; with 3 mols. of acid to 2 mols. ot
potash, 2476 units ; with 2 mols. of acid to 2 mols. of ammonia,
' The' number found by Thomsen for the heat of neutralisation of
succinic acid was 24-8 nnits; the author considers that this number is
incorrect. The foregoing numbers may, if required, be referred to a
reaction between the solid constituents.
With soda 40-02; with potash 46-37; with ammonia gas 39-42.
As reo-ards the amount of heat evolved on nentralisation succinic
acid occupies a position intermediate between benzoic and tartaric
'''^^'^^- NaHO. KHO. NH3 gas.
Acetic acid, 18-3 219 18-5
Benzoic acid 17*4 22-5 U U
i succinic acid 20-01 23-19 19-7
I oxalic acid 26-5 29-4 24-4
i tartaric acid 22-9 27-1
Sulphuric „ 34-7 40-7 3o-8
By determining the heat of solution of the anhydride and of the
hydrated acid in potash, the heat of combination of the anhydride with
Avater was obtained by difference: C4H6O4 = 20-06; CJi.O, = 29 78;
difference = 9-72 units. j j j. j
If the heat of solution of the hydrated acid m water be deducted
from the heat of solution of the same acid in potash, the number ot
units obtained should be equal to the heat of neutralisation by potash
in solution.
Heat evolved on solution in potash = + 20-06
water = — 6 4
55 "
Difference = 26-46
This indirect verification of the number 26-4 supports the author's
results as against Thomsen's figure, 24-8.
INORGANIC CHEiUSTRY. 158
Succinic acid appears to be completely displaced from its combina-
tions by sulphuric acid ; but doubtful results only were obtained in
the case of hydrochloric acid, fui'ther data are in fact required respect-
ing the heat evolved or absorbed in diluting succinic acid and its
salts. J. W.
Inorganic Chemistry.
Silicon Nitride. By P. Sghutzenberger {Cornet, rend., 89, C44
— 64t>). — The composition of the silicon nitrides discovered by Sainte-
Claire Deville and Wohler, not having been experimentally determined,
the author has sought to prove the existence of two- compounds by the
following expea*iments : —
By heating crystallised silica with gas carbon in a blast furnace for
some time, a mass is obtained consisting of unaltered silica, a white
substance soluble in cold concentrated hydrofluoric acid without evolu-
tion of gas, and a green substance which is insoluble in hydrofluoric acid
and caustic alkalis, and, after successive treatment with hydrofluoric
acid and dilute potash, is obtained as a green infusible powder : this is
not attacked by water or by solution of caustic alkalis, but is dissolved
by potash at a red heat with formation of potassium silicate and
evolution of hydrogen and ammonia. The analyses agree with the
formula (SijS')j-.
The white substance soluble in hydrofluoric a^. 'd cannot be obtained
in the pure state, but most probably it has the formula SisN^ ; this is
rendered probable by the fact that on heating (SiN)j: in a current of
chlorine, it loses 22 per cent, of its weight of silicon,. and a white sub-
stance, soluble in hydrofluoric acid, is left. The equation, (SiX)4 +
CI4 = SiCb + SisNi, represents the loss of 22*4 per cent, of silicon.
By passing ammonia gas into a flask containing silicon tetrachloride,
a very light white powder is obtained soluble in water with separation
of Si(H0)4; when heated in a current of hydrogen, ammonium chlo-
ride sublimes. The results of analyses compare fairly with those
required bv the formula SigN^ioClaH. Its formation may be expressed
thus : SSiCU + lOXH, = SigN.oClsH + 29HCT, and its decomposi-
tion by water, thus: SigN.oClaH + 16H,0 = SSiO. + IONH3 -f
oHCl. When heated to bright redness in a current of ammonia, a
white powder is obtained which is not attacked by water, and only
sHghtly soluble in alkalis; its formula is SiaNgH. These experiments
show the existence of two silicon nitrides, one (SiN)^ corresponding
to CN, the other probably of the formula Si.Xi. L. T. O'S.
Action of Metallic Nitrates on Nitric Acid. By A. Ditte
{Cuinpt. rend., 89, -57(3 — 579). — Ammonium nitrate dissolves readily
in fuming nitric acid, forming a liquid which does not solidify at 6° ;
below this tempei-ature crystallisation takes place, when the ther-
mometer immediately rises to 18". The crystals melt regularly at 18°,
but generally exhibit the phenomenon of surfusion, in which condition
154 ABSTRACTS OF CHEMICAL PAPERS.
a crystal of aramoiimm nitrate will not determine solidification. The
composition of the salt is NH4NO3.2HNO3; when melted the liquid
closely resembles nitric acid, bub does not fame in the air ; it is capable
of dissolvincr a large quantity of ammonium nitrate to form the salt
NH4NO3.HNO3, melting at 9°-, this latter remains liquid at 4°, and a
crystal of the di-ardd salt does not induce crystallisation. The same
compounds are pi-oduced when dry ammonium nitrate is placed ia an
atmosphere containing nitric acid vapour.
Potassium nitrate, in like manner, produces the salt KN'03.2HN03,
melting at — 3° ; when carefully cooled the whole will remain liquid
at —10", bat the temperature rises to — 3" as soon as crystallisation
sets in. The monacid salt, KNO3.HNO3, could not be prepared.
Thallium and rubidium nitrates also combine with nitric acid to form
the salts TINO3.3HNO3 and RbNOa.SHNOs respectively ; their
melting points are not given, but in general properties they resemble
the potasi-ium and ammonium salts previously described. J. W.
Action of Metallic Nitrates on Nitric Acid. By A. Ditte
(Coiiqjt- rend., 89, (341 — 643). — -The author has shown (see previous
abstract) that certain metallic nitrates combine with nitric acid to
form acid salts. There are, however, other salts which behave dif-
ferently. Magnesium nitrate, ]Mg(N03)26H20, for example, which
contains 6 mols. of water of crystallisation, melts and begins to
decompose when heated ; under certain circumstances, however, when
heated, it yields a syrupy mass, which suddenly solidifies, evolving a
large amount of heat ; it consists of Mg(N03)23H20. It is decom-
posed by heat, leaving a residue, from which is separated by water a
nitrate having the composition MgO.Mg(N03)2 ; this decomposes
Avithout melting, leaving magnesia.
If the decomposition of the neutral nitrate be stopped the moment
nitric oxide begins to be evolved, a deliquescent mass is obtained,
which dissolves in nitric acid, and on cooling deposits transparent
prisms, consisting of Mg(N03)2'2H20.
The basic nitrate, when treated with nitric acid, yields the neutral
salt, but owing to the qunntity of water set free it is impossible to
obtain acid salts ; the author therefore proposes to saturate a solution
of the neutral salt with nitric anhydride, which will combine with the
Avater, and thus a solution of the anhydrous salt in nitric acid will be
obtained.
To this group besides magnesium nitrate belong the nitrates of
manganese, aluminium, zinc, uranium, copper, and iron, which give
the following salts : — -
Mg(N03)..3H.O 2[Mn(N03)2].5H20 (UO.) (N03)2.3H20
Mg(N03)o.2HoO MnfNO-O-HoO Cu(N03)o.3H,0
2[Zn(N03)2].3H,0 Al23(N03)2.4H20 Fe23(N03)2.t)H20.
Of these, the nitrates of manganese, aluminium, and iron leave a
residue of oxide when heated ; the others yield basic nitrates.
Secondly, there exists a class of nitrates which are insoluble, or
only sparingly soluble in nitric acid, to which belong the nitrates of
INORGANIC CHEJUSTRY. 155
sodiain, lithium, calcium, strontium, barium, uickel, cobalt, bismuth,
cadmium, mercury, and silver. L. T. O'S.
Contributions to our Knowledge of Clays and Earthenware
Goods. (Dingl. polyt. /., 234, 465 — 473). — Bischof mentions a new
source of bauxite at Kleinsteinheim, in the Offenbach district. The
following is the composition: —
AI2O3. SiOo. Feo03. Loss on ignition.
56-02 10-97 6-19 26-42 = 99-60
Lesrer gives the following analyses (p. 156) of clay substances used
for the preparation of tine white goods. A and B are French goods,
C and D are Belgian goods, the former being used for fine goods, the
latter for ordinary ; and E is German.
Lindhorst states that, besides lime and the flue gases, the alumina
and alkalis contained in clay also influence the coloration of clay ;
whereas -gypsum is inactive. Experiments were made with various
oxides, the colour produced being red with iron, green with chromium,
grey with copper, white with zinc, yellowish-grey with nickel, brown
with manganese, pink to violet with gold, and greyish-white with
platinnm. Mixtures of these substances produce intermediate shades.
The black-burning of Indian goods is explained by Sarnow as follows :
— When earthenware goods are polished by rubbing them, the surface
of the clay is rendered more compact ; by subsequently placing the
clay in a sooty atmosphere, and exposing it to a temperature high
enough to expel the combined water, the pores produced are filled with
coal. The latter cannot ignite in a reducing atmosphere, and becomes
fixed in the pores as the clay shinnks. A shining mass is produced,
which is so dense that it resists even the penetration of water.
D. B.
Ultramarine. By Kxapp (Dmr/Z. polyt. J., 234, 479— 486).— In
the first part of his investigation of this subject {ibid., 229, 69, 173),
the author considered mainly the changes taking place during the
formation of ultramarine, and its subsequent conversion into blue.
The object of the jDresent paper is to consider the cases, which, although
not strictly connected with ultramarine, represent properties common
to the same. These are well known, and the author merely mentions
a few instances, which have not yet been noticed.
Dressel found that nosean assumed a pure blue colour, when heated
with coal. (Nosean is a mixture of haiiyne and sodalite.) During the
fusion of borax with sodium sulphide, i.e., the yellow colouring of glass,
it was noticed that after the addition of boracic acid to the fused mass,
a black product was formed, which on continued heating assumed a
blue colour. The same colour was produced when potassium thiocya-
nate was fused, and also when sulphur was introduced into potassium
cyanide and the mixture heated. The formation of blue with fused
borax led to the following important deductions: — 1. Silicic acid can
be replaced by boracic acid, in order to produce the blue. 2. The
borate gives a blue as stable in properties as the silicate. 3. The blue
of the borate is not altered by fusion, its melting point being high
156
ABSTRACTS OF CHEMICAL PAPERS.
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INORGANIC CHEMISTRY. 157
enough to avoid the destruction of colour. 4. Alumina is not abso-
lutely requisite for developing the blue colour. Silica without aluminn,
and alumina without silica form the bku! colour. Besides these, other
bodies gave similar results, e.g., aluminium borate, calcium phosphate,
and stannic oxide produce the blue colour. D. B.
Erbium. By P. T. Cleve {Compt. rend., 89, J'OB— 709).— This is
an acknowledgment of Soret's claims to priority in the discovery pub-
lished by the author {ibid., 15th September, 1879). He points out
that the substance called by him liolmium is the same as that called x
by Soret. L. T. O'S.
Tungsten Bronze. By J. Philipp and P. Schwebel {Ber., 12,
2234 — 2236). — Although tungsten bronze (the golden-yellow com-
pound obtained by fusing acid sodium tungstate in a current of
hydrogen) resists the action of acids and of alkalis, it is readily de-
composed by an ammoniacal solution of silver nitrate. By making
use of this fact in analysing the substance, the authors find that its
composition is NaWOr^, instead of Na2W04 + W2O5, as stated by
Malaguti {Ann. Chim. Phys., 60, 284). W. C. W.
New Basic Salts of Mercuric Sulphide. By W. Spring
{Annalen, 199, llG — 120). — The yellow amorphous substance, which
is precipitated on the addition of mercurous nitrate to an aqueous
solution of tetrathionic acid (Wachenroder, Annalen, 60, 190), has,
after drying and treatment with carbon bisulphide, the composition
Hg4S404. Its formation is due to the following reactions : —
H,SA + Hg,(N03)2 = Hg^S^Os + 2HNO3
2Hg2S40s + 3H,0 = HgiS^Oi + 2H2SO4 + H.SO,, -f S.
When perfectly free from tetrathionic acid, this substance undergoes
no change on exposure to the light or to a temperature of 12U°. The
amount of heat evolved on treating tkis body with sodium sulphide
shows that it is not a mixture of mercuric sulphide and s-nlphate, but
a definite compound, viz., trithiohasic mercuric sidphate. The salt is
insoluble in water and in most acids. It is soluble in aqua rccjia and
in a mixture of hydrochloric acid and bromine, and it is converted by
the action of warm nitric acid into a white insoluble salt, monothiobasic
trimerc.uric sulphate, HgS(HgS04)3.
Trithiobasic mercuric sulphate is decomposed by alkaline solutions,
forming black mercuric sulphide. On boiling with barium nitrate,
mercuric sulphide and barium sulphate are obtained. Wlien the salt
is boiled in water, sulphuric acid passes into solution and a dark yellow
product remains, which has the composition (HgS)3HgO. Trithio-
basic mercuric oxide turns black, and evolves sulphuretted hydrogen
when brought in contact with dilute hydrochloric acid.
It is suggested that, for the purpose of classification, the basic mer-
curic sulphates may be considered to be derived from the following
types, in which the 0 or S is replaced by the group SOi.
158 ABSTRACTS OF CHEMICAL PAPERS.
Thiobasic. Oxjbasic.
Hg.S.Hg S.Hg.S /Hg.O.Hg' O.Hg.O
^Hg.S.Hg/ Hg.S.Hg ^Hg.O.Hg/ Hg.O.Hg
W. C. W.
Oxidation of Gold by Galvanic Action. By Berthelot
(Gompf. rend., 89, 683— 684).— Grottliuss (Anu. (Jhim. Pjuis., 58, 60)
observed that a gold wire is dissolved when employed as the positive
terminal of a circuit in sulphuric acid. The author confirms these
results, and shows that under similar circumstances nitric acid al.so
dissolves gold. This is due neither to ozone nor, as suggested by
Chovreul, to persulphuric acid, for neither of them has any action on
gold. L. T. O'S.
Organic Chemistry.
Normal Paraffins. By C. Schoelemmek (Annalen, 199, 139 —
144). — By chlorinating pure hexane (from secondary hexyl iodide
prepared by the action of hydriodic acid on mannitol), a mixture of
monochlorides is obtained (b. p. 121 — 134"), which yields hexylene
and ethyl-hexyl ethers on decomposition with alcoholic potash. The
define combines with hydrochloric acid at the ordinary temperature,
forming a chloride which boils at 124° without decomposition ; whiLst,
according to Morgan {Ann., 161, 275), the corresponding chloride
from petroleum boils at 116^ with decomj^osition. The acetate from
the chloride yields an alcohol boiling at 130 — 135° and another at
135 — 140^, which split up on oxidation into acetic and butyric acids;
propionic acid could not be detected.
The fact that the paraffins from petroleum have a higher specific
gravity than those from other sources, and that the specific gravity
diminishes when a portion of the hydrocarbon is oxidised by nitric
acid, indicates that the normal paraffins from petroleum probably con-
sist of a complicated mixture of homologous and isomeric hydro-
carbons. W. C. W.
Constitution of Dibrom-ethylene. By E. Demole (Ber., 12,
2245 — 2247). — By the action of aluminium chloride on a solution of
dibromethylene in benzene, unsymmetrical diphenylethylene, CHo '. CPhj,
b. p. 174 — 176°, and a liquid boiling above 350°, are formed. The
})roduction of the former hydrocarbon shows that dibromethylene is
also unsymmetrical, BrjC '. CHj. This result agrees with the con-
clusions arrived at by Anschiitz (Ber., 12, 2073). W. C. W.
Glucose. By Feanchimont {Gompt. rend., 89, 713 — 714). — In
applying Liebermann's method for the preparation of the acetyl deri-
vatives of the phenols to the carbohydrates, the author obtained with
ORGANIC CHEMISTRY. 159
o;lucose a crystalline acetyl compound soluble in benzene, alcohol,
acetic anhydride, and acetic acid ; sparingly soluble in ether and iu
petroleum spirit, and insoluble in Avater. It is octo-acetyl diglucose,
Ci;:Hi,03(CvH302)s, (m. p. 10U°). It has a bitter taste, is dextrorota-
tory, and unlike glucose it is oxidised only with great difficulty ;
boiling chromic mixture does not attack it, and phosphorus penta-
chloride acts on it but slowly. L. T. O'S.
Cellulose. By Franchimont (Compt. rend, 89, 711 — 712). — Not
being able to obtain any reaction between cellulose, acetic anhydride,
and sodium acetate, the author substituted concentrated snlphui-ic acid
for the last substance, when a violent reaction set in, and the cellu-
lose was dissolved, the solution becoming coloured. On adding water
to the solution, a white precipitate is formed, which is filtered and
washed Avith cold alcohol until the washings are no longer coloured.
The residue is then dissolved in hot alcohol, and from the solution
microscopic needles or plates separate out (m. p. 212°). These are
soluble in benzene, sparingly soluble in cold alcohol, and insoluble in
ether. It has the empirical formula C4(,H340/;, and appears to be a
derivative of triglucose, containing the acetyl-group eleven times. An
acetyl-derivative is also obtained by substituting zinc chloride for sul-
phuric acid. This corresponds with a triacetyl-compound, but it is
more probable that it is a saturated acetyl-derivative of w-molecules of
glucose —{n — 1)0H2. It has not yet been identified with Schiitzen-
bergcr's triacetyl-cellulose. The author has applied the same reaction
to other carbohydrates. L. T. O'S.
Commercial Trimethylamine. By E. Dcvilliee and A. Bur-
.siN'i: {Cuiiqjt. rend., 89, 7u9 — 711j. — To detect the presence of ethyl-
amine in commercial trimethylamine, which escaped the authors' notice
in their previous research (this Journal, Abst., 1879, 912), from being
present only in very small quantity (2 per cent.) ; the mother-liquors
from the purification of the oxamides are decomposed with potash and
the bases converted into sulphates ; these are treated with absolute
alcohol, which dissolves, all with the exception of mouomethylamine
sulphate. The soluble sulphates are distilled with potash, the bases
collected over absolute alcohol, and the solutions treated with oxalic
ether. The oxamic ethers are decomposed with lime, when crystals
of calcium monethyloxamate sepai'ate out. This is the sixth base
found in commercial trimethylamine. The authors also reply to
Vincent's remarks (this Journal, Abst., 1879, 913) on their previous
publication. L. T. O'S.
Ethylamine. By H. Kohler (Ber., 12, 2208— 2211).— When a
solution of mercuric chloride is boiled with ethylamine and the hot
mixture filtered, the filtrate deposits on cooling white pearly scales,
which have the composition Cl.HgNHEt. The insoluble precipitate
which is formed at the same time is converted by boiling with water
into yellow oxymercurethylamine chloride, ClHg.O.HgNHEt.
Hence it appears that the action of ethylamine on mercuric chloride
160 ABSTRACTS OF CHEMICAL PAPERS.
is analogous to that of ammonia ; the product, however, is much more
readily oxidisable than is the case with white precipitate.
w. c. w.
Action of Potassium Dichromate on Acetic Acid and
Potassium Acetate. By L. jy\yEsi.(Gazzetfa, 9, 420— 421).— The
author finds thaty w^hen acetic acid is boiled with a solution of potas-
sium dichromate, the acid is oxidised at the expense of the chromic
acid, and carbonic anhydride is produced. In one experiment, the
author employed eqiual weights of potassium dichromate and acetic
acid ; the latter (in.uted with water, but how much is not stated. The
dichromate acts on potassiiim acetate in a similar manner, the chromic
acid liberating acetic acid, which is subsequently oxidised.
C. E. G.
Action of Hypochlorous Acid on Acrylic Add. By P.
Melikoff (Ber., 12, 2227—2228). — The monochloro-lactic acid ob-
tained by the action of hypochlorous acid on a dilute aqueous solution
of acrylic acid and the acid formed by treating glyceric acid with
hydrochloric acid {Ber., 12, 178,. this Journal, Abst., 1879, 521) are
shown to be identical, by a comparison of their amido-derivatives and
of their barium and tin salts (both of which are amorphous). The
amido-acid, which is produced by heating ethyl chlorolactate and
ammonia at 120'',. crystallises in long, thin prisms, and also in four-
sided plates. It resembles serine in most of its properties, but is
somewhat less soluble in water. W. C. "W.
Acetylenedicarboxylic Acid.- By E. Bandrowski (Ber., 12,
2212 — 221G). — Copper acetijlenedicarhorylate, CuCiOi + 3HoO, foi'ms
glistening blue scales, which are spai'ingly soluble in cold water, and
are decomposed by hot water. This salt slowly undergoes decom-
position at the ordinary temperatui'e. The silver salt dissolves in
sti'ong nitric acid, but th^e solution rapidly becomes turbid, owing to
the deposition of silver cyanide.
Acetylenedicarboxylic acid is converted into succinic acid by the
action of nascent hydrogen. When heated with water, it splits up
according to the equation C4II2O4 = COo + C3H2O2. The new acid
melts at 145°, and is soluble in water, alcohol, and ether. It is crys-
talline, and forms well crystallised salts.
When bromine is added to an aqueous solution of acetylenedicar-
boxylic acid, the dibromo-acid, C4H2Br204, is formed, together with
small quantities of bromoform, and a crystalline compound of unknown
composition.
Dibromacetylenedicarhoxyllc acid is deposited from its aqueous solution
in transparent crystals, which dissolve freely in ether and in alcohol.
The silver salt, C4Br204Aga + -^HiO, crystallises in small needles,
which explode when heated. The lead salt, C4Bro04Pb, also forms
needles which are soluble in water. The acid begins to blacken at
217°, and melts with decomposition at 220°. On distillation it yields
hydrobromic acid and Kekule's dibromomaleic acid (m. p. 108^)
(Annalen, 130, 3), hence it may be regarded as dibromofumaric
acid.
ORGANIC CHEMISTRY. IGl
Attempts to prepare tetrabromosuccinic aeid hj the action of bro-
mine on acetylenedicarboxylic acid were unsuccessful.
W. C. W.
Carbamido-palladious Chloride, or Palladoso-uramonium
Chloride. By E. Dkechsel (/. pr. Chem., 20, 469— 476).— This
sub.stauce is obtained by mixing solutions of palladious chloride and
urea. It forms a brownish crystalline powder, sparingly soluble in
water, and has the formula PdCV2CN,,H,0 = Pd[NH,(Cb.NHOCl],.
As it is nearly insoluble in water, attempts were made to found a
method of estimating urea and palladium by its formation, but with
no success in the former, and unsatisfactory results in the latter case.
When boiled with water, it undergoes the following decomposition : —
PdCU.2XH3(CO.XH,) + 2H,0 = PdCl,.2NH3 + 2NH3 + 2CO2.
When evaporated with excess of palladious chloride, the urea appears
to be partially deccimposed with formation of free cyanic acid. Some
urea combining with the cyanic acid, biuret is produced : —
NHo.CONH, + HCXO = (NH.,.CO)oNH.
An attempt was made to prepare hydantoic acid by evaporating
glycocine with carbamido-palladious chloride, but without success.
Besides small quantities of biuret, urea hydrochloride, and palla-
dium bases, palladious amidoacetate was formed. No hydantoic acid
could be detected. W. R.
Relative Displaceability of Bromine in the Monobromo-
benzyl Bromides. By C. L. Jacksux {Ber., 12, 2243—2245).—
When sodium acetate acts on the ortho-, meta-, and para-monobromo-
benzyl bromides under similar conditions, the bromine replaced in
these compounds in a given time is in the ratio 52 : 77 : 100.
w\ c. w.
Tolylphenol. By G. Mazzaija (Gazzetta, 9, 421— 423).— The
xylene employed for the preparation of the tolyl chloride is obtained
from commercial xylene by fi-actional distillation, and agitating the
portion boiling at 136 — 139° with concentrated sulphuric acid. On
redistillinof the undissolved hvdrocarbon, it yields a fraction boilinc at
137 — 139°, which is treated with chlorine while boiling to convert it
into tolyl chloride (b. p. 190 — 195°). When equal parts of tolyl
chloride and phenol are heated with zinc filings, a violent reaction takes
place, with evolution of hydrochloric acid and formation of tolyl-
phenol, OH.CfsHi.CeHi.CHoMe, which may be separated from the pro-
duct by fractional distillation. It is a colourless liquid of feeble
odour, boiling at 250 — 255° under a pressure of 8 — 10 mm. It is in-
soluble in water, but dissolves in alcohol, ether, chloroform, and alkaline
solutions. It gives no coloration with ferric salts. When tolylphenol
is treated with acetic chloride, it yields an acetate,
AcO.CeHi.CsH^.CH^Me.
This is a colourless liquid, boiling at 250° under a pressure of 9 mm.,
and decomposing on exposure to moist air, with formation of tolyl-
phenol and acetic acid. C. E. G.
1G2 ABSTRACTS OF CHEMICAL PAPERS.
Action of Nitrosodimethylaniline on Phenols which do not
contain the Methyl Group. By R. Meldola (Ber., 12, 2065 —
2UG6). — 'TVlien nitrosodimethylaniline hydrochloride (1 mol.) is slowly
added to a solution of iS-naphthol (1 mol.) in sflacial acetic acid at
110'', a blue mass is produced. This is washed with water, dissolved
in hot alcohol, and mixed with hydrochloric acid. On cooling, bronze-
coloured needles are deposited, which dissolve in alcohol and in water,
forming a bluish-violet solution.
Similar compounds are obtained by the action of nitrosodimethyl-
aniline on resorcinol and on a-naphthol. W. C. W.
Action of Ferric Chloride on Orthodiamidobenzene. By
C. Rudolph (Ber., 12, 2211— 2212).— By the action of ferric chloride
on orthodiamidobenzene, a hydrochloride is formed which has the com-
position C24H1glSrcO.2HCl.6H2O. The base combines with sulphuric
acid, yielding several different salts. The formula of the neutral sul-
phate is C24Hi8NeO.Ho.SO4.3H2O. W. C. W.
Tolylenediamines. By R. Nietzki (Ber., 12, 2236—2238).—
Paradiamidotoluene (m. p, 64°) from nitro-orthotoluidine (m. p. 130°)
is identical with the tolylenediaraine from amidoazotoluene. The
para-diamines can be distinguished from the ortho- and meta-diamines
hj their forming quinones on oxidation with ferric chloride, whilst the
ortho-compounds yield a coloured crystalline precipitate having a
metallic lustre.
When treated with nitrous acid, para-diamines form diazo-compounds,
whilst the meta-derivatives yield colouring matters analogous to
phenylene brown, and the ortho-diamines give colourless stable com-
pounds containing nitrogen. W. C. W.
Occurrence of Paraleucaniline in the Manufacture of
Rosaniline. By C. Graebe (Ber., 12, 2241— 2242).— Considerable
quantities of paraleucaniline are found in the rosaniline manufacture
in the mother liquors from which the chrysaniline has been precipi-
tated. Whether leucaniline is the first product of the reaction of
arsenic acid on a mixture of aniline and toluidine (the colouring
matters being afterwards formed by oxidation), or whether it owes its
orio-in to the reduction of pararosaniline is uncertain, but the author
considers the tirst hypothesis the more probable. W. C. W.
Dimethylphenyl Glycocine or Phenylbetaine. By J. ZnniER-
MANN (-Ber., 12, 22U6 — 2207). — Plienylheta'hie hydrochloride,
C,oH,30.,N.HCl,
formed by digesting an ethereal solution of dimethylaniline (2 mols.)
with monochloracetic acid (1 mol.) can be obtained in white needles
by addino- ether to the concentrated aqueous solution of the compound.
The platinochloride forms beautiful dark red crystals.
CH2
Plienvlletatne ethylchloride, \ /N'.(Me)2PhEtCl, is deposited in
CO/
hyo-roscopic ciystals when a mixtux-e of ethyl monochloracetate and
ORGANIC CHEMIST KT. 163
dimethylaniline is heated at 100° for four honrs. On treatment with
silver oxide, the ehh>rine is eliminated from this substance, and a
powerful base is produced, which is very deliquescent, and does not
appear to form crystalline salts. W. C. W.
Hydroxyazobenzene and Paramethylhydroxyazobenzene. By
G. Mazzaka (Gazzetta, 9, 424 — 425). — Hydroxyazobenzene or phenol-
iJiii:ohen:ene, Ci2HioN^20, has already been obtained by Griess (Annalen,
137, 84), and by Kekule and Higed (Ber., 4, 233). The author finds
that the most convenient mode of preparation is to dissolve 3 parts of
potassium nitrite in 400 of water, and pour in a solution of 2 parts of
aniline nitrite and 2 of phenol in 200 of water. The solution soon
becomes turbid and deposits the azo-compound, which should be
collected after 24 hours, dissolved in dilute ammonia to separate
resin, and the filtered solution precipitated with hydrochloric acid.
After recrystallisation from boiling- dilute alcohol the substance melts
at 148—154°.
Paramethylhydroxyienze7ie or Paracresoldiazohenzene,
CeHs.NiKCeHsMe.OH,
may be prepared in a similar manner, substituting pure paracresol for
phenol. The pi-oduct is purified from an oily substance by repeated
crystallisation from boiling alcohol. It forms lustrous red crystals
• (m. p. 108 — 109°) which are but little soluble in cold and only mode-
rately soluble in hot alcohol. It is soluble in ether, in alcohol, and in
alkaline solutions. C. E. G.
Cymenecarboxylic Acid. By E. Paterxo and P. Spica (Gaz-
zetta, 9, 400). — It has been shown (Gaz., 5, 30) that when sodium
cymenesulphate is distilled with potassium cyanide, an oil is produced
which may be converted into the amide CeH3Me(C3H7).CONH2 (m. p.
138 — 139°) by the action of alcoholic potash. Although this com-
pound resists the action of alcoholic potash in a remarkable degree, it
splits up when fused with potash, yielding an acid of the formula
C6H3Me(C3H7).COOH, crystallising in slender needles (m. p. 63°) and
isomeric with Rossi's homocuminic acid (m. p. 52°). The amide is
converted into the acid much more readily by heating it with concen-
trated hydrochloric acid at 180° than by fusion with potash. The
authors have endeavoured to prepare cymenecarboxylic acid by other
methods, such as fusing the cymenesulphate with sodium formate,
and by the action of sodium and carbonic anhydride on bromocymene,
but without any satisfactory result. C. E. G.
Metamidocinnamic Acid. By G. ]\Iazzara (Gazzetta, 9, 425 —
428). — The metauitrocinnamic acid from which the amido-acid was
obtained was prepared according to Schiif 's method by heating uitro-
benzoic aldehyde with acetic aldehyde and sodium acetate. On re-
ducing the nitro-group in the acid by boiling it with tin and hydro-
chloric acid, and subsequently removing the tin by means of hydrogen
sulphide, the metamidocinnainio acid hydrochloride,
HC1.NH,..C6H,.CH: CH.COOH,
104 ABSTRACTS OF CHEMICAL PAPERS.
was obtained in thin plates, permanent in the air and soluble in hot
alcohol from which it crystallises in needles. The amido-acid sepa-
rated from the copper salt by hydrogen sulphide was very unstable.
Attempts were made to oxidise the amido-acid with nitrous acid, so
as to obtain the corresponding metahydrosycmnamic acid, which
with cumaric and paracnmaric acids would complete the series ot
the three possible hydroxycinnamic acids. It was found, however,
that the action went much further, metahydroxybenzoic acid,
C6H4(OH).COOH (m. p. 196—197°) being produced. O. h. (j.
Synthesis of Phenylconmarin. By A. Oglialoeo (Gazzetta 9,
498— 432).— On heating 20 parts of salicylaldehyde with 28 ot dry
sodium alphatoluate and 70 of acetic anhydride ^t 150 for 8 hours,
a red-brown crystalline mass is obtained which is boiled with water
for some time and then allowed to cool. The insoluble portion, when
treated with a hot solution of sodium carbonate, partly dis^solyes, and
onacidifving the liquid, acetylpheni/hotirnaric acid, Ci^a.iiOi, is Tpr-eci-
pitated in the crystalline state. The portion remaining undissolved,
Avhich is the chief product of the reaction, is impure phenylcou-
^ Acetyl phenylcoumaric acid, when purified by crystallisation from
boiUno- water, in which it is moderately soluble, forms long, white,
very slender needles. It is soluble in alcohol and in ether, but only
sparino-ly so in cold water. When heated, it begins to soften and give
off gas" at 170°, but at 180° it fuses to a transparent liquid; it after
beino- allowed to cool it is again heated, it melts at 130^ From this
the author is inclined to believe that when the acid is heated, it loses
acetic acid and is converted into phenylcoumarin. The silver acetyl-
phenylcoumarate, CnH„0,Ag, obtained by precipitating the sodmm
salt with silver nitrate, crystallises from boiling water m tutts ot
slender, colourless needles, which become yellowish-red on keeping-.^
The phenylcoumarm, CaH^.O^, after purification by crystallisation
from boiling alcohol, with addition of animal charcoal, forms large
transparent colourless prisms (m. p. 139-140°), soluble in ether. It
is odourless. Like coumarin, it dissolves when boiled with potash
solution, and is precipitated unchanged on adding an acid. When
treated with sodium-amalgam in dilute alcoholic solution, plienyl-
eoumarin is converted into a new acid, which may be isolated by
acidulating the solution and agitating it with ether. It crystallises
in prisms (m. p. 120°), and is, perhaps, phenylmelilotic acid, but has
not as yet been further examined.
From its mode of formation the author_ believes that acetylphenyl-
coumaric acid has the rational formula AcO.CeHi.CH . CFh.OOUM,
whilst phenylcoumarin, if regarded as the anhydride of phenylcoumaric
acid, would be Oq |1 • rt -ci n
\C0 .CPh C. B. G.
Pittical and Eupittonic Acid. By A. W. Hofmann (Ber 12
2216— 2222).— The formation of eupittonic acid is analogous to that
of pararos"anillne, as is shown by the following equations :—
t
ORGAXIC CHEMISTRY. 165
2aH,oO, + C9H,,03 = CsHseOs + Ho
Dimethyl- Dimethyl- Eupittonic
pyrogallate. methvlpyro- acid,
gallate.
The sodium and barium salts of this acid have the composition
CjsHnXaoOg and C25H24Ba09 respectively. The diacetyl derivative,
C25Ho4Ac209, is best prepared by the action of acetic anhydride on an
alcoholic solution of sodium eupittonate ; it crystallises in yellow
needles, which melt at 265° and decompose with evolution of violet
vapours. The crystals are soluble in alcohol and are decomposed by
alkalis and by acids.
The yellow amorphous substance (Ber., 12, 1371) obtained as a bye-
product in the preparation of diacetyleupittonic acid by heating a
mixture of acetic anhydride and eupittonic acid is insoluble in water,
but dissolves freely in alcohol, ether, and acetic acid. It is also dis-
.'iolved by alkalis and by strong sulphuric acid ; on neutralising the
alkaline, or diluting the acid solutions, the original substance is repre-
cipitated.
BibenzoyJenpittonic acid, C05H04BZ2O9, remains as a yellow powder
when a mixture of benzoic anhydride and sodium eupittonate is fused
and the product exti-acted with alcohol. The compound dissolves in
chloroform, and may be obtained in golden needles (m. p. 232^) by
addine alcohol to the chloroform solution. By the action of benzoic
chloride on eupittonic acid, a white crystalline powder is f)btained.
Methyl eupittonate prepared by the action of methyl iodide on sodium
eupittonate is deposited from alcohol in golden needles (m. p. 242°).
The ethyl salt fm. p. 202°) resembles the preceding compound in its
mode of preparation and in its properties.
When a concentrated alcoholic solution of iodine is added to a cold
acetic acid .solution of eupittonic acid, brown glistening prisms are
deposited which have the composition C25H3SO9I4. This compound is
decomposed by heat. By the action of strong alkalis and acids, eupit-
tonic acid is regenerated. On treating an alcoholic solution of the
iodine-compound with sulphurous acid, hydriodic, sulphuric, and eupit-
tonic acids are formed, but on heating the liquid, the original .substance
is again formed, since the sulphurous acid decomposes the hydriodic
acid with formation of iodine, which at once combines with the eupit-
tonic acid.
Eupittonic acid is decomposed by the action of water at 270°, with
formation of dimethyl pyrogallate and a crystalline body which is
soluble in alcohol, ammonia, and soda. The dimethyl ether of methyl
pyrogallol is not produced by this reaction. Eupittonic triamine
undergoes no change on boiling with aniline. When heated at 200"*
with water, it splits up into ammonia and eupittonic acid.
w. c. w.
Hydroxylation by Direct Oxidation. By R. Meyee and A.
Baur (Ber., 12, 2238 — 2211). — The following experiments support
the hypothesis that it is only atoms of hydrogen occupying a ter-
tiary po.sition which are capable of uudergoLng direct oxidation to
hydroxy] : —
VOL. xxxviii. n
166 ABSTRACTS OF CHEMICAL PAPERS.
Iformal propylbenzenesulplionic acid is oxidised to carbonic anhy-
dride and potassium sulphate by the action of potassium permanga-
nate in an aniline solution, whilst, under similar conditions, cumene-
sulphonic acid is converted into hvdroxypropylbenzenesulphonic acid,
C6H4(S03H)C3H6.0H.
By treating the product of the action of phosphorus pentachloride
on this acid with ammonia, propenylbenzenesulphamide,
CeH,(SO,.NH2)C3H5,
is formed. This sulphamide melts at 152°, and combines readily with
bromine. W. C. W.
Cuinenes-ulphonic Acids and a New Cumol. By P. Spica
(Gazzetta, 9, 433 — 444). — All observers who have hitherto studied
the action of sulphuric acid on cumene are agreed that only one sul-
phonic acid is formed ; although there is great discrepancy in the
description of the salts which this acid forms, and especially with regard
to the amount oi water of crystallisation they contain. As, how-
ever, it has been show by Paterno and Spica (Gaz., 7, 21, and this
Journal, 1877, 1, 70?) that normal propylbenzene forms two sulphonic
acids, and analogous results have been obtained with butylbenzene,
&c., it seemed highly improbable that cumene (isopropylbenzene)
should give such a different result, especially as the author had
observed, in the preparation of cumol from the crude cumenesulphate,
that a small portion of the product passed over below 220°, and that
this did not completely solidify at a low temperature.
The cumene employed in the research was prepared by distilling
cumic acid with lime and iron filings and rectifying over sodium.
The pure cumene, boiling at 150 — 155°, was converted into the sul-
phonic acid by agitating it with twice its weight of a mixture of equal
parts of ordinary and of fuming sulphuinc acid, the action being com-
pleted by heating it at 100° for a few minutes. The sulphonic acid
was diluted, neutralised with pure barium carbonate, and the product
submitted to a careful fractional crystallisation. By this means the
author succeeded in isolating two barium cumenesulphates ; the one
which is formed in larger quantity crystallises in micaceous scales,
somewhat unctuous to the touch, and containing 1 mol- H2O, thus
confinning the observations of Fittig, Schaeffer, and Koenig ; the other,
formed only in small quantity, remains in the mother-liquors from the
crystallisation of the first salt, being much more soluble. It crystal-
lises in microscopic nodules, and contains SHjO or S^HoO, which can-
not be driven off completely without decomposing the salt. The cor-
responding lead salts are very similar, containing 1 mol. HoO and
3 mols. H2O respectively. By treating the sodium salts with phos-
phorus pentachloride and converting the chlorides thus formed into
the amides by the action of alcoholic ammonia, two sulphamides are
obtained corresponding with the two barium cumenesulphates. The
one from the less soluble barium salt is a solid substance which, by
crystallisation from dilute alcohol, may be separated into two definite
compounds, both containing sulphur and nitrogen, and having the for-
mula C6H4(C3H7).S02NH2. The less soluble compound which occurs
ORGANIC CHEMISTRY. 107
in largest quantity forms white micaceaus scales (m. p. 107°), very
soluble in alcohol, soluble also in boiling sodinm carbonate solution
without alteration ; the more soluble compound obtained from the
mother-liquOT's of the first is relatively small in quantity and crys-
tallises in white scales (m. p. 96''). The sulphamide corresponding
with the barium salt with SH^O is a brown oily liquid which could
not be purified, but the author believes it to be identical with the crys-
talline sulphamide mentioned above as melting at 96°. The sulpha-
mide (m. p. 107°), when oxidised by fusion with potash, appears to
yield a inixture of salicylic and parahydroxybenzoic acids, whilst the
oily sulphamide gives a small quantity of a very impure acid, melting-
bet ween 150° and 170°.
C'unwl, C6Hi(C3H7).OH.-The crystallisable cumol (m. p. 61°) ob-
tained from the cumenesulphonic acid formed in largest quantity has
already been described by Patemo and the author. The small quan-
tity of the sodium salt of the second sulphonic acid at the author's
disposal yielded about 5 grams of a new phenol by fusion with potash
in the ordinary way. This new cumol is an almost colourless liquid,
and boils at 218*5° (cor.) under a pressure of 756T8 mm. It does not
solidify when cooled with ice and salt. It is slightly soluble in water,
and the solution is coloured violet by ferric salts.
In order to> ascertain the constitution of the two cumols, they were
converted into the corresponding ethyl ethers in the usual way and
then oxidised with chromic mixture. The ethylcumol, CuHn-OEt, from
the solid cumol (m. p. 61°) is a colou_t*less, mobile liquid (b. p. 220°
cor. at 757 mm.) and sp. gr. at 0° = 094377, at 100° = 0-86369.
By oxidation it yields paraethoxybenzoic acid (m. p. 194 — 195°).
The ethylcumol from the liquid cumol boils at 213° (uncor.), and on
oxidation gives an oily acid soluble in alcohol and in ether, besides a
small quantity of an acid melting at 194°. Ethysalicylic acid melts at
19-5° C. From these results it would seem that the solid cumol is
paraisojjropyl'plienol, and the liquid cumol ortlioisaproi-iylfhenol. It is
evident also that the perfect separation of the isomeric barium cumene-
sulphonates cannot be effected without great difficulty.
C. E. G.
Empirical Formula of Skatole. By M. ISTencki {J. pr. Chem., 20,
466 — 469). — This product is the result of long putrefaction of animal
matter, and its formation is subsequent to that of indole and phenol.
The author prepared it by the putrefaction of pancreas and muscle for
five months. The putrefied mass was acidified with acetic acid and
distilled, and the skatole, which volatilised with water-vapour, was
separated from the distillate by acidifying it with hydrochloric acid
and adding picric acid. On analysis, it gave numbers agreeing with
the formula C9H9N, and its picric derivative has the formula
C9H9i^.C6H2(N03)30H. The author thi-ows out the suggestion that
skatole is methylindole. W. R.
Action of Chlorine on Naphthalene-a-sulphonic Chloride :
7-Trichloronaphthalene. By 0. Widmann (i?er,, 12, 2228—2231). —
The tetrachloride of the oL-sidphonic c/iZun'de, (CioH5Cl2S02Cl)Cli, formed
n 2
168 ABSTRACTS OF CHEMICAL PAPERS.
when chlorine (2 mols.) is passed into a solution of naphthalene-
a-sulphonic chloride in carbon bisulphide : it is an oily liquid, freely
soluble in the usual solvents: it has not yet been sohdified. The
potassium dichlorosnlphonate, which is obtained by the action of alco-
holic potash on the tetrachloride, yields on treatment with phosphorus
pentachioride, dicliloronaphthalene-cc-sidphotiic chloride, CioHoCU.SOoCl.
After recrystallisation from boiling glacial acetic acid and from ben-
zene, the chloride is deposited in glistening needles or scales (m. p.
145"). Heated in sealed tubes with water, it yields dichloronaphtha-
lene-a-sulphonic acid. ^i.Trichloronaphtlialene, C10H5CI3, previously de-
scribed by Atterberg {Ber., 9, 316), is formed when the sulphonic
chloride is distilled with phosphorus pentachioride. This derivative
yields dinitrodichlorophthalic acid on nitration, which indicates that
the 7-trichloronaphthMlene contains two chlorine atoms in one benzene
nucleus and one chlorine atom in the other. Hence it is probable that
the only difference in the constitution between the 7 and f compounds
is that the isolated chlorine atom occupies the a position in the one
compound and the (3 position in the other. W. C. W.
Dichloronaphthalene-a-sulphonic Acid, By 0. Widmann
{Ber., 12, 2231— 2233).— This acid, CoHsCL.SOgH, is deposited in
colourless needles when dichloronaphthalene-a-snlphonic chloride is
heated with water at 140°.
Its salts are crystalline and sparingly soluble in water. They lose a
portion of their water of crystallisation at the ordinary tenaperature,
but, to remove the whole, they must be heated nearly to 200°.
CoHsCU-SOgK + 2HoO forms needle-shaped crystals. The anhydrous
salt dissolves in 115 parts of water at, 15°. CinHsClo.SOsNa + H2O
crystallises in prisms, and CoHsClo.SOsAg -h 2H2O in silky needles.
The barium salt also forms needles which require 1650 parts of water
for complete solution. The lead salt (needles) dissolves in 700 parts
of water. (C,oH5Cl2.S03)oCa-|- 4HoO crystallises in quadratic plates,
1 part of the salt dried at 100° dissolves in 1270 parts of water at 14 ,
and in 145 at 100°. The zinc salt forms pearly scales containing 7
mols. of H.O.
The amide, CoHjClo.SOoNH,, forms feathery ^crystals soluble m
water and alcohol, which melt and blacken at 250°. W. C. W.
Phenylnaphthylcarbazol. By C. Geaebe and W. Knecht {Ber.,
12, 2242— 2243).— The carbazol, C.sHuN, discovered by Brunck {Ber.,
1% 341) in crude anthracene, is formed synthetically when ^-phenyl-
naphthylamine is passed through a red-hot tube. W. C. W.
Balsamum Antarthriticum Indicum. By B. Hirsch {Arcli.
Pharm. [3], 15, 27 — 47). — Three specimens, labelled Balsamum antar-
thriticum Indicum, Wapa balsam, and oil of Wapa, together with a
l»lock of wood of the same sort as that from which the above were
prepared, Eperna falcata, came under the author's observations. He
concludes from careful comparison that the balsams and oil closely
resemble one another in their chemical and physical properties, but
ORGANIC CHEMISTRY. 1(J9
that the wood in its present state (being without bark or centre) could
not, without the addition of other materials produce the balsam.
E. W. P.
Coca. By G. W. Kennedy {Pharm. J. Trans. [3], 10, 65).— The
physiological action of coca in small doses is to produce excitement
i>f the functions, to relieve or prevent muscular fatigue, and, to some
extent, to take the place of 'food ; large and frequent doses produce
effects similar to those of opium. Attempts have been made to isolate
the narcotic principle which produces these effects. Neumann dis-
covered an alkaloid named cocaine ; a volatile alkaloid, hygrine, has
also been separated, and an essential oil which imparts the peculiar
odour to the leaves. Cocaine or erythroxyline appears to be the active
principle ; it is soluble in 704 parts of water, more soluble in cold
alcohol, and quite soluble in hot alcohol and ether. The author gives
proportions and directions for the preparation of a fiaid alcoholic
extract, and an elixir. F. C.
Berberine Salts. By J. IT. Lloyd (Pharm. J. Trans. [3], 10,
125 — 127). — The finely powdered roots of Mydrustis canadetisis are
extracted with alcohol by percolation; the extract is cooled by ice, and
mixed with excess of sulphuric acid ; and after it has been kept cool
for about twelve hours the precipitate is separated by filtration and
stirred up with cold alcohol ; and the impure berberine sulphate is
separated and dried by exposure to the air.
Sulphate of berberine in the pure state is obtained by adding the
above impure product to 16 parts of water, dropping in ammonia in
slight excess, with constant stirring, and allowing the liquid to stand
in a cool place for twelve to twenty-four hours. The liquid is then
filtered, cooled by ice, and exactly neutralised with sulphuric acid :
the crystals can be strained off in a few hours. The sulphate is orange-
red, soluble in about 100 parts of water at 21' C. ; it is readily decom-
posed by alkalis, yielding free berberine. It is unaffected by exposure
to the air, but becomes moist if extractive matter or sulphuric acid is
present. From 18 to 20 ounces are obtained from lOU pounds of
hydrastis.
The author prepares pure berberine from the sulphate by treating it
with slight excess of ammonia, dissolving in alcohol, and precipitation
with ether. Berberine is soluble in about 4^ parts of water at 21^,
moderately soluble in alcohol, and insoluble in ether and chloroform.
It readily yields salts with acids : the pyrophosphate is very soluble,
the picrate insoluble in water. The phosphate, hypophosphite, and
chloride are readily prepared by adding the respective acids in
slight excess to an aqueous solution of berberine. The ortho-phos-
phate is soluble in 2bO, and the hypopho&phite in about 60 parts of
water.
Berberine hydrochloride, prepared by precipitation, is soluble in about
500 parts of water ; almost insoluble in cold alcohol, ether, and chloro-
form.
Berberine nitrate is greenish-yellow, it is made in a similar wav to
the chloride, and resembles it closely in solubility.
Remarks. — The alcoholic extract of Hydrastis canadetisis contains,
170 ABSTRACTS OF CHEMICAL PAPERS.
besides berberine, a greenisb fixed oil, an acrid resin, a wbite alkaloid,
a vegetable acid, yellow colouring' matter, and small amounts of other
substances. These substances are probably combined in the root, but
on adding an acid, the alkaloids are converted into sulphates, with
separation of the vegetable acid, the resinous matters and the colouring
matter. In the process given above for preparing berberine, the
impure berberine sulphate is decomposed by ammonia, a slight ex-
cess of which precipitates the white alkaloid hydrastine, together
with the resin and oil. The berberine sulphate made from the filtrate
by cooling and adding sulphuric acid, contains some ammonium sul-
phate and foreign matters ; it may be purified by dissolving in hot
alcohol and recrystallising.
The volatile oil is obtained by distilling the root witli water. When
the mother- liquor of the berberine sulphate crystals is mixed with its
own bulk of -water, and the alcohol removed by evaporation, the green
fixed oil rises to the surface, and the resinous substances settle to the
bottom : the water contains the hydrastine as sulphate. Hydrastine is
separated from this solution of its sulphate l)y adding ammonia in
excess in the cold ; it is purified by converting it once more into sul-
phate, reprecipitating with ammonia, and crystallising from boiling
alcohol. The crystals are coloured yellow by admixture with a yellow
substance ; they are not bitter, but acrid ; hydrastine is almost -insoluble
in water, somewhat soluble in cold alcohol, and freely soluble in boil-
ing alcohol and in chloroform : it forms salts with acids, which are, as
a rule, very soluble and difficult to crystallise. F. C.
Veratrnm viride. By C. Bullock (Tharvi. J. Trans. [3], 10,
180).^ — The powdered rhizome and rootlets of this plant were exhausted
with alcohol, and after evaporation, the residue was freed frem alcohol
by a continued moderate heat : the resin which separated from the
soft extract was removed and allowed to drain for several weeks during
warm weather.
The Soft Extract. — 86 per cent, was soluble in water; 43 percent, of
fatty matter was removed by light petroleum. The aqueous extract
was concentrated and made alkaline with sodium carbonate : after
filtering ofi'the precipitated alkaloids, the solution was heated to 'o^° C.
and a little soda added ; the additional precipitate was then filtered off
while the liquid was warm : the precipitated alkaloids from 1 pound of
root amounted to 19'3 grains, abou^ one-ninth of which was precipi-
tated by warming after addition of soda. Colouring matter was
removed by dissolving in acetic acid and reprecipitating from the warm
.solution : and the united mother-liquors, after being acidified and
evaporated, were mad^e alkaline, treated with ether, the ether product
dissolved in acetic acid, filtered, and precipitated as before. The total
weight of mixed alkaloids obtained was 12"4 grains, of which 1"7
grains had been separated from the mother-liquors.
The jervine was precipitated as nitrate from an acetic acid solution
containing 3 grains in each fluid ounce, by addition of an equal volume
of saturated potassium nitrate solution. The precipitate was filtered
off after six hours, washed with potassium nitrate solution, pressed
between bibulous paper, and dried : its weight was 7'9 grains, and the
ORGAXIC CHEMISTRY. 171
weight of alkaloids precipitated from the concentrated filtrate by
warming with soda was 3"2 grains.
The aqueous solution, after removal of the alkaloids, was treated
with subacetate of lead, the excess of lead separated, and the free acid
neatralised with barium carbonate ; the filtered solution was then
evaporated to a syrup, and thrown into alcohol. The filtered alcohol
solution, evaporated and dried at lUO°, yielded a product with sweet
and somewhat bitter taste, energetically reducing copper and silver
salts, and apparently consisting almost entirely of glucose : its weight
amounted to 8"5 per cent, of the total aqueous extract.
The alkaloids were then removed from the resin, both that from the
soft extract and also the hard resin. Fatty matter was first dissolved
away by light petroleum, then the powdered resin was made into a
smooth paste with water, and dissolved in a solution of sodium car-
bonate containing soda. The alkaline solution was twice agitated with
ether, and the ether extract dissolved in acetic acid, filtered, and the
alkaloids precipitated as above ; the alkaloids were also extracted from
the mother-liquor, and the jervine separated from the alkaloids as
nitrate. A further minute quantity of alkaloids was obtained from
the alkaline solution of the resin.
The total amount of alkaloids obtained from the extract representing
1 pound of root was 46"6 grains, and from this, 31"2 grains of nitrate of
jervine and 11 grains of other alkaloids were obtained, the loss of
10 per cent, representing loss and removal of foreign matter. About
oncrquarter of the total weight of nitrate of jervine was obtained from
the soft extract and from the resin from the soft extract, the hard
resin yielding about one-half of the total weight. Wright obtained
only U"80 gram of alkaloids per kilogramme of the root employed ;
the author obtains 6'612 grams : the excess being due probably to the
alkaloid separated from the resin by the author.
The alkaloids, after separation of the jervine and crystallisation
from alcohol, showed under the microscope crystalline forms differing
from jervine, the substance probably being Wright's pseudojervine :
when purified, it amounted to 5 per cent, of the mixed alkaloids.
Sapotiiticatio7i of the Hard Itesin by Lime. — From 1 pound of the
hard resin the fatty matter was removed by light petroleum ; it was
then rubbed into a smooth paste with 2 pounds of slaked lime, water
added, and the mixture boiled for a few minutes. After evaporation
and drying on the steam-bath, the powdered mass was exhausted with
3 gallons of hot alcohol. The alkaloids obtained from the alcoholic
extract, when purified by reprecipitation, amounted to more than 485
grains, a quantity 20 per cent, greater than that yielded by the ether
process, and corresponding to 4'21 grams per kilogram of the root.
F. C.
On Casein, and the Action of Rennet. By 0. Hammahstem
{Bitd. Centr., Ib7y, 147j. — Pure casein may be prepared by preci-
pitating with acetic acid, care being taken to avoid excess of acid, dis-
solving the washed precipitate in alkali, so that the solution remains
.slightly acid, filtering from separated fats, reprecipitating several times
bv acetic acid, and washing with alcohol and ether. The casein thus
172 ABSTRACTS OF CHEMICAL PAPERS.
prepared appears to be a weak acid, dissolving calcium, and barium
carbonates, and calcium phosphate. Salts appear to keep casein in
solution, and this accounts for the fact that, in the precipitation of
casein by acids, the amount obtained is not equivalent to the acid em-
ployed. Rennet, when it precipitates casein, appears to break it up
into two albuminoids, one which is greatest in quantity is combined
with calcium phosphate, and appears as cheese ; the other (a peptone)
remaining dissolved in the whey. For complete precipitation, the
presence of calcium phosphate is necessary, and this accounts for the
fact that dilute milk cannot be coagulated. The presence of calcium
chloride also partly aids cui^dling, and one part of rennet ferment is
capable of curdling 800,000 parts of" casein. E. W. P.
Fibrinogen. By O. Hammarsten (P/Z%er's Arch. /. PIii/s., 19,
563 — 622). — The author's researches have led him to regard para-
globulin and fibrinogen as entirely distinct substances, each charac-
terised by well-marked properties. In the present communication, he
describes his method for preparing fibrinogen from venous blood, and
claims for the substance so prepared that it is perfectly free from
hgemoglobin, serum, albumin, and paraglobulin, that it is> in no way
altered by the process of preparation, and that it is the true parent
body whence fibrin is derived.
To prepare fibrinogen, the author mixes 3 vols, of blood with 1 vol.
of a saturated solution of magnesium sulphate, filters, and precipitates
by addition of an equal volume of a saturated solution of sodium
chloride. After continued shaking, the precipitated fibrinogen is
removed, broken in very small pieces, and shaken up with a half-
saturated sodium chloride solution.. This process of washing with
sodium chloride solution is repeated five or six times, care being taken
that no lumps are allowed to form in the fibrinogen. The fibrinogen
is finally collected on filters, strongly pressed, dissolved in water, and
the solution is filtered.
Slight modifications of this method are elescribed, and the process
is compared, at great length, with those of Gautier and A. Schmidt.
The properties of pure fibrinogen are scarcely mentioned in the
present paper, but are reserved for a further communication. The
author states that a solution of fibrinogen is altered by long-continued
dialy.sis; that it niiay be frozen without inducing any turbidity, but
that if a trace of altered fibrinogen is present, small solid particles
separate when the mass is melted; that fibrinogen readily undergoes
fermentative changes ; and that when precipitated by sodium chloride
and allowed to remain in contact with the supernatant liquid, its solu-
bility diminishes. M. M. P. M.
Note on Hyraceum. By W. H. Greene and A. J. Parker
(Pharm. J. Trans, [ti]., 10, 188). — Hyraceum is believed to be the
inspissated urine of the Cape Hyrax (Hyrax capensis), the urine col-
lecting in hollows of rocks and gradually evaporating ; its medicinal
effect is reported to be the same as that of castoreum. It is a dark-
brown, brittle, resinous substance, with aromatic odour and bitter
taste. About 56 per cent, of it is soluble in water, and nearly one-
PHYSIOLOGIC.VL CHEMISTRY. 173
third of the residue (14 per cent.) in alcohol, ether, and chloroform ;
of the 3U per cent, of insoluble matter, 14 is woody tibre and inso-
luble organic material, and 10 coiisLsts of sand and other inorganic
substances. On ignition, h3'raceum leaves 34 per cent, of ash, con-
sisting of chlorides, sulphates, phosphates, and carbonates of sodium,
potassium, calcium, and magnesium. Small quantities of nitrates are
also present.
When the organic matter in the aqueous extract was precipitated by
lead acetate, and the precipitate was decomposed by sulphuric acid, a
hard, horny, resinous, brown, transparent substance, emitting a faecal
odour, was obtained.
Hyraceum consists of various salts and organic substances ; the
latter constitute about one-half, and contain urea in small quantity,
besides uric, hippuric, and benzoic acids ; probably also glycocol, derived
from the breaking up of the hippuric acid. Hyraceum is, therefore,
undoubtedly derived from a urine ; but the large amount of calcium
salts in proportion to the other salts, and the character of the organic
matter, indicate the presence also of faecal matter. F. C.
Physiological Chemistry.
Assimilation of Ordinary Horse Fodder. By E. v. Wolff and
Others {Lied. Ceuti\, lb7'J, ooo — 667). — After a series of experiments
given in detail, it was found that, generally speaking, the various
component parts of oi-diuary fodder were digested as well by horses
as by sheep. J. K. C.
Fattening of Animals. By E. v. Wolff (Bied. Centr., 1879, 661—
663j. — The author makes some observations on the results given in
a paper by Henneberg and others on the fattening of sheep (this
Journal, 36, 811), showing by a comparison of the food given and the
resulting increase of fat, that at least one-third of this arose from the
absorption and assimilation of the carbohydrates contained in the
fodder used. J. K. C.
Source of Hippuric Acid in the Urine of Herbivora. By
0. LoEW (.7. yr. CheiK., 20, -170 — 479),. — The author discovered an
acid in meadow hay closely resembling quinic acid, but was not success-
ful in demonstrating the identity of the two. On repeating his expe-
riments, he found it impossible to effect a satisfactory separation from
a substance resembling peptone ; but the impure substance resembles
quinic acid by giving hydroquinone with lead peroxide, and proto-
catechuic acid with bromine. Researches by several chemists have
shown that hippuric acid is not increased in the urine of an animal
by giving it quinic acid in its food ; and hay, after treatment with
soda, is still a source of hippuric acid in urine. But after treatment
with sulphuric acid, the source of hippuric acid is removed from hay.
174 ABSTRACTS OF CHEMICAL PAPERS.
The only definite compound which the author was able to isolate
from an extract of haj made with dilute sulphuric acid was some acid
resembling quinic acid.
It has been suggested by Weiske that the real source of hippuric
acid may be the meadow plants with which hay is mixed. The author,
therefore, investigated the officinal extract of dandelion, and again
found the acid resembling quinic acid along with some succinic acid,
and an acid oil, heavier than water, which gradually became resinous.
W. R.
Analysis of a Calculus from a Horse. By P. Peters and
K. ^liJLLER {Bled. Ceiitr., 1879, 714). — A calculus formed in con-
centric layers and weighing 84 kilos.^was analysed by the authors
with the following results : —
Magnesium
Soda and
Organic
ammonium
Ferric
Calcium
potash
Water.
matter.
phosphate.
phosphate.
phosphate.
Silica.
salts.
4-22
6-10
87-37
0-29
0-11
1-36
J.
0-45
K. C.
Physiological Influence of Adulterated Wine. By A. Schmitz
(Bii'iJ. Centr., 1879, 712 — 713). — The unfermentable residues of grape-
sugar, which are used for the adulteration of wine, were subjected to
experiment "with reference to their physiological action. Sub-
.cutaneous injection in the case of dogs was found to produce vomiting
and general derangement. The autlior is of the opinion that these
residues contain a poison similar to that in fusel oil. J. K. C.
Chemical Cause of the Toxicological Action of Arsenic.
By C. Bixz and H. Schulz {Ber., 12, 2199— 2202).— The authors are
of opinion that arsenic owes its poisonous nature to the alternate
oxidation of arsenious to arsenic oxide and reduction of arsenic to
arsenious oxide, which produces a rapid oscillation of the atoms of
oxygen in the molecules of albumin, causing their complete destruc-
tion. Arsenic acts as a carrier of oxygen, resemblins: nitric oxide in
this respect. Phosphorus and the other members of the nitrogen
group appear to act in a similar manner. The authors base their
opinion on the following obsei'vations : — (1,) That in cases of arse-
nical poisoning, it is those portions of the system which have the
power of taking up oxygen from the blood which suffer most
severely; (2) and that egg albumin, blood tibrin, and brain reduce
arsenic oxide to arsenious at a blood heat, and that the salivary glands
and liver not only reduce arsenic to arsenious oxide, but also oxidise
arsenious to arsenic oxide, whereas blood, h£emoglobin, and fat have
no action on the oxides of arsenic. W. C. W.
Presence of Alcohol in Animal Tissues during Life and
after Death. By J. Bechamp (Compt. rend., 89, 573 — 574). — In
order to verify the truth of the statement that flesh superficially coagu-
lated would rapidly putrefy under conditions in which well-cooked
tlesh would remain sound for many weeks, some horseflesh was coagu-
lated by immersion for ten minutes in boiling water, then wrapped in
VEGETABLE PHYSIOLOGY AXD AGRICULTURE. 175
a closely woven cloth, and placed aside for eight days. At the expira-
tion of that time, the meat was found in an advanced state of decom-
position, and the muscular striation had disappeared, although the air
had not penetrated to the interim- of the substance, whilst bacteria and
\'ibrios abounded. By methods described in the original memoir, the
author isolated and characterised about 0*8 gram of alcohol and
10 grams of sodium salts formed by acetic, butyric, and other acids.
The alcohol was converted into aldehyde, and oxidised to acetic acid, so
that its identity was established beyond doubt ; within certain limits
the quantity obtained was larger, the further the extent of the decom-
position.
It would seem, therefore, that the phenomena accompanying putre-
faction are very closely allied to those belonging to fermentation
properly so called, perhaps more directly with those of the butyric
fermentation. By the same process alcohol was obtained from the
n-e.^/i tissues. The brain of sheep gave a larger quantity than the
liver, but the largest quantity was obtained from the brain of an ox,
which furnished sufficient alcohol to measure with the hydrometer.
It may be argued, therefore, that in medico-legal cases, the detection
or separation of alcohol from putrid or healthy tissues, is not sufficient
evidence to show that alcohol has been administered at all. still less
that this liquid has been the cause of death. J. W.
Chemistry of Vegetable Physiology and Agriculture.
Unorganised Ferments in Plants. By C. Kracch {Bied. Centr.,
IbT'J, IlIU — 1-2.-2). — The ferments from various plants were obtained by
the method of Wittich, or by that proposed by Erlenmeyer, For the
detection of diastatic fermentation, the decomposition of starch into
sugar, and dextrin was employed. The action of the ferments on albu-
minoids could be studied only when free acids (2 : 1000) were present ;
to detect and recognise the ferments -which act on fats, the decompo-
sition (1) of an emnlsion of gum arable water ; (2) of oil with free acid
and glycerol; (3) of oil in the state of an emulsion, were taken advan-
tage of.
The substances which came under examination were buds and twigs
of horse chesnut, which were sepai-ated into wood and bark : the same
also of the birch ; the young and old bark and wood of oak, the leaves
of hawthorn ; bulbs and tubers ; starchy grains, as barley and maize, the
endosperm and embryo being in the last grain examined separately ;
oily seeds, as pumpkin. In no case could albuminous or fatty ferments
be detected. A strong diastatic ferment is found in the horse chesnut
at all periods of growth. Slight I'ermenting action in the leaves of
oak and hawthorn, whilst the birch is free of ferment. In onions and
potatoes, a weak ferment is present, but during the period when there
is no growth, the onion alone possesses a ferment. Diastase is present
in unsprouted barley, but the action is weaker than that of malt
176
ABSTRACTS OF CHEMICAL PAPERS.
diastase ; in Tinsproiited. inaize diastase is found only in the embryo
and hiluin. It would seem, therefore, that in all starch-containing
plants, diastase is present more or less, the quantity being dependent
on the amount of starch present ; but the change of starch into glucose
does not necessitate the presence of diastase : for example, the birch
contains no diastase at any time. Further experiments were directed
towards determining the action of the ferment of the above plants on
gum arabic and qaince emulsion ; in all cases sugar v/as formed. The
ferment of oak and hawthorn leaves, mailt and pumpkin seeds, affected
salicin, but the action was most energetic in the case of the pumpkin
seeds ; only oak leaf ferment had any action on amygdalin, and that
only after 48 hours' contact. The coniposition of diastase is given as
C, 45-68; H, 6-90; K, 4-57; ash, 6-08;. O, 3677 parts per hundred;
sulphur is also present in small quantities. E. W. P.
Chemical Composition of Bacteria in Putrefying Liquids.
By M. Nencki and F. Schakfer (/. pr. Chem., 20, 443— 465).— The
authors have found that on adding a few drops of acid (sulphuric,
bydrochloric, or acetic) to a liquid containing bacteria, and boiling it
for a few minutes, the bacteria shrivel up, and settle ; the liquid may
then be filtered, and the bacteria separated in a " chemically pure "
condition. Of course the fluid must contain no substances precipi-
table by boiling, such as albumin. Ordinary gelatin was therefore
chosen as a suitable medium for propagating the growth of bacteria.
Tlie dried mass of bacteria was first exhausted with alcohol, and
the alcoholic extract then treated with ether. A slight brownish
residue of a substance resembling peptone was left. The ethereal
exti-act contained the fat, the elementary composition of which
— 72'54 per cent. C, and 11*73 per cent. H — corresponds fairly with
that of vegetable and animal fats,, but contains 1"5 per cent, too little
carbon.
In order to ascertain whether any change in the composition of
bacteria occurs in the course of their development, analyses were made
of undeveloped granules, of a niixtui'e of granules and rod-like bodies,
and of the rod-like bodies after full growth. The results are as
follows : —
Water
Fat (contained in dry
substance)
Ash (in substance de-
prived of fat) ....
Elementary com-^ p
position of the I tt
substances de- f^-^
prived of fat J
Grranular mass
Pure gi'anular
with partially
mass
developed
Perfect
(Zooglcea).
bacteria.
bacteria.
84-81
84-26
83-42
7-89
14-34
14-60
6-41
3-25
53-07
7-09
13-82
a.
6-04
5-03
53-82
7-76
14-02
13-82
An estimation was made of the albuminoid substance contained in
VEGETABLE PHYSIOLOGY AXD AGRICULTURE. 177
the bacteria, by exhausting: the mass with very dilute alkali, separating
the soluble from the insoluble portion by filtration, neutralisation with
hydrochloric acid, and precipitation by addition of crystals of salt.
The precipitate consists of anew albuminoid, soluble in excess of acetic
acid, and has been named by the authors mycoprote'in. It contains
52'32 percent. C. ; 7'55 per cent H., and 14"75 per cent N., and corre-
sponds well with the formula C25H40N6O9. It was proved that neither
sulphur nor phosphorus were- present. Freshly precipitated my co-
protein is easily soluble in water, alkalis, and acids, but after beincr
dried at 110°, it is no longer perfectly soluble in water. It exhibits
the usual properties of an albumin, and is lasvorotatory, [a] = — 79.
Acids convert it into peptones. The authors believe that this simple
form of albumin is obtained from a simple organism ; a general law
may be deduced, the more complex the organism, the more complex its
proximate chemical constituents.
The residue left insoluble on treating the bacteria with dilute alkali,
consists of cell-membrane, and amounts to about 5 per cent, of their
weight; it contains a little nitrogen. This may point to some albumin
nob removed, for Loew analysed similar cell-membranes, and found
them to contain a mere trace, or no nitrogen. W. R.
Germinating Power of Beetroot Seeds. By A. Petermann
(Bied. Gentr., 697 — 699). — The author is of opinion that beetroot seeds
of good quality should have a germinating power of not less than
85 per cent. ; he also observes that this depends very largely on the
ripeness of the seeds at the time of gathering. J. K. C.
Influence of Smoke on the Development of Blossoms. By
E. DA Canto (Bied. Centr., 1879, 715). — It is found in the Azores that
the entrance of smoke into the conservatories causes a rapid develop-
ment of the buds in the case of roses, ananas, &c., and this fact is now
made use of in hastening the blooming. J. K. C.
Causes of the Change in the Form of Etiolated Plants. By
E. GoDLEWSKi (Bied. Centr., 1879, 715 — 716). — The author shows that
want of light stops the growth of the cotyledons, and favours that of
the stems ; hence the changes of form observed. J. K. C.
Notes on Cinchona Bark. By D. Howard (Pharm. J. Trans.
[3], 10, 181). — The author has been enabled to compare the proportion
of quinine and other alkaloids contained in the " natural " bark and
in that formed by " renewing," i.e., growing after the artificial removal
of the bark. This renewed bark is termed "' mossed bark," because the
tree, after being stripped of its bark, is usually protected by a covering
of moss, whilst fresh bark is being formed. The natural bai'k was
found to be generally inferior to the mossed bark, since it had been
collected either from the upper stem, or from inferior old trees,
whereas the mossed bark represents the product of the main stems of
the oldest trees. As far as the eifect of age was concerned, it was
found that both the quinine and total crystallisable alkaloid steadily
increased in quantity with the age of the trees ; this is probably due to
178 ABSTRACTS OF CHEMICAL PAPERS.
the greater maturity of the trees. The trees from which the bark was
taken were specimens of Cinchona officinalis: The author, on the other
liand, confirms from recent experience an opinion previously expressed,
that the bark of succiruhra deteriorates in quality when the tree has
passed a certain age. Root bark shows a marked tendency to develope
the dextrogyrate alkaloids. A sample of renewed bark, which had
been formed without " mossing," or any kind of protection, was also
examined, and was found equal in quality tO' the best mossed bark ;
hence it appea;rs that the only advantage of mossing is to enable the
tree to form bark again with a minimum injury to its health ; the
process does not appear to improve the quality of bark formed. The
author also compares the proportions of alkaloids contained in outer
and inner bark ; the outer bark not only contains a larger quantity of
alkaloids, but these contain a larger proportion of quinine ; hence it
has been suggested to shave off only the outer layers, without cutting
quite through the bark. F. C.
Relation of Yield of Beet to Rain and Sunshine. By J.
Hanamann (Bied. Gentr., 1879, 694 — 697). — The author has made
observations in Bohemia, on the relation of beetroot produce to the
weather during the last twelve years, and arrives at the following
conclusions. A mean temperature of from 14 to 18° C, from May to
October inclusive,^ and a warm and w^t spring, together with a not too
dry stimmer, are tke best conditions under which beet can be grown.
J. K. C.
Researches on the Ripening of Grapes and Fruits. By
C. PoETELE {Bied. Centr., 1879, 123 — 131). — The composition of
apples, pears, and other fruits was determined at various periods of
their growth. The results are as follows : — The absolute weight of
pears and apples increases, whilst that of grapes increases only up to
the time when colour appears, and then begins to decrease. The per-
centage of dry matter iu the pear at first increases and tlien diminishes,
whereas with apples the decrease is sudden and then remains constant.
In the same way alteration of the amount of insoluble residue occurs.
The percentage of ash constantly sinks, which with the apple is twice
as great as with the pear. The amount of free acid is greatest in the
young pear, gradually sinking, but again slightly increasing at the end
of ripening ; this last does not occui' in the apple. Grapes differ from
kernel fruit in that with them there is not only a change in the rela-
tive percentage of the various acids present, but also a decided decrease
in the total free acid. Pears appear to contain at first only tannic
acid, which gives place to malic acid as growth pi'oceeds, whilst the
apple appears to contain both, and these diminish regularly. Sugar
increases as apples, pears, and grapes ripen, but with grapes it is the
dextrose which increases most, whilst laevulose increases in greatest
proportion in other fruits.
Comparing the constitution of the leaves with the fruit, we find
that the acid in the leaf is present in greatest quantity when that in
the fruit is lowest. Sugar increases in the leaf and then decreases,
and there is more present in the leaf at first than in the fruit ; l^evu-
lose and dextrose are pi'esent in equal quantities.
VEGETABLE PHYSIOLOGY AND AGRICULTLTIE. 179
Other specimens of fruit were examined whicli had been plucked
and put aside to ripen, and it was found that the loss in weight was
less, the riper the fruit was when plucked. Fibre, &c., and acid de-
crease, but sugar increases, and dextrose is converted into laevulose.
Various otlier fruits, as strawberries, peaches, &c., were also
examined, and with similar results. E. W. P.
Depreciation of Barley by Overgrowth. By Lauensteix
(Bied. Centr., 1879, 676 — 681). — The difference between barley
gathered at the right time and barley which has been allowed to lie
out on the field for some time after it was ripe is not clearly shown
by direct chemical analysis. An examination of the separate con-
stituents is necessary in order to ascertain the changes which have
taken place. In carrying out this plan the author turned his attention
first to the starch present in the seed. Ordinary barley contains 64
per cent. ; in the overgrown corn was found, however, only 58 per
cent., the remainder having been converted into dextrin and sugar: a
loss of lO per cent., therefore, on the total quantity of starch was dis-
covered. The change which the starch had undergone would of course
not affect the nutritive value of the barley ; this, however, was not the
case with the albumin, nearly one-foui'th of which was found to be
converted into amido-compoands, which are of very little nutritive
value. The worth of barley for the preparation of malt depends to a
very large extent on its powers of germinating. This was found to
have suffered a loss of 53 per cent, in the overgrown corn.
J. K. C.
On the Quantities of Acid and Sugar in Grapes cut at
Various Stages of their Growth. By P. Wagner and W. Rohx
(JJii'd. Ctidr., 1679, 681 — 6b6). — These researches have been so far
only of a tentative character, the object being to discover if possible a
practicable method of examining various sorts of grapes at different
stages of their growth, and chieflj" at the ripening stages. The authors
carried out their researches at six difierent places, with vines of
various kinds. The grapes were cut four times during the last month
of ripening, and the relative quantities of sugar and acid determined
in the sap. In some cases the relation improved, in others it remained
constant for some weeks. The authors hope, by repeating these obser-
vations for some time to come, to arrive at results of great practical
value. J. K. C.
Ripening of Apples after Gathering. By F. Tschaplowitz
(Bied. Centr., 1879, 686— 689),— The author finds that the loss of
weight undergone by apples on keeping is dependent on the position
in which they are left and the dryness of the surrounding air. It may
be almost entirely considered as loss of moisture, the amount of car-
Ixmic anhydride which is given off being but very small. It is notice-
able that smaller apples lose more in weight than those of a larger
description. The temperature of the frait is also the same as that of
the air.
The results of various analyses show that the quantity of sugar in
180 ABSTRACTS OF CHEMICAL PAPERS.
the apples increases during the ripening process at the expense of the
pectin and acid, J. K. C.
Decomposition of Albuminoids in Pumpkin Sprouts. By
E. ScHULZE and J. Barbieri (J. pr. Chem., 20, 385 — 418). — The seeds
of plants contain albuminoids, starch, and oil, by which the sprouts,
which are not able to decompose carbonic anhydride and water, are
nonrislied. During germ.ination the starch and fat decrease, whilst
sugar, dextrin, and cellulose are formed, and carbonic anhydride and
water are eliminated. From more recent observations, it has also been
discovered that the albuminoids become soluble, and that in many
plants, especially in Papilionaceae, asparagine is produced. As that
body decomposes on boiling with hydrochloric acid into aspartic
acid and ammonia, its amount may be determined by estimating the
ammonia. Gorup-Besanez afterwards found leucine amongst the de-
composition-products of albuminoids. In pumpkin sprouts, which
contain no asparagine, Sabania and Laskowski supposed that another
amide existed ; this was shown to be correct by the authors and by
Uli-ich. In the beetroot this amide has been shown to be glutamine,
and the object of the present paper is to show that it is also present in
germinating pumpkin sprouts, along with asparagine, leucine, and
tyrosine.
The albuminoids and fatty oil form 86 — 88 per cent, of the weight
of dry pumpkin seeds, the former being present as protein granules.
When the crushed seeds are treated with ether, the fat dissolves and
the protein substances sink to the bottom of the vessel. They are in-
soluble in water, but dissolve in a 10 per cent, solution of salt. On
addition of solid salt, a small quantity of vegetable myosine separates,
and on dilution with water, vegetable vitelline is deposited. Non-
albuminoid principles containing nitrogen are present in very small
amount in pumpkin seeds.
The sprouts after germination were dried, boiled with alcohol, and
the evaporated extract was treated with lead acetate. The filtrate
from the lead precipitate was boiled for several hours with hydro-
chloric acid, and again mixed with lead acetate to remove hydrochloric
acid. The filtrate from the lead chloride after evaporation was mixed
with alcohol, and the precipitated lead salts were decomposed with
sulphuretted hydrogen. The solution filtered from the lead sulphide
and treated with silver oxide to remove traces of hydrochloric acid
was evaporated, when glutaminic acid, C5H9NO4, separated in the
crystalline state. It was shown that this acid was not present as such
in the sprouts, but was formed by the action of hydrochloric acid on
glutamine, a body bearing the same relation to glutaminic acid as
asparagine does to aspartic acid. From sprouts which had germi-
nated for eight days, 100 grams gave only a few decigrams, but 16
days' growth increased the amount to 1"75 gram of acid, representing
1-74 gram of glutamine. The ammonia produced by the action of
hydrochloric acid on glutamine corresponds to twice that amount, and
to account for it a search was made for substances which would
undergo a similar decomposition with hydrochloric acid. Aspart-
ate of copper, amounting to 05 gram in 400 grams, was separated
VEGETABLE PHYSIOLOGY AXD AGRICULTURE. 181
from the mother-liquors of the glutamic acid, and leucine and tyro-
sine were isolated by boiling the juice from sprouts 2 — 3 weeks old ;
and after precipitating with alcohol and evaporating the filtrate, wart-
like crystals were deposited, consisting of tyrosine. From 1,000 grams
of fresh sprouts (60 grams when dried), 0'15 gram of tyrosine was
obtained, and leucine was isolated from the mother-liquor of the tyro-
sine, but in much smaller quantity.
The nature of the decomposition products is thus the same as when
the albuminoid is heated with baryta-water or hydrochloric acid ; but
the proportion of each product diffei's greatly. Un decomposing the
albuminoids from pumpkin seeds with hydrochloric acid and stannous
chloride, 120 grams yielded leucine, 24 grams ; tyrosine, 25 grams ;
aspartic acid, 3 grams ; glutamic acid, 4 grams; and an uncrys-
tallisable residue of 40 grams, the sum being 75 grams. The differ-
ence between 120 and 75 = 45 grams, was lost. If these amounts
represent even appi'oximately the pi'oportions in which the nitrogenous
materials are present in the mixture, it is seen that they differ greatly
from the proportions produced by the decomposition of the albuminoids
during germination. The author's explanation is that in a growing-
plant albuminoids are being formed as well as decomposed, any one of
the decomposition products serving as material for their foi'mation.
The co-existing decomposition products of albuminoids may, however,
not be equally used in the formation of new albuminoids, and those
which resist the process of regenerating albumin longest accumulate
in largest quantity. Thus leucine, which is produced in large quan-
tity by the artificial decomposition of albumin, is probably one which
lends itself best to the natural formation of albumin, and is therefore
present in germinating plants in small amount, whilst such, substances
as asparagine and glutamine are comparatively stable, and resist ab-
sorption to form new albuminoids.
In conclusion, the authors remark that as ferments are capable only
of changing albuminoids into peptones, some other reason must be
sought for to account for their decomposition into much more simple
products, and quotes a sentence of v. Niigcli, in which such changes
are ascribed to the molecular force of living tissue. W. R.
The Most Advantageous Method of Sowing Corn. By F.
Haberlandt (Bied. C'entr., 1879, 689 — 694). — The author has made
several experiments with wheat, rye, and barley, with a view of ascer-
taining the number of seeds per square meter which will give the best
yield. His results have necessarily only a special value for the soil
and climate in which the experiments were carried out. He was able
to obtain a yield twice as great as that usually obtained, and thinks
that this might be effected in most cases where the proper conditions
are observed. It was noticed that the latest development occurred
where the seed was most sparsely sown. J. K. C.
Proper Thickness and Depth to Sow Corn. By Schenk-
Baiiiof (Bied. Ceutr., 187'J, 717).
Amount of Carbonic Anhydride in Shingle. By G. Wolff-
hug el {Bied. Cent)-., 1879, 709).— The author brings forward tables
VOL. XXXVIII. 0
182
ABSTRACTS OF CHEMICAL PAPERS.
already publi.slied in defence of his view that the amount of carbonic
anhydride in tlie ground air is a measure of the degree of impregna-
tion of the soil with, organic matter and of the progress of its decom-
position. J. K. C.
Peaty Soils. By A. v. Schwarz (Bied. Gentr., 1879, 84—93;.—
The analyses of 26 Austrian peaty soils are given, in which
the ash varies from 2'30 to 76'08 per cent. To one soil the author has
paid special attention, and he has determined the physical properties
(which are here appended) of soil from the moorland of Kirchberg a. W.
He also finds that this soil when treated with artificial manures yields
average crops. The physical properties of the soil were compared
with those of alluvial sand from Rotz, loam, and clay, and are as
follows : —
Weight of
Capillary saturation
100 e.c. in
Contraction and
capacity.
grams.
expansion.
Satui'ated with capil-
Sp. gi-.
lary water.
wntpi*
SoU.
at 17 -5
Air
drv.
Satu-
rated.
= 1 -00.
100 e.c.
saturated
after dry-
100 e.c.
. dried,
when satu-
100 CO.
contain
100 gnns.
contain of
rated in
of water
water
ing in e.c.
e.c.
Peaty
28-7
105-6
1-470
39-8
_
82-0
77-6
Sand
157-9
190-6
2-569
100 -0
100 0
34-9
18-3
Loam ....
1.55-2
192-9
2-729
83-9
119-2
43-2
22-6
Clay
140 -1
179-8
2 -714
70-2
142-1
51-5
28-6
In the determination of cohesion by Haberlandt's process, clay
was found to stand highest and loam lowest, sand naturally possessing
none. In the case of adhesion by Schlibler's method, clay stands first,
then loam, peat, sand.
Masses of soil 10 cm. deep, and exposing a surface of 10 square cm.,
allowed the passage in 24 hours of 1 e.c. water in the case of peat,
Hygroscopieity
100 gi-ams
dry soil
absorb of
water
Equal weights specific heat.
Equal volumes
Soil.
Dried at
100^
Saturated
with
capillary
water.
Dried at
100°.
saturated
with
capillary
water.
Peaty
Sand
Loam
Clay
21-6
11
3-7
9-2
0-592
0-209
0-218
0 -225
0-909
0-3oi
0-395
0-417
0-140
0 -325
0-326
0-289
0-960
0 -675
0-762
0-804
>t:getable physiology and agriculture. 183
5,760 in the case of sand, 1,674 in the case of loam, and 0-7 in the case
of clay.
Conductivity for heat was determined (1) by the increase of tem-
perature of the unheated soils, and (2) by the loss of temperature
experienced in cooling. In this the soils were experimented on when
dry, and when moist, or saturated with capillary water, the source of
heat was 60°, and the original temperature 16-3 — 16-7°.
From the results, it would appear that under direct action of solar
radiation peaty soil when dry a.<5sumes a higher temperature than
either of the others, but the case is reversed if the soils be moist. As
regards the rising of water in columns of sand, loam, and clay, it is
found that in 100 days water had risen to the height of 408 mm. in
sand, to 1,627 in loam, and to 770 in clay. E. W. P.
Composition of Maize. By L. Graxpeau {Bled. Centr., 1879,
149). — Analyses of various specimens of maize used as feeding stuffs
are given. The best appear to be the Hungarian (nutrient ratio,
1 : 88), then American (nutrient ratio = 1 : 8"6), but the American
is very hard to crush. E., W. P.
New Plant for Fodder. By J. Deinixgbe (Sled. Centr., 1879,
700 — 702). — Seeds of a plant known in India as "gram," a variety of
chick-pea, were planted in various kinds of soil in Hungary. The
plant thrived exceedingly well, especially in sandy soils, which were
worthless for other purposes, and proved very productive. The
following analysis of the seeds show that they ai-e very valuable as
fodder : —
Water.
Protein.
Fat.
Tfitrogen-fret
extmct.
1
Fibre.
Ash.
First year . . . .
Second year . .
10-72
9-80
12-88
17-68
4-39
3-77
58-02
54-32
10-20
10-89
3-79
3-54
J. K. C.
Analysis of Materials used for Fodder. By P. Wittelshofeu
(Bied. Centr., 1879, 713). — Analyses were made of soured cabbage
leaves, dried sprigs of broom, concentrated residues from a starch
manufactory, and potato pulp. The fir.st two proved to be excellent
for fodder, but the last was too poor in nutritive matter to be used
alone. J. K. C.
Feeding Value of some Manufacturers' Waste. By J.
MosER (Bied. Cent)-., 1879, 114—117). — The analyses of several
feeding-stuffs, which however do not appear in large quantities in the
market, are given, and are as follows : —
0 2
184
ABSTRACTS OF CHEMICAL PAPERS.
Album.
Water.
Fat.
Ether,
oil.
Non-
nitrog.
Fibre.
Ash.
Sand.
extract.
Fennel seed caKe . .
9-23
15-28
12-0
0-15
33-12
20-15
8-14
1-93
Sunflower cake :
(1.) As powdery
mass
10 -62
38-00
6-44
~
28-11
10-48
4-96
1-39
(2.) As coherent
cake
807
37-69
23-73
^■^
19-29
6-05
5-10
0-62
Pumpkin seed cake .
Loosely coherent
mass
11-25
32-56
25-57
—
9 13
15-68
4-79
1-02
Decorticated. . . .
11 01
38 -74
23-55
—
10-75
10-33
5-39
0-23
Tobacco seed cake,
containing no ni-
cotine
10 -fiO
25 -60
14 60
—
15-08
22-43
5-31
6-29
Wine lees cake. .
51 04
2-54
8-54
—
7-41
11-10
1-74
9-20
Dried brewers'
grains :
Mixed with meal
and dried ....
12-94
18-69
G-30
—
38-00
16-95
4-31
2-81
Fresh and un-
dricd
79 -22
4-92
1-35
—
9-36
3-44
0-89
0-52
Brandy manufac-
turers' waste*,
pressed and dried
12-42
24-50
11-87
—
39-30
8-78
1-52
1-61
Suet grieves :
Boiled and press-
ed
4-77
48 06
41-10
—
—
—
4-88
0-41
Same not pressed
58-29
11-75
24-20
-"^
—
—
E. W. P.
Certain Sorts of Pumpkin. By C. 0. Harz {Bied. Centr., 1879,
717). — The author recommends Cucui'hita maxima Brasiliensis and
G. m. elliptica as tlie best kinds to grow, because the fruit does not
putrefy and can be kept many years. Analysis of tlie dried fruit gave
tlie following results : —
Nitrogen -free
Protein.
Fat.
extract.
Fibre.
Ash.
10-87
1-64
72-75
9-39
5 -.35
J. K. C.
Influence of Fodder on the Quantity and Quality of Milk
Fat. By H. Wki^ke, M. .Scukodt, and B. DEiniEii (Bicd. Centr.,
1879, 110 — 113). — The present opinions concerning the influence of
fodder on milk pi'oduced are, that dry food produces more solid gly-
cerides in butter than the green feeding of summer, and that a hard
butter is produced when the feeding has been scanty, or poor in albu-
minoid matter. The analyses of the milk of a cow which had been
* Note hy Abstractor. — There is evidently a printer's error here, as the above
analysis is said to he that of a substance undricd, whereas the analysis of the sauu^
material which is called " dry," shows a percentage of 6141 water.
VEGETABLE PHYSIOLOGY AND AGRICLTLTURE. 185
fed at different periods with various kinds of food, show that a high
melting point of butter is not dependent on scanty feeding ; the
melting point, and also the quantity of the butter fats, and of the
fatty acids, show no regularity, even when the feeding remains the
same. Highly albuminous fodder produces the highest yield of milk ;
addition of albuminoid matter to fodder increases the amount of fat
in milk, but addition of oil and of stearic acid causes a much greater
amount of fat and diy substance to be formed. Comparing mornino'
and evening milk, no difference in the amount of solid matter or fat
could be detected ; and the melting points of the fats were the same
on the same days, the melting point of the cream fat being 2^ lower
than that of the fat of the skimmed milk. The amount of fatty acid
insoluble in' water varied very considerably, varying from 84 — 88"9
per cent. . E. W. P.
Pour-yearly Rotation of Crops. By A. Voelcker (Bwd. Cent,-.,
1879, 658 — 661). — These experiments were conducted at Woburn on
behalf of the English Agricultural Society ; the plan of rotation
was the following: — 1st year, clover; 2nd year, wheat; 3-rd yeai*,
roots (turnips, &c.) ; 4th year, barley. The results obtained in 1878
were mostly of a normal character. The author has found that
manure obtained after a fodder of cotton seeds is of more value to the
land than if the animals had been fed on maize ; and that the mate-
rials for plant nutriment have a better effect when applied directly to
the land than when they have been mixed with fodder and allowed to
pass into dung. J. K. C.
Manuring of Oats on Fen Lands. By H. J. Garsten (Bied.
Centr., 1879, 97 — 99). — Oats were found to be most prolific on moor
land when manured with stable manure.
Comparing the two methods of cultivation, " Veen" and " Damm
kultur," it was found that the " Damm" method (covering the moor
with a layer of sand), in all cases when the manuring with artificial
manures was employed,, gave better results than the " Veen" method
(where the surface to a depth of 10^ — 12 cm, is mixed with sand).
E. TT. P.
Effect of Gypsum on the Quantity and Quality of Clover
Crops. By A. Pasqualini (Bied. Centr., 1879, 99).— Clover manured
with gypsum is not affected as regards its feeding qualities, although
the total yield is increased. E. W. P.
Manuring of Su.gar Beet. By. J. Moser (Bied. Centr., 1879,
100 — lU6). — This paper contains an account of the manures used
(salts of potash, sorla, and magnesia)^ the yield of roots, tops, and
sugar obtained in experiments made in the years 1876-77 ; but no
conclusions are drawn, as the experiments are still being carried on.
The manures were employed in quantities equal to one-eighth of the
capacity of the soil for potash. E. W. P.
Manuring of Beet. By H. Brtem (Bied. Centr., 1879, 656—658).
— Two kinds of lime manui-e are used in this investigation, the object
186
ABSTRACTS OF CHEMICAL PAPERS.
of which was to compai'e their action. One of these was the ordinary
lime-scum from sugar works, and the other a mixture of lime-dust
with the residues from a beet and molasses distillery : the latter con-
taining about 43 per cent., and the former 30 per cent, of lime: they
were applied to a soil very poor in lime, containing about 4 parts per
thousand, the experiments being carried out in two successive years :
the mean results are as follow : —
Manure used.
Weight of the beet
in grams.
Polai'isation of
sap.
Percentage
of
Total.
Leaves.
Root.
Degrees.
Sugar.
Not
sugar.
Water.
Ash.
None
440
506
946
105
122
210
335
384
736
14-2
15 0
14 1
10-95
11-67
9-66
3-25
3-23
4-44
82-8
84-7
Lime from sugar
works.
Lime with distil-
lery residues. . .
0-80
0-91
The difference in the effects produced by the two manures is very
marked : the distillery residues produced a wonderful effect in in-
creasing the total weight of the yield, at the same time, however,
deteriorating greatly the quality of the juice obtained, as is observed
on comparing the ratio of the quantities of sugar and non-saccharine
matter present in the juice : this relation is of the greatest importance
to the manufacturer, as a juice containing such a quantity of extra-
neous matter would be found very difficult to work. J. K. C.
Influence of Soluble and Insoluble Phosphates as Manure
for Turnips. ByT. Jamfeson {JJied. CeiUr., lb7U, 652 — QlJCy). — These
investigations were carried out near Aberdeen, with a view of com-
paring the effect of phosphoric acid in the soluble and insoluble form
applied as manure to turnips. Five fields, lying at considerable dis-
tances from one another, were selected, and each made the subject of
eighteen experiments, each of which was carried out on two separate
plots. The experiments were conducted in the years 1876 and 1877,
the latter proving a bad year for turnip crops. No difference was
observed between the effect of animal and mineral phosphates. From
the results obtained, the author shows that the effect of insoluble phos-
phates varied little from that produced by soluble phosphates : —
Yield per acre in kilos, after
treatment with
1876.
1877.
Insoluble
pliosphate.
Mean of 30 experiments at 15 places . . 17,270
6 ., 1 place . . 18,290
„ 4 „ „ .. 8,430
Soluble
phosphate.
18,290
17,260
9,860
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 187
Addition of nitrogenous manures to the phosphates yielded the
followino: results in 1876 : —
o
Sulphate of ammonia Cliili saltpetre
with with
~^ r
Soluble Insoluble Soluble Insoluble
bone-ash. bone-ash. bone-ash. bone-ash.
Mean of 10 experiments . . -20,720 20,720 21,130 18,tJ99
„ 2 „ .. 24,380 24,380 23,350 22,350
The increase in the yiehl produced by the addition of nitrogenous
manures is, however, only an appai'ent one, as it arises merely from an
increase of the percentage of water in the product. The same increase
in the yield may be obtained when the phosphate is very finely
powdered.
The author also finds that the highest percentage of nitrogenous
matter and the smallest quantity of sugar was the result of manuring
with soluble phosphate, whilst insoluble phosphate produced the exactly
opposite effect, and a medium result was obtained when nitrogen had
been added to either.
Those plots which were manured in 1876 were left unmanured in
1877 in order to observe the after-effects of the various materials used.
It was observed that those fields which gave the best yields in the
former year w^ere the least productive in the latter, and vice versa.
Animal phosphate also appeared to have a better after effect than
phosphates of mineral origin. The highest produce as a total of both
years was obtained by using raw dried bone-ash, which is more effec-
tive when applied in spring than in autumn. The results obtained by
the use of this manure show that it is the best that can be applied in
the case of turnips. J. K. C.
Action of Different Manures on the Yield of Potatoes. By
W. Paulsek (Bied. Centr., 1879, 106 — 108). — Sheep's dung produces a
yield 50 per cent, higher than that produced by various other artificial
manures, and 60 per cent, higher than if no dung be applied. Extra
supplies of ammoniacal superphosphate pi'oduce no increase, and
•"compost" does not appear to be capable of producing larger yields
than unmanured land. But, on the other hand, manures increase the
amount of starch. The number of diseased potatoes was highest in
the plots which were unmanured, and raore especially high in the
crops of " Fiirstenwalder ;" amongst the " snow flake " potatoes there
were also many diseased. Of the seven soi-ts grown, " 7\urora " seems
to have been the most satisfactory. E. W. P.
188 ABSTRACTS OF CHEMICAL PAPERS.
Analytical Chemistry.
Method for the Continuous Measurement of the Intensity of
Daylight, and of its Application to Physiological and Botanical
Researches. By M. Krelsleu {Bied. Centr., 1^79, 117—120). — In
the tirst portion of this article an instrument is described whereby the
intensity of daylight can be estimated for any hour; it consists of a
hollow dram in which is cut a slit parallel to the terrestrial axis ;
behind this slit is a strip of sensitised paper, across whose surface the
slit IS caused to pass by means of clockwork. To be able to compare
the shades of colour, several tints are produced also on sensitised
paper, by causing the direct rays of the sun to fall on the paper at
various angles for twenty seconds, this being the length of exposure
for each part of the registering paper. An inclination of 60° (cos. 0'5)
produces half-tint, &c., the tints being numbered 1, 2, 3 — 10 ; 10 re-
presenting full sunshine.
In tiie second portion, the author states that brightness of light is
accompanied by increased assimilation on the part of the plant ; but
this regularity of increase continues only up to the point when the
intensity of light is one-eighth that of the full sunshine, and after
that assimilation goes on less rapidly, not keeping pace with the in-
creased intensity. Now, as increased intensity of light is accompanied
by increased chemical intensity, the former may be used as an indi-
cator of the latter, as regards plant physiology, as it was found tliat
assimilation increased as chemical intensity increased, at first rapidly,
but afterwards in a less degree. Sub-aquatic plants are not of value
in determining assimilation, as they are not sensitive enough to small
changes of light ; an apparatus has therefore been devised in wliicli it
is possible to expose whole plants to the light, and is on the principle
of an aspirator. E. W. P.
Estimation of Chromium. By T. Willm (Ber., 12, 2223— 222G).
— When chromium is estimated as sesquioxide by precipitation with
ammonia, boiling off the excess of alkali, and ignition of the precipi-
tated hydrate, the results obtained are invariably too high if the
precipitation is carried on in a glass vessel. The small quantity of
lime v.liich is taken up by the ammonia from the glass enables the
chromium sesquioxide, during ignition, to combine with the oxygen of
the air to form chromic acid. Calcium chromate can be dissolved out
of the ignited residue by treatment with hot water. 'W. C. W.
Separation of the Heavy Metals of the Ammonium Sulphide
Group. By C. ZiMMERMANN (Anvale/i. 199, 1 — 16). — Zinc from the
other Mt'tals. — The solution is made as nearly neutral as possible (this
is absolutely essential) with sodium bicarbonate, and mixed with a not
too dilute solution of ammonium thiocyanate. After being heated to
60^ to 70°, a gentle stream of sulphuretted hydrogen is passed into
the liquid at intervals until it smells distinctly of the gas. It is then
ANALYTICAL CHEMSTRY. 180
left to stand for some hours at a gentle heat, when the whole of the
zinc is found to be deposited as sulphide, and perfectly free from the
other metals of the group. An excellent method of estimating the
zinc is to convert the sulphide into the chloride, and to heat the latter
with mercuric oxide, by which means the zinc is converted into oxide
and may be weighed as such.
Iron from Nickel and Cobalt. — The solution is mixed with excess of
ammonium thiocyanate, and sodium bicarbonate is added until the
red colour disappears. The iron is thus completely precipitated as
ferrous hydrate, and is free from nickel and cobalt. The nickel and
cobalt are then separated by Liebig's mercuric oxide method.
Iron from Uranium. — The boiling hot solution is mixed with excess
of ammonium thiocyanate, and sodium bicarbonate is added until the
red colour disappears. The iron is precipitated entirely as hydrate, and
is free from uranium.
Precipitation of Uranium, Oxide by Ammonia. — Addition of ammonia
in presence of ammonium chloride causes precipitation of uranium
oxide in solution so dilute that the former reagent alone produces no
effect. G. T. A.
New Method of Estimating the Air Space in Seeds and
Fruits. By J. Adamec and E. Klose (Bied. Centr., 1870, l-JU). — The
volume of the sample is calculated from its specific gravity ; the volume
of the several constituents is calculated from their specific gravity ;
these added together give the volume of the solid, and, subtracting
this from the original volume, the air enclosed is calculated.
E. W. P.
Composition of Bohemian Beer-wort, determined by
Chemico-optical Processes. By T. Haxamann (Lied. Centr., 1870,
138). — The author in this paper comes to the conclusion that by the
early processes of determination, the amount of dextrin present in
wort was too high ; by the modern proce.'^s, the amount is too low ;
the true quantity is to be found between, and can be closely determined
by the polariscope. E. W. P.
Determination of the Acid in Sugar of Lead and in Lead
Vinegar. By F. Salomox (I>u,rjl. poli/t. J., 234, 222— 220 j.— What
the atithor claims as novelty in tiiis paper is (1) that as standard acid
a solution of acetic acid should be used, which contains exactly
50 grams of acetic anhydride in 1 liter ; (2) that the solution of potash
used should be equivalent to the acetic acid solution. The following
are the details of the method : — 10 c.c. of the solution to be examined
are treated with an excess of the standard potash in a 100 c.c. flask,
and the mixture is made up to 100 c.c. with distilled water. The
portion of the lead which is dissolved by the excess of potash used is
separated from the hydrate by filtration, and 50 c.c. of the filtrate
titrated with standard acetic acid^ using phenolphthalem as indicator.
In the case of the solution containing sugar of lead, the total acid may
be estimated at once, providing the salt is neutral ; if acid, it is best to
estimate the qiiantity of free acid with standard alkali, using litmus
as indicator in this case. To apply the method to determinations of
190 ABSTRACTS OF CHEMICAL PAPERS.
acid in lead vineprar, it is necessary to neutralise the basic solution
with the titrated acetic acid solution. D. B.
Analysis of Cinchona Barks. (Chem. News, 40, 209—210.)—
1. EtJier jirocc-'s. — i,Ui.»U grains of very finel^'-powdered bark are
mixed with sufficient alcohol to form a paste, and when the fibres are
thoroughly saturated with the liquid, it is intimately mixed with
.500 grains of calcium hydrate, and heated to drive off the alcohol.
The dried mass is exhausted successively with ether, the ethereal
solution evaporated, and the residue fused at 125° C. The mass is
weighed and dissolved in absolute alcohol, and the solution neutralised
with standard sulphuric acid (loO c.c. = 10 grams crystalline quinine
sulphate). The alcoholic solution of basic quinine sulphate is eva-
porated to dryness and treated with a quantity of standard acid
equal to that pi-cviously used ; water is added, and the salt com-
pletely dissolved by boiling. Animal charcoal to the amount of 15 per
cent, of the original weight of bark is then added ; the whole digested
for 10 minutes, filtered, and washed with acidulated water. The fil-
trate containing acid quinine sulphate is concentrated, nearly neu-
tralised with dilute ammonia (3 per cent.), and allowed to crystallise.
The crystals of basic quinine sulphate are collected and weighed.
Weight of air-dried crystals ^ amount of crystalline quinine sulphate
in the bark. Dried at lOO'', 8-r5 = 100 crystals.
2. Acid process. — 1,000 grains of finely-powdered bark are treated
twice with boiling dilute sulphuric acid, and once with water ; the
extracts are evaporated to a small bulk, neuti-alised with milk of lime,
and filtered. The residue is dried and boiled repeatedly with alcohol
of 90 per cent. ; the alcoholic solutions are evaporated to dryness, and
the residues treated with acidulated water and filtered; the filtrate is
neutralised with caustic soda and shaken with chloroform ; the chloro-
form solution is separated and evaporated in a tared capsule. The
residue consisting of the total quantity of quinine, cinchonine, and
quinidine is treated with ether to extract the quinine, which is esti-
mated by the ether process. The residue is dissolved in dilute acetic
acid, and treated with a concentrated solution of potassium iodide.
The precipitate consists of quinidine iodide, of which 100 grams =
71'69 quinidine, or 94'o quinidine sulphate. The quinidine and cin-
chonine may be separated by treating the residue with proof spirit,
in which the quinidine is soluble, whilst cinchonine and cinchonidine
remain undissolved.
Owing to the rapidity with which the ether process may be worked,
it can be used with greater advantage than the acid proce.ss. The
object of the former is to extract that alkaloid only on which the
value of the cinchona bark depends, and is achieved without pro-
ducing amorphous quinine, which is so liable to be formed by pro-
tracted boiling, as in the acid process.
Calisaya and red cinchona barks may be analysed by the ether pro-
cess, but it is not applicable to the Losa or grey barks.
L. T. O'S.
Estimation of Albuminoid Nitrogen in Fodders. By F.
SlsTINI {Bled. Ceitlr., Ib79, 711).— The author recommends boiling the
TECnXICAL CHEMISTRY. 195
since the spirit was too weak to dissolve the full proportion of oil.
This tincture was examined bj diluting with water, clarifying with
calcium chloride and sodium carbonate solutions, distilling the alcohol,
and estimating benzoic acid in the residue by acidifying it and shakino-
several times with ether. On evaporating the ether, the benzoic acid
was left in a pure state ; the opium was roughly estimated colorime-
trically by adding proof spirit and a few drops of ferric chloride, and
comparing with a similarly treated standard opium solution. The per-
centage of alcohol found in this tincture by the distillation process
never exceeded by two degrees that deduced from the density of the
original tincture. The proportion of oil of anise present may be
roughly judged by the readiness with which the liquid is precipitated
on dilution with water. With a proper proportion of oil, precipitation
occurs on very slight dilution. F. C.
Technical Chemistry.
Recent Improvements in the Iodine Industry. Bv B. Wetzig
(Dingl. polyt. J., 234, 216 — ^^220). — The heavy pressure which has been
put on the Eui'opean market by the production of iodine in South
Ameinca is mostly due to the fact that the treatment of the plant, its
burning to ashes, and the lixiviating operations are conducted in a very
imperfect manner in Europe. Various methods have been proposed
whereby the loss of iodine, experienced in the first treatment to which
the plant is subjected, is reduced considerably. The plants are gene-
rally collected during the winter months, and are dried and burnt tcj
ashes in June aiid July. During this interval a large quantity of iodine
is lost through the action of fogs and rain on the plant. Pellieux and
Maze-Launcey subject the plant to a fermentation process, whereby
the loss of iodine is reduced considerably in the after treatment. At
the beg'inning of the fei^mentation, all sulphides present are said to be
converted into alkaline sulphides or hydrogen sulphide ; the latter acts
on the organic iodine-compounds which may be present, forming
hydrogen iodide. This body destroys all alkaline sulphides, potas-
sium and sodium iodides being the final product. Similar methods
have been proposed by Thiercelin and Herland.
As to the separation of iodine from varec, potassium chloride
has been adopted very largely, the results being most satisfactory.
In practice the proportion of potassium chloride to the iodine is 1 : 4
(theory 1:6).
It is stated that the methods which are generally used for deter-
mining iodine are of but little pi'actical value in varec analyses.
Wallace and Lamont's method of precipitating iodine with silver
nitrate and washing with ammonia gave satisfactory results ; however,
Fresenius's method is the simplest, safest, and best. Instead of dis-
solving nitrous acid in sulphuric acid, the author uses a solution of
19G ABSTRACTS OF CHEMICAL PAPERS.
ferric cliloride with the addition of a small quantity of sulphuric acid
for precipitating the iodine. D. B.
Introduction of Nitric Acid into the Sulphuric Acid Cham-
bers along with the Steam. By M. Liebig {Dingl. polyt. J., 233,
01 — 03). — The author says bis apparatus has stood the test of experi-
ence in one sulphuric acid manufactory in Westphalia. It consists of
a leaden steam-pipe with platinum nozzle whose opening is fi-om
4 to 5 mm. diameter, which penetrates the leaden wall of the chamber
for 5 or 10 cm. in a straight line. Immediately underneath this, and
also penetrating the chamber wall, is a glass tube 5 mm. diameter
drawn to a fine point ; this tube is bent upwards, so that the point
terminates in the centre of the opening in the steam-pipe ; outside the
leaden chamber, the glass tube is bent downwards at an angle of 30" from
the horizontal, and is passed at the same angle into another tube, the
junction of the two tubes being made tight by a piece of india-rubber
tube ; the tube into which it passes is bent into a U and connected with
the bottom of the apparatus for regulating the flow of acid. This con-
sists of a glass bulb, into the top of which projects a tube of 2 mm.
diameter, and furnished with a glass stopcock having a projecting arm
moving over a graduated scale so as to regulate the flow of acid. The
tap is connected with a syphon passing to the bottom of a flask filled
with nitric acid. When the glass tap is opened sufficiently to allow
the required amount of nitric acid to be delivered from the flask into
the bulb, and the steam is turned on, it blows across the fine opening
in the glass tube, producing a partial vacuum in the bulb ; the nitric
acid in the flask then rises in the syphon tube, passes through the stop-
cock and bulb, and issues at the point of the glass tube fixed in front
of the nozzle of the steam-pipe, when it is blown by the steam into a
spray which mixes thoroiTghly with the sulphurous acid coming from
the burners ; by this means the exact quantity of nitric acid pro-
jected into the chamber can be accurately determined and any excess
obviated. W. T.
Observations on Sulphur-baths. By P. de Clermont and
J. Fbommel (Bull. Soc. Chim. [2], 31, 485.- — Becquerel has stated that
the electromotive force of polj^sulphides to monosulphides is in the
proportion of 163 to 248. As the therapeutic action of sulphur-baths
has been ascribed to their electromotive force, some physicians have
prescribed baths of sodium monosulphide instead of polysulphide.
The authors have shown that the amount of sulphuretted hydrogen
evolved from the bath of monosulphide bears to that evolved by poly-
sulphide, the inverse proportion to their electromotive forces. By
adding manganese chloride to a solution of monosulphide of sodium at
34° C, O'OllS gram of sulphuretted hydrogen was liberated, whilst
from a solution of polysulphide of similar strength, 0'0206 gram
escaped. As the polysulphide is less efficacious from the medical
point of view than the monosulphide, it is evident that the quantity of
sulphuretted hydrogen liberated is not, at least in the case cited, pro-
portional to its therapeutic action, and to the strength of the electric
current. W. R.
TECHXICAL CHEMISTRY. 197
Use of Copper Phosphide in the Refining of Copper. By C.
RossLER {Dingl.polyt. J., 233, 48 — 53). — The object of this process is
to separate all the oxide of copper from the metal, and so to make it
tougher and more ductile. Amorphous and ordinary phosphorus have
been proposed for this purpose, but their use is now superseded by that
of copper phosphide of known composition : this has been employed
several years at Chatham dockyard with satisfactory results. The
advantages of using copper phosphide in preference to free phosphorus
are, that with the former the whole of the phosphorus present is avail-
able for reducing the copper oxide present in the molten metal, and
the possibility of accurately determining beforehand the quantity of
copper phosphide required ; the danger to the health of the workmen
caused by the use of phosphorus is also avoided.
According to Hampe, when copper phosphide comes in contact with
cupric oxide, one equivalent of phosphorus combines with the oxygen
of five equivalents of copper oxide, forming phosphoric anhydride,
which combines with another equivalent of copper oxide, forming
copper phosphate, which rises to the top of the molten metal as a
fluid slag.
In the refining furnace 1,700 kilos, of copper was first " poled " in
the usual way until the required point of deoxidation had been reached,
which was ascertained by taking a quantity out and testing it. The
quantity of phosphide added was 9 kilos., containing II' 7 per cent, of
phosphorus. It was introduced in five separate portions, the whole
then stirred by a protected iron crook, covered up with wood charcoal,
and the door and every other opening of the furnace closed. A portion
was then drawn off, and when cold tested by being bent by repeated
strokes of the hammer. This showed a marked difference in the con-
stitution of the metal before and after the addition of the phosphide.
In the latter case it had an amount of toughness which was quite
astonishing. Its cleavage was finely toothed, of salmon-red colour,
and silky lustre, like that of chemically pure copper, in contrast to
the cleavage of the other specimen, which could not be distinguished
from that of copper refined in the ordinary manner for commercial
purposes.
The specific gravity of the sample before the addition of copper
phosphide was 8' 731, and after the addition it was 8'906. With a
view to determine the actual percentage of oxygen in each sample,
portions of each were ignited in a stream of hydrogen. The loss of
weight in the sample taken before the addition of the phosphide was
0*190, and the loss after was 0"042 per cent. The author infers that
the whole, or at least part, of the loss in the latter was due to the
phosphorus and not to oxygen.
The author further ascertained that much less than the theoretical
quantity of copper phosphide required to decompose the oxide present
suffices to produce the necessary deoxidation, and this is owing to the
fact that when the copper phosphate comes to the surface, as it does
in small, very fluid drops, it meets with and is reduced again to
phosphide by the action of the red-hot charcoal which is put on the
surface, and is again absorbed by the metal, and so repeats its deox-
idising action. The minimum quantity of phosphide required to do
VOL. xxxviii. p
198 ABSTRACTS OF CHEMICAL PAPERS.
the work can fcherefoi-e only be determined by practical experience.
Its use, however, does not end here, because, when the metal is cast
into the mould, it protects the casting from the action of the oxygen
of the air, and only ceases to act when it has come entirely to the
surface in the form of phosphate of the protoxide of copper.
W. T.
On Belgian Phosphorites. By A. Peterman^^ (Bied. Cerit., 1879,
53 57). — Of the four sorts of phosphorites which occur at Ciply, in
Belo-ium, " craie grise," containing 11"25 per cent. P2O5, occurs in
laro-est quantities. It appears to be almost insoluble in solutions of
various salts, and when used in the raw state as a manure is of no
great value. E. W. P.
On Cement. (Dhigl. polyt. /., 234, 473— 478).— Tomei has
studied the question as to the influence which sulphates are said to
exercise on the time of setting and the firmness of cement, and con-
cludes that the addition of sulphates is not favourable, as it retards
the setting and decreases the firmness of cement.
Erdmenger in discussing the points as to the methods of improving
the quality of cement, especially by stowing it or adding various sub-
stances to it, gives a series of experiments which show that cement
can often be improved very materially by the addition of gypsum,
&c.
Behrmann has tried the influence of sea water on cement and finds
its action favourable, especially on Roman cement. D. B.
Peculiar Changes of Gas-pipes. By K. Birnbaum (Dingl.
pohjf. J., 234, 460 — 463). — At the St. John Gas Works, near Saar-
briick, some gas-pipes which had been in use for ten years showed
peculiar phenomena. The cast-iron of which the pipes were made had
assumed the form of a regular, brittle, and graphite-like mass of mag-
netic oxide, which could be cut with a knife and had a shining
surface. The latter disappeared after a few weeks' exposure to the
air.
The author explains this alteration by the fact that, owing to the
softness of the soil, it was necessary to surround the pipes with some
hard material in order to keep them in their position, and for this
purpose cinders were employed. These were obtained from the Saar
coals, which are noted for the large amount of pyrites they contain.
The latter coming into contact with rain-water, and also being partly
exposed to atmospheric influences, readily acted on the metal and
brought about these changes. D. B.
Action of Water on Lead Piping. By E. Reichardt (Arch.
PJiann. [3], 15, 54 — 63). — The examination of a lead pipe which had
been employed during 300 years at Andernach for the conveyance of
water, showed the formation of a coating on the interior sui-face
05 mm. thick ; the colour of this coating was yellowish-white, and
had the composition: —
PbO. BiOa. CdO. CuO. Fe^Os. Al-A-
73-962 0-453 0120 0-323 1-552 1-035
TECHNICAL CHEMISTRY. 199
CaO.
MgO.
P2O5.
C0„.
Cl.
H.,0.
1-095
0-283
8-446
1-iio
1-254
6-141 :
besides organic matter = 0-388 ; insoluble SiOo and clay = 4-399.
The source of the phosphoric acid is unknown, as the analysis of the
water at the present time, which has a hardness = 5-25, shows no
trace of it. This encrustation has a peculiar fatty acid smell, but no
definite organic compound could be obtained from it ; the presence of
this substance, whatever it may be, is considered to be due to eels,
which were formerly employed to free the pipe from rootlets with
which it became clogged.
Concerning the various modes of coating the interior of lead pipings,
so as to preserve them fi'om the action of water, the author has ma^le
experiments with piping coated with a layer of lead sulphide in the
interior surface, by the action of an alkaline sulphide. He finds that
distilled water becomes contaminated in such a pipe^ but this does not
occur if the water contains large quantities of magnesium and calcium
carbonates. On the contrary, this water deposits salts on the inte-
rior, and preserves it ; but they are removed together along with
lead by water containing carbonic acid. E. W. P.
Tungsten -Manganese Bronze. By F. P. Vexables (Clem.
Nev:s, 40, 187 — 188). — An analysis of an alloy from Hanover, bearino-
the above name, proves that it contains no manganese, and onlv an
insignificant quantity of tungsten. It consists of ordinary gun-
metal, in which part of the tin is replaced by zinc, as is seen from the
results ; —
Cii.
Sn.
Zn.
Fe.
W.
86-51
9-04
3-47
0-26
0-23
It is of a light golden-yellow colour, and close grain, and is susceptible
of a fine polish. Its sp. gr. = 8-04. L. T. O'S.
Petroleum. By H. Horler (Liugl. polyt. ./., 2-34, 52— 61).— This
paper is based on a report to the authorities of Zurich by V. Merer
respecting the sale of petroleum and other inflammable liquids.
Various points are taken into consideration, such as the limit of tem-
perature at which petroleum ignites, the consti'uction of petroleum
lamps and stoves, the size of petroleum stoves, their distance from
dwelling-houses, and regulations requisite in case of fire.
As to the flashing point of petroleum, it is stated that although a
large number of apparatus for determining this point are known, the
results obtained are very unsatisfactory. Meyer recommends the use of
an apparatus, which is said to give the true flashing point of inflam-
mable liquids. A corked glass cylinder is fitted with two thermometei's,
one dipping in the petroleum, the other being above it. One-tenth of
the cylinder only is filled with the petroleum to be examined. It is
next placed in warm water for a few minutes, then taken out and well
shaken, until the temperature of both thermometers is the same. The
cork is now removed and a flame introduced into the cylinder. The
flame burns at the end of a small glass tube drawn out to a very fine
200 ABSTRACTS OP CHEMICAL PAPERS.
point. If the vapour iguites the operation is repeated at a lower tem-
perature, until a point is reached at which the vapour no longer
ignites.
Meyer is of opinion that the flashing point of petroleum should not
exceed 36°. D. B.
Improvement of Italian Tobacco by permeating the Leaves
with the Juice of Exotic Tobacco. By A. i>e Negr[ (Gazzetta,
9, 418 — 420). — The author proposes to place the indigenous leaves in
an autoclave, and after exhausting the air to allow a strong infusion
of exotic leaves to flow into the apparatus, subsequently increasing the
pressure to two or three atmospheres, so that the juice may thoroughly
permeate the leaves. When the operation is finished, the leaves are
removed from the liquid and dried in a centrifugal machine. In this
way the aroma is greatl}^ increased, whilst the exotic leaves from
which the infusion was made, if only partly exhausted, are still useful,
although of somewhat less value. C. E. G.
Preparation of Wind. By A. Blankenhorn and Others (Bied.
Centr., 1879, 706 — 707). — The authors recommend the aeration of
must Avhich is rich in sugar and albumin during the earlier part of the
fermentation. The colouring matter of red wine is much more soluble
between 15 and 20° C. than between 0 and 10° C. J. K. C.
Bleaching of Jute. By M. Singer (Dingl. potyt. J., 234, 486).—
The author recommends the follo-rt^ing method: — The yarn is first
placed into a weak slightly warm soap-bath for 10 minutes, and trans-
ferred to a chloride of lime bath of 1"0035 sp. gr. After 40 minutes,
the jute is taken out and the operation repeated, if necessary. Finally,
it is washed with warm, then with cold water, and dried in the air.
D. B.
Application of Potatoes and Undried Malt in the Pre-
paration of Yeast. By J. Krieger-Delft (5«ecZ. Gentr., 1879, 718). —
The mash used for preparing yeast should not contain much more
than 10 per cent, of fermentable sugar, with peptone and ash in proper
proportions. The author recommends also the use of undried in pre-
ference to dried malt. J. K. C.
Influence of Light on Beer. By 0. Net {Bied. Gentr., 1879,
152). — Black, yellow, blue, white, green represent the order in which
the colours influence beer, when it is enclosed in bottles of the above
colours. Green has least influence, and therefore it is recommended
that green bottles are the best in which to store beer. E. W. P.
Adulteration of Rye Bran with Rice Husks. By J. Konig
{Bied. Centr., 1879, 149). — A specimen of rye bran M^as found to con-
tain 40 per cent, of rice husks, causing the albuminoids to fall from
14-7 to 9-6, and raising the fibre from 57 to 17-5. E. W. P.
201
General and Physical Chemistry.
Dark Lines in the Solar Spectrum on the Less Refrangible
Side of G. By J. C. Draper (Am. J. Sci. [3], 17, 448— 452).— The
author refers to a former paper on this subject (Am. J. Sci, 16, 256 —
265, this JourDal, 1879, Abst., p. 997). He now discusses the region
o
of the solar spectrum between X 431G and X 4320 of Angstrom's scale.
Five photographs, taken in November, 1878, and January and February
1879, show faint lines in this region which agree in position with
lines in the electric spectrum of oxygen. Similar lines are visible in
Rutherfurd's photograph of the same region, and in Chi-istie's map of
the prismatic spectrum. A diagram is given showing the coincidence
of the lines noticed by these three observers, -wdth the lines in the
oxygen spectrum as observed by Angstrom, Draper, Pliicker, and
Huggins. A table is also given of the solar lines between X 4313
and \ 4325, in which all the lines corresponding with those of known
elements are marked. The author considers (1) that the regions in the
solar spectrum at X 4317 and \ 4319, claimed as bright lines of oxygen,
are not as bright as others in their immediate vicinity ; (2) that the
solar spectrum shows faint dark lines in the region about X4317 and
X 4319 ; (3) oxygen is the substance which can produce dark lines in
this region, therefore we must attribute them to the presence and
action of that element. J. ]\1. H. ]M.
Ultra-violet Limit of the Spectrum at Various Heights. By
A. CoRXU {Compt. rend., 89, 808—814). — From photographs of the
solar spectrum taken at different heights, the author draws the follow-
ing conclusions : — The ultra-violet limit of the solar spectrum varies to
a small extent with the height above the sea-level, owing to the absorp-
tive power of the atmosphere for ultra-violet rays. The rate of varia-
tion corresponds to theoretical values deduced from the hypothesis of
a homogeneous absorbing atmosphere, provided equally clear days be
chosen. The extension of the spectrum expressed in wave-lengths is
one-millionth of a millimeter for a rise of about 900 meters, within
the limited differences of height observed by the author. W. R.
Examination of Essential Oils. By TV. X. Hartley and A. K.
HuxTiNGTON (Chem. News, 40, 269). — The following is a list of sub-
stances examined by the authors with respect to their optical pro-
perties : —
Oils and Hydrocarbons transmitting Continuous Spectra. — Australene
from oil of turpentine ; birch-bark, cajputene dihydrate, caraway
hydrocarbon (Xo. 2), calamus, citron, citronella, cedar-wood, cedrat
hydrocarbon, cubebs, elder, hesperidene from oil of orange peel, Indian
geranium, juniper, lavender, lign-aloes, melaleuca ericifolia, menthol
from oil of mint, nutmeg hydrocarbon, oils of patchouli (Nos. 1 and 2) ;
rose, rosewood, rosemary, santal wood, terebene, terebenthene, viti-
vert. In the.se experiments, photographs were taken of the spectrum
transmitted by the undiluted liquid, and then of that transmitted by
VOL. XXXVIII. qr
202 ABSTRACTS OF CHEMICAL PAPERS.
the liquid in various states of dilution, the dilutions ranging in some
cases from 1 in 50 to 1 in 500,000 volumes of alcohol.
Hydrocarhons showing the Absorption-hands of Cymene. — Thyme,
lemon, nutmeg, caraway (No. 1).
Substances shmving Strong Bands of Absorption in the Spectncm
transmitted by Dilute Solutions. — Oils of aniseed, bay, bergaraot, bitter
almonds, cassia, cloves, peppermint, pimento and thyme. Carvol, the
oxidised derivative of caraway oil, myi'isticol, the same from nutmeg
oil, and blue oil of patchouli.
The authors attach great interest to the examination of these bodies,
since they consider it to be proved from the character of the spectra
they transmit, that the nucleus of menthol is a terpene, whilst the
benzene ring is the inner basis of carvol and myristicol. Bergamot
appears to be a terpene mixed with some derivative of the aromatic
series ; but the oil of peppermint, on the other hand, is essentially a
substance belonging to this latter class.
The following is a summary of the author's observations with re-
gard to the terpenes : —
(].) The terpenes with the composition CmHis possess in a high
degree the power of absorbing the ultra-violet rays of the spectrum,
although they are inferior in this respect to benzene and its deriva-
tives, to which class of bodies they are closely allied.
(2.) Terpenes with the composition C15H04 have a greatly increased
absorptive power for the more refrangible rays, that is to say, they
withstand dilution to a greater extent, the greater the number of carbon
atoms in the molecule.
(3.) Neither the terpenes themselves nor the oxidised nor hydrated
derivatives occasion absorption-bands under any circumstances when
pure, but always transmit continuous spectra.
(4.) Isomeric terpenes transmit spectra which usually differ from
one another in length, or show variations on dilution.
(5.) The process of diluting with alcohol enables the presence of
bodies of the aromatic series to be detected in essential oils, and in some
cases even the amount of these substances present may be estimated.
D. B.
Ultra-violet Absorption Spectra of Ethereal Salts of Nitric
and Nitrous Acids. By J. L. Soret and A. A. Rilliet (Gompt.
rend., 89, 74:7 — 748). — The nitrates of ethyl, isobutyl, and amyl, have
a very great absorptive power for the ultra-violet rays, as is seen from
the table : —
Thickness
of 1
iquid requir
3d to
produce
extinction witli nit
rate of
Rays of
Ethyl.
Isobutyl.
Amyl.
cadniiuin.
Wave-lengths.
mm.
mm.
mm.
12
325-8
15-6
14-45
9-9
13
)9
2-0
1-9
2-3
14
51
0-7
0-85
0-92
17
2747
0-22
0-37
0-25
18
257-2
0-07
0-2
0-07
The alcoholic solutions of the nitrates (5 grams per litre) are more
GEXERAL AXD PHYSICAL CHEMISTRY. 203
transparent than the undiluted liquids, and are more fit for compari-
son with the metallic nitrates, yet there exists some difference in
chemical construction of the two classes of chemical compounds, the
maximum of absorption between the lines 12 and 18, so distinct! j
recognisable for calcium nitrate both in alcoholic and aqueous solu-
tions, is absent with the ethers, which are more transparent for the
rays 12 — 14, less transparent for the rays 17 — 20, and again more
transparent for the rays 22—24.
Thickness of liqiiid required to produce extinction
with alcoholic solution of nitrate of
Eays of
Wave-
cadmium.
lengths.
12
• 325-8
13
»
14
>j
17
274-7
18
257-2
20
)>
22
282-2
24
226-6
I
Calcium. Etlivl. Isobutyl. Amvl.
mna. mm. mm. mm.
or^.o J ray passes through a thickness of
\ O'l m.
15-1 57-95 59-7 37-6
7-9 17-1 17-85 15-0
20-35 7-1 7-82 5-72
4005 4-9 3-97 3-7
7-82 3-52 2-6 1-9
0-52 0-57 0-45 0-32
0-05 0-15 0-15 0-15
The vapours of the ethereal nitrates show absorbing powers even at
the ordinary temperature.
Solutions of nitrites of amyl and ethyl act very energetically on the
ultra-violet rays : the alcoholic solution of amyl nitrate gives rise to an
absorption spectrum, there being six bands at nearly equal distances
between the solar rays H and R, varying in distinctness. The first
and sixth between H — L and Q — R are the most indistinct. The
second and fifth at M and P — Q are more distinct, and the third and
fourth at X and 0 are most distinct. Ethyl nitrite gives a similar
spectrum.
The vapours of amyl nitrite at the ordinary temperature present
the same spectrum as the alcoholic solution, but sharper.
L. T. O'S.
Electric Discharge of the Chloride of Silver Battery. By W.
De la Rue andH. Muller {Coni-pt. rend., 89, G37 — 641). — By a series
of experiments on the discharge in air, hydrogen, and carbonic anhy-
dride, details of which are given, the authors have established that
there is a minimum pressure for each gas corresponding with a mini-
mum resistance to the passage of the discharge, but if the pressure be
diminished beyond this minimum, the resistance increases with ex-
treme rapidity. Although there appears to be no condensation or
expansion of the gaseous medium in the neighbourhood of the elec-
trodes, the discharge is accompanied by a sudden expansion of the gas,
which, however, does not seem to be due merely to heating, as it lasts
the whole time of the discharge, and ceases instantaneously with it.
The relation which exists between the pressure and the difference of
potential necessary to produce discharge between two plane surfaces at
a constant distance, may be represented by a hyperbolic cui've, taking
2 2
204 ABSTRACTS OF CHEMICAL PAPERS.
the pressures as abscissje and the numbers of elements as ordinates.
It is the same for the difference of potential and the distance of dis-
ruptive discharge when the pressure is constant. The resistance to
the discharge between two plates varies as the number of interposed
molecules. The law is the same for points. The authors have pre-
viously shown, that for a constant pressure equal to that of the atmo-
sphere, the potential varies as the square root of the distance. With a
constant pile of 11,000 elements, the distance at which disruptive dis-
charge takes place, varies inversely as the pressure, from 1 — 15 mm.
The electric arc and the stratified discharge in a vacuum appear to be
modifications of the same phenomenon. C. E. G.
Phosphorescence produced by Electrical Discharges. By
E. WiEDKMANN (Ann. Fhys. Cheni. [2], 9, 157— 1(50).— Most of the
platinocyanides exhibit fluorescence under the influence of electrical
discharges, but the fluorescence is dichro'ic only as the result of a
partial decomposition. Dichro'ism is induced in barium platinocyanide
without any electrical action, by placing the salt in a vacuum for a
time. The author attributes this effect to the loss of water, by which
loss the optical differences of the several directions in the crystals
are more strongly brought out. That dichro'ism is so much more
quickly developed in the salt when it is subjected to electrical dis-
charges, he explains by the warming of the crystals by the discharge.
The superficial parts of the crystals thus losing their water become
dichro'ic, whilst the deeper-lying parts fluoresce under the influence
of the electric discharge.
These experiments were suggested by a research of Crookes's, from
whose view of the cause of the phenomena, however, the author
dissents. Instead of a stream of projected molecules, we have here,
the author contends, to do with electrical disturbances or waves, com-
municating their motion to the ether of the solids in which vibrations
are thus set up, that appear partly as heat, partly as light. A striking-
proof of the incorrectness of Crookes's theory is an experiment in
which the positive current of a Holtz machine is passed through a
discharge-tube, made with thick glass, in such a manner that it may
be diverted within the tube by the finger. A feeble phosphorescence
then appears in the inside of the tube, but on the outside a very bright
green light is seen. Closely connected with this phenomenon, is that
which appears when a spherical positive electrode is used within a
glass globe, and a collecting point touches the external surface of the
globe. On the opposite part of the globe is seen a well-defined shadow
of the electrode, surrounded by a circle of beautiful green rays. The
starting point for a theory of these phenomena is supplied in Maxwell's
equations (Wied. Galv., p. 1226). An electrical discharge effected by
the motion of material particles is out of the question, as the velocity
of electricity in gases is immensely greater than that of any molecular
motion whatever. The reflection of the negative discharge from sur-
faces on which it impinges, is likewise in accordance with Maxwell's
theory, if we attribute to the waves of electric polarisation sufficient
energy ; and that they do in fact possess this may be inferred from
their melting the glass upon which they strike. R. R.
GENERAL AND PHYSICAL CHEMISTRY. 205
Action of Ozone on some Noble Metals. By A. Yolta
(^Gazzelta, 9 ,o21^bo2) . — In IS^jJ? Sclionbein, whilst studying the action
of ozone on some of the noble metals (gold, silver, and platinum)
found that they became polarised negatively, and in a gi'eater degree
as the metal was less oxidisable; this polarisation, moreover, was not due
to any pfeculiar electrical state of the metal, but to the presence of ozone.
The author's method is to take two plates of the metal having the
same area, and after exposing one of them to the action of ozone for a
certain time, to connect the two wdth interposed galvanometer, and to
plunge the two plates into a vessel containing distilled water.
When silver is submitted to the action of moist ozone, the surface
becomes coated with black silver peroxide, as Andrews and Tait have
observed ,- but when the ozone is dry, no sensible decomposition of the
ozone can ever be detected, although the chemists above mentioned
state that the silver is not oxidised, but that the ozone is completely
decomposed by the metal. The polarising action of the ozonised silver
is found to be invainably negative, whether dry or moist ozone had
been used, and there is a deviation of the galvanometer, persisting for
some time after the immersion of the plates.
Gold is quite unaltered by ozone, whether moist or dry, and the gas
is also unaffected by the metal. The polarisation is always negative,
but there is no permanent deflection of the galvanometer, as with
ozonised silver.
With platinum both the ozone and the metal are unaltered. The
polarisation is negative, and there is a permanent deflection, but this
is much more feeble than with silver.
With palladmm which is quite free from hydrogen, neither the gas
nor the metal is attacked, if the former is dry, but in moist ozone the
surface of the palladium becomes covered with an iridescent him,
resembling that formed on steel when it is heated ; like the other noble
metals, palladium is negatively po-larised, and it gives a large perma-
nent deflection.
Hydrogenised palladium, even after the action of ozone, is found to
be polarised positively, and to give a large permanent deflection, which
is very persistent, lasting for days. Hydrogenised platinum behaves
in a similar manner, but the deviation is not so persistent.
Dry ozone attacks mercury readily. When a tube containing the
metal is plunged into the ozonised oxygen, the meniscus instantly dis-
appears, and the surface becomes quite plane ; after a few minutes'
contact with the ozone, however, the edges become depressed, and the
meniscus again reappears with a clean surface, the convexity gradually
increasing until it far exceeds the normal curvature ; this lasts for a
couple of hours, and then the meniscus returns to its ordinary state.
This phenomenon the author believes to be electrical, the period of
maximum convexity corresponding with the maximum polarity of the
metal ; this, as in the case of the other metals, is negative, but there is
no permanent deflection. Analogous results were obtained with moist
ozone, but they were much less strongly marked. C. E. Gr.
An Electro- Capillary Thermometer. By E. Debefn (Compt.
rend., 89, 755). — The principle on which this instrument is based
206 ABSTRACTS OF CHEMICAL PAPERS.
is tliat of Lippmann's electrometer, in wliicli any mechanical move-
ment vvliich alters the form of the mercury meniscus cause an electric
current.
A fine capillary thermometer tube is filled with acidulated water,
and mercury introduced so as to foi-m a chain of beads, the first and last
of which are in connection with platinum wires. When the water
expands or contracts it pushes the globules, and in consequence of
their contact with the sides of the tube, distorts them, when a current
is generated in the direction of the expansion or contraction of the
water. This current may be measured on a Lippmann's electrometer,
and thus the variation of temperature registered. The advantages of
this instrument are (1) the thermometer can be placed in one spot,
and observation taken in another ; (2) it works without a battery, and
is very sensitive. L. T. O'S.
Mendelejeff s Periodic Law and the Magnetic Properties of
the Elements. By T. Caenelley (Ber., 12, 1958— 1961).— T/iose
elements ivhich helonrj to the even series of Mendelejeff's classification of
the elements {Ann. Chem. Pharm. Swppl., 8, 133 ; Watts^s Dictionary of
Chemistry, Sec. Siipp.} are always paramagnetic, ivhereas those which
helonrj to odd series are always diajnar/neiic. This rule holds good with
all the 38 elements to which it can at present be applied. In the case
of the odd members of the same group, the diamagnetism increases
with the atomic weight. T. C.
Thermal Absorption and Emission of Flames, and the Tem-
perature of the Electric Arc. By F. Rossetti {Compt. rend., 89,
781 — 7e3j. — Flame is very diathermous, and consequently its absorbing
power for heat-rays is small. If the radiation from a flame (lumi-
nous or non-luminous) traverses another of the same nature, having
a thickness of 0"01 m., the coefficients of absorption and transparence
are respectively 0"135 and 0"8G5.
The transparence and absorptive power decrease and increase respec-
tively, in proportion to the thickness of the flame. An infinitely thick
flame is athermous, and its absorptive power unity. This limit is
nearly reached with flames of finite thickness, for a flame 1 m. in thick-
ness is abnost completely athermous to rays fi'om a flame of the same
natiire.
1 — A;*
The formula y = a — , represents the intensity of radiation of
— log. k
a flame having a given thickness e, expressed in centimeters. The
coeflicient of transparence k = 0'865 ; a = a constant, the value of
wbich depends on the nature of the flame.
The intensity of radiation of a luminous white flame of infinite
thickness, compared with the intensity of radiation of lampblack at the
same temperatui'e, is equal to unity. This is the absolute power of
emission.
The absolute power of emission of the non-luminous pale-blue flame
of the Bunsen burner is equal to 0"3129.
The relative power of emission of a flame is determined by multiply-
ing the ratio between its intensity of radiation and the maximum inten-
GENERAL AND PHYSICAL CHEMISTRY.
207
sitij (the intensity of radiation if the same flame were of an infinite
thickness), by the absolute power of emission of the class of flame to
which the one in question belongs.
The electric light emits two classes of rays, one from the incandes-
cent carbon, which are white, the other from the voltaic arc, which
are bluish-purple ; these together give a bluish-white light.
The temperatures of the two carbon poles differ, and they may be
calculated from the formula y = i?iT* (T — 9) — )i(T — 0), on the sup-
position that the emission power of the carbon is a maximum. The
power of emission of the voltaic arc is very small, like that of non-
luminous flames. Its temperature may be calculated from the above
formulee, but it is necessary to introduce the value of the emission
power of the arc proportional to its thickness.
Experiments show that the maximum temperature of the incan-
descent portion of the positive pole is about 3,9u0'' C, and that of the
negative, 3,150° C The temperature of the voltaic arc between the
poles is always the same, about 4,8U0° C, whatever the volume of the
arc or the intensity of the current. L. T. O'S.
Specific Heat of Concentrated Solutions of Hydrochloric
Acid. By H. Ham.merl {Coinpt. rend., 89, bll — 683 j. — The author
has determined the specific heat of strong solutions of hydrogen
chloride between the temperatures — 12' and + 12° with the following
results : —
HCl
pc.
32
28
25
23
18
12
6
4
37
18
37
82
30
50
53
80
for
IHCl.
4-23
5-20
5-96
6-49
9-05
14 19
29-02
47-67
HCI +
«H.,0.
112
•7
130
•2
143
■8
153
■3
199
•4
291
■9
558
•8
894
5
Sp. heat
Sp. heat
by
by
heating.
cooling.
0 -6270
0 -6602
—
0-6797
—
0 -6868
0 -6895
0 -7436
0 -7502
0 -8076
0 -8132
— .
0 -8983
—
0-9310
Value in
water
for 1 CO.
of
solution.
C.
Molecu-
lar heats.
C.
Molecu-
lar heat
of water
(wHsO).
•727
70-70
-752
85-95
•765
97-75
-769
105 -45
•814
148 ^95
-860
236 -60
-925
501 -95
-950
832 ^80
76-20
93 -70
107 -35
116 -80
162 -95
255 50
522-35
858 -10
C-C.
5-50
7 75
9-60
11-35
14-00
18-90
20-40
25-30
The following formula expresses the molecular heats of strong as
well as of weak solutions of HCT : —
C = 18/i - 28-39 +
151-3 242-1
n
W. R.
Heat of Formation of Ammonia. By Berthelot {Gonipt. rend.,
89, 877 — 883). — The heat evolved during the formation of ammonia,
water, carbonic anhydride, and hydrochloric acid are among the most
important data of thermo-chemistry. The last three have been fre-
quently measured, but the heat equivalent of the formation of am-
monia has been measured only twice, and the determinations are
208 ABSTRACTS OF CHEMICAL PAPERS.
therefore o doubtful value. Favre and Silbermann, and Thomsen
have determined it by means of the reaction between chlorine and
ammonia, supposing the reaction to be complete. The difference
between the determinations of these independent observers is about
20 per cent. In determining the heat evolved by the action of hypo-
bromites on urea, numbers were obtained which did not coincide with
those of the former experimenters on ammonia, for by this indirect
method 22'8 kil. -degrees of heat were evolved for 14 grams of nitrogen,
instead of 31'5 found by Favre and Silbermann, or 35"15 by Thomsen.
These results are so abnormal that the author investigated the action
of chlorine on ammonia. In- aid of which the other experimenters had
determined the heat equivalent of ammonia. He found that when chlo-
rine is passed through a dilute solution of ammonia, considerably less
than half the nitrogen equivalent to the chlorine is liberated, whilst
ammonium hypochlorite, and possibly bases intermediate between am-
monia and nitrogen chloride, are formed. Satisfactory results were,
however, obtained by burning ammonia in oxygen, the sole products
being nitrogen and water. The average of five detei'minations, closely
concordant with one another, gave, for 17 grams of ammonia, an evo-
lution of 913 kil. -degrees. Now (H2 + O = H.O liquid) evolves 69-0,
or 345 for each atom of hydrogen, hence N + H3 = NH3 (gas)
evolves (34"5 x 3) — 9r3 = 12"2, and as solution of NH3 in water
evolves 8'82 kil. -degrees, the total heat of formation of N + H3 +
solution in water is 210 kil. -degrees. W. R.
Relation between the Heat Developed on Solution and
that Developed on Dilution, with Complex Solvents (Gompt.
rend., 89, 9(37); Thermo-Chemistry of Cuprous Chloride (ibid.,
89, 967 — 971). By Bkuthklot. — Let D = heat evolved by dissolv-
ing a salt in any solvent not water; and A =: heat evolved on dilution
with water; and similarly let A' be heat evolved by addition of water
to the solvent, and D' the heat evolved on dissolving the substance in
the dilute solvent ; then D' — D = A' — A. For example, cuprous
chloride dissolved in hydrochloric acid gives off a certain amount of
heat, and on dilution, a further amount ; or if the hydrochloric acid
be diluted, it evolves a certain amount, and subsequent solution of
cuprous chloride in it evolves a further amount : the difference between
that evolved by dissolving the salt in strong acid and that evolved on
dissolving in weak acid is equal to the difference between the dilution
of the concentrated solution and that evolved by diluting the acid. In
the second paper Berthelot gives details of this experiment. On dis-
solving CunCls in hydrochloric acid the absorption of heat increases as
the dilution of the acid increases until it reaches its maximum, when
the solution is no longer stable, but begins to give a precipitate. This
phenomenon is the resultant of various distinct actions. 1st. CuoCU
forms a definite compound with a portion of the solvent, developing a
constant amount of heat which is termed +A. 2nd. This compound
dissolves, absorbing heat approximately constant if a large excess of
solvent be used, termed — B. 3rd. If the relation between water and
acid in the new compound differs from that of the original solvent,
the definite hydrates contained in the latter undergo partial decomposi-
GENERAL AXD PHTSTCAL CHEMISTRY.
209
tlon and absorb a variable quantity of heat = C. 4th. Those portions
of the hydrate, decomposed by the formation of the new compound,
cause hberation of water, which unites with the iinsaturated hydrates
of hydrochloric acid and developes heat +K; this is equal to 0" when
the liquid is so dilate that saturated hydrates may be formed, and in such
a case the formation of a new cuprous compound is possible only when
its heat of formation is greater than that of the hydrates which it de-
composes. This explains the decrease of solubility of cuprous chlo-
rides with dilution of the solutions. Thus the resultant, D = A — B
— C + K = (A + K) — (B -1- C), is the algebraic sum of two posi-
tive quantities, one constant. A, and one decreasing with dilution, K ;
and two negative quantities, — B, almost constant if the amount of
cuprous chloride is small compared to the solvent, and — C, which
increases with dilution up to a certain limit. D therefore increases
with dilution up to a point where the tendency of cuprous chloride to
form a definite compound with the hydracid is balanced by the insolu-
bility of the chloride. The experimental data for determining the
heat of formation of CuoCU is given in the follo'O'ing two tables, which
themselves explain the method of determining it : —
i(BaO + 0 = BaOo) erolres .. 6-0
H + CI + -svater = HCl, dilute 39 -3
Reaction on ^Cu^CU 44 '0
89-3
iBaO + dihite HCl 27 8
i(H., + 0 = H.O) 34-5
iCuiCL, + CI + water = CuCL,
dissolved x
X + 62 3
Hence x = 27-0.
was made : —
To check these results the following measurement
i(H,0 + 0 = HoOo), dilute . . -10-7
H + CI + water = HCl, dilute 39 -3
Reaction on iCu2Cl2 33-0
61-6
-i(H.2 + 0 =H..O) 34-5
iCuoCU + CI + water = CuCLj,
dissolved
X
+ 34-
Hence x = 27 1, corresponding with the former result. From former
experiments it has been found that ^(Ca -\- CU = CuCli) evolves
62"6 c, hence -KCus -|- CI2 ^ CU2CU) anhydrous evolves 35"6.
W. R.
The Temperature of Decomposition of Vapours. By H. St.
Claire Deville {Compt. rend., 89, 8U3 — 806). — This paper has special
reference to the long-disputed question of the dissociation of chloral
hydrate when heated. The author remarks that change of tempera-
ture cannot be taken as proof of combination or decomposition, and
the observation made by Wurtz that no change of temperature accom-
panies the mixing of chloral vapour with vapour of water, does not
prove that combination has not taken place, nor would a rise of tem-
perature have been conclusive that combination had occurred. If two
vapours, e.rj., vapours of carbon bisulphide and of ether be mixed,
contraction takes place and liquid may even be seen to condense. This
of course is accompanied by change of temperature, yet no combina-
tion is supposed to take place.
Granting even that water- vapour and chloral vapour do not com-
210 ABSTRACTS OF CHEMICAL PAPERS.
bine, Wartz's assertion that sucli componnds, including ammonium
chloride, cannot exist in the gaseous state without decomposition is
evidently incorrect ; for nitrogen chloride, which absorbs 38,478 gram-
degrees per equivalent during its formation should be incapable of exist-
ing in the state of vapour, yet it can be boiled ; and had Troost and the
author had any method of sealing the vessel in which it was contained,
its vapour-density could have been determined, and, on the other hand,
Avater, which evolves 33,500 gram-degrees, shows decomposition aboiit
1,000°, and can be resolved into its constituents by diffusion. It is thus
evident that the heat evolved by a compound dui'ing formation has no
connection with the temperature of its decomposition, and that the
old confusion between heat and temperature is the ground of Wurtz's
objections. W. R.
Solubility of Solids in Gases. By J. B. Hannay and J. Hogarth
{Chem. Neics, 40, 256). — This investigation was undertaken in the
hope that, by an examination of the conditions of liquid matter up to
the "critical" point, sufficient knowledge might be gained to enable
the authors to determine under what particular conditions liquids are
dynamically comparable, in order that the microrheometrical method
might be applied, to determine their molecular mass and energy rela-
tions. The question as to the stato of matter immediately beyond
the critical point being considered by Andrews to be at that time
incapable of receiving an answer, the authors imagined that some
insight might be gained into its condition by dissolving in the liquid
some solid substance, whose fusing point was much above the critical
point of the liquid, and noticing, whether, on the latter passing its
critical point, and assuming the gaseous condition, the solid was pre-
cipitated or remained in solution. It was found that the solid was not
deposited, but remained in solution or rather in diffusion, in the at-
mosphere of vapour. Experiments were made with strong gaseous
solutions of solids, using as solvents alcohol, ether, carbon bisulphide
and tetrachloride, paraffin and olefines, and as solids, sulphur, chlorides,
bromides and iodides of the metals, and organic substances such as
chlorophyll and the aniline dyes. It was found that, when the side of a
tube containing a strong gaseous solution of a solid is approached by
a red-hot iron, the part next the source of heat becomes coated with a
crystalline deposit, which slowly redissolves on allowing the local dis-
turbance of temperature to disappear. The authors also examined the
spectroscopic appearances of solutions of solids when their liquid
menstrua Avere passing to the gaseous state ; but as all the substances
they have yet been able to obtain in the two sfcites give banded spectra
with nebulous edges, the authors are only able to state that the sub-
stance does not show any appreciable change at the critical point of
its solvent. It was considered to be most interesting to experiment
on a body such as sodium, which besides being an element, yields in
the gaseous state sharp absorption lines. It was found that on work-
ing with the blue solution of sodium in liquefied ammonia, and raising
the ammonia above its critical point, the sodium combined with some
constituent of the gas, forming a white solid, and yielding a perma-
nent gas, probably hydrogen.
GEXERAL AXD PHYSICAL CHEIUSTRY. 211
When the solid is precipitated by suddenly reducing the pressure
it is crystalline, and may be brought down as a " snow " in the gas, or
on the glass as a "frost," but it is always easily redissolved by the gas
on increasing the pressure.
The above, therefore, is the phenomenon of a solid with no measur-
able gaseous pressure dissolving in a gas, and not being affected by
the passage of its menstruum through the critical point to the liquid
state, showing it to be a true case of gaseous solution of a solid.
D. B.
Tension of the Vapours of Saline Solutions. By E. Pauchojt
(^Compt. rencl., 89, 7b'l — 754). — In examining certain thermodynamic
formula, particularly those of Kirchhoff, the author has found it
necessary io determine the vapour-tension of different saline solutions
between the temperatures of 0 and 50^. The method employed was
that of Regnault, with slight modifications. An ordinaiy barometer
is placed between two others, one containing the solution, the other
water. Up to 30 — 35° the parabolic relations represent the results
very exactly, but above that temperature irregularities occur, which
increase rapidly with the temperature, the diminution in the elastic
force being always less than that given by the empirical formula. Earch-
hoff's formula for low temperatures is of the form d — a (^ + b (jy^, in
which d = the diminution of tension referred to the unit weight of salt
dissolved in 100 parts of water, 0 = maximum tension of aqueous
vapour at the same temperature, a and h certain coefficients determined
by experiments, which are given for certain salts. These coefficients
are found in some cases to increase, and others to decrease with the
weight of salt. To find the formula for any solution containing a
given weight of salt tt, let a and (3 be the constants to be determined,
and let a and 6, a' and &', be the coefficients of two solutions containing
weights P and P' of the same salt given in the table, of which P <^ tt
and P' ^ TT, then if P' = tt -f p we have —
a = a + (ft' — ft) ^ , and
iS = & + {h' -h)
V
P'-P
All things being equal, the diminution of tension is not strictly pro-
portional to the quantity of salt dissolved. L. T. O'S.
Passive State of Iron. By L. Varenne (Gompt. rend., 89, 783—
786). — From a series of experiments, the author concludes that the
passive state of iron is due to the formation of a gaseous envelope,
which surrounds the surface of the metal when plunged into strong
nitric acid. He shows that the action of dilate nitric acid on iron in
the passive state may be established not only by rubbing the surface of
the metal, but also by setting up a series of vibrations or by causing a
current of gas to come in contact with the metal. A piece of iron
rendered passive, after being placed in a vacuum, is readily attacked
by dilute nitric acid. The gas which envelopes the metal is nitric
oxide. L. T. O'S.
212
ABSTRACTS OF CHEMICAL PAPERS.
Relation of the Volumes of Solutions of Hydrated Salts to
their Water of Composition. By R. J. Southwokth (A^n. J. Sci.
[3], 17, 399 — 401). — The author has tested by experiment the follow-
ing theorem :— If a hydrated salt be dissolved in a given volume of
water, the volume of the solution will exceed the original volume of
the water by a bulk equal to the bulk of saline water contained in the
salt dissolved. The expression saline toater is used to mean all the
water contained in the salt, both water of crystallisation and water of
constitution. The results of the experiments are exhibited in the fol-
lowing table. The first column of numbers gives the weight of each
salt tried which contains 1 cc. of saline water, calculated from the
formula. The second column gives the weight of each salt, which
was found necessary to increase the volume of the solution by 1 cc.
The calculated numbers agree closely with the experimental ones in
all instances except bai'ium chloride and sodium hydrogen sulphate,
thus proving the general truth of the proposition.
Salt used.
N"a.CO3.10H..O
NaoSOj.lOHOo
Na.,S04.H..S04.3HoO
Na..BiO7.10H,O
Na..HP04.12H.>0
BaCl.,.2H,0
SrClo.6H,0
MgSb4.7H..O •
ZnS04.7H..b
NiS04.7H.,0
reS04.7H,0
Cu804.5H,0
AL(S04)3.i8H..O
A1.(S04)3.K,S04.24H,0 ....
AL(S04)3.(NH4).S04.24H.,0
Cr2(S04)3.K.>S04.24H..O . . .
" M.
Six Lecture Experiments. By C. v. Than {Ber., 12, 1411 —
141G). — (1.) The conductivity of hydrogen for heat may be shown by
rendering incandescent, by a current of suitable strength, a fine plati-
num wire which joins the upper and out-bent extremities of two stout
copper wires fixed parallel and vertically in a cork by means of glass
tubes. The glow of the wire disappears on inverting over it -a cylinder
of hydrogen, while the gas burns at the mouth.
(2.) By interposing short bars of different metals in the circuit, the
difference in their conducting powers will be shown by the more or
less lively glow of the platinum wire.
(3.) A jet of oxygen may be burnt in a two-necked glass balloon
containing sulphur, which is vaporised by the heat of a Bunseu. The
gas is best kindled by means of a morsel of charcoal fastened to the end
of the jet. This is ignited befoi'e introducing the jet into the balloon.
(4.) The indestructibility of matter may be demonstrated by pre-
paring two sealed glass tubes of equal weight, one of them containing
Calculation.
Experiment.
1-588 1
^rams
1*59 grams
1-788
5>
1-63
4-083
3-25
2-122
2-12
1-591
1-59
Q-777
3-89
2-468
2-47
1-954
1-95
2-277
2-28
2-228
2-23
2-206
2-20
2-771
2-77
2-058
2-06
2 196
2-20
2-099
2-10
2-31
2-31
J. M.
H. :
INORGANIC CHEMISTRY. 213
oxygen and a little powdered charcoal. The charcoal may be caused
to bum away completely by heating it by means of a small flame ; on
placing the two tubes on a balance it will be seen that there has been
no variation in weight.
(5.) The usual experiments for illustrating the laws of diffusion of
gases through porous plates, are apt to convey to the minds of begin-
ners false ideas as to the rate at which one gas propagates itself
through another by diffusion alone. That this is extremely slow,
owing to the numerous collisions between the molecules, mar be
proved by suspending a slip of paper, moistened with lead solution,
from the bottom of a tall inverted cylinder into which the stopper is
inserted. In the hollow of the latter a little hydrogen sulphide solu-
tion is placed. Blackening of the lead-paper does not occur for ten to
fifteen minutes. Chlorine water and potassium iodide paper may also
be used.
(6.) The diffusion of gases through colloid membranes may be
demonstrated by fastening a piece of thin india-rubber (from a toy
balloon) over the ruouth of a funnel, which is then placed in an
inverted bell- jar. The stem of the funnel is connected (best by a
side tube) with a U-tube containing a little mercury. If the bell-jar
be filled with carbonic anliydride, there will be increased tension
within the funnel, and theref(jre a rise in the mercury. If one ter-
minal of a voltaic circuit including an electric-bell be plunged into
the mercury, matters may be so arranged that the mercury in rising-
shall come in contact with the other, a fact announced by the ringing
of the bell.
The paper is illustrated by diagrams. Ch. B.
Inorganic Chemistry.
Non-production of Ozone in the Crystallisation of Iodic
Acid. By A. R. Leeds (Chem. Neus, 40, 257).— It has been stated
by Croft that air over crystallising iodic acid becomes ozonised. The
author has repeated Croft's experiments, and explains this reaction
quite differently. When the difficulty of getting rid of every trace of
extraneous matter by chemical operations — however carefullj- con-
ducted— is borne in mind, it appears to the author that the simplest
explanation of the apparent ozonic reaction is that the phenomenon is
not due to ozone produced in the act of crystallising — which, as Croft
remarks, is anomalous — but to a trace of chlorine or nitrous acid, or
possibly some lower oxide of iodine formed in the process of manufac-
ture, and eliminated by successive crystallisations of the acid. After
washing, the air did not manifest the ozone reaction, a fact which
strongly corroborates this view. D. B.
Solubility of Ozone in Water. By A. R. Leeds (Ber., 12, 1831—
1834). — The author concludes that ozone is soluble in water, for when
strips of paper are moistened with lead acetate, the latter converted
214 ABSTRACTS OF CHEMICAL PAPERS.
into sulphide, and tlie strips fastened, under a layer of water 1 cm.
deep, and tlien exposed for several hours to a current of air contain-
ing' ozone, oxidation takes place, lead peroxide and sulphuric acid
being formed. Bright silver foil similarly ti-eated also shows evidence
of the actio^i of ozone. P. P. B.
Behaviour of Chlorine at High Temperatures. By V. Meter
and C. Meyer (Ber., 12, 1426 — 1431). — In order to meet the objection
that might be advanced against their method of determining vapour-
densities at very high temperatures, viz., that the molecules of the
nitrogen gas in which the substance is volatilised might themselves
undergo dissociation, the authors have made several determinations of
the density of mercury vapour at 440 and 1,567°. According to
current theories the molecules of that metal consist of single atoms.
Agreement between the determinations of its density at the above
two tempei'atures would therefore show that nitrogen gas is not itself
dissociated at the higher one. Experiment gave, for mercury at 440°
density =6-86, at 1,567° density = 6-81. Theoretical for Hg = 6-91.
The following determinations of the sp. gr. of oxygen were made : —
Oxygen was weighed and introduced into the apparatus in the form of
silver oxide, previous experiments having shown that silver gives off
no appreciable vapour at the highest temperature reached. At 1,392°
= 1-06 and 1-04; at 1,567° = 1-04 and 1-10. Theoretical for
O2 = 1-05.
In determining the density of chlorine most remarkable results
were arrived at. Chlorine was weighed and introduced in the form of
platinous chloride, a salt easily prepared, and having the great advan-
tage over other easily decomposible chlorides of not being deliquescent.
It was found that xip to about 020° the density of chlorine is constant,
corresponding with the molecular formula CU. A little above this
temperature dissociation commences, and at 800 and 1,000° inter-
mediate numbers are obtained. Above 1,200° the density again
becomes constant, the molecular weight being exactly f CI2. The
following are the actual numbers observed : —
At 620° = 2-42 and 2-46
55
808 = 2-21 „ 2-19
1,028 = 1-85 „ 1-89
At 1,242° = 1-65 and 1-66
„ 1,392 = 1-66 „ 1-67
„ 1,567 = 1-6 „ 1-63
Theoretical for CI2 = 2-45 ; for f CI2 = 1-63.
The molecular weight of chlorine, which at low temperatures = 71,
becomes therefore at high temperatures = 47"3.
That the walls of the porcelain vessel were not attacked during the
experiment was proved by exposing a piece of porcelain at about 1567°
to a current of dry chlorine for an hour and a half, after which not
the least change in its weight could be detected.
The authors postpone discussion of their results until experiments
with iodine and bromine have been completed. Already they have
ascertained that iodine at high temperatures behaves like chlorine ; a
fact of great importance, since it renders necessary a revision of the
determinations of Deville and Troost, in which the constancy of the
density of iodine vapour is assumed. In order to test the truth of the
INORGANIC CHEMISTRY. 215
old ^Murium theory, in wMcli chlorine is regarded as an oxide, they
purpose causing dissociated chlorine to diffuse through a porous
diaphragm. Ch. B.
Solidifjring Point of Bromine. By J. Philipp (Ber., 12, 1424).—
Pure bromine solidities at —7'- to —7-3°. This determination agrees
well -with that of Regnault ( — 7'32°) and that of Pierre
( — 7*5 to — 7'8°), but differs much from those of other chemists.
The melting point is slightly raised by addition of iodine, but con-
siderably lowered by the presence of chlorine. Solid bromine is brown
in colour, and has a concho'idal fracture. Exposure to air (moisture ?)
gives it a grey colour and crystalline appearance. Ch. B.
Non-existence of Pentathionic Acid. By W. Spring (Annalen,
199, 97 — 115). — After referring to the researches of Wackenroder
(Ann. Gliim. Phys. [3], 20, 144. and Annalen, 60, 189), Fordos and
Gelis (Ann. Ghim. Phys. [3], 22, m, and Annalen, 64, 249), Kessler
(Annalen, 68, 233), and Risler-Beunat (Pogg. Ann., 116, 470) on
pentathionic acid, the author describes his attempts to prepare this
acid.
When sulphuretted hydrogen and sulphurous anhydride are simul-
taneously passed into water, finely divided sulphur separates out
(which may be removed by the addition of freshly precipitated metallic
copper), and an acid remains in solution which Wackenroder believed
to be pentathionic acid. The acid liquid is concentrated, to 1"30 sp. gr.
and extracted with ether. On the addition of a dilute aqueous solution
of potassium carbonate to the ethereal solution mixed with alcohol a
white precipitate oi potassium tetrathionate is obtained. If the aqueous
solution of the acid is neutralised with potash or baryta, the salt which
is produced invariably contains free sulphur. This explains the fact
that Wackenroder found the relation between the atoms of sulphur
and potassium to be greater than 4 to 2.
Kessler distinguished penta- from ^e#?-a-thionic acid by the ammonium
salt of the former pi'oducing with sulphuretted hydrogen a precipitate
of sulphur, and with silver nitrate a precipitate of silver sulphide.
These reactions are, however, also exhibited by ammonium tett'a-
thionate, but not by barium tetrathionate. The precipitate which is
deposited by a solution of barium tetrathionate does not consist of
pure sulphur, as was formerly supposed, but contains almost half its
weight of barium sulphate and sulphite.
The reaction which really takes place when sulphuretted hydrogen
and sulphurous anhydride act on each other in presence of water, is
the formation of thiosulphuric acid and the oxidation of this acid to
tetrathionic by the excess of sulphurous anhydride : —
(1) SO2 + H.3O + S = HS.SO2.OH.
TTQ Qn HTT boUo.Uid
(2) SO. + HS SO OR = S3SO, + I
HS.SO3.OH SSO3.OH
The presence of hypo.sulphurous acid, H0SO2, can be detected by its
property of bleaching indigo both in acid and in alkaline solutions.
216 ABSTRACTS OF CHEMICAL PAPERS.
Fordos and Gelis's method of acting on sulphurous acid with sulphur
dichloride, and neutralising the product with freshly precipitated
barium carbonate also yields barium tetrathionate and not the penta-
thionate. W. C. W.
Action of Lime on Silica in Mortar. By W. B. Roberts
(^Cheni. News, 40, 250). — Having found in the recent analysis of some
specimens of old mortar from the walls of a building erected about
200 vears ago, considerable traces of hydrated silica, it occurred to
the author that possibly the hardening or setting of mortar might be
due to some chemical action occurring between the lime and the
silica when these ingredients were mixed, whereby some proportion of
the silica was caused to assume the gelatinous form ; that this being
then incorporated by the usual mixing process, subsequently solidified,
binding the whole bulk with a hard network of silica. Experiments
were made to test this point, and the author's general conclusions may
be summarised as follows : —
(1.) Practically no gelatinisation of silica occurs in the manufacture
of mortar.
(2.) Under the ordinary conditions of access of air the lime in
mortars becomes gradually dehydrated, absorbs carbonic acid, and
forms neutral carbonate.
(3.) The absorption of carbonic acid is very slow.
(4.) A slight action takes place between the lime and the silica,
although very small.
(5.) Although even the small proportion of dry silicates slightly
increases the hardness of a mortar, the ordinarily sufficient hardness
of mortar is obtained by simple dehydration and carbonation.
These conclusions appear to be confirmed by the fact that lime
already containing a small proportion of carbonate is preferred to pure
lime for making mortar. D. B.
Arsenates of Zinc and Cadmium. By H. Salkowski (Bar., 12,
1446 — 1449). — Arsenates of the f orm 5R"0, 2As205 + «H20, were long
since prepared by the author (J. pr. Gheni., 104, 109). — The only
similar compound occurring in nature is perhaps picropharmacolite,
5 (Ca.Mg)0.2As>05 + 12H20, corresponding with the natural phosphates,
hureaulite and heterosite, 5(Mn.Fe)0, 2P2O5 + 5H2O, and the artificial
phosphates, 5Mn0.2P-,03 +5H2O (Erlenmeyer and Heinrich, Annalen,
190, 195) and 5Zn0.2P205 + SH.O (Demel, Ber., 12, 1174). Quite
recently Demel {Ber., 12, 1279) has described the arsenates,
5Zn0.2As205 + SHoO, and 5Cd0.2As205 + 5H2O, already prepared by
the author, although in a difi^erent way (Joe. cit.). In addition to these
Demel has described the salt AsOi.HZn + H2O. This salt the author
had also prepared by a different method, viz., by allowing common
zinc arsenate to remain for more than a year in contact with a solution
of arsenic acid. The deposit, after washing with cold water and dry-
ing at 120°, consisted of the above salt ; and by evaporating the
filtrate, allowing the residue to deliquesce, washing it with cold water
and alcohol, and boiling it with water, a second arsenate, probably
Zn(As03)2 was obtained as a heavy white powder.
Setterberg by evaporating solutions of arsenates in arsenic acid and
INORGANIC CHEMISTRY. 217
heatiug the residues, lias obtained arsenates, Ba0.2Aso05 + 4H2O and
AgaO. AS3O5 + 2H2O, analogous to Maddreil's metaphosphates. Hurtzig
and Geutlier (Annalen, 111, 168) obtained by the same metliod the
salt Ag20.As205. Both silver salts were decomposed by water. By
dissolving various compounds ; oxides (Mn), chlorides (Ba, Sr, Ca, Cd,
Cu), nitrates (Ag), and arsenates (Zn, Cd, Cu, Ag) in arsenic acid,
evaporating", heating the residue for some time at 200°, and washing
with water and alcohol, the author claims to have prepared the fol-
lowing in addition : — Of the form R"0.Aso05, salts in which R" =
Sr, Ca, Zn, Cd, or Aga ; also Ba0.2As20o and 2CUO.AS2O5. Only the
silver salt was washed with dilute nitric acid. All these salts are
either sparingly soluble, or quite insoluble, in water. I^o peculiar
modification of arsenic acid could be detected in them.
The analyses are mostly very unsatisfactory. Ch. B.
Arsenates of Zinc and Cadmium. By W. Demel (Ber., 12,
1949). — A reply to Salkowsky (Ber., 12, 1446) as to priority of
discovery.
Ultramarine Compounds. By K Heumann (Annalen, 199,
2.53 — 281). — That portion of the paper which refers to the mode of
preparation and to the properties of silver ultramarine has appeared in
the Berichte (10, 991, 1345, 1888, and 12, 60) and in this Journal
(1877, 2, 572, 707; 1878, Abst., 113; 1879, Abst., 437).— By the
action of the alkaline haloids and of methyl and ethyl iodides on
silver ultramarine, the silver is replaced more or less conapletely. When
silver ultramarine is heated in a current of chlorine gas or iodine
vapour, a flesh-coloured mass is formed which yields green ultramarine
on fusion with potassium iodide. Heated to redness in an atmosphere
of hydrogen, silver ultramarine blackens and evolves a small qiaantity of
sulphuretted hydrogen. The ultramarine is completely decomposed
by the action of sulphuretted hydrogen. W. C. W.
Roussin's Salt. By 0. Pawel (Ber., 12, 1407— 1411).— The salt
named dinitrosulphide of iron by Roussin has been investigated by
Porczinsky (Annalen, 125, 302), Rosenberg, and recently by Demel
{Ber., 12, 461), but with widely discrepant results. Roussin's method of
preparation gives it in a very impure form ; the following is therefore
recommended by the author : — A solution of 80 grams of potassium
nitrite (50 per cent.) in 300 c.c. of boiling water, is mixed with a cold
solution of 30 grams of sodium sulphide in 300 c.c. of water. 70
grams of ferrous sulphate dissolved in 300 c.c. of water is gradually
added to the mixture with constant shaking, the whole heated on a
water-bath for half an hour at 70 — 80°, and filtered. After forty-
eight hours the salt is deposited from the filtrate. The neutral potas-
sium sulphide, or the hydrosulphide of potassium, sodium, calcium or
barium, may be used as a substitute for the sodium sulphide. The salt
may also be prepared by adding a dilute solution of potassium hydro-
sulphide to a very dilute solution of nitric oxide in ferrous sulphate,
and slowly warming. The impure black crystals from either opera-
tion must be recrystallised from warm water, air-dried, and dissolved
VOL. XXXVIII. r
218 ABSTRACTS OF CHEMICAL PAPERS.
in etlier. The dried and powdered residue from the evaporated
ethereal filtrate is digested with pure carbon bisulphide, and after
washincr with chloroform recrjstallised from warm water, to which a
few drops of potash solution have been added. The crystals, which
are hard, brilliant, monocliuic prisms, are not affected by sunUght, and
but little by exposure to air. Analysis leads to the formula,
Fe7S5(NO)ioK3 + 2H2O, which maybe put in the i^tional form —
3Fe(N0),r*:^|
Fe.(N0)4|f-
When ammoninm sulphide is used in its preparation, as by Roussin,
Rosenberg and Demel, the product contains both potassium and am-
monium : hence the discrepancies between the results of those chemists.
The potassium and ammonium salts resemble each other closely ; but
tlie former, being more soluble than the latter, may bo completely con-
verted into it by digestion with ammonium carbonate. The sodium
salt is easily soluble, and is identical with the iron nitrosulphocarhonate
of Low {Ghem. Centr., 1865, 948). Ch. B.
Roussin's Salt. By 0. Pawel (5er., 12, 1940— 1956).— It has
been previously shown (see previous abstract) tliat the compound
described as nitroso-ferrous sulphide is a mixture of several salts
with sulphur, and that it always contains an alkali-metal. The
author in the present communication describes methods for preparing
the potassium, sodium, ammonium, ferrous, and other salts of the
above compound. These have the general formula, Fe7S5(NO)i2M2
+ 2H2O, except that the ferrous salt crystallises with 8 instead of
2 mols. of water.
The ammonium salt is less soluble in water than the potassium salt,
and like the latter crystallises in brilliant monoclinic crystals, which
dissolve in water with a light brown colour : it begins to decompose
at 80°. Of all these salts, the potassium and ammonium compounds
are the most stable.
The so-called nitroso-sodio-ferrous sulphide was also prepared
and investigated. It is best obtained by heating the ammonium salt
above referred to on a water-bath with soda, until ammonia is no
longer evolved. It forms dark-red crystals, which are insoluble in
ether but soluble in alcohol and water, giving a neutral solution. It
begins to decompose on heating at 115"', and gradually at the ordinary
temperature on exposure to the air (on account of the carbonic acid
present), after which the aqueous solution becomes alkaline ; in all
these cases, the sodium salt first referred to is formed with evolution
of sulphuretted hydrogen.
The paper concludes -with theoretical considerations as to the con-
stitution of these various compounds. T. C.
Roussin's Salt. By W. Demel (2?er., 12, 1948).— This is merely
a reply to Pawel's remarks (ibid., 1410) on the paper by Roussin,
Rosenberg, and Demel (ibid., 461) concerning the salt prepared by
them from ferrous sulphate, potassium nitrite, and ammonium sul-
nhide. ' T. C.
IXORGAXIC CHEMISTRY. 219
Composition of the Weldon Manganese " Mud " and some
Similar Compounds. By J. Post (Ber., 12, 1454 — 1459). — Accord-
ing to Weldon, the manganese dioxide olitaiaed in his regenerative
process exists in combination with lime as CaO.MnO.., or CaO(Mn02)2.
Gorgeu too (Ann. Chim. Phys. [3], 66, 153) has described a " vian-
ganous acid" (manganese dioxide), which he formed by repeated
treatment of the red oxide with boiling concentrated nitric acid. This
acid was said to redden litmus, to dissolve lime and baryta, and to
decompose carbonates. Various neutral salts were rendered acid by
the addition of " manganous acid," and Gorg-eu even described some
of its salts, such as _(Mn02)5MnO, (MnOjsCaO, (MnOOsKoO.
By careful analysis of some of these compounds, the author shows
the theories of Weldon and Gorgeu to be incorrect. The composition
of the Weldon mud is not such as to lead to the conclusion that it
contains a definite compound of lime and manganese dioxide ; and in
the so-called salts of Gorgeu, he has not found so muchi as half the
amount of base stated by that chemist to be contained in them. They
are rather to be regarded as mixtures of manganese dioxide with,
various compounds. Tables of analytical results are given.
Ch. B.
Behaviour of Bismuth containing Arsenic towards Nitric
Acid, and the Preparation of Basic Bismuth Nitrate, free
from Arsenic. By R. Schneider (/. pr. Chem., 20, 418 — 434). —
Many varieties of commercial bismuth, contain a small quantity of
arsenic, and in the ordinary process of preparing officinal bismuth sub-
nitrate, the arsenic is incompletely eliminated. In dissolving metallic
bismuth by aid of heat in strong nitric acid, the arsenic present is
oxidised to arsenic acid, and combines with bismuth, forming bismuth,
arsenate, wliich is insoluble in a strong solution of bismuth nitrate,
although more soluble in water. To oxidise the arsenic to arsenic acid,
excess of acid must be employed, otherwise the oxidation is incomplete,
and the arsenite of bismuth formed is not insoluble. The author there-
fore recommends that 2 kilos, of bismuth should be treated with 10
kilos, of hot nitric acid, and after solution, decanted from the sediment
containing arsenic. On evaporation, the crystals of bismuth nitiate
which separate are quite free from arsenic. W. R.
Vapour-density of Stannous Chloride. By T. Carnelley
( Bei-., 12, 183t3 — 1837) . — From the determinations of the vapour-density
of stannous chloride (Ber., 12, 1195), V. and C. Meyer attribute to it the
molecular formula SuaCU. This the author shows is due to the tem-
perature at which the determination was made, being too near the
boiling point of stannous chloride (617 — 628°), as determined by
Carleton-Williams and him.self (this Journal, Trans., 1879, 563).
This is probably the cause of the low numbers obtained by Rieth (Ber.y
3, 668), and not that the temperature had produced decomposition.
P. P. B.
Action of Phosphorus Pentachloride on Molybdic Anhy-
dride. By A. PiuTTi (Gazzetta, 9, 538—543). As Teclu (Annalen,
188, 255) had obtained tungsten hexchloride by the action of phos-
V 2
220 ABSTRACTS OF CHEMICAL PAPERS.
phorus pentacliloride on tnngstic anhydride, according to the equa-
tion WO3 + 3PCI5 = WCle + 3POCI3, the author thought it pro-
bable that molybdenum hexchloride might be obtained m the same
way. Accordingly, a mixture of molybdic anhydride (1 mol ) with
phosphorus pentachloride (3 mols.) was heated m a_ sealed tube at
180° for about 5 hours. On cooling, the tube contained a reddish-
brown liquid, and crystals of a dark green colour with metallic reflex.
As these crystals were rapidly disintegrated on exposure to moist air,
and became covered with a film of blue oxide, it was necessary to pour
off the liquid in an atmosphere of dry carbonic anhydride, and subse-
quently to dry the crystals in a current of the same gas ; this was done
without removing the crystals from the tube. When the whole of the
liquid had been removed, the crystals were transferred to tubes also
filled with carbonic anhydride, which were at once closed before the lamp
On analysis, the substance was found to contain molybdenum, phospho-
rus and chlorine in proportions corresponding with the formula,
Mo'ch POCI3, so that it is a combination of molybdenum pentachlo-
ride and phosphorus oxychloride. It is soluble in carbon bisulphide and
phosphorus oxychloride, but insoluble in chloroform ether, and ben-
zene When heated, it melts at 125-127=, and at 170° it enters into
ebullition, and is decomposed, phosphorus oxychloride distilling over.
When all the oxychloride has passed off and the residue is exposed to
a hio-her temperature, magnificent black needles with metallic reflex
sublime; these on analysis were found to be molybdenum penta-
chloride MoCl. They melt at 170-175° (Debray, 185°). The liquid
formed at the same time as the compound, M0CI5.POCI3, was found to
be phosphorus oxychloride containing chlorine in solution, so that the
reaction which takes place may be expressed by the equation—
2M0O3 + 6PCla = 2(MoCl5.POCl3) + 4POCI3 + Ch
c ht. U".
Mineralogical Chemistry.
- Explosion in a Coal Mine due to Carbonic Anhydride. By
Deles^e (Go^pt. rend, 89, 814-817).-On the 28th of uly las^ an
explosion took place in a coal mine at Rochebelle (Gard) at a depth
of 345 meters. There was no fire-damp in the mine, ^^^ «« f.^^J^f^
produced by the explosion, but the mine was afterwards fi^ed ^;t^
choke-damp. The author accounts for it by supposing ^1^^* ^^^ ^J;;^'
phur of thL iron pyrites contained in the coal, or ^f ^^mg m its iieigh-
bourhood, becoming oxidised to sulphuric acd, had attacked some
layers of limeston! beneath the coal, and the generated carbonic
anhydride had found vent in the mine, producing the explosion. ^
Analysis of Tetrahedrite from Huallanca, Peru. By W. J.
COMSTOCK (Am. J. Sci. [3], 17. 401).-Tlie mineral caves of iMlanca
are situated upon the eastern flank of the Peruvian Andes, at a height of
MIXERALOGICAL CHEMISTRY.
221
14,700 feet above the sea. The ores average 800 ounces of silver to
the ton. The walls of the cavities are studded with crystals of tetra-
hedrite, some of which are two inches long. A portion of one crystal
(sp. gr. 4*7) gave the following results: —
Sulpliui".
s ....
. . 26-74
S.
Sb . . . .
9-06
3-56
Sb
As ... .
. . 13-49
8-57
As
Ao-....
3-86
0-57
Ag
Cu . . . .
. . 39-09
9-87
Cu
Fe . . . .
5-46
3-12
Fe
Zn . . . .
2-14
1-06
Zn
Atomic ratio.
8356
07431 .o.
1785/ -^
28
0179
3083 .
0975 f
0330 J
4567
99-84
26-75
Prom, these numbers is deduced the ratio —
•2528 ks, : -9134 RS or USs : 3-6 RS.
J. M. H. M.
Genesis of Cinnabar Deposits. By S. B. Christy (.4m. /. ScL
[3], 17, 453 — 463 j. — The ores of mercury have been generally re-
garded as formed by sublimation. The author, however, considers
that the facts already known and the results of his own experiments
favour the theory that cinnabar has been deposited from solutions of
alkaline carbonates containing alkaline sulphides.
The following are the chief reasons adduced by the author in sup-
port of this theory : —
Cinnabar deposits are almost always found in metamorphic instead
of in igneous rocks, and in immediate proximity to such substances as
earthy carbonates, quartz, and bitumen, the presence of which cannot
be explained on the sublimation hypothesis. On the other hand, the
minerals which are associated with cinnabar in the ore-stuff — blende,
galena, fahlore, iron pyrites, horn quicksilver, quartz, heavy spar,
dolomite, spathic iron, gypsum, calcspar, and magnetic iron pyrites —
have all, excepting the last, been produced in the wet way by various
experimenters. Cinnabar volatilises only at just below a red heat
(500° C.) at ordinary pressures. Assuming the temperature of the
earth to increase 1° C. for every 100 feet in depth, it would take a
depth of nearly 50,000 feet to give this temperat'are. At New Alma-
den, therefore, where the cinnabar crops out on the summit of a hilL,
we should have to assume an erosion of nearly nine miles and a-half
of strata. Moreover, at such a depth the enormous pressure of super-
incumbent strata would greatly raise the temperature of sublimation.
PfaflP, for example, has shown that the increase of temperature due to
internal heat can at no depth be great enough to convert water into
steam. The cinnabar deposits themselves do not usually show the
signs of true fissure veins, but are found irregularly disseminated in
layers and impregnations. Meix3ury has been recognised as a con-
stituent (although in very minute quantity) of at least one mineral
water, that of the spring " du Rocher," St. Nectaire-le-haut, Puy-de-
Dome. It is well known that mercuric sulphide is soluble in solutions
222 ABSTRACTS OF CHEMICAL PAPERS.
of alkaline sulphides c-oufaiuing free alkali, and is reprecipitated when
the solution is saturated with carbonic anhydride or sulphuretted
hydroo-en. When mercuric sulphide is slowly deposited from such
solutions, cinnabar is formed, but when rapidly deposited, as by dilution,
the black or amorphous modification is produced ; moreover, the black
sulphide is clianged into cinnabar by being heated v/ith alkahnepoly-
sulphides. As free alkali is not known to exist in any natural mineral
waters, the question still remains, from what solution has the cinnabar
been deposited ? It occurred to the author that mercuric sulphide,
although insoluble in alkaline sulphides under ordmary conditions lu
the absence of free alkali, might dissolve under pressure. Some black
amorphous mercuric sulphide, heated in a sealed tube with a solution
of potassium-hydrogen sulphide at 180° for five hours, at a pressure ot
180 lbs. to the square inch, was changed into a coherent mass ot
cinnabar crystals, recocjnisable by the naked eye, and closely resembling
the crystals of native cinnabar. Similar experiments were made with
other solutions, with the following results :— Solutions of sodium
bicarbonate did not change the amorphous sulphide to cinnabar ; solu-
tions of water-glass were equally powerless; but when sulphuretted
liydrogen was Jassed through either of these solutions and the tubes
were again heated in the digester, the transformation was complete.
Polysulphide of potassium effected the change very rapidly and com-
pletely. The presence of carbonic acid seemed to retard the formation
without being able to prevent it. In all cases when the transforma-
tion had taken place, the liquid would stain the skm deep black as is
usual when mercuric sulphide is dissolved in alkaline sulphides.
Finallv, the experiment was tried of heating mercuric sulphide
with the New Almaden Vichy water, which contains considerable
quantities of sodium bicarbonate and free carbonic acid. Sulphuretted
hvdrogen was passed into this water, and some black mercuric
sulphide heated in the solution both at ordinary pressure and m
the digester (pressure 140—150 lbs., temperature 180 C). Ihe
sulphide, which was treated in the open air, was unchanged even when
examined with the microscope, whilst that treated in the digester was
brownish-red even to the naked eye, and when examined under the
microscope proved to be in great part changed into crystals of cin-
nabar. J- ^^- ^- ^^•
Emplectite. By F. R. W. Daw (Chem. Neivs, 40, 225).— The
author has recently discovered this mineral at the Aamdal copper
mines in Norway. It gives on analysis : —
Bi. Cu. Ag. Pb. S. SiO,.
5772 17-23 2-91 a trace 19-20 1-30 = 98-36
The formula of this mineral would be CuS + BioSj. D. B.
Artificial Laurite, and Platiniferous Iron. By H. St. Claire
Deville and H. Debuay (Comi^t. rend., 89, 587— 592).— Wohler, a few
years ago, succeeded in isolating a new mineral which he termed
laurite, from the osmiridium of the platiniferous sands of Borneo ;
this mineral, which eventually proved to be ruthenium sulphide, was,
MIX'ERALOGICAL CHEMISTRY. 223
like osmiridium itself, insoluble in aqwi regia-. The authors have
succeeded in preparing laurite artificially. A mixture of ruthenium
and iron pyrites with a little borax is heated to brig-lit redness during
IS or 10 hours; the ruthenium is converted into sulphide, and dissolved
by the molten ferrous sulphide. On treating the latter after cooling*
with, hydrochloric acid, a mixture of the two sulphides of ruthenium is
left undissolved : the one occurs as a black powder, soluble in nitric
acid, with conversion into ruthenium sulphate ; the other, crystallised in
cubes or regular octohedrons, has the metallic lustre and bluish colour
of laurite ; it is insoluble in all acids and in aqua regia.
Its analysis gave Ru ■= 63'0, S = 37'0 per cent. ; the formula RuSs
requiring Ku = 01 "9, S = 38'1 per cent.
By igniting this sulphide in an earthen crucible to a temperature at
which the crucible begins to soften, it is decomposed, with formation of
crystallised metallic ruthenium.
Platinum Sulphide. — Platinum melted with ten times, its weight of
pyrites and its own weight of borax, is converted into a sulj^hide which
may be extracted from the ferrous sulphide by treatment with acids.
It is of a grey colour, crystallised in needles, and wholly insoluble in
aqua regia. It corresponds in composition with the monosulphide
PtS, and not with the bisulphide as is the case with ruthenium.
The foregoing mixture of platinum and iron sulphides when very
strongly heated leaves, after the action of acids, a crystalline- metallic
substance, which is platinum containing about 11 per cent, of iron.
This alloy, which resembles certain natural specimens of platiniferous
iron both in percentage of iron and in many other characteristics, is
soluble only in aqua regia, and is so feebly magnetic, that it is only
under the influence of a powerful electro-magnet that its magnetism
can be detected at all.
The absence of magnetic properties in native platiniferous iron
was noticed by BerzeliuS; and it is now well known that ferro man-
ganese containing 30 per cent, of iron has no appreciable action on
ihe magnet. Artificial alloys of plattnuin containing as much as 17 to
20 per cent, of iron are, however, strongly magnetic, so that experi-
ments are still wanting in order to determine the precise relations
existing between the magnetic intensity of the alloy, and the percent-
age of iron it may contain. J. W.
Artificial Production of Oligist. By M. Coppola (Gazzettu, 9,
452 — 455). — When the vapour of water and of sodium chloride is al-
lowed to act slowly on pieces of Vesuvian lava at a very high, tempera-
ture, the author has found that the surface becomes covered with
haematite, and that in some cases crystals of oligist are formed. The
most favourable conditions for the production of the latter are attained
when a small platinum crucible containing sodium chloride is placed
at the bottom of a large earthen one, and covered with pieces of the
lava. The crucible is then intensely heated for several days, whilst
water is allowed to drop in slowly : under these circumstances, minute
crystals of oligist are formed on the lava, and especially on those
pieces which are most exposed to the action of the sodium chloride
vapour. C. E. G.
224 ABSTRACTS OF CHEMICAL PAPERS.
The Mica Group. By C. Rammelsbeeg (Ann. Phi/s. Chem. [2], 9,
113 — 14G>. — This paper is the first instalment of a mouograph on the
group of silicates distinguished as micas, the author's purpose being
to embody the knowledge of the chemistry of micas which has been
acquired since the publication of his Handhuch der Mineralchemie in
1875. He considers that, in the classification of micas, the proper
ground of division is to be found, not in their crystalUne forms or
optical properties, but in their chemical constitution. From this
point of view the micas may be permanently divided into two great
groups : —
1. Micas which consist of silicates of aluminium and of univalent
metals (to which last must also be added hydrogen). These are called
the alkali-micas.
2. Micas which, in «,ddition to the above-named silicates, contain
also silicates of bivalent metals (Mg, ¥e, Ba, &c.). These are called,
according to their compos-ition, magnesia-, ii-on-, and baryta-micas.
The alkali group of micas has three sub-divisions : — (A) soda-
micas ; (B) potash-micas; (C) lithia-micas. The analytical figures,
atom-ratios, and notes of physical characteristics of members of these
and of other groups are contained in the original paper. Here only
the general formulae which the author has assigned to each group will
be given, M representing a univalent atom (Na, K, Li), R" a bivalent
atom, and R'^* the sexvalent AL, Fco. It must be understood also
that 0 may be replaced by Flo.
A. Soda-^iicas have the formula 2(HiSi04)(NaiSiOi)3(Al2Si30i2), or
MoAlSisOg.
B. Potash-micas. — First division. Usually the formula is —
(MiSiOi.Al.SiaO,,), or MoAlSioO«.
In most cases these hss/ve H : K = 2 : 1, but the piX)portion M : R^'
= 2 : 1 is not invariable. To this division belong micas from Pontivy,
Union\'ille, Lichfield, Uto, Goshe'n(Mass.), Lane's Mine, Lisens (Tyrol),
Bengal, Horrsjoberg, East Indies, Ballygihen, Grindelwald, Easton
(Pennsyl.), Ceux, Leinster, Glendalough, &c. The second division of
the potash-micas is sub-divided into two series, the first of which con-
tains micas from the Zillerthal, Royalston, Aschaffenburg, Broddbo
near Fahlun, Soboth, Ochozk, and Ytterby (Sweden). Their general
formula is 5(]\I.>Si03,R^'Si309).(R"Si03)
+ 3{5(M4S104.R^Si30,2)-(R"2Si04)}, or MioR"R^5Sii2043.
The second series of the second division of the potash group are less
basic than the first division. Their foi'mula is —
7(MoSi03).2(R"Si03).G(R^'iSi309) + 7(M4SiO4)(2R"2Si006(R^Si30io),
or MuR'^.R^'sSii^Oes.
C. The Lithia-micas. — These contain no hydrogen, and appear to
consist of 1 mol. of orthosilicate with 3 mols. of bisilicate. The locali-
ties and formula3 are these : —
Rozena; Paris: (M4Si04.R^'2Si30,2) -f 3(MoSi03.R^'Si30,),
, or MioR^'^oSiieOso.
Juschakowa : {7(M4Si04)6(R^2Si30,,)} + 3{7(M.,Si03)6(R^Si309)},
or MiiR^'eSiioOss.
MIXERALOGICAL CHEMISTRY. 225
In the second great division of the micas, the inagyiesia-micas con-
taining nearly 30 per cent, of magnesia and little or no iron, are first
considered. The specimens referred to are from Rossie, St. Lawrence,
N.Y. ; Gouverneur, St. Lawrence, N.Y. ; Jefferson Co., N.Y. ; Edwards,
St. La\\Tence, N.Y. ; Paragas, Finland ; Pennsbury, Pennsyl. : and
Ratnapura, Ceylon. The author hesitates whether to regard this
group as consisting of 4 or of 3 mols. of orthosilicates with 1 mol.
of bisilicate. He pronounces finally, however, for the latter view, as
more closely representing the analyses. The most general formula of
the group is MuR"KR^'7Si360i33.
Iron-magnesia- micas. Magnesia -iron -m,icas, and iron-micas, form
another section of the groups discussed in the present paper, which
contains, however, only the first division, viz., the iron-magnesia-micas.
The specimens mentioned belonging to this first division are from
Vesuvius; Morawitza ; Tscheterkul, Siberia ; Monzoni ; Lake Baikal,
Siberia ; Mainland ; Arendal ; and Greenwood Furnace, Monroe, N.Y.
All the micas of this section consist entirely of orothosilicates. The
general formulte for the numbers of the first division (iron- magnesia-
micas) is —
(M4Si04),4(R",Si04)(R^'.-Si30io), or M2R"4R"SiiOi6.
R. R.
Composition of Cymatolite from Goshen (Mass.). By A. A.
JrLiEN (aim. /. Sci. [3], 17, 3l;'8j. — A specimen identical in physical
character with that found by Shephard in the granite veins of Hamp-
shire Co., Mass., yielded the following results : —
Oxygen.
Water 2-58 229
Nitrogenous organic matter .... 0'43 —
KoO 8-38 1-42
Na,0 2-57 066
Liob 009 0-05
CaO 0-48 014
MgO 0-75 0-30
MnO 0-18 0-04
FesOa 1-66 0-49
ALOs 24-38 11-38
SiOj 58-11 30-99
99-61
These numbers correspond with the formula —
3H20..3(Na)20.4Alo03.18SiOo,
The author proposes to retain the name aglaite for this peculiarly
brilliant and micaceous variety of cymatolite. J. M. H M.
Associated Minerals contained in certain Trachytes from
the Ravine of Riveau Grande, at Mont Dore. By F. Gounaed
(Compt. rend., 89, 614 — 010). — In a memoir by Koch, Professor of
Mineralogy at Klausenberg, on andeslte from Mount Arany, and on
the minerals associated therewith, two new specimens are described,
namely, szaboite and pseudobrookite. One of these, szaboite, having
been found by the author in a specimen of trachyte accidentally
226 ABSTRACTS OF CHEMICAL PAPERS.
picked up in the ravine of the Riveau Grande at Mont Dore, it was
thought that a more careful investigation of the rocks of that locality
might lead to the discovery of a similar association of minerals as. that
described by Koch as emanating from Mont Arany. Without pre-
tending to describe the situation and the exact circumstances under
which they were eventually found, it will be sufficient to say that
both minerals, szabo'ite and pseudobrookite, undoubtedly exist in the
trachyte of the Riveau Gi'ande, associated with tridymite, altered
hornblende, and sometimes with breislakite. Szabo'ite has since been
discovered by Lasaulx on the lava of Biancavilla, to the south of
Etna. J. W.
The Lavas of the Volcanos of Ernici in the Valle del
Sacco (Rome). By S. Speciale (Gazzetfa, 9, 393—395). These
lavas are of a dark-grey colour, that from the volcano Giuliana having
a sp. gr. 2-0, and that of Poti 2"81 at 15°. The analyses of the two
lavas gave the following results : —
SiO,.
Giuliano .. 46-22
Pofi 47-59
Giuliano
Pofi ...
V,0,. Al^Oa.
FcOs-
FeO. CaO.
0-52 22-47
8-97
0-78 12-18
0-51 18-02
6-44
1-19 11-66
MgO. CuO. KoO.
Na^O.
CO., and H-P.
3-35 0-30 5-42
1-02
0-56
2-41 0-23 1005
1-82
0-72
C. E. G.
A Meteorite which fell on January 31, 1879, at la Becasse ;
Commune of Dun-le-Poelier (Indre). By Daubr^e (Compt.
rend., 89, 597 — 598). — The fall of this meteorite was accompanied
by a violent detonation, audible at a distance of 20 kilometers ; its
path was nearly vertical, and its velocity such that it embedded itself
in the soil about 0-3 meter. It weighed 2-8 kilograms ; in form it
roughly resembled a pyramid with a square base, the angles being
rounded ofF ; the surface was covered with a black hard crust similar
to that of other meteorites. The interior of the meteorite presented a
finely-grained structure and a clear grey colour, throughout which
numerous metallic grains were distributed. The matrix was chiefly
peridote and a bisilicate such as pyroxene or enstatite ; the metallic
portion consisted of nickeliferous iron and troilite. The meteorite
consequently belongs to the group of sporadosiderites, and to the sub-
group of oligosiderites, numerous representatives of which are known.
J. W.
Water of the Oberbrunnen, Flinsberg, Silesia, By T.
PoLECK {Be,:, 12, 1902— 1906).— This spring yields about 1,000
litres per hour ; the water is clear, sparkling, and colourless, has a
chalybeate taste, but no odour. Its temperature is 7°, that of the air
being 14-5°. It has a slightly acid reaction, but after boiling its
action is alkaline.
Its analysis gave the following results.
10 litres of the water contain : —
MIXERALOGICAL CHEMISTRY. 227
Sodium chloride 0"0618 Sfram
Potassium chloride 0'0253
Potassium sulphate 0'1041
Sodium, carbonate 0"470o
Lithium ,, O-OIOl
55
))
Ammonium. ,, O'OIO? „
Calcium ,, 0-9648 „
Magnesium ,, 0v245 ,,
Iron „ 0-2442 „
Manganese ,, 0'0067 ,,
Aluminium phosphate 0'0087 .,
Silica 0-3995
'5
5)
Titanic acid 0-0026
8 0356 „
Half-combined carbonic acid 0"1055 „
Free carbonic acid 25-429 grams corresponding to 13.229 c.c.
at V.
The folloTving are also present, bat in quantities too small to be
"weighed, viz., iodine, boric and arsenic acids, antimony, tin, nickel,
bismuth, barium, and strontium.
The analysis of the ochre-sediment from the spring gave the follow-
ing- results : —
o
Water (expelled at 120°) 32 15 per cent.
Iron oxide 43"75 ,,
Calcium carbonate 0-57 ,,
Magnesium carbonate O'oO ,,
Barium sulphate 0-014 ,,
Manganese 0-027 :,
Copper 0-015 ,,
Nickel 0-003 „
Bismuth 0-003 ,,
Phosphoric acid 1-43 ,,
Silica 3- 16 ,,
Titanic acid 3-13 ,,
Insoluble residue, sand, &c 7-86 ,,
Loss on ignition 7-35 „
Aluminium (not estimated)
Arsenic acid, antimony, and tin, are present, but in quantities too
small to be Aveighed.
These results are of interest, inasmuch as they show the presence in
the water of this spring of constituents of the minerals which are
found in the mountains in its neighbourhood, and also as one of the
lew instances we have of springs containing titanic acid.
P. P. B.
228 ABSTRACTS OF CHEMICAL PAPERS.
Organic Chemistry.
Halogen Derivatives of Ethane and Ethylene. By J. Denzel
{Ber., 12, 2207 — 2208). — Chlorpenlahroniethane, CoClBi's, prepared by the
action of bromine on chlorotribrom- and tetrabrom-etliane, is deposited
from carbon bisulphide in crystals which melt, with decomposition, at
170°. a.-'Diclilorotetrabromethmie, CBr3.CBrCl2, obtained by the action
of bromine on a-dichlorodibromethane, forms colourless crystals, which
evolve bromine at 175°, and melt with complete decomposition at 180°.
Hexbromethane, CsBre, pentabromethane, CoHBrs (colourless crystals,
m. p. 54°, b. p. 210°, under 300 mm. pressure), and tetrabromethane
(b. p. 195° under 300 mm., and 225° under 732 mm. pressure), are
derived from /3-tribromethane. Unsymmetrical tribromethane has not
yet been prepared. Chlorotribromethylene., C2ClBr3, from chlorotetra-
bromethane, melts at 34°, and boils at 203 — 205° under 734 mm.
pressure (comp. this Journal, 1879, Abst., 368). W. C. W.
Action of Silver Cyanate on Isobutyl Iodide. By B. Brauner
(Bcr., 12, lb74 — lb77j. — lu a former communication, the author and
Linnemann (Ber., 11, 1243) demonstrated that the product of the
action of silver cyanate on isobutyl iodide, when treated with potash,
yields both trimethylcarbinylamine and isobutylamine. When isobutyl
iodide and silver cyanate react on one another in a vessel connected
with a reversed condenser, a volatile liij^uid is first formed, which after-
wards disappears, gaseous butylene and cyanic acid being given off.
The products of this reaction when treated with soda give tertiary
butylamine and a little isobutylamine.
When isobutyl iodide is distilled repeatedly over fresh silver cyanate,
tertiary butyl cyanate, CMes.NCO, is obtained. It is a colourless
liquid of aromatic odour, b. p. 85'5° (corr.), and sp. gr. 0-8676. The
determination of its vapour-density gave 3'48, the calculated being
3"42. With hydrochloric acid, it yields tertiary butylamine hydrochlo-
ride, and by the action of water it is converted into the urea,
(CMe3.NH)2CO, m. p. 242°, which is also formed by the action of
tertiary butylamine on the cyanate, whereas by isobutylamine the
cyanate is converted into a ui-ea of the formula,
CMe3.KH.CO.NHCH.,CHMe2,
ni. p. 163°. Tertiary butyl cyanate, when heated at 180°, is resolved
into butylene, cyanic acid, and cyanuric acid.
In the residue from the distillation of isobutyl iodide over silver
cyanate, solid isomerides of butyl cyanate and of cyanuric acid have
been detected.
Silver cyanate, when gently warmed with an excess of isobutyl
iodide, yields a product which is converted into isobutylamine by the
action of soda. When isobutyl iodide is distilled over silver cyanate
mixed with sand, the reaction is less violent, and the chief product is
isobutyl cyanate. P. P. B.
ORGANIC CHEMISTRY. 229
Constitutional Changes in the Molecule of the Isobutyl
Group. ByB. Bradner (Ber., 12, 1877— 1879). -The author ex-
plains the results described in the previous abstract by supposing that
intramolecular change takes place at the commencement of the reac-
tion as follows : —
c(CH3)2;H.cH2i + AgN : c : 0 = C(CH3)3.J^ : c : 0 + Agi.
(2.) Another portion decomposes thus : C4H9I + AgXCO = Agl -|-
C4H8 + HXCO. And finally both the cyanic acid and the butyl
cyanide form solid polymerides. P. P. B.
Octyl Derivatives. By E. Eichler (Ber., 12, 1879— 18S9).— In
the preparation of the following octyl derivatives the author used the
alcohol prepared from the oil of Heracleum spho)idylium.
Mercuric dioctyl, lIg(C8Tii-,)2, prepared fi'om octyl iodide by the
action of sodium-amalgam, is a cleai', colourless, oily liquid, of
feeble odour, producing slight headache. Its sp. gr. is 1'342 at 17°.
It cannot be distilled, as it decomposes at 200° into dioctyl and mer-
cnry. It is insoluble in water, but soluble in alcohol, ether, and
benzene.
Mercuric octyliodide, Hg.CsHnl. — Obtained as a white silvery pre-
cipitate on treating mercuric dioctyl with iodine and alcohol.
Mercuric ocfylchloride, HgCsHnCl, formed as a white j^recipitate by
the action of mercuric chloride on mercuric dioctyl. When this
chloride is treated with moist silver oxide, mercuric octyl hydrate,
Hg.CsHnOH, is formed. It crystallises in beautiful yellow leaflets,
m. p. 75°, is sparingly soluble in hot water, but abundantly in
alcohol. Its solutions have an alkaline reaction, expel ammonia from
its salts, and produce precipitates in solutions of ferric, aluminic, zinc,
and copper salts. In the last case the precipitate is grey, and on
boiling is reduced to copper.
Dioctyl, (CsHn)?, is prepared by the action of zinc on octyl iodide
at 180°. On distilling the product, a liquid is obtained which, on
cooling, solidifies to a crystalline mass (m. p. 14°, b. p. 277 — 279°).
Its sp. gr. is 0"74.S8° at 15°. Its properties agree generally with those
attributed to it by Zincke (Aiinaleti, 152, 16) ; it appears, however,
that some other comjjound is present, perhaps a small quantity of
dioctylene.
Nitro-octane, CsHnNOj. — This body was prepared by V. Meyer's
method (Aiuialen, 171, 23), viz., by the action of silver nitrite on octyl
iodide ; the product of this reaction is a bright yellow liquid which,
when distilled, yields two fractions, the first consisting of octyl nitrite
(b. p. 171— 180"), the second of nitro-octane, boiling at 205—212°.
The latter with nitrous acid and alcoholic potash gives the reactions
shown by Meyer to be characteristic for primary nitro-compounds.
Octylnitrolic acid was obtained as a syrup by the action of nitrous
acid on the nitrolic acid : when treated with sulphuric acid it gave
octylic acid.
Ocfylamine, CsHnXHo. — This the author prepared by reducing the
nitro-octane with iron filings and acetic acid ; it has already been
230 ABSTRACTS OF CHEMICAL PAPERS.
obtained by Van Renesse, accordiug to whom it unites with water,
foi^ming a crystalline compound, CgHisN + HoO. This compound,
however, the author finds to be the carbonate, (Ct,Hi4N)2C02, as it
gives off carbonic anhydride when heated with acid.
Ochjl nitriie, C^HnO-NO, is prepared by passing nitrous acid into
octyl alcohol, and heating in closed vessels at 100°. It boils at
175 — 177° ; its sp. gr. is 0*862 at 17". It is insoluble in water, but
easily soluble in ether and alcohol.
Octyl cyanide, CgHpCN. — Prepared in the usual manner from octyl
iodide and potassium cyanide; it is a liquid boiling at 214 — 216°; its
sp. gr. is 0"7'SG at 1G° ; is insoluble in water, but easily soluble in
alcohol and ether, P. P. 13.
Fluoboretbylene. By C. Couxclkr (Ber., 12, 19G7).— The
formula, CdlalJlUj, ascribed by Landolph (Ber., 12, 1580) for fluobor-
ethvlene is incorrect, since it contains an odd number of pcrissad
atoms. The formula, BF(0H).0C.H5, which also represents its con-
stitution, airrees better, both with the mode of formation and with the
reactions of the compound. T. C.
Isotributylene. By A. Butlerow (Ber., 12, 1482— 148G).— Whilst
tTimethylciubiuol is formed as an intermediate product during the
conversion of isobutylene into isodibutylene, Iri-inohutylene is readily
obtained at ordinary temperatures, and apparently without hydra-
tion, when isobutylene is absorbed by a moderately cool Tnixture of
5 parts of oil of vitriol and 1 part of water. The oily layer which
separates yields pure isotributylene as a colourless mobile strongly
refracting liquid, of b. p. 177"5 — 179° and sp. gr. 0*774 at 0°, 0'74G at
50°. This hydrocarbon slowly absorbs oxygen when exposed to air or
when heated with it at 190°. Bromine combines with it energetically,
but the product soon begins to evolve hydrobromic acid. It does not
readily combine with hulo'id acids nor with sufficient hydrogen for
saturation. By oxidation with chromic mixture at ordinary tempera-
tures it yields carbonic, acetic, and trimethylacetic acids, acetone and
indifferent oils, but principally a feebly acid body of the composition
CiiHooOo. This is crystalline, insoluble in water, soluble in alcohol
and ether, and distils unclianged at 266° (m. p. && — 70°). Although
it can decompose carbonates in the cold, it is precipitated from its
solutions in alkalis by carbonic anhydride, and its ammouiacal solution
on evaporation over oil of vitriol leaves tlu free acid. The sodium salt
has the composition 2(CiiHoiNa02) + H^O. Potassium and magnesium
salts are also described. The alkaline compounds are decomposed by
the carbonic acid of the atmosphere. They yield white precipitates
with solutions of barium, strontium, calcium, lead and silver salts.
The methyl salt boils at 217—220°, the ethyl salt at 227—230°.
The indifferent oils above mentioned boil between 100 and 200°,
and have all the characters of ketones.
The experiments of Frl. Lermontoff" {Ber., 11, 1255) tend to prove
that isotributylene is a tertiary-butyl derivative of isodibutylene, pro-
bablv thus constituted: —
ORGANIC CHEMISTRY. 231
CH, : CMej. CH.CMeo : CMe,. C(CMe3)o ! CMeo.
Isobutylene. Isodibutylene. Isotributjlene.
i.e., it is unsyrnmetrical dimethyl-dikatahutylethylene, analogous to the
hexylene (tetramethylethylene) corresponding with and convertible
into pinacone (Paulow). Now, when pinacone is acted on by an acid,
one of its metliyl groups is transferred from one carbon atom to the
other, producing a derivative (pinacolin) in which one carbon atom
is united to three methyl groups. Admitting that a similar intramole-
cular transposition takes place during the oxidation of isotributylene,
the first product from it would be the pinacolin CH3.CO.CMe(CMe3)2,
which would be further oxidised to methyl - dilcatahutylacetic acid,
CMe(CMe3)2.COOH, the crystalline acid described above. The inter-
mediate pinacolin may be present amongst the oily neutral products
of the reaction. It is also possible that part of the hydrocarbon may
be oxidised without transposition, and, the splitting of the molecule
taking place at the point of double union of carbon atoms, acetone and
dikatabutyl-ketone would result, the first giving acetic acid, the second
trimetbylacetic acid, by further oxidation.
If this theory be correct, the acid CuHo^Oo should not be produced
by oxidising isotributylene in neutral or alkaline solution, and the oxi-
dation of other tetra-substituted ethylenes in acid solution should yield
acids containing an atom less of carbon. Both anticipations have been
confirmed. When isotributylene is oxidised with potassium permanga-
nate, it yields only acetic and trimethacetic acids, tugether with indif-
ferent oils, whilst tetramethylethylene by oxidation with chromic
mixture gives acetone^ acetic acid, and some trimethacetic acid.
The conversion of isobutylene into isotributylene is probably brought
about by successive hydrations and dehydrations, although these have
not been demonstrated. Ch. B.
The Hydrocarbon, Ci„Hif„ from Diamylene. By Tugolessofp
(Ber., 12, 1486). — This hydrocarbon is not identical with terebene,
as Bauer states, since it is not convertible into cymene and does not
yield terephthalic acid by oxidation. Ch. B.
Action of Ferro- and Ferri-cyanic Acids on Amines. By L. J.
EiSEXBERG {Ber., 12, •2-lo^).—AniliHeferrocyauide, 4(C6H5)NH,.H4FeCy6,
crystalhses in white scales. The ferro- and ferri-cyanides of ortho-
and meta-toluidine, acetamide, naphthylamine, and bromaniline were
also prepared. W, C. W.
On the Addition of Oxygen to Unsaturated Compounds.
By L. Heney {Ber., 12, 1838 — 1844).— From tetrachlorethyl oxide,
CCl,.CHC1.0Et {Ber., 4, 101 and 435), the compound CCl, ! CCl.OEt
{ihid., 11, 445 and 750 ; 5, 1054) has been obtained. This and the
corresponding methyl derivative, CCI2 '. CCl.OMe, on exposure to the
air give off hydrochloric acid, become moist, and are finally converted
into oxalic acid. Pui'e dry oxygen unites with the oxy-derivatives of
perchlorethylene, apparently forming an acid chloride of the consti-
tution COCI.CCl^COCHzn+i), wdiich is therefore easily resolved into
232 ABSTRACTS OF CHEmCAL PAPERS.
oxalic acid. This compound is a dichloro-derivative of oxalovinyl
chloride (ibid., 4, 598).
The author also criticises the views of Demole (ibid., 11, 315) and
of Fittig (Annalen, 195, 176) upon the compounds formed by the ad-
dition of oxygen to the haloid-derivatives of ethylene. The formation
by these reactions of bodies exhibiting the properties of oxychlorides
and bromides, COCl and COBr, and of analogous bodies by the action
of heat on perchlorinated ether, the author considers to belong to the
same class. P. P. B.
Preparation of Propylene Glycol from Glycerol. By A.
Beloiioci'.ek (Iter., 12, lb72 — 187-4). — According to Letts, the gum-
like mass obtained by treating glycerol with sodium amalgam is
sodium glycerate. This substance, when submitted to dry distilla-
tion, fields as chief pi'oduct a colourless liquid, most of which on frac-
tionation passes over at 186 — 188°. The analysis and physical pro-
perties of this liquid show it to be propylene glycol ; it boils at 187°
(cor.), its sp. gr. is 1*054 (Wurtz, 1'051), and the vapour-density
i!-68. When it is heated with hydrochloric acid the corresponding
chlorohydrin is formed, which yields propylene oxide, b. p. 36°, by
treatment with potash.
This formation of propylene glycol from glycerol the author regards
as uninfluenced by nascent hydrogen, laying particular stress on the
formation of water. When glycerol is distilled with soda, propylene
glycol is also formed, together with some acids and hydrocarbons.
P. P. B.
Some Properties of Glucose. By Peltgot (Compt. rend., 89,
918 — 922). — Saccharose, when treated with lime, gives a compound,
but glucose yields glucate of calcium and tribasic glncate of calcium,
coloured brown by melassic acid, a humus-likc body. The author has
succeeded in isolating a substance of the formula C12H22O11, an isome-
ride of saccharose, by the following process : — After boiling a solution
of glucose and lime, and filtering to separate a brown precipitate,
enough oxalic acid is added to throw down all the lime. After allow-
ing the filtrate to stand for a long time, crystals separate and the
adhering syrup is removed by means of blotting-paper. The crystals
are dissolved in hot water, and the solution is decolorised by animal
charcoal. On spontaneous evaporation, the new substance, to which
the author has given the name saccharin, separates in bulky prisms.
It may also be purified by dialysis. Another method is to add sub-
acetate of lead to a neutral solution of calcium glucate and saccharine ;
tribasic glucate of lead separates out, and the filtrate on addition of
ammonia gives a deposit of a compound of saccharin and lead oxide,
from which the former may be isolated by sulphuretted hydrogen or
by sulphuric acid.
Saccharin is not a sugar ; it does not ferment ; it has not a sweet
taste, but a slightly bitter after-taste, recalling Glauber's salt. It is
sparingly soluble in cold water, but easily in hot water. It is partly
volatile without decomposition ; it is almost unattacked by nitric acid,
and is dissolved by sulphuric acid without alteration. It reduces
Fehling's solution, but not until after prolonged ebullition. The
author remarks in conclusion, that saccharin and glucic acid ditler
ORGANIC CHEMISTRY. 233
from glucose only by elimination of water, and imagines tlie action of
lime on glucose to be analogous to saponification. W. R.
Remarks on the Saccharoses. By Berthelot (Gompt. rendU^
89, 965 — 966). — The author draws attention to the close resemblance
in crystalline form of the sacchari)ie recently discovered by Peligot,
and trehalose, the crystalline form and angles being nearly identical,
although the stability is different, and the formula of trehale^se shows
it to be hydrated. He also offers some remarks on the relaifive sta-
bility of the saccharoses under the action of dilate f^ulphuric acid.
W. R.
On Tunicin. By Feaxchimont {Compt. rend., 89, Too — 756)- —
By the action of sulphuric acid on tunicin or animal cellulose-, Berthe-
lot, and lately Schafer, have obtained a sugar which the authc-r ©.n
examination finds to be dextrose. The difference between aaimal! amd
vegetable cellulose is to be attributed to a difference in the naaniiier
in which the groups CeHioOs are connected, and not to a difference- in
the individual groups. L. T- O'S.
Calcination of Beetroot Molasses. By C. Vincekt (Cnmpi.
rend., 89, 788 — 790). — The author replies to Duvillier and Buisine's
remarks (ihid., 89, 48 ; this Journal, 36, 912), and contirms his
previous statement that the basic products consist chiefly of ammonia
and trimethylamine, the amount of dimethylamine being but small.
L. T. O'S.
Action of Cyanamide on Dimethylamine Hydrochloride.
By P. Tatat;ixoff (Conqjt. rend., 89, COS). — As methylgnanidine is.
formed by the action of cyanamide on methylamine hydrochloride, s&
dimethylguanidine is formed by the action of the same subsrance on
dimethylamine hydrochloride. An alcoholic solution of the two sub-
stances is heated for several liours at 105 — 110^, the excess of di-
methylamine is removed, and the dimethylguanidine separates in the
form of the platinochloride.. Its analysis calculated accurately to
the formula (CsHgNj.HCO.PtClj. J. W.
Chloro-derivatives of Amines. By H. Koblek {Ber., 12,1869 —
1872).— Wurtz {Compt, rend., 11, 810) and Wilm {Ber., 8,427) state
that dichlorethylamine undergoes decomposition when kept ; whilst
Tscherniak (Ber., 9, 143) attributes this decompasition to imparities.
The author has prepared dichlorethylamine according to the- method
proposed by the latter, and obtained it pure. After this- preparation
had stood some months in a stoppered bottle, the liquid bad become
solid, and amongst the products of decomposition the following were
observed : — Hydrochloric acid, ammonium chloride, monethylamine
hydrochloride, chloroform, acetonitril and acetic chloride. The for-
mation of some of these compounds may be explained as follows : —
(1.) CH3.CHo.N"Cl2 + H,0 = CH,.C0C1 + HCL
(2.) CH3.CH2.NCI0 = CH3.CN + 2HC1.
(3.) CH3.CH0.NCI2 + 2HC1 = CH3.CH...NH0 + 2CI2.
(4.) CH3.CH,.NClo + 3Clo = CClsCH^NHo + 3HC1.
(6.) CCI3.CH2.NCI2 = CHCI3 + CNCl -I HCl.
P. P. B.
VOL. XXXVIII. .c
234 ABSTRACTS OF CHEMICAL PAPERS.
Ethylidenamine Silver Sulphate. By W. G. Mixter (Am. J.
Sci. [3], 17, 4"2? — 429). — lu order to prepare this compound, alde-
hyde-ammonia is dissolved in a small quantity of water, and silver
sulphate, in the proportion of 1 molecule to 4 molecules of aldehyde-
ammonia, is slowly added with constant asfitation ; after some hours,
the small black residue is filtered off, and the filtrate is left to spon-
taneous evaporation, when colourless transparent crystals separate,
which give the aldehyde reaction strongly. At summer temperatures,
tabular crystals, and at 10 — 15°, prismatic crystals, pi'cdorainate.
The tabular crystals, dried between blotting-paper, and then washed
with alcohol and ether successively, gave on analysis results from
which the author deduces the formula Ag2S04(C2H4 '. NH)4,3H20,
whilst the elongated crystals gave results agreeing with the formula
Ag2S04(CoH4 !NH)4,6H20. Some crystals apparently of the same
form as the tabular crystals, gave the formula,
AgSO,(C,K, : NH)3NH3,3H20.
Eth/lidenamine silver sulphate is soluble in water, and yields alde-
hyde when treated with acids. The hexhydrated salt loses water more
readily in dry air than the trihydrated. J. M. H. M.
Bases from Fusel Oil. By H. Schrotter (Ber., 12, 1431 —
1432). — By agitating with hydrochloric acid that part of fusel oil
(from beetroot molasses) which boils above 200°, the author has ex-
tracted, a mixture of basic bodies boiling between 180 and 230°. This
appears to include at least two bases having the composition C8H12N2
and CioHifiN2, respectively. The first of these forms a crystalline sul-
phate, C»Hi>N2(H2S04)o. Their examination is not yet completed.
Ch. B.
Hydrazines of the Fatty Series. By E. Fischer (Annalen, 199,
281 — 325). — The substance of this paper has appeared in the BericMe
from time to time and has been abstracted in this Journal.
(S-Chloropropaldehyde. By Krestowxikoff {Ber., 12, 1487—
1488). — This aldehyde, formed by the union of hydrochloric acid with
acrolein (Ber., 10, 1104), crystallises from alcohol in long thin
coloui4ess needles (m. p. .34'5 — 35'5°), which decompose on keeping;
it is sparingly soluble in water, easily in alcohol and ether, and gives
/S-chloropropionic acid when oxidised with nitric acid of 1"4 sp. gr.
By acting on acrolein with phosphoric chloride, Geuther believed
that he had formed acrolein chloiide, and a compound of dichloro-
glycide and trichlorhydrin isomeric with it. The author, however,
suspects that this so-called compound was in reality isotrichlorhydrin,
produced by the successive reactions —
CH, : CH.OHO + PCI5 = CHo : CH.CHCI2 + POCli
CH2 : CH.CHCI3 + POCI3 + 3H.,0 = CH2CI.CH2.CHCL +
H3PO4 + 2HC1.
He notes that the boiling point of this compound (144 — 148°) is
lower than that of trichlorhydrin, agreeing with the law that the
boiling points of all halogen derivatives of hydrocarbons, in which the
ORGAXIC CHEMISTRY. 235
halogen atoms are united to one carbon atom^ are lower than those of
their isomer ides.
Dichloroglycide, he considers^ is formed by separation of HCl from
this isotrichlorhydrin —
CH,Cl.CH,.CHCl2-HCl = CH.Cl.CH : CHCl,
a decomposition which may be assumed to take place in presence of
certain bodies, although isotrichlorhydrin, when pure, may be dis-
tilled unchanged. Greuther and Reboul state that trichlorhydrin may
be formed by addition of HCl to the isomeric dichloroglycides
CH.Cl.CH : CHCl (b. p. 109°) and CHo : CC1.CH,C1 (b. p. 94°) ; but
this is not in harmony with the law which regulates such syntheses,
and requires confirmation. Tlie author thinks that these chemists really
had to do with two isomerides of trichlorhydrin, CHoCl.CHo.CHCIo
and CH3.CCL.CH.CI. Ch. B.
/S-Chlorobutyraldehyde. By Karetxikoff (Ber., 12, 1488 —
1489). — This body is formed" by the union of hydrochloric acid and
crotonaldehyde.
CH3.CH : CH.CHO + HCl = CHa.CHCl.CH^.CHO,
and yields /S-chlorobutyric acid by oxidation with nitric acid (1-4 sp. gr.).
From this the author infers that when addition of HCl to a mole-
cule takes place, the chlorine unites with the atom of carbon most
remote from the oxygenised group ; whilst the reverse occurs when a
halogen is introduced by substitution. This generalisation is con-
tradicted by Hemilian's observation that a-derivatives are chiefly pro-
duced by the union of HBr and HI with solid crotonic acid ; whilst
Linnemann obtained ,S-compounds alone by the action of haloid acids
on acrylic acid. The author refex's these diiFerent results to differences
of temperature. Ch. B.
Some Reactions of Acrolein and Glycerol, By Tawildaroff
(Ber., 12, 1487). — The author cannot confirm Alsberg's statement,
that triethylglycerol is produced by heating acrolein with absolute
alcohol and acetic acid. "When acted on by lime, glycerol yields ace-
tone, a compound of the formula CeHiiO, boiling at 160°, and gases
containing carbon, which are not absorbed by bromine. The author
IS studying the action of zinc chloride on glycerol. Ch. B.
Oxidation of Formic Acid and Oxalic Acid by Ammoniacal
Cupric Oxide. By P. Cazexeuve (Bull. Soc. Chim. [2], 32, -277—
278). — The author gives the first results of a research into the oxida-
tion of the acids of the acetic series by ammoniacal cupric oxide, a
reagent which has already been employed by Loew for the oxidation of
nric acid, creatinine, &c.
Both formic and oxalic acids, when heated for five hours at 150°
m sealed tubes with excess of ammoniacal cupric oxide, are com-
pletely transformed into carbonic acid, the following equations beino-
realised : — °
H.COOH -f 2CuH,02 + 2XH3 = (XHO-^COs + Cu^O + H,0.
HoCoOi + 2CUH2O3 + 4NH3 = 2(NH0.^CO3 + CuoO + H,0.
s 2
236 ABSTRxVCTS OF OHEMTCAL PAPERS.
If cupric oxide is not present in excess, part of the copper is ob-
tained in the metallic state. J. M. H. M.
Dry Distillation of Sodium Trichloracetate. By L. Henry
(Ber., 12, 1844 — 1848). — According to the observations of Kolbe
(Annalen, 49, 341), the salts of trichloracetic acid are resolved by
distillation into chloride of the metal, carbonic oxide, and carbonic
chloride. Besides these substances, the author has observed the for-
mation of carbonic anhydride, trichloracetyl chloride, CCI3.COCI, and,
as secondary products, trichloracetic acid and its anhydride. Carbon
tetra- and hexa-chloride have also been isolated. P. P. B.
Action of Aluminium Chloride on Acetic Chloride. By W.
WiNOGEADOFF (Ber., 12, 1486 — 1487). — One mol. aluminium chloride
and 4 mols. of acetic chloride react ■when gently heated together,
gi\nng off 4 mols. of hydrochloric acid and forming a solid mass. The
latter evolves 1 mol. of carbonic anhydride on treatment with vi^ater,
and the distillate from the aqueous solution contains an oil lighter
than vi^ater, which smells like acetone, and forms a crystalline com-
pound with potassium bisulphide (bisulphite?). The investigation is
being continued. Ch. B.
Characteristic Reaction of Thioglycollic Acid. By R.
Andreasch (Ber. ,12, 1300 — 1302). — If a drop of dilute ferric chloride
solution is added to a slightly acidified solution of a thioglycoll-ate, a
transient indigo-blue colour appeai-s, and on adding ammonia in
excess, the solution takes a deep violet-red colour, which becomes more
intense on agitating it with air, oxygen being absorbed. The colour
disapjoears on standing, but may be reproduced by shaking with air.
If much ferric chloride is added in the first instance, and then
ammonia in excess, the red colour at once appears. As before, it
gradually fades, but may be recalled by agitating it with air. These
colour-changes may be alternately produced many times, but they
finally cease when the acid is comjiletely destroyed, and all iron is
then precipitated as sesquioxide.
In this reaction, amtnoniiim f err id-thiogly collate,
Fe'" (S.CHo.COONHi)^,
is probably first formed. On standing, this is reduced to a colourless
feri'ous compound, part of the acid being at the same time oxidised.
Contact with air reproduces the ferric compound, which again de-
composes, these changes continuing until all the acid has been oxidised.
Claesson (Annahn, 187, 120) has observed that the cupric salt of
thioglycollic acid gradually decomposes into a cuprous salt.
These reactions are not exhibited by the thiodigly collie acid of
Schultze and Wislicenus (Animlen, 146, 15G). Ch. B.
Decomposition of Thiohydantoin by Barium Hydrate. By
K. AxiiREASCH (Ber., 12, 1380' — 1300). — When thiohydantoin and
barium hydrate are boiled together in molecular proportion, decom-
position ensues; a precipitate of basic larium thiorjhj collate \ /Ba,
COO^
ORG-ANIC CHEMISTRY. 237
falls, and the filtrate, wteii fi^eed from, barium by carbonic anbydride
and evaporated, leaves an orange residue, from which dicyanamide
may be extracted. The precipitate, when suspended in water and
treated with carbonic anhydride, is converted into the soluble normal
hariinn thioyh/ collate (HS.CH2.COO)2Ba; and a solution of the latter,
treated with mercuric chloride as long as the precipitate formed is re-
dissolved, yields the chai-acteristic mercury salt, Hg(S.CH2.COOH)2,
described by Claesson. Thioglycollic acid was discovered by Carius
(Aitiialen, 124, 43), and fiTrther studied by Heintz (ibid., 136, 223j,
Wislicenus (ibid., 146, 145), Claesson (ibid., 187, 113), and others.
The author considers that dicyanamide is not directly formed from,
thiohydanto'in, but is produced by the action of the alkali on cyan-
amide. He represents the reaction as occurring in three stages, in the
first of which barium tliioliydanto'inate is formed. This is subse-
quently converted into barium cyamidoacetate by removal of HjS ; and
the latter finally decomposed into cvanamide and barium thiogly collate.
.NH.CHj
(1.) CS< I + baOH = XHo.CS.NH.CHo.COOba.
^NH.CO
(2.) NH..CS.XH.CH,.COOba + baOH = baSH + H.O +
CX.NH.CH.,.COOba.
(3.) CN.NH.CHo.COOba + baSH = CX.XH2 + baSCH2.C00ba.
This experiment explains why all attempts have failed to convert
thiohydanto'in- into glycolyl-cyanajnide by the action of alkalis.
Ch. B.
Spontaneous Oxidation of Nitrolactic Acid.' By L. Henry
(Ber., 12, 1837 — 1838). — Xitrolactic acid on keeping is resolved into
oxalic and hydrocyanic acids and water, thus : CH3.CH(N03).COOH
= C'..04H2 + HCN -r H2O. Light appears to influence this decom-
position. P. P. B.
Reduction of Carbon Dioxide by Phosphorus at the Ordi-
nary Temperature. By A. R. Leeds (Ber., 12, 1834 — 1836). —
The author has observed the formation of carbon oxide and small
quantities of phosphoretted hydrogen when phosphorus partially
covered with water stands for some time in an atmosphere of carbonic
anhvdride. He expresses the change by the equation, 6P + 5C0o +
SHjb = P2O5 + P2O3 + 2PH3 + 5C0. P. P. B.
Oxidation of Carbon Oxide by Moist Air in Presence of
Phosphorus at the Ordinary Temperature. By A. R. Leeds
(Ber., 12, 1836). — The author finds that carbon dioxide is formed
when carbon oxide and air are allowed to stand in contact with moist
phosphorus for some time. P. P. B.
Decomposition of Mesoxalic Acid by Sulphuretted Hydro-
gen. By C. BoTTiNGER (Ber., 12, 1956— 195s).— Thioglycollic and
thiodiglycollic acids are obtained, together with a little oxalic acid,
when sulphuretted hydrogen is passed for many hours through a
dilute aqueous solution of mesoxalic acid previously treated with silver
oxide. T. C.
238 ABSTRACTS OF CHEMICAL PAPERS.
Homoitaconic Acid. By Markownikoff and Keestownikoff
(Ber., 12, 1489). — By arldmg- sodium etbylate or metliylate, dried at
200°, to warm ethyl a-cliloi^opropionate, the authors obtained alcohol,
ethylic ethyllactate, and an -ethereal salt which by saponification
yielded a crystalline dibasic acid, CbHbOi (m. p. 170 — 171°). The
ethereal salt is thus produced : —
2CMeHCl.C00Et + 2EtON"a = COOEt.CMe : CMe.COOEt +
2NaCl + 2EtOH.
The acid is therefore unsaturated, and related to adipic acid as
itaconic is to pyrotartric acid. Hitherto the authors have not succeeded
an combining it either with halogens or with haloid acids. The acid
may therefoi'e contain a closed chain —
CHo.CH.COOH
I I
COOH.CH.CHo. Ch. B.
New Metliod of Preparing Thiodilactic Acid. By C. Bot-
1 iXdKR (Jnr., 12, 1425^1-12G). — In his former papers (Annahn, 188
and 196) the author described the preparation of thiodilactic acid
fi'om pyroracemic acid (by the action of silver oxide and hydrogen sul-
phide), and from a-chloropropionie acid. He finds that it may also
be obtained by treating pyroracemic acid in strongly alkaline solution
with hydrogen sulphide for a long time. On acidifying, shaking witli
ether, dissolving the ethereal extract in water, and evaporating, the
acid is obtained as an uncrystallisable bright-yellow syrup. Its
identity was established by the analysis of its barium salt, and by
converting it into thiolactic acid. Ch, B.
Influence of Nitro- and Amido- Groups on a Sulphonic
Group entering the Benzene Molecule. By J. Post (Ber., 12,
1460 — 1462). — It has already been observed by the author that the
same bodies are produced by sulphating ortho- and para-amidophenol
(Ber., 6, 397), and orthobromamidobenzene (ibid., 8, 15-57), as by
sulphating and subsequently reducing the corresponding nitro-deriva-
tives. In each of these cases, the molecule contained a negative group
(OH or Br) besides the nitrogen group ; but in experiments which the
author has since made with nitro-amido- and diamido-benzenes (meta-
and ortho-), in which the second radicle is 'positive, similar results
were obtained, the same diamidohenzene-sulplwnic acid being produced
from corresponding nitro- and amido-compounds. These experiments,
as well as others with corresponding phenols, are as yet incomplete.
Hiibner explains these phenomena by supposing that when an
araido-compound is sulphated, the ISTH. group, by its union with sul-
phuric acid, acquires negative properties, and henceforth acts like a
nitro-group. To test this theory the author has repeated the experi-
ments of Meyer and Stiiber (Annalen, 165, 165) and of Limpricht
(ibid., 177, 794). According to these, on sulphating either nitroben-
zene or aniline, the three possible isomeric acids are produced, but one
of them always predominates. By reducing the monosulphonic acid
ORGANIC CHEMISTRY. 239
most abundantly formed from nitrobenzene, an acid is obtained
different from sulphanilic acid, the principal product from aniline.
Sulphanilic acid, on the other hand, corresponds to Limpricht's 8-nitro-
benzenesuljihonie acid, produced in relatively small quantity from nitro-
benzene. The author completely confirms these results. He finds
that nitrobenzene yields 786 per cent, of cc-nitrohenzenesulphonic acid,
whilst aniline yields 5o"2 per cent, of sulphanilic acid. The acids
were prepared and puritied by well-known methods.
Hiibner's theory, although, not contradicted by these results, is not
confirmed by them. Ch. B.
Compounds of Benzotrichloride with Phenol and Tertiary
Aromatic Bases. By O. Doebxer (Z?er., 12, 1462— 14ti8j. — In his
first communication on this subject {Ber., 11, 1236), the author de-
scribed the remarkable colouring matters produced by the action of
benzotrichloride, CeHs.CClj, on phenols and tertiary aromatic bases, and
concluded that they are all of the same type, i.e., derivatives of tri-
phenylmethane or of its homologues. Malachite-green, C22II24X2, for
example (the basic colouring matters are all green) is formed by the
union of 1 mol. of benzotrichloride and 2 mols. of dimethylaniline with
elimination of 3 mols. of HCl. Here the author seeks to ascertain the
constitution of the red colouring matter from phenols, henzaurin.
When 1 mol. of benzotrichloride and 2 mols. of pbenol are gently
heated in an open dish, streams of hydrochloric acid are evolved. The
reaction being completed on the water- bath, the red mass is freed from
phenol by steam, and heated repeatedly with hydrogen-sodium sulphite
solution, which dissolves out the red colouring matter, leaving a pale
tenacious resin. By boiling the solution with hydrochloric acid, the
coloaring matter is precipitated in hard, metallic, red crusts. It is
slightly soluble in water, easily in alcohol, ether, and glacial acetic
acid, less easily in benzene. It forms violet-red solutions in alkalis,
which become colourless on expostu-e to air. The colour of these
alkaline solutions cannot be fixed, but the free compound dyes a
golden-yellow. It melts a little above 100^, and decomposes at a
higher temperature.
Since the colouring matter could not be obtained in a crystalline
form, it was reduced in alcoholic solution with zinc and hydrochloric
acid. A crystalline leuco-compound, insoluble in water, but crystal-
lisable from alcohol, was thus obtained. It forms brilliant pale-yellow
needles, which dissolve without colour in alkalis and are reprecipitated
by acids. It is easily soluble in alcohol, ether, and acetic acid. It has
the composition CigHieOo, and is therefore formed from the colouring
matter CigHuOa by fixation of two atoms of hydrogen. Heated above
its melting point in contact with air, it becomes red-coloured, and then
yields fuchsin-coloured solutions with, alkalis. Potassium dichromate
and acetic acid partially oxidise it to the original colouring matter ;
but potassium ferricyanide converts it into a body like cedriret, insoluble
in alkalis. The relation between the colouring matter and its leuco-
compound is the same as that between malachite-green and its leuco-
compound, or between rosolic and leucorosolic acids. Although the
240 ABSTRACTS OF CHEMICAL PAPERS.
number of OH groups in the molecule of the leuco-compound has not
been determined, tlie latter doubtless has the constitution —
C6H5.CH(C6H,.OH).,.
It will probably be formed by the action of benzal- chloride or benz-
aldehyde on pbenol.
The colouring matter combines directly witb acetic anhydride on
heating, producing a colourless body, C19H14O2 + AcaO (m. p. 119°),
which is slightly decomposed by boiling with water, slowly by alkalis,
but rapidly by strong oil of vitriol. Fusing potash decomposes it, with
evolution of benzene. On dissolving the fused mass in water, and
acidifying, crystals of Staedel's dilujdroxyhenzophenone, CO(C6H4.0H)2
(Annalen, 194, 335), are obtained. This body has also been obtained
by the decomposition of mcrin {Ber., 11, 1348), and of pheuolphthale'm
(ibid., 11, 1299). From the titrate parahydroxijbenzoic acid and phenol
may be extracted. The decompositions are represented by the equa-
tions : —
C.gHuO^ + H.,0 = C,.H,o03 + CeHe
CgHuO. + 2H.0 = CHgOa + CsHeO + CsHe.
Reviewing these facts, the author concludes that the colouring
matter is produced according to the equation —
CHsCla + 2CcH60 = CaHuO^ + 3HCI,
and that it and its acetyl compound have the constitutions —
fCeH^OH rC„H4.0H.
C6H5.C<^ CeHi. and C6H5.C<^ C6H4.O.AC,
[O — ^ LO.Ac
also assigned to them by Graebe and Care (Ber., 11, 1351). Triphenyl-
methane and the leuco-compounds of malachite-green and of the
phenol colouring matter are thus related : —
CPhH(C6H5)2. CPhH(aH4NMeo)2. CPbH(C6H4.0H)2.
The colouring matters are anhydrides of similar derivatives of tri-
pbenyl carbinol —
rCcHs r CeHil^Mea rC6H4.0H
Ph,C<^ CeHa Ph.C<^ CoH4NMe Ph.C<^ C6H4 OiHl
I OH L|(JHH;CH2 UUH
Benzo-trichloride seems also capable of reacting with only two
molecules of benzene in presence of metallic chlorides, producing only
triphenylmethane in small quantity, but no tetraphenylmethane.
Ch. B.
Separation of Orthoxylene from its Isomerides. By
Wroblewsky {Ber., 12, 1487). — This is effected by means of its
acetyl-derivative. No details are given of the method. Ch. B.
Aniline Dithionate. By Maltschewsky (Ber., 12, 1487). — This
salt is formed by mixing aqueous solutions of aniline sulphate and
ORGANIC CHEMISTRY. 241
barium dithionate. It may be precipitated by etlier from an alcoholic
(98 per cent.) solution in almost colourless needles, which resinify and
become bro\vn on exposure to air, giving off sulphurous anhydride.
It is soluble in water and alcohol, but not in ether. At 74° it decom-
poses, withou.t melting, into aniline sulphate and sulphurous anhy-
dride. Ch. B.
Amines Corresponding with a-Toluic Alcohol. By P. Spica
(Gazzetta, 9, 555 — 569). — Benzyl chloride, prepared from, toluene and
boiling at 227 — 230°, when dissolved in alcohol and treated with zinc
and hydrochloric acid at a gentle heat is very slowly reduced, ten days
being required for the completion of the reaction when 10 grams of
the cyanide is employed. After removal of the alcohol by evapora-
tion, the product is mixed with excess of soda, and the bases thus set
free are extracted with ether in the usual way. On agitating the
ethereal solution with dilute hydrochloric acid, white micaceous
plates make their appearance in the ether ; these are identical in
every respect with the dijjhenylethylamine hydrochloride —
(Ph.CH,CH2)2NH.HCl,
described by Fileti and Piccini (this Journal, 36, 922, and Gaz., 9,
294), the crystals melt at 260° if the temperature be slowly raised,
but at 265° if heated quickly. The platinochlaride forms yellow crys-
tals, moderately soluble in water. The dilute acid separated from the
supernatant layer of ether, and evaporated to dryness, leaves a crys-
talline residue, a portion of which is soluble in absolute alcohol, and
a portion insoluble, the latter being ammonium chloride. By evapo-
rating the alcoholic solution, treating the hydrochlorides with soda and
ether, and the ethereal solution with hydrochloric acid, a further
portion of the diphenylethylamine hydrochloride may be separated,
and by a long series of fractionations on the residues, small quantities
of two other hydrochlorides may be isolated, the one melting at 217°,
and identical with Fileti's monophenylethylamine hydrochloride —
Ph.CH0.CH0.NH2.HCl
(this Journal, 36, 719, and Gac, 8, 446), whilst the other (m.p. 137 —
138°) is triphenylethylamine hydrochloride (Ph.CHo.CHoJsN.HCl. It
crystallises in long slender iridescent needles, sparingly soluble in
water, easily in alcohol or chloroform, moderately in benzene, and but
very slightly in ether. By spontaneous evaporation of its solution in
dilute alcohol, it is sometimes obtained in long, hard, transparent
prisms, which probably contain water of crystallisation, as they effloresce
in a vacutim.
From these results, it is evident that the reaction is not merely the
simple one expressed by the equation Ph.CHo.CH + 2N2 =
Ph.CHo.CHo.KHo, but that the phenylethylamiue as soon as it is
formed takes part in the reaction, thus —
Ph.CHo.CHo.NHo + Ph.CHo.CN + 2H2 = (Ph.CHo.CHOaNH+NHa,
and that the diphenylethylamine then yields triphenylamine by a
similar reaction.
242 ABSTRACTS OF CHEMICAL PAPERS.
When the oilj product, obtained on passing hydrogen sulphide for
some time through an alcoholic solution of benzyl chloride and adding
water, is reduced with zinc and sulphuric acid and treated exactly in
the manner previously described for benzyl cyanide, the hydro-
chlorides of mono- and di-phenylethylamine are formed besides some
ammonium hydrochloride, but no triphenylethylamine salt. The fact
that the tertiary amine is not formed in this reaction may be explained
by a consideration of the different manner in which the nitrogen and
carbon in the thioamide (produced by the action of the hydrogen sul-
phide on the nitrile), and in the nitrile are united thus : — C'^-m-tt- and
— C:^. With the thioamide the action of the nascent hydrogen
tends to produce the monamine Ph. CHo.C^^^r , by displacement of
the sulphur by liydrogen. and it is not improbable that the presence of
the small quantity of diphenylethylamine observed is due to un-
altered benzyl cyanide in the crude thioamide.
Mo7W2)henyIethylanmie, Ph.CHn.CHo.NHs, obtained by the decompo-
sition of the hydrochloride with potash and extraction with ether, is a
colourless liquid somewhat lighter than water, and boiling at 193°
under a pressure of 757"8 mm. (corr. to 0°). It is easily soluble in
alcohol or ether, and sparingly in water, to which it communicates a
strongly alkaline reaction. The free base rapidly absorbs carbonic
anhydride from the air, and becomes converted into a crystalline mass
of the carbonate. Bernthsen {Amialen, 184, 307) states that the
base crystallises in small plates, but it is not improbable that it was
reallv the carbonate which he was examininsf.
Diplievyletliylamine, (Ph.CH2.CH2)2NH, is a colourless liquid
(b.p. 335 — 337° at 603 mm.), somewhat heavier than water. It is
soluble in alcohol and in ether, but only very sparingly in water. It
combines readily with acids, but does not appear to absorb carbonic
anhydride from the air.
Triphenylethylamine, (Ph.CHo.CH2)3N, is an oily body, soluble in
ether, alcohol, and chloroform, but almost insoluble in water. The
quantity obtained was too small to determine its boiling point.
2Iono2)he7iylethylcarbamtde, NHo.CO.NH(CH2.CH2Ph), prepared by
mixing hot solutions of potassium cyanate and monophenylethylamine
hydrochloride and boiling for a few minutes, crystallises from its alco-
holic solution in long flat prisms (m.p. 112°). It is very soluble in
alcohol and in hot water, moderately so in cold water.
^-Dipheirylethylcarhcunide, ]SrH2.CO.N(CH2.CH2Ph)o, obtained from
diphenylethylamine hydrochloride in a similar manner to the corre-
sponding- monophenyl compounds, ciystallises from boiling water in
tufts of long slender prisms (m.p. 108 — 109°). It is easily soluble in
alcohol and in hot water, sparingly soluble in cold water.
The corresponding thiocarbamides were also prepared, but the
quantities of material at the author's disposal were too small to
enable him to examine them carefully. 0. E. G.
Ethyl Derivatives of Phenylhydrazine. By E. Fischer and
W. Ehehard (Aiiiudeii, 199, 325 — 332). — The mixture of volatile
ORGAXIC CHEMISTRY. 243
"bases •which are produced, together with diethylphenjlazoninm
bromide, Ph.XaHoEtoBr, by the action of ethyl bromide on phenyl-
hydrazine contains symmetrical and unsymmetrical ethylphenyl-
hydrazine, and a series of more highly ethylated derivatives.
In order to isolate the symmetrical ethylphenylhydrazine or
hydrazo-phenylethyl, the following process was adopted : — Ethyl
bromide and phenylhydrazine are heated together in a flask pro-
vided with an npright condenser until the mixture solidifies ; the
product is dissolved in water, and the excess of ethyl bromide distilled
off. A small quantity of soda is added and the solution extracted with
ether. On the addition of a concentrated solution of soda to the alka-
line liquid, diethylphenylazonium bromide is deposited as a white
crystalline mass. The ethereal extract is evaporated to dryness, and
the unaltered phenylhydrazine removed from the residue by treat-
ment with strong hydrochloric acid. After the addition of soda to the
filtrate, it is shaken up with ether and an excess of yellow mercuric
oxide is added to the ethereal solution. This reagent converts the
unsymmetrical ethylphenylhydrazine into a non-volatile tetrazone,
and the symmetrical into a volatile azo-compound, PhX '. NEt. After
treatment with dilute (Gpercent.) hydrochloric acid, the ethereal liquid
is evaporated, when diethylphenyltetrazone, PhEtX.X ! jST.XEtPh, is
deposited in white monoclinic prisms, m.p. 108''. The mother-liquor
is warmed with dilute sulphuric acid (to decompose any tetrazone con-
tained in it), diluted with water, and extracted with ether.
By distilling in a current of steam the residue which is left on
evaporating the ether, azophenylethyl, PhX2Et, is obtained. The first
portion of the distillate is pure, the later portion must be purifi.ed
by treatment with dilute acids. The azo-compound is a pale yellow
oil lighter than water. It boils between 175 and 18b^ with partial
decomposition, and decomposes slowly on exposure to the air. It is freely
soluble in alcohol, ether, and benzene, and in concentrated acids, and
is rapidly attacked by reducing agents. By the action of sodium
amalgam on the alcoholic solution, it yields hydrazophenylethyl,
Ph.XH.NH.Et, which may be extracted with ether after diluting the
mixture with water. The crude product is purified by precipitation as
the acid oxalate, CgH,2X2.C2H204.
By decomposing the oxalate with an alkali, the free base is obtained
as a colourless oil, soluble in alcohol, ether, and benzene. It distils
without decomposition, Fehling"s solution, mercuric oxide, nitrous
acid, and even exposure to the atmosphere convert it into the azo-
compound. It is decomposed by the action of zinc and acetic acid,
forming ethylamine and aniline.
Oxidation of Phenylhydrazine hy MercAi.ric Oxide. — In the decompo-
sition of phenylhydrazine by Fehling's solution, nitrogen, benzene,
and aniline are formed {Ann., 190, 101) ; if mercuric oxide is substi-
tuted as the oxidising agent considerable quantities of mercury
diphenyl are produced in addition to the above products of decomposi-
tion. Four grams of mercurv diphenyl were obtained from 10 grams
of the base. " W. C. W.
Synthesis of Substituted Guanidines. By E. Eelexmeter
(Ber., 12, 1981— 19^5).— A claim of priority.
244 ABSTRACTS OP CHEMICAL PAPERS.
Orthotoluidine-Guanidines and their Cyanogen-Derivatives.
By F. Bebger {Ber., 12, 1854 — 1860). — Bi-orthotohjlthiocarhamide,
CS(NH.C7H7)2, was prepared by acting with carbon bisulphide on an
alcoholic solution of orthotoluidine in presence of an alkali. It is
insoluble in ether and water, but dissolves freely in hot benzene,
acetic acid, and alcohol, from which it crystallises in long needles.
The author finds its melting point to be 158° (uncor.), and not 165° as
stated by Girard (Ber., 5, 985).
Liorthotolylguanidine, NH '. C(NH..C7H7)2, is obtained by the action
of lead acetate on an alkaline solution of the above carbamide, ammonia
gas being at the same time passed into the solution. On adding alkalis
to the hydrochloric acid solution, a white curdy precipitate is thrown
down, which, after crystallisation from alcohol, melts at 179°. It forms
well crystallised salts, and a platinochloride, (Ci5Hi7N6.HCl)PtCl4,
which is of a bright yellow powder, insoluble in the ordinary solvents.
Dicyanodiorthotolyhj^mnidine^'^iL'.Gi^^C-Jl-^'i + 2CN, is obtained
by passing cyanogen into the ethereal solution of the above guanidine ;
it separates out in small, needle-shaped crystals ; easily soluble in alco-
hol and benzene : when heated, it becomes brown at 160^, and melts
at 173'5 — 174'5° to a dark brown resinous mass.
NMe.CcH^CO
Diorthotolyloxahjlguanidine, NH '. C\^ | , is formed when
^NMe.C6H4CO
hydrochloric acid is added to the dicyanogen compound ; it separates
out in greenish flocks, which, when crystallised from alcohol, form
long, white branching needles, m.p. 206 — 207'5°. Amnaonia. is formed
at the same time. By boiling the alcoholic solution with concentrated
hydrochloric acid, it is converted into diorthotolylparabanic acid,
CnHuNsOs; it crystallises from alco-hol in small white, branching
needles, m.p. 202"5 — 20;3'5". It is insoluble in water, sparingly in cold,
but more soluble in hot alcohol, soluble in glacial acetic acid and
carbon bisulphide, from the last solution it separates needles united in
rosette-like groups.. From an examination of the mother-liquors, it
appears that ammonia, oxalic acid, and diorthotolylguanidine are
formed,
Triorthotnlylguanid.me, (06114116.^11)30 LN.OeHiMe, obtained by treat-
ing an alcoholic solution of diorthotolylthiocarbanaide with lead oxide
in presence of orthotoluidine. It ci'ystallises from alcohol in leaflets,
or microscopic prisms, melting at 130 — 131°. Its platinochloride,
(022H23N'3HOl)2PtOl4, is a bright yellow, fine powder ; and from alcohol
it crystallises in tufts- of prisms.
The a-dicyano-derivative, Cs^HosKg -f 201^, ha» been obtained from
the triorthotolylguanidine by evaporating its ethereal solutions, as a
crust consistiiigof rounded masses formed of yellow needles, m.p. 141°;
whentreated\vithhydrochloricacid,.it yields triorthotolyloxalylguanldine,
O24H21N3O2, crystallising in yellow rhombic plates, m.p. 179°. In the
preparation of this body, the formation of scarlet needles was observed,
the nature of which is doubtful, but they may be the hydrochloride of
|(3-dicyantriorthotolylguanidine. This osalyl-derivative, when boiled
with hydrochloric acid for a long time, yields the diorthotolylpara-
banic acid.
ORG-^'IC CHEMISTRY. 245
By heatinsf ortliotoluidine livdrochloride with cyanamide in sealed
tubes at 100° for some hours, diorthotolylcarbamide is obtained ; it is
insoluble in ether and water, and but sparingly in hot alcohol, from
which it separates in light violet coloured needles, m.p. 252° (uncorr.).
It is identical with the body obtained by Lachmann (Ber., 12, 1350),
by the decomposition of diocyanorthotolylchloride. By continued
action of potash at 150 — 160° it is resolved into carbonic anhydride
and orthotoluidine.
In conclusion, the author states that the dinaphthylthiocarbamide
described by Delbos {Annalen, 64, 371) and Schiff (/. fr. Ghem., 70,
271, and 71, 109), melts at 197 — 198° (uncorr.), and is sparingly
soluble in hot alcohol and hot glacial acetic acid. The attempts to pre-
pare guanidine derivatives from this compound have not been successful.
P. P. B.
Carbamides Derived from the Isomeric Toluidines. By J.
COSACK (Ber., 12, 1440 — 14oO). — The following have been prepared by
the author : —
Paratoli/lcarh amide, CO(NH2)NH.C7H7, from potassium cyanate and
paratoluidine hydrochloride. Crystallises in thick needles ; m. p. 172°.
Already prepared by Sell {Annalen, 126, 158).
Metatolyl carbamide, prepared in a similar manner, crystallises from
water in plates ; m. p. 142°.
Metaditohjlcarbamide, C0(NH.C7H-;)^. from metatoluidine and ethvl
chlorocarbonate, 2C;H7.NHo + COClEt = CO(NH.C7H,)2 + EtOII
+ HCl ; crystallises from hot alcohol in brilliant colourless needles ;
m. p. 217°.
Orthotohjlurethane, CO(OEt)NH.C7H7, from orthotoluidine and ethyl
chlorocarbonate. Crystallises from light petroleum in colourless tables ;
m. p. 42°. Described by Lachmann and by Merz {Ber., 6, 444).
Ch. B.
Action of Oxalic Acid on Carbazol. By W. Suida {Ber. 12,
1403 — 140G).— When carl^azol is fused with ten to twelve times its
weight of oxalic acid, the mixtui'e becomes intensely blue ; and by
washing it with hot water and benzene, and extracting with hot alcohol,
a blue substance may be obtained in microscopic crystals which show
a coppery lustre when rubbed. This body has the composition
C13H9NO, and is formed according to the equation —
C.oH.N + CH^Oi = CisHsNO + CO^ + H^O.
It is insoluble in water, benzene, and petroleum ether, but soluble in
alcohol and glacial acetic acid. Its solution in alcohol is precipitated
by platinic chloride. Alkalis dissolve it, forming colourless solutions.
Cold sulphuric acid also dissolves it : nitric acid colours it brown, and
on heating dis.solves it with carmine-red colour. Nitrous anhydride
throws down a green precipitate from its solution in acetic acid.
Judging by its reactions and mode of formation, this body is best
24G ABSTRACTS OF CHEMICAL PAPERS.
regarded as an internal anliydride of ortliamidophemjlhenzoic acid,
CbH^.CO
I I . Under the influence of various reagents it assimilates the
C6H4.NH
elements of water, giving derivatives of the acid,
NHo.CsHi.CsHi.COOH.
Thus alcohol precipitates the salt CisHipNOoK from its solution
in potash. Bromine converts it into a derivative, Ci3H8l?r3"Nr02, and
warm nitric acid converts it into a mixture of a dinitro- and a tetra-
nitro - compound, Ci3H9(N02)2XO, and Ci3H7(N02)4lSrOj. Acetic
anhydride, however, converts it into an insoluble compound,
CiaHsAcNO.
When separated from its alkaline compounds, this body again
parts with the elements of water just as isatic acid passes into isatin
when set free from its salts. Ch. B.
Bromoxyl Derivatives of Benzene. By R. Benbdikt {Annalen,
199, 127 — 138). — Trihromopheiiol bromide, CeHoBra.OBr, is obtained
by the action of excess of bromine- water on a dilute aqueous solution
of phenol or salicylic acid (1 in 1,000) as a heavy yellow precipitate.
As it is decomposed by alcohol, it must be purified by recrystallisation
from boiling chloroform or carbon bisulphide. In this way, it is
obtained in lustrous lemon-coloured plates which melt at 118*^ and
decompose at 125°. The crystals are insoluble in ether and in water,
they undergo no change on boiling with ammonia or with fixed alkalis.
Tribromophenol bromide is converted into broraopicrin and picric acid
by boiling with nitric acid, and is changed into tribromophenol by the
action of warm alcohol. Tribromophenol is also produced when tri-
bromophenol bromide is treated with tin and hj-drochloric acid. Tri-
bromophenol bromide dissolves in aniline with liberation of heat : on
pouring the product of the reaction into a dilute solution of soda, and
extracting with ether, tribromaniline is obtained, and tribromophenol
remains in the alkaline aqueous solution. Tribromophenol bromide
is transformed into tetrabromophenol (m. p. 109") when heated with
sulphuric acid. By the action of heat alone, the phenol bromide
loses an atom of bromine and leaves a resinous-looking substance
which is probably hexabromophenoquinone, CeBrsHjO.OCeBrsHo, but
has not yet been obtained in the pure state. The author also points
out that the chemical properties of pentabromoresorcinol may be best
explained by the assumption that this substance is tribromoresorcinol
bromide, CsBraHCOBr)^. W. C. W.
Products of the Oxidation of the Ethers of Thymol. By E.
Paterno and F. Canzoneri (Gazzetia, 9, 455 — 462). This paper gives
the results obtained on treating the methyl and ethyl ethers of natural
and of artificial thymol with dilute nitric acid.
When the methyl ether of natural thymol, CfiH3Me(C3H7).OMe, is
digested with dilute nitric acid (1 : 4) for several days, it is converted
into a colourless crystalline substance which on analysis was found to
be a niethoxynitrotoluic acid, C6H2(N02)Me(MeO).COOH. It forms
ORGANIC CHEMISTRY. 247
very slender needles (m. p. 173 — 175 ), very soluble in alcohol, ether,
or benzene. Its barium salt may be obtained in straw-coloured crystals
containing 2 mols. H2O. Besides this, small quantities of methyl-
metahomosalicylic and methoxyterephthalic acids seem to be formed.
The corresponding ethyl compound of thymol (b.p. 227'8 at 7b6'7 mm.),
when oxidised in a similar manner, yields ethoxynitrotoluic acid in long
silky needles (m. p. 161—162°), ethoxytoluic add, C6H3Me(EtO).COOH
in minute quantity, and a third acid melting at 252 — 253°, and ha^ig
all the characters of ethoxyterephthalic acid. From these experiments,
taken in conjunction with the known difficulty of oxidising thvmol by
means of chromic mixture (Gazzetta, 5, 13), it would seem that the
action of nitric acid first produces a nitro-derivative, which, beinof
more easily oxidisable, is converted into the methoxy- or ethoxy-
nitrotoluic acid.
The methyl ether of artificial camphothymol, when treated with dilute
nitric acid in the manner above described, yields metJioxijterephtlialic
acid, C6H3(MeO)(COOH)2. It is a white crystalline powder consist-
ing of minute prisms (m. p. 274 — 275°), only very sparingly soluble
even in boiling water, but easily in alcohol : it is probably identical
with Schall's acid (Ber., 12, 828). The ethyl ether of camphothymol,
C6H3Me(C3H7).OEt, prepared by treating the thymol with ethyl iodide
and alcoholic potash in the usual way, is a colourless, transparent
liquid of aromatic odour, and lighter than water. Its boiling point at
656"58 mm. is 228'^° (corr.), being almost identical with that of the
corresponding derivative from natural thymol. When oxidised it
yields ethoxyterephthalic acid in stellate clusters of minute white
crystals. The acid melts at 253 — 254°, is almost insoluble in cold
water, very sparingly soluble in ether or benzene, and but moderately
soluble in alcohol.
It would seem that the synthetical thymol is more readily oxidised
than the natural, and from this the author infers that in the synthetical
camphothymol [CH3 : OCH3 : C3H7 =1:2:4], whilst in the natural
thymol it is [CH, : OCH3 : CsH; =1:3:4]. Attention is also drawn
to the fact that the melting points of the methoxy-acids is higher than
that of the corresponding ethox y-a,cids. C. E. Gr.
Formula of Quinhydrone. By R. Nietzki (Ber., 12, 1978—1983).
— A reply to Wichelhaus's remarks (Ber., 12, 1500) on a previous com-
munication of the author. The latter still maintains the correctness
of his formula, CuHioOi, for quinhydrone, and of his method for
determining the amount of sulphurous acid necessary to convert a
given weight of quinhydrone into hydroquinone, and thus settlino- the
formula of the former compound. From an application of the same
process to phenoquinone, he concludes that the latter is Ci^HioOi. From
these facts it would appear that quinone can unite with 2 mols. of a
monatomic, or 1 mol. of a diatomic phenol. This is confirmed by the
formation of a compound of quinone when resorcin and quinone in
equal molecules are dissolved in warm benzene ; if an excess of either
be present it remains unacted on. Resoqtdnone, C12H10O4, consists of
almost black, dark red needles (m. p. about 90°) ; it is moderately
soluble in alcohol and water, but less easily in cold benzene.
T. C.
248 ABSTRACTS OF CHEMICAL PAPERS.
Amidomethylenecatechols. By O. Hesse (Annnlen, 199, 341
— 343). — Amidometliylevecatecliol hydrocliloride, C7H5(NH3)Oo, is ob-
tained in white crystals freely soluble in water and in alcohol, by
the action of tin and hydrochloric acid on nitromethylenecatechol
or on nitropiperonylic acid. In the latter case the followiug' reaction
takes place i—CsHsCN-OOOi + 3H2 =.C,H5(NH2)02 + 2H,b + CO,.
The aqueous solution of the hydrochloride gives a cherry-red colora-
tion with ferric chloride, a precipitate and a blue coloration with excess
of silver nitrate, and a purple coloration with chloride of gold. Plati-
num chloride throws down a pale-yellow crystalline precipitate.
The free base is an oily liquid soluble in ether, alcohol, and chloro-
form. The oxalate and sulphate form needle-shaped crystals soluble
in water.
The dinitromethylenecatechol, obtained as a bye-product in the
nitration of piperonylic acid {Ann., 199, 75), yields a diamido-deriva-
tive on reduction. The hydrochloride of this base crystallises in white
plates, which dissolve in strong sulphuric acid ; on the addition of
water the solution is coloured blue.
The aqueous solution of the hydrochloride is coloured green by
ferric chloride, and. reddish-brown by platinum chloride. The free
base has not been obtained in the pure state. W. C. W.
Behaviour of Hsematoxylin on Destructive Distillation. By
R. Meyer (Ber., 12, 1302 — 1393). — Baeyer has already pointed out
the analogy between gallein (the phthalein of pyrogallol) and the
colouring matters brasilin and ha3matoxylin. The composition of
brasilin, CieHuOs, and the fact that on destructive distillation it yields
resorcinol, without a trace of pyrogallol, would point to its being a
resorcinol-succinein isomeric with that artificially prepp^red by Baeyer.
Hsematoxylin, dfiHuOe, may then be a mixed succinein of pyrogallol
and resorcinol ; and the author has found that on destructive distilla-
tion it actually yields a mixtui-e of these two phenols, easily recognised
and separated as gallein and fluorescein. This view of the constitu-
tion of the two colouring matters does not account for the existence
of the hexacetyl-haamatoxylin described by Reim, and the tetracetyl-
brasilin described by Liebermann and Burg. Both bodies require
further examination. Ch. B.
Methylpyrogallol Acid and the Formation of Pittacal. By
A. W. HoFMANX {Ber., 12, 1371- — 1385).— From former experiments
{Ber., 11, 329 and 1465) the author concluded that the colouring
matters cedriret and pittacal, discovered by Reichenbach, were both
derivatives of the dimethyl ether of pyrogallol. Pittacal, he found,
was formed when the crude liquid dimethyl pyrogallate from beech-
wood tar was heated witti caustic alkali and carbon sesquichlorlde.
The two latter reagents when heated together yield oxalic acid, and it
was therefore conjectured that pittacal was formed by the action of
this acid on the pyrogallate, iust as rosolic acid is formed by heating
oxalic acid with phenol. Pittacal has in fact the composition of a
hexamethoxylated rosolic acid, Ci9Hg(OMe)fi03; and this view of its
constitution harmonises with the observations of Liebermann {Ber., 9,
ORUxVNIC CHEMISTRY. 249
334), who describes it under the name Eupittone. It has since been
observed by the author, however, that neither of the two dimethyl-
pyrogallic ethers extracted from beech- wood tar (by a process not yet
published) yields any trace of pittacal by the above process. He also
found that the crude ether when mixed with alkali and exposed to air,
or better, heated in contact with it, yielded the blue colouring matter
without the addition of any carbonaceous substance. The formation
of pittacal must therefore be due to the pi'esence of some third sub-
stance contained in the crude ether, which, bearing in mind the origin
of rosaniline from aniline and toluidine, he suspected to be a homo-
logue. Since this body could not be isolated by fractional distillation,
the crude ether was treated with benzoic chloride, and the benzoyl
compounds separated by crystallisation. He thus obtained the benzoyl
derivatives of the dimethyl ethers of pyrogallol and propylpyrogallol,
and finally a body melting at 118 — 119°, which, when decomposed by
potash, yielded benzoic acid and dimethylmethyl pyrogallate,
C6H2"Me(OMe)2.0H,
melting at 36° and boiling at 265°. Its constitution was proved by
its yielding a dibrominated derivative (m. p. 126^) and the above-
mentioned benzoyl derivative, C6H2Me(OMe)2.0Bz (m. p. 118^). By
heating with concentrated hydrochloric acid at 150-^160°, it is re-
solved into methyl chloride and metliylpyrogallol, C6H2Me(OH)3.
This body (m. p. 129°) is soluble in water and volatilises unchanged.
It bears a strong resemblance to ordinary pyrogallol, its alkaline solu-
tion turning brown on exposure to air.
The sodium derivatives of dimethyl pyrogallate and dimethyl
methylpyrogallate are best obtained by adding soda to their alcoholic
solutions. Separately, they may be heated in air without forming a
trace of pittacal ; but if a mixture of the two with excess of soda is
heated, pittacal is formed, sometimes to the extent of 10 per cent, by
weight of the mixed ethers. On treating it with water, the mass dis-
solves forming a deep indigo-blue solution. On adding hydrochloric
acid the solution becomes carmine-red, and deposits a resinous mass
which when purified furnishes eupittonic acid (pittacal) in beautiful
crystals. The pittacal may also be extracted from the acidified solu-
tion with boiling benzene, unaltered pyrogallate having been finst
removed by agitation with ether. The quantity of colouring matter
formed is not increased by the addition of oxidising agents, chiefly on
account of the extreme ease with which these convert dimethyl pyro-
gallate into cedriret. The reaction may be thus represented —
2CsHic03 + C9H10O3 = CosH^eOg -h 3H2,
-nd may be compared wdth that by which rosaniline is produced —
2C6H,X + CHgN = C.^HnNa + 3Ho.
In the former case the oxygen necessary to remove hydrogen is
derived from the atmosphere, as may be proved by attempting to con-
duct the reaction out of contact with air.
Eupittonic acid appears to be bibasic. Salts of it with the alkaline
ma alkaline-earthy metals, ammonium, copper, nickel, cobalt, lead
VOL. xxxviii. t
250 ABSTRACTS OP CHEMICAL PAPERS.
and zIbc, have been prepared. The alkaline salts are blue with green
reflexion. The ammonium compound is decomposed when its solu-
tion is boiled, and after a time crystals of pittacal are deposited.
In virtue of the deep blue colour of the alkaline compounds of
pittacal, paper steeped in a solution of it and dried, furnishes an ex-
ceedingly sensitive test for free alkalis. Unfortunately concentrated
hydrochloric acid also colours it blue.
When boiled with acetic anhydride, eupittonic acid j'ields a yellow
diacetyl-derivative, which strangely enough is insoluble in alkalis,
although its molecule ought still to contain four hydroxyl groups.
The triamine CojHoglSrsOs.HoO, previously described (loc. cit.), is ob-
tained with surprising ease from eupittonic acid. Its salts give pure
blue solutions aud might be used as dyes.
A homologue of eupittonic acid, C29H34O9 (which was not analysed),
was prepared by heating diethyl pyrogallate and dimethyl methylpyro-
(jcdlate with soda.
It differs from its prototype in being soluble in ether and less easily
crystallisable, and in the less stability of its ammonium compound.
It also forms a triamine when heated with ammonia, probably a
dimethoxyl-tetrethoxyl-pararosaniline,
Ci9Hu(OMe)2(OEt)4N3.H30.
The salts of this base are blue. Ch. B.
Ethylene Ether of Pyrogallol. By G. Magatti (Ber., 12, 1860
— 1863). — This ether is prepared by heating 2 mols. pyrogallol, 3 mols.
ethylene bromide, and 6 mols. potash with ethyl alcohol at 100° for
15 — 20 hours : the ether is obtained from the product by acidifying
with hydrochloric acid and extracting with ether. The ethereal extract
on rectification yielded the monetln-lene pyrogallate, as a colourless,
heavy, strongly refractive liquid of a burning taste, and having the
odour of beech-wood tar; it boils at 267°.
Its analysis and vapour-density determination show its formula to
be C6H3(OH) '. O-z '. C2H4. It resembles the phenols in its properties,
forming crystalline compounds with alkalis, benzoic chloride, and
bromine.
The benzoyl compound, CeHTOyBz, is a white crystalline substance,
easily soluble in boiling alcohol and ether (m. p. 109°). The bromo-
compound crystallises from glacial acetic acid in ti'ansparent tables
(m. p. 67°).
A compound, which is insoluble in alkalis, is formed at the same
time as the ethylene ether ; it is soluble in alcohol and ether, and from
the former is obtained in ill-defined crystals (m. p. 83"). It appears
to have the composition CmHnOsBr.
Monethylene pyrogallate is easily oxidised by ferric chloride and
potassium dichromate ; the oxidation-product is, however, apparently
not uniform in composition. It is not dissolved but blackened by sul-
phuric acid, aud therefore differs from the class of compounds to which
cedriret belongs.
By the oxidation of diphenol, CioH8(OH)2 (m. p. 270°) with potas-
sium dichromate and acetic acid, a compound is obtained which dis-
ORGANIC CHEMISTRY. 251
solves in sulphuric acid, forming a beautiful blue solution, a character-
istic property of cedriret. The author is engaged with the further
study of this reaction. P. P. B.
Nitrocuminaldehyde and its Derivatives. Part II. By E.
LiPPMAXX and W. Strecker {Wien Alcad. Ber., 78, 570 — 572). — With
a view of obtaining a nitrocuminaldehyde in -which the NOo should
take the place of hydrogen in a fatty group, similar to the two isome-
rides, CsH3(N0.,).CbH and CeHs.C.fXOo) OH, previously obtained by
the nitration of benzaldehyde, the latter of which yields benzoic and
nitric acids on oxidation, the authors have prepared pure cuminalde-
hyde from the commercial article by treatment with hydrogen
sodium and sulphite, &c. It boils at 217° (corr. 222"^), and may be
nitrated by dropping it into a cooled mixture of nitric and sulphuric
acids, and subsequently washing with soda solution ; a crystalline body
is thus obtained, together with an oil, easily removable by alcohol,
in which the crystals are insoluble.
The crystalline substance is a nitrocuminaldehyde,
CeHsCCaHOCNOO-COH,
and gives a compound with sodium hydrogen sulphite, after separa-
tion, from which it forms sulphur-yellow crystals melting at 54°, and
exhibiting a tendency to remain liquid after fusion.
According to Ditscheiner the crystals are doubly oblique prisms.
On oxidation with chromic mixture, a nitrocuminic acid is formed
(m. p. 158°), identical with the acid obtained by nitration of cuminic
acid, C6H3(X02)(C3ll7).COOII, and probably it crystalUses in oblique
prisms —
a : & : c = 1-57133 : 1 : 1-26742.
On reduction, it gives an amido-acid forming a hydrochloride iden-
tical with the one described by Cahours (Annalen, 109, 10).
As a mixture of two amido-acids was obtained by Paterno and Fileti
(Gazzetta, 5, 383) by reduction of nitrocuminic acid, the authors
intend to examine the reaction more carefully to ascertain if the nitra-
tion products from the aldehyde contain two isomerides.
W. R. H.
Fittica's Nitrobenzoic Acids. By C. Bodewig (Ber., 12, 1983
1984). — The author has examined the physical properties of the four
nitrobenzoic acids described by Fittica (/. pr. Chem., 1878, 184).
The acid (m. p. 127°) separates from solution in acetone as an un-
stable a-modification of the meta-acid (m. p. 142°). This a-modifica-
tion forms monosymmetrical crystals (m. p. 141'^).
The meta-acid on crystallisation from a mixture of alcohol and ether
or fi'om acetone, g-ives an unstable /^-modification and a stable '/-modi-
fication, both of which are monosymmetrical.
The nitro-acid (m. p. 136°) on crystallisation, from acetone gives the
stable 7-modification of the meta-acid. The lemon-yellow acid (m. p.
142°) under similar cii'cumstances is converted into the unstable
^-modification .
The ethers of the meta-acid (m. p. 142°), of the acid m. p. 127°,
t 2
252 ABSTRACTS OF CHEMICAL PAPERS.
and of the lemon-yellow acid (m. p. 142°), are identical as regai'ds
their physical properties.
Measurements of the above crystals are given. T. C.
Xylic Acid, its Preparation and Derivatives. By E. Ador
and F. Meier (Bcr., 12, 1968 — 1971). — The most ready method for
preparing xylic acid [COOH : CH3 : CH3 = 1 : 2 : 4] (m. p. 126°, b. p.
267", bar. 727 mm.) is by passing a current of carbon oxychloride into
pure [1 : 3] xylene in presence of an excess of aluminium chloride, and
occasionally heating to 100°, thus r—CeHiMeo + C0Cl2= CgHaMeo.COCl
+ HCl. The chloride thus produced gives the acid on decomposition
with water. The barium, calcium, ammonium, and silver salts were
prepared and described.
Xyhjlic ehloriJe, C6H3Me2.C0Cl is obtained by treating the acid with
j)hosphorus pentachloride. It is a colourless liquid (b. p. 235°),
which on cooling crystallises in needles (m. p. 25°).
Xyhjlamide, CsHsMeo.OISrHn, was prepared by triturating the preced-
ing compound with ammonium carbonate. It is almost insoluble in
cold water, and separates from the hot solution in needles (m. p. 181°),
which are very soluble in alcohol. After sublimation it melts at 179°.
This amide is a very stable body, not being decomposed by soda even
on boiling ; it is, however, readily acted on by hydrochloric acid with
reproduction of xylic acid. It dissolves in acids, forming somewhat
unstable salts. The a)dUde, obtained by adding the chloride gradually
to aniline, consists of crystals (m. p. 138), which are but sparingly
soluble even in hot water, but more easily in alcohol. On boiling
with hydrochloric acid, it is partially decoraposed. T. C.
Parahydroxyphenylacetic Acid. By H. Salkowski (Ber., 12,
1438 — 1441). — Amongst the putrefaction products of horn, the author
and his brother {Ber., 12, 648) found a hydrox ij])lienylaGetLc acid different
from those previously known. This acid now proves to be identical
with hydroxyphenylacetic acid, obtained synthetically by the author
in the following way : — Phenylaceiic acid is nitrated, the isomeric
para- and ortho-nitro-compounds formed (Radziszewski, ibid., 2, 207,
and 3, 648) are reduced, and the amido-acids separated by Baeyer's
method {ibid., 11, 583). The 2'><^'''(^'*nid')i}henyJ acetic acid (which has
already been described by Radziszewski) was easily converted into the
hydroxy-acid by boiling with potassium nitrite and dilute sulphuric acid.
Parahydroxyphenylacetic acid crystallises in brittle, flat, prismatic
needles (m. p. 148°), which are very soluble in water, alcohol, and
ether, and may be volatilised unchanged. With ferric chloride it
gives a grey- violet colour, rapidly changing to dirty green. Its ammo-
nium salt is soluble and crystallisable ; its solution gives no precipitate
with zinc, cadmium, or cupric sulphates. The silver salt is soluble in,
and crystallisable from, boiling water. Lead and calcium salts have
also been prepared. The ethyl salt is an oily liquid ; by heating it
wdth ethyl iodide and potash, and saponifying, ethoxypheiiylacetic acid
has been obtained (m. p. 88°).
Parahydroxyphenylacetic acid yields paracresol when distilled with
soda-lime. It is pi-oduced during the putrefaction of serum albumin
as well as of horn. Ch. B.
ORGANIC CHE:\nSTRT. " 253
Paramethoxyphenylcinnamic Acid and Methoxystilbene.
By A. Ogluloro {Gazzetta, 9, 533 — 537). — -On heating a mixture
of 17 parts of anisaldehyde with 20 of sodium phenvlacetate and 70 of
acetic anhydride for 8 hours at 150° a crystalline mass is obtained,
Avhich, after being boiled with water, is treated with excess of solution
of sodium carbonate ; this leaves undissolved a small quantity of
methoxystilbene, whilst the filtered solution, after being twice washed
with ether, yields a precipitate of pararaethoxyphenylcinnainic acid,
OMe.CsHi.CH.CPh.COOH,' on addition of hydrochloric acid. It may
readily be purified by crystallisation from boiling absolute alcohol,
when it is deposited in hard yellowish prisms if the solution is not too
concentrated. The acid is but moderately soluble in ether, and only
very sparingly in water, as are also the greater number of its salts.
Although it is dissolved but slowly by sodium cai'bonate solution,
ammonia and solutions of potash or soda dissolve it readily. Heated
with a hot saturated solution of barium hydroxide, it yields the barium
salt, but at the same time a portion of the acid loses the elements of
carbonic anhydride and becomes converted into methoxystilbene. Its
acid properties are relatively feeble, the ammonium and barium salts
being decomposed by a current of carbonic anhydride. The acid melts
at 188 — 189", but at a somewhat higher temperature it is decomposed,
splitting up sharply into carbonic anhydride and methoxystilbene,
which distils over.
Methoxystilbene, OMe.C6H4.CII I CPh, which, as just stated, may be
readily prepared by distilling the methoxyphenylcinnamic acid, is
insoluble in water, but dissolves easily in ether and in hot alcohol,
crystallising out in exceedingly thin micaceous scales (m. p. 136°).
From its constitution and formula, it will be seen that this compound
is the methyl ether of a phenolic compound, which may be tenned
stilhojphenol.
As no reaction takes place between benzaldehyde, cadmium para-
toluate and acetic anhydride, it would seem necessary that the acid
should contain the group CH2.COOH, as is the case with all the acids
which have yielded successful results hitherto. The author hopes to
be able to definitively establish this hypothesis by further experiments.
C. E. G.
Metaisatic Acid (Metamidophenylglyoxylic Acid). By L.
Claisex and C. M. Thompson {Ber., 12, 1942— 1948).— This is an
account of the application of the reaction (Ber., 12, 350) by which
nitrobenzoic acid was converted into isatin, to the corresponding
meta-compound. Metanitrobenzoic chloride was first prepared from
metanitro benzoic acid by heating the latter with an equivalent quan-
tity of phosphorus pentachloride and distilling oft' the phosphorus oxy-
chloride formed. Metanitrobenzoic chloride thus obtained crystallises
in brilliant rhombic pyramids (m. p. 33°, b. p. 184°, under a pressure
of about 50 — 55 mm.), and on distillation over silver cyanide yields
the corresponding cyanide as a thick yellow liquid (b. p. 231° under a
pressure of about 145 mm.) which does not solidify at — 17^. This
dissolves in concentrated potash with formation of potassium nitro-
benzoate and potassium cyanide. On long standing in contact with
strong hydrochloric acid, it is converted into a mixture of metaisat-
2,34 ABSTRACTS OF CHEMICAL PAPERS.
amide, C6H4(CO.CO.NH2).N02 (1:3), and nitrobenzoic acid. The
former consists of white or slightly yellow prisms (m. p. 152°),
sparingly soluble in cold water, only moderately in ether, but easily
soluble in alcohol, chloroform, benzene, and boiling water.
Meta-uatic add, CfiH4.(CO.COOH).N02 = [1:3] was obtained
from the above amido-acid in the usual way. It crystallises in prisms
(m. p. 78'', with previous intumescence at about 65°), and like phenyl-
glyoxylic acid gives, when treated with benzene and sulphuric acid,
an intense carmine and afterwards a violet-red colour, but is charac-
terised (and also its salts) by a far more bitter taste. The potassium,
barium, (C8H4X05)2Ba + HoO, silver, and ethyl salts were prepared.
Meta-isatic acid was converted into the corresponding amido-acid,
CgH4(CO.COOH).NH2, by reducing the alkaline solution of the acid
with ferrous sulphate. It is a strong acid and crystallises in colour-
less prisms and needles, which, when heated, are first discoloured
and afterwards partially melt at 270 — 280°, and are not completely
volatile at 300°. It is sparingly sokible in cold, but more easily in hot
Avater, and is practically insoluble in alcohol, ether, benzene, and chloro-
form. The barium and silver salts were prepared. The hydrochloride,
C6H4(CO.COOH).NH2.HCl, forms groups of prisms, and gives with
platinic chloride a precipitate of the platinochloridc. T. C.
Formation of Hydroparacoumaric Acid from Tyrosine. By
E. BADMANN(i?er., 12, 1450 — 14-54). — In conjunction with Brieger, the
author has already shown (Zeit. Fliys. Ghem., 1, 60) that paracresol
and a little common phenol are produced dui-ing- the putrefaction of
albumin. The former is in all probability a decomposition-product of
tyrosine, which Weyl has proved to yield these phenols by putrefac-
tion {Ber., 12, 354). The author has also proved, that paracresol,
when administered to dogs, appears in the urine partly as para-
hydroxybenzoic acid (Zeit. Phys. Ghem., 3, 250) chiefly as paracre-
Siilsulphonic acid (ibid., 1, 244). Parahydroxybenzoic acid is decom-
posed partly by digestion (ibid., 3, 250), wholly by putrefaction
{ibid., 1, 60) into phenol and carbonic anhydride. To establish the
connection between phenol and tyrosine, it only remained then to
trace the changes by which paracresol is produced from it.
Six grams of pure tyrosine were mixed with five liters of water and
a little putrefying pancreas and exposed to air for two days in an incu-
bator. The tyrosine had then been completely dissolved, and by con-
centrating the filtered liquid, acidifying with sulphuric acid and ex-
tracting with ether, hydroparacoumaric. acid was obtained. This change
is evidently of the same kind as the formation of succinic acid from
aspartic acid by fermentation, and furnishes an additional proof that
tyrosine belongs to the paracresol series (Barth, Aniialev, 136, 110;
152, 96; and 163, 296), although Barth failed to obtain it syn-
thetically.
From fresh concentrated urine also, ether extracts an acid which
gives Plugge's phenol-reaction (Zeit. Anal. Ghem., 1872, 173), and
after this has been removed and the urine boiled with hydrochloric
acid as long as phenol is given off, a similar acid may again be ex-
tracted by ether. These acids are probably identical with, or related
to, hydroparacoumaric acid.
ORGANIC CHEMISTRY. 255
The series of phenol- derivatives obtained by the putrefaction of albu-
min (tyrosine) has been rendered complete by the author's discovery
{Ber., 12, 1438) of parahydroxyphenylacetic acid amongst the products
from putrefying horn.
The several stages of the conversion of tyrosine into phenol may be
thus represented : —
C9Hu]S^03 -^ H, = C^H.oOa + NH3.
Tyrosine. Hydropara-
coumarie acid.
C9H10O3 = CsHinO + CO2.
Para-etliyl-
plienol.
CsHioO + 03 = CsHsOa + H2O.
Paraliydroxy-
phenylacetic acid.
CbHsOs = C:H,0 + CO2.
Paracresol.
CHsO + 03= C,H«03 + H.O.
Parahydroxy-
benzoie acid.
C,He03 = CeHeO + CO,.
Phenol.
Of these bodies, paraethylphenol and parahydroxybenzoic acid alone
have not been traced directly to albumin or tyrosin.
Such a series of changes is quite in accordance with Hoppe-Seyler's
theory of fermentation and its connection with vital processes (Pji'iiger's
Arch., 12, 1). Similar oxidations and reductions have been eifected by
Tiemann in the protocatechuic series {Ber., 11, 659). Ch. B.
Californian Orcella Weed. By 0. Hesse (Annalen, 199, 338 —
341). — This lichen, which is a variety of Boccella fucijormis, contains
erythrin and a small quantity of roccellic acid. An alcoholic solution
of erythrin has no action on joolarised light. W. C. W.
Products of the Dry Distillation of Calcium Phthalate.
By 0. Miller (Ber., 12, 1489— 1490).— By this operation, the author
has obtained benzene, benzophenone, a crystalline compoiind (m. p.
145"5 — 146"), apparently identical with Hemilian's diphenylene-
phenylmethane, and a body (m. p. 243 — 244°) having the properties
of the hydrocarbon C13H10, which Thorer and Zincke prepared by
acting on a-benzpinacoue with soda-lime ; the two latter in very small
quantity. The first three of these are also obtained by distillation of
calcium benzoate, from which it mioht be inferred that this salt is
produced during the distillation of calcium phthalate ; the author,
however, was unable to detect it. The object of his research was to
obtain the ketone C6H4 ! CO ; the fact that he did not succeed con-
firms Kekule's view concerning the non-existence of benzene deri-
vatives containing the group (CeHi)" united with an elementary
atom. The author is studying the distillation-products of calcium
succinate. Ch. B.
256
ABSTRACTS OF CHEMICAL PAPERS.
Toluenemonosulphonic Acids. By P. Claesson and K. Wallin
(Ber., 12, 1848— 1854).— On treating toluene cooled to 10° with sul-
phuric cliloride, the following reaction takes place, 2C7H8 +
3(H0.S0,C1) = C-Hv.SO^Cl + CH^.SOsH + H0SO4 + 2HC1. The
sulphonic chlorides were separated from the rest by pouring the pro-
duct into ice-cold water, and from the mixed sulphonic chlorides, the
solid paratoluenesul phonic chloride separated on standing, and by
cooling to —20°, leaving the liquid chlorides. From the aqueous
solution, the potassium salts of the sulphonic acids were prepared, and
these again converted into the chlorides by means of phosphorus pen-
tachloride, and the solid para-compound separated as before. The
fluid chlorides were converted into the corresponding amides, from
which, by fi-actional crystallisation, the ortho-amide and meta-araide
were obtained. This method of separation was proposed by Beckurts
(Ber., 10, 943) and Fahlberg (ibid., 12, 1048), and the melting points
of the derivatives agree with those given by Fahlberg (loo. cit.) and
Midler (ihid., 12, 1348). From tolueneparasulphonic chloride, after
Para-series.
Meta-series. Ortho-series.
Acids
CjH^.SOgH + H.p.
Crystallises betterthan
the isomerides. Long
thick leaflets, or flat
prisms. Deliquescent.
C^Hy.SOaH + HoO.
Thin crystalline scales.
Yery soluble and de-
liquescent.
C7H7.SO3H + 2HoO.
Tliin leaflets. Very
easily soluble. Deli-
quescent.
Potassium
salts
C;II;.S03K + H.jO.
Long prisms, like
nitre. Soluble.
C-H-.SO3K + HoO.
Needles or thin plates,
united to form no-
dules. Very easily
soluble.
C;B";.S03K + H2O.
Tables of rhombic or
almost quadratic habit.
Soluble.
Calcium salts
(C7H;.S03)2Ca + 4H.,0.
Crystallises well in ap-
parently monoclinic
prisms. Easily solu-
ble.
(C;II;S.03)cCa+3H.20.
Long fine needles ;
very easily soluble.
(C9H7.S03)2Ca.
Separates from its so-
lutions on cooling, in
leafy crystals.
Zinc salts . .
(C-H7.S03),Zn + 6H,0.
Crystallises in quad -
ratic acuminated
prisms. Easily solu-
ble.
(C7H7.S03).,Zn + 7H20.
Rectangular, thin leaf-
lets. Easily soluble.
(C-H-.S03)2Zn + 7H20.
Lai'ge prisms. Easily
soluble.
Amides ....
C;H-.SO..NHo.
Crystallises from water
and alcohol in leaflets.
Sparingly soluble in
water; more so in
alcohol. 1 pt. amide
in 515 pts. of water
at 4\ or in IS'S pts.
of alcohol at 5°. M. p.
136°.
CVH^.SO^NHa.
Crystallises from alco-
hol and water in long,
leafy forms. Sparing-
ly soluble in water ;
more so in alcohol.
1 pt. amide in 248 pts.
water at 9°, or in
5'7 pts. of alcohol at
5°. M. p. 107—108°.
C7U;.S02NH2.
From water and alco-
hol in quadratic octa-
hedrons and prisms.
Insoluble in cold
water ; sparingly solu-
ble in alcohol. 1 pt.
amide in 958 pts.
water at 9°, or in
28 pts. of alcohol at
5°. M. p. 153—154".
ORGANIC CHEMISTRY. 257
crystallisation from ether, the acid was obtained bj boiling with
watei", and the corresponding acid from toluene ortho-sulphamide bj
heating it with hydrochloric acid at 135 — 140°, and in a similar
manner at 150°, the toluenemetasulphonic acid was obtained from the
toluenemetasnlphamide. The authors have by this means obtained
excellent yields of the above compounds ; whilst Beckurts and Otto
(ibid., 11, 2061) found the para-derivative to be the chief and almost
the only product of the action of sulphuric chloride on toluene. A
table is given containing the results of the comparative study of the
three isomeric toluenesnlphuric acids, from which the foregoing (p. 256)
are taken.
From these results, the authors conclude that the metatoluenesul-
phonic acid is not, as supposed by Fahlberg, a mixture of the para-
and ortho-acids. Further, the ortho- and meta-acids may be separated
by means of the barium, calcium, or silver salts, as well as by their
amides. The properties attributed to the salts of the ortho- and meta-
toluenesulphonic acids, prepared indirectly from bromo-, nitro-, and
amido-toluenes, do not agree with the above descriptions.
P. P. B.
Oxidation-products of Cymene-sulphonamide. By L. B.
Hall and I. Remsex (Ber., 12, 1432 — 1436). — It has been previously
shown that when xylenesulphonamide is oxidised, it yields sul-
phonamidometatoltiic acid and some sulphonamidoparatoluic acid.
The former acid has been pavtially examined by lies and Remsen
(Ber., 11, 229), who converted it into paratoluic acid by treatment
with hydrochloric acid.
Sulphonamidoparatoluic acid is also readily furnished by oxidation
of cymenesulphonamide [CH3 : C3H5 : SOj.NHo = 1:4:2]. The
group SO2.NH2 appears to protect the methyl (ortho-) groiip from
oxidation, the propyl being converted into carboxyl.
By fusion with potash, this acid is converted first into the a-oxy-
paratoluic acid of v. Geriehten and Rossler (Ber., 11, 1586), which is
further oxidised to the oxyterephthalic acid of Burkhardt (Ber., 10,
144). The first of these acids crystallises from hot water in needles,
does not volatihse with steam, and gives no colour with ferric chloride.
Its lead salt was prepared and analysed.
By oxidising sulphonamidometatoluic acid with potassium perman-
ganate, Remsen and lies obtained sulphonisophthalic acid. When free
sulphonamidoparatoluic acid is similarly oxidised, it yields a salt,
CfiH3(CO0H)3.SO3K + HoO, presumably of .mJphontereplithalic acid,
still containing two displaceable hydrogen atoms. But when the cor-
responding potassium salt is treated with permanganate instead of the
free acid, the result is diiferent. Very little ammonia is evolved, and
a salt having the constitution, CeHsCCOOKX^Q >NH + HoO, is
the principal product. The molecule of water is given off at 240° ;
it is probably not constitutional. On this view, the free acid, anliy-
drosulphonamido-terephthalic acid, would be analogous to the anhydro-
CO
compound, C6H4<^p. >NH, obtained by the oxidation of ortho-
toluenesulphonamide (Remsen and Fahlberg, Ber., 12, 469). If, how-
258
ABSTRACTS OF CHEMICAL PAPERS.
ever, the water given off at 240^ be constitutional (see next Abstract),
the salt will have the formula, C6H3(CUOK)(COOH).S02NH2.
Ch. B.
Anhydrosulphonamidoisophthalic Acid. By I. Remsen and
R. D. CoALE {Ber., 12, 1436 — 1438). — According to Remsen, when
sulphonamidometatoluic acid is treated with potassium permanganate,
it yields only sulphonisophthalic acid ; while Jacobsen asserts that
sulphonamidoisophthalic acid is the product. In the authors' opinion,
this latter acid cannot exist, since on being set free it is at once con-
Yerted into an anhydride. This anhydro-acid. (m. p. 283^5°) is ob-
tained by oxidising sulphonamidometatoluic acid in strongly alkaline
solution with permanganate on the water-bath, and acidulating the
hltered and decolorised solution with hydi^ochloric acid. Its potas-
slum salt, CgH3(C00K)<^P^'"^NH + 2H2O, may be formed by cau-
tiously adding hydrochloric acid to its solution in potassium carbo-
nate. As proved by titration, this salt is capable of taking up an
additional atom of base.
The authors conclude that a sulphonamide and a carboxyl grotip
cannot exist together in the ortho-position, but may in the meta- or
para-position. Ch. B.
Solubility of some Constituents of Coal-tar. By G. v. Bechi
(Ber., 12, 1976—1978).
100 parts of Toluene dissolve
100 parts of absolute Alcohol
dissolve
At the ordinary
temperature.
At 100°.
At the ordinary
temperature.
At 78°.
Naphthalene. . . .
Anthracene ....
Phenanthrene. . .
Pyrene
31-91
■92
33 02
16-54
■24
•55
Scarcely soluble
•19
In all propor-
tions
12-94
In all propor-
tions
Very soluble
5 -.39
5-46
•39— -57
2-56
5-29
•076
2-62
1-37
•097
•92
Scarcely soluble
•05
In all propor-
tions
•83
10^08
3 08
Clirrscne
Carbazol
Plienyl-naphthyl-
carbazol,
Anthraquinone. .
•17
3-88
•25
2-25
T. C.
Skatole. By L. Briegeb (Ber., 12, 1985— 1988).— This compound,
which was previously obtained by the author (Ber., 10, 1027) from
human excrement, crystallises in brilliant white plates (m. p. 93°),
and has an intense fsecal odour. It has great resemblance to indole,
from which it differs, however, in being much less soluble in water, in
having a higher melting point, in its odour, and also in the fact that it
does not give a coloration with chlorine- water, or a red precipitate with
ORGAXIC CHEMISTRY. 259
fuming nitric acid, but only a white cloud. On warming wdtli dilute
nitric or hydrochloric acid, it assumes a violet colour. An analysis
gave numbers which were the mean of those required by the formulae
CioHioN and CioHuN. An analysis by Nencki (Centr. Med. Wissen-
schaft, 1878, No. 47) of the same substance obtained by the fermenta-
tion of flesh in the presence of pancreas infusion, led to the formula
C9H9N. The best method for preparing skatole is by the fermentation
of blood-albumin with a little pancreas and water, indole being also
formed at the same time. Several analyses of the skatole thus obtained
gave numbers corresponding with the formula C9H9N, and a vapour-
density determination gave 65'2 instead of 65'5.
Administered in small doses, skatole appears to have no deleterious
effect on the animal system, but in larger quantities it produces
tetanus. An examination of the urine showed that the proportion of
ethylsulphates to sulphates had considerably increased. T. C.
Peculiar Formation of Tolane Tetrachloride. By C. Liebek-
MAXN and J. HoMEYER (Ber., 12, 1971 — 1976). — Tolane tetrachloride
was obtained as a bye-product in the preparation of a lai-ge quantity
of benzotrichloride by the action of chlorine on boiling toluene. It
crystallises in rhombic prisms (m. p. 163"^), and is remarkable for its
gi'eat stability, not being attacked by boiling nitric acid, nor by a mix-
ture of chromic and acetic acids, nor on heating the alcoholic solu-
tion with oxide of silver or with potash. On heating with dimethyl-
aniline and zinc chloride, it gives a violet colour. The author confirms
Zinin in the observation that tolane tetrachloride gives two isomeric
dichlorides, CuHjoCL, when its alcoholic solution is boiled with zinc.
The compound least soluble in alcohol crystallises in rhombic tables
(m. p. 143°; 153°, Zinin; also Limpricht and Schwanert, Ber., 4,
379), and the other in needles (m. p. 63 '). Tolane tetrachloride in
alcoholic solution gives tolane (v. d. = 6'34, calculated for CuHio =
6'18) on treatment with sodium amalgam, thus confirming the earlier
observations of Zinin; stilbene and dibenzyl are also formed at the
same time. Tolane, on oxidation with chromic mixture, gives benzoic
acid, and when its solution in chloroform is treated with chlorine the
chloride (m. p. 143°) is obtained. Tolane dibromide, CuHioBr2 (m. p.
207° ; 205° according to Limpricht and Schwanert), is produced by the
action of an excess of bromine on a solution of tolane in carbon bisul-
phide. Stilbene is obtained when tolane tetrachloride is heated with
zinc-dust, and benzil when the same substance is acted on by glacial
acetic acid for a long time at 230 — 250°, or by concentrated sulphuric
acid at 165°, small quantities of benzoic acid being produced at the
same time. T. C.
Synthesis of Diphenylpropane : New Method of Forming
Dibenzyl. By R. D. Silva {Gompt. rend., 89, 606--608).— By
acting with ordinary propylene dichloride on benzene in presence of
aluminium chloride according to the method suggested by Friedel
and Crafts, diphenylpropane is obtained as a slightly viscid liquid of
figreeable odour, boiling without decomposition between 277° and 279°.
2(50 ABSTRACTS OF CHEMICAL PAPERS.
Its density is 0"9256 at 0°. The same hydrocarbon is obtained when
allyl chloride is substituted for propylene chloride ; it is most likely,
therefore, that the allyl-benzene combines with the liberated hydro-
chloric acid to form the compound CoHs.CHo.CHCl.CHs, which after-
wards reacts with the excess of benzene to form diphenylpropane.
Ethylene dichloride reacts in a similar manner with benzene and
aluminium chloride, forming diphenylethane, which should be identical
with dibenzyl. This was proved to be the case by comparing its
reactions with that of dibenzyl prepared by the action of finely
divided silver on benzyl iodide. The melting points of both com-
pounds was 52"5°, and their boiling points 276 — 277°. Diphenyl-
ethane crystallises from an ethereal solution in prisms belonging to
the orthorhombic type. J. W.
Di- and Tri-derivatives of Naphthalene. By R. Meldola
(Ber., 12, 1961 — ll»65). — A continuation of the author's previous work
on this subject.
a^-DibromonapJithylamine, doH-BraN, is obtained by heating dibrom-
acetonaplithalide with concentrated soda-lye at 140 — 150° for several
hours. It crystallises in large white needles (m. p. 118"), which are
easily soluble in benzene, petroleum, alcohol, ether, and chloroform ;
it has no basic properties. On oxidation with chromic and acetic
acids, it gives an evanescent indigo- blue coloration, and by oxidation
with dilute nitric acid, it yields phthalic acid, showing that the bi'omine
and amido-groups are all in the same benzene ring, and since Rother
and Liebermann have shown that in bromacctonaphthalide the bromine
atom and the NH.C^HaO group occupy the position (1:4), it is pro-
bable that in the new dibromnaphthylamine the arrangement is
NH2 : Br : Br = 1 : 2 : 4.
al3-DibromovaphthaIe72e was obtained from the preceding compound
by means of the diazo-reaction. It ciystallises in white needles
(m. p. 64°). From considerations based on the lowness of this melt-
ing point as compared with that of the isomeric /3-compound (ra. p.
81°) prepared by Glaser and afterwards by Jolin (Bull. Soc. Chim.
[2], 28, 514), the author concludes that it is a meta-compound, as
we should have expected from the constitution above ascribed to
a/3-dibromonaphthylamine.
a-Bromonaphthalenesulphonic acid, obtained by the action of
fuming sulphuric acid on a-bromonaphthalene, gives phthalic acid on
oxidation with an alkaline solution of potassium permanganate, thus
proving it to have the constitution HSO3 : Br =: 1 : 4.
Sodium bromonaphthalenesulphonate on fusion with soda does not
give bromonaphthol, but resinous products, and by treatment with
sodium amalgam in alkaline solution it is partially reduced to naphtha-
lene. T. C.
Some Naphthol-derivatives. By C. Marchetti (Gazzetta, 9,
544 — 545). — Ethyl monohrom-cc-naphfholate, doHgBr.OEt, is prepared
by adding a^ chloroform solution of bromine in theoretical proportion
to a solution of ethyl a-naphthyl ether, CmHv.OEt, also in chloroform.
After evapoi'ation, the oily product is washed with sodium carbonate
ORGANIC CHEMISTRY. 261
solution, cooled bj a freezing mixture, and the crystalline mass thus
obtained purified by pressure and recrystallisation from ether con-
taining a little alcohol. It forms long thick prisms (m. p. 48") very
soluble in ether and in carbon bisulphide, but insoluble in water.
Metlujl a-naptliolate or methyl a-nuphtlbijl ether, CioHv.OMe, may be
prepared by Shaeif'er's process {Ber., 2, 90), except that it is necessary
in order to complete the reaction to digest the mixture for 8 — 10
hours under a pressure of about 800 mm. of mercury. It is a colour-
less liquid (b. p. 265 — 266°) which remains liquid at - 10'^. It is
very soluble in ether, carbon bisulphide, and chloroform, less soluble
in ethyl alcohol, sparingly in methyl alcohol, and almost insoluble in
water.
Methyl ^-naphtholate or methyl (3-naphthyl ether crystallises in colour-
less plates (m. p. 70°, b. p. 274°) having an odour of pine-apple. In
solubility, it resembles the a-compound ; it is volatile in the vapour of
water. C. E. G.
Nitronaphthoic Acids. By A. G. Eckstraxd (Ber., 12, 1.393—
1396). — "When fuming nitric acid is added to the hot concentrated
solutions of the isomeric a- and ,<3-naphthoic acids in glacial acetic
acid, each yields two isomeric monouitro-derivatives, which may be
separated by fractional crystallisation from alcohol and ether, &c.
a-Xaphthoic acid thus gives — first, a more soluble nitro-acid, which
crystallises in colourless prisms (m. p. 195 — 196°), and forms a
sparingly soluble anhydrous calcium salt (1 in 47), and a crystalline
ethyl salt (m. p. 63°) easily soluble in alcohol and ether; also a less
soluble yellowish coloured acid, in fine prisms (m. p. 233°), soluble
in alcohol, ether, glacial acetic acid, and benzene; it forms a very
sparingly soluble calcium salt (1 in 160), and a crvstalliue ethyl salt
(m. p. 92°).
/3-Naphthoic acid gives — first, a yellowish easily soluble nitro-acid
(m. p. 220°), readily dissolved by alcohol, ether, acetic acid, and ben-
zene, forming a slightly soluble calcium salt (1 in 388), and an ethyl
salt (m. p. 82°) ; also a sparingly soluble acid (m. p. about 280°),
forming a very slightly soluble calcium salt (1 in 930), and an ethyl
salt (m. p. 107°).
The alkaline salts of all four acids are easily soluble in water, their
silver salts insoluble. Their constitution is as yet unknown.
Ch. B.
Synthesis of Phenylnaphthalene. By W. Smith (Ber., 12,
1396 — 1398). — When a mixture of monobromonaphthalene and ben-
zene is passed through an empty tube heated to rednes.s, very little
change takes place. But when the tube is filled with soda-lime at the
same temperature, the three following reactions occur simultane-
ously : —
(1.) 2C,oH,Br + 2CoH6 + 2XaOH = 2XaBr + 2H2O +
CeHs.Cella -f C10H7.C10HT.
(2.) C.oH;Br + CeHe + NaOH = NaBr + H.O -f CoH^.CeHs.
(3.) CioH.Br + 2C6H6 -|- NaOH = NaBr + H.O -f CoHs +
CeHj.CeHo.
262
ABSTRACTS OF CHEMICAL PAPERS,
In the actual experiment, a little diphenyl and a considerable quan-
tity of naphtlialene were formed.
When a mixture of naplithalene and monobromobenzene is passed
tbrouo'li a combustion tube, filled with pumice stone and heated to
strono- redness, diphenyl, isodinapldliyl, and a new hydrocarbon of
lower boiling point than the dinaphthyls, are obtained mixed with the
unchanged original bodies. The new hydrocarbon is soluble in hot
spirit, and separates on cooling in microscopic plates, which may be
sublimed in transparent scales showing blue fluorescence (m. p. 101 —
102°). It smells like pomegranate. It is yyroh&hlj phenylna'phtlialene,
produced by the second of the reactions occurring in the process : —
(1.) 2C,oH8 + 2C6H5Br = 2HBr + C.oHv.CioH, + C^Hj.CeHs.
(2.) CoHs + C6H5Br = HBr + C,oH,.C6H5. Ch. B.
Synthesis of Anthracene. By C. L. Jackson and J. F. White
(Bet., 12, 19G5 — 19G7). — A solution of orthobromobenzyl bromide in
toluene when acted on by sodium ^-ields a product which may be sepa-
rated into three parts: — A, an oil which after some time becomes crystal-
line (m. p. about 51°), this has not yet been investigated. B, a mixture
of anthracene and anthracene dihydride. C, a bituminous residue.
The formation of anthracene by this reaction proves that the two car-
hon atoms in anthracene are combined with both benzene-rings in the
ortho-position. T. C.
Constitution of Alizarin-blue. By C. Gkaebe (Ber., 12, 1416 —
1418). — The anah'ses of the salts and ethers of alizarin-blue have con-
firmed the author's foi-mula for it, CnH9N04, and shown that its
molecule contains two ketone oxygen atoms and two hydroxy! groups.
The two atoms of oxygen which nitroalizarin loses in its conversion
into this body by the action of glycerol (Ber., 11, 1646 and 1945) are
therefore those of the nitro-group.
The author considers that alizarin-blue bears to alizarin the same
relation that chinoline bears to benzene, and ascribes to it and the base
derived from it by heating with zinc-dust the constitution and
names,
:CH H ch:
ch:
:CH
H
H
.CO.
/\ A--nTT TT /\ CTT /\
^'•CH
CO . I J OH
H OH
Alizarin-blue.
CH
n:ch
h h
Anthracliinolin e.
on the following grounds : — Alizarin-blue yields phthalic acid on oxi-
dation, showing that only one benzene nucleus contains lateral chains.
Moreover, the nitroalizarin of Rosenstiehl and Caro, used in preparing
it, which also yields phthalic acid on oxidation, cannot be converted
into purpurin like its isomeride prepared by Perkin : it must there-
fore contain the groups OH : OH : NO? in the positions 1:2: 3, since
according to Baeyer, the corresponding groups of purpurin have the
arrangement, 1:2:4.
Anthrachinoline (m. p. 170°, b. p. 446°) is a tertiary base. It can
ORGANIC CHEMISTRY. 263
be readily oxidised into a quinone "which reacts with zinc- dust and soda
like anthraquinone.
The synthesis of chinoline from aniline and allyl iodide, effected by
Konigs {Ber., 12, 453), is to a certain extent analogous to the syn-
thesis of alizarin-blue from nitro-alizariu and glycerol. Ch. B.
Action of Ammonia on Anthraquinonesulphonic Acids.
By R. BouECART (-Be?-., 12, 1418 — 1420). When sodium anthraquinone-
monosulphate is heated at 180° with aqueous ammonia for 48 hours,
the group HSO3 is eliminated, and a body having the composition
CuHgOsN is formed. This substance is dark-red in colour, crystalline,
insoluble in water, ether, and alkalis, but soluble in alcohol and ben-
zene (m. p. 301°). By sublimation it is obtained in crystals strongly
resembling those of alizarin. It has the composition of amido-oxyarv-
thraquinone, but diffei's fi'om known bodies of that type in beinf in-
soluble in alkalis.
Acetic anhydride converts it into a yellow triacetyl- compound
(m. p. 257°) soluble in alcohol and ether ; by the action of potassium
nitrite and sulphuric acid, it yields a volatile nitro-derivative —
CuHsOaNCNOo) (m. p. 240°).
The latter when heated with zinc-dust is converted into a basic body
containing oxygen (m. p. 210°), which dissolves slowly in dilute
sulphuric acid ; its solutions in alcohol and ether are dichroic. Its
constitution is not known.
Sodium anthraquinonebisulphate (analogous to isopurpurin) when
similarly treated with ammonia yields a nitrogenous body, still con-
taining the group HSO ; it dissolves in ammonia with cherry- red
colour, and is precipitated again by acids in pale violet flocks. The
new acid probably has the constitution —
C6H,(SO,H)<^g>C6H,(OH).XH,,
with which formula the analysis of its ammonium salt also agi'ees.
Ch. B.
Products from Brown Coal-tar and some Derivatives of
Chrysene. By A. Adler (Ber., 12, lb89— 1895).— The author has
discovered chrysene to be the chief constituent of the residue from the
rectification of the tar, prepared by distilling a variety of brown coal
known as pyropissite ; the following derivatives have been prepared
from the chrysene so obtained.
Dihromochrysoquinone, Ci8HaBi'202. — Bromine acts directly on the
quinone, and by crystallisation from carbon bisulphide, the dibromo-
derivative is obtained in small red leaflets, which dissolve in alcohol
and benzene, but less easily in ether. It melts at 160 — 165°.
Birdtrochrysoquinone, CisHs(XOo)202. — By dissolving chrysoquinone
in nitric acid (sp. gr. 1"4; a red solution is formed, from which the
dinitro-derivative is precipitated on addition of water. By crystallisa-
tion from hot acetic acid and alcohol, it is obtained in red needles
(m. p. 230°) sparingly soluble in benzene and ether.
Trihromodinitrochrysene, CiBH;(X03)3Br3. — This compound is formed
264 ABSTRACTS OF CHEMCAL PAPERS.
by tlie direct action of bromine on tetranitrocbrysene ; it dissolves in
alcobol, from whicb it crystallises in yellowish-red needles, is sparingly
soluble in benzene and ether. It is not decomposed by alcoholic
potash.
The action of reducing agents on tetranitrochrysene yield but un-
satisfactory results.
Barium chrysoquinonedisulphate, Ci8H802(S03)2Ba, is formed by
treating the sulplionic acid with barium carbonate : on concentration
in a vacuum it is obtained in well-formed ciystals, viz., I'egular octa-
hedrons. It is unstable, takes up moisture from the air, and becomes
red. P. P. B.
Hydration of Terpenes. By F. Plawctzky (Ber., 12, 140(3 —
1407). — The hydration of terpenes, shown by the author to take place
under the influence of hydrochloric and sulphuric acids (^Ber., 12,
1022), is also effected by hydriodic and phosphoric acids, but not by
oxalic and acetic acids. Using alcoholic sulphuric acid, the amount
of hydrate formed is greater the more soluble the terpene is in that
mixture. Thus, one part of French oil of turpentine ([aJD = — 30°)
mixed with one part 90 per cent, alcohol and one half part oil of
vitriol (sp. gr. 1"64) and allowed to stand for ten days, is dissolved to
the extent of more than one half; and on adding a little water to the
solution a liquid layer separates, which solidifies when left for a few
days in an open dish. By washing with water, distilling with steam
and fractional distillation, an optically-inactive, pleasantly-smelling
compound, CioHisO, is obtained, which is soluble in all proportions in
alcoholic sulphuric acid of the above strength.
Sulphuric acid also acts on certain terpenes ([^^Jd = — 36° and [ajn
= + 24°) from Russian oil of turpentine, but very slightly on oil of
lemon ([a]D =^ + 55°). Alcoholic nitric acid also dissolves oil of tur-
j3entine. Ch. B.
Abietic Acid. By 0. Emmerling (Ber., 12, 1441— 1446.— The
most important work with reference to this acid is that of Maly
(Annalen, 132, 249), who ascertained its composition, C44H54O5, and
considered that it is produced by hydration from colophonium,
C44He40^. ]\laly prepared several of its compounds, including the
ethyl salt, Ci4H62(CoH5)>05 + -11120, and the glycerol salt, abietin.
By the action of sodium amalgam, he converted it into hydroabietic
ttcid, C44H8g05 ; and by fusion with potash obtained, besides some pro-
pionic acid, a potash salt which was soluble in water, but insoluble in
potash solution, and was not a protocatechuate. By the action of
phosphoric chloride, he obtained various hydrocarbons. Amongst
later investigators (Fliickeger, Schreder and others) Ciamician (Ber.,
11, 269) heated it with zinc-dust and obtained toluene, metetliylmethijl-
henzene, metliijlnaplithalene and methylantJiracene.
Abietic acid is best obtained pure by digesting colophonium with 70
per cent, alcohol for a couple of days, washing the undissolved portion
A\-ith weak spirit, and dissolving it in the smallest quantity of glacial
acetic acid. From this solution, the acid gradually separates in crusts.
By adding a little water to its solution in hot alcohol and stirring, the
ORGANIC CHEMISTRY. 265
acid may be obtained in crystalline scales (m. p. 139°; Lievert, Jahres-
hericht, 1859, 508, gives 150°; Maly 165°, and Fliickeger 135°). By
slow evaporation of its alcobolic solution, it is obtained in equilateral
triangular crystals.
Abietic acid probably contains bydroxyl-groups. When heated
■with acetic chloride or anhydride it yields a neutral oil which could
not be purified, and was therefore not analysed. Since, however, it
gives up acetic acid to boiling potash, it is evidently an acetyl com-
pound. By adding bromine to a solution of abietic acid in carbon
bisulphide a bromine derivative is formed, probably C«H62Br205,
which separates from alcohol as a red powder (m. p. 131:^).
When abietic acid is distilled with zinc chloride, a heavy oil is pro-
duced, which has the properties of Anderson's resin-oil (Jahresbericht,
1869, 787). A portion of this liquid, boiling between 70° and 250°,
may be separated by water vapour ; the part which comes over between
80° and 100° contains heptylene, since on treatment with hydriodic acid
it yields liepiyl iodide.
Strong hydriodic and hydrochloric acids at 145° appear to dehydrate
abietic acid, reproducing colophonium. Fusing potash does not attack
it. By oxidation with permanganate, carbonic, acetic and formic
acids are produced. When it is boiled with chromic mixture, acetic
acid is formed in large quantity ; and after this has been removed by
distillation, ether extracts from the liquid a little trimellitic acid,
CbH3(COOH)3, which was converted into barium salt and analysed.
The acid separated from this salt is crystalline, and by sublimation
yields trimellitic anhydride (m. p. 158°). Ch. B.
The Glucoside from White Mustard-seed, By H. Will and
A. Laubexheimer (Annalen, 199, 150 — 164). — Sinallin, CsoHuN'oSoOie,
is prepared by extracting with warm alcohol white mustard- seed
{Sinajns alba) from which the oil has been removed by pressure and
by treatment with carbon bisulphide. The crystals which are deposited
are washed with carbon bisulphide and dissolved in a small quantity of
hot water : the solution is then boiled with animal charcoal, filtered, and
mixed with strong alcohol, and the precipitate which is formed is recrys-
tallised from alcohol, when pale-yellow needle-shaped crystals of sinal-
bin are obtained. The mother-liquor from the crude sinalbin contains
sinapin thiocyanate. Sinalbin is insoluble in ether and carbon bisul-
phide, sparingly soluble in cold absolute alcohol, but freely soluble in
water. The aqueous solution has a neutral reaction ; when brought
in contact with a trace of an alkali, it acquires an intense yellow
colour which is turned red by nitric acid. Silver nitrate throws down
a white precipitate which consists of the silver compounds of sinapin
and of sinalbin thiocarbimide ; the filtrate, which has a strongly acid
reaction, contains sinapin (which may be precipitated by mercuric
chloride) and grape-sugar. When the precipitate is decomposed by
sulphuretted hydrogen, sinajmi suli^hate, C16H04NO5.HSO4, and the
cyanide, 06114(011)01120^, pass into solution ; the latter can be ex-
tracted with ether. After recrystallisation, from benzene, the cyanide
forms colourless plates (m. p. 69°) soluble in ether, alcohol, warm
benzene, and warm water. On boiling with potash, ammonia is evolved
VOL. XXXYIII. u
266 ABSTRACTS OF CHEMICAL PAPERS.
and orthohydroxi/phefiylacetic aa'tZ, CsHi (OH) CH2.COOH, is produced.
The acid crystallises in colourless prisms (m. p. 144"5°), soluble in
alcohol, ether, and hot water, and bears some resemblance to Salkowski's
parahydroxyphenylacetic acid (Ber., 12, 1438). The calcium salt,
(C8H703)2Ca + 4H2O, forms glistenino- prisms, sparingly soluble in
cold water : the bariitm salt, (C8H703)2Ba + H2O, triclinic prisms,
slightly soluble in cold water. The silver salt, C8H703Ag, is almost
insoluble in water, and is decomposed by heat.
On the addition of mercuric chloride to a warm aqueous solution of
sinalbin, a precipitate is produced which contains, in addition to com-
pounds of mercury with sinapin sulphate and the cyanide, CtHvOCN,
a double chloride, viz., dsHosNOsHCl.HgClj.
If ground white mustard-seed is treated with water and filtered, an
acid liquid is obtained which contains myrosin, sugar, sinapin thio-
cyanate, and sulphate. The myrosin may be precipitated from this
solution by alcohol. An aqueous solution of sinalbin is decomposed
by myrosin, thus : —
C3oH«N2S20,6 = C,H;O.NCS + C,6H23N05.H2S04 + C6H.2O6.
Sinalbin. Sinalbin tliiocai-bimide. Sinapin sulpliate. Sugar.
The pungent principle in the mustard-seed is contained in the
albuminous precipitate, which separates out on the addition of the
myrosin ; by extraction with alcohol and ether it can be obtained in
the impure state as a yellow oil insoluble in water. W. C. W.
Chlorophyll. By A. Gautiee (Compt. revd., 89, 861— 866).— The
author succeeded in obtaining pure crystallised chlorophyll in the year
1877, by the following process. The green leaves of spinach and
cresses were bruised in a mortar, with addition of sodium carbonate,
so as to neutralise the acidity of the juice, and then pressed. The solid
residue was suspended in alcohol of 55°, and again pressed, and the
process repeated with alcohol of 83°. Chlorophyll, wax, fats, and
pigments dissolve. The liquid is filtered, and then shaken with pure
animal charcoal. The green colouring matter is absorbed after several
days ; the charcoal is washed with alcohol of 65°, which removes a
yellow crystallisable substance. It is then washed with dry ether, or
light petroleum, when the chlorophyll dissolves, and is deposited in
dark-green crystals by slow evaporation.
It forms needles of as much as half a centimeter long, of soft con-
sistence ; on keeping it turns yellowish- or greenish-brown. Some of
the smaller crystals transmit green light, and some lilac. The crys-
talline form appears to be an oblique rhomboidal prism, the rhombohe-
dral angle being about 45°. As thus obtained, chlorophyll presents
striking analogy to bilirubin ; it is soluble in the same solvents ; it is
removed from its solutions by animal charcoal, and may be again
recovered by treatment with ether or petroleum ; it forms salts with
bases ; it is easily oxidised in presence of light ; it undergoes numerous
changes, accompanied by alteration of colour ; and it combines directly
with nascent hydrogen. When digested with hydrochloric acid, it
splits up into plujlloxanthin, a brown substance, crystallising from ether
or hot alcohol, and Fremy's phijllocijanic acid, an olive-green substance,
ORGANIC CHEMISTRY. 2G7
soluble in alcohol and ether, and forming salts with bases. Chlorophyll
thus prepared is absolutely free from iron. The " chlorophyllane "
discovered by Hoppe-Seyler (an account of which is published in Ber.,
12, 1555), closely agrees in its properties with the substance separated
by the author. The analyses of the two bodies are also fairly con-
cordant. Hoppe-Seyler's chlorophvllane contains C = 73'4 ; H =
9-7; N = 5-62; P = 1-37; Mg = 6-34; 0 = 9-57; and the author's
analysis of chlorophyll which had turned yellow from exposure to light
is C = 73-97 ; H = 9-80 ; N" = 415 : ash = 175 ; 0 = 10-33. The
author concludes by remarking that his discovery was two years prior
to that of Hoppe-Seyler, and he has been induced to publish in con-
sequence of the latter's recent paper. W. R.
Colouring-matter of Anguria and Colycynth. By A. and G.
DE Negri {Gazzefta, 9, 506 — 507). — -In the fruit of Cucumis anguria,
a very unstable red colouring-matter exists, which the authors have
named riibiJine. It may easily be obtained by exhausting the fruit
with ether, evaporating, and treating the residue with absolute alcohol ;
this dissolves a yellow colouring-matter, and leaves the rubidine in the
crystalline state. It is insoluble in water, but easily soluble in benzene,
chloroform, or carbon bisulphide ; the solutions giving a characteristic
spectrum, with two absorption-bands in the green, and another less
distinct in the blue. It crystallises in beautiful red needles with yel-
lowish-green metallic reflex ; it is not altered by the action of am-
monia, but becomes blue when treated with concentrated sulphuric or
nitric acid. It is not volatile, but carbonises when strongly heated.
It is probable that rubidine exists in other plants : in fact the
authors have extracted a red crystalline substance from colycynth,
very closely resembling rubidine in its properties, and apparently
identical with it. C. E. G.
Lapachic Acid. By E. Paterno (Preliminary Notice) (Gazzetta,
9, 505 — 506). — This acid is obtained from the " lapacho " wood,
furnished by a tree of the order Bigoniace^, indigenous to the Argen-
tine Republic and other parts of South America. The formula of the
acid is CisHuOs, and that of its silver salt, CisHigAgOa ; treated_with
acetic chloride or anhydride it yields a crystalline acetate, CisHi^AcoOs,
whilst with bromine it gives the compound CisHi^BrOa, crystallising
in orange-coloured plates. It is almost entirely converted into
phthalic acid by the action of nitric acid, and yields naphthalene and
isobutylene when distilled with zinc turnings. The acid appears to
be identical with Stein's groenhartin and with Arnoudon's taigulc acid.
C. E. G.
Compounds from Animal Tar. By H. Weidel (Ber., 12,
1989 — 2012). — Since the oxidation- products (nicotinic acid, cincho-
meronic acid, oxycinchomeronic acid, berberonic acid) of certain
alkaloids gave chiefly pyridine by the dry distillation of their lime-
salts, whilst others (cinchonine and chinolic acid) gave chinoline, a
more minute examination of the bases from animal tar than had
hitherto been made appeared very desirable. Animal tar begins to
boil at about 80°, when an oily distillate mixed with water passes over
u 2
2(58 ABSTRACTS OF CHEMICAL PAPERS.
aecompanied by a considerable evolution of ammonia. The tempera-
tnre then rises gradually to 250°, beyond which the distillation cannot
be carried conveniently on account of the rapid sublimation of am-
monium cyanide, ammonium carbonate, &c. The bases (picoline,
pyridine, &c.) were sepai'ated and isolated from the above distillate
by a process described in the original paper. 1,400 kilos, of tar gave
18"5 kilos, of the dry bases, boiling between 95° and 250°.
The picoline obtained boiled at 133 — 139°. Several analyses and a
vapour-density determination of the lowest and highest boiling portions
gave niimbers corresponding with the formula, C6H7N, but different
oxidation-products were obtained from each, showing that they were
not identical. Devar (Zeits. Chem., 1871, 116) obtained pyridinedi-
carboxylic acid, CtHsN^Oj, by the oxidation of picoline with potassium
permanganate ; the author, however, using exactly the same process,
did not obtain this acitl, but two other acids having the composition
CeHjNOj ; he afterwards succeeded in obtaining Devar 's pyridinedi-
cai'boxylic acid, but only from those portions of the distillate from the
tar having the composition of lutidine. The two acids obtained above
by the oxidation of picoline were separated by means of the difference
in the solubility of their copper salts which were then decomposed by
sulphuretted hydrogen.
Picnlinic Add, CeHsNOo. — This is the acid obtained from the less
soluble copper salt. It crystallises in prismatic needles (m. p. 135°)
which are easily soluble in alcohol and in water, but almost insoluble
in ether, benzene, chloroform, and carbon bisulphide. It is odourless,
and has an acid taste, afterwards bitter. On adding a copper salt to
a not too dilute solution of this acid or its salts, a precipitate of
brilliant violet-blue needles or plates is produced : this characteristic
action may be used for the identification of the acid. It is monobasic ;
the potassium, sodium, ammonium, calcium [(C6H4N02)2.Ca-)-liHiO],
barium [(C^HiNOOi-Ba-HHoO], magnesium [(CGH4N02)..Mg + 2H,0],
cadmium, and copper salts, were prepared and desci-ibed. The hydro-
chloride, CgHsNOj.HCI, crystallises in large colourless crystals, and
gives a platiuochloride, (CsHsNOj.HCOz.PtCU + H2O, of sp. gr. 2-0672
at 22°.
Picolinic acid may be considered as pyridinecarboxylic acid,
CsHfN.COOH, being obtained by the oxidation of picoline or methyl
pyridine, C5H5N.CH3. This view is further confirmed by the fact that
pyridine, together with a small quantity of dipyridine, is formed by
the dry distillation of its calciam salt with quick-lime, or on heating
the acid with alcoholic potash in sealed tubes at 240°. The sodium
salt of picolinic acid by reduction with sodium-amalgam, gives a new
acid, oxijsorhic acid, CeHsOa, whilst ammonia is evolved. Oxysor-
binic acid crystallises in colourless needles (m. p. about 85°) which are
exceedingly deliquescent and very soluble in water, but almost in-
soluble in hot or cold alcohol. It reduces Trommer's copper solution.
The calcium, barium, and cadmium salts were prepared ; they are all
amorphous.
Nicotinic Acid, C6H3NO2. — This acid, obtained together with pico-
linic acid by the oxidation of picoline, crystallises in needles (m. p.
228°), and is identical with the acid previously obtained by the author
ORGANIC CHEMISTRY, 2Q9
(Aiinalen, 165, 328), and also by Laiblin (Ber., 10, 2136). Nicotinic
acid, like picolinic acid, by the dry distillation of its calcinm salt,
yields pyridine, whilst reduction with sodiuin-amalgam converts it
into oxysorbinic acid. A table is given showing the more important
differences between picolinic and nicotinic acids.
The formation of two distinct acids from picoline shows that the
latter is a mixture of two isomeric compounds, which cannot be sepa-
rated by fractional distillation. This can, however, be attained by
making use of the different solubilities of their platinochlorides. The
a-picolive compound being less soluble than that of ^-picoline.
a-Picoline (b. p. 134°, uncorr.) is optically inactive, and gives on
oxidation only picolinic acid. The platinochloride, according to the
condition of its formula (C6H7jSr.HCl)2 + PtCU + HjO), can be
obtained either anhydrous or with water of crystallisation.
^-Picoline (b. p. 140°) is slightly laevorotatory, and on oxidation
gives only nicotinic acid ; it is less soluble in water than a-picoline.
The picoline which Baeyer obtained synthetically by the dry distilla-
tion of the ammonia compound of acrolein {Annalen, 155, 281), is not
identical with either a.- or /i-picoline, and therefore forms the third of
Korner's three possible picolines. T. C.
Some Derivatives of Cinclionine. By A. "Wischxegradsky
(Ber., 12, 1480 — 1482). — Batlerow and Wischnegradsky have shown
(Ber., 11, 1253) that cinchonine, under certain as yet undefined con-
ditions, is decomposed by fusing potash into chinoline and a base
which they have further resolved into a fatty acid and ethyl- pyridene.
The latter base is a pleasantly-smelling liquid (b. p. lt)6°), soluble
in water with difficulty. It combines with platinic and mercuric
chlorides, and by oxidation with a 30 per cent, chromic acid solution
in presence of sulphuric acid, yields Laiblin's monocarhopyridenic
(nicotinic) acid, C7H9X + 30^ = CeHsO.N + CO, + 2H.,0. It is
isomeric, or identical with Anderson's lutidAne.
With regard to chinoline, the author finds that by oxidation with
chromic and sulphuric acids, it yields Ramsay and Dobbie's dicarho-
pyridenic acid (this Joarual, 35, 189), obtained by oxidation of cincho-
nine. This reaction harmonises with Korner's view of its constitu-
tion, confirmed by Baeyer and Konig's synthesis, viz., that it is
naphthalene in which the group CH has been replaced by 'N. By
reduction with zinc and hydrochloric acid, chinoline yields a resinous
base, which forms uncry.stallisable salts, and a base having nearly the
same boiling point as itself, and forming a crystalline compound with
hydrochloric acid.
These experiments lead to the conclusion that cinchonine contains
a metJiylchi)ioh'ne and an ethylpyridine nucleus. By the addition of
hydrogen, the double union of carbon and nitrogen in the two nuclei
may be supposed to be loosened ; and from the hypothetical secondary
bases thus formed, cinchonine may be constituted by the intervention
of the acid radicle CH3.CH.CO or CHo.CH,.CO, thus :—
EtCsHs.N.Co.BU.CO.N.CoH^.NHs.
By oxidation, these hydrogenated bases are reconverted into the
270 ABSTRACTS OF CHExMICAL PAPERS.
tertiary bases (or their derivatives), pyridine and chinoline. Fusing
potash acts on cinchonine in two ways, partly by oxidising it to cin-
chonic acid, and partly by decomposing it, with reduction, into methyl-
chinoline. The potash further decomposes the cinchonic acid with
formation of chinoHne. As a fact, cliinoline prepared from cinchonine
always contains methylchinohne or lutidine (Williams and Wisch-
negradsky).
If the constitution of cinchonine given above is correct, it should
be obtained synthetically by acting with dihydrolepidine and dihydro-
ethylpyridine on the chloranhydride of one of the chloropropionic
acids. Ch. B.
Homocinchonidine. By Z. H. Skraup (Annalen, 199, 359 —
3G8). — Cinchonidine and Hesse's homocinchonidine (Ber., 10, 2156)
are identical in crystalline form and melting point, and they have the
same composition, CigHjoNoO, and rotatory power. The determina-
tions of the solubility of the alkaloids in water, ether, and alcohol,
yield slightly varying results. Since the salts of homocinchonidine
and cinchonidine resemble each other in every respect, the author con-
cludes that the two bases are identical. W. C. W.
Quinamine. By O. Hessb {Annalen, 199, 333 — 337). — Analyses
of the free base and of the hydriodide and platinochloride show that
quinamine has the composition Ci9H2iN.202.
The alkaloid is dextrogyrate ; the rotatory power of its solutions is
seen from the following numbers, ^ = 2 and t 15° : —
Solrent. aD.
97 per cent, alcohol + 104-50°
Chloroform + 93-50
Water + 1 mol. HCl . , + 116-03
Water + 3 mols. HCl. . + 117-18 W. C. W.
A New Organic Acid, Lithobilic Acid. By C Roster
(Gazzetta, 9, 462 — 471).— In the author's paper on lithofellic acid
(this vol., p. 131), he mentioned that in recrystallising the crude pre-
cipitated barium lithofellate, a substance remained undissolved, appa-
rently the barium salt of a new acid ; this is of a resinoid nature,
and after being thoroughly washed with boiling water, in which it is
almost insoluble, is obtained as a yellowish amorphous semiti^ansparent
mass. It melts at 109'', and on treatment with acids, it is decomposed
with liberation of the new acid. Although this barium salt is usually
amorphous, it was on one occasion obtained in a crystalline state,
on allowing a hot filtered solution of crude barium lithofellate to
evaporate spontaneously. The crystals, which were exceedingly
minute, were of rhombohedric habit, but owing to their smallness, but
few measurements could be taken. Two analyses of the barium salt
were made, the results agreeing with the formula CsoHstOb.H.
Lithohilic acid was prepared by decomposing the barium salt with
dilute hydrochloric acid, and after carefully washing with warm water,
crystallising it from alcohol. The acid foi'ms tufts of long needles,
ORGANIC CHEMISTRY. 271
of a slightly yellowish tinge (m. p. 199°). It is insoluble in water,
moderately soluble in ether, and readily in alcohol even in the cold.
Heated with concentrated hydrochloric acid, it is decomposed and dis-
solved with a very beautiful violet-rose coloration. Its alcoholic solu-
tion is dextrorotatory ; the specific rotatory power for D being greater
than that of lithofellic acid.
In conclusion, the author points out the difference in properties
between lithofellic and lithobilic acids, such as the difference in the
solubility of the barium salts, the difference in melting points, &c.
The new acid would seem to belong to the group of biliary acids, as it
gives Pettenkofer's reaction, and, when burned, emits the peculiar
aromatic odour characteristic of the biliary acids. C. E. Gr.
Constitution of Stag's Horn. By A. Blennaed {Gompt. rend.,
89, 953 — 954). — Purified stag's horn gave the following numbers on
analysis : —
I. C, 4503 ; H, 7-3 ; N, 16-01 ; Ash, 2-4.
IL C, 44-90 ; H, 7-0 ; N, 15-5 ; Ash, 2-3.
On digestion with baryta in an autoclave at 150° for 48 hours, it
gave —
NH3, 2-7; COo, 3-0; CoHA, 3-2; C^HA, 1-2
Analysis of the residue, which amounted to 95 per cent, of the puri-
fied horn, gave —
I. C, 448; H, 7-5; N, 13-9; Ash, 0-37.
II. C, 44-5; H, 7-45; N, 13-8.
These results correspond with the equation —
CissHaoaN-^TOss + 13H,0 = 7NH3 + 3C02 + CoH.Oa -f
l-5CoIl204 + C150H300N40O35.
Comparing this equation with that deduced by Schiitzeuberger from
similar experiments with albumin, viz.,
Ciy^HsueNjaOeo + 48H2O = I3NH3 + 3C2H0O4 + 300^ +
3C2H4O3 + Cn7H34«N4o081,
the following inferences are drawn : — that stag's horn is a lower homo-
logue of coagulated e^g^ albumin, and is more hydrated ; and each
molecule of carbonic and oxalic acids formed corresponds approximately
to two molecules of ammonia; whilst oxalic and acetic acids are
evolved in nearly equivalent amounts. W. R.
272
ABSTRACTS OF CHEMICAL PAPERS.
Physiological Chemistry.
Gaseous Nitrogen, a Product of the Decomposition of
Albuminoids in the Body. By J. Seegex and J. Nowak (Pjiuger's
Archiv. f. Fhys., 19, 347 — 415). — The authors criticise, at great
length, the -work of Viot and Pettenkofer, especially Viot's statement
that the whole of the nitrogen resulting from the decomposition of
albuminoids within the body is to be found in the urine and excre-
ment. They point out possible sources of en'or in the experimental
methods adopted by Viot, and in the respiration apparatus of Petten-
kofer. An apparatus is minutely described, composed entirely of glass
and metal, all joints being made tight by means of mercury, and by
the use of which they claim to have established the facts, that a por-
Grams of
Duration of
experiment in
hoiu-s.
Animal
employed.
Weight in
grains
of animal.
gaseous nitro-
gen expired
per hour
per kilo, weight
of animal.
Total grams
of nitrogen
expired.
15
Rabbit
2010
0 -0058
0-176
36
Do.
2010
0 -0064
0-465
29
Cock
1950
0-009
0-525
23
Do.
1800
0-007
0-288
16
4 Pigeons
1500
0 -0077
0-187
55
Do.
1500
0-007
0-583
72
2 Fowls
2011
0-007
1-004
12
Dog
4100
0-008
0-396
17
Do.
4100
0-008
0-551
24
Do.
4100
0 0081
0-804
60
Do.
4100
0-0081
1-997
40
4 Rabbits
7900
0-005
1-595
18
Do.
7900
0 0043
0-628
25
Fowl
1520
0 -009
0-351
16
5 Fowls
5500
0 -0089
0-779
62
Dog
4200
0-009
2-384
60
4 Fowls
4400
0 -0084
2-200
72
3 Do.
3500
0-0087
2 197
46
8 Pigeons
3600
0-009
1-532
70
Dog
3500
0 -0085
2-085
60
Do.
3500
0 -0081
1-726
56
Rabbit
2050
0-004
0-435
60
Fowl
1000
0-008
0 -515
108
Do.
1000
0 -0083
1-995
48
Fowl
1350
0-008
0-527
43
3 Pigeons
1300
0 -0077
0-432
96
Rabbit
2200
0 -0053
1-130
110
Do.
2800
0-006
1-896
32
Dog
6500
0-0076
1-585
68
Do.
6500
0 -0063
2-868
98
5 Rabbits
10400
0 -0047
4-767
70
5 Fowls
6000
0 -0078
3-300
PHYSIOLOGICAL CHEMISTRY. 273
tion of tlie nitrogen which results from the decomposition of albu-
minoids in the bodies of animals passes out of the system in the
gaseous form ; and that the amount of nitrogen thus expired increases,
within narrow limits, in direct proportion to the duration of the expe-
riment and the weight of the animal employed.
As the point discussed is of importance, a table is given in whicli
the actual results obtained are grouped together.
The cubic contents of the apparatus were determined, and thus the
total nitrogen, in grams, could be found from analysis of the air
passing through the apparatiis. M. M. P. M.
Chemical Composition of Milk. By L. Schischkoff (Ber., 12,
1490 — 1492). — Adopting the view that milk is an emulsion of fat, the
author has made attempts to emulsify different fats. A weak solution
of potassium or sodium carbonate (fth per cent.) will only emulsify
those fats which contain free fatty acid, even though in minute
quantity. The richer the fat is in solid constituents, the more easily
is it emulsified ; fats poorer in solids require a larger proportion of
free fatty acids. A fat must, however, be liquefied before it can form
an emulsion ; the ease with which it does so depends therefoi'C not on
its firmness at ordinary temperatures, but on the superior attraction
exerted by the emulsifying liquid on a solid over a liquid fat. An
alkaline solution emulsifies a fat, when its smallest particles exert a
sufficient attraction on any one constituent of the fat, even though
absolutely indifferent to the remainder. Thus, oil of turpentine,
mineral oil, &c., may be easily emulsified if mixed with a little stearic
acid. A fat which cannot be emulsified in an alkaline liquid will be
so easily when a different fat has been previously emulsified in the
same liquid. The fat extracted from cow's milk by a mixture of
alcohol and ether contains a certain quantity of fatty acids, and lience
easily forms an emulsion. Melted butter, which contains relatively
little free acid and solid fat, is emulsified with much less ease. The
liquid part of butter is almost incapable of forming an emulsion, but
does so easily when mixed with solid fat and a little free fatty acid.
Conversely, cow fat completely loses its power of forming an emulsion
after washing: with a solution of an alkaline carbonate. It is singular
that alkaline carbonates are chiefly attracted by, and combine with,
the solid fats of butter. The author has not yet accurately determined
what acids render milk fat emulsifiable : but amongst them are
myi'istic, capric, caproic, and perhaps butic acids, as may be concluded
from some of the properties of their salts, and from their melting
points. An emulsion may be pronounced good when it is brilliantly
white, adheres strongly to glass, and on standing slowdy separates a
layer considerably thicker than the original fat. Under the micro-
scope it appears to be formed of small globules, nearly uniform in
size.
The formation of an emulsion thus evidently depends on the divi-
sion of the fat into minute globules, and the fixation of the emulsifying
liquid on their surface by the molecular attraction exerted upon it by one
of their constituents. The greater this attraction, the smaller will be the
globules, but the more unstable the emulsion. Shaking favours the
274 ABSTRACTS OF CHEMICAL PAPERS.
division of the globules, and therefore 'the decomposition of the emul-
sion. The most permanent emulsions are furnished by fats containing
fatty acids which do not easily combine with alkalis, since the alka-
line salts of fatty acids attract fats but feebly. By prolonged shaking
an emulsion is completely decomposed into fat and soap, which do not
further act on each other.
Intermediate products are obtained by partial decomposition. An
emulsion is decomposed on keeping, by cooling, and by dilution with
water, alcohol, or ether, and by such operations as hasten saponification,
viz., heating, addition of strong alkali, &c. Albuminous matters
added in excess decompose it very easily, forming soap-like compounds
containing fatty acids, fat, albumin, and alkalis, or even salts. These
compounds have little attraction for the excess of fat, wherefore the
latter separates. The fat contained in these compounds cannot be
extracted by alcohol or ether alone, but may be so by a mixture of the
two. Albuminous matters decompose emulsions less easily in presence
of calcium salts, since a mixture of albumin with these salts, especially
the phosphates, strongly attracts fats.
That milk is an emulsion of fat in a liquid containing albumin,
salts, and sugar, the author has proved by preparing a similar artificial
emulsion closely resembling it. The changes taking place in milk
■when kept depend on the formation of various new emulsions. The
composition of the cream is different at ditFerent periods of its forma-
tion. The first portions give the best butter, and consist of fat, alka-
line phosphates, and albumin, forming a compound insoluble in water
and weak acids ; the later portions are richer in albumin and lime
salts. These latter emulsions consist of smaller globules, contain free
fatty acid, and yield a much coarser butter. About the time of their
separation the milk begins to turn sour, and consequently all the sub-
stances which are insoluble in weak acids, and have a sufficiently low
specific gravity, pass into the cream. If the souring of the milk be
prevented, very little cream will be formed. Butter consists of fat,
and an emiilsion containing lime, insoluble in water.
Finally, the author has discovered in whey an albuminoid which is
diff"erent from common albumin and from casein. Synthetic experi-
ments have shown that casein without albumin may form milk, but
not cream. These two albuminoids together go to form milk and
cream ; bat the latter is only obtained in its natural form, when the
third modification is present. Ch. B.
Combinations of Phosphoric Acid in the Nervous Substance.
By L. Jolly (Compt. rend., 89, 756 — 758). — Phosphoric acid occurs
in the nervous substance as glycero- or oleo-phosphoric acid, and on
ignition of the brain substance a residue, consisting of phosphoric acid
and alkaline phosphates, and carbonates is left. The results obtained
by the ignition of 100 grams of the brain substance of the ox and calf,
and the spinal marrow of the ox are as follows : —
PHYSIOLOGICAL CHEMISTRY.
275
Free phosphoric acid
Potassium phosphate
Sodium ,,
Magnesium.
Iron
j>
-
Spinal marrow
Brain of calf.
Brain of ox.
of ox.
, .
0-095
0-874
.. 4-774
1-851
2-310
. . 0-104
0-206
0-105
. . 0-054
0-178
0-076
, . 0-088
0-309
0-154
5-020 2-639 3-519
The phosphoric acid in combination with alkahs is calculated as
potassium phosphate.
These results show that in the young animal, the brain is very rich
in phosphates, whilst in the full grown animal, the spinal cord contains
more phosphoric acid, and that after the alkaline phosphates, phos-
phate of iron is most abundant. L. T. O'S.
Distribution of Phosphates in the Muscles and Tendons. By
L. Jolly {Compt. rend., 89, 958 — 959). — Although the total amount
of phosphates in muscle has been determined, analyses are wanting
in which the separate phosphates have been estimated. The author
has analysed the muscle of the calf, and of thin and fat oxen, with the
following results : —
100 grams of dried muscular tissue contain : —
Calf. Thin ox. Fat ox.
Alkaline phosphates 0-971 0-021 1-201
Calcium „ 0-099 0-060 0-350
Magnesium ., 0-135 0-073 0-430
Iron ,, 0-042 0-040 0-065
Iron oxide, uncombined with
phosphorus — — —
1-247 0-394 2-046
The ash of tendons was also analysed —
Calf. Ox.
Alkaline phosphates 0-480 0-185
Calcium „ 0-048 0--396
Magnesium „ 0-060 0-136
Iron „ 0-110- 0-061
0-698
0-776
W.
E.
Distribution of Copper in the Animal Kingdom. By M.
GiUNTi {Gazzetta, 9, 546 — 555). — After noticing the statements of
various chemists as to the existence of appreciable quantities of copper
in various parts of the human system, Cloez' researches on the blood
of the goat, and Church's on the red pigment in the feathers of cer-
tain of the Musophagidge, the author describes his own experiments,
which he was induced to undertake on discovering copper in some
bat's guano from a cave at Santagata d' Esaro ; various samples of
276 ABSTRACTS OF CHEMICAL PAPERS.
this were found to contain from 0"348 to 0"403 per cent, of cnpric
oxide, CuO. The next step was to examine the bats whose excrements
had formed the guauo ; several of these were incinerated and the
copper estimated in the ash : it was found to be 0"039 per cent., equiva-
lent to 0"0014 on the original weight of the bats. It is worthy of note
that the proportion of copper found in these animals is much less than
in the guano, which confirms the observations of Paul and Kingzett,
that when copper is exhibited internally, the greater portion passes
out with the excrements. Lastly, the food of these insectivorous
animals was examined. Various species of insects (more than 20 in
number) belonging to the natural orders Hymenopteraj, Coleopterae,
and LepidoptertE, were tested for copper, and it was found in every
case.
Other animals examined were the hedgehog, of which the ash
yielded 002 per cent. CuO, and a species of lizard {Fodercis muralis).
In the latter the amount of copper was very variable, but the mean of
18 individuals gave 005G5 per cent, on the ash. Two species of
Coleopterae were examined, Anomala vitis giving 0"095, and Blatta
orientalis 0"826 per cent, on the ash. The very large quantity of
copper in the last named insect is accounted for by their coming in
contact with copper vessels in their excursions about the house in search
of food. Two Myriapods were examined (Jiilus terrestris and Armidilli-
dium vnlr/nre), the ash of the former containing 0"221, and that of the
latter 0"197 per cent. Cu. A mollusc {Helix pisana) gave 0'089. The
results already obtained are sufficient to show that copper is very
widely distributed in the animal kingdom. C. E. G.
Chemistry ofVegetable Physiology and Agriculture.
Alcoholic Fermentation, liy D. Cochin (Compt. rend., 89,
786 — 787). — To prove the existence of a soluble ferment, yeast-water
was prepared from beer-yeast, according to Pasteur's method, by boiling
it with water in the proportion of 100 grams per litre, and filtering at
once. The filtrate was mixed with beer-wort, at a temperature of
25 to 30°, no fermentation set in, but on sowing some of the residue
in beer-wort, fermentation took place with great rapidity. This ap-
pears to contradict Berthelot's statement (ibid., 83, 9) that a soluble
ferment does exist. L. T. O'S.
Remarks on Cochin's Note relating to Alcoholic Fermenta-
tion. By Berthelot (Cumpt. rend., 89, 806—808). — Cochin has
attempted to continue Claude Bernard's work by some observations on
the actual process of fermentation of sugar with beer-yeast, and failed
in separating a soluble ferment from an extract of beer-yeast, in which
the yeast itself was growing. Now a liquid in which yeast is actually
growing does not cause alcoholic fermentation, and if a soluble fer-
ment exists at all, it must be sought for under conditions analogous
VEGETABLE PHYSIOLOGY AXD AGRICULTURE. 277
to those in which digestive ferments are formed, viz., under the influence
of the food which the ferment is intended, to digest. W. R.
Alcoholic Fermentation : Reply to Berthelot. Bj D. Cocnm
(Gompt. rend., 89, 992— 994).— The author replies to Berthelot's
criticism, that yeast actually growing does not provoke fermentation,
by stating that the ferment he used was stable, contained no organisms
in the state of growth, and although capable of inverting sugar, did
not induce alcoholic fermentation. W. R.
Vital Power of ScMzomycetes in Absence of Oxygen.
By J. W. GuxxiNG (,/. p/-. Cheiii., 20, 484 — 443;. — The author has
previously published, an account of his researches (this Journal, 1878,
Abst., 267, 907), from which he di-aws the conclusions that sub-
stances capable of putrefaction when enclosed in vessels from which
nearly all oxygen has been removed act for only a short time ; and.
when oxygen has been completely removed by means of a solution of
grape-sugar in caustic soda mixed with indigo, no putrefaction
occurs, and the organisms which produce putrefaction are killed. The
present paper is a reply to Nencki's objections, who stated that Gun-
ning's experiments were inaccurate.
Gunning has shown that the apparatus employed to produce what
Nencki termed " space freed from oxygen" is insufiicient for that
purpose, and contains enough oxygen to colour ferrous ferrocyanide
deep blue. Nencki also supposed that the presence of products of fer-
mentation stopped all action of the organisms. To controvert this state-
ment. Gunning adduces experiments which were already in progress
before Nencki had published his objections. These consisted in keeping
putrefying matter in tubes in which oxygen, hydrogen, and air were
enclosed. As was to be expected, fermentation proceeded furthest in
the tubes containing pure oxygen, less far in those containing air,
and very much less in those containing hydrogen. The amount of
decomposition was ascertained by estimating the carbonic anhydride,
ammonia, and volatile acids. Nencki's last objection was that by some
chance the liquids infected may have come in contact with only those
bacteria which require oxygen for their existence. This objection is
shown by Gunning to depend on a misunderstanding of Pasteur's
researches, viz., that two such varieties exist. Pasteur believes that
such ferments as exist at the surface of a putrefying medium obtain
oxygen from the air, and those in the interior of the liquid derive
oxygen from the decomposing substance, but does not imagine two
varieties to exist. Besides, even were there such different organisms,
it is impossible to believe that from some chance a liquid should,
become infected with only one variety, and that the germs of the
other variety, which would, be just as likely to be present in air to the
same extent, should have no influence. W. R.
Nitrification. By T. Schloesing and. A. Muntz (Compt. rend.,
89, 891—894, 1074— 1077).— Por the preceding researches of the
same authors see this Journal, 34, 597. The authors have separated
the organism producing nitrification from the other organisms existing
278 ABSTRACTS OF CHEMICAL PAPERS.
in soil by systematic cultivation in suitable solutions, wbich had been
previously sterilised by beat. The nitrifying organism consists of
minute corpuscles, round or slightly elongated ; they occur frequently
in pairs, and appear to propagate by budding ; they are not easily
distino-uished from other organisms of the same class.
The nitrifying organism is somewhat easily destroyed by heat ;
exposure for ten minutes to 100° is certainly fatal, and even 90° is
generally sufficient. Desiccation also arrests nitrification, and appa-
rently kills the ferment. A soil actively nitrifying may be effectually
sterilised by drying at the temperature of the air. Long deprivation
of oxysren also kills the ferment, at least in liquid mediums. In
mediums rich in organic matter, mucor is its chief enemy. Until the
life of the fungus has run its course, no nitrification will occur.
The nitrifying organism is not normally present in the air. In no
case has nitrification been started in a sterilised solution by the access
of ordinary air. It is abundant in soil, in sewage, and in waters con-
taminated with organic matter. In running water, it is sparsely
distributed, attaching itself to the surfaces of solid bodies. It collects
at the bottom of tlie vessel, when the water is allowed to rest.
The effect of temperature on nitrification in liquid mediums was
ascertained. Below 5°, the action is extremely feeble; it becomes
appreciable at about 12^. With a rising temperature, the action
rapidly increases, reaching its maximum at 37°, at which point the
production of nitrates is ten times as rapid as at 14°. Beyond 37°, a
speedy diminution of action takes place ; at 45°, less nitrate is formed
than at 15°; and at 50°, the action is very slight. Beyond 55°, no
nitrification occurs.
Free access of oxygen is essential for rapid nitrification. Other con-
ditions being equal, nitrification in liquids will be in proportion to the
surface exposed. In soils, nitrification will be greater in proportion to
the amount of water present, up to that point at which the pores of
the soil become filled and air excluded. Feeble alkalinity is another
essential condition. This condition is generally satisfied by the pre-
sence of carbonate of calcium, but may also be fulfilled by alkali car-
bonates, including carbonate of ammonium ; if, however, the amount
of alkali carbonate exceeds two or three thousandths of the solution,
nitrification is arrested. Small quantities of neutral salts are without
effect. Sugar, glycerol, alcohol, tartrates, and albumin are all capable
of furnishing the organic carbon required by tbe organism. There is
no constant relation between the carbonic and nitric acids produced.
Strong light is prejudicial to nitrification, but feeble illumination has
little effect.
Nitrites are seldom formed in soils, but frequently in liquids if the
temperature is below 20°, or the access of air is limited. A thin layer
of liquid may produce nitrates, and a thicker layer nitrites.
R. W.
Note hy Ahi^trador. — At Rothamsted, the maximum temperature at
which nitrification occurs was found to be much lower than here
stated. Solutions kept for 54 days at 40° refused to nitrify though
twice seeded. The difference may perhaps be explained by the
different depths of the solutions ; this at Rothamsted was about five
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 279
incTaes, and in tlie case of the above experiments was (apparently) but
a few millimeters. The production of nitric or nitrous acid is shown
by the Rothamsted esperiments to be determined in some cases by
the condition of the ferment, rather than by the conditions of the
medium. R. W.
Nitrification. By E. W. Davy (Chem. News, 40, 271).— Experi-
ments were made in reference to the addition of animal impurities in
potable waters, and to ascertain the circumstances which were favour-
able or otherwise to the formation of nitrites and nitrates in waters,
which were so polluted. By using Price's well-known test for nitrites,
the author in most cases obtained the evidence of the formation of
nitrites.
Warington concludes from some experiments made that darkness is
an essential condition to the development of those low forms of vege-
table life which are supposed in many instances to give rise to nitrifi-
cation, but from the results of several comparative experiments made
in this way, the author came to the conclusion that the condition of
light or darkness exercises but little influence one way or the other in
this process.
The author mentions that as regards nitrification occurring in water
containing organic matters, it is necessary to have a certain amount of
air or free oxygen to cany on the process. It was also found that the
quantity of animal matter which is held in solution in the water exer-
cises a considerable influence on nitrification ; the influence of tem-
perature, however, is still greater, for it has been observed that in cold
weather nitrification is very slow, whilst in warm weather, it is much
quicker, and that by the application of artificial heat, the process can
be greatly accelerated.
In conclusion, the author calls attention to another fact noticed in
connection with this subject, viz., the rapidity with which nitrites are
sometimes formed in water contaminated with sewage impurities.
D. B.
Albumin and Amido-compounds in Plants. By 0. Kellner
(Bied. Cent)-., 1879, 671 — 676). — The author made a series of investi-
gations on plants at different stages of their growth with respect to
the amount of albumin and amido-compounds they contain. His
results confirm conclusions already arrived at (Bied. Gentr., 1879, 370 ;
this Journal, 1879, Abst., 819), namely, that the amount of albumin
reaches its maximum only when tlie plant has arrived at full maturity.
With regard to the conversion of nitrogen from inorganic sources into
albumin, the author finds that with nitrates, a certain quantity is con-
verted into amido-compounds. The plant investigated was the common
pea. After soaking the seeds in water, they were divided into three
lots, and sown in sand, the first lot being treated regularly with dis-
tilled water, the second with solution of nitre, and the third with a
solution of ammonium nitrate.
Nine different kinds of potatoes grown on unmanured land gave
the following mean results on analysis : —
280 ABSTRACTS OF CHEMICAL PAPERS.
Percentage of
Percentage of Percentage of nitrogen nitrogenoiis albu-
dried substance. in dried substance. min in total.
Xcs. 1—5 .... 19-45 2-117 49-1
„ 6—9.... 22-29 1-619 57-1
These figures show that the total quantity of nitrogen decreases as
the total solid matter increases, while the albumin undergoes not merely
a relative, but also an absolute increase. J. K. C.
Resistance of Seeds to the Prolonged Action of Chemical
Agents. By I. Giglioli (Gazzetta, 9, 474 — 505). — The seeds em-
ployed in this research were chiefly those of lucerne, as they offer
great resistance to the action of reagents, and germinate quickly.
They were carefully selected, and trial experiments made during the
course of the investigation showed that 90 per cent, germinated under
favourable conditions. In all the experiments, the seeds were sown in
quartzose sand kept moist.
Action of Gases. — The seeds, either dry or moist, were placed in a
glass globe furnished with two tubes, through which a current of the
gas was passed until the air was entirely expelled, when the orifices
were hermetically sealed. The gases employed were oxygen, nitro-
gen, hydrogen, carbonic oxide, carbonic anhydride, methane, nitrous
oxide, nitric oxide, ammonia, sulphurous anhydride, hydrogen sul-
phide, chlorine, hydrochloric acid, and arseniuretted hydrogen, and
the time during which the seeds were left in contact with the gas
varied from 1 to 593 days. Full details of the experiments are
given, and from the results the author infers that all seeds do not
resist the action of the same gas equally well, those being least
affected which, like lucerne, have an involucre not easily permeable
by gases. If softened in water, they invariably die when exposed to
the action of any other gas than air, and that whatever may be the
structure of the involucre.
Of the different gases, chlorine, hydrochloric acid, and ammonia act
comparatively rapidly on seeds normally dry, although these may be
able to resist the action of nitric oxide, sulphurous anhydride, and
hydrogen sulphide for a considerable time, whilst the other gases act
but slowly on them ; moreover, those seeds which have resisted for a
long time the action of the more energetic gases do not germinate in
the normal manner, the root being but slightly developed if at all, and
the cotyledons ai*e often green.
Action of Liquids. — The author had completed his investigation of
the action of liquids on seeds before the publication of Nobbe's
results. These he can confirm by his own observations, which embrace
a much wider field, and include the action of water, methylic, ethylic,
and amylic alcohol, ether, chloroform, carbon tetrachloride, carbon
bisulphide, ethyl iodide, glycerol, benzene, nitrobenzene, and aniline,
both at the ordinary temperature and at their boiling point, the seeds
being dry in some cases, and in others previously steeped in water.
The results show that various kinds of seed differ in their power of
resisting the action of liquids, this depending exclusively on the
structure of the integument. Of the seeds tried, lucerne is least
VEGETABLE PHYSIOLOGY AXD AGRICULTURE. 281
affected, whilst the vitality of wheat is most easily destroyed. Of all
the liquids employed, water is the most readily absorbed, and it is
the only one which causes the seeds to swell ; moreover, if the other
conditions for germination are wanting, it is the liquid which most
quickly destroys the vitality of the seed. Seeds which have been
steeped rapidly lose their power of germination in contact with
other liqtiids. When the temperature of ebullition is comparatively
low, as is the case with ether and carbon bisulphide, the seeds with
sensibly impermeable involucre, such as those of lucerne, can resist
the action of the boiling liquid for a long time, no appreciable
quantity of fatty or waxy substance being extracted.
Action of Solutions. — Alcoholic solutions of iodine, of potassium
bromide, sulphide, and cyanide, of zinc and mercuric chlorides,
copper sulphate, ammonium sulphide, arsenious anhydride, camphor,
and phenol were tried, using seeds of lucerne and wheat. It was
found that the latter were rapidly killed (except when treated with
a glycerol solution of copper sulphate) whilst the lucerne resisted
the action of most of the solutions for a long time. They were, how-
ever, quickly destroyed by alcoholic solution of iodine when concen-
trated, by potassium and ammonium sulphides, and by an alcoholic
solution of sulphurous anhydride. C. E. G.
Mode of Action of Sulphur as a Remedy against Vine-
disease. By J. MoRiTZ (Ber., 12, 19o8). — The efficacy of sulphur in
protecting vines against the destructive attacks of the fungus O'idium
Tuckeri is due to the evolution of sulphurous anhydride, w^hich occurs
when that substance is sprinkled over the living vine. T. C.
Note. — Pollacci (this Journal, 1876, ii, 540) states that hydrogen
sidpldde is produced when vines are sulphured, and that it is to this
that the destruction of the oidium is due. — C. E. G.
Analysis of Soils from the Bunter Sandstone Formation.
By E. Weber (Bied. Centr., 1179, G50 — 651). — The soils under inves-
tigation were produced by the weathering of bunter sandstone from
Spessart and Vogesen. Samples were taken from poor and good
plots, and analyses were made from the surface and subsoil of each.
The author finds that the upper layers of soil taken from plots planted
with oak and beech contain more humus than is the case when the
ground is overgrown with fir; also that soils from the latter yield less
potash when treated with hydrochloric acid, and contain only about
one-half the amount of soluble silica present in the former case. It is
also remarkable that the quantity of phosphoric acid present is in
direct proportion to the fertility of the soil. J. K. C.
VOL. xsxviii. z
282 ABSTRACTS OF CHEMICAL PAPERS.
Analytical Chemistry.
Application of the Galvanic Current in Analytical Chemistry.
By C. LuoKOW (Zrifs. Anal. Ghent., 1880, 1 — 19). — The subject is
divided into — (1) the qualitative behaviour of various soluble and
insoluble compounds of the commonly occurring elements under the
influence of the galvanic current, and (2; the electrolytic quantitative
separation and estimation of various metals, partly in the metallic
state and partly in the state of compounds of constant composition.
Either a constant battery or a thermo-electric pile is used for the pro-
duction of the electricity. Of all constant batteries Meidinger's is
most suitable for analytical purposes (ibid., 8, 81). Among thermo-
electric piles, Clamond's, in the form of a cylinder, using gas, petro-
leum, or charcoal, is best (il/id., 15, 834), A voltameter is used to
measure the strength of current.
(1.) The Qualitative Behaviour of various Soluble aiid Insoluble
Compouiuls of the commonly occicrrimj Elements under the influence of
the Galvanic Current. — The action is different, according as it takes
place in a simple cell, in which both poles are immersed, or in a divided
cell. The strength of the current, the concentration and temperature
of the solutions, also in some cases influence the nature of the decom-
position. In the simple cell, the products of decomposition are allowed
to freely mix with each other and hence secondary products arise.
The p-alvanic current in acid solutions has mainly a reducing,
and in alkaline .solutions an oxidising action. For instance, a solu-
tion of potassium chromate acidified with sulphuric acid is reduced
when in the simple cell, all the chromic anhydride being converted
into chromic oxide, whilst a solution of chromic oxide in potassium
hydrate is converted into potassium chromate.
In the electrolysis of cyanides, the cyanogen undergoes a further
decomposition, the final products consisting of carbonic anhydj-ide and
nitrogen. Prussian blue is deposited on the positive pole from solu-
tions of ferro- and ferri-cyanides. In dilute solutions of metallic
chlorides, hypochlorous acid is alone produced, in concentrated solu-
tions chlorine is also liberated ; chlorates are produced from the
chlorides of the alkalis and alkaline earths as soon as the reaction of
the solutions has become alkaline, from the evolution of the chlorine
and hypochlorous acid.
If dilute chloride solutions contain a little free h3'drochloric acid,
hypochlorous acid is alone produced, and the solution after a time
acquires an alkaline reaction. Iodine and bromine are separated from
solutions of iodides and bromides. lodatcs and bromates are pro-
duced simultaneously from the iodides and bromides of the metals of
the first two groups, especially in concentrated solutions. Potassium
cyanide is decomposed by the galvanic current into potassium and
ammonium carbonates. When the solutions of the chlorides, bromides,
and iodides contain free alkali, only chlorates, bromates, and iodates
are produced. From the insoluble compounds of chlorine, bromine,
iodine, cyanogen, ferro-, and ferri-cyanogen with the metals suspended
ANALYTICAL CHEMISTRY. 2'83
in dilute sulphuric or nitric acids, the metal is separated at the nega-
tive pole, whilst the acid radicle appears at the positive.
Concentrated nitric acid is decomposed with production of nitrous
acid ; in the acid of sp. gr. 1"2, this decomposition does not occur, at
all events under the influence of a feeble current. No ammonia is
produced from dilute nitric acid, either j>er se or in presence of sul-
phuric acid ; but if a solution of cupric sulphate is added in sufiicient
quantity, ammonium sulphate and metallic copper are produced simul-
taneously until all the nitric acid is converted into ammonium sul-
phate. In the presence of free alkali, nitrates are not converted into
ammonia, but the latter is converted to nitric acid. Concentrated
(English) sulphuric acid is decomposed with deposition of sulphur.
Sulphurous acid in aqneo'us solution decomposes into sulphur and
salphuretted hydrogen; the sulphites- are gradually converted into
sulphates. Tbiosulphates are converted into their corresponding
sulphates with separation of sulphur. The alkaline sulphides, accord-
ing to their richness in sulphur, are decomposed with or without sepa-
ration of sulphur, sulphates being' formed. In the alkahne sulphates
and thiosulphates, in addition to sulphides, polythionates are always
pi'oduced. Phosphoric acid or phosphates undergo no change in dilute
solutions. Cairbonic anhydride is very incompletely evolved at the
positive pole from the solutions of hydrogen potassium carbonate.
Silicic and boric anhydrides are separated from their concentrated
solutions in tree-like crystals at the positive pole.
The metals of the sixth group are all separated from their solutions
by the galvanic current in the metallic form. In the electrolysis of
the chlorides of antimony and arsenic, some antimoniuretted and
arseniuretted hydrogen are produced at the negative pole. If the three
metals occur together, first arsenic, then antimony, and lastly tin is
precipitated. Platinum is deposited from its solutions in the reguline
form at first, but as the solutions become more dilute, in the form of
platinum black. From the solution of their sulphides in alkaline sul-
phides, tin and antimony are separated complete^, arsenic not quite
completely, in the metallic form. The oxide of tin produced by the
action of nitric acid, and the oxide of antimony formed in the same
way, dissolve on heating in concentrated potash or soda : the metallic
separation from these solutions is very incomplete, unless sulphuretted
hydrogen is passed intt)- the alkaline solutions or they ai-e acidified with
hydrochloric acid.
Of the metals of the fifth group, copper is precipitated from solu-
tions containing free sulphuric, nitric, or aicetic acid when the
amount of acid in the solution, calculated as anhydride, does not
exceed 8 per cent. Also all copper is separated from solutions con-
taining free hydrochloric acid, on the addition of ammonium or sodium
chlorides or sodium acetate. Similarly from solutions containing ex-
cess of ammonia, ammonium carbonate, or potassium cyaruide.
Silver is separated from solutions containing 8 — 10 per cent, nitric
acid in a very bulky metallic state ; at the same time somie peroxide is
precipitated on the positive pole, which, however, can be prevented by
the addition of glycerol, sugar of milk, or tartaric acid. From the
ammonia or ammonium carbonate solutions, the metal is precipitated
284 ABSTRACTS OF CHEMICAL PAPERS.
in a very bulky form, peroxide being deposif-ed at the positive pole;
this, however, is soon reduced to the metallic state. From potassium
cyanide solutions, the silver separates in the metallic form with a dull
lustre.
Mercury is precipitated in the form of drops from all its salts ; in
presence of other metals, amalgams are formed.
Lead is precipitated from neutral solutions partly as metal at the
— pole, partly as peroxide at the + pole. A pure metallic separation
occurs only in the presence of easily oxidisable substances which pre-
vent the formation of the peroxide. From alkaline solutions, the lead
is separated as metal only, in a somewhat bulky form ; a slight sepa-
ration of the peroxide occurs in a pure lead solution only in the
presence of not more than 10 per cent, of free nitric acid. If the
solution contains copper, even in very small quantities, in addition to
lead, all the lead is separated as peroxide in presence of smaller quan-
tities of free acid. Other metals, as silver and mercury, behave in a
similar manner, but carry some lead down with them.
Bismuth is precipitated in the metallic state from its solution in
presence of free nitric acid, some peroxide being formed at the same
time.
Cadmium is completely precipitated from its acid or ammoniacal
solution in the metallic state.
If all the above-mentioned morals of the fifth group are present
simultaneously, mercury and silver are first precipitated, bismuth and
copper only after the greater portion of the first two mentioned metals
is separated.
Of the metals of the fourth group, zinc, nickel, and cobalt are incom-
pletely separated in the metallic form, from tlieir sulphates in neutral
solution, manganese and uranium not at all. On the addition of potas-
siuna acetate, tartrate, or citrate, zinc, nickel, and cobalt separate com-
pletely, uranium to a slight extent. In the electrolysis of the ammo-
niacal or potassium cyanide solution of cyanides, both zinc, nickel,
and cobalt, are completely separated. Zinc is furthermore completely
separated in the metallic state from its potash solution, to which some
potassium cyanide has been added.
Manganese is not separated in the metallic state from its neutral or
acid solution, but is deposited as hydrated manganese peroxide. In
very dilute solutions of manganese containing much nitric or a mix-
ture of nitric and sulphuric acids, permanganic acid is formed, and
imparts its characteristic red colour to the solution.
Uranium is obtained in small quantity only, even from the completely
neutral solutions of the oxide, as a yellowish-grey metallic precipitate,
soluble in hydrochloric acid.
Iron is incompletely separated in the metallic form from neutral
solutions of ferrous salts, some ferric salt being formed. If to the
neutral solution of ferrous sulphate, some ammonium citrate be added
containing free citric acid, and care be taken that free citric acid
remains in the solution, the iron will be deposited in the lustrous
metallic form, even when a portion of the iron Avas present originally
in the ferric state. No iron is separated from potassium ferrocyanide,
but Prussian blue at the — pole. From the solution of ferrous oxide
ANALYTICAL CHEMISTRY. 285
iu sodium thio-sulphate all the iron is separated, chiefly as ferrous
sulphide. From the fluoride dissolved in sodium fluoride, metallic iron
is pi-ecipitated.
The solutions of the metals of the Hrst three groups offer but few
characteristics.
The alkaline earths are distinguished from the alkalis by the pro-
duction of precipitates of their carbonates on the electrolysis of their
salts of organic acids in neutral or slightly acid solutions.
In the solutions of ammonium salts, ammonia is produced at the
negative pole. F. L. T.
Estimation of Chlorine in Grains and Forage. By R.
NoLTE {Compt. rend., 89, 955 — 956). — In estimating chlorine in grain,
the author finds it necessary to neutralise the phosphoric acid liberated
on ignition by adding sodium carbonate before ignition ; otherwise
the chlorine is evolved. The table which follows shows comparative
results with and without the use of sodium carbonate : —
Without Na^COj. AVith XaiCO^.
Oats 0-016 0-0605
Wheat 0-007 0-0630
French beans 0-0345 0-0455
Maize 0-00 0-037
Barley 0-0135 0-0396
Buckwheat 0-021 0-026
Rye 0-006 0-054
Bran O'OO 0-080
W. R.
Method for the Detection and Estimation of Iodine in
Presence of Chlorine and Bromine. By E. Doxath {ZeiU.
Anal. Chem., 1880, 19 — 23). — The author was led to the present pro-
cess from some observations of C. Zulkowsky in a paper " On an
lodometric Estimation of Chromic Acid " (J. pr. Chem., 103, 351).
The process consists in the distillation of the mixed chlorides, bro-
mides, and iodides with chromic acid solution, when the chlorides are
found to be entirely and the bromides almost entirely unacted on,
especially in dilute solution, the iodides being decomposed according
to the equation 6KI -j- 8Cr03 = le -j- Cr-^Oa -|- oKoCr^Or, the resulting
iodine being collected in a solution of potassium iodide and deter-
mined in the usual manner. F. L. T.
Titration of Iodine by Stable Standard Solutions. By E.
Allary {Bull. Soc. Ghim. [2], 32, 273 — 276). — The author's process
is a modification of that joroposed by Pellieux and Allary, in which
bromine is made to replace combined iodine, which is removed as fast
as liberated by agitation with carbon bisulphide, the termination of
the reaction being reached when, after an addition of the bromine
solution, a fresli drop of carbon bisulphide ceases to be tinged violet.
In place of the alterable solution of free bi'oraine, the author uses a
solution containing a definite mixture of alkaline bi'omate and bro-
mide, which is easily pi'epared, and may be kept any length of time
■X 2
2Si^ ABSTRACTS OF CHEMICAL PAPERS.
without alteration in strengtli. This solution is made to act upon the
iodide to be determined, in the presence of free hydrochloric acid,
when the following reactions take place : — -'SKBr + KBrOs + 6HC1 =
6KC1 + 3H2O + 6Br and 6KI + 6Br = 6KBr + 61. The liberated
iodine is transformed into bromide of iodine by continued addition of
the broraated solution, and starch-paste is used as an indicator. The
mixture of bromate and bromide is made by saturating a concentrated
solution of pure sodium hydrate with excess of pure bromine, and
evaporating to dryness, without igniting. Two grams of this saline
mixture are dissolved in water and made up to 1 litre. The standard
solution of potassium iodide contains 1'308 gram of the pure salt
(= I'OOO gram iodine) in 1 litre. The starch solution is made ac-
cordins" to Mohr's formula. To standardise the bromated solution,
10 c.c. of the standard potassium iodide are measured into a test-glass,
and an excess of pure hydrochloric acid added, together with a few
drops of starch solution. The bromated solution is now run in cau-
tiously from a burette, with constant stirring. The liquid is suc-
cessively coloured blue, the tint of wine lees, cinnamon, and very pale
yellow. The point of maximum decoloration is easily seen, and the
reading should be confirmed by ailding a very slight excess of the
bromated liquid, and titrating back with standard potassium iodide,
added drop by drop until the slightest deepening of tint is observed.
The strength of the bromated solution should be adjusted so that
1 c.c. = 1 c.c. of the standard potassio-iodide. If free iodine has to
be estimated by this method, it should be transformed into hydriodic
acid by addition of sulphurous acid. Iodic acid mny be reduced to
hydriodic acid by the same reagent. The author describes the appli-
cation of this method to the determination of the iodine in kelp.
J. M. H. M.
Separation of Phosphoric Acid from Iron and Aluminium.
Jiy P. Dkkome (Compf. rend., 89, I'.j^ — 1)53). — The substance con-
taining phosphoric acid is mixed with five or six times its weight of
dry sodium sulphate, and strongly ignited for ten minutes. On cooling,
the mass is treated with water, when the phosphoric acid all dissolves
as tribasic sodium phosphate, the iron and aluminium remaining as
oxides. The exactness of this process is attested by numerous
analyses. W. R.
New Process for Analysing Commercial Potash. By B.
CoRKNWiNDEK and G. CoNTAMixK {CoDipt. rend., 89, 9U7— 9u8). — This
process is to acidify the solution with hydrochloric acid, add platinic
chloride, and evaporate. The potassio- platinic chloride is washed
with alcohol and ether, and then dissolved on the filter with hot water.
The platinum in the solution is reduced to the metallic state with a
hot solution of sodium formate, and is weighed as such. The advan-
tage is that it is unnecessary to remove sulphuric and phosphoric
acids and silica from the potash before precipitation with platinic
chlorides. W. R.
Detection of Cobalt and Nickel in presence of each Other.
B}' G. Pai'asogm {Gazzetta, 9, oU9 — 513). — The author has observed
ANALYTICAL CHEMISTRY. 287
that when a plate of zinc is immersed in a solation of the double
cyanide of nickel and potassium, hydrogen is evolved, and metallic
nickel is deposited on the plate as a black powdei* ; at the same time a
dense cloud of a deep red- coloured liquid is formed around the latter,
and gradually sinks to the bottom, until finally the whole liquid be-
comes of a blood-red colour. No such phenomenon takes place with
the corresponding cobalt compound.
In order to test an acid solution containing the two metals, a slight
excess of potash is first added, so as to pi^ecipitate the m.etals as basic
salts ; these are well washed by decantation, and after adding a little
ammonium chloride solution and ammonia, the precipitate is dissolved
in a very slight excess of a concentrated solution of potassium cya-
nide, taking care to avoid agitation as far as possible, to prevent the
double cobalt cyanide from absorbing oxygen from the air. The solu-
tion is th.en divided into two parts, one of which' is tested for cobalt
in the manner previously suggested by the author, that is, by adding
a few drops of ammonium polysulphide, so that it may float on the
cyanide solution ; if cobalt be present, an intense red coloration will
be seen at the point of contact of the two liquids. This reaction is
very sensitive, and quite independent of the presence of nickel. To
test for nickel, a plate of zinc is immersed in the other portion of the
cyanide solution, when, if it be present, an evolution of gas will take
place, and the red coloration above mentioned will be observed. This
reaction is not interfered with by the presence of cobalt ; but if too
much cyanide has been used to dissolve the basic salts, a violent evolu-
tion of gas will take place from the zinc plate, which disperses the
red-coloured liquid formed at its surface, and renders it impossible to
detect the presence of the nickel if the quantity is but small.
C. E. Gr.
New Method of Separating Nickel from Cobalt. By P. Dirvell
{Compt. read., 89, 9u3 — 9U5). — This process depends on the fact that
a solution of microcosmic salt, saturated in the cold, mixed with a
solution of ammonium bicarbonate saturated with carbonic acid, pro-
duces with salts of cobalt a bluish precipitate ; after boiling for some
seconds, a few c.c. of ammonia ai'C added, and on heating to 100°, all
the cobalt is precipitated as CoNH4P04.H.>0, which is changed to
CooPOt on ignition. If nickel is present, the whole of it remains in
solution, as nickel salts give a blue colour, but no precipitate. The
nickel remaining after separation of cobalt may be precipitated as sul-
phide. Full details of the method for separating the two metals are
given. In a note appended to this paper, Pisani states that ammo-
nium acetate mav be substituted for ammonium carbonate.
W. R.
Estimation of Cobalt and Nickel. By E. Doxath {Ber., 12,
1868-1869). — This method is a modification of Fleischer's (./. pr. Chem.,
1870, Bd. 2, 48), and depends on the fact that when a solution of a
cobalt salt is heated with potash or soda and iodine, cobalt sesquioxide
is formed, whilst nickel salts ai-e not changed. Therefore, in order to
determine both the cobalt and nickel, the solution containing the two
metals is divided into half, one half is boiled with potash and bromine,
which precipitates both the cobalt and nickel, and the other half with
288 ABSTRACTS OF CHEMICAL PAPERS.
potash and iodine, whereby the cobalt alone is thrown doAvn. The
sesquioxides thus obtained are in each case heated with hydrochloric
acid, and the liberated chlorine passed into potassium iodide solution,
and finally the free iodine determined by titration with decinormal
sodium thiosulphate solution. From the equation, R2O3 + 6HC1 =
2RCI2 + 3H2O + CI2, it is seen that 1 atom of iodine equals 1 atom oi"
cobalt or nickel. Further, as the atomic weight of each metal is 59,
so the difference of c.c. of decinormal thiosulphate solutions used in
the two cases, when multiplied by 0'0059, gives the quantity of
nickel. And the number of c.c. used in the second case, multiplied
by 0-0059 gives the quantity of cobalt. P. P. B,
Estimation of Chromium and Tungsten in Steel, and in
their Alloys with Iron, liy R. Schofffx (Ber., 12, 18G8— 1867).
— Estimation of Chromium. — The material finely powdered in a steel
mortar is treated with a solution of the double chloride of copper and
sodium or ammonium, by which means the greater portion of the iron
is removed and a porous mass is left containing the chromium : the
chromium is determined in this by fusion with sodium carbonate and
nitre, extraction with Avater, and after carefully neutralising the filtrate
■with nitric acid, precipitating the chromate by mercurous nitrate.
When silica is present, the aqueous solution obtained by extracting the
fused mass is acidified with hydrochloric acid, a little alcohol added,
and the whole evaporated to dryness : in the filtrate from the silica the
chromium is precipitated by means of ammonia.
The above method is not applicable in cases where the amount of
chromium present is more than 8 per cent., as then the residue left
after treatment with the double chlorides of copper and sodium is not
easily oxidised by fusion. In such cases, it is better fii'st to digest the
steel with concentrated hydrochloric acid ; the insoluble portion is then
fused AA-ith sodium carbonate and nitre, and the solution of the fused
mass in hydrochloric acid added to the hydrochloric acid solution of
the steel. To separate the iron and chromium in such a solution, the
author uses a method similar to that described by W. J. Sell (Ber., 12,
847), which consists in almost neutralising with sodium carbonate,
and after adding sodium acetate solution, which must not produce a
precipitate, the solution is boiled with potassium permanganate solu-
tion. Thus the greater portion of the iron separates out, and the
supernatant liquid must have a red colour, indicating the presence of
an excess of permanganate, which excess is destroyed by means of
alcohol, and sodium carbonate is added to pi-ecipitate all the iron. In
the filtrate from the iron, the chromium exists as chromate. A similar
result is more advantageously obtained by using bromine instead of
potassium permanganate.
Estimation of Tungsten. — The estimation of this element may be made
in a manner similar to the above ; the residue obtained by treating the
steel with solution of the double chlorides of copper and ammonium,
is fused with sodium carbonate. The aqueous extract of the fused
mass is neutralised with nitric acid and the tuugstate precipitated by
mercut'ous nitrate. If silica is present, then the weighed tungstic
acid is fused with potassium hydrogen sulj^hate, and the weight of the
ANALYTICAL CHEMISTRY. 289
silica left on extracting the fused mass with water, deducted from the
first weighing, gives the weight of tungstic acid. When the amount of
tungsten is higher than 12 per cent., it is better to digest the material
with aqua regia, a portion of the tungsten then going into solution, whilst
some separates out as tungstic acid ; if the solution is allowed to stand
for some days, the whole of the tungsten separates out, and may be
filtered off, and the residue fused with sodium carbonate and treated
as above. In case of an alloy containing 10 per cent, of tungsten, aqua
regia does not produce a complete solution, but yields a black residue
containing some tungstic acid, which is, however, decomposed by
fusion with sodium carbonate. P. P. B.
Influence of Acetic Acid on the Separation of Iron as Basic
Acetate from Manganese, Zinc, Cobalt, and Nickel. By J.
Jewett (Chem. Neius, 40, 273). — It has often been observed, when
manganese is separated from iron by precipitating the latter as a basic
ferric acetate, that some manganese is carried down with the iron pre-
cipitate. Eggertz states that this can be obviated, at least to a great
extent, by the presence of free acid. The author experimented in this
direction and found that the presence of free acid decreased the
amount of manganese in the iron precipitate, but at the same time
prevented complete precipitation of the iron. Asei'iesof experiments,
in which the only variable factor was the acetic acid, was undertaken
to ascertain to what extent free acetic acid is eflBcient in keeping
manganese, likewise zinc, nickel and cobalt, in solution, when present
in quantities not too great to prevent precipitation and washing of the
iron. It was found that, by using 4 per cent, of volume of acetic acid
(sp. gr. 1"044) and adhering to the necessary precautions of the pro-
cess, a complete separation by one precipitation can be obtained of
zinc, and one sufficiently accurate for most purposes of manganese,
whilst the amount of nickel and cobalt that goes down with the iron
lessens with increase of acetic acid. D. B.
New Method of Separating Manganese and Iron. By
Beilstein and Jawein (Ber., 12, 1487). — Iodine is added to the solu-
tion, previously treated with potassium cyanide in excess, when the
manganese is precipitated as peroxide. Ch. B.
Estimation of Carbon in Cast-Steel. By S. Kerx (Chem. Neiv.<!,
40, 225). — The following analyses show the ditference in Eggertz's
method and the combustion method, in estimating the amount of
carbon in steels. For the combustion method, chromic acid was
used : —
Combustion used. .
0-14
0-17
0-27
0-38
0-37
0-46
0-64
102
Eggertz's method
0-12
0-15
0-24
0-34
0-36
0-45
0-60
D.
1-03
B.
Clarke's Method for the Separation of Tin from Arsenic and
Antimony. By F. P. Dewey {Chem. Ne^is, 40, 257 — 259). — In
experimenting on the separation of tin, arsenic, and antimony, the
author decided to make a thorough investigation of the method proposed
290 ABSTRACTS OF CHEMICAL PAPERS.
by Clarke as the most favourable. Owing to tbe want of time, tlie
separation of tin from antimony was the only one that could be under-
taken. Some qualitative experiments were made to test the influence
of free hydrochloric acid on the separation, and also the statement of
Clarke that antimony could not be detected in the filtrate from the anti-
mony trisulphide, either by the Marsh test or the black stain on pla-
tinum with zinc, and that oxalic acid did not interfere with either of
these tests. It was found that, to get the best separation, no hydrochloric
acid should be present, although a vei'y small amount does not exert
any very great solvent action on the antimony trisulphide. Oxalic
acid obscured the platinum and zinc test, forming a dense white coat-
ing on both the platiimm and zinc when the acid became nearly neu-
tralised ; this completely masked any black stain that might have been
produced on the platinum. It did not, however, obscnre the Marsh
test in the least. Another series of experiments showed that solutions
of stannic chloride and antimony trichloride containing free hydro-
chloric or nitric acid, or both, can be safely evaporated to dryness if a
sufficient amount of potassium chloride is present.
Other points of minor importance are considered in the original paper.
D. B.
Methods for Indicating the Presence of Organic Matter in
Water. By V. Tiemann and C. Pkeusse (Be)-., 12, 1UU6— 1924).—
The authors have submitted some of the varioas methods proposed for
this purpose to a critical examination, with the following results : —
I. Determination by Ignition of the Solid Residues dried at 180°. —
To this method it is objected that (1) the organic matter not expelled
by evaporation is alone taken into account. (2) S-ilica present dis-
places carbonic acid, and this is not again taken up on evaporation
with ammonium carbooate. (3) Different mineral matter will retain
dilferent amounts of moisture at 180°. (4) Some of the chlorides of
the alkalis will be volatilised. Finally, the organic matter will react
on the inorganic matter present, e.g., deco-mposing nitrates and nitrites
into cyanates and cyanides.
II. Frankland and Armstrong^ s, and III, Dittmorr and Robinson's
(Chem. News, 1877, 26). — To these methods the authors raise the
objections, th it they do not take into consideration the organic matter
volatilised by boiling in acid solution, nor the decomposition which
the organic matter undergoes by evaporation in presence of sulphu-
rous acid and ferrous chloride. Further, since the amount of car-
bon and nitrogen differs in organic compounds, this method gives
no evidence of the absolute quantity of organic matter present ; and
only comparative results, when the mixture of the organic compounds
in the waters compared is similar. This latter objection applies also
to the following methods.
IV. Methods in which Fvtassium Permanganate is used as an Indi-
cator.— (a.) Kubel's method (Kubel-Tiemanu, Anleit. zr. Untorsuchimg
von Wasser, II Anfl., 104). The water is acidified with sulphuric acid,
and boiled with a quantity of centinormal potassium permanganate
solution for 10 minutes ; the unused permanganate is destroyed by
centinormal oxalic acid ; and the excess of oxalic acid is determined by
titration with permanganate solution. Thus the amount of potassium
ANALYTICAL CHEMSTRY. 291
permang'anate reduced by the organic matter is determined and con-
sequently the oxygen required for the latter's oxidation.
(b.) Schulze's method (ibid., 102). This method differs from
Kubel's, inasmuch as the water is rendered alkaline by adding a little
soda, instead of being acidified with sulphuric acid. After boiling for
ten minutes, the water is acidified with sulphuric acid, and the amount
of unused potassium permanganate determined as before.
(c.) Tidy's method (this Journal, Tra7i.<!., 1879, 66).
The advantage of these methods is that both the volatile and the
non-volatile organic matter is taken into consideration. Of the three
methods the authors prefer that of Kubel, as being the most free from
sources of error, and at the same time the simplest.
Y. Fleck's method {J. pr. Chern. 4, 364). The oxidising agent used
in this method is a solution of silver nitrate in sodium thiosulphate,
made alkaline by soda. The water is boiled with this solution for ten
minutes, and the silver in solution determined by titrating with a
■g'o normal solution of potassium iodide. The end of the reaction is
reached when a drop of the solution, added to a drop of a mixture of
hydrochloric acid, potassium permanganate, and starch- paste, produces
a blue coloration.
The authors have made a series of experiments with solutions of
various organic bodies, in order to compare the methods of Kubel and
Fleck. The results obtained show that organic matter reduces potas-
sium permanganate more quickly than the alkaline silver solution.
Fleck claims that his method indicates the presence of volatile organic
matter very delicately. These two methods have been compared with
water saturated with coal gas, the result being that Kubel's method is
judged the better of the two.
In order to settle the question whether the organic products offer-
mentation reduce potassium permanganate more strongly than the
bodies from which they are formed, the authors have made the follow-
ing experiments : — A dilute solution of albumin was titrated with
permanganate solution when freshly made, and then after putrefaction
had taken place. These experiments indicated that the products of
putrefaction have a slightly stronger reducing action than the origi-
nal compound.
In order to settle the question of the presence of volatile organic
matter in waters, the authors have made experiments with some of the
w^aters in Berlin, the mode of procedure being to distil the water
alone, (2) after acidifying with sulphuric acid, and (3) after making
it alkaline by the addition of soda.
The following results were yielded by the water of a brook in the
north-west of Berlin: —
100 c.c. of the water reduce 4T98 mgrm. KMnO^ = 10'G2 mgrm.
(a.) Distillation of the Neutral Water.
1st. 100 c.c. required 5"05 mgrm. KMnOi = 1*28 mgrm. 0.
2nd. „ „ 2-59 „ „ = 0-65 „
3rd. „ ., VhQ ., ., = 0-39 „
4tb. „ „ 1-06 „ „ = 0-27 „
292 ABSTRACTS OF CHEMICAL PAPERS.
(b.) Distillation of the Acidified Water.
1st. 100 c.c. required 4'51 mgrm. KMnOi = 1*14 mgrm. 0.
2nd. „ „ 273 „ „ = 0-69 „
3rd. „ „ 1-78 „ „ = 0-45 „
4th. „ „ 1-61 „ „ = 0-4
(c.) Distillation of the Alhaline Water.
1st. 100 c.c. required 4-28 mgrm. KMnOi = 1-08 mgrm. 0.
2ud. „ „ 1-92 „ „ =0-48 „
3rd. „ „ 1-07 „ „ = 0-27 „
4th. „ „ 1-04 „ „ = 0-26 „
As (a) and (c) contain quantities of ammonium salts, the effect which
these salts have on potassium permanganate was investigated. As a
result, it was found that 100 cc. of a solution containing 100 mgrms.
ammonia required 0"91 mgrm. K]Mn04, which is equivalent to0"24mgrm.
of oxygen ; whereas a solution containing 1 mgrm. ammonia in 100 c.c.
had no effect.
The disadvantage of Kubel's method is that from it no idea can be
formed of the nitrogenous organic matter present; this, however, may-
be attained by the use of Wanklyn, Chapman and Smith's method of
distilling with an alkaline solution of potassium permanganate. This
latter method, the authors have tried with solutions of such bodies as
quinine sulpliate, ethylamine hydrochloride, aniline hydrochloride,
aspartic acid, urea, allauto'in, leucine, tyrosine, and some others. As
a result, the authors find that the ammonia given off is always less than
that required by theory ; but in such cases as leucine, aspartic acid,
and tyrosine-com])Ounds (resulting from the putrefaction of albumin-
ous matter), the quantity of ammonia approaches the theoretical very
nearly. The results of this method yield no clue to the absolute
quantity of nitrogenous organic matter in a sample of water, and the
results obtained in two cases can be compared only when the mixtures
of organic compounds in the different waters are similar.
P. P. B.
Use of the Polariscope in testing Crude Anthraquinone
for Anthracene. By B. Nickels (Chem. News, 40, 270). — By
examining anthracene and anthraquinone with the polariscope, both
compounds are said to present very beautiful objects, the former as
crystallised in the tabular form exhibiting a supei'b play of colours,
whilst anthraquinone, similarly viewed, presents coloured bands only,
crossing the needles individually or grouped. Other substances accom-
panying crude anthracene, such as carbazol, acridine, phenanthrene,
pyrene, chrysene, &c., also exhibit to some extent distinctive and cha-
racteristic forms, but as compared with anthracene, whether as hydro-
carbons or oxidised products, so entirely different that limited obser-
vation readily distinguishes them. Naphthalene is the only body in
any way resembling anthracene, but here again with equally charac-
teristic difference, and to a careful observer there need be no error in
judgment. D. B.
293
General and Physical Chemistry.
Motion produced by the Diffusion of Gases and Liquids
By St. Claire-Deville (Compt. rend., 90, 18 — 22). — If a tube of
platinum or cast steel filled with hydrogen is heated to 1000° in an
atmosphere of nitrogen, the hydrogen escapes from the tube and a
vacuum is produced. If, on the other hand, the tube is filled with
nitrogen and exposed to an atmosphere of hydrogen at 1000°, the
hydrogen penetrates the platinum or steel, and the pressure inside the
tube is equal to 2 atmospheres.
As a second experiment to illustrate the diffusion of gases, a U-tube,
10 metei's high, one limb of which has been sealed at the blowpipe, is
partly filled with water ; the level of the liquid in the two limbs should
be identical. The apparatus is placed under a bell- jar, through which
a current of ammonia passes ; the water in the tube absorbs the
ammonia, and finally becomes saturated by it, the ammonia gas then
diffuses into the air contained in the closed limb, and increases the
pressure until the liquid is forced out of the closed limb.
If the closed limb is fil led with ammonia gas, and the other with a
saturated solution of ammonia, on exposing the apparatus to the atmo-
sphere, the liquid will gradually rise and till the closed limb.
The well-known apparatus of Uebray for illustrating the diffusion
of gases through a porous cell is also described, W. C. W.
Temperature of Decomposition of Vapours. By A. "Wurtz
(Compt. rend., 89, 1062 — lOHo). — In reply to Deville's remarks on the
vapour of chloral hydrate, the author quotes the following experiments
to show that the vapour is a mixture of water and chloral : — 1. The
vapour diffuses like a mixture of steam and chloral (Wiedemann and
Schulze, Annalen [2], 6, 293). 2. The water can be separated
from the chloral by distillation (Naumann, Compt. rend., 89, 285).
3. When anhydrous potassium oxalate is heated in the vapour of chloral
hydrate, at a temperature at which the tension of the vapour is greater
than the tension of dissociation of the hydrated salt, the hydrated
oxalate is formed. 4. No rise in temperature takes place when, chloral
vapour and steam are brought together. W. C. W.
Heat of Formatioa of Chloral Hydrate. By Berthelot {Compt.
rend., 89, 1099 — 1102j. — The author denies that the experiments of
Wurtz were sufficiently delicate to prove that no heat is evolved when
the vapours of chloral and water are brought together.
w. c. w.
Heat of Formation of Chloral Hydrate. By A. Wurtz {Compt.
rend., 90, 24, 25). — A reply to the criticisms of Berthelot.
w. c. w.
Relations between the Physical Properties of Organic
Bodies and their Chemical Constitution. By J. W. Bruhl
{Ber., 12, 2135 — 2148). — Gladstone and Dale, as well as others, have
VOL. xxxviii. y
294 ABSTRACTS OF CHEMICAL PAPERS.
n —1
shown that the fraction — - — (where n stands for the index of re-
d
fraction, and d for the density of the body) gives a numerical value
which is independent of the temperature. This number may be called
the specific refractive index. In the case of bodies of small refractive
power, n may be replaced by the refractive index of any wave-length
(colour), but when the body has strongly refractive properties, disper-
sion interferes. If, however, m^i be called the observed index of the
wave-length, Xi and /<a2 that of wave-length X^, then as /«xi = A +
B B ^^- ~ ^''^ B
— and /iA.2 = -^ + — , B = 1 i and A = /tixi — — , where B is
the coefficient of dispersion, and A the required index for a beam of
infinite wave-length. This value of A can now be introduced into the
formula ^ instead of n, as the true coefficient of refraction, inde-
A— 1 .
pendent of dispersion. For every substance, therefore, — -— is a con-
stant which is influenced only by the chemical nature of the substance.
If this constant be multiplied by the molecular weight P of any body,
A— 1
then P. — - — , referred to chemically comparable quantities, is the mole-
cular refractive index, called in the rest of this paper the molecular
refraction of the body.
Landolt has shown that the atoms of all compounds maintain their
own refractive index, independently of the manner in which they are
grouped ; and Gladstone has also shown that the molecular refractive
power of compounds is the sum of the refraction of the atoms. Many
exceptions, however, were found to this law, such as benzene-deri-
vatives, terpenes, many alkaloids, ethereal oils, and other compounds
rich in carbon. The molecular refraction of these bodies is greater
than that calculated from the sum of atomic refraction. The author
has, however, succeeded in discovering an interdependence between
the composition and optical relations of these bodies ; that in unsatu-
rated bodies atoms which are more than once directly combined with
each other possess a more active influence in the propagation of light
than atoms which with the same quantivalence are linked to different
atoms. If, for instance, hydrogen-atoms are taken away from a saturated
hydrocarbon, so that their removal induces a double combination of
neighbouring carbon-atoms, the molecular refraction is greater than
that calculated from the percentage composition of the body. If R^
represents the refractive equivaleut of the hydrocarbon calculated from
its empirical formula, a the influence of a double combination upon the
molecular refraction, and x the number of atoms removed, the mole-
cular refraction of a body of the composition (C„H2„+2) — xH^ is
= R. -|- x.a. Further, in unsaturated bodies in which
{^)-
there is no manifold attraction of neighbouring carbon-atoms, but
where the removal of constituents of the saturated body produced a
linking of carbon-atoms previously not directly combined with each
GENERAL AND PHYSICAL CHEMISTRY. 295
other, the constitution of the body has no particular influence on its
optical properties, and its molecular refraction corresponds with its
empirical composition PI — 1 = R^- Bodies of the formula
(C„H2H+2) — a;Ho, in which several combinations of neighbouring
carbon-atoms, and likewise attractions of non-neighbouring atoms
are present, have the molecular refraction Pi — - — | = R^ + (x — y).a,
where y stands for the number of hydrogen-pairs whose removal pro-
duced the rinsr-formed linking.
Tables are appended from which the following results are ob-
tained : —
The molecular refraction of bodies which contain one carbon-pair is
greater by 2 than the value calculated from the sum of the specific
atomic refraction, M^ = P| — | = R^ + 2. For bodies con-
taining two carbon-pairs the formula is M^ = P( — - — J = R ^ + 4 ;
for those containing three carbon-pairs, M^ ^ P( - — - — J = R^ + 6.
The atomic refraction of carbon in saturated bodies is 4'86, and there-
fore the refraction equivalent of the group C ! C is 2 X 4"86 + 2 =
llv2
11'72 : hence the refraction-equivalent of the carbon-atom is — =:
5"86, and this shows that the atomic refraction of carbon is variable.
The molecular refraction of propargyl-derivatives is M^ = P| " — ~ — ' =
HCH
Ra + 1'8, which would show that their constitution is /\ , or
HCziCH
CH : c— CH3.
The value of the optical properties of a body in determining its
chemical constitution may be seen from the following example : —
A hydrocarbon of the formula (CnHin + o) — 4H may contain either
(1) two ring-formed combinations ; (2) one ring-formed and one double
combination ; or (3) two double combinations. Its molecular refraction
would give us (1) M^ = R^; (2) M^ = R^ + 2; (3) M^ = R^ -I- 4.
G. T. A.
Chemical Constitution of Organic Compounds in Relation
to their Refractive Power and Density. By J. W. Bkuhl
(Annalea, 200, 139 — 231). — After referring to the reseiarches of Glad-
stone and Dale (Proc. Boy. Soc, 12, 448 ; 16, 439 ; and 18, 9 ; Phil.
Trans., 18-58, 887 ; and this Journal, 3, 108 ; 8, 101 and 147) ; Landolt
(Pogg. Ann., 117, 368, and 123, 595) ; Wiillner (ibid., 133, 1), and
others, the author gives the details of his investigation on the
specific refraction of a large number of liquid organic compounds.
The refractive indices of the substances were determined for the yellow
sodium line D, the red and srreen hydrogen lines C and F, and for the
y 2
206
ABSTRACTS OF CHEMICAL PAPERS.
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INORGANIC CHEMISTRY. 297
violet hydrogen line wliicli occupies a position between the Fraunhof er
lines F and G. These determinations were made at 20°. The specific
gravities were also taken at this temperature, and referred to water at
4°. The weighings were reduced to vacuo.
In the table (p. 296), Column IV gives the index of refraction for
the sodium line ; Y the coefficient of refraction for a ray of infinite
wave-length (consequently not influenced by dispersion) calculated by
"D
Cauchy's formula /«a. =^ A + -^ ? in which /i = index of refi'action,
X. the wave-length, A coefficient of refraction, and B = coefficient of
dispersion. Yl shows the coefficient of dispei'sion. VII, specific
A — 1
refraction, — - — VIII, molecular refraction ; and IX, the molecular
a
refraction R^, calculated from the following atomic refractions : —
C 4-86, H 1-29, 0 2-9, CI 9-53, Br 1475, and N 5-35.
The followinof conclusions amono-st others were deduced from a con-
sideratiou of the above data : — I. When an orgauic body loses 2 atoms
of hydrogen, forming a compound in which two of the carbon-atoms
are united together by a double affinity, the specific gravity is increased
by004 (circa), the coefficient of refraction by 0'02, and the coefficient
of dispersion is also larger. 2. The atomic refraction of monad
elements is constant. W. C. W.
Inorganic Chemistry.
Preparation of Hydroxylamine. By G. Bertoni (Gazzelfa, 9,
569 — 570). — In order to avoid the inconveniences attending the pre-
cipitation of the tin by hydrogen sulphide and the evaporation of large
quantities of solution containing fi'ee hydrochloric acid, as in the usual
method of preparing hydroxylamine hydrochloride, the author employs
lead oxide to precipitate the tin and hydrochloric acid ; it has more-
over the additional advantage of entirely removing the iron chloride
which is always present and causes the decomposition of a large
proportion of the hydroxylamine salt during the evapoi-ation. The
product of the reaction of the tin and hydrochloric acid on the nitrate
is poured into a large basin, and hydrated lead oxide or carbonate added
in successive portions until there is a slight excess with respect to the
tin originally employed in the reduction : when the precipitation is
completed, which happens in the course of a few days, the liquid is
neutral or slightly alkaline, and after removal of the lead by sulphuric
acid, should give no precipitate of tin sulphide with sulphuretted
hydrogen. The liquid is then decanted, the residue heated several
times with water to dissolve out the hydroxylamine salt, and the small
quantity of lead which is present is precipitated by hydrogen sulphide.
After filtration and evaporation to dryness, the hydroxylamine salt is
extracted from the residue in the manner described by Lessen.
C. E. G.
298 ABSTRACTS OF CHEMICAL PAPERS.
Conversion of Hydroxyl amine into Nitrous and Nitric Acids.
By G. Bkktoni (Gazzetta, 9, 571 — 674). — When a dilute solution of
hydroxy] amine is rendered alkaline with baryta and treated with
potassium permangfanate, it is immediately reduced, and on examining
the solution it will be found to contain nitrous acid. If the hydroxyl-
amine solution is rendered acid with sulphuric acid, its reducing
action on the permanganate is very much slower, and in this case
nitric acid is formed. In neither reaction, however, is the whole of the
hydroxyl imine converted into the acid. Chromic acid behaves in a
somewhat similar manner, producing nitric and nitrous acids, whilst
the oxides of the noble metals yield nitrous acid only. The author
hopes to found a quantitative process for the estimation of hydroxyl-
amine on this reaction. Red blood-corpuscles are deoxidised by
hydroxylamine, but the products formed have not been examined.
The powerful reducing action of hydroxylamine causes it to act as an
energetic poison when injected subcutaneously, and also when exhibited
internally. C. E. G.
Reduction of Carbonic Anhydride by Phosphorus at Ordi-
nary Temperatures. By A. K. Lkkls (7>V/-., 12, 2131).— The
author finds that, although large quantities of phosphine are produced
under the conditions stated in a previous paper (this vol. 237), no
reduction of carbonic anhydride to carbonic oxide takes place.
G. T. A.
A New Hydride of Silicon. By J. Ogier (Compt. rend., 89,
1068 — 1U70). — Silicon tetrahydride is decomposed by the electric
discharge, liydrogen being liberated, and a yellow deposit formed
which has the composition SiHa. The new compound ignites on per-
cussion, and burns when heated in the air: it also takes fire in an
atmosphere of chlorine.
Whnn exposed to a temperature of 400°, the tetrahydride splits up
into hydrogen and silicon.
Phospnoretted and arseniuretted hydrogen are also decomposed by
the eiect/ic discharge, with formation of solid hydrides.
W. C. W.
Luminosity of Phosphorus. By W. Mijller-Erzbach (Ber.,
12, 2180).— The statement of Joubert (Compt. rend., 79, 693) that
the luminosity of phosphorus is due to oxidation of its vapour is not
new. The author has stated the same fact in Pogg. Ann., 141. 95,
and Ber., 3, 84. G. T. A.
Pentathionic Acid. By F. Kessler (Annnlen, 200, 25G— 259).
— In re|)lying to Spring's paper on the non-existence of pentathionic
acid (Ann., 199, 79) the author points out that his analyses (Pogg.
An7i., 74, 271) proved that the acid which is produced by the action
of sulphuretted hydrogen on sulphurous acid was penta- and not tetra-
thionic acid. W. C. W.
Reduction of Metallic Oxides by Hydrogen. By W. ;Mi;LLER-
Erzbach {Ber., 12, 2130). — The statement made by Wright and Luff
in their papers on " Researches on some Points in Chemical Dyna-
INORGAXIC CHEMISTRY. 299
mics (this Journal, 1878, 1 and 504), that the initial temperature for
the reduction of oxides depends on their physical nature, has been
already published by the author (Pogg. Ann., 136, 51). Also their
statement that precipitated copper oxide is not reduced by hydrogen
at a temperature below 83° has been forestalled by the author, who
gave it as 82° (Pogg. Ann., 153, 332). G. T. A.
Copper Hydride. By Berthelot (Compt. rend., 89, 1005 — 1011).
— The anomalous results observed in the amount of heat absorbed in
the formation of copper hydride (which was found to vary from
— 2"7 to — 8'7 in different specimens) induced the author to analyse
the substance. A sample prepared by the addition of sodium hypo-
phosphite to a solution of copper sulphate and dilute sulphuric acid,
purified by washing with water containing carbonic acid, and dried on
porous plates over sulphuric acid in an atmosphere of carbonic anhy-
dride, had the following composition :
Cu 87-2 H ; 0-08 ; HoO 1-3 ; S 0-28 ; P 1-34 ; 0 combined with
Cu 4"6. O combined with S and P, loss, &c., 5-2 per cent.
It may be regarded as a complex compound of hydroxide and phos-
phate of copper.
When boiled in water, the so-called hydride gives off hydrogen, and
leaves a residue which contains besides copper,, small quantities of
oxygen, sulphur, and phosphorus. W. C. W.
Copper Hydride. By A. Wcetz (Comjjt. rend., 89, 1006—1068).
— In reply to Berthelot's criticisms, the author points out that pure
cuprous hydride can be obtained by the electrolytic decomposition of
a dilute solution of copper sulphate, or by the action of sodium hypo-
sulphite, NajSO), on copi^er sulphate. When the hydride is treated
with hydrochloric acid, the volume of hydrogen liberated is twice
that set free when the hydride is decomposed by heat.
W. C. W.
Copper Hydride. A Reply to Wurtz. By Berthelot (Compt.
rend., 89, 1097 — 1099). — The author maintains that the existence of
cuprous hydride is purely hypothetical, since the so-called compound
invariably contains constitutional water. W. C. W.
Copper Hydride. By A. Wurtz (Compt. rend., 90, 22 — 24). —
In the preparation of cuprous hydride at the ordinary temperature, the
portion which is first deposited contains only very slight traces of
phosphate. The mean of two analyses gave —
Found. Calculated.
Cuo 98-52 98-45
H.> 1-48 1-55
w. c. w.
Atomic Weight of Antimony. By F. Kessler (/. pr. Chem. [2],
20, 114 — 123). — (Comp. this Jour., 36, 772.) A critical discussion of
the methods and results of the five more important investigations of
this constant, leads the author to the following conclusions : — The
determinations of Schneider, by the ignition of a native sulphide
300 ABSTRACTS OF CHEMICAL PAPERS.
( Arnsberg glance), in hydrogen gas, are untrustworthy, he having over-
looked the presence of calcspar as an impurity in the ore : so also
are Cooke's numbers ; both those obtained from the synthesis of SbjSa
m the wet way, and subsequently heating to 2i0° in a stream of
hydrogen, through the oxidation of a portion of the sulphide in the
latter process, due to the presence of nitrogenous impurity (NoO) in
the hydrogen used; and also those obtained from the analyses of
halogen compounds on account of the contamination of the silver pre-
cipitates with the sparingly soluble salt, AgSbO.CiH.O^, and probable
impurities in the SbClsCH.O), SbBra, and SblsCSBr^.SL), the two
latter compounds having been prepared in presence of carbon bisul-
phide. On the other hand, after applying a correction to the number
obtained by Dumas for the AgSbO.C.H.Oe, here also most probably
contained in the silver precipitate, we obtain Sb = ] 22-29 The number
assigned by Dexter, l22:i3, the author regards as trustworthy, whilst the
mean value obtained by the author himself from three series of experi-
ments was 122-29. The final conclusion to be drawn is that 122-3 re-
presents the atomic weight of the metal ; or, on the assumption of
htas (H = 1, O = 15-90; the integral 122. C. F. C.
Atomic Weight of Antimony. By J. P. Cooke (Ber., 12, 2123
— L124;.— A reply to the objections of Kessler to the author's results.
(bee preceding abstract, and this Joui-nal, 36, cio-i and 772.)
Galvanic Experiments (Platinmn Bases). By E. Drechsel
(J.pr. Chem [21 20, 37S-y,su;._The method employed is to con-
tinuously and rapidly reverse the galvanic cuiTent from platinum
poles through the solution operated upon. By acting in thi.s manner
on commercial ammonium carbonate (containing ammonium carba-
mate) for a period of eight hours, and tlien evaporating on the water-
bath a salt crystalhsing in fine white needles was obt^iined It was
found to contain (;4-(J9 per cent, platinum, and is the salt of a plati-
num base; its composition could not be satisfactorily settled on
account of want of material. Concentrated hydrochloric acid gives a
bright green, nitric acid a sky-blue crystalline precipitate with its
solution. About Ul gram platinum was dissolved in ten hours by the
ammonium carbonate.
On working the commutator more slowly, the temperature of the
liquid rises and no precipitate is formed, but by simultaneous cool inc^ a
crystalline precipitate occurs, which contains 38-6 per cent, platinum
and IS also the salt of a platinum base; this yields no bright green pre-
cipitate, but an almost colourless one with hydrochloric acid, consist-
ing of microscopic needles. By operating on a solution of glucose
mixed with sodium phosphate, with very large platinum electrodes,
prevented from touching each other by a sheet of filter-paper, the
places on the platinum where the paper had rested were found at the
end ot the experiment to be covered with a brownish translucent sub-
stance easily removable in large plates ; this on ignition left a large
amount of platinum, but its properties have not as yet been inves-
tigated. "^
H. Kolbe remarks in a note to the paper that these interestincr
MIXERALOGICAL CHEMISTRY. 301
results have induced him to extend his earlier galvanic experiments,
and to study the action of rapid change of poles on a number of
salts. F. L. T.
Mineralogical Chemistry.
Mineralogical Notes on the Ores of Chanarcillo, North
Chili. By A. Streng (Jahrb. f. Min., 187«, b;»7— 927). — The speci-
mens examined by the author were obtained from the Dolores I Mine,
Chanarcillo, Atacama. The veins and deposits of the various ores of
this district were described by F. A. Moesta (Jahrh. f. Min., 1870,
489). According to him, the silver ores are irregularly distributed
over Atacama, some occurring in the neighbourhood of the coast, and
others in the Cordillera in greenstone, sti'atified porphyiy, sedimentary
and metamorphic rocks. The most considei-able deposits of ore occur
in the stratified formations of Chanarcillo, in limestone of the Upper
Jura fonnation, in which there are vertical veins and intrusive layers
of eruptive rocks. There are numerous veins of greenstone penetrat-
ing the limestone (their direction being from the south towards the
north) and in these veins, where the rocks are still undecompo.sed,
there are considerable quantities of iron-pyrites, galena and zinc-blende,
all of which contain small quantities of silver, varying from four to six
ounces to the centner. There are three occurrences to be taken into
consideration, which are of great importance, viz. : (1) the veins ;
(2) the so-called " mantos ; " (3) the intrusive deposits.
The Veins. — These consist of rich silver veins, ferruginous barren
veius, and rock veins more or less of decomposed greenstone. The
rock veins are undoubtedly the media through which the metalliferous
deposits were brought about, as they cause an enrichment of the silver
veins penetrating them.
The Maxtns. — These are layers and zones of rock interposed with
great regularity in the stratified formation ; they contain silver ore,
and are always metamorphosed through the action of silicates.
The Intrusive Layers. — These also are " mantos," consisting, how-
ever, of greenstone, and enriching the silver veins which penetrate
them. The distribution of ore in the veins is very irregular, owing to
the unmistakeably intimate connection existing between the " manto "-
formation and the ore deposits, as the latter occur only where the ad-
jacent rock (nebengestein) is " manto," or where a vein of greenstone
penetrates a vein of ore. Where the adjacent rock is not "manto," the
veins are filled with barren rock substance, and, speaking generally,
the veins increase in richness with the depth. The silver-ores of the
above locality may be divided into two large groups, viz., the uppermost,
and those near the surface consisting mostly ot native silver, or the
compounds of silver with chlorine, bromine, iodine and mercury, whilst
the lowermost deposits are either sulphides of silver or arsenical silver
compounds, such as sdver-glance, polybasite, proustite and pyrargyrite.
£02 ABSTRACTS OF CHEMICAL PAPERS.
The accompany iBg vein- mass can also be divided into two groups :
(1) in the upper zone it consists mostly of a loam coloured yellow by
ferric oxide, of a purer iron-ochre, ferruginous bitter spar, calcite,
barytes and some malachite; (2) in the lower zone it is black or grey,
and consists of calcite, much zinc-blende, galena, arsenic, and occa-
sionally iron-pyrites. . -1x4.1,^.
It is characteristic of the deposit of silver ore that it ends at that
depth or spot where the decomposition or alteration of the rock strata
can no longer be detected. From these observations the author con-
cludes that the ores in the veins are the product of the decomposition
of the adjacent rock. The silver in them arises from the silver enter-
ing into the composition of the metallic sulphides distributed in the
caTcite and greenstone, as it appears that the richer the deposit in the
veins, the poorer is the adjacent rock in iron-pyrites, galena and zmc-
blende. These conclusions fully confirm the theory of Bischoff that
" the metalliferous veins obtained their material from the adjacent
rocks," and the recent researches of Sandberger, who proved that
silver, copper, nickel and cobalt are present in many rock-forming
minerals, accounting for the presence of these metals m the veins by
showing conclusively that they must have been taken away from the
adjacent rocks bv the action of water, and deposited in the veins.
1. Proustite.— This mineral often occurs attached to pyrargyrite, and
is accompanied with argentite, calcite, fluorspar, irou-pyntes, feuer-
blende, &c., the proustite being generally completely enveloped by
felt-like asbestos. Its crystals vary in size, from short crystals or fine
needles to individuals 25 mm. in length, and the forms observed being
the predominating scalenohedron R^ combined with
iR . -in . R . -2R . coR . GoP2 . ooP^
The comparative length of the vertical axis c was found by the
author to be 0-80839, and this result agrees exactly with the length
of the axis c, obtained by calculation from Miller's measurements.
The rhombohedron — 2R occurs sometimes almost predominating,
and on these crystals good measurements can be obtained. The rhombo-
hedron + ^R, occurs generally as a modification of the terminal edges
of — -iR, but it occurs sometimes independently. Its faces are always
distinctly striated parallel to the shorter diagonal, that is, parallel to
the combination-edge of -iR with + ^R- This striation is caused by
the alternating combination of ^R and -^R. The rhombohedron R is
a rare occurrence, and its faces are not generally well adapted for accu-
rate measurements of the interfacial angles. A scalenohedron |-R ,
which occurs sometimes with R', and the other rhombohedrons already
referred to, is characterised also by a peculiar roundness and mdefiuite-
ness of its interfacial angles. This peculiarity of the interfacial angles
of the two forms is confined mostly to the same portion of a crystal,
whilst on other crystals nothing of the kind is observed. As a rarity
there occurred a negative rhombohedron immediately beneath —ZK
on R^ its combination-edges being very nearly parallel to the obtuser
terminal edges of the scalenohedron : consequently it must be an obtuser
rhombohedron than — 5R. There were also slight indications of a
rhombohedron f R. Amongst the scalenohedrons, R^ predominates,
MINTi:RALOGICAL CHEMISTRY. 303
the faces of which possess a magnificent lustre, and often exhibit a
striation parallel with the combination-edge with coP2, this striation
being caused on some individuals by the alternating combination of
the scalenohedrous W and R*, whilst on others it is due simply to the
alternating combination of R^ and ooP2. The scalenohedron R* does
not occur independently. The scalenohedron -f R* is a common occur-
rence on the obtuser terminal edges of R^, and exhibits a striation on
all its faces parallel to the combination edge with -^R, caused by
the alternating combination with the latter form. The^scalenohedron
|R^ is a rare occurrence ; it modifies the combination edges of R with
— gR- On a few crystals, a scalenohedron (new to red silver ore)
— 2Rf occurs; it combines with R^ in such away that the combination
edges with R^ are only approximately parallel to the obtuser ter-
minal edges of that form. The faces of — 2R| are horizontally striated,
owing to its alternate combination with a scalenohedron — wiRf (pro-
bably - 4Rf ). The author observed also a scalenohedron Rl«-, occur-
ring in alternate combination with ooP2, and points out that Sella
(Quadro delle forme cristalline dell Argento rosso, del Quarzo e del
Calcare di Q. Sella : estratto da una memoria sulle forme cristalline
dell' argento rosso letta davanti alia R. Academia delle scienze di
Torino, li 10 febbraio, 1856) had already observed a scalenohedron R^-,
but Streng's measurements were of suHicient accuracy to show that
his scalenohedron was really R^. The " prism zone " is very fully
developed, but the individual faces are not very clearly defined, and
occur m alternating combination, thus causing a very irregular, strong,
vertical striation. Amongst the prisms coP2 predominates, its faces'
being generally striated parallel to a prismatic edge, or else parallel
to the combination-edge with R. Sometimes the latter striation is
caused by the alternate combination of ooP2 with R', and sometimes
with the scalenohedron R-i^. A prism ooP-J occurs tetartohedral.
The prism ooR is a rare occurrence, and is observed generally as a ti-i-
gona,l prism. The author could not ascertain whether proustite was
hemimorphous (as might be expected with a hemihedral or tetarto-
hedral habit of the " prism zone ") owing to one end only of the crystal
being developed, whilst the other end was invariably attached to the
supporting surface. The basal terminal plane OR is one of the rarest
occurrences on proustite crystals. Proustite crystals occur also
twinned according to two laws, the first being " the twin-plane a face
of -f-R." The twins according to this law have their vertical axes
inclined to each other at an angle of 94° liS', and one individual pre-
dominates largely and forms a nucleus round which other smaller
twins arrange themselves, parallel to the three directions corresijonding
with the three pairs of rhombohedral faces. A polysynthetical twin-
formation was also observed occasionally, tabular crystals occurring as
thin lamina? being interpolated parallel to a face of R, in the principal
or predominating crystal. The second twin-law is "the twin-plane a
face perpendicular to the terminal edge of --^R." The twin-axis is a
terminal edge of -^R. The two crystals have a face of -f^R in
common, but the twin-plane is the one given above, and the vertical
axes of the two crystals intersect at an angle of 26° 7'. A similar
grouping of crystals, round a central prcdominatiug individual, was
304 ABSTRACTS OF CHEMICAL PAPERS.
observed with twins accordino: to tbe second twin-law, as was the case
^vith those according to the first law; also for the first tune a poly-
synthetical twin-formation. The author considers proustite to be one
of the best examples of three kinds of striatiou on the crystal-faces as
the latter are striated (1) throagh the alternate combination of two
faces- (2) throuo-h the occurrence of sub-individuals ; and {.6) tnrougii
polysynthetical twin-formation. The author appeuds a table ot m_ter-
facial angles for all the forms observed on proustite from Chanar-
^' 2.' Purnrniinte.— This mineral occurs simultaneously with proustite at
Chaii:.rcillo,'the latter being generally attached to the former i he
crystals of pyrargyrite are less lustrous than thoscof proustite, and there-
fore not well adapted for accurate measurement, but the fo lowing forms
were observed, viz., R' . -^R • ooP2 and coR as a trigonal prism. 1 he
terminal edges of -^R are either replaced by i K, or else by very obtuse,
striated scalenohedrons, which could not be measured, ihe taces oi
R3 are strewn over with small excrescences, which aggregate into
narrow swellin.rs on the acuter edges, whilst the faces of coF_ project
so much that R occurs above it, with a re-entering angle in combination
with R3, whence it follows that the faces of R' are sunken, as in a
crvstal skeleton. Some pyrargyrite crystals are encased m a ligHt-
grey, lustreless covering, on which proustite crystals have formed.
Twins occur, the twin-plane being a face c,f R. On analysis of a pyrar-
gyrite crystal, the following results were obtained, viz. :—
A". Sb. As. S.
60-53 lH-i7 3-80 18-17 = 100-97
from which the formula Ag.AsSa + SAgaSbS, is deduced. From this
formula it appears that the Chaiiarcillo pyrargyrite occupies an inter-
mediate position between pyrargyrite and proustite, as the autnor
considered might be the case, from its occurrence simultaneousfy witti
proustite. .,
2 Feaerhlende.— This mineral occurs attached to pyrargyrite, m
very small, isolated, hyacinth-red crystals, in a rhombic form resembling
stilbite. The largest crystals attained a length of To mm., and a
breadth of f mm. Breithaupt describes this mineral in his una-
rakteristik des Mmeralsystems." 3 Autl. 1832 ; Phillips, m his Ele-
mentary Introduction to' Mineralogy " (Brooke and Miller) 5 '/^^J' "J
his " System of :^lineralogy," and Roemer {Jahrh.J. Mm., ib48, 6i^)
are of the same opinion. " Phillips gives the following forms:—
-f P . coiw^co . Poo . coPoo . ooP . ^Pc
oo.
and states that ooPoo is striated parallel to its combination-edge with
Poo. The forms given by Dana are ooP . coPoo . P2 . Poo . -Poo,
and he al^o states that ooPoo is striated parallel to the chnodiagonal,
the cleavage-plane being also ooPoo. Roemer also considers the
mineral to be monosymmetrical, on account of the striation being
feather, like, and parallel to a terminal edge of P, whilst he was of
opinion that the cleavage-plane must be a face of P.
Kenngott, however, concluded from his observations " (Uebersicht
der Resultate mineralogischer Forschungen in den Jahren 1844-49,'
MINERALOGICAL CHEMISTRY.
305
249), tliat it crystallised in the rhombic system, the forms observed
being P . ooPoo . ooPco, the cleavage direciiion parallel to coPco, and
the feather-like striation on ooPco was parallel to the combination
edge with P. The crystals examined by Streng exhibited two types,
i-iz., a distinctly rhombic type and a monosymmetrical type. There
were three pyramids in the same zone, a pi-isin whose obtiiser edge was
modified by a dull, lustreless pinacoid, aud the acute edge by a pina-
coid having a strong pearly lustre ; no striation was observed, how-
ever, on the latter face. A dome occurred on all the pyramids. An
exfoliation was observed on the crystals, parallel to the pinacoid, exhi-
biting a pearly lustre (cxsPco), and this exfoliation causes a striation
on the other pinacoid, and also on the faces of the domes and pj^ramids,
parallel to the combination edges with ooPoo. The author concluded
from the measurements obrained by him, and the results of the optical
examination of the crystals, that they crystallised in the rhombic
system, and did not exhibit any twin-formation. The most obtuse
pyramid was chosen as primary pyramid, and the axial ratio a : h : c =
0-370(5 : 1 : 0-1944.
The following table gives the various forms and the interfacial
angles observed according to the authorities above named : —
I
Streng.
Brooke and
MiUer.
(Mono-sym-
metrical.)
Dana.
(Mono-sym-
metrical.)
X.
Y.
Z.
(Rhombic.)
Calculated.
Found.
Calculated.
Qofoo
xBoo
ocPao
___
ooPao
aPx
aPx
—
— •
—
—
ocP
ocP
xP
40° 40'
—
139° 20'
—
P
—
—
125 32
—
160 28
58° 30'
4P4
ip30
£x
—
—
110 52
—
5Po
—
138 46
137° 58'
98 32
95 42
1 .5 tt 1 .5
2 2
530
2Px
— .
—
75 28
—
9f9
P
P2(?)
150 50
—
65 44
122 32
Pso
—
124 371
124 37i
55 221
~^~
All the forms given in the first column were observed by the author,
excepting 4P4 and ^^-P^~, which he converted into rhombic forms,
from Brooke and Miller's measurements.*
* Note hji Abstractor. — Since the above paper was written it has been shown that
if the crystals be placed in the position assigned to those of rittingerite by Schrauf
(viz., tabular through OP), the interfacial nngles will be almost identical, and the
crystal system monosymmetrical, the forms being OP . ocPx . -^^^Pao . P . yP . xP . f P.
Owins;, however, to the presence of sulphur in Streng's feuerblende. and its entire
absence in rittingerite, it is still an open question whether the two minerals are iden-
tical. Below are given the interfacial angles of feuerblende (in Schrauf's position)
compared with the interfacial angles of Schrauf's rittingerite, viz. : —
ooP -
P -
i&p _
Streng.
xP = 5.5° 23i'
OP = 49 7
OP = 81
OP = 69 14
Schrauf.
55°
40'
48
52
81
6
70
32i
C. A. B.
306 ABSTRACTS OF CHEMICAL PAPERS.
4 Magnetic iron pyrites.— Sm^W crystals of this mineral, exliibitirig
the characteristic colour aiul forms, were observed on proustite ihe
forms observed were ooP . P and 4P (the latter on a crystal from
Kont^sbero-), and the interfacial angles coincided with those ot silber-
kies° The author could not, however detect the slip^htest trace of
silver in any of the crystals, althou.srh he is strongly of opinion that
magnetic iron-pyrites crystallises in the rhombic system, and is isomor-
phous with silberkies. ^- ^- ^•
Water of the Ferdinandsbmnnquelle at Marienbad, Bolie-
mia. By W. F. Gintl (,/. pr. Chem. [2], 20, 356-370)— The ex-
amination of this water was made in August, 1876. The spring, on
August 2nd at 4.20 p. m., was yielding 1458-34 litres per hour, as the
mean of three determinations. The temperature of the spring was
10•3^ the temperature of the air being 20-2°. The water was clear
colourless, and showed only a slight yellow tint m long columns, it
had a feebly acid reaction, slightly sharp taste, afterwards very salt,
leaving a distinctly inky after-taste. The sp. gr. of the water at 20-b
was found to be 1-0085.
Result of the analysis : 10,000 grams of water contain—
Potassium sulphate 0-49262 gi-am.
Sodium „ 47-15345 „
Calcium „ 0;14899 „
Sodium nitrate 0 12355 „
Sodium chloride 17-11257 „
Magnesium chloride 0 77146 ,,
Sodium carbonate 14-54793 „
Lithium „ 0-19061 „
* Ammonium „ 0-05099 „
Calcian, 48034 „
Magnesium ,, "^ voooo „
Fei^-ous „ 0-53464 „
Manganous „ ^ "^^qqi "
Basic aluminium phosphate 0-06334 ,,
Silicic anhydride 0-77645 „
Organic matter 1-00521 „
Arsenic traces
Boric anhydride traces
Bromine traces
Strontium oxide trace^
Half-combined carbonic anhydride. . 10-60759 „
Free carbonic anhydride 31-79302 ,,
which corresponds to 1672867 c.c. at 760 mm. b. p., and 10-3°.
The gases rising in the spring in 1000 c.c. contained —
Carbonic anhydride 938-4/ c.c.
Oxygen -^^ ^ ( "
Nitrogen (with a trace of a hydrocarbon) 42 46 „
F. L. T.
* With traces of mettiylamine.
ORGANIC CHEMISTRY. 307
Organic Chemistry.
I
Dioxyethylmethylene. Preparation of Methylene Chloride.
Bj W. H. Greene {Coynpt. rend., 89, ll»77— 1078).— J/"f/%/e?ie chloride,
CHoClo, is best obtained by cautiously adding hydrochloric acid to a
mixture of alcohol, chloroform, and metallic zinc contained in a flask
connected with a condenser. An active reaction takes place, and
sufficient heat is evolved to distil over a considerable quantity of
methylene chloride and chloroform. When the action ceases, more
acid is added to the zinc, and the mixture is gently heated until
alcohol begins to come over. On fractionating the distillate, methylene
chloride (b. p. 40 — 41') is isolated, and the higher boiling liquid is
again treated with zinc and hydrochloric acid. Dioxyethi/bnethi/lene
ether, prepared by the action of sodium on a mixture of methylene
chloride and absolute alcohol, boils at 89° under 709 mm. pressure, and
its sp. gr. is 0'851 at 0°. The ether dissolves freely in alcohol and in
common ether, and is somewhat soluble in water, but it separates from
the aqueous solution on the addition of calcium chloride.
w. c. w.
Action of Potassium Permanganate on Potassium Cyanide.
By E. Baudeimont {Curnpt. rend., 89, 1115 — 1117). — Four equivalents
of potassium cyanide are required to decolorise 5 mols. of potassium
permanganate ; the rate of decomposition increases with the tempera-
ture and with the strength of the solutions, but it is diminished by
strongly acidifying the mixture with sulphuric acid.
Urea, ammonia, and carbonic, nitric, nitrous, oxalic, and formic acids
are the products of the decomposition. The formation of urea, nitric
and nitrous acids, is represented by the following equations : —
(1.) 4KCN + KoMn^Os + 5HoO = •2C0(NHo), + 2K2C03 + 2KH0
+ Mn.Os.
(2.) KCX + KoMnoOs = KXO3 + K,CO:, + Mn.Os.
(3.) 4KCN + oKoMn.Oa + H,0 = 4K^^03 + 4K0CO3 + 2KH0
-f MnoOs.
In an alkaline solution, a considerable quantity of nitrite, and but a
small quantity of urea is produced, but when the mixture is acidified
with sulphuric acid, the yield of urea is greatly increased.
w. c. w.
Cyanamide. By E. Drechsel (/. pr. Chem. [2], 20, 77—97). —
The author gives, in the first instance, details of improved methods
for the preparation of cyanamide, both from potassium cyanate and
from ammonium thiooyanate. Volhard's method of preparation from
the latter salt, viz., conversion into thiocarbamide and treatment of this
compound with mercuric oxide, is supplemented by treatment of the
residues ftom the first of these processes, thus : — A crude melam is
obtained by heating until the mass becomes solid ; it is then finely
powdered and heated with an equal weight of quick-lime ; the result-
ing cyanamide is isolated by the ordinary treatment. By the method
308 ABSTRACTS OF CHEMICAL PAPERS.
thus completed the author obtained from 4*5 kilos, ammonium thio-
cyanate, 1010 grams thiocarbamide (yielding about 400 grams cyan-
amide), and from the 727 grams melani obtained from the residues,
292 grams cyanamide ; the total yield of cyanamide being thus 15 per
cent, of the salt employed.
Bodies of the formula ??(CN.NH2), are converted into cyanamide by
similar treatment, probably yielding in the first instance melam (the
formation of ammonia accompanied by evolution of heat being always
observed).
The formation of calcium cyamide from melam and lime may be
represented by the equation —
CeHgNu + 4CaO = 4CaCN'o + 3NH3 + 2COo,
or as occurringr in the following stagres : —
I. CeHgNn + 4CaO = 2Ca(OCN)2 + SNHs + (2Ca + 2CN
+ N3).
II. 2Ca(0CN)o = 2CaCN. + 200^.
TTT / (a) 2Ca + 2CN + N. = 2CaCX,, or
^^^- 1 (6) Ca(CN)2 + Ca + No = 2CaCN,.
The last of these equations was verified (so far as the analogy
holds good) by passing the vapours of sodium over potassium cyanide
kept at a red heat in an atmosphere of nitrogen, when a cyamide was
formed, thus : KCN + N + Na = KNaCNa. The conversion of
barium cyanide into cyamide, and the possibility of the direct removal
of the carbon-atom, by which the formula of the first diifers from
that of the latter, were investigated by the following experiment : —
Pui'e barium feiTOcyanide was heated to redness in an atmosphere of
nitrogen or hydrogen ; cyanamide was identified amongst the products
of the reaction. The direct observation with barium cyanide was beset
with the difficulty of obtaining it. Two methods of preparation were
attempted : first, dry hydrocyanic acid was passed into a solution of
barium oxide in anhydrous methyl alcohol, the reaction taking place in
an atmosphere of hydrogen. The product, however, was a methoxy-
cyanide, crystallising with 1 mol. of the alcohol in white shining
plates Ba(OMe)CN + MeOH ; on heating, it was resolved according
to the equation : 2Ba(0Me)CN = CNBa.O.BaCN + Me.O. The
oxycyanide, heated in an atmosphere of nitrogen, yielded cyanamide.
Secondly, cyanogen gas was passed over heated barium-amalgam, air
being previously expelled by a stream of hydrogen. In this case also
cyanamide was formed. The conversion of barium cyanide into
cyamide is thus established : the non-formation of cyanogen, when
the compounds investigated were heated in an atmosphere of nitro-
gen; and of acetylene when hydrogen was employed, negatives the
hypothesis of the direct removal of a carbon-atom. On the other
hand, the reaction is attended with evolution of gas and formation
of bariiim carbonate. The explanation of these phenomena, adopted
by the author after a long investigation, lies in the presence of
traces of moisture in the streams of nitrogen or hydrogen gas in
which the substances were heated (Dibbits, Zeits. Anal. Ghem., 15,
ORGAXIC CHEMISTRY. ' 309
121). The presence of water would probably determine the following^
reactions : —
1. Ba(CN). + 2HoO = Ba(0H)2 + 2HCN.
2. Ba(CN)2 + 2Ba(OH)2 = BaCOs + BaCN, + BaO + H,.
In confirmation of this supposition, by analogy, the author found
that on heating a mixture of potassium cyanide with potash to low
redness in an atmosphei'e of nitrogen, a cvaraide was formed, thus :
2KCN + 4K0H = Ko.CN'o. + K^COs + "K,0 + H^. It was also
observed that on fusing together potassium cyanate and potash in a
silver dish, potassium cyamide was formed, thus r
2KCN0 + 2K0H = K.CXj + KoCOg + H,0,
which bears on the question of the analogy of the alkali-metals to
those of the alkaline earths in their relations to cyanamide.
Although the hypothesis of a direct removal of a carbon-atom from
barium cyanide was rejected, the inverse problem of the addition of a
carbon-atom to a cyamide appears to be solved by the observation, that
on heating disodium cyamide with lamp-black, sodium cyanide is
formed. The author also mentions incidentally, that on heating sodamide
with carbon in a stream of hydrogen, cvanide is formed, thus: XaHoN
+ C = XaCX + H..
Constitution of Cyanamide. — The view of the constitution of this body
advanced by the author in a previous paper {ibid. [2], 11, 347), viz.,
that it is actually cyanamide, CN.XH,. and not carbodiimide, C(NH)2,
has been strengthened by the subsequent investigations of others,
especially those of Schiff and Fileti (Ber., 10, 425), and may now be.
regarded as established. Tiie lengthy discussion of the value to be
attached to the greater stability of the mono-, as compared with the
disodium and potassium compounds of cyanamide, is concluded by
assigning as the cause of the difference, the characteristics of the metals,
rather than a corresponding difference of function of the two hydrogen-
atoms.
The compound of cyanamide with hydrochloric acid, CX.NH2.2HCI.
appears to contain a CCl-group, to be constituted, therefore, similarly
to the imido-chlorides of Wallach (Ber., 1875, 302), thus :
CN.NHo.2HCl = HN: CCl.NHo.HCl, and
CN.NH.C00Et.2HCl =^ HN : CCl.NH.COOEt.HCl.
These bodies are decomposed by water, with formation of urea deri-
vatives, the former yielding dicyanodiamidine, the latter ethyl allo-
phanate.
The author aLso extends this view of the constitution of the hydro-
chlorides of cyanogen derivatives to the following : —
(I.) Nitrils—
H.CN.HCl = H.CCKNH, i.e.. Formo-imidochloride.
EtCN.HCl = Et.CCKNH, Propio-imidochloride.
(2.) Carbamines —
H.NC -f HCl = H.CCKNH, Formo-imidochloride.
Et.NC + HCl = H.CCi:NEt, Formoethyl-imidochloride.
VOIi. XXXVIII. 2
;U0 ABSTRACTS OF CHEMICAL PAPERS.
(3.) Carbimides —
CO.NH.HCl = H,X.C0C1, Carbaminvl cliloride.
CO.NEt.HCl = EtHN.COCl, Ethylcarbaminyl cliloride.
(4.) Cijanates —
N : COEt.HCl = HN : CCl.OEt, Cai-bamidocliloride etliyl ether.
On this hypothesis, an investigation of the action of ammonia and
its derivatives upon these anhydro-chlorides, would lead to interest-
ing' results, the nature of which is evident.
The action of the compounds under (3) upon sodium-cyamide should
vield true cyanocarbamides, thus : —
H.X.COCl + NaHCXa = H.N.CO.NHCN + NaCl.
C. F. C.
Action of Sulphuric Monochloride on Alcohols. By P.
Kkhulnl. (J.jji: Cheia. [2], 20, o82— :^84).— The author, in reply to
Claesson, says that by acting on sulphuric chloride with alcohol, he ob-
tained the body EtO. 80.^01; by the action of this body, many of the
alcohols may lie converted into sulphates of the alcohol-radicles.
Claesson did not obtain this latter result. The author complains that
Claesson did not prepare the ethyl chlorosulphonate according to his
(the author's) method, but prepared it by M. Miiller's method, by
;i-etitig with ethylene on chlorosulphonic acid. The results of Claesson
differ so much from his own, that he considers there is some proba-
bility that these bodies are isomerides. F. L. T.
Combinations of Lithium and Magnesium Chlorides with
Alcohols. By S. E. SiMOxV {J. pr. Chem. [2], 20, 371— 377).— On
ac-tijig with the pure lithium and magnesium chlorides on dry ethyl
and methyl alcohols, heat is evolved, and on cooling with ice or freez-
ing mixtures, alcoholates of these chlorides crystallise out. These
iilcoholates are crystalline, deliquescent bodies. The formulae repre-
f>enting the composition of the ethyl compounds are: LiC1.4EtOH ;
Mgdz.GEtOH, and of the methyl compounds :
LiC1.3MeOH; MgCl,.6MeOH. F. L. T.
Oxidation of Alcchoi by an Ammoniacal Solution of Cupric
Oxide. By A. Lktellier {CuidjA. rend., 89. llU.j). — Ethyl alcohol
is oxidised to acetic acid by the action of an ammoniacal solution of
copper oxide at 18U^.
The blue colour of the ammoniacal solution is destroved by treat-
racnt with glycerol, benzene, oil of turpentine, and by all alcohols.
w. c. w.
Action of Diastase on Starch-paste. By A. Herzfkld (Ber.,
12, 2120 — 2123;. — Tlie final products of the action of diastase on
starch are maltose and achroodextrin. As regards the preparation of
maltose, it is found that crystallisation takes ])lace much more readily
when the solution in hot alcohol of 80 — 85 per cent, is left standing in
the cold for some time in a closed vessel before the alcohol is eva-
porated.
ORGANIC CHEMISTRY. 311
Above a temperature of 65°, besides maltose, another body, soluble
in diluted but not in strong alcohol, seems to be formed by the action
of diastase on starch. It forms a slightly coloured uncrystallisable
gummy mass, very soluble in water. It has a faint sweet taste, which
may be due to its conversion by the saliva into suarar. It is evidently
identical with. Bondonneau's 7-dextrin, but the author prefers to call
it maltodextrin. It has about one-third the reducing power of
maltose on Fehling's solution. Its acetyl compound differs from those
of erythro- and achroo-dextrin, in that when considerable quantities of
it are dissolved in hot alcohol, none of it separates out.
The author has also formed acetyl-compounds with cane- and milk-
sugar, maltose, and dextrose, which he is further investisratinsr.
G. T. A.
Spontaneous Decomposition of Dichlorethylamine. Bv J.
TsCHEENiAK (Ber., 12, 2] 29 — 2130). — Dichlorethylamine can be kept
for a long time unchanged if it is perfectly pure, or if it is covered by
a layer of water, G. T. A.
Desulphuration of Guanidine Thiocyanate. By S. Byk (/.
jir. Chem. [2], 20, 328 — 351). — Attempts were made to obtain cyano-
guanidine from guanidine thiocyanate by the desulphurising action of
the oxides of mercury and lead, but without success. Guanidine thio-
cyanate cannot be desulphurised in alcoholic or aqueous solutions by
mercuric or plumbic oxides: mercuric oxide in aqueous solutions pro-
duces a compound (CNS),Hg(CNSH.CN3H5)HgO, ammonia and car-
bonic anhydride being given off. On treating this compound with acetic
acid, guanidine thiocyanate is formed, and also a mercuric acetothio-
cyanate, Me.COOHg.CXS. Hydrochloric acid produces a double salt of
guanidine hydrochloride and mercuric chloride, CN:iH5.HC1.2HgCL^. By
the action of lead on molten guanidine thiocyanate, a de.sulphuration
occurs, no cyanoguanidine however being produced, but ammonia,
hydrocyanic acid, plumbic thiocyanate, and a compound CvNisHiaO,
termed cyanomelamidine by the author. By oxidation, it is converted
into melamine, with production of hydrocyanic acid. Hydrochloric and
sulphuric acids yield salts of melamine; nitric acid, by assimilation of
water, gives ammeliue nitrate, CaHjNsO.HNO:,. Silver nitrate gives
with cyanomelamidine, ammeline nitrate and ammeline-argentic oxide,
CjHsNsO.AgOH. F. L. T.
Action of Ethyl Chlorocarbonate on the Amines. By L.
ScHREiNER (/. pr. Chem. [2 J, 20, 124— 126).— The product of the
action of methylamine (aqueous) on ethyl chlorocarbonate is methyl-
amidoethyl formate ; it is a colourless liquid, with an ethereal smell,
specifically lighter than water, and boiling at 170°. It is resolved, on
Ijoiling with pota.ssium or barium hydrate, into alcohol, methylamine,
and carbonic anhydride ; the alkaline carbonates and the hydrated
oxides of lead and copper are without action upon it. The following
homologues were prepared : —
- o
312 ABSTRACTS OF CHEMICAL PAPERS.
Methjl-amidoethyl formate, boiling at 170°
Ethyl- „ „ „ 175-5
Propyl- „ „ „ 186
Dimethyl- ,, „ „ 139'5
The vapour- density of each was determined, and found to coincide
with the theoretical.
It is to be observed that the above compounds are liquid at ordinary
temperatures, whereas the urethanes are solid crystalline bodies. The
low boiling point of the dimethyl-compound is in harmony with other
cases pointed out by the author (Annalen, 197, 1 — 20).
C. F. C.
Preparation of Glyceryl Triacetate. By H. Schmidt (Annalen,
200, W — lul). — A good yield of triaeetin is obtained by gently
boiling anhydrous glycerol for 40 hours with twice its weight of
glacial acetic acid in a flask provided with an npright condenser.
The mixture is distilled, and the portion of the distillate boilino: at
257 — 260° purified by solution in water and extraction with ether :
1 gram of triaeetin dissolves in 5*6 c.c, of water at 27°.
w. c. w.
Some Derivatives of Propionic Acid. Bv B. Freytag (J. pr.
Ghem. [2], 20, 380— 382).— On heating thiocarbamide and ethyl
monochlornpropionate in sealed tubes at 100" for 5 hours, a com-
pound crystallises out on cooling which appears to be lactylthiocar-
NH.CoHi
bamide hydrochloride, CS^ | .HCl. On repeated crystallisation
^NH.CO
from alcohol or water it loses hydrochloric acid and is converted into
lactylthiocarbamide. The aqueous solution yields a difficultly soluble
crystalline platinochloride.
Thiocarbamide is dissolved by propionic anhydride at 100", and on
cooling a crystalline mass of propionyl thiocarbamide —
NH^.CS.NH.CsH.O,
is obtained.
The aqueous solution has a neutral reaction, and yields a crystalline!
platinochlotide.
On heating equal numbers of molecules of potassium thiocyanate and
et'iyl a-monochloropropionate in tubes at 150 — 160° for 4 — 5 hours,
the following reaction occurs : — •
Me.CHCl.COOEt -f KSCN = KCl -f Me.CHS.CN.COOEt.
The ethyl thiocyanopropionate thus formed is decomposed on distil-
lation, but may be purified by distillation in a current of steam. The
amyl thiocyanopropionate is obtained in a similar manner.
Further experiments have been commenced with the diethjd ketbn*'
obtained from calcium propionate ; an oxycaproic acid is obtained by
the action of hydrocyanic and hydrochloric acids, which the author
intends comparing with the one obtained by Frankland and Duppa.
F. L. T.
ORGANIC CHEMISTRY. 313
Nitrils from Hydrocyanic Acid and Acetaldehydeammonia.
By S. C. Passayant (Aniuilen, 200. 120— 138).— When a solution of
aldehjdeammonia in 30 per cent, hydrocyanic acid is acidified -with
dilute sulphuric acid, a-aniidopropionitril immediately separates out as
a colourless unstable oil. In the course of a few days needle-shaped
crystals of imidopropionitril are deposited, and if the mixture is
frequently shaken and is exposed to diffused sunlight for four or five
weeks hydrocyanaldine and parahydrocyanaldine crystallise out.
a.-Imidopropionitril forms glistening colourless needle-shaped crys-
tals which dissolve in ether and alcohol, and also, although less freely,
in water. The acid melts at 68^, and sublimes when cautiously heated.
The aqueous solution is not precipitated by silver nitrate at the ordi-
nary temperature, but on heating the mixture silver cyanide is thrown
down. The hydrochloride, CeHciX^j.HCl, obtained by passing dry hydro-
chloric acid gas into an ethereal solution of imidopropionitril is a
white crystalline powder, soluble in absolute alcohol, insoluble in abso-
lute ether, and decomposed by water.
CL- hnidopropicmic or diethylidenelactamic acid —
Me(C00H)HC.NH2<^-j^^j^>C0,
isomeric with the ethylenedilactamic acid of Heintz (ibid., 152, 42)
is prepared by decomposing with dilute sulphuric acid the barium salt
which is formed by boiling a-imidopropionitril with baryta-water.
The barium salt and the free acid are hygroscopic amorphous powders,
insoluble in alcohol. The nitril, when treated with sodium nitrite and
nitric acid, yields a nitroso-compound in the form of a pale-yellow oil
Avhich is heavier than water and is soluble in alcohol and ether. It is
decomposed by heat, with evolution of nitrous fumes, aldehyde, and
hydrocyanic acid.
Hydrocijanaldine, described by Strecker (ibid., 91, 349), melts at
11-5° and sublimes when cautiously heated. It is freely soluble in
glycerol, in acetone, and in hot alcohol and hot acetic acid. It is
deposited in triclinia prisms from an ethereal solution containing
imido-propionitril. It is the nitril of triethylidenelactamic acid or
nitrilopropionitril, Is (CHMe.CXja, and can be prepared by adding
hydrochloric acid to a mixture of amido- and imido-propionitril in
their molecular proportions. If the liquid is warmed, parahyd.ro-
ryanaldine is also formed. This bodv crvstallises in the rhombic
system and is .sparingly soluble in absolute alcohol, water, and g'lycerol,
but dissolves freely in acetone. It melts at 232" and sublimes when
cautiously heated. It resembles hydrocyanaldine in its behaviour with
silver nitrate and with potash.
Attempts to prepare Strecker's base, CgllisN's (ibid., 130, 122), by
the action of hydrocyanic acid on aldehyde-ammonia were unsuc-
cessful. W. C. W.
Synthesis of Normal Nonoic Acid and of an Isomeride
of Palmitic Acid. By F. Jolrdan. — Ethylic heptylacetoacetate,
Me.CO.CH(C7H,5).COOEt., is formed by heating to lOO" the theo-
retical quantities of ethylic acetoacetate, normal heptyl iodide, and an
o
U4 ABSTRACTS OF CHEMICAL PAPERS.
alcoholic solution (8 per cent.) of sodium ethylate. When the reac-
tion is completed, the alcohol is distilled off and water added to the
residue. Tlie lighter layer of liquid is dried over potassium carbonate
and fractionated. The pure ethereal salt is a colourless, oily liquid,
b. p. 271—273° (uncorr.), sp. gr. 09324 at 177°. By the action of
alcoholic potash it yields methyloctyl ketone, Me.CO.CHo.CTHis, and
potassium acetate and heptylacetate. The ketone is a clear mobile
liquid, not miscible with water, boils at 214°, and solidifies to a crys-
talline mass when cooled in a freezing mixture. Its sp. gr. at 17' 7° is
0-8294.
A concentrated aqneous solution of potash decomposes ethylic
heptvlacetoacetate, forming acetic and heptylacetic acids and a small
quantity of methyloctyl ketone. Heptylacetic acid melts at 12°, boils
at 253°, and is identical with the nonoic acid of Zincke and Franchi-
moiit (Annalen, 164, 335; this Journal, 1872, 300).
Eflujlic dihept iflacetoacetate, Me.CO.C(C7H,5)2.COOEt, is prepared by
boiling for two days in a flask, provided with an upright condenser,
a solution of sodium ethylate in absolute alcohol, ethylic heptylaceto-
acetate, and normal heptyl iodide. To prevent moisture loeing ab-
sorbed during the operation, the open end of the condenser is con-
nected with a drying tube containing solid potash. After distilling
oflF the alcohol and adding water to the residue, an oily liquid is ob-
tained which contains heptyl iodide, methyloctyl ketone, ethylic heptyl-
acetoacetate, ethylic diheptylacetate, CH(C,H,5)..C00Et (b. p. 308-5—
3ir), and ethylic diheptylacetoacetate, Me.CO.C(C7H,5)2.COOEt.
These bodies were separated by fractional distillation. Ethylic diheptyl-
acetoacetate is an oily liquid, sp. gr. 0-8907 at 175°, b. p. 331 — 333".
When boiled with a 20 per cent, aqueous .solution of potash, it
splits up into carbonic anhvdride and methyl diheptylcarbinketone,
Me.CO.CH(C7H,5).', a colourless liquid, sp. gr. 0-826 at 17°, boiling at
300— 304\
A concentrated solution of potash decomposes the ethereal salt with
formation of ethyl alcohol and acetic and diheptylacetic acids.
IHhepti/lacetic acid, CH(C7Hi5)2.COOH, melts at 27°, and boils be-
tween 240° and 250" under 80— 90 mm. pressure. It dissolves freely
in alcohol, ether, and benzene, but is insoluble in water. Copper
dilieptijlacetate, Cu(C]6H3i02)2, is deposited from an alcoholic solution
as a granular crystalline mass (m. p. 227 ). It is the only salt of this
acid which has characteristic properties. W. C. W.
Hydroxyvaleric Acids and Angelic Acids. By W. v. Miij.ki;
{Annn]e)i, 200, 2t31 — 285). — The oxidation of valeric acid (prepared
from isobutyl carbinol) by potassium permanganate was investigated
some time since by Neubauer, and stated by him to yield Bijchner's
angelic acid {Annalen, 106, 02; 42, 226). The author, doubting
Xeubaner's results, has repeated the investigation. On distillation
with dilute sulphuric acid, the mixed products of oxidation yielded
a volatile acid (m. p. 69-5^), crystallising in prisms of the monosym-
raetric system {a : h : c =l 1-535 : 1 : 0"706 ; 3 = 7413°), and having
the composition of an angelic acid; the barium salt crystallised in
needles containing 2 mols. H2O. The observed melting point of the
ORGANIC CHEMISTRY. ?>\'t
acid diffei's widely from that of Biichner's isomeride (-Ao"). It also
lies above that of methylcrotonic acid (62'5° — Frankland and Dappa),
but the difference is not sufficient to exclude the probability of iden-
tity. To solve this point, the latter acid was prepared by Frankland's
method (Ann., 136, 36) and by Rohrbeck's (ibid., 188, 229) ; the pro-
ducts were identical ; the acid was found to crystallise in plates (m. p.
65°), belonging to the asymmetrical system, and yielded a barium
salt crystallising with 4 raols. H5O. The acid in question was there-
fore investigated as a new isomeride. The valeric acid studied by
Neubauer being a mixtui'e of ethylmethylacetic acid and isobutyl-
formic acid, these acids were prepared bj synthetic methods and
severally oxidised by permanganate. From the latter an acid was
obtained identical in properties with that under discussion.
A further examination of the products of oxidation of the original
valeric acids showed that a hydroxy-acid was also present; this was
isolated in the crystalline form (m. p. 63°) and found to be identical
with that obtained by Saytzeff (ibid., 197, 72) by the action of phos-
phorus trichloride on ethylic /3-hydroxyisobutyl formate. It would
seem, therefore, that the isomeride in question is dimethylacrylic acid,
Me2C '. CH.COOH, and that it is formed through the medium of /3-hy-
droxyisobutyl formic acid, MeoC(0H).CH2.C00H. The formation of
isobutyric acid, which is stated by Neubauer to accompany that of
angelic acid, is also denied by the author on the grounds of his
experimental results.
The oxidation of the second constituent of oi'dinary valeric acid,
viz., ethylmethylacetic acid, was next investigated. The acid was pre-
pared by the synthetic method of Saur (ibid., 188, 259), and oxidised
in dilute alkaline solution by permanganate. The mixed product was
treated by the distillation metliod, as well as by exhaustion with ether,
and in both cases a crystalline acid was obtained (m. p. 68°), which
was identified as a-hydroxyethylmethylacetic acid ; the absence of
methylcrotonic acid was also established. This hydroxy-acid, there-
fore, does not yield the corresponding angelic acid on distillation with
sulphuric acid, and differs in this respect from the previous isomeride.
The conversion is brought about, however,, by the prolono-ed action of
.sulphuric acid at 115—130". " C. F. C.
Pyroterebic Acid. By J. Bredt and R. Fittig (Annalen, 200,
269, 260).— The liquid uhich is produced by the destructive distilla-
tion of terebic acid is a mixture of lactoiie and pyroterebic acid.
w. c. vr.
Action of Methyl Iodide on Asparagine. By P. Griess (Ber.,
12, 2117 — 2119). — In endeavouring to introduce methyl into aspara-
gine in place of hydrogen by the action of methyl iodide (and methyl
alcohol) on a solution of this body in potash, a new acid was obtained
in addition to tetramethylammonium iodide. This acid, C4H5NO3, is
tolerably soluble in hot water, but less readily in alcohol, and is almost
insoluble in ether. It has a strongly acid taste ; and when heated,
first melts and then blackens with evolution of pungent vapours.
If the constitution of this body is rightly expressed by the formula,
31(3 ABSTRACTS OF CHEMICAL PAPERS.
C00H.C2Hs^— — — T*^H, it bears the same relation to aspartic acid that
lactimide does to alanine.
The harium salt, (C4HiN03)2Ba + 6HoO, forms white foliated solublf
i-rystals. The neutral silver salt, C4H-N03Ag, is obtained in the form
of minute needles or plates Avhen a neutral solution of the ammonium
salt is decomposed by silver nitrate. When this salt is dissolved in
hot water, a basic silver salt, C4H;,N03Ag2, separates out on cooling-.
It is also obtained, but in an amorphous state, when silver nitrate is
added to a solution of the acid in excess of dilute ammonia.
G. T. A.
Preparation of Bromobenzene and lodobenzene. By W. H.
Grkknk {Cninpt. reiuL, 80, 4u — ±1). — The best method of preparing
raoniodobenzene, is to allow chloride of iodine to drop slowly into
l)enzene containing a small quantity of aluminium chloride. To avoid
the formation of higher iodides, a large excess of benzene should be
used.
Mono- and dibrorao-benzene are easily obtained by warming a mix-
ture of benzene and bromine with some aluminium chloride in a flask
)unected with an upright condenser. W. C. W.
(•<
Action of Cyanogen Compounds on Diazobenzene. By P.
(rUiKSs (Bcr., 12, lill'J — 212U). — The author has obtained a compound
of diazobenzene with hydroferricyanic acid and another with hydro-
uitroprussic acid. The first consists of (C6H4N2)3H6(Fe2Ci2Ni2), the
.•;ecoud of (C6H4N,)H2(FeC5N5.NO) + H,0.
They both crystallise well, and are tolerably stable. Diazobenzene
and similar bodies also yield with potassium permanganate salt-like
compounds which have remarkably explosive properties. Similar
compounds have been obtained by Gabriel (Ber., 9, 132, and 12,
1(337). " G. T. A.
Ethylene Derivatives of Phenol and Salicylic Acid. By
A. W.EiiDi(.iK {J. pr. (Jlieni. [2], 20, 127 — 128). — Ethijlcnediiyaranitro-
phenol, C2H4(O.C6H4.N02)2, formed on heating ethylene bromide
with the sodium derivative of paranitrophenol, crystallises from its
alcoholic solution in small needles (m. p. 143*^), but is insoluble in
water. On treatment with tin and hydrochloric acid, it yields a base
which crystallises from its alcoholic solution in reddish needles. In
the first-named reaction there is formed in addition, a body which
appears to be hroinetluiliHiranitropliCHol, C^l:^i(J^O-i)0.(joH.Jiv \ it crys-
tallises in large yellowish tables (m. p. 62 — 63°), and reacts with
paranitrophenol sodium in alcoholic solution to form ethylenediparani-
tropheuol.
The corresponding ortho-compounds were prepared by the analogous
reaction. The nitro-compound melts at 162 — 163°, and yields a crys-
talline base (m. p. 127*^) on reduction. The bromethylorthonitro-
phenol is a ciy.'-talline body which melts at 38 — 40°, and remains in
ihe molten state for some time after cooling.
Diethylic eilnjlenesalicylate, C2H4(O.C6H4.COOEt)2, is formed by
heating sodium ethyl salicylate with ethylene bromide at 120 — 130°. It
ORGAXIC CHEMISTRY. 317
t-r-ystallises from alcoholic solution in thick plates (m. p. 96 — 97°). On
saponification with alcoholic potash, it yields ethijlenedisalicylic acid,
C'2H4(O.C6H4.COOH)2, which crystallises from a hot saturated aqueous
solution in long silky needles (m. p. 151 — 152'').
The author is engaged in completing and generalising his results,
of which this is a preliminary communication. C. F. C.
Quinic Acid, Quinone and Allied Compounds. By 0. Hessf:
(Annalen, 200, 282 — 255). — Tetracetylquiiiide, C7H6Ac403, obtained
by the action of acetic anhydride on quinic acid at 170°, is a vitreous
amorphous mass insoluble in cold water. It is deposited from a solu-
tion in boiling alcohol, in which it is sparingly soluble, in granular
crystals (m. p. 124°). The compound melts in boiling water, under-
going slight decomposition. When bromine acts on an aqueous solu-
tion of quinic aci-d, protocatechuic and a brominated acid are formed.
These acids are easily separated by the greater solubility of the pro-
tocatechuic acid iu hot water. The new acid crystallises in colourless
needles and plates, which are insoluble in cold water, but dissolve
freely in ether. Quinic acid dissolves in hot hydrochloric acid, and
the solution when heated at 150° decomposes with formation of quinol
and parahydroxybenzoic acid. Protocatechuic acid is produced when
quinic acid is fused with potash or soda.
Quinone can be readily purified by recrystallisation from ligroin or
light petroleum, when it is obtained in beautiful yellow prisms. The
author states, in contradiction to Sarauw (Ber., 12, 6b0) that this
body is not converted into >an acetyl-derivative by the action of acetic
anhydride.
He regards it as the aldehyde of the unknown quinonic acid,
C6H4O4.
Quinol melts at 168 — 169° (uncorr.), and begins to sublime at 158°.
When a very narrow tube is used in the determination of the melting
point, a portion of the quinol decomposes.
Diacetjjlquiiiol prepared by Radkowski (JV. Handw^rt f. Chem., 2,
560) by warming a mixture of acetic anhydride and quinol, crystal-
lises in colourless plates (m. p. 121°), which ai'e soluble in benzene,
ether, chloroform, hot alcohol, and in boiling acetic acid. It is not
acted on by ferric chloride or by silver nitrate, but by the action of
strong nitric acid it is converted into dinitrodiacetylquinol,
CeH^CNOO.CAcO),.
This compound crystallises in yellow, plates (m. p. 94^), which dissolve
freely in chloroform, ether, and alcohol. The crystals are soluble in
ammonia, soda, and milk of lime, forming yellow liquids.
Uipropionylquinol is obtained in colourless crystalline plates (m. p.
113*) by heating a mixture of propionic anhydride and quinol at 150'.
Jt dissolves in chloroform, ether, and acetone. Mononitrodipropio7iyl-
quinol, C6H3(N02)(C3H50)202, prepared by treating the preceding com-
pound wdth strong nitric acid, crystallises in pale-yellow plates (m. p.
86°) soluble in chloroform, ether, alcohol, and hot water. With sodn,
it produces a blue coloration, and with ammonia a brown coloui-,
(^hanging to purple and blue.
o
18 ABSTRACTS OF CHEMICAL PAPERS.
Quinliy drone. — When this compound is treated with acetic anhydride
it splits up into equal molecules of quinone and diacetylquinol. This
reaction confirms the accuracy of Graebe's {Ann., 146, 36) formula,
C6H4(OH).0.0.(OH)C6H4, for qninhydrone.
Phennqninone may be pi'epared by adding a hot solution of phenol
to quinone dissolved in boiling petroleum ether, and is deposited in
red needle-shaped crystals when the mixture cools. Neither quin-
hydrone nor quinol is formed, and no hydrogen is evolved in the
reaction.
CeHiOo + 2C6H60 = CaHjOa^ZCfiHsO. According to Wichelhaus the
following equation represents the formation of phenoquinone —
2C6H,0, + 2CeHeO = C,bHu04 + C'K.O,.
The author also disputes the correctness of the formula CjoHjgOfi,
assigned by Wichelhaus (Ber., 12, 1500) to methylquinhydrone, since
his analytical results and the reaction which takes place in preparing
the compound, both indicate C2oH2o06 as the true composition of
methylquinhydrone. W. G. W.
Action of Acetic Anhydride on Phenolic Aldehydes. By P.
Barrier (Co)npt. rend., 90, 37 — 39). — When a mixture of two equiva-
lents of acetic anhydride and one of salicaldehyde is heated at 180°
for six hours, a triacetyl-derivative is formed, which on distillation
splits up into acetosalicylal (b. p. 254 — 25'6°) and acetic anhydride.
The triacetyl compound cry.stallises in white needles (m. p. 100°) ; it
yields the diacetyl-derivative (m. p. 104 — 105°) on treatment with
soda. Similar compounds have been prepared from parahydroxybenz-
aldehyde, and from the liquid and solid hydroxytoluic aldehydes. The
monacetyl-derivatives are colourless liquids boiling respectively at 260°,
267°, and 275°. They all form crystalline compounds with sodium
hydrogen sulphite. W. C. W.
Synthesis of Saligenol. By W. H. Greene (Gonipt. rend., 90,
40). — Saligenol is formed when a mixture of methylene chloride (30),
phenol (30), soda (40), and water (50 grains), is heated at 100° for
six hours. The crude product is acidified with hydrochloric acid and
extracted with ether. The residue which is left on evaporating the
ethereal solution is treated with hot water, which dissolves out the
saligenol (saligenin), leaving the greater part of the phenol undis-
solved. The aqueous solution is concentrated by evaporation and
allowed to cool ; after removing any phenol which has separated out,
the liquid is left in a bell-jar over sulphuric acid until crystals of
saligenol are deposited. W. C. W.
Phenoxyacetic Acid. Bfy P. Pritzsche (J.pr. Chem. [2], 20, 267—
300). — The preparation of phenoxyacetic acid is described at length :
sodium phenolate (10 pts.) is added to a hot concentrated solution
of sodium chloracetate (12 pts.), and the whole heated with con-
stant stirring for about an hour and a half ; the product is then
dissolved in water, and hydrochloric acid added, which throws down
the phenoxyacetic acid as an oil, which soon solidifies. The acid
ORGANIC CHEMISTRY. 319
crystallises in large needles, melting at 96", and distilling with partial
decomposition at 285°. Supersaturated aqueous solutions are easily
prepared.
The acid is scarcely attacked by boiling solutions of potash ; it is
not poisonous, and has marked antiseptic properties. Various salts are
described. The potassium salt, CH2(0Ph).C00K, crystallises in bril-
liant scales, "vrhich may be heated to 300° without melting or decom-
posing. The lime salt, 2[CHo(OPh).COO]2Ca.7HoO, crystallises in
long needles, moderately soluble in water, melting at 120°. The
barium salt crystallises with 3 mols. of water. The salts of the heavy
metals melt in hot water, and are therefore prepared with difficulty ;
none ai'e described in detail.
Methyl and ethyl phenoxyacetate are readily prepared by heating a
solution of the acid in methylic or ethylic alcohol, in a stream of
hydrochloric acid ; the former is an oily liquid, of somewhat pleasant
odour, boiling at 245°, and having a sp. gr. of I'lS at 17"o"; it is inso-
luble in water, and mixes in all proportions with alcohol, ether, and
carbon bisulphide. The ethyl salt boils at 2-51°, and has a sp. gr. of
1-1()4°.
Phenoxijacetamide, CH2(OPh).CONH2, is best prepared by mixing
1 vol. of ethyl phenoxyacetate with 2 vols, of aqueous ammonia. After
3 — 5 days, the amide crystallises out in rhombic tables, melting at
101"5", insoluble in cold water, slightly soluble in hot water, and easily
soluble in hot alcohol. By heating the amide with phosphoric anhy-
dride, jj/i!.ewoa;!/ace/«i^?"i7, CHo(OPh).CN, distils over mixed with phenol.
The nitrile is an oily, colourless liquid, boiling about 235 — 238", and
having a sp. gr. of 1"09 at 17'5°. Hydrogen sulphide acts on this
nitril with production of pheno^ei/acefothiaynide, CHo(OPh).CSNH.>,
which crystallises from alcohol in rhombic prisms, difficultly soluble in
water and cold alcohol ; easily soluble in hot alcohol.
Pfienoxyacetanilide, CH2(0Ph).C0NHPh, is produced by heating
equivalent weights of phenoxyacetic acid and aniline at 150", and
crystallising the product from hot alcohol ; it forms long needles
(m. p. 99°), insoluble in cold water, but easily soluble in hot alcohol.
Fuming nitric acid reacts readily with phenoxyacetic acid, but with-
out the production of a substituted nitro-compound ; the main product
of the action is dinitrophenol.
Or thonitrophenoxii acetic acid, CH2(O.C6H4.N02).COOH, may be pre-
pared by heating together sodium orthonitrophenolate with excess of
.sodium monochloracetate, dissolving the fused mass in water, precipi-
tating by addition of hydrochloric acid, and crystallising from hot water,
after filtration through animal charcoal. The acid is with difficulty
soluble in water, crystallising therefrom in regular octahedrons, which
melt at lo6'5°.
The salts of orthonitrophenoxyacetic acid resemble those of phenoxy-
acetic acid in crystalline form and solubility; the salts of the alkaline
earth metals of the nitro acid are somewhat more soluble, and those
of the heavy metals less soluble than the corresponding salts of phe-
noxyacetic acid. The sodium, barium, and copper salts of orthonitro-
phenoxyacetic acid are described.
Paranitrophenoxyacetic acid may be prepared by the same method as
?dO ABSTRACTS OF CHEMICAL PAPERS.
that used for preparing the ortho-acid, only substituting sodium para-
nitrophenolate for the ortho-compound. This acid crystallises in
microscopic forms, belonging either to the rhombic or to the mnno-
clinic system (m. p, IBS'"). The properties of the acid and its salts
resemble those of the ortho-acid.
By the action of reducing agents, paranitrophenoxyacetic acid
appears to yield an amido-acid, easily decomposible by water ; whilst
the ortho-acid yields an anhydride, C8H7N02 (m. p. 143 — 144°), analo-
gous to oxindole, which is obtained by the action of reducing agents
on the orthonitro-derivative of phenylacetic acid.
The action of bromine-water on a hot aqueous solution of phenoxy-
acetic acid appears to give rise to more than one isomeric compound. By
dropping bromine into a solution of ethyl phenoxyacetate in carbon
bisulphide, boiling the product with soda, decomposing with hydro-
chloric acid, and crystallising from hot water,
Mo7iobruinophenoxy acetic acid, CH3(O.C6H4Br).COOH, is obtained in
brilliant rhombic plates (m. p. 153 — 154°). This acid is scarcely
soluble in water, but is easily dissolved by alcohol. That the bromine
is substituted in the phenyl group is shown by the fact that boiling
with caustic alkali does not cause the bromine to be displaced by
hydroxyl. A few of the metallic salts and the ethyl salt of the acid
are described.
No phenoxybromacetic acid could be obtained by the direct action
of bromine on phenoxyacetic acid, even in sealed tubes at 150°.
M. M, P. M.
Action of Fused Alkalis on Aromatic Sulphonic Acids. By
P. Degenbr (/. pr. Chem. [2], 20, 300— 32u).— From the results of
the action of fused potash and soda on phenolorthosulphonic and ben-
zeuedisulphonic acids respectively, the author concludes that the
exchange of SO^H for OH is brought about at a lower temperature,
with a smaller quantity of alkali, and in shorter time by the use of
potash than of soda ; but if continued for a considerable time, the
difference between the actions of the alkalis becomes less. In many
reactions, the use of soda is preferable to that of potash, as the
secondary reactions which frequently occui* when the latter is used do
not take place. The difference between the action of soda and potash
is less marked in the replacement of SO3H by OH, than in reactions
which involve a more complete molecular decomposition, e.g., the pro-
duction of salicylic acid from phenoL M. M. P. M.
Sulphanilic Acid. By C. Laar (/. p-. Ckem. [2], 20, 242—267).
— Besides the ordinary rhombic crystals with 1 mol. of water, the
MUthor describes a monoclinic form of sulphanilic acid, which crystal-
lises from very dilute solutions with 2 raols. of water.
The crystalline forms of many metallic salts of the acid are de-
tailed. The sodium salt, CeHijNHOSUsNa + 2H2O, crystallises
from concentrated solutions in leaf-shaped crystals, and from dilute
solutions in plates, both belonging to the rhombic system,
OP . P . coPoo . coPoo . Poo.
ORGANIC CHEMISTRY. 321
The potassium salt, with l-^HoO, forms rhombic prisms ; the ammonium
salt also crystallises iu rhombic prisms, with 1^ mols. of water. The
barium s-alt, [C6H4(NH2).S03]2Ba + S^HoO ; rhombic prisms,
coPoo . coP . Poo ;
the cop^jer salt, [C6H4(]S'H2).S03']2Cn + 4HnO, does not give off watet-
at 100°. The aniline salt, [CeHjCN'HoJ.SOaHJo.CeH,]^, crystallises in
needles, and is dissociated on boiling with water. When the dry .sale
is heated to 150°, the aniline is i-emoved, and the free acid remains.
By the action of phosphorus pentachloi-ide on snlphanilic acid, under
dry benzene, smalt colom-less crystals are obtained, soluble in ether
and hot chlox-oform, and having the composition
(NH.POCy.CsHi.SOaCl.
This chloride is decomposed by ethyl or methyl alcohol, with forma-
tion of the ethyl or methyl salt of fjliosphanilidesulphonic acid,
PO(OC„H2„+02.NH.C6H4.SO3C„H2.+i.
Both salts are soluble in the ordinary solvents, with the exception of
carbon bisulphide and petroleum ether. The phosphaMilidesidplionir.
iMoride, mentioned above, is better prepai^ed by heating phosphorus
pentachloride with potas.sium sulphanilate on the water- bath, dissolving
in absolute alcohol, and precipitating with water. After purification,
the chloride forms small leaf-shaped crystals (m. p. 102°).
Ethyl phosphanilidesulphonate is decomposed bv boiling water, with
production of sulphanilic acid, alcohol, and ethyl phosphate.
An oily diazo-compound, which has not yet been further examined,
is produced by the action of nitrous acid on the same compound.
The action of phosphorus pentachloride on dibromosulphanilic acid
gives rise to a chloride which is decomposed by ethyl alcohol, in a
manner not exactly analogous to that noticed in the case of the
chloride of sulphanilic acid, inasmuch as the compound formed still
contains the group SOoCl, and has the formula
PO(OEt)o.NH.C6H2Br2.SO,Cl.*
But along with this chloride, small quantities of the efJn/l salt of
dihromophospUanilldesidphonic acid, PO(OEt)2.NH.C6H2Br;;.S03Et) are
produced.
When potassium dimethylsnlphanilate is heated with phosphorus
pentachloride, and alcohol is added, the product consists simply of the
ethyl salt of the original acid, i.e., of ethyl dimethylsnlphanilate,
NMe.iC6H4.S03Et. This compound is easily soluble in benzene, chloro-
form, and acetone, and moderately soluble in ether and carbon bisul-
phide ; it crystallises in small brilliant scales, which melt at 85°.
Barium dimethyhidphanilate, (NMei.CeHi.SOsj-iBa, crystallises in
needles with 3 mols. of water, OP . Pco . ooP, or in palates with
11 mols., OP . P; the latter form readily loses 8 mols. of water, and
changes into the former.
* The author belieyes this to be the first instance of an atomic compound contain-
ing eight different elements.
322 ABSTRACTS OF CHEMIC.VJL PAPERS.
Potassium sulphanilate is readily oxidised in the cold by an aqueous
solution ot potassium permanganate to potassium azophenyldisulphonate,
SOjK.CeHi.N : N.C6H,.S0:,K + 2iHoO, a salt which is but slightly
soluble in cold water, and seems to belong to the class of colouring
matter known as tropaolins. M. M. P. M.
Trimethylparamidobenzenesulphonic Acid. By P. Griess
(Ber., 12, 211(3 — 2117). — The author ])ropose3 the name of "betaines"
for a peculiar class of bases derived from the amido-acids of the ben-
zoic acid and fatty acid series by replacement of three atoms of hydro-
gen by methyl. Amido-acids which contain the SO3H group in place
of carboxyl, also yield similar bodies, one of which may be obtained
as follows: — Paramidobenzene-sulphonic acid is dissolved in a strong-
solution of potash, and after dilution with methyl alcohol, excess of
methyl iodide is added. The alcohol is next removed by distillation,
and the residue is mixed with a solution of iodine in hydriodic acid, by
which means the base is obtained as a periodide in the form of gold-
green tabular crystals. The periodide is decomposed by sulphuretted
hydrogen, the solution neutralised with ammonia, and evaporated until
it crystallises. The crystals thus obtained consist of brillianr, white,
four-sided plates, which dissolve readily in water, but are almost inso-
luble in alcohol, and completely insoluble in ether. They have an
extremely bitter taste and a neutral reaction. Trimethylparamido-
lienzcnesulphonic acid has probably the constitution expressed by the
formula CfiHi<^ o^ ^^0. It is a much weaker base than trimethyl-
amidobenzoic acid, inasmuch as it does not form simple salts with
acids ; but it forms a well characterised aurochloridc, and platino-
chloride, (CcH,.XMe3.S03.HCl)2PtCl4 + 8H,0. The latter crystallises
in thin, yellowish-red, hexagonal plates, which are readily soluble.
The new acid above described is decomposed when heated, and yields
a heavy, oily base, together with much carbonaceous residue.
^ r - G. T. A.
Phenyl-lactimide. By E. Posen (Annalen, 200, 97 — 99). — Araido-
hydrocinnamic acid (Annalen, 195, 143; this Journal, Abst., 1879,
378) cry^^tallises unchanged from dilute hydrochloric acid, but a
hydrochloride, PhCjH:,.NH2-C()011.1lCl, can be obtained by dissolving
the amido acid in warm hydrochloric acid diluted with its own bulk
of water, and pouring the solution into three times its valume of
fuming hydrochloric acid. The new compound is de])osited in glisten-
ing pri.sms which dissolve freely in water.
When amidohydi'ocinnamic acid is treated with a mi.xture of equal
volumes of water and sulphuric acid at 6U — 70°, it is converted into
NH ,NH
phenijladimide, PhCH.,.CH<( | , or CPhH<( ^CO. This substance
crystallises in silky needles (m. p. 146^), soluble in alcohol, ether,
carbon bisulphide, and hot water. Attemjits to prepare metallic
amidohvdrocinnaniatt'S were unsuccessful. W. C. W.
ORGANIC CHEMISTRY. 323
Constitution of Anthraquinone. By H. v. Peckmann (Ber., 12,
■^124 — 212y). — Following a method similar to that adopted by Graebe
iu determining the constitution of naphthalene {Annalen, 149, 20),
the author shows that in anthraquinone the pair of carbon-atoms is
combined with both of the benzene-groups in the ortho-position. Since
the oxyanthraqtiinones which contain hydroxj-l in one benzene-nucleus
yield on oxidation phthalic acid, it follows that in this reaction the
nucleus containing hydroxyl in place of hydrogen is destroyed, and.
that the other must contain the carbon pair in the ortho-position. For
the artho-position of the carbon pair in the other benzene group, a
proof was found by preparing an oxyanthraquinone which had under-
gone substitution in the benzene nucleus containing the two carbon-
atoms in the ortho-position, and obtaining from it by oxidation phtha-
lic acid, whilst still retaining the other benzene group. Orthobromo-
phthalic acid was first prepared and then converted by the action of
benzene and aluminium chloride into orthobromobenzoylbenzoic acid.
This acid contains bromine in place of hydrogen in the benzene-group
with which both the CO-groups are combined in the orcho-position.
The orthobromobenzoylbenzoic acid, when acted on by concentrated
sulphuric acid, yielded an orthobromanthraquinone, from which
phthalic acid was obtained by the action of nitric acid.
This orthobromanthraquinone by the action of potash is converted
into an oxyanthraquinone, having the same projjerties, except the
melting point (190°), as the erythroxyanthraquinone of Baeyer and
Caro (Ber., 7, 968). The two bodies were also found to give almost
identical results when examined by the spectroscope.
Since Liebermann obtained erythroxyanthraquinone (m. p. 190°) by
reduction of quinizarin, the hydroxyl must occupy the ortho-position
with respect to the ketone-group, and therefore the bromine-atom must
occupy the same position iu the bromanthraquinone above described.
G. T. A.
Action of Haloid Acids on Isoprene, Formation of Caout-
chouc. By G. BouCHARUAT (Conipt. rend., 89, 1117— 1120j. — Iso-
prene, obtained by the dry distillation of caoutchouc, combines with
hydrochloric acid gas to form tlie chloride C5H9CI (b. p. 86 — 91°,
sp. gr. 0"868 at 16°), which is converted by the action of moist silver
oxide into an alcohol boiling betwT'cn 120' and 1-30". The chloride
absorbs bromine vapour, forming the compound CsHgClBr;, which de-
composes on distillation. When isoprene is treated with concentrated
hydrochloric acid, a mixture of mono- and di-chlorides is formed,
together with a solid compound, which appears to be identical witii
caoutchouc. The dichloride, CsHsCL, boils between 145'' and 153*^',
and has a sp. gr. of 1-065 at 16°. A saturated solution of hydro-
bromio acid has a similar action on isoprene ; the monobromide,
GsHgBr, boils at 104 — 105° (sp. gr. l'17o at 15°), and combines with
2 atoms of bromine. The dibromide, CoHgBra, boils at 175 — 180", and
is heavier than water (sp. gr. 1"601 at 15°). When treated with potash,
it loses half its bromine, and gives rise to a liquid which boils at 110°.
The action of hvdriodic acid on isoprene appears to be analogous to
that of hydrochloric acid, but the prodw^ts of the reaction were not
obtained in a state of purity. W. C. W.
324 ABSTRACTS OF CHEMICAL PAPERS.
Relations of the Camphenes obtained from Borneol and
from Camphor. By J. Kaculer and F. Y. Sfitzer (Annalen, 200.
34Q — 36<J). — The authors having independently prepared hydrocarbons.
C10H16, the one from borneol chloride, dnHnCl, the other from cam-
phor dichloride, dnHieCl. (Annalen, 197, 86 and 126 resp.), have
jointly invef>tigated the question of their probable identity. The pre-
paration of the former, by decomposing the chloride with warm water,
has been several times repeated with uniformly the same result ; the
pure caraphene melts at ol — 52", and boils at 160 — 161° ; these points
are iinaffected by recrystallisation. From the higher fractions, a small
quantity of borneol was isolated : this is formed simultaneously with
the caraphene. The hydi-oohloride of the camphenc was prepared by
passing hydrochloric acid gas into its solution in anhydrous ether ; it
melts at 156 — 157°; a column of 201*7 mm. of its solution in ethyl
acetate (1 gram-molecule in 1,000 c.c.) caused a left-handed rotation
of 6"1°. It is decomposed by warm water, with formation of the
original caraphene, and a small quantity of borneol. Its properties
generally are those of borneol chloride. The hydrochloride of the
second caraphene was prepared in a similar manner; the product,
however, was in the first instance impure, the chlorine being 1^3 per
cent, below the theoretical, and this was not alte-i*ed by prolonged con-
tact with hydrochloric acid gas ; by recrystallisation from alcohol and
subsequent exposure in ethereal solution to the> gas, a hydrochloride
was obtained with the theoretical percentage of chlorine, melting at
153", and yielding, on decomposition with water, a camphene melting
at 51 "2° and boiling at 161°. A column of 1003 mm. of the molten
caraphene causes a right-handed rotation of only 24'', whereas that
prepared directly from camphor dichloride gives, under similar circum-
stances, a rotation of 50°.
The results may be summed up as follows : — The camphene, of
melting point 51 — 52", obtained from borneol chloride by decomposi-
tion with water and fractionation of the product, is the pure hydro-
carbon, C,nHif„ and yields directly, with hydrochloric acid, the pure
hydrochloride, CioHirHCI ; that obtained by the action of sodium on.
camphor dichloride is in the first instance mixed with a hydrocarbon
which does not combine with hydrochloric acid ; the hydrochloride
may be obtained pure by crystallisation, &c., and then yields on de-
composition a camphene melting at 51 — 52", which combines directly
with hydrochloric acid to form a pure product identical with the first-
named hydrochloride. It is therefore concluded that the camphenes
in question are identical.
The next point investigated was the constitutional relationship of
camphene hydrochloride to borneol. The hydrochloride was heated
with silver acetate and glacial acetic acid in a sealed tube at 70°; an
acetate was obtained identical with that prepared by Baubigny {Zeits.
Ghera., 1866, 408) and by Montgolfier {Avn. Chiin. Phys. [5], 14, 5). On
heating this with solid soda at 120 — 150°, a sublimate of pure borneol
was obtained ; the residue, on distillation with sulphuric acid, yielded
acetic acid. It appears, therefore, that camphene hydrochloride is
borneol chloride.
The formation of borneol in small quantity, which attends that of
ORGANIC CHEMISTRT. 325
camphene in the decomposition of borneol chloride by water, may be re-
ferred either to double decomposition between the constituents of the
two latter causing the replacement of CI by (OH), or to a hydration
of camphene under the influence of the hydrochloric acid simulta-
neously formed. Qualitative experiruents showed that camphene does,
in effect, yield borneol on heating with dilute acids, and the authors,
therefore, adopt the latter explanation.
The identity of the camphenes was borne out by the investigation
of the products wliich they yield on oxidation with chromic acid.
These were in both cases chiefly camphor, and in addition small quan-
tities of camphoric and camphoronic acids, together with acetic and
carbonic acids.
In conclusion, the authors observe with reference to the constitution
of camphene, that it is an unsaturated hydrocarbon containing the
atomic group peculiar to the camphor-group ; yielding, by addition of
oxygen, camphor, by addition of chlorine, camphor dichloride. (They
anticipate soon being able to furnish direct proof of the latter point.)
From the manner in which camphene is converted into camphor, it is
probable that the oxygen of the latter is not present in the form of a
CO-group, but rather that it is united b}^ a single aSinity to two
carbon-atoms. The reactions of camphor are most completely to be
expressed by a modified form of the formulae proposed by V. Meyer
and by Armstrong (Ber., 3, 121, and 11, 1698 resp.J, which the
authors intend shortly to publish. C. F. C.
Palmellin and Characin Extracted from Algae by Water.
By T. L. Phipson (Comjjt. rend., 89, 1078— 1079).— Xanthophyll (the
yellow colouring matter of leaves in autumn), chlorophyll, and palmel-
lin, may be respectively extracted from Palmella crtienta by successive
treatment with carbon bisulphide, alcohol, and water. The prepara-
tion of characin has already been described (this volume, 58).
w. c. w.
Coto-barks and their Characteristic Ingredients. By J.
JoBST and O. Hesse {AnnaJen, 199, 17 — 90). — Two kinds of coto-bark
are found in the market, both of which are exported from Bolivia :
the one which was first examined comes from the interior of Bolivia,
and from its resemblance to the true cinchona barks was called " Cin-
chona Coto." According to Wittstein, however, it would appear to be
derived from some plant belonging to the orders La'uracesB or Tereben-
thinaceae, rather than to the Rubiacese. The powder or tincture is
used in cases of diarrhoea and colic, also for neuralgia, rheumatism,
and gout. Another variety of coto-bark, snid to come from the shores
of the Mapiri, closely resembles the other in appearance, bnt its phy-
siological action is considerably weaker. It is called by the authors
" Paracoto-bark," and differs greatly from the true coto-bark in its
chemical nature, for alrhough piperon} lie acid is found in both (this
Journal, Abstr., 1878, 73oJ the cotoin and dicotoin contained in the
true coto-bark are absent in paracoto-bark, being replaced by paracoto'in,
hydrocotone, dibenzoylhydrocotone, leucotin, and oxyleurotin. As the
two barks very closely resemble one another in appearance, and are
sold under the common appellation of " coto-bark," the crystallised
VOL. xxxYiii. 2 a
^•2[] ABSTRACTS OF CHEMICAL PAPERS.
coto'in of commerce maTmfactnred from them necessarily varies greatly
m its physiological effects, according as it is prepared from the true or
false coto-bark or mixtures of the two.
Cotoin. — The method of preparing this compound, which is onlv
contained in true coto-bark, has already been described (this Journal,
1877, i, 480). Its melting point is 130°, and its solutions have no
action on polarised light. The results of the analyses of the substance
itself, and of the lead compound, correspond very closely with the
formula C22H,k06. The action of bromine in chloroform solution
gives rise to trihromocotnin, C'ioHisBrsOe ; this crystallises in yellow
prisms (m. p. 114°), almost insoluble in cold watei*, but easily soluble
in alcohol. Triacetylcoto'in, C.2H,5Ac306, is formed by the action of
acetic anhydride on cotoin at 170°: it forms large prisms (m. p. 94°)
easilv soluble in chloroform, in ether, and in hot alcohol. Benzoic
acid is formed when cotoin is heated witli concentrated hydrochloric
acid at 140°, also when it is fused with potash.
Bicoto'in, C44H:,40ii. — When the crude cotoin is treated with boiling
water, at first nothing but cotoin crystallises out from the cooled solu-
tion, but when the insoluble residue is treated again and again with
the mother-liquors, large plates make their appearance: these may be
to a great extent separated from the cotoin by means of a sieve which
retains the plates. When pure, it melts under boiling water, and is but
sparingly soluble in it ; by boiling with water, however, it appears to
be converted into cotoin. Dieotoin crystallises in lustrous, almost
colourless plates (m. p. 74 — 77°), easily soluble in alcohol, ether, and
chloroform.
Paracouihi, doHioOg. — This compound, which melts at 152°, has
already been described (this Journal, 1877, ii, 201). When bromine
is gradually added to a chloroform solution of paracotoin, it is at first
absorbed, with evolution of hydrobromic acid, but on continuing the
addition of bromine, a scarlet cry.stalline precipitate is formed, which,
on being dried between filter paper becomes yellow, whilst hydrobromic
acid continues to be given off. The analyses agi-ee with the formula,
CiteHjiBraOio, but it is probably a brominated derivative of paracotoin,
as when gently heated with potash-solution, it yields the characteristic
odour of paracoumarhydrin, a substance produced on decomposing
paracotoin itself with potash {loc. cit.). Paracotoic acid, as already
noticed, is produced by the action of baryta- water on paracotoin, but
may be more conveniently prepared by means of potash. The solution
is first treated with, ether to remove paracoumarhydrin, and the crude
paracotoic acid may then be precipitated with hydrochloric acid.
When pure, it melts at 108° ; its barium, calcium, lead, and silver salts
are yellow amorphous precipitates.
Lencofiii, C^uHsaOio (loc. cit.). — When leucotin is treated with bro-
mine in chloroform solution at the ordinary temperature, it yields
dibromohucntiii, CgiHaoBr.Om, crystallising in small white prisms
(m. p. 187°), very sparingly soluble even in boiling alcohol, more
soluble ill ether or chloroform. When gently heated with excess of
bromine in acelic acid solution for a long time, it is converted into
tetrabromoleucotin, C34B[:6Br40io (m. p. 157°).
Cotogenin, C14H14O5. — When leucotin is fused with potash, it gives
ORGANIC CHEMISTRY. 327
off hydrogen, and the product contains benzoic acid, and small quan-
tities of formic and protocatechuic acids, protocatechiiic aldehyde and
cotogenin. In order to extract the latter, the solution of the fused
mass is acidified with hydrochloric acid and treated with ether : the
ethereal solution is then agitated with soda to remove the acids, and
evaporated. The protocatechuic aldehyde and the cotogenin in the
crystalline residue are separated by means of alcohol, in which tl'je
last-named substance is bu^". spainngly soluble. After being purified
by crystallisation from boiling acetic acid, cotogenin melts at 210°,
l)nt at the same time turns brown and decomposes ; at a higher tem-
perature, pyrocatechol distils over. When fused with potash, it is
entirely decomposed into protocatechuic acid, whilst hydrogen is given
off" in abundance. Attempts to prepare a bromine-derivative of coto-
genin were unsuccessful.
Hi/drocotone, C18H24O6. — "When the fusion of the leucotin with potash
takes place in a retort, an oil distils over which solidifies on standino-.
The hydrocotone thus obtained may be easily purified by distillation or
by crystallisation from alcohol, in which it is readily soluble, as well as
in ether and in chloroform : it is but sparingly soluble in boiling water,
and almost insoluble in potash solution. It forms colourless prisms
(m. p. 48 — 49° ; b. p. 24.¥). When gently heated with nitric acid, it
is converted into dinitrocotone, C|RH2n(N02)iOB. This compound crys-
tallises in plates which explode when strongly heated. It dissolves in
water, alcohol, and concentrated nitric or hydrochloric acid with
magnificent blue colour. The author considers hydrocotone to be a
substance of the nature of a quinol, whilst dinitrocotone is probably a
dinitro-derivative of the corresponding quinone. The formation of
hydrocotone and cotogenin from leucotin may be represented by the
equation CaiHs.Om + 5H,0 = C,8Ho40b + CuHuOj + 2CH,02, whilst
the benzoic acid is produced thus : C34H30O11, + 4H2O = CisHojOs +
2C\H602 + 2CH2O2.
Oxylencotin, C34H320i2 (l.oc. cit.). — Protocatechuic acid is found
amongst the products of the action of concentrated hydrochloric acid
on oxyleucotin at 140°. Dibromoxylencotin., C34H3oBroOi2, and tetra-
hromoxi/le^icotin, C34H2BBr40i3, are colourless crystalline substances
melting at 190" and 159° respectively : they may be obtained by a
process similar to that described for the corresponding leucotin deri-
vatives. When oxyleucotin is fused with potash, it yields the same
products as leucotin.
Dihenzoylhyrh-ocotone, C32H33O8, is contained in the crude leucotin,
and is left undissolved on treating it with a small quantity of acetic
acid. When purified by crystallisation from hot acetic acid, it forms
colourless prisms (m. p. 113°) easily soluble in chloroform, ether, or
boiling alcohol. When fused with potash, it is in great part resolved
into hydrocotone and benzoic acid, iDut some cotogenin is produced at
the same time. Dihromodibenzoylhydrocotnne, C32Ho,|Br208, formed on
adding bromine to an acetic acid solution of dibenzoylhydrocotone,
crystallises in colourless prisms (m. p. 147°), and is converted into
tetrahromodihevzoylhydrocotfyne, C32H28Br408 (m. p. 84°), by treating it
with excess of bromine in chloroform solution.
Hydrocotoin, C15H14O4 (loc. cit.), yields two bromine derivatives, of
2 a 2
328 ABSTRACTS OF CHEMICAL PAPERS.
which monohromhydrocotoin, CisHisBrOi, crystalHses in pale yellow
needles and very short monoclinic prisms (m. p. 147^), whilst dibrom-
hydrocotoin, Ci5Hi2Br204, forms sulphur-yellow six-sided prisms (m. p.
95°). AcetylJtydrocofo'in, Ci5H,3Ac04, obtained by the action of acetic
anhydride on hydrocotoin at 150°, forms colourless crystals (m. p.
83°), which yield a crystalline monobrominated derivative (m. p. 166°).
When heated with potash, hydrocotoin yields hydrocotone and benzoic
acid.
An account of the piperonylic acid existing in paracoto-bark and of
the various derivatives obtained from it, has already appeared (this
Journal, Abstr., 1878, 733).
The etherenl oil obtained by distilling paracoto-bark with water
appears to differ somewhat from that existing in true coto-bark. Bj
fractional distillation, it was separated into five portions, two of which,
named a- and /3-paracotene, are hydrocarbons boiling at 160° and 170°
respectively : the analyses and the fact that they do not absorb hydro-
chloric acid, show that they are not terpenes. The other three por-
tions, a-, |8- and 7-paracotol are oxygenated oils boiling at 220°, 236°,
and 240° respectively. Full details of the physical properties and
action of reagents on these five compounds are given in the paper.
In conclusion, the authors state that the various constituents of the
coto-bai'ks may be arranged in three groups.
The first, or hydrocotone group, includes hydrocotone, which is a
hexhydric alcohol, dibenzoylhydrocotone, leucotin and oxyleucotin ;
the three last-named yield cotogeniu and hydrocotone when fused with
potash.
The second, or cotoin group, includes cotoin, dicotoin, and hydro-
cotoin, which arc distinguished by giving a dark brown-red coloration
with ferric chloride in alcoholic solution.
The third, or paracoto'in group, contains but two members, para-
cotoin and paracotoic acid. Both these compounds give a deep
yellow or brown-yellow coloration with concentrated nitric acid.
Besides these compounds, piperonylic acid, which had been already
prepared by synthesis, exists ready formed in the bark, and also
various oily bodies volatile in the vapour of water. C. E. G.
Cinchona-barks. By O. Hesse (^nnaZe^i, 200, 302—310).—
This is a continuation of previous researches (Annaleu, 185, 296)
into the characteristics and identity of the bark of a vaiiety of
cinchona, the cusco-bark. A comparative analysis of a specimen of
the Quinquina jaune de Cusco of Delondre and Bonchardt (obtained
from G. pelletierana), which the author found to contain 0"37 per cent,
cusconine, 0"24 ariciue, no traces of quinine, and 0'50 of an amorphous
alkaloid (in all 111 per cent, alkaloids), showed the close mutual
resemblance of these varieties. The amorphous alkaloid present
in the latter appears to be identical with the cusconidine previously
isolated by the author from the cusco-bark (Ber., 10, 2162). It is
.soluble in acetic acid, and is precipitated from the concentrated solu-
tion on the addition of nitric acid, as nitrate, in the form of brownish
drops.
irom a cusco-bark, presented some time since by J. E. Howaid
PHYSIOLOGICAL CHEMISTRY. 329
to the Pharmaceutical Society, and obtained according to Holmes,
from C. pelletierana, the author has isolated two new alkaloids,
which he terms cuscamine and cuscamidine. A determination
of the quantities of alkaloids present gave the following numbers :
0"21 per cent, aricine, 0"35 per cent, cusconidine, and 0v8 per cent, of
a mixture of the new alkaloids. These were separated as nitrates, bv
adding nitric acid in small quantity to their solution in dilute acetic
acid. They are separated from one another by taking advantage of
the difference of solubility of the oxalates, cuscamine oxalate beinf
comparatively insoluble in water. Cuscamine is readily isolated from
the oxalate, and after recrystallising from alcohol is obtained in colour-
less prisms (m. p. 218°). These are dissolved by sulphuric acid to a
yellowish solution, which changes to brown on warming; if molybdic
acid be also present, a bluish-green colour is developed, changing to
brown on warming, this again becoming violet-brown on cooling. The
crystals are dissolved by concentrated nitric acid to a yellow solution,
which does not alter on standing. The charactei'istics of several of the
compounds of this alkaloid are described.
Hydrochloride, gelatinous and transparent, easily soluble in water.
Aurochloride, a yellow amorphous precipitate.
PlatinocMoride, yellow and flocculent, difficultly soluble in water.
Sydrohromide crystallises in large colourless plates.
Hydriodide crystallises from hot aqueous solution in microscopic
needles.
Nitrate crystallises in needles which are almost insoluble in water.
Sulphate crystallises in needles, the hydrogen sulphate in prisms.
Oxalate crystallises in white needles, which are freely soluble in hot
water, only slightly in cold.
The second alkaloid, cuscamidine, closely resembles cuscamine in
its properties, the only important difference between them being that
the former is precipitated by nitric acid from dilute, cuscamidine only
from its concentrated solution.
The species of cinchona, C pelletierana, from which the above alka-
loids are obtained, has the additional characteristic of yielding neither
quinine, cinchonine, quinamine, nor paricine, and is therefore to be
regarded as extraordinary. The author suggests that in the classiti-
cation of the cinchona group, regard should be paid to chemical as
well as morphological characteristics. C. f . C.
Physiological Chemistry.
Nutritive Value of Grass at Various Stages of Growth. By
E. V. Wolff and Others {Bied. Centr., 187U, 7oG — 741). — The grass
was cut three times in the early summer, in the years 1874 and 1877 ;
the first cutting took place about the middle of May, the second at the
beginning and the third at the end of June. The second cutting
appeared to give the best results in the case of the animals experi-
330 ABSTRACTS OF CHEMICAL PAPERS.
merited upon, namely, sheep and horses ; and as a rule it was found
that ;nore nitrogenous matter was excreted by the latter than by the
former. J. K. C.
Nutritive Value of Asparagine. By H. Weiske and Others
(Bied. Ceutr., 1879, '/44 — 74i>). — Asparagine when given in conjunc-
tion with glue, was found to support life in the case of rabbits and
sheep, the latter digesting about twelve per cent, of the nitrogen.
J. K. C.
Digestive Power of Geese for Fibrin. By H. Weiske (Landw.
VersacJis.-Stat., 24, "ill — 213). — Geese, according to the author's former
researches, are not able to digest the fibrin of dandelion or horsetail.
In order to confirm this result, analyses were made of the fibrin of
the food and of the faeces, showing the composition to have remained
unaltered. J. K. C.
Ptyalin and Diastase. By T. Defresne (Compt. rend., 89, 1070).
— Ptyalin converts starch into sugar in presence of impure gastric
juice, as rapidly as it does in the mouth. Its action is, however, sus-
pended by pure gastric juice, but on passing into the duodenum the
ptyalin again becomes active. Diastase on the other hand is com-
]iletely deprived of its power of converting starch into sugar, by hydro-
chloric acid, or by pure gastric juice. W. C. W.
Carbonic Anhydride from Muscle. By R. Stintzing (Pfluger's
Archiv. f. Phi/s., 20, 189 — 200). — Muscle of rabbits was employed.
Every precaution was taken in the experiments, which were conducted
by passing either air or nitrogen through boiling" water containing
the muscle. When air was employed 18"3 per cent., by volume, of
carbonic anhydride was obtained as the mean of several experiments,
and 15'8 per cent, when nitrogen was used. Mean of all experiments
= 17 2. M. M. P. M.
Milk-secretion and the Amount of Fat in Milk. By W.
Fleischmaxn and P. Vieth (Luiida-.-Versuchs. Stid., 24, 81 — 97). —
The absence of an extended series of such observations npon a large
number of cattle induced the authors to avail themselves of an oppor-
tunity of making and recording certain investigations upon the herd
of Count von Schiefien, consisting of 119 cows. They observed and
registered the daily yield of milk, the percentage of fat, the specific
gravity, and the difference between the morning and evening milkings,
with which they combined the results of a change of fodder and general
treatment. Their observations extended over a whole year, and should
be of value to students in this branch of chemistry.
The herd was of the dun- red Mecklenburg breed; their average
weight during the stall-feeding season being 4.53'5 kilos. Taking into
account their dry period, a mean of 55 days per year for each cow, the
milk production of the whole herd was 2582"34 kilos, each, or ignoring
their dry time, the whole number, year in year out, averaged 2191*73
kilos, each animal, equal to 569 times its own living weight.
The winter stall-feeding lasted from the commencement of the
PHYSIOLOGICAL CHEMIbTRY. o31
observations (Isfc January, 1878) until loth May; pasturag^e upon, the
town commons, not very good land, commenced on 16tli Mav and con-
tinued to 17tli July, when the cattle were put upon stubble and after-
grass; on loth October they were again housed, and were stall-fed
until the authors ceased their record. Their daily food from 1st January
to 5th March consisted of 12 kilos, of chopped fodder, viz., one-fifth
clover hay, one-tifth meadow hay, three-fifths oat and barley straw;
together with 0875 kilo, long oaten straw, I kilo, wheat bran, 1 kilo,
cocoa cake. The same rations were continued to loth May, with the
single addition of 0'375 of fieshraeal ; from loth October to 31st
December the rations consisted of 4'165 clover hay, l"7o meadow hay.
5"985 oaten straw, all long, | kilo, cocoanut cake, -^ kilo, rye meal ;
the hay was of good quality, the straw had been hand threshed, and of
course contained some grains of corn.
The herd had an epidemic of cow-pox from the middle of September
until the beginning of November, every cow being more or less affected.
During its prevalence, the milk fell off very considerably, those cows
which were only slightly affected by the disease did not show any
marked departure from the normal butter or cheese produce, but the
skim milk and cheese made during this time suffered from not ripen-
ing. The milbings took place with great regularity at 5 o'clock
morning and evening, and it was the custom of the dairy to exactly
weigh the milk ; the samples of 60 to 80 c.c. were carefully drawn
from the dairy receptacles containing about 100 kilos, of well
mixed milk, the general determinations were only made weekly,
double experiments being generally made. Particular search was
made for the brownish substance first extracted from milk by ether,
by Mannetti and Musso {Zeitschr. Anal. Chem., 16, 397).
The subjoined table shows the influence of the fodder and changes
of location ; the average of the evening shows a higher sp. gr. and
fat than the morning milk, which, however, is larger in quantity,
except during the third period, when the days were longest ; the pro-
jxirtion of fats in the evening yield oscillated within wider limits
than in the morning ; from March to July the morning milk was
richer in fats than in the evening, being the period of the greatest
activity of the lacteal glands, which fell partly in the floshmeal and
partly in the grazing periods. Search was made for the brown sub-
stance in every determination ; it was, however, found only five times
in the morning and eight times in the evening ; from other experiments
the authors believe it to exist in considerable quantities iu buttermilk
to as large a proportion as 2'0o3 of the total weight.
The experiments were to be continued in 1879, and a report is pro-
mised.
332
ABSTRACTS OF CHEMICAL PAPERS.
Periods.
SiJecific gravity.
Percentage of fat.
Remarks.
Morning.
Evening.
Morning.
Evening.
Dec. 30, 1877, to
irar. 5, 1878
Mar. 6 to May 15
May 16 to July 16
July 17 to Oct. 14
Oct. 15 to Dec. 31
1 -0311
1 -0311
1 -0319
1 -0319
1 0318
1 -0314
1 0316
1 -0318
10321
1 -0321
3-387
3 373
3-314
3-341
3-460
3-489
3-365
3 145
3-450
3-627
Ordinary stall-feeding.
Addition of fleshmeal.
Pasturage on commons.
Pasturage on clover after-
grass.
Stall-feeding.
Day's average. .
1 -0317
3-395
Periods.
Milk per cow.
Fat per cow.
Remarks.
Morning.
Evening.
Morning.
Evening.
Dec. 30, 1877, to
Mar. 5, 1878
Mar. 6 to May 15
May 16 to July 16
July 17 to Oct. 14
Oct. 15 to Dec. 31
Kilos.
3-543
4-013
4-285
3-357
2-648
Kilos.
3-304
3 -854
4-393
3-26S
2-469
Kilos.
0-120
0 136
0 143
0 112
0 092
Kilos.
0 115
0-129
0-138
0-112
0-090
Ordinary stall-feeding.
Addition of fleshmeal.
Pasturage on commons.
Pasturage on clover after-
grass.
Stall-feeding.
Day's average. .
7-091
0-236
J. F.
Abnormal Composition of Human Milk. By C. Marchand
(Bied. Centr., 1872, 7G*J — -770). — According to the author, the usual
composition of human milk is as follows : — butter, 36-8 : lactose, 71'1 ;
proteiu, 17; salts, 2-04, and water 873 parts per thousand ; when the
amount of butter rises to above 52 parts, the milk is injurious to the
child. The quantity of protein, which is much less than in cow's milk,
cannot be exceeded without ill effects. J. K. C.
Occurrence of a Reducing Substance in the Urine of
Herbivorous Animals. By B. Dehmel (Landw. Versuchs.-Stat., 24,
44 — 48). — These experiments were undertaken in consequence of the
isolation, by Hofmeister, and afterwards by Kaltenbach, of a re-
ducing substance in the urine of recently confined women suffering
from milk-fever, this substance after several recrystallisations giving
the reactions of milk-sugar. It was therefore thought desirable to
ascertain if a stoppage of milk caused the same effect in animals. A
goat which produced daily 5 litres was left unmilked for some days
until a decided suppression of milk was obtained ; the urine col-
lected at intervals of 14 — 24 hours, each day's collection being sub-
PHYSIOLOGICAL CHEMISTRY. 333
mitted to examination with the result of finding an amount of the
.substance, which calculated as milk-sugar gave in proportion per 1,000
parts : — first day's sample, 0492 ; the second day's, 0"401 ; the third,
0'231. The substance, after drying over sulphuric acid, appeared as a
glassy yellowish mass without any trace of crystalline structure. Sub-
jected to dialysis the reducing body passed freely into the dialysate,
and on again evaporating this liquid, the same vitreous amorphous
substance was reproduced. In order to compare the results with the
kidney secretions of a non-milk-produciug aninial, the urine of an
ordinary wether sheep was collected and treated in the same way,
with the result of obtaining on the first day a proportion per 1,000 of
0"137 ; at the end of the second 0'124 of the substance reckoned as
milk-sugar.
The quantity found in the urine of the goat in this case was trifling,
and does not come near the amount obtained by Hofmeister from the
woman's urine ; the amount found in the milk-producing animal at the
beginning of the experiment was, however, about four times that
found in the male animal, but at the end of the third day it was
not double.
The author is not certain that the substance is milk-sugar ; he only
considers it proved that it is a strongly reducing dextrorotatory sub-
stance. J. F.
Analysis of Concretions taken from an Abscess on the
Jawbone of a Horse. By G. Thoms (Landw. Versuchs.-Stat.,
24, 4y). — The concretions were of irregular form, of a whitish colour,
with a red-brown shade of blood corpuscles ; in one instance they had
formed round a particle of straw, so that the author concludes that
the abscess and concretions were caused by a wound sustained by the
animal in taking its food. The principal constituent was calcium
carbonate. J. F.
Action of Dehydrating Agents on the Crystalline Lens of
the Eye. By E. Heubel {Pjiwjers Arch. f. Phys., 20, 114—188).—
The general result arrived at by the author is that cataract may be
artificially produced in frogs, and also in warm-blooded animals, by
the introduction into the eye of substances which act as dehydrating
agents, and that the action of these bodies is physical, depending as it
does on a process of osmose between the saline liquid in the aqueous
humour and vitreous body, and the water in the lens, whereby the
amount of the latter is reduced, whilst simultaneously a small quantity
of the salt injected finds its way into the lens. The action is confined
to the eye itself, and is not, as supposed by Guttmann, an action on
the general organism. A list is given of a large number of potassium
and sodium salts, &c., which cause cataract if injected into the eye of
the frog or rabbit. Many sodium salts produce cataract when injected
under the skin, while other salts do not act in this way under the same
conditions. The author explains this by the facts that sodium salts are
not readily expelled from the blood, because their i-ate of diiFasion is
comparatively low, and that their dehydrating action is not rapid ;
these salts therefore eventually find their way to the eye in a state in
334 ABSTRACTS OP CHEMICAL PAPERS.
which they are still capable of withdrawing water from the lens.
Very many physiological details are given in the original, and the
results of other workers are discussed at length. The author thinks
that cataract in the human subject is cau.sed by the presence in the
aqueous humour and vitreous body of an excess of mineral matter
which reacts on the lens and diminishes the amount of water therein.
M. M. P. M.
Chemistry of Vegetable Physiology aud Agriculture.
The Butyric Ferment f Bacillus Amylobacter) in the Car-
boniferous Period. By P. v. Tieghem (GotiqjL rend., 89, 1102—
1104). — Bacillus amiilohacter is soon developed when fragments of the
young roots of cypress or yew are immersed in water. It attacks the
tissues and cellular membranes of the roots, dissolving the cellulose
which undergoes butyric fermentation, and finally leaving nothing
but the cuticle and the vessels. The different stages of development
of the bacillus naay be traced in the interior of the destroyed organ,
from the slender threads in a state of active division to the free spores
floating in the liquid which tills the space once occupied by the cells.
A microscopical examination of the numerous rootlets of coniferas.
found in the fossil state in the coal measures of St. Etienne, exhibits
visible traces of the ravages committed by the Bacillus ann/lobacter.
w. c. w.
Formation of Vinegar by Bacteria. By E. Wurm (Dinyl.
]iolijt. J., 235, 22-5). — The author lias investigated this matter, and
his results prove, without doubt, that an active formation of vinegar
from alcohol is obtained by means of Mycoderma aceti {Bacterium
■iiiycodemui — Colin), thus supporting Pasteur's view. The author
then discusses the practical details of the process given by Pasteur,
and compares the process with others. J. T.
Starch-altering Ferments in Plants. By J. Baranktzky (Bied.
Centr., 18?9, 790 — 791). — Ferments were obtained from the germinat-
ing seeds of many plants and their action on starch examined. In
many cases it was found possible to convert 70 per cent, of the starch
into glucose. The author is of opinion that the starcti is first con-
verted into dextrin alone, and not into dextrin and glucose together.
J. K. C.
Organisms in Beet Sap. By L. Cienkowski (Beid. Gent., 1879,
767). — The bodies known as " frogspawn," which make their appear-
ance after a time in the sap of beetroot, prove on microscopic exami-
nation to be a species of bacterium, called by the author Ascococcus
Bilrothii. J. K. C.
Carbonic Acid in the Air. By Makie-Davy (Compt. rend., 90,
32— o5). — An exumiiiatiou of the determinations of the amount of
VEGET-LBLE PHYSIOLOGY AXD AGRICULTURE. 835
carbonic anbydride iu tbe air, wbicb bave been made daily during' tbe
last four years at Montsouris, seems to sbow that tbe best crops
bave been produced iu tbose years wben tbe amount of carbonic anhy-
dride has been below tbe average. Tbe carbonic anhydride varies in-
versely with clearness of the sky. and is influenced by the oscillations
of the great equatorial atmosphei'ie currents. W. C. W.
Respirative Power of Marsh and Water Plants. By E. Frev-
liEKci {Utid. Centr., IbTy, 7-i5 — 75u;. — It is a well-known fact that
these plants are able to thrive in media which contain little or no
oxygen. They are all very poor in nitrogen, and tbe author has
shown by a number of experiments that this latter property accounts
for the former. His investigations prove that the respirative power
of plants varies with the amount of nitrogen they consume, and this,
taken in conjunction with the fact that water plants contain large air
chambers which do not often need refilling, accounts for their being-
able to exist in media which contain very little oxvgen.
J. K. C.
Influence of Nutritive Material on the Transpiration of
Plants. By A. Burgeestein {Bied. Centr., 1879, 7-50— 752).— The
author shows that plants transpire more when placed in a 0"2 per
cent, solution of any nutritive salt than in pure water alone, but that
the transpiration diminishes as the percentage increases, also that if
the 0'2 per cent, be made up of more than one salt the transpiration is
less than in pure water. J. K. C.
Influence of Salicylic Acid and other Bodies on Germina-
tion. By E. Meckel {Bied. Centr., 1S7L', 789). — Small doses of sali-
cylic acid appear to have a favourable influence on the gennination of
.seeds, whereas phenol and thymol have an opposite, although not a
lasting effect. J. K. C.
D
Passage of Plant-material in Seedlings. By W. Detmer
(Bied. Centr., 1879, 788 — 789). — Glucose by itself can pass only fi-om
cell to cell, and must enter into some combination before being able to
pass through the septum of the plasma. Vegetable casein is insoluble
in water, but is rendered soluble by organic acids and neutral alkaline
phosphates. J. K. C.
Course of the Nitrogen and Mineral Constituents in the
Development of the Early Shoots. By J. Schroder {Bled. Centr.,
1879, 7o2 — 7o4). — -It was found that from the oth of April to tbe 18th
of May the axial organs of the plants under investigation bad lost a
great quantity of their nitrogen and mineral contents, which had
passed into the young shoots. In the cases of phosphoric acid, the
loss was greatest, amounting to nearly 50 per cent. ; nearly one-third
of the potash, and more than one-fourth of the magnesia and nitrogen
had also been given up. The amount of lime and silica was, however,
greater at the end than the beginning of the period under observation,
and as some at least bad passed into the shoots, the I'oots must have
been more active in absorbing these constituents. J. K. C.
336
ABSTRACTS OF CHEMIC.VL PAPERS.
Development of Oats. By P. Deherain and Nantibr (Bled.
Centr., 187\), 765 — 766). — Oats grown ou land which had not been
manured since 1875, showed a great falling off in the percentage of
nitrogen, 3*12 per cent, of nitrogenous substances being found instead
of 8 or 9 per cent, as usually obtained. With respect to the loss of
weight which the plants undergo at the ripening period, the authors
express their opinion that it is proportionate to the goodness of the
crop. J. K. C.
Influence of the Leaves on the Production of Sugar in the
Beet. By B. CorExVwixder and Gr. Contamine {Bied. Centr., 1879,
792). — The leaves of the beetroot contain small quantities of glucose,
and those roots which have well-developed leaves are the richest in
sugar.
J. K. C.
Ripening of Grapes. By C. Portele {Bied. Centr., 1879, 758 —
764; comp. this volume, p. 178). — The chief object of this series of
investigations was to ascertain the changes which the acids of the
grape undei-go during the ripening process. Examinations were made
of the must and aqueous extract of the Negrara grape at various times
from the 26th of July to the 21st of October, 1878. The results show
that the total quantity of free acid in the must and aqueous extract
increases until the grapes begin to soften, and then regularly diminishes.
The tannic acid disappears altogether in the must, but not entirely in
the aqueous extract, as it is still present in the skins and seeds. The
free tartaric acid, from the time the berries begin to soften, gradually
diminishes, and finally disappears when the grapes are fully ripe.
Malic acid is still present in the ripe berries, and then forms two-thirds
of the total free acid : it is not found in the combined state. Sulphuric
acid and phosphoric acid are present in the ash in sufficient quantity
to combine with the lime and magnesia, whilst potash is found in
excess of the amount required for the cream of tartar. The following
table gives the weight in grams of the various constituents in lOU
berries plucked at different times : —
2Gtli July
tJth „ ■ ....
16rh „
12tli August
23rd „
31st „
9th September
28th
12th October
21st
Siijrar.
0 16
0-29
0-41
1-64
1(3 -00
21-70
28-60
31-20
38-20
38-30
Precipitate
with
alcohoL
0-32
-65
-59
•08
•15
•16
•28
•36
-67
Insoluble
in water.
119
1-80
3 02
5-28
-68
•27
•45
-60
-96
7-45
Total
free acid
calculated
as tartaric.
0-79
-14
•09
•40
51
•12
•83
•54
•48
•03
Free
tartaric
acid.
31
41
78
81
65
30
25
04
02
VEGETABLE PHYSIOLOGY AXD AGRICULTURE.
30 —
Malic acid found.
Total
Cream of
tartar.
Tartaric
acid.
free and
Directly.
Indirectly.
combined
tartaric
acid.
''6th July
0-19
0-23
0 35
0-31
0 -46
fith '
0
0
0
27
13
17
06
0-48
0-39
0-68
0-75
0 -90
2-17
0-45
0 -92
2 00
113
0-61
1 fit h ,
1 -12
12th August
23rd „
119
1-49
31st „
18
0-82
119
1-04
1-24
9tli September
28th „
25
0-81
0-70
0-98
0-86
0 -8(1
0 -08
1-24
119
12th October
1 -53
0-79
0-73
0 00
1-24
2l3t „
i-:7
0-79
0-48
0-20
1-25
The grapes gathered on the 2Gth of July were from a very backward
plant.
It appears from the above table, that the total quantity of tartaric
acid remained pretty constant after the berries began to soften, the
free acid being gradually neutralised by the pota.sh, and thus dis-
appearing.
Experiments on the after-ripening of grapes showed that the amount
of sugar and tartaric acid in the berries remained constant, unless
kept until decomposition set in : the malic acid, however, diminished
in the same manner in the case of unripe grapes as if they were still
attached to the vine stock. J- K. C.
Growth of Plants in Artificial Solutions. By F. Farskt (Bied.
Centr., 1879, 6*^9 — 671). — The conclusions which the author draws
ffom his experiments on the replacement of potash by soda in the
plant, and the influence of various substances on the growth of plants,
such as chlorine, chloride of calcium, &c., agree in all respects with
former investigations. J. K. C.
Formation of Fat in the Growth of Fungi. By C. v. N.Kgeli
and 0. LoEW (-/. 2^''- Chem. [2], 20. 1»7 — 114). — Previous investiga-
tions of the phenomenon of the foj'mation of fat in vegetable cells
have established the following points : — That it is a secretion, and not
a product of fermentation or other action external to the life of the
cell ; that it is formed in quantity varying with the activity of the
growth, and of the oxygen respiration of the plant. On the chemistry
of the process, especially in respect of the proximate sources of this
product, but little light has been thrown. The fact that the starch
which is present in the immature condition, e.g., of the rape seed, is
replaced in the mature condition by oil, has been regarded as the result
of the conversion of the carbohydrates into fat ; this conclusion is,
however, unwarranted. There is weightier evidence of the origin of
fat in the splitting up of cell proteids in the cells of penicillium and
other fun^i which are proteid in the earlier stnges, and contain abun-
dance of fat at later periods ; the development of the latter is observed
838
ABSTRACTS OF CHEMICAL PAPERS.
to occur iin.ri passu with a loss of proteids ; and since the cell- wall
often undergoes considerable increase during the same periods, i.e.,
carbohvdrates are secreted, a causal connection between the former
phenomena is extremely probable. The relation of fat formation to
the nutrition of the plant is obscure, and throws no light on the
problem ; plants nourished with albuminoids evince a scarcely more
active fat secretion than those fed on non-nitrogenous organic bodies
(suo-ar, mannitol, glycerol, &c.), together with ammonia or nitric acid.
The investigation of these and other points bearing on the question, is
the purpose of the following experimental work : —
I. To determine the quantitative relations between the matter con-
sumed as food, and that elaborated both in the aggregate, as cells with
their contents and as fat.
Penicillium was selected as a simple cellular structure. The spores
were sown in solutions (1 — 3 per cent.) of the several food-stuffs con-
taining a sufficient quantity of ash constituents (K2H.P04.MgSOi and
CaCL), and in addition 0"5 — 1 per cent, of free phosphoric acid, the
presence of which is fatal to schizomycetes. The solutions were placed
in flasks loosely closed with cotton wool, and agitated from time to
time. After the expiration of several weeks the cells were filtered off,
dried at 100°, and weighed ; the filtrate evaporated and the residue
weio-hed. The amount of organic matter consumed is the weight
orio-mally present less that ol^ the residue. The fat was determined
by weighing as fatty acid, after destroying the cell- walls with hydro-
chloric acid. The results are enumerated in the table (p. 339).
The conditions of gi-owth, temperature, access of air, &c., were kept
as constant and uniform as possible, so that those experiments in
which the degree of concentration of the nutrient solution is the same
may be regarded as strictly comparable.
In a second series the secretion of fat was more closely investigated
in relation to nutrition by sugar and tartaric acid plus inorganic
nitroo-en on the one hand, and albumin, soluble and insoluble, on the
other. The duration of the experiment was two months ; at the end
of this period the total growth of the penicillium and the fatty acids
seci-eted by the cells were in each case determined. The details are
tabulated below : —
Nutrient solution.
(a.) 500 c.c. water, 5 grains ammonium tartrate, 5 grams
tartaric acid
(&.) 500 c.c. water, 50 grams sugar, 0 5 phosphoric acid,
5 grams potassium nitrate, 2 grams nitric acid
(c.) 300 c.c. water, 15 grams sugar, 3 grams ammonium
tartrate, 3 grams tartaric acid
(d.) 300 grams water, 3 grams peptone, 2 grams pliosphorie
acid
(p.) 300 c.c. water, 3 albumin, 2 piiosphoric acid
(/.) 300 c.c. water, 3 albumin (insol.), 2 phosphoric acid . .
Fat acids
per cent.
of dry
cells.
8-08
7-12
12-35
7-32
8-79
0-53
VEGETABLE PHYSIOLOGY AXD AGRICULTURE.
339
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340
ABSTRACTS OF CHEMICAL PAPERS.
(The solutions contained in addition, O'lOO per cent. K2H.PO4,
0-01(3 MgSOi, 0-005 CaCIa, 0-017 (NH4),S0, in each case.)
In the case of (c) the residual sugar and tartaric acid were esti-
mated in the filtrate; of the latter there remained 13-9 percent, of the
original weight, whereas of the sugar, although added in so much
larger quantity, only 6 per cent, remained. No products of oxidation
or fermentation could be detected.
II. To determine the formation of fat in relation to a varying suppl}'
of cane-sugar, that of nitrogen and the necessary inorganic salts being
kept constant.
The solutions (1,000 c.c.) contained in each of the six experiments,
0-7 gram (NHij^SOi; 2 grams K2H.PO4 : 0-3 gram MgSOi; 0-1
gram CaClo ; and 0-9 gram phosphoric acid. The duration of growth
was six weeks. The quantities of sugar and other details are given in
the table : —
Sugar
per cent, of
nutrient
solution.
(^'■) I 0-1
(A.) 0-5
(r:) 1-0
(d.) 5-0
('.) 10-0
(/.) I 15-0
Total
growth.
0-210
0-305
0-230
0-772
2-700
2-215
Fat acids
per cent, of
cells.
Sugar
assimilated
per cent, of
total con-
sumption.
15-84
14 -36
23 13
34-3
n 34-;
8-8
The increase of yield, it will be seen, has no constant relation to the
increase of concentration of the sugar solution. Comparison of (a) and
(/") in respect to the quantity of sugar burned, shows that this increases
with the concenti-ation. As regards the inversion of sugar during the
growth of penicillium, the authors found that in a 1 per cent, solution
the growing plant caused the inversion of GO per cent, of its weight
(estimated as dry) of sugar in eighteen hours.
III. To investigate the " degradation " (" involution ") of penicillium
in relaticm to the fatty contents of the cells, one-fourth of the product
of growth in a solution containing sugar (2 per cent.) and p.lbumin
(1 per cent.) was analysed in the fresh state (after drying) ; the re-
mainder was placed in phosphoric acid solution (1 per cent.), and set
aside for four weeks : the originally compact mass of hyphse was by
this time resolved into loose threads ; these were filtered off, dried, and
weighed, and found to represent about 15 per cent, of the original
weight.
The following constituents were estimated ; —
VEGETABLE PHYSIOLOGY AXD AGRICULTURE. 341
Before After
degradation. degradation.
Albumin 427 IGS
Fat 18 5 50-5
Cellulose, &c 388 33-0
100-0 100-0
proving a considerable formation of fat at the expense of prote'ids.
The only general conclusion the authors at present draw from their
results is, a classifieation of the nutrient matters investigated, in an
ascending series representing the successive degrees in which they
favourably influence the formation of fat, viz. (passing from those less
to the more favourable), (1) ammonium acetate; (2) ammonium tar-
trate and succinate and asparagine ; (3) leucine ; (4) peptone ; (5)
ammonium tartrate, plus sugar; (6) leucine, plus sugar ; (7) peptone,
plus sugar.
The problem of the proximate origin of fats remains very much in
statu quo. C. F. C.
Formation of Vegetable Albumin. By A. Emmerlixg (Landw.
Versuchs.-Stat., 24, 113 — 160). — This long paper describes the
author's investigations into the presence of albumin in the roots,
stalks, leaves, blossom.s, and seeds of the Vicia faba mnj., or common
buff bean, with the view of throwing light upon the interesting and
little known question of the production of prote'id substances in plants,
and how the nitrates and ammonium salts from the soil on the one
side, and from decomposed nitrogenous organic substances on the
other, are assimilated by the growing vegetable.
The author's experiments are very numerous, and show most careful
and painstaking observation; his apparatus, of which he gives drawings,
are eminently adapted to the purposes of his investigation, but they
contain no new principle ; and his results, althouo-h most interesting,
being chiefly of a negative character, will be sufliciently understood
From the summary with which he concludes the paper.
He finds the nitric acid taken up from the soil abundant in the
roots and stems, gradually becoming less, until in the buds, blossoms,
and fruits it is seldom to be met with, and he believes that the leaves
are the particular organs charged with its transformation into albumi-
noids ; that the most active agent is not nitrogen in the form of
ammonium salts. As he has found the latter most frequently in the
leaves from which the more active nitric compound had already dis-
appeared, he thinks that had the ammonium salts been the most active
agents, they would have been as.similated at an earlier stage. He
thinks the absorbed nitrates, which are very unstable, are acted upon
by the vegetable organic acids, which combine with the lime of the salt,
and free the nitrogen, but he admits that his researches have not
advanced our knowledge of the matter greatly, the only certain con-
clusion being that albumin is the result of the end reactions, of which
we do not know the steps. The presence and distribntion of the
amides appear to point to a step in the process, as their distribution
seems to follow a simple law, which is that those parts of the plant
VOL. XXXVIII. 2 b
342 ABSTRACTS OF CHEMICAL PAPERS.
which are of quickest growth, and which increase their bulk most
rapidlr, are invariably richest in amides. The young leaves contain
more than old ones, the stem than the root. More particularly are
the buds, sprouts, and blossoms rich in this product, and where new
cells are about to be built up, there is previously collected upon the
spot an accumulation of material for their construction, not only of the
matters required to form their membranous portions, but of proto-
plasmic matter; it appears certain that the amides form the nourish-
ment of the young cells ; even the flower-buds accumulate these sub-
stances for the nourishment of the future seeds, but the manner in
which the process is carried out still remains unknown. J. F.
Leucine and Tyrosine in Potatoes. By E. Schclze and
J. Barbieri (Lanchv. Versuchs.-Stat., 24. 167 — 160). — The purified
alcoholic extract from potatoes, when allowed to stand, was found to
deposit after some time a crystalline substance, which on further
examination proved to be impiire tyrosine, giving all the characteristic
reactions of that substance. The mother-liquor on further evaporation,
and standing for a few days, yielded a crystalline crust of leucine.
J. K. C.
Amount of Oil in Grass-seeds, and its Relation to their Germ-
ination. By H. Breiuolz (Bied. Centr., IbTV, 756 — 757). — The
various kinds of seeds examined contained oil in quantities varying
from 0*8 to 158 per cent. Two hundred specimens of each sort were
sown under the same conditions, and their germinating power and
quickness of growth observed, the former of which, however, was found
to bear no constant relation to the richness of the seeds in oil, whilst
qiiickness of growth after a certain period was found to be to some
extent dependent on the quantity of oil present. J. K. C.
Analysis of Parsnips. By B. Coeexwinder and G. Contamine
(Bied. Centr., 1879, 794). The following is the result of the analy-
sis : —
Water 79-34
Kitrogenous substances .... 2"36
Crystallisable sugar 8'25
Grape-sugar 1'57
Fibre 20 '
Starch I'O
Pectin, &c 4-33
Mineral matter 1 '02
100-00
The ash contained 40 per cent, of potash, and 50 per cent, of phos-
phates. J. K. C.
Mineral Constituents of the Riesling Grape. By A. Hilger
(Bied. Centr., 1879, 793). — The amount of dried substance was found
to vary between 13 and 15 per cent., and the ash from I'l to lo per
cent. Analyses of the ash gave the following results : —
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 343
Eiesling at Riesling at Sylvaner at
Stein. Leisten. Mulheim.
Potash 3304 34-67 48-46
Soda 1-84 1-21 0-45
Lime 8-55 11-00 7-33
Magnesia 2-61 142 3-75
Ferric oxide 104 0-45 O'lO
Phosphoric acid 21-08 19-72 7-36
Sulphuric acid 4-54 4-19 4-89
Silica 1-00 0-45 1-71
Carbonic anhydride .. 22-51 23-78 24-38
Hydrochloric acid 2-29 2-53 0-96
J. K. C.
Mineral Constituents of Fir and Birch. By J. Schroder
(Bied. Centr., 1879, 754 — 756). — As regaixls the distribution of the
ash of the fir in the tree, the author finds that the leaves are the
richest, and that the bark is richer in ash than the wood. A concen-
tration of the phosphoric, sulphuric, and silicic acid takes place in the
direction of the branches, as these acids have a tendency to pass into
the leaves. Magnesia and potash are found in largest quantities in the
wood, and lime in the bark. Similar results were obtained in the case
of the birch, as regards the distribution of the ash constituents,
although not in so marked a degree. The fir gives more ash than the
birch, the excess being due to the larger amount of silica present.
J. K. C.
Ash Analyses. By G. Thoms (Lanchtr. Versuchs.-Stat., 24, 53).—
The ash of the seed capsules and stems of the flax plant were submitted
to analysis, and compared with that of the hay of the Galeopsis tetrahit,
or common "hollow tooth," a plant coming greatly into use as a fodder
in Russia ; the whole of the specimens were grown in Livonia. The
following are the principal constituents :-
Pota?h.
Flax seed capsules . . 22-39
„ stems .... 19-75
Galeopsis 41-26
Analyses of Feeding Stuffs. By G. Thoms (Landw. Versuchs.-
Stat., 24, 50 — 52). — The author communicates the result of his exami-
nation of nine samjjles of feeding cakes of Russian manufacture, con-
sisting of linseed-oil cake and a so-called starch cake. Of the nine
samples he describes four as adulterated, two of medium quality, and
three as good ; the adulterations consist of the seeds of various weeds,
and in some of the samples particles of straw. From these results
the author urges the employment of the microscope, a botanical exami-
nation, treatment with warm water, and the judging of the samples by
smell and taste. He agi-ees with Voelker, that an ordinary chemical
analysis is not sufficient in such cases ; he particularly recommends
careful search for mildew in the centre of the cake. In some parts of
Russia, it is the custom to stove the seeds previous to pressing them, in
2 6 iJ
Phosphoric
Silicic
Soda.
Lime.
acid.
acid.
6-69
27-41
25-14
5-21
0-56
31-84
8-85
15-87
1-75
23-43
9-74
10-79
J. F.
344 ABSTRACTS OF CHEMICAL PAPERS.
order to get a better yield of oil, thereby injuring tlie quality of tlie
cake, and probably forming matters injurious to the cattle which
use it. J' F.
Spent Hops as Fodder. By 0. Kellner (Bied. Centr., 1879,
(3()7'). — A diet of hops and hay was daily given to two sheep, and after-
wards for a short time hay alone, in order to ascertain the digestibility
of the spent hops. The composition of the dried substance was as
follows : —
Nitrogen Ash and
Protein. Fibre. Fat. free extract. sand.
Hops.. 197 217 7-8 461 4-6
Hay .. 87 34-5 27 45-2 8-9
Of these constituents the animals digested —
Organic Nitrogen
Hops. substance. Protein. Fibre. Fat. free extract.
Animal No. 1 . . 28-6 38-9 — 77-2 43-2 per cent.
„ No. 2 .. 377 347 lO'l 75-9 458 „
Hat.
Mean of both .. 59-4 527 54-5 48-6 65-0 „
The above numbers show that only a comparatively small percentage
of the hop constituents was digested by the animals. Taking also
into consideration the fact that the animals showed great objection to
this food, spent hops cannot be highly recommended as fodder (comp.
this Journal, 36, 1050). J. K. C.
Nitrogen in Turf. By M. v. Sivers (Landw. Versitchs.-Stat., 24,
183 — 210). — The author comments at considerable length on the
several results of 26 analyses of turf taken at different depths, and
formed from various vegetable growths. The source of the nitrogen
is attributed to the albuminoids of the decaying plants, the amount of
these being sufficient to account for most of the nitrogen present, and
they are not destroyed in the process of decay. The nitrogenous sub-
stances are soluble in potash. J. K. C.
On various Manures. By J. Moser (Bied. Centr., 1879, 721 —
72t)). — As foreign manures are in general too high-priced in Austria,
an investigation of various materials to be obtained in that country,
both natural and artificial, which may be used as manure, has been
made at the agricultural station in Vienna.
The beds of phosphorite examined, found chiefly in Idria and East
Galicia, were not suSiciently rich to allow of being worked. The pro-
duct obtained by treatment of sewage with lime was found to be
valuable. Waste products from various manufacturing processes were
also examined, such as fish-guano, dried blood, glue waste, &c., the
I'esults showing that they are very valuable as manures. Bat-guano,
which occurs in very large quantities in some parts of Austria,
proved on analysis to be a manure of excellent quality. J. K. C.
ANALYTICAL CHEMISTRY. 345
Manuring Experiments. By F. Bilck {Bied. Centr., 1879,
729 — 73tj). — In order to institute a comparison between cow and
sheep dung in their influence on the growth of vegetables, a series of
experiments was made in Silesia. Details of the effects on various
plants are given, from which it appears generally that the application
of cow-dung delays the ripening and reduces the yield,, whilst sheep-
dung has in most cases the op|K)site effect. J. K. C.
Composition of Fowls' Dung, By A. Petermanx {Bied. Centr.,
1879, 784). — The samples analysed were collected on dry sand, and
mixed into a homogeneous mass with 10 per cent, of gypsum. The
following results were obtained on analysis : —
Water 11-76
Organic matter and ammonium salts. 24'59
Mineral matter soluble in acids 34 04
„ insoluble „ 2821
100-00
J. K. C.
Bat-guano from Various Sources. By A. Volckee (Bied Centr.,
1879, 783. — 784). — This kind of guano occurs in large quantities in
the Southern States, Jamaica, Ea.sc India, &c. ; the analysis showed
great variations, the principal constituents ranging as follows : —
moisture, Q'7 to 64; organic matter and ammonium salts, 5-"8 to Qb;
phosphoric acid, from 1'4 to 24'9, and nitrogen from 0'3 to 8'9 per
cent, in 21 samples. J. K. C.
Analytical Chemistry,
Gasometric Methods. By D. Amato and P. Figueara {Gazzetta,
9, 4ij4 — 418). — In the centre of the Valle del Bove of Etna there is a
small lake, called the Lago di Xaftia or Lago dei Palici, formed by
the streams from the hills with which it is surrounded, but which is
occasionally quite dry after a hot and dry summer. At the bottom of
this lake are three large openings and many smaller ones (about 40),
from which gas constantly issues, so that the lake appears to be in a
state of ebullition. As animals which by chance go to drink of the
water, have been noticed to drop down dead, it is believed in the
district that the water is poisonous. The authors therefore determined
to examine it, and for this purpose collected samples of the water, and
also of the gas issuing from one of the larger openings.
Before making the examination of the gases it seemed desirable to
study the gasometric methods ordinarily employed, some of which the
authors have modified, besides introducing new ones. A modification
of Bunsen's apparatus for collecting the gases in water is described
which entirely obviates any chance admixture with air. The 41 known
gaseous substances, of wliich a table is given, were examined with
346 ABSTRACTS OF CHEMICAL PAPERS.
respect to their behaviour towards reagents, the details of which are
fully described.
It was found that acetate of lead was blackened by hydrogen sul-
phide, selenide, telluride, and arsenide, and also by liquid hydrogen
phosphide, but neither by phospliine nor by antimouiuretted hydrogen.
The four gases first named are absorbed by manganese peroxide,
which moreover decomposes antimoniuretted hydrogen with liberation
of the hydrogen. Silver nitrate decomposes arseniuretted, antimoniu-
retted, and phosphoretted hydrogen, setting free hydrogen. A coke
Imll impregnated with ammonieal chronious sulphate absorbs acetylene
and allylene, but has no action on the gaseous oletines or paraffins. A
coke ball with fuming siilphuric acid absorbs gases of the acetylene
group as well as the olefines. The authors find also that a dry gas,
when exploded with twice its volume of oxyhydrogen mixture, is com-
pletely saturated with aqueous vapour after the explosion.
Details ^re then given of the analysis of the gas collected from the
openings (I), and from the water (II) with the following results: —
I. II.
Carbonic anhydride 94-23 84-58
Hydrogen sulphide — 6-17
Methane 1-82 2-42
Oxygen 0-28 4-52
Nitrogen 3-79 1-89
100-12 99-58
Qualitative analysis showed that the gases were free from nitrogen
oxides, arsenic, antimony, a,nd the hydrocarbons of the acetylene and
define series. The sudden death of the animals which had been
observed must be referred therefore not to any poisonous effect of the
water, but rather to the carbonic anhydride which constantly streams
from the numerous openings, and in a calm atmosphere forms a stratum
over the surface of the lake. C. E. G.
Extension of Dietrich's Table for the Calculation of Nitro-
gen. By E. Tkachsel {-Zelts. Anal. Chem., 1880, 48). — This table
gives the weight of a c.c. of nitrogen for temperatures varying from
5—25° C, and pressures from 705—720 mm. C. E. G.
Determination of Carbonic Acid in Carbonates. By G. W.
WiGXER {Analyst, 1879, 228 — 230). — In the case of white lead, where
the proportion of carbonic acid present is really the standard by which
to judge of its suitability for use as a paint, the results obtained with
the ordinary forms of carbonic acid apparatus are not of a satisfactory
character. The only satisfactory process by which carbonic acid can
be estimated in such samples is by measuring the volume of the gas
evolved on treating the sample with dilute nitric or hydrochloric acid,
and ascertaining that this gas is entirely carbonic acid. The author
has for some time used an apparatus, in which the decomposition of
the carbonates is entirely performed in a partial vacuum, so that the
ANALYTICAL CHEMISTRY. 347
liberation of the cai'bonic acid proceeds rapidly and freely at a tem-
perature considerably below the ordinary boiling point of the solution.
By this means the time necessary for the decomposition is greatly
shortened, and the risk of the evolution of any other gases than car-
bonic acid is also decreased. Details of the apparatus required and
the mode of tteatment are sfiven. D. B.
o
Volumetric Estimation of Manganese and Cobalt. By C.
RosSLER {Annalen, 200, 323 — 340). — This is an investigation of cer-
tain points in connection with the author's method for the volumetric
estimation of manganese (Abst., 1879, 746). The manganese is pre-
cipitated as a definite compound, AgiO.MnoOa (Pogg. Anti., 41, 344,
and 101, 229), by adding decinormal silver solution in excess followed
by an alkali; the excess of silver is removed by ammonia and esti-
mated by means of a standard thiocyanate. The author finds that the
presence of ammonium salts at the time of precipitation has the effect
of retaining a large proportion of the manganese in solution, and must
therefore be carefully avoided. Accurate results are obtained by the
following method : — The silver solution is added in excess to the man-
ganese solution, the whole is then heated on the water-bath, and
sodium carbonate is added in excess. The excess of silver above that
required to form the compound with the manganese is removed by
means of ammonia and estimated with thiocyanate. The presence of
iron (Fe'") does not affect the results obtained.
It was ascertained by direct experiment that the compound
AgiO.MuoOs gives up none of its silver to ammonia, provided this
already contained silver in solution ; this condition obtains in the
above method.
Applications of the Method. — Where the nature of the substance per-
mits, as in the case of iron (metal), spathic ore, and blast-furnace
slag's, nitric acid should be em])loved in effecting its solution. Man-
ganese dioxide, in its several forms, is digested at a gentle heat with
aqueous sulphurous acid ; concentrated sulphurous acid is then added
and the liquid boiled ; lastly, the solution is oxidised with nitric acid.
In cases where it is necessary to decompose with aqua regia, the solu-
tion must be boiled, after adding sulphuric acid, until the whole of
the chlorine is expelled. Cast iron is dissolved in nitric acid and the
iron precipitated as basic acetate in the usual way; this has the effect
of entirely decolorising the solution by the removal of the carbon-
aceous matter, the presence of which in solution would prejudice the
results.
Estimation of Cohalt. — This metal is also precipitated by silver
nitrate in presence of alkali (H. Rose, Pogg. Ann., 101, 498), and upon
the formation of this compound the author has based a volumetric
method for the estimation of cobalt, differing fi'om that adopted in the
case of manganese only in the substitution of alkaline hydrate for
carbonate.
The method gives fairly accurate results in presence of nickel, pro-
vided the quantity of the latter does not exceed that of the cobalt.
Perfect accuracy is attained by previously separating the metals by
means of potassium nitrite. The precipitate may be dissolved in
348 ABSTRACTS OF CHEMICAL PAPERS.
nitric acid, without washing, and the cobalt estimated in the solution
lay the method described. C. F. C.
Decomposition of Arsenic and Antimony Compounds. By
E. DoNATH {Zeits. Anal. Chem., 1880, 23). — The excellent method of
fusing with sodium carbonate and sulphur sometimes gives doubtful
results, owing to the large quantity of free sulphur separated from the
aqueous solution before and on the addition of hydrochloric acid. This
difficalty is avoided by using sodium thiosulphate (proposed for a
similar process by Froehde), well dried and finely powdered, instead
of the sulphur fusion mixture. J. T.
Rapid and Easy Process for Simultaneously Detecting
Nitrogen, Sulphur, and Chlorine in Organic Compounds.
By P. Spica {Gazzetta, 9, 574 — 575). — The substance to be examined
is heated with sodium in a test-tube, and the product dissolved in
water, as in the ordinary way of testing for nitrogen by Lassaigne's
process ; the solution will then contain the nitrogen in the state of
cyanide, the sulphur as .sulphide, and the chlorine, bromine, or iodine
as chloride, bromide, or iodide if these elements be present. A drop of
the alkaline liquid placed on a clean silver surface will at once pro-
duce a black stain if a sulphide has been formed, whilst the cyanogen
may be detected by the Prussian blue test in a portion of the liquid.
If neither of these is present, the halogen may be at once tested for in
another portion of the solution by adding nitric acid and silver nitrate,
but if a sulphide or cyanide is present it must be first destroyed by
mixing the solution with about half its bulk of pure sulphuric acid
and heating for a short time before adding the silver nitrate.
C. E. G.
Examination of the Will-Varrentrap Method of Nitrogen
Determination. By A. Prehx and E. Huknberger (Laitdio. Versuchs.-
Stat., 24, 21 — S^). — The doubts thrown upon the accuracy of the soda-
lime process have induced the authors to make a series of experiments
in order to verify the results of the Will-Vax'rentrap and Dumas sys-
tems, to ascertain the defects of the former, and to remedy them if
possible. They considered fiat the first experiment should be as to the
behaviour of free ammonia in the combustion-tube, for which purpose
they employed salts of ammonia, and commenced the series with
chemically pure sulphate, — the usual routine being followed, the
ordinary precautions taken, and a dull red heat employed, the tube
being arranged so as to be aspirated at the termination of the experi-
ment. The results were too low by about 1^ per cent. The hinder
end of the tube was then filled with soda-lime mixed with sugar, from
which better results were obtained, but still below the theoretical
numbers. In the next experiment the hinder end was fused to a
round-shape, sugar and soda lime being placed at the opening; the tube
was heated to expel the atmospheric air, and after the combustion,
the other portion lying behind the substance ignited to clear the tube
of gas. Notwithstanding all precautions, however, the results were
too low, distillation with milk of lime yielding more exact numbers.
Similar results followed the employment of ammonium oxalate, the
ANALYTICAL CHEMISTRY. :U<)
theoretical numbers being never reached ; the operations with this salt
also succeeded better with sugar than without, and better results still
were obtained when the sugar was not mixed with, but separated
from, the substance. The low results ])oint, in the authors' opinion,
to some unexplained decomposition by which free nitrogen is lost,
and think it proved that the Will-Varrentrap method is attended
with danger of incorrect results when employed for estimation of cer-
tain salts of ammonia. They recommend distillation with milk of
lime as a convenient and correct substitute. It was with ammonium
chloride that the results looked for were first obtained.
In the first experiment with the chloride, sugar was not employed
and air was sucked through ; the results were low. Employing
.sugar to expel the gas after the operation, but not before, the re-
salts were better ; but with sugar employed, both before and after
the combustion of the substance, the whole theoretical amount was
obtained. The same satisfactory result was obtained by connecting
the tube with an easily regulated hydrogen apparatus to clear it before
and after the combustion, which leads to the belief that a great dilu-
tion of the substance is not so important as a thorough expulsion of
atmospheric air. With substances naturally poor in nitrogen the
system would be successful, using only the ordinary precautions, pro-
bably because the gases given off, even at a gentle heat, would drive
out the air and remove the oxygen, so that the loss of ammonia would
either be very small or none. In fact, the objection to the method
that it gives too low results applies only to substances rich in nitro-
gen ; with matters containing small proportions the authors think the
trustworthiness of the method incontestable.
Equally good results were obtained from potas.sium ferrocyanide, a
substance for many reasons suitable for testing the method.
The remaining experiments were made to learn the effect of longer
or shorter tubes and higher degrees of heat upon the combustion, and
are explained in the tables accompanying the article, in which short
tubes are held to mean those of 35 — 40 cm., and long those from 55 —
<»0 cm. ; by ordinary heat is meant the usual dark red glow ; high heat
is the greatest obtainable from a gas-combustion furnace.
General recommendations of the authors are the careful expulsion
of air before as well as of the gas after the combustion ; not to employ
the longrer tubes where there is danger of excessive heat, but with ordi-
nary heat good results may be obtained from long as well as short
tubes ; to proportion the amount of sugar to the richness of the sub-
stance in nitrogen, and to have the heat neither too strong nor too
weak.
Abstract of Tables.
Amtnonium Sulphate containing 21-21 jjer cent. N.
Found.
Without sugar, aspirated, low temp., 5 experiments 19"61
With sugar, without aspiration, low temp., 9 experiments. . . . 20'67
Ammonium Oxalate containing 19' 71 per cent. N.
Without sugar, aspirated, low temp., 3 experiments 191i
350 ABSTRACTS OF CHEMICAL PAPERS.
Found.
With sugar mixed with substance,* not aspirated, low temp.,
7 experiments 19'03
With sugar, not aspirated, low temp., 8 experiments 19'59
Do. do. high temp., 3 „ 19'54
Ammonium Chloride containing ^&\Q per cent. N".
Without sugai", aspirated, low temp., 4 experiments 24*97
With sugar in fore part of tube, aspii'ated, low temp., 2 experi-
ments 26-01
With sugar in liinder part, not aspirated, low temp., 4 experi-
ments 23-57
With sugar before and behind substance, low temp., 6 experi-
ments 2G-12
With sug-ar before and behind long tube, high temp,, 5 experi-
ments "... 23-54
Potassium Ferrocyanide containing 19-87 ^er c&ni. N".
Without sugar, aspirated, short tube, low temp., 2 experiments 19-50
AVith sugar both extremities, short tube, low temp., 8 experi-
ments 19-80
With sugar both extremities, short tube, very low temp., 2 ex-
periments 19-58
With sugar both extremities, long tube, very low temp., 2 ex-
periments 19-85
With sug"ar both extremities, short tube, high temp., 10 ex-
periments 19-36
With sugar both extremities, long tube, high temp., 5 experi-
ments 18-90
J. F.
Estimation of Nitrogen in Albuminates. By U. Kreusler
(Landiu. Versuchs.-Stdt., 24, 85 — 40). — This paper is almost a continua-
tion of tlmt by Prehn and Hornberger (see preceding Abstract), and
has also been called forth by the controversy on the respective merits
of the Dumas and Will-Yairentrap methods of nitrogen estimation.
The author in previous experiments has obtained very satisfactory
results from the soda-lime process without the employment of any
extraordinary precautions, and his experience makes him doubtful of
the great value of sugar in a combustion. He, however, refers to
some as yet unpublished experiments of the same chemists, Prehn and
Hornberger, with the casein of milk, as proving more clearly the trust-
worthiness of the combustion with soda-lime process, and as proving
the value of sugar. His experiments were instituted with a view of
adapting the volumetric plan as a verification of the other system.
His experiments were, he asserts, numerous and exhaustive, and from
the experience gained he has become aware of sources of error in the
Dumas process, not only such as are generally admitted, but othei'S
scarcely so well known. One of the worst is the presence of atmospheric
*
The only experiment in which sugar was mixed diiectlj^ with the substance.
ANALYTICAL CHEMISTRY. 351
air in the carbonic acid gas. which is passed through the arrangement.
He considers the gas as generally prepared to be unfit for the purpose,-
and advises emplovraentof carbon dioxide obtained from sodium bicar-
bonate. A second he states to be the common neglect of repeated
annealing of the copper reduced bj hydrogen. Far more serious and
more difficult to be avoided is the persistent adherence of particles of
air to the walls of the tube, the copper oxide, and to the substance
itself ; he gives examples of the difficulty of its removal. The ex-
haustion of the tube by a Sprengel pump to -^ of an atraosphei'e does
not seem to lemove the air sufficiently to affect the result. The use of
a larger quantity of" material lessens the amount of the error, but gives
rise to another, as the longer time required for the operation allows
decompositions to take place, which vitiate the results. Another
difficulty in the way of the use of the Dumas method is to prevent
loss in the form of carburetted hydrogen. It is a common experience
in elementary analysis that an unavoidable loss of carbon generally
takes place, and when it is remembered that every equivalent of carbon
which is consumed as marsh-gas equals 2^ equivalents of nitrogen in
the estimation, it becomes a serious matter. The employment of mer-
cury, leading to an intermittent passage of the gases, and a large
quantity of copper oxide, is another source of error. The author
recommends the use of asbestos coppei-ised by steeping in a strong
solution of copper nitrate acd ignition. These errors, calculated to
increase the nitrogen numbers in an analysis, are not compensated by
others of a contrary nature, unless such arise from careless manipula-
tion, which of course are as likely to be in one direction as the other.
In the author's opinion, the method of Dumas cannot be accepted as a
check upon the soda-lime process, as the eriors of the two tend in
opposite directions, even with the greatest precautions, and without
great care, the small differences may amount to large discrepancies.
The author believes that both methods are in need of and capable
of being perfected, and of yielding fairlv satisfactory results.
J. V.
Determination of Dry Substances toy the Use of Alcohol.
By F. TsCHAPLOWirz (Lundiv, Versuchs.-Sfdt., 24, -i? — 48). — The author
having been previously unsuccessful in obtaining a perfectly dry
residue from apples by means of a stream of hydrogen, devised at last
the following method, which gives satisfactory results : — A few small
portions are cut from an apple, contained in a small weighed covered
glass, with a sharp knife, which is wiped upon a dried and tared
filter, afterwards used for the filtration. The slices are then treated
in a small beaker with absolute alcohol, containing about 10 to 20 per
cent, ethylic ether; and the liquid is repeatedly boiled and- filtered into
a 500 — 1,000 cc. flask; the fragments of substance can then be easily
broken into minute particles on the filter, and, with the aid of a small
wash-bottle, transferred to the beaker and again boiled. Should an
oil determination be desired, it can be readily made at this point, it
being only necessary to employ more ether. The solid residue is dried
at 100 to 110° with the filter; the filtrate in the flask is filled to the
mark ; 50 to 100 cc. taken, dried in an air-bath, the heat of which at
first should not exceed 60", but which at the end of three or four days
352 ABSTRACTS OF CHEMICAL PAPERS.
may be raised to 85 or 90°, a higher, temperature leading tc decompo-
sition. The author considers the results very satisfactory. J. F.
Detection of Salicylic Acid in Wine and in Fruit Juices.
By L. Weigert (Zeits. Anal. Chem. 1880, 45). — Ferric chloride
S(jlation, the best reagent for salicylic acid, cannot be added directly to
strongly coloured wines and fruit juices, as a coloured precipitate is
formed. Previous decolorisation by means of animal charcoal also
removes the greater part of the salicylic acid - 50 c.c. of v?ine and
5 c.c. of amyl alcohol are well shaken together for some minutes.
After standing, the upper layer of amyl alcohol is- removed and treated
with an equal quantity of alcohol. To this solution some drops of
dilute ferric chloride solution are added, when the characteristic deep
violet coloration, if salicylic acid is present, is pi'oduced.. J. T.
Determination of the Fat in Milk by the Lactobutyrometer.
By F. Schmidt and Others {Bied. Ccntr., IS/t*, 770— 772).— The
authors recommend the following modifications of Marchand's original
method : — Non-addition of caustic soda, use of alcohol of 91 per cent.
instead of 8(J, measuring the liquids in pipettes, and employment of
(jther formulae which they furnish. In answer to Marchand's defence
of his original method, they bring forward the results obtained by the
use of the modifications proposed. J. K. C.
Quality of Milk. By H. Schulzs, R. Feijhltng, and J. Schli>z
(Bied. Centr., 1879, 780 — 782). — A controversy between tlie first-
named and the two latter analysts has been going on with reference to
the percentage of solids in milk, the former asserting that under some
circumstances this percentage in unadulterated milk may fall under 10,
and the latter refusing to acknowledge milk as genuine which contains
less than 11 per cent, of total solids. J. K. C
Estimation of Albuminoids in Vegetable Substances. By
B. Dehmel (Landiv. Versucha.-Stat., 24, 214 — 225). — After giving
some account of the methods already known for the determination of
albumin, the author proceeds to recommend precipitation whilst hot
with copper sulphate solution, adding potash until neutral, filtering,
and estimating the nitrogen in the filtrate by heating with soda-lime.
Asparagine was found under these circumstances to remain entirely in
solution. Potatoes, however, appear to contain some other nitrogenous
body, which is precipitated along with the albumin, as the results
obtained by the author were much higher than those obtained by
other investierators. J. K. C.
&•■
New Method of Ascertaining the Ripeness of Grapes. By
E. PoLLACCi (Bied. Centr. , 1879, 7G4 — 705). — The skins of unripe
grapes contain two colouring matters, phylloxanthin, which is yellow,
and phyllocyanin, which is green ; the latter disappears when the
grapes are ripe. To ascertain the absence of the latter body, the
author treats the skins with dilute sulphuric acid, to dissolve out any
i-ed colouring matter, and removes the phylloxanthin with carbon bi-
ANALYTICAL CHEMISTllV. 3j3
sulphide. Treatment with ether will then extract the phyllocyanin, if
any be present. « J. K. C.
Examination of Coffee. By A. H. Allex {Anahjat, 1880, 1 — 4).
— In IS"^ the author described (Chem. Neir.s, 29, 140) three methods
an likely to be of service for the approximate determination of chicory
in samples of mixed coffee, viz. : (1) determination of the soluble
ash; (2) comparison of the tint of an aqueous solution of the sample
with that furnished by similarly treating a standard specimen ;
(3) determination of the density of a 10 per cent, infusion in hot
water. Since the publication of these methods, the author has
iicquired a large amount of additional experience in their use, and has
arrived at the following conclusions : —
With respect to method (1), experience has shown that it is only
capable of furnishing l-esults of the roughest possible kind. This fact
iH due to the varintions in the percentage composition of the ash of
both coffee and chicory, as well as to differences in its total amount.
The differences shown by coffee are, however, exceeded by those ex-
hibited by chicory, owing to the considerable and very variable pro-
portion of silica present in the latter substance. This method can
therefore be employed only as a check on the proportion of chicory in
a mixture.
Method (2) is capable of giving rapid and fairly trustworthy estima-
tions of the proportions of chicory present in mixed samples, but in
practice it is open to the very serious objection that a standard mix-
ture of various coffees and chicories is apt to undergo a change which
gravely affects the colour of the infusion.
Method (3) is one which further experience has proved to be very
valuable. The author has reason to think that exhaustion of the
sample is usually tolerably perfect, but it is better to boil well, filter
and wash the residue with hot water until the filtrate measures 10 c.c.
for every gram of the sample operated on.
In sorting coffees for further examination, the author makes the
following tests : —
(a.) Treatment of the sample with hot water and determination of
the density of the 10 per cent, infusion, which should not exceed
1009. (6.) Search for starch in strained infusion, which should give
negative results. (c.) Examination of the insoluble residue under
the microscope, (d.) Determination of the ash, which ought not to
exceed 5 per cent. D. B.
Analysis and Composition of English Beers. By T. A.
PooLEY {AiLalijst, IfcSU, 4 — 7). — The author hus made analyses of
various beers brewed in different parts of the kingdom under various
systems and with a variety of materials, the object in view being to
ascertain the exact proportions of all the more important constituents
in the typical descriptions of beers brewed in this country, in order that
a comparison may be made as to their respective values as foods and
wholesome stimulants. No claim is made to any originality of method
of analysis, for as a rule, the best methods as laid down by well known
authorities on chemical analysis have betn clo.sely followed; but when
354 ABSTRACTS OF CHEMICAL PAPERS.
the exigency of the occasion required it, a modification has been intro-
duced. The determinations usually made have been as follows: —
Sp. gr., original gravity, carbonic acid, alcohol-extract, acetic acid,
glucose, dextrin, lactic acid, ash including silica, lime, phosphoric
acid and sodium chloride, nitrogen, and the corresponding quantity of
albuininoid bodies. In the second part of this paper the author
describes the raethod of analysis employed, and gives the results
obtained with a sample of bee: purchased from a public house in
Messrs. Truman, Hanbury, and (/o.'s trade. D. B.
Adulteration of Bone-Meal. By Krocker (Bied. Centr., 1879,
726 — 729). — It is usual in the manufacture of bone-meal to increase
the percentage amount of nitrogen by the addition of horn and other
nitrogenous bodies; the nitrogen contained in horn is, however, not
so valuable as a manure as that present in bone-glue, and therefore
the quality of the meal is reduced. The author proposes an easy method
of detecting the presence of foreign nitrogenous substances in bone-
meal, by the differences in specific gravity. The sp. gr. of bone-meal
containing glue is 1*9, whilst that of dried blood and horn is about
l"o : if then we shake up a sample of meal with chloroform (sp. gr.
1'48) and allow it to settle, the blood, horn, and other impurities, will
float on the liquid, and can be removed, and their amount roughly
estimated. J. K. C.
Behaviour of Fruit-Juices of Different Ages with Reagents.
By F. V. Lbpel {Zeits. Anal. Chem., 1880, 24— 44).— The juices
examined were those of raspberry, wild strawberry, cherry, and red
currant. Absorption-spectra were observed by means of a pocket
spectroscope.
Fresh Juice. — There is nothing peculiar in the absorption-spectra of
these juices to distinguish them from the juices of other red berries
and fruits. Raspberry gives reactions with lead acetate, silver nitrate,
ferric chloride, and manganic chloride. Cherry gives reactions with
alum, lead acetate, ferric chloride, manganic chloride, and ether.
Wild strawberry gives reactions with caustic alkalis, lead acetate,
alcohol, chloroform, and benzene.
Red currant gives reactions with aluminium acetate, lead nitrate.
By means of these reactions mixtures of the juices can be examined ;
but a known mixture of the juices should be simultaneously ex-
amined.
The presence of sugar, and of hard water, if such have been used in
preparing the juices, have no effect on these reactions. By adding
very dilute alkaline solution to slightly acidified juice, an indefinite
number of absorption-spectra can be obtained.
Old, Juice. — In course of a year, raspberry juice changes in colour
and in its reactions with metallic salts, so that coloured precipitates
change in intensity of colouring (lead acetate) or in definiteness of
colouring (copper sulphate), or precipitates obtained in fresh juice,
fail altogether in the old (ferric chloride, uranium nitrate, and man-
ganic chloride). Cherry juice is very stable. At the end of three
years, metallic salts give almost the same reactions as with the fresh
TECHNICAL CHEMISTRY. 355
juice, manganic chloride however gives no precipitate. Wihl straw-
berry juice is much changed at the end of four years ; and the cha-
racteristic reactions with chloroform or benzene only hold for very
fresh juice. Red currant juice is very stable, and its colour is intense
after four years. The reactions with metallic salts are almost the
same as in the case of raspberry. All the juices in course of time
give an absorption-spectrum cnt off at the line G, and a more or less
perceptible line in the orange. The absorption near E — F becomes less
sharp towards D, and extends somewhat more in this direction.
The reactions with acids are the same with old as with new juices,
but on careful addition of alkalis, the deep violet-blue colour, and in
the case of strawberry, the deep orange-red colour, are not obtained ;
similarly by adding acid and carefully neutralising with alkali, the blue
colour is not obtained.
As a general reagent, silver niti'ate gives with old raspberry a blue
fluorescence, and with the others a dirty green one, and with a large
excess of the reagent reduced silver. J. T.
Determinations of Nitrogen in Explosive Ethereal Nitrates.
By TsCHELZAFF (Ber., 12, 1486). — The author modifies Champion and
Pellet's method (Ber., 9, 1610) by conducting the decomposition in a
stream of carbonic anhydride, and determining the ferric chloride
formed, by adding stannous chloride in excess and titrating back with
iodine. Ch. B.
Technical Chemistry.
Oxidation of Sulphur in Gas on Combustion. By TV. C.
Young (Analyst, 187y, 201). — In a former communication the author
published an account of some experiments, made for the purpose of
ascertaining whether sulphurous or sulphuric acid was produced by
the combustion of gas containing sulphur, the results of which led
him to the conclusion that practically the whole of the sulphur present
was at once converted into sulphuric acid. On absorbing the acid
fumes by passing the products of combustion over zinc in a fine state
of division, the author hoped to find a very simple method of estimat-
ing sulphur.
In practice it was found, however, that the zinc was quite unaffected
except in places where moisture had condensed, and there sulphate
had formed. It was noticed, moreover, that whei'ever sulpha£e was,
there also was carbonate to be found. In investigating the subject
further, the author determined to avoid using any alkaline or basic
substance as an absorbent of the acid. Numerous experiments were
made, the results showing beyond doubt that sulphurous acid only is
formed when gas is burned in a Bunsen burner under the " gas
referees " apparatus, as the small quantity condensed as sulphuric
acid by water alone may reasonably be assumed to have been oxidised,
;i5G ABSTRACTS OF CHEMCAL PAPERS.
during its passage througli the apparatus. In all the experiments
where alkali or alkaline carbonate was used as the absorbent, no trace
of the sulphite could be detected, the whole of it being oxidised to
sulphate. D. B.
Norwegian Phosphorite. By A. Petermann (Bied. Centr., 1879,
783). — This is one of the richest pbospliorites known to commerce,
and contains 86 per cent, of calcium phosphate. J. K. C.
Preparation of Phosphorite. By P. Vorster (Bied. Centr.,
1879, 783). — To prevent the soluble phosphoric acid being rendered
again insoluble by the iron and alumina present, the phosphoiite is
roasted with pyrites until the latter is quite decomposed : in this pro-
cess the sulphur is oxidised to sulphurous and sulphuric acids, which
in contact with calcium carbonate and iron phosphate, form calcium
sulphate and a soluble phosphate, the iron and alumina being rendered
insoluble. J. K. C.
Constitution and Properties of Dialysed Iron. By M. Per-
soNNE (/. Fhann. Ghhn. [4], 30, 332— 334).— The liquid sold under
this name is a pseudo-solution of modified ferric oxide, which differs
from the ordinary oxide by having a less specific heat and being inso-
luble in acids. This modification of ferric oxide was discovered
twenty- five years ago by Pean de St. Gilles, who obtained it by heating
feri'ic acetate; subsequently Bechamp obtained it by heating ferric
nitrate. The purest commercial sample of this liquid prepared by
dialysis still contained 6'75 per cent, of ferric chloride, and 076 per
cent, of ferric sulphate. Acids, strong or dilute, precipitate ferric
oxide from this solution ; the same effect is produced by solutions of
salts. It is completely insoluble in gasti-ic juice. A quantity of it
was injected into the stomach of a dog during digestion, and after two
liours the stomach was opened, when flocculent particles of ferric
oxide were found adhering to the undigested food, whilst no trace
could be found in solution in the acids of the stomach or along the
surface of the alimentary canal. The author concludes that this sub-
stance is medicinally inactive, and that its commercial .'•uccess at the
jjresent day, after having been abandoned for many years, is due to
the manner in which it has been advertised. J. M. H. M-
Bessemer Steel Plates. By S. Kern (CJiem. Neivs, 40, 206).—
For the rolling of boiler plates out of Bessemer ingots, it is preferable
to use ingots hammered after casting. The reasons for doing so may
be explained as follows: —
1. The plates obtained by the rolling of hammered ingots have a
smooth, fine surface. Flaws, scale or excavitions, are seldom ob-
served, and, if present, must be attributed to imperfect rolling.
2. Plates from hammered ingots have a higher density, a good
structure, and are more uniform in their mechanical qualities, such as
tensile strength per square inch, elongation, &c. Such y)latcs, even
uuiinnealed, will always stand the test within the limits of the Lloyd's
regulations.
TECHXICAL CHEMISTRY. 357
On the other hand, plates rolled directly out of unham.mei'ed: ingots
show much fluctuation in their mechanical properties. D, B.
Comparison of Various Milk Coolers. By Wust (Bted. Centr.,
1879, 778 — 780). — The coolers examined were those of Lawrence,
Rossler, and Neubecker. Of these, Rossler's appeared to combine the
advantages of the other two as being applicable where cold water is
obtainable only in small quantity or in an impure state.
J. K. C.
Machines for Milk Churning. By Eugling and Others (Bied.
Centr., 1879, 772 — 778). — Lefeldt's and Winstrup's machines are
highly recommended, as also the "separators" of Xielsen and de
Lavalle. By means of these 90 — 96 per cent, of the butter can be
separated in the course of an hour's working. J. K. C.
Analysis of two Ancient Samples of Butter. By G. W.
WiGNER and A. Church {Analyst, ISSO, 17 — 21). — The authors have
examined a sample of Irish bog-butter, which cannot be traced with
any certainty to a particular locality. There is no doubt, however,
that it is a perfectly authentic specimen, probably 1000 years old.
The following results were obtained : — Volatile fatty acids, calculated
as butyric, 0-6 per cent. ; soluble fatty acids, not' volatile, 0'42 per
cent. ; insoluble fixed fatty acids, 99"-i8 per cent. ; glycerol, minute
traces. The insoluble fatty acids contained 9 per cent, oleic acid, and
91'0 per cent, stearic and palmitic acids.
The other sample of butter, which is much older, was taken some .
time ago from an Egyptian tomb. It dates from about 400 or
600 years before Christ. It was contained in a small alabaster vase,
and had apparently been poured in while in a melted state. In appear-
ance, colour, smell, and taste it corresponds closely with a sample of
slightly rancid butter. Analysis shows that the sample has not under-
gone any notable decomposition. D. B.
Manoury's Method of Desugarising Molasses. {Bied. Centr.,
1879, 768). — The lime, after being slaked by the addition of a little
water, is added to the molasses along with a small quantity of sodium'
or potassium carbonate. The sugar-lime is then purified by addition
of alcohol. J. K. C.
Changes Effected by Fermentation in the Nitrogenous Con-
stituents of Sweet Mash. By P. Behrexd and A. Mokgex {LanJur.
Versuchs.-Stat., 24, 171 — 181). — More than half the nitrogen of sweet
potato-mash exists in the form of albumin ; on boiling and filtering,
the filtrate is found to contain the amido-compounds along with a small
quantity of peptone, and fermentation removes about one-fifth of these'
from solution, whilst the albumin present becomes increased. The
acid amides are converted by fermentation into amido-acids, with
formation of ammonia, which goes to nourish the yeast, whilst the
amido-compounds as a whole are partially converted into albuminoid
bodies, and thus the nutritive value of the mash is materially in-
creased. J. K. C.
VOL. XXSVIII. 2 c
358 ABSTRACTS OF CHEMICAL PAPERS.
Influence of Varying Pressures on Grape-Must and Wine.
By C. Weigelt (Landw. Versuchs.-Stat, 24, 13— 19).— The author
having formerly made experiments on the aeration of the mnst, observed
during their progress that the ninsts which run from the press at
different stages of the pressure exhibited remarkably varying amounts
of sugar, and he undertook his present series of experiments in order
to ascertain if the separation of the juice obtained at different stages of
the operation would improve the wine.
The experiments were made with 1 hectolitre of mash, containing
berries in all stages of ripeness. The use of mashed grapes of course
affected the results to a certain extent, but it was thought advisable
to follow the custom of the country in its mode of wine manufacture.
The press used was an ordinary iron aiTangement, and operations were
commenced some hours after the mashing had finished, but before
fermentation had commenced. The juice from the press was divided
into three portions — that which flowed without pressure ; that obtained
by slight hand pressure on the screw ; and that which was obtained
by the greatest amount of leverage obtainable on such an instru-
ment.
The results of the experiments were contrary to the author's expec-
tation, as the different portions showed an almost constant proportion
of sugar, a slight diminution taking place at the second pressure.
The increase in tannin and colouring matter was constant, but so
also was the decrease in acidity. The behaviour of the tartar was
peculiar ; that remaining in solution gradually increased, the deposited
tartar, on the other hand, diminished with each accession of pressure ;
the sum of the two shows a regular increase, which, taken in con-
nection with the decrease of acidity, convinces the author of the presence
of a large amount of malic acid in the must taken for the experiment,
which he considers surprising.
The practical results of the investigation were that it was undesira-
ble, at least unprofitable, to separate the yield of the different pressures
in a year of bad vintage, such as that in which the experiments were
made ; the author, however, hopes that he may be enabled to repeat
his experiments on better fruit in a more favourable year, and compare
the results. J. F.
Use of Thiocyanates in Calico Printing. (Dingl. polyt. J.,
235, 156.) — These compounds serve as resists for aniline colours, as
previously shown by Storck and Strobel, and they give a method for
extracting the ammonium salt from gas liquors. The liquid is first
slightly acidulated Avith hydrochloric acid, and after the effervescence
has ceased, cuprous chloride, or a mixture of cupric chloride and
sodium bisulphite is added to the clear liquid, and the grey precipitate
of copper thiocyanate is collected. On treating with baryta-water,
and concentrating, barium sulphocyanate is obtained in the crystalline
state, and can easily be converted into other thiocyanates.
J. T.
New Coal-tar Colours. (Dingl. polyt. J., 235, 154.)— Przibram
and Co., in Vienna, have patented a method of preparing red, violet,
and blue colours from mono- and diamido-anthraquinones, and rela-
TECHXIC.VL CHEMISTRY. 359
tively from mono- and dinitro-anthraquinone. The amido-compoonds
are prepared by known methods, or better by one of the two following
ones : — 100 kilos, nitroanthraquinone, 2,000 kilos, water, and 300 kilos,
ammonia solution are heated to boiling in a closed vessel, and tin-dnst
is added ; after the reduction is ended, the liquid is filtered, and air is
blown through the filtrate ; the amido-compound thus precipitated is
filtered ofi" and washed. By the second method 100 kilos, anthraqui-
none (?) are heated with 300 kilos, concentrated ammonia solution,
the excess of ammonia is blown off. 10 kilos, of mono- or diamido-
anthraqninone are heated to 100^ with 50 kilos, of sulphuric acid of
40 per cent, strength, until all quinone disappears ; the mass is then
thrown into water, sodium chloride added, the whole cooled, filtered,
and washed. With stronger acid, less of it and a lower temperature
are required ; on the contrary, if the heating be continued too long,
sulpho-compounds of the colours are produced. From monamido- or
nitro-anthraquinone, red colours are thus produced, and from the
diamido- or dinitro-anthraquinone, blue ones. According as a tin,
aluminium, or chromium mordant is used, can shades from red to
violet vrith the red colour be obtained, and shades from violet to blue
with the blue colour. J. T.
New Azo-colours. (Bingl. polyt. J., 235. 155.) — Meister,
Lucius, and Briining have patented a process for the production of a
new series of azo-colours. The colours are obtained by the action of
the two naphthalenedisulphonic acids on the diazo-compounds of
phenol and naphthol, as well also on their corresponding methyl- and
ethyl-ethers. To obtain the diazo-compounds of phenol the correspond-
ing amidophenol is obtained from nitrophenol by reduction with zinc
and hydrochloric acid, and the diazophenol is then produced by the
action of nitrous acid. The nitrophenol ethers obtained from potassium
nitrophenol, and ethyl or methyl bromide, serve as starting points for
the preparation of the amidophenetols and amidoanisols ; and these are
converted into the corresponding diazophenol ethers as above. These
diazo-compounds, treated w^th a solution of a |3-naphthalenedisul-
phonic salt (see Bingl. polyt. J., 232, 544), yield the azo-colours, which
are sent into commerce as potassium or sodium salts. J. T.
Soluble Essence of Ginger. By J. C. Thresh (Pharm. J. Trans.
[3], 10, 193). — To prepare an essence which does not become turbid
by keeping, and which has not lost any appreciable quantity of the
active principle of ginger during preparation, the author recommends
the following process as an improvement on one previously suggested
by him : — To 1 pint of strong tincture (1 to 1) of finest Jamaica
ginger, slaked lime is added in a finely-powdered state in small quan-
tities at a time. The addition is continued -with vigorous agitation
until the tincture ceases to lose colour ; the whole is then thrown upon
a filter, and the residue washed with proof-spirit until the filtrate
measures two pints. Sulphuric acid is then added drop by drop until
the rich yellow colour of the tincture suddenly disappears, and after
standing for 24 hours, the liquid is filtered, diluted with water to four
360 ABSTRACTS OF CHEMICAL PAPERS.
pints, sliaken with a little powdered pumice or silica, and filtered at
0° C, if possible.
In this process, the lime removes the greater part of the resin, and
the sulphuric acid removes the lime. The dilution with water sepa-
rates the neutral resin, wax, fat, and peculiar extractive, and also the
excess of volatile oil ; the filtration at a low temperature prevents
tui'bidity from separation of essential oil. The pale colour of the
essence can be changed to rich orange by addition of a few drops of
potash. F. C.
Mineral Constituents of Cinnamon and Cassia. By 0. Heh-
NER (Analyst, 1879, 225 — 228). — The discrimination between ground
cinnamon and cassia being a matter of some importance, but of con-
siderable difiiculty, the author determined to investigate this subject
more minutely. The only test which has been in use is that founded
on the alleged difference in the behaviour of the decoctions towards
iodine ; but the fact is that decoctions of both cassia and the cheaper
kinds of o-enuine cinnamon turn blue with iodine.
To find, if possible, some real difference between the two kinds of
bark, the author examined their mineral constituents, believing that
the more woody bark, cassia, would contain a larger amount of salts
of lime and magnesia than the delicate membranous cinnamon. The
following analyses show, however, that this supposition was not entirely
substantiated. An analysis was made upon the ash obtained at the
lowest possible temperature, but not recarbonated : —
Coal. Sand. SiOo. CO.. PsOj.
(1.) Cinnamon, Is. lOfZ. per lb. 0-27 1-09 0-27 29-29 3-52
(2.) „ 3s. „ 0-41 0-53 0-31 32-27 2-20
(3.) „ 3s. 6c?. „ 0-31 0-52 0-25 3240 300
(4) Cassia lignea 1-26 3-16 0*90 27-18 3-67
(5.) „ vera — 0-24 0-20 36-26 1-13
SO3. CI. FeoO-s. MngO^. CaO.
(1.) Cinnamon, Is. lOcZ. per lb. 2-42 0-18 0'78 0-86 40-09
(2.) „ 3s. „ 2-73 0-51 0-41 0-97 36-98
(3.) „ 3s. 6cl „ 2-84 0-76 0-46 0-13 40-39
(4.) Cassia lignea 2-02 0-14 1-23 5*11 25-29
(5.) „ vera 0-71 0*09 0-14 1-13 52-72
MgO. KoO. NaoO. Totals. Ash.
(1.) Cinnamon, Is. lOd. per lb. 2-65 14-22 3-98 = 99-62 4-78
(2.) „ 3s. „ 3-30 16-70 2-97 = 100-29 4-59
(3.) „ 3s. 6d. „ 386 10-35 4-65 = 99-92 4-66
(4.) Cassia lignea 5-48 20-58 3-98 = 100-00 1-84
(5.) „ vera I'lO 5*60 0-90 = 100-16 4-08
D. B.
3G1
General and Physical Chemistry.
Spectroscopic Researches. By G. L. Ciamician (Wieji. Ahad.
Ber. [2], 79, S — lu). — By passing induction sparks from a small coil,
connected with a weak battery, between electiodcs made of the
metals of the earths contained in tubes filled with hydrogen, the
author obtained calcium and strontium spectra which had an extra-
ordinary resemblance to the snectrum of magnesium. These spectra
appeared also to contain the lines of the less refrangible half of the
oxygen spectrum. The author thinks that his observations support
the view which regards the so-called elements in each natural gioup
as really compounds containing some common principles. R. R.
A New Chemical Photometer. By J. M. Eder {Ber., 13, 16G—
168). — A solution of mercuric chloride is decomposed by exposure to
sunlight. The presence of certain organic compounds gr(;atly facili-
tates the reduction.
In order to make use of this reaction in estimating the chemical
activity of light, a mixture is prepared whioh consists of 2 volumes
of a solution of 40 grams of ammonium oxalate in 1 litre of water,
and 1 volume of mercuric chloride solution (50 grams per litre).
The liquid is exposed to the light until it becomes slightly turbid;
it is then filtered, and may be preserved in the dark- without under-
going any change.
The red, yellow, and yellowish-green light have no action on this
solution ; nine-tenths of the mercurous chloride reduced by exposure
to ordinary daylight is due to the action of the ultra-violat rays.
Since the quantity of mercurous chloride precipitated increases
with the temperature and with the concentration of the reagent, cor-
rections must be made for th( se variations.
The intensity of the light is expressed by the number of milligrams
of mercurous chloride precipitated for each square centimetre of the
surface of the liquid exposed to the light. W. C. W.
Heat of Formation of Cuprous chloride {f:ic). By J. Tiiomsen
, (Ber., 13, lo8 — lu'.*). — A reply to Berthelot's statement that the heat
evolved in the formation of an aqueous solution of cupric chloride by
the actiim of chlorine and water on cuprous chloride is equal to
54,200 c. (this vol.. 208), and not 69,625 as found by the author (./. pr.
' Ghem. [2], 12, 281). W. C. W.
Heat of Formation of Cyanogen. By J. Tiiomsen {Ber., 13,
I 152). — The author points out that th' first determination of the heat
I of formation of cyanogen was made by Dulong {Fogg. Ann., 92, 55).
W. C. W.
On the Carbonates. By J. Thomsen {J. pr. Chem. [2], 21, 3S— 45).
— The heat of solution of carbonic anhydride, and the evolution of heat
during its neutralisation by soda, have been described in a former
VOL. XXXVIII. 2 d
362
ABSTRACTS OF CHEMICAL PAPERS.
paper {Fogg. Ann., 140, 516). The present paper givesan account of
experiments on the heat of, neutralisation of carbonic anhydride for
other bases, i.e., of the heat of formation of the carbonates of barium,
strontium, calcium, manganese, cadmium, lead, and silver.
The decomposition in the case of the barium salt is instantaneous,
and the precipitate is amorphous and anhydrous. In the case of stron-
tium, the precipitate is at first amorphous, but a further evolution of
heat takes place as it becomes crystalline. Calcium carbonate is also
at first amorphous, but the change to the crystalline state is accom-
panied by absorption of heat.
The following tables give the results obtained : — _
(1 ) An aqueous solution of carbonic anhydride acting on an
aqueous solution of oxides and hydrates. (2.) Gaseous carbonic
anhydride on anhydrous oxides.
(1) R. R + COsAq.
Na.O.Aq 20180 heat-units
BaO.Aq 21820
SrOAq 205.50
CaOAq 18510
MnOoHa 13230
CdCH, 12990
PbO 16700
AgaO 14180
(2) RO
BaO .
SrO .
CaO .
PbO .
AgoO.
(RO + CO2).
55580 units
53230 „
52490 „
22580 „
20060 „
(3.) Evolution of heat during formation of anhydrous carbonates
(a) from metal, oxygen, and carbonic anhydride; (&) from metal,
oxygen, and carbonic oxide.
R. (R + O + CO2.)
K, 184130 units
Na, 175680
Ba 185960
Sr 184210
Ca 173850
Mn 113880
Cd 84550
Pb 72880
Ag2 25960
(R + O., + CO.)
250940 units
242490
252770
251020
240660
180690
151360
139690
92770
The following table shows the difference between the evolution of
heat during formation of sulphates or nitrates and of carbonates :
R.
K3 ..
Naz . .
Ba ..
Sr ..
Ca ..
Pb ..
Ag2..
Cd ..
Mn ..
(R + O2 + SOo) -
(R + O2 + CO.)
22620 units
15020
13720
8800
8310
5440
3430
-1150
-1900
(R + O2 + CO) -
(R + O2 + N2O4.)
7980 units
15990
23020
27160
33420
30180
31290
GENERAL AND PHYSICAL CHEMISTRY. 363
The great difFerence between the heat of formation of the carbonates
and the corresponding nitrates and sulphates would indicate a differ-
ence in constitution between the former and the latter.
G. T. A.
Thermo-chemical Researches. By J. Thomsen (,/. pr. Chevi.
[2], 4G — I'd). — In this article the author gives a summary in seven-
teen tables of his thermo-chemical researches which have been pub-
ILshed at various times in the Annalen and ./. pr. Ckem. As transla-
tions or abstracts of these tables have appeared from time to time in
this Journal, it is unnecessary to give more than a list of the tables
and their contents.
Tables 1, 2, 3 contain the heats of formation and solution of the
anhydrous and hydrated compounds of chlorine, bromine, and
iodine.
4. The heat of formation of various hydracids of the haloid
metals.
5. Heat of formation of the oxides and their hydrates.
6. Heat of formation of sulphides and sulphydrates.
7. Heat of neutralisation of bases for suJphuric, hydrochloric,
nitric, and acetic acids.
8. Evolution of heat in the reaction of gaseous hydracids on anhy-
drous oxides.
9. Evolution of heat during the formation of sulphates of the formula
R.02.S02.nH20, and their heat of solution.
10. Evolution of heat during the formation of anhydrous nitrates
from their elements.
11. Evolution o meat during the formation of nitrates of the formula
R.Oj.XjOi.JiHoO, and their heat of solution.
12. Evolution of heat during the formation of sulphates and nitrates
in aqueotis solution, of formula R -f 0 -f- QAq.
13. Heat of formation and solution of the dithionates.
14. Heat of formation of carbonates.
15. Heat of formation and solution of some double salts.
16. Evolution of heat during decomposition of metallic salts by sal-
])huretted hydrogen.
17. Energy of various galvanic combinations. G. T. A.
Condensation of a Liquid at the Wet Surface of a Solid.
By A. ScHLEiEKMACHER (Lhngl. pobjt. J., 234, 471;. — For the deter-
mination of the standard weights, numerous investigations have been
carried out regarding the weight of the unity by volume, viz., water.
These investigations, although made with great care, showed that the
value of a kilo, had been determined with a probable error of + 7^6
mgrms. All determinations which give the value of the kilo, are de-
rived from hydrostatic weighings of accurately measured bodies. It
is known, however, that the state of a liquid is different at a limiting
surface from what it is in the interior of the liquid. Whilst the par-
ticles in the interior of the liquid are influenced to the same extent on
all sides, those in contact with a solid surface are simultaneously ex-
posed to the action emanating from that surface. If the attraction of
the solid particles surpasses that existing between the liquid ones, a
2 fZ 2
3fi4
ABSTRACTS OF CHEMICAL PAPERS.
layer of condensed liquid will be formed at the surface of the solid
body, the weight of which has hitherto not been considered.
Fi'om the accounts respecting the determination of the new English
standard pound, the author calculates the value of the coefBeients of
condensation for water on brass ot /3 = 0-00092 g. sq. c. The sepa-
rate values of the kilo, are freed from the influence of surface-conden-
sation by adding to each one of them the corresponding correction
—j3. This is more fully illustrated by the following table : —
Shape.
Volume.
Surface.
0
V
Value of
1 kilo.
Corrected.
England
»
5)
France
cube
spliere
cjHnder
)>
)>
j>
)»
c.c.
2046
18:.0
1234
11264
1234
387
822
402
sq. cm.
968
729
64-8
2781.
648
294
486
301
0 -473
0-394
0-5-6
0-217
0-526
0-760
0-592
0-750
g-
+ 0-555
+ 0-555
+ 0-334
±0-000
+ 0-296
-0-348
-0-065
+ 0-041
g-
+ 0-990
+ 0-917
+ 0-817
+ 0-227
Sweden
Austria
Russia
+ 0-779
+ 0-350
+ 0-478
+ 0-729
Average . .
—
—
—
+ 0-171
+ 0-661
The author shows that the thi.ckness of the condensed Liyer for
water and glass does not amount to 0 001 mm. D. B.
DifFasion of Liquids. By J. Stefan (Wien. Al-ad. Ber., 78 [2],
9.57 — 975, and ihid., 79 [2], 161 — 214). — la these papers, the author
enters into a full mathematical discussion of the numerical results
which have been obtained in the principal experimental researches into
the diffusion of soluble substances through their liquid sol/ents.
Fick (Pngg. Ann., 94, 50) had pointed out that the formulge of the
propagation of heat in solid conductors were applicable to diffusion
phenomena ; the formula, which is the starting point of the discussion,
is therefore
S = Jcqt
U\
Ui
I
where S represents the quantity of salt which has passed through the
section q in the time t between horizontal strata, the concentration of
which is represented by Ui and Uo respectively, and their distance by I;
k is a coefficient, depending only on the nature of the salt and of its
solvent.
The first paper relates to investisfations conducted by optical
methods ; those, namely, in which the concentration of the various
horizontal layers is inferred from the refractive power, or in the case
of saccharine solutions, from the polarising power. The researches
chiefly discussed are those of Voit (Fogg. Ann., 130, 227) and of
Hoppe-Seyler {Medicinisch-cheniische TJntersucliungen, I, Berlin, 1866)
GENERAL AND PHYSICAL CHEMISTRY. 365
on sugar solutious; auJ those ot Johanni.sjaiiz (^Wiedemann's Annolen,
2, 24) and of Fick, on saline solutions. The author's conclusion from
the results of the discussion is, that the optical methods of investiga-
tion are wholly untrustworthy. Not only are they liable to extra-
ordinary errors, but their inaccuracy may, in certain cases, be con-
cealed by an apparently tolerable agreement of the results with each
other and with the theoretical formula), whilst these results may, never-
theless, be very far fi-om the truth. The au hor describes some ex-
periments of his own to prove that rays of light passing through a
solution wherein diffusion is prijcceding do not retain their hori-
zontality ; and he remarks that this fact may also be deduced from the
known laws of refraction.
The second paper is occupied by a minute discussion of Gi'aham"s
researches on liquid diffusion (Phil. Tran"^. for 1861, 188 — 224; Phil.
Mag. [4], 33, 204—233, 290—306, 368—380). The original paper
should be consulted for the results of the mathematical discussion of
the several series of Graham's experiments, as these do not well admit
of abstraction. The general conclusion, however, is, that Graham's
results do show a satisfactory, and in some relations a remarkably
close, agreement with theory. R. R.
Some Chemical Constants. By J. V. Janovsky (Wloi. Ah.uL
Ber., 78 [2], 1004 — 1012). — If by qiiantivalence we understand the
maximniii capacity of saturation of an atom or of a molecule, the
quanti valence will then have a constant value, and it will be the
quotient which results from dividing the atomic weight by the equi-
valent. Also, the quanti valence of carbon compounds will be equal
to the sum of the quantivalences of the several constituent elements,
plus a constant. These laws are illustrated and discussed at large in
the paper. R. R.
Limits and Velocities of Chemical Reactions. By A.
PoTiLiTZiN (^Ber., 12, 2371 — 2374). — The mutual reaction of bodies
depends on the atomic weights (whicii are related to the energy of
the atomic naotion) and on the mass (the number of impacts in tho
unit of time). Reactions are therefore independent of the direction
of the heat-change produced by the reaction, the speed of the reaction
only being influenced by the absorption or evolution of heat, A re-
action between two bodies present in equivalent quantities proceeds
up to a certain limit, which depends on the occurrence of a state of
unstable equilibrium between two opposite reactions. Heat-change
accelerates the motion of the molecules and atoms, and therefore
causes the limit to be attained more quickly. The commencement of
a reaction depends on the ratio of the masses of the acting bodies to
the velocity of the molecular motion. If tlus be true, the necessity
of a preliminary heat-change, whether of absorption or of evolution,
is fully accounted for. T. C.
Mutual Replacement of the Halogens. By A. Potimtzin
{Ber., 12, 2369 — 2371). — A continuation of the author's previous
work on this subject (ibid., 9, 1027; tliis Journal, 1877, ii, 109). — Bro-
366 ABSTRACTS OF CHEMICAL PAPERS.
mine displaces chlorine from the anhydrous metallic chlorides, and if
the bodies be present in equivalent quantities, then the percentage of
chlorine displaced depends on the atomic weight of the metal, and the
atomicity of the latter in such a way that
-— — = constant.
Where A =: atomic weight, p = percentage of chlorine displaced,
and E = the atomicity of the metal. The following table contains
the results obtained, and from these the above rule was deduced : —
RCl.
A.
A
J-
A
Li
7
1-84 3-80
3-80
Na
23
5-56 4-13
9-78 4-00
413
K
39
4-00
Ag
... 108
27-28 3-98
RClo.
3-98
A.
A
2). —
A
Ca
. . . . 40
2-5 16-0
4-0
Sr
87
5-21 16-7
7-78 17-6
4-2
Ba
... 137
4-4
B.cr
... 200
1202 16-6
12-43 16-6
4-2
Pb
... 207
41
RCI3.
A.
A
p
A
Bi
... 208
5-38 38-66
ECh.
4-3
A.
A
p
A
Sn
. ... 118
1-49 79-19
xvsCle.
4-9
A.
A
A
P- — •
P
pH'
Fe,
.... 112
0-72 155-.5
4-3
T.
c.
Lecture Experiment. By H. Schulze (Bcr., 13, 44 — 45). —
This is a description of a simple apparatus to show the liquefaction of
such a gas as ethyl chloride, and consists of a tube closed at one end
by a stopcock, and connected at the other by means of a stout
caoutchouc tube with a reservoir containing mercury, which may be
raised or lowered. P. P. B.
IXORGANIC CHEinSTRY. 367
Inorganic Chemistry.
Non-existence of Pentathionic Acid. By W. Spring (Amialen,
201, 377— oSUJ. — A reply to Kessler's remarks {Annalen, 200, 256;
this vol., 298) on the author's research on this subject (^Annalen,
199, 97—115; and this vol., 215). W. C. W.
Phosphoric Acid. By W. F. Horn (Phai-m. J. Trans. [3], 10,
468 — 469). — Piiosphoric acid may be readily prepared by covering a
stick of vitreous phosphorus with water, adding a crystal or two of
iodine and some nitric acid, and allowing the mixture to stand for
24 — 36 hours. After the oxidation is complete, the solution is eva-
porated and treated as the Pharmacopoeia directs. The advantages
presented by this method are economy of material, and consequent
safety, and the indefinitely large quantities of phosphorus which can
be oxidised by a very small quantity of iodine. The theory of the
process is based on the discovery of Brodie (this Journal, 1852, 289)
that the iodine converts the vitreous phosphorus into the amorphous
variety, which is oxidised by the nitric acid. This method dilfers
from, that of Pettenkoffer, who treats phosphorus iodide with water,
and obtains phosphorous acid, which, is oxidised by nitric acid.
L. T. O'S.
Sodium Hypophosphite. By Botmond {Pharm. J. Trans. [3],
10, 407 — 408). — Pure sodium hypophosphite may be prepared by
treating 25 grams commercial sodium hypophosphite (containing
phosphite) and 1 gram barium hypophosphite with water, and making
the volume up to 50 c.c. After some time, 200 c.c. of absolute alcohol
are added, the mixtui-e allowed to stand, and then filtered from the
barium phosphite and hypophosphite. The last traces of barium are
removed from the solution by adding the requisite quantity of sodium
sulphate and 100 c.c. absolute alcohol, and decanting the clear solu-
tion, which is mixed with 500 c.c. absolute alcohol and sufficient
absolute ether to allow of the mass being well ■ agitated. Sodium
hypophosphite is thus completely separated, and, after being collected,
is dried in a current of air. Thus prepared, the salt is entirely free
from phosphite, which is always present when the usual methods are
employed. L. T. O'S.
Ultramarine Compounds. By K. Heumann {Annalen, 201,
262 — 291). — The results of the experiments on the decomposition of
silver ultramarine (from ultramarine blue) by dilute hydi'ochloric and
nitric acids and by solutions of sodium chloride and soda {Ber., 12,
60, and this Journal, 1879, Abst., 437) show that in this compound
one-third of the silver is present as sulphide and two-thirds as
aluminium-silver silicate. On fusion with potassium iodide, the silver
ultramarine is converted into potassium ultramarine (Ber., 12, 784,
this Journal, 1879, Abst., 692). By a similar reaction, lithium ultra-
marine can be prepared. It has a beautiful blue colour, and resembles
the corresponding potassium and sodium compounds in its properties.
368 ABSTRACTS OF CHEMICAL PAPERS.
When heated witli sulphur in a current of air, its colour changes to
green, and finally to pink. A red compound is obtained by heating
the blue lithium ultramarine in a current of hydrochloric acid and air,
but its colour is changed to blue by exposure to sulphur vapour or
hydrogen.
B7 long-continued digestion with an ammoniacal solution of silver
chloride, blu3 sodium ultramarine is converted into a yellow compound,
in which two-thirds of the sodium in the ultramarine have been re-
placed by silver. On exposure to hydrochloric acid gas, this product
turns blue.
The silver can be replaced by an alkali by fusion with an alkaline
iodide.
By the action of silver nitrate on green ultramarine at 120°, a
yellow compound is obtained which bears a strong resemblance to the
ordinary silver ultramarine, bub differs from it in yielding a green
product on fusion with potassium iodide. W. C. VV.
Spontaneous Oxidation of Manganese Oxides with reference
to the Manganese Eecovery Process. By J. Post (Ber., 13, 53—
56). — The author finds that when a solution of manganese chloride is
treated with lime water in excess, and a current of oxygen passed
through the solution, it gradually becomes less alkaline, the man-
ganese beintr oxidised at the same time. This he regards as ex-
plained by the formation in the fii^st place of a manyanese oxychlo-
ride, which is oxidised, with liberation of hydrochloric acid, the
latter uniting with the alkalis. The existence of an oxychloride is
supported by the fact that the precipitate formed by adding an alkali
to manganese chloride contains chlorine, and is decomposed by wash-
ing and exposure to the air. This formation of an oxychloride the
author thinks explains the formation of the " red charge " in the
Weldon process, which takes place when an insufficiency of lime is
added. The " red charge " after washing is found to conta'n no chlo-
rine. In this case the oxygen expels the chlorine from the molecule
as hydrochloric acid, and enters it: to form a species of anhydride :
the hydrochloric acid so liberated reacts with an oxide of manganese
to form manganous chloride. The formation of this latter body has
been demonstrated by experiment.
The formation of the " thick charge " takes place in the Weldon
process when too much lime is added and the blast of air is not strong
enough. This phenomenon is due to the formation of calcium oxy-
chloride; for when calcium chloride solution is mixed with twice the
quantity of slaked lime, and then heated to 60°, a thick mass is
produced consisting of crystals of calcium oxychloride.
P. P. B.
Composition of Weldon Mud and Similar Compounds.
By J. Post (Bn\, 13, 50 — 58). — The author gives some analyses of
unheated and but slightly washed Weldon mud, which bear out his
conclusion (Ber. 12, 1454) that the quantity of lime present is smaller
than is required to form a compound with mauganese dioxide. Fur-
ther, that the compound described by' Rammclsberg as (MnO..)5K20
(Ber., 8, 2'62), and obtained by heating potassium manganate, yields
MIXERALOGICAL CHEMISTRY. 3(39
after washinor mncli less potash tlian is necessary for tlie above
formula. The author couuludes that the existence of a maiiganous
acid is doubtful. P. P. P.
Mineralogical Chemistry.
The Meteorite of Albarello. By P. Maissen {Gnzzetta, 10, 20).
— This meteorite, which fell at Albarello in July, 1766, has been analysed
by the author with the followiug results : —
Fe. Ni. Co. S. SiO.,. FeO. Al.O.v MgO. CaO.
4-332 0730 0-105 2-36i 35-yi3 24313 4-47i) 22-773 2073
K,0. lYajO. Loss. Mn and Cr.
0-440 l-o"37 0-840 traces.
The silicate soluble in hydrochloric acid appeared to be analogous to
olivine, and the insoluble silicate to brouzite. C. ij. G.
Niobite from the Isergebirge. By J. V. Jaxovsky {Ber., 13,
139 — 142). — The following niineials are found jn the Iser- and llicsen-
gebirge. I. Niobite, a coinbination of ooPoo, ooPoo . P . OP . 00P3 . coPg ;
sp. gr. 5-74-. II. Iserite, sp. gr. 4-52, P . Pco . ooP . coPcx3, cleavage
cx>Pco. III. Iserine, sp. gr. 4-742, magnetic ; and IV. Zircon, cx>Poo . P
and ooPoo . ??/P . wP/i. ; sp. gr. 4-027 — 4635 : —
I. 11. III. IV.
Nb.,0, 62-04 0-44 — —
Ta.,05 16-25 _ _ _
TiO — 68-99 38-84 —
FeO 13-06 28-57 2981 —
FcoOa — — 27-35 0-53
MnO 6-11 1-41 3-33 trace
ZrO 0-48 0-00 — 65-01
SnO., 0-41 — — 0-54
WO3 l-Ol _ _ _
HO 0-34 _ _ _
:MgO — 0-32 115 —
SiO, — — — 33-63
The following numbers show the composition of red and blue
spinelle : —
Red. Blue.
AloOa 71-37 71-05
Crbs 1-34 —
MgO 2711 25-97
FeO 0-25 3-36
MnO — trace.
W. C. W.
370 ABSTRACTS OF CHEMICAL P.\PERS.
Organic Chemistry.
Action of Phosphonium Iodide on Carbon Bisulphide. By
H. Jahn (Ber., 13, 127 — 135). — A new synthesis of methane is accom-
plished when a mixture of phosphonium iodide and carbon bisulphide
is heated at 120 — 140° in a sealed tube from which the air has been
expelled by carbonic anhydride or carbon bisulphide vapour. A red
crystalline deposit is formed, and on opening the tube phosphoretted
hydrogen, marsh gas, and sulphuretted hydrogen are evolved : —
CSo + 4H2 = CH4 + 2H2S.
Baeyer {Annalen, 155, 266) ascribes the formula PI to the red crys-
talline compound, but it really appears to be a complex molecular
compound of carbon bisulphide and phosphorus di-iodide, since it is
decomposed by water, with liberation of sulphuretted hydrogen, and
with formation of hypophosphorous and hydriodic acids, and of a
white solid compound having the composition CsStPsHbOu-
5CSo + 6PI0 -h I2H2O = CsS^PeH^Ox^ -F 3H,S -f 12HI.
This substance is also produced by the action of alcohol on the red
crystals. When heated in sealed tubes with water free from air, it is
decomposed according to the equation : —
CsS^PeHeOi, + 6H2O = 7HoS + 500, -f 4HP0o. + P^.
It appears that when phosphonium iodide acts on carbon bisulphide,
phosphoretted hydrogen, phosphorus di-iodide, and hydrogen are pro-
duced.
2HiPI = PH3 + PL. + 5H. W. C. W.
Reactions due to the Presence of Aluminium Bromide and
Chloride. By G. Gustavson {Ber., 13, 157— 159).— The author
claims priority in reference to Kekule's explanation {Ber., 12, 2280)
of the conversion of propyl bromide into isopropyl bromide by alumi-
nium bromide, viz., that the aluminium bromide forms addition-pro-
ducts with non-saturated hydi'ocarbons. W. C. W.
Constitution of Diallyl. By W. Sorokin {Ber., 12, 2374).—
Diallyl, on oxidation with potassium permanganate, gives chiefly
succinic acid, from which its constitution would appear to be repre-
sented by the formula CHo : CH.CH0.CH2.CH '. CHj. T. C.
Cyanamide. By G. Pratorius-Seidlee (/. pr. Chem. [2], 21, 129 ;
see this vol., ;^)07). — (I.) The author has investigated the reaction of
cyanamide with the following compounds : —
Hydroxylamine Hydrochloride. — The reagents were heated, in alco-
holic solution, on the water-bath. After removing the ammonium
chloride which had been formed, as platinochloride, the filtrate
from the latter, containing excess of platinum chloride, yielded on
spontaneous evaporation ruby-red prisms of a platinochloride
ORGANIC CHEMISTRY. 371
(CN3H50.HCl)j.PtCl4, i.e., oxyguanidine platiaochloride. Cjanainide
and ammonium chloride react under similar conditions (Erlenmejer,
Annalen, 146, 258) to form guanidine, in complete analogy, there-
fore, to the present case. It was attempted, but without success, to
isolate a simpler compound of the base, viz. :— (1) by precipitating
the platinum of the platinochloride in alcoholic solution as sulphide,
filtering and evaporating; (2) by the action of cyanamide on hy-
droxylamine sulphate in both aqueous and alcoholic solutions; and
(3) by the action of cyanamide on hydroxylamine itself. In the two
latter ca.ses no decomposition occurred.
Formic acid was found to react with cvanamide-according to the
equation H.COOH + CN.NH, = CO + CO(NH,),, cyanamide playing
the part of a dehydrating agent.
Lactic acid decomposes cyanamide, in alcoholic solution also, with
formation of urea, probably according to the equation —
C2H,(0H).C00H + CN.NH^ + EtOH = COX2H4 +
C,Hi(OH).COOEt.
Phenol was heated with a solution of cyanamide (in anhydi'ous
alcohol) ; the result was a polymerisation of the latter, dicyanodiamide
being formed.
Salicijlic acid resLcts with cyanamide in presence of alcohol, according
to the equation : —
C6H,('0H).C00H + CN.XH, + EtOH = C5H,(0H).C00Et +
CbXoH^.
The isomeric hydroxybenzoic acids were without action on cyan-
amide, even under pressure.
Thiacetic acid reacts energetically with cyanamide, forming thio-
carbamide and acetylthiocarbamide.
(II.) The author further contributes the following to the chemistry
of thiocarbamide. That obtained as the product of the last-mentioned
reaction was observed to melt in the first instance at 170°; but, on
again heating, it melted at 149°, the latter being the melting point
observed by Reynolds {Annalen, 150, 220) ; thiocarbamide prepared
from ammonium thiocyanate gives the same result : 149° is therefore
the permanent, although not the original melting point.
Platinochlorides. — A mixture of saturated solutions of platinum
chloride and thiocarbamide yielded microscopic red prisms of the com-
pound PtCl2(CSH4N2)2.HCl, as stated and described by Reynolds
{ibid.). The filtrate from this salt yielded on evaporation yellowish
prisms of a new platinochloride, (CSHiN2.HCl)2PtCl4. This com-
pound is soluble in water and in alcohol ; it resists a temperature of
100°, but cannot be fused without decomposition. The author attempted
to prepare the compound PtCla.CSHiNj, but without success. The
corresponding aurochloride was prepared according to Reynolds' direc-
tions.
Cuprosulphate. — On mixing together concentrated solutions of
thiocarbamide and cupric sulphate and leaving the solution to evapo-
rate spontaneously, colourless prisms of the compound (CSHiN2)2CuSOi
372 ABSTRACTS OF CHEMICAL PAPERS.
are obtained. On heating the aqueous solution of this salt, it is decom-
posed with se))aratioii of copper sulpliide.
Thalliosuljiiiate. — The double salt, CSH4N2.TISO4, was prepared in a
similar manner. It is only slightly soluble in water and in alcohol.
The aqueous solution may be boiled without decomposition ; the salt
melts a.^' 1-40 — 145'', but not without decomposition. C. F. C.
Normal Propyl Alcohol from Glycerol. By A. Fitz (Ber.,
13, 3G). — Amongst the fermentation-products of glycerol, the author,
besides ethyl and normal butyl alcohol, has also obtained propyl
alcohol. It boils at 95 — 100°, and the form of the barium salt of the
acid obtained by its oxidation corresponds with that of barium pro-
pionate. P. P. B.
Allylmethylpropyl Carbinol. By Semlianizin (Ber., 12, 2375).
— This compound, prepared from allyl iodide, zinc, and methyl-propyl
ketone, is a mobile colourless liquid (b. p. 160° ; bar. = 743 mm.),
smelling somewhat of camphor. It is optically inactive, combines
energetically with bromine, and is insoluble in water. Its sp. gr. at
0° = 0"8486 ; at 20° =: 0*8345 ; and its coefficient of expansion be-
tween 0° and 20° = 0'00084 for 1°. On oxidation with chromic mix-
ture, it is converted almost wholly into carbonic anhydride.
^.Mcthi/ljjropylethijUaGtic acid, CMeH,.CH2.CM.e(0H).CHo.C00H, is
obtained by oxidising the preceding compound with potassium per-
manganate. It is a thick syrup. The silver, calcium, and barium
salts are described. T. C.
Methyl and Ethyl Ethers of Diallyl Carbinol. By RjABtNix
(Ber., 12, 2374 — 2375). — These compounds are obtained by the action
of methyl iodide and ethyl iodide respectively on the sodium compound
of diallyl carbinol. Both are mobile liquids, of peculiar odour. The
methyl ether boils at lo6° (bar. *7^o mm.); its sp. gr. is 0'8258 at 0*^,
and 0"S096 at 20" ; therefore, its coefficient of expansion between
0 and 20° is 0-0010 for 1°. The ethjl Hher boils at 144° (bar. 759 mm.) ;
its sp. gr. is 0-8218 at 0°, and 08023 at 20° ; and therefore its co-
efficient of expansion between 0° and 20° = 0-00121 for 1°. Both
ethers, on oxidation with chromic mixture, are converted almost
entirely into carbonic anhydride. On oxidation with potassium per-
manganate, the methyl ether gives
(S-iMethoxyr/lutari-G acid, C00H.CHo.CH(0Me).CH2.C00H, as a
syrupy liquid, which after some time becomes partly crystalline. The
calcium, barium, and silver salts are described. T. C.
Composition of Pyroxylin. By J. M. Eder (Ber., 13, 169 —
180). — After referring to the researches of Hadow (J.pr. Chem., 68,
51; 58, 15), Bechamp, Wolfram {Dingl. pohjt. J., 1878,. 230), and
many others, the author describes the properties of five cellulose
nitrates.
Cellulose hexnitrate, Ci2ETu04(N03)6, is prepared by immersinsf dry
cotton wool in a mixture of 3 volumes of sulphuric acid (sp. gr. 1-845 j
and 1 volume of nitric acid (sp. gr. IS) at a temperature of 10° for 24
ORGAXIC CHEMISTRY. 373
hours. The product is thoroughly washed with cold and finally with
hot water. 100 parts of cotton yield from 175 to 180 of pyroxylin. A
small quantity of oxalic acid and other organic compounds rem.ain in
the niti'osulphuric acid. The gun-ootton contains from 1'2 to 5'8 per
cent, of pcnta- and tetra-nitrate, vvhicli may be removed by repeated
digestion with a mixture of ether and alcohol (3 : 1).
The hexnitratc is insoluble in ether, alcohol, acetic acid, methyl
alcohol, ether-alcohol, and ethyl acetate.
With acetone it forms a transparent jelly, which dissolves in a laro-e
excess of the solvent.
Thoroughly washed gun-cotton may be heated at 100° for several
days without undergoing any change ; its temperature of ignition is
between 16'J° and 170"^. Attempts to prepare the hexnitrate by treat-
ing the cotton with nitre and sulphuric acid did not yield satisfactory
results.
Cellulose pentanitrate, Ci2Hi505(NO:,)5. is formed, together with the
tetranitrate, by digesting cotton wool for five hours at the ordinary
temperature in a mixture of eqiial volumes of strong sulphuric and
nitric (sp. gr. 1"4) acids. The product is washed and treated with
ether to which a small quantity of alcohol has been added ; in a few
days a gelatinous mass is obtained which is poured into thi'ee times
its volume of alcohol, when the pentanitrate separates out, leavino- the
lower nitrates in solution.
The pentanitrate can also be obtained by dissolving collodion-cotton
in nitric acid (sp. gr. 1*4) at 60° ; the turbid solution is cooled down
to 0°, filtered through asbestos, and tlie filtrate is mixed with four
times its volume of sulphuric acid (sp. gr. 1'84), care being taken to
prevent the temperature of the mixtui-e rising. The acid liquid is
largely diluted with water and the precipitated pentanitrate collected
on a filter and purified by solution in alcoholic ether and reprecipita-
tion by water.
This compound is insoluble in alcohol and in ether, but dissolves in
ether-alcohol, in acetic acid, and in ethyl acetate.
The solution in alcoholic ether leaves on evaporation a transparent
film; potash converts it into the dinitrate.
Cellulose tetra- and tri-nitnUes, Ci2H,6(''6(N03)4 and Ci2Hn07('NO:,)3,
have not yet been obtained in the pure state. The tetranitrate is insoluble
in alcohol and in ether, but dissolves in methyl alcohol, ethyl acetate,
alcoholic ether, and in a mixture of acetic acid and alcohol or acetic
acid and ether. The trinitrate dissolves freely in ethyl acetate, methyl
alcohol, and boiling acetic acid. It is slowly dissolved by absolute
alcohol, and the solution becomes turbid on the addition of ether in
excess.
Cellulose clinifraie, Ci3Hi308(NO;j)2, is formed by the actiim of am-
monia or potash on the higher nitrates. It is also prepared by adding
alcoholic potash to collodion; the product is diluted with water and
the aqueous solution neutralised with acetic acid, when the dinitrate
is precipitated. After being dissolved in alcoholic ether, it forms a
yellowish-white powder which explodes at 175°. It is soluble in alco-
holic ether, absolute alcohol, methyl alcohol, acetic acid, ethyl acetate,
acetone, and also in potash, but in the latter case a considerable por-
374 ABSTRACTS OF CHEMICAL PAPERS.
tion of the substance is decomposed. The solution in alcoholic ether
deposits an opaque film on evaporation. The dinitrate appears to
form compounds with alkalis which are insoluble in alcoholic ether,
but dissolve in water.
The cellulose mononitrate could not be obtained.
In order to estimate the nitrogen in these compounds the following
method was employed : —
0"2 — 0"3 gram of the substance are brought into a flask of 150 c.c.
capacity, clo.sed by a cork through which passes a tube bent twice at
right angles. To this tube a piece of caoutchouc is attached so that the
opening may be closed by means of a pinchcock. The flask, which is half
tilled with water, is heated until the air is completely expelled and only
a small quantity of water remains in the flask. The end of the tube is
now placed in a concentrated solution of ferrous sulphate in hydrochloric
acid and the source of heat removed from the flask. The solution of
ferrous salt is allowed to flow into the flask until it is one-third full,
when the tube is closed by the pinchcock. A small quantity of water
is afterwards admitted into the flask in order to wash the iron out
of the tube, but care must be taken to avoid the entrance of air. The
apparatus is heated and the nitric oxide is collected in a graduated
cylinder filled with a strong solution of soda. The number of cubic
centimeters of gas at 0° and 760 mm. multiplied by 062693 gives the
milligrams of nitrogen, and multiplied by 1'72649 gives the milligrams
of nitrogen tetroxide, N2O4. W. C. W.
Synthetical Formation of Formic Acid. By Y. Meez and J,
Tii!iRi<;!A (Ber., 13, 23 — 33). — The authors have investigated the con-
ditions under which the formation of formic acid takes place by the
action of carbonic oxide on caustic alkalis. They find that the absorp-
tion of this gas by alkalis with production of formic acid takes
place at about 200°. In order to saturate the soda completely, it is
best to use it as soda-lime, which must be porous. Another essential
is that the carbonic oxide must be moist, and further, that the tem-
perature must not be raised above 220°. Above this temperature the
formate is decomposed into carbonate and hydrogen. With caustic
potash or potash-lime, this secondary decomposition takes place below
220", and more easily than with soda or soda-lime. Since the absorp-
tion of carbonic oxide by soda-lime, when the necessary precautions are
taken, takes place very rapidly, the authors think that formic acid
might be made on the large scale in this manner.
Experiments made in the hope of obtaining benzoic acid from
sodium phenylate and carbonic oxide yielded negative results. Sodium
ethylate absorbs carbonic oxide at 200°. The investigation of the
products of this reaction is as yet unfinished. P. P. B.
Maleic and Malic Acids from a-Dibromopropionic Acid.
By S. Tanater (Ber., 13, 159 — 161). — A mixture of maleic and malic
acids is formed when a solution of a-dibromopropionic acid is boiled
for six hours with potassium cyanide and an excess of potash. The
acids are obtained from the alkaline solution by acidification with
hydrochloric acid and extraction with ether, and may be separated
ORGANIC CHEMISTRY. 375
by precipitating the maleic acid with barium acetate, when the malic
acid will be found in the filtrate.
The barium and calcium malates are crystalline and dissolve readily
in water. The silver salt is also soluble ; the lead salt is insoluble in
excess of lead acetate and does not melt in boiling water. The acid
crystallises in needles (m. p. 100°), which are freely soluble in alcohol,
ether, and water. In many respects it appears to resemble the isomalic
acid prepared by Schmoger from isosuccinic acid. W. C. W.
Etherification of Unsaturated Monobasic Acids. By N,
Mexscuutkix (Ber., 13, llj2 — 1G;>). — The initial rate of etherification
of the unsaturated monobasic acids is greatest for the primarv and
lowest for the tertiary acids, so that in this respect the non-saturated
acids resemble the saturated.
Initial Limit of
Primary unsaturated acids : rate, etherification.
Hydrosorbic acid, CeHioOa 430 70-83
Phenylacetic acid, CeHs CH..COOH 48-82 7387
Phenylpropionic acid, C6H5(CH2)2.COOH . 40-26 72-02
Secondary acids :
Crotonic acid, CMeH ! CH.COOH 12-12 72-12
Cinnamic acid, CPhH ! CH.COOH 11-55 74-61
Tertiary acids :
Sorbic acid, CbH.O, 7-96 74-72
Benzoic acid, Ph.COOH 862 72-57
Paratoluic acid, CgHiMe.COOH 6-64 76-52
Cumicacid, C6H4(C3H7).COOH 6-26 75-91 '
W. C. W.
Unsaturated Monobasic Acids -with Six Atoms of Carbon.
By R. FiTTiG and others {Amialen, 200, 21 — 65). — Ethjlcrotonic
Acid. — In preparing ethylic diethoxalate by the action of amalgamated
zinc and ethyl iodide on ethyl oxalate (Frankland and Duppa, Annalen,
136, 2) the author recommends that the zinc should be only slightly
amalgamated by a very brief immersion in a dilute solution of mercuric
chloride. The ethylic ethylcrotonate obtained from this by the action
of phosphorus chloride (for small quantities preferably by Geuther
and Wackenroder's method with hydrochloric acid {Zeit. CJiem., 3,
709) need not be separated, but may be at once saponified by potash,
the ethylcrotonic acid set free by acidifying the solution being distilled
o£P with steam.
Ethylcrotonic acid is not attacked by nascent hydrogen from sodium
amalgam, and combines but slowly with hydrobromic acid. To bring
about this combination the acid must be saturated at 0° and used in
large excess (200 c.c. to JO grams). On standing for some weeks the
addition product, CgHiiBrOs, separates from the mixture as a reddish
oil, which solidifies when cooled to 0°, and may be dried over sulphuric
acid and potash (m. p. 25°). When this addition-product is treated
S76 ABSTRACTS OF CHEMICAL PAPERS.
•with sodium-araalgam, under snitable conditions (Annalen^ 195, 117),
it is convprted into a saturated acid, ChHuO., (b. p. 194 — 195°). Tliis
is a colourless oily liquid, which is volatile with steam. Barium and
calcium salts were prepai^ed and analysed; the latter, fCBHii0.j)2Ca
+ H.O, is less soluble in hot than in coll water. The ethyl salt,
CeHiiO.Et (b. p. 15r5°), is obtained by dissolving' the acid in twice
its volume of absolute alcohol, and heating this solution with an equal
volume of sulphuric acid on the water-bath for half an hour. On
dilution, the salt separates.
If th3 formula of ethylcrotonic acid is CH,.CH ! CEt.COOH, the
saturated acid derived from it is probably diethylacetic av;id. An
acid of this composition lias been prepared by Frankland and Duppa
(Annrde7i, 138, 221) by the action of sodium and ethyl iodide on ethyl
acetate; bv Schnapp {Ber., 10, 195.3) by heating a-diethyl-jS-hydroxy-
butyric acid; and by Saytzeff (Annaleii., 193, L!4-9), from the cyanide
corresponding with diethv Icarbinol ; but since this new acid does not
ao"ree in all points with the description of these chemists, the authors
name it Jii/droethi/Jcrofonio acid.
A solution of sodium carbonate at once decomposes bromhydro-
ethylcrotonic acid into hydrobromic acid, carbonic acid, and amylene.
The reaction must be conducted at 0°, as otherwise the amylene is
almost entirely carried off by the escaping carb )nic anhydride. This
amylene is identical with the hydrocarbon eth/lpr ipt/lenp- (b. p. 36°)
obtained by Wao^ner and Savtzeff {Annalen, 175, 378 ; 179, 302) by
treating the iodide from diethylcarblnol with alcoholic potash, and by
Wurtz from allyl iplide and zinc ethyl, bat has a higher boiling point
than other known amylenes (Wischuegradski, Ber., 9, 102S; Annalen,
190, 328; Le Bel. B'dl. Soc. Chim., 23, 546; Gnynpt. read., 85, 853;
Zijidler, ^/maZe/i, 133, 245; 197,243; Eltakoff, Be,:, 10, 706, 1904,
2057; 11, 414; Flawitzky, Annalen,, 139, 205; 179, 340; Ber., 11,
992 ; Etard, Compt. rend., 86, 488). A little ethylcrotonic acid is
also pi'oduced in rhe reaction together with a third acid of doubtful
composition. Heating the acid with five times its weight of water
at 100° effects a simiLir decomposition, but in this case a relatively
large quantity of ethylcrotonic acid and a little hydroxyciproic acid
are also formed. As in the case of bromhydrocinnamic acid (^Annalen,
195, 135), therefore, three reactions occur: —
CoH.oBr.COONa = aH,„ + CO^ + NaBr
CoHioBr.COONa = CH^.COONa + HBr
CaH.oBr.COONa + H,0 = aH.n(OH).COOXa + HBr.
A solution of ethylcrotonic acid in carbon bisulphide rapidly absorbs
bromine, and on evaporation dibromethyicrotonic acid, CoHgBr-j.COOH,
remains in large crystals (m. p. 80'5°). This acid also is decom-
posed by a cooled solution of sodium carbonate, or by digestion with
water at 100"^ for 24 fiours. In both cases, bromamylene, CsHgBr, is
the principal product; in the latter, on evaporating the water and
shaking with ether, an acid, C6tli^04, named by the authors hexenic
acid, is obtained in small colourless rhombic prisms which have been
accurately measured (m. p. 141°). Hexenic acid is probably a homo-
ORGANIC CHEMISTRY. 377
logue of glyceric acid ; its salts are unciystallisable and esceedingly
soluble in water.
Hi/drosorhi'c and Sorhic Acids. — Hjdrosorbic acid (Annalen, 161,
309) dissolves with evolution of heat iu a solution of hydrobromic acid
saturated at 0°, and after a few hours monobromocaproic acid, CsHuBrO.,
separates. When washed and dried, it forms a feebly odorous, colour-
less oil, which does not become solid at —18°, and decomposes on dis-
tillation. In an analogous way moniodocaproic acid, C6HnI02, may be
obtained as a colourless oil which turns yellow on exposure to light.
AVhen sorbic acid is shaken with concentrated hydrobromic acid for
some days, a light oil, doubtless monohromohydrosorhic acid, at first
separates, but after a time becomes heavier, sinks and crystallises,
being converted into dihromocaproic acid, CeHmBroOo, which is de-
posited from carbon bisulphide or benzene in large clear compact
crystals (m. p. 68°).
Isodibromocaproic acid has been prepared by Fittig and Barringer by
the action of bromine on hydrosorbic acid in a freezing mixture ; the
two substances may also be brought together in solution in carbon
bisulphide. It forms a thick uncrystallisable syrup, which decomposes
slowly in the cold, rapidly at 50°.
Fuming hydriodic acid dissolves sorbic acid, and after some time an
oily body is deposited, whilst much iodine is set free. The oily body
is moniodocaproic acid, CoHiJOi : the sorbic acid is therefore first
reduced to hvdrosorbic acid, which is then converted into the iodo-
acid. Diiodocaproic acid could not be prepared.
When sodium amalgam is added in small quantities to a very dilute
solution of monobromocaproic acid, the caustic soda formed being
repeatedly neutralised with sulphuric acid, it yields a mixture of
hydrosorbic and normal caproic acids, the latter of which has been
described by Lieben and Rossi (Annalen, 159, 75), b. p. 204*5°; m. p.
—2° (Freund, J. pr. Chem., N.F., 3, 232). This experiment proves
that the addition-compounds of sorbic and hydrosorbic acids must all
be derivatives of normal caproic acid.
Boiling water or a dilute solution of sodium carbonate rapidly dis-
solves monobromocaproic acid : part of the acid is decomposed into
hydrobromic and hydrosorbic acids, whilst another portion is converted
into hydro^ei/capj-otc acid, C6Hi,(OH)02. The former having been re-
moved by distillation with steam, the latter may be extracted by ether,
from which it is deposited on evaporation as a brown-yellow syrup.
Its salts are uncrystallisable and very soluble in water and alcohol. A
solution of the free acid on sjwntaneous evaporation apjiears to leave
an anhydride, which only redissolves on the addition of much water. In
this behaviour the acid resembles lactic acid. It is not identical either
with leucic acid or with the hydroxy caproic acid of Erlenmever {Bar.,
9, 1840), and Ley (ibid., 10, 231), prepared from normal caproic acid.
Dibromocaproic acid is decomposed by heating with water at 100°, or
by warming with sodium carbonate, yielding sorbic acid and a syrupy
acid which is not volatile with steam. Isodibromocaproic acid, on the
other hand, is only partially decomposed by prolonged heating with
water, yielding two acids, both volatile with steam. One of these is
sorbic acid, the other probably bromhydrosorbic acid. These havino-
VOL. xxxviu. " 2 e "
378 ABSTRACTS OF CHEMICAL PAPERS,
been removed by distillation, tbe residue gave up to ether a liquid non-
volatile acid. Analysis of a crystalline calcium salt of the acid showed
that it was probably a hi/droxy-hydrosorhate, (C6H903).Ca + l^HjO.
Evidently the isodibromocaproic acid is first resolved into hydro-
bromic and bromhydrosorbic acids : the latter is then decomposed
partly into sorbic acid, partly into hydi'oxyhydrosorbic acid.
Tetrabromocaproic acid (the addition-product of sorbic acid) is very
slowly attacked by water. It yields sorbic and brominated acids,
together with an indifferent oil containing bromine. These products
were not examined.
Pyroterehio acid is immediately dissolved by fuming hydrobromic
acid with evolution of heat. On diluting and distilling, a neutral oily
body passes over into the distillate, from which it maybe separated by
saturation with potassium carbonate. This body is isomeric with
pyroterebic acid, and is the internal anhydride of hydroxyisocaproic acid,
C5H1CL
I yO (b. p. 206°), bearing to that acid the same relationship that
CO— ^
terebic bears to diaterebic acid (Ber., 7, 649; Annalen, 180, 66).
With the possible exception of the amidotrimethylbutyllactide of
Heintz {Annalen, 189, 231 ; 192, 329 and 339), it is the first repre-
sentative of its class in the lactic series. For this class of anhydrides
the author proposes the name " lactones ;" and as examples of lactones
in other series, he instances paraconic, terebic, aconic, and muconic
acids, the lactones of itamalic, diaterebic, hydroxyitaconic, and hy-
droxyhydromuconic acids, respectively.
Amongst aromatic bodies, umbelliferone, the phthalide of Hesserfc,
Zineke's orthobenzhydrylbenzoic anhydride, Wreden's oxycamphic
anhydride, and santonin, are also lactones. It is to be noted that the
experiments of Henry {Ber.. 7, 753) have proved that lactide is not a
lactone, as commonly assumed, but is really an anhydride derived from
tioo molecules of lactic acid. The neutral reaction and solubility of
the lactones of the lactic series are probably the cause of their having
been hitherto overlooked. Like other bodies of its class, the lactone
of hydroxyisocaproic acid yields a salt of that acid when boiled with
alkalis. In its formation from pyi'oterebic acid, an addition-product of
that acid with hydrobromic acid is probably first formed, viz., bromiso-
caproic acid, which immediately exchanges bromine for OH : the
liydroxy-acid then passes into an anhydride. The intermediate brom-
isocaproic acid may be formed by saturating pure pyroterebic acid
with dry gaseous hydrobromic acid, and exposing it to the air for some
time : colourless crystals then separate in small quantity. These may
be recrystallised from carbon bisulphide. Cold water does not dis-
solve them ; but they are quickly decomposed by warm water. The
acid was not analysed. Ch. B.
Methacrylic Acid. By F. Engelhobn {Annalen, 200, 65 — 74). —
This acid gradually combines with hydriodic acid {Annalen, 188, 59),
but not so easily with hydrobromic acid. Much of the acid becomes
polymerised, unless it is treated with five times its volume of hydro-
bromic acid and the mixture allowed to stand surrounded by ice. On
I
ORGANIC CHEMISTRY. 379
diluting, a small quantity of oily condensation-products separates, and
from the residue carbon bisulphide extracts a colourless oil which may
remain long without solidityint^'. This the author names /3-bromiso-
butyric acid (m. p. 22 ) to distinguish it from ordinary or a-bromiso-
butyric acid (m. p. 45°). Only two isomerides are theoretically
possible: the a-acid is with certainty CH3.CMeBr.COOH ; the f3- acid
must therefore be CHoBr.CHMe.COOH. The iodobutyinc acid pre-
viously obtained also belongs to the |(3-series, since its melting point
(36°) is lower than that of the a-bromo-acid, whereas it would be
higher were they of similar constitution.
Unlike the a-acid (Markownikoff, Atinalen, 153, 228), /3-bromiso-
butyric acid does not yield a hydroxy-acid when boiled with barium
hydrate, but breaks up into hydrobromic and methacrylic acids.
Moreover the conversion of the a-acid into hydroxy-acid is never com-
plete; in one experiment only 54 percent, of it underwent this change,
the remainder yielding methacrylic acid. Hydroxybutp-ic acid is
formed in large quantity when sodium carbonate is substituted for
barium hydrate.
Methacrylic acid becomes polymerised by distillation (Annalen, 188,
47), by long keeping, by the action of acids, and when its aqueous
solution is heated at 130°. The product in the latter case is a white
porcelain-like mass, insoluble in all neutral menstrua, but swelling up
like gum or starch in contact with water. The mixture with water,
although transparent, yields up the substance on filtration or on heat-
ing. The substance separated by heating dries up to a brittle trans-
parent colourless mass, having the composition of methacrylic acid.
This decomposes at 300'' witliout yielding a trace of methacrylic acid.
The polymeride is a feeble acid; it dissolves in ammonia and is repre-
cipitated by hydrochloric acid. Barium and calcium chlorides give
with the ammoniacal solution white precipitates which coalesce to
gummy masses, and become very hard when heated, but resume their
elasticity on cooling. When dried at 100°, these precipitates have the
composition —
(C4H502)2Ba -f 2H2O and (C4H502)2Ca -f- ^H^O.
The soluble alkaline salts remain as gums when their solutions are
evaporated.
Neither oxidising agents nor fusing potash yield any defined pro-
ducts with the polymeride. Ch. B.
Decomposition of the Substitution-products of the Lower
Fatty Acids by Water. By G. C. Tu<».\ksu.\ (A/malen., 200, 75 — 87).
— A solution of chloracetic acid is slowly decomposed on boiling, more
rapidly as the solution is more dilute. A lO per cent, solution is about
lialf converted into glyoollic acid at the end of 30 hours ; a 5 per cent,
solution to the extent of 86 per cent, after four days' boiling, com-
pletely after eight days' boiling.
This affords the simplest process for preparing glycollic acid. It is
only necessary to evaporate the solution several times with water to
the state of syrup, and on standing in a desiccator the mass solidifies
to pure glycollic acid. Occasionally the acid separates from the syrup
in large transparent deliquescent monocliuic prisms. If the svmp be
2 e 2 '
380 ABSTRACTS OF CHEMICAL PAPERS.
heated too long, it will on addition of water deposit the anhydride (m. p.
128—130°) described by Fahlberg (/. pr. Chem., N.F., 7, 335) ; but
even then the solution, on filtration and careful evaporation, will yield
pure glycollic acid. The anhydride is crystallisable from boiling water,
although Fahlberg states that boiling water reconverts it into glycollic
acid.
a-Bromofropionic acid, prepared by heating propionic acid with
bromine at 120 — 140° and fractional distillation, is completely con-
verted into hydrobromic and ethylidene-lactic acids after 30 hours'
boiling with water.
iS-Iodoprcfionic axid (4 per cent, solution) is completely decomposed
after 16 hours' boiling with water, yielding 9-5 per cent, of acrylic
acid and 90-5 per cent, of hydracrylic acid. The former acid may be
removed by distillation with water : the latter may be separated from
the hydrio'dic acid by conversion into calcium salt and precipitation by
zinc chloride as zinc-calcium double salt (Heintz and Wislicenus).
oi-Bromohutyric acid (Erlenmeyer, Ber., 10, 636) is converted on
prolonged boiling with water into volatile crotonic acid and non-
volatile a-hydroxyisobutyric acid (Markownikoff, Annalen, 153, 244).
The former could not be obtained in a crystalline form.
a-Bromisobutyric acid (m. p. 45—46°) in 4 per cent, solution is
decomposed, after 27 hours' boiling, into hydroxyisobutyric acid and
volatile methacrylic acid (=8 per cent.).
Theoretical Remarls (by R. Fittig). — The above brominated acids (see
preceding Abstracts) may serve as types of three different classes : —
1st. Those which are decomposed on neutralisation by sodium car-
bonate at 0° into unsaturated hydrocarbon, sodium bromide, and car-
bonic anhydride, with traces of unsaturated acid and hydroxy-acid.
Such are, bromhydroethylcrotonic, bromhydrotiglic, and bromhydro-
cinnamic acids, and the addition-compound of Perkin's homologue of
cinnamic acid.
2nd. Those which are decomposed by boiling water or alkalis, partly
into unsaturated acid and hydr(?bromic acid, partly into hydroxy-acid.
The former decomposition is predominant in the case of bromisobuty-
ric acid, the latter in the case of the substitution-products of tbe lower
fatty acids, bromhydratropic acid, &c.
3rd. Those which cannot exist in presence of water, but are con-
verted by it into hydroxy-acids or into lactones.
As the author has elsewhere pointed out, members of the first class
are derived from acids containing the gi'oup C '. C(H or G).COOH,
and contain the bromine and carboxyl united to the same caT'bon atom.
The ground for the second of these statements is, that two of these bodies,
bromhydrocinnamic and iodhydrocinnamic acids, are undoubtedly ana-
logous to Glaser's phenylactic acid, CH2Ph.CH(0H).C00H, contain-
ing Br in the place of OH. Erlenmeyer, however (Ber., 12, 1607),
gives to bromhydrocinnamic acid the constitution
CHBrPh.CH2.COOH,
because the corresponding amido-acid is decomposed by hydrochloric
acid into ammonia and cinnamic acid, whereas a-alanine,
CHMe(NH2).C00H,
ORGANIC CHEMISTRY. 381
to which it is closely allied, is not so decomposed. The author replies
that even ,t3-alanine has not been proved to undergo a similar change ;
and, moreover, that a-alanine, although not attacked by hydrochloric
acid, evolves ammonia when heated with barium hydrate at 180"^.
Erlenraeyer also remarks that bromhydroparacoumaric acid is not con-
verted by ammonia into tyrosine, CH.>Ph.CH(NHo).COOH. Although
not attaching any value to this objection, the author states that Posen
in his laboratory has never been able to obtain this bromo-acid, para-
coumai'ic acid being invariably converted by hydrobromic acid into an
anhydride, CigHuOs, analogous to dilactic acid. The chlorostyrenes,
to which Erlenmeyer (/oc. cit.) alludes, have not yet been sufficiently
examined.
Only in the case of acrylic and crotonic acids is the constitution of
their addition-compounds known. Meth acrylic acid is convertible into
bromisobutyric acid, CH-2Br.CHMe.COOH : and since it corresponds
with atropic acid, the addition-compound of the latter is probably
CH2Br.CHPh.COOH. This latter is not converted into a hydrocarbon
by sodium carbonate, but passes into atrolactic acid. The bromine
addition-compound, CHoBr.CBrPh.COOH, gives off carbonic anhy-
dride with the greatest ease.
The fact that acrylic acid combines with hydrobromic acid to form
,/3-broraopropionic acid, CHoBr.CHi.COOH, would be in Erlenmeyer's
favour, were it not that its honiologue, solid crotonic acid, yields a-bro-
mobutyric acid, CH>Me.CHBr.COOH and a-iodobutyric acid (Hemi-
lian, Anncden, 174, 3'22) ; and since solid crotonic acid is related to
cinnamic acid as atropic is to methacrylic acid, bromhydrocinnamic
acid is probably CH2Ph.CHBr.COOH. Erlenmeyer's view would have
the undoubted advantage of explaining the formation of unsaturated
hydrocarbon from these acids without assuming a transfer of hydrogen
from one carbon-atom to another, thus : CHPhBr.CHo.COOXa =
CHPh : CH. + CO2 -f NaBr.
For hydrosorbic acid, the choice of a formula lies between
CHMe : CH.CH2.CH2.COOH and CH2Me.CH2.CH : CH.COOH, either
of which would explain its decomposition into butyric and acetic acids,
and its reduction to normal caproic acid. The first is probably correct ;
for if the second were so, then either its hydrobromo- or dibromo-
compound should give off carbonic anhydride when treated with
alkalis.
The case of pyroterebic acid is more obscure. Having the consti-
tution CHMe2.CH '. CH.COOH (since it is decomposed by potash into
isobutyric and acetic acids, and is reducible to isocaproic acid) its
bromhydro-componnd might be expected to give off carbonic anhydride
in contact with alkalis, whereas it actually forms a lactone. The two
reactions are, however, of the same nature : for both primarily de-
pend on the union of the bromine-atom with the hydrogen of the
carboxyl-group, the free bond of the oxygen being in one case trans-
ferred to the carbon of the carboxyl to form carbonic anhydride, in
the other to the carbon of the principal chain to form a lactone.
The peculiarity of constitution which determines the formation of
lactones in all probability cannot be expressed by our present constitu-
tional formulae. In the aromatic series the " ortho " constitution is
382 ABSTRACTS OF CHEMICAL PAPERS.
commonly supposed to predispose to it. But Perkin (Ghem. Soc. J.,
1877, 1, 417) has shown that coumarhi is the lactone, not of orthocou-
maric acid, but of an isomeride as yet unknown, salts of which have
been prepared by Williamson, and its stable methyl salt by Perkin.
Santonin, again, is the lactone of santoninic acid, which may be iso-
lated, but easily decomposes into water and santonin. But this santo-
ninic acid by long" boiling with barium hydrate passes into santonic
acid, which is perfectly stable and corresponds in all respects to ortho-
coumaric acid. At present this is inexplicable. Ch. B.
Structure of Sorbic and Hydrosorbic Acids. By N. Men-
SCHUTKIN {IJer., 13, 163 — 105).— The low initial rate of etherification
(7'96) of sorbic acid shows that this acid is tertiary, and the high
initial rate of etherification of hydrosorbic acid (43 '0) indicates the
primary nature of the latter acid. The author explains the conversion
of tertiary sorbic acid into primaiy hydrosorbic acid by reduction with
sodium-amalgam, by assuming the existence of a bivalent atom of
carbon in the former acid. W. C. W.
i8-Dipropyl- and /S-Diethyl-ethylenelactic Acid; Oxidation of
Allyldimethylcarbinol and Diallylcarbinol. By Schirokoff
{Ber., 12, 2375 — 237t>). — li-JJipropylethijlenelactic acid,
(CMeHo.CH,)2C(OH).CH3.COOH,
is obtained by oxidising allyldipropylcarbinol with potassium perman-
ganate. It is a syrup, which is but sparingly soluble in water, and
forms a ci'ystalline silver salt.
B-Bleihijlethylenelactic acid, CEt2(OH).CH2.COOH, is obtained in a
similar manner from allyldiethylcarbinol. It crystallises in needles
(m. p. 72°). The silver salt forms microscopic needles, whilst the
potassium salt is not crystalline.
Allyldimethylcarbinol gives hydroxyvalerianic acid on oxidation
either with chromic mixture or with potassium permanganate ; the
yield in the latter case, however, is much better than in the former.
Diallylcarbinol on oxidation gives oxalic acid and a non-volatile acid
wbich has not yet been investigated. T. C.
Stereocaulon Vesuvianum. By M. Coppola (Gazzetta, 10, 9 —
12). — This plant, after being thoroughly cleansed from dust and dried
at 100°, gave 11-16 per cent, of ash of the following composition : —
SiO.,.
SO3.
Fe,0,.
ALOg.
CaO.
MgO.
K2O.
Na.,0.
46-40
1-07
20-40
11*13
14-78
2-41
2-25
0-97
besides traces of phosphoric acid, manganese, &c.
By macerating the plant with milk-of-lime, precipitating the filtrate
with basic lead acetate, and decomposing the precipitate with hydro-
gen sulphide, a reddish-yellow solution was obtained from which ether
extracted a white crystalline substance mixed with a brown resin. The
crystalline substance after purification melted at about 180°, and on
analysis gave numbers closely agreeing with those required by the
formula C4H6O4. It would seem therefore to be succinic acid, but the
ORGANIC CHEMISTRY. 383
author tliinks it necessary to more completely investigate the proper-
ties of the substance before pronouncing a decided opinion as to its
nature. C. E. G.
Preparation of Pure Dioxyfumaric Acid. By S. Tanater
(Ber., 13, lo'J). — In order to separate dioxyfumaric acid from oxalic
and fumaric acids, the mixture of free acids is digested with freshly
precipitated nickel oxide and filtered whili^t hot. The liquid on cool-
ing deposits crystals of nickel dioxyf amarate, which may be purified by
recrystallisation. W. C. W.
Formation of /S-Methyloxyglutaric Acid from Diallylmethyl-
carbinol. By W. Sorokin (Ber., 12, 2374). — (S-Methyloxi/glutaric acid
is obtained by the oxidation of diallylmethylcarbinol with potassium
permanganate. It has the consistence of a syrup, decomposes car-
bonates, and forms salts, of which only those of silver and copper are
crystalline. The copper salt, (C6Hs05)2Cu + CUH2O2 + H^O, crys-
tallises in small plates. Its mode of formation indicates the following
constitution for the acid :— COOH.CH-.CMe(OH).CHo.COOH.
T. C.
Ethyl-carbamide and some of its Derivatives. By R. Leuckart
(J. pr. Chem. [2], 21, 1 — S6). — The author has not been able by his
numerous experiments to show that the ethyl-carbamides, obtained
from ethyl cyanate by the action of ammonia, and from ethylamine
cyanate by the re-grouping of its elementary constituents, are isomeric
and not identical bodies : but it must be noted that accurate quantita-
tive researches on their relative solubilities, and crystallographic
measurements have not been fully carried out.
The natui e of the diphenyl-carbamide obtained from both bodies by
heating with aniline, and of the diphenyl-biuret prepared by the same
reaction from the ether of ethyl-allophanic acid, as well as the consti-
tution of the acetyl-ethyl and benzoyl-ethyl compounds, renders it
probable that if urea is to be regarded as the amide of carbamic acid,
both ethyl compounds must be considered to be ethylamides of the same .
acid.
It is possible that the tolerably high temperature which comes into
play in the formation of the amide of ethyl-carbamic acid converts it,
as well as the ethyl-ammonium cyanate, into the more stable ethyl-
amide of carbamic acid. The author had intended to include in his
investigations the products which are formed by the action of am-
monia on the ether of ethyl- cai'bamic acid, and of ethylamine on ethyl
carbamate, but was unable to do so.
If an ether of ethyl-carbamic acid containing phosphorus could be
obtained by the action of ethylphosphine on ethyl chlorocarbonate, and
from this by the action of ethylamine a diethyl-phospho-carbamide, and
on the other hand if ethyl cyanate would combine with ethylphosphine
to form diethyl-phospho-carbamide, the first body would probably be
derived from ammonia, whilst the second would have the character-
istic properties of a phosphine.
Ethyl -carbamide itself closely resembles ordinary urea in nearly all
its reactions : it unites with acids to form salts, and combines with
384 ABSTRACTS OF CHEMICAL PAPERS.
metallic oxides. Acted on by etliyl chlorocarbonate, it yields an ether
of ethylalloplianic acid, and under the action of acid chlorides ethyl-
carbamides with acid radicles are formed, closely resembling the
corresponding compounds of ordinary urea. It resembles urea in its
behaviour with oxidising agents and on addition of water, but it
diifers in this, that condensation products resembling biuret cannot be
obtained from it : when heated, it passes directly into a mixture of
ethers of cyanuric acid. The melting point of ethyl-carbamide and its
compounds generally is lower, but their solubility, especially in ether,
is greater than that of the compounds of ordinary urea : the specific
gravity of urea is also slightly lowered by the substitution of alcohol
radicles for hydrogen. G. T. A.
Synthesis of Cumene. By A. Liebmann (Ber., 13, 45—46). — By
the action of an ethereal solution of zinc methide on benzal chloride,
the author has obtained cumene, C9H12. It boils at 152"5 — 158°, its
sp. gr. at 17"5° is 0"86576. The sulphonic acids prepared from this
hydrocarbon and its barium salt agree in their properties with those
prepared from cumene, and this would therefore seem to be isopropyl-
benzene. P. P. B.
Crystallographic Constants of some Benzene Derivatives.
By Gr. La Valle (Gazzetta, 10, 1 — (j). — Nitro 1:2:3 tribromobenzene,
C6H2Br3.N02, The crystals obtained by slow evaporation of the alco-
hol and ether solution belong to the triclinic system a : b : c_=
1-00552 : 1 : 0-48230. Observed forms 010, 001, 100, 120, 101, 122;
combinations 010, 001, 100, 120, 101, 122 ; cleavag-e parallel to 100 ;
dichroism feeble.
Nitro 1 : 3 diiodobenzene, CeHsL.NOj. The sulphur-yellow crystals
obtained by slow evaporation of the alcoholic solution, mixed with
very little ether belong to the trimetric system a : & : c = 0-64734 :
1 : 0-45819. Observed forms 010, Oil, llu ; combinations 010, Oil,
100 -, cleavage parallel to 110.
Monovitrochloro2yJienol, C6H3C1(N02).0H. Lemon-yellow crystals be-
longing to the monoclinic system a : b : c = 2-8293 : 1 : 1-50923. jf =
+ X : + S = 112° 29'. Observed forms 100, 101, 001, 101, 110, 112 ;
combinations 100, 101, 101, 110, 112 and 100, 101, 101, 110 ; fracture
vitreous. The plane of the optic axis is parallel to the plane of sym-
metry ; dichroism feeble.
Dinitroiodobenzene, C6H3l(N02)2- Two of these were examined : the
tirst was obtained by the action of nitric acid on [I : NO2 = 1:2]
nitroiodobenzene. The sulphur-yellow crystals belong to the triclinic
system a : b : c = 1-63461 : 1 : _0-939_687. Observed forms 001, 100,
110,190, 010, 110, 101, Oil, 101, 201; cleavage perfect parallel to
110. The pinacoids 190, 010, are striated parallel to their intersec-
tion ; dichroism scarcely sensible. The dinitro derivative obtained
from 1 : 4 nitroiodobenzene by the action of niti-ic acid, when ex-
amined crystallographically gave results almost identical with those
just described, and thei'o can be no doubt but that the minute differences
observed were due to the presence of a small quantity of some impurity.
C. E. G.
Anethol Derivatives. By P. Landolph {Ber., 13, 144—148).—
ORGANIC CHEMISTRY. 385
Boronflaoride decomposes boiling anetho], with formation of anisol,
and anethol dihydride, CioHuO.(b. p. 220^). Anetltol tetrahydride or
anethol camphor, CioHigO, is obtained together with anisaldehyde by
oxidising anethol wnth nitric acid. This compound boils at 190 — 193°,
and yields on oxidation with sulphuric acid and potassium dichromate
an acid crystallising in long needles (m. p. 175°), probably anisic acid.
The tetrahydride is converted into the hexhydride, CioHisO, by heating
with alcoholic potash in sealed tubes ; a potassium, salt crystallising in
needles is also formed at the same time. The hexhydride is a syrupy
liquid at the ordinary temperature. Tt boils at 198°, and solidifies at
0°, forming needle-shaped crystals, which melt at 19°.
Two compounds are produced by the action of alcoholic potash on
anethol in sealed tubes, viz., CieHi^Os and CuHigOe. The former is
sparingly soluble in hot water, but dissolves freely in alcohol, ether,
and benzene, and is volatile in a current of steam. The crystals melt
at 87°. The acetate of this diphenol is a yellowish syrupy liquid,
which is easily decomposed by heat.
The compound, CuHieOo, is a yellow brittle resin (m. p. 65°), not
volatile in a current of steam.
The acetate, CisHi^Os, is a reddish-yellow resin (m. p. 40°).
Two substances are also formed by the action of alcoholic potash on
monochh^ranethol, prepared by treating anethol with phosphorus
pentachloride. The chief product is a colourless liquid, CieHooOa,
of ethereal odour. It is insoluble in water and potash, and boils at
270".
The second product, a liquid soluble in potash, has not been obtained
in the pure state. W. C. W
Resorcinol Isosuccinein. By J. Rosicki (Ber., 13, 208 — 209).
— This compound is prepared by heating at 120 — -loO" a mixture of
isosuccinic acid, resorcinol, and sulphuric acid. The unaltered iso-
succinic acid and resorcinol are removed from the crude product, by
treatment with boiling water; the residue is dissolved in ammonia,
and reprecipitated by hydrochloric acid. Resorcinol-isosuccinein,
CieHijOj, is a yellowish-brown amorphous substance, soluble in alco-
hol, in ether, and in alkalis. In the latter case, a liquid having a
faint red colour and green fluorescence is formed.
The isosuccinic acid used in these experiments was prepared by
boiling a-bromopropionic acid (Friedel and Machuca, AiDialeii, 120,
286) with 2 parts of potassium cyanide dissolved in 4 parts of water.
The cyanopropionic acid obtained in this way is converted into pro-
pionic acid by the usual method. W. C. W.
Bromine Derivatives from Quinone. By Saraitw (Ber., 13,
209). — A mixture of mono- and dibromo-quiuols is formed by the action
of concentrated hydrobromic acid on solid quinone. Under certain
conditions an acetic acid solution of quinone yields only the mono-
product. Dibromoquinone is prepared by bringing together equal
molecules of bromine and quinone, also by the action of 2 molecules
of bromine on one of quinol. Tetrabromoquinol is formed when
bromanil is heated with hydrobromic acid. W. C. W.
386 ABSTRACTS OF CHEMICAL PAPERS.
Action of Sulphur on Phenylbenzamide. By A. W. Hofmann
(Ber., 12, 2359 — 2365). — Bemijlamidopheuyl ?nercaptan, C13H9NS, is
obtained by boiling 1 part of sulphur with 2 parts of phenylbenza-
mide for several hours, thus: CigHnNO + S = C13H3NS -h HjO. It
crystallises from alcohol in colourless needles (m. p. 115° ; b. p. ^
about that of mercury). It distils without decomposition, and is
soluble in ether and in carbon bisulphide. It has feeble basic proper-
ties, dissolving in acids to form salts, which are decomposed on addi-
tion of water. The platino- and auro-chlorides are described, the
latter having the composition, 2[Ci3H9NS.HCl]AuCl3. The free base
has an agreeable odour of tea-roses and geraniums, which is consider-
ably increased on warming. Its constitution is represented by the
formula : C6H4<' "yCPh, the nitrogen being in the ortho-position
as regards the sulphur. This substance is therefore analogous to
the compound which Ladenburg obtained (Ber., 9, 1524; 10, 1123) by
the action of benzoic chloride on orthamidophenol, for it merely con-
tains sulphur in place of oxygen. On fusion with potash, it gives
benzoic acid and amidopJienyl mercaptan, C6H4(NH2).SH [1 : 2], the
latter of which undergoes oxidation on exposing its solution to the air,
crystals of the &/.s»/|iM/f?, (C6H4.NH2)2S2, being deposited; this I'eaction
takes place more readily if a feeble oxidising agent such as ferric
chloride is used ; when this latter agent is employed, the bisulphide-
hydrochloride is first obtained. The hydrochloride crystallises in
plates, which are difficultly soluble in very dilute hydrochloric acid,
but easily soluble in hot water. By decomposition with ammonia, it
gives the bisulphide crystallising in plates (m. p. 93°), which are in-
soluble in water, but soluble in boiling alcohol. Reducing agents
convert it into the mercaptan. This bisulphide is isomeric with the
pseudo-dithioaniline (m. p. = 79°), obtained by E. B. Schmidt {ibid.,
11, 1168) by the action of sulphur chloride on acetanilide.
An impure amidophenylmercaptan has already been obtained by
Glutz and Schrank (J. pr. Chem., 2, 223). T. C.
Constitution of Nitrosodimethylmetatoluidine. By C. Riedel
(Ber., 13, 126 — 127). — Dimethyltolylenediamine obtained by the re-
duction of nitrosodimethylmetatoluidine, yields on oxidation with sul-
phuric acid and manganese dioxide, a crystalline compound (m. p. 67'^)
which IS identical with the toluquinone, which Nietzki (Ber., 10, 833,
and this Journal, 1877, ii, 476) prepared from paramidotoluene. This
shows that dimethyltolylenediamine is a dimethyl derivative of par-
amidotoluene, and since this body was obtained by the reduction of
nitrosodimethylmetatoluidine, the nitroso-group must occupy the para-
position with regard to the amido-group in the latter compound. The
constitution of nitrosodimethylmetatoluidine is consequently —
C6H3Me(NOj.NAle2[Me : NO : NMco = 1:2:5].
w. c. w.
Ortho- and Para-toluidine Derivatives. By G. Staats (Ber.,
13, U6— 138).— OrthotolyWiiocurbamide, H2N.CS.NH.C7H7, obtained
ORGANIC CHEMISTRY. 387
by tbe action of ammonia on orthotolylthiocarbimide (b. p. 236°), melts
at 155°, and is soluble iu hot water and in alcohol. The para- com-
pound crystallises in thick needles (m. p. 182"), which are soluble in
hot water and alcohol.
OrthotolyJefhiflthiocarbamide, HEtN.CS.NH.C7H7, prepared by treat-
ing tolylthiocarliimide with ethylamine, crystallises in pale yellow
prisms (m. p. 84°), which dissolve in alcohol and ether, but are in-
soluble in water. Tlie /)a?-a-compound forms crystalline plates (m. p.
93°) soluble in ether and in boiling' water.
Orthofolylphevylthiocarbaniide, HPhN.CS.NH.C7H7 (m. p. 139°),
crystallises in yellow needles freely soluble in alcohol and ether. Para-
tolylpheiit/lfhiocarhamide (m. p. 137'') is sparingly soluble in water and
easily soluble in alcohol and ether.
Orthotoh/lglycocine, C7H7.NH.CH3.COOH, is produced when ortho-
toluidine monochloracetate is boiled with water for 15 minutes, and
is deposited from the mixture on cooling in white acicular crystals
(m. p. 150°). Orthotolylglycocine forms a crystalhne compound with
copper salts ; it reduces nitrate of silver solution, and throws down a
red precipitate when boiled with ferric chloride.
Acetorthohomoparoxyhenzaldehyde, C6H.,Me(0Ac).C0H, is obtained
in needle-shaped ciystals (m. p. 4U°) by adding an ethereal solution of
acetic anhydride to the potassium salt of orthohomoparaoxybenzalde-
hyde. W. C. W.
A New Base. By E. F. Smith (Ber., 13, 33— 34).— By the per-
chlorination of toluene, the author has obtained a carbon chloride,
C21CI26, vvhich crystallises in large colourless prisms, m. p. 152 — 153°
(Am. Phil. Soc, May 4, 1877; Jahresh., 1877, p. 420). By the
action of this chloride on aniline in sealed tubes at 180°, the new
base is obtained. It is easily soluble in water and other solvents,
and has been obtained from concentrated aqueous solutions in thin
leaflets, which blacken at 225° and melt at 230°. When warmed with
aqueous solution of chromic acid, it is converted into a reddish-brown
mass, only sparingly soluble iu water, but soluble in alcohol with an
intense red coloration. The new base forms well crystallised salts ;
the hydrochloride forms long thick needles, easily soluble in alcohol
and water. P. P, B.
A Series of Aromatic Bases Isomeric with the Thiocarbi-
mides. By A. \V. Hoi-manx {Jier., 13, 8 — 22).— The author has
already described (this Journal, 1879, Abstr., 805) the production of
chlorophenylthicjcarbimide, C7H4CINS. It is a liquid which crystal-
lises on cooling (m. p. 24°). It has basic properties; its solution in
concentrated hydrochloric acid is precipitated by gold and platinum
chlorides, the double salt so formed being decomposed by water, form-
ing chlorijphenylthiocarbimide.
Chlorophenylthiocarbimide is decomposed by water at 200°, aniline,
hydrochloric acid, carbonic anhydride, and sulphur being amongst the
products of the reaction.
Chloronitrophenylthiocarbimide, C7H3C1(N02)NS, is obtained by the
action of nitric acid on the solution of the thiocarbimide in concen-
388 ABSTRACTS OF CHEMICAL PAPERS.
trated sulphuric acid. It crystallises in yellow needles, m. p. 192°,
and is destitute of basic properties. The chlorine in this compound
may be replaced, e.g., by aniline, forming a compound melting
at 247°.
EthoxiiplienyJthiocarhimirJe is obtained by treating the chlorophenyl-
thiocarbiiuide with solution of sodium ethylate in alcohol. It forms
at first an oil, which finally becomes crystalline, m. p. 25°. It has
feeble basic properties, being dissolved by hydrochloric acid, and yields
unstable auro- and platino-chlorides.
AcetoxypheniiUhiocai'bimide, C7H4(OAc)NS, is obtained by heating
hydroxyphenylthiocarbimide (loc. cit.) with acetic anhydride. It crys-
tallises from alcohol in prisms, and from hot acetic acid in needles,
melting at GO^. It has no basic properties.
AniidophenyUhiocarhim.ide (loc. cit.) is precipitated from its alcoholic
solutions in shining leaflets melting at 129°. It may be distilled with-
out decomposition. It is a feeble base, dissolving in concentrated
acids. Platinum and gold chlorides precipitate its hydrochloric acid
solutions ; the double salts so obtained are not decomposed by water.
The platinochloride has the composition [C7Hi.(N"Il2)NS.HCl]3PtCl4.
Auilidoplieyiylthiocarhimide (loc. cit.) after repeated crystallisation
melts at 159°, not 157° as formerly stated. It is very stable, may be
distilled, and is not decomposed by boiling with alkalis or acids. Its
platinochloride has the composition [C7H4(NIIPh)NS.HCl]2PtCl4.
The 1 . 2, 1 . 3, and 1 . 4 chloranilines were converted into carba-
mides by means of carbon bisulphide, and the corresponding chloro-
phenylthiocarbimides obtained from them.
1"2 chloraniline yields a thiocarbamide (m. p. 145 — 146°), and a
soKd thiocarbimide (m. p. 44—45°, b. p. 249—250°).
1"3 chloraniline yields a thiocarbamide (m. p. 121 — 122°), and a
liquid thiocarbimide (b. p. 249 — 250°).
1'4 chloraniline yields a thiocarbamide (m. p. 108°), and a solid
thiocarbimide (m. p. 44-5°, b. p. 249—250°).
None of these chlorophenylthiocarbimides exhibit the same properties
as that prepared from phenylthiocarbimide {he. cit.). The chlorine
in this compound maybe replaced by hydrogen, e.g., when it is treated
with tin and hydrochloric acid or hydriodic acid and phosphorus, and
thus a new base is obtained isomeric with phenylthiocarbimide and
phenylthiocyanate.
This base, C7H5NS, is a liqaid heavier than water, in which it is
scarcely soluble; alcohol and carbon bisulphide dissolve it easily. It
has a burning taste, and an odour resembling that of the pyridine
bases. It boils at 230°. It forms salts, and its hydrochloride yields a
crystalline, sparingly soluble platinochloride, [C7ll5NS.HCl]3PtCl4, and
an aurochloride, CtHsNS.HCI. AuCla, also double salts with tin and mer-
curic chlorides. Moreover, this base differs from phenylthiocarbimide,
ins(Jmtich as the sulphur is not removed by alkalis or by lead. It
forms addition-products with bromine and with methyl iodide ; the
latter crystallises in needles melting at 210°, and having the formula
C7H5NS.MeI. The base, treated with phosphorus pentachloride, yields
the original chlorophenylthiocarbimide.
I
ORGAXIC CHEMISTRY. 389
Pheiiyl-pJienylthiocarbimide, CTHifCeHj^NS. — This body is obtained
in small quantities when phenvlthiocarbitnide is heated with benzoic
chloride at 250—300°, thus : CtH-,NS + PhCOCl = C,H4PhNS +
CHOCl. It crystallises from alcohol in beautiful needles havintr the
odour of roses and g'eraniums. This body is identical with that ob-
tained by the action of sulphur on phenylbenzamide (this vol., p. 386).
The new base, C7H5NS, when fus^d with alkalis is resolved into
formic acid and amidophenyl mercaptan, and further it may be pre-
pared by heating these two compounds together. Therefore it is
methenylamidophenyl mercaptan, C6H4\ ^CH.
The author has prepared the amido-mercaptans from the 1 . 2, 1 . 3,
and 1 . 4 nitrobenzenesulphouic acids described by Limprlcht (Anna-
len, 177, 60).
1.2C6H4(NOo).S03Hgaveanamide, C6H4.(N02).S03NH„m.p.l88°,
which on reduction gave an amido-mei'captan. Similarly 1 . 3-
C6H4(NO,).SO;,H yielded an amide, m. p. 164°, and finally 1 . 4-
C6H4(NO)2.S03Hgave an amide, m. p. 131°, from both of which amides
raercaptans were obtained by reduction. The mercaptans from 1 . 3
and 1 . 4 uitrostilphonic acids are not acted on by acids or by acid chlo-
rides, whereas the 1 . 2 mercaptan when heated with formic acid yields
the base CTniNS. Thus the constitution of this base being repre-
sented by the above formula, those of the chloro-, hydroxy-, and
amido-derivatives are as follows : —
C6H4< ^CCl. CB/ ^C.OH. C6H4/ ^C.NH...
^S^ ^s^ ^s^
And the formation of the chloro-derivative from the thiocai'bimide
may be represented thus : —
C5H5.N : c : s + CL = CeHs.N : cci.sci = CeHi/ ^ci + hci.
The following homologues of methenylamidophenyl mercaptan have
been prepared : —
EtheyiylamifJ oyihenyl mercaptan, CJi-^S, is obtained by the action of
acetic anhydride on the amidomercaptan. It resembles the methenyl
compound in its properties, and boils at 238°. The platinochloride,
(C8H,NS.HCl).,PtCl4, forms yellow needles.
PropeyujJamidnphenyl mercaptan, C9H9NS, obtained from the amido-
mercaptan and propionic chloride. It is a colourless heavy liquid,
boiling at 252°. Its platinochloride forms large pi-isms.
PentenyJ amidophenyl mercai^tan, CnHisNS, is obtained from the
amidomercaptan and valeric chloride. It has less marked basic
])roperties than the lower homologues ; its platinochloride is obtained
as a crystalline precipitate by treating the alcohol solution with
hydrochloric acid and platinum chloride. P. P. B.
Some Azo-derivatives. By F. Stecbins {Ber., 13, 43 — 44). —
Azubenzenetriicilro-uxybeuzene, CoH5.N2.C6H(X02)3.0H, is obtained by
390 ABSTRACTS OF CHEMICAL PAPERS.
treatiug an alcoholic solution of picric acid with diazobenzene nitrate.
It is an unstable compound, crystallises in long;' brown prismatic
needles, having metallic lustre ; when heated to 70° it explodes. It
is insoluble in cold water, slightly soluble in hot water, and easily in
alcohol. It dyes silk and wool orange-yellow.
Azoheiizenepiirogallol, C6H5.No.C6Ho(OH)3, is obtained by treating an
alkaline solution of pyrogallol with diazobenzene nitrate. When
crystallised from glacial acetic acid, it forms small red needles, inso-
luble in water, but easily soluble in alcohol and in nitrobenzene.
It also dyes silk and wool orange-yellow. P. P. B.
Dye-stuffs of the Rosaniline Group. By E. and 0. Fischer
(Ber., 12, 2344- — 2o53). — lu a previous communication (ibid., 800),
the authors described a green dye-stuff obtained from paranitro-
benzoic chloride and dimethylaniline ; this they considered to be the
ijaraniti'o-derivative of malachite green. By reduction with zinc-dust
and acetic acid, this body gives a violet dye-stuff very similar to the
violet dei'ivatives of rosaniline. On further reduction, a leuco-base is
obtained, which appears to be a methylated leuco-aniline. This on
oxidation yields a violet-red dye, and by heating with methyl iodide
gives an ammonium base as a final product identical with the com-
pound obtained from paraleucaniline in a similar way. The final
methylated product of ordinary leucaniline is a nono-, and not an
octo-niethylated compound, as stated by Hofmann and Girard {ibid.,
2, 448).
Ndnomefhi/lated paraleucaniline, Ci9Hi3Me6CMeI)2, crystallises from
hot water in colourless needles, and possesses properties similar to
those of its homologue. On heating the iodide, it loses methyl iodide,
and is partially converted into methyl violet. These properties are
also exhibited by the body obtained from the leuco-base of paranitro-
bitter almond oil green by heating with methyl iodide and methyl
alcohol at 100—110°.
The ammonium iodides of both compounds when heated quickly in
capillary tubes assume a feeble blue colour, and melt with evolution
of gas at 185° to a dark violet- blue liquid. They are therefore iden-
tical, and the relative position of the three nitrogen groups in the
green nitro-compound is the same as in pararosaniline, and further, it
is very pi'obable that the two amido-groups have the same position as
in malachite green, there being in fact no essential difference between
the constitution of the two bodies. Their direct conversion by reduc-
tion into a violet methylated rosaniline derivative shows that the
whole class of dye-stuffs derived from bitter almond oil green has a
constitution similar to that of rosaniline.
From considerations for which the original paper must be consulted,
it appears that the colour-forming group in all the basic derivatives of
triphenyl carbinol is essentially the same.
In regard to the caase of the difference in colour of methyl- violet
and methyl-green, the following conclusions are drawn : — Since the
colour of the paranitro-benzaldehyde green is not essentially different
from that of benzaldehyde oil green, it would seem that the colour is
independent of the nitro-group ; but when the latter becomes an
ORGANIC CHEMISTRY. 391
amido-gronp, the green changes to reddish-violet. The two methylated
amido-groups in benzaldehyde green are therefore the cause of the
greed colour, and these, when in combination with a third amido-
greup present in the para-position, give a red. When, however, this
third amido-group is destroyed, the green colour is reproduced, as is
the case when the third amido-group is changed into a quarternary
ammonium-group, which, like the nitro-group, is without infinence on
the colour, but increases the solubility of the dye-stuii".
Hofmann's (ibid., 7, 364) tri-iodomethylated trimethylrosaniline is
totally different from methyl-green. T. C.
Safranine. By R. Bindschedler (Ber., 13, 207— 208).— Safranine
is best prepared by the action of potassium chromate on a dilute boil-
ing solution of paradiamidotoluene hydrochloride (1 mol.) and ortho-
or para-toluidine hydrochloride (2 mols.). On neutralising the liquid
with sodium carbonate, the safranine remains in .solution. A similar
colouring matter is produced by oxidising a mixture of dimethyl-
phenyldiamine (1 mol.) and aniline hydrochloride (2 mols.). The
alcoholic solutiou which is strongly fluorescent dyes silk bright red.
By oxidising a cold dilute hydrochloric acid solution of dimethyl-
phenylenediamine (1 mol.) and dimethylaniline (2 mols.) in presence
of zinc chloride, beautiful crystals are produced, having a cupious
or green lustre. The aqueous solution has an intense green colour ;
when heated with aniline hydrochloride, it yields a reddish-violet
fluorescent liquid. W. C. W.
Colouring Matters from Furfuraldehyde. By H. Schiff
(Annalev, 201, 355 — 369). — Furfuraldehyde combines with 2 mole-
cules of diphenylamine at 150° to form an oily liquid, which solidifies
at 0"" to a crystalline mass. With hydrochloric acid this substance
yields a bronze-coloured compound, which dissolves in alcohol, forming
a deep-red coloured solution. The hydrochloride is unstable, and cannot
be purified by recrystallisation.
When an alcoholic solution of metanitraniline and furfuraldehyde is
gently warmed, the compound C6H4(N03).NH2.C5Hi02 separates out
as a chrome-yellow crystalline crust. The hydrochloride of this base
ciystallises in small plates, having a metallic lustre. The deep car-
mine colour of the alcoholic solution is destroyed by strong hydi'o-
chloric acid.
Hydroxijfui-furaniline is deposited in pale yellow prisms, when
aqueous solutions of furfuraldehyde and paramidophenol are mixed
together, CeHiCOHj.NH, -f C,B.,0, = H,0 + C6H4 : (OH)N".C5H40.
The crystals are soluble in alcohol ; they melt at 180°, undergoing
decomposition. The hydrochloride could not be obtained by direct
union of the base with hydrochloride acid, but it may be easily pre-
pared by evaporating at 60°, an alcoholic solution of the base con-
taining a small qimntity of ammonium chloride. It forms a beetle-
green crystalline mass, sparingly soluble in water, but dissolving freely
in alcohol, producing a red solution.
Difurfuroioh/leHedia/niiie, C7Hf;X2(C5H40)2, prepared by adding fur-
furaldehyde to an alcoholic solution of melatolylenediamine, crys-
392 ABSTRACTS OF CHEMICAL PAPERS.
tallipes in orange- coloured needles, which decompose at 120° without
melting. The carmine-coloured hydrochloride is soluble in alcohol
and in water, but is decomposed by a large excess of the latter solvent.
The platinochloride has the composition, H,PtCl6.C7HioN2.2C5H402.
The preparation of furfur obenzidine (C6H4N)2(C5H40)2 resembles that
of the pi'eceding base. It forms pale yellow needles, which are only
sparingly soluble in water and in cold alcohol, but dissolve freely in
benzene. The salts of furfurobenzidine are very unstable ; they form
carmine-coloured alcoholic solutions. The hydrochloride has the com-
position C,2H,oN2.2C5H40o.2HCl.
Fvrfuraiiii(Johenzoic acid, Ci5H4(N"H2)COOH C5H4O2, is deposited in
dichroic needle-shaped crystals, when fuifuraldehyde is added to an
aqueous solution of amidobenzoic acid. The compound is soluble in
alcohol, forming a red solution. It has neither acid nor basic pro-
perties. If in the preceding reaction a salt of amidobenzoic acid is
used instead of the free acid, no coloured derivative is obtained until
hydrochloric acid is added to the mixture.
Amidocinnamic and the amidosalicylic acids also yield crystalline
compounds with furfuraldehyde. W. C. W.
Nitration of Metachlorosalicylic Acid. By E. F. Smith and
G. K. Peirce (Ber., 13, 34 — 30). — By the nitration of metachloro-
salicylic acid, metachloronitrosalicylic acid and two isomeric dinitro-
chloroplienols were obtained. The two phenols were separated by
means of their potassium salts, the less soluble one proving to be the
a-monochlorodinitrophenol described by Faust and Saame. The
isomeride of this phenol crystallises in orange needles (m. p. 78 — 80°, '
and solidifying at 25°). Its potassium salt crystallises in orange-
coloured needles, containing 1^ mol. of water, and is easily soluble in
water. The silver salt of the a-derivative forms long red needles,
whilst that of the isomeride forms bronze, lustrous needles.
The vitrocliloromh'cyh'c acid, crystallises in needles (m. p. 162 — 163°),
and is identical with metachloronitrosnlicylic acid described by Hiibner.
The potassium salt, C«H2Cl(N02)(OH).COOK, forms yellow needles,
having a bitter taste; is easily soluble in water. The harium salt
[C6H2Cl(N02)(OH).COO]oBa "forms oranffe-red needles sparingly
soluble in water. The ethyl salt, CeH2Cl(N02)(OH).COOEt, crys-
tallises in colourless needles, melting at 89° ; from it the amide,
C6H2Cl(N02)(OII).CONH2, has been obtained; it is easily soluble in
alcohol, but sparingly in water (m. p. 199°).
a-Monocldorodinttrophenolaniline, CeH.Cl (NOo) . OII2. CgHs.N'Hs, is
obtained by mixing the phenol with aniline, when a deep-red solu-
tion is formed. By evaporation, it is obtained in hard yellow crystals
which are easily soluble in hot water, and melt at 137°. It is resolved
into its constituents by continued boiling with water. P. P. B.
Action of Phenols on Halogen-derivatives of Patty Acids. By
L. Saakbach {J.pr. Clem. [2], 21, 151— 171).— The reaction of phenol
with monochloracetic acid, yielding phenoxyacetic acid, was regarded
by Heiutz, who first studied it (Pogg. Ann., 109, 489), as typical of
ORGANIC CHEMISTRY. 393
the whole series of possible homolosrous reactions. The investigation
of certain of these forms the subject of this communication.
Phenol and a-Monochloropropionic Acid. — These bodies, in the form
of their sodium compounds, react in the cold with formation of
phenoxypropionic acid (m. p. IIC'5"), thus: —
CMeHCl.COOXa + Ph.ONa = ]N'aCl + CMeH(PhO).COOXa.
This acid is freely soluble in alcohol, ether, and in hot water ; slightly
soluble in cold water. It is volatilised by steam. The aqueous solu-
tion gives a yellowish precipitate with ferric chloride. The sodium
salt, the product of the above reaction, crystallises on evaporation of
its aqueous solution in concentric groups of needles ; the potassium
salt also in long needles containing 1^ mol. HjO. Ethyl phenoxy-
propioymte, CMeH(OPh).COOEt, is easily prepared by passing hydro-
chloric acid gas into the alcoholic solution of the acid kept boiling on
the water-bath. It is a colourless liquid of sp. gr. ISfJO at 17"5° ; it
boils undecomposed at 243 — 244° ; it is volatilised by steam. In con-
tact with aqueous ammonia it is decomposed, yielding the corresponding
amide :
CMeH(OPh).COOEt -f NH3 = EtOH -f- CMeH(0Ph).C0NH2.
It is freely soluble in alcohol, ether, and hot water, crystallising
from its solutions in needles (m. p. 130°). On adding bromine to the
hot aqueous solution of phenoxypropionic acid, monobromphenoxy-
jrropionic arid, CMeH(OC6H4Br).COOH, is formed. On recrys-
tallising from dilute alcohol, it is obtained in long transparent needles
(m. p. 105 — 10G°), which are freely soluble in ether and alcohol : on
the addition of water to its solution in the latter, the acid is separated.
The acid is not decomposed by boiling with concentrated solution of
soda.
Eugenol and Mono chlor acetic Acid. — These bodies were heated toge-
ther on the water-bath, and soda (sol. sp. gr. 1"34°) added, until the
decomposition was complete. The reaction which occurs is expressed
by the equation : —
C6H3(OMe)(C3H5).OH -1- CH2CI.COOH + 2NaOH = NaCl +
2H.0 4- C6H3(OMe)(C3H5).O.CHoCOO]S'a.
The new acid crystallises from its aqueous solution in long needles
(m. p. 80 — 81°), which are easily soluble in ether and in alcohol.
Thymol and Monochloracetic Acid. — The reaction which occurs is
exactly analogous to the preceding. The thymoxyacetic acid foi-med,
C6H3Me(PrO).CHo.COONa, is freely soluble in alcohol, ether, and hot
water, and crystallises from its solution in long needles (m. p. 148°).
Orcinol and Monochloracetic Acid. — The reaction between these bodies,
which is equally smooth, takes place according to the equation : —
CeHsMeCOH), + 2CH0CI.COOH + 4XaOH = 2NaCl + 4H2O +
C6H3Me(O.CH,.COONa)2.
The acid is easily isolated, crystallising from its hot aqueous solu-
tion in microscopic needles (m. p. 216 — 217°). Its analogy with the
acid previously desci'ibed suggests the name diorcoxydiacetic acid ;
VOL. XXXVIII. 2 /
394 ABSTRACTS OP CHEMICAL PAPERS.
the term diocroxy- representing the hypothetic diatomic radicle,
(CeHaMe { g)".
The normal sodium salt crystallises from its aqueous solution with
3 mols. HoO. The calcium salt crystallises with 2 mols. H2O in thin
plates. EtJujl cUorcoxydiacetate is prepared by passing hydrochloric
acid gas into the hot alcoholic solution of the acid. It is freely
soluble in alcohol and ether, crystallising from these solutions in
needles (m. p, 107°) ; on the addition of water, it separates as an oil.
In contact with aqiieous ammonia, it is converted into the corresponding
amide.
Two isomeric mononitrodiorcoxydiacetic acids are formed when the
acid is added slowly to warm concentrated nitric acid ; one of these
is separated as a red powder on diluting the solution ; the second is
obtained in the form of colourless monoclinic prisms by evaporating
the filtrate from the first, allowing to crystallise, and recrystallising
from alcoholic solution,
Pltenol and I) ihromo succinic Acid. — The mutual reaction of these
bodies was investigated ; but the results obtained were not of a definite
character. C. F. C.
Condensation-products of Gallic Acid. By J. Oser and F.
BocKER {Wien. Ahid. Ber., 79 [2], 148— 155).— By mixing gradually
and with certain precautions a solution of potassium permanganate
with one of gallic acid containing sulphuric acid, the authors obtained
a yellow substance, which in a pure state formed minute acicular crys-
tals. Its composition agreed with the formula CuHioOs, and when
heated with zinc powder in hydrogen, it yielded a hydrocarbon cor-
responding with the formula CuHio, and identical with that which
Rembold obtained by a similar reduction of ellagic acid (Ber., 1875,
1494), and proposed to designate by the name of ellagene. The
authors consider, therefore, that their new substance is not to be
ranked in the series of condensation-products of rufigallic acid, but
belongs to the ellagic acid series, its relation to ellagic acid, C14H6O8,
being that of a reduction-product to an oxidation-product.
R. R.
Sulphonic Acids from Isomeric Nitramido- and Diamido-
benzenes. By J. Post and E. Hardtung {Ber., 13, 38 — 41). —
Ori]iOiiitramidobenze7ie-swl'pho7i{c acid, prepared from orthonitraniline by
the action of fuming sulphuric acid, is easily soluble in alcohol and water.
The barium salt, [C6H5(N02).NHoS03]2Ba.2|H.,0, forms dark yellow
brittle needles. The calcium salt, [C6H3.(N02).NH2S03]2Ca.2^H20,
is soluble in 4 — 6 times its weight of boiling water ; it crystallises in
bright yellow needles. ThQ potassuon salt crystallises with 1 mol. of
water in dark yellow short needles which are more soluble than the
above.
Ortliodiamidohenzene-sulplioyiic acid is obtained by the reduction of
the nitramido-acid ; it forms rose-coloured needles. Its barium salt,
[C6H:i(NH..,).]SrH.SOs]2Ba5^H30, is very soluble in water; crystallises
in thin, light brown leaflets. It is precipitated from its aqueous solu-
tions by alcohol in the form of brittle, bright brown needles. The
calcium salt, [C6H3(NH2).NH2S03]oCa.3Il30, is also easily soluble in
ORGANIC CHEMISTRY. 395
water. The orthodiamidobenzene-snlplionic acid, prepared from ortlio-
diaiuidobenzene, is identical with the above, showing that the sul-
phoxj-group replaces the same atom of hydrogen in the aromatic
nucleus, whether there be a nitro- and an amido-group present, or two
amido-groups.
Metanilramidohenzene-sidphonic acid is prepared by heating meta-
nitraniline with fuming sulphuric acid in sealed tubes at 175°. The
free acid prepared from its barium salt crystallises in large yellow
brown prisms. The barium salt, [C6H3(N02).]S'H2S03]oBa.2H,.0, is
soluble in 6 — 8 times its weight of hot water, crystallises in dark
brown needles. By slow evaporation of its aqueous solutions, it is
obtained in tables. The caZci«??i. salt, [C6H3(N02).NHjS03]2Ca.4HoO, is
easily soluble in hot water, from which it crystallises in small, dark
yellow needles.
Metadiainidobeiizene-»idplionic acid, prepared by the reduction of the
metauitroamido acid, has been obtained in two dimorphous modifica-
tions. Its barium salt, [C6H3(NH2).NH2S03]2Ba.6H20, is easily
soluble in water, less soluble in alcohol and water ; it crystallises in
brown prisms. The calcium salt, [C6H3(NH2).NH2S03].Ca.5iH20,
crystallises from a mixture of alcohol and water in colourless, compact
prisms, which are very soluble in water.
The metadiamidobenzene-sulphonic acid, prepared from meta-
diamidobenzene, is identical with that obtained from metanitramido-
benzene sulphonic acid, as was the case with the orthodiamidobenzene
sulphonic acids. P. P. B.
Synthesis of Methylketole, an Isomeride of Skatole. By
A. Baeyer and 0. R. Jackson (Ber., 13, 1S7— 189).— 3Iethylketole,
C6H4'v. ^C.Me, is formed by treating the nitro-derivative of the
methylketone of phenylacetic acid (Ber., 3, 198) with ammonia and
zinc-dust, at a temperature just below the boiling point of the mix-
ture. When the product is distilled in a cuii-ent of steam, the methyl-
ketole crystallises from the distillate in colourless plates or needles,
which have a strong odour, resembling that of indole.
The crystals melt at 59'^, and distil without decomposition at a
higher temperature. They are soluble in hot water and in cold hydro-
chloric acid. The acid solution j-ields a crystalline platinochloride,
and a deposit of yellowish-red needles with picric acid. With nitrous
acid a yellowish, and with bleaching powder a fugitive blue, coloration
is produced. W. C. W.
Monophenylboron Chloride. The Quantivalence of Boron.
By A. !MiCHAELi.s and P. Becker (Ber., 13, .5s — 'o\).—Moiwpheniilhoron
chloride is prepared by the action of mercury diphenyl on boron chloride
at 180— 200°, the following reaction taking place, Hg(CsH5)> + 2BCl3
= 2C6H5BCI2 + HgCU. It is a colourless liquid, becoming red on
exposure to the air ; it boils at 175°: like boron chloride, it fumes in
the air, and decomposes with a hissing noise when treated with water.
2/2
396 ABSTRACTS OF CHEMICAL PAPERS.
By this action monophenylhonc acid is proclaced, wliioh crystallises
from water in needles. Chlorine is not absorbed by monophenylboron
chloride at the ordinary temperature, but a small quantity of the
chloride is decomposed as follows : CeHsBCL + CI, = CsHsCl + BCI3.
If monophenylboron chloride be placed in a freezing mixture, it soli-
difies, and in this state absorbs chlorine, becoming at the same time
liquid, owing to the formation of a tetrachloride, C6H5BCI4, which
when removed from the freezing mixture decomposes, forming boron
chloride and chlorobeuzene, thus : CeHsBCli = CeHsCl + BCI3. At
the saTQe time a portion decomposes into the monophenvlboron chloride
and chlorine, thus : CeHsBClj = CeHjBClo + CU.
The formation of this tetrachloride and its decomposition, the
authors regard as evidence of the quinquivalence of boron.
P. P. B.
Aromatic Arsenic Compounds. By W. La Coste and A.
MiCHAELis (Annalen, 201, 189 — 261). — After referring to the re-
searches of Bunsen (Annalev, 24, 271; 31, 175; 37, 1 ; 42, 25; 46,
1), Dumas {ibid., 27, 148), Cahours and Riche (Compt. rend., 36,
1001 ; 39, oil ; 49, 87, and 50, 1002), Landolt (Annalen, 89, 301 ;
92, 365), Wohler (ibid., 103, 375), Hofmann (ihid., 103, 357, and
Supplement, 1, 306), and Baeyer (ihid., 105, 265), on the organic
arsenic compounds, the authors give an account of the mono-, di-, and
tri-phenyl- and of the mono-tolylarsinic derivatives. Most of these
bodies have been previously described (J5e?-., 8, 1316; 9, 1566; 10,
622 ; 11, 1883, and this Journal, 1876 [i], 610 ; 1877 [i], 311 ; [ii],
452; 1879, Abstracts, 161).
Monophenylarsinic acid, PhAsO(OB[)2, is soluble in aqueous ammo-
nia, potash, soda, and baryta-water.
When a concentrated solution of the ammonium salt is allowed to
stand over sulphuric acid, it slowly deposits transparent needle-shaped
and prismatic crystals, which lose ammonia and effloresce on exposure
to the air. The potassium salt, PhAsO(OH).OK is very hygroscopic,
aud has not been obtained in the crystalline state. The harium salt
(PhAs03H)2Ba forms anhydrous needle-shaped crystals, which are
less soluble in hot than in cold water. Monophenylarsinic acid forms
two calcium salts ; the acid salt, (PhAs03H)oCa, prepared by adding
ammonia to a boiling concentrated solution of calcium chloride and
phenylarsinic acid, until the mixture is but slightly acid, is sparingly
soluble in hot water. By recrystallisation from hot dilute hydrochloric
acid, the salt is obtained in colourless needles. The neutral calcium
salt, PhAsOaCa + 2H..0, is deposited in clusters of needle-shaped
crystals, when a layer of ammonia is cautiously poured on a dilute
mixture of calcium chloride and phenylarsinic acid. The copper and
lead salts are insoluble in water.
I)ip]ieii ij I arsendous chloride, PhoAsCl, is prepared by the action of
mercury-diphenyl on an excess of monophenylarsenious chloride ; the
best yield is obtained when the temperature of the mixture is rapidly
raised above 320°. The pure chloride is a pale yellow oil (b. p. 333°,
sp. gr. 1'42231 at 15°) insoluble in water, but soluble in alcohol, ether,
and benzeue. It combines directly with chlorine and bromine to form
solid addition products. It is attacked by zinc at 100*^ with the pro-
ORGANIC CHEMISTRY. 397
fluction of a small quantity of a crystalline compound (m. p. 154°),
which dissolvos freely in benzene.
Biphenylarsinic acid, PhoAsOoH, is deposited from an aqueous solu-
tion in needles and from an alcoholic solution in prisms (m. p. 174'^).
The acid resists the action of oxidising agents.
The amiivynium salt separates from a concentrated solution in
feathery crystals which rapidly lose ammonia at the ordinary tempera-
ture. The sodiitm salt, PhoAsOoNa is very hygroscopic.
The barium salt (Ph2AsO-.)2Ba forms a gum-like mass soluble in
water and alcohol, the calcium salt is deposited in woolly needles on
the addition of ether to its solution in alcohol.
The lead salt is sparingly soluble in boiling water ; anhydrous silky
crystals are deposited from the solution on cooling. The copper salt
is insoluble in water.
Triphenylarsine, AsPhs, is most easily prepared by the decomposi-
tion of the monophenylarsenious oxide, 3PhAsO = AsPhs + AS2O3.
The mixture of mono- and di-phenylarsenious chlorides obtaiued by the
action of arsenious chloride on benzene is converted into oxide by
boiling with sodium carbonate. The oxide is heated at 180° for some
time and then slowly distilled until the temperature reaches 360°, the
residue in the retort is dissolved in alcohol and treated with animal
charcoal. On evaporating the solution, triphenylarsine ciystallises
in transparent colourless plates (m. p. 58°). The cr3-stals are insoluble
in water and in hydrochloric acid, but dissolve freely in benzene and
ether. Triphenylarsine is not attacked by ethyl iodide, but it com-
bines directly with sulphur to form PhjAsS. The sulphide is best
prepared by boiling triphenylarsenious dichloride with yellow ammo-
nium sulphide ; the mixture is aciditied with hydrochloric acid, and
on recrystallising the precipitate from alcohol the sulphide is ob-
tained in silky needles (m. p. 162°).
The monotoJijlarsenious oxides, CcHiMe.AsO, are prepared by boiling
the ortho- and para-tolylarsenious chlorides with a concentrated solution
of sodium carbonate. The resinous product is extracted with hot
water and dissolved in alcohol ; on evaporating the alcoholic solution
to dryness and washing the residue with cold ether, the tolylarsenions
oxide remains as a white powder. The ortho-compound melts at 145°,
and at a high temperature decomposes into arsenious oxide and a
resinous mass, probably orthotritolylarsine. The para-compound
melts at 156°, and at a higher temperature splits up into arsenious
oxide and a substance crystallising in plates (m. p. 130°), probably
para-tritolylarsine. The oxides combine directly with chlorine and
bromine to form tolylarsenions oxychlorides, CoHiMe. AsOClj, and oxy-
bromides, C6H4Me.AsOBr2.
The monotolylarsinic acids, C7H7.ASO3H2, produced by the action of
water on the oxy- and tetra-chlorides, crystallise in needles or prisms,
which are soluble in water and alcohol, but are insoluble in ether.
The orthotolylarsinic acid is converted into the anhydride by being
heated at its melting point (159°) for some houx's. This acid forms an
amorphous silver salt, C7H7. As03Ag2. The barium salt (C7H7.As03H)2Ba
does not form well defined crystals. When ammonia is added to a
cold solution of calcium chloride and orthotolylarsinic acid, no change
398 ABSTRACTS OF CHEMICAL PAPERS.
takes place, but on heating the mixture a crystalHne precipitate of
(C-H7.As03)Ca is deposited. The para-acid passes into the anhydride
at 113°, and may be heated to 300° without melting. It forms a non-
crystalline potassium salt ; the silver salt becomes crystalline when
boiled with dilute alcohol. The harium salt, (C7H7.As03H)2Ba, is de-
jDosited from an aqueous solution in anhydrous needles. The calcium
salt, (C7H7.As03H)2Ca, is obtained in anhydrous plates on the addition
of ammonia to a hot mixture of calcium chloride and paratolylarsinic
acid. The copper and lead salts are insoluble in water.
w. c. w.
Acridine. By C. Gr^ibe and H. Caro {Ber., 13, 99— 103).— By
the oxidation of acridine wath potassium permanganate solution, care
being taken to avoid the presence at any time of an excess of the
latter, the authors have obtained an acid which they term acridinic
acid. It separates from hot saturated aqueous solutions in thin long
needles of the composition C11H7NO4 + 2HoO. It is sparingly soluble
in cold water, more easily in hot. When warmed with water in quan-
tities insuflBcient to dissolve it, the needle-shaped crystals form brown
tables, which contain 1 mol. of water of crystallisation. At 120 —
130° acridinic acid loses both molecules of water of crystallisation and
also carbonic anhydride, forming a monobasic acid, CioH7N02.
Acridinic acid is dibasic, it crystallises from hydrochloric acid and
platinum chloride as the free acid. When distilled wdth slaked lime,
it yields quinoline as chief product : hence acridinic acid is qninoline-
dicarboxylic acid, CaH5N(C00H)o + 2H,0.
Acridinic acid at 120-^130" is resolved into carbonic anhydride and
quinolinecarboxylic acid, C111H7NO2, which crystallises in small ill-
defined tables ; it melts at 275°, is easily soluble in alcohol, soluble in
hot water, but only sparingly in the cold. It forms salts with acids
and bases, and yields quinoline on distillation.
The silver salt, CgHeN.COOAg, crystallises in small colourless
prisms, very sparingly soluble in cold, more easily in hot water.
Its copper salt, (C9H6N'.COO)2Cu, forms a greenish-blue precipitate.
The platinochloride (CioH7N02.HCl)2PtCl4, crystallises from water,
in which it is easily soluble, in reddish-yellow tables. The properties
of this acid show it to be different from Weidel's cinchoninic acid
(Annalen, 173, 84).
From the above, it is seen that acridine is a quinoline derivative,
and for it the authors propose the following constitutional formula —
H
HC C CH
I II I
HC C CH
^c/^c^^
I I
HoC CH
H
Acridine is attacked by the long-continued action of chi'omic and
ORGANIC CHEMISTRY. 399
acetic acids ; tlie same product being obtained if a solution of acridine
in glacial acetic acid be treated with potassium permanganate. The
product has neither basic nor acid properties, and the authors regard it
as a ketone having the composition C12H7XO. It crystallises from
acetic acid in yellow needles ; it does not melt at 320°, but sublimes.
It is soluble in acids and alkalis, dissolving in concentrated sulphuric
acid with a yellow colour. P. P. B.
The a- and /3-Positions in Naphthalene. By F. Reverdix and
E. NoLTiKG (Ber., 13, 36 — 38). — In support of the present view that
the a- and /^-positions in naphthalene are the following —
the authors advance the following argument.
Beilstein and Kurbatow (Ber., 12,. 688) have shown that by the
oxidation of a-nitronaphthalene, a nitrophthalic acid is obtained, melt-
ing at 212°. According to theory, two such acids can exist, viz. :
[NO2 : COOH : COOH] = [1 : 2 : 3J or [1 : 3 : 5].
0. Miller (Ber., 9, 1191) has prepared a nitrophthalic acid melting
at 165°, which he shows to correspond with the oxyphthalic acid of
Baever. Further, Schall (Ber., 12, 816) has shown that this oxy-
phthalic acid has the constitution : [OH : COOH : COOH] = [1:3:5].
Hence the nitrophthalic acid, m. p. 165°, has the constitutional
formula [1:3: 5], whilst the acid melting at 225° corresponds with
the formula [1:2:3], and as this corresponds with a-nitrophthalene,
the a-position is adjacent to the carbon atom common to the two
nuclei. P. P. B.
Diphenyldiimidonaphthol. By B. Goes (Ber., 13, 123—125).
Diphenyldiimidoiuqjhthol, CioH5(NPho).OH, is prepared by heating a
mixture of equal parts of aniline and diiraidonaphthol hydrochloride,
until the evolution of ammonia ceases. The excess of aniline is re-
moved from the crude product by distillation in a current of steam ;
the residue is extracted with boiling water and then purified by re-
crystallisation from alcohol and treatment with animal charcoal. Pure
diphenyldiimidonaphthol crystallises in red needles which dissolve
freely in benzene and ether, but are sparingly soluble in alcohol. The
crystals melt at 1S2°, and can be sublimed without undergoing decom-
position. The platinochloride crystallises in brown plates insoluble in
water but soluble in alcohol.
Similar compounds are obtained by the action of ortho- and para-
toluidine on diimidonaphthol hydrochloride. W. C. W.
The Third Anthracenecarboxylic Acid. By C. LiEBERiiAXN
and A. Bischof (Ber., 13, 47 — 50). — Of the three anthracenecarboxylic
acids two have been prepared, one from anthracene and carbonic
chloride (Graebe and Liebermann), the second from an anthracene-
400 ABSTRACTS OF CHEMICAL PAPERS.
sulphonic acid by distillation witli potassiatn ferrocyanide (Lieber-
mann and v. Ratb). The third acid has been obtained from an
anthracenesulphonic acid obtained by the reduction of a commercial
anthraquinonesulphonic acid with hydriodic acid. The anthracene-
sulphonic acid so obtained was distilled with potassium ferrocyanide,
and the resulting nitrile saponified by means of alcoholic potash. The
acid is obtained as a flocculent precipitate by acidifying the solution
of the potassium salt ; it consists of a mixture of two isomerides,
which were separated by means of the different solubilities of their
barium salts.
The acid from the soluble barium salt is identical with that prepared
by Liebermann and v. Rath ; the acid from the insoluble barium salt
forms the greater portion of the mixture. This new anthracene-
carhoxylic acid has a brownish colour, is less soluble in alcohol and
glacial acetic acid than the isomeride; it sublimes in leaflets and
needles, and melts at about 280° without decomposition.
The sodium salt, CuHg.COONa, is soluble in cold water, but is pre-
cipitated in spangles by boiling ; its aqueous solutions are fluorescent.
The ammonium salt loses ammonia on evaporation, its solutions
yield flocculent precipitates with barium chloride, ferric chloride,
lead acetate, and copper acetate. The barium salt is slightly soluble
in hot water.
The ethyl salt, CuHg.COOEt, is easily soluble in alcohol, melts at
134°, and distils without decomposition.
This new anthracenecarboxylic acid, like the one described by Lie-
bermann and V. Rath, yields an anthraquinonecarboxylic acid,
C14H7O2COOH, on oxidation. It crystallises from glacial acetic acid
in long, light yellow needles, melting at 285°, like its isomeride, from
which it is distinguished by the insolubility of its barium salt. The
solution of its alkaline salts do not fluoresce. With zinc-dust and
soda, it yields the characteristic red coloration, distinguishing all un-
coloured anthraquinone derivatives from those of anthracene.
The authors conclude that the carboxyl groap in the new anthra-
cenecarboxylic acid occupies the same position as the hydroxyl in
oxyanthraquinone. Since the sulphonic acid from which it was pre-
pared yields chiefly oxyanthraquinone on fusion with potash, the for-
mation of the second carboxylic acid is probably due to the presence
of a sulphonic acid which yields erythroxyanthraquinone on fusion with
potash. The sulphonic acid used in this investigation is the one pre-
pared for the manufacture of alizarin. P. P. B.
Fluoranthene, a New Hydrocarbon from Coal-tar. By R.
FiTTiG and H. Liepmann (Annalen, 200, 1 — 21). — The preparation of
this hydrocarbon from the crude mixture of pyrene, fluoranthene, &c.,
by crystallisation of their picric acid compounds, is much facilitated
by a previous fractional distillation under reduced pressure. Pure
fluoranthene boils at 250 — 251" under 60 mm. pressure, at 217° under
30 mm. ; pure pyrene at 260° under 60 mm. The portion boiling
between 240'' and 250° under 60 mm. may be treated as already
described (Annalen, 193, 142). The vapour-density of the hydro-
carbon corresponds with the formula CisHjo.
ORGAXIC CHEJnSTRT. 401
As previously mentioned, chromic mixture oxidises fluoranthene
into diphenyleneketone-carboxj-lic acid and a quinone wliich is only
produced iu small quantity. By suitably moderating the reaction, the
acid, quinone, and unaltered hydrocarbon are obtained together as an
insoluble deposit. The acid may be extracted from the mixture by
sodium carbonate, and on crystallising the residue from hot alcohol
and "washing the crystals with light petroleum to remove adhering
hydrocarbon, a compound of the quinone with fluoranthene was ob-
tained, CioHsOa + 2C15H10 (m. p. 102"). Repeated crystallisation from
alcohol resolves it partially into its constituents ; hydrogen sodium
sulphite decomposes it at once. The quinone crystallises iu red needles
(m. p. 188°).
Treatment with cbromic mixture converts this quinone completely,
and apparently directly, into carbonic acid and water ; it is not there-
fore a product intermediate between the hydrocarbon and diphenylene-
ketone-carboxylic acid, but may be formed along with the latter,
which is exceedingly stable towards oxidants. In virtue of this
stability, the acid may be readily obtained from the crude mixture
of pyrene and fluoranthene. 100 grams of hydrocarbon are treated
with 600 gi-ams of dichromate and 1000 grams of sulphuric acid
diluted with five times its volume of water, and the mixture slowly
heated to boiling, avoiding too violent an action. From the powdered
and washed deposit, the acid may be extracted by sodium carbonate,
precipitated by hydrochloric acid, and boiled with barium carbonate
and animal charcoal. From the solution thus obtained, hydrochloric
acid precipitates it in a nearly pure state.
Fuming nitric acid dissolves this acid on gentle heating, and on
cooling deposits nitrodiphenyleneketone-carboxylic acid, CiiH7(N0..)0:j,
in long yellow needles, which may be purified by conversion into the
barium salt. The nitro acid crystallises from alcohol in brilliant
golden-yellow needles (m. p. 245 — 246°) which are insoluble in water,
but dissolve in glacial acetic acid. Its barium salt was analysed.
The conversion of diphenylene-ketone-carboxylic acid into isodi-
phenic acid, and the various salts of the latter, have been already de-
scribed. Analyses of the free acid are now given. Its methyl salt,
Ci2H6(COOMe)2 (m. p. 69"5°), and its etliijl salt (an uncrystallisable
syrup) are obtained by the action of sulphuric acid on solutions of the
acid in the corresponding alcohols. Isophenic acid is easily oxidised,
yielding isophthalic acid in theoretical quantity, together with car-
bonic acid and water. By this behaviour, it is distinguished from its
isomeride diphenic acid, which yields only carbonic acid and water
(Hummel, J.u«aZe/i, 193, 130). Its general characters also distinguish
it from its other isomeride diphenyl-dicarboxylic acid (Doebner,
Annalen, 172, 117).
When treated with nascent hydrogen (from sodium amalgam), di-
phenylene-ketone-carboxylic acid passes into a carboxyl derivative of
CeH^.
fluorene (diphenylene-methane), | /'CH2 which the author.s
CeHs-COOH'
name fluorenic acid (m. p. 24.5 — 246°). The new acid is scarcely
soluble in boiling water, but easily in hot alcohol ; it may be sublimed
402
ABSTRACTS OF CHEMICAL PAPERS.
unchanged. Barium and calcium salts and a crystalline ethyl salt
(m. p. 53"5°) were prepared. The acid yields fluorene with the greatest
ease when distilled with lime. Chromic mixture destroys it completely,
but potassium permanganate in alkaline solution reconverts it into
diphenylene-ketone-carboxylic acid. It is isomeric with Friedlander's
fluorene-carboxylic acid (Ber., 10, 537) obtained by reduction of di-
phenylene glycollic acid.
Isodiphenic acid decomposes so easily into diphenylene-ketone and
carbonic anhydride, that one of its carboxyl-groups must be in the
ortho-position with respect to the point of union of the two benzene
nuclei ; and since it yields isophthalic acid by oxidation, the second
carboxyl-group must occupy the meta-position in the second nucleus.
The latter position must also be assigned to the carboxyl-groups of the
closely allied diphenylene-ketone-carboxylic and fluorenic acids. The
constitution of fluoranthene having been previously ascertained
(^Annalen, 193, 142), the relationship of these bodies may be exhibited
as follows : —
V^CH
II
^-CH
Fluorantliene.
/\
/\.
CO
COOH
Diphenylene-ketone-
carboxylic acid.
><^CH2
. .COOH
Fluorenic
acid.
'COOH
iCOOH
Isodiphenic
acid.
Finally, the author points out the parallelism between the deriva-
tives of dijDhenylmethane and fluorene : —
C6H5.CH2.C6H5
Diplienylmethane.
C6H5.CH(OH).C6H5
Benzhjdrol.
Cells. CO. CsHs
Benzophenone.
CeHs.CO.CeH^.COOH
Benzoylbenzoic acid.
CeHs.CHo.CeHi.COOH
Benzylbenzoic acid.
(CsHi.CgHi) '. CH2
Diphenylenemethane.
(CeH^.CeHO : CH.OH
Fluorenyl alcohol.
(CeH^.CeHo : CO
Diphenyleneketone.
[CeH^.CsHsCCOOH)] : CO
Diphenylene-ketone-carboxylic acid.
[CeH^.CeH^CCOOH)] : CH2
Fluorenic acid.
Ch. B.
Changes produced by Hydration and Dehydration in the
Lsevorotary Terpene from French Turpentine Oil. By F.
Flawitzsky (Ber., 12, 2354 — 2359). — Lcevorotary terpene hydrate,
CioHigO, is obtained by treating the rectified liBvorotary terpene
from French turpentine oil with a mixture of 1^ parts of alcohol
(90 per cent.) and ^ part of sulphuric acid (sp. gr. 1-64°). After
removal of the undissolved terpene the colourless solution is decom-
ORGANIC CHEMISTRY. 403
posed with water and fractionated in a current of steara, and finally dis-
tilled, the portion boiling at 211 — 215° being collected. This terpene hy-
drate boils at 218 — 221^ (corr. bar. 766'3 mm.), and its action on polar-
ised light is represented by ap = — 51'7°. Its coefficient of expansion
between 0 and 18° = - 0-00083, therefore [ccl^ = ~/^'^ = -56-2°.
^ -■ 0-9201
(Sp. gr. at 0° 0-9339, and at 18° 0-9201.) It is insoluble in water, but
dissolves in a mixture of alcohol and sulphuric acid, its optical activity
being thereby diminished, and finally disappearing altogether; on dis-
tillation, it undergoes slight decomposition, leaving an almost colourless
residue. The dihijdrochloride alone is obtained by saturating the above
hydrate with gaseous hydrochloric acid, when the liquid assumes a
violet-red colour and the dichlorhydrate separates out in crystals
(m. p. 49°). The alcoholic solution of this compound is optically
inactive.
The application of the acetic anhydride reaction to tevorotary ter-
pene hydrate, although not conclusive, appears to show that the latter
body contains a hydroxyl-group. The more volatile portion of the
product obtained by this reaction contains a new substance, viz.,
Icevorotary isoterpene, CioHie (b. p. 179, corr.: bar. 762-6 mm.), which
readily undergoes oxidation, so that after standing several days and
being redistilled over sodium, it always yields a brown precipitate. It
has a feeble odour, different from that of the terpene from turpentine
oil. It dissolves in alcoholic sulphuric acid. The chief points of differ-
ence between this substance and ordinary la3vorotary terpene are as
follows : —
Terpene. Isoterpene,
Boiling point 155^ 179°
[a]i, - 43-4 - 61-0°
Sp. gr. at 0° 0-8749 0-8639
„ at 20° 0-8587 0-8486
Coefficient of expansion 0-00096 0-00091
On treatment with gaseous hydrochloric acid, the terpene of b. p.
155° gives only the solid monochlorhydrate, the liquor remaining
colourless, whereas the new terpene of b. p. 179° gives the crystalline
dichlorhydrate, the liquid at the same time becoming red. The author
considers that the presence of moisture plays an important part in the
formation of the dihydrochloride, which is readily converted into
terpene hydrate on treatment with water. In many respects Isevoro-
tary isoterpene resembles the terpene from essence of elemi and that
from oil of citron, but the former has a larger laevorotary power whilst
the latter is dextrorotary. T. C.
Compounds in Animal Tar. By H. Weidel and G. L.
CuMiciAN (Ber., 13, 65 — 85). — II. The Noti-basic Constituents. — The
material used in this investigation was obtained from bone-oil by shak-
ing it up with dilute acid and then separated by distillation into the
following fractions :— I. 98—150°; II. 150—220°; III. 220—360°.
Each fraction was then boiled with solid potash until the evolution of
404 ABSTRACTS OF CHEMCAL PAPERS. .
ammonia ceased, and was thus separated into potassium salts of fatty
acids, an aqueous portion, and an oil consisting of hydrocarbons.
I. The potassium salts of this fraction yielded the following acids: —
Propionic, normal butyric, pentoic, and isocapi-oic acids. The aque-
ous portion contained valeramide. The oil was further separated into
two fractions, one boiling at 110^130°, and the other at 180 — 180°.
The first yielded toluene, ethylbenzene, and pyrroline, which boils at
126'2° (bar. 746"5 mm.) and not at 133°, as usually stated ; its sp. gr.
is 0"9752 at 12"5°. The authors also confirm the observation of Ander-
son as to the formation of pyrrol-red, but are unable to attribute to it
a definite composition.
The higlier fraction yielded some pyrroline and three hydrocarbons :
— Metadihydroethylbenzene, CgHu, a colourless mobile liquid, of sweet
ethereal odour, and boiling at l-53"5° (bar. 748"7 mm.) ; on oxidation
it forms isophthalic acid. Metadihydromethylcymene, CmHie, a colour-
less liquid, having an odour resembling that of turpentine, and boiling
at 165"5° (bar. 748'8 mm.) ; oxidising agents convert it into isophthalic
acid. It forms an addition compound with bromine, which, when
heated in sealed tubes at 180° with aniline, yields an isomeride of
cymene, boiling at 174 — 175°. The third hydrocarbon, which has also
the composition CmHie, boils at 172"5° (bar. 748*5 mm.), and yields
isophthalic acid on oxidation.
The fraction II, when similarly treated, yielded isocapric acid,
phenol, two homologues of pyrroline, naphthalene, and a hydrocarbon,
CiiHig.
HomopyrroUne, CiHsMeNH, is a colourless liquid with an odour re-
sembling that of chloroform, and boiling at 145"5° (bar. 742"8 mm.).
' Its pi'operties are similar to those of pyrroline, but it is attacked by
acids less easily than the latter ; it forms a white curdy precipitate with
mercuric chloride. The acetyl derivative, C4H3MeNAc, forms a crys-
talline mass (m. p. 4 — 6°).
Dimethylpyrroline, C4HoMe.,NH, the second homologue of pyrroline,
is an almost coloui'less liquid of a somewhat disagreeable odour
(b. p. 1C4°, bar. 792 mm.). Its acetyl derivative, CjHoMe.iNAc, is
a vi.«cous, almost colourless liquid, slightly soluble in water, and
remaining liquid at — 20°.
An isomeride of homopyrroline has been described by Bell (Ber., 9,
935, and 10, 1861) ; it is methylpyrroline, C4H4NMe.
The hydrocarbon, CuHig, is a colourless, strongly refractive liquid
(b. p. 182°). It does not combine with hydrochloric acid, and on
oxidation yields a small quantity of isophthalic acid. A small quantity
of an isomeride of this body has been also obtained from this fraction ;
it boils at 202—203°.
III. This fraction yielded chiefly palmitic and stearic acids.
P. P. B.
Conversion of Piperidine into Pyridine. By W. Kqenigs (Ber.,
12, 2341 — 2344). — On heating piperidine, C5H11N, for several hours at
.300° with concentrated sulphuric acid, it is oxidised to pyridine. The
same result is obtained, although not so readily, by heating an aqueous
solution of piperidine with silver oxide. Hofmann (Ber., 12, 984) has
previously shown that a body having the composition of dibromoxy-
ORGANIC CHEMISTRY. 405
pyridine, CsHsBrNO, is obtained when piperidine hydrochloride is
treated with an excess of bromine at 200 — 220°, but he was unable to
prepare this compound directly from pyridine. These facts show that
the alkaloid from pepper is a derivative of pyridine. The author con-
siders that the oxidation of piperidine to jiyridine is analogous to the
behaviour of aromatic hydro-derivatives, in which the double attach,
ments in the benzene ring are changed to single ones by addition of
hydrogen, and which on oxidation lose these hydrogen atoms, and are
again converted into compounds with double attachments. So far,
however, it has not been possible, from want of material, to convert
pyridine back into piperidine. The following formuhe show the rela-
tion between pyridine and piperidine : —
HC CH H.C CH2
II I 'II
HC CH H.C CH2
\c/ '\c^
H H.
Pyridine. Piperidine.
Now, since piperine on boiling with potash gives piperidine and
piperinic acid, it may be considered as piperonyl-piperidine,
CsH.oN.CO.CuHeNO^,
and is, therefore, analogous to the corresponding benzoyl-compound.
As the constitution of the two radicles, C5H10N (_vide sujira), and
CO.CiiHgNOo (Fittig), has ah'eady been determined, we know that of
piperine, which is therefore the first alkaloid of which the constitution
is known with comparative certainty.
Experiments are in progress with the object of obtaining pyridine
synthetically from the ethyl-allylamine isomeric with piperidine, by a
reaction analogous to that bv which quinoline has been obtained from
allylaniliue (Kojnigs, Ber., 12, 453). T. C.
Pyridinecarboxylic Acids. By S. Hoogewerff and W. A. v. Dorp
(Ber., 13, Gl — Go). — ^Pyi-idinetricarboxylic acid, obtained by oxidatioii
of quinine (this Journal, 1879, Abst., 541) when heated at 185 — lOO'',
is resolved into carbonic anhydride and pyridinedicai^boxyUc acid. Pyri-
dine-dicarboxylic acid crystallises from water in needles ; it melts with
decomposition at 250° ; is sparingly soluble in alcohol, ether, and ben-
zene ; with ferrous sulphate it gives no coloration. The properties of
this acid show that it is identical with the cinch omeronic acid described
by Weidel and v. Schmidt (Ibid., 1879, 947). The authors attribute to
the barium salt the formula C7H:iN04Ba + 1-|-H20, and to the calcium
salt CvHsNO^Ca -h S^HoO. Besides the silver salt, C^HaNOiAgj, de-
scribed by "VVeidel and Schmidt, the authors obtain an acid salt,
C^HiXOiAg, by treating the aqueous solution of the acid with silver
nitrate, as a white crystalline precipitate. The aqueous solution of the
acid in presence of acetic acid gives with copper acetate a light blue
406 ABSTRACTS OF CHEMICAL PAPERS.
cloud, which increases on heating and disappears when the solution
cools. The identity of this pyridinedicarboxjlic acid with cinchome-
ronic acid is further shown by the fact that it also yields a pyrocin-
chonic acid (m. p. 94 — 97°) ; Weidel and v. Schmidt found the m. p.
to be 90".
This pyridinedicarboxylic acid is resolved by heat into carbonic and
■piiridenemonocarhoxijlic acid, which crystallises from water in nodules.
This acid the authors style pyrocinchomeronic acid ; it is sparingly
soluble in water and alcohol, and very slightly in ether and benzene ;
its aqueous solutions yield no coloration with ferrous sulphate. The
hTjdrocMonde, C6H5NO2.HCI, forms large shining crystals. The
plathiochloride, (C6H5NOo)o2HCl.PtC]4 + 2H2O, forms red crystals,
resembling the corresponding salt of nicotinic acid.
Beside this pyridinemonocarboxylic acid, a small quantity of an acid,
apparently nicotinic acid, is formed at the same time.
The acid obtained by the authors from quinoline (this Journal,
Abst., 1879, 731) and described as pyridinedicarboxylic acid, has
proved on further investigation to be nicotinic acid.
The three possible pyridinecarboxylic acids are now known, viz.,
pyrocinchomeronic, nicotinic, and picolinic acids (Weidel, Ber., 12,
1989). And of the six possible pyridinedicarboxylic acids, five are
already known, viz. (1), the a-acid (Dewar, Ztit.f. Chem., 1871, 116),
(2) the (S- and 7-acids (Ramsay, this Journal, Trans., 1879, 289), the
fourth is cinchomeronic acid, and, finally, the fifth acid is that obtained
from quinoline by the authors (Joe. cit.). P. P. B.
Pyridinetricarboxylic Acid from Cinchona Alkaloids. By S.
HooGEWERFF and W. A. v. Dorp (Ber., 13, 152 — 154). — The acid
obtained by the oxidation of quinine, quinidine, cinchonine, and cin-
chonidine, by potassium permanganate is identical with the pyridine-
tricarboxylic acid, CsHsNOg + UH2O, which Skraup (Ber., 12, 2331)
prepared from cinchonic acid. The acid is soluble in 83" 1 parts of
water at 15". The solutionis optically inactive. The metallic salts have
the following composition :—(C8H2N06)2Ba3 + 16H,0 ; (C8HoN06)2Ca3
+ 14H.0 ; CsHoAgoNOG + 2H2O ; CBHsAg.NOe + H2O ; CHiAgNOe
-f CgH^NOe + H2O, and CgHoKaNOe + 3HoO. W. C. W.
Synthesis of the Homologues of Hydrocarbostyril and Qui-
noline. By A. Baeyer and 0. R. Jackson (Ber., 13, 115 — 123). — By
the action of sodium-amalgam on phenylangelic acid (prepared from
normal butyric acid and benzaldehyde) sodium plienijletlnilpriypionate is
obtained. The free acid, CHoPh.CHEt.COOH, is an oil which boils
at 272°, and does not solidify in a freezing mixture. The silver salt is
amorphous and insoluble in water ; the barium salt dissolves freely in
water, but is not crystalline.
CHo.CHEt
Ethylhydrocarhostyril, C6Hi<^ | , formed by treating nitro-
^NH.CO
phenylethylpropionic acid with tin and hydrochloric acid, dissolves
freely in alcohol, ether, and benzene, and is sparingly soluble in hot
ORGANIC CHEMISTRY. 407
water. It dissolves easily in strong acids, bat is reprecipitated on the
addition of water. The crystals melt at 88° ; if they are heated again
soon after solidification, the melting point falls to 7&°, but gradually
rises if the specimens are kept for some time at the ordinary tempera-
ture.
CH : CEt
EtJiijlchloroquinoline, C^x^ \ , m. p. 72°, is produced by the
^N" : cci
action of phosphorus pentachloride on ethylhydrocarbostyril. It is a
weak base, sparingly soluble in water, but dissolving freely in other
solvents.
The platinochloride is soluble in alcohol, but is decomposed by water.
In the preparation of the chloroquinoline, ethylcarbostyril (m. p. 168°)
appears to be formed as a bye-product.
CH : CEt
^-EthyJqidnoline, C6H4<^ | , is obtained by acting on ethyl-
^N : CH
chloroquinoline with a solution of hydriodic acid in acetic acid, render-
ing the product alkaline, and distilling off the base in a current of
steam. The free base resembles quinoline ; the platinochloride is in-
soluble in alcohol, and less soluble in water than the correspondino*
quinoline compound.
Hydrocinnamylacrylic acid, previously obtained by Perkin (this
Jonrnal, 1877, i, 405j by the reduction of cinnamylaerylic acid with
sodium-amalgam as an oily liquid, solidifies in a freezing mixture,
forming colourless plates (m. p. 29°). The acid combines directly
with bromine in a carbon bisulphide solution, with production of
an addition-product (m. p. 109°), crystallising in prisms, which are
soluble in light petroleum and in chloroform. It also combines
directly with hydrobromic acid. When hydrocinnamylacrylic acid is
treated with a solution of hydriodic acid in acetic acid at 160°, and the
product diluted with water and mixed with sulphurous acid, normal
p}ie)iylvaleric acid separates out as an oily liquid which solidifies, forming
rhombic plates (m. p. 59°) sparingly soluble in water. The barium
salt of this acid is slightly soluble, and the silver salt insoluble in
water.
Nitrophenylvaleric acid on reduction with tin and hydrochloric acid,
does not yield a derivative analogous to hydrocarbostyril.
w. c. w.
Action of Benzoic Chloride on Morphine. By K. Pobstorff
(Ber., 13, 98 — 99 j. — By the action of benzoic chloride on morphine
free from _water, in sealed tubes at 109 — 110°, tribenzoylmorphine,
C17H16KO3BZ3, is obtained; it forms large, colourless, columnar crys-
tals (m. p. 186°). It is insoluble in water, sparingly soluble in cold
alcohol, more easily in hot alcohol. It has no basic properties. By the
action of benzoic acid and benzoic anhydride on morphine, Beckett
and Wrigh_t (this Journal, 28, i, 23) obtained monobenzoylmorphine,
CitHibXOoBz, and dibenzoylmorphine, Ci-HnNOaBza respectively, to
which bodies they attribute basic properties.
The author concludes that as morphine is a nitril base, as shown
by the preparation of methylmorphine hydroxide, therefore there is
408 ABSTRACTS OF CHEMICAL PAPERS.
no hydrogen combined directly witli the nitrogen, so the benzoyl com-
pounds indicate the existence in morphine of three hydroxyl-groups.
P. P. B.
Action of Potassium Ferricyanide on Morphine. By K. Pol-
STORFF (Ber., 13, 86 — 88). — The action of an alkaline solution of
potassium ferricyanide on morphine, observed by Kieffer (Annalen,
103, 254), converts it into oxydimorphine, thus : 2CnHi9N03 +
2KH0 + 2K3Fe(C]S')6 = SH^O + 2K4Fe(CN")6 + CaiH^eNo.Oe.
Oxydimorphine is obtained by precipitating its hydrochloric acid
solution with ammonia as a colourless heavy crystalline powder. It is
insoluble in ordinary solvents, and is precipitated from the solution of
its salts by caustic alkalis, but is soluble in excess ; on warming its
solution in aqueous ammonia, it is precipitated. Oxydimorphine has
the composition C34H36N3O6 + 3H2O.
Oxydimorphine sulphate, C34H36N2O6.H3SO4 + 8HaO forms small,
concentrically-grouped needles, sparingly soluble in cold, more easily
in hot water.
Oxydiviorphine hydrochloride, C34H36N206.2HC1 + (PHoO), is a
shining white, indefinitely crystalline powder. It is easily soluble in
water ; the addition of acid lessens its solubility. Preparations have
been obtained with varying amounts of water of crystallisation, e.g.,
with 6^ mols.,1 moL, and 2 mols. of water. P. P. B.
Schiitzenberger's Oxymorphine {Ber., 13, 88 — 90) ; Action
of Potassium Permanganate on Morphine {Ber., 13, 91) ; Ac-
tion of Atmospheric Oxygen on Morphine in Ammoniacal
Solution {Ber., 13, 92 — 93). By K. Broockmann and K. Polstorff.
The oxymorphine prepared by Schiitzenberger {Bull. Soc. Cliiin.,
1865, 176) by the action of silver nitrite and hydrochloric acid on
morphine, to which he ascriljed the formula CnHi9N04, is found to be
identical with oxydimorphine, C34H3BN0O6, prepared from morphine
by the action of potassium ferricyanide ; its formation may be ex-
pressed as follows : 2CnHi4X03.HCl + AgNO, = 034H36N,06 + 2AgCl
+ 2H2O -f 2N0.
The authors find that oxydimorphine is formed when morphine is
oxidised by means of potassium permanganate in presence of an
alkaline carbonate.
The authors find that oxydimorphine is also obtained when an
ammoniacal solution of morphine is exposed to the air. The identity
of the base in each of the above instances with that obtained by the
action of potassium ferricyanide on morphine is shown not only by its
properties but also by those of its sulphate and hydi'ochloride.
P. P. B.
Methylmorphine Hydroxide. By K. Broockmann and K. Pol-
STOKEF {Ber., 13, 96 — 98). — Methylmorphine hydroxide is obtained by
first converting the iodide into sulphate by means of silver sulphate,
and then heating the sulphate with bai'yta-water. After removing
the excess of baryta by carbonic anhydride, the filtrate was concentrated
to a syrup, taken up with alcohol, and from the alcoholic solution the
hydroxide was precipitated by ether in the form of brittle yellow
ORGANIC CHEMISTRY. 409
needles, having the composition Ci7Hi9"N"03.CH30H + 5H2O. It is
very sohible in water, the aqueous sohition decomposes on exposure to
the air, forming coloured uncrystallisable products. P. P. B.
Action of Potassium Ferricyanide on Methylmorphine
Iodide. By K. Pulstorif (7>V/-., 13, U3 — VG). — Methyhnorphine,
when oxidised by potassium ferricyanide in an alkaline solution, yields
the basic iodide of methyloxydimorphine, thus : 2C17H19NO0.CH3I +
2K3Fe(CX)6 + 3K0H = (CnH„N03)2.CH3l.CH30H + 2K,Fe(CN)G
+ KI + 2H,0.
Basic methyloxydimorphine iodide, (Cn'H.isN0o.C'H:i)2l.0I{ + SHjO, is
obtained by treating its solution in hydrochloric acid with ammonia. It
forms small colourless tablets, easily soluble in hot and sparingly
soluble in cold Avater ; its aqueous solutions have an alkaline reaction.
The neutral iodide, (CnHi.NOa.CHsI).. + 4H2O, is obtained by treating
the basic iodide with hydriodic acid ; it forms small yellow quadratic
prisms. It is sparingly soluble in cold, and easily in hot water. It is
also prepared by heating the basic iodide with methyl iodide in sealed
tubes at 125°.
The neutral su/ph ate, (CnHi8N03.CIl30),SOo + 4H.>0, is obtained by
treating the basic iodide with sulphuric acid, and then with a boiling-
solution of silver sulphate. It crystallises in yellowish, shining leaflets,
easily soluble in hot water, but less easily in cold. By treating its
concentrated solution with ammonia, the basic sulphate separates out
in colourless shining scales.
Metlujloxydimorpliine hydroxide, (CnHi),N03.CIl30II)3 + 7H2O, can-
not be prepared by treating the iodide with moist silver oxide, since
oxidation takes place ; but it is obtained by treating the sulphate with
an excess of baryta- water and removing the excess of the latter by
means of carbonic anhydride. The base is precipitated from its
aqueous solutions by alcohol as an indistinctly crystalline powder. It
is easily soluble in water, but insoluble in alcohol. P. P. B.
Constitution of Cinchonine and Cinchonidine. By Z. H.
Skraup {Annalen, 201, 291 — 333). — The following conclusions were
deduced from the results of the author's investigations on the oxida-
tion products of cinchonine, cinchonidine, and cinchonic acid (Ber.,
11, 1510; 12, 230, 1107, 2231; Annalm, 197, 226, 352, and 374;
and this Journal, 1879, Abstr., 71, 656, 810, 948). In the
oxidation of chinoline and cinchonidine by chromic mixture, the
methoxyl group is fii'st attacked, with formation of formic acid
and carbonic anhydride, probably of cinchotenine and cinchotenidine
or closely allied compounds as intermediate products. Cinchonic
(quinolinemonocarboxylic) acid, CioHtNOo, and a non- crystalline acid
which forms exceedingly hygroscopic salts, are the results of the reac-
tion. Cinchonic acid is monobasic, and does not form acid salts as
stated by Weidel (Wien. Akad. Ber., 1874, Part II). On further
oxidation it yields pyridine-tricarboxylic acid, which is identical with
Weidel's oxycinchomeronic acid, and with the pyridine-tricarboxylic
acid obtained by Hoogewerff and van Dorp {Ber., 13, 152 : this vol.,
p. 406), by the action of potassium permanganate on quinine, quird-
VOL, XXXYIII. 2 g
410 ABSTRACTS OF CHEMICAL PAPERS.
dine, cinclionine, and cinclionidine. The constitution of these acids
and of cinchonine and cinchonidine may be represented by the follow-
ing formulae : —
HC:CH.C.(COOH)C COOH.C.(COOH)C
I II II II II
Hc: ch.c.n: CH.cH cooH.c.iir :ch.ch
Cinclionic acid. Pyridinecarboxjlic acid.
CeH^.CaHoN.CgH.aN.OCHa
l3-
Ciuchonine and Cinclionidine.
The tricarboxylic acid decomposes when heated at its melting point,
with evolution of carbonic anhydride and production of the dicarboxylic
and 7-monocarboxylic acids. The latter acid melts at 305° and sub-
limes without decomposition. W. C. W.
Belladonnine. By K. Kraut (Ber., 13, 1G5 — 166). — Commercial
belladonnine appears to be a mixture of belladonnine and atropine,
since, on boiling with baryta-water, atropic acid and tropine pass into
solution, while the belladonnine remains undissolved. Belladonnine
appears to be isomeric with atropine ; it may possibly be identical with
hyoscyamine. W. C. W.
Artificial Alkaloids, By A. Ladenburg {Ber., 13, 104 — 110). —
In a former communication (this Journal, Abstr., 1879, 733), the
author desci'ibed the artificial preparation of atropine. Further experi-
ments prove that atropine so prepared is chemically identical with
natural atropine, and that this identity holds with regard to its
physiological action. The author has prepared by similar reactions the
following bases analogous to atropine.
Sah'cyltrojyeine, C15H19NO3, from tropine salicylate. It crystallises
in white silky leaflets, sparingly soluble in water, but easily in alcohol,
m. p. 57 — 60°. Its production is represented as follows : — CgHisNO +
CvHeOa = C15H19NO3 + II2O. It is a strong base ; the hydrochloride
crystallises fi'om water in slender shining needles, the aqueous solu-
tions giving a crystalline precipitate with platinum chloride. It forms
a yellow crystalline aurochloride. Picric acid gives an amorphous pre-
cipitate, potassium mercuric iodide a white gelatinous precipitate, and
tannic acid a white precipitate soluble in dilute acids. Solution of
iodine in potassium iodide produces separation of a brown oil. Salicyl-
tropeine is a feeble poison, but has no action on the eye.
Oxytoluyltropeine or homatropine is obtained from tropine mandelate.
It is purified either by means of the aurochloride or the picrate, from
both of which the base is separated by treatment with potassium car-
bonate as an oil.
Homatropine aurochloride, C16H21NO3.HCI. AitCIs forms first as an oil,
which becomes crystalline on standing ; it crystallises from water in
prisms.
The picrate, Ci6HoiN'03.C6H2(NOn)3.0H, is obtained as an oil, which
becomes crystalline ; it is soluble in hot water, from which it crystal-
lises in yellow shining leaflets.
i
ORGANIC CHEMISTRY. 411
The solutions of its hydrochloride yield no precipitate with tannic
acid ; with potassinrn mercuric iodide, a white curdy precipitate ;
with mercuric chloride, a white oil ; and with iodine, yellow crystals
and a black oil. In concentrated solutions platinum chloride gives an
amorphous precipitate, the filtrate from which on concentration yields
beautiful needles.
Homatropine acts on the pupil of the eye as energetically as
atropine.
PhthahjUwpeine, C24H30N0O4, is obtained from tropine and phthalic
acid. It forms white silky needles, sparingly sohible in water, but
easily in alcohol, m. p. 70°. Its reactions are similar to those of atro-
pine ; its platinochloride crystallises in needles, and is sparingly
soluble.
Hyoscyamine, which the author purified by means of the aurochlo-
ride, is isomeric with atropine, as shown by its analyses and those of
the aurochloride. It crystallises in smaller and less well formed
prisms than atropine, and melts at 113'5°, atropine melting at 108'5°.
Its aurochloride, CnHi^NOs.HCl.AuCls, crystallises from water in
beautiful leaflets, which have a golden lustre on drying. It melts at
154°, whilst the atropine salt melts at l.So°.
The author is engaged with the further study of hyoscyamine.
P. P. B.
Erythroxylon Coca. By D. F. Shull (Pkarm. J. Trans. [.3], 10,
408. — The leaves of tliis plant, a native of South America, resemble
those of the tea plant, have an astringent and aromatic taste, and pro-
duce a smarting and numbness of the tongue, due to the presence of
an alkaloid, cocaine.
The leaves are exhausted with alcobol, the colouring matter pre-
cipitated with lime, and the filtered solution evaporated to a small
bulk ; water is then added, and the evaporation continued to expel the
alcohol ; after adding potassium carbonate, filtering, and saturating
the solution with potassium carbonate, the alkaloid may be ex-
tracted by agitation with ether. The ethereal solution is decolorised
with animal charcoal, and allowed to stand, when cocaine is obtained
in colourless prismatic crystals, odourless, and of a bitter taste. It is
soluble in alcohol, ether, chloroform, and water, has strong stimulating
properties, produces a feeling of intoxication and a smarting and
numbness of the tongue. A light brown amorphous substance is also
obtained from the leaves, having a strong smell, a sharp burning
taste, and an alkaline reaction. It is soluble in alcohol, ether, chloro-
form, and water. The leaves also contain gum, tannin, wax, and
resin. L. T. O'S.
Baptisia Tinctoria. By F. Y. Greene (Pharm. J. Tram. [3], 10,
584 — 585). — Failing to isolate the alkaloid of Baptisia tinctoria, either
by the method of Smedley {Am. J. Pharm., 1862, 310) or of J. A.
Warner (ihid., 1871, 251), the following method was adopted: — The
powdered root is exhausted with water, the extract evaporated with
calcined magnesia, the dried residue extracted with alcohol (95 per
cent.), and the solution concentrated: distilled water is added, and
filtered from precipitated resin. To the filtrate, tannic acid is added,
2 rj 2
412 ABSTRACTS OF CHEMICAL PAPERS.
which precipitates tlie alkaloid ; the precipitate is intimately mixed
with lead oxide, dried, and exhausted with ether. On evaporating
the solution a resinous mass is left, from which the pure alkaloid is
separated by means of oleic acid at 100°. The oily solution is poured
off and treated with benzin (? petroleum), which dissolves the
oleate and excess of acid. This solution is shaken with water, acidu-
lated with hydrochloric acid, and on standing acicular crystals sepa-
rate out from the acid solution.
Octohedral crystals may be obtained by treating the root with
sodium bicarbonate and evaporating the extract to dryness. The
residue is exhausted with ether, the ether evaporated, the mass treated
with water and filtered: after neutralising the aqueous solution with
hydrochloric acid and extracting the colouring matter with ether, the
solution is allowed to crystallise.
The alkaloid gives a precipitate with Mayer's reagent, potassium
iodo-iodide, potassium-cadmium iodide, phosphomolybdic acid, sodium
phosphotungstate, tannic and picric acids. It is soluble in water,
alcohol, and ether, but insoluble in benzene and chloroform.
L. T. O'S.
Phytolaccin. By T. E. Claessen {Pharm. J. Trans. [3], 10, 566).—
Phytolaccin, a crystalline substance contained in the seeds of poke-
berries (PJtijtoJacca deeandra) , is obtained in needle-shaped crystals by
extracting the seeds with alcohol, distilling the extract, washing the
residue with light petroleum, pulverising the dried residue, exhausting
with ether, and evaporating the solution. It is pui^ified by recrystallisa-
tion from alcohol. Phytolaccin is tasteless, colourless, soluble in ether,
chloroform, and alcohol, sparingly soluble in light petroleum, insoluble
in water, dilute acid, strong acetic and hydrochloric acid, soda solu-
tion, and ammonia. Concentrated sulphuric acid dissolves it with a
brownish-yellow colour, changing to red when heated ; and in warm
nitric acid, it dissolves with a yellow colour. It is precipitated in a
flocculent state by water from its alcoholic and ethereal solution. On
ignition, it first melts, then chars. It leaves no residue when burnt,
and contains no nitrogen. L. T. O'S.
Phytolacca Deeandra. By A. C. Ehrhard (Pharm. J. Trans.
[3], 10, 426 — 429). — An ethereal extract of the powdered root was
evaporated to dryness, and the residue exhausted with alcohol. The
alcoholic solution was found to contain potassium, calcium, sulphuric
acid, and a fat or wax. The residue left after treating the ethereal
extract with alcohol coiitained a crystalline acid resin, soluble in sul-
phuric acid with an olive-green colour, changing to purple- on heating,
and to red on addition of nitiic acid.
After exhaustion w^ith ether the root was treated with alcohol, and
the extract obtained yielded two crops of crystals ; the first consisted
of the potassium salt of an organic acid, and the second of cane sugar.
The mother-liqnor contained a resin and a substance, the reactions of
which are described, but no conclusions ari'ived at. L. T. O'S.
Apiol. By H. C. Whitxey (Pharm. J. Trans. [3 J, 10, 585—586).—
The method adopted by Joret and Homolle for preparing apiol does
ORGANIC CHEMISTRY. 413
not yield the pure substance but a mixture of apiol and guatin (oil
of parsley). Pure apiol is obtained by distilling parsley seed with
water, and satui-ating the distillate with sodium chloride, when all
the volatile oil separates out, which corresponds very closely to the
apiol of Joret and Homolle. The residue in the retort was filtered,
and the solution on cooling yielded a large quantity of apiin. The
residuary seed when treated with petroleum spirit gave 9'114 per
cent, of a green fatty oil and resin ; further quantities of oil and resin
were separated by ether, the resin being separated by alcohol. The
alcoholic extract gave on evaporation a greenish-brown oily liquid,
lighter than water, and easily saponitied by alkalis. The author has
failed to isolate the parsley camphor described by E. v. Gerichten.
L. T. O'S.
Colouring Matter of the Caryophyllacese. By H. Bischofp
(Bied. Cenfr., IbTl', 875). — The colouring matter of the Caryophyllaceae
has been spectroscopically examined, the appearances with maximum
and minimum absorption, and the action of acids and alkalis noted.
The same colouring matter appears to be present in all the meTnbers of
the family. " E. W. P.
Putrefaction-products of Albumin. By E. and H. Samcowski
(Btr., 13, I8y — 11'3). — In continuing their research {Ber., 12, GIS
and 1438, this Journal, 1879, Abst., 6-5^), the authors find that the acetic
and benzoic series of acids may be best separated from the liydroxy-
acids in the products of putrefaction, by distillation in a current of super-
heated steam. The non-volatile portion contains, besides the hydroxy-
acids, a crystalline compound which melts at 1C1° with simultaneous
decomposition into carbonic anhydride and skatole.
The quantity of parahydroxyphenylacetic acid, formed by the
putrefaction of blood albumin and the hj-drocinnamic acid from the
putrefaction of fiesh, is diminished by the presence of air during the
process, whilst the amount of cresol is increased. W. C. W.
Guanidine. an Oxidation-product of Albumin. By F. Lossen
{A^inaleii, 201, 3(ji) — 'S7i)). — In order to settle the disputed question
of the formation of urea by the action of potassium permanganate on
albumin, an aqueous solution of purified egg albumin was treated
with a mixture of potassium permanganate and magnesium sulphate,
until a permanent colour was imparted to the liquid. The magnesium
sulphate was added with a view of keeping the solution feebly alka-
line. After filtering the mixtui'e and acidifyii^g with dilute sulphuric
acid, a bulky precipitate is thrown down ; the filtrate contains gaani-
di7ie, which Bechamp (Journ. de Fharm. [3], 31, 32) mistook for
urea. W. C. W.
414: ABSTRACTS OF CHEMICAL PAPERS.
Physiological Chemistry.
Digestion of Food by the Horse when at Work. By E. v.
Wolff and others (Bled. Cent, 1879, 827— 835).— The result of the
experiments on the digestion of food by the horse, when performing
diiferent amounts of work, was that the digestion of food is not in-
fluenced by muscular exertion. Comparing the amount of matter
assimilated during the digestion of various foods by the horse and sheep,
the following facts are arrived at : — Tlie horse makes less use of hay
than ruminants, the difference being 11 — 12 per cent. ; but crude
protein is equally digested in both horse and sheep. On the other
hand, there is a wide difference as regards fibre ; although the digestion
of the non-nitrogenous extractive matter is more equal. Comparison
of the digestive capacity for various kinds of hay shows that they are
alike in both animals as regards the total organic matter ; but as
regards the various constituents, there is a difference, viz., with smaller
absolute quantities of protein the difference is smaller ; but in a few
sorts which are difficult of digestion, the horse makes a better use of
the protein than the sheep. There does not appear to be much dif-
ference between the digestibility of the fat and non-nitrogenous ex-
tract in either aximal, but the opposite is the case as regards the fibre.
Oats and beans and steeped maize are digested with like ease. Feeding
the horse continuously with the same sort of hay appears to have no
influence on the digestion of that food, whether it be given in large or
in small quantities. E. W. P.
Absorption of Food. (Di7igl. polyt. J., 234, 486— 489).— Nutri-
tion, as is well known, has to solve tw^o problems, viz. : — (1) to build
up and sustain the organism, and (2) to introduce and utilise latent
energy so as to preserve the actual forces of the body and its organs,
i.e., production of heat, electricity, mechanical labour, &c. The
albuminoids have to fulfil the first-named task, whilst all organic sub-
stances develop force in proportion to the latent energy liberated
during their conversion in the organism. The non-nitrogenous sub-
stances which take a subordinate part in the building up of the body,
and consequently possess the largest amount of latent energy, are
mainly utilised for the production of the vital forces, the chief agent
of which is animal heat.
In order to estimate the nutritive value of a food, it does not suffice
to ascertain the amount of nitrogen and carbonic acid, or to know the
quantity of albumin, fat, and carbohydrates contained therein ; but
it is necessary that we should know the amount of every nutritive
principle really absorbed into the system. To form a correct opinion
as to the absorption of these different pi'inciples, we must further con-
sider the quantity necessary for the preparation of a diet, in order to
obtain the proper proportions of nitrogen and carbon. Meat, eggs,
and white bread form the most favourable diet, whilst maize, potatoes,
and black bread may be included in this group. As a rule, fat is
absorbed into the ^vstem with but little residue. Larger quantities of
PHYSIOLOGICAL CHEMISTRY. 415
fat appear to influence the utilisation of the carbohydrates. How-
ever, the absorption of the latter into the system is of great import-
ance, since they represent the greater part of the dry substances in
the food of most men. Vegetable diet, which generally is poor in
nitrogen, gives excrements with more nitrogen than animal food.
In conclusion, it is stated that the causes of the differences in the
absorption of alimentary principles contained in various food-stuffs
have still to be explained more satisfactorily. D. B.
Feeding Experiments with Pigs. By E. v. Wolff, "W". v.
FuNKE, and G. DiTTMANN (Bied. Centr., 1879, 835—841). — The results
of the experiments in which the fattening values of potatoes and
flesh-meal are compared, are as follows : — The amount of dry matter
given caused the live weight to increase in five months from 27'2
to 89"2 kilos. ; the mean daily increase per head was 0"403 kilo.,
when the mean daily feedins: was 0"450 kilo. By a judicious mixture
of flesh-meal and boiled potatoes, a larger amount of solid matter is
retained than when potatoes alone, or with split peas, are given.
Likewise the nourishing influence of a given quantity of dry matter,
together with flesh-meal, is greater than without the latter. Young
pigs fatten better on potatoes than older ones. Beyond a certain
range, there is no advantage in using flesh-meal, as a like quantity of
carbohydrates will do as well ; the minimum ratio appears to be 1 of
flesh-meal to 33 of potatoes. Beyond this, 4" 78 kilos, of potatoes seem
to do the work of 1 kilo, of flesh-meal. The ratio of flesh-meal to
potatoes = ] : •2-5 yields good results. It appears, then, that flesh-meal
may with advantage be mixed with any food poor in albuminoids.
E. W. P.
Activity of Bees. By E. Eelexmeter and A. v. Planta-Reichexau
(Bied. Cent]-., 1879, 841 — 844). — The points to be determined were,
whether bees find honey and wax ready formed in flowers or not, and
whether they alter, wholly or in part, these substances. Several
specimens of honey were examined, and the pollen separated by mixing
the honey with water and then filtering, and in the filtrate were deter-
mined the coagulable albumin, total nitrogen, ash, and phosphoric
acid. Fresh honey apjsears to contain moi-e water than old honey ;
the coagulable albumin represents only part of the total nitrogen. Of
the remaining nitrogenous matter, a part is soluble in alcohol, a part
insoluble ; the proportions which these bear to one another are "0208 :
"0337 : '0230; the nectar of plants contains no albumin. The amount
of wax in honey was determined by means of ether, the extract so
obtained being treated with alcohol to remove oils ; the purified wax
melted at 6(J^C., and was present in varying quantities : '1603 : '0357 :
•0967 part per 100 dry substance. The presence of cane-sugar was
microscopically detected, but is present only in small quantities;
the greater portion which is at first collected having been changed
into glucose by the saliva of the bees, and by the ferment contained in
the pollen. The authors consider that the wax is produced by the bees
from sugar. E. W. P.
Physiological Action of Borax. By E. de Cvox and Gr. le Bon
(Bied. Centr., Ib79, 8G8j. — Cyon states that meat preserved by borax
416 ABSTRACTS OF CHEMICAL PAPERS.
is not diminished in its power of nourishing, and that the suhstitution
of borax for salt greatly aids assimilation of food ; Avhereas le Bon
asserts that meat cured with borax is useless as a food ; in fact, is
harmful. E, W. P.
Chemistry of Vegetable Physiology and Agriculture.
Alkaloid of Lupinus Luteus. By H. C. Schulz (Bied. Gentr.,
1879, 874). — The recognition of an alkaloid in lupines will account for
the several fatal results of feeding cattle with them. In the seed of
yellow lupines a cry stalli sable base has been found of the composition
Ci(]H2iN0o, soluble in water, melting at 62"5°, and boiling at 269 —
270°. Besides this, two other amorphous alkaloids have beeu found,
CgHnl^O and C7H15NO. None of the three bear any resemblance to
coniine. E. W. P.
Increase of Dry Matter in Several Agricultural Plants dur-
ing Growth. (Bled. Ceutr., 1879, 844— 847 j.— This paper contains
a mere statement of the points investigated by various persons. The
only research described is that by Messi'S. Kreusler, Prehn, and Horn-
beyer on maize. It is found that the first great increase of dry matter
is attained at the period of maximum development of the male flowers ;
and that a retrogression of the growth- takes place when the seed sets.
E. W. P.
Absorption of Oxygen and Expiration of Carbonic Anhy-
dride by Plants. By H. Moissan (Bied. Gentr., 1879, 874).— Every
organ of a plant inspires oxygen and gives out carbonic anhydride ;
expiration of carbonic anhydride is not always accompanied by ab-
sorption of oxygen ; generally at low temperatures the volume of oxy-
gen absorbed is greater than that of the carbonic anhydride expired ;
for every species of plant there is a definite temperature at which a
given volume of oxygen is replaced by a like volume of carbonic
anhydride. ■ E. W. P.
Constitution of Frozen Beech - leaves. By J. Schrodek
(Bied. Gentr., 1879, 875). — The leaves of a beech tree which had
been frosted in May appeared to have the same amount of nitrogen
and johosphorus as a normal leaf in the same month. E. W. P.
Composition of Leaves of Diseased Vines. By E. Rotondi and
A. Galimbkrti (Bied. Gentr., 1879, 876). — Diseased vine leaves con-
tain more moisture than healthy leaves, and in the dry matter there is
a higher percentage of nitrogen, ash, phosnhoric acid, potash, and
soda. E. W. P.
Dry and Wet Rot in Potatoes. By J. Reinke and G. Berihold
(Bied. Gentr., 1879, 851 — 855). — The two classes of rot to which pota-
toes are subject, namely the dry, in which the tuber becomes loose and
spongy, coated on the outside with mould, and the wet, in which the
=V^GETABLE PHYSIOLOGY AND AGRICULTURE. 417
interior of the tuber becomes partially liquid, the outside being also
coated with mould, are not due originally to the fungi Phytophtora
infestans and Saprophi/te, but to Bacteria (Bacillus suhtilus and Bac-
terium navicula). The disease is generally accompanied and aided by
the presence of Phytophtora, but not ahvays. If a healthy and
Phytophtora-free potato be inoculated with Bacteria by means of the
fluid from a diseased potato, disease will be communicated. Potatoes
having a maximum of starch resist the disease most effectually.
Potatoes grown on moist soils, and soils containing much organic
matter, such as stable manure, are most liable to disease. The starch
from diseased potatoes is yellow, but it can be used for the prepara-
tion of dextrin of a second quality. ' E. W. P.
Comparative Investigation of Hops. By C. 0. Harz (Bied.
Centr., lS7y, 8-i8 — 850). — The proportion in weight of the various
parts to one another of several species of hops has been determined,
and tables are given of the results. The sp. gr. of the alcoholic
extract is about 0"795. The percentage of leaf is about 79, but
there appears to be no definite relationship between the lupulin, fruit,
or leaves, neither can any be found between lupulin, fruit, and tannin,
which last is present to the extent of about 3 per cent. E. W. P.
Supposed Presence of Catechol in Plants. By C. Preusse
(Bicd. Ctiitr., laJV, 87-i). — The author denies the presence of cate-
chol in the leaves of Ampelopsis hederacea, and considers that some
kind of tannin was mistaken for catechol. E. W. P.
Influence of Manures on the Combustibility of Tobacco.
By G. Cantoni (Bied. Centr., 1879, 812— 814).— The manures em-
ployed were, potassium ammonium and calcium sulphates, potassium
and sodium nitrates, and potassium and sodium chlorides. The
nitrates had most effect as regards vigour of growth, whereas the
chlorides and gypsum were prejudicial, the yield in weight being
even higher when no manure was applied than when ammonium sul-
phate or sodium chloride was added. As regarding combustibility,
the leaf was almost totally incombustible when the plant had been
manured with gypsum, but that produced by potassium sulphate and
chloride was completely combu.stible. E. W. P.
Combustibility of and Amount of Chlorine in Manured
Tobacco. By A. Mayer (Bled. Ccdr., lb7L', 814— 81Gj. — Tobacco
manured with chlorides may contain as much as 0"52 per cent, of
chlorine, whilst an unmanured plant will only contain about 0"21 per
cent, in the leaves of the plant. The author confirms the statement
that chlorides have a prejudicial influence on the combustibility of
tobacco, as expressed by Cantoni (vide preceding paper) ; it is there-
fore recommended that no chlorides should be used to manure the
tobacco plant, but nitrates in preference. E. W. P.
Application of Natural Products as Manures. By F. Ullik
(Bied. Centr., 1879, bOl — 8U4). — Some basalts contain a considerable
418
ABSTRACTS OF CHEMICAL PAPERS.
quantity of potassium and phosphoric acid, but in such a form as
not to be easily dissolved by acetic acid, and therefore not readily
absorbable by plants ; but if the finely ground stone be treated with
a 2 per cent, solution of potassium chloride, calcium is eliminated,
and the phosphoric acid rendered more soluble. Thus the ratio of
the difficultly soluble to the readily soluble potassium in the original
basalt is 7 : 1, whereas after treatment the ratio is 4 : 1. In the same
way the ratios of the phosphoric acid are 90 : 1 before treatment, and
4-8 : 1 afterwards. E. W. P.
Determination of the Chemical Peculiarities of Soils and
Manures requisite for them; and on the Action of Soluble
and Reduced Phosphates. By D. v. Koth {Bied. Centr., 1879, 805 —
812). — The soil on which the experiments were performed contained
50 per cent, of clay and sand, and only 0'039 phosphoric acid ; the
manures were dug in to a depth of 10 — 12 cm. The special results
are naturally only of local interest. Of the three forms in which
phosphoric acid is applied, viz., superphosphate, precipitated phos-
phate, and patent " humus superphosphate" (dried peat saturated with
free phosphoric acid), precipitated phosphate seems to have been the
most successful.
Another series of experiments was devised to determine the relative
value of soluble and reduced phosphates. The results were as follows :
— The application of soluble phosphate alone in a calcareous soil has
no effect ; the application of reduced phosphate has considerable
effect ; when potash is present, the soluble phosphate still yields the
worst results ; but when potash and nitrogen were added, the results with
barley were equal, except that the straw was increased by the reduced
phosphate. E. W. P.
Manuring of Sugar-Beet in America. By C. A.. Goessmann
(^Bied. Centr., 1879, 816). — The following are the tabulated results of
experiments on sugar-beet : —
Soil.
Manure.
Sand J loam
Loamy cla}
Alluvial . .
Light sand
AUuTial . .
Heavy ....
Free stable uiaaure
Fresh pigs' dung . . . .
None
Brighton's artificial
manure
Stable manure
Sp. gr. of
juice of
root in deg.
Brix.
16-50
15-50
12-75
13-50
18-50
14-50
12-25
Percentage
of sugar
in juice.
12-50
10-05
9-17
9
13
53
73
11-15
8-15
Percentage
of foreign
matter
in juice.
4-00
4-15
3-58
■97
•77
3-35
4-10
Percentage
of sugar
in soluble
matter
of juice.
75-08
71-30
71-92
70 96
74-21
76-90
66-53
E. W. P.
Raising Vines from Seed. By A. Blankenhorn (Bied. Centr.,
1879, 850). — It is recommended that vines be raised from seed to
ANALYTICAL CHEMSTRY. 419
avoid the effect of Phylloxera. Attempts to do this have often failed,
by reason of the fact that the seed does not ripen until long after the
period of ripening of the grape itself The seeds of a vine which
resists the attacks of Phylloxera are sti'onger iu habitus, and raore
regularly formed. E. W. P.
Analytical Chemistry.
Determination of the Specific Gravity of Liquids, By H.
SoMMERKOEX (Ber., 13, 143 — 144). — The apparatus consists of a tube
of thin glass of 3 to 4 cm. diameter, the lower end of which is closed
by a thin disc of glass or platinum, having the same circumference as
the tube. The disc is held in its position by a thread. The apparatus
is immersed in the liquid under examination to such a depth that the
pressure is great enough to sustain the disc in its position without the
aid of the thread. It is then gradually raised until the point is
reached, when the pressure of the liquid is no longer strong enough to
support the disc. The length of tube immersed is read off by means
of a millimetre scale etched on the glass. The sp. gr. can now be cal-
culated with the aid of the formula — ^ = sp. gr., whei'e G represents
the weight and a the area of the disc, and h the length of tube im-
P 1
mersed. Since — is constant, and only — varies with the sp. gr., the
a h
specific gravities calculated for the different values of h may be etched
on the tube.
This apparatus yields more correct results than ordinary hydro-
meters do. W. C. AY.
New Method of Determining the Fusing Points of Organic
Substances. By G. Roster (Gazzetta, 10, 13 — 16). — The author
points out that the ordinary method of ascertaining the melting point
of a substance as well as Terrell's (this Journal, 1879, Abst., 693),
where the substance is attached to the bulb of the thermometer, which
is then cautiously heated over a small gas flame, is liable to give in-
accurate results. He has, however, modified the last-mentioned pro-
cess by fixing the thermometer horizontally and placing the substance
on the bulb, which is then heated in an air-bath. This air-bath con-
sists of two stout brass tubes, the inner one 3 cm. in diameter and
35 long, closed at one end, and having a small glazed apertui-e 5 cm.
from the open end ; the external tube is 8 cm. in diameter and 17
long, and is closed with annular rings at each end, so that it may slide
over the internal tube, and is also furnished with a glazed aperture
larger than that in the internal tube ; when these two windows are
brought opposite to one another the interior of the inner tube can be
easily seen. To use this apparatus a thermometer with large bulb is
fixed horizontally, and a small quantity of the substance whose melting
420 ABSTRACTS OF CHEMICAL PAPERS.
point is to be determined, is placed on it. The air-bath above
described is also fixed on a movable stand at such a height that the
axis of the internal tube shall correspond exactly with the thermometer
stem ; it is then moved forward until the bulb of the thermometer is
opposite to the glazed apertures. The extremity of the internal tube
remote from the glazed apertu're is then heated by means of a gas-
lamp, and as soon as any trace of moisture there might be in the in-
terior has escaped, the open extremity of the tube is closed by a loosely-
fitting plug which surrounds the stem of the thermometer. The
temperature then rises slowly and gradually, and as the substance and
the bulb of the thermometer ai"e always at exactly the same tempera-
ture the fusing point can be determined with very great accuracy.
C. E. G.
Estimation of Carbonic Acid in the Air. By M, Katosstin
(Ber., 12, 2376). — This method depends on the fact that when air
containing carbonic anhydride is shaken with a solution of caustic
soda in alcohol (90 per cent.) the whole of the sodium carbonate
formed is precipitated ; sufficient water is then added to redissolve this
precipitate, and from the amount of water required, the quantity of
carbonic anhydride present is deduced. In an actual experiment,
5 litres of air are shaken for half an hour with 75 c.c. of alcoholic
soda (1 litre of this solution = 0'5 gram. NaHO), 25 c.c. of the
liquid are withdrawn, and water added gradually from a burette until
the liquid becomes clear. The amount of carbonic anhydride present
in the original volume of air is then found from the equation
ic = — — - — , where n = the c.c. of water required by the whole 75 c.c.
of the soda solution. This method is recommended especially for
sanitary purposes, where the number of determinations is of more
importance than the great exactness of a single experiment.
T. C.
Estimation of Aqueous Vapour in the Atmosphere. By
F. Rddorff (Ber., 13, 149 — 152). — In order to determine the amount
of moisture in the atmosphere, a three-necked Wolff's flask of 1 litre
capacity is used. Each neck is provided with a perforated ground
glass stopper ; to one of these a manometer containing sulphuric acid
(sp. gr. 1-30) is attached. A burette containing strong sulphuric acid
passes through the second, and a glass tube provided with a stopcock
passes through the third stopper to within a short distance of the
bottom of the flask. The first stopper is fitted with a two-way stop-
cock, so that the flask may be placed either in communication with the
manometer or with the external atmosphere.
At the beginning of each determination the stoppers are removed
from the perfectly dry flask, and air is blown in to the apparatus from
a pair of hand-bellows, the stoppers are replaced, and the manometer
placed in communication with the interior of the flask. A small
quantity of sulphuric acid is allowed to flow from the burette into the
flask, aqueous vapour is absorbed, and the manometer is depressed.
After an interval of six minutes sulphuric acid is again slowly added
until the manometer regains its normal position. The volume of acid
added is equal to the volume of aqueous vapour in the flask.
w. c. w.
ANALYTICAL CHEMISTRY. 421
Estimation of Oxygen dissolved in Water. By J. Konig
{Ber., 13, 154 — loG). — The author jiiakes the folhjwing observations
on the paper of Tiemann and Prensse {Ber., 12, 17(58, antl this vol.,
137). The use of Reichard's apparatus (Zeits. Anal. Chem., 11, 271;
and this Journal, 26, 412) for expelling the dissolved gases from
water in the gasometric method of estimating oxygen yields too high
results.
Mohr's process yields slightly too high and Schiitzenberger's too low
numbers. Mohr's method is well adapted for those cases in which an
interval elapses between the diiferent analyses, since the strength of
the volumetric solutions does not change rapidly. Where a large
number of determinations are made in immediate succession, it is ad-
visable to use Schiitzenberger's process. In this case, it is recommended
to ascertain the strength of the sodium hyposulphite solution (NaoSOa)
by titration with water saturated with air instead of copper oxide
solution. W. C. W.
Volumetric Estimation of Arsenic Acid. By "W". A. H. Naylor
(Phann. J. Trans. [3], 10, 441 — 443). — Hydriodic acid exerts a re-
ducing action on arsenic acid, and under certain circumstances may be
applied to its estimation. The hydriodic acid solution must contain at
least 20 per cent. HI, and the iodine estimated as quickly as it is
liberated.
To determine the value of an arsenate, a portion equal to O'Oo — 0"03
gram of arsenic acid is weighed and dissolved in water and a little
hydrochloric acid, 5 c.c. of a 20 per cent, hydriodic acid solution are
added, and the iodine titrated with sodium hyposulphite. To prevent
the oxidation of the hydriodic acid, the operation must be performed
in an atmosphere of carbonic anhydride. Towards the end of the
reaction, the iodine is liberated at increased intervals, and before
taking the final reading 15 minutes should be allowed to elapse. The
reaction may be represented by the equation HgAsOi + 2III =
HsAsOs -f- HoO 4- l2- The method may be employed in presence of
phosphates and arsenites.
The results given are satisfactory, varying from 2 to "25 per cent.
As a qualitative test it may be used to detect O'OOOl gram AsoOo in
1 gram AsA- L. T. Ci'S.
Valuation of Wine. By Houdart and T. Petit (Bied. Centr.,
1879, 858 — 85'J). — To assign a value to wine, the following must be
determined: — (1) the density D at 15"; (2) the amount of alcohol
a present ; (3) the weight of the dried extract p per litre ; (4) the
mean density c of this extract. Then let P = weight of water,
Pi = weight of alcohol contained in 1 litre of wine, whose sp. gr. = D,
and containing a of alcohol; also let d = density of water, and Dj =■
density of a mixture of pure water and the quantity a of alcohol : then
the weight of a litre of wine will be expressed by the equation
1,000 D = P -h Pi +p. Suppose the extract to be replaced by water,
then a mixture will be obtained containing the same amount of alcohol
as the wine ; let Di be the density of such a mixture, and this is
found by reference to tables of density. The weight then of a litre of
422 ABSTRACTS OF CHEMICAL PAPERS.
this mixture is 1,000 Di = P + Pi + ±- (Z. Subtract the second
c
from the first equation and we have 1000 (D — Di) ^ p — -l^d, then
c
c = • — — — . Another formula may be employed, viz.,
p - 1,U00 (D - Di) ^ 1 J ' '
^j = 20G2 (D-D,). E. W. P.
Estimation of the Decolorising Power of Animal Charcoal.
By Reixecke and G. Meyer (Biecl. Cenfr., 1879, 857). The decolorising
poTver of bone charcoal appears to be inversely as its specific gravity.
E. W. P.
Adulteration and Examination of Food and Drink. By
F. Fischer {Dingl. polyt. /., 235, 140— 1.50).— J'/oHr.— In the Im-
perial German Act concerning the adulteration of food, &c., flour
ilenotes the grain of corn as prepared in the grinding process. As
adulterants the following substances have been used : —
a. Flour of peas, lentils, beans, maize, and potatoes. These are not
injurious to health.
h. Gypsum, barytes, chalk, magnesium carbonate, and other mineral
constituents, the use of which is injurious.
c. Alum, copper sulphate, and similar metallic salts, which when
used in the preparation of bread, are very injurious to health. The
colouring of macaronis for soups with picric acid instead of yolk of eg^
or saffron is also condemned. The methods for analysing flour have
been noted elsewhere {Hid., 231; 85, 287).
Confectionery. — The following colours are not injurious : — For white :
fine meal, starch ; red : cochineal, carmine, madder-red, beet-root jiiice,
and cherry-juice ; yellow : safiron, safilower, turmeric ; blue : indigo,
litmus ; green : juice of spinach and mixtures of non-injurious yellow
and blue colours ; for brown : burnt sugar, juice of liquorice ; black :
Indian ink.
Meat: sausages. — Under the following conditions meat is injurious
to health : —
1. The meat of animals that have died.
2. The meat of animals afilicted with mania, glanders, splenitis, or
with inflammation of the inner organs or outer parts of the body.
3. The meat of animals slaughtered while in a diseased state having
shown signs of typhoid appearances or of emaciation.
4. The meat of animals suffering from poisoning, or having been
treated with large quantities of poisonous substances previous to being
slaiightered.
5. Meat affected with trichinosis or tuberculosis.
G. Meat tainted considerably.
The value of meat is diminished, but without being dangerously
injurious: —
1. In all cases of fever and chronic diseases in which consumption
has set in.
2. In the case of calves less than eight to ten days old.
ANALYTICAL CIIEMISTRY. 423
3. The nutritive value of sausages is decreased by the addition of
flour (ibid., 209, 238).—
4. Horseflesh is often, sold as an adulterant for beef (ihid.,
203—231).
5. Milk. — It vronld seem that adulteration is of more frequent
occurrence with this article than with all other foods or drinks {ibid.,
6, 391; 40,234; 74,157; 224, 554; 227, 316). The following
adulterations are mostly noticed : —
a. Skimmed milk contains less fat than unskimmed milk, and is not
suitable for the nourishment of sucklings.
b. Dilution : unskimmed milk and even skimmed milk is often
adulterated with water, whereby the nutritive value is lowei-ed.
c. The addition of foreign ingredients to milk (starch, chalk,
gypsum, wheat flour, &c.) is not often practised, and is iisually made
with the view of preventing the detection of the adulteration with
water, as they impart to the diluted milk the normal degree of non-
transparency and thickness. The author refers to the various methods
known for the analysis of milk. He states that milk containing less
than 3 per cent., or even 2"8 per cent, fat, or 11"5 per cent, dry sub-
stances, should not necessarily be called adulterated.
Butter. — According to the German Act, butter is the fat obtained
from the milk of manniferous animals. The increase in weight by
adding foreign substances to butter is not allowed. Various other
conditions of adulteration of butter are considered in the original, all
of which have been published previously. D. B.
Presence of Sulphuric Acid in Milk. By G. Musso and F.
Schmidt (Bied. Centr., 1879, 865). — Both authors prove that sulphates
are present in milk, although it was formerly stated that they were
only present in milk to which spring water had been added. The
amount naturally present amounts to 0'0831 — 0"0391 per cent.
E. W. P.
Butter Adulteration. By W. G. Crookes and others {Bied.
Centr., 1879, 861 — 865). — The processes recommended divide them-
selves into three classes: — (1) microscopic; (2) specific weight;
(3) estimation of the fatty acids.
Microscojnc Test. — Mylius proposes to examine the butter with a
polarising apparatus, in which the Nicol's prism is replaced by one
of herapathite. Pure butter which has not been melted shows no
signs of polarisation, but if lard, suet, &c., which have been melted,
and are therefore crystalline, are present, the crystals appear light on
a dark ground.
Estimation of Spp-cific Gravity. — Konig has determined the sp. gr.
of several fats at 100°, and finds the sp. gr. of pure butter to be
0-865— 0-868 ; artificial butter 0-859 ; suet 0-860 ; mutton suet 0-860 ;
lard 0-861 ; horse fat 0-861. Mixtures gave intermediate numbers.
Estimation of Fatty Acids. — F. Jean saponifies the butter wdth
alcoholic potash, and adds magnesium sulphate after evaporation of
the alcohol, washes the precipitate on a filter, and decomposes with
hot dilute sulphuric acid. Pure butter should only contain of these
solid fatty acids 87 — 88'2 per cent., whereas oleo-margarin contains
424 ABSTRACTS OF CHEMICAL PAPERS.
941 — 95'7, and butter of poor qiialifcy 90 ; so that butter having more
than 88 per cent, of solid fatty acids may be considered as being
adulterated. Reichart saponifies 2"5 grams of butter with 1 gram of
solid potasb and 20 c.c. 80 per cent, of alcohol and distils the result-
ing soap with sulphuric acid ; the first 50 c.c. of the distillate should
require, if the butter be pure, about 14 — 16 c.c. of decinormal soda
solution, but cocoaniit fat only 3" 7 c.c, and oleo-margarin 0'25 —
0"95 c.c. ; if, then a butter require only 12"5 c.c. of soda it is impure.
Koettstorfer's process has already been described (this Journal, Abstr.,
1879, 1069). E. W. P.
Testing of Pepsin. By A. Petit (Pharm. J. Trans. [3], 10,
583 — 584). — After revievving the various methods of testing pepsin,
namely : — (1) By coagulation ; (2) by coagulated white of egg ; (3) by
fibrin, the author concludes that the first method should be rejected,
since the principle in rennet which coagulates milk differs from that
which dissolves and transforms fibrin.
The second method whicli is generally adopted has one objection, that
it does not establish sufficient gradation in the transformation ; it may,
however, be used as follows : — An egg is boiled for half an hour, the
white passed througli a sieve, and 5 grams of the coagulated albumin
are treated with 25 grams of hydrochloric acid (1'5 HCl per litre)
at 40''. The albumin should be dissolved in four or five hours by
OTO pepsin. The mixture should be shaken every half hour.
The third method is the most suitable. All the phemonena are dis-
tinct and comparable; whatever be the nature of the ferment, all things
being equal, its exact equivalence may be determined by reference to
other specimens. 5 grams of moist fibrin strongly dried are treated
with 25 c.c. of hydrochloric acid (3 grams HCl per litre), and to several
flasks thus prepared quantities of pepsin, varying from 0*10 to 0"60
gram, are added and heated to 50°, at which temperature the action of
pepsin is a maximum. Agitate every half hour until dissolved, and
then every hour : no precipitate should be produced by nitric acid after
6 hours' heating with 0"5 — 0'6 gram pepsin. L. T. O'S.
Detection of Alizarin, Iso- and Flavo-purpurins ; and the
Estimation of Alizarin. By E. Schunck and Roemer (Ber., 13,
41 — 43). — These compounds may be separated by fractional subli-
mation, since alizarin begins to sublime at 110°, flavopurpurin at
160'^, and isopurpurin at 170°. The first is easily removed by keeping
the temperature below 160°; in the sublimate obtained above 170°
the two purpurins may be distinguished by the aid of the microscope,
flavopurpurin subliming in fine reddish-yellow needles, whilst iso-
purpurin sublimes in compact, well-formed rhombic crystals ; or they
may be separated by means of benzene, in which the latter is inso-
luble, whilst the former is easily soluble.
The authors propose to apply the above to estimate alizarin. The
mixture is heated at 140° as long as a sublimate is obtained and the
residue weighed, and thus the alizarin estimated by loss. In applying
this method to commercial alizarin, it is necessary first to remove
anthraquinune, oxyanthraquinone, authra-, and isoanthra-flavic acids.
P. P. B.
TECHNICAL CHEMISTRY. 425
Technical Chemistry.
Action of Sulphuric Acid on Phosphates, especially Calcium
Phosphate, in connection with the Manufacture of Super-
phosphates. By J. PubT (Bir., 13, 57 — 58). — The author iinds that
by the use of an acid containing 19"8 per cent. H2SO4, a very com-
plete reaction takes place between it (2 mols. H2SO4) and calcium
phosphate (1 mol.). After a few minutes, the alcoholic extract of the
jjroduct yields but traces of sulphuric acid.
In various experiments, 54"4o, 55"66, 57'1, 58"75, and 61'2 per cent,
of phosphoric acid was found, the theoretical being 6&67 per cent.
P. P. B.
Electro-brass Plating. By J. J. Hesz (Dtngl. pohjt. J., 235,
47). — The author uses the following bath, which differs materially
from former formulae : — 84 grams sodium bicarbonate, 54 grams
ammonium chloride, and 13 grams potassium cyanide are dissolved
in 2 litres of water. To render the bath active, the sides of the vessel
are covered with a sheet of brass which serve as anode, whilst another
piece of brass hangs in the bath and forms the cathode. The current
is allowed to pass through the bath for one hour, when it is ready for
use. It is better to employ cast brass.
In order to tin directly on zinc, the author uses the following mix-
ture : — 50 grams sodium phosphate, 50 grams salammoniac, 25 grams
sodium bicarbonate, and 25 grams tin salt dissolved in 1 litre of water.
Instead of sodium phosphate, Rochelle salt may be employed.
D. B.
Composition of Must at different Stages of Ripeness of the
Grape. By E. Rotondi and A. Galimberti {Bied. Centr., 1870, 877). —
As ripening proceeds, the total acid and free tartaric acid diminish,
whilst the ash and sugar increase. E. W. P.
o
Patent Process for Preparing Inverted Sugar. By Maumene,
Cail, and Co. (Bied. Centr., 1879, 856). — Sugar dissolved in four times
its weight of water is boiled with -goVo concentrated sulphuric acid in
silvered or tinned boilers, then neutralised with barium carbonate,
filtered, and evaporated. To separate the salts which may be present
in solution, alcohol is added, which may be recovered by distillation.
By such a process, the crude product obtained in the first stage of the
manufacture of sugar may be made available for the making of pre-
.serves. E. "W. P.
Extracts of Narcotic Plants. By H. Bretbt (Pharm. J. Trans.
[3], 10, 565 — 566). — To determine the value of various extracts of
narcotic plants, extracts were made by the different processes in vogue
and the proportion of alkaloid contained in them determined.
Comparative experiments on conium with the extract of the defe-
cated juice and extract by infusion, show that 10 grams of the former
yield from 0'01309 to 0'0159 gram conicine, and the latter, 0"01857 to
b-0329 gram.
VOL. xxxviii. 2 h
426 ABSTRACTS OP CHEMICAL PAPERS.
Analyses of belladonna and datura were made with more uniform
results.
1 kilo, of fresli leaves of belladonna : —
Per cent. Grams
Grains. Containing atropine, atropine.
On clarification of juiceyield 5'16 coagulum = — = 0*0580
„ 29-60 juice extract . . = 0-305 = 0-1067
Deprived of juice .... ,, 15-50 aqueous extract = 0-721 = O'lll?
When dried „ 54-94 „ „ =0-721 = 0-3961
„ „ 48-54 alcoholic „ = 1-352 = 0-6562
Alcoholic extract of datura yields 1-442 per cent, alkaloid.
„ ,, belladonna yields 1-081 — 1-4 per cent, alkaloid.
Defecated juice of „ „ 0-090 — 0-27 „ ,,
Aqueous extract of datura yields 0-451 per cent, alkaloid.
,, ,, belladonna yields 0-721 — 0-180 per cent, alkaloid.
These results show that the alcoholic extract is much the richest in
alkaloid, the extract by infusion ranks next. The extracts of the non-
defecated juice are richer in alkaloid than the defecated ; this confirms
the opinion that the extracts of Storck are more active than those of
the defecated juice. L. T. O'S.
Manufacture of Resorcinol and Colouring-matters derived
from it. By Bindschedler {Bingl. polyt. J., 234,484). — An abstract
on this subject {Chem. News, 38, 226) has already appeared in this
Journal (Abst., 1879, 291), but from the article in Dingier it would
seem that the temperatures formerly given (^loc. cit.^ are in degrees
Fahrenheit and not Celsius. C. E. Gr.
New Class of Phenol Colours; By C. Reichl {Dlnql. polyt. J.,
235, 532 ; from the Berich. d. Oster. Chem. Ges., 1879, 12)'.— The pro-
perty which phenol has of giving beautifully coloured compounds with
aldehydes, acids, and anhydrides of polybasic acids, induced the author
to investigate the action of polyatomic alcohols on the same group of
bodies. Similar results were obtained in the case of glycerol, and it
appeared, during the investigation, that carbohydrates, mannitol,
quercite, erythrol, and ethylene glycol give colours with phenols. The
author describes the colours obtained with glycerol and the compounds
thymol, cresol, phenol, quinol, orcinol, resorcinol, and pyrogallol, and
to these coloured bodies he gives the name of "glycereines."
Two parts of phenol, 2 parts of glycerol, and 1 to 2 parts of sul-
phuric acid heated at 110 — 120° for a long time, give a dark reddish-
yellow resin-like mass ; this is well washed and dissolved in alcohol or in
soda- lye; the colour is then obtained by diluting the alcoholic solution
or by the addition of hydrochloric acid to the soda solution. The
substance gave the formula C9H10O2, formed as follows : —
CeHsO + C3H8O3 = C9H10O.. + 2H2O.
This " phenolglycerein," a brownish-yellow, amorphous mass, is
soluble in acetic acid, alcohol, and in boiling water, but insoluble in
benzene and carbon bisulphide. Its solutions acquire a splendid red
TECHXICAL CHEMISTRY. 427
coloui" on the addition of alkalis. With alumina, lead oxide, and
other oxides, coloured lakes are produced, and fibrous textures are dyed
bj it of a violet or yellow tint.
On warmins: this compound with concentrated sulphuric acid, no
sulphur dioxide is evolved, and a sulpho-salt, soluble in cold water,
is produced ; this solution shades red with alkalis, and is not precipi-
tated with alum.
By heating the mixture of phenol and glycerol with less sulphuric
acid, a yellow powder is produced insoluble in ether, benzene, carbon
bisulphide, acetic acid, and alkalis : it turns red with the last class of
reagents. But its sulpho-compound behaves like that of " phenolgly-
cerein," the sulpho-salt given above.
Five parts of glycerol, 2 — 5 parts of sulphuric acid, and 6 parts of
cresol, heated at 110 — 120°, yield a dark, glistening, amorphous mass
which gives a dark-brown powder. With alkalis it becomes violet-red,
and its other properties agree with those of the phenol-colour.
Three parts of thymol, 1 part of glycerol, and .5 parts of sulphuric
acid give a corresponding glycere'in, similar to the phenol compound
as to its solubility, and giving a splendid violet-coloured solution with
alkalis. Wool and silk can be dyed violet wnth this compound.
In a similar manner, 1 mol. each of quinol, glycerol, and sulphuric
acid produce the glycere'in of quinol. Its alcoholic solution has a
beautiful green fluorescence, and becomes brown with alkalis, without
losing the fluorescence. In the same way the corresponding com-
pounds of resorcinol and orcinol are obtained. Their alcoholic solu-
tions become red with alkalis, and then show a green fluorescence. On
wool and silk they afford pure yellow, reddish- and greenish-yellow
colours.
Seven parts of pyrogallol, 5 parts of glycerol, and 2 — 3 parts of
sulphuric acid, heated at 120 — 130°, give the corresponding compound.
The red product contains a new dye which gives a beautiful red shade
with tin-salt. ' J. T.
Action of Infusorial Earth on Colouring-matters. By G.
ExGEL (Dinrjl. fohjt. J., 235, 1-50). — The author thinks that the
physical properties of dyeing woven fibres are of much more import-
ance than the chemical. To support this view he has investigated the
behaviour of infusorial earth when treated according to the various
processes of cotton and wool dyeing, the results of the experiments
being noted in Bull, de MulJiouse (1879, 659) : mordanted and dyed in
the same way as wool and cotton, it takes up the dyes quite as well as
these substances. Formerly infusorial earth was considered a product
of animal origin ; but recent investigations have shown that it emanates
from the vegetable kingdom. This, however, does not affect its
chemical composition. D. B.
Mineral Tanning. By C. Heinzbrltng {Bhujl. iwJyt. ./., 235,
•51 — 53). — The author has patented a process for tanning calf-skin,
using (1) alum, (2) zinc-dust, for separating amorphous alumina from
the former, (3) chromates, (4) baryta or lead salts, and in case it is
necessary to colour the leather black, potassium ferrocyanide. For
428 ABSTRACTS OF CHEMICAL PAPERS.
the actual tanning process the three first-named substances only are
nsed, the baryta and lead salts being evidently intended only to impart
weight to the leather, so that such leather may compete with ordinarily
tanned leather. The effective agent appears to be the chromate, but
no details of the process are given. Sole-leather cannot be tanned
according to this process. D. B.
Linaloes-wood. By J. Moelleb {Binf/l. polyt. J., 234, 468 — 470).
— The author has obtained a sample of this wood, the ethereal oil of
which is at present largely used in perfumery. The wood is extremely
light, porous, almost spongy, has a light yellow colour, with darker,
denser, and harder portions, which are quantitatively very subordinate.
The wood is without taste. Its aqueous extracts are almost colour-
less, and do not contain any trace of tannin. The alcoholic extracts
also are but slightly coloured, and the author could not succeed in
proving the presence of resinous substances with certainty. The
examination with the microscope shows, without doubt, that it is only
the dense and darker coloured portions of the wood which contain
the ethereal oil, whilst the specifically lighter and paler coloured por-
tions— the chief portion in the sample — contain empty cells. The
author has not yet been able to collect evidence as to the origin of the
wood, and the mode of distillation and preparation of the oil.
D. B.
Wild Croatian Hops. By C. O. Cech (Bied. Centr., 1879, 792).—
These cannot be used alone in the preparation of beer, but must be
mixed with at least twice their weight of ordinary hops ; as they con-
tain large quantities of tannic acid, they may be used with advantage
for clearing purposes. J. K. C.
Glycerina Cement. By T. Morawski (Dingl. polyt. J., 235, 213).
— Litharge, ground with glycerol, forms a cement which hardens
rapidly. The author found, under various conditions, a glyceride of
lead in the form of fine needle-shaped crystals of the formula
CsHePbOs ; but much litharge usually remains uncombined. The
combination takes place more rapidly on the water-bath. To prepare
the compound quickly, a hot saturated solution of PbO in potash solu-
tion is mixed with glycerol, more PbO added to saturation, and the
solution quickly filtered : occasionally the compound crystallises out
immediately. Heated to 130°, the compound becomes coloured, and
at 200 — 210"^ it slowly carbonises. Decomposition soon begins on
boiling with water, glycerol and lead oxide being separated. It is
easily soluble in acetic acid with decomposition, and potash-lye easily
dissolves it, especially on warming. It is acted on by nitric and sul-
phuric acids, although not very rapidly when the acids are concen-
trated.
The greatest tenacity of the cement is obtained with 50 grams of
litharge to 5 c.c. of glycerol.
The author is investigating compounds of glycerol and other metallic
oxides. J. T.
429
General and Physical Chemistry.
Photograph of the Ultra-red Portion of the Solar Spectrum.
By Captain Abney (Compt. rend., 90, 182 — 18o). — The photographs
«)f the portion of the solar spectrum, less refrangible than the A line,
were obtained by the use of a silver-compound prepared speciall}" for
the purpose, but of whick no. further details are given.
The wave-lengths are approximately correct; they were obtained
by covering half of the slit, and exposing the sensitive surface to the
extreme red of a spectratn of the first order, a suitable absorbing
medium cutting off the blue end of the spectrum of the second order.
The second half of the slit was then opened and the first covered. In
this manner the two spectra are superposed, and the wave-lengths
were obtained without the possibility of any great error.
This photograph of the prismatic spectrum is in harmony with the
thermic observations of Lamansky, and perhaps also with those of
Sir J. HerscheL J. W.
Existence of Carbon in the Coronal Atmosphere of the
Sum. By J. N. Lockyer {Proc. Boy. Soc, 27, 308). — Photographs
have been obtained of the spectrum of carbon, in oxygen and in
chlorine, which correspond with the supposed carbon lines in the solar
spectrum.
The carbon lines in the solar spectrum are not reversed, showing
that the vapour exists at a lower temperature and pressure than the
metallic vapours in the sun's atmosphere. It must, therefore, exi.'it
above the chromosphere. C. W. W.
Acceleration of Oxidation caused by the Less Refrangible
End of the Spectrum. By Captain Abney (Froc. Boy. Soc, 27^
291, 451). — The author is of opinion that Bccquerel's coloured
spectra and Draper's reversed spectra are due to the increased oxida-
tion caused by red rays.. Silver bromide, spread on a plate and ex-
posed first to diffused daylight and then to the solar spectrum under a
layer of some oxidising solution (hydrogen peroxide, potassium per-
manganate, nitric acid, &c.), gave a reversed spectrum, extending
from D into the ultra-red. No reversal was obtained in an atmo-
sphere free from oxygen.
Silver bromide, which, under ordinary circumstances, is not sen-
sitive below B, when exposed under sodium sulphite, was sensitive to
M, the lowest limit (about w. 1. 12,000) yet photographed. Silver
iodide, under the same conditions, was sensitive to a point between
A and a.
Solarisation is in reality due to the increased oxidation produced by
the red rays, and this effect, as is well known, cannot be produced in
reducing solutions. It may therefore be concluded that the whole
spectrum exercises a reducing action on the sensitive compound, and
VOL. XXXYIII. 2 i
430 ABSTRACTS OF CHEMICAL PAPERS.
that the redneed compound can also be reoxidised, the relative power
of these actions appearing to vary with the part of the spectrum em-
ployed. C. W. W.
Spectra of Metalloids. Spectrum of Oxygen. By A. Schuster
(Proc. Boy. Soc, 27, 383). — Four different spectra of oxygen must
be distinguished. At the lowest temperature at which oxygen becomes
luminous it gives a continuous spectrum. ; but as the temperature is
gradually raised, the continuous spectrum is successively transformed
into two distinct line spectra, which the author names i^espectively the
compound line spectrum and the elementary line spectrum. The
fourth spectrum is that which is always seen at the negative pole in
vacuum tubes containing oxygen.
The existence of the continuous spectrum is proved by tbe following
facts : — The wide part of a Pliicker tube generally shines with a faint
yellow light, which gives a continuous spectrum. A weak spark from
a coil taken in oxygen at the ordinary pressure gives a continuous
spectrum, having its maximum in the greenish-yellow. The point of
an oxyhydrogen flame has a yellow colour when excess of oxygen is
present (Becquerel) ; when excess of hydrogen is present, the hydrogen
lines are seen (Pliicker).
The elementary line spectrum is seen when a strong spark is passed
through oxygen at the atmospheric pressure. There are some strong*
lines which do not appear in Thalen's list. The author has made
careful measurements of all the lines.
The compound line spectrum of oxygen consists of four principal
lines and a number of fainter ones. The four principal lines, one in
the red, two in the green, and one in the blue, are always the first to
appear (Wiillner). The following is the appearance of an oxygen tube
as it undergoes exhaustion : — When the pressure is sufficiently
diminished to allow the spark to pass, it has a yellow colour and gives
a continuous spectrum ; then the four lines make their appearance,
gradually becoming stronger, while the continuous spectrum becomes
weaker until at last the lines stand out on a perfectly black background.
If now a Leyden jar and air break be introduced, the elementary line
spectrum at once comes out. There is a blue line in this spectrum
closely, biit not exactly, coincident with the blue line in the compound
line spectrum ; the complete disappearance of the compound line
spectrum has, therefore, hitherto escaped notice.
The spectrum of the negative pole consists of fine bands, made up
of lines at about equal inteiwals.
The author considers that the separate spectrum generally seen at
the negative pole in gases is due to separate molecular groupings
which are formed at that pole. In support of this view, he adduces
the fact that when the ciirrent is suddenly reversed, the peculiar
spectrum is persistent for some time at what was previously the nega-
tive pole. C. W. W.
Absorption of the Ultra-violet Rays of the Spectra by
Organic Substances. By W. N. Hartley and A. K. Huntington
{Proc. Eoij. iSoc, 28, 233). — The apparatus employed was a combina-
GEXERAL AND PHYSICAL CHEMISTRY. 431
tion of Miller's with Soret's, modified to suit the particular require-
ments of this research. The object of the research was to trace a
connection between the chemical constitution of a body and its actinic
absorption. The following conclusion.s have been drawn : —
(1.) The normal alcohols of the series ChHo„+i.OH are remarkable
for transparency to the ultra-violet rays, pure methylic alcohol being
nearly as much so as water.
(2.) The normal fatty acids exhibit a greater absorption of the
more refrangible rays of the ultra-violet spectrum than the normal
alcohols containing the same number of carbon-atoms.
(3.) There is an increased absorption of the more refrangible rays
corresponding with each increment of CHo in the molecule of the
alcohols and acids.
(4.) Like the alcohols and acids, the ethereal salts derived from
them are highly transparent to the ultra-violet rays, and do not exhibit
absorption-bands.
(5.) Benzene and bodies derived from it and its homologues are
remarkable firstly, for their powerful absorption of the ultra-violet
rays ; secondly, for the absorption-bands made visible by dissolving
them in water or alcohol and diluting ; and thirdly, for the extra-
ordinary intensity of these absorption-bands, that is to say, their
power of resisting dilution.
(6.) Isomeric bodies containins: the benzene nucleus exhibit widely
different spectra, inasmuch as their absorption-bands vary in position
and in intensity.
(7.) The photographic absorption spectra can be employed as a
means of identifvinQf organic substances, and as a most delicate test
of their purity. The curves obtained by co-ordinating the extent of
dilution with the position of the rays of the spectrum absorbed by
the solution, form a strongly marked and often highly characteristic
feature of many organic substances. C. W. W.
Thermo-electric Properties of Liquids. By G. G-ore (Proc.
Eoij. Sue, 27, 513). — When two plates of tlie same metal are immersed
in a liquid which does not act chemically on them, and one of the
plates is heated, an electric current is generated, the direction of which
depends on the nature of the liquid. In strongly acid solutions the
cold metal is positive to the hot ; in strongly alkaline solution the hot
metal is positive to the cold. The direction of the current depends
on the nature of the liquid ; its magnitude is often greatly affected by
the kind of metal employed, although no chemical action takes place.
The strength of the current is often greatly increased by main-
taining the temperature of the hot plate for some time ; in a few cases
it was decreased.
The heat applied seems to be the sole cause of the electricity gene-
rated. C. W. W.
Density of Chlorine at High Temperatures. By J. M. Crafts
(Compt. rend., 90, 183 — 186). — The modification of Meyer's apparatus
for the determination of vapour-densities, devised by the author, con-
sists in connecting the porcelain cvlinder with two U-tubes, which are
2 i 2
432 ABSTRACTS OF CHEMICAL PAPERS.
calibrated and divided in tenths of cubic centimeters. One branch of
these tubes is connected with a moveable vessel by which the pressure
can be controlled, and the other branch terminates in a bulb or re-
servoir of 9 or 10 c.c. capacity, which communicates by means of a
capillary tube with the cylinder. One of the tubes delivers its gas
through a narrow tube of platinum or clay to the bottom of the
cylinder, while the expelled air passes into the second U-tube to be
measured. The tubes are filled with mercury, water, or sulphuric
acid, according to circumstances, and are surrounded by cold water to
maintain them at an equable temperature.
Two experiments, conducted at the highest temperature of the fur-
nace, showed that 10 c.c. of chlorine occupied the same volume as
10*37 c.c. and 10'24 c.c. of air at the same temperature. There was,
however, a small progressive diminution of volume, so that six minutes
after the first observation the volume had contracted by 0'04 c.c, and
after the second 0'05 c.c. This alteration in volume is probably owing
to some action of the chlorine on the tobacco-pipe stem used to convey
the gas down the cylinder.
When the apparatus was filled with dry chlorine and heated as
before, 10 c.c. of air displaced 9"98 c.c. and 10 c.c. of chlorine. The
density of chlorine, according to Meyer, requires in the first series of
experiments an expulsion equal to 15 c.c, and in the second to 6'6 c.c.
Two other experiments with a thick platinum tube gave 10"43 c.c.
and 10"3 c.c. of air displaced by 10 c.c of chlorine. Bromine, the
density of which at 445° was 5"24 (theory 5'57), had at the same tem-
perature as the chlorine, densities of 4"39 and 4'48. Iodine, the density
of which at 445° was 8"657 (theory 8*795), gave in a similar manner
results which showed that its density was reduced to 6*01 and 5*93.
It must therefore be admitted that at the highest temperature of
Perrot's furnace iodine diminishes in density to increase in volume in
the proportion of 1 : 1*5, and bromine in the proportion of 1 : 1*2 ; in
the case of chlorine the increase in volume is 0, or at most only a few
hundredths, and therefore nothing like an augmentation of 50 per
cent., as originally obtained by Meyer. J. W.
Behaviour of Chlorine at High Temperatures. By V. Meyer
and H, ZUblin ( Ber., 13, 399 — 401). — The dissociation of chlorine to
molecules of the size -|Cl2, which occurs (Ber., 12, 1430) in the case of
nascent chlorine obtained from platinous chloride at or above 1200",
does not take place at similar temperatures if read]] -formed chlorine be
employed ; in the case of iodine, however, this dissociation takes place
even v.'hen the element is used in the free state. These results agree
with those of Crafts (preceding abstract). T. C.
Density of Bromine at High Temperatures. By Y. Meyer
and H. ZUblin (Ber. 13, 405 — 407). — At a temperature of about
1570° the density of bromine in the nascent state (evolved from platinic
bromide) corresponds to fBro, so that bromine exhibits exactly the
same phenomenon of dissociation as nascent chlorine and free iodine
under similar conditions.
The density of bromine when employed in the free state was very
GEXERAX, AND PHYSICAL CHEMISTRY. 433
difficult to determine at the same high temperature, owing to the
explosive violence with which the element is converted into gas. The
several numbers obtained, however, all lie between those for Br,
(5'o2) and f Bro (3'64), and this agrees with the results of Crafts
(this vol., p. 4:o\l). T. C.
Behaviour of Iodine at High Temperatures. By Y. Metee
(£er., 13, 3'J-i — 399). — At high temperatures iodine behaves exactlv
like chlorine. Up to at least 600°, its density corresponds to L, at 800""^
it is much less, but remains constant between 1027" and 1567°, when
the density corresponds to -flo. It differs from chlorine, however, in
that the temperature at which the density is diminished by one-third
is much lower, being 1000° in the case of iodine, whilst for chlorine it
is 1200°. These results agree with those of Crafts (Compt. rend., 90,
184, comp. preceding abstract), but are at variance with those ob-
tained by Deville and Troost (Ann. Chini. Phys. [3], 58, 293), accord-
ing to whom iodine has a normal density at 1040°. T. C.
Density of Iodine at High Temperatures. By J. M. Crafts
and F. Meier (Covrpt. rend., 90, 690 — 692). — According to the well-
known experiments of Deville and Troost the density of iodine is
normal at 860° and 1040°, whilst, according to Y. Meyer, the densitv
of this element is abnormal above 590°. The authors have found thai
Meyer's method of determining the temperatures by measurino- the
volume of gas consumed in a given time gives inaccurate results. In
their own experiments they have employed the method previously
described (this vol., p. 431), the determination of the temperature
being made immediately before that of the density. The iodine used
was prepared by Stas's method. The numbers obtained are given
in the following table as compared with those of Y. Meyer. The
third column shows the ratio between the experimental and theoretic
densities : —
T. Merer.
/' ' >. ^
Temperatue. Density. _
4.50° 8-85 —
586 8-72 0-99
842 676 0-77 '
1030 5-75 0-66
1570 5-70 0-65
From the authors' results, it would appear that the density of iodine
gradually decreases with a rise of temperature up to 1400", and is not,
as Meyer's figures would show, constant between 1000° and 1570".
Probably at still higher temperatures the density would be reduced to
half its normal value, or L. would become 21. C. H. B.
Observations on Vapour-densities. By Y. Meyer (Ber., 13,
40l — 404). — The author endeavours to account for the conflicting-
results obtained by himself (see previous abstracts) and by Deville
Crafts
and Meier.
Temperature.
Density.
D'
445°
8-74
830 880
8-07
0-92
1020—1050
7-01
0-80
1275
5-82
0-66
1390
5-28
0-60 •
434 ABSTRACTS OF CHEMICAL PAPERS.
and Troost (Ann. Ghim. Phijs. [3], 58, 293) in reference to the vapour-
density of iodine at high temperatures, by the fact that the conditions
of the experiment were very different in the two cases. Deville and
Troost placed the iodine in the cold apparatus, which was then slowly
heated, whereas, in the author's experiments, the element was throimi
directly into the red-hot vessel, and hence passed almost instantaneously
from tlie solid to the gaseous state. It is therefore not improbable
that in this latter case a dissociation would occur which, under other
conditions, would not be observed, or only at much higher tempera-
tures. Further, in the author's experiments, the iodine vapour was
always in contact with a foreign gas, which was not the case in
those of Deville and Troost. Now it is well known that the presence
of a foreign, chemically indifferent gas sometimes exercises a very
remarkable influence on the molecular condition of the gas ; so that
the dissociation of complicated molecular groups, which under other
circumstances can only be obtained at a high temperature, takes place
at a comparatively low temperature if a foreign gas be present, pro-
bably owing to the latter diminishing the partial pressure on the vapour
in question. This is the case with the vapour of acetic acid, as shown
by Horstman (Ber., 3, 78; 11, 1278). This effect appears to be inde-
pendent of the nature of the indifferent gas. T. C.
Vapour-densities of the Alkali-Metals. By Y. Meyer (Ber.,
13, 391 — 394?). — The vapour-densities of potassium and sodium
cannot be detenuined in vessels of glass, porcelain, iron, silver, or
platinum, as all these substances are attacked by the metals at the
temperature necessary for the determinations. The author is now
trying vessels of giraphite. T. C.
Calorimetrical Temperature-determinations. By Y. Meter
(Ber., 13, 407 — 4U8). — This is a reply to Crafts's remarks (Compt.
rend., 90, 184) on the author's method of determining the tempera-
ture in his vapour-density investigations. From his own observations,
as well as those of Roscoe (Ber., 11, 1196), the author considers that
the measurements of temperature given by the calorimeter are accu-
rate enough for the pui^iose in question, as only an approximate and
not an exact knowledge of the tempei'ature is necessary.
T. C.
Density of some Gases at a High Temperature. By J. M.
Crafts (Compt. rend., 90, 309 — 312). — By means of a modification of
Y. Meyer's vapour-density apparatus, the author has proved that car-
bonic anhydride and hydrochloric acid have a normal density even at
the highest temperature of a Perrot's furnace (about 1360"). He finds
that at veiy high temperatures porcelain is permeable to hydrogen
and aqueous vapour, and suggests that the small quantity of oxygen
obtained by Meyer in his experiments on the vapour-density of chlo-
rine may have been due to the action of the chlorine on a small
quantity of aqueous vapour which had diffused into the apparatus.
C. H. B.
Further Remarks on the Heat of Formation of Gaseous
Chloral Hydrate. By Bekthelot (Compt. read., 90, 491).— A
GEXERAL AND PHYSICAL CHEMISTRY. 435
contimiation of the discussion with M, Wurtz. The author points
out that by operating at a low pressure, the mass of matter reacting is
so far reduced that the total elevation of temperature cannot he more
than one or two-tenths of a degree, a quantity within the limits of
experimental error. Moreoverr the quantity of matter passing through
the apparatus in a given time was probably only small, and the rela-
tion between the vapour of water and that of chloral was uncertain.
Then, again, everything tends to show that chloral hydrate is partly
dissociated at 100°, and at a low pressure this dissociation would pro-
bably become complete. C. H. B.
Reply to Berthelot concerning Chloral Hydrate. By A.
Wurtz {Compt. rend., 90, 572). — Since Berthelot admits that chloral
hydrate is dissociated at 100°, and that the decomposition tends to
become complete at this temperature when the pressure is low, it is
useless to continue the discussion. The author points out that when
operating at ordinary pressures he always noticed a slight decrease in
temperature, and that he employed a low pressure in order that the
vapours might be dry. The quantity of chloral hydrate formed varied
from 20 — 40 grams in ten minutes. C. H. B'.
Action of Water on Silicon and Boron Fluorides : Solution
of Cyanogen in Water. By H. Hamjierl {ComiJt. rend., 90,
312 — 313). — The decomposition of an equivalent (104 grams) of
silicon fluoride by water evolves 22"34 cals. The decomposition of an
equivalent (68 grams) of boron fluoride evolves 24'51 cals. A mole-
cular volume of cyanogen gas (22"3 liters) develops heat = + 6'8 cals.
on solution in water. C. H. B.
Comparison of the Curves of the Tensions of Saturated
Vapours. By P. he Moxdesir (Comjjt. rend., 528 — 531). — If instead
of constructing the curves on the same scale of temperature a con-
venient scale is chosen for each one, the points of agreement and dis-
agreement become more marked, and classification is rendered much
easier. C. H. B.
Specific Heats of Solutions of Potash and Soda. By Ham-
MERL (Compt. rend:, 90, 694 — -695). — The following results were
obtained by Berthelot's method : —
Potash. Soda.
KoO per 100 gi-ams
"^
Ka20 per 100 grams
* ■
solution.
Sp. heat.
solution.
Sp. heat.
32-72
0-697
38-34
■ 0-816
25-48
0-737
25-54
0-852
17-60
0-780
19-82
0-869
14-98
0-807
14-40
0-886
1116
0-845
7-21
0-924
9-85
0-869
7-78
0-8-33
6-28
0-900
C- H. B.
436 ABSTRACTS OF CHEMICAL PAPERS.
Oxidation of Haloid Salts. By H. Schulze {J.pr. Chem. [2], 21,
407 — 443). — Action of Oxygen on Haloid Salts. — The chlorides of the
alkali-metals, and of barium, mercnrj, and silver, are not altered when
heated in a glass tube through -which a current of dry oxygen is pass-
ing. The chlorides of lithium, strontium, and calcium lose a very small
amount of chlorine. The chlorides of magnesium, aluminium, and
zinc are partly decomposed. Lead cbloi'ide is converted into an oxy-
chloride of constant composition. The chlorides of iron, nickel,
cobalt, manganese, copper, and chromium are converted into oxides.
The determination of the energy with which oxygen acts on the
various chlorides is beset with insuperable dilficulties ; but some other
points brought out by the experiments are worth notice. Silver oxide
is converted at the ordinary temperature into chloride by the action
of chlorine gas, and calcium oxide when heated in chlorine forms a
chloride with incandescence, whilst ferric oxide is only converted with
difficulty to the chloride by free chlorine.
The action of oxygen on these chlorides is quite in accordance with
the affinities thus shown, for it is known that ferric chloride is easilv
decomposed by oxygen, calcium chloride very slowly, and silver
chloride not at all. When the protochlorides of iron, tin, and barium
are heated in air, they suffer partial oxidation together with formation
of a higher chloride. Similarly when chlorine acts on such oxides
as are capable of a higher state of oxidation, e.g., oxides of lead and
antimony, protoxides of iron, manganese, and tin, a higher oxide is
formed in addition to a chloride.
The author's results agree with those which Kunheim obtained by
the action of water- vapour at high temperatures on various chlo-
rides, only that water-vapour is more energetic in its action than
oxygen.
Tiie bromides are much more easily decomposed by oxygen than
the chlorides, and the iodides than the bromides.
The fluorides experimented on were those of sodium, calcium, mag-
nesium, iron, and nickel, and the results obtained throughout were
negative. Calcium fluoride, however, is partly decomposed if a trace
of aqueous vapour is present, even that derived from the burning gas
employed in heating the tube being sufficient.
Action of Nascent Oxygen on the Haloid Salts. — Pieces of various
chlorides, bromides, and iodides were dropped into melted potassium
chlorate, and oxidation took place to a greater or less extent in each
case, the iodides being most easily oxidised, and the chlorides with the
greatest relative difficulty. The oxidation was least in case of the
alkalis, and increased through the groups of calcium, magnesium, &c.,
but silver and mercury chlorides were unacted on.
Behaviour of Oxygeio to Haloid Salts in presence of Acid Avliydrides.
— Iodides, which are only slightly acted on by free oxygen (potassium
iodide for instance) are decomposed if an acid anhydride is present
with formation of a potassium salt, thus 2KI + SO2 +20 = KoSOi-f L.
Bromides are less readily acted on, and chlorides, especially those of
the alkali-metals, even less readily than the bromides, although the
heating of mixtures of chlorides and acid anhydrides, in presence of air
has been proposed as a means of preparing chlorine on the large
I
GEXERAL AXD PHYSICAL CHEJIISTRY. 437
scale. Fluorides are decomposed by some acid anhydrides (silicic and
boric), but this happens also when free oxygen is not present.
Behaviour of Ackl Anhydrides ivith Haloid Salts in absence of Oxygen.
— Potassium iodide is oxidised by some anhydrides, whilst a part of
the anhydride is itself reduced to a lower state of oxidation ; arsenic
anhydride, for instance, yields iodine, potassium arsenate, and
arsenious acid. Tungstic anhydride when beated with potassium
iodide forms a lower oxide of a deep steel-blue colour, the composition
of whicb has not been determined. From molybdic anhydride an
oxide of the composition MoiOn has been obtained, while silicic,
boric, stannic, titanic, and chromic anhydrides are without action
when heated alone with potassium iodide.
Chlorides are decomposed by the anhydrides of chromium, arsenic,
sulphur, and phosphorus in absence of air, but chromic anhydride
under this condition scarcely acts on the chlorides of the alkali
metals. When carbonic anhydride is passed over a heated mixture of
calcium chloride and tungstic anhydride, a dioxychloride of tungsten is
formed: a dioxybromide is easily obtained by a similar method.
Molybdic anhydride acts on fluorides with formation of molybdic
dioxyfluoride, MoOoFo, and phosphoric anhydride forms a phosphorus
oxyfluoride, which will be described in another paper. G. T. A.
Chemical Stability of Matter in Sonorous Vibration. By
Beethelot (C'o/Hjj^. rend., 90,487 — 491). — The author has made expe-
riments to determine the influence of sonorous vibrations on chemical
decomposition or combination. Two notes, one corresponding to 100^
the other to 7,200 simple vibrations per second, were without effect on
ozone, hydrogen arsenide, ethylene in the presence of sulphuric acid,
tydrogen peroxide, and persulphuric acid, even after a considerable
interval of time, and although decomposition or combination, as the
case may be, is in each instance attended with an evolution of heat.
It would appear that matter is stable under the influence of sonorous
vibrations, but not under the influence of ethereal vibrations, a dif-
ference probably due to the much greater rapidity of the latter.
C. H. B.
Researches on Chemical Equivalence. Part I. Sodium
and Potassium Sulphates. By E. J. Mills and T. W. Waltox
(Froc. Roy. Soc, 28, 268). — The conception of a chemical equivalent
employed in this research is that given in Fhil. 2Iag. [5], 1, 14, viz.,
that the chemical equivalent of a body is that weight of it whicb does
the unit of work.
The method employed in the case of the sulphates of sodium and
potassium is the efiiect produced on the rate of formation of ammonia
when nascent hydrogen is made to act on potassium nitrate.
The conclusions which the authors draw are : —
(1.) That sodium and potassium vsulphates have a well-marked
influence on the above reaction.
(2.) That as more sulphate is added the reaction is accelerated.
(3.) That equal weights of sodium and potassium sulphates have,
as nearly as possible, the same working effect.
The last conclusion may be otherwise expi'essed thus : —
438 ABSTRACTS OF CHEMICAL PAPERS.
If the equivalent of potassium sulphate be represented by a certain
number, then the equivalent of sodium sulphate is represented by the
same number. C. W. W.
Researches on Chemical Equivalence. Part II. Hydrogen
Chloride and Sulphate. By E. J. Mills and J. Hogakth (Proc.
Hoy. Soc, 28, 270). — The effects of these bodies on the rotatory
power of lactin were used as the measure of work done.
Varied quantities of solutions of hydrogen chloride (73 grams HCl
per liter) and of hydrogen sulphate (196 grams H2SO4 per liter) were
made to act on a solution of 5 grams of lactin at 100°, and the change
in rotatory power noted after half an hour.
The results obtained show that although 2HC1 may be the " equiva-
lent " of H..SO4 in weight of saturation (i.e., in the ordinary sense) it
certainly is not the equivalent in the dynamical sense. They also
render it highly probable that HCl is equal dynamically to H0SO4.
c. w. w.
The Speed of Reactions. By B. Pawlewski (Ber., 13, 334—335).
— Boguski and Kajander {ihid., 10, 34) have shown that when acids
(hydrochloric, hydrobromic, and nitric) act on marble, the rate of the
reaction is inversely proportional to the molecular weights of the acids.
The author concludes from his experiments on the action of hydro-
chloric and nitric acids on the carbonates of calcium, strontium, and
barium, that the rate is not inversely proportional to the molecular
weights, but to the atomic weights of the metal in the respective car-
bonates. T. C.
Supersaturated Saline Solutions. By C. Tomlinson (Proc. Boy.
Soc, 27, 121, 290). — The author has observed that with a southerly
or westerly wind, the action of oils on a supersaturated solution of
sodium sulphate is to throw down the seven-atom salt, in a powdery
form, during damp weather, but in crystals during fine weather. With
a northerly or easterly wind,, the oil determined the immediate solidifi-
cation of the solution.
The author attributes these results to the presence or absence of
ozone in the air, and cites various experiments adverse to the con-
clusions of different observers, that they are due to particles of sodium
sulphate in the oils employed.
Oil of cajuput, previously inactive, was rendered active by the
action of phosphorus in presence of water. Castor-oil and benzene
gave the same result.
Various essential oils and other substances, which were powerfully
active, w^ere rendered totally inactive by distillation ; but the distillates
quickly became active when exposed for a short time to the air, or
when a few drops of ozonised water were added.
The solution of sodium sulphate did not solidify by itself even when
dropped through the open air while a south-east wind was blowing.
Ozone prepared by means of electricity was found to render inactive
oils powerfully active in a very short time. On one occasion when
there was a lai-ge quantity of ozone in the air (wind N.E.) a paraffin
GENERAL AND PHrSICAL CHEMISTKT. 439
oil "was distilled, and the distillate was found to be powerfully active ;
the same oil distilled during a south-west wind was quite inactive.
Sodium sulphate solution mixed with inactive oil of cajuput was
shaken with hydrogen dioxide, but the solution did not solidify.
Inactive cajuput and paraffin oils shaken up with pure oxygen were
I'endeved active, ozone being formed at the same time. Castor-oil
did not act in the same way.
Charcoal, heated and cooled out of contact of air, was inactive
when first exposed to the air, but became active after a short exposure
during a north-east wind. C. W. W.
Influence of Coal-dust in Colliery Explosions (No. 2). By
W. Galloway (Proc. Hoy. Soc, 28, 410). — Colliery explosions often
occur in mines, the air of which contains a very small percentage of
fire-damp, and in which the character of the coal precludes the proba-
bility of any sudden outburst of that gas. These mines are without
exception of a dry and dusty character. The explosion is accompanied
by the production of large volumes of smoke and soot, and the timbers,
&c., of the mine are found after the explosion (in those cases which
are not followed by fire) to be covered by a deposit of coked coal-dust,
presenting the appearance commonly called "charred."
The author has made a number of experiments on the conditions of
explosion in a dusty mine, the air of which contains a small percent-
age of fire-damp. He finds that a local explosion in such a mine, by
mixing the coal-dust with the air, may extend through an indefinite
distance, more especially if the air of the mine contains a small
quantity of fire-damp (2 per cent, or even less). If the length of a
gallery is very great compared with its diameter, the flame is extin-
guished in a short time.
The most effectual means of preventing these explosions is to keep
the floor of the mine continually wet, either with water alone, or with
a weak solution of calcium chloride. C. W. W.
Dry Fog. By E. Franklaxd (Proc. Boy. Soc, 28, 238).— It has
been frequently noticed that during fogs near large towns the air is
not saturated with moisture, the dew point in one instance being as
much as 10° C. below the temperature of the air.
Seeing the possible connection between this phenomenon and the
fact that the evaporation of water is greatly retarded by its surface
being covered with a film of coal-tar, the author made a series of ex-
periments on the comparative rates of evaporation of water, when
freely exposed to a current of air, and when covered with a film of
coal-tar or of coal-smoke. It was found that the film retarded the
evaporation from 92" 7 per cent, to 66 6 per cent.
The results of these experiments point out a condition of very
common occurrence, competent to produce " dry fog," whilst they also
explain the frequency, persistency, and irritating character of the fogs
which afflict our large towns. C. W. W.
440 ABSTRACTS OF CHEMICAL PAPERS.
Inorganic Chemistry.
Researches on Nitrous Anhydride and Nitrogen Tetroxide.
By G. LuxGE {Ling, polijt. J., 233, 63 — 75 ami 155— 165).— It has
not yet been conclusively proved whether or no nitrous anhydride can
exist in the gaseous condition, or whether the gas which shows the
empirical composition, N2O3, is simply a mixture of nitric oxide and
nitrogen tetroxide, and that this mixture combines and forms nitrous
anhydride on being condensed to the liquid form by cooling, or on
coming in contact with sulphuric acid to form nitixjsyl sulphate or
with alkalis to form nitrites.
The solving of this problem has been attempted by physical means
(by the absorption spectra) by Luck and Moses, but the author has
shown {Reports, German Chemical Society, 1878, p. 1643) that these
results are not satisfactory because of the difficulty of obtaining
nitrous acid free from nitrogen tetroxide, and even if this difficulty
could be easily removed, any partial dissociation of the vapour would
make the distinction by spectrum analysis unreliable.
The author based his line of research on the well ascertained fact
that niti-ic oxide cannot remain as such in presence of oxygen. Ac-
cording to many chemists, nitrogen tetroxide is exclusively produced,
whilst others, e.g., Berzelius and Weber, assert that the tri- and tetr-
oxide of nitrogen are always simultaneously formed, the former being
produced in proportion as the nitric oxide outweighs the oxygen in
the mixture. When, however, there is an excess of oxygen, it is
generally believed that nitrogen tetroxide is exclusively or almost
exclusively formed.
It is clear, however, that if nitrogen tetroxide is passed into concen-
trated sulphuric acid, the quantities of nitrosulphuric and nitric acids
formed must differ from the quantities of those bodies produced, if nitro-
gen trioxide or a mixture of nitric oxide and nitrogen tetroxide in the
proportions to form the trioxide be treated in a similar manner; and if
it be correct that the tetroxide is invariably formed with nitric oxide
in presence of an excess of oxygen, then by passing a mixture of nitric
oxide with an excess of oxygen through sulphuric acid, and subse-
quently examining the products so formed in the sulphuric acid, the
problem would be solved. This is the process which the author has
followed.
A consideration of the composition of the gases which leave the last
leaden chamber and enter the Gay-Lussac tower, together with the
composition of the resulting sulphuric acid compound, and of the
gases which escape from the Gay-Lussac tower, prove almost conclu-
sively not only that the nitrogen compounds have mainly the empirical
formula N0O3, but that nitrogen trioxide actually exists as a gas in
presence of free oxygen. The conditions in the sulphuric acid
chamber are, however, too complicated for the above inference to be
taken as demonstrated beyond doubt.
The author prepared liquid nitrous anhydride and rectified it :
INORGANIC CHEMISTRY. 441
2 liters of ordinary air at 17° were then passed through 50 c.c. of this
liquid, which on analysis was found to have suffered no chana-e in
composition. In other experiments several cubic centimeters of the
liquid nitrous anhydride were placed in a U-tube and evaporated
by passing through it a rapid stream of dry air, the mixture of air
and vapour was then passed through sulphuric acid, sp. gr. ISi, and
the last named analysed. The total nitrogen pi-esent in the sulphuric
acid was determined as nitric oxide in the nitrometer, and the oxyo-en,
from the amount of potassium permanganate required to oxidise°the
nitrogen compounds into nitric acid : from these determinations, the
composition of the nitrogen compound or compounds which existed
in the sulphuric acid was calculated.
A table of the results of experiments is given from which it is
shown generally — •
First. That nitrogen trioxide is partly decomposed by simple
evaporation, yet a complete decomposition is never effected, either bv
mixing with a very large excess of air or by submitting the mixture
to high temperatures : in all cases a very considerable proportion, up
to three-fourths of the total nitrogen trioxide, remains unaffected.
Secondly. The greater the excess of air, the greater the amount of
trioxide decomposed, but there are exceptions to this rule.
Thirdly. Cceteris paribus, temipera.ture appears to have little or no
influence in bringing about the decomposition, and the trioxide exists
in presence of a large excess of air even at the temperature of 1.50".
W. T.
Action of Hydrogen Peroxide on Silver Oxide and Metallic
Silver. By Beuthllut {Cumpt. rend., 90, 572— .577).— When hydro-
gen peroxide acts on silver oxide in any proportion, the volume of the
oxygen evolved is exactly equal to the active oxygen in the peroxide,
provided the latter be sufficiently dilute to avoid local elevation of
temperature. The result is the same whether the hydrogen peroxide
acts on the moist silver oxide, or whether the former be mixed with a
solution of silver nitrate and an alkaline hydrate added to the mixture.
The residue consists of a mixture of metallic silver and a sesquioxide
AgiOs, in the proportion of 1 mol. of the former to 1 moi. of the
latter.
Silver Sesquioxide when hydrated forms black flakes, which are
soluble in dilute acids with evolution of oxygen and formation of ordi-
nary salts of silver. Hydrochloric acid converts it into silver chloride,
without evolution of any free chlorine or the production of hydroc^en
dioxide. It is decomposed by the carbonic anhydride in the air, with
formation of silver carbonate. When dried, it slowly loses oxyo-en
and is transformed into the monoxide. The formation of this com-
pound may be represented by the equation : SAgaO + .SH^Og =
AgiOs + Ago + 3HiO -I- O3. The same substance is probably pro-
duced when ozone acts on the monoxide.
The reaction may be explained by supposing that a compound is
formed analogous to the double compound of barium and hydrogen
peroxides, thus : 3H,0, + 3AgoO = AgiO,.3R.O,Ag,* This compound
* In a subsequent paper the author assigns to this compound the formula
Ag^Os-SH^O. — C. H. B.
442 ABSTRACTS OF CHEMICAL PAPERS.
is at once decomposed into free oxygen and hydrated silver sesqui-
oxide. If the hydrogen peroxide is in excess, the sesquioxide again
forms the double compound, which is again split up, and so on until
the whole of the hydrogen peroxide is decomposed.
The existence of such a double compound is rendered probable by
the fact that if an alkali be added drop by drop to a mixture of hydro-
gen peroxide and silver nitrate solution at a low temperature, a brown
precipitate is formed, but no gas evolved. In a short time oxygen is
given off and the precipitate turns black.
Whatever the relative proportions of hydrogen peroxide and silver
monoxide, the heat evolved is sensibly the same as that developed by
the spontaneous decomposition of the former, viz., + 21'6cals. Since
the heat of formation of silver monoxide is + 7"0 cals., it follows that
that of the sesquioxide is + 21 '0 cals.
When hydrogen peroxide acts upon finely divided metallic silver, a
small quantity of the same oxide is formed, and this may be regarded
as the active agent which brings about the decomposition of the di-
oxide. C. H. B.
Silver Sesquioxide. By Berthelot (Compt. rend., 90, 653 — 656).
— This compound was obtained by the electrolysis of a 10 per cent,
solution of silver nitrate, in the form of large, thick, black, lamellar,
striated needles, of brilliant metallic lustre. When exposed to the air
at ordinary temperatures, it decomposes with evolution of oxygen, and
the formation of a black amorphous powder ; a little above 100° the
decomposition takes place with explosive violence. Prolonged wash-
ing with water also brings about decomposition, removing silver nitrate.
Analysis of the freshly prepared substance, rapidly dried by means of
blotting paper, without pressure, showed that it is really a compound
of silver sesquioxide with the nitrate, and has the composition
4Ag203.2AgNO:).HoO, or is probably a salt of argento-nitric acid, cor-
responding to phosphomolybdic acid, thus —
The substance AgoOa or Ag406 is probably identical with the unstable
oxide described in the preceding abstract {Compt. rend., 90, 572).
C. H. B.
Compound of Calcium Iodide with Silver Iodide. By Max-
well Simpson (Proc. Boy. Soc, 27, 120). — This salt is prepared by
saturating a hot concentrated solution of calcium iodide with moist
silver iodide, and crystallises on cooling in long white needles having
the composition CaL.2AgI.6H2O. It is completely decomposed by
the addition of even a few drops of water, silver iodide being pre-
cipitated ; this reaction affords an easy method of analysing the
salt. C. W. W.
Dicalcium Phosphate. By A. Millot (Bull. Soc. Glum. [2], 33,
194 — 198). — Dicalcium phosphate dried at 100° contains SH^O, which
it does not lose below 115°. It is soluble in ammoniacal ammonium
citrate, whilst the phosphate containing 1 mol. of water is only sparingly
soluble in ammoniacal ammonium citrate. When boiled with water.
INORGANIC CHEMISTRY. 443
dicalcium phosphate is partially decomposed, calcium phosphate
goes into solution and tricalcium phosphate is formed. The whole of
the dicalcium phosphate can be converted into tricalcium phosphate
by decanting the acid solution, and boiling the residue of dicalcium
phosphate and tricalcium phosphate with more water, or by neutra-
lising the acid with chalk. By mixing boiling solutions of sodium
phosphate, calcium chloride, and acetic acid, CaoH.,(P04)o.HoO is
formed, and in the cold, Ca,Ho(P04)..5H,0. L. T. 6'S.
Effect of Heat on Mercury Di-iodide. By G. F. Rodwell and
H. M. Elder (Proc. Hoy. Soc, 28, 284). — ^Mercuric iodide, as is well
known, is capable of existing in two crystalline foi'ms belonging to
different systems, and of passing from the one form into the other by
change of temperature or by mechanical means. On heating a mass
of the crimson amorphous iodide, it turns yellow at 126°, and of a
red-brown colour just below the melting point, 200°. The fused
substance has the colour of bromine, solidifies at 200° to a red-
brown solid, which speedily becomes yellow, and at 126° passes into
the crimson octohedral variety, this last change being accompanied
by distinct cracking sounds. The change from the red iodide to the
yellow is accompanied by an absorption, the reverse change by an
evolution of heat.
The coefficients of expansion of mercuric iodide were determined
in the manner and with the apparatus employed in the case of silver
iodide (ibid., 25, 280), The index of the apparatus showed a regular
expansion of a bar of the iodide (red variety) until the temperature
of 126° was reached, when the bar began to change from the octo-
hedral to the prismatic condition, and rapid expansion took place
without further rise of temperature. When the change was complete,
the temperature was again slowly raised, and regular expansion con-
tinued under a higher coefficient than before the molecular change,
and this continued until the melting point was reached. The ex-
pansion in passing from the solid to the liquid state was also de-
termined. The following are the results obtained : —
Coefficient of cubical expansion for 1° from O'' to 126° (the point
of change) = 0-0000844706.
At 126°, during the passage from the red to the yellow variety,
the body increased in bulk to the extent of 0'00720407.
Coefficient of cubical expansion for 1° from 126° to the melting-
point (200°) = 0-0001002953.
The changes in volume in a mass of liquid mercuric iodide in cool-
inor from 200° to 0° would be as follows : —
o
1J
Volume at 200° of the liquid mass = 1-1191147
200° of the solid mass = 1-0190453
126° (yellow prismatic) = 1-0115378
126° (red octohedral) = 1-0043837
0" = 1-0000000
The authors give a curve illustrating these changes.
The specific gravities corresponding to the five marked conditions
shown above are as follows : —
51
444 ABSTRACTS OF CHEMICAL PAPERS.
Sp. gr. at 0° = 6-297
126° (octohedral) . . = 6276
126° (prismatic) = 6-225
200° (solid) =6-179
200° (liquid) = 5-286
Schiff gives the sp. gr. of the octohedral variety as 5*91 ; Karsteh
gives 6-2009, and Boullay 6-320. C. W. W.
Cubic Alum and Chrome Alum. By A. Polis (Ber., 13, 360^
357). The necessary conditions for obtaining alum crystallised either
in cubes or in octohedrons are described in detail, and also the over-
o-rowth of chrome alum with potash alum. T. C.
Certain Bichromates. By K. Preis and B. Ratman (Ber., 13,
340 343). — Barium diehroinate, BaCr>07, is obtained by dissolving
barium chromate in concentrated chromic acid, and diying the crystal-
line product at 100°. It is decomposed by water into chromic acid
and ordinary barium chromate. This fact explains the observation of
Schulerud (/. pr. Gheni., 19, 36) that only barium monochromate is
obtained, by precipitating barium solutions with potassium dichromate.
The mother-liquid from the precipitate of barium dichromate on
standino- deposits crystals having the composition of the salt, BaCrjOv +
2HoO obtained by Bahr and Zettnow {Jahresb., 1853, 358 ; Fogg. Ann.,
145, 167).
Strontium dichromate, SrCr.Or + H2O, is identical with the salt
described by Bahr (loc. cit.), and was obtained like the barium salt.
It consists of easily soluble dark-red crystals. A salt containing 3H2O
was obtained in one experiment in the form of granite-red delique-
scent crystals.
The compounds PbCroO: and PbCr20';.2H20 are alsa described,
T. C.
Decomposition of Potassium Permanganate by Hydrogen
Peroxide. By Berthelot {Comjjt. rend., 90, 606 — 660). — It is well
known that potassium permanganate and hydrogen peroxide in acid
solutions mutually decompose one another. Thenard has shown
(Compt. rend., 75, 177) that if the two acid solutions be mixed at
a low tempei'ature, the liquid is decolorised, but no oxygen is given
off ; if the temperature rises, oxygen is rapidly evolved. If the hy-
drogen peroxide be added to the permanganate, the colour is dis-
charged when the proportion of the peroxide and the permanganate
is such that they Ijoth contain the same amount of active oxygen,
and the whole of this oxygen is evolved when the temperature
rises. These facts would seem to indicate the formation of a highly
oxidised compound, stable at —12°, but decomposed at the ordinary
temperature. The colourless character of the compound, and the
non-production of any colour during its decomposition, render it im-
probable that it is a higher oxide of manganese. It cannot be persul-
phuric acid, for if the permanganate has been added until the solution
just ceased to be decolorised, the liquid retains no trace of any oxidi-
sino- agent, whereas when permanganate is decomposed by persul-
MIXERALOGICAL CHEMISTRY. 445
phuric acid the residual liquid always liberates iodine from potassium
iodide. Again, it cannot be ozone, for this substance is insoluble in
water, and is not present in any considerable quantity in the oxygen
evolved. It would appear, then, that the unstable compound is a
sesquioxide of hydrogen, H0O3, foi'med according to the equation
i\ln20: + 5H3O2 = 2MnO + 0H2O3, and corresponding with H.S3 and
with various metallic oxides. C H B
Platinic Bromide. By V. Meyer and H. Zublin {Ber., 13, 404—
405).— This compound can easily be obtained by heating spongy
platinum with bromine and aqueous hydrobromic acid at 180° in sealed
tabes. The residue left on evaporation of the filtered liquid is ex-
tracted with water so as to separate any platinous bromide, and the
clear liquid again evaporated and dried at 180°. Platinic bromide
IS a black-brown powder, which is not in the least deliquescent. It
is readily soluble in water, and stdl more easily in alcohol and iu
ether. m p
Mineralogical Chemistry.
Examination of the Yellow Incrustation found on the
Vesuvian Lava of 1631 : Vesbium. By A. Scacchi (Gazzetta, 10,
21 — 37). — The fissures in the immense lava torrent of 1681 are often
found coated with an extremely thin green crust, with which one of a
yellow colour is occasionally associated. In his attempts to ascertain
the composition of this crust, the author has observed reactions differ-
ing from those of the known elements, and which he attributes to the
presence of a new element, vesbium, so called from Vesbio, the ancient
name for Vesuvius.
As the crust is too thin to separate mechanically, the pieces of lava
are treated with very dilute hydrochloric acid, which dissolves off the
crust, forming a blue solution, containing abundance of copper, silica,
and other constituents of the lava ; the acid solution is evaporated to
dryness, heated to 170°, and exhausted with water. The residue
consists principally of silica and a vesbium compound, together with a
finely divided pulverulent matter which can easily be separated by
elatriation ; after this has been done, the product is treated with hydro-
chloric acid, filtered from undissolved silica, and again evaporated to
dryness and heated to 170°: the small quantity of copper present is
removed by repeated washing with hot water, when the purified
vesbmm compound remains as a dark-green powder, called vesh'tne by
the author. This is hygroscopic, and when ignited becomes brown
^H^- °^^ ^"sing. It is soluble in acids, yielding a green solution ; the
addition of potash or ammonia to this" solution precipitates a ferric
compound of vesbium, partly soluble in excess of the precipitant,
forming a yellow solution. When vesbine is fused with an alkaline
carbonate or nitrate, it dissolves with effervescence, forming an alka-
VOL. .\xxviu. 2 k
446 ABSTRACTS OF CHEMICAL PAPERS.
linevesbiate soluble in water ; on adding an acid to the colourless
^tflnf frnonuires a yellow colour similar to tliat of a cliromate ; this
becon"' b u"h-gr enVn heating. Alkaline vesbiates give precipitates
ofvarious colours with solutions of metallic salts that with silver
b in' Wbt red, whilst the zinc salt is greenish. Attemp s to obtain
rtassiunrvesbiate in the crystalline state were unsuccessful. _
^ On mTshig hydrogen sulphide through an acid solution of vesbme,
a brown Pi-elitate i^ produced consisting chiefly of sulphur, but con-
Wiirsnall quautitiis of lead and copper sulphides; the filtrate from
tSss°o a bright blue colour, but becomes colourless on adding excess
of ammonia whilst a brown precipitate is thrown down. When a
mTTS^c irimmersed in the blue solution, the colour is changed to
§ ep brow" so as to appear almost opaque. Even a very arge excess
of hydro-e; sulphide produces no change m the blue solution. All
theves^^^um compounds, when fused with microcosmic salts give a
yeUow bead tinged with brown in the outer flame, and a g-J-^^^^^ ^
the reducing flame.
Phosphates and Boro-phosphates of Magnesia and Lime^n
the Guano Deposit of Mejillones (Lat. 23-24 S.)- By Do-
n^KO^Gnrnpt rend., 90, 544-547). -Whereas the guanos found i„
C 12-13° S. retain the nitrogen of their orgamc matter, those n
at 23-24° S. contain mere traces of this element, but are largely
charted with phosphates. The most important deposit of these phos-
Sntrco-uanos forms a belt round the mountain Moiro de Mfjillones,
1th is composed of granitic and syenitic rocks t-ve-ed by dyke^^
of compact or porphyritic felspars. The deposit is about 50 meters
t breadth, and varies in depth. It rests on banks of disintegrated
rock of which there are two well-marked varieties, tosca, a oose white
:ml'ytbstance free f-m guano and phosphates, and j.o^^^^^^^^
earthy substance mixed with a considerable quantity of guano and
often containing fragments of the neighbourmg rocks. The ripio also
fontVnTtn rations^ of gypsum, phosphates, and borophosphates of
wTnd mao-nesia The great mass of the guano proper is brown,
earthy anrcCsists mainly%f calcium phosphate and sulphate com-
mon salt, and organic matter, with traces o magnesium phosphates,
Sumima, oxide of "iron, and nitrates. The phosphates and borophos-
Tihates found in the interior of this mass are—
^IGnaTo en roche, a hard, compact, somewhat crystalline substance,
of a o-rev colour, and consisting mainly of tri-calcium phosphate
i '^G7anoeMizado, ^h^ch includes douUe phosphate of calaun.
andLgnesium, (CaO,MgO).P.O. + 6H.0, found - f^-^-^^^f
the rock or in the interior of cavities m hard masses of guano, ihe
crys'ls are colourless, more or less transparent, and have a vitreous
Se Their faces are indistinct, but the dominant form appears to
be a rectangular prism. They have the .^«-P°f ^'^?.^. .^^^^'^V/g'
CaO 5-80 • PoOs, 40-13. Water and organic matter 3b 00 _ iuu^o.
Maqnesium pfwsphate, Mg.P.O,, sometimes fibrous, «o«^^*'^f ?,^,^;^^
form of long pyramidal crvstals, having a greyish cohnir and vitieous
lustre The fibrous varieties have a silky lustre. The pure mineral
contains MgO, 35-11, and F,0„ 64-89 per cent.
MINERALOGICAL CHEMISTRY. 447
3. Boi'oplwspliate of magnesium and calcium.^ whicli occurs in the
form of spherical and kidney-shaped concretious, seldom more than
6 cm. in diameter. The exterior of these concretions is soft, but the
interior is hard and compact. The mineral is amorphous and of a
yellowish- white colour. It is soluble in acids, but after stronsf ignition
is not attacked by nitric acid. On analysis it was found to have the
composition : —
MgO 24-38
CaO 0-14
P0O5 27-60
B0O3 6-80
Water and organic matter . . 38'30
AI2O3 and FesOa 230
99-52 C. H. B.
Artificial Production of Spinel and Corundum. By S.
Meunier (Comjyt. rend., 90, 701 — 702). — By the action of steam on
aluminium chloride at a red heat in the presence of magnesium, minute
crystals are obtained which have the composition and properties of
spinel. They consist of colourless and transparent cubes and octohe-
drons, have no action on polarised light, are extremely hard, and are
not attacked by boiling nitric acid. Periclase, and possibly corundum,
are formed at the same time. Attempts to obtain gahnite by substi-
tuting zinc for magnesium were unsuccessful, probably on account of
the low temperature, but the white powder left in the tube consisted
mainly of very distinct hexagonal plates, having no effect on polarised
light. They contained no zinc, but consisted simply of alumina.
Similar crystals can be easily obtained by the action of steam on
aluminium chloride heated to redness in a porcelain tube.
C. H. B.
Martite from Brazil. By Gorgeix (Compt. rend., 90, 316—318).
— The crystals of martite, which are generally octohedral, are found in
the talcose rocks of Boa- Vista in the province of Minas Geraes. They
have a brilliant lustre, and are sometimes slightly magnetic. Asso-
ciated with them are found crystals of limonite, hematite, and magne-
tite, having all the forms common to pyrites, from which they have
evidently been derived. The interior of one large cubical crystal
composed of a mixture of quartz and limonite, contained octohedral
crystals of sulphur. The crystals of martite are composed of a mix-
ture of haematite and magnetite, and in all pi'obability have also been
derived from pyrites. C. H. B.
Ne-w Silicates of Aluminium and Lithium. By P. Haute-
FEciLLE (Compt. rend., 90, 541— 544).— I. 5SiO.>.Al203.'Li,0, may be
obtained by heating silica and alumina with lithium vanadate for
several hours to a temperature slightly above the fusing point of the
i after. If the alumina and the silica be in the proportion of at least
1 mol. of the former to 5 mols. of the latter, the crystals are large and
well defined. They have the composition SiOa, 69-03 ; AUG,, 23-74 ;
2 A- 2
448 ABSTRACTS OF CHEMICAL PAPERS.
Li^O, 6-08 ; loss, 1"15 = lOO'OO, corresponding with that of oligoclase.
They resist the action of acids, scratch glass easily, and. have a sp. gr.
of 2"40 at 10°. The crystals are transparent, sometimes milky. The
general form is an octohedron with a square base, the ratio of the
vertical to the lateral axes being about 0'824. They are bi-refractive,
and the faces are frequently striated in a direction parallel to the
intersection of the faces of the octohedron with those of the prism.
Similar crystals are formed when mica is heated with lithium vana-
date.
II. 6SiO2.AloO3.LioO, may be prepared by heating lithium tung-
state or vanadate with alumina and silica in the proportion of 1 mol.
of the former to 6 mols. of the latter. The crystals have the compo-
sition SiOa, 72-60 ; AI2O3, 22-00 ; Lio.O (by diiff .), 5-40, and stand in
the same relation to orthoclase and albifce that the preceding com-
pound stands to oligoclase. They have the hardness of orthoclase,
and offer the same resistance to the action of reagents ; their sp. gr.
is 2-41 at 11°. When prepared by means of the vanadate, this com-
pound crystallises in octohedra, the angles of which are identical with
those of the preceding compound. When obtained from the tungstate,
the usual form is a very obtuse prism, the edges of which are truncated
by the faces of the octohedron observed on the crystals obtained from
the vanadate.
These two silicates, which have not yet been found in nature,
furnish another example of geometric isomorphism similar to that
observed in the case of the triclinic felspars.
The crystals of the first compound differ from those of the second,
in that they are bi-refractive, and depolarise polarised light.
The author proposes to class these compounds with amphigene.
C. H. B.
Artificial Production of a Leucitophyr identical with the
Crystalline Lavas of Vesuvius and Somma. Incipient Crys-
talline Forms of Leucite and Nepheline. By F. Fouqu^ and
A. M. Levy {Compt. read., 90, 698 — 701). — By fusing for twenty-four
hours at a bright red heat, and then for twenty-four hours at a cherry-
red heat, a mixture of silica, alumina, potash, soda, magnesia, lime, and
oxide of iron, in proportions representing one part of augite, four of
labradorite, and eight of leucite, a crystalline mass is obtained, the
optical properties of which correspond exactly with those of the natural
lavas. The augite is in small green microliths, the labradorite is in
large microliths, twinned according to the same law as albite, and the
leucite is in large and small trapezohedrons. Octohedral crystals of
magnetite and picotite are also present. If the fused mass be allowed
to cool slowly after the first twenty-four hours' fusion, the formation of
the crystals of leucite can be distinctly observed.
When thin slices of leucite thus obtained are examined under the
microscope, arborescent forms, generally at right angles, are observed.
With polarised light, the two series of elements of the right angle are
differently tinted, and extinction takes place in the direction of the
branches of the cross. Less complicated forms are obtained with
artificial nepheline. C. H. B.
MIXERALOGICAL CHEMISTRY. 449
Artificial Production of Felspars containing Barium, Stron-
tium, and Lead. Bv F. Fouquk and A. M. Levy {Gompt. rend.,
90, 620 — 622). — By heating mixtures of silica, alumina, sodium car-
bonate, and strontia, baryta, or lead oxide, in the requisite proportions
to a temperature just below their fu.sing points for forty-eight hours,
crystalline masses are obtained which correspond in composition to
oligoclase, labradorite, and anorthite, but contain baryta, strontia, and
lead oxide in the place of lime. These crystals resemble felspathic
microliths in their behaviour with polarised light, and one of the axes
of elasticity coincides with the direction of elongation. The anorthite
of baryta is probably orthorhombic, the labradorite of lead is decidedly
triclinic, but the determination of the crystalline forms of the other
compounds could not be made with certainty. The made of albite,
characteristic of triclinic felspars, was not observed on the artificial
products. They all scratch glass, and, with the exception of the
oUgoclases of baryta, strontia, and lead, and the labradorite of strontia,
are attacked by acids. Their specific gravities are given in the fol-
lowing table : —
Strontia. Baryta. Lead.
OH^oclase 2-619 2-906 3-196
Labradorite 2-862 3-333 3-609
Anorthite 3043 3-573 4093
None of these artificial products corresponds with the natural tri-
clinic barytic felspar recently described by Descloizeaux (Bull. Soc.
Min., 1878). C. H. B,
Production of Amphigene. By P. Hautefeuelle (Gompt. rend.,
90, 313 — 316). — A'ery distinct crystals of amphigene were obtained
by fusing potassium vanadate and aluminate with fragments of
strongly ignited silica at a red heat in a platinum crucible for several
days. Some of the faces of these crystals showed striae similar to
those observed on twinned crystals of triclinic felspars. Goniometric
measurements proved that the faces and angles are strictly comparable
with those of the crystals from Mount Somma described by von Rath.
The action of the artificial crystals on polarised light showed that,
like the natural crystals from Frascati, they are composed of several
systems of repeated twins. The oxygen ratios determined by analysis
were 1:3:8. The crystals have a sp. gr. 2-47, that of the natural
crystals being 2-48. Like the latter, they are dissolved by sulphuric
acid. C. H. B.
Formation of Soils by Weathering. By J. Hazard (Landvj.
Versuchs.-Stat., 24, 225 — 251);. — The author has analysed three rocks,
weathered portions from them, and the soils to which they have given
rise. First a greywacke consisting of an aggregate of quartz-grains
and felspar with mica fragments, a little carbon and crystallised silica.
Second, a tolerably coarse-grained granite,, consisting of quartz fel-
spar plagioclase mainly, and biotite, w'ith fissures charged with iron
oxide ; a little apatite and iron pyrites also occur. Third, phyllite^ a
fine-grained schistose rock, consisting mainly of a lamellar mineral of
450
ABSTRACTS OF CHEMICAL PAPERS.
the mica group-, minute quartz needles permeate the mass, and other
minerals occur sparingly. The following results were obtained: —
Moisture . . .
H.O combined
C...
SiO.>
Al,03
FeA
MnaOa
CaO
MgO
KoO
Na.,0
1.
2.
3.
4.
5.
0-13
1-30
2-40 \
1-23/
1-53
1 2-27
2-49
213
0-29
2-42
4-87
73-95
72-32
77-42
63-39
64-06
14-30 "1
3-72 /
14-37
15-39
/ 18-25 1
1 5-94/
16-74
0-22
0-12
0-12
0-14
0-97
1-15
123
4-27
1-52
1-07
0-75
0-80
1-88
1-54
1-37
1-65
1-77
1-38
1-23
2-86
1-57
1-68
3-25
1-19
Loss on ig-nition, less
water and carbon . .
100-18 99-58 99-94 100-77 95-77
— _ _ _ 4-87
100-64
jVIoisture
HiO combined.
c
SiO.,
ALO,
Fe,0,
Mn.Os
CaO
MgO
K.,0
Na.O
Quartz
P.O5
Loss on ignition, less
water and carbon. .
6.
.7.
8.
a
0-30
1-65
2-58
29-5
3-23
,3-53
—
3-00
72-87
33-54
1914
63-58
1 19-04
/ 23-641
1 7-40 /
25-05
27-23
0-18
0-13
0-14
1-73
0-86
1-30
1-41
1-75
1-89
1-29
1-40
1-40
2-99
1-68
1-83
1-35
1-16
0-75
0-82
—
25-42
39-35
0-28
100-72
100-33
96-57
9^94
3-00
99-57
1. Fresh greywacke from a quarry, the mean of two analyses. 2.
Soil above, taken in a tir-wood. Hnmus calculated from the C found
given as 4-03 per cent. : loss on ignition 7-66 per cent. 3. The in-
organic constituents of 2, with the water of 1, calculated to 100
approximately. 4. Mean of two analyses of fresh granite. 5. Soil
above the granite, estimated to contain 9-74 per cent, of cellulose and
humus, with a loss on ignition of 14-36 per cent. 6. The inorganic
constituents of 5 with the water of 4 calculated to 100 approxi-
MIN'ERALOGICAL CHEMISTRY. 451
mately. 7, 8, 9, tlie corresponding results for the phyllite and its
soil.
From the analysis we have the following proportions : —
Greywaclce.
Silica. Sesquioxides. Monoxides.
Stone 1179 292 1
Soil 14-13 2-84 1
Granite.
Silica. Sesquioxides. Monoxides.
Stone 578 2-21 1
Soil 11-69 2-OG 1
Phyllite.
Silica. Sesquioxides. Monoxides.
Stone 8-54 4-53 1
Soil 11-64 5-02 1
In all three soils, the silica has increased, whilst the oxides have
diminished ; possibly the increase of lime in the phyllite soil may be
due to additions made to the soil. The separation of silica into free
and combined was only successfully made in the case of phyllite, from
which it appears that there is less combined silica in the soil than in
the stone.
By neglecting quartz in the analyses of phyllite and its soil, and
calculating up to 100, we get : —
Sesqui- Mon-
SiOo. oxides. oxides. Humus. H.^O.
Unweathered silicate in fresh
stone 44-78 41-68 9-20 — 4-34
Unweathered silicate plus
weathered products in soil 31-78 41-83 8-33 9-96 8-10
Unweathered silicate in soil* 31-78 29-68 6-53 — 3-08
Weathering products in soil — 12-15 1-80 9-96 5-02
■ The bottom line shows base in excess of that required for the silica.
This may be combined with humic acid, so that the phyllite soil may
have the following composition :—
Quartz 39-35
Silicate undecomposed 42-74 (19-14 SiO. + 17-81 sesquioxide +
3-93 monoxide + 1-86 H^O.)
Humic salts 14-46 (6-00 humic acid + 7-37 sesquioxide
+ 1-09 monoxide.)
Water 3-02 (1-35 of which is moisture.)
99-57
* Obtained by taking the same proportions with the silica of the second line as
are found in the first line.
452
ABSTRACTS OF CHEMICAL PAPERS.
Determination of ahsorption, soluble bases, moisture, combined water,
carboyt, humus (calculated), and loss on ignition. — The material used
was well air-dried and freed from root fibres as far as possible. For
the absorption of nitrogen, 50 grams were treated with ammonium
chloride solution of known strength ; after two days the nitrogen left
in the solution was determined, and the c.c. absorbed by the material
gives the number in the table. The soluble bases wex'e determined by
treating with dilute hydrochloric acid, evaporating to dryness, taking
up with concentrated hydrochloric acid and water, &c. The water
and carbon determinations were made by elementary analysis.
Absorption
Solid bases
Moisture
HcO combiufd
C'
Humus (calculated)
Loss on ignition . . .
Granite.
1.
11-32
•27
2-27
2.
13
14 00
0-68
2-06
2-74
3.
30
12-64
0-88
2-48
3-36
29
65
62
33
86
72
5-67
5.
37
11-35
1-73
2-48
1-15
2-30
6-51
6.
40
12-10
1-87
2-48
2-70
5-40
9-75
41
9
2
2
4
9
14
-60
-49
-13
■87
-74
-36
PhylUte.
8.
Absorjjtion 2
Soluble bases 8 -87
Moisture 0-30
HoO combined .... 2 '95
C ".
Humus (calculated)
Loss on ignition .... 3 "25
9.
10.
9
12-40
0 80
4-44
5-24.
25
14-36
22
67
73
46
6-35
11.
13
1
3
3
6
10
36
-38
•65
•23
•00
-00
-88
Greywacke.
12.
8
6-62
0-13
1-30
0-29
1-72
13.
40
12.-29
1-23
3-55
0-25
5-03
14.
15.
19
17
-11
2
-18
3
•94
0
-58
1
•16
7
•28
28
6-80
2-42
2-03
4-77
9-55
14-00
16.
24
8-73
2-40
1-23
2-42
4-03
7-66
Nos. 1, 8 and 12 are the fresh rocks; 2 to 6 are rubble, gradually
diminishing in size; 9 and 13 are also rubble; 7 is the granite soil
before given; 10 subsoil, and 11 upper soil, both above phyllite ; 14,
subsoil about 0-80 meter deep, 15, the soil above it, both in a fii'-wood,
and 16, soil from a meadow, all three being over greywacke.
All three soils are fertile ores. The absorption of the rocks increases
with rate at which they weather ; the greywacke soils show a diminish-
ing absorption probably due to the effect of rain, as they were taken
from a hill side.
The absorption increases generally with the increase of the soluble
bases, but not invariably. By degrees, the silicates of the sesquioxides
pass into clay, which absorbs, whilst the monoxides are partly washed
out, and the soluble bases are diminished. From this it happens, as
in the granite, that the last weathering product with 9'6 per cent, of
soluble bases has an absorption of 41. J. T.
MIXERALOGICAL CHEMISTRY, 453
Examination of Volcanic Dust which fell January 4th, 1880,
at Dominica, and of the Water which accompanied it. By
Daubeee {Comjjt. rend., 90, G24 — 626;. — The powder collected after
the rain was fine-grained, and resembled pnzzuolana. Microscopic
examination revealed the presence of colourless grains of labradorite
and sanidine, greenish grains of pyroxene, crystals of gypsum, and
very distinct cubic crystals of pyrites from 0'2 to O^oS mm. diameter.
Grains of galena were also present. The sand was impregnated with
highly deliquescent salts. Analysis of the powder collected in the dry
state gave the following results : —
KCl. XaCl. CaSO^. Organic.
Soluble in H,0 1-96 0-63 0-28 OvO = 3-57
FeS04. CaCOs. MgCOj.
Soluble in dilute HCl 6-20 3-60 080 — =^ 9-60
FeSo. PbS.
Soluble in KN'Os S'SO 0-65 — — = 5-95
Insoluble in acids 80"30
Total 99-42
No copper was detected.
The rain received in a rain gauge was charged with about 20 per
cent, by weight of a somewhat coarser powder. It held in solution 20
parts per 1000 of the salts found in the dry powder.
The presence of jiyrites and galena in the powder is a fact worthy
of special notice. The former has probably been recently produced in
the volcano by the action of the sulphurous vapoui's, and resembles in
appearance the pyrites found in the fumerolles of Iceland.
C. H. B.
Sketch of the Origin of the Mineral Waters of Savoy. By L.
Jjtw {Compt. rend., 90,628 — 630). — The mineral waters of the Savoy
Alps may be arranged in three classes : (1) sulphui'etted ; (2) saline
(chlorides and sulphates) ; (3) carbonated (alkaline, calcareous, or
ferruginous). To the first class belong the springs of Aix, Marlioz,
and Challes, in Savoie, and of Bromines, la Caille, and Menthon, in
Haute-Savoie. Analyses of the three first give the following results
in parts per liter : —
Aix-les-Bains.
Sulphur spring. Alum spring.
Temperature 43-5° 44-6°
Hydrogen sulphide, free . . 3'37 — 4'13 mgrm. 3'74 mgrm.
Sulphur as thiosulphate . . 3-84 mgrm. 3'60 mgrm.
Total solid matter 0-4925 ^r. 0-4443 ffr.
Marlioz. Challes great spring.
Temperature 11" 10-5°
Sodium sulphvdrate 0-0285 gr. 0-3594 gr.
Total solid matter 0-6383 1-3453
In the second class are the waters of Bride, Salin.s, I'Echaillon, and
454 ABSTRACTS OF CHEMICAL PAPERS.
Bonneval (Tarentaise) in Savoie, and of Saint Gervais in Haute-
Savoie. These contain from 16 (Salins) to 5 (Saint Gervais) grams
of solid matter per liter, consisting principally of sodium and mag-
nesium chlorides, and calcium and sodium sulphates. Their tempera-
ture varies from 30° to 40°, except in the case of Saint Gervais, where
the temperature is 20°.
To the third class belong the springs of Saint Simon, Coise, Farette
and la Bauche in Savoie, and of Evian and Amphion in Haute-Savoie.
These always contain less than one gram of solid matter per liter, and
their temperature is from 10° to 12". The waters of Evian are alkaline
and calcareous, those of la Bauche are highly ferruginous.
The sulphuretted springs are found to the east of the axis of eleva-
tion of the Western Alps, which stretches from Grenoble to Sallanches,
in a district occupied by Jurassic and cretaceous limestones traversed
by faults. The waters acquire their sulphuretted character whilst
percolating through the limestones, which contain concretions of
gypsum and pyrites, and also bituminous organic matter.
The saline springs are found to the west of the same axis in a dis-
trict occupied by triassic beds which consist of white grits, magnesian
limestones, glossy schists, gypsum with common salt, and ferruginous-
clayey schists.
The waters of the third class are, comparatively speaking, of sur-
face origin, and ai'e found in the old alluvium or in marshes. They
derive their carbonic anhydride mainly from the air, and their iron
from oxidised pyrites. C. H. B.
Composition of the Waters of Cransac (Aveyron). By E.
WiLLM (Gom^^t. rend., 90, 547—548).
April 15tli, 1879. July 14th, 1879.
Grams. Grrams.
Free carbonic anhydride 0"0175 —
Magnesium sulphate 1-7920 1-9985
Calcium „ 1-5640 1-5623
Aluminium „ 0-2800 0-1760
Manganese ., 0-0158 0-0704
Nickel , 0-0007 0-0008
Potassium ,, 1 --v.qooh / 0-1446
Sodium „ r 1 0-0908
Lithium ,,
Rubidium „ > traces traces
Zinc ,, J
Sodium chloride 0-0151 0-0161
Silica 0-0790 0-0870
Phosphoric and boric acids. . . . traces traces
Total per liter . . 3-9696 4-1465
Amount directly determined . . 3-9820 4-1820
The mineral matter of the water of Cransac consists mainly of
sulphates, and contains sulphates of manganese and aluminium,
MIXERALOGICAL CHEMISTRY.
455
together with small quantities of the sulphates of nickel and zinc.
Copper, iron, and arsenic are absent, although the mineral matter is
probably derived from iron pyrites undergoing decomposition. The
amount of potassium present is considerably greater than that of
sodium. The analyses (p. 454) of the principal spring (source Basse
Richard) made at different dates seem to indicate that the composition
of the water is subject to variation.
The temperature of the water is 12"4^ C. C. H. B.
Mineral Waters of Bussang (Vosges). By E. Willm (Compt.
rend., 90, 630—633).
Source Source Source
Salmade. cl'eii haiit. Marie.
Temperature ' 12° 12-5° 11°
Total CO2 2-8719 2-1890 2-4934
(a.) Portion of residue insoluble in water : —
SiO, 0-0641 00634 00536
Fe^Os 0-0059 0-0024 0-0024
Mn304 U-0019 00019 0-0020
Al 0-0012 0-0010 0-0011
Ca 0-1519 0-1495 0-1880
Mg 0-0506 0-0506 0-0540
C63 0-3589 0-3546 0-4196
As 0-00047 0-00026 0-00043
(b.) Portion of residue soluble in water: —
CO3 0-3801 0-3912 0-3081
SOi 0-0904 0-0896 0-0806
CI 00507 0-0572 0-0497
Na 0-3495 03580 0-2890
K 0-0346 0-0360 0-0264
Li 0-00116 0-0013 0-0010
P2O5, BjOs, and F . . traces traces traces
Total 1-54143 1 55696 147593
The " source Marie " rises in the bed of the Moselle. C. H. B.
Waters of Bourboule. By A. Riche (./. Pharm. Chim. [5], 1,
302 — 306). — The springs of Bourboule, viz., Choussy, Perriere,
Sedaiges, La Plage, and Fenestre owe their healing properties to
the large quantities of arsenic they contain, viz., 00068 gram per
liter in Perriere and 0-0064 in Choussy. In the case of Perriere and
Sedaiges, the quantity of arsenic does not appear to alter ; but in the
springs of Choussy and La Plage it is slowly decreasing. Periodic
analyses made during the year show that the total mineral matter
decreases as it has done since 1867 from 5-886 gram per liter in that
year to 4-970 gram per liter in 1879. The quantity of mineral matter
in the Choussy and Perriere springs is about the same, as is also the
pi'oportion of lithium. L. T. O'S.
45(1 ABSTRACTS OF CHEMICAL PAPERS.
Organic Chemistry.
Direct Formation of the Chlorobromides of the Olefines
and other Unsaturated Compounds. By Maxwell Simison
(ProG. Roy. Soc, 27, 118, 4<24>) .—Ethylene chlorobromide, C.HiClBr.
Chloride of bromine was prepared by passing cblorine into a solution
of bromine in aqueous hypochlorous acid ; on passing ethylene into
this solution, an oily liquid separated, boiling after purification at
108 — 110'^, and giving on analysis numbers agreeing with the above
formula.
Propylene chlorobromide, CsHeClBr, is prepared in a similar way, and
boils at 118—120°.
Allyl rhlorodihromide, CsHjClBro, is formed by'the action of bromine
chloride on allyl bromide at the ordinary temperature. It boils at
197 — 199°. If the mixture be heated to about 100°, allyl bromo-
dichloride, CaHsClsBr, b. p. 180 — 187°, is produced.
Ethylidene cldoriodlde, CHa.CHClI, may be prepared either by th.e
action of a weak solution of iodine chloi-ide on ethylidene iodide or
of aluminium iodide dissolved in carbon bisulphide on ethylidene
iodide, also dissolved in carbon bisulphide. After purification, the
product distils at 117 — 119° without decomposition, and has a density
of 2-054 at 19°.
Ethylidene hromiodide, CHaCHBrI, may be prepared in the same
way as the chloriodide, substituting the bromide of iodine for the
chloride. It boils at 142 — 144°, and does not solidify in a freezing
mixture. C. W. W.
Preparation of Acetylene. By Juxgfleisch (Compt. rend., 90.
364—367, and /. Pharm. Chhn. [5], 1, 307— 310).— This is a descrip-
tion of a special lamp for the preparation of acetylene by the incom-
plete combustion of coal-gas, the supply of air being limited by
virtually burning a jet of air in an atmosphere of coal-gas, so as to
avoid any excess of oxygen being carried over into the ammoniacal
cuprous solution. A description of the apparatus would be incomplete
without the diagi^ams, which are given in the original paper.
L. T. O'S.
Action of Bleaching Powder on Propyl, Butyl, and Amyl
Alcohols. By J. Regnault and E. Hardy (/. Pharm. [4], 30, 405 —
408). — To determine the part played by the above alcohols in intro-
ducing impurities in the preparation of chloroform from ethyl alcohol,
they were severally treated with bleaching powder. Isopropyl
alcohol (b. p. 82"), isobutyl alcohol (b. p. 109°), and amyl alcohol
(b. p. 130^132°), were distilled with bleaching powder; in each case
the distillate separated into two layers, the lighter consisting of an
alcoholic solution of a chlorine compound and the heavier of water.
The upper liquid was again distilled with bleaching powder, when
the distillate separated into three layers. The heaviest liquid con-
sisted of a chlorine compound, and the other two of the alcoholic solu-
tion of the same and water ; they were again treated with bleaching
ORGAXIC CHEMISTRY. 457
powder and so on until all the alcohol had been converted into the
chlorine compound.
The chlorine compounds in each case have properties similar to
those of chloroform, but differ from it and from each other. These
results show that the isomeric alcohols have some influence on the
purity of chloroform. The authors purpose giving a more detailed
account of their research in a future communication. L. T. O'S.
Action of Bromine on Epichlorhydrin. By E. Grimaux and
P. Adam (Bull. Soc. Chim. [2], 33, 257— 259).— By treating epichlor-
hydrin with bromine at 100°, the latter is rapidly absorbed and an oily
liquid obtained, which decomposes on distillation in a vacuum, but
deposits crystals on adding water and cooling at 0°. The crystals sepa-
rate from a heavy oil, and recrystallised from alcohol, consist of
chlorotrihromacetone, C3H2ClBr30.4H20 (m. p. 55°). Dried in a current
of air, the crystals lose their water of crystallisation, and anhydrous
chlorotrihromacetone is obtained as a heavy, colourless oil, which
attacks the eyes.
The oilv liquid which is separated from the crvstals consists of
chlorobromhydrin, CHoCl.CH(OH).CHoBr (m. p. 190—195°).
The action of bromine on epichlorhydrin may be expressed thus : —
2(C3H5C10) + 3Bro = CsHoClBrsO + CaHeClBrO + 2HBr.
L. T. O'S.
Action of Sodium on Epichlorhydrin. By Haxriot (Bull
Soc. Chim. [2], 32, 552). — By the action of sodium on epichlorhydrin,
a yellow insoluble body, C6H10O2 + 2XaCl, is produced, from which
the sodium chloride cannot be removed by washing. If, however, the
reaction is allowed to take place in the cold, a product is eventually
obtained which is soluble in cold water. On heating this solution,
the yellow substance is precipitated, but by evaporating the cold solu-
tion in a vacuum, the sodium chloride crystallises out alone, and an
oily liquid is obtained, having a sweet taste and corresponding with
the formula CeHioO,. The author thinks it is the anhydride of a
tetratomic alcohol, which he hopes to obtain from it by hydration.
J. M. H. M.
Constitution of Epichlorhydrin. By Haneiot (Bull. Soc.
Chim. [2], 32, 551 — 552). — In order to decide by experiment be-
tween the two formulse for epichlorhydrin, CHoCl.CH<^ | and
^0
CH2Cl.C.CIl2(OH), proposed by Reboul and by Berthelot respectively,
the author mixed gradually 92 grams epichlorhydrin with 1 30 grams
phosphorus trichloride. A violent reaction occurred, and on coolino-
the mixture and submitting the product to distillation under reduced
pressure, a liquid was obtained (b. p. 133 — 140'' at 100 mm.) which
proved to be a compound of epichlorhydrin and phosphorus trichloride,
C3H5OCI.PCI3; it is decomposed by water into epichlorhydrin and phos-
phorous acid. If Berthelot's foi-mula be correct, the hydroxyl should
be replaceable by chlorine, isoallylene dichloride, CH2CI.C.CH2CI
being formed, but no such body was produced in the reaction.
J. M. H. M.
458 ABSTRACTS OF CHEMICAL PAPERS.
Inactive Glucose or Neutral Sugar. By U. Gayon (Ball.
Soc. Chim.. [2], 33, 253— 256).— Horsin-Deon (ibid., 32, 121) shows
that inverted and inactive sugar have the same composition, and that
in the formation of inverted sugar, inactive sugar is first formed and
subsequently converted into inverted sugar by hydration. In answer
the author refers to previous notes by himself on the same subject, in
which he arrives at the same conclusions as Horsin-Deon, but in dif-
ferent ways. Details of the experiments are given in the paper.
L. T. O'S.
Inactive and Inverted Sugar. By P. Horsin-Deon (Biill. Son.
Cki'in. [2], 33, 25G — 257). — lu reply to Gayon, the author points out
that although their results agree, the diifereuce between their commu-
nications is, that Gayon states the fact and the author gives the expla-
nation. L- T. O'S.
Method of Producing Acetal. By R. Engel and De Girard
(Compt. rend., 692 — 694). — Aeetal may be obtained in considerable
quantity by passing a current of uon-spontaneously inflammable
hydrogen phosphide through a mixture of equal volumes of aldehyde
and absolute alcohol, cooled to —21°. A small quantity of ethyl ether
is also produced. It is probably not necessary to work at so low a
temperature, but the authors promise further details. C. H. B.
Researches on Lactin. By E. J. Mills and J. Hogarth (Pwc.
Roy. Soc, 28, 273). — The permanent specific rotation of lactin (milk-
sugar) as determined by Jellett's polarimeter is 59' 17° (mean of
21 experiments). Berthelot gives 59'3°.
If the rotatory pow^(!!r of freshly prepared aqueous solution of lactin
be examined at short intervals of time, it is found to gradually de-
crease. This phenomenon was quantified by a series of determinations
made at intervals of two hours, in some cases with addition of sodium
or potassium chloride ; and it was found that the change could be ex-
pressed by the equation y = a + Ix + c^'\ in which y is the angle of
rotation, x the time in half hours, counting from the first contact of
the lactin with water, and a, b, and c are constants. From the results
obtained, the initial specific rotation of lactin is calculated to be
92'63°. When the specific rotation 64"8 is reached, the law of change
must be expressed by a different equation ; this fact pointing to the
dual nature of lactin mentioned by Fudakowski. Increase of tem-
perature hastens the change. The presence of sodium or potassium
chloride increases the amount of lactin in solution, but has no apparent
effect on the rate of change.
The study of the action of hydrogen nitrate on lactin is attended by
great experimental difficulties, but the authors have succeeded in ob-
taining results which are expressed in a curve. This curve shows a
rise in the rotatory power on first addition of nitric acid (due to
galactose ?), then it falls below zero (formation of mucic acid, and
perhaps of lasvo-tartaric acid) ; then a second rise (dextro-tartaric
acid), and finally a fall to zero (oxalic acid).
Water at 17° shaken with excess of lactin takes up a quantity cor-
responding to a solubility of one part lactin in 10'64 parts water, the
ORGANIC CHEMISTRY. 459
quantity gradually increasing until it reaches the limit of 1 part
lactin in 3"23 parts water. C. W. W.
Action of Acetic Chloride on Valeraldehyde. By Maxwell
Simpson (Froc. Hoy. Snc, 27, 120). — Equivalent proportions of acetic
chloride and valeraldehyde were heated in a sealed tube at 100° for
about three hours, and the product distilled. About half the liquid
passed over between 115 and 145°; the remainder refused to distil
even at 300°. On redistillation, the first portion boiled for the most
part at 118 — 128"^. It gave on analysis numbers leading to the for-
mula CoHioO, AcCl. Its sp. gr. is about 0-987 at 17°. It is
gradually decomposed by water with formation of hydrochloric acid,
acetic acid, and valeraldehyde. C. W. W.
Action of Dehydrating Substances on Organic Acids. By
B. Vangel (Ber., 13, 355 — 358). — It is well known that many poly-
basic organic acids, either when heated or when subjected to the
action of dehydrating agents, give carbonic anhydride, and frequently
also carbonic oxide and water, whilst a residue is left depending on
the nature of the acid. A more detailed investigation of these facts
has led to the following results, attention being paid merely to the
nature of the gas evolved :■ — •
Monohasic acids when heated with dehydrating agents (sulphuric
acid or syrupy phosphoric acid) are either not decomposed at all, or
only with difficulty, in which case they give either carbonic anhydride
or carbonic oxide ; thus stearic and benzoic acids give neither gas by
the action of phosphoric acid, and with sulphuric acid they give car-
bonic anhydride, but no carbonic oxide. Dilujdric monohasic acids also
give either carbonic anhydride or carbonic oxide ; thus salicylic gives
carbonic anhydride, whilst lactic acid gives carbonic oxide. Dibasic
acids give equal volumes of carbonic oxide and anhydride, according
to the following eqiiation :— R"(C00H)2 = R" -|- CO. + CO -|- HoO,
as in the case of oxalic and camphoric acids. Dumas and Piria found
that tartaric acid by treatment wath sulphuric acid gave 3 vols. CO,
1 vol. COo, and 2 vols. SOo, but by the action of phosphoric acid,
the author states that it gives equal volumes of carbonic oxide and
anhydride. Trihasic acids give 2 vols, of carbonic anhydride to 1 vol.
of carbonic oxide, thus: R'"(C00H)3 = R'"H + 200^ + CO + HoO.
This is the case with citric acid, the same result being obtained
whether sulphuric or phosphoric acid be employed as the dehydrating
agent. Dumas, however, found that citric acid when heated with
sulphuric acid gave pure carbonic oxide. Should the above rules be
confirmed by further experiments, the author believes that the deter-
mination of the nature of the gas evolved on treatment with dehydrating
agents would serve as a very ready method for ascertaining the
basicity of organic acids. T. C.
Action of Carbonic Oxide on Alkaline Hydrates at High
Temperatures. By A. Geuther {Ber., 13, 323— 324).— A claim to
priority of discovery over Merz and Tibirica (this vol. p. 374).
460 ABSTRACTS OF CHEMICAL PAPERS.
Synthesis of Formic Acid. By 0. Loew (Ber., 13, 324 — 825). —
Formic acid, ferrous sulphide, ferrous formate, carbonic anhydride,
and trithiomethylene are obtained when carbon bisulphide and
water are heated with iron filings in sealed tubes at 100°. This
method is recommended for preparing formic acid on the large scale.
T. C.
Action of Titanium Tetrachloride, Stannic Chloride, and
Antimony Pentachloride on Acetic Acid and Acetic Anhy-
dride. By A. Bertrand (Bull. Soc. Clilm. [2], 33, 252— 253).— The
above chlorides act on acetic acid and acetic anhydride, forming
mixed anhydrides, which are probably similar to the sllico-acetic
anhydride of Friedel and Ladenburg {Ann. Ghim. Phys. [4], 27,
428). ii. T. O'S.
Compounds of the Myristic Series. By F. Masino {Gazzetta,
10, 72 — 78). — As commercial oil of ntitmegs is usually more or
less adulterated, it was considered preferable to prepare myristin
directly from nutmegs by extracting the powdered seeds with ether,
which was found to be a far better solvent than either benzene or
light peti'oleura for this purpose. Obtained in this way, it crystallised
in colourless lustrous silky plates (m. p. 55° ; Playfair found 31°,
probably from his substance containing impurities derived from the
commercial oil of nutmegs employed). The myristic acid obtained
from this by saponification with potash had the melting point (53 — 54°)
o-iven by Heintz.
Myristamide, CuHotO.NHo, prepared by boiling myristin with alco-
holic ammonia for three or four days, crystallises in lustrous scales
(m. p. 102°). It is insoluble in water, but easily soluble in alcohol,
ether, and benzene. Myristanilide, Ci4H270.NHPh, obtained by long
continued heating of aniline myristate, crystallises in long slender
silky needles (m. p. 84°), which are very soluble in ether, benzene,
and chloroform.
Myristolic acid. — Bromine does not act on myristic acid even at
120°, but it is readily attacked by chlorine at 100° if exposed to sun-
shine, hydrochloric acid copiously evolved, and a chlorinated deriva-
tive being formed. This was separated from unaltered myristic
acid by crystallisation, and heated with alcoholic potash for eight days
at 180° ; the product contained myristic acid and an oily body, which
gave Pettenkofer's reaction, and solidified at a low temperature
(m. p. 12°) ; it united readily with bromine, forming the tetrabro-
minated derivative Ci4H24Br402. This is a yellow oily substance,-
which gradually gives olf hydrobromic acid when exposed in a vacuum
over solid potash, leaving a residue of the composition CuH22Br202,
which is reconverted into myristolic acid (m. p. 12°) by nascent hydro-
gen. The quantity of substance was too small to allow of the
myristolic acid, C14H04O2, to be purified for analysis. C. E. G.
Products of the Oxidation of Wool : Cyanopropionic Acid.
By J. A. Wanklyn and W. J. Cooper (Phil. Mag. [5], 7, 35G).—
When wool, dissolved in water by means of three times its weight of
potash, is oxidised by four times its weight of potassium permanganate,
ORGANIC CHEMISTRY. 4G1
there are produced carbonic acid, oxalic acid, and ammonia ; when
only two parts of permanganate are employed at least two new acids
are produced, one of which, cyanopropionic acid, has been obtained
pure.
The free acid, obtained by decomposing the barium salt with sul-
phuric acid, has the formula 2C4H5NO2.3H2O. It is an amorphous
solid, brittle at ordinary temperatures, but softening at 100". In mass,
it has a pale brownish-yellow or straw colour, in powder, it is almost
white. It is very soluble in water and in strong alcohol. It has a
strongly acid taste and reaction, decomposes carbonates, and dissolves
magnesium in the cold. It is oxidised by potassium dichromate and
by permanganate.
Heated to 140"^, it gives off all its water ; at higher temperatures, it
is decomposed, evolving ethyl cyanide, and forming a brown mass,
soluble in potash.
Most of the metallic cyanopropionates are soluble in water, and con-
tain water of crystallisation.
Barium CTjanopropionate, Ba(C4HiN02)2-3H20, is a white powder,
very soluble in water, but sparingly soluble in alcohoK It loses 1 mol.
of water at 160 — 170°. There is also a basic salt,
[Ba(C4H4N02)2.3H20]2.BaHo02.
Silver cyanop-oioionate, 2C4H4AgN02.-|-H20, is nearly insoluble in
water; the dry salt quickly absorbs 2 per cent, of water. There is a
basic salt, 2C4H4AgNO2.AgIIO.II2O, obtained by adding silver nitrate
to the basic barium salt.
Lead, cyanoproinonate, Pb(C4H4N02)2-H20, is also nearly insoluble in
water ; it is a white powder.
The magnesium salt, Mg(C4H4N02)2.3H20. is extremely soluble in
water, drying up first to a jelly, and finally to a brittle mass, yielding
a white powder.
Potassium cyanopropionate, C4H4NKO2.H2O, forms a straw-coloured
transparent solid. Dried at 100", the salt contains five molecules of
water; at 190°, it contains only one ; deposited from strong alcohol
and dried at 100°, it contains 4H2O. It is very soluble in water and
in 40 per cent, alcohol, sparingly so in strong alcohol. Heated at
200 — 220° with twice its weight of potash, it is completely decomposed,
giving off ethylamine and leaving potassium oxalate, C4H5NO2 +
2KHO = K2C204-t-C2H5.NH2, proving the acid to be isocyanopropionic
acid.
Calcium cyanopropionate, Ca(C4H4N02)2-4H20 (dried at 100°), is
very soluble in water, and is preci})itated from its aqueous solution
in 84 percent, alcohol. It loses about 4 per cent, (half a molecule) of
water at 200°. C. W. W.
Amides and Anilides of ,3-Hydroxybutyric Acid. By L. Bal-
BiAxo {Ber., 13, 312 — 314). — i3-Amidohutyramide,
NH2.CHMe.CH2.CONH2,
is obtained by heating ethyl /3-chlorbutyrate with alcoholic ammonia
in sealed tubes at 70 — 80°. It is a syi'upy liquid, which is easily
VOL. XXXVIII. 2 I
462 ABSTRACTS OF CHEMICAL PAPERS.
soluble in water and in hot alcohol, but only sparinp^ly soluble in
ether. Its platinochloride crystallises in orange-coloured tables,
which are but little sokible in alcohol, and insoluble in ether. The
aqueous solution of the free base evolves ammonia when boiled, and on
boiling with lead hydroxide, it gives lead /3-araidobutyrate, from
which the free acid may be obtained by treatment with sulphuretted
hydrogen. It crystallises in deliquescent plates. The hydrochloride
of /3-amidobutyramide may be obtained by decomposing the platino-
chloride with ammonium chloride ; it forms a crystalline hygroscopic
mass.
On heating ethyl /:{-chlorbutyrate for several hours with 3 to 4
mols. of aniline a crystalline mass is obtained, which is only partially
soluble in ether. The insoluble portion consists of aniline hydro-
chloride, and the hydrochloride of /3-amidobutyranilide,
NHPh.CHMe.CH2.CO.NHPh.HCl,
the latter of which crystallises in brilliant, colourless fatty plates
(m. p. = 206°), which are insoluble in ether, and but sparingly soluble
in boiling water. ,
The portion of the above product which was soluble in ether con-
sisted of unchanged ethyl chlorbutyrate and aniline, together with
(3-hutyranilhetame, CmHisNOo, which was purified by means of its
oxalate. It is a crystalline neutral mass, and forms a hydrochloride
and platinochloride, PtCli-CCioHiaNOoHCl),. The free base on boiling
with bai'ium hydrate gives barium acetate and resinous products.
The oxalate, CioHisNOj.C.HoOi, crystallises in nodules (m. p. 138"),
which are easily soluble in hot water and in hot alcohol, and shows a
strono- acid reaction. On treating the oxalate with barium hydrate
it gives, in addition to the free base, the crystalline barium salt of
^.anilobuhjric acid, NHPh.CHMe.CHg.COOH, isomeric with the above
base. It crystallises in needles (m. p. 128°), which are but sparingly
soluble in cold, but more soluble in hot water ; it is easily soluble in
alcohol and in ether. T. G.
Electrolysis of Malonic Acid. By E. Bourgoin (Cornpt. rend., 90,
g08 — 611).- — -When an alkaline solution of sodium malonate is electro-
lysed, the gas evolved at the positive pole consists simply of a mixture
of oxygen, carbonic anhydride, and carbonic oxide without any hydro-
carbon, whatever the degree of alkalinity or concentration of the solu-
tion. With a neutral solution of the salt, carbonic anhydride alone is
evolved and the liquid becomes strongly acid in the positive part of
the cell. After a time, the carbonic anhydride is accompanied hy car-
bonic oxide and oxygen. With free malonic acid, the gas consists
mainly of oxygen with small quantities of carbonic anhydride. Malonic
acid, then, difi'ers from succinic acid in that no hydrocarbon is pro-
duced when it is electrolysed, and it differs from oxalic acid in its
greater stability and in that it concentrates itself in the positive part
of the cell. C. H. B.
Inactive Malic Acid. By G. J. W. Beemer (Ber., 13, 351—353).
— The inactive malic acid obtained by the author (ibid., 8, 151t4) by
the reduction of tartaric acid with hydriodic acid consists of a mixture
ORGANIC CHEMISTRY. 463
of dextro- and Igevo-rotary malic acids. The two are best separated by
means of their ciiu-bonine salts, that of the former being the least
soluble in water. The specific rotations of the two acids are +6"316
and — 2'596 respectively. T. C.
Succinin. By A. Fuxaro and L. Danesi (Gazzetta, 10, 58—60). —
When equal parts of succinic acid and jrlycerol are heated at 200°, a
product is obtained wliich may be purified by dissolving- it in water
and adding animal charcoal ; on cooling, the cleai' solution becomes
turbid and gradually deposits the succinin as an amorphous buty-
raceous mass of pale-yellow colour. It may be obtained almost coloui'-
less by a second treatment with animal charcoal. Succinin, CtHioO.,,
forms an opaque mass resembling wax in appearance, insoluble in
\*ater or alcohol when cold, but easily soluble in the boiling liquid, in-
soluble in ether, benzene, and chloroform. It is saponified by the
action of alkalis in the same manner as other ethereal salts, yielding
glycerol and succinic acid. C. E. G.
Synthesis of Ethylbenzene from Ether and Benzene, By M.
Balsohx (Bull. Soc. Chivi. [2], 32, 01" — 618). — The author has previ-
ously shown that in presence of aluminium chloride, ethylene unites
direct!}' with benzene, forming ethylbenzene, diethylbenzene, and tri-
elhylbenzene. He now shows that ethylbenzene is produced by heat-
ing together in sealed tubes at 180° for 12 hours a mixture of 1 part
ether, 2 parts zinc chloride, and 4 parts benzene. A small quantity
of a crystallisable substance is produced at the same time, together
■with ethylene, and hydrocarbons boiling at higher temperatures than
ethylbenzene. J. M. H. M.
Action of Iodine on Aromatic Compounds with Long Side-
chains. By B. Ratman and K. Peeis (Ber., 13, .344—347).—
On treating cymene with iodine at high temperatures, it gives the
same hydrocarbons as turpentine oil under similar conditions (Ber.,
12, 219 ; this Journal, 1879, Trans., 623), viz., hydrides of toluene
and xylene, meta- and para-xylene, mesitylene, pseudocumene, cymene
hydride, propyldimethylbenzene, and a high boiling hydrocarbon
winch gives benzoylbenzoic acid on oxidation.
Amylbenzene and camphor by a similar treatment give in general
the same products as cymene and turpentine oil. T. C.
Fittica's Fourth Nitrophenol. By S. Nataxson (Ber., 13, 415 —
417). — The author is unable to confirm Fittica's statement (ibid., 12,
2183) as to the existence of a fourth nitrophenol, for he has several
times repeated Fittica's experiments and has only been able to obtain
ordinary orthonitrophenol (m. p. 45°), mixed with a little of the cor-
responding para-compound (m. p. 114°). T. C.
Ethyl-derivatives of Orthamidophenetol and Orthamido-
phenol. By M. Foster (/. pr. Chem. [2], 21, 341— 375).— Ortho-
amidophenetol is prepared by reducing the nitrophenetol with tin and
hydrochloric acid, and after adding soda distilling off the base in a
current of steam. Orthamidophenetol is a colourless, oily liquid,
2 I 2
464 ABSTRACTS OF CHEMICAL PAPERS.
which becomes brown on exposure to the air; it has an aromatic
odour and a burning taste, and boils at 229° (bar. 756 mm.). It does
not sob'dify at — 21 °.
3Ionefhylorthumidophenetol,Ceiii(0'Elt).N'KlS,t, is obtained by heat-
ing amidophenetol and ethyl bromide in closed vessels at 60° for four
or five hours ; the free base is liberated from the salts so obtained by
means of sodium carbonate. It is a colourless, highly-refractive
liquid, and boils at 234 — 235° (bar. 751 mm.) ; its sp. gr. is 1"021
at 18'3°. Water and alcohol dissolve it but sparingly; with other
ordinary solvents, it mixes in all proportions. It is volatilised by
steam. The base becomes brown on exposure to the air, a change
also produced by various oxidising agents. With bleaching powder
and chloroform the base undergoes a change similar to that observed
by Schmitt (/. pr. Chem. [2], 18, 196) in the case of aniline ;
the chloroform solution on evaporation yields a crystalline residue,
which is probably an azo-compound. Acetic chloride reacts on the
base. This base forms well-crystallised salts, which ai-e easily soluble
in water and in alcohol, but insoluble in a mixture of alcohol and ether.
Its ]/2/drobro7nide, CioHjsIS^O.HBr, crystallises in beautiful colourless
rhombic tables, which redden on exposure to air.
The lajdriodide, CiuHisNO.HI, forms yellowish rhombic leaflets.
The hydrochloride, C10H15NO.IICI, forms long colourless prisms. Its
solutions, when treated with platinum chloride and concentrated hydro-
chloric acid, give a platinocJdoride, (CioHi5NO.HCl)2PtCl4, in long,
yellow, opaque, rhombic prisms or tablets. It is easily soluble in
water ; the aqueous solutions are decomposed on boiling ; alcohol
dissolves it easily, but it is insoluble in a mixture of alcohol and ether.
The oxalate obtained by mixing alcoholic solutions of the acid and
base crystallises in colourless, short, thick prisms, which are easily
soluble in water.
The sulphate crystallises in small rhombic plates, and the nitrate in
long colourless rhombic columns.
Monethylnitro-orthamidomtrosophenetol, C6H3(N02)(OEt).]S'(NO)Et,
is obtained by the action of nitrous acid on an alcoholic solution of
ethylorthamidophenetol hydrochloride ; it is insoluble in water, slightly
soluble in alcohol, from which it crystallises in yellowish prisms. It
is not acted on by acids or alkalis. The nitro-group in this body is
reduced by tin and hydrochloric acid, forming a base which is easily
attacked by the air.
Monethylortliamidophenol, C6H4(OH).NHEt, is prepared by heating
the phenetol with concentrated hydrochloric acid in sealed tubes at
130°. The free base, prepared by treating the hydrochloride so ob-
tained with caustic soda, crystallises from ether or benzene in small
white rhombic plates, which become brown on exposure to the air ; it
melts at 167"5°, and is decomposed by distillation. It is only sparingly
soluble in chloroform, but easily in alcohol. Bromine reacts with the
base, forming brown resinous products ; a similar change is produced
by potassium dichromate and sulphuric acid. Bromine-water and
bleaching powder produce a violet, changing to a brown coloration.
Monethylorthamidopheuol is a weak base, its salts crystallise well,
but appear to be decomposed by the evaporation of their aqueous solu-
ORGAXIC CHEMISTRY. 465
tions ; they are prepared by adding acids to the alcoholic solution of
the base and allowing it to evapoi'ate slowly. The salts are easily
soluble in water and alcohol, but only sparingly in concentrated acids ;
they become brown on exposure to air.
The hydrocliloride, CgHnNO.HCl, crystallises in colourless needles or
acute rhombic prisms, and may be sublimed by heating carefully.
The platinochloride, (C8HiiNO.HCl)2PtCl4, crystallises in long yel-
lowish needles united in rosette-like groups. It is easily soluble in
water and alcohol, and is decomposed on boiling with separation of
platinum.
The hydrobromide, CgHnlSrO.HBr, forms small colourless prisms,
which, when carefully heated, may be sublimed.
The hydro-iodide crystallises in yellow acuminated needles ; it is
very unstable. The oxalate resembles that of the phenol.
OrthamidonttrosophcnoJ, C6H4(OH).N(NO)Et, is obtained by the
action of nitrous acid on the alcoholic solution of orthamidopbenol
hydrochloride ; it is precipitated from its alcoholic solutions by water
in greyish leaflets (m. p. 121"5°). It is insoluble in water, but soluble
in other ordinary solvents, and is not acted on by alkalis or acids. Tin
and hydrochloric acid convert it into amidophenol.
Biethylorthamidoplienetol, C6H4(OEt).NEto, obtained by heating an
alcoholic solution of orthamidophenetol and ethyl iodide in sealed tubes
at 120 — 130°, and decomposing the iodides so obtained with sodium
carbonate. The free base is a colourless oily liquid, boiling at 227 —
228° (bar. 754'3 mm.), and having an aromatic odour. It is insoluble
in water, but soluble in other ordinary solvents. On exposure to air,
it becomes yellow ; bleaching powder gives a red dish- violet coloration,
changing to a red ; and bromine-water and other oxidising agents pro-
duce a red solution. It is not acted on by acetic chloride. Concen-
trated sulphuric acid dissolves it, forming a violet solution, which
becomes yellow when diluted. Its salts form thick gelatinous masses.
Diethyl or thamidophenol, C6H4(OH).]SrEt2, is obtained from the phe-
netol bv the action of concentrated hvdrochloric acid. It is a colour-
less liquid of aromatic odour boiling at 218 — 220", and becomes green
on exposure to air ; the green solution when heated becomes yellow,
and on cooling assumes the green colour. It is insoluble in water, but
soluble in alcohol, ether, &c. Oxidising agents produce a reddish-
brown coloration in its solutions. Bleaching powder gives a red-
coloured solution, from which a dark resinous body separates. Bro-
mine water gives a yellow cloudiness, then a blackish-brown resin, and
leaving a reddish- violet solution. Like the other bases already de-
scribed, it does not expel ammonia from its salts. The salts of this
base crystallise well, are easily decomposed, and easily soluble in
water and alcohol.
The hydrobromide, CioHisN'O.Br, forms colourless rhombic tables,
which become violet on exposure to the air.
The hydrochloride, C10H15XO.HCI, crystallises in colourless acumi-
nated rhombic prisms, often united in twin-growths.
The platinochloride, (doHisNO.HCljoPtCU, crystallises in slightly
yellow rhombic prisms ; soluble in water and alcohol, but only sparingly
soluble in a mixture of alcohol and ether.
4(36 ABSTRACTS OF CHEMICAL PAPERS.
The hydrioclide crystallises in yellow tablets or prisms, and the
oxalate in small colourless pi'isms.
The attempts to prepare triethylammonium derivatives of orthamido-
phenetol and orthamidophenol have proved unsuccessful.
In conclusion, the author draws attention to the relations between
the boiling points of these bases and those of the corresponding sub-
stituted anilines. The monethylamidophenetol boils 7'5° higher than
the diethyl base, and monethylamidophenol 10° higher than the
diethylphenol. The diethylorthamidophenetol has the same boiling
point as orthamidophenetol. Efchylaniline boils 10^ lower than
diethylauiline. P. P. B.
Nitroorth- and Nitropara-azophenetols. By H. Andreae
(/. 2-"'- CViem., [2], 21, ol8 — o41). — By the nitration of orthazophene-
tol, two dinitro-dei'ivatives were obtained, which were separated by
means of the difference of solubility in alcohol. The dinitrazo-
phenetol, CioHieNiOB, which is soluble in alcohol, and forms about one-
fourth of the yield, crystallises in bright reddish-yellow needles
(m. p. 190°). Its isomeride, which is insoluble in alcohol, crystallises
from hot chloroform or benzene in lustrous brownish-red prisms
(m. p. 284 — 28o°), which under the microscope appear blue when
viewed by reflected light. It sublimes with partial decomposition,
and is not acted on by concentrated hydrochloric or nitric acid ; con-
centrated sulphuric acid, however, dissolves it, forming a bright-red
solution, from which it is thrown down by water as a yellow flocculent
precipitate.
This dinitrazophenetol (m. p. 284—285°), when reduced by ammo-
nium sialphide, yields a dinitroliydrazophenetol, CieHisI^iOe, which is
insoluble in water and in alcohol, sparingly soluble iu boiling alcohol,
and largely soluble in chloroform, benzene, and ether. It crystallises
from concentrated alcoholic solutions in brilliantly lustrous prisms
(m. p. 201 — 202°), and by slow evaporation from dilute solutions, it is
obtained in long iridescent prisms, having a vitreous lustre. When
heated for a considerable time in the water-bath with hydrochloric
acid, it is resolved into dinitrazophenetol and nitramidophenetol hydro-
chloride—
C6H3(I^O,)(OEt).HN CeH3(N'0o)(0Et).N'
2 I + 2HC1 = II
CeHaCNO.) (OEt) .HN CeHaCNO.) (OEt).N
-f 2C6H3(N02)(OEt).N'Ho.HCl.
At the same time a small quantity of a weak base is formed, the salts
of which are decomposed by water.
Niiramidoplienetol, CfiH3(OEt)(N02).N"H2, prepared by decomposing
the hydrochloride, obtained in the manner already described, with an
alkali, and extracting with ether. It crystallises from aqueous alcohol
in long yellow needles (m. p. 96 — 97°). It forms well crystallised
salts. Nitrous acid converts it into a diazo-compound, which when
boiled with alcohol yields paranitrophenetol, thus showing the com-
pound to be a nitramidophenetol, and not a diphenyl-derivative ;
ORGANIC CHEinSTRY. 467
further, that the dinitrazoplienetol, which was prepared from orthazo-
pheuetol, has the constitutional formula,
C6H3(OEt).(NOo).iq' : N.CNOOCEtOjCsHs =[1:4:2:2:4:1].
And the dinitrohydrazo- and nitramido-phenetols contain the groups
in similar positions.
Nitramidophenetol when heated with concentrated hydrochloric
acid at 155°, is resolved into ethjl chloride and nitramidophenol.
Parazophenetol, prepared according to Schmitt's method {J. pi:
Chem. [2], 18, 198), is scarcely acted on by cold concentrated nitric
acid; both hot concentrated and fuming nitric acid attack it, forming
(1) dinitrophenetol, soluble in water; (2) trinitrazoxyphenetol,
soluble in alcohol, and an isomeride of the latter insoluble in alcohol.
These three products were separated by the difference of solubilities in
water and alcohol.
Linitrophenetol, C6H3(iS'02)2-OEt, crystallises from alcohol in white
silky leaflets (m. p. 85°), and is volatile in steam. It is sparingly
soluble in hot water. "When heated at 150° with concentrated hydro-
chloric acid in sealed tubes, it yields a dinitrophenol (m. p. 102 — lOS"").
This is probably an isomeride of the a- and /3-dinitrophenols prepared
by Hiibuer, melting at 63 — 64° and 113 — ■114'^ respectively.
Triuitrazoit'ij-phenetol, Ci6Hi5N509, crystallises from alcohol in long fine
yellow needles, united in stellate groups. It is sparinglj^ soluble in
alcohol, easily soluble in hot alcohol, ether, chloroform, benzene, and
glacial acetic acid, and insoluble in water. The isomeride of this
trinitro-dei'ivative, which is insoluble in alcohol, dissolves in glacial
acetic acid, chloroform, and benzene, and very easily in ethyl acetate,
from which it crystallises in bright yellow needles (m. p. 187°). It
dissolves in concentrated sulphuric acid, and is reprecipitated from
this solution by water. Xitric acid oxidises it with the production of
the dinitrophenetol described above. Concentrated hydrochloric and
hydrobromic acids do not act on it, whereas it is acted on by
hydriodic acid. Alcoholic potash and soda also attack it. It is
reduced by means of ammonium sulphide.
In conclusion, the author draws attention to the fact that the appa-
rently abnormal behaviour of parazophenetol with nitric acid is
similar to the behaviour of azobenzene and azotoluene when treated
with nitric acid. (H. Petriew, Ber., 6, 557.) P. P. B.
Occurrence of Vanillin in certain kinds of Raw Beetroot
Sugar. By C. Scheibler {Ber., 13, 3a5 — 340). — The author finds
that a substance (m. p. 79^") identical with vanillin occurs among
the soluble non-saccharine constituents of the juice of beetroot sugar,
and especially in such as are neutral or slightly acid, but rarely in
those which are strongly alkaline. T. C.
Synthesis of Aromatic Aldehydes : Cuminaldehyde. By A.
Etaed {Oompt. rend., 90, 534 — 536). — The author has previously
shown that the oxidation of cymene derived from terebenthene by
chromic dichloride in solution in carbon bisulphide, yields an oil
forming a crystalline compound with sodium hydrogen sulphite ;
468 ABSTRACTS OF CHEMICAL PAPERS.
this, when decomposed "by sodium carbonate, gives an aldehyde fusing
at 80°, and resembling camphor in appearance. If the temperature
be allowed to rise as high as the boiling point of the carbon bisulphide,
the character of the reaction is completely changed.
Cymene and chromic dichloride, when dissolved in carbon bisul-
phide and mixed in the proportion of 1 mol. of the former to 2 mols.
of the latter, give a chocolate-brown granular precipitate containing
CioHi4.2Cr02Cl2. This is decomposed by water with the production of
cuminaldehyde which boils at 223° (uncorr.), and may be purified by
combining it with sodium hydrogen sulphite and decomposing the
compound formed by means of sodium carbonate. Benzoic, isocu-
minic, and anisic aldehydes may be easily obtained by this method.
The chromic dichloride attachs the group CH3 connected ivith the radicle
jthenyl, and hy the further action of water transforms it into the group
COH, characteristic of the aldehydes.
Dimethylbenzene, oxidised in this manner, yields metamethylbenz-
aldehyde, which when purified boils at 200''.
In these reactions a small quantity of the corresponding chlorine-
derivative is generally formed. The chromic acid produced by the
action of the water on the chromic dichloride gradually oxidises the
aldehydes if allowed to remain in contact with them. C. H. B.
Action of Acetic Anhydride on some Aromatic Aldehydes.
By P. Babbier (Bull. Soc. Chim. [2], 33, 52— 56).— Three classes of
acetyl-derivatives maybe obtained from aromatic aldehydes: (1) in
which the aldehyde function is destroyed by substitution ; (2) in which
the phenol function is desti'oyed by substitution ; and (3) in which the
substitution takes place in both functions. Bodies of the first class
behave as monatomic phenols, those of the second c.lass as monatomic
aldehydes, and those of the third class as ethers. It is from the
derivatives of the second class only that coumarin and its analogues
can be obtained. The author's experiments have been made with
salicylic aldehyde, paroxybenzoic aldehyde, and the two oxytoluic
aldehydes formed by the action of chloroform on an alkaline solution
of liquid cresol. These two bodies had been isolated in the pure state
by him when the note of Tiemann and Schotten appeared. The liquid
aldehyde boils at 206 — 208°, the crystals of solid aldehyde melt at
120°. All these aldehydes, when heated in sealed tubes with excess
of acetic anhydride at 180° for six hours, give acetyl-derivatives of the
second class, of which acetosalicylol, C6H4(AcO).COH, is a type.
The new bodies thus obtained by the author are —
Acetylparoxybenzaldehyde, CgHgO;,. — A colourless oily liquid (b. p.
260"), with an odour like that of the phenyl acetate. It combines
with sodium hydrogen sulphite.
Acetyl derivative of liquid oxytoluic aldehyde, C10H10O3. — A colourless
slightly oily liquid (b. p. 267°), combining with sodium hydrogen
sulphite. It does not solidify in a mixture of ice and salt.
Acetyl derivative of solid oxytoluic aldehyde, CioHioOa. — A liquid
similar to the preceding (b. p. 275^^). All these compounds, when
boiled with baryta-water, yield the corresponding aldehyde and acetic
acid. The reaction which gives rise to these acetic salts is similar
ORGANIC CHEMISTRY. 469
to that observed in the case of salicylic aldehyde. An acetate of the
third cjass is _ first formed, C6H4(HO).COH + 210^0 =
C6H4(OAc).C(OAc)oH + Ac.OH. It may be isolated by prolonged
"washing of the product with sodium carbonate solution, and crystal-
lises in 6ne white needles (m. p. 100°). On treating this compound
with potassium hydrate, the acetyl of the phenol portion is removed,
and .an ether of the first class produced, C6H4(OAc).C(OAc)oH +■
KO^ = C6H4(OH)C(OAc)oH + KOAc. Diacetic salicylol forms
large colourless crystals (m. p. 104 — 105 ). On the other hand, by
distilling the original acetyl- derivative, an ether of the second class is
produced, C6H4rOlc).C(OAc),H = AcO + C6H4(OAc).COH.
J. M. H. M.
Action of Nascent Hydrogen on Orthonitrobenz aldehyde.
By C. Rudolph (Ber., 13, 310 — 311). — Orthonitrobenzaldehyde, on
treatment with tin and glacial acetic acid, gives a base, C7H5N, which
crystallises in colourless plates. Its constitution is most probably
represented by the formula | | /C6H4.
A monochlorinated derivative of this base is obtained by the action
of stannous chloride and hydrochloric acid on orthonitrobenzaldehyde.
It melts at 83°, and forms a hydrochloride, C:H,ClX.HCl.HoO, which
crystallises in reddish-coloured plates. The author is continuing his
investigation. T. C.
Formation of Cinnamic Aldehyde during Fibrin-pancreas
Digestion. By J. Ossikgvszky (Btr., 13, 326— 328).— The author
has found cinnamic aldehyde among the volatile products obtained by
fibrin-pancreas digestion, and considers that this fact accounts for the
formation of phenylpropionic and phenylacetic acids by the putrefac-
tion of albuminous substances as observed by the Salkowskis.
T. C.
Limited Oxidation of Ethylbenzene. By C. Friedel and M.
Balsohn {Bull. Soc. Chim. [2], 2, 615—617). — The sole aromatic pro-
duct of the oxidation of ethylbenzene, according to the observations
of Fittig and of Kekule, is benzoic acid. All the attempts made by
Kekule to obtain an intermediate aldehyde, CeHo.CHo.COH, were un-
successful. The authors show that the CH2 group is the first to
oxidise, the product of incomplete oxidation being mefchylphenylketone.
This substance is produced by the action of chromic acid in insuflBcient
quantity on ethylbenzene in acetic solution. The reaction is complete
in about fifteen minutes, and the mixture must be cooled in water to
prevent too rapid action. Twenty grams of ethylbenzene furni.shed
about 2 grams of methylphenylketone obtained in a pure state by
agitating the oxidised mixture with water and fractionally distillincr
the supernatant liquid. J. M. H. !M
o
Conversion of Bromostyrolene into Methylphenylketone.
By C. Friedel and M. Balsohx (Bull. Soc. Chim. [2], 32, 613 — 61-!)).
By the action of sodium and carbonic anhydride on the bromostyro-
lene obtained from styrolene bromide by treatment with alcoholic
470 ABSTRACTS OP CHEMICAL PAPERS.
potash, Swart a obtained cinnamic acid, and hence assigned the for-
mula PhCH ; CHBr to bromostyrolene. The authors, however, show
that the formula PhCBr! CHo is the correct one, since by the action
of sulphui'ic acid or water on this substance, methylphenylketone is pro-
duced, just as acetone is obtained from chloropropylene, MeCCl '. CH2.
The reaction of bromostyrolene with sulphuric acid yields methyl-
phenylketone in very small quantity, but about 66 per cent, of the
theoretical proportion can be easily obtained by heating bromosty-
rolene in sealed tubes with a lai^ge excess of water at 180° for 12
hours.
CeHs.CBr : CH, + H,0 = CeHs.CO.CHs + HBr.
By means of this reaction, methylphenylketone can be obtained
from ethylbeuzene. The authors explain the production of cinnamic
acid in Swart's experiments by supposing either that the crude bromo-
styrolene contains PhCH '. CHBr, as well as PhCBr '. CH2, or that
the acid CeHs.C : CCOOH is formed first, and that this becomes
cinnamic acid by fixation of hydrogen. ' J. M. H. M.
Isophthalophenone. By E. Ador (Bull. Soc. Chim. [2], 33, 56
— ol*). — This substance was prepared by treating isophthalic chloride
with benzene in presence of aluminium chloride ; the product was
washed with water, the excess of benzene distilled off, and the product
treated with dilute soda. The residue is isophthalophenone, and the
solution contains sodium isophthalate and the sodium salt of an acid
which melts at 161°, and is less soluble in boiling water than iso-
phthalic acid. The barium salt of the new acid crystallises in scales
having the formula (CuH903)2Ba + 2Aq. The silver salt is very slightly
soluble in boiling water, easily soluble in ammonia, and crystallises
in white filaments, of the formula Ci4H903Ag. The reaction of iso-
phthalic chloride with benzene therefore takes place in two stages: —
(1) CeHiCCOCl). -t- CeHe = C6H,(C0Ph).C0Cl + HCl;
(2) C6H,(C0Ph).C0Cl + CeHe = CeHi (COPh)^ + HCl.
The benzoylbenzoic acid obtained in the first of the above reactions
is a meia-derivative ; the acid melting at 194°, obtained on oxidising
tolylphenylketoue, is a para- derivative ; therefore Plascuda and
Zincke's acid melting at 127 — 128°, obtained by oxidising benzyl-
toluene should be the ortho-acid.
Isophthalophenone, purified by distillation, boils at about 260° ;
crystallised repeatedly from, alcohol, it melts at 99*.5 — 100°. Treated
with alcoholic potash or soda, it furnishes a reddish resin, insoluble in
alcohol and water. Baeyer, by treating phthalophenone with soda,
obtained triphenylmethane-carboxylic acid, CH(C6H5)2.C6H4.COOH.
Fused with potash, isophthalophenone furnishes benzoic acid, but no
isophthalic acid. Treated with hot fuming nitric acid, it gives two
isomeric derivatives: a-dmitroisnphthalopJienone, C6H2(N02)-.(COPh)8,
melts at about 260°, is almost insoluble in boiling alcohol, and crys-
tallises from glacial acetic acid : ^-dlii.itroisop]ith,alophenone is formed
at a lower temperature, melts at about 100°, is more soluble in
alcohol and in acetic acid than the a-derivative, but does not crys-
tallise.
ORGANIC CHEMISTRY. 471
(3-D{amidoisophthaloj)henone, obtained by reducing- an acetic solution
of the corresponding nitro-compound with metallic tin, is a yellowish
amorphous powder, fusing at about 100°, but partially decomposing at
abont 70°, soluble in alcohol and in acetic acid, giving a reddish
coloration, which is diminished by addition of hydrochloric acid. By
the action of potassium nitrite on this compound, isophthale'in appears
to be formed.
a.-Diamtdolsophthalophenone behaves like the (3-derivative, and
appears also to give a phthale'fn. On reduciug isoplithalophenone
with phosphorus and h3-driodic acid at 200°, a colourless hydrocarbon
is obtained, distilling above 360°, easily soluble in ether, slightly
soluble in cold alcohol, aud separating from boiling alcohol as a tliick
oil, which does not crystallise at — 1S°. Baeyer considei's that when
phthalic chloride is treated with benzene, it is the oxygen of the
former which is replaced by phenyl groups, whereas the above experi-
ments show that in the case of isopbthalic chloride, it is the chlorine
atoms that are replaced.
To escape this anomaly, the author suggests for phthalic chloride
CCl . ^
the formula C6Hi<^ CO^^' ^^ place of that usually received.
J. M. H. M.
Solubility of Benzoic and Salicylic Acids. By E. Burgoix
(J. Pharm. Chim. [4], 30, 488— 490).— According to Ost (/. pr. Chem.
[2], 17, 288) 1 part benzoic acid is dissolved by 640 parts of water at
0°, and 1 part salicylic acid by 1,050 — 1,100 parts water. In reply, the
author confirms his previous results (i&z'cZ. [4], 27, 528, and 29, 10),
that at 0° 1 part of the former acid requires 580 water, and salicylic
acid, 606.
The solubility of these acids from 0° to 35° may be represented by
parabolic curves, and. may be expressed by algebraic formula in func-
tions of the temperature, that for salicylic acid being xt = 0-002(t'^ +
lot + 750), which at 0° gives x =. 1-5, i.e., 1 liter of water dissolves
1'5 grams salicylic acid instead of 1 gram as stated by Ost.
L. T. O'S.
Dinitrobenzoic Acid. By F. Beilstein and A. Kurbatow {Ber.,
13, o5o). — Metadinitrobcnzoic acid (m. p. 202°) is obtained by the
oxidation of either a- or /S-diniti'onaphthalene. Eilnjl metadinitroheti-
zoate, C6H3(N02)2.COOEt, crystallises in brilliant colourless needles
(m. p. 91°) ; 100 parts of alcohol (90 per cent.) dissolve 0'562 part
of the salt at 13°. The formation of this ether serves as a ready
method for detecting- the acid. T. C.
&
Phenyl-lactic Acid. By E. Erlexmeter (Ber., 13, 303—305). —
Glaser's phenyl-lactic acid (m. p. 93°) is phenyl-/3- and not phenyl-a-
hydroxypropionic acid, and has therefore the constitution —
CHPh(0H).CH2.C00H (Ber., 12, 1637).
Plienyl-a.-hydroxypropionic acid, CH2Ph.CH(0H).C00H (m. p. =
98") is obtained from phenylethaldehyde and hydrocyanic acid by
the general reaction with hydrochloric acid. It is less soluble in water
472 ABSTRACTS OF CHEMICAL PAPERS.
than the |8-acid, and a similar remai'k applies to the zinc salts of the
two acids. When heated with dilute sulphuric acid in sealed tubes,
it remains unaltered at 100°, but at 130° it splits up into phenyleth-
aldehyde and formic acid, and at 200° it gives carbonic oxide, sul-
phurous anhydride, and a condensation-product of phenylethaldehyde,
C24H2o02, which crystallises in silky plates (m. p. = 102°). The
/3-acid on the other hand is decomposed by dilute sulphuric acid at
100° into cinnamic acid, styrolene, cinnamic acid, and carbonic anhy-
dride.
These facts show that in the hydrohalogen addition-products of
cinnamic acid, the halogen must be in the /3-position. This would
explain the formation of styrolene from a phenylhalogen-propionic
acid on treatment with sodium carbonate. T. C.
Phenylbromolactic Acid. By E. Erlenmeyer (Ber., 13, 305 —
310). — The author adduces facts which show that Glaser's phenyl
oxyacrylic acid (^Annalen, 147, 98) is a true oxy-acid, which stands to
phenyldibroraopropionic acid in the same relation that ethylene oxide
does to ethylene bromide, and that the oxystyrolene obtained by
Glaser {loc. cit.) from the above phenvloxy acrylic acid is phenyleth-
aldehyde. " T. C.
Artificial Formation of Tropic Acid. By A. Ladenbukg and
L. RuGHEiMER {Ber., 13, 373 — 37!)). — Hydratropic acid when oxidised
with an alkaline solution of potassium permanganate gives atrolactinic
acid, thus:— CHPhMe.COOH + O = CPhMe(OH).COOH, and this
fact, taken in conj auction with the results of R. Meyer {Ber., 11, 1283,
1787) on the hydroxylation of acids which contain the CH-group in
the side-chain, would seem to show that tropic acid has the constitu-
tion assigned to it in the foregoing equation, and not —
CH2(0H).CHPh.C00H,
as ascribed to it by Fittig and Wurster {Annalen, 195, 145). If this be
true, then tropic acid must be represented by the last-named formula.
Atrolactinic acid on boiling with concentrated hydrochloric acid
gives atropic acid, C9Hg02 (m. p. = 106°), thus: —
C00H.CPh(0H).CH3 = COOH.CPh: CH2 + H2O,
which shows that atrolactinic acid is not identical with Glaser's
phenyl-lactic acid, for the latter under similar circumstances gives
cinnamic acid. By the action of hypochlorous acid atropic acid is
converted into chlortropic add, C9H9CIO3 (m. p. := 129°), thus : —
CH2 : CPh.COOH + HCIO == CH.(OH).CClPh.COOH.
Chlortropic acid is very soluble in water, and on reduction with
zinc dust and iron filings in an alkaline solution, gives tropic acid
(m. p. 118°), thus :—
CH2(0H).CClPh.C00H + Ho = CH.,(OH).CHPh.COOH -f HCl.
We have thus passed by a series of reactions from hydratropic acid to
tropic acid, and the authors hope that by the synthesis of one of this
ORGANIC CHEMISTRY. 473
series of compounds to be able to settle finally the constitution of all of
them. T. C.
Aromatic Amido- Acids. By V. Tiemann and L. Friedlaxder
{Ber., 13, o81 — 385). — Strecker {Annalen, 75, 27) prepared alanine
by the following general reactions : —
R.CH(OH).NH, + HCN = R.CH(CN).NHo + HoO and
R.CH(CN).NH2 + 2HoO + HCl = R.CH(NH,).COOH + NH4CI.
The intermediate amido-cyanide, R.CH(CN).NH2, can, however, be
better obtained from the aklehydcyanhydi'in, bv the action of ammo-
nia, thus:— R.CH(CN").OH + NH3 = R.CH(CN).NH, + H-A and
this reaction is applicable not only to the acetic acid series, but also to
aromatic aldehydes and even to ketones.
Phemjl-aviidoacetic acid, CPhH(NHo).COOH, is obtained by digest-
ing 1 mol. of benzaldehydcj'anhydrin w-ith 1 mol. of ammonia dissolved
in absolute alcohol at 60 — 80°. It crystallises in prisms or sometimes
in six-sided tables (m. p. 256°), -which are only sparingly soluble in
cold, but more soluble in hot water. It is sparingly soluble in alcohol,
but more easily in ether. On distillation, it yields an oil which
becomes crystalline on standing (m. p. below 100°). Distilled with
lime, it gives benzylamine ; it forms ci'ystalline copper and lead com-
pounds, and a hydrochloride which crystallises in prisms, and is
soluble in water. These facts show that this acid is identical with the
amido-acid obtained by Stockenius {Ber., 11, 2002) from phenyl-
bromacetic acid and ammonia. T. C.
Oxidation of Sulphaminemetatoluic Acid. By I. Remsex
(Ber., 13, 347 — 351). — The author maintains the correctness of his
statement (Hid., 11, 1328, 2088), that sulphaminemetatoluic acid gives
sulphoisophthalic acid on oxidation, and denies the validity of Jacob-
sen's conclusions to the contrary. He also shows that Jacobsen's
assertion, that Lassaigne's reaction is not applicable to the detection
of nitrogen in bodies containing sulphur, is incorrect, and that the
method proposed by Jacobsen for this purpose, viz., the substitution
of iron filings for sodium, cannot be depended on. T. C.
Constitution of Tyrosine and Skatole. By J. Ossikoyszkt (Ber.,
13, 328—334).
Constitution of Phthalic Chloride. By E. v. Gerichten (Ber.,
13, 417 — 422). — There are two possible formulae for phthalyl chloride,
CClo
viz. : — C6H4(C0C1)2 and C6^i<Cr^r\ "^0, but it has not yet been defi-
nitely settled which of these is correct (comp. this vol., p. 471). The
present investigation was begun with the object of throwing further
light on this subject. Phthalide, although not attacked by chlorine
at a boiling temperature, is easily decomposed by phosphorus penta-
chloride, even at 60 — 80°, with the formation of a compound, CsHiCUO,
consisting of large monosymmetric crystals (m.p. 88°, b. p. =275°,
with slight decomposition), which are readily soluble in alcohol, ether,
and in light petroleujn, but insoluble in water. It is not acted on by
474 ABSTRACTS OF CHEMICAL PAPERS.
boilino' wafer, and only slowly by boiling potasli, bnt when g-ently
heated with concentrated sulphuvic acid, it is easily decomposed into
hydrochloric acid and phthalic acid. It reacts with phenol, forming
hydi'ochloric acid and phenyl phthalate (m. p. 70°). A compound,
C8H4CI4O, isomeric with the above (m. p. 88°), is obtained, together
with a smaller quantity of the latter when 1 mol. of phthalic chloride
is heated with rather more than 1 mol. of phosphorus pentachloride in
sealed tubes at 210 — 220° for 50 hours. It crystallises in colourless
tables (m. p. 47°, b. p. 2G2°, with slight decomposition), and in most
of its chemical properties it has great resemblance to its isomeride
(m. p. 88°). Both compounds, when ti-eated with aniline, give the
same product, which crystallises from hot alcohol in brilliant yellow
scales (m. p. 152°), soluble in cold alcohol, more easily in hot alcohol,
readily soluble in ether, and in chloroform, less so in light petroleum,
and insoluble in water. It is reprecipitated by water unchanged from
its solution in concentrated hydrochloric acid or glacial acetic acid.
On heating with concentrated hydrochloric acid, alcoholic potash, or
aqueous ammonia, it gives phthalic acid and aniline. Analysis led to
the formula C6H4<^p|^ >NPh. It is shown that the difference
between the two bodies, CgHiChO, cannot be due to physical meta-
merism or to polymerism ; and it seems most probable that the one
(m. p. 88°) is CgHi : (CCUJo : O, and the other (m. p. 47°)
C6H4(CCla).COCl. Since phthalic chloride gives both these com-
pounds, it cannot have the constitution C6H4(C0C1)2, as such a body
could not yield a substance having the second of the above formula3 :
hence it must have the only other possible constitution, viz. : —
A New Series of Dye-stuffs. By E. Fischee (Ber., 13, 317—
319). — Phenauthrenedisulphonic acid, when treated with phenols, and
more especially with resorcinol, gives a series of condensation-products,
having the properties of dye-stuffs, very similar to the phthaleins
described by Baeyer. In the case of resorcinol, the product (phenan-
threnesuljjhein-resorcin, C26H10O7S2) is a brittle mass, with a can-
tharidian lustre, yielding a dark red-brown powder. Its solution,
especially in alkalis, exhibits a fluorescence greater than that of
fluorescein, and by transmitted light has a blood-red, and by reflected
light a green colour. A constitution analogous to that of resorcinphtha-
C IT rOTT^
lein is ascribed to this substance, viz.: — 0<^p''TT^>^-rT< ^-OiSoCuHs.
It is sparingly soluble in cold water, but more easily soluble in hot,
giving a golden-yellow liquid ; it is still more easily soluble in alcohol.
These solutions dye silk yellow, whilst its alkaline solution dyes red.
It combines with bromine to form a dark violet-red powder, which is
less soluble in water than the sulphein, but more soluble in hot
alcohol ; this bromine derivative gives a bluish-red solution with
alkalies, which imparts the S'^me colour to silk. Both the sulphein
and its bromo-derivative become colourless on reduction. With rosani-
line in alcoholic solution, the sulphein gives a characteristic cherry-
ORGANIC CHEMISTRY. 475
red liquid, wliich dyes silk a beautiful red. The bromo- compound
gives a bluish product when treated in a similar manner.
With pyrogallol, phenanthreuedisulphonic acid gives a body which
dissolves in alkalis with a brown-red colour. The author proposes to
utilise the fact of the production of these coloured compounds in the
detection of a disulphouic acid in the presence of the mono-acid. A
method is described for preparing phenanthreuedisulphonic acid on
the large scale, and as a source of the above-mentioned dye-stuffs.
T. C.
Potassium Hydrindigotin- Sulphate and Potassium Indoxyl-
sulphate. By E. Baumaxn and F. Tiemaxx (Ber., 13, 408—415). —
This is a reply to Baeyer's remarks on a previous communication of
the authors {Ber., 12, 1098 — 1192), in which they had advanced the
opinion that hydrindigotin-sulphuric acid and indoxylsulphnric acid
were not identical as stated by Baeyer. Further experiments now
confirm their first conclusions.
Potassium hydrindigotin-sulphate is best obtained by dissolving
about 25 grams of moist but well-pressed hydrindigotin (indigo- white)
in 25 grams of a solution of potash (1 : 2), a current of hydrogen
being simultaneously passed through the liquid ; the latter is then
decomposed by the addition of 12 — 15 grams of potassium pyrosulphate
and continuous shaking with air for an hour. The filtrate, after
agitation with ether, is mixed with alcohol to get rid of the bulk of
the sulphate, the remainder being removed by means of barium
chloride. The quantity of the potassium hydrindigotin-sulphate
formed was in all cases very small. A comparison of solutions of the
potassium salts of hydrindigotin-sulphuric acid and indoxylsulphnric
acid gave the following results : — (1.) Both solutions remain unchanged
when agitated in contact with air. (2.) On the addition of dilute
hydrochloric acid to the hydrindigotin-sulphate solution, indigo-white
is at once thrown down, and this, on agitation with air or by treating
with a small quantity of ferric chloride, is oxidised to indigo-blue.
The indoxylsulphate, on the other hand, remains unchanged on the
addition of dihite hydrochloric acid, and on warming an oil of faecal
odour is precipitated, which after some time cbano-es to a red
amorphous substance, soluble in alcohol and in ether. If ferric
chloride is not added previous to treating with dilute hydrochloric
acid, this compound contains only a very small quantity of indigo.
This very different behaviour of the potassium salts of the two acids
towards hydrochloric acid serves as a very ready method of separating
the two when present together in solution. (3.) Indigo-blue is at
once precipitated when a solution of the hydrindigotin-sulphate is
decomposed with a mixture of ferric chloride and hydrochloric acid ;
whereas the indoxylsulphate, under similar conditions, does not give
a precipitate of indigo until it is warmed. The aqueous or alcoholic
solution of the hydrindigotin sulphate is decomposed on evaporation,
even in the presence of an excess of alkali, with the separation of
indigo ; whereas the indoxylsulphate does not undergo decomposition
either on repeated evaporation or even by heating with excess of
alkali in sealed tubes at 160"^. These facts show conclusively that the
two acids are not identical as stated by Baeyer.
476 ABSTRACTS OF CHEMICAL PAPERS.
The urine of rabbits fed with food containing finely powdered
indigo gives a precipitate of indigo on the addition of a few drops of
hydrochloric acid, and the filtrate, like the normal urine, gives Jaff 's
indican reaction. The urine of dogs fed in a similar manner does not
give indigo on addition of hydrochloric acid, but it does if fed with
damp indigo- white wrapped in paper. These experiments show that,
in virtue of some powerful reducing action in the intestines of the
rabbit, the indigo is partially reduced to indigo-white ; whilst in the
case of dogs such a strong reducing action does not occur. When
rabbits are fed for a long time with indigo, symptoms of palsy set in,
and the urine becomes albuminous ; whilst in the loins a considerable
deposit of indigo takes place, showing that the indigo-white first
formed is reconverted into indigo, and in great part, therefore, does
not behave like other phenol compounds forming ethereal sulphates.
In the cases of animals fed with indol, and whose urine then contains
potassium indoxylsulphate, similar phenomena are not observed. The
above experiments, although not conclusive, render it very probable
that a salt of hydrindigotin- sulphuric acid is present in the urine of
animals fed with indigo-white. T. C.
Sulphur-derivatives of Diphenyl. By S. Gabriel and A.
Deutsch (Ber., 13, 386 — 31*1). — Diphenylmonosu^^lionic chloride,
C13H9.SO2CI, is obtained by treating potassium diphenylmonosul-
phonate with an equivalent quantity of phosphorus pentachloride. It
crystallises in pale yellow prisms (m. p. 115°), which are soluble in
alcohol, ether, and carbon bisulphide. Digestion with alcoholic ammo-
nia in sealed tubes at 100° converts it into diphenylmonosidijliamide,
C12H9.SO2NH2, which crystallises in needles (m. p. 228°), and is easily
soluble in ether and carbon bisulphide, but almost insoluble in water
and in benzene.
Diphenyl mercaptan, C12H9.SH, is obtained from the sulphonic chlo-
ride by reduction with tin and hydrochloric acid, and subsequent dis-
tillation in steam. It is a white mass (m. p. 110°), which, when
freshly prepared, is completely soluble in alkalis, but on keeping
gradually loses this property, owing to its conversion into the disul-
phide by the action of the air ; it is soluble in alcohol, glacial acetic
acid, and ether, and more easily in benzene and carbon bisulphide ; it
forms crystalline mercaptides with lead and mercury.
Diphenyl sulphide (012119)28, is obtained by the dry distillation of
the lead mercaptide. It crystallises in brilliant plates (m. p. = 171°),
which are moderately soluble in alcohol, ether, glacial acetic acid,
carbon bisulphide, and benzene.
Diphenyl sulphone (012119)2802, is formed by the oxidation of diphenyl
sulphide with potassium permanganate in glacial acetic acid solution.
It crystallises in colourless plates (m. p. = 215*^), and is easily soluble
in alcohol, carbon bisulphide, and benzene, but only sparingly soluble
in ether. A compound, apparently identical with this sulphone, may
be prepared by heating diphenylsulphonic chloride with diphenyl in
the presence of aluminium chloride.
Diphenyl disulpliide (012119)282, is the product obtained by the spon-
taneous oxidation of diphenyl mercaptan. It is, however, moi'e con-
ORGANIC CHEMISTRY. 477
veniently prepared by employing dilute nitric acid as the oxidising
agent. It crystallises in colourless needles (m. p. 149°), whicli are
easily soluble in alcohol and carbon bisulphide, but less soluble in
ether or glacial acetic acid.
Diplieni/lnionnsidphiiiic acid, C10H9.SO2H, is obtained, together wifh
diphenyl and the following compounds, by the reduction of an ethereal
solution of the monosniphonic chloride with sodiam amalgam. It is a
crystalline powder, which, is decomposed even at 70°, and is soluble in
hot water.
Ethi/hJtphen7jhvonosu1phonate, CioHgSOsEt, obtained as above
described or by the action of ethyl iodide on the correspond in cr silver
salt, crystallises in needles (m. p. == 7'6°), which are easily soluble in
dilute alcohol, ether, carbon bisulphide, and benzene.
Trisu1j}hondiphenyl hypovitrite (Ci2H9.S02)3NO is formed, together
with diphenylmonosulphonic acid, by oxidising diphenylrnonosul-
phinic acid with dilute nitric acid. It crystallises in needles (ra. p.
178°), which are but sparingly soluble in ether, benzene, or carbon
bisulphide.
Diphenyl sulpTiocyanide, Ci2H9.S.CISr, is prepared, together wdth the
bisulphide, by the action of an ethereal solution of cyanogen iodide on
the lead mercaptide at 100". It has not yet been obtained in a pure
state. The impure substance melts at about 84°.
DijyJienylmonosuJphncetic acid, djHg.S.CHj.COOH, is obtained by
mixing the mercaptan with monochloracetic acid, each being dis-
solved in caustic soda. The acid (m. p. 169°) is sparingly soluble in
water and in alcohol, but more easily in carbon bisulphide, benzene,
and ether.
DiphejiyldisulpJwnic cJdoride, Ci2H8(SOoCl)2, is obtained by the
action of phosphorus pentachloride on potassium diphenyldisulpho-
nate. It crystallises in lustrous prisms (m. p. 203°), soluble in alcohol,
ether, and benzene, bnt less soluble in carbon bisulphide.
Diplienyld'LsulpJwmide, Ci2Hf,( 802X112)2, prepared like the mono-
sulphamide, crystallises from boiling water in sleLder white colourless
needles (m. p. above 300°),. which are only sparingly soluble in
alcohol and benzene, but more easily in carbon bisulphide or ether.
Diphenyl dif^idphydrate, Ci2H8(SH)2, prepared by reduction of the
disulphonic chloi-ide with tin and hydrochloric acid. It forms colour-
less plates (m. p. 176°), which are soluble in alcohol, ether, and carbon
bisulphide, and still more easily in benzene. It forms a brown mer-
captide with lead.
Diphenyldisulphacetic acid, Ci2BrH(S.CH2.COOH)2, obtained like the
corresponding mono-compound, forms crystals (m. p. = 252°), which
are sparingly soluble in water and alcohol, and almost insoluble in
carbon bisulphide, benzene, and tther.
Diphenyldisulphonic acid, on reduction with sodinm-amalgam, does
not give a disulphinic acid, but diphenyl and diphenylnionosal-
phinic acid. T. C.
Dinitronaphthalene. By F. Beilstein and A. Kuhbatow (Ber., 13,
353 — 354). — a-Dinitronaphthalene, on oxidation with dilute nitric acid
in sealed tubes at 150° gives ordinary nitrophthalic acid, together
VOL. }txxvili. 2 m
478 ABSTRACTS OF CHEMICAL PAPERS.
with ordinary dinitrobenzoic acid and a little picric acid, ^-dinitro-
naphthalene under similar circumstances gives dinitrophtlialic acid,
dinitrobenzoic acid, and a little picric acid.
Binitrophthalio acid, C6H2(N02)2(COOH)2, crystallises in large
prisms (m. p. 226°), which are easily soluble in water, alcohol, and
ether, but insoluble in carbon bisulphide, low boiling petroleum, or
benzene. The calcium salt. CRHoNsOBCa, is sparingly soluble in water.
The harium salt, CsHjNaOsBa, is a crystalline precipitate, which is
insoluble in water and dilute acetic acid. Ethyl dinifrophthalate,
C6H2(NO..)2(COOH).COOEt, crystallises in needles (m. p. 186^), which
are easily soluble in alcohol, but less so in chloroform. T. C.
Condensation of Benzhydrol and Naphthalene. By A. Lehnb
(Ber., 13, 358 — 360). — Najyhtliyldiflienylmethane, CasHig, is obtained
by heating 10 parts of benzhydrol and 15 parts of naphthalene with
15 parts of phosphoi'ic anhydride in an oil-bath at 140 — 145° for
several hours. According to the process employed and the amount of
solvent used, two sets of crystals may be obtained, the one melting at
134° and the other 149° ; the first modification is easily converted into
the second either l)y recrystallisation or by fusion. The hydrocarbon
is only sparingly soluble in absolute alcohol and in light petroleum,
more easily in ether, and in glacial acetic acid, and very easily in
benzene ; it sublimes without decomposition. On oxidation, it gives
an acid in small yellow crystals (m. p. = 206°), which has not yet
been completely investigated.
a-Naphthylpiienyl carbinol, CnHuO, is obtained by the reduction of
a-naphthylphenylketone in alcoholic solution with sodium amalgam.
It forms nodular crystals (m. p. 86°, b. p. over 360°), which are
readily soluble in alcohol, ether, and benzene, but only sparingly
soluble in light petroleum. On treatment with concentrated sulphuric
acid or phosphoric anhydride, it gives beautiful violet-blue condensation
products ; but by the action of phosphoric anhydride in sealed tubes at
120°, either with or without the presence of benzene, it gives a-naph-
thylphenylketoue, and not naphthyldiphenylmethane as Avas expected.
By incomplete reduction with sodium amalgam, a-naphthylphenylketone
gives a compound crystallising in needles (m. p. 61°). T. C.
Phenanthrenedisulphonic Acid and its Derivatives. By
E. Fischer (Ber., 13, 314 — 316). — Pltenanthrenedisulphonic acid,
CuHef S03H)2 (compare Grtebe, ^/ma/en, 167, 152, and Rehs, Ber.,
10, 1252), is obtained by adding one part of phenanthrene gradually
and with continual shaking to four parts of pyrosulphuric acid, and
then allowing the liquid to stand for about half an hour on a water-
bath. It forms a yellowish-brown non-crystallisable .syrup. Its salts,
including the barium salt, are, as a rule, easily soluble in water, but
insoluble in alcohol and ether. The potassium salt when distilled with
potassium cyanide, or better with dry potassium ferrocyanide, gives
the nitril, and a substance which crystallises in white needles, and is
only sparingly soluble in alcohol. The nitril crystallises in bright
yellow plates, which are easily soluble in hot alcohol; on saponification
it gives an acid which with resorcinol yields a body which has great
ORGANIC CHEMISTRY. 479
resemblance to Baeyer's fluorescein ; tins same substance was also
obtained by fusing the potassium disulphonate with sodium formate.
It is still under investigation. T. C.
Electrolysis of Terebenthene. By A. Kenard {Com.pt. rend.,
90, 531 — 531). — When a solutiou of terebenthene (25 c.c.) in alcohol
(80 c.c.) is mixed with sulphuric acid diluted with an equal volume of
water (20 c.c), and subjected to the prolonged action of a powerful
electric current, hydrogen is evolved at the negative pole, but no gas
appears at the positive pole. The addition of water to the liquid
causes the separation of a dark-coloured oil, which consists of ethyl
acetate, formed by oxidation of the alcohol, a small quantity of un-
attacked terebenthene, cymene boiling between 178 — 180", and tere-
bentkene monohydrcrte, CioHigO, a yellowish, somewhat oily liquid, boil-
ing between 210 and 214°; sp. gr. at 10° 0-9511; vapour-density
5"191. This compound is insoluble in water, but dissolves in alcohol,
ether, and acetic acid. Oxygen gas is without action on it even after
prolonged contact. It is attacked by bromine with great violence,
hydrobromic acid being evolved. If, however, the bromine and the
terebenthene monohydrato be both dissolved in carbon bisulphide before
mixing, no hydrobromic acid is given off, but water is formed, to-
gether with a compound which could not be isolated, but which pro-
bably has the composition CioHisBro. This substance is decomposed on
erapoi-ation of the carbon bisulphide, and the residue when distilled
with zinc-dust yields cymene. Terebenthene monohydrate is dissolved
by concentrated sulphuric acid with deep brown colour. On the
addition of water a black viscid mass separates out. ^Vllen distilled
with phosphoric anhydride the monohydrate jnelds terebenthene. It
forms no hydrochloride with hydrochloric acid, and is not acted on by
anhydrous acetic acid. Concentrated nitric acid attacks it with great
violence, but the moderately dilute acid gives rise to oxalic acid and
ctimidic acid, C10H10O4 + H2O, slightly soluble in Avater, but soluble in
alcohol. From these reactions, it would appear that terebenthene
monohydrate is a pseudo-alcohol, CioHjeH.OH.
The aqueous liquid from which the oil had been separated contained
(1) terpin ; (2) an acid forming a lead salt of the composition
CnHooSOvPb ; this maybe regarded as the lead-salt of asulpho-ethylic
derivative of hydroxycampholic acid, C10H20O4, and probablv has the
CO
constitution Pb<oQ'>C8Hi7.COOEt. (3) An acid giving a lead-
saU of the composition C 38-84, H 8-04, S 11-14, Pb 14-40.
G. H. B.
Podophyllin. By I. Gcareschi {Gazzetfa, 10, IG— 20).— The author
has examined the podophyllin of commerce obtained from Podophjllum
peltatum, and finds that it consists of two substances, a resin soluble
in ether, and a glucoside which is not soluble in ether. This
glucoside is decomposed by the action of emulsin, or when boiled
with dilute sulphuric acid ;. in the latter case, the solution on coolino-
deposits a white powder, whilst the sugar remains dissolved. The
product of the decomposition of the glucoside is soluble in alcohol and
2 m 2
480 ABSTRACTS OF CHEMICAL PAPERS.
also in boiling water, being deposited again as the solution cools ; it
lias not "been examined.
When commei'cial podophyllin is fused with potash and treated in
the usual way, it yields a small quantity of a product, which seems to
contain hydroxy salicylic acid, parahydroxybenzoic acid, and pyro-
'catechol.
The author considers that the glucoside in podophyllin resembles
•convolvulin and turpethin. C. E. G.
Bases of the Pyridine Series. By A. Richard (Bidl. Soc. Ghiw.
[2], 32, 486— 489).— The author has undertaken the study of these
bases, and especially of collidine, with a view to determine whether
the pyridine, picoline, and collidine which occur in Dippel's animal
oil, are identical or isomeric with bases of the same composition which
have recently been prepared synthetically. 200 kilos, of bone-oil
were digested with sulphuric acid, the acid liquor boiled to reinove
pyrrol, saturated with sodn, and distilled in a current of steam : 2 kilos.
of crude bases were obtained, from which the pyridine, picoline, luti-
dine, and coUidine wei'e easily isolated by fi-actional distillation in an
apparatus with eight washers. In order to separate the higher bases
(boiling above 180°) it was necessary to conduct the distillation under
reduced pressure. These higher bases form but a small fraction of the
entire product, of which pyridine and lutidine constitute about 40 per
cent., picoline and cnllidine being ])resent in smaller proportion. The
'first three bases of the series, freed from foreign substances by treat-
ment with oxidisine aeents, and purified by fractional distillation,
o-ave the following results: —
B. p. Density at 0°.
Pyridine 115° 0-9802
Picoline ]35 0-9660
Lutidine 156-5 0-9377
The density therefore diminishes as the moleeular weight increases,
a result in accordance with Anderson's observations, but not agreeing
with those of Thrnius. Some diflBculty was experienced in purifying
collidine. The fraction boiling at 176 — 180° was treated several
times in succes.sion with strong nitric acid, but the residue was still
considerably acted on by that acid. Fuming nitinc acid converrs this
base into a product which explodes on concussion. The best agent
for the purification of collidine appears to be chromic acid, the base
being dissolved in sulphuric acid. After four purifications by chromic
acid the base was obtained as a colourless liquid, becoming slightly
tinted by action of the air: b. p. 179—180°; density at 0° 0-9291.
The platinochloride was obtained as a viscous, uncrystallisable,
yellow-brown precipitate, insoluble in water and acids, from which
the author could not succeed in regenerating the base. Collidine
platinochloride is described by Anderson as a salt crystallising in
prisms. On comparing the collidine purified as above with (1) the
(ildehi/dine of Baeyer, (2) the base obtained by Wurtz in distilling
aldol-ammonin, and (3) the base CsHuN, obtained by Greville Williams
from the products of the distillation of cinchonine with potash, the
ORGANIC CHEMISTRY. 481
following differences were observed : — Aldehydine, prepared according
to Baeyer's directions, is a colourless liquid boiling at 179°. Its
platinochloride is identical with that of ^Vurtz's base, and is much
more soluble in water than the platinocKloride of the base from ciu-
chonine. One c.c. of water at 60° dissolves 0'0213 gram of the ])la-
tinochloride of the base from cinchonine, 0'U495 of the platinochloride
of the base from aldol-ammonia, and. 0"5U0 gram of the platinochloride
of Baeyer's aldehydine. Analysis of Baeyer's aldehydine gave
C 7924 per cent, and H 9'90 per cent., and of the base from cinchonine
C 79"O0 per cent, and H 919 per cent. The author concludes that
the collidine obtained by him fi-om Dippel's oil is not identical with
either of the above bases having the same formula. Dippel's oil con-
tains a small quantity of ethyl alcohol. J. M. H. M.
Alkaloids of the Pomegranate. By C. Taxret {Compt. read.,
90, t)9o — 698). — The bark of the pomegranate tree contains four
alkaloids : —
(1.) Metlajlpelletierine, CgllnNO, a liquid boiling at 215°, and
forming very deliquescent salts. It dissolves in 25- times its own;
weight of water at 12^, and is very soluble in alcohol, ether, and
chloroform. The hvdrochloride has a rotatory power for [a]T>.
of + 22°.
(2.) Pseudopelletierine, C9H15NO, a crystalline solid.
(3.) Pelletierine, C^isNO^a colourless liquid, boiling at 195? under
ordinary pressure, with partial decomposition, but may be distilled un-
changed under reduced pi-es.sure. It dissolves in 20 times its own
weight of water, and is soluble in all proportions in alcohol, ether,
and chloroform ; its sp.gr. at 0° is 0'988. When exposed to oxygen,,
it is rapidly converted into a resinous mass. The salts of this alkaloid
become acid when heated either in the dry state or in solution. The
sulphate has a rotatory power for ao of —30°. If the free alkaloid,
be heated to 100°,. this rotatory power disappears.
(4.) Iso-pclletierine. d-HisNO, a liquid without action on polarised
light. Its specific gravity, solubility, and boiling point are the same
as those of pelletierine, of which it is an isomeride. C. H. B.
Daturine. By E. Schmidt (iJer., 13, 370 — 373). — According to>
Planta (Annalen, 74, 252.) atropine and daturine are identical, whilst,
according to Poehl {Chem. Ce)itr.,.lS78, 108), they are not. The author
has carefully compai'ed samples of daourine and atropine from various
sources, and so far has been unable to detect any difference between
the two. This conclusion is ba.sed on the following facts : —
The melting points of several samples of atropine varied from 112"5?
to 1155 (115'5°,.LadenburgJ, and those of several samples of daturine
113'5° to 115"5°. Both gave the same results on analysis, viz., CnHjsNOs,.
and both are slightly la^vorotatory, although Poehl states that atropine
is inactive towards polarised light, whilst Bnignet {Jahresb., 1861,
49) agrees with the author. The platinochlorides of the two bodies
have both the composition (Ci7B[o3NCK,.HCl)2PtCl4,. and the same melt-
ing point (208^). The gold salts also are to all appearance identical.,
and have the composition CnH23XO3.IlCl.AuCU. Both bases behave
482 ABSTRACTS OF CHEMICAL PAPERS.
in a manner exactly similar towards all ordinary reagents, and on
boiling- witk baryta-water both yield atropic acid, CgH^Oo (m. p.
10(j'5^), and tropine (m. p. 63° ; Kraut gives 61'2° as the melting
pointof tropine from atropine), the platino- and auro-chlorides of the
latter base were also found to be identical, the composition of the
platinochlorides being (CVH,5NO.HCl),PCl4, ard m. p. 109° with de-
composition, and that of the auro-chlorides, CsHisNO.HCl.AuCU, 211°.
T. C.
Daturine. By A. Ladenburg and Gr. M^tbr (Ber., 13, 380—381).
— Daturiue is not identical with atropine, as stated by Planta (Annalen,
74, 252), but with hyoscyamine and duboisine. This conclusion is
based on a comparison of the respective melting points of the free
bases (atropine = 113"5°, daturine = 105 — 108°, hyoscyamine = 108'5°),
and on the properties and composition of the auro-chlorides, the melt-
ing points of the hyoscyamine and daturine compounds being identical,
viz., = 159°. Daturiue and hyoscyamine also behave in an exactly
similar manner towards reaofents. T. C.
o
Synthesis of Ulmic Substances. By A. Millot (Compt. rend.,
90, 611 — 612). — When a 5 percent, solution of ammonia is electro-
lysed, the negative pole being of platinum and the positive pole of
purified gas carbon, the carbon becomes disintegrated and a black liquid
is obtained ; the addition of a mineral acid to this produces a precipi-
tate which, when purified by solution in wa,ter and reprecipitation,
has the composition C 5475, H 4-00, N 12-40, 0 28-85. It is entirely
soluble in water, especially if warm, but is insoluble in alcohol, which
precipitates it from its solutions. When dried it becomes partially
insoluble in water, but dissolves complettely in solutions of ammonia.
After drying at 150° it is altogether insolable in water. When boiled
with alkali it does not evolve ammonia. Heated with potash it gives
potassium cyanide.
By substituting potash or soda for ammonia, substances are obtained
which have similar properties, but contain no nitrogen.
C. H. B.
Gluten. By T. Weyl and Bischoff (Ber., 13, 367— 369).— The
gluten which is obtained by the action of water on flour does not
exist ready formed in the latter, but is due to the action of some fer-
ment on the vegetable myosin present in the flour. This ferment,
however, has not yet been isolated. T. C.
Products of the Decomposition of Proteids. By Bleunabp
(Compt. rend., 90, 612—614). — The mixture having the general for-
mula C„H2„N>04, obtained by the action of baryta on stag's horn,
consists mainly of a glucoprotein of the composition C6Hi2l!^o04, cor-
responding with the compound C7HuISr204, obtained by Schiitzenberger
from albumin. When treated with bromine, it is converted into a
substance, CeHisiSrsOo which is a mixture of glycocine, C2H5NO2, and a
compound, C4H7NO3, in equivalent proportions. A body such as
CeHisNoOi may be regarded as a mokcular combination of C2H5XO2
PHYSIOLOGICAL CHEMISTRY. 483
■with a luceine, C4H7NO2, which, on oxidation is converted into
C4H7XO3. The reaction with, bromine may serve as a means of deter-
mining the constitution of glaco-proteins. C. H. B.
Chemical Composition of Aleurone Grains, By S. H. Vinks
(Proc. Roy. Soc, 28, 218). — When the ground seeds of the blue lupin
(Lupinus varius) are treated with a 10 per cent, solution of common
salt, a fluid is obtained which gives the characteristic reactions of
globulin. From this liquid water precipitates vitelliu, and excess of
common salt precipitates myosin.
The author concludes from an experiment, which is not very clearly
explained, that conglutin is a product of the alteration of the reserve-
prote'ids (globulins) and does not pre-exist in the seed.
In addition to vitellin and myosin there is another substance present
in the 10 per cent, sodium chloride solution, -which is not precipitated
either on boiling or by addition of water or of salt. It is extracted
from the seeds by boiling water. Its reactions indicate that it is
allied to the peptones, most nearly resembling Meisoner's a-peptone
(hemialbumose, Kuhne). It is precipitated from its aqueous solu-
tion by alcohol, but retains its solubility in water even after keeping
in alcohol for three months. C. W. \V.
Physiological Chemistry.
Specific Heat of Animal Tissues. By I. Rosenthal (Bied.
Centr., 1879, 633).
Specific heat.
Compact bone substance O'oOO
Spongy „ „ 0710
Fatty tissues 0-712
Stri-rited muscle 0'825
Defibrinated blood 0-927
Dried muscle gave 0*30 specific heat, and calculating the active
muscle as consisting of three parts water and one part organic sub-
stance, the specific heat would be 0-82.5, a result which exactly corre-
sponds with the experimental number.
The influence of water on the specific heat of a substance is shown by
the approximation of its specific heat to that of water. The above de-
terminations were made with Bunsen's ice-calorimeter at an initial
point of 40^, and can be regarded as only appro.ximate on account of
the ditticulty in fixing the initial temperature. A. J. C.
The Function of Respiration at Various Altitudes on the
Island and Peak of Teneriflfe. By AY. Marcet {Proc. Boy. Soc,
28, 498). — The experiments were performed by the author on himself
and his guide at three stations, respectively 7,090, 10,700, and 12,200
feet above the sea-level. The functions investigated were the number
484 ABSTRACTS OF CHEMICAL PAPERS.
of respirations, the volume of air, amount of carbonic acid and amount
of water expired per minute at the three stations, both while at rest
and while doing' a definite amount of work. By the comparison
of the results with those obtained in a previous series of experi-
ments on the Alps, the effects of increased temperature were deter-
mined.
The results obtained may be summarised as follows : —
The carbonic acid ex]iired is, under all circumstances, proportional
to the weight of the body ; for the subjects of these experiments it was
676 mgrms. per 100 kilos. The amount was greatest during the first
or second hour after eating, afterwards gradually diminishing.
The amount of carbonic acid expired was greater at Teneriffe than
on the Alps, the increase amounting" to 14"0 and 17"5 per cent, for the
author and his guide respectively. There was no increase in one case
at the greater elevations such as was experienced on the Alps, the
inci'ease in the latter case being probably due to reduced temperature.
In the other case, however, 17 per cent, more carbonic acid was
expired at the sea-level than on the Peak of Teneriffe. This was due
to increased perspiration at the higher altitudes.
The volume of air expired per minute, and also the number of respira-
tions decreased at the higher elevations. The percentage of carbonic
acid in the air expired increased from 41 per cent, at the sea-level to
4-9 per cent, at 11,945 feet.
With respect to the effect of work, it was found that the relation
between the volumes of air expired while sitting and while engaged on
a regulated amount of muscular work, was the same as the relation
between the weights of carbonic acid expired under such circum-
stances.
The amount of w^ater expired increases considerably from the lower
to the hio-her level; this causes a very great loss of heat at the higher
elevation^ C. W. W.
Digestion of Albuminoids. By A. Schmidt (Bied. Centr.,'[879,
887 — 890). — Six dogs of the same breed, after two days' fasting, were
fed each with 200 grams of flesh and killed with potassium cyanide at
various intervals after the meal. The stomach and intestines were
then examined. It was found that, after a lapse of more than nine
hours, some of the food still remained undigested in the stomach. As
regards the digestion of the albumin, it was observed that a constant
quantity of dissolved albumin remained in the stomach during the
digestive process, arid the peptone varied from one and a half to
twice the amount of dissolved albumin. The food passed through the
dogs in about nine hours. J. K. C.
Digestion in Sheep. By E. v. Wolff and others (Bied. Centr.,
1879, 890 — 901). — The i)bject of these researches was to ascertain the
influence which the addition of bye-fodder, such as potatoes and beet-
root, has on the digestion of ordinary raw fodder, hay, straw, and the
like. For two months beet was given to two sheep along with clover
hay : the composition of each was as follows : —
PHYSIOLOGICAL CHEMISTRY.
485
Clover hay
Beet
Nitrogen
.'roteiu.
Fat.
Fibre.
free extract.
Ash.
19-37
3-84
24-45
43-92
8-42
13-60
0-56
7-04
70-35
8-45
The plan of the experiment and the results as mean of both animals,
are appended in the following table : —
Fodder per
diem.
Percentage of clover hay
digested.
'
Kitrogeii
Clover.
Beet.
Organic
free
Period, grams.
grams.
Solids.
matter. Protein.
Fat.
Fibre.
extract.
I.. 1000
57-76
59-53 60-28
55-01
55-25
63-43
II.. 1000
2000
54-02
55-62 54-68
50-62
45-69
61-82
III . . 500
2000
53-94
56-10 5316
Percentage o
39-90
f beet diges
48-11
ted.
62-90
II.. —
85-78
85-00 71-35
96-19
III..
85-92
86-53 71-59
96-17
Similar experiments with potatoes as bye-fodder showed that in
this case also a lowering of the digestive coefficient of the hay took
place, the percentage of total solids digested being reduced from 60-2
to 47-3, and of protein from 63-/ to 45-9. In other experiments, the
clover was replaced by hay and pasture grass, and the potatoes by
sugar beet, turnips, and swedes. In all cases a lowering of the diges-
tive coefficient of the raw fodder resulted, varvinsr in each case
according to the absolute amount of each constituent present in the
bye-fodder. J. K. C.
Nutritive Value of Asparagine. By H. Weiske, M. Schrodt,
and St. v. Daxgel {Zeits. f. Blolngie, 15, 261 — 296). — Various experi-
menters have found that araido-compounds, as glycocine, leucine, tyro-
sine, asparagiue, and aspartic acid, are converted into urea in the animal
system. Kuieriem also found that when asparagine was given to a
dog receiving an insufficient diet, it diminished the previous loss of
albumin in the body. Gelatin has been shown by Voit and others to
discharge the same function. As amides are generally present in
succulent and immature vegetable food, the authors made the follow-
ing experiments to ascertain their value in the animal economy.
Four rabbits were fed on a mixture of 50 grams starch, 10 grams
oil, and 2 grams vegetable ashes. To this mixture was added in one
case 5 grams asparagine, in another case 10 grams gelatin, and in a
third case 5 grams of both asparagine and gelatin. The rabbit receiv-
ing gelatin died on the 38th day, but without any serious loss in
weight. The rabbit receiving no nitrogenous food died on the 49th
day, having diminished in weight from 1125 to 640 grams. The rabbit
with the asparagine ration died on the 63rd day, after a gradual
diminution in weight, which became rapid towards the close. The
fourth rabbit, receiving both asparagine and gelatin, increased in
weight, and was alive on the 72nd day, when the experiment closed.
Asparagine thus merely somewhat retarded death, while asparagine
486 ABSTRACTS OF CHEMICVL PAPERS.
mixed with gelatin was apparently capable of forming albumin in the
animal body, and thus permanently sustaining life. A mixture of
tyrosin and gelatin has been similarly found by Escher to be capable
of replacing albumin.
Experiments were next made with hens, the diets employed being
similar to those just described. The hens did not consume enough
food to maintain their body weight, those receiving asparagine and
gelatin were however quite healthy at the end of 17 days. With
gelatin as the only nitrogenous food there was less success.
The final experiments were made on sheep. Two full-grown sheep
received in the first experimental period 500 grams hay, 200 grams
starch, and 50 grams sugar per head per day. In three succeeding
periods the nitrogen in the diet was doubled by the respective addi-
tion of albuminoids, asparagine, and gelatin. Towards the end of each
period, the solid excrement and urine were collected and analysed. It
appeared that the asparagine was perfectly digested, the albumin (sup-
plied as pea-meal) was also almost completely taken up, while the
gelatin was less perfectly assimilated. By comparing the quantity of
nitrogen and sulphur supplied in the food with that voided in the
excrements, the amount retained as albuminoids in the body was cal-
culated. On the first diet, the average amount of nitrogen retained
by the sheep was 0'275 gram, and of sulphur 0'029 gram per day.
With gelatin, the nitrogen retained amounted to 1'330 gram, and the
sulphur to 0"038 gram. With asparagine, the nitrogen retained was
1"6G4! gram, and the sulphur 0"112 gram. With albumin, the nitrogen
retained was 2'048 grams, and the sulphur 0*176 gram. It appeared,
therefore, that the supply of both asparagine and gelatin increased
the amount of albumin stored up in the body. The authors believe
that asparagine and gelatin protect albuminoids from oxidation in the
animal economy, and thus allow albumin to be stored up even under a
poor diet, R. W.
Physiology of Sugar in Relation to the Blood. By F. W.
Pavy (Froc. Roy. Soc, 28, 520). — After a comparison of the results
obtained by various processes for the estimation of sugar in blood, in
which he gives the j^reference to the ammoniacal cupric test, the
author examines Bernard's hypothesis that the natural seat of destruc-
tion of sugar in the system is in the systemic capillaries. If this is
the case, then a disappearance of sugar should occur in the blood
after removal from the vessels ; and, according to Bernard, such a
disappearance does actually take place. The results obtained by the
author, however, directly contradict those of Bernard, and point to
the conclusion that the gradual disappearance of sugar which takes
place in putrefying blood is the result of ordinary decomposition, and
does not arise from any physiological cause.
The author also concludes, from the results he has obtained, that
there is in the blood a reducing substance besides sugar, which is of
a sufficiently stable character to resist advanced decomposition,
c. w. w.
Muscular Activity and Waste. By O. Kellner (Bied. Centr.,
1880, 24 — 27). — A record of observations on a horse, regularly fed
PHYSIOLOGICAL CHEMISTRY. 487
and worked, in order to throw some light on the question whether
muscular activity is caused simply by the oxidation of uon-uitrogenous
substances in the body or by the increase of albuminous matters in
the food, as held by two schools of physiologists. The horse was
periodically carefully weighed, his work estimated by a specially in-
vented dynamometer, his consumption of food and water recorded,
and his urine carefully collected and tested for nitrogen. The general
results of the experiments show that with an increase of work, changes
of albuminoid matters become more active. An increase of water
drunk by the animal causes an increase in the evacuation of albu-
minoids.
The author draws an inference from the present and his former
observations, that the source of muscular strength in general is the
waste of organic matter. In the first place, the non-nitrogenous
substances, hydrocarbons and fats, are called into requisition, the
organic albuminoids not being attacked until the other materials capable
of oxidation are no longer present in sufficient quantity. J. F.
Observations on the Milk of a Large Herd of Cows. By W.
Fleis^chmann and P. Vilih {Bled. Centi\, 1879, 908 — 911. The mean
results of a year's examination of the milk of several cows are given in
the following table : —
Morning milk. Evening milk.
Specific gravity lUolG 10318
Percentage of fat 3-374 3-420
Yield per cow in kilograms 3-552 3-439
Yield of fat in grams .... 120 116
The percentage amount of fat varied from 2-844 to 3-927 per cent.
J. K. C.
Influence of Ground Nats on the Production of Milk. By
W. J. KiKCHXEK and P. dd Koi (Bied. Ctntr., 1879, 903—906).—
Ground nut cakes, containing 52 per cent, of protein, gave favourable
results as regards the production of milk, but seemed to have no
special effect on the quantity of fat produced. J. K. C.
Influence of Shearing on Yield of Milk. By H. Weiske
(Bied. Centr., 1880, 31, 32). — Previous observations convinced the
author that the effect of shearing was to cause a greater appetite, but
not a better digestion of the fodder. The removal of the hair neces-
sitates a greater internal warmth in the body, which must be sustained
by digested food; consequently, fodder, which should go to increase
the production of flesh, is expended in producing heat, so that a dimi-
nution in the amount of flesh formed takes place.
The frequent shearing of fattening sheep is, therefore, not profitable,
except for the purpose of increasing the animal's appetite and con-
sumption of food, in order to indirectly increase the production.
The present observations were made upon a 2^ year old Southdown
ewe, which lambed on 22nd April, unshorn, milked carefully three
times daily, receiving regularly each day 1 kilo, of turnips, i kilo, of
hay, and ^ kilo, of groats ; she yielded on each consecutive — ■ '
488 ABSTRACTS OF CHEMICAL PAPERS.
Day ... . 1 2 3 4 5 6 7 8 9
Grams . . 523 G20 736 768 840 910 924 992 987 milk.
From 10 — 20th of May the daily yield was very regularly 1,000 grams.
On the 21st of May the ewe was shorn, the same food and treatment
was continued, and a decided falling off was evident.
Date, May . . 20 21 22 23 24 2-5
Grams 1006 913 854 781 750 712
On the 26th of May ^ kilo, of linseed cake was added to the other
food, with very beneficial results.
May 26 27 28 29 30 31
Grams 687 760 889 950 910 961
The yield of milk evidently suffered from shearing, and the addition
of the linseed cake brought it up to its normal amount.
It appears reasonable from this that when the lambing season coin-
cides with the time of shearing, the ewes should be generously fed
with artificial food, unless they have the run of a good meadow, where
they have food ad lihituvi. J. F.
Influence of Impure Water on Health. By R. Emmerich
(Bii'd. Centr., 1880, 4 — 12). — A belief that such diseases as typhus
and cholera are propagated by means of impure water is prevalent
not only amongst medical men, but the general public, and exercises
an important influence on the expenditure of town corporations and
similar bodies in the endeavour to supply the pure and remove the
impure water. The author of the present paper, believing from the
experiments of Pettenkofer and others that this deleterious influence
either does not exist at all, or if at all, in the most trifling degree,
undertook the experiments recorded on the bodies of animals and his
own person, in order to contribute to the settlement of the question.
The experiments on animals consisted of subcutaneous injections of
distilled, ordinary, and impure waters. The first experiments showed
that with rabbits weighing from 7tiO to 1,500 grams, the injection of
40 — 70 c.c. of distilled water produced no observable alteration in
their health, and that it i-equired a considerable quantity, fully 200 c.c,
to kill them. With impure water different results were obtained. The
water selected was from the drain which collects the sewage of part of
Munich, and discharges it into a brook ; the temperature before injec-
tion was kept at blood heat, and the results were uniform, viz., that
with animals weighing 550 to 1,500 grams, quantities of 6 to 60 c.c.
invariably caused death in shorter or longer periods, the symptoms
differing o-nly according to the amount of the dose and the weight of
the animal operated on ; the tempei'ature of the body rose in each ex-
periment, but the author hesitates to ascribe that effect to the oxida-
tion of the impurities of the water. With hoiled sewage water the
results were very similar to those with clean water, 14 — 24 c.c. pro-
ducing but slight sickness, quickly recovered from, and death taking
place only after injection of comparatively large quantities, say 150 c.c.
Two other experiments were made with the residue of evaporated
PHYSIOLOGICAL CHEMISTRY. 489
sewage water ; 500 c.c. evaporated on the water-bath and dissolved in
a small quantity of distilled water; the injection of this matter pi'o-
duced strong convulsious and speedy death. The net result of this
first series of experiments shows that the snbeutaneous injection of
impure water causes symptoms quite analogous to those produced by
putrid fluids, and that its effects are the more intense the greater the
quantity of oxidisable impurity contained in the water.
These experiments do not show whether the poisonous matter is in
solution or suspension, or whether or not it is an organised ferment ; but
the author inclines to the opinion that it is not an organism, and that
the similarity of the behaviour of the boiled sewage and its extracted
residue with other preparations of putrid solutions leads him to the
belief that the poisonous qualities are due to putrefactive matter in
the sewage.
The author next directed his attention to the introduction of impure
■water into the stomachs of animals, and the results agree very closely
with other experiments made with putrid poisons, viz., that a much
larger quantity can be introduced into the stomach than either into
the veins or under the skin. In the present case a rabbit weighing
1,500 grams received daily 600 c.c. of sewage water in four doses of
150 c.c. At the end of two days the animal appeared unharmed.
The author thinks it would be unsafe to say that the effects on
human beings would be the same as on animals, and if the poison be
an alkaloid or anything of that nature — say, similar to morphine — its
toxical effects would vary very considerably; and taking into account
the slight effect of large doses on such small animals as rabbits, he is
of opinion that human beings could with impunity partake daily of a
considerable quantity of sewage water. To test the matter, he deter-
mined to drink daily one-half to one whole liter of water taken from
one of the small brooks or water-courses of Munich, which received
the drainage from kitchens, wash-houses, urinals, cattle-sheds, &c.,
moreover, there were cases of typhoid in some of the houses draining
into it ; on the surface floated cabbage and lettuce leaves, hum.an and
animal hair, &c. He continued the experiment "a long time," not
exactly defined, but without feeling any injurious effects. A slight
stomach coucrh with which he was affected at the bearinning' of the
observations did not become any worse; and he inclines to the opinion
that the unpleasant effects experienced by other people ma)" have
arisen from feelings of nausea at the appearance of the water. The
author invites other investigators to continue similar experiments.
Injections of largely diluted sewage yield negative results, and the
author agi-ees with !Nageli that the addition of large quantities of
water to sewage renders the poisonous matter innocuous.
The author proposes a rough method of estimating the evil effects
of impure water, which is, that the suspected water or its residue dis-
solved in 40 to 8U c.c. be injected under the skin of a full-grown
rabbit ; if the increase of temperature is no greater than 1° C, or if
death do not follow in a very short time, there is no hurtful matter
present, or it is pi-esent in trifling quantity.
He has examined the worst of the Munich waters by this method
and thinks it fairly trustworthy, but that it, in common with all known,
490
ABSTRACTS OF CHEMICAL PAPERS.
processes for estimating organic impurities in water, must be co-q-
sidered as temporary expedients to give way to some method yet to be
devised, J- F.
Presence of Copper in Food. By A. Gauthier {Bled. Gevtr.,
1879, 937 — 938). — Experiments on dogs sbowed that doses of some
decigrams of copper sulphate could be given daily without pro-
ducing death, but further researches are necessary to ascertain whether
])ermanent derangement of health is not produced. It was found that
Avheat, coifee, starch, &c., contain about 1 mgrm. of copper per kilo.
J. K. C.
Injury to Fishes by Waste Liquids. By Weigelt (Landiv.
Verstichs.-Sfat., 24, 424 — 427). — Trout weighing 5 — 20 grams die in
a few minutes in water containing 0-005 gram chlorine per liter, and
even 0-0002 gram per liter is undoubtedly fatal to small fish ; and
this is near the limit of the amount of chlorine that can be detected
by chemical means. Soda-lye, and even ammonium carbonate, act much
less injuriously ; fish kept in solution of soda containing 3 grams
and 0-1 gram of crystallised soda per liter for 15 and 45 minutes re-
spectively seemed to be uninjured ; at least they were living six weeks
afterwards in a running stream. Sulphuric acid was more fatal by far
than hydrochloric acid, but the fish soon recover themselves when
removed from the contaminated water. "Waters charged with car-
bonic anhydride, neutral salts (calcium chloride and sodium chloride),
with a concentration of 3 parts per 1,000, have no injurious influence.
J. T.
Cobra Poison. By A. Pedler (Pi-oc. Boy. Soc, 27, 17), A. W.
Blyth {Analyst, 1, 204), and T. L. Bruxton and Sir J. Fayrer (Froc.
Boy. Soc, 27, 188). — The poison of the Cobra de Capello {Naja tri-
jmdians), which may be obtained by pressing the parotid glands of the
snake while its fangs are erected, is an amber-coloured, syrupy, frothy
liquid, of sp. gr. 1-046 (Blyth), 1-095 at 23° (Pedler). When eva-
porated, either in the air or in a vacuum, or at 100°, it leaves a solid
residue amounting on the average to 28-82 per cent. (Pedler) ; about
33 per cent. (Blyth). The fresh liquid has no action on polarised
light. It may be kept for two or three months without alteration, but
after a year or 18 months it alters considerably, becoming insoluble,
and losing to a great extent its poisonous action (Pedler).
Dried in a vacuum over sulphuric acid, it gave by analysis : —
C. H.
49-32 7-01
N. Ash.
17-39 6-68
0 witli
trace of S.
19-60 = 100
acting the ash : —
C. H.
62-87 7-51
N.
18-29
0 and S.
21-33 = 100
This composition does not differ greatly from that of various kinds
of albumin ; the proportion of nitrogen, however, is rather greater
than in egg-albumin.
; The liquid poison, treated with strong alcohol, yielded a precipitate
PHYSIOLOGICAL CHEMISTRY. 491
of albuminous matter, amounting to about 17 S per cent, of the whole,
which was only slightly poisonous, whereas the portion soluble in
alcohol (10'9 per cent, of the whole) was excessively poisonous : hence,
as the total quantity of solid matter in the poison is about 28 per cent.,
it follows that about 60 per cent, of the poisonous liquid is of an albu-
minous nature, and only about 40 per cent, consists of pure poison.
No crystallisable substance could be obtained from the poison, either
by the use of solvents or by dialysis through parchment paper, although
slight indications of crystallisation were obtained by both methods.
The liquid remaining in the dialyser left on evaporation a gummy
mass, having all the physiological characters of the poison ; and the
liquid outside the dialyser appeared to be rather more poisonous than
the original virus (Pedler).
According to Blyth, cobra poison contains albumin, and a minute
quantity of fat, and yields about 1"4 — 1"5 per cent, of ash, mainly con-
sisting of sodium chloride. It dries up quickly on exposure to the air,
leaving a yellow acrid pungent powder, amounting to about 83 per
cent, of the whole. This substance is not decomposed at 100^, but
blackens at 270°, and yields a sublimate at higher temperatures. A
similar substance, crystallising in needles, niay be obtained by dialvsing
the poison. It exists therein to the amount of 10 per cent., and is
highly poisonous, appearing to be the only active principle. It is ob-
tained pure by conversion into a lead-salt, separation therefrom, and
evaporation in a A'acuum. Blyth designates this substance as cohric
acid. He finds that a weak solution of potash, or a weak alkaline
solution of potassium permanganate, destroys the physiological activity
of cobra poison.
Pedler describes a long series of experiments on the raodification of
the active properties of the poison by various substances, undertaken
with the view of discovering an antidote to its action. When the
poison was digested with etliyl iodide, a residue was obtained which
exhibited an increase of weight, indicating combination, and was
much less active than the original poison. The residue obtained by
mixing the poison with hydrochloric acid and leaving the liquid to
evaporate, was also much less active than the original poison. By
slow evaporation in a vacuum, distinct traces of crystals were obtained,
but they were mixed with a large quantity of amorphous soluble
matter, from which they could not be separated.
A much greater diminution of the activity of the poison is pro-
duced by the addition of platinic chloride. "When a quantity of fresh
cobra poison was treated with alcohol to precipitate the albumin, the
alcoholic filtrate acidified with hydrochloric acid, and a solution of
platinic chloride added, a small quantity of a yellow amorphous pre-
cipitate was formed, and the solution evaporated in a vacuum yielded
a semicrystalline residue, which was freed from excess of platinic
chloride by washing with weak spirit. O'l gram of the solid platinum
compound administered internally to a chicken exerted no poisonous
action, and the solution containing the excess of platinic chloride was
Hkewise without action when injected hypodermically. A considerable
number of experiments upon chickens and dogs showed that even
considerable quantities of cobra poison mixed with platinic chloride
492 ABSTRACTS OF CHEMICAL PAPERS.
ini_^ht he injected hypodermically without producing- a fatal result,
pre. ided a shoi't time was allowed to elaps« hefore the mixture was
injected. In one experiment, the quantity of poison thus injected was
sufficient, if administered alone, to kill 120 chickens. When, on the
other hand, the injection was performed immediately after mixino;,
the results were less favourable, the fatal effect being not prevented,
but merely retarded. The seme effect of retardation, but not pre-
vention of the fatal result, was obtained when the cobra poison was
first injected alone, and the platinum solution a few minutes (1 to 5)
afterwards. The poison indeed seems to diffuse itself through the
organism so rapidly that no antidote can be afterwards injected
quickly enough to counteract its effects.
The platinum salt of the cobra poison gave by analysis numbers
nearly agreeing with the formula, (CnH35N407.HCl)3.PtCl4 (Pedler).
Brunton and Fayrer find that auric chloride behaves similarly to
platinic chloride, rendering the poison nearly inactive if mixed with
it before injection. Permanganate of potassium also prevents the fatal
effect, probably by destroying the poison. Zinc chloride, mercuric
chloride, silver nitrate, and carbolic acid also diminish the activity of
the poison, and slightly prolong life if mixed with it before injection.
Ferric chloride has a weaker action. Potash prolongs life for several
hours. With large doses of the poison, none of these substances have
any appreciable effect, even when applied immediately.
c. w. w.
Chemistry of Vegetable Physiology and Agriculture.
Locality of Albumin Secretion in Plants. By H. Mullbr
Thukgau {Bled. Cttdr., 1880, 42 — 43). — The author endeavours to
decide whether the formation of jyrotoplasm takes place in the leaves
or other portions of the plant ; for this purpose he devises an arrange-
ment by which the seeds of maize, wheat, beans, &c., are germinated
over water, and the rootlets led out in two divisions, and immersed in
separate vessels ; the two vessels contain solutions which are identical
as reo-ards mineral constituents, but to one of them is added a nitro-
o-enous substance of easy assimilation, the other contains none. The
o-rowth of the rootlets was measured regulai'ly every day.
If the development of the albuminoid was due to absorption from
the air, or had its origin in the upper portions of the plant, both
divisions of the root should grow equally. If, however, it proceeded
from the roots, the portion immersed in the solution containing nitro-
o-enous matter should grow quicker than the other; this was actually
the case. The leaves do not appear to play any part in the assimilation.
To prevent mistakes, the roots were alternately immersed in one
solution, and changed to the other; their growth varied exactly
and daily as they were placed in one or other solution. The same
results were obtained from placing the rootlets in sand saturated with
a nitrogenous solution.
VEGETABLE PnYSIOLOGY AXD AGRICULTURE.
493
The practical application of these experiments shows that there is
advantage in the use of a nitrogenous manure in cases where quick
and strong development is desirable, as for example in turnip and tree
culture. J. F.
Decomposition of Albuminoids in Plants. By E. Schulze
(liied. Cent)-., 1879, GU'J — 61u;. — The author advances the theory of
the alternate decomposition and re-formation of albuminoids in the
organism of plants, and to this end he discusses the production in the
lupine of asparagine from conglutine. A. J. C.
Passage of Nutritive Material in Plants. By L. Desbarbes
(Bied. Centr., 1879, 946 — 947). — The wood of young branches of
Ehus elegans was examined in winter and spring with the following
results : —
In winter. In spring.
Dry substance .... 72T6 66' 70
Protein 9-42 2-25
Starch 17-31 1-57
Ash 1-60 1-20
The woody parts of the plant seem, therefore, in winter to form a
reservoir for assimilable material for the nourishment of the yonng
organs in spring. J. K. C.
Amount of Dew on Plants. By L. Haiipel {Bied. Centr., 1879,
G.jO). — The observations were made in July and August.
With dew.
Pinus austriaca, four needles gave ,
Tilia grandifolia, one leaf gave. . . . ,
Tubercux peduncidata, one leaf gave ,
Abies excelsa, a small bougli gave . . .
centigrams.
45-60
106 -80
96 06
85-10
Without
dew.
centigrams.
40-76
82-40
71-50
75-30
Dew by
difference.
centigrams.
4-84
24-40
24-56
9-80
A. J. C.
Fertilization of Rye. By W. Rimpau {Bied. Centr., 1879, 911—
912). — The author finds that the flowers on the same plant cannot
fertilize each other, and that pollen from other individuals is necessary
for this purpose. J. K. C.
Result of Drying Seeds. By E. Wollxy {Bled. Centr., 1880,
36 — 42;. — Many experiments have shown that the seeds of several
plants including flax, cucumbers, pumpkins, and melons, yield very
plentifully when they have been dried at a temperature of 30° to 50° C,
notably flax seed, growers of which always seek old seed, as yielding
a better and longer flax ; the author presumes this is because of the
natural drying of the moisture originally contained in the seeds. This
fact led the author to undertake a series of experiments with the seeds
VOL. xxxviii. 2 n
494 ABSTRACTS OF CHEMICAL PAPERS.
of many foorT plants in order to learn tlie effect of artificial drying- on
their productiveness.
In view of the danger of too high a temperature killing some of the
seeds, they were not heated above 32 — SS'' C, so that a long time was
necessary to dry them ; the undried seeds were meanwhile kept in
airtight bottles, and lost scarcely any moisture. The experiments were
arranged in two series, firstly, to ascertain the effect upon the grmidh
of the plant, and, secondly, the effect upon the productiveness. The
answer to the first question is that the drying of the seeds delays the
growth of the plant, and that the plants produced from the dried are
much more irregular in size than those from undried seeds, and that
notwithstanding the greatest care in drying, the seeds so treated have
a less percentage of germinating power. The effect on the crop, how-
ever, is very different, the figures showing clearly that the effective
produce of the dried seeds is greater than from the undried.
The author confesses his inability to reconcile the different conclu-
sions, but suggests that a great deal depends on the state of the soil,
whether it contains abundance of natural moisture or not, and suggests
that after all it is to a great extent dependent on the nature of the
locality and the facilities for obtaining water, and hopes that practical
farmers will carry out further experiments. J. F.
Normal Presence of Copper in the Plants which Grow on
Primordial Rocks. By Dieulafait. — The author has previously
shown that all rocks of primordial formation contain copper. He finds
that this element is present in plants growing on such rocks to such
an extent that it may be recognised by the ammonia reaction in 1 gram
of ash. Copper is also present in the ashes of plants growing on
marls, the sand of which has been derived from primordial rocks.
Other researches have led the author to conclude that heat has had
nothing to do with the formation of dolomites. They are marine
formations, sedimentary in the ordinnry sense of the word, but often
deposited in concentrated marine waters. He has previously found
that deposits found in such waters always contain copper, therefore
dolomites ought to contain this element. Plants growing on dolomites
contain copper to such an amount that it can be detected in 1 gram of
ash. On the other hand, plants growing on pure limestones contain
but traces of this metal, requiring at least 100 grams of ash for its
detection. C. H. B.
Formation of Nitrates in Sugar Beets. By A. Pagnoul {Bied.
Centr., 1880, 17). — These salts when found are not always derived from
mineral manures added to the soil, but may come from organic nitro-
genous substances, such as stable manure. Beets which were sown
in ground manured with sodium nitrate, although containing a con-
siderable quantity of the salt immediately after germination, contained
no trace at a later period, whilst some from the same seed, sown in
ground which had been heavily manured with stable dung, contained
0'7 per cent of the salt.
Very great care must be taken when cultivating beets to avoid every
cause that might lead to late vegetation ; the leaves should attain
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
495
tlieir full development by the end of August ; if a slowly working
manure be employed, or the season be mild, dull, and damp, and the
development is delayed until September or October, it is at the expense
of the saccharine matter of the roots ; they continue to grow, and
take up salts from the soil which they have not vigour to assimilate.
When nitrates are found in the roots under such circumstances,
allowance should be made for the season and the slow or quick nature
of the manures employed. J. F.
Nitrates in Sugar-Beets. By J. A. Barral (BiecL Cenir., 1880,
44 — 4.5). — An English farmer sent to the French Agricultural Society
in December, 1878, a number of large beets, some of them weiehino-
14 kilos. They were found poor m sugar and were employed for feeding
purposes ; they were analysed, and it was found that nitrates were
most abundant in those which were poorest in sugar, the proportions
being very constant. The sugar manufacturers have for a lono- time
forbidden the use of nitrate of soda on the farms which supply them
with roots, and the author's researches prove them to be right, the
beets experimented on having been heavily manured with sodium
nitrate. He also believes that the feeding of cattle largely with such
roots would be attended with injurious consequences. In the follow-
ing table the amounts of nitrogen, nitrates, and sugar are the percen-
tages contained in the dry substance, the nitrates being calculated as
nitric acid : —
Name.
Weight
of root,
kilos.
Mammoth 14 'V>0
Berkshire 10 600
Ox-hcart 11-390
Tankard 8 "920
Yellow globe 1 2 082
Horn I 1-782
Giant ' 2 -444
White green top i 3 '124
White red top 0-730
Kohl Rabi 6 200
Dry
substance
per cent.
5-81
7-95
6-35
7-88
11-54
12-60
9-46
11-92
16-73
9-56
Nitrogen Nitric acid
per cent. per cent.
-54
13-
•27
4^
-44
9^.
-12
11-
-51
1^
■40
0-(
•75
o-(
•11
0^
•97
0^(
-33
4-.
89
98
21
39
37
64
68
13
09
55
Sugar.
17
25
31
12
34
31
52
58
48
20
21
16
50
92
66
75
86
72
10
92
J. F.
Beetroot. By P. Wagxer (Bied. Cenfr., 1879, 947).— Sugar beet-
root from various sources w'as examined ; the percentage of sugar
varied from 10—14. J. K. C.
Researches on Beetroot. By A. Baudeimont (Bied. Gentr.,
1879, 916). — On cutting open a beetroot, two series of concentric rings
are observed, the one white and opaque, the other clear, transparent,
and mostly coloured ; in the former the sugar is chiefly aggregated,
and in the latter the albumin. The author has endeavoured to pro-
mote the special growth of one or the other set of rings by the appli-
2 n 2
496 ABSTRACTS OF CHEMICAL PAPERS.
cation of suitable manures. The roots were grown on four plots of
land ; one of these was treated with water, the rest in order with so-
lutions of bicarbonate of ammonia, bicarbonate of potash, and a
mixture of these. It was observed that the roots which had been
watered with bicarbonate of potash solution were very large and hard,
and consisted chiefly of the sugar bearing rings ; those which had re-
ceived bicarbonate of ammonia were much softer, hollow in the
centre, and the albuminous rings were more strongly developed ; those
treated with a mixture of both were not so hard, and showed clear
albuminous rings, whilst those which had received water alone were
the strongest, and showed both kinds of rings clearly. J. K. C.
Composition of Ash of two kinds of Beet Seed. By H. Boden-
BENDER and Ihlee (Bied. Centr., 1879, 948). — In 100 parts of the seed
were contained (1) 7'80 and (2) 7'67 parts as ash.
The percentage composition of the ash was as follows : —
Na.p.
KoO.
CaO. MgO. FeoOs.
CI.
CO..
SO3.
RO5. SiO.,.
(1)
25-73
6-75
22-18 5-72 1-77
1-07
15-39
4-46
2-56 13-59
(2)
32-93
4-97
13-44 3-91 3-86
4-19
22-54
2-50
6-47 5-11
J. K. C.
Effect of Acid Gases on Vegetation. By R. Hasenclever (Bied.
Centr., 1880, 57 — 58). — The author has collected a number of analyses
of leaves of trees from the neighbourhood of chemical works, and
from districts where such manufactories are not carried on. The
results are interesting ; but consisting as they do of different kinds of
plants do not afford sufficient grounds for comparison, the author re-
commends the analysis of healthy and unhealthy plants from the same
neighbourhoods when complaints of damage from acid vapours are
made, and also wishes that the rain and air of such districts could be
compared with samples of the same from other localities. J. F.
Injury to Vegetation caused by Acid Gases. By J. Schroder
(Landiv. Vermclis.-Stat., 24, 392 — 421).— The author is of opinion
that Stockhardt's view is correct, namely, that the injurious effect of
smoke from smelting works, chemical works, and from coal fires, is
mainly due to sulphurous anhydride and other acid gaseous products.
Wood-smoke does not injure vegetation, and the less sulphur is pre-
sent in bituminous and brown coals the less injurious it is. A very
short exposure to acid gases produced perceptibly injurious effects on
the leaves ; an alcoholic extract of the leaves then shows the absorp-
tion-bands of acid chlorophyll. All plants thus damaged show a
diminished transpiration, depending on the amount of acid and time
of exposure.
^Numerous experiments show that sulphurous anhydride acts most
strongly in presence of light, warmth, and moisture, but darkness is
more efficacious as a preservative than dryness. Sulphui'ous anhy-
dride is strikingly worse than hydrochloric acid. Sulphuric acid is
less injurious than an equivalent amount of sulphurous anhydride, so
that oxidation of the sulphurous anhydride present in smoke by the
action of air and moisture is favourable.
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 497
Plants growing in an atmosphere containing sulpliurous anliydride
or hydrochloric acid show an excess of sulphur or chlorine respectively.
Thus a young fir-tree growing in the laboratory in presence of sul-
phurous anhydride gave in 100 parts of dry needles 0'72L of sulphuric
acid, whilst a healthy young tree gave 0"240 part. Different plant"?
do not suffer equally in presence of sulphurous anhydride. In the
following list those least influenced are placed first: — Oak, maple, ash,
alder, poplar, lime, birch, red beech ; then we have needle-leaved trees,
pine, fir. The list agrees with observations made in the neighbourhood
of metallurgical works. The effect of hydrochloric acid is probably
the same.
The amount of sulphur and chlorine in healthy plants may vary
within tolerably wide limits ; thus an alder grown under the water-
culture system gave 0'75 per cent, of sulphuric acid, whilst another
grown in the soil gave 0'19 per cent., both being healthy plants. The
presence of gypsum and salt in the soil affects the results of analysis ;
so that healthy plants grown under similar conditions as to soil should
be examined along with susjiected plants. Two maps of the Upper
Harte smelting district were shown. In one the district was coloured
to show the damage done to trees as determined by inspection. One
colour showed trees destroyed, or very seriously damaged, another
tint showed the region of trees perceptibly injured, and a third the
region in which the damage from smoke was somewhat questionable,
whilst a fourth tint showed the uninjured districts. 150 samples of
leaves were taken, and the sulphuric acid determined in them : those
giving O'o per cent, and upwards were found to fall within a district
marked out on the second map, those with from 0"5 to 0"3 occupied
another region, 0"3 to 0'21 a third, and all below 0"21 formed a fourth
region ; on comparing the two maps they were found to agree very
closely indeed. The samples were taken during a week of autumn in
1878, and were mainly of fir-needles. In the discussion following,
M. Freytag reported similar results founded on nearly 20 years' obser-
vation, but he was of opinion that sulphuric and hydrochloric acids
were more injurious than sulphurous anhydride. J. T.
Injurious Effect of Industrial Effluent Water and of Gases
on Soils and Plants. By J. Koxig {Bied. Centr., 1879, 504—567).—
The author shows the importance of ascertaining that the water used
for iri'igation is free from any constituent which has a prejudicial
action on vegetation. Effluent water from a zinc blende mine contains
an appreciable amount of zinc sulphate, formed by oxidation of the
sulphide, and the result of irrigating a meadow for sonae years with
a stream which received such effluent water was to cause a consider-
able decrease in the yearly produce. Moreover, certain parts of the
meadow became almost barren. The soil of the meadow was found to
contain O'lS — 0-964: per cent, zinc oxide, whilst the grass and plants
(beech and maple) gave 4"13 — 6-53 per cent, of ash and 0'037 — 0'15G
per cent, zinc oxide, which is equal to 0'86 — 2-78 per cent, in the
ash. The soil and the plants from the apparently sound part of the
meadow contained no zinc oxide.
The ash of three specimens of the white " erzblume " which grew
498 ABSTRACTS OF CHEMICAL PAPERS.
in places iu tlie meadow on
which zinc-
■ore had
been spil
respectively : —
Ash in dried plant
. 13-29
1275
9-29
Zinc oxide in the plant.
1-49
2-68
1-46
Zinc oxide in the ash .
. 1127
21-40
15-81
gave
Waste water from dye works, wire drawers, and from pyrites
washing has an injuiious action on vegetation : the first-named con-
tains a large quantity of sodium sulphate and organic colouring
matter, and the two last much ferrous sulphate ; the pyrites v/aste
water probably also contains a small quantity of free sulphuric acid.
The destructive influence of sulphurous acid fumes on plant life,
which is observable in the neighbourhood of chemical works, has been
investigated by the author, who states that the leaves, needles, and
young twigs of the trees are first affected, and that these injured
parts contain about 11 — 50 per cent, of sulphuric acid in excess of
the 'normal quantity, and a proportional increase in the amount of
ash. A. J. C.
Grass Mowing. By E. Wollny (Bled. Centr., 1879, 617—619).—
It is the custom of some agriculturists to discontinue mowing grass
land during a continuance of dry weather, as they hold the opinion
that the grass retains the moisture which would be removed by mow-
ing, and the after crop would be endangered in consequence. This
erroneous idea has no doubt arisen from the fact that the upper surface
of grass-covered land is damper than that of the fallow land (16-08
per cent, moisture against 11 -93 per cent, in the author's experiments) ;
but this is the case at the surface only, for at a lower stratum, whence
the plants replace the water which has evaporated from their upper
organs there is less moisture (22 54 per cent.) than from a similar
stratum (28-59 per cent.) m a fallow land. The conclusion which is
drawn from several experiments of the moisture contained at different
depths in grass land and in fallow land is, that the amount of moisture
in all kinds of soil covered with vegetation, grass for example, is
always less than that in the same soil which is not covered with vege-
tation. As it is the vegetation which dries up the soil, it necessarily
follows that the retention of the moisture is assured to the soil if the
mowing takes place under the above condition of weather.
A. J. C.
Relation of the Grasses of Meado-ws and Pastures. By
Speer (Bled. Gentr., 1879, 919 — 921;. — The author gives an account
of the various weeds, sour grasses, &c., occurring on meadow and
pasture land. J. K. C.
Digestibility of Steamed Hay. By U. Kreuslee and others
{Bled. Centr., 1880, 27 — 29). — Amongst the various methods em-
ployed for tjie cooking of fodder, none has hitherto been in use which
does not diminish the quantity of nutritive matter and injure its
digestibility ; this frequently happens when it is sought to make the
fodder more palatable and urge the animals to consume larger quanti-
ties. The usual methods are souring, fermenting, boiling, scalding,
VEGETABLE PHYSIOLOGY AND AGRICULTURE, 499
and steaming. The first two occasion a loss of the raw maferial, the
others diminish the digestibility and nutritive effect by tlie addition of
large quantities of water. Steaming appears to be the least deleterious.
Two oxen were chosen for purposes of experiment ; the quantities
given them were calculated from observation of their previous ordinary
consumption. The experiments were divided into three periods, when
the animals were fed first upon raw, secondly upon steamed, and
thirdly on damped hay.
Their consumption of water does not seem to have been affected by
the quantity taken up in the steamed or moistened fodder, the animals
consuming their normal quantity.
From the calculated results of the droppings, it appears that the
amount of protein substances digested in the raw and damped hay is
about the same, and much greater than is found in steamed hay.
The authors summarise thus : the steaming of hay diminishes
facility of digestion, is in fact injurious, and the desire of the animals
for it, which has been asserted, is not found, but on the contrary, the
animals liked the steamed hay less than either of the other kinds.
J. F.
Permanent Pasture a Substitute for Clover. By J. Godefroy
and others (llitd. C'entr., IbbU, 5U — 5o). — French agriculturists have
for many years found the soil in some localities worn out, and, as it is
called, " clover sick." On the other hand, foreign competition in
cattle rearing forces them to raise large quantities of fodder materials.
They have therefore turned their attention to laying down permanent
pastures, or at least meadows for two to five years. The experiments
of which this paper is the record, were carried out for this purpose,
and were made at St. Onen, near Pontoise, by two of the authors, and
at Yilleneuve le Roi by two others. The mixtures used were of
English origin, consisting of leguminous and graminivorous plants,
feseue rye-grass, &c. In one experiment the plot was divided into
two portions, one of them being manured with stable manure, the
other with artificial fertilizers ; the latter gave far better i-esults.
The observations are not complete, but so far they lead to the belief
that it is quite possible to lay down meadows which wdl yield excel-
lent crops the first year, with increasing produce the second and third
years. J, F.
Composition of Red Clover and Maize. By H. Weiske and
others {Bied. Gentr., IttbU, 4b — 48). — The clover plants were 25 days
old at the commencement of the observations, 24th May. Some of
them bloomed on 21st June, and 5th July the flowering was general,
and on 12th July it was nearly over. The nitrogen percentage de-
clined until the time of bloom, remained tolerably constant for a short
period, and then rapidly fell off ; the behaviour of the cellulose was
exactly the reverse. The sulphur and phosphorus compounds vary in
much the same manner as the nitrogen, but not with such regularity.
The figures show a steady progression in productive power until
the termination of the flowering period, when it ceases, except as
regards the cellulose. Therefore, when the plants were in blossom.
500 ABSTRACTS OF CHEMCAL PAPERS.
about the 5th July wonld have been the most economical period to cut
them.
The maize plants were observed from six days old, 24th May ; the
nitrogen diminished more quickly than in the case of the clover, and
more rapidly in the first than in the second half of the period of ob-
servation. The diminution in the nitrogen was, however, not accom-
panied by so large a formation of cellulose as in the clover, a large
proportion of the non-nitrogenous substances consisting of extractive
matter : as the secretion of nitrogenous substances ceases at an
early stage, the author thinks it economical to cut maize intended
for green fodder not later than the end of August, as is actually the
practice. J. F.
Nutritive Value of " Elodea canadensis." By W. Hoffmeister
(Bled. Centr., 1879, 915 — 916). — This plant (the water pest) is greedily
devoured by cattle ; when fresh it contains 12, and when air-dried
from 73 — 83 per cent, of solids. The composition of the solid con-
stituents was found to be as follows : —
Protein.
Fat.
Nitrogen
free extract.
Fibre.
Ash.
•
I—I
.. 17-37
2-32
44-17
16-98
19-22
2 ..
. . 19-56
2-26
41-48
16-54
20-16
The percentages of cellulose and starch were found to be 16 and
19-4 respectively. In nitrogenous constituents, water pest compares
favourably with clover. J. K. C.
Cotton-Seed Cake as Fodder. By Bitter (Bied. Gentr., 1878,
902). — Bitter found that by using this cake, the cows yielded more
milk and of a better quality. J. K. C.
Culture of the Lentil Vetch. By E. v. Bodiczky (Bied. Centr.,
1880, 49 — 50). — This plant, known under various names, has always
been considered in Germany a weed, Vicis ervilia. In sandy districts
of Spain, parts of Switzerland, and in the south of France, it has some-
times been sparingly cultivated as a winter fodder. It appears to be less
liable to injury from insects than peas and lentils, and can be cultivated
without supports, a circumstance not without weight.
The author is not enabled from actual experiment to pronounce an
opinion on the results of this crop under the climatic conditions of
Germany, his analyses having been made on French, Spanish, and
Grecian seeds.
Although the beans of this plant are a very valuable food, it is
chiefly employed as a green fodder and as hay, the tender stems and
numerous young fresh leaves rendering it peculiarly useful for the
purpose. A partial experiment showed a result — 2 hectoliters of seed
per hectare after two months, when the plants were in bloom — 13,700
kilos, green fodder, and 2,500 kilos, dry hay. Winter pease showed
4,500 and lentils 5,3U0 kilos. Considering the short time required to
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 501
bring this plant to maturity, and its suitability to ligbt sandy soils, it
is certainly worth some attention from practical farmers.
J. F.
Seeds of the Corn Cockle as Fodder and Distillery Material.
By E,. Ulbricht (Bied. Centr., 18SU, 34 — 3(3). — The seeds of this
plant, Agrostemma Gifhago, are largely bought by farmers on account
of its low price as a fodder material, and is also offered to distillers,
and sometimes purchased by them, notwithstanding it is known to
have frequently had very injurious effects.
Analyses of two samples show the nutritive properties of the
material to be very valuable, and in a chemical sense to stand about
equally between grain and leguminous plants, a prominent feature
being the large proportion of fat and the extraordinary quantity of
mineral matter, particularly potash and phosphoric acid, which is
higher than in any other grain yet analysed.
An old milch goat was fed with the grain of A. Githago, 300 to 500
grams given daily with clover hay. It was then fed for 12 days
entirely on the seeds. During the whole of this period there was no
disturbance of the animal's health, nor was the production of milk in
any way lessened ; but three weeks afterwards, when the animal had
been put back to her normal food, she sickened and died ; a post mortem
showed severe inflammation of the large intestine and lesion of the
spinal marrow.
A pig weighing 9'24 kilos., to whose food was added 20 — 100 grams
of the seed daily, died in 14 days, and showed a strong inflammation
of the coats of the stomach. Another and larger pig, weighing 12'32
kilos., was fed with gradually increased quantities of the material up
to 350 grams per day, gained weight and continued in good health.
Geese and ducks were also experimented on, but with negative results.
The observations show that great caution is necessary in the use of
this product for feeding purposes. The author believes that the
poisonous principle may be extracted in a manner similar to that in
which the bitterness is removed from lupins, but it is a thing of the
future, and might at the same time diminish the value of the article as
fodder.
The author made other experiments as to its value for distillery pur-
poses, but they are incomplete. J. P.
Digestibility and Nutritive Value of the Soja Bean. Bv H.
Wkiske and others (Bied. Cenfr., 1880, 30—31). — The experiments
were made on two full grown Southdown wethers with the object of
determining the food value of the article. Analysis shows the com-
position of the straw to resemble in valuable constituents that of good
meadow hay, and analysis of the excrement of the animals shows that
a large proportion was digested. The cultivation of this bean is very
largely carried on in Germany ; it yields a large produce, and these
experiments prove it to be a valuable addition to the fodder materials
at the farmers' command. J. F.
Flesh-meal as Fodder for Milch Cows. By Fehlau (Bied.
Centr., 1879, 590).— Flesh-meal added to other stall-fodder in the
502 ABSTRACTS OF CHEMICAL PAPERS.
daily proportion of 0"5 kilo, per cow, increased the yield of milk'and
the weight of" the cow when compared with the results obtained from
cows that received no flesh-meal, but its comparative action on the
same cows was not ascertained. A. J. C.
Spent Hops as a Fodder for Cattle. By M. Maercker and E.
Wein (liiud. Ceutr., 1879, 60l — 6l'2). — Spent hops are recommended
as a valuable addition to lich nitrogenous cattle fodder, such as
grains, &c., on account of the large amount of extractive matter they
contain, viz., 4o"UG per cent, soluble in water, which contained 14'7l per
cent, sugar from the wort ; 339 per cent, protein, and 2"05 ash. Wein's
analysis further showed water ll'ti percent., fat 4'52 percent., ash 3"39
per cent., protein i-i'OG per cent., fibre 16"39 per cent., non-nitro-
genous matter 50'08 per cent, (see also this Journal, Abst., 1879,
1050). A. J. C.
Spent Hops as Fodder. By H. Weiske and others (Bled. Centr.,
1879, 906 — 908). — Further researches confirm the results already pub-
lislied that spent hops do not make good fodder, although in unfavour-
able seasons they may be useful. J. K. C.
Cacao Rind as Fodder for Calves. By Samek (Bled. Centr.,
1879, 9lG). — The milk was gradually replaced by extract of cacao
rind in the fodder of calves. The animals appeared to thrive on
the change of diet, although they showed considerable distaste for it.
An analj'sis of the pulverised rind gave the following results. In 100
parts substance : — -
Nitrogen
Water. Ash. Protein. Fat. Fibre. free extract.
11-13 7-28 25-87 8-22 13-35 34-15
J. K. C.
Influence of the Potato Blossom on the Amount of Pro-
duce. (Bied. Centr., 1879, G34). — 2u8 centrs. 19 lbs. of tubers were
obtained fi-om potato plants from which the blossom had been re-
moved and only 181 centrs. 49 lbs. of tubers from plants not so
treated. A. J. C.
Gro-wth of Beets. By P. Behrend and A. Morgen {Bied. Centr.,
1879, Gi2 — GloJ. — TUe results of the analyses show that a better pro-
duce was obtained from a sandy soil than from a beet soil. The
amount of sugar in the two cases from two varieties of beets was
from a sandy soil 10-4G and 13-90 jjer cent., from a beet soil 8-35 and
8-39 per cent. A. J. C.
Planting of Sugar Beets. By J. Haxamann {Bied. Centr., 1879,
614 — ol7j. — The experiments were made on seven different kinds of
soil and with seed under various conditions of sowing, and the results
confirm what has been stated previously by other observers that in thick
sowing — in the author's experiments the minimum area to each plant
was 555 square cms. and the maximum 1,000 square cms. — the produce
VEGETABLE PHYSIOLOGY AND AGRICLXTURE. 503
of the beet crop is smaller in quantity, bat of Higher value in the amount
of sugar and in the density and purity of the juice than in thin sow-
ing. According to the space allotted to each plant it was found that
on one and the same soil the sugar quotient varied from 86 — 91 per
cent, and in another case from 88 — 98 per cent., and this important
sugar factor is said to be more affected thereby than by the manuring
or even by the kind of beet grown. The distance between the plants
should be small on a humid and matured land, but great on a dry,
high ground and poor soils. A. J. C.
Results with Stall-feeding of Sheep. By F. Schxoekenpfeil
(Bled. Centr., 1880, 33 — 34). — The feeding of 10 sheep for purposes
of exhibition allowed the following comparison between the results of
tbeir luxurious feeding and that of other members of the same flock
ordinarily foddered. The tlock consisted of 247 Southdown Merinos,
which were well fed and cared ; tive of the best formed wethers and.
five two-year old ewes were carefully selected for stall-feeding. Up
to 13th of January they received the same food as the remainder of
the flock, and on that day were shorn and yielded 3'87o kilos, of wool
in the grease ; from this day they had unlimited supplies of peas, lin-
seed cake, and rye bread, out of constantly replenished mangers. Each
day they were littered and fed four times, and each morning the litter
removed. From_ the beginning of May, in order to increase their ap-
petite, the turnips and acorns were sliced and pared and the crust
removed from the bread ; about the 20th of May the animals took an
instinctive dislike to over-feeding, but it was continued, and on the
11th of November the 10 sheep were valued ; the result was, all costs
of feeding calculated, a sm-plus of the stall-fed over the ordinary
sheep of 15'14 marks each.
The author thinks that it would pay the farmer to liberally nourish
sheep of good breeds with food similar to human food and in large
quantities, even so far as to supply it ad lihituru, if the farmer could
find a ready outlet for the unconsumed fodder. J, i\
Decomposition of Silicates. By J. Lemberg (Bied. Centr., 1879,
567 — 577j. — In the first part of the original paper, of which this is an
abstract, the author gives a series of analyses of minerals in various
conditions of decomposition. His experiments on the absorptive power
of soils lead him to the conclusion that it is a purely chemical action,
in which the influence of mass is to be regarded according to Berthel-
lot's views. On account of the complex character of sods and the dif-
ferent behaviour of one and the same silicate towards different solu-
tions of salts, it is impossible to express the absorptive action by an
empirical rule. The decreased absorptive power which a calcined soil
has, cannot be due to the decomposition of humus substances or to an
alteration in the capillarity of the soil. It is even possible that many
kinds of soils have their absorptive power for some substances increased
after calcination.
By treating a potassium silicate with an aqueous solution of car-
bonic acid, the greater part of the potash is abstracted, hence it is
504 ABSTRACTS OF CHEMICAL PAPERS.
assumed tliat basic water has been substituted for tlie potasTi, and as
a silicate so treated can re- absorb the base, tbe author concludes that
the strong absorptive power of such soils for free potash is partly due
to the re-formation of the decomposed silicate by the substitution of
basic water by the fixed base. This action is more complicated in the
soil, as a part of the potash combines with free silicic acid to form a
soluble silicate, which again combines with hydrated alumina and
kaolin compounds ; therefore it would be expected that a calcined soil
having lost its basic water has undergone a great decrease in its power
to absorb free potash.
The supposition that potassium carbonate, when brought into con-
tact with a silicate which has been deprived of the greater part of its
jDotash by the action of carbonic acid water is partly detomposed into
free carbonic acid and potash, which latter is taken up by the silicate,
was confirmed by a series of experiments which showed that the sili-
cate behaved in fact as an acid salt, the carbonic anhydride and the
silicate being apportioned to the potash according to their mass and
affinity. The substitution of basic water by a fixed base, and moreover
the possibility of the direct addition of alkaline carbonates to silicates
without substitution, explain the fact that in many cases more sub-
stances are absorbed by a soil than correspond with the substances
eliminated. As ammonia behaves similarly to potash in the replace-
ment of basic water in silicates, the absori^tion by a soil of free am-
monia cannot be regarded as favouring the theory of mechanical absorp-
tion, nor can the retention by a soil of easily soluble salts. W. Knop's
method for estimating humus substances in soils {Landw. VersucJis.-
Stat., 8, 40), which consists in treating the soil with an ammoniacal
solution of calcium nitrate and calculating the amount absorbed as
calcium humate, would, according to the author's statement, give
incorrect results, as silicates containing basic water behave like weak
acids, and in this case would retain the lime which would be incor-
rectly calculated as humate.
The author controverts at some length the various points which are
alleged by some observers to be evidence in favour of the theory of
mechanical absorption. It is evident that silicates in soils undergo the
same metamorphosis as all other minerals without exceyjtion, but a part
of the silicate is specially prone to enter into chemical exchange with
dissolved substances. Silicates of the zeolite class are among the most
rapid absorbents, and on this account Mulder has placed the absorbing
silicates in this category ; but this property is not confined to zeolites,
being possessed by several felspatic silicates.
The author disagrees with the statement of A. Knop that micaceous
silicates are produced in a soil by the absorption of potash, also with
the sxipposition that the degree of absorption is in concordance with
the amount of bases dissolvable by dilute acids, showing that although
silicates, which quickly undergo change with solutions of salts, are easily
decomposed by weak acids, yet the contrary fact does not necessarily
follow. The degree of absorption is quite arbitrary, and depends
rather on the substance employed ; some constituents of soils can
quickly absorb potash, others again behave altogether differently. It
is rather the rule that minerals which are decomposed with difficulty
VEGETABLE PHYSIOLOGY AXD AGRICULTURE. 505
by acids very slowly undergo chemical cLange, but this only occurs so
long as the period of action is proportionally short.
Potash is more readily absorbed by soils and silicates than lime,
magnesia, or soda. If a silicate which contains potash and soda be
decomposed by carbonic acid water, the soda is always the first base
abstracted ; again, the latter is frequently replaced in a soil by potash,
but potash is seldom replaced by soda.
The fusion of silicates with fusible salts of the alkalis, alkaline
earths, and of iron, is analogous in its chemical action to that of an
aqueous solution of the salt at the ordinary temperature.
A. J. C.
Free Carbonic Anhydride in Soils. By J. Moller {Bied. Gentr.,
1879, 631). — The amount of carbonic anhydride in the air in soils is
not much above that contained in the atmosphere. Organic soils con-
tain in themselves a constant source of carbonic anhydride, and the
external conditions remaining the same its formation there proceeds
without much variation. Dry quartz sand has not the property like
other kinds of soils of condensing carbonic anhydride, the amount of
which in soils is dependent to a great extent on the porosity of the
soil and the natui'e of its stratification. It decreases in amount as the
soil dries up, but a damp soil produces as much as a soil saturated
with water ; rainfall causes an increase at first, but it quickly declines
in proportion to the rate of surface-evaporation ; the carbonic anhy-
dride absorbed by the rain is set free and enriches the atmosphere of
the soil. The amount of carbonic anhydride does not perceptibly in-
crease with the depth of the soil ; it is higher in unmanured than in
manured soils. A. J. C.
Clover Sickness. By A. Emmerling and R. Wagner {Bied.
Cent)-., 1879, 578 — 582). — The I'esults of the analyses of the soil and
of the ash of the affected red clover at first seemed to indicate that the
cause of the disease was due to the poorness of the soil in potash, but
further investigation, more especially the results obtained with white
clover growing in the same soil, showed that no direct conclusions
could be drawn from the chemical examination. In this particular
instance the clover sickness is ascribed to a want of proper culture of
the plant. Red clover requires a matured soil, deeply tilled, damp,
and in good culture ; it seldom repays direct dunging. The land had
only been for a short time in cultivation, and having regard to its
stony nature had not been tilled sufficiently deep ; whilst in many-
parts the soil was poor in humus, and contained an abundance of lime,
a state conducive to sterility. The general conditions of the soil beino-
unfavourable to the growth of red clover, the plant was less able to
endure the povei-ty of the soil in potash.
White clover requires very different conditions ; it thrives in soils
not so deep and less cultivated, and once planted, it withstands the
summer di'oughts.
The remedy to be generally applied is to increase the amount of
humus and nitrogenous matter, to give a supply of phosphoric acid
and potash with greater depth of soil.
50G ABSTRACTS OF CHEMICAL PAPERS.
The poorness of the soil hpA exercised no perceptible influence on
the composition of the organic constituents of the clover.
A. J. C.
Manures for Cabbages and Fruit Trees. By Lauche (Biecl
Centr., 1879, 591—593).
Amount of Nitrogen in Forest Trees, and in the Under Litter
of Leaves. By J. Schroder (B;ed. Centr., 1879, 634— 635).— The
avernfe amount of nitrogen required to be supplied to forest trees is
aboutequal to that given to stalk crops in the form of manure. This
is supplied to the former in the under litter of leaves, which serves
the same purpose to the trees as artificial manures to field crops, both
in its supply of nitrogen and ash constituents. Hence the importance
of not removing the under litter. A. J. C.
Employment of Peat as Manure. By T. Neelinger (Bied.
Centr., 1879, 883 — 885). — Direct application of peat alone to sandy
soils does not give such good results as to allow of dispensing with,
other kinds of manure, although the yield obtained is greater than if
the soil had not been manured at all. The author recommends that
before use the peat should be first mixed with, lime and stable drain-
incs. "• ^- ^'
D
Guano from the Island of Ichaboe. By B. C. Niederstadt
(Lruiihv. Ver-'^rirli.'^.-Sfat., 24, 269 — 270). — The gnano is quite recent
as a rule ; the nitrogen is mainly in organic combination. An original
sample, known in commerce as " ammonia-fixed Ichaboe guano," No. 2,
was analysed witb tbe following result : —
CaO. Fe.Oa. MgO. Sand. KCl. NaCl. P2O5.
21-04 1-52 0-65 3-35 1-40 3-25 —
Total. 11'25 (8'13 soluble, 3'12 insoluble) ; organic compounds, 21'46
(with 7'99 of N, of wliicb 2'89 was present as ammonia) ; SO3, 20'33,
moisture at 105°, 1575 per cent. = lOO'OO. J. T.
Natural Phosphates and their Value in Agriculture. By J.
Haxaman^' (Bied. Centr., 1879, 631—632).
Experiments with Artificial Manures. By v. Bulow (Bied.
Centr., 1880, 18 — 21). — This paper gives the results of certain experi-
ments on manuring potatoes and beetroots, carried out at the instance
of an agricultural society in Posen.
For the potatoes, the soil was well dug in with strong stable manure
in the autumn, left fallow until the following May, and then divided
into three portions, the first of which received no artificial manure, the
second was treated with nitrate of soda only, the third received equal
parts of 20 per cent, superphosphate and nitrate of soda. The several
quantities dug were : — Unmanui-ed plot, 89, Schifflast ; nitrate, 102 ;
nitrate and superphosphate, 107. It follows that the employment of
nitrate of soda with potatoes pays, the addition of superphosphate
increases the yield, but at a greatly augmented cost, and could only be
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 507
recn-mmended on larsre distillery farms, where the freight of a quan-
litv would be an appreciable consideration.
In the experiments with beetroots, a very similar conrse was pursued.
In the autumn, the plot which contained some unfavourable soil, was
well tilled with plenty of cowdung. In the spring of the following
year, three plots were measured off, and all treated with artificial
manures. No. 1 with 100 lbs. superphosphate; No. 2, 100 lbs. super-
phosphate, and 400 lbs. kainit ; No. 3, 100 lbs. superphosphate, and
150 lbs. nitrate soda ; another plot received no artificial manure; the
seeds were carefully sown and tended, hoed, and cultivated. The
results were: without artificials, 200o0 centner ; with superphosphate,
226 92 ; superphosphate and potash, 243 ; superphosphate and nitrate
soda, 25970.
Everything calculated and allowed for, the additional cost of the
artificial manures was fully paid, and the three plots left a surplus ;
the superphosphate paid the best, and in localities where beets are
largely raised, and the value of them at least 1 mark per centner, super-
phosphate would amply repay liberal use. J. F.
Chili Potash Saltpetre. By G-. Drechsler {Bied. Centr., 1879,
682 — 584). — The application of this manure, which contained
34"26 p.c. potassium nitrate, and oG"18 p.c. sodium nitrate, to sugar
beets, increased the amount of sugar in the beet by 2"11 and 1"47 p.c.
above that yielded by beets that were unmanured and manured with
Chili saltpetre respectively. A. J. C.
Manure Experiments with Superphosphate and Chili Salt-
petre. By Count Schwerin-Putzar (Bied. Centr., 1879, 584 — 585). —
Chili saltpetre as a manure for rye, especially on ill-conditioned land,
gives a greater produce than superphosphate. A. J. C.
Lupine Seeds as a Manure. By A. Selmi, C. Costa-Reghixi and
F. Oppenau (Bied. Centr., 1879, 585 — 587). — An experimental inquiry
as to the relative value of lupine seeds in comparison with bone meal
and linseed cake meal mixed with sewage, in which the results are in
favour of the first named. Details are given, showing the pecuniary
profit accruing from the produce (beans and maize) by the use of each
kind of manure. A. J. C.
Action of Various Manures on the Composition of Must.
By E RoTOXDi and A. Galimberti (Bied. Ctvtr., 1879, 590—591). —
The manures employed were respectively lime phosphate, a mixture of
equal parts of lime phosphate, potassium nitrate, and gypsum ; potassium
nitrate, potassium chloride, sodium nitrate, and ammonium sulphate.
The conclusions are (a) that the must of the manured vines is slightly
richer in suo-ar than that of the unmanured ; (h) potash in combina-
tion with chlorine appears the most materially to increase the amount
of sugar in the must ; (c) lime phosphate apparently increases the
tartar, and lessens the amount of free tartaric acid. There is no rela-
tion between the total acidity of the must and the manure employed.
508 ABSTRACTS OF CHEMICAL PAPERS.
The ash of the must was increased by all the manures, more espe-
cially by potassium chloride, and less so by sodium nitrate.
Manuring Experiments on Wheat and Rye. By A. Thaer
(Bied. Centr., 1879, 94-5). — The manures used were as follows: —
Decomposed guano, with 10 p. c. of soluble phosphoric acid, and the
same quantity of nitrogen ; dried bone-meal, with 20 p. c. of phosphoric
acid. From each half acre were obtained —
Wlieat.
Grains. Straw. Chaff. Total.
Kilos. Kilos. Kilos. Kilos.
Unmanured 161-0 .340 43-0 549
With guano 232-5 480 60-5 773
Bye.
With guano 251-0 720 45 1016-0
With bone-meal . . 222-5 714 42 983-5
J. K. C.
Manuring of Oats. By Brenning {Bied. Centr., 1879, 881—882).
— The soil on which the experiments were conducted had been sown in
1877 with potatoes, and in 1878 with rye. In the spring of 1879 it
was divided into eight plots, of 518 square meters each, and treated
in the following way : — ISTo. 1 was unmanured ; No. 2 received
3-75 kilos, soluble phosphoric acid ; N"o. 3 was manured with 2*25 kilos,
nitrogen as ammonia, and 225 kilos, soluble phosphoric acid ; No. 4,
with 5 kilos, soluble phosphoric acid (as guano-superphosphate) ; No. 5,
2 kilos, nitrogen, as nitrate of soda ; No. 6, 1-95 kilo, nitrogen (in the
form of decomposed guano), and 7-38 kilos, soluble phosphoric acid;
No. 7, 1-75 kilo, nitrogen, and 2*38 kilos, soluble phosphoric acid, both
in the form of decomposed guano ; No. 8, 1-95 kilo, soluble phosphoric
acid, and 1'60 kilo, nitrogen as nitrate of soda.
The oats on plots 3, 5, 6, 7, and 8 thrived the best, having a darker
colour and better growth than the plants on the other plots. On
plot 4, the plants had during the whole time of growth a very poor
appearance, and were more backward than those on the unmanured
plot. The following yields were obtained : —
Total
weight of
Plot. Grootl oats. Poor oats. corn. Straw. Chaff.
Kilos. Kilos. Kilos. Kilos. Kilos.
1 1470 15-5 162-5 3125 11-5
2 145-5 6-0 151-5 283-0 10-0
. 3 166-5 17-5 1840 3460 12*5
4 110-0 8-0 118-0 20575 11-25
5 170-0 12-5 182-5 325-0 10-0
6 149-5 12-0 161-5 309-0 10-0
7 159-5 80 167-5 3-20-0 15-0
8 156-0 11-0 1670 250-0 13-0
J. K. C.
ANALYTICAL CHEMISTRY. 509
Manuring of Beetroot, By J. HAXAMA>^y (Bied. Centr., 1879,
91 7 — 919)- — As the results of three years' experiments on the manuring
of beet, the author finds that in the ripe plant there is a constant i-ela-
tion between the sugar produced and the potash absorbed by the root of
about 100 to 2 ; and that a strong nitrogenous manure in a calcareous
soil produces the same effect as potash. No constant relation between
the phosphoric acid and sugar was observed. J. K. C.
Effect of Manures on Growth of Larches and Pines. By
Hkss and L. Hampel (Bled. Centr., 1880, 21 — :23j. — This paper gives
the results of two sets of experiments ; one by Hess, on the effect of
manures on the growth of larch seedlings, carried out in the Collegiate
Gardens at Giessen ; and the other by L. Hampel on pine seedlings,
at Gusswerk, in Austria.
In both cases, three garden beds were prepared, one left unmanured
and the other two manui'ed. The results show a balance in favour of
the latter, but the differences are not very striking and the experi-
ments not sufficiently extensive to base any broad conclusions on.
J. F.
Analytical Chemistry.
Method of Measuring High Temperatures. By J. M. Crafts
and F. Meier (Compt. rend., 90, 606— G08).— This method is de-
signed specially to determine the temperature employed when using
V. Meyer's method of determining vapour-densities, but is generally
applicable to other cases. A tube of glass or platinum is passed down
to the bottom, of the apparatus, and the air is driven out by a cur-
rent of some easily absorbable gas, collected in a eudiometer, and
measured at the ordinary temperature. The vapour-density determi-
nation is made immediately afterwards in the same apparatus, as soon
as the gas has been displaced by dry air or nitrogen. Hydrochloric
acid gas is preferable, since its complete absorption by water serves as
an indication of the total expulsion of the air. This gas does not
attack glass or porcelain vessels, and is not dissociated at 1300°. In
calculating tbe temperature, the apparatus must be regarded as con-
sisting of two parts, one of which is at the temperature to be measured,
whilst the other is at some lower temperature. The method gives
satisfactory results. C. H. B.
Detection and Estimation of Chlorine in presence of Iodine
and Bromine. By G. Vortjiann (Ber., 13, 32.5— 326).— The method
proposed is based on the different behaviour of the halogen elements
towards the peroxides of lead and manganese in the presence of acetic
acid. Iodides are decomposed by the oxides even in a neutral solu-
tion, and the separation of the iodine is complete if the liquid be boiled
with acetic acid. When peroxide of lead is employed, a portion of the
VOL. xxxviii. " 2 0
bio ABSTRACTS OF CHEMICAL PAPERS.
iodine is converted into iodic acid, whereas this is not the case with
peroxide of manganese. Bromides are not decomposed by either
oxide in a neutral solution. In acetic acid solution only the lead per-
oxide causes tbe separation of the bromine, the other oxide having no
action, and only in the presence of large quantities of bromine is any
bromic acid formed. Chlorides, on the other hand, are affected by
neither oxide either in neutral or acetic acid solution.
In order to detect chlorine then in the presence of the other halo-
gens, the substance is boiled with lead peroxide and acetic acid until
the liquid becomes colourless, and smells no longer of bromine or
iodine, any iodic acid which may have been formed is got rid of by
filtering the mixture from the lead iodate and the excess of oxide used.
The filtrate now contains all the chlorine free from both bromine and
iodine. The method also serves for the quantitative determination of
chlorine in presence of the other two halogens.
When the chlorine is present in large quantity together with iodine,
it is better to use manganese peroxide so as to avoid tlie formation of
the difficultly soluble lead chloride ; and when there is a large
quantity of chlorine together with bromine, a little potassium sulphate
should be used along with the lead peroxide, so that all the chloride
may be present as potassium salt. T. C.
Parkes's Method of Estimating Copper. By R. Ulbricht
(Landtv. Versuclis.-Stat., 24, 253 — 267). — The first and only part here
given of an article on must arid wine analyses is taken up with detailed
results of an examination of Parkes's method. Very good results are
obtained when the standardising of the cyanide solution and titration
of the copper solution are made under the same conditions, that is,
when in both cases the same quantity of nitric acid, the same quantity
of free ammonia, and the same quantity of ammonium salts are
pi'esent ; also when the resulting solutions have the same volume, the
cyanide solution is added in the same time and in the same manner,
and the amount of copper is about the same in both. The cyanide solu-
tion is standardised daily. Under these conditions the method serves
very well for the determination of the copper precipitated by Fehling's
sugar determination process. J. T.
Use of Smithson's Pile for the Detection of Mercury in
Mineral Waters. By J. Lefort (Compt. rend., 90, 141 — 143).—
Ortila objected to the voltaic couple of tin and gold, devised by Dr.
Smithson for the detection of small quantities of mercury, alleging
that when it was allowed to remain for some time in the suspected
solution, traces of tin were dissolved, which, re-depositing upon the
gold plate, caused the latter to become whitened even in absence of
mercury.
The author shows that this deposition of the tin is liable to take
place, but that no real error can result, since the metal not being vola-
tile cannot be sublimed, there is therefore no sublimate to be sub-
mitted to the vapour of iodine, whereby an essential part of the
operation as conducted by Smithson is omitted. Such, however, is
not the case with arsenical solutions ; the arsenic deposits upon
ANALYTICAL CHEMISTRY. 511
the gold with great readiness, and the coated foil when heated in
a closed tube, yields a sublimate, which, although not exactly I'esem-
bling the mercurial sublimate, becomes red from formation of arsenic
iodide, when acted on by iodine vapour. The colour of the arsenic
iodide under these conditions is very similar to that of mercuric iodide,
and it becomes necessary to use the microscope in order to distinguish
them.
The wat«r from the Rocher spring at St, Nectaire (Puy-de-D6me)
was examined by this process some time ago, and was stated to con-
tain mercury ; this statement is now contradicted, it being shown to
contain arsenic and not mercury.
In a similar manner, the presence of arsenic has been detected
in the mineral water of Bourboule ; and doubtless this element
might be shown to be present in many other waters if they were
carefully examined by this process, or by some other method of equal
delicacy. J. W.
Separation of Minerals of Greater Density than Quartz, by
means of Fused Mixtures of Lead and Zinc Chlorides. By R.
Bkkox (Comjit. rend., 90, G2G — 027). — The density of lead chloride in.
a state of fusion is 5, of zinc chloride 2"4 ; by mixing these two sub-
stances, a liquid of any required density between the two extremes is
easily obtained and may be employed to separate minerals of different
densities. The mixture of salts is fused in a test-tube, and the powdered
mineral is thrown in little by little : after some time the tube is allowed
to cool, and is then broken. In this way, a solid cylinder is obtained
in which the various minerals are arranged in the order of their
densities. The lead and zinc salts may be easily removed by boiling
with pure water or with dilute acetic acid. C. H. B.
Physico-chemical Analysis of Clay-soils. By F. Sestini {Gaz-
zetta, 10, 57). — The author regards Schloesing's method (Compt.
rend., 78, 1276), although tedious and troublesome, as the only one
which permits of a satisfactory determination of the amount of clay in
a soil. He finds, however, that it is better to give twelve washings
instead of six, and to diminish the time of settling from 24 to 12
hours. He also recommends that a camel's hair pencil should be used
when rubbing up the soil with the water. In this way very satisfac-
tory rssults are obtained. C. E. G.
Physico-chemical Analysis of Clay-soils. By N. Pellegrini
(^Landiv. Versuchs.-Stat., 25, 48 — 52). — The author compares the
methods of Noebel and Schloesing. With a clay- soil from Orciano,
near Pisa, Noebel's method gave sand 1"471 per cent., clayey consti-
tuents 87'315, soluble and Joss 1'560, organic and volatile 9'654.
Schloesing's for the same clay gave sandy constituents 32075 per
cent., clayey 37'670, earthy carbonates 20"200, organic and volatile
10'255. With the same soil, Masure's method gave sandy constituents
13"358, clayey constituents 71'899. Knop's method, sandy constituents
21-208, clayey constituents 64'432 ; the differences are enormous.
Schloesiug's method is the best. J. T.
512 ABSTRA-CTS OF CHEMICAL PAPERS.
Estimation of Glycerol in Wine. By H. Raynaud (Bidl. Soc.
'■Ghim. [2], 33, 259— 262).— The wiue is evaporated to one- fifth of its
original volume, and the alkalis precipitated with hjdrofluosilicic
acid and alcohol. The filtered solution is treated with a slight excess
of baryta, mixed with sand and evaporated in a vacuum. The residue
is extracted with a mixture of equal volumes of alcohol and ether; the
extract is evaporated, and the residue kept in a vacuum over phos-
phoric anhydride for 24 hours to eliminate the last traces of moisture
and then weighed. The glycerol obtained sometimes leaves an ash on
evaporation. The impure glycerol, after extracting the alkalis, does
not contain one-tenth of its weight of non-volatile substances.
L. T. O'S.
Estimation of Glucose. By Battandier (/. Pharm. Chim. [5],
1, 221—222). — Grlucose in urine may be estimated with greater cer-
tainty by using ammoniacal Fehling's solution than with the ordinary
solution. 100 c.c. of Pehlins:'s solution are treated with 250 c.c. ammo-
Ilia, and the mixture made up to 1 liter. 200 c.c. of this solution (= O'lO
grain glucose) are put in a flask, provided with a cork in which two
tubes are inserted, one is connected with a Mohr's burette containing
tbe urine, the other allows access to the air. The contents of the
flask are brought to boiling, and the urine added drop by drop from
the burette until the colour of the solution disappears.
L. T. O'S.
Volumetric Estimation of Sugar by an Ammoniacal Copper
Test, giving Reduction without Precipitation. By F. W. Pavy
{Proc. Hoy. Soo., 28, 260). — By adding ammonia to Fehling's solution,
a clear blue solution is obtained which is reduced by sugar to a per-
fectly colourless solution without any precipitation of cuprous oxide.
With the solution prepared in this way, it is found that 1 atom of
sugar reduces 6 atoms of cupric oxide instead of S. When, however,
caustic potash^ in the proportion of 5 grams to 20 c.c. of the ammo-
niated test (one-tenth of Fehling's solution), was added, the amount of
copper reduced was brought back to the normal 5 atoms.
c. w. w.
Estimation of Starch in Potatoes. By Siewert (Landw.
Yersuchs.-lStat., 24, 427 — 431). — The author criticises methods given
by Heidepriem and Holdefleiss, and remarks that his results differ
fi'om those of Maercker. He treats the potato cut up into small
])ieces with li- per cent, solution of tartaric acid for four hours on a
]>araffin-bath at 112 — 115° C, sliaking it frequently. After cooling, it
is made up to a fixed volume, filtei-ed, and a measured volume again
heated gradually with 30 drops of concenti'ated sulphuric acid up to a
temperature of 112 — 115° C, by which the sugar becomes inserted.
A slight excess of Fehling's solution is used, and the cuprous oxide
filtered off, roasted for 1 — 1^ hours, and weighed until constant.
By this process, the use of diastase and two sugar determinations is
avoided. At a lower temperature than 110° C, and in less than four
hours, all the starch is not converted into sugar ; whilst at a tempera-
ture above 115° C, the liquid begins to be discoloured : on heating for
six hours, most of the sugar is inverted. J. T.
AXALYTICAL CHEMISTRY. 513
Estimation of Starch in Potatoes. By P. Behrexd, M.
Maeecker, and A. Morgex (Landw. VersiKhs.-Stat., 25, 107 — 165). —
The authors find that all the starch can be extracted by water alone
by heating at 135 — 140° G. for four hours, and after cooling to 90°,
filtering it quickly through an asbestos plug by the aid of a Bunsen
pump. To convert into sugar, the filtrate is heated with hydrochloric
acid on the water- bath for three hours. After ?(etir?;/ neutralising with
potash solution, lead acetate is added, the precipitate separated by
filtration, and the excess of lead removed by sulphuric acid. The
sugar is determined by Fehling's solution, which only gives good
results when' used under constant conditions. The precipitated copper
oxide is reduced in hydrogen and weighed as metal. Working always
with the same volume of Fehling's solution and sugar solution, the
amount of sugar is obtained from the weight of copper by reference
to a curve previously prepared.
The amount of starch averages about 5' 75 per cent, less than the
dry substances in the potato, but the amount can only be very roughly
estimated from the specific gravity. J, T.
Estimation of Urea. By A. FArcoNxiER (Bull Soc. Chim. [2],
33, 103 — 105).- — On repeating the experiments of Mehu on the action
of alkaline hypochlorites and hypobromites on urea in presence of
saccharose and glucose, the author confirms the results of Esbach,
that the theoretical quantity of nitrogen is not evolved when saccha-
rose is present ; but in presence of glucose, results corresponding with
theory were obtained. This is due to the formation of a small
quantity of nitric acid which is reduced by glucose, but not attacked
by saccharose. L. T. O'S.
Estimation of Urea in Urine, By Jay (Bull. Soc. Chim. [2], 33,
105 — lOG). — The quantity of gas evolved by urea when treated with
sodium hypobromite, is influenced by the quantity of cane-sugar
present, notwithstanding that cane-sugar alone when treated with
sodium hypobromite yields no gas. When grape-sugar is treated with
sodium hypobromite, appreciable quantities of gas are evolved^; con-
sequently,, neither cane-sugar nor glucose can be emploj-ed in tlig
determination of urea. L. T. O'S.
Lactic Fermentation. By P. Cazeneute (/. Pharm. Chim. [5],
1,212 — 215j. — Saccharose, glucose, and lactose, in presence of urine
in which the urea is converted into ammonium carbonate, undergo
lactic fermentation, which, if sufiicient sugar i& present, continues
until all the ammonia is converted into ammonium lactate. The
microscopic examination has .shown that besides bacteria, the lactic
ferment discovered by Pasteur is present ; and experiment proves that
dilute urine is best suited for its development. In estimating glucose
in diabetic urine, errors are likely to occur from this source.
L. T. O'S.
Estimation of Non-albuminous Nitrogen- compounds in.
Plants. By 0. Kellxer {Landw. Verstcchs.-Stat., 24,. 439—453).—
The author discusses various methods, but gets the best results with
2 0 2
514 ABSTRACTS OF CHEMICAL PAPERS.
the following : — Ten grams of the finely pulverised substance is heated
for Ij — li hours with 300 c.c. of a 30 — 40 percent, solution of alcohol
containing a few drops of acetic acid ; after cooling, an aliquot
part is taken, filtered, evaporated, taken up with water, and treated
with lead acetate to precipitate albuminous compounds. Kern pro-
posed phosphotungstic acid, instead of lead acetate, but the author
found that they gave almost identical results, except in the case of
plants containing alkaloids, as peptones were found to be absent from
the extracts, or present in traces only. The different results given by
the two methods will serve as a direct measure of the amount of
alkaloid nitrogen present in the plant during the period of flowering
and afterwards; but during earlier plant- life, the presence of peptone,
not precipitated by lead acetate, gives a difference in the results. To
the alkaloids and peptones, a third nitrogen-compound must be added,
whose presence has frequently been observed, namely, nitric acid; in
cases where it occurs, a slight loss in nitrogen may result on evapo-
rating the acid plant extract, due to the reaction of nitric acid on amides.
The nitrates should be decomposed before evaporating by dropping the
extract into a solution of ferrous chloride, mixed with hydrochloric
acid, and heated on the water-bath ; the residue is heated for ten
minutes at a temperature of 100°. The nitrogen is then determined
in the residue. J. T.
Analysis of Milk. By L. Janke (Bied. Centr., 1879, 927).— The
author remarks that a very large number of analyses at various times
should be made for each locality, in order to fix a minimum in the
quality of the milk. Out of 103 samples, the poorest milk had a
sp. gr. of 1"0275, 904 percent, of solids and 1"G0 percent, of fat.
J. K. C.
Adulteration of Coffee with Chicory. By Prunier (J. PJiarm.
Chim. [5], 1, 222 — 224). — To detect the presence of chicory in coffee,
the microscopic examination is the best method, but as this is not
always possible, the following method may be employed. The ground
coffee is spread on a sheet of white paper. The grains of coffee
present an angular fracture, whilst chicory has an amorphous appear-
ance, and is of a darker colour ; the suspected grains are picked out
with a needle ; the coffee grains jump away from, or are split by it,
whereas the chicory grains, being softer, are easily penetrated. The
softer grains when crushed carefully between the teeth produce a gritty
sensation like fine sand. If chicory is present, its fiavour also is more
of an acid bitter, than the aromatic bitter taste of coffee.
Chicory may be estimated in coffee as follows : — About 2 grams of
dried ground coffee are sifted in a hair sieve from the fine dust, which
consists of pure coffee ; the larger grains are macerated with cold water
for some hours, and then thrown on a piece of stretched cloth and rubbed
with the fingers, when the chicory is forced through, whilst the coffee
grains remain on the cloth. The coffee is then collected, dried, mixed
with the dust, and weighed ; the loss in weight gives the weight of
chicory. L. T. O'S.
TECHNICAL CHEMISTRY. 515
Determination of Wine-extract. By Nessler (Landw. Versuchs..
Stat., 24, 284 — 289). — The amount of extract may vary from 1"2 per
cent, to 3 per cent, or more ; 1'7 per cent, may be taken as a normal
amount, and it may be made up as follows : — Non- volatile acids, 0"5 ;
salts, albuminoids, and other constituents, 0"5 ; glycerol, 0*7 ; acetic
acid, which boils at 120°, is often present in wine, a considerable
amount of it goes off during the evaporation, but the la.st portions
are not expelled by several hours' drying. The presence of glycerol
causes a loss of weight during the drying at 100° ; 1 gram of gly-
cerol lost on an average "043 gram per hour for 18 hours. It is not
advisable to heat until all the glycerol is expelled, and so to exclude
it from the extract. The author proposes evaporating to a syrup,
and then heating^ at 100° for four hours.
The following process is employed at the Versueh-Station, Weis-
baden : — A weighed porcelain-boat, charged with dry quartz-sand, is
heated in the water-bath, and 5 c.c. of wine are slowly dropped into
it. The boat is then placed in a stream of coal-gas previously passed
over calcium chloride. The boat is then cooled and weighed.
Halenke evaporates for six hours on the water- bath, and then stands
in a vacuum over sulphuric acid for twelve hours. J. T.
Technical Chemistry.
Rapidity of Germ-diflFusion in the Air. By I. Sotka (Bied. Centr.,
1880, 71 — 72). — The close connection between putrefactive and disease
germs led the author to make some experiments intended to test the
rapidity of dissemination of the former. The apparatus employed was
of extreme simplicity, consisting of a pear-shaped flask partly filled
with a solution of meat extract. Into this flask was led a tube which
communicated with the outer air, first passing over a quantity of dried
and powdered putrid blood. The air did not pass tkrowjh the solution
which was being experimented on.
The experiments were made with air currents of different velocities,
and the author found it impossible to determine minimum rate of speed
which, would not convey the germs. He concludes that a very slight
motion of the air almost, if not altogether imperceptible, is sufficient
to convey them ; much, however, depends on the lightness of the
putrefactive matter, and the liability of the receptive substance to
infection. He asserts also, and this appears worthy of further investi-
gation, that when the air is thoroughly saturated with aqueous vapour,
the putrefactive effects were not visible. J. F.
Antiseptic Action of Salicylic Acid. By A. Schultz (J. 2'>r.
Chem. [2], 21, 380 — 382). — In order to ascertain what substances
combine with salicylic acid, the author has treated solutions of bodies
tabulated below, with given weights of salicylic acid. The amount of
unaltered acid was determined by extracting the solutions with a given
516
ABSTRACTS OF CHEMICAL PAPERS.
volume of ether, and that of the combined acid bj extraction with ether
after acidifying with hydrochloric acid.
I. Nitrogenous Subsiances. — Asparagine, amygdaline, allantom, urea,
albumin, and gelatin.
II. Organic Salts. — Ammonium tartrate, sodium tartrate, Rochelle
salt, dipotassiam tartrate, potassium hydrogen tartrate, calcium tar-
trate, ammonium, sodium, and potassium malates.
III. Inorganic Salts. — Ammonium, sodium, and potassium phos-
phates, calcium pyrophosphate, ammonium, sodium, and potassium
chlorides, and ammonium nitrate.
The experiments show that amongst the nitrogenous bodies, only
gelatin and urea combine with salicylic acid. And in the case of salts,
that only the sodium and ammonium salt of acids having weaker acid
properties than salicylic acid, can combine with it. Potassium and
calcium salts do not combine at all with salicylic acid.
The author concludes that the power of salicylic acid to prevent
fermentation is greater than it was supposed to be by Kolbe and
E. Meyer (J. pr. Chem. [2], 12, 134). P. P. B.
Adulteration of Bone Meal witk Phosphorite.- By A.
Wachtel {ibicL, 032).
V.
Chemical Technological Notes. By E. Donath (Dingl. polyt. J.,
233, 78 — 81). — 1. On the Use of Heavy Spar in tJie Manufacture of Glass.
■ — An Austrian firm brought out" a product which they called " plate
glass composition," as a substitute for lime and soda in the manufac-
ture of glass. The authors on analysis declared it to be an intimate
mixture of powdered heavy spar and wood charcoal.
Baryta cannot take the place of potash or soda, but by increasing
the number of bases in glass, a greater proportion of basic oxides may
be introduced, and therefore less alkaline salts would be necessary.
Glass made with barium compounds has a higher specitic gravity
and brighter lustre than ordinary glass, but their high price stands
in the way of their being largely used.
2. The Composition of Various Kinds of Mirror Glass. — Analysed by
the author.
German
So-called
Constituents.
plate
glass.
French.
Rhenish.
German
plate-mass.
English.
Silicic acid
71-45
73-64
72-22
71-02
72-32
Oxides of iron and alumina
0-51
1-40
1-53
1-22
115
Lime
11 16
14-58
15-45
9-15
12-64
Magnesia
traces
0-30
traces
traces
traces
Soda
16-17
10-90
10-80
18-61
13-18
The author concludes that owing chiefly to the proportion of silica
and lime, the French glass is the best and the Rhenish next to it, and
very nearly as good.
TECHNICAL CHEMISTRY. 517
3. A Test for Free Mineral or Organic Acids. — Potassium iodide is
decomposed with liberation of iodine by potassium dichromate only
when there is present free chromic acid, and as the latter is only pro-
duced by the action of free mineral acids, this may serve in many
ways as a mode of analysis. The author employs carbon bisulphide
as the test for free iodine in the solution. W. T.
Explosion of a Platinum Still used for Concentrating Sul-
phuric Acid. By F. Kuhlmann (Bull. Soc. Chim. [2], 33, 50—52).
— A platinum still, holding about 300 liters, and capable of concen-
trating 6,000 — 7,000 kilos, of acid in 24 hours, was stopped for repairs,
and all the acid run out except about 40 kilos. Some water was in-
troduced into the still by a syphon, and the mixture gently heated
for three or four hours in order to clean the apparatus.
An explosion suddenly occurred which tore the still and still-head
into fragments, projecting some to a distance of 30 meters, and dis-
persed the brick setting on all sides. The explosion was pi-eceded by
a slight hissing sound, which warned the workmen just in time for
escape.
The author explains the occurrence by the liberation of a large
volume of vapour caused by the sudden mixture of the acid and water
at a high temperature. Taking the figures of Favre and Silbermann,
he shows that enough heat would be produced by the mixture of
40 kilos, of sulphuric acid with water at 18'^ to generate 18 — 20 cubic
meters of vapour. At 100^, the temperature at w4iicb the explosion
occurred, the effect would of course be much greater. Experiments on
a small scale show that an explosion is always produced when not less
than 10 eqriivalents of water are suddenly mixed with 1 equivalent of
acid. J. M. H. M.
Picking of Grapes. By C. Weigelt (Bied. Cenir., 1879, 931).—
From analytical results, the author entertains favourable opinions of
the stripping off of the berries and allowing the skins to ferment, in
the production of wine. J. K. C.
Time of First Drawing of Wine, By C. Wemelt and 0. Saare
(Bied. Centr., 1879, 930). — The authors arrive at the conclusion that
all wines which are obtained from niu.st rich in nitrogen should be
drawn early. J. K. C.
Clearing Action of Spanish Earth. By C. Weigelt and
0. Saaee (Bied. Centr., 1879, 932). — Experiments on the clearing of
wine by means of Spanish earth showed that the quantity of nitro-
gen in the wine was much diminished by its addition. J. K. C.
*
Density of the Mash. By M. Maecker (Bied. Centr., 1879,
619 — 621). — Comparison is made between the two methods of mash-
ing in alcoholic fermentation, viz., thick and thin mashing, and the
advantage which is said to lie with the latter method is not confirmed
by the author, who is in favour of a thick mash at a concentration
of 22 — 24° Sac, -which appears to be the working limit most favour-
518 ABSTRACTS OF CHEMICAL PAPERS.
able to fermentation, both with regard to the purity and the amount
of alcohol obtained. There is the objection, however, that so concen-
trated a mash necessitates larger mash-tubs. A. J. C.
Apparatus for Quick Fermentation. By Hammer (Bied. Centr.,
1879, 939 — 940). — By means of this arrangement, of which a full
description is given, the percentage of sugar in mash after ten hours'
fermentation may be reduced from 18 to 10. J. K. C.
Malt Combings a Source of Yeast. By F. "W. Marquardt (Bied.
Centr., 1880, 69—71). — Dried malt combings contain a certain amount
of protein substances soluble in not too dilute solutions of potato-sugar,
and not too dilute molasses, which serve as nourishment to the fer-
ments generated.
Working upon this fact, the author has deduced and perfected a
plan, which he has patented, for the preparation of yeast for dis-
tillery purposes, and also for the manufacture of compressed yeast
for domestic use.
The method employed may be briefly described as the saturation of
the combings with the requisite quantity of potato-sugar or molasses
solution (say a solution of the strength 15 per cent. Boiling to every
6 — 7 parts takes 1 part of combings), which contains as much actual
sugar as combings employed. It is left for 18 hours, with frequent
stirrings; the filaments are then separated, the liquor heated to 20 —
24° Reaumur (25 — 30° C), a little fresh working barm added, and the
mixture left in fermenting tubs or other suitable vessels with access
of air, the head-barm removed, and the bottoms pressed, with or
without the addition of starch according to the use for which it is
intended. For extensive distillery purposes, a mash of potatoes, maize,
or neutral molasses is at once added instead of the sugar solution.
100 kilos, of combings are calculated to produce 25 — 35 kilos, of
fine active pressed yeast, and the author believes that 1 kilo, of dry
malt combings contains as much protein matter as 2^ kilos, of dry
malt. J. F.
On Frothy Fermentation. By E. Bauer (Bled. Centr., 1879,
941 — 944). — The reason of the frothing which sometimes occurs in
the fermentation of potato mash lies, according to the author, in the
peculiar organisms developed, and not in the mechanical condition of
the liquid. When mash mixed with bottom-yeast, and kept for some
time without additional yeast food, is suddenly supplied with yeast
nutriment at a temperature which favours top fermentation, frothy
decomposition at once sets in. By careful selection of the yeast this
may be altogether prevented. J. K. C.
Surface Fermentation of Potato Mash. Souring of Yeast.
By M. Delbruck and others (Bied. Centr., 1879, 621— 627).— It is
shown that potato spirit and pressed yeast can be advantageously
prepared with the same mash, and that there are no grounds of objec-
tion against such a process (see also Bied. Centr., 1879, 220 ; this
Journal, 1879, Abst., 843).
TECHNICAL CHEMISTRY. 519
The souring of yeast proceeds very actively if the temperature
happens to reach 40' R., and if the mash has been made at 50° R.
no after cooling of the yeast will aiTest it. It is suggested to ensure
a uniform aciditication by adding soured yeast to the yeast at 40° R.,
and in order to avoid excess of acidity, a saccharine mash is added
to it on the second day after it has been cooled. A. J. C.
Fermentations produced in preparing Syrups from Beet
Juice by Diffusion. By A. Millox and MAyiEX-NK (Bull. Soc. Chim.
[2], 32, 611 — G13j. — In treating beetroots (some of which had been
frozen) by the diffusion process, the authors noticed a deficiency of
about 1 per cent, of sugar in the liquors and residue as compared with
that originally in the beet juice. They have traced this loss to fer-
mentations set up during the diffusion, the products of which are car-
bonic acid, hydrogen, and butyric acid. Ethyl butyrate was also
found, bat this was probably formed during the analysis. The authors
suppose that the acetous fermentation goes on as long as oxygen is
present in the diffusion vat, and that when this is exhausted the
bntvric fermentation commences, of which hydrogen is one of the pro-
ducts. J. M. H. M.
Proportion of Sugar to the Weight of Beetroots. By
E. Feltz and H. Bpjem {Bied. Centr., 1880, .59— 60).— Feltz made
13 exhaustive laboratory experiments, but on a large scale, using
18 kilos, in each, in order to determine the relation between the
weights of the roots and the sugar contained in their juice. The
general results arrived at are that the richness of the juice in the
sugar is the greater as the juice is thicker, that the smaller sized
roots generally yield the thickest and consequently the richest juice,
although it cannot be given as an absolutely fixed rule that the smaller
the root the greater the proportion of sugar, but it is sufficiently proved
for technical purposes. The most satisfactory results were obtained
from roots weighing 200 — 300 grams; those from 300 — 400 were but
slightly inferior ; above that weight, however, the percentage of sugar
rapidly declined. J. F.
Analyses of Sugar. By J. Moser and others (Bied. Centr., 1879,
926). — Very many samples of raw sugar from various sources have
been analysed by means of Sachsse's modification of Knapp's method.
The solution used consisted of 18 grams mercuric iodide, 25 potassium
iodide, and 80 potash, dissolved up to a liter. 40 c.c. of this solution
correspond to 0T342 gram of dextrose. J. K. C.
Bassia Longifolia. By A. Riche and A. Remont (/. Pharm. CMm.
[oj, 1, 215 — 218).- — Bassia lonr/ifolia, a tree of the order Lapelece, con-
tains a large amount of sugar. The bark and leaves are used in
medicine, and the seeds contain a fatty substance known as " butter of
AUipa." The flowers when dry have much the appearance of dried
raisins, and contain about 61 per cent, of fermentable sugar and about
8"5 per cent, of crystal Usable sugar. The fatty substance melts at a
higher temperature than other similar bodies, and therefore might be
used in the manufacture of tapers. L. T. O'S.
520 ABSTRACTS OF CHEMICAL PAPERS.
Valuation of Raw Sugar. By K. Stammer (Bied. Centr., 1879,
029). — The author thinks that 5 is too hio;h a multiple of the quantity
of salts contained in raw sugar to be used in valuation, and considers
that only 3"5 times the percentage of salts present should be subtracted
from the total quantity of sugar present in order to give the possible
yield of refined sugar. J. K. C.
Suint. By E. Schulze and J. Barbieri (Bled. Centr,, 1879, 596 —
598). — The authors have investigated a peculiar kind of sheep sweat
of a " pitch-like " character, containing a large quantity of fatty
matter, of which 84 per cent, is described as being difficultly soluble
in alcohol. The portion soluble in alcohol differed from that of
ordinary saint in containing no cholesterin in the free state, and in
o-ivino- only a very small quantity even by saponification. In other
respects there was no essential diifereuce in the nature of this kind of
suint and the ordinarv sheep sweat as described in Schulze's previous
papers (this Journal,'^ 1873, 920 and 1219; 1874, 1079). Expressed
on the raw wool, the amount of fatty matter w^as in these cases found
to be 34-19 per cent. (m. p. 35-5°), 35-16 (m. p. 37°), and 36-31
(m. p. 44°), and the amount soluble in water 9-76, 13 77, and 12-15
per cent, respectively, whilst ordinary wool, in two examples quoted
amongst others, contained 7-17 and 14-66 per cent, fatty matter, with
21-13 and 21'83 per cent, soluble in water. The aqueous solution con-
tained no potash soap, and this peculiarity, together with the large
amount of fatty matter, explains the fact that this kind of wool is so
imperfectly cleansed by water. The ether extract of the wool con-
sisted of pure fatty matter, whilst that of ordinary wool always con-
tains potassium oleate. In addition to inorganic compounds, the
aqueous solution is said to contain an organic acid, the nature of
which has not been examined. A. J. C.
Destructive Action of Wood on Salicylic Acid. By H.
KoLBE {J.pr. CJiem. [2], 443 — 447). — Water, to which salicylic acid
has been added in proportion of 0*1 gram to the liter, may be kept for a
year in a glass vessel and will then be found to be quite fresh ; but if
double the amount of the acid is added to water in a wooden cask or
in a o-lass vessel containing wood, the water becomes bad, and the
acid totally disappears ; it cannot be detected either in the water or
the wood. The same result was obtained on substituting wine for
water.
In what way the acid is destroyed is an open question.
G. T. A.
Analyses of Milk. By J. Moser and F. Soxhlet (Bied. Centr.,
1879 934 — 937). — In the samples of condensed milk analysed, the
percentage of water vai-ied from 24 to 30, fat from 7-5 to 11, and
casein from 9 to 11. The sp. gr. of goat's milk varied from 1-027 to
1-045. Mare's milk was found to contain 92 per cent, of water, and
about 15 per cent, of casein. J. K. C.
A
521
General and Physical Chemistry.
Effect of Light on Chemical Compounds. By T. P. Blum
(Anahjst, 1880, 7\) — 81). — The author finds that solutions of certain
compounds when exposed to the light undergo decomposition. A
solution of oxalic acid may be kept for any length of time in the dark,
whereas if exposed to the light it rapidly undergoes decomposition ;
some solutions exposed to the light for six months in test - tubes
stoppered with cotton wool, lost all ti'aces of acidity. Dilute solu-
tions of alkaline oxalates undergo similar oxidation, notably ammo-
nium oxalate.
In the dark, dilute permanganate solution may be kept for months
unchanged.
From experiments with potassium iodide, the author concludes that
the oxidation is due to the effect of light alone, without the interven-
tion of any acid.
Ferrous iodide, however, requires exposure to the brightest possible
light to prevent decomposition. L. T. O'S.
A New Voltaic Condenser. By — D'Arsonval (Compt. rend.,
90, 166 — 167). — The action of secondary piles, such as those devised
by Plante, is very energetic for a short time, but not lasting. An
attempt was therefore made to discover the causes which limit the
condensing power of the lead-plate couple, and if possible to rectify
them. The gaseous state of the oxidisable metal (hydrogen) unques-
tionably limits the action, and this soon attains a maximum, which it
is impossible to exceed, the lead plate becoming covered with a layer
of dioxide which protects the metal from further oxidation. A cell
was therefore devised in which a zinc plate was used in connection
with a carbon one, the latter being surrounded with very fine leaden
shot (dust-shot) in order to increase enormously the surface of the
lead, and the whole was excited with a solution of zinc sulphate. On
passing a current fi-om the carbon to the zinc through a couple thus
constructed, the zinc salt is decomposed, and the metal deposited on
the zinc plate, the oxygen forms lead dioxide, whilst the sulphuric
acid remains free ; the deposit of oxidisable metal is thus unlimited,
and the oxygen can be accumulated in very large quantity. With a
couple containing only 1 kilo, of shot, the author succeeded in work-
ing a Deprez electromotor for four hours.
In practice, the zinc plate may be replaced by a mercury pole ; the
electromotive force of such a couple was found to be 21 volts. The
lead plate also may be replaced by several other substances, but
nothing else seemed to give such satisfactory results. J. W.
Determination of High Temperatures, By H. St. Claire
Deville and L. Troost (Compt. rend., 90, 727 — 73U). — The thermo-
metric apparatus consists of a cylindrical reservoir of porcelain, of at
least 50 c.c. capacity, furnished with a capillary porcelain tube about
VOL. XXXVIII. 2 p
522
ABSTRACTS OF CHEMICAL PAPERS.
0'3 mm. long, to wliicli is attached a tliree-way stopcock communicat-
ing witli the air, and, by means of an almost capillary lead tube, with
a Sprengel pump. The thermometer is placed in a refractory glazed
earthen tube, packed with asbestos and heated in a furnace fed with
petroleum. The teinpei'ature of this furnace can be adjusted by regu-
lating the flow of oil by means of a sensitive stopcock. When the
temperature has become constant, communication between the reser-
voir, the air, and the pump is cut olf. The tube connecting the
thermometer to the pump is first rendered vacuous, the stopcock is
then opened, and the gas (nitrogen) contained in the thermometer is
pumped out into a graduated tube, and its volume determined with
the greatest possible accuracy. The necessary cori-ection for the
capillary portion of the thermometer is ascertained by determining
the volume of gas in a tube of the same length and diameter, placed
at its side, and which the authors term a compensator.
C. H. B.
Heat of Formation of the Oxides of Nitrogen. By Bsrthelot
(Compt. rend., 90, JTi' — 784). — The author has determined the heat
of formation of nitric oxide by exploding cyanogen and ethylene
respectively, first Avith this gas and afterwards with oxygen, and
measuring the amount of heat evolved in each case. The heat of
formation of nitrous oxide was determined by exploding it with carbon
monoxide. The results, together with those of experiments on the
heat of formation of other nitrogen compounds are given in the follow-
ing tables : —
I.
No -f 0 = NoO gas
N, + Oo = N0O2 gas
No 4- O3 = N2O3 "gas
No -f Oi = N.Oi gas
No -F O3 = N0.O5 gas
Cals.
-20-6
-43-2
-22-2 dis.
—
8-4
- 5-2 liq.
+
3-4
- 1-2 liq.
+
3-6
i(No-)- O5 + H,0) = HNO3 gas - 0-1 liq
N + O3 + H . .
N + H3
N -h H3 + 0 . .
C + N
HNOsgas +34-0 liq.
NHsgas +12-2 dis.
NH3O dis. +19-0
-37-3
3-6soL -f 11-8 dis. -h 28-6
+ 7-1 sol. -t- 7-7 dis. +14-3
+41-6sol. +42-2 dis. +48-8
-I- 21-0
CN gas
II. Nitrates.
Cals.
KNO3 -h 118-7
NaNOg .... +110-6
NH,N03 .... + 87-9
Sr2N03 .... +219-6
Ca-2N03 .... +202-4
Pb2N03 .... +105-6
AgNOa .... + 28-7
C2H5NO3 . . . . + 52-4
nitroglycerine + 96'4
nitrobenzene + 4-2
Cs + Hs + N2 + O'l = dinitrobenzene + 12-7
N + O3 + K .
N + O3 + Na
No. + O3 + H,
N2 + Oe + Sr
N2 + Oe + Ca
No + Oe + Pb
N + O3 + Ag . . ^
N + O3 + C2 + H5
Na + O9 + C3 + Hs
Co + H5 + N + O
GEXERAL AXD PHYSICAL CHEMISTRY. 523
III. Ainmoniacal Salts.
Gals.
N + H4 + CI. . . . := iS^HiCl +767
I^ + Hi + Br gas = NH.Br +71-2
N + Hi + I ^as = KHJ +560
N + Hi + Sgas = :N'HiS +42-4
C. H. B.
Thermochemical Study of Sulphides of the Earth-metals.
By P. Sabatier (Compt. rend., 90, 819 — 821). — Magnesium sulphide,
obtained by the action of carbon bisulphide on the oxide at a red heat.
The solution of one equivalent in hydrochloric acid causes development
of heat = + 21"8 cals. at 13°, hence the heat of formation of MgS
(56 grams) = + 73"6 cals. The conversion of MgS into Mg(H0)2 by
the action of water develops + 10 '4 cals.
Aluminium sulphide, prepared by heating the metal to redness iu
the vapour of sulphur. When one equivalent is decomposed by water
at 12*^, + 74'0 cals. are developed, which gives the heat of formation
of AI2S3 (150-8 grams) = + 124-4 cals.
Silicon sulphide, obtained in the form of long silky needles by the
action of carbon bisulphide on silica heated to redness. The decom-
position of one equivalent by water causes development of heat =
+ 38-5 cals. at 9-5°, which gives the heat of formation of Si So (92 grams)
= + 40-4 cals., a number much lower than the heat of formation of the
corresponding oxide. C. H. B.
Freezing Point of Alcoholic Liquids. By P. M. Raoult
(Con/pt. rend., 90, 865 — 868 J. — Mixtures of alcohol and water when
subjected to low temperatures congeal but never completely solidify.
That which solidifies consists of plates of pure ice, and can be freed
from alcohol by simple mechanical means. The temperatures at which
congrelation begfins in mixtures of alcohol and water containing
different percentages of the former, are given iu the following table,
which may be used for the determination of the strength of such
mixtures : —
Vol. alcohol
A"ol. alcohol
Temperature.
per cent.
Temperature.
per cent.
-0-0°
0-0
- 9-0°
21-9
-0-5
1-6
-10-0
23-3
-10
3-2
-12-0
26-4
-1-5
4-8
-14-0
29-1
-2-0
6-3
-16-0
31-3
-2-5
7-8
-18-0
33-8
-3-0
9-2
-20-0
36-1
-3-5
10-6
— 22-0
38-3
-40
11-8
-240
40-0
-4-5
131
-26-0
41-6
-5-0
14-2
-28-0
43-7
-6-0
16-4
-30-0
46-2
-7-0
18-7
-32-0
47-9
-8-0
20-4
2 p 2
524 ABSTRACTS OF CHEMICAL PAPERS.
In solutions containing from 0 gram to 10 grams of alcohol to 100
grams of water, the addition of 1 gram of alcohol lowers the point of
congelation by 0'377°, and the distance of this point below zero is
proportional to the weight of alcohol dissolved in a constant weight of
water. The alcohol behaves like anhydrous salts, and therefore pro-
bably exists in the liquid uncombined with water. In solutions con-
taining 24 to 51 grams of alcohol to 100 grams of water, the addition
of 1 gram of alcohol lowers the congelation point 0"528°, but the total
distance of this point below 0° bears no relation to the amount of
alcohol in the liquid. This fact indicates that the alcohol dissolves in
the hydrated condition. Applying Rudorff 's method of calculation, it
is found that this hydrate has the composition CoHeO.HoO.
The following table gives the points of congelation of various fer-
mented liquors, compared with those of aqueous solutions of alcohol of
the same strength : —
Per cent. Congelation Cong, point,
alcoliol, point. Aqueous alcohol.
Cider 4-8 -2-0° -1-5°
Beer 6-3 - 2-8 -20
Vin rouge ordinaire 6'8 — 2*7 — 2"2
Viu blanc ordinaire .... 7'0 — S'O — 2"3
Beaugolais 10-3 —4-4 —3-4
Red Bordeaux 11-8 - 52 -40
Red Burgundy IS'l - 57 -4-5
Red Roussillon 15-2 - 6-9 -5-5
Marsala 207 -101 -8-1
Fermented liquors require a lower temperature for congelation than
the corresponding aqueous solutions of alcohol, and the difference is
greater the greater the proportion of alcohol ; it is about 0*1° for each
percentage of that liquid. That which solidifies is pure ice, and by
removing this as fast as it is formed, the alcohol in the liquid may be
gradaally concentrated. C. H. B.
Some Properties of Mixtures of Methyl Cyanide with Ethyl
and Methyl Alcohols. By C. Vincent and Delachanal {Coiwpt.
rend., 90, 747 — 750). — The following table gives the boiling points
and specific gravities of various mixtures of ethyl alcohol and pure
Alcohol. Methyl cjanide. Sp. gr. Contraction. B. p.
0 100 0-8052 0-0 81-6°
10 90 0-8059 0-00007 76-8
20 80 0-80G7 0-00017 74-8
80 70 0-8075 0-00029 73-8
40 60 0-8083 0-00046 73-2
50 50 0-8092 0-00071 72-7
60 40 0-8102 0-00111 72-7
70 30 0-8114 0-00177 73-2
80 20 0-8127 0-00251 74-1
90 10 0-8130 0-00211 75-4
95 5 0-8130 0-00138 75-4
100 0 0-8120 0-0 78-4
GENERAL AST) PHYSICAL CHEMISTRY. o25
methyl cjanide obtained from coal-tar naphtha (this Joui-nal, 34, 3". '2,
and boiling at 81'6°.
The boiling points of these mixtures are lower than that of either
constituent. When subjected to fractional distillation, a distillate is
obtained which at tirst contains 5t3 per cent, of alcohol, and afterwards
a higher or lower percentage according as the mixture in the retort
contains more or less than 56 per cent. The methyl cyanide may be
separated from the alcohol by repeated treatment with calcium chloride,
and finally with phosphoric anhydi-ide. In this way, it may be ob-
tained in large quantities in a state of purity from coal-tar naphtha.
The followinsf table srives the results obtained with mixtures of
methyl cyanide with pure anhydrous methyl alcohol, boiling at
64-8° .—
Alcohol. Cyanide. Sp. gr. Contraction. B. p.
0 100 0-«052 0-0 81-6°
10 90 0-80G3 0-00076 74-0
20 80 0-8073 0-00148 69-2
30 70 0-8083 0-00218 67-1
40 60 0-8093 0-00278 65-7
50 50 0-8102 0-00332 64-8
60 40 0-8110 0-00378 64-2
70 30 0-8115 0-00384 63-8
80 20 0-8115 0-00318 63-7
90 10 0-8109 0-00192 64-0
100 0 0-8098 0-0 64-8
C. H. B.
Relation bet-ween Molecular Weight and Density of Gases.
By A. Naumanx {Ber., 13, 468 — 470). — A reply to Schmidt's assump-
tion (Ann. PIdjs. Chem. [2], 6, 612, this vol , p. 87), that V, i.e., the
molecular weiyht of gas divided by its density referred to air as unity,
equals 28-8384 instead of 28-88. W. C. W.
Absorption of Gases by Liquids. By A. Naccart and S. Pag-
LIANI (Guzzetta, 10, 119 — 120). — From the experimental results ob-
tained by Bunsen and others the authors show —
1. That the absorption of carbonic anhydride by water follows
Henry's law for pressures of from one to four atmospheres.
2. That scarcely any experiments have been made at pressures less
than one atmosphere.
3. That gases which are absorbed by water to a considerable extent
vary from Henry's law when the pressure is low.
On making experimental determinations, however, of the solubility
of carbonic anhydride in water at temperatures between 17° and 27",
and at pressures from 257"7 to 663-6 mm., they found that the results
obtained approximated closely to those calculated from Henry^'s law.
The coefficient of absorption of carbonic anhydride by water between
17° and 27°, as deduced from the author's experiments may be repre-
sented by the formula —
a = 1-5062 - 0-036511 t + 0-0002917 f,
52G ABSTRACTS OP CHEMICAL PAPERS.
which differs somewhat from that given by Bunsen for temperatures
between 0° and 20°.
A table is given of the observed and calculated values for different
temperatures, reduced to 760 mm. pressure, on the supposition of the
truth of Henry's law. C. E. G.
Determination of High Temperatures. By H. St. Claire
Deville and L. Tkoost (Gompt. rend., 90, 773 — 778). — The authors
give the results of experiments made some years ago to determine the
boiling point of commercial zinc. The air-thermometer employed was
constructed of Bayeux porcelain, glazed within and without, and pro-
tected by screens to prevent loss by radiatio-n. Several kilograms of
zinc were distilled at each operation, and care was taken to prevent the
overheating of the vessel in which the thermometer was placed. The
numbers obtained were 916 — 925°, when the thermometer was filled
with hydrogen, 929—954°, with dry air, and 1067—1079° when
carbonic anhydride was the gas employed, indicating dissociation of
this gas. C. H. B.
Researches on Diffusion. By L. Joulin {Gompt. rend., 90,
741 — 744). — The author has studied the influence of pressure, ranging
from a few centimeters of mercury to four atmospheres, and tempe-
rature between 0" and 100°, on the condensation of gases by porous
solids, the solution of gases in liquids, and the equilibrium between
the condensed or dissolved gases and the surrounding atmosphere,
with the following results: — ^(1.) Wood Gharcoal. — The aniomit by
weight of dry OEygen, nitrogen, and hydrogen condensed, is directly
proportional to the pressure and inversely proportional to the tempe-
rature. The time necessary for saturation is too small to admit of
measurement. With carbonic anhydride, the amount condensed in-
creases more rapidly than the pressure up to 300 mm., and decreases
more rapidly than the temperature rises, between 0° and 100°, but
above these limits it obeys the same law as the other three gases. The
time necessary for saturation increases with the pressure, and decreases
with a rise of temperature. The condensation of gaseous mixtures is
slower than that of each constituent, and the amount of each gas
absorbed bears no relation to the proportion in which it exists in the
mixture. The quantity of gas required to replace a given volume of
carbonic anhydride is much less for nitrogen and hydrogen than for
oxygen. Air behaves like a mixture of its constituents. The time
necessary for the establishment of equilibrium varies with the nature
of the atmosphere, being very short for hydrogen, longer for nitrogen,
and still longer for oxygen. When the gases are saturated with
vapour, the phenomena are of the same order, but differ in degree.
The amount of carbonic anhydride condensed, when saturated with
aqueous vapour, is one-half, and when saturated with vapour of alcohol,
one-fifth that of the dry gas. (2.) Gharcoal saturated with liquid. —
When the liquid is water, the absorptions are almost the same as with
dry charcoal ; but with carbon bisulphide the amount of gas con-
densed is smaller, and still smaller with alcohol. The author has
experimented with other porous substances, such as spongy platinum
INORGANIC CHEMISTRY. 527
and palladium, but as yet withnut any definite results. At ordinary
temperatures and pressures, different specimens of earth absorb notable
quantities of the gases in the air, the oxygen being absorbed to twice
the amount of the nitrogen. C. H. B.
Inorganic Chemistry.
Sulphides and Selenides of Chromium. By H. Moissax
{Compt. rend., 90, 817 — 819). — Chromium sesquisidphide, Cr^Ss. — Ob-
tained as a brownish-black amorphous powder by passing dry hydrogen
sulphide over heated, hut not calcined, sesquioxide. It is but slightly
attacked by acids, with the exception of nitric acid and aqua regia.
When heated in chlorine gas, it is converted with incandescence into
chromic chloride. On heating it in the air, the sesquioxide is formed ;
but if it be heated in a closed vessel, a portion of the sulphur is given
off in the free state. By the action of hydrogen sulphide on chromic
chloride, this compound is obtained in black brilliant plates, which
retain the form of the chloride.
Chromium monosulphide, CrS. — A black powder, attacked with diffi-
culty by acids, but readily converted into chromic chloride by chlorine,
obtained by heating the preceding compound in hydrogen. When
heated in the air, it is converted into tlae sesquioxide, but does not
lose sulphur when heated in a closed vessel. By heating chromous
chloride at 440^ in hydrogen sulphide, the monosulphide is obtained
as a gi'eyish- black substance, retaining the micaceous appearance of
the chloride.
Chromium sesquiselenide, Cr2Se3, is a black powder, obtained by the
action of hydrogen selenide on chromic chloride, or by heating the
sesquioxide in selenium vapour. It is very slightly attacked by acids,
and readily converted into a beautiful green-coloured sesquioxide
when heated in the air. Heated out of contact with air, it loses a
portion of its selenium.
Chromium, monoselenide, CrSe. — Obtained by heating the preceding
compound in a current of hydrogen, or by the action of hydrogen
selenide on chromous chloride. It is easily converted into the ses-
quioxide on ignition, and is readily attacked by chlorine.
C. H. B.
A New Property of Vanadates. By P. Hautefeuille (Compt.
rend., 90, 744 — 747j. — The acid vanadates of potassium, sodium, and
lithium, have the property of " spitting," like metallic silver, when
cooled after fusion in presence of air. The gas thus given off is
oxygen, and the amount absorbed by a given quantity of vanadate is
constant ; lithium bivanadate, for example, when fused at a dull-red
heat, absorbs nearly eight times its own volume of oxygen, which is
again given off at about 600° during the process of cooling. The fol-
lowing table shows the volume of oxygen given off when an amount of
vanadate containing 1 gram of vanadic acid is fused in a vacuum : —
528 ABSTRACTS OF CHEMICAL PAPERS.
Product.
c.c.
Product.
c.c.
Product.
c.c.
2V,05.KoO . .
. 0-4
2V,05.NaoO . .
. 3-8
2V.305.Li.,0 . .
. 3-3
3V2O5.K0O . .
. 0--^
3V205.NaoO . .
. 5-0
3V205.Li20 . .
. 37
4Vo05.Ko,0 . . .
. 27
5Vo03.K,0 . .
. 3-4
It will be seen that the volume o£ gas disengaged increases as the
relative proportion of base diminishes.
When vanadic acid is acted on by an alkaline carbonate, oxygen is
also evolved. The following table shows the amount of gas given off
when 1 gram of vanadic acid is acted on in a vacuum by alkaline
carbonates : —
Pi'oduct. c e. Product. c.c. Product. c.c.
V,05.K20 . .
. 0-0
VsOs-Na^O . .
. 0-4
V205.Li,0 . .
. 2-5
2y205.K20 . .
. 07
2V.,03.Na-,0 . .
. 40
2V205.Li,0 . .
. 47
3V205.K00 . .
. 1-5
3Vo05.Na^O . .
. . 5-4
3Vo05.Li.O . .
. 5-8
4V,.05.KoO . .
. . 3-3
5V2O5.K0O . .
. 4-8 '
The volume of oxygen absorbed by a crystalline vanadate, when
fused in presence of air, serves as an indication of the relative propor-
tions in which a vanadate and vanadic acid may be fused together
without combination taking place. These observations render it advi-
sable to redetermine the atomic weight of vanadium, since this quan-
tity has been fixed by ascertaining the loss of weight which vanadic
anhydride experiences when passing to the state of trioxide.
C. H. B.
Composition and Analysis of the Binoxide of Manganese
recovered in the Weldon Process. By G. Lunge (Dingl. polyt.
J., 235, 300—311). — Post (Ber., 12, 1454 and 1537) publishes
some researches on Weldon-mud, which seem to sliow that Weldon's
theory of the " manganites," i.e., saline compounds of Mn02 with
bases, which he applies as a definition of his process, is not only un-
founded, but that the methods used in works for the analysis of
Weldon-mud must be totally wrong. Post states (p. 1539) that he
has obtained a wide difference between the ferrous sulphate method as
laid down by the author and Bunsen's iodine method. The present
paper is devoted entirely to this statement, and in a very complete
series of experiments the author discusses this question, and proves
without doubt that the methods formerly described by him for analysing
Weldon-mud are perfectly trustworthy.
Post in his researches entirely ignores the existence of a base, and
regards the Weldon-mud as a mechanical mixture of MnOj with MnO
and a small proportion of lime, magnesia, and ferric oxide, the former
present probably as carbonates, but the total sum not sufiicient to form
Weldon's "acid manganite " (R02Mn02).
The author refers to this assumption very briefly, and mentions that
Post did not analyse Weldon-mud itself, but a product obtained by a
very troublesome process of washing (100 times with 40 times its
Aveight of water), which had probably been altered by this treatment
MINERALOGICAL CHEMISTRY. 529
to a considerable extent. VaiMOus circumstances undoubtedly show
that this binoxide of manganese is a salt of manganous oxide with
manganic acid or permanganic acid, i.e., MnO, MnOs or 3MnO, Mn^OT.
In this case Weldon's manganous salts would represent basic manga-
natesor " permanganates," i.e., CaO, 2MnOo would be CaO, MnO.MnOj,
&G. D. B.
Mineralogical Chemistry.
Step-like and Skeleton Growth of some Regular Crystals.
By F. ScHARFF {Jahrb. f. Mho., 1878, 953 — 954). — The development
of the various crystals of the regular system is dependent on a varying
disposition of the building material, and the proof of this is seen in
the common occurrence of striations in different directions, of poly-
hedral elevations on the faces, and of hollow faces. These peculiarities
are brought about by the influence exerted on the crystals during
their growth by the working one into the other of the various systems
of "directions of activity" (thatigkeitsrichtungen), thus causing the
formation of edges, faces, and cleavage directions. These actions of
the directions of activity can be retarded or interfered with externally,
so that the formation of one or other face is promoted or induced.
Cubical and octohedral forms are most easily produced. On the faces
of the cube, there is often observed a quadruple concentration in the
polyhedral elevation ; whilst on the faces of the octohedron only a
triple concentration is observed. In iron pyrites, the pentagon-dode-
cahedron takes up an intermediate position between these two concen-
trations ; for instance, the horizontal striation on some of the faces
points to cubical structure, whilst the inclined or vertical striation
points to octohedral structure. Hemihedral formation appears to be
due to the partial coincidence of two different systems of " directions
of activity " in one place. The complete crystal is built up exactly
similar to the form of its minutest particle. The development of
secondary faces is generally intimated on the polyhedral elevations
observed on the neighbouring faces. In a similar manner the hollow
faces remaining behind are intimately connected in forjn with the
neighbouring faces, and they can easily be distinguished fi'om " etch-
figures." Intersecting or reticulated striation is caused by the inter-
secting of systems of " directions of activity," good examples of such
a striation being often observed on fluorspar crystals, resulting occa-
sionally in the formation of a tetrakis-hexahedron and at other times
in the formation of a hexakis-octohedron. C. A. B.
Sensitiveness of Alum-crystals to Variations in the Strength
of their Mother-liquor. By F. Klocke (Jahrb. f. Min., 1878, 958
— 959). — The author made some experiments in order to ascertain the
correctness of the law of Lecoq de Boisbaudran, viz. : " A crystal face
can remain unchanged — that is, neither increase nor decrease in size —
530 ABSTRACTS OF CHEMICAL PAPERS.
in a fluid whose degree of concentration chans^es within determinable
limits." In order to test the accuracy of this statement, Klocke
placed alum crystals in a saturated solution of alum and examined
them microscopically, in order to ascertain whether any variation
in the concentration of the solution would produce " etch-figures " on
the crystals. The result proved the inaccuracy of the above-men-
tioned law, as " efcch-figures " were easily and distinctly produced; the
so-called inertia of the crystal faces therefore is not a fact. An appa-
rent inertia of the ci'ystals can be brought about by layers of liquid
(differing in degrees of concentration, owing to the oscillations of
temperature) being present in the solution, but the crystal dissolves
in an adjacent non-saturated layer until the resulting solution about
the crystal is saturated, or it grows in an adjacent saturated solution.
A crystal which is rounded off at one end sometimes exhibits sharply-
defined faces at the other end ; and if the whole crystal then grows
fui'ther, new faces grow on the rounded end which do not occur at the
other end, thus producing an apparent hemimorphism. C. A. B.
Chemical Composition of the Pitchblende (Uraninite)
from Branchville, Conn., U.S. By W. J. Comstock (Amer. J.
Sci. [3], 19, 220). — The crystals, which were very distinct, were
octohedral, modified by the planes of the dodecahedron and cube. Their
sp gr. is 9'22 — 9'28, and their composition as follows: —
U. Pb. Fe. O. HjO.
81-50 3-97 0-40 13-47 0-88 = 100-22
The formula indicated by this composition is 3R'^02 + 2R^03, in
which R'"^ represents tetrad uranium, replaceable by two atoms of lead
or iron and R^', hexad uranium. C. W. W.
Crystallography of Calcite. By Irby (Jahrb. f. Min., 1878, 952
— 953). — The author continued the investigations commenced by
Hessenberg, and directed his attention particularly to the inner con-
stitution of calcite crystals, and from the results obtained, was of
opinion that Hauy's theory was more worthy of the consideration
which German mineralogists had hitherto declined to bestow upon it.
Irby exarained the development of the crystal forms from the primary
rhombohedron, and also the combinations of the different forms
with each other. He accounts for the great rarity of the primary
rhombohedron occurring independently, by the fact that foreign sub-
stances present in the solution of calcium carbonate exert a retarding
influence on the independent formation of the primary rhombohedron,
and conduce to the simultaneous occurrence of other forms. Irby
gives tables of all the rhombohedrons and scalenohedrons known (49
of the former and 100 of the latter), with their interfacial angles.
C. A. B.
Chemical Composition of Amblygonite. By S. L. Penfield
(Amer. J. Sci. [3], 18, 295). — In describing triplo'idite. Brush and
Dana (Amer. J. Sci. [3], 16, 42 ; this Journal, 36, 20) showed
that the hydroxyl-group which enters into its constitutional formula
MIXERALOGICAL CHEMISTRY. 531
•must play the same part as the fluorine in the allied species, wagnerite
and triplite. In this paper, the author shows that the hjdroxyl in
amblygonite also replaces fluorine. This conclusion is deduced from
a very large number of analyses, the particulars of which are given in
the original paper. For more easy comparison, the ratio for phosphoric
acid, alumina, alkalis (sodium and lithium oxides), and of hydroxyl
and fluorine, are given below, as also the localities from which the
minerals were obtained : —
P.,05. Al.Oa. NaoO.LijO. OH.F.
I. Penig, Saxony I'OO 0-9G 6-98 I'lG
II. Montebras, France (A) 1-00 0-97 0-98 1-17
III. Auburn, Maine 1-00 096 097 1-06
IV. Hebron, Maine (A) .. I'OO 0-97 0-95 1-13
V. Paris, Maine 1-00 0-96 0-97 1-17
VI. Hebron, Maine (B) .. I'OO 0-98 0-95 1-27
VII. Branchville, Conn I'OO 0-97 0-96 1-09
VIII. Montebras, France (B) 100 0-96 0-96 1-21
It will be seen that all these ratios approach very nearly 1:1:1:1;
therefore the author proposes the formula ALPoOs + 2R(0H,F) or
3AloP,0al , rAlo(0H,F)6 ,, , „ 1 I " n • .• ^ .,
2R p6 II '^Rf OH F) ^^ formula for all varieties of the
mineral.
To explain the fact that the (OH,F) is in every case too high, whilst
the alkalis and alumina are constantly, although slightly, too low, he
supposes either that a small quantity of accidental water is always
present, or that some of the water is basic. C. W. W.
Analyses of some American Tantalates. By W. J. Comstock
(Amer. J. Set. [o], 19, 131). — Of these minerals, the first came from
Yancey Co., N.C. ; it was a massive piece, of sp. gr. 6-88 ; the second
was from IN'orthfield, Mass., a fragment of a large crystal having the
angles of ordinary columbite ; sp. gr. 6'84. No. Ill was from Branch-
ville, Conn. ; slightly translucent in thin fragments, and giving a
brownish-grey powder ; sp. gr. 6-59.
TaoOj. NbA- FeO. MnO. MgO. CaO.
I . . 59-92 23-63 12-86 3-06 0-34 — = 99-81
II . . 56-90 26-81 10-05 5-88 — — = 99-64
III . . 52-29 30-16 0-43 15-58 — 037 = 98-83
These all agree with the formula (Fe,Mn)(Ta,Nb)o06.
c. w. w.
T-wo New Silicotitanates of Sodium. By P. Hautefetjille
{Gomi^t. rend., 90, 868 — 870). — By heating one equivalent of sodium
titanate to bright redness with sodium tungstate, and heating this
product to dull redness with two equivalents of silica, two definite
compounds are produced. One of these, 4Si03.5Ti02.2Na20, is ob-
tained in nodules formed of radiating fibres, or in flat finely Channelled
prisms. The faces of the prisms and the sections of the nodules have
a brilliant silky lustre. The crystals are always opalescent, and
strongly birefractive ; they are very fragile, but scratch glass and
532 ABSTRACTS OF CHEMICAL PAPERS.
resist tlie action of acids which attack the native silicotitanate of
calcium.
The other compound, 3SiO2.2TiO2.Na2O, forms colourless, trans-
parent, very refractive orthorhonibic prisms, isolated or united in druses-
The faces a and e are found on all the crystals, but are often very-
small. The cleavage is parallel to the faces of a prism of 91°, and the
ratio, 6 to /;, =: 1 : 0'544. Optical examination proves that the crys-
tals belong to the orthorhombic, and not to the quadratic system.
By replacing tungstates by vanadates it will probably be possible to
obtain compounds between those described and sphene. The silico-
titanates diif er from the natural .silicates in fusing to a colourless limpid
bead before the blowpipe. When fused, they devitrify very rapidly
with separation of rutile. C. H. B.
Simultaneous Reproduction of Quartz and Orthoclase. By
P. Hautefeuille {Compt. rend., 90, 830 — 831). — Many phosphates
bring about the crystallisation of silica in the form of tridymite. The
phosphates of potassium and sodium also attack the aluminosilicates.
Potassium aluminosilicate, at about 1,000", crystaHises in the form of
orthoclase adularia. The simultaneous production of quartz and
orthoclase cannot be accomplished by means of a pure phosphate, since
the latter only acts on the silica at a very high temperature. By the
addition of a fluorine compound, however, the temperature necessary
to effect this is lowered, and crystals of quartz are obtained associated
with those of felspar. The most highly developed faces of the quartz
crystals are e~, jj, and e-, and these are very deeply striated. The
orthoclase has a stony appearance, and the crystals are generally
twinned like those found in trachytes- The author considers it pro-
bable that the crystals of orthoclase found on the bricks of metallurgi-
cal furnaces have been foi-med by the action of alkahne fluophosphates
volatilised and carried away in the furnace gases. By heating a mix-
ture of acid potassium phosphate (previously fused with silica and
alumina) with silica and a small quantity of potassium fluosilicate in
a glass tube, one part of which contained fragments of porcelain, he
obtained crystals of orthoclase together with quartz, not only on the
part of the tube containing the mixture, but also on the pieces of
porcelain. C. H. B.
The Micas. By G. TscnERMAK (Jah-h.f. Miyi., 1878, 950—952).—
In a previous paper, the author considered the crystallographical and
optical properties of the micas (Jahrb. f. Min., 1878, 71). The present
communication treats of the composition of the various combinations
occurring in the different micas, and shows that most of the micas are
complicated compounds, all containing the same nucleus or kernel,
round which the other combinations are grouped. Tschermak ar-
ranges the micas m the following groups, viz. : —
Blotite group {inagnesia-mica jjajf/y). — Monosymmetrical ; typical
forms OP, + P, — -ip, 00^00. Optically negative, the first bisectrix
" a " differing very little from the normal on " c." The sp. gr. increases
with the amount of iron, and varies from 2-8 to 3-2.
Anomite. — The plane of the optical axes is parallel to " &," p>u-
MINERALOGICAL CHEMISTRY. 533
Composition = SisAleKa&jO;;! + SieMgi^-O.! in the proportions 1 : 1
or 2 : 1.
liahellan, voigtite, eicJcamptite, aspidolite, hallite, raHolite, are more or
less altered meroxene.
Lepidoinelane. — The plane of the optical axes is parallel to "J."
Chemical composition = SisAlnKoHiO.i + SieAli-.Oji. Sometimes
varying amounts of the iron-compound corresponding to the first-
mentioned silicate occur vicariously. The pterolite of Breithaupt is
probably lepidomelane.
PhJngc'pite Group. — Monosymmetrical typical forms =: OP. -fP —
^P.oo^co. Optically negative; "a " deviating 2^ from the normal to
" c." The plane of the optical axes is parallel to " b." Sp. gr. varies
from 275 to 297.
Phlocjopite. — Composition = SieAl^KBOai + SiioH^Oji and SieMgijOoi,
these compounds often occurring in the proportions 3:1:4. Some-
times the isomorphous compound, SiioOsFl24, occurs in the place of the
second compound, p<Cv. The reddish-brown phlogopites all contain
fluorine, whilst the green ones contain very little, hence it is often
diflficult to distinguish between the latter and meroxene. One charac-
teristic of the phlogopites is their occurrence in granular limestone.
The vermiculite of Webb, and the jefferisite of Brush are most likely
decomposed phlogopite.
Zinnii-aldite (Hthionite of von Kobell, rabenglimmer of Breithaupt,
and kryophyllite of Cooke). — Chemical composition = SigAleKsOoi +
Si6Fei.>024 + Siion2408, these compounds occurring in the proportions
10 : 2 : 3. The potassium compound is occasionally half replaced by
the analogous lithium compound, and the fluorine compound bj the
corresponding hydrogen compound, p^i".
Muscovite Group. — Monosymmetrical ; typical forms OP. — 2P.coPco.
Optically negative, " a " deviating slightly from the normals. The
plane of the optical axes perpendicular to " i," p^v. Sp. or varies
from 2-83 to 2-89. ""
Lepidolite (lithia-mica). — Chemical composition = SSieAlgKeOn +
Siio08F]24, where the potassium compound is partially replaced by the
corresponding lithium compound, and the fluorine compound partially
replaced by the corresponding hydrogen compound. Probably the
cookeite of Brush is a variety of this mineral.
Muscovite (potash-mica, diaxial-mica, phengite, fuchsite, chromium-
mica). — Chemical composition = SieAleKoHiOai + SiioH8024 ; both of
these compounds occurring in the proportions of 3 : 1 in phengite.
Didymite and amphilogite are names for varieties of muscovite. Mar-
garodite and euphyllite are mixtures of muscovite with the followino-
micas, viz., cellacherite, a muscovite containing barium ; sericAte a
muscovite containing magnesia-mica ; damourite, a massive muscovite
sometimes called onlcoslne ; liehenerite and pinite are composed mostlv
of muscovite.
Paragovite (pregrattite, sodium-mica). — Chemical composition =
Si«Al6Na2H4024.
Cossaite is massive paragonite.
Margarite Group. Margarite (perlgllmmer, corundellite, clingman-
nite, emerylite, diphanite). — Monosymmetrical; typical forms
534 ABSTRACTS OF CHEMICAL PAPERS
OP.oo^oo— iP. + 5P. Optically negative, " a " deviating as raucli as
6° from the" normals to "c,"p<'y. Sp. gr. varies from 2-95 to 3'1.
Chemical composition = Si4Al6Ca2H4024. A sodium silicate is inter-
mixed with it in minute quantity. The dudleyite of Genth is probably
an altered margarite. Margarite is nearly related to the clintonite-
group on account of its brittleness and. optical properties, although its
oxygen-ratio is that of a true mica. AstrophylUte, which is also nearly
related to clintonite, is not a mica. C. A. B.
Crystal-system of Cyanite. By G. Rath (Jahrb. f. Min., 1878,
952). — Owing to the absence hitherto of terminal faces, the relation
between the vertical axis and the lateral axis could not be ascertained.
The author obtained the missing infoi-mation from the examination of
a fine crystal from the Greiner in Tyrol, and a crystal from Monte
Campione led to the discovery of a new twin-law. The axial ratio of
the brachy-axis, macro-axis, vertical axis = 09164 : 1 : 0' 70996. The
vertical and macro-axes intersect at an angle of 90°. Besides the
already well-known forms, the following new ones were observed, viz.,
,P, . P, . 2,P2 . 2,P . ,P2 . 2,P2 . oo'P2 . 'P,ob . ,P'ob . 2,P,c^ . P'c5b .
|,P,cd . ooPcb : OP = 101° 161' , ooP : OP = 99° 17' (calculated).
The new twin-law observed on the Monte Campione crystal was "the
twin-plane the basal terminal plane." C. A. B.
Crystal Forms of Epidote. By H. Bucking (Jahrh.f. Min., 1878,
9o6 — 958). — The author adopts the orientation of Marignac,and takes
also the axial ratios of von Kokscharow, viz., a : b : c = 1"5807 : 1 :
1"8057. j3 = 64° 36' as the basis of the various calculations.
Epidote from the Snlzhacldlinl. — The crystals from this locality attain
sometimes a length of 120 mm., and are always developed in the
direction of the ortho-axis, whilst the zone of the hemidomes is very
prominent. The common forms observed are OP . ooPoo . Poo . and P.
The crystals are either single, or twinned parallel to the orthopinacoid.
The author was enabled to add many new forms to the great number
already known, the final result proving that epidote from this neigh-
bourhood exhibits 172 distinct forms.
Epidote from Ai-endal is characterised by the great size and a peculiar
shell-like or zonal structare of the crystals. The number of forms
exhibited by epidote from this locality is 29. The crystals are gene-
rally rich in faces, sometimes single and sometimes twinned (twin-
plane coPco) ; OP predominates in the zone of the hemidomes, whilst
ooPco is often very slightly developed ; the commonest domes are
Poo and 2Poo, and with these P and ooP occur.
Epidote from Striegau. — Crystals from this locality are curtailed in
the direction of the ortho-axis. Twin formation is not observed, whilst
the number of forms is 17.
Epidote from the Fassathal and Allochetthal. — These crystals are occa-
sionally complete at both ends, and attain sometimes a length of from
5 to 10 mm. The forms commonly observed are Poo . -^Poo . 2Poo .
OP . ooPoo and ooP. No twins.
Epidote from Guttannen in the Bernese Oberland. — Two types of crys-
tals are observed here, the first and commonest being characterised by
MIXERALOGICAL CHEMISTRY. 535
the prominence of the clinopinacoid ; whereas in the second type it is
entirely absent. The crystals of the first type are generally tabular,
through the predominance of OP or coPoo ; coPoo is very prominent
and strongly striated. P is also much developed, and the prisms
coP and ooP2 occur often together.
Epidote from TraverseUa is characterised by the occurrence of a long
vertical pi'ismatic type, through the predominance of cxsP, the crystals
sometimes attaining a length of 20 mm. There is also a second type,
the crystals in this case being developed in the dii'ection of the ortho-
axis, with ooP very much developed. The faces in the zone of the
hemidomes are strongly striated. Twins common according to the
usual laws. The epidote from TraverseUa exhibits 17 distinct forms.
Epidote from Bourg d'Oisans. — The crystals from this locality have
long been known, and are characterised by a peculiar development
parallel to the axis of symmetry (clino-axis) ; they are very strongly
striated, grouped together almost parallel to each other, and in sheaves.
The clinopinacoid is the predominating side form. The author o-ives
the results of his examination of epidote from other localities, which
are, however, of less interest than those above referred to. The result
of Biicking's labour is the addition of 147 distinct forms to the 73
already known, making the total number of forms known to occur on
epidote 220. He arranges a'l these in tables according to their zones,
giving at the same time the interfacial angles with corrected angles
for the previously known forms. C. A. B.
Lintonite and other Forms of Thomsonite. By S. F. Peck-
ham and C. W. Hall (Amer. J. Sci. [3], 19, 122). — These varieties of
thomsonite occur in cavities in a dark-coloured rock related to dia-
base, at Grand Marais, Lake Superior; considerable quantities are also
found on the beach beneath the rock, in the form of round, smoothly
puhshed pebbles. Three principal varieties were distinguished.
(I.) Opaque, white, almost conchoidal in fracture, structure but
very slightly fibrous.
(11.) Ordinary thomsonite, of various colours, but always hard and
fibrous ; and (III) opaque and chrome-green in colour, shadino- out in
some to colourless, and translucent with a conchoidal or uneven
fracture.
The hardness of all these varieties is generally between 5 and 6.
Some fibres scratch quartz (H = 7). The sp. gr. is 2"33 — 2"3o. Frac-
ture of I and II fibrous, of III very uneven, and in all directions with
equal facility. With hydrochloric acid they form a thick jelly.
Grains of metallic copper frequently occui' in them, especially in
No. III.
(I.) This form is, as already mentioned, opaque and porcelain-like
in appearance, sometimes banded with trans2:)arent or with yellow
bands ; its composition is as under —
SiO.2. AI2O3. FeoOs. CaO. KoO. XaoO. Hp.
40-45 29-50 0-232 10- 75 0-3'57 4766 13-93 = 99-985
(II.) Specimens of this type are fibrous and radiated from one or
more centres ; the mineral sometimes fills seams and cavities, the
536 ABSTRACTS OF CHEMICAL PAPERS.
centres of radiation then being close together, and the mineral break-
ing easily at the points of juncture of the various systems of concre-
tion. Transparent needles often occur penetrating the masses from
the surface to about halfway towards the centre ; these act strongly
on polarised light.
The composition of this variety is — .
SiO.>. AI2O3. Fe^Og. CaO. K.O. Na.p. H2O.
46-020 26-717 0-813 9-400 0-390 3-756 12-800 = 99-896
(III.) This vai'iety was first supposed to be prehnlte, but its com-
position and sp. gr. show that it is, at any rate closely allied to,
thomsonite. Its sp. gr. is 2-32 — 2-37, and its composition as fol-
lows : —
SiO.,. AI2O3. FeO. CaO. KoO. NaoO. HoO.
40-605 30-215 0-40 10-370 0-49 4 055 1375 = 99-885
In its structure, however, it differs greatly from thomsonite, being
finely granular instead of fibrous. The iron also is combined as
ferrous oxide, instead of being a mechanical admixture of ferric
oxide.
The mineral, -which the author proposes to call Jintonite, occurs
either in small rounded pebbles, or as a crust on tlie exterior of the
previous minerals.
The silica in No. II is considerably higher than in I and III, but it
is probable that, taking its exceptional hardness into account, it con-
tains free silica. If the composition of II be calculated with 40-43
per cent. SiOa, and the iron in all three be omitted, their compositions
come out practically identical. Compared with ordinary thomsonite,
these minerals have a higher percentage of silica and of water, part of
the latter being probably basic. C. W. W.
Some Points in Lithology. II. Ccmposition of the Capillary
Volcanic Glass of Kilanea, Ha-waii, called Pele's Hair. By J.
D. Daxa {Amer. J. Sci. [3], 18, 134). — The composition of this sub-
stance closely resembles that of ordinary dolei'ite ; the following
fit^ures show the relative composition of the two substances, the first
line giving the mean of two analyses of Pele's Hair, the second the
results of an analysis by G. W. Hawes of the " trap " of West Rock,
New Haven, Conn., U.S. : —
II
SiOs.
ALO3.
Fe^Oj.
FeO.
MnO.
MgO.
50-75
16-54
2-10
7-88
trace
7-65
OaO.
Na-.O.
K2O.
P2O5.
Ign.
11-96
2-13
0-56
0-35
= 99-92
SiOj.
AI.P3.
FeoOg.
FeO.
MnO.
MgO.
51-80
14-21
3-55
8-26
0-42
7-63
CaO.
Na.O.
K„0.
P2O5.
Ign.
10-68
2-i5
0-39
0-14
0-63
= 99-72
MIXERALOGICAL CHEMISTRY. 537
The " trap " consists essentially of labradorite and augite, with
some magnetite.
The following details respecting the microscopic characters of Pele's
Hair are given bj C. F. W. Kruckenberg : — The fibres are sometimes
bent and coalesce into loops ; they are often tubular, frequently
contain air-bubbles, and occasionally microlites. The fibre is usually
enlarged where a crystal (or microHte) or an air-bubble occurs. The
crystals are mostly rhombic. C. W. W.
The Eruptive Rocks in the Saar and Moselle Districts. By
A. V. Lasaulx (Jnhrb.f. 2Iin., 1878, 9o5 — 'Jo^). — Tlie eruptive rocks
of the devonian formation between the Moselle and the Saar, consist
(in the northern portion of the neighbourhood of the Moselle) of
diorite and diabase. These rocks are also common to the west of the
Saar as far as the Ardennes. Further south, near the younger " Zech-
stein " and '' rothliegenden " formations, melaphyr and porphyry
occur. The diorites are characterised throughout by light green and
mostly fibrous hornblende, whilst augite is generally absent. The
diabase contains light-grey or reddish augite, which has occasionally
a diallagite-like cleavage ; hornblende is also observed in it sometimes.
Between the two rocks mentioned stands the rock of Kiireuz, which
is a diorite-diabase containingr the aug'ite of the diabase, the horn-
blende of the diorite, and in addition dark-green hornblende, some
biotite, and as a characteristic, uralite. The secondaiy products of
the decomposition of the diabases are viridite, calcite, and very little
epidote. The viridite is a chloritic mineral in both rocks, and has
not a constant composition ; it sometimes resembles dilessite and
sometimes helminth.
Titanic-iron, magnetite, and iron-pyrites are present in both, rocks,
the latter pi'edominating in the diabase, whilst the titanic-iron is pre-
sent in greater quantity than the magnetite. The melaphyrs are
characterised by a preponderance of " base," but its amount varies.
Some melaphyrs are poor in olivine. Three stages of decomposition
are observed on these melaphyrs, viz. : (1.) Where the augite and
plagioclase is clear, the " base " partially unchanged and partially
altered into viridite, the olivine mostly fresh, but the granules are
penetrated with veins of viridite, lastly the magnetite is still fresh,
but surrounded with a brown zone. Calcite is rare. (2.) The plagio-
clase appears clouded in zones, the augite and " base " is changed
into viridite, the olivine is completely converted into viridite, and con-
tains freshly formed magnetite, " brown-iron " in and about the
olivine, but only sparingly in the " ground-mass," primary magnetite
completely changed into oxide of iron, and lastly, calcite in large
amount. (.3.) The plagioclase appears completely clouded, the cha-
racteristic striation being scarcely apparent, whilst the outlines only
of the plagioclase are defined by oxide of iron, all the vii"idite has dis-
appeared, and is changed into oxide of iron, which now imparts its
colour to the whole rock, the olivine is also converted into oxide of
iron, there is no newlj^-formed magnetite, almost all the calcite has
been washed away, whilst silicic acid has more or less replaced it.
The final products of the various processes of decomposition are: —
VOL. XXXYIII. 2 q
538 ABSTRACTS OF CHEmCAL PAPERS.
(1.) Fi'om the ih'orites, limestone rich in epidote (epidosite). (2.)
From the diabase, limestones containing serpentine and dolomite
(ophicalcite). (3.) From the melaphyrs, aluminous and quartzose
brown-ironstone. C. A. B.
Organic Chemistry.
Action of Potassium Carbonate on Isobutaldehyde. By F.
Urech (Ber., 13, 483 — 484). — The author attempts to determine the
rate of polymerisation of isobutaldehyde by measuring the contraction
which a given volume of isobutaldehyde undergoes when left in con-
tact with potassium carbonate for intervals of time varying from
5 minutes to 10 hours. W. C. W.
Diiodopropyl Alcohol and Moniodoallyl Alcohol. By H.
HiJBNER and B. Lellmann (Ber., 13, 460 — 401). — Diiodopropyl alcohol,
C3H5I2.OH, is prepared by adding a solution of iodine in chloroform to
allyl alcoliol dduted with three times its volume of chloroform. The
compound crystallises in colourless needles, which are insoluble in
water, but dissolve in alcohol. The crystals decompose under the
influence of light or heat.
Moniodoallijl alcohol, C3H4I.OH, prepared by warming the solution of
the preceding compound in chloroform, or by treating the solution
with dilute sodium carbonate, forms needle-shaped crystals (m. p.
160°). A third body appears to be formed by the action of a con-
centrated solution of potash on diiodopropyl alcohol. W. C. W.
Ulmic Compounds formed from Sugar by the Action of
Acids. By F. Sestini {Gazzetta, 10, 121— 136).— The author dis-
cusses the results hitherto obtained in this reaction, and as they are
far from concordant, resolved to reinvestigate the subject. He finds
that the formula attributed to the pi"oduct by Mulder is incorrect, for
this chemist dried the substance at 140 — 165", whilst it is decomposed
a little above 100", giving ofE volatile carbon compounds, and amongst
others, formic ncid. Moreover, the criide product of the action of
acids on cane-sugar consists of at least two substances, one of which,
saculmi'c acid, is soluble, whilst the other, saculmm, is insoluble in
cold alkaline solutions.
Following Malaguti's process, a brown voluminous pi'oduct was
obtained, amounting, however, to only about 3 per cent, of the cane-
sugar employed. A microscopic examination showed that it consisted
of numei'ous minute spheres or vesicles, and not of scales or plates, as
might be supposed from the appearance to the naked eye. This pro-
duct is formed abundantly during the first 12 hours' boiling of the
acidulated sugar solution, but the quantity produced then gradually
decreases, and ceases almost entirely after 40 hours with acid 1 : 30.
This is due to the conversion of the sugar into other products, and not
ORGANIC CHEMISTRY. 539
to exhaustion of the acid. The quantity of sugar transformed int«
this product is relatively small, it being very difficult to obtain as
much as 10 per cent, from the sugar. In the course of this action,
the principal product during the first period is saculmin, then saculmin
and saculmic acid are formed in nearly equal portions, and at last
much more saculmic acid is produced than saculmin. The author has
made experiments -which show that the saculmin is formed from the
cane-sugar, whilst the saculmic acid is a product of the decomposition
of the glucose arising from the inversion of the cane-sugar: pure
glucose gave a pi'oduct which was completely soluble in potash
solution.
-During the ulmification of sugar, an appreciable quantity of volatile
acids is produced, besides some carbonic anhydride : the acids are
formic acid, a little acetic acid, and perhaps acids higher in the series ;
at the same time there appears to be present a substance which be-
comes converted into formic acid in. contact with the air, possibly
formic aldehyde. The carbonic anhydride observed is in all probability
due to decomposition of the formic acid.
From these results it would seem most probable that the ulmic
matters instead of being formed from the carbohydrates by simple
dehydration, are really formed from saccharine substances by the
simultaneous elimination of the elements of water, and of volatile
carbon compounds. C. E. G.
Compound of Levulose with Lime. By E. Peligot (Gompt.
rend., 90, 153 — 156). — In order to obtain the lime-compound of levu-
lose in a state of purity, a 6 or 8 per cent., solution of inverted sugar
is mixed with milk of lime, the liquor quickly filtered and cooled to
0°, when the so-called calcium levulosate crystallises out in abundance.
The crystals must be washed quickly to prevent absorption of carbonic
anhydride, and dried in a vacuum. 100 parts of water at 15° dissolve
0"73 part of the salt, producing a solution which is exceedingly prone
to alteration, its alkaline reaction becoming gradually weaker, and its
amber-yellow colour passing to deep brown. When boiled, the solu-
tion quickly becomes neutral, and a precipitate is obtained similar to
that which appears always to accompany the formation of glucic
acid.
The analysis of the pure yellowish-white lime compound, dried in a
vacuum, leads to the formula CeHi-iOe.CaO.HaO, containing 22*0 per
cent, of lime : when dried in presence of quicklime only, a dihydrate
is obtained, which, unlike the stable monohydrate above mentioned,
cannot be preserved even in well-closed bottles ; it is slowly trans-
formed into a brown viscous substance, which appears to contain both
glucic and saccharic acids. By means of calcium levulosate and oxalic
acid, a solution of pure levulose can be prepared, but all attempts to
induce this solution to crystallise have hitherto proved unsuccessful.
J. W.
Rate of Substitution by Bromine in the Acetic Acid Series.
By C. Hell (Ber., 13, ool — 541). — Small tubes containing weighed
quantities of bromine and the acid were heated at 100° for a given
time, the tubes were then opened in a solution of potassium iodide,
2 q 2
540 ABSTRACTS OF CHEMICAL PAPERS.
{ind the amount of iodine libei'ated by the free bromine was deter-
mined by titration with a solution of sodium thiosulphate. From
these experimental data the rate of substitution can easily be calculated.
The process is divided into three stages, 1st, a period of feeble action,
which lasts until 10 — 20 per cent, of the bi'oraine present has entered
into the reaction ; 2nd, a period of rapid substitution, during which
from 10 to 60 per cent, of the bromine combines. In the final stage
the rate of substitution diminishes.
The duration of the first stage of substitution diminishes as the
molecular weight of the acid increases. In the case of isobutyric and
valerianic acids, the number of molecules which have taken part in the
reaction is proportional to the time. The rate of substitution increases
Avith the temperature.
The author believes that when bromine is brought into contact with
a fatty acid, the two bodies exist together in a comparatively inert
state until a certain amount of hydrobromic acid has been liberated,
which promotes the formation of an addition compound. Substitution
now takes place rapidly, since the fatty acid and the bromine are now
in close juxtaposition.
The preparation of substitution products is greatly facilitated by
saturating the fatty acid with hydrobromic acid gas before sulimitting
it to the action of bromine. W. C. W.
The Acids which are formed by the Distillation of the Crude
Fatty Acids in a Current of Superheated Steam. By A. Cahours
and E. Demak^ay (Go'mj't. rend., 90, 156 — 158). — By redistillation in
a current of superheated steam, the crude fatty acids resulting from
the saponification of the neutral fats, are partly resolved into a num-
ber of simpler acids of the acetic series. Thus, butyric, valeric,
caproic, oenanthylic, and caprylic acids are formed, all apparently be-
longing to the normal series. The predominating acids in the first
sample were caproic and oenanthylic, whilst butyric, and perhaps
pelargonic, were present in small quantity only.
Another specimen of 135 grams resulting from the distillation of
nearly 200,000 kilos, of crude acids, gave as pi-incipal product a
liquid boiling between 162° and 164°, which had the composition and
properties of normal butyric acid ; the last portions wliich distilled
between 180° and 190^^ were chiefly valeric acid. From the more
volatile portions of the distillate, two liquids were obtained boiling
between 106 — 122° and 135 — 145", these after a most careful in-
vestigation were proved to be acetic and propionic acids respectively.
A third sample of 180 grams boiling between 102° and 168° was
etherified by distilling it with methyl alcohol and sulphuric acid. On
fractionating the product, ethers were obtained boiling at 35°, 55° —
58'', and 76° — 80°, which on saponification were found to contain
respectively formic, acetic, and propionic acids.
The authors therefore have proved that in the distillation of the
more complex fatty acids in a current of superheated steam, a partial
resolution into simpler terms of the acetic series takes place, they have
isolated and prepared in a state of purity all the acids from formic to
caprylic ; while they do not doubt the presence of higher members of
ORGANIC CHEMISTRY. 541
the series such as pelargonic and capric, they have not been able on
account of their small proportion and high boiling point to effect
their satisfactory separation.
Independently of the acids of the fatty series, a small quantity of
acids belonging to the succinic series appears to be produced ; sebacic
acid was certainly recognised, but the other acid or acids could not be
purified sufficiently to admit of their recognition. They appeared to
be lower homologues of sebacic acid. J. W.
Preparation of Ethyl Acetate. By J. A. Pabst (Bull. Soc. Cldra.
[2], 33, o50 — 351J. — A. cooled mixture of 50 c.c. sulphuric acid and
50 c.c. alcohol is placed in a flask and heated at l4o°, a mixture of
equivalent parts of alcohol and acetic acid, being allowed to run in
slowly ; at tirst a little ether distils over, but after a shoi"t time ethyl
acetate is given off. The reaction commences at 130 — ISo"", whilst at
145° sulphurous anhydride is evolved.
The distillate is washed with a .saturated solution of calcium chlo-
ride, and dried over fused calcium chloride. Pure ethyl acetate is in-
soluble in a solution of calcium chloride, but if it contains oO per cent,
alcohol, calcium chloride solution dissolves appreciable qaantities. A
mixture of 1 vol. ethyl acetate, and 1 vol. alcohol, forms a homogeneous
mixture with 2 vols, of a solution of calcium chloride. By the above
method 90 per cent, of the theoretical yield of ethyl acetate may be
obtained. The reaction which takes place is similar to that in the fm'-
mation of ether by the action of sulphuric acid on alcohol.
Methyl acetate may be prepared in a similar manner. When a
mixture of alcohols is used, a. mixture of acetates is produced,
corresponding with the alcoiiols taken. L. T. O'S.
Action of Ethyl Iodide on Ethyl lodoacetate. By L. Arox-
STEiN and J. M. A. Keamfs {Her.., 13,489 — 4'Jlj. — When a mixture
of ethyl iodide and ethyl iodoacetate is heated in sealed tubes at 130°,
ethyl acetate, ethane, and ethylene iodide (m. p. 82°) are produced—
CHJ.COOEt -1- EtI = CHj.COOEt + CHJ,.
Ethylene iodide is also formed in small quantity when either ethyl
iodide or ethyl iodoacetate is heated at 130°. W. C. W.
Some Derivatives of .3-Chlorobutyric Acid. By L. Balbiano
{Gazzetta, 10, 137 — 148j. — When alcoholic ammonia in large excess
acts on ethyl /:?-chlorobutyi'ate, taking care that the teraperatui'e does
not rise above 7u'"'. it yields ammonium chloride and >S-amidoh utii raiuide
thus: CHMeCl.CHo.COOEt + 3NH3 = CHMeCNHO.CHs.CONH,.
The amide may be separated as platinochloride in distinct yellowish-
red crystals, sparingly soluble in alcohol, and insoluble in ether. On
decompo.sing the platinochloride with the theoretical quantity of pot-
ash a syrupy substance is obtained which is probably the amide, but it
does not crystallise. It is decomposed when boiled with lead hydrate,
ammonia being evolved, and after removing the lead by hydrogen sul-
phide and evaporating, a deliquescent mass of crystals of j3-amiclobn-
tijric add, CHMe(NH,j.CHo.COOH, is obtained." The hydrochloride
542 ABSTRACTS OF CHEMICAL PAPERS.
of /3-amidobutyramide obtained by decomposing the platinochloride
with the theoretical amount of ammonium chloride is a crystalline
deliquescent mass. The yield of the amide obtained in the above reac-
tion is but small, by far the larger portion of the /3-chlorobutyric acid
being converted into resinous products.
In a similar manner, when aniline acts on (3-chlorobutyric acid the
anilide of jS-anilobufyi-ic acid is formed, and may be obtained in the
form of the hydrochloride, CHMe(NHPh.HCl).CH2.C0NPhH. This
substance, which is with difficulty purified from the resinoiis matter
which accompanies it, crystallises in small lustrous plates, only mode-
rately soluble in cold alcohol, but very readily when it is hot, very
sparingly soluble in hot water, and insoluble in ether; it melts at 207°.
A small quantity of another crystalline substance of the formula
CioHisOgN is also produced in the reaction between aniline and dichlo-
robutyric acid. It is only sparingly soluble in cold water, moderately
in water or alcohol when hot. It crystallises in large nodules (m. p.
137 — 139°). This substance, on examination, was found to be the
oxalate of a base, C10H13O2N, which undergoes decomposition when
boiled with baryta, forming the barium salt of anilohutijric- acid,
CMeH(N'PhH).CH2.C00H. The aiithor regards this base as analo-
gous to a betaine of the butyric series in which only one of the
nitrogen valencies is satiTrated by a negative radicle, and proposes for
it the formula O <C]vrpu[j '^CHMe, that of (S-butylhydrophenylhe-
tauie. The base forms a hygroscopic crystalline mass, very soluble in
alcohol and ether. The platinochloride is obtained as a crystalline
precipitate by adding ether to its alcoholic solution, ^-anilobutyric
acid crystallises from its aqueous solution in tufts of needles (m. p.
128°), sjiai'ingly soluble in cold water, more so in alcohol or ether.
The hariavi salt, (CiiiHi202N).jBa, crystallises in scales which are only
very sparingly soluble in cold water and almost insoluble in alcohol
even when boiling. The mechanism of the reaction in which these
compounds is produced is far from simple, as is shown by the amount
of resinous products formed. C. E. G.
Action of Finely Divided Silver on Ethyl Monobromobuty-
rate. By C. Hell and O. Mulhauser {Ber., 13, 473—479). — A com-
plicated reaction occurs when ethyl monobromobutyrate is subjected to
the action of finely divided silver; ethyl bromide, ethyl alcohol, ethyl
butyi^ate, and a mixture of isomeric ethyl suberates (b. p. 245 — 247°)
are formed.
In order to isolate the isomeric acids, the portion of the crude pro-
duct, boiling between 238° and 290°, is treated with strong hydro-
bromic acid at 100", when a crystalline deposit separates out on cooling.
The contents of the tube are neutralised with soda and boiled to
remove the undecom posed ethereal salts, the liquid is then acidified
with dilute sulphuric acid and distilled in a current of steam, when an
oily, uncrystallisable acid passes over. Ether extracts two acids from
the residue, which can be separated by recrystallisation from hot
water. The moi-e soluble acid melts between 110 — 125°, the less
soluble acid melts between 170—180°.
ORGANIC CHEMISTRY. 543
A liydroxysuberic acid, CgHuOs, is formed as a secondary product if
the hvdrobromic acid contains free bromine. W. C. W.
Acids of the Formula CHuO^, derived from Bromobutyric
Acid. By C. Hell and 0. Mulhauser (Her., 13, 479— 432).— The
formation of three acids by the action of hydrobromic acid on the mix-
tare of ethereal salts, which is produced by treating ethyl bromobuty-
i-ate with finely divided silver, has been described in the preceding
abstract.
The volatile acid is a clear oil which is soluble in alcohol, ether, and
also to some extent in water. It has almost the same sp. gr. as water.
The silver salt has the composition CsHnOiAg,. The small quantity
of the substance obtained did not permit of its identity with isocro-
tonic acid being clearly established, although it closely resembles the
latter in certain points.
The two crystalline acids can be easily separated by recrystallisa-
tion from 20 parts of hot water, or by adding dilute sulphuric acid to
a solution of the sodium salts, when the less soluble acid is pi-ecipitated
and the acid of low melting point remains in solution.
The sparingly soluble acid crystallises in white, microscopic needles,
m. p. 184 — 185°; at a higher temperature a portion of the acid sub-
limes, but the rest decompo.ses, forming an oily anhydride soluble in
alcohol, ether, and hot water. The ethyl salt of this acid is not attacked
by alkalis at 100°, although it is saponified by hydrobromic acid at
this temperature.
On heating the acid, m. p. 127", it changes into a liquid anhy-
dride. The ethyl salt of this acid is slowly saponified by alkalis at
100°. The discovery of those two crystalline acids increases the number
of isomeric suberic acids to five. W. C. W.
Amido-acids from a-Bromocaproic Acid. By E. Duvillier
(Cumjjt. rend., 90, 822 — 824j. — Mcth)jl-amido-2(..caproic acid,
CH3.(CHo)3.CH(IS'HMe3).COOH,
is obtained by heating a-bromocaproic acid with an aqueous solution
(if methylamine in a closed tube at 10')° for several hours. It is a
white crystalline substance soluble in 9'8 parts of water at 1 1°, and
much more soluble in boiling water ; slightly soluble in cold, but
readily soluble in hot alcohol, from which it is deposited in nacreous
plates, insoluble in ether. The acid may be heated to 110° without
change, but at a higher temperature it volatilises without fusing,
and gives off ammonia. It gives no reaction with niercurous or silver
nitrate, but with ferric chloride an intense red coloration is produced,
and on boiling a yellowish-brown precipitate is thrown down. The
hydrochloride crystallises in anhydrous transparent flakes, very soluble
in water and alcohol, but insoluble in ether. The platinochloride
forms orange crystals extremely soluble in water, very soluble in
alcohol, but only sparingly soluble in ether. With cnpric oxide this
acid forms a beautiful pale-blue salt, containing 2H2O, which it loses
at 110°.
EtJiijl.amido-x-caproic acid, is obtained in the same way as the pre-
544 ABSTRACTS OF CHEMICAL PAPERS.
ceding compound, and has almost identical properties. It is, how-
ever, but little more soluble in hot than in cold water; the liydrochlo-
ride crystallises with difficulty, and the copper compound contains no
water of crystallisation. The aqueous solutions of both acids have a
neutral reaction and a bitter taste. C. H. B.
Crystallised Oxalic Acid. By A. Villters (Cnmpt. rend., 90,
821 — 822). — Crystallised anhydrous oxalic acid, C0H0O4, may be ob-
tained by dissolving 1 part of the ordinary acid in about 12 parts
of warm concentrated sulphuric acid, and allowing the solution to
stand for several days. The anhydrous acid is deposited in remark-
ably transparent voluminous crystals of the form of octohedra with a
rhombic base, generally modified by the face p of the prima,ry prism,
with a cleavage parallel to this face. When exposed to the air, the
crystals take up two molecules of water and fall to powder.
C. H. B.
Reducing Properties of Potassium-ferrous Oxalate. By J. M.
Edek (Ber., 13, oOU — 502). — A solution of potassium ferrous oxalate is
easily prepared by adding a concentrated solution of potassium oxalate
to ferrous sulphate until the precipitate which is first produced redis-
solves, forming a dark-red liquid. It is a powerful reducing agent,
not only in neutral but also in acid solutions. Platinum chloride,
potassium platinochloride, and silver nitrate are rapidly reduced, and
the chloride, bromide, and iodide of silver are slowly reduced to the
metallic state by potassium ferrous oxalate. This reagent also reduces
warm solutions of copper and mercuric salts, and rapidly decolorises
Prussian blue and converts indigo blue to indigo white.
w. c. w.
Oxypropionic Acid (Oxacrylic Acid). By E. Erlenmeyek
Ber., 13, 457— 460).— /3-Chlorolaetic acid, CH,Ci.CH(OH).COOH,
obtained by the action of nitric acid on monochlorhydrin, is identical
with Richter's acid from epichlorhydrin (J. pr. Ghem., 20, 193), but
is quite distinct from Melikoff's acid (Ber., 12, 2227) prepared by
treating acrylic acid with hypochlorous acid. Both acids yield the
same oxypropionic acid, | /CH.COOH, when acted on by alcoholic
O
potash or soda.
On boiling the solution of the sodium or potassium salt, it is converted
into glycerate. On distillation with dilute sulphuric acid, the acid is
also changed into glyceric acid and a trace of aldehyde is formed, while
sodium phenyloxypropionate under similar treatment yields phenyl-
ethaldehyde.
The ready conversion of oxypropionic acid into /3-chlorolactic acid,
and of epichlorhydrin into unsymmetrical dichlorhydriu, seems to
indicate that the epicyanhydrin of Pazschke (J. pr. Chem. [2], 1, 82)
and Hartenstein (ibid. [2], 7, 297) is a polymeride, since it has not the
property of combining directly with hydrochloric acid.
A crystalline compound, soluble in 72 parts of cold water, is formed,
together with ammonium chloride, by heating /3-chlorolactic acid with
ammonia. W. C. W.
ORGANIC CUEMISTUY. 545
Reaction of Acetone with Potassium Cyanide, Thiocyanate,
and Aqueous Hydrochloric Acid. By F. Urixh (Ber., 13, 485 —
48t)). — The name acetomjlsulpkocarbaminate is given to the compound
C5H:N02S, wliieli is formed by the action of potassium thiocyanate,
cyanide, and aqueous hydrochloric acid on acetone {Ber., 11, 467, this
Journal, 1873, Abst., 488). The sulphur in this substance can be
replaced by oxygen by means of lead oxide forming acetonyl carba-
minate (m. p. lii^). Its melting point falls to 'o7°, if it is heated at
120° in a sealed tube for some hours. Both strong hydrochloric acid
and baryta-water split up the compound into carbonic anhydride,
acetonic acid and ammonia.
Acetonylcarbamic acid is not decomposed by freshly precipitated
oxide of silver, but combines with the metal forming CsHsAgNOs.
When nitrate of silver is added to the solution of a carbaminate, a
crystalline double salt having the composition (C5H7N03)2AgNOr„ sepa-
rates out. W. C. W.
Formation of Tetramethylammonium Nitrate. By E. Duvil-
LTER and A. BuisiNE {Corapt. rend., 90, 872— b74j. — According to
Juncadella {Compt. rend., 1859), methylamine may be obtained by the
action of methyl nitrate on an alcoholic solution of ammonia. The
authors have substituted wood spirit for ethyl alcohol to avoid the
formation of ethylamine. They tind that when 1 mol. of methyl nitrate
is heated in a closed tube at 10U° with 1 mol. of ammonia, monomethyl-
araine is the main product, but small quantities of the di- and tri-
amines are also produced, together with a small quantity of tetra-
methylammonium nitrate.
When 1 mol. of methyl nitrate acts on 1 mol. of monomethyl amine,
about half the latter remains unchanged ; small quantities of the di-
and tri-metbylamines are found, but the principal product is the tetra-
methylammonium nitrate. This substance is produced in still larger
quantities when dimethylamine is heated with methyl nitrate. The
liquid is heated with potash to expel volatile bases, neutralised with
sulphuric acid, and the potassium salts are removed by concentration
and repeated treatment with ab.solute alcohol. The tetramethylam-
monium nitrate is obtained in tine, anhydrous, lamellar crystals, which
may be dried at 130° without undergoing alteration. It is not deli-
quescent, is \evy soluble in water, slightly soluble in cold, but more
soluble in hot alcohol. It burns without leaving any residue, and is
not decomposed by boiling with potash. When an aqueous solution of
the substance is treated with hydrochloric acid and platinic chloride
the platinochloride is deposited in the form of large orange-red
regular octohedrons. C. H. B.
Amines containing Tertiary Radicles. By W. Rudkeff (Bull
Sor. Chlm. [2], 33, ■J.VT—SiJUj.—Trunethijlcarbamine, CMes.NH.,
(b. p. 45°), is obtained as a secondary product in the pi'cparation of
trimethylacetic acid from tertiary butyl nitrile. It is a mobile colour-
less liquid, having the characteristic odour of the amines. Its sp. gr.
at 0" is 0-7137 ; 07054 at 8^ ; and 0-6931 at 15°, giving the coefficient
of dilatation 0-00217 between 0° and 15°, Its salts with hydrochloric,
')iC) ABSTRACTS OF CHEMICAL PAPERS.
nitric, and hydriodic acids are soluble in alcohol, ether, and water, and
are not decomposed on boiling their aqueous solutions. The sulphate
and oxalate are partially decomposed by cold water. By treating sul-
phuric acid with excess of the amine a mixture of neutral and acid
sulphate is obtained. Trimethylcarbinamine readily unites with
(rarbon bisulphide, forming a mixture of a salt of a thiocarbamine,
CS(NH.C4Ho)(S.NH3.C4H9), and dibutylthiocarbamide,
. CSCNH^.aHg)^.
The thiocarbamide cannot be obtained free from the urea.
Dimethi/lethijlcarbaviiiie, CHMcoEt.NHo (b. p. 78°) ; its sp. gr. is
0"7611 at 0° and Ov475 at 15°. It is obtained as a bye-product in
the preparation of dimethylethylacetic acid, and also by the action of
mercuric cyanate on isoamyl iodide in presence of hydrochloric acid,
which the author prefers to potash. Carbonic anhydride is evolved
and isoamyl carbamide,- CO(NH2.C5Hii)2, is formed, which is heated
at 140° with hydrochloric acid under pressure. The amine is a liquid
dissolving in water with evolution of heat. Its properties and salts
correspond with those of the isoamylamine of Wurtz.
Dihutijlamine, (C4H9)oNH. — By allowing a mixture of trimethylcar-
bamine and isobutyl iodide to stand for some time at the ordinary
temperature crystals of dibutylamine hydriodide separate out. The
I'eaction is not accelerated by heat, since the composition takes place
with evolution of butylene. Dibutylamine yields trimethylcarbamine
when treated with potash.
Butijlamylamine. — Crystals of the iodide are obtained by allowing
equal molecules of trimethylcarbamine and amyl iodide to stand at
the ordinary temperature for about a week. The iodide decomposes
spontaneously. Caustic soda and water decompose the amine with
formation of amyleue and trimethylcarbamine. L. T. O'S.
Oxalethyline and Chloroxalallyline. By 0. Wallach and
G. Stricker (Ber., 13, 511 — 514). — The chlorine-atom in chloroxal-
ethyline resists the action of nascent hydrogen, metallic magnesium, or
aluminium, but it can be replaced by treating an alcoholic solution of
the compound with sodium, or better by the action of phosphoiiium
iodide on chloroxalethyline hydriodide, CgHhCINo.HI + H^O. This
substance crystallises in beautiful transparent prisms, which melt in
their water of crystallisation when heated on a water-bath. The
anhydrous salt is hygroscopic.
Oxalethyline, CgHioN^2) is produced by heating this compound in
sealed tubes with phosphorus and hydriodic acid. The crude product
is rendered alkaline by the addition of potash, and the free base
extracted with chloroform. Oxalethyline is a thick oily liquid miscible
with water. It boils at 213", and has the sp. gr. 0'9820. The aqueous
solution produces precipitates with metallic salts. The hydrochloride,
C6Hin]S"2.HCl, is deliquescent ; it forms a beautiful double salt with
cadmium chloride. The platinochloride, (CoHinNs.HCO.PtCU, forms
reddish-yellnw crystals, soluble in hot water. The crystalline silver
salt, (CeH,n]Sr2)2AgN03, is soluble in alcohol and in hot water.
Two modifications of chloroxalethyline appear to exist, the ordinary
ORGANIC CHEMISTRY. 547
variety, which is freely soluble in light petroleum, and an isomeride
insoluble in that solvent.
A solution of diallyloxamide (m. p. 154'', b. p. 274') in chloroform
combines with bromine to form the tetrabromide,
CHoBr.CHBr.CHj.NH.CO.CO.NH.CH^.CHBr.CHaBr,
a white compound insoluble in chloroform and the usual solvents. It
can, however, be recrvstallised from glacial acetic acid. It decomposes
at 220°.
Chloroxalhjline is formed by the action of phosphorus pentachloride
on diallyloxamide, but it has not vet been obtained in a state of
purity. ^ W. C. W.
Bases of the Oxalic Acid Series. By 0. Wallace and
E. ScHULZE (Ber., 13, 514 — 51o). — Claloroxalethyline is decomposed
by sulphuric acid at 220'' with evolution of hydrochloric acid. The
mixture does not blacken. On oxidation with potassium permanganate,
monethyloxamide and an acid melting at 111° are formed. The
soluble compound with zinc chloride, (CgHrjClXo.HCljiZuClo, yields
pyrrol and ammonia when distilled with potash.
Oxalethyline and methyl iodide combine with explosive violence, but
if the substances are diluted with alcohol or ether the addition pi-oduct,
CflHioNo.Mel, is obtained in white hygroscopic crystals, soluble in
alcohol. The polyiodide crystallises in dark-green lustrous needles.
Oxalethyline combines with bromine to form an oily compound, which
yields an insoluble brominated base when treaxed with alkalis.
Chloroxalpropyline, CsHiaClXj (b. p. 235°), is sparingly soluble in
water. Both the platinochloride and the silver salt are crystalline.
Chloroxalamijline, CioHojClXo (b. p. 265 — 270°), is insoluble in water,
but is volatile in a coj-reut of steam. W. C. W.
Formation of Bas^s from Acid Amides. By 0. Wallach and
J. Kamexski {Ber., 13, 6l6—b->rj).~Acetefhijlamide, MeCCNHEt,
on treatment with phosphorus pentachloride, forms the base CpHijClX-j,
which splits up when liberated from its salts, yielding the amidiue,
C'iHiiX.;, and acetic acid.
Triclduracetethylamide, CCl3.CO.NHEt, prepared from ethylamine
and ethyl trichloracetate, crystallises in large colourless plates
(m. p. 74^"), which boil at 229 — 230°. With phosphorus pentachloride
it vields an imide chloride, CCl^.CCl '. NEt, but no base. The di-
chloracetethylamide, CClTI.CO.XHEt (m. p. 67°, b. p. 227°), yields
with phosphorus pentachloride the imidechloride, CCLH.CCl '. NEt
(b. p. 161—164°), and the compound CCLH.CC.lo.NEtPOCl,, which
boils between 140° and 150°.
It has been previously shown (Annalen, 184, 196) that acetanilide
under similar treatment gives the base C1BH15CIN2.
TricJtl or acetanilide, CCIs.CO.NHPh, when treated with phosphorus
pentachloride does not yield a base; but vinnorJdoracetan'dide,
CClH2.CO.NHPh, forms a crystalline hydrochloride, which is deposited
from hot alcohol in yellow needles.
o48 ABSTRACTS OF CHEMICAL PAPERS.
AcebnethyJanilide, MeCO.N]MePh, also produces a liydrocliloride
under like conditions.
Phosphorus pentachloride acts on ethylamine camphorate,
C,„Hie04(NH.,Et)2,
forming a pale yellow liquid, which yields on distillation phosphorus
oxycbloride and a resinous mass containing a base, having the com-
position CuHoiNjO or CUH22N2O. The base is an oily liquid (sp. gr.
1-01 at 20°, b. p. 284—28(3°) insoluble in water. It forms crystalline
addition-compounds with silver nitrate, with methyl iodide and with
bromine. The hjdrochloride crystallises in prisms or plates, which
are soluble in alcohol, and it forms a platinochloride. ^Y. C. W.
Remarks on the Preceding Papers. By 0. Wallace {Ber., 31,
522 — 524). — The author points out the relation between the bases of
the oxalic series and some of the alkaloids, e.g., pyridine and piperi-
diue. W. C. W.
Thiocarbamides with Tertiary Radicles. By W. Rddneff
(Bull. Soc. Chim. [2], 33, 3U0). — Tertiary buti/lthiocarbamide,
ilcaCNCS (m. p. 10-5°, b. p. 104"), is obtained by the action of mer-
curic chloride on the compound CS(NH.C4H9).(S.NH3.C4H9) this
vol., p. 546). It crystallises in large plates, having an aromatic
odour. When treated with ammonia it yields the thiocarbamide,
GS.(NH.CMe3).NH3, crystallising in prisms, and very soluble in
alcohol ; it melts at 165°. By the action of trim ethyl cai'binamine on
the thiocarbimide, di-isobutyl thiocarbamide, CS(NH.CMea)3, is formed,
which is also obtained by heating the compound
CS(NH.aH,)(S.NH,C,H9),
with alcohol. It is soluble in water, alcohol, and ether, and melts at
162".
Tertiarij amyWa'ocarhamide, CMe2Et.NCS. — The salt of the thio-
carbamine, obtained by the action of carbon bisulphide on the amine
CMeaEt.NHj, when treated with mercuric chloride, yields tertiary
amyl thiocarbimide. It is a liquid boiling at 166°, and having a
pleasant odour. L. T. O'S.
Crystalline Form of Nitrosothymol, Lapachic Acid, and
CumicAcid. By R. Panebianco (Gazzetta, 10, 78 — 82). — Nitrosothy-
mol, C6H2Me(C3H7)(NO).OH. — This was prepared from the synthetic
thymol obtained from cumic alcohol cumene, and from camphor
cymene, the compounds from the two sources being identical. The
crystals are monoclinic a : h : c = 1-9874 : 1 : 0-8941, 7, = 94° 57' 20".
Observed forms 100, 010, OUl, 101,101, 110 ; observed combinations
100 010 with the cleavage plane lOl, and the same with 110; 100
010 101 101; the same with OOl. Cleavage parallel to 101. Twin
plane parallel to 100. Positive double refraction 2H„=86° 10' for the
red and 82° 20' for the violet. The colour of the crystals is straw-
yellow.
Lapachic add belongs to the monoclinic system. a : h : c =
0
—
73'' 21'
/3
—
75° 8
7
=
72° 56'
ORGAXIC CHEMISTRY. 549
0720G : 1 : 0-6192 ; ,; = 97° 9'. Obserred forms 100, 001, 101, iOl,
110, 130, 150, 133, 133, h Sh I. Observed combinafions 100 001 101
101 150, the same with 110 130 133 133. Cleavage takes place
easily parallel to 100. The twin plane is parallel to 100.
Cumic Isnpropylhenzoic Add, C6H4(CH2.CHo]\[e).COOH. — The
crystals belong to the triclinic system a:h: c = 207825 : 1 : 1*34669 : —
r = 103° 13'
^ = 100° 50'
r = 103° 44' 30"
Observed forms 100, 001,010, 110, 101, 470, 201. Observed com-
binations 100 001 110 110 470, the same with 010 and with 010 201.
Cleavage plane parallel to 100 imperfect. The crystals are colourless,
and usually have the form 100 greatly developed. C. E. G.
Nitration of Paranitrobenzoic Acid. By H. Hubxbe and A.
Stromeyer (Ber., 13, 461 — 462). — Paraorthodiniti-obenzoic acid,
described by Tieraann and Judson {Ber., 3, 232), and by Griess (ibid.,
7, 1223), can also be obtained by saturating a mixture of fuming
nitric and sulphuric acids with paranitrobenzoic acid. The solution
is warmed on a water- bath and afterwards heated at 170° for 12
hours, the unchanged paranitrobenzoic acid is precipitated by diluting
the mixture with water. Soda is added to the filtrate until a fourth
of the acid present is neutralised ; the liquid is evaporated to drvness,
and the residue extracted with alcohol. From the alcoholic solution
barium nitrobenzoate is prepared, from which the lead salt and the
free acid can be derived. W. C. W.
7-Sulphoisophthalic Acid and the Corresponding 7-Hydroxy-
isophthalic Acid. By K. Heine (Ber., 13, 491— 497).— 7-,S'wZp/io-
isophthalic acid, C6H3(S03H)(COOH)fCOOH) = [1:3: 5], prepared
by heating a mixture of sulphuric anhydride and isophthalic acid, and
purified by conversion into its barium and lead salts, is a thick un-
crystallisable syrup. It forms three potassium salts ; the normal salt,
CgHaKsSO:, crystallises in needles, which are very soluble in water.
A solution of this substance in hot hydrochloric acid deposits beautiful
needles of the mono-potassium salt, CsHsKSOt + 3H2O, on coolint)-.
The crystals are insoluble in alcohol and ether ; they dissolve fi-eely in
hot and sparingly in cold water. C8H4K0SO7 crystallises in lono-
prLsms. The salts of 7-snlphoisophthalic acid, with the exception of
lead sulphoisophthalate, are soluVjle in water.
Trimesic acid appears to be produced by fusing together 7-potassium
formate and 7- sulphoisophthalate.
'l-Hi/droxyisophthalic acid, CfiH3(0H)(C00H)(C00H) =[1:3:5],
is formed by fusing the mono-potassium 7-sulphoisophthalate with
10 times its weight of potash for five minutes. By dissolvino- the
product in water and acidifying the solution with hydrochloric acid,
the new acid is obtained as a colourless crystalline deposit, which
melts at 285°, and begins to sublime at the same temperature. If the
fu.sion is carried on too long, a-hydroxyphthalic acid is produced.
The 7-acid contains 2 mols. of water of crystallisation which are
550
ABSTRACTS OF CHEMICAL PAPERS.
expelled at 100°. It forms three series of salts : CsHsAgOs is de-
posited in slender needles when silver nitrate is added to a hot aqueous
solution of the acid : CsHiAgoOg is thrown down as an insoluble crys-
talline precipitate, when silver nitrate is added to the corresponding
ammonium salt. Calcium chloride does not produce a precipitate in
neutral solutions of the acid, but on addition of ammonia, (0^11305)200.3
separates out. Barium chloride yields an immediate precipitate with
the alkaline solution, and when added to a hot neutral solution a white
salt is formed, which is deposited in needle-shaped crystals from the
liquid on cooling. Lead nitrate produces a white precipitate in neutral
solutions.
Diethyl 7-liydroxyisophthalate, C6H3(OH)(OOOEt)2, crystallises in
monoclinic prisms, which melt at 103° ; the dimethyl salt forms
needle-shaped crystals (ra. p. 169 — 160"^). The following table
exhibits the points of difference between the three isomeric hydroxy-
isophthalic acids : —
Water of crystallisation
Melting point
Solubility in hot water .
Aqueous solution
Ferric chloride
Neutral barium salt. . . .
Diethyl salt
None
Above 300° .
Freely
Non-fluorescent .
Red coloration . .
Very soluble ....
Melting point 52°
/3.
1 molecule
Anhydrous, 243'
Air dried, 239°
Freely
Fluorescent . .
Red coloration
Insoluble ....
2 molecules
1 284—285°
Sparingly
Non-fluorescent
No change
Sparingly soluble
Melting point 103°
W. 0. w.
Acetobenzoic Anhydride. By W. H. Greene (Bull. 80c. CJdm.
[2], 33, 424 — 426).^ — On repeating the experiments of Loir (this
vol., 31) on the action of hydrochloric acid and chlorine on acetoben-
zoic anhydride, the author finds that it behaves in a precisely similar
manner, whether the anhydride is prepared from acetic chloride and
sodium benzoate or from benzoic chloride and sodium acetate. By
treating the anhydride with hydrochloric acid at a temperature below
100^ the liquid solidifies ; between 55° and 60°, acetic chloride distils
over, the distillate which comes over below 120° contains acetic
chloride and acetic acid, and by heating the residue more strongly,
and increasing the current of hydrochloric acid, a small quantity of
benzoic chloride distils over, and it is also found in the residue.
By passing hydrochloric acid into acetobenzoic anhydride in the
cold, the liquid solidifies, and consists of acetic chloride, acetic acid,
benzoic chloride, and benzoic acid. With chlorine, acetobenzoic anhy-
dride, prepared by either method, gave the same products of decompo-
sition, namely, acetic chloride, monochloracetic acid, benzoic chloride,
and nionochlorobenzoic acid. If the reaction takes place between 140°
and 155° the two first bodies are the principal products. There is
some difficulty in separating the chloracetic acid and benzoic chloride,
owing to the boiling points being nearly the same. These results
)
ORGANIC CHEMISTRY. 551
prove the identity of the so-called acetylbenzoic anhydride, and the
benzoylacetic anhydride of Loir. L. T. O'S.
Digallic Acid. By H. Schiff (Ber., 13. 454—4.57). — In replying
to Freda's criticisms (Gazzetta, 9, 327, and Ber., 12, 1576), the author
points out that when sulphuretted hydrogen is passed through a hot
solution of natural or artificial digallic acid, decomposition may take
place in two different ways, viz., that either the digallic acid is simply
converted into gallic acid or sulphur separates out and another acid is
formed in addition to the gallic acid.
Artificial digallic acid is more easily decomposed by sulphuretted
hydrogen, than tannin containing 3 per cent, of glucose.
Hot alcoholic or aqueous solutions of gallic acid can dissolve small
quantities of arsenic sulphide. ]N^o change occurs when the liquid is
boiled. W. C. W.
Chemical Constituents of Stereocaulon Vesuvianum. By
E. PATF.E^6 {Gazzetta, 10, 157). — The author states that by exhausting
this lichen with ether he obtained a colourless crystalline compound,
which after purification by crystallising it from chloroform, appeared
to be identical with atranoric acid, CigHisOg, from lecanora. utra.
Coppola (this vol., .382), found nothing but succinic acid, and although
it is possible that this acid may be present as some salt insoluble in
ether, the fact remains that Coppola missed the principal constituent
oftheHchen. C. E. G.
Homofluorescein, a new Colouring Matter from Orcinol.
By H. SCHWARZ (-Be/-., 13, 543 — 56^). — Sodium homojiuorescei/i, pre-
pared by gently boiling 10 grams of orcinol dissolved in 20 c.c. of a
saturated solution of common salt, with 8 grams of chloroform, and
80 c.c. of a 10 per cent, solution of soda. The liquid soon acquires a
red colour, and after boiling for 10 minutes begins to deposit red
needle-shaped crystals. A second crop of crystals can be obtained
by boiling the mother-liquor with chloroform and soda.
The aqueous or alcoholic solution of the salt has a reddish-yellow
colour. 1 mgrm. imparts a pale yellow colour, and a green fluorescence
to a liter of water. The silver salt is thrown down as a dark red
precipitate when silver nitrate is added to a solution of sodium homo-
fluorescein.
When a concentrated aqueous solution of the sodium compound is
boiled with 150 parts of glacial acetic acid, dark red crystals having a
green metallic lustre are deposited, which, when heated at 100°, lose
32 per cent, of acetic acid and leave pure homofluorescein, C23H1SO5.
This compound dissolves sparingly in water, alcohol, and cold acetic
acid, and it combines with the alkalis and alkaline earths to form
fluorescent solutions, which deposit red needle-shaped crystals on
evaporation. The ammonium salt is very unstable, splitting up at the
ordinary temperature into ammonia and homofluorescein. The barium
salt, CjsHisBaOa -f- SHoO, crystallises in brownish-red needles or scales
which exhibit a golden lustre.
The salts of the heavy metals are insoluble in water.
I
552 ABSTRACTS OP CHEMICAL PAPERS.
The fluorescence of homofluores(^ein is destroyed by reduction with
sodium amalgam, and also by oxidation with potassium permanga-
nate or dicliromate.
Tetra- and hexa-hromohomoeosm are produced by adding the calculated
amoiint of bromine mixed with hot acetic acid to a boiling solution of
sodium homofluoresce'xn in alcohol or glacial acetic acid. The alco-
holic solution of these compounds has a cherry-red colour and a pale
yellow fluorescence. Tetrabromohomoeosin, CoaHuBriOs, forms a pale
red crystalline sodium salt, CosHisNaBriOs + 4H2O.
On adding a solution of iodine in potassium iodide to an aqueous
solution of sodium-homofluoresce'in, a black precipitate is deposited,
which turns red when heated. It consists of tri-iodohomoeosin,
C23H15I3O5. The sodium salt is a red crystalline body, dissolving in
alcohol or water, forming a cherry-red liquid which is not fluorescent.
With acetic anhydride, homofluorescei'u yields a resinous compound
having the composition, CssHe^AciOs + 2H2O or C^sHi^Og .+ 2C4H6O3.
On addition of water to the alcoholic solution of this substance, a
brown syrup separates out, which solidifies, forming brownish-yellow
crystalline plates.
Warm nitric acid (sp. gr. 1"4) dissolves sodium horaofluorescein, but
the liquid rapidly deposits hexanitromonox^jhomofluoresc&in nitrate,
C23H,2(N02)o06.HN03,
as a yellowish-red crystalline powder, which explodes without melting
at 180°. The nitrate is soluble in alcohol, but is decomposed by water
into hexanitrohomofluorescein and nitric acid. The nitro product is
less soluble in nitric acid than in water, and it may be obtained in
golden-coloured rhombic plates having the composition —
by adding dilute nitric acid to the hot aqueous solution. The sodium
salt, Co3Hn(N02)6Na06, and the silver salt, C23Hu(]Sr0o)6Ag06, crys-
tallise in glistening red plates.
Diammonium pentanitrodiazoamidomnnoa'jjliovtnff.uorescehi is deposited
in red or yellow ciystalline plates when a solution of the preceding
nitro- product in boiling ammonia is acidified with acetic acid. From
this compound the ij-i- and the d,i-potassium. salts, CosHnKsNsOie and
Co3Hi2K..NhOi6, were prepared : the former resembles potassium picrate
in appearance, the latter forms pale yellow crystals.
He.rmnidooxyfliwresceinhydrochlonde, C23Hi2(NH2)606 -f HCl + H2O,
prepared by the reduction of the nitro-compound with tin and hydro-
chloric acid, forms transparent colourless crystals, which readily lose
hydrochloric acid and acquire a brown colour. If the reduction
is carried on in an alkaline solution an intense purple colour is pro-
duced.
When treated with a warm aqueous solution of potassium cyanide
the hexnitromonoxyhomofluorescein yields hexanitrohomofluorescein-
cyamic acid. W. C. W.
Xylene Derivatives. By R. Nietzki (Ber., 13, 470—473).--
Amidoazoxylene, prepared by treating xylidine with nitrous acid, crys-
ORGANIC CHEMISTRY. 553
tallises in orange-coloured plates (ra. p. 115°) ; it dissolves in alco-
hol and ether, forming dark yellow solutions which are changed to
carmine colour by the addition of an acid in excess. The hydrochlo-
ride forms red needles, soluble in alcohol. It is decomposed by water.
On reduction with zinc and hydrochloric acid, paraxijlenediamine is
produced together with xylidiue. The crude product is made alkaline
and extracted with ether, and that portion of the residue (remaining
after evaporating off the ether) which boils at 270 — 300° is recrystal-
li.sed from hot benzene. In this way paraxylenediamine is obtained
in colourless needles (m. p. 150°), soluble in alcohol and in hot water.
The salts of this base are very soluble.
Xyloqitiiioue, CgHsO.., formed by the oxidation of xylenediamine or
xylidene melts at 125°, and sublimes even at the ordinaiy temperature,
producing golden-yellow needles. It bears a strong resemblance to
its lower homologues, and is perhaps identical with the metaphloron of
Rommier and Bonilhon (^Compt. rend., 55, 214).
Xyloqriinol, pi'epared by treating xyloquinone with warm sul-
phurous acid solution, is deposited from a hot aqueous solution in
silvery plates (m. p. 212°). It is converted into the quinone by oxida-
tion. Xyloquinone combines with hydrochloric acid, forming mono-
chloroxyloquinol. W. C. W.
Constitution of Rosaniline Salts. By A. Rosenstiehl (Bull.
Soc. Chim. [2], 33, 342—349 and 426— 435).— E. and 0. Fischer
(Annalen, 194, 285) have shown that paraleucaniline is the triamido-
derivative of diphenylmethane, the amido-groups being equally divided
among the phenyl-groups, and moreover parai'osaniline bears the same
relation to paraleucaniline that triphenylcarbinol does to triphenyl-
methane.
Triphcnvlmethane. Triplienylcarbiuol.
H.CPha OH.CPha
Paraleucaniline. Pararosaniline.
H.C(aHi.NH2)3 OH.C(CoH4.NHo)3
In discussing the constitution of the salts of rosaniline, they show
that the base loses the elements of water when it combines with an
acid, and this separation of w^ater they conclude is accompanied by a
rearrangement of the atoms. The formula they give for the combined
base may be either —
C TT
(CeH^.NHOaC : CeHa.NHo, or (CoH4.NHO-.C<^ { \
Of these they prefer the latter, since the former formula would make
rosaniline to be a derivative of the hydrocarbon, Ph.C '. CgHj, which
does not exist. There is therefore one formula for the uncombined
base, and another for the combined, and according to the formula,
^igHnNa, for pararosaniline, it contains two atoms of h^^drogen less
than paraleucaniline, whereas in reality it contains the same number
of hydrogen atoms, and differs by an atom of oxvgen. In the forma-
tion of the salts from the base, CigHnNa, E. and 6. Fischer (Ber., 12.
VOL. XXX VIII. 2 r
554 ABSTRACTS OF CHEMICAL PAPERS.
2351) assume tlaat one atom of nitrogen becomes peutatomic, the
liydrochloride being (C6H4.NH2)2C<( |
Starting Tvitli pai'arosaniline bydrocliloride having the above for-
mula, the formation of paraleucaniline, the diazo-derivative and the base
from it are all attended with a rearrangement of the aromatic group,
the double linking of the nitrogen atom being in each case broken,
and an amido-group formed. If (C6H4.NH2)2C;^ | , is the con-
NH.Cl
stitution of pararosaniline hydrochloride, then (C6H4.NH2)2C<^ |
^NHo.OH
would be the base, and it is no longer a tertiary alcohol, but if the
base is a carbinol, (C6H4.NH2).,C(6H).CfiH4.NH',, then the chloride
should be represented thus : (C6H4.NH,,)2CC1.C6H4.NH2, as the haloid
ether of a tertiary amido-alcohol. The reactions can, by the above
formula, be explained without any alteration in the grouping of the
atoms.
The formation of (1) paraleucaniline, (2) the diazo-derivatives, and
(3) the base from the hydrochloride, may be represented as fol-
lows : —
(1) (CcHi.NHOsCCl + B, = (C6H4.NH2)3CH + HCl.
(2) (C6H4.NH,)3CC1 + 3HNO2 + 2HC1= (C«H4.]S"2C1)3C.0H + 5H2O.
(3) (C6H4.NH2)3CC1 + NaHO = (C6H4.NH2)3C.OH + NaCl.
That the substitution of the alcoholic OH group by chlorine, and
vice versa, is not a new function of these bodies, is seen by the forma-
tion of methyl chloride and benzyl chloride, and notably triphenyl-
chloromethane, which is so unstable as to be decomposed by the
moisture in the atmosphere; it is also readily reduced by hydrogen.
The question of the group, (C6H4.NH2)3C, playing the part of an
electropositive element, only needs reference to the reaction of nitro-
form with potash, forming (N02)3C.K, in which the nitro-group
(N03)3C plays the part of an electronegative element ; such being the
case, it is not impossible that the amido-group, (C6H4.NH2)3C, should
play the part of an electropositive element.
Leucaniline forms a series of triacid salts, each of the groups
(C,;H4.NH2) acting as a primary amine, and uniting with one molecule
of a monobasic acid, paraleucaniline hydrochloride being —
(C6H4.N.H3C1)3CH.
Pararosaniline ought to form two series of salts, the monacid salts
and the series corresponding with the chloride (C6H4.NH3C1)3CC1.
This is in accordance with fact and with the views of Hofmann, although
he considered the polyacid salts as triacid, based on his analyses,
which were only approximative owing to the instability of the salts,
and on his idea that rosaniline was a triamine. Pararosaniline there-
fore as a carbinol forms two series of salts, (1) ethers of a tertiary,
ORGANIC CHEMISTRY. 555
aromatic amido- alcohol, and (2) salts of the ether, which is a trlacid
amine.
In explaining the constitution of malachite-green, E. and 0. Fischer
have again resorted to the double linking of the nitrogen atom when
the base is combined. At first ihej proposed for the combined base
Me.N.CeH, CeH,
the formula, y^\ I » O" ^^^ assumption that formyl alde-
Ph^ ^NMe
hyde was formed when the leuco base is oxidised, this beino- denied by
P\ CeH,
Doebner: the j suggest the foi-mula, ,r „ / \l , , which
is derived from the carbinol, PhC(OH)(CeH4.XMe2)2, by the hydroxyl
uniting with an atom of hydrogen of one of the methyl groups leav-
ing the unsaturated link of the carbon of the methane to unite with
the nitrogen (which becomes pentavalent) of the group 06114.1^^16.
thus formed. When this base unites with an acid, the hydrogen of
the acid unites with the group CH2, forming methyl, and the acid
radicle saturates the vacant nitrogen link, the hydrochloride beino-
Ph^ CsH,
;C<^ I . A body having such a formula belongs to
MeoT^.CeH/ ^NMe.Cl
the class of quartemary ammonium compounds, in which the chlorine
is only replaced by OH with great difficulty. In this case, however,
the change is easily effected. To meet this objection, E. andO. Fischer
assume that since the nitrogen is united to triphenylcarbinol, it has
special properties, and that the reaction takes place in two stages, the
ammonium hydroxide, !C<^ I , which readily undergoes molecular
^NMeo.OH
change, the double link breaking up, and the result being the carbinol
; C(0H).C6H,.XMeo.
Starting with that formula for malachite-green, the author explains
the above reactions on the same principle as he does the constitution
of the pararosaniline salts, namely, by considering the salts as ethers
of the carbinol. Thus malachite-green hydrochloride is —
PhCClCCeHi.NMes)..
By so doing, the formation of a hypothetical base is not necessary,
and the nitrogen in the salts derived from both bases has the same
properties, which is not the case according to the views of E. and 0.
Fischer, in the one case nitrogen being trivalent, and in the other
pentavalent.
Regarding E. and 0. Fischers views on the identity of the violet
from methylaniline and Hofmann's violet, the author does not con-
sider the evidence in support of them conclusive, but maintains rather
that the violet from methylaniline would be —
PhMeN.CCl(C6H,.NMe2)2,
556 ABSTRACTS OF CHEMICAL PAPERS.
whilst Hofmann's violet from pararosaniline would be—
MeHN.C6H4.CCl(C6H4.NMe2)2.
To establish their identity, a molecular change would be necessary.
Discussing the theory of the double linking of the atoms and its
bearing on the colour of bodies, the author maintains that the views
of Graebe and Liebermann (Ber., 1, 106, 1868) have not been con-
firmed, for since the constitution of anthracene is fully established,
the cause of the coloration of the anthraquinones cannot be due to
double linking. Again, there are nitroform, the nitroanilines, and the
nitrophenols, colouring matters which have no double linking.
L. T. O'S.
Conversion of Azoxybenzene into Oxyazobenzene. By 0.
Wallach and L. Belli (Ber., 13, 525 — 527). — When water is added
to a solution of azoxybenzene in warm sulphuric acid, unaltered
azoxybenzene and an isomeride are precipitated. The new compound
ciystallises in red pyramids, which have a metallic lustre, and appears
to be identical with the oxyazobenzene of Griess (Ber., 3, 233). The
formation of this substance is probably due to the following reac-
tions : —
(PhN)oO + HoSOi = PhOH + PhN':N.S03H + 0
PhOH + PhNlN.SO^H = PhN : N.CeHi.OH + HoSOi-
w. c. w.
Nitration of Salicylanilide. By C. Mensching (Ber., 13, 462—
4(yo) .—a-Nifrosal icylaniUde (m. p. 224°) produced by the action of
nitric acid on salicylanilide, is converted into a-metanitrosalicylic acid
by treatment with alkalis.
SaUcylorthonitranilide, C6H4(N02).NH.CO.C6H4.0H, obtained by the
action of phosphorous chloride on a mixture of orthonitraniline and
salicylic acid, crystallises in yellow plates, which dissolve freely in
benzene, but are only sparingly soluble in petroleum and in alcohol.
Nascent hydrogen converts salicylorthohitranilide into an anhydro-
NH
compound, C6H4<' ');,C.CJIi.O'£i, which forms colourless needle-
\ N^
shaped crystals (m. p. 222'5°), readily soluble in ether and alcohol.
This substance combines with acids forming colourless salts.
w. c. w.
Thiamides. By O. Wallach (Ber., 13. 527— 530).— The sodium
compounds of the isoihiaviirles, SR".R.C;isR' are easily obtained in
colourless glistening crystalline plates by adding ether to a mixture of
a concentrated alcoholic solution of tlae thiamide (1 mol.) with a
freshly prepared concentrated alcoholic solution of sodium (1 atom).
The sodium compounds dissolve freely in water. "V\'"hen cai"bonic
anhydride is passed through the aqueous solution, the thiamide is
deposited in a state of purity.
Sodium thiacetanilide exhibits the following reactions. It produces
with silver nitrate a black, with lead acetate a white precipitate, which
turns black on boiling, with copper sulphate a yellowish-green, with
ORGANIC CHEMISTRY. 557
mercuric chloride a white precipitate, which changes to yellow when
boiled, with mercurous nitrate dark brown, ferric chloride white, and
with cobalt nitrate a greenish- white precipitate.
Metliijlisothiacetanilide, SMe.MeC '. NPb, prepared by the action of
methyl iodide and sodium on thiacetanilide, boils at 244 — 246°. Thi-
acetmethylanilide, SMe.CNi^IePh, from acetmonomethylanilide, crystal-
lises in colourless monoclinic plates soluble in ether, chloroform, and
alcohol. This compound melts at 58 — o9\ and boils at 290°. The
two isomerides, thiacetorthotoluidide and thiacetparatoluidide, melt at
07° and 130° respectively.
The isothiamides combine with the iodides of alcoholic radicles at
the ordinary temperature, forming a crystalline mass.
w. c. w.
Orthochlorobenzparatoluide and its Derivatives. By H.
ScHREiB (Ber., 13, 4G5 — 408). — By the action of orthochlorobenzoio
chloride on paratoluidine, colourless crystals of orthochlof-uhenzpara-
toluide are obtained. This compound melts at 131°, dissolves freely in
alcohol, and yields several nitro-prodacts.
OrthocJiIorobenzmetanitroparatoluide prepared by dropping the pre-
ceding compound into a mixture of 1 part of fuming and 3 parts of
concentrated niti'ic acid, forms yellowish-green crystals (m. p. 139°)
soluble in glacial acetic acid. It yields metanitrotoluidine on decom-
position with alcoholic potash.
Diiiitro-orthocldorohenzparatoluide, obtained by treating the mono-
nitro-derivative with hot fuming nitric acid, forms colourless silky
crystals (m. p. 228°), soluble in chloroform and in glacial acetic acid.
The trinitro-prodact, CuHgiSTiOTCl (m. p. 239°) is prepai-ed by heat-
ing a solution of orthochlorobenzparatoluide in fuming nitric acid,
and resembles the preceding compound.
Orthochlarobenzaniidoparatoluide (m. p. 153^) is formed by the reduc-
tion of the mononitro-derivative by tin and glacial acetic acid saturated
with gaseous hydrochloric acid. When an aqueous solution of hydro-
chloric acid is used, chlorobenzoic acid and diamidotoluene are pro-
duced. The amido- compound is soluble in alcohol.
By the action of benzoic chloride on the preceding substance, colour-
le.ss needles (m. p. 178°) are obtained, w'hich have the composition,
CeHaMe.NHCOPbNHCO.CeHiCl. This base yields on distillation
anhijdro-ortliocTilorohenzmetamidoparatoluide, C6H3Me.]S';C(isH).C6H4Cl.
w. c. w.
Action of Alcohols and Phenols on Acid Imide Chlorides.
By 0. Wallach and A. Liebmann {Ber., 13, 506 — 511). — If oxame-
thane chloride, COOEt.CClo.NHo, is covered with an equivalent quantity
of benzyl alcohol, it dissolves in the alcohol, and a sudden evolution of
ethyl chloride and hydrochloric acid takes place. The mixture on
cooling deposits white needle-shaped crystals (m. p. 135°), which
have the composition NHi.CO.COO.CHaPb.
Oxamethane chloride yields similar compounds with isobutalde-
hyde, fermentation amyl alcohol and anhydrous phenyl, viz. : —
XH,.C0.C00.CiH9 (m. p. 90°), NH.,C0.C00.C5Hu (m. p. 93'),
558 ABSTRACTS OF CHEMICAL PAPERS.
and NHo.CO.COOPh (m. p. 132°). The first of these three compounds
is also produced by saponifying isobutyl oxalate with ammonia.
By heating together phenol and benzanilidimide chloride, a green
syrupy liquid is obtained, which solidifies in a few days to a yellow
mass (m. p. above 260°) insoluble in ether, chloroform, and benzene.
On exposure to moist aii-, it rapidly decomposes into phenol, phenyl
benzoate, benzenyldiphenylamidine hydrochloride, and aniline hydro-
chloride. If the syrupy liquid is protected from the influence of
moisture by immersion in anhydrous ether, it is found to have the
composition OPh.PhC '. NPhHCl.
Its decomposition is represented by the following equations : —
OPh.PhC : NPhHCl + H.O = Ph.COOPh + NH,PhHCl
OPh.PhC :NPh + NHoPhHCl = NHPh.PhC: NPhHCl + PhOH.
w. c. w.
Synthesis of Phosphenyl Sulphochloride. By H. Kohler
(Ber., 13, 463 — 464). — Phosphenyl sulphochloride can easily be pre-
pared by allowing sulphur chloride to drop slowly into a flask (fitted
with an upright condenser) containing phosphenyl chloride, 3PhPCl3
+ SjCl, = 2PhPCloS + PhPCli.
When the reaction is complete, the flask is cooled down in a freez-
ing mixture, which causes phosphenyl tetrachloi'ide to crystallise out.
The liquid portion of the product is shaken up with water, di'ied, and
rectified ; the phosphenyl sulphochloride boils at 270°.
w. c. w-
Action of Bromine on Diphenylm ethane. By C. Friedel and
M. Balsohn (Ball. Soc. C/iim.[2], 33, 337— 342).— Diphenylmethane,
prepared by the action of benzoic chloride on benzene in presence of
aluminium chloride, when treated with 2 mols. of bromine, yields
ili'l'ilieiiuhUhroviomeUiane, CBrjPhj, a brown liquid which solidifies on
standing. It is decomposed by repeated distillation or by continued
heating, being converted into a crystalline solid (m. p. 214*^) contain-
ing 4 per cent, of bromine, which is obtained ia orthorhombic plates
when heated at 150° with alcohol under pressure. It consists of
impure tetraphenylethylene, PhoC '. CPho, from which the pure sub-
stance may be obtained by treating the solution of it in toluene with
sodium for some time.
When heated with water at 150° for some time, diphenyldibromo-
methane is in great part converted into benzophenone.
Diphenylmonobromomethane, CKBrPho. (m. p. 45°). — By the action
of 1 mol. bromine on 1 mol. diphenylmethane, a brown liquid is
obtained, from, which crystals of the monobi^omo-compound separate
on cooling ; it is very soluble in benzene. By the action of alcoholic
potash, the bromo-compound is converted in the ethyl ether of di-
phenylcarbinol, CHPhj.OEt, an oily liquid boiling at" 288°. Linne-
mann (Annaleii, 133, 17) obtained the same body by the action of
sulphuric acid on a mixture of benzhydrol (diphenylcarbinol) and
alcohol, and describes it as a liquid boiling at 183°, and turning green
when exposed to the light ; that prepared by the authors is not affected
by sunlight. The same ether is obtained by tlie continued boiling of
the bromo-compound with alcohol.
ORGANIC CHEMISTRY. 559
The amyl ether is obtained bj the aotion of amyl alcohol and potash
on diphenylmonobromomethane. It is an oily colourless liquid
(b. p. sur).
Diphenylmethylacetate, CHPho.OAc, is obtained as a liquid (b. p.
310°) by treating- the bromo-compound with potassium acetate. The
continued action of alcoholic potash on the acetate converts it into
diphenylcarbinol, CHPho.OH (m. p. 65^).
When heated with water at 150° for some time, diphenylmonobromo-
methane yields diphenylcarbinol and the corresponding ether. The
latter is sparingly soluble in alcohol, from which it crystallises in
small prisms. It melts at 110° (Linneman, 118°), and on cooling
remains liquid at temperatures much below its melting point ; it finally
solidifies to an opaque crystalline mass, which melts at the original
temperature. The ether crystallises in anorthic prisms from its solution
in a mixture of alcohol and benzene.
Diphenylcarbinol is obtained in fine needles by adding water to the
mother-liquors of the ether.
Diphenylmonobromomethane is gradually converted into the car-
binol by contact w'ith water at the ordinary temperature.
L. T. O'S.
A New Colouring Matter. By W. v. :\[iller (Ber., 13, 542—543).
— '■ Biebrich Scarlet ' is a mixture of " mandarine yellow" with several
red colouring matters, two of which proved to be the di- and tri-
sulphonic acids of the compound PhX '. N.CoHi.N ! I^.Ci„Hn.OH.
W. C. W.
Laevorotary Terebenthene from French Turpentine Oil. Bv
F. Flavitzky (Bull. Soc. Chim. [2], 33, 21tG).— This terebenthene
yields hydrate of terebenthene not only when treated with nitric acid,
but also with sulphuric or hydrochloric acid. The reaction takes place
more quickly when hydrochloric acid is used than with either of the
other acids. By treating lasvorotary terebenthene with alcohol and
sulphuric acid (sp. gr. 1'64), the rotary power disappears, and a sub-
stance boiling at 175'^ is obtained, proljablv an isomeride.
L. T. O'S.
Adipic Acid from Camphor. By J. Kachler (Ber., 13, 487—488).
— Camphor yields on oxidation with chromic or nitric acid, cam-
phoronic acid, C0H12O5, hydro-oxycamphoronic acid, CigHuOfi, and some
syrupy acids which were not investigated. This confirms the accuracy
of the author's former experiments (Annale^i, 200, 340), but does not
agree with Ballo's observ^ation (Ber., 12, 1597, and this vol., p. 50)
that adipic acid is formed wheil camphor is oxidised with chromic
acid. W. C. W.
Resin from Rosewood. By A. Terreil and A< Wolff (Bull.
Soc. Chim. [2], 33, 435 — 436). — The resin obtained from rosewood
has a brilliant black colour with a brown reflection, a vitreous fracture,
and a balsamic odour; its sp. gr. at 15° is 1*2662, and it melts at 95°.
It dissolves in all proportions in alcohol, but is less soluble in ether,
chloroform, and carbon bisulphide, and is insoluble in water.
Soda and potash dissolve the resin, forming brown-coloured .solutions,
from which it is again separated in brown flakes on adding an acid ;
5(U) ABSTRACTS OP CHEMICAL PAPERS.
on boiliiio- tlic solution an odour resembling benzaldeliyde and haw-
thorn is evolved. Sulphuric acid also dissolves the resin with a blood-
red colour ; by adding water, the resin is precipitated without alter-
ation. W'hen treated with nitric acid, it yields an acid of an orange
colour crystallising in needles.
On distillation, white vapours are evolved at first, having an odoar
resembling those from gum benzoin, but containing no benzoic acid,
then an essential oil passes over, and finally tarry matters. Its analysis
corresponds with the formula CjiHoiOe ; it forms salts with lead and
barium.
By extracting other coloured woods, such as amaranth wood, iron
wood, ebony, &c., with alcohol, resins resembling that from rosewood are
obtained, but not in so large a proportion; rosewood yields 35 per cent,
of its weight of resin. L. T. O'S.
Chlorophyll. By Pringshein {Covipt. rend., 90, IGl — 165). — By
exposing a portion of vegetable tissue under the microscope to bright
sunlight concentrated by means of a large lens, the author has been
able to follow by direct observation the effects of light on chlorophyll,
and on the protoplasmic contents of the living cell. In this manner
he has proved the existence in chlorophyll of a colourless, crystallisable,
oleaginous substance, hitherto unknown, which appears to have a
direct relation with the assimilation of carbon by the green parts of
plants. This substance, named liijpocldorin, has not been isolated in
a pure condition, but it has been shown to be the only carbon com-
pound, in phanerogams at least, which cannot be formed without the
aid of light.
Researches on chlorophyll itself have fairly proved that this pigment
is not decomposed in the act of carbon assimilation, and that it cannot
be considered as the mother-substance of all or any of the carbon com-
pounds found in plants.
It is true that its decomposition in the isolated cell can be directly
observed, but this decomposition is due to the action of oxygen, and is
quite independent of absorption of carbonic anhydride, or even of the
presence of this gas.
The author's micro-photochemical researches on the green cell show
that respiration or inspiration of oxygen increases in a corresponding
ratio with the intensity of the light, and that this absorption may
become so great as to be positively injurious to the plant; the energy
of oxidation becomes then greater than the energy of assimilation, the
hypochlorin disappears, and the other combustible substances which
together make up the contents of the cell, are rapidly oxidised and
destroyed. But the chlorophyll by its power of luminous absorption
counterbalances these two functions ; it acts as a protective screen,
absoi'bing tlie chemical rays and diminishing respiration, thereby
enabling the assimilation of carbon by the plant to keep pace with the
oxidation of its carbon compounds.
When the particles of chlorophyll are examined carefully under the
microscope they are seen to be porous bodies, the solid portion of
which, like a sponge, is impi-egnated throughout with an oil, in which
the green pigment is dissolved, and which generally contains the
ORGANIC CHEMISTRY. 561
crystallisable substance termed hypochlorin. Protected by the
coloured pigment, the hypochlorin, which appears to be the mother-
substance of the carboliydrates, does not undergo rapid combustion,
but either remains unaltered in the chlorophyll, or suffers only a regu-
lated oxidation, such as may be properly said to be one of the life
functions of the plant ; in concentrated solar light, however, the
hypochlorin is instantly destroyed before even the chlorophyll has
had time to be attacked.
The protective action of the chlorophyll is the new point which the
author considers he has satisfactorily demonstrated. J. W.
Analyses of Cliloropliyll. By Rogalski (Compt. rend., 90,
881 — 882). — Chlorophyll obtained by Fremieux's method from Lolium
perenne gave the following results on analysis. The numbers in the
second column are the results of an analysis of crystallised chlorophyll
made by A. Gautier in 1879 : —
Rogalski. Gautier.
C 73015 73-97
H 10-377 9-80
X 414 4-1.5
O X 10-33
Ash (Ca) 1-6.57 (Phosphates) 1-75
C. H. B.
Alkaloids of Belladonna, Datura, Jusquiame, and Duboisia.
By A. Ladexburg {Gompt. rend., 90, 874 — S7t3). — BeUadonna, as is
well known, contains atropine and hyoscyamine ; Datura stramoniura
contains hyoscyamine, and probably atropine ; jusquiame contains
hyoscyamine and another alkaloid, which gives a compound with gold
chloride, fusing at 200"^. Duboisia viyoporoides contains hyoscyamine.
Hyoscyamine crystallises in small needles, fusing at 108'5°. It is iso-
meric with atropine, from which it is distinguished by forming a com-
pound with gold chloride, which fuses at 159°, and has a brilliant
lustre, whilst the corresponding atropine compound melts between
135 and 137°, and has no lustre. "When treated with baryta, it is
easily transformed into tropine and tropic acid, products identical with
those obtained from atropine, which, moreover, may be artificially re-
produced by heating a mixture of tropine and tropic acid with hydro-
chloric acid, Hyoscyamine, which comes into commerce as li'jJit
atropine, affects the pupil of the eye in the same way as atropine.
C. H. B.
Composition of Diastase and Beet Mucilage. By C. Zul-
KOw.sKi and Gr. Rexxer {Bied. Centr., 1879, 929j. — Diastase was
extracted from malt by glycerol, precipitated and washed with alcohol,
redissolved and reprecipitated. A product soluble in water was ob-
tained, having the following composition: — C, 47-57; H, 6-49;
N, 8-16; O, 37-G4; ash, 3"1G per cent., and a little sulphur.
From beetroot has been extracted by similar means a body contain-
ing 5 per cent, of nitrogen, and bearing a great resemblance to
Scheibler's " frog spawn." J. K. C.
562 ABSTRACTS OF CHEMICAL PAPERS.
Diastase. By J. Kjeldahl (Dingl. polyt. J., 235, 379 — 387, and
4'.52^4G0). — This research comprises a considerable amount of experi-
mental work undertaken by the author with a view of solving several
questions which have arisen as to the active fermenting principle of
malt, known as diastase. A normal solution of malt-extract was pre-
pared. As to the influence which diastase is said to exercise on the
production of sugar, the author in his investigations arrived at the
following law. The proportion of the amount of diastase of two malt-
extracts may be expressed by the reducing power which, they effect,
providing that both act on the same quantity of starch at the same
temperature, during the same period of time, and that the reduction
does not surpass 25 — 30. With regard to the influence of temperature
on tlie yield of sugar, a series of trials was made, showing that at tem-
peratures above 63"^ the fermenting power is weakened, whilst below
63'^ it does not appear to be affected. It was further proved that by
long- continued digestion the same yield can be obtained at all tem-
peratures below 63" as that obtained at 63°, and that the action of
diastase at all these temperatures is the same, inasmuch as the yield
of sugar may reach the same proportions in each of these cases.
Other questions of minor importance are considered in the original
])aper, such as the fermenting power of barley, the formation of diastase
during the preparation of malt, the diminution of the fermenting
power during the baking process, the influence of the concentration on
the production of sugar, the influence of foreign ingredients on the
yield of sugar, viz., sugar, dilute acids and alkulis, salts of the heavy
metals, other salts, alkaloids, alcohol, &c.
In conclusion, the authoi* bi-iefly refers to a substance called ptyalin,
the diastase of saliva, which resembles the diastase of malt in several
of its properties. D. B.
Oxidation of Cholic Acid. By P. L.vrscprrxoFF (Bull. Soc Chim.
[2], 33, 21J7). — The formation of stearic and palmitic acids, &c., by
the oxidation of cholic acid with potassium permanganate and sul-
phuric acid (Tappeiner, this Journal, 36, 388), is due to impurities
contained in the acid, which are not removed by washing with ether.
The acid purified by means of its barium salt does not yield any fatty
acids on oxidation. L. T. O'S.
Albuminoids. By W. Knop (Bied. Centr., 1879, 885—887).—
Assuming for albumin the formula CeoHiooNieOM, for the purpose
of comparison, the author obtains the compounds C6(,H97Br3Ni20.>i,
C6oH96B!-4Ni20jn, and CfioHgfi.aBrs.sNiaOoi, by the action of bromine-
water in the cold on albumin. Other brominated products obtained
from horn, glue, feathers, &c., differ from albumin by one or more
molecules of tyrosine, leucine, and water. " J. K. C
PHYSIOLOGICAL CHEMISTRY. 563
Physiological Chemistry.
Digestibility and Nutrient Power of Caroba Beans. By H.
Weiskk and others {Bled. Centr., 18!^0, 110 — 115). — The experiments
were made with two Southdown Merino sheep. The food given con-
sisted of wheat straw, caroba beans, peas, beans, sugar, and starch in
various proportions, and the amount of each digested and the influence
of the caroba beans on the absorption of the albumin of the other foods
observed. In all cases the caroba beans had a depressing influence, so
that the albuminoid matter was not so freely digested as when it was
absent. Even when large quantities of albuminoid matter were given,
such as linseed cake, there was a considerable depression.
E. W. P.
Quantitative Estimation of Digested Protein. By 0. Kellxer
(Bied. Centr., 1880, lo7 — llO). — Schulze has only determined the
nitrogen in the biliary secretions which occurs in the fseces of Herbi-
vora fed on food poor in nitrogen. The author has, therefore, under-
taken the estimation when the food was poor and rich in nitrogen.
The following are a few of his results : —
N in biliary
Daily food. secretiou.
Oat straw 0257 gr.
Wheat straw 0"396 ,,
Ditto, + 400 gr. beans . . 0-660 „
Ditto, + 800 gr. beans . . I'Oo? „
According to the above figures, the nitrogen which is contained in
the faeces is very variable, but appears to be directly proportional to
the dry matter digested. When food poor in nitrogen is given, the
pei'centage of nitrogen in the fasces appears to increase. It lias also
been remarked that tbe outer surface of the fteces of sheep when dry
cracks and peels off in thin layers ; this outer coating appears to contain
a large quantity of mucous matter. E. W. P.
Absorption of Various Alimentary Materials in the Human
Intestinal Canal. By M. Klbxer (Zeits.f. Biulugie, 15, 115 — 204).
— The diet of the persons experimented on was carefully regulated,
and the fasces periodically collected and analysed. The difference
between the amount of nitrogen, carbohydrates, &c., entering, and that
leaving the system in the fseces was thus determined ; this difference
was regarded as affording a measure of the aliment absorbed in the
intestinal canal. The following tables contain the more important
numerical results. A lengthy discussion of these results will be found
iu the original. The quantities of food, &c., are stated in grams.
Digested.
Dry fsecal
matter.
Dry matter.
Albuiuiu.
212 gr.
2gr.
319 gr.
560 „
66 „
318 .,
651 „
141 „
315 „
838 ,.
222 „
359 „
564
ABSTRACTS OF CHEMICAL PAPERS.
Table I. — Absorption of Fat.
Pc'rcentage
Fat in Fat in
Diet. food. faeces. loss.
Bacon 96-0 17-2 17-i
191-2 lo-2 7-8 .
'' and butter ... . 350;5 44-6 127
Rice and marrow .... 74'1 5'3 7"1
Eo-o-s 118-5 5-2 4-4
Butter 234-3 5-8 2-7
Potatoes and butter . . 143-8 5-3 3-7
Non-nitrogenous food
with butter 157-8 2-5 i-8
Cabbages and butter. . 88-0 8-2 G'l ^
Maccaroni with gluten 73-4 5-1 6-96
with butter 72-2 4*2 5-7
Carrots and butter . . 47-0 2-5 6-4
Maize and butter .... 43*6 8-0 17-5
Milk 160-0 7-4 4-6
119-9 6-7 5-6
, 95-1 3-0 3-3
„ 79-9 5-7 7-1
and cheese .... 213-5 24-6 11-5
138-6 3-8 2-7
133-6 10-4 7-7
Animal food and butter 23-4 4-0 17-0
20-7 4-4 21-1
Table II. — Absorption of Carbohydrates.
Carbohydrates Carbohydi-ates Percentage
Diet. in food. in faeces. loss.
White bread 670 5 0-8
„ 391 G 1-4
Rice 493 4 0-9
Maccaroni 462 6 1-2
SpatzeJ} 558 9 1-6
I'at' 259 4 1-6
Diet free from nitrogen 674 11 1*7
Maccaroni with gluten 418 10 2-3
Maize 563 18 3-2
Fat^ 226 14 6-2
Tat^ 221 14 6-2
Fat* 234 16 6-8
Potatoes 718 55 7-6
Black bread 659 72 109
Cabbages 247 38 15-4
Carrots 282 50 18-2
1. Prepared by mixing lueal, water, milk, and eggs to a stiff paste,
passing through a wide sieve, and boiling with water.
2 and 3. Fat supplied in form of bacon, eaten alternately with
bread and with animal food. 4. Fat supplied in form of butter. 5.
In form of butter and bacon.
PHYSIOLOGICNX, CHEMISTRY. 565
Table III. — Absorption of Nitrogen.
J^itrogen in Nitrogen in Percentage
Diet. food. faeces. loss.
Animal food 48-8 1-2 2-5
400 1-1 27
Egffs : . . 22-8 0-6 2-6 •
Milk and cheese 23-4 0 7 2-9
24-1 0-9 37
38-9 1-9 4-9
Milk 12-9 0-9 70
„ 15-4 10 6-5
„ 19-4 1-0 77
„ 25-8 3-1 12 0
Leguminous vegetables — " — 10'5
Maccaroni with gluten 227 2'5 11-2
Maccaroni 11-2 19 171
Cabbages 13-2 2-4 18-5
White bread 13-0 2-4 187
147 2-3 19-2
Maize 12-0 23 20-5
Spdtzel 8 4 2-1 25-1
Eice 77 1-9 257
Black bread 133 4-3 32-0
Potatoes 11-4 37 39 0
Carrots 65 2-5 39-0
A similar table is given showing the difference between the ash in the
food and in the feeces, but the author does not think that the results
throw much, light on the question of the absorption of mineral matter,
M. M. P. M.
Interchange of Material in the Animal Organism. By A.
Adamkiewicz (Bied. Centr., 1880, 103— 105).— The fact that the
animal organism can produce from ammonium salts the more complex
constituents of urine has long been known. The author now shows
that the quantity of sugar whicli is produced in urine by diabetic
patients, and which is formed by the "rapid degeneration of tissue, can
be in great part diminished if not altogether caused to cease, by doses
of ammonium salts. He considers that the sugar is produced from the
albuminous matter, as more sugar is formed than can possibly be
formed from the cai'bon contained in the food. Experiments prove
that ammonia when administered does not appear in any form in the
urine, and that the sugar also ceases to appear, therefore the conclu-
sion is drawn that the ammonia and the sugar are employed in re-
generating the destroyed tissues. After a time, however, the action
of the ammonia diminishes ; this appears to be due to the presence of
a third substance : concerning this point, further investigations are
being made. E. W. P.
o
Distribution of Copper in the Animal Kingdom. By G.
Bizio {Gazzetta, 10, 149 — -157). — This is a claim of priority for his
father, B. Bizio, as being one of the first workers in this field, and as
5G6 ABSTRACTS OF CHEMICAL PAPERS.
having' made most extended investigations. The paper gives a very
complete historical survey of the labours of the various chemists vrho
have examined the subject from Sarzeau, w^ho discovered copper in
the blood of the bull in 1830, to Giunti whose researches vrere pub-
lished in the GazzeUa in 1879 (this vol., p. 27o). C. E. G.
Chemistry of Vegetable Physiology and Agriculture.
Light, Shade, and Soil studied in their Influence on the
Growth of Forest Trees. By M. Gurnand (Gompt. rend., 90,
144 — 14G). — The experiments, which lasted during 17 years, were
instituted with a view of ascertaining the periodic cubical increase in
the wood of a forest of young fir trees extending over an area of 13'3
hectares. The young trees, which were intermingled with leafy copse-
wood, were reckoned as forest trees when they measured 0'6 metre in
diameter, at a distance of 1"33 metre from the ground.
First period of si.v years : The coppice was from four to ten years
old, and covered the ground imperfectly. There were 1,457 trees,
the cubical contents of which were 1,424 cubic metres at the begin-
ning, and 2,266 cm. at the end of the period. The mean yearly in-
crease was 140 cm. of wood, or 71'5 cm. of carbon, reckoning 51 per
cent, of carbon for every 100 parts of wood.
Second period of five years : The coppice was from 11 to 15 years
old, and covered the ground completely. Allowing for wood cut
down, there were 1,336 fii-s containing 1,700 cm., which increased to
2,207 cm. The mean annual increase was 101"4 cm. or 51*7 cm. of
carbon, instead of 71"5 cm. as in the first period, notwithstanding that
the actual bulk of wood (1,700 cm. against 1,424 cm.) was larger to
start with.
Third period of one year : During the winter a considerable clear-
ance was made in the underwood, all the oblique or horizontal
branches being suppressed, leaving only the vertical branches. The
trees numbered 1,057 containing 998 cm., which at the end of the
year measured 1,096 cm. The increase was 98 cm. or 50 cm. of
carbon.
In the fourth period of three years, with 1,155 trees, the mean
annual increase was 87 cm. or 44-4 cm. of carbon fixed ; and in the
fifth period of tivo years, when there were 1,348 trees, the yearly
increase was only 47'5 cm. or 24-2 cm. of carbon.
The conclusion drawn from these experiments is that the fixation of
carbon by the forest tree diminishes in proportion as the shade pro-
duced by the underwood becomes more intense, and that this diminu-
tion is not prevented by the subsequent suppression of the lateral
branches of tlie coppice. The experiments of Saussure have proved
that the carbon or carbonic anhydride required by the plant is not
derived from the soil, it is therefore useless to look in that quarter for
a solution of the difiiculty ; it is, on the contrary, much more probable
VEGETABLE PHYSIOLOGY AXD AGRICULTURE. 567
that a certain increase of carbonic anhydride in the atmosphere is
beneficial to the life of the tree, and that this increase of carbonic
anhydride results from the decomposition, under the influence of
liofht, of the substances which form humus ; if access of lisrht to the
soil is prevented by the presence of a leafy undergrowth, the humus-
forming substances are not decomposed ; carbonic anhydride is not
produced, and the trees suffer in consequence, or at least do not
flourish to the extent that they would do under opposite conditions.
The author likens humus kept closely in shade to farm-yard manure
which has been too deeply ploughed in ; both are liable to remain
almost inert for several years. J. W.
Growth of Legumes. By R. Pott (Landw. Versuclis.-Skit., 25,
57 — 106). — For the ibilowing investigation, 50 sq. m. were sown with
horse beans and the same amount with common vetch. Plants were
collected at six different periods during their growth from all parts of
each field, an average sample being taken. The plants were divided
as follows : — The stem cut off close to the crown of the root was
divided into three parts, except during the first period. In the first,
fifth, and sixth periods the leaves were taken all together: in the
other cases the leaves were divided into lower and upper. The flowers
were examined separately, also the young pods ; and in the last period,
the seeds and husks were examined separately.
Numerous tables of results giving the amount of woody fibre, fat,
nitrogen-free and nitrogenous compounds, mineral constituents, and
nitrogen are given, showing the state of the different parts of the plant
at the six periods.
For the horse-bean plant, the author finds that the plant continually
increases in weight, most, just before beginning to ripen and least, just
about the end of flowering. The formation of woody tissue has its
relative and absolute maximum with the ripening of the fruit. Most
woody tissue appears in the lower part of the stem. The fatty sub-
stances are greatest at the end of the vegetation, but are relativelv
greatest during flowering time. The absolutely and relatively greatest
quantity of nitrogen-free compounds appears before the ripening.
The stems are relatively richer in nitrogen-free compounds than the
leaves, and these are poorer than the flowers and the pods. The whole
plant is richest in nitrogen-compounds during the flowering and is
poorest before ripening. The upper parts of the plant are richer in
nitrogen than the lower ; the least nitrogen relatively is found in the
lower part of the stem. With increased age, the leaves become de-
cidedly poorer in nitrogen. Mineral constitaents increased during the
whole growth of the plant ; the absorption was greatest during the
flowering period, but the relatively greatest quantity was found during
the first period.
In the case of the vetch, the plants were collected at the end of five
different periods. Tabular results are given, as in the case of the
horse bean, and the author draws the following conclusions : — The
plants increase in weight during the whole time. The greatest in-
crease comes just before the ripening is completed, the least at the
beginning of ripening. The increase in weight ceases first in the
568 ABSTRACTS OF CHEMICAL PAPERS.
lower leaves. The absolute maximum of the woody fibre formation
occurs at the end of the flowering. The fat is found in greatest
quantity after flowering, and is highest in the leaves. The absolutely
greatest production of nitrogen-free compounds occurs after flowering,
and generally less is found in the leaves than in the stem. Up to the
end of flowerinc, the nitrogen increases, then decreases, again increases,
and finall}^ decreases ; the maximum occurs when the fruit begins to
ripen. The amount of nitrogen per cent, is least at the time when
pods cease to grow, whilst it is greatest shortly after the end of flower-
ing. Generally the lower part of the plant is poorer in nitrogen than
the upper ; the leaves contain more than the stem, and the seeds more
than the leaves; but the older the leaves, the le.ss they contain. The
ripe plants are richest in ash (per cent.) ; the maximum absorption
compared with the growth takes place at the beginning of ripenino-.
J. T.
Formation of Fatty Matter and Ripening of the Olive. By
A. FuNARO {Gazzetta, 10, 82 — 85; also Land iv. Versuclis.-Stat., 25, 52 —
56). — The author made cai-eful analyses of the pulp and kernel of the
olive and also of the leaves of the plant at intervals between the 25th
of July and 25th of February, the results of which are given in three
tables. The author finds, with De Luca and Roussille, that the forma-
tion of the kernel precedes that of the pulp, and that as the weight of
the olive and of the fatty matter it contains increases, the water slowly
diminishes. Mannitol is found in small quantity in the fruit, but can-
iiot be detected in the leaves until the greater part of the fatty matter
has been formed in the fruit. From this it is inferred that the pre-
sence of mannitol has no relation to the formation of the fatty matter,
but rather that it is a product of the metamorphoses of the carbo-
hj'drates. Its presence in the olive is accounted for when we consider
that it belongs to the same family of plants as the ash.
C. E. G.
Amount of Albuminoids in Potatoes. By F. Holdefleiss
{Bled. Centr., 1880, 120— 122).— Analyses of 19 different sorts of pota-
toes show that the amount of albuminoids (calculated by N x 6"25)
is not dependent on the sp. gr. nor on the starch ; the quantity varies
from 6 — 11 per cent, of the dry matter, the mean being 2'31 per cent,
of the original material. E. W. P.
Existence of Ammonia in Vegetables. By H. Pelet (Compt.
rend., 90, 876— 879).— The leaves of the beetroot contain 0-0138, the
root 0'029, and the seeds 0'192 per cent, of ammonia. Phosphoric acid
is in each case present in the proportion required to form magnesium
ammonium phosphate, whilst the magnesia is in slight excess. Wheat
contains 0*16 per cent, of ammonia and 0"?4 per cent, of phosphoric
acid. The whole of the magnesium is probably in the form of magne-
sium ammonium phosphate, whilst the excess of ammonia exists as
double salts of ammonium and potassium. C. H. B.
Lime in Plant-Life. By E. v. Raumer and C. Kelleemaxn
(Landw. Versuchs.-Stat., 25, 25— 38). — Stohmann has shown {Annalen,
121) the necessity of lime for the development of plants, but its func-
\t:getable physiology and agriculture. 569
tion has not been fully made out. Bolim has shown that h'me is neces-
sary, in the earliest stages of plant life, for the consumption of the
non-nitrogenous reserve stuff ; he also concluded that lime was as neces-
sary to the building up of plant structure as to the change of cartilage
into bone. From the rapid absorption of lime by sprouting bulbs, and
the simultaneous appearance of calcium oxalate, Kellermann supposed
that lime might act on the solution of the starch by the formation of a
ferment. The experiments on bean plants detailed in the paper were
conducted by Raumer. Some of the plants were grown in acid- washed
quartz-sand and fed with different solutions, both free fi'om and con-
taining calcium salt ; others were grown in water and solutions with
or without calcium salt ; the plants produced were examined micro-
scopically only. The results agree essentially with those of Bohm
and others, and show specially that the function of the lime is closely
connected with the consumption of carbohydrate ; further, the amount
of lime present in the seed is not sufficient for the use of the non-nitro-
genous reserve stuff. Whether the lime acts in the dissolving and
transport of the reserve starch, or in the decomposition of the starch to
form cellulose, is a difficult question to answer, but the weight of evi-
dence is in favour of the latter view. The investigation is to be con-
tinued. J. T.
Relation between the Sugar and Mineral and Nitrogenous
Matters in Normal Beetroot and in Beetroot Run to Seed.
By H. Pellet (Compt. rend., 90, 824— 827).— The author considers
that a constant relation exists between the amounts of sugar and
phosphoric acid (100 to 1"15), and that the latter is the most important
constituent in the manures to be applied. The amounts of lime and
magnesia in the plant vary but slightly, but the potash and soda are
liable to much greater variations, replacing each other in equivalent
proportions, so that the amount of sulphuric acid necessary to combine
with the mineral matter in the ash remains almost the same. Next to
phosphoric acid, magnesia and lime are the most important constitu-
ents of the manures employed, then come potash and soda, and lastly
nitrogen. The richer the lieetroot is in sugar, the less mineral matter
does it contain, but the quantity of leaves is greater and they leave
more ash. If, however, the leaves are left on the soil, proportionally
more mineral matter is restored to it. In other words, the hig-her the
yield of sugar, the less is the soil impoverished. The German roots
contain less chlorine and much less nitrogen than those grown in
France, but are richer in sulphuric acid. The Siberian roots contain
much more soda than is found in the French roots. The phosphoric
acid probably exists in the root in the form of ammonium magnesium
phosphate, since the acid and the magnesia are always present in the
proportions in which they exist in this compound. C. H. B.
Manuring of Field Beans. By L. Ridolfi (Bled. Centr., 1880,
153). — Field beans were grown on four plots manured as follows : —
I, unmanured ; II, 100 kilos, nitrogeii as ammonia salts ; III, 65
kilos, nitrogen as ammonia, and 50 kilos, phosphoric acid as super-
VOL. xxxviii. 2 s
570
ABSTRACTS OF CHEMICAL PAPERS.
phosphate ; IV, 200 kilos, phosphoric acid as superphosphate. Th'd
results per ha were as follows : —
Beans.
Straw.
Plot.
Litres.
Kilos.
Kilos.
Weight of hectol.
■ in kilos.
I
2,000
2,540
3,060
3,200
1,575
1,524
5.204
2,8fi0
2,000
2,244
2,700
2,757
78-75
II
60-00
IIT
71-99
lY
89-37
The percentage composition of the beans did not greatly vary ; plot
II gave a maximum 5-26, and I only 4-275 of nitrogen, while III
gave maximiim of ash .S'S.
In 100 parts ash was found : —
Beans.
. J
I.
II.
III.
TV.
p„0
45-5
6-46
1-3
32-61
5-89
27 -48
8-23
3-8
45-79
6-59
4-3
6-1
4-3
33-33
5-6
41 -4
so,
5-6
CI
NaoO, K.,0
1-64
38-97
CaO . . . .'.
5-75
Straw. ■
I.
II.
III.
IV.
P.,0-
5-15
8-57
0-91
49-34
30-25
3 92
5-05
1-78
51-25
32-70
4-00
5-05
1-73
45-87
33-21
3 -2
SO,
0 16
CI
KooO, K.O
0-14
36-43
CaO
48-33
E. W. P.
Experiments with Manures. By M. Leclerc and M. Moreau
{Bied. Gentr., 1880, 100 — 103).— The following were employed as
manures through a six years' course of potatoes, oats, flax, cole-rape,
beans with vetches, oats: (1) stable manure; (2) artificial manures;
(3) stable and artificial manures mixed. These were sown with the
seed on plots of 7\ ars, and a similar plot was left unmanured for
comparison. The yield of the various crops, with their money value,
and also that of the manures, are carefully enumerated.
In each year, a slight change in the quantities of the manure was
made, but the materials employed were the same. A second series of
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 571
experiments is also detailed ; in tliis series, the crops were grown upon
land which Avas less rich in organic matter, and the course consisted
of potatoes, wheat, clover, oats, potatoes and oats ; in neither case is
any inference drawn from the experiments. E. W. P.
Note by Abstractor. — In many cases it appears, according to the
figures in the above paper, that the expense of the manure more than
counterbalanced the gain of the manured over the unmanured crop ;
as for example, value of unmanured crop of oats was 358 marks, that of
the crop manured with ammonium sulphate was 430 marks, whereas
the value of the manure was 164 marks. — E. W. P.
Reduction of Superphosphates, and the Behaviour of Phos-
phoric Acid in Soils. By H. Joulie, H. Albert, and H. Yoll-
BRECHT {Bled. Centr., 1880, 81 — 87). — JouHe states that all aluminium
phosphates are soluble in ammonium, citrate, but that the iron phos-
phates are less soluble, the more basic they be ; they dissolve, however,
if treated with ammonium citrate and sulphide. In a mixture of
mono- and di-calcium phosphates with aluminium and ferric hydrates,
the greater part of the phosphates are no longer soluble in water and
citrate, which proves the combination of part of the phosphoric acid
with the last-named oxides ; hence tricalciura phosphate must be
formed. Tricalcium phosphate is also less soluble in ammonium
citrate, the drier it is. It is further shown that if superphosphate be
prepared with the requisite quantity of sulphuric acid, a moist pro-
duct is the result when the phosphate contains large quantities of
iron and calcium compounds. If a dry compound is produced, and
this occurs when there is an in.suificiency of acid, the superphosphate
is rapidly reduced to the tribasic salt. The same occurs, if calcium
carbonate be added.
Albert and VoUbrecht show that in a calcareous soil the reduction
takes place most rapidly under the influence of light, and that the
dicalcium salt also becomes tricalcium phosphate in the soil.
All the phosphates, including ferric and aluminium, whether
originally insoluble or only partly so, become soluble in very peaty soils,
the cause being in all probability the action of the humic acid. It is
therefore most economical for the manuring of peaty soils to use only
one-third of the sulphuric acid generally employed when preparing
soluble phosphate, so that dicalcium phosphate only may be produced.
Hence, composts of turf, or stable manure with insoluble phosphates, are
valuable. E. W. P.
Agricultural Value of Reduced and Insoluble Phosphates.
By A. Petermaxx and others (Bied. Centr., 1880, 87— 99).— Peter-
^ mann's experiments were made with (1) superphosphate containing
about 1-5 per cent, of soluble phosphoric acid; (2) superphosphate
, containing 7 per cent, of phosphoric acid soluble in water, and 2 per
I cent, soluble in ammonium citrate ; (3) precipitated phosphate con-
taining about 20 per cent, of the acid soluble in citrate ; (4) ignited
precipitated phosphate containing about 3 per cent, soluble in citrate ;
the crops were jjeas and barley. He comes to the conclusion that in
2 s 2
572 ABSTRACTS OF CHEMICAL PAPERS.
many cases the " redaced " phosphate is of greater value than the
superphosphate. In sandy soils the soluble phosphate is washed away
from the roots ; if the superphosphate does not show marked action,
on limey soils, it is due to the formation of tricalcium salt, while the
" reduced " on the same soil remains unaltered. On sandy soils
having a small percentage of lime, the " reduced " often shows a better
result than the " soluble." This is probably due to the production of
ferric and aluminium phosphate. The results with ignited phosphates
are unsatisfactory.
De Leeuw finds that on a soil containing no lime and much humus,
the insoluble phosphates are the most satisfactory. Fleischer states
that when the same sort of manures as above are applied to a peaty soil,
the difficultly soluble phosphate is of more value than on other soils.
E. Wein has employed the same manures, with the addition of Chili
saltpetre to " soluble " and " reduced " phosphates, on a sandy lime
soil, and finds that the yield of grain (rye being the crop) is increased
by the addition of phosphates, and the yield of straw trebled on those
plots to which the nitrate had been added. The nitrate and reduced
phosphate yielded the best crop. Phosphates increase the amount of
dry matter ; for cereals, on the above class of soils, phosphorite phos-
phate is better than guano superphosphate ; bibasic phosphate is best
for peas ; aluminium and ferric phosphates produce a better crop than
if no phosphates had been added ; tricalcium phosphate gives no re-
sults. With oats, the results are similar. On light, calcareous soils
reduced phosphate is better than soluble phosphate for all crops.
E. W. P.
Sulphurous Acid as a Remedy for Bunt in Wheat. By A.
ZoEBL (Bied. Centr., 1880, 129— 133).— The spores of bunt or "stink-
ing smut" {tilletia caries) are readily destroyed by fumigation with
sulphurous anhydride. It is recommended to burn sulphur in a large
cask, which is then half or three-quarters filled with the grain, and
subsequently rolled. The spores are destroyed in a few minutes,
whereas the vitality of the wheat remains for the most part unimpaired
even if exposed to the gas for o — 4 hours. E. W. P.
Analytical Chemistry.
Determination of Specific Gravity. By A. W. Bltth (Analyst,
1880, 76). — The sp. gr. of solid butter fat may be determined at 15°
with great accuracy as follows : — A short wide test-tube is weighted
with lead or mercury and weighed in water, the height of the water
in the beaker being noted and kept constant in future determinations.
The tube is now filled with a weighed quantity of butter fat and
weighed again in water. The sp. gr. of other organic solids may be
determined by this method. A section of the solid is cut with a cork
ANALYTICAL CHEMSTRY. 573
borer, so that it tiglitly fits the weighed test-tube containing mercury,
and is covered by the latter. It is then weighed in water as above.
If the solid is porous, the tube containing the solid is fitted with a
doubly perforated cork, in which is inserted a stoppered funnel con-
taining mercury, and a glass tube connected with a Sprengel pump ;
the air is exhausted, and a stream of mercury allowed to pour in, the
pores are thus completely filled with mercury. L. T. O'S.
Filter-paper and Filtering, By K. Kraut (Zeits. Anal. Ghem.,
1879, 543 — 546). — Independently of mechanical means for hastening
filtration, the author finds that attention to the quality of the paper
used and to the shape of the funnel employed, will produce very con-
siderable increase in the rapidity of filtration. The angle of the funnel
must be a right angle, and the paper fit it evenly without interposed
air-bubbles; but further, the tube of the funnel must be of the right
diameter and uniform throughout, any enlargement or constriction
retarding the passage of liquid : in one series of experiments the time
of filtration was increased fourfold by the use of a badly shaped fun-
nel. The paper should be uniform in quality, and should not swell
too rapidly when wetted ; it should also readily allow the passage of
liquid whilst retaining fine particles of precipitate. The quality of
the paper used, and the length of time it had been wetted, produced
very great variations in the rapidity of transmission of the liquid.
The best paper experimented on by the author was of Danish make.
F. C.
Estimation of Carbonic Anhydride in Gases. By A. Gawalovski
{Zeits. Anal. Chem., 1879, 560 — 56o). — An apparatus is described for
determining the proportion of carbonic anhydride present in the gas
used for " saturation " in sugar refining, or for making mineral water
or for other purposes, where the carbonic anhydride is mixed with
other gases not absorbed by caustic alkali. Its claims over other
existing forms of apparatus are that it is less fragile, it dispenses with
stopcocks, is of smaller dimensions, and is cheaper ; at the same time
it is sufficiently accurate for commercial purposes.
The apparatus consists of an upright graduated measuring tube
closed above, into the lower end of which a U-shaped funnel tube can
be fitted, the whole forming a U-tube. Two measuring tubes are pro-
vided each of 2U0 c.c. capacity, the one broad above and narrow below,
the other narrow above and expanded below, the enlarged part being
divided by 50 c.c. graduations and the narrow part into J- c.c. One or
other of these tubes is used according as the pi'oportion of carbonic
anhydride present is large or small. The measuring tube is filled with
the gas over salt-solution up to the 200 c.c. mark, then removed into
a vessel containing caustic soda solution, and after the soda solution
ceases to rise by further agitation, showing the absorption to be com-
plete, the funnel tube is connected under the solution ; the tempera-
ture of the gas is then lowered by immersion of the apparatus in a
vessel of cold water, the levels of liquid in measuring tube and
funnel tube are equalised, and the volume of unabsorbed gases is read
off. To avoid error by caT^illarity, the tubes must be of the same
diameter at the upper surfaces of the liquid. F. C.
574 ABSTRACTS OF CHEMICAL PAPERS.
Reduction of Carbonic Anhydride to Carbonic Oxide by
Red-hot Stannous Oxide. By A. Wagner (Zeits. Anal. Ghem., 1879,
559 — 560). — In the course of experiments made to ascertain whether
stannous oxide could be substituted for chromic oxide in the autlior's
jirocess for estimating nitrates, it was noticed that carbonic anhydride
was reduced to carbonic oxide by the heated stannous oxide. The
author describes in the present paper experiments whicli fully confirm
this result. Heuce the method of dehydrating stannous hydrate by
heating it in a stream of carbonic anhydride is unsatisfactory, since it
furnishes stannous oxide more or less mixed with stannic oxide.
Similar experiments proved that carbonic anhydride is reduced in
an analogous manner by red-hot ferrous oxide. F. C.
Formation of Nitric Oxide by Ignition of Nitre. By A.
Wagxee {Zeits. Anal. Chem., 1879, 552 — 558). — The method already
described by tlie author (ibid., 11, 91) for estimating nitric acid by
igniting a nitrate with excess of chromic oxide and alkaline carbonate
in a stream of carbonic anhydride, is found to give accurate results
either by estimating the chromate formed or the nitric oxide evolved.
In the case of other gases being evolved, the author suggests oxidising
the nitric oxide by oxygen gas over standard alkali solution, and
titrating the excess of alkali : and he suggests adapting the process to
the estimation of nitric acid in drinking-water by oxidising the organic
matter by potassium permanganate tirst in alkaline then in acid solu-
tion.
A direct experiment in which the nitre was estimated by reading off
the volume of nitric oxide liberated, gave 0'7 per cent, excess of nitre.
A series of trials with other oxidisable oxides in place of the chromic
oxide, proved that with all other oxides a deficiency of nitric oxide
was obtained ; cuprous oxide yielded 3 per cent, deficiency, manga-
noso-manganic oxide 4 per cent., and manganous carbonate about 15
per cent. F. C.
Contribution to the Knowledge of "Reduced" Phosphoric
Acid. By C. F. Mkyer {Zeits. Anal. Chem., 1880, 1-15— 15U).—
1. Process of Reduction. — Wagner explains the so-called "reduction"
of phosphoric acid in ferriferous and aluminiferous superphosphates
by the conversion of ferric and aluminic sulpliates, in tlae })resence of
monobasic calcium phosphate, into acid ferric and aluminic phosphates
with sepai-ation of gypsum. The two last-named phosphates consider-
ably influence the quality of the superphosphate, as they occasion the
formation of an insoluble precipitate.
In investigating this point, the author found that the concentration
of the solution containing the calcium phosphate materially retards the
forniation of this pi-ecipitate. He explains the " reduction " of the
phosplioric acid by the simultaneous action of tribasic calcium phos-
phate, monobasic calcium phosphate and ferric vsulphate on one
another, and proves by a series of chemical equations that this action
is facilitated by the presence of ferric and aluminic sulphates in ferri-
ferous and aluminiferous superphosphates.
.2, Separation of Ortho- and Fijro-phosphoric Acids. — In these ex-
ANALYTICAL CHEMISTRY. 575
periments dibasic calcium phosphate was used. 5 grams of the
phosphate were ignited until constant in weight. The resulting
calcium pyrophosphate was decomposed with sulphuric acid, and the
lime separated with alcohol. The solution was diluted to 200 c.c.
1. 10 c.c. neutralised witli ammonia gave, when heated with
ammonium (or sodium) acetate and uranium nitrate, a perfectly
clear solution. On cooling, the salt was partly separated.
"2. 10 c.c. diluted to 120 c.c. with water and treated with ammonium
chloride, magnesia mixture, and ammonia, did not give a precipitate.
1 gram of the above phosphate was ignited, dissolved in hydrochloric
acid, neutralised with ammonia, and the solution made up to 200 c.c.
1. By heatijig the solution with ammonium acetate, the calcium
pyrophosphate was separated almost entirely, so that ammonia pro-
duced only a slight turbidity in the hltrate.
2. 50 c.c. treated with ammonium citrate and chloride did not give
a precipitate with magnesia mixture and ammonia.
3. By heating the resulting precipitate with ammonium acetate and
uranium nitrate, it could only be dissolved with great difficulty.
It was impossible to obtain a complete solution with sodium acetate.
Fresenius states that ammonium molybdate with the -addition of
nitric acid does not precipitate pyrophosphoric acid ; the author, how-
ever, constantly obtained a yellow precipitate.
In conclusion, he says that he has not yet been able to ascertain how
far these methods ai"e capable of. being applied for the quantitative
separation of ortho- and pyro-phosphoric acids. Further trials are
being made. D, B.
Volumetric Determination, of Phosphoric Acid by Means of
Uranium in the presence of Iron. By C. Mohr {Zeits. Anal. Chem.,
1880, 1.50 — 153). — 2 or 5 grams of the finely-powdered mineral are
boiled repeatedly with small quantities of dilute nitric acid, and the
solution is made up to 250 c.c. When soluble phosphoric acid is deter'-
mined in superphosphates, the same proportion is used, except that
distilled water is employed instead of nitric acid. 10 or 25 c.c. of the
filtered solution are treated with a solution of sodium acetate until the
turbidity first formed no longer disappears. The solution of acetate
of uranium is then added, and the mixture heated gradually to the
boiling point. Before the end of the total precipitation has been
reached, a few granules of potassium ferrocyanide are added. The
ferric phosphate is thus decomposed, the phosphoric acid goes into
solution, the ferric oxide forms Prussian blue, and becomes mixed
Avith the uranium phosphate. It is essential not to proceed with the
precipitation of the phosphoric acid until all the iron has been pre-
cipitated, which is easily recognised by treating a drop of the
supernatant liquid with potassium ferrocyanide on a porcelain plate.
In this way determinations of phosphoric acid may be made with a
standard solution of uranium in cases where its use was hitherto not
practicable, and although this process cannot compete with the molybdic
acid method, its application may be recommended especially for
laboratories in connection with sewage and manure works on account
of its simplicity and rapidity. D. B.
570 ABSTRACTS OF CHEmCAL PAPERS.
Analysis of Mineral Superphosphates and of "Phosphate
Preclpite." By Brunner {Zeits. Anal. Chem., 1880, 141 — 145). — The
methods described by Fresenius, Neubauer, and Luck, for determining
the " assimilable " pliosplioric acid in superphosphates {ihid., 10, 133)
appear to have been surpassed by the improvement recently made by
Petermann, who succeeded in removing several weak points, inherent
in the above methods. The object of the present paper is to describe
this improved method, which was accepted as a commercial test by
the Belgian Government in February of last year. A certain per-
centage of " acide phosphorique anhydride assimilable " is guaranteed.
This includes the total phosphoric acid in the compounds soluble in
water and in ammonium citrate.
The solution of ammonium citrate is prepared by dissolving citric
acid in ammonia, and making it up to a density of 1'09, taking care
that the solution has a distinctly alkaline reaction. It is then filtered
and kept in a well-stoppered bottle: 100 c.c. of this solution are
brought into a small wash- bottle. A weighed quantity of the mannre
to be analysed is then washed into a small porcelain mortar, ground
up with the pestle, and the mixture transferred to a flask, using the
remaining citrate solution to wash out the mortar. After warming
the flask for one hour at 35° C. exactly, and repeatedly agitating it, the
mixture is made up to 500 c.c. and filtered. The first portion of the
filtrate is rejected, as the mixture never filters clear in the commence-
ment ; 50 or 100 c.c. of the clear filtrate are then precipitated with a
sufficient quantity of magnesium chloride rendered strongly alkaline,
and filtered after six hours' standing. The ammonia is removed by
washing, and the precipitate ignited and weighed in the usual manner,
as magnesium pyrophosphate. D. B.
Volumetric Estimation of Sulphates. By H. Precht (Zeits.
Anal. Chem., 1879, 521 — 523). — Normal barium chloride solution is
added until the sulphate is exactly precipitated, the final reaction
being evident in a clear solution : if the liquid is not clear, the standard
solution is added in excess, and the excess is estimated by adding
standard potassium chromate solution in quantity more than sufficient
to precipitate as chromate the barium present in solution, and then
titrating the excess of chromate by standard ferrous sulphate. The
potassium chromate is made of half the strength of the barium
chloride ; 10 c.c. of it are added to the precipitated solution, and the
liquid is neutralised by addition of sodium hydrate, an excess of which
is harmless. If the yellow colour of the solution is not permanent,
10 c.c. more of the chromate are added, and the addition continued, if
necessary, until the yellow colour remains. The liquid is made up to
half a litre, and 50 c.c. are filtered off, acidified with dilute sulphuric
acid, and titrated with irou solution of one-tenth the strength of the
chromate ; the end of the reaction is seen by the change of colour
from yellow to green, and is exactly found by adding a drop of it to
potassium ferricyanide on a white porcelain surface. 10 c.c. FeO,
divided by 2, gives the excess of barium chloride added, and each cubic
ceutimetre of the latter indicates 40 mgrms. SO3. The method is very
AXALYTICAL CHEMISTRY. 577
exact, and is applicable in the absence of substances, "whicb would
reduce the chromate or oxidise the ferrous solution. F. C.
Estimation of Potassium as Platinochloride. By H. Precht
(Zeits. Anal. Chem., 1879, 509 — 521). — This method of determining
potassium seems to be the only one in general use, all others having
proved to be less trustworthy. The author gives an account of a
careful examination into the sources of error, and into the best mode
of conducting the analytical processes.
1. Preparation of the Platinic Chloride. — If the alcoholic washings
are evaporated to recover the platinum they contain, it is impossible
to precipitate all the platinum with potassium or ammonium chloride,
since the compound CoH^PtCL is formed, and is not thus precipitable ;
an explosive compound is also liable to separate. The evaporated
washings are best reduced by mixing them with sodium carbouate
solution, glycerol, formic acid, or grape-sugar, and boiling. Potassium
platinochloride if present is gradually reduced if shaken up occasionally
viith the liquid, but it is more rapidly reduced by being boiled witlx
caustic soda solution of 1'2 sp. gr., containing 8 per cent, of glycerol.
The reduced platinum-black is washed with lu'drochloric acid and
water until it is free from sulphuric acid and potassium salts ; it must
never be reduced by potassium instead of sodium carbonate or hydrate,
or a large quantity of potassium is retained. Platinum reduced
from alcoholic solution contains some of the above explosive com-
pound, and glows when dried on the water-bath ; it is only quite
freed from this body by heating to redness, and this is necessary to
remove any carbonaceous substances which would hinder the solution
in acids. If reduced by soda and glycerol, the platinum appears to be
pure, and is easily soluble in aqua regia. After dissoh-ing the
platinum by hydrochloric and nitric acid in the usual way, the excess
of nitric acid is removed by alternate evaporation with hydrochloric
acid and water; its removal is necessary because it leads to formation
of 2N0Cl.PtCh, and promotes the crystallisation of the platinic
chloride. The above double chloride forms a yellowish-brown deposit
of cubic crystals ; it is very deliquescent and soluble, and is decom-
po-sed by water, yielding ultimately 2HCl.PtCl4, nitric acid, and nitric
oxide ; so that the evolution of nitric oxide on dilutingr the solution
with water is a proof of the presence of this double chloride. A pla-
tinic chloride solution should be as free as possible from nitric acid,
hydrochloric acid, and platinous chloride ; the presence of platinous
chloride yields too high results, since it separates on addition of
alkaline chlorides ; the presence of nitric acid to the extent of 4 per
cent, of strong acid was found to make the results 0'05 to 0"1 per cent,
too low by increasing the solubility of the platinochloride. The
presence of platinous chloride is more detrimental than that of nitric
acid. Although ignited iridium is not soluble in aqua regia, it is
soluble if alloyed with platinum ; it maybe separated from the solution
by Gibb's method, but its removal is scarcely necessary, since potassium
chloride precipitates platinum from the solution before iridium ; and
even if iridium should partially replace platinum in the precipitate,
the atomic weights of the two metals are suflBciently close to prevent any
578 ABSTRACTS OF CHEMICAL PAPERS.
considerable error arising. The platinum chloride used for estimating
potassium should dissolve entirely in alcohol, and give the theoretical
quantity of potassium platinochloride when precipitated with pure
potassium chloride. A table is given showing the percentage of
platinic chloride contained in a solution of known sp. gr. ; the deter-
minations required for this table were made with solutions containing
2'24 parts of free hydrochloric acid to every lUO of platinic chloride :
the solutions were evaporated and the residue ignited in hydrogen,
2. Solubility in Alcohol of the Platinoehlurides of the Alhall and
Alkaline Earth Metals. — The solubility of potassium platinochloride, as
determined by Fresenius, is such as to render necessary a correction
for what is dissolved by the alcohol used in washing ; the author
determined the solubility of the pure salt with every precaution, and
found it to be much less than Fresenius stated, 1 part of the salt dis-
solving in 42,600 parts of absolute alcohol, or in 37,300 parts of alcohol
of 96 per cent, by weight, or in 26,400 parts of alcohol of 80 per cent,
by weight.
Sodium platinochloride crystals contain 6 mols. H2O, and are
triclinic prisms or tables. The dried salt when dissolved in hot
alcohol crystallises free from excess of sodium chloride. This salt
dissolves to almost any extent in boiling water ; the aqueous solution
saturated at 15° C. contains 3'.;''77 percent, of anhydrous salt : addition
of alcohol causes separation of the salt in a crystalline condition. A
saturated solution in 50 per cent, alcohol contains 17"85 per cent, of
salt. The water of crystallisation is almost entirely expelled at a tem-
perature below 100°; the anhydrous salt dissolves much more copiously
in alcohol than the crystalline, and with evolution of heat. The salt
perfectly freed from water by drying at 150° dissolved in absolute
alcohol to the extent of 48'3 per cent. ; after being dried on the water-
bath 32'8 per cent, was dissolved ; on addition of a few drops of water,
these solutions solidify to a mass of the hydrated crystalline salt. As
the temperature rises the solubility of the salt is much increased ;
addition of ether to the alcohol solution causes separation of the salt,
and in a mixture of alcohol and ether in equal proportions, only 2-43
per cent, remains dissolved. The salt is insoluble in ether free from
alcohol; it is unchanged by boiling with alcohol, but if ether is present,
it is partially decomposed into sodium chloride and a combustible
compound of hydrogen and platinum chloride.
Magnesium platinochloride was prepared by mixing the two chlorides
in molecular proportions ; it crystallises with 6H2O ; it dissolves in
absolute alcohol to the extent of 43-2 per cent., and when dried at
ISO'^ is less soluble, only 37'8 per cent, entering into solution.
Barium platinochloride can only be obtained from a solution which
contains excess of barium chloride ; the crystals contain HjO ; they
are partially decomposed by water and entirely by boiling.alcohol into
the two chlorides. The presence of four times the theoretical propor-
tion of platinum chloride was found insufficient to convert barium
chloride into the platinochloride soluble in alcohol. The anhydrous
salt yielded 94-8 (?) per cent, of insoluble barium chloride when washed
with absolute alcohol.
AXALTTICAL CHEMISTRY. 579
Strontium platinocTiloride is a salt soluble in water, and decomposed
to a less extent by absolute alcohol than the barium salt. The crystals
after being well washed with alcohol left 4-2 per cent, of insoluble
sti'ontium chloride.
Calcium platinocliloride ciystallises with 8H2O, is deliquescent in the
air; its alcoholic solution contains 53 per cent.
3. Operations in estimatiny Fotassiiim. — When potassium is to be
separated from sodium and magnesium salts and weighed as pla-
tinochloride, the metals must be present as chlorides : sulphates are
best removed by addition of barium chloride solution of known
strength to the boiling liquid, which contains 0"5 of hydrochloric acid
to every one part of salt. The precipitation is carried out in a half-
litre flask, which is cooled and filled to the mark as soon as neither
barium chloride nor sulphuric acid causes any precipitate, a further
quantity of water is added equal in volume to the barium sulphate
precipitate, whose sp. gr. is 4"2. The use of standard barium chloride
solution serves to determine the amount of sulphates present during
their separation ; its strength is 104 grams of anhydrous salt in a
litre. The coprecipitation of potassium salts leads to a very slight
minus error, amounting to 0"046 per cent, of potassium chloride in
kieserite containing 12 — 14 per cent.
Finkener's method is to be recommended when sulphates or sodium
salts are present in large proportion, since it economises platinum
chloride solution and alcohol. According' to this method, sufficient
platinum chloride is added to entii'ely precipitate the potassium, the
precipitate is washed with alcohol, reduced, and the well washed
platinum weighed. It requires little more time than the process
already described with preliminary precipitation of the sulphates.
The presence of magnesium chloride does not occasion error in the
estimation of potassium, since magnesium platinochloride is much
more soluble in alcohol than the sodium salt. But as barium pla-
tinochloride is decomposed by alcohol, yielding insoluble barium
chloride, the presence of barium always leads to high results. It may
be stated generally that the presence of barium chloride or of sulphuric
acid is inadmissible in estimating potassium.
In working with pure potassium salts, lo2805 grams are dissolved
in a half litre, and 10 c.c. of the solution are taken, each milligram of
the platinochloride then corresponds to 0"1 per cent, of potassium
chloride; if the potassium is retuimed as sulphate, 17847 grams are
dissolved. Larger quantities are necessary for determining potassium
with accuracy in carnallite, 20 grams being dissolved in 500 c.c, and
25 c.c. of this solution being employed. After adding platinum
chloride, the solution is evaporated until it crystallises on cooling, the
formation of large crystals being avoided; if sodium platinochloride
alone has to be separated, it is best to evaporate quite to dryness, since
the sodium salt is more soluble when anhydrous, the use of hot alcohol
renders the washing more rapid for the same reason. The use of a
mixture of alcohol and ether is to be avoided, since the sodium salt is
only dissolved by it with difficulty.
The precipitate may be weighed on a filter previously dried for two
hours at loU"" C. ; if washed with absolute alcohol, it is perfectly dried
580 ABSTRACTS OF CHEMICAL PAPERS.
by heating for 20 minutes at 130° C. The use of glycerol is not
recommended.
Small quantities of potassium chloride in presence of much sodium
chloride are best estimated by adding sodium platinochloride solution
to the solution of from 10 — 100 grams of the salts, and evaporating :
the precipitate is washed with absolute alcohol, and the platinum
contained in the sodium platinochloride present in the washing is
separated, washed, and weighed. This is the only method which
gives correct results when less than 2 per cent, of potassium chloride
is present. F. C.
Direct Determination of Soda in Potashes. By A. v. Hasselt
(Ze/f.N\ Anal. Chem., 1880, 156 — 159). — It is known that sodium
cliloride is but sparingly soluble in concentrated hydrochloric acid ;
this applies also to potassium chloride, which nevertheless is much
more readily soluble than the sodium salt, as illustrated by the follow-
ing table : —
10 cc. of the saturated solution of sodium chloride in hydrochloric
acid of 1'189 sp. gr. contain when prepared —
at 13-G° 0-009 1 gram NaCl
15-2° 0-0092 „
25-0° 0-0114 „
10 c.c. of a similar solution of potassium chloride contain —
at 15° 0-1280 gram KCl
15-5" 0-1284 „ „
A hydrochloric solution of potassium chloride, saturated at a tempe-
rature of 15-3", was treated with solid sodium chloride, and 10 c.c.
evaporated to dryness. The residue amounted to 0-1380 gram " salt-
mixture." This shows that the solubility of sodium chloride is not
increased by the amount of potassium chloride present in the solution ;
the solubility, moreover, of sodium chloride in hydrochloric acid of
the above strength is not appreciably increased by raising the tempe-
rature of the solution.
Fi'om these results, the author inferred that 100 c.c. of hydrochloric
acid of the above strength, previously saturated with sodium chloride,
would dissolve the quantity of potassium chloride obtainable from
1 gram of potash, whilst the sodium chloride formed from the soda
present would remain undissolved. The sodium chloride is allowed to
settle, and after removal of the bulk of the acid solution is collected
on a vacuum filter, washed M'ith some of the hydrochloric acid solu-
tion of sodium chloride, dried at 150°, and weighed. A simple and
ingenious apparatus, which greatly facilitates this operation, is
described in the paper. As to the other impurities present in potash,
it is mentioned that they can be removed by treating the potash with
water and filtering the solution. Silicic acid if present could be re-
moved by evaporation in the usual manner. D. B.
Removal of Large Quantities of Sodium Chloride in Mineral
Analyses. By F. Muck (Zeits. Anal. Chem., 1880, 140).— In
ANALYTICAL CHEMLSTRY. 581
fusing with alkaline carbonates, neutralising the free acid with sodium
carbonate, precipitating iron and alumina with sodium acetate, &c.,
the resnlting solutions often contain as much as 40, 50, and 00 grams
of sodium (and potassium) chloride. Under such conditions an accu-
rate determination of magnesia, which requires all possible concentra-
tion, cannot be carried out successfully. The author removes the
alkaline chlorides as follows : — The filtrate containing the magnesia is
evaporated to dryness, treated with cold fuming hydrochloric acid,
and the mixture allowed to stand for a few minutes, having previously
well stirred it. The whole is then filtered through a filter formed of
alternate layers of coarse glass and cotton, and finally washed on
the filter with furaing' hydrochloric acid. The residue from the
evaporated filtrate contains, besides magnesium chloride, only very
small c^uantities of fixed chlorides, and requires but little water to
dissolve it. D. B.
Action of Fused Alkaline Carbonates on Platimim. By L.
KoxixCK (Zeits. Anal. Chem., 1879, o&J). — Fusion of 6 grams of
KNaCOs in a platinum crucible over a Bunsen flame and blowpipe
flame, removed 1 mgrm. of platinum. The presence of manganese
raised this loss to 1'5 mgrm. and 17 mgrm. in two other fusions,
probably owing to the formation of alkaline manganate. By keeping
2-3 grams of KXaCOs in fusion for flfteen minutes at a high tempe-
rature by means of the blowpipe, 38 mgrms. of platinum were ren-
dered soluble in water, and in this case, as in those cited above, this
weight of platinum was found in the solution of the fused mass.
Hence when a substance is decomposed by fusion with alkaline car-
bonates in a platinum crucible, it is necessary to allow for platinum
entering into solution and to precipitate it with sulphuretted hj drogen
in the copper and arsenic group. F. C.
Lithium Phosphates. By G. Meelixg (Zeits. Anal. Chem., 1879,
663 — 568). — The accuracy of the method of estimating lithium as
orthophosphate having been called into question, the author has con-
firmed its trustworthiness by preparing pure lithium carbonate from
lepidolite, and precipitating a known quantity as phosphate : after
observing all due precautions detailed below, 104'53 per cent, was
found instead of 104 "SO.
Lithium carbonate, prepared from lepidolite, was dissolved in hydro-
chloric acid ; all metals except magnesium were separated by treat-
ment successively with sulphuretted hydrogen, ammonia, ammonium
sulphide, and small quantities of ammonium carbonate. The magne-
sium was completely separated by boiling with lithium hydrate,
prepared by the action of silver oxide on the chloride. The solution
was then considerably concentrated by evaporation, and precipitated
by ammonia and ammonium carbonate : the lithium carbonate was
boiled 20 times with small quantities of water to free it from chloride,
then disseminated in a large quantity of cold water through which a
stream of washed carbonic anhydride was passed. The clear filtered
liquid was boiled, and the precipitated lithium carbonate several times
582 ABSTRACTS OF CHEMICAL PAPERS.
■washed %Tiili boiling water and dried : no foreign substances could
be detected in this salt.
The process of estimation was carried out as follows : — A known
weio-ht of this salt was dissolved in hydrochloric acid, and the solu-
tion was mixed with 10 times the weight of crystallised sodium
phosphate and sufficient caustic soda to make it decidedly alkaline :
it was then evaporated to dryness on the water-bath, and the residue
was allowed to stand for 12 hours with sufficient 2'5 per cent, ammo-
nia solution to dissolve all the soluble salts ; the phosphate was then
washed for a long time with dilute ammonia. The filtrate and wash-
water wei'C united and subjected twice to the same process after
addition of a little caustic soda; the third treatment yielded only
O'G mgrm. of phosphate. All evaporations were conducted in pla-
tinum, but the ignited phosphate left I'l mgrm. of silica on solu-
tion in hydrochloric acid, the silica probably arising from the caustic
soda.
Lengthened washing of the precipitated phosphate with dilute
ammonia is indispensable. Lithium orthophosphate dissolves when
boiled with ammonium chloride solution with evolution of ammonia,
and its purity may thus be ascertained. The decomposition which
occurs is as follows :— Li^POi -f 2NH4CI = LiH.PO^ + 2LiCl + 2NH3.
Lifhium metaplwsphate was obtained by evaporating the solution of
lithium carbonate in excess of phosphoric acid. The most suitable
proportions are two molecules of lithium oxide to three of phosphoric
anhydride. When the temperature during evaporation reaches 130°,
a soluble crystalline salt separates, which contains 6Li20.5P;05.8H20,
it consists of ortho- and pyro-phospliate. On continuing the evapora-
tion, this salt redissolves, and as soon as excess of metaphosphoric
acid begins to be evolved as white fumes the lithium metaphosphate
crystallises : the thick mass is boiled with water, and the metaphos-
phate remains as an insoluble heavy powder. The crystals are large
or small according as more or less than the above projDortion of phos-
phoric acid has been employed. It is probably a monometaphosphate.
This process also yields the sodium and potassium metaphosphates
in a crystalline condition.
Analysis of the lithium salt by the method of Kraut, Kahnsen, and
Cuno (Avnalen, 182, 165) proved its composition to be that of lithium
metaphosphate.
Lithium metaphosphate is a white crystalline powder, consisting
of well-formed microscopic tables. It is insoluble in boiling water,
slightly soluble in acetic acid, and easily soluble in hydrochloric,
nitric, sulphuric, and phosphoric acids. Its sp. gr. is 2"461. At an
incipient red heat, it melts to a colourless hygroscopic glass of 2"226
sp. gr., which is soluble in water with feebly acid reaction, and
insoluble in alcohol.
lAthinm 'pyropliospliate was prepared by dissolving Kraut's (loc. cif.)
sodium lithitim pyi-ophosphate in acetic acid and precipitating with
alcohol : the bulky precipitate was washed with alcohol and dried.
The salt contains 2H..0 ; heated to 100° it loses 7"03 per cent., and if
melted 14'65 per cent, of water. The salt dried at 100° is still pyro-
phosphate. F. C.
AXALYTICAL CHEMISTRY. 583
Estimation of Ferrous Oxide in Presence of Organic Acids
or Sugar. By J. M. Eder (JJer., 13, 502—506). — Ferrous oxide
can be accurately determined in mixtures containinp;' organic acids
by means of tlie reducing properties of potassium-ferrous oxalate.
Neutral potassium oxalate is added to the solution, which should not
contain a large quantity of free mineral acid. Excess of silver nitrate
and ammonia are then added to the mixture. Metallic silver is pre-
cipitated in the proportion of 1 atom of silver for each molecule of ferrous
oxide present, 'iFeO + Ag20 = Aga + FcoOa (after the addition of
the silver nitrate the liquid should be protected from direct sunlight).
The precipitate consisting of metallic silver and ferric hydrate is col-
lected on a filter, washed, dissolved in nitric acid, and the silver
precipitated as chloride. If the liquid contains sufficient tartaric acid
to prevent the precipitation of ferric hydrate, the silver may be
weighed directly as metal. If the precipitate of metallic silver does
not filter clear, ammonium chloride is added to the mixture.
W. C. W.
Valuation of Pyrites by the Gravivolumetric Method. By A.
HoDZEAU {Compt. rend., 90, 870 — 872). — 1 gram of finely powdered
pyrites is fused in a platinum crucible with 4 grams of pure potassium
nitrate and 3 grams of pure sodium carbonate. The saline mass is
dissolved in warm water, filtered to separate ferric oxide, and the
solution diluted to 500 c.c. 10 c.c. are withdrawn, acidified with
acetic acid, and the sulphuric acid estimated by means of a standard
solution of barium chloride, measured by a gravivolumeter, in Avhicli
the standard solution is weighed. Results accurate. C. H. B.
o
Electrolytic Estimation of Cobalt, Nickel, and Copper, By
W. Ohl (Zeits. Anal. Chem., 1879, 523— 531).— After enumerating
the sources of error and inconvenience in the estimation of these
metals by any but the electrolytic process, the author describes his
method of procedure. The current was produced by a small Gramme
machine, the rate of revolution of which was under control ; a moderate
speed producing a current which caused a deflection of 70° on an
interposed sine-compass. When nickel is to be deposited in the
presence of little or no cobalt, a very strong current is necessary, but
if the quantity of cobalt is large, a weaker current must be employed
to secure a firmly adherent deposit. Copper may be separated by
means of a very strong current if it does not exceed 400 mgms. in
weight. The metal should be deposited on a platinum cone formed
by rivetting the parts together, any folding together or curving of the
edges being avoided, as they tend to retain the metallic deposit.
As an example of the application of the electrolytic process, the
analysis of a cobalt-nickel ore is given. After decomposing the ore
by heating it with strong nitric acid or aqua regia, preceded if neces-
sary by fusion with sodium carbonate, the solution is evaporated to
dryness ; the residue is then dissolved in a little strong hydrochloric
acid, diluted, and sulphuretted hydrogen passed through the hot
solution until it is cold : the passage of the gas through the hot solu-
tion should be repeated, when all arsenic and copper present will
settle rapidly as sulphides. If by the colour of the precipitate copper
584 ABSTRACTS OF CHEMICAL PAPERS.
is -iuclf^cd to be absent, the excess of sulphuretted hydrogen should be
removed by heat before filtering, since arsenic sulphide is somewhat
soluble in a solution of this gas. If copper sulphide is present, the
removal of the gas is omitted, and a slight error arises from the
arsenic sul])hide present in the filtrate.
The filtrate is evaporated with addition of a little potassic chlorate
to oxidise the iron : the residue is taken up with dilute hydrochloric
acid, soda is then added to alkaline reaction, and the precipitate
dissolved by addition of acetic acid ; the liquid is then diluted
and heated to boiling to precipitate the iron. The filtrate from the
iron is evaporated to dryness, and the residue dissolved in water and
dilute sulphuric acid, mixed with excess of ammonia and subjected to
electrolysis; as soon as the liquid has been free from colour for some
time, and a few drops yield no precipitate or dark coloration with
ammonium sulphide, the platinum cone with the deposit of nickel and
cobalt is removed, washed with water, then with absolute alcohol,
dried by holding it over a heated surface and weighed. The nickel is
then estimated in the dry way by Plattner's method, and the cobalt
found by difference. This method of estimating the nickel is liable to
an error of only 0"2 per cent. : the alternative plan is to dissolve the
electrolytic deposit in dilute nitric acid, and separate the cobalt with
potassium nitrite.
The pi'ecipitate of basic ferric acetate is free from, nickel and cobalt
or contains mere traces of those metals ; and even if the iron should
not be completely precipitated, a small amount of ferric hydrate pre-
cipitate present during electrolysis is harmless.
The separation of nickel, cobalt, and copper from the solution of
any substance is efi'ected by passing sulphuretted hydrogen slowly
into the cold solution, which has been freed from silicic acid, until the
copper sulphide separates ; the arsenic remains almost entirely in
solution : the copper precipitate is filtered off rapidly, and with the
filter is heated with nitric acid, then evaporated to dryness; the residue
is dissolved in nitric acid, diluted, and the copper precipitated by
electrolysis : any arsenic present separates after the copper, the cur-
rent is therefore stopped when the copper is completely separated, and
the solution, freed from nitric acid by evaporation, is mixed with
the former filtrate, from which the arsenic is then precipitated as
sulphide and estimated as ammonium magnesium arsenate. Iron, if
present in any quantity, is precipitated as basic ferric acetate, and
nickel and cobalt are then separated from the ammoniacal solution by
electrolysis, any^ ferric hydrate precipitate which forms on addition of
ammonia being added to the iron precipitate. The alkaline earths can
be determined in the liquid from which the nickel and cobalt have
been separated.
Zinc is the only metal which need be separated before estimating
nickel and cobalt. It must be separated by passing sulphuretted
hydrogen into the acetic acid solution ; the filtrate is evaporated, the
residue dissolved in dilute sulphuric acid, and the ammoniacal solution
is then electrolysed.
Copper is separated from arsenic as described above : antimony
should be removed by twice evaporating with nitric acid : and lead, if
ANALYTICAL CHEMISTRY. 585
present iu any quantity, should be precipitated as sulphate ; ti-aces of
lead will not interfere, since the metal separates as peroxide on the
positive pole. Silver is separated as chloride, and bismuth as basic
chloride.
The author's experience iu the application of the electrolytic method
to the quantitative analysis of metal ores leads him to recommend it
on the grounds of economy of time and great accuracy. F. C.
Blowpipe Assay of Silver Lead. By F. M. Ltte (Analyst, 1880,
99). — The inconvenience arising from the smallness of the silver
button obtained in the assay of lead ores by the blowpipe, may be
avoided by digesting 1 to 5 grams of the iinely powdered ore with
strong hydrochloric acid until all the lead is converted in chloride. It
is then evaporated to dryness, and the residue is boiled with a concen-
trated salt solution (50 — 60 c.c. for each gram of ore taken). The
solution containing the lead and silver chlorides is filtered, and the
residue washed with boiling salt solution. Pieces of spongy lead (pre-
cipitated from lead acetate by zinc) are placed in the hot solution,
and digested on the water-bath for a few hours ; these precipitate and
absorb the silver, becoming changed in colour to silver grey. The
end of the reaction is known by no change of colour taking place in
freshly added lead sponge. The lead is collected, heated with sodium
carbonate on charcoal, and finally cupelled before the blowpipe.
L. T. O'S.
Voliunetric Analysis of Red Lead. By F. Lux (Zeits. Anal.
Chem., Ib^U, loo — loO). — By ti-eating plumbic peroxide with an
aqueous solution of oxalic acid in excess, decomposition takes place
with formation of plumbic oxide, water, and carbonic anhydride.
Warm dilute nitric acid dissolves the plumbic oxalate formed by the
excess of oxalic acid originally used, and the quantity of the latter
may be easily determined in the nitric acid solution. The author
applies this method in conjunction with that of titrating lead by means
of potassium dichromate iu an acetic acid solution, for the ready deter-
mination of the practical value of red lead. Details of the method
are given in the original paper. D. B.
Presence of Arsenic in the Atmosphere. By H. C. Bartlett
(Analyst, 1880, 81 — 82). — Experiments were made to show that
arsenic would be present in the atmosphere of a room papered with an
arsenical wall-faper. By placing the paper in a jar through which a
current of pure hydrogen was passed containing a small quantity of
ammonia, and directing the effluent gas on to a piece of filter-paper
moistened with slightly acid silver nitrate solution, a deep brown
mark is produced. In blank experiments, no mark appeared on the
prepared paper. Hydrogen evolved from sodium amalgam and water
is the most convenient to use, since that from zinc and sulphuric acid,
even when it gives no reaction with ^Jarsh's test, is liable to contain
minute traces of arsenic and antimony. L. T. O'S.
Volhard's Permanganate Method of Titrating Manganese.
ByA.E. Haswell (Dinrjl. polyt. J., 235. 3^7— 891;.— The author
VOL. xxxvin. 2 t
086 ABSTRACTS OF CHEMICAL PAPERS.
mentions that this method surpasses all recent improvements made in
this direction. He has carefully investigated the method, and finds it
quick and convenient in execution, and the results very accurate. The
method is based on the following facts. By treating a dilute solution
of a salt of manganous oxide heated to 100° with a few drops of a
solution of zinc sulphate, coloured pink hy a few drops of a solution of
potassium permanganate, and adding a solution of potassium perman-
ganate drop by drop to the mixture, with constant agitation, the sepa-
ration of a brown peroxide mixed with zinc oxide occurs in the form
of large flakes, which readily separate from the clear supernatant
faintly pink coloured liquid as soon as all the manganese has been pre-
cipitated. If the pink colour of the clear solution no longer disap-
pears after standing for some time and repeated heating at 100°, the
reaction may be considered to be complete, and the total manganese con-
tained in the solution to be precipitated as peroxide. From the number
of c.c. of standard potassium jjermanganate used, the quantity of man-
ganese can be calculated very easily. Volhard gives the solution a
concentration of 2 mgrms. manganese in 1 c.c, consequently dissolves
3"883 grams crystallised potassium permanganate in 1 liter of water.
The solution to be standardised for manganese should not contain more
than 0'25 per cent, of manganese. Iron appears to interfere with the
accuracy of the results. It is, however, recommended to separate this
metal by precipitation with zinc oxide.
The standard solution of potassium permanganate is titrated by
treating it with a solution of potassium iodide acidified with hydro-
chloric acid. The iodine equivalent of the active oxygen in the per-
manganate is immediately liberated, provided that excess of iodide is
used, which may easily be recognised by the circumstance that no
iodine separates from the brown solution. The iodine liberated is then
estimated by means of sodium thiosulphate, &c. D. B.
Must and Wine Analysis. By R. Ulbricht (Landw. Versuchs.-
Stat., 25, 5 — 24). — Determination of Chlorine. — With precautions, the
gravimetric method gives good results. The liquid is diluted, treated
with 5 per cent, of milk of lime, and after an hour the solution is
filtered off, heated to 70° with nitric acid and slight excess of silver
solution, and the precipitate is washed with precaution and weighed.
Determination of SutpJmric Acid. — Very exact results can be obtained
with care. The filtrate and wash water from the lime precipitate are
mixed and acidified with a little hydrochloric acid, heated to boiling,
and a very slight excess of barium chloride is added, the whole
warmed for 2 hours, and then allowed to stand for 36 hours.
J. T.
Examination of Sugar-beet and the Amount of Sugar the
Roots contain. By F. Schulze (Died. Centr., 133— 135).— If during
the expression of the juice from sugar-beet the amount of sugar pre-
sent be estimated in the different portit)ns, it will be found that the first
and last portions contain the smallest quantities. When Scheibler's
diftusion process is employed, the whole amount of sugar in the root
can be determined, and if from this the amount of sugar in the juice
be subtracted, the difference is the sugar i-etained in the mark. When
ANALYTICAL CHEMISTRY. 587
the root was sliced, a juice poorer in sugar was obtained by pressure ;
but these slices when pressed yielded a juice which when examined at
different stages of pressing, contained more sugar in the first portions.
E. W. P.
Scheibler's New Process for the Determination of Sugar in
Beet. By C. Scheibler and others (Bled. Centr., 1880, 136 — 143). —
By the expression of the juice from the sugar-beet 4"5 — 5 per cent,
of "mark " is left, so that np to the present time 95 — 95'o per cent.
have been the figures which were supposed to represent the true amount
of juice in which the sugar was to be estimated. But this quantity is
now shown to be considerably above the true quantity, which Scheibler
and several others find to be only about 90 per cent. The excess is
due to water forming a hydrate of the mark (colloid water). The
following process is recommended for the better extraction of the
sugar. 20 — 25 grams of the crushed root are placed in a tube, the
lower end of which is closed by a piece of felt. This tube is again
enclosed in a larger tube ending in an upright condenser, the lower
end of the outer tube being connected with a 50 cm. flask, in which
is placed 25 c.c. of 95 per cent, alcohol. The alcohol is boiled,
allowed to cool and run back through the tube containing the sugar-
beet for three-quarters of an hour. At the end of the operation the
fluid is filtered, and the sugar determined by the polariscope (see this
vol., p. 144). E. W. P.
Separation of Fats from Soaps. By J. Wolff (Zeits. Anal.
Chem., 1879, 570 — 571). — In the ordinary method of soap analysis
small quantities of unsaponified fats and resins are usually not esti-
mated nor even detected. The author determines them by treating
the soap with cold aniline, which does not dissolve soap, but readily
dissolves fat and resin.
To free commercial aniline from benzene and nitrobenzene, several
kilograms are mixed with a slight excess of hydrochloric acid, then
diluted with 500 parts of water, and shaken until all aniline salt has
been dissolved. The solution is then filtered through several thick-
nesses of well wetted filter-paper. The clear liquid is made just alka-
line with sodium hydrate solution, and nearly saturated with sodiom
chloride. As soon as the aniline has separated it is run oif and dis-
tilled, the portion boiling above 180'' being preserved for use.
The finely divided soap is twice treated with about 20 parts of
aniline for half an hour on the water-bath, being well stirred mean-
while, and hard particles being pressed. It is each time filtered when
cold. The united aniline solutions are acidified with hydrochloric acid,
mixed with four times their weight of water, stirred well, cooled, and
shaken with ether. The clear ether solution is sepai-ated, the ether
evaporated, and the residue of unsaponified fats and resins weighed.
F. C.
Testing Butter. By L. Medicus and S, Scheree (Zeits. Anal.
Chem., 1880, 159 — 162). — Of the three methods recently published by
Hehner, Reichert, and Koettstorfer for the determination of butter
fat, Reichert's method appears to be the most useful and accurate, as
588 ABSTRACTS OF CHEMICAL PAPERS.
it determines that ingredient which distinguishes butter fat from other
animal and vegetable fats of the same category, namely, the volatile
acids.
The object of this paper was to see whether melted butter fat sepa-
rates on cooling, so as to indicate to some degree any adulteration
which may have taken place, and for this purpose Reichert's method
was employed. It was found that the more difficultly fusible ia,H
separated in places where the cooling first originated, whereas the
more readily fusible fats separated towards the centre of the mass.
The quantity of volatile fats had been increased in the centre and
lower parts of the melted mass, whilst in the ujDper parts a decrease
had taken place.
These experiments indicate the necessity of using the utmost care in
sampling fatty substances for analysis. D. B.
Woody Fibre Estimation and its Defects. By C. Krauch
(Landw. VersucJts.-Siat., 25, 221). — After remarking on the unsatis-
factory state of fodder analysis, and the want of accuracy in classing
the results as protein, fat, non-nitrogenous extract, and woody fibre, the
author details experiments made on residues obtained from rye grain,
meadow hay, and red clover respectively, by treatment with ether and
alcohol, cold and warm water, and infusion of malt. The residues
were analysed, and were treated with dilute acids, potash solution, and
Schulze's reagent in various orders, and the results are discussed
without leading to any definite conclusions. J. T.
Estimation of the Non-albuminoid Nitrogen in Fodder. By
E. ScHULZE (Lavdiu. Versiichs.-Stat., 25, 173 — 176). — Kern has shown
(ibid., 24, 368) that in Sachsse's method of estimating amides, the
presence of ammonium salts causes error in the results, owing to the
action of nitrous acid on these salts. On decomposing asparagine by
means of nitrous acid, one-half its nitrogen is converted into ammonia,
and this under the action of the acid increases the amount of nitrogen
obtained, so that the result for asparagine is too high. The author
finds that the amount of nitrogen obtained from ammonium salts
depends on their state of concentration, and on the temperature at
which the reaction takes place. J. T.
Estimation of Proteids in Fodder. By R. Wagner {Land.
Versuchs.-Shit., 25, 195— 219).— In papers by F. Sestini (ibid., 23,
305) and B. Dehmel (ibid., 24, 214), the process given by the author
is unfavourably criticised in part. The author gives numerous ex-
amples to show that the method he has previously described (ibid.,
21, 259) gives accurate results. The fodder may be extracted either
by a 0'04 per cent, solution of hydrochloric acid or a 0'125 per cent,
solution of potash ; the latter gives the best results. The extraction
takes a day, and should be made at the lowest possible temperature, with
frequent shaking. The alkaline solution is treated with dilute acetic
acid until a white precipitate appears, then a saturated solution of tannin
in acetic acid is added to precipitate the proteids. After 12 — 24 hours
filtei', and to the filtrate add a considerable amount of common salt to
ANALYTICAL CHEMISTRY. 589
collect the proteids in suspension : after 24 — 48 lionrs this residue may
be collected. J. T.
Examination of Mineral Oils. By O. Brenkex (Zeits. Anal.
Chem., 1879). — The author describes his method of examining such
oils as are used chiefly for lubrication of railway axles and of ma-
chinery. He claims for his process the advantage of detecting the
presence of tar-oils, which resemble mineral oils in not being saponified
by caustic soda solution ; it also shows whether the oil is properly re-
fined and is free from undissolved substances. The presence of undis-
solved particles in very small quantity is objectionable, since by set-
tling they render the lower stratum of oil in a vessel useless for many
purposes ; they also clog the woollen feeder which stipplies oil to rail-
way axles.
The examination consists of the following parts : —
1. Determination of the Specific Gravity.
2. Determination of the Temperature at which Vapour is Evolved tvMch
mil Burn contimiously . — The oil is heated on a sand-bath in a porce-
lain crucible 6'4 cm. in diameter and 4" 7 cm. deep, which is filled to
within 1"2 cm. of its edge. A small flame is passed once over the top
of the crucible without touching the edge or the surface of the oil ; it
should take as many seconds in passing as the number of cm. breadth
of the crucible. This test is conveniently repeated for each 5° rise of
temperature of the oil, and is then, if necessary, repeated for each 1°
rise between the limits thus found. The oil should froth only slightly,
or not at all, when thus heated.
3. Determination of Solidifying Point.
4. Determination of Undissolved Bodies. — 10 c.c. of oil are dissolved
in 10 c.c. of ether, filtered through a weighed filter, and the filter and
residue weighed after having been washed with ether and dried.
5. Behaviour with Soda Solution. — 5 c.c. of soda solution of 1"4 sp.
gr. are poured into a graduated test-tube, 10 c.c. of oil are added, and
the whole is well shaken and heated in a water-bath ; the solution
must separate perfectly from the oil in a few minutes or when the
water boils ; the tube is then removed and once more shaken and re-
placed in the water-bath ; after the soda solution has once more per-
fectly separated it must be clear and show no alteration of volume
after cooling ; an increase of volume indicates unwashed tar-oils. The
inside of the tube must be perfectly clean, to insure the rapid and com-
plete separation of the solution from the oil.
6. Behaviour with Nitric Acid. — On mixing the oil with nitric acid
of l'4o sp. gr., the rise of temperature observed must be very
slight, or better none ; if much rise occurs, the presence of washed
tar-oils is indicated. If a small preliminary trial shows that no very
violent reaction occurs, 75 c.c. of oil are poured into a graduated
20 c.c. tube and are brought to 15" C. ; 7"5 c.c. of the nitric acid at
15° C. are then added, the tube is closed with a cork through which a
thermometer passes, and the liquids are well shaken. If a violent
reaction occurs a larger vessel is used and a glass tube passes through
the cork, which is closed with the finger during the agitation.
7. Behavioiir with Sulphuric Acid. — This test is earned, out in the
2 t 2
500 ABSTRACTS OF CHEMICAL PAPERS.
same way as that with caustic soda (5), 10 c.c. of oil being mixed
with 10 c.c. of acid of I'SS sp. gv. The acid must not be coloured
black or brown, otherwise insufficient refining is indicated, or the pre-
sence of tar-oils, already indicated by nitric acid, is confirmed.
8. Examination of the Aqueous Extract for Slime and Free Acid. —
Water, which has been violently agitated with the oil, must separate
clear and must show no acid reaction. Slimy particles will make the
water turbid, they are not removed by filtration, and settle after a
time.
The author does not consider the above method perfect, and intends
to publish further papers on the reaction with nitric acid and on the
determination of the consistency of the oil. F. C.
Determination of Ash in Coal. By F. Muck (Zeits. Anal.
Chcm., 18<S0, 131 — 149). — The determination and incineration of ash
is in many cases accompanied with great difficulties, such as —
1. The difficulty of incinerating bodies like anthracite, graphite.
2. The formation of carbon, Avhich cannot be burnt off without
difficulty (with fusible organic substances).
3. The presence of certain mineral substances which retard the
incineration, e.g. silica, phosphates, fusible salts.
4. The tendency to decrepitate, shown by some plants and almost
all kinds of coal.
b. The greater or less solubility of some ash-constituents.
6. The chemical changes which the ash may experience, according
to the time and degree of heat and the draught of air.
The author has investigated this subject very fully, and gives a
detailed account of his experiments, which tend to show that the
following conditions should be observed in order to obtain accurate
results : —
1. The substance to be incinerated must be pulverised very finely
and heated very gradually.
2. In order to completely incinerate the ash it is advisable to moisten
it with alcohol, after incineration, and to continue the burning,
3. Other conditions are considered in the original paper, which are,
however, mostly known to practical analysts. D. B.
Technical Chemistry.
Potassium Ferrous Oxalate and its Use for Developing Pho-
tographic Bromide of Silver Plates. By J. M. Eder (Diugl.
polyt. /., 235, 37G — 379). — Potassium ferrous oxalate has more pow-
erful reducing properties than any acid or neutral ferrous compound
hitherto examined, its power of reduction approaching that of an
alkaline solution of pyrogallic acid. Hence it has been introduced
in photography for developing bromide of silver plates. The author
found that this developer, when applied correctly, gives better nega-
TECHNICAL CHEMISTRY. 591
tives than those developed with the usual alkaline pyrogallic acid
mixture. It is essential to use a solution of slightly acid reaction,
otherwise the development of the plates will not be successful. Gelatin
plates are at present mostly developed with this salt. The plates are
dipped into a solution of potassium feri'ous oxalate and the picture
develoj^ed in about two to five minutes. Several plates can be placed
and developed in the same solution. Since this solution is somewhat
more expensive than pyrogallic acid, the author has been investigating
various modes whereby the developer may be recovered. He succeeded
in devising; a method of recoverino- the most valuable insfredient of the
solution, viz., potassium oxalate, by the very simple process of preci-
pitating the iron with potash, evaporating and crystallising.
D. B.
Analyses of Four Waters for Turin. By A. Lieben (Gazzetta,
10, 86 — 115) and S. Caxxizzako (ibid., 115 — 118). — The municipality
of Turin having decided to introduce a new water supply for the city,
sent samples of four waters from different sources to the authors of
these two papers for analysis. Lieben gives a long dissertation both
on potable waters in general and on the methods of analysis, the
analytical results being given in tabular form. The permanganate
method (Schulze's process) was employed for the organic matter, as
the author considers that of Frankland and Armstrong to be liable to
error, both from loss of volatile organic matter during evaporation
and from the action of the sulphurous acid. Cannizzaro's results
agree with those obtained by Lieben, with the exception of the
nitric and nitrous acid ; the former chemist having taken all the pre-
cautions indicated by Kammerer (/. pr. Chem., 1875) found that no
nitrous acid was present. Both chemists insist upon a knowledge of
the history of the water as a most important factor in pronouncing
an opinion as to its potabiHty. C. E. G.
A Peculiar Water. By W. Wallace (Analyst, 1880, 79).— This
deep well water, which penetrates the strata of sedimentary rocks of
the lower coal formation, is entirely free from sulphates, but contains
large quantities of free ammonia, of chlorine, and of barium, giving a
precipitate with calcium sulphate. The analysis gave the following
results in parts per million : — •
BaCOa. CaCOg. MgCOs. CaCl,. MgCl2.
54-1 262-6 23-0 92-4 78-0
Organic Total
KCl. NaCl. AI2O3, &c. iiiO.2. and volatile. solids.
24-0 1783-0 8-0 7-0 85-0 2417-1
Hardness, degrees per million 537-00
Oxygen required to oxidise oi'ganic matter 1-67
Ammonia, free, per million 0-95
„ organic 007
One month later the water had not altered in its composition, not-
withstanding large quantities had been withdrawn from the well.
L. T. O'S.
592 ABSTRACTS OF CHEMICAL PAPERS.
Evolution of Carbonic Oxide from Red-hot Iron Stoves.
By F. Fisher (Dingl. loohit. J., 235, 438 — 443). — This question was
first cousidered by Pettenkofer in 1851, and Morin in 1869 proved
that iron stoves evolve carbonic oxide, which escapes into the air of
the room when they are heated to redness, thus becoming injurious to
health. The presence of carbonic oxide and hydrogen in the air
heated by iron stoves is explained by the diifusion of these gases
through the red-hot metal, which can be avoided by lining the in-
terior of the stoves with refractory bricks or stone and regulating the
fire so as to prevent the formation of carbonic oxide in the stove as
much as possible. D. B.
Mode of Desulphurising the Crude Soda-lyes obtained in the
Le Blanc Process. (Dingl. pohjt. J., 235, 299.) — The oxidation of
the sulphides in the soda-lyes has recently been facilitated by the ad-
dition of manganese. 1 liter of the lye is treated with 1 gram of
manganous chToride at a temperature of 50° to 60°. A strong current
of air is then passed through the mixture, the manganous oxide
formed being converted into a higher stage of oxidation, which, how-
ever, immediately gives up again its oxygen to the metallic sulphides
in the lyes. As soon as these are desulphurised they are drawn off
from the manganese oxide, which can be used for fresh quantities of
the lye. In this way considerable quantities of the latter can be
desulphurised, using comparatively little manganous oxide.
D. B.
Preparation of Soda from the Sulphate by Means of Lime
and Sulphur. By F. Gdtzkow (Dingl. polijt. J., 236, 148—158).
The author has patented a method of preparing caustic soda from
sodium sulphate by treating the latter with calcium sulphite and in-
troducing sulphurous acid gas into the mixture. Soluble calcium
bisulphite is thus formed, which reacts with the sodium sulphate,
forming calcium sulphate and sodium bisulphite. These are separated
by filtration, and the gypsum washed out with hot water. The sodium
bisulphite is then treated with milk of lime, whereby a solution of
caustic soda is obtained, which contains a certain proportion of sodium
sulphite and sulphate and also calcium sulphite. It is evaporated in
the usual manner, and the calcium sulphite which is left after decanta-
tion is used in another operation. The following two questions pre-
sented themselves to the author in working out this method: — (1.)
To what extent can sodium sulphate be transformed into the sulphite
by means of lime and sulphurous acid ; and (2) to what extent can
sodium sulphite be rendered caustic by lime ? As regards the first
question, the conversion of sodium sulphate into sulphite is very
satisfactory, and might be regarded as complete, if it were not for the
solubility of the calcium sulphate, which is greater in the solution than
in pure water. In the subsequent treatment with lime, this has a ten-
dency to reconvert part of the sodium sulphite into sulphate. The
second question could not be solved in a satisfactory manner, although
success depends in a great measure on the solution being sufficiently
dilute, but even with 14 grains per liter only 87 per cent, was converted.
The results obtained, however, were only approximate, and, therefore,
TECHNICAL CHEMISTRY. 59,^
could not be nsed as proper data for answering this question. It was
found that sodium sulphite requires a greater dilution than the car-
bonate.
Details of the apparatus used and the mode of working are
given. D. B.
Dephosphorisation of Pig Iron, Bj- R. v. Wagner (Dingl.
poJi/t. J., 236, l-i"). — Bull has recently discovered a pi'ocess of de-
phosphorising pig iron, which depends on the conversion of the
phosphorus into phosphoretted hydrogen. The process is said to have ,
Ijeen very succes.sful as far as it has been tried at the present time. It
consists in introducing into the fluid metal, after separating ciirbon,
silicon, &c., by means of a cuiTent of air. a stream of steam mixed
with hot air. The steam is decomposed, the hydrogen combining
with the phosphorus, and escaping in the form of vapour as phospho-
retted hydrogen.
It is mentioned that this method, should it continue to give .satis-'
factory results, would become of great practical importance, as it
would probably compete with the Thomas-Gilchrist process. The
author, however, points out that C. Winkler is really the originator of
this idea. In the first part of his Auleitwng zur Uvtersuchung der In-
dustrie-Gase (Freiberg, 1876, 6) Winkler in describing the Bessemer
process distinguishes (1) combustion of the carbon and silicon by
means of a current of air, and (2) removal of phosphorus in the form
of a hydrogen compound, by forcing superheated steam through the
metallic column, which is identical with the process pronosed by
Bull. . 'D. B.
Preparation of Nickel. (Bingl. polyt. /., 235, 444.) — According
to Laroche and Prat, tlie composition of the nickel ore of New Cale-
donia is as follows : —
SiOo. CaO. Al.^Cv MnO. Ee^Oa. CoO. KiO. MgO. K-jO.LiCCu. HjO combined
, 41-0 .3-0 7-0 9-0 14-0 1-3 8-9 6-0 1-1 87 = lOO-OO
46-0 0-5 1-3 4-0 5-2 00 17-3 9-0 07 16-0 = 100-00
The powdered ore is treated with an equal weight of sulphuric acid
of 56° to Q&° B. The mixture is boiled out ivith water and treated
with a quantity of ammonium sulphate equivalent to the amount of
nickel sulphate present. After concentration, nickel ammonium sul-
phate crystallises out, which when rccrystallised, is obtained in a
chemically pure form. The latter is boiled with an equivalent quantity
of an alkaline oxalate, and the precipitate treated with sodium or
potassium carbonate at 110°. The oxalic acid is thus recovered, and
can be used again for a fresh operation, whilst the carbonate of nickel
is reduced to the metallic state in the usual manner. D. B.
Examination of the Effect of Hard and Soft Water on the
Brewing of Beer. By E. R. Southby {Bierl. Cevtr., 1880, 145—
147). — Composition of the worts (unhopped) prepared with distilled
water, and with hard water containing 66"9 grains calcium sulphate,
and 16"5 grains magnesium sulphate per gallon, was compared, the
594 ABSTRACTS OF CHEMICAL PAPERS.
result being that neither of the above salts in solution has any appre-
ciable influence on the amount of extract obtained, or on the compo-
sition of that extract ; but the wort prepared with hard water settles
more quickly, and remains unfermented longer, than if it had been
prepared with soft water. E. W. P.
Amount of Sugar in Sorghum, Maize, and Melons. By C. A.
GOESSMANN (Bied. Ce7itr., 1880, 122 — 124). — The amount of sugar
(cane and grape) contained in several varieties of the above plants at
different periods of growth was estimated, and the result arrived at
was that they are unfitted for the manufacture of sugar by reason of
the small quantity which they contain. E. W. P.
Formation of Fat in Ripening Cheese. By 0. Kellner
(^Lanclw. Versuchs.-Stat., 25, 39 — 46). — The author criticises the
results of several investigators, and then gives results obtained by
comparing the proportion of fat in chalk-like and fatty-looking cheese
from the same block, with that of two of the unchangeable constituents,
viz., phosphoric acid and lime. The amount of fat was almost the
same, being slightly less, but not materially so, in the riper portion.
Samples from an older cheese gave a similar pair of results. The melt-
ing points of the fats obtained from the same block were almost iden-
tical, the melting points of the fatty acids also ; so that the fats were
found to be the same in quality and quantity in ripe and in less-ripe
cheese. J. T.
Estimation of the Value of Grain. By J]. Wollnt (Bied.
Centr., 1880, 116 — 120). — It is usual to estimate grain by its volume-
weight, but this is shown to be a false method ; the results of careful
experiment are, that the volume-weight is not proportional to the size
of the grain ; with barley and wheat, it diminishes with the size of the
grain, whereas with certain sorts of oats it increases as the size of the
grain diminishes : the volume- weight of a mixture of large and small
grains is a mean of the volume-weight of both sorts ; the volume-
weight of grains of like size is greater the less water they contain ; it
is likewise greater the riper the crop be, and also higher in the case of
translucent wheat : the volume-weight of the grains of cereals of
difierent varieties is different, and is independent of the size of the
grain.
As the volume- weight cannot be taken as a true indication of the
value of grain, neither can the specific gravity, which is less in pro-
portion as the grain is riper, and contains more moisture.
The only true guarantee is the absolute weight of the grains. Of
grains of like weight and size, those which are most globular, are the
most valuable. E. W. P.
Analysis of Various Tinned Foods. By Gr. W. Wigner
{Analyst, 1880, 99 — 102). — From the analysis made of different
American and Australian tinned meats and vegetables, the author
considers them to be very slightly, if at all, inferior to raw meat and
vegetables as articles of food. L. T. O'S.
TECHNICAL CHEMISTRY. 595
New Coal-tar Colouring Matters. (Dingl. poh/t. J., 235, 316.)
— Meister, Lucius, and Briining prepare from secondary and tertiary-
amines of the aromatic compounds new colouring matters by the action
of tri- and teti'a-chloroquinone or of crude chloranil.
To prepare violet colouring matters, 1 part chloranil is added gra-
dually with constant stirring to 2 parts dimethylaniline, and the
mixture heated at 60^ to 70° for some time. Blue colouring matters
are formed by the action of chloranil on methyldiphenylamine. To
obtain green colouring matters, chloranil is allowed to act on benzy-
lated diphenylamine and its horaologues, benzytolylphenylamine, &c.
Colouring matters are also obtained according to Herran and
Chaude by the action of nitrobenzene on mixtures of aniline and
double metallic chlorides. D. B.
Some Analyses of Starchmakers' Residues. By F. Holde-
FLEiss (Bied. Centr., 1880, 66). — The author has analysed two samples
of these residues with the view of estimating their value as fodder ; one
sample was in the state in which it left the factory ; the other had been
put under pressure to extract all the water possible. The analyses of
the wet and dry substances show a striking difference in the percentage
of albuminous substances and carbohydrates : the former largely di-
minishing, the latter increasing in the dried substance, which is easily
accounted for by the water carrying off the albumin. The employ-
ment of pressure in order to bring the substance into portable and
marketable condition would not be found injurious, but when it is used
for feeding pui-poses, it should in every case be supplemented by highly
concentrated starchy foods.
The author compares the value of both with raw potatoes ; taking
the residue from one centner of these at 0"17 mark, the wet starch
residue is worth 0'44 mark, the dry residue 1'15 marks. J. F.
On Explosives for Blasting, especially Nitroglycerine. By
B. C. NiEDERSTADT (Diiu/l. polyt. J., 233, 7-5 — 78). — The most -widely
used dynamite is Noble's hieselguhr dynamite. When used ia solid
rock it has from 6 to 7 times the force of blasting-powder.
The " kieselguhr " in its natural state has the following percentage
composition : — Insoluble silica, peroxide of iron, alumina, and calcium
sulphate, 15'43; soluble silica, 77*30; water, 7"27. Green hieselguhr
has the following percentage composition : — Insoluble silica, (fee,
10"97; soluble silica, 62-92; organic matter, 17"76; water, 8 35.
The kieselguhr is first burned in a furnace to destroy the organic
matter and expel water. The mingling of the nitroglycerine with the
burned earth is done by hand labour in wooden troughs lined with
lead or india-rubber. The cartridges are prepared at the manufactory,
of size corresponding with that usual for the bore-hole. The strongest
cartridges are made with 75 per cent, nitroglycerine, the absorbent
material being nitrocellulose or kieselguhr. The weaker sorts contain
about 50 per cent, of nitroglycerine.
Bhexite consists of a mixture of 30 to 65 per cent, of nitroglycerine
with saltpetre, chalk, and sawdust.
59() ABSTRACTS OF CHEMICAL PAPERS.
Recently there has been brought into use in mining a mixture of
nitroglycerine and dissolved gun-cotton.
Lithofradeur consists of 52 per cent, of nitroglycerine, mixed with
kieselguhr, coal, Chili saltpetre, and sulphur.
Dimlin is better fitted for practical work than lithofracteur. It
contains 50 per cent, of nitroglycerine, with sawdust and potassium
nitrate.
The sp. gr. of dualin is only half that of dynamite, and it has per
volume about 50 per cent, less explosive power. W. T.
Liquid for the Preservation of Botanical Preparations.
By J. Nesslee (Landiv. Vei\<Hc]is.-Stut., 24, 275 — 277). — The author
has used a 20 per cent, solution by volume of alcohol with 1 — 2
drops of an 8 per cent, solution of sulphurous acid in the form of
acid calcium sulphite to every 200 c.c. of alcohol. This is suitable
for green parts which are easily bleached ; for roots which are brown,
3 — 4 times as much of sulphurous acid is used. The solution has
behaved very well since 1875. So far as observations go, animal pre-
parations may be preserved in the same way. J. T.
Primavera-wood. By J. Moellee {Dingl. pohjt. J., 236, 146),
— This wood comes from Navidad (west coast of Mexico), and was
obtained by Exner in Hamburg, where it had been sent into the market
as furniture-wood.
The author has examined this wood. As to its botanical origin
nothing is known, and from its anatomical structure also sufficient
data could not be obtained for tracinof its orio^in. The colour of the
wood is yellow on its split or sawn surfaces ; its polished sections,
however, are coloured light reddish-brown, and the naked eye dis-
cerns elegantly marked rays of a light colour, in which minute yellow
spots are scattered about. The sp. gr. of the wood is 0'99, and its
hardness vei-y great. D. B.
597
General and Physical Chemistry.
New Hydrogen Lines and the Dissociation of Calcium. By
H. W. VoGEL {Ber., 13, 274 — 276). — The spectrum of hydrogen has
l)een hitherto considered to consist mainly of four lines : but in his
photographic examination of Greissler's tubes containing hydrogen, the
author has detected a number of other lines, some of them in the
violet and ultra- violet of remarkable intensity and sharpness. Almost
the same lines are observed in the photographed spectrum of pei"fectly
pure electrolytic hydrogen, and hence must be considered characteristic
of that element.
One of the most brilliant of these lines is slightly less refrangible
than the Fraunhofer line H', which, together with H ', is usually
ascribed to calcium. The author designates it Hde, the symbol Hd
representing a hydrogen Hne.
According to Lockyer (Proc. Boy. Soc, 28, 157), the element
calcium, when submitted to the enormous temperature of the white
fixed stars, which are regarded as the hottest, undergoes dissociation
into two bodies X and Y, to which the lines H' and H" respectively
belong. This dissociation cannot be artificially effected. Lockyer
relies on the observation of Huggins, that in the spectra of Sirius,
Vega, and other stars, the first of these lines is present, while the
other is absent or scarcely visible.
The author interprets the facts otherwise : the so-called H' line in
the stellar spectra being, in his opinion, identical with the hydrogen
line Hde, and not belonging to calcium. The remaining hydrogen
lines are also much more intense in these stellar spectra than in the
spectrum of the sun.
This view is borne out by an examination of the published observa-
tions of Huggins (Compt. retul., 1880, No. 2). Huggins there gives
the wave-lengths of twelve stellar lines in the violet and ultra-\'iolet.
The first two of these are the acknowledged hydrogen lines, Hdy and
Hd ; and the others agree so closely with the hydrogen lines dis-
covered by the author, that there can be no doubt as to their identity
with them.
Huggins' stellar lines.
New hydrogen lines,
3968
3968
3887-5
3887
3834
3834
3795
3795
3767-5
3769
The rest of Huggins' lines have not been observed by the author,
who used glass prisms which strongly absorb violet and ultra-violet
rays. Huggins used quartz prisms.
Whether these lines are contained in the solar spectrum must be
ascertained by using more highly dispersive instruments. Doubtless
the presence of the Hne H' will render diificult the detection of Hde.
VOL. xxxviii. 2 w
598 ABSTRACTS OF CHEMICAL PAPERS.
Lockyer explains the frequent occurrence of the line H' " injected
into the chromosphere " without H", observed by Toung, as due to
the dissociation of calcium. In the author's opinion the line noticed
to occur singly by Toung was Hd^, and not H'. Ch. B.
Dichroic Fluorescence of Magnesium Platinocyanide. By
E. LoMMEL (Ann. Phys. Chem. [2], 8,634 — 640). — A particularly well-
formed crystal (a four-sided prism) of this salt being at the disposal of
the author, various optical phenomena exhibited by it were carefully
noted as follows : —
(1.) Viewed by reflected light, the side faces were green, the end
faces blue-violet.
(2.) A ray of transmitted light was broken up into an ordinary
bright carmine-red ray, and an extraordinary dark blood-red ray.
(3.) In ordinary blue or violet light, the crystal showed splendid
orange fluorescence.
(4.) When this orange light is viewed through a T^icol prism it
appears orange-yellow when the plane of polarisation of the Nicol is
perpendicular to the axis of the crystal, scarlet when it is parallel to
the same axis.
(5.) If the violet light employed be first polarised, the fluorescent
light is orange-yellow when the plane of polarisation is perpendicular
to, scarlet when it is parallel to the axis of the crystal.
(6.) If a polarised violet ray falls normally on one of the end faces,
a scarlet fluorescent light is obtained, and this colour is unchanged
when the plane of polarisation is turned about the axis of the crystal.
(7.) If the ray falls obliquely, the plane of polarisation remaining
perpendicular to the end-face and therefore containing the axis of the
crystal, the colour remains unchanged ; if, however, the plane of
polarisation be inclined to the axis, the colour changes. From this it
would appear that the light vibrations must be perpendicular to the
plane of polarisation. The same conclusion results from the following
considerations : — Red fluorescent light is obtained when the violet i-ay
falls normally on the end-face, and when consequently the plane of
vibration is perpendicular to the axis of the crystal ; red light is also
obtained from the side-faces when the plane of polarisation is parallel
to the axis of the crystal ; but since, in the first case, the plane of
vibration is perpendicular to the axis, it should be the same in the
second : it is therefore perpendicular to the plane of polarisation.
F. D. B.
Phosphorescence. By B. Sturtz (Ann. Phys. Chem. [2], 8, 528).
— In high vacua, the following substances exhibit phosphorescence : —
Magnesium phosphate, wolframite, cerusite, adularia, doublespar, apa-
tite, franklinite, dolomite, red spinel, cohalt-glanz, stannite, baryta,
chrome-ironstone, lazulite, lepidolite, zinnwaldite, ankerite, greenockite,
pektolite, borax, leucite, sanidin, and the meteorite of Java, 1869.
Cerusite is deprived of this property bj'- ignition ; while on the other
hand the following substances exhibit no phosphorescence, or but a
faint trace, until after they have been heated to redness : — Brucite,
magnesite, orthoclase, kaolin, axinite, kieselzink, fergusonite, apophyl-
GENERAL AND PHYSICAL CHEMISTRY. 599
lite, and coelestin. A long list of minerals is also given which do not
exhibit phosphorescence. R. R.
Electro-optic Observations on Various Liquids. By J. Kerr
(Phil. Mag. [5], 8, 85 — 102 and 229 — 245). — Some years ago two
papers were published by the author (ibid., 1875) describing experi-
ments in which a power of double refraction was induced in glass,
carbon bisulphide, and other dielectrics by the application of electric
force ; since then observations have been made with improved appara-
tus, and with the advantage of previous experience.
The liquid to be examined is contained in a glass cell formed by boring
a hole one inch in heisrht and five-eighths of an inch in v/idth through
a piece of plate-glass three-quarters of an inch thick; the ends of the hole
are covered with thin pieces of plate-glass gently pressed against the
main piece by suitable screws. In the centre of th& cell thus formed
two brass buttons, each one-quarter of an inch in diameter, oppose their
slightly convex and heavily plated surfaces. The distance between
the two surfaces is one-eighth of an inch, whilst the line joining their
centres is horizontal and parallel to the surfaces of the plate-glass.
One of the buttons is connected with an electrical machine, the other
with the earth by means of wires passing through holes drilled in the
glass. Similar holes serve to fill and empty the celL A ray of light
emitted by a flat pai'affin flame presented edgeways,, passed, first through
a polarising Nicol having its principal section at an angle of 45° to the
horizon, then through the cell above described, then through one or
more slips of thin plate-glass so arranged that they could be subjected
to strain by means of weights, and finally through the analysing Nicol.
In order thoroughly to undex'stand the results of these experiments,
we must remember that when a ray of light polarised in a plane
inclined at 45^ to the horizon passes through a slice of a uniaxial
crystal having its principal axis vertical, the ray is broken up into
two parts, one of which (the ordinary ray) has its vibrations in a
plane perpendicular to the axis ; the other (tlae extraordinary ray) has
its vibrations in a vertical plane containing the axis. In negative
uniaxial crystals, such as calcspar, the velocity of the extraordinary
ray is greater ; in positive uniaxial crystals, such as quartz, it is less
than that of the ordinary ray. Precisely the same effect can be ob-
tained with a piece of glass subjected to strain in one direction ; if
stretched vertically or compressed horizontally, the light, having its
vibrations vertical, will travel faster ; if compressed verticallv, or
stretched horizontally, the light, having its vibrations vertical, will
travel slower than that which has its vibi'ations horizontal. In the
first case, therefore, the glass acts as a negative, in the second, as a
positive uniaxial crystal, with the principal section vertical.
Since this birefringent action induced in the glass varies with the
strain to which it is subjected, it is evident that we are provided with
a means of exactly compensating any similar action of the electrified
liquid in the cell, and so observing the nature and measuring the
amount of such action. This is the object of the slips of glass placed
in the path of the ray of light, as above described.
As an illustration of the effects observed when a liquid is submitted
2 u 2
600
ABSTRACTS OF CHEMICAL PAPERS.
to electric force, we may select those obtained with carbon bisulphide.
The cell being filled with this liquid, the slips of glass being subjected
to no strain, and the analysing Nicol being tamed to perfect extinction,
the electrical machine is set in motion, and immediately the light is
restored in the form of a fine vertical line ; as the potential rises, the
light increases steadily until it is quite brilliant ; but if a spark be
taken upon the knuckle from the prime conductor the phenomenon
vanishes instantly. One of the compensating slips is now subjected
to strain, and it is found that horizontal tension strengthens the effect
of electrical action, whilst horizontal compression weakens it, and when
strong enough reproduces sensibly perfect extinction. It would,
therefore, seem that the electric tension has the same effect on the
liquid as a horizontal tension on the glass, in other words, the electric
force sets up a birefringent action in the carbon bisulphide; the light
which is polarised in the plane parallel to the lines of force, that is to
say, the vibrations of which take place in the plane perpendicular to
the lines of force, is relatively retarded.
Carbon bisulphide when electrified acts therefore as a positive
uniaxial crystal with the axis perpendicular to the lines of force.
Other liquids, such as colza and olive oils, with which the glass cell
was filled, yielded opposite results, behaving- as a negative uniaxial
crystal with the axis in the same relative position.
Experiments were made with a large number of liquids, with the
general results given in the following table, where the positive
liquids are arranged as neai-ly as possible in the descending order of
electro-optic power, the larger and clearer intervals being marked by
separating lines. The negative liquids are not so arranged, but colza
and seal oils are certainly among the strongest, and linseed is the
weakest.
Positive liquids.
Carbon bisulphide, v. g.
Cumene, f/.
Paraffin oil (sp. gr. 0"890), v. g.
Carbon dichloiide, v. g.
Xylene, v. rj.
Toluene, v. g.
Cymene, v. g.
Benzene, v. g.
Amylene, v. g.
Paraffin oil, v. g.
Sperm oil, p. g.
Terebene, v. g.
Bromotoluene, b.
Negative liqviids.
Vegetable fixed oils.
Colza, V. g.
Sweet almonds, v. g.
Olive, V. g.
Poppy-seed, g.
Rape-seed, p. g.
Nut.
Mustard-seed, p. g.
Linseed, jp. g.
Animal fixed oils.
Seal, g.
Cod liver.
Lard, p. g.
Neatsfoot, g.
Valeric acid, h.
As it is admitted that very slight changes in the conditions of the
GE>nERAL AND PHYSICAL CHEMISTRY. 601
experiment produce large variations in the electro-optic power, and as,
moreover, no care seems to liave been taken to obtain pure liquids,
further than to purchase the best readily obtainable, the above order
of the positive liquids may require much alteration.
The electrical conductivity of the various liquids was roughly esti-
mated by drawing sparks fi-om the prime conductor of the electrical
machine, firstly when the conductor was in connection with one of the
brass buttons of the cell, while the other was in connection with the
earth ; and secondly when the conductor was entirely disconnected.
If the sparks are in each case of about the same density and length,
the liquid in the cell must evidently be a good insulator ; if the sparks
are smaller in the first case the liquid is not a good insulator, whilst if
no sparks at all can be obtained, the liquid evidently conducts elec-
tricity without difiiculty. The letters v. g., g., p. g-, and b., placed
after the names in the table, signify that the insulation obtained with
the liquid is veiy good, good, pretty good, or bad.
When experiments were made with nitrobenzene, it was found
that no optical effect could be obtained in the usual way, the liquid
conducting electricity with the greatest facility. An interesting
phenomenon was, however, observed when the wire connecting the
machine with the cell was interrupted by a small air-space. In this
case a momentary restoration of the light takes place at the instant
of the passage of a spark across the air-space, and this restoration is
the brighter the greater is the distance across which the spark has to
travel.
By means of a Thomson's long-range electrometer, the electric
potential during the experiments with non-conducting liquids was
measured, and the tension of the compensating glass slips being at the
same time noted, it was possible to obtain at any rate a general idea of
the relation between potential and birefringent action. As regards
the glass slips, it was inferred that the straining weight and the
optical effect are sensibly prop(jrtional as long as the weight does not
exceed 12 lbs. The weight, therefore, may be regarded as a measure
of the optical effect. This being so, quantitative experiments with
carbon bisulphide proved that as the potential increases the intensity
of the corresponding birefringent action also increases, and that the
increments of potential corresponding to a constant increment of
birefrinorent action have sensiblv smaller values at high than at low
potentials. Experiments with other liquids gave similar results, and
it was remarked that in some cases the optically equivalent potentials
for two liquids were respectively proportional. F. D. B.
Specific Heat of Water. By Baumgartner {Ann. Phys. Cliem.
[2], 8, 648 — 653). — At Prof. Pfaundler's suggestion, new determina-
tions were made, in which the method of mixtures was employed,
precautions being taken to render the results as accurate as possible.
Tables of the numbers obtained are given. The values of the true
specific heat of water at 100° (the specific heat at 0° being taken as
unity) as given by different observers are as follows : —
602 ABSTRACTS OF CHEMICAL PAPERS.
Regnault's experiments and calculation 1"0130
,, ,, and Bosscha's calculation 1'0220
V. Miincliliausen's experiments and Wiillner's calculation. ... ] -0302
Baum^artuer's experiments and Pfaundler's calculation .... 1-0307
Henriclisen's experiments and calculation 1"0720
Jamin and Araaury's experiments and calculation 1-1220
Marie Stamo's experiments and calculation 1*1255
F. D. B.
Freezing Mixtures of an Acid and a Hydrated Salt. By
A. DiTTE {Gom.pt. rend., 90, 1163 — 1165). — The reduction of tem-
perature observed when sodium sulphate is mixed with hydrochloric
acid is not due simply to the solution of the salt. Double decom-
position takes place in accordance with the principle of maximum
work ; sodium chloride is produced, and this, being insoluble in
concentrated hydrochloric acid, is precipitated : the water which
existed in the salt as a solid is set free as a liquid, and it is mainly
this passage of the water from the solid to the liquid condition which
causes an absorption of heat. If the hydrochloric acid be not suffi-
ciently concentrated, a portion of the salt formed is dissolved, the
decomposition is not complete, and the maximum reduction of tem-
jDerature is not obtained. When 16 parts of sodium sulphate are
mixed with 12 parts of the commercial acid, the temperature of the
mixture is redu-ced about 33°. Similar effects are produced with
mixtures of sodium phosphate or sulphate with nitric acid, and the
alums or sodium phosphate with hydrochloric acid.
Pure phosphoric acid may be easily obtained by saturating a solution
of sodium phosphate with hydrochloric acid gas, decanting the clear
liquid from the precipitated common salt, and distilling oflf the excess
of hydrochloric acid. C. H. B.
Compounds of Hydrogen Peroxide. By Berthelot (Compt.
rend., 90, 334 — 337). — The paper gives the measurements of the
thermic relations of certain combinations of hydrogen peroxide with
alkalis, recently discovered by Schone. The combination BaO^.H-jOo,
decomposes with development of heat = + 14'2 cal. into BaOj.HoO
+ 0 ; this hydrate of barium peroxide then combines with more
water, BaOs.HoO + OH.O = BaOa.lOH.O = + 29-6 cal., and finally it
breaks up into BaO.H,0 and oxygen, BaOo.lOHoO = BaO.lOHoO +
0 = + il"8 cal., each of these reactions being attended with develop-
ment of heat. The same series of reactions serves to explain the
instability of hydrogen peroxide in the presence of a trace of baryta,
or of any other alkali, the following series of reactions taking
place : —
2HoOo + BaO.HoO = BaC.HaO^ + 2H2O
BaOo.HoO., = BaOo.HoO + O
Ba02.H,0 = BaO.Ho.6 + 0.
All these reactions are attended with a disengagement of heat, and
thus the alkali reverts to its original condition, when it reacts upon a
fresh quantity of hydi-ogen peroxide, continuing a series of reactions
which individually and collectively are exothermic. R. R.
GENERAL AXD PHYSICAL CHEMISTRY.
603
Heat of Formation of Ammonia, of the Oxides of Nitrogen,
and of the Nitrates. By J. Thomsex (Ber., 13, 498— 500).— Ber-
thelot {Corrvpt. reml., 89, 877, this volume, p. 207) has recently shown
that the heat of formation of ammonia cannot be accurately deduced
from experiments based on the action of chlorine on aqueous
ammonia. Satisfactory results are obtained by burning ammonia in
oxygen ; the heat of combustion for 1 mol. NH3 equals 91300. The
heat of formation of N + H3 is 12200.
The author has repeated Berthelot's experiments, and obtains 90650
for the heat of combustion, and 11890 as the heat of formation for
1 mol. NH3.
Since the heat of formation of ammonia enters into the calculations
for the heat of formation of the acids and oxides of nitrogen, the fol-
lowing numbers must be substituted for those contained in the pre-
vious communication {Ber., 13, 498 — 500, and this vol., 81).
Table I.
Reaction. Heat of formation.
Nitrous oxide N^ + 0 -18320
„ N + NO + 3255
Nitric oxide N+0 -21575
. „ „ NoO -h 0 -24830
Nitrous acid No + O3 + Aq. — 6820
„ NoOj + 0 + Aq. -36330
„ N + Oa-fH + Aq. +30770
„ NO + 0+H-fAq. +52.345
Nitrogen dioxide N + 0, — 2005
„ NO + O +19570
Nitric acid N, + O5 + Aq. +29820
„ N3O + O, + Aq. +48140
„ N.O^ + O3 + Aq. + 72970
„ N.O4 + 0 + Aq. +33830
„ N + O3 + H +41510
, NO + O2 + H +63085
„ NO, + O + H +43515
„ N^Oi + 0 + H2O +18670
„ N+03 + H + Aq. +49090
„ NO + Oa + H + Aq. +70665
„ NOa + O + H + Aq. +51095
„ NO^HAq. + 0 +18320
Table II. — Real of formation of Metallic Nitrates by direct union of their
Elements.
Anhydrous nitrates.
Potassium . .
Sodium ....
Heat of formation.
119480
111250
111620
58150
28740
Anhydrous nitrates.
Barium
Strontium. . . .
Calcium
Heat of formation
225740
219850
203230
Thallium ....
Silver
Lead
105500
w. c. w.
604 ABSTRACTS OF CHEMICAL PAPERS.
Heat of Formation of Chloral Hydrate. By A. Wurtz
(Conipt. rend., 90, 337 — .342). — The experiments described in the
paper lead to the following conclusions. The vapours of water and of
anhydrous chloral may be mixed without giving rise to any sensible
change of temperature. This fact supports the view entertained on
other grounds that the vapour of chloral hydrate is a mixture and not
a compound, and that it forms therefore no exception to the law of
Avogadro and Ampere.
Sainte-Claire Deville considers that the experiments detailed in the
foregoing paper do not determine the point at issue. He declines to
accept either Avogadro's law, or any doctrine concerning atoms,
molecules, forces, peculiar states of matter, &c., refusing to believe in
what he cannot see or even imagine. As a matter of fact, the vapours
of ammonium chloride, of the chlorides of the compound ammonias,
and of many volatile organic bases, correspond with 8 vols., and it has
not yet been proved that any one of these vapours is a mixture.
R. R.
Heats of Combustion of Glycerol and of Ethylenic Glycol.
By W. LoPGUiNiNE {Compt. rend.. 90, 307). — The heat of combustion
of glycerol in the reaction CsHsOa liquid + 70 gaseous = 4H2O liquid
+ 3CO2 gaseous, is 392,455 ; that of ethylenic glycol in the reaction,
CvHeOo liquid + 50 gaseous = 3H2O liquid + 2CO2 gaseous, is
283,293. R. R.
Volatile Metallic Chlorides. By v. Meter and H. ZiIblin
(Ber., 13, 811 — 815). — The authors have endeavoured to settle the
question as to whether such chlorides as Fe2Cl6, Sn2Cl4, become FeClj
and S11CI2 at higher temperatures, and claim to have proved the
existence of SnClo at a temperature of about 800°. Gr. T. A.
Compression of Gaseous Mixtures. By L. Catlletet {Comp.
rend., 90, 21U). — When a mixture of air and carbonic anhydride is
submitted to pressure, the liquefaction of the carbonic anhydride is
often greatly retarded. Thus, a mixture of eqtial vols, of air and car-
bonic anhydride will suppoi't a pressure of 400 atmo.spheres at 0°
without visible change. When, however, 5 vols, of carbonic anhy-
dride are mixed with 1 vol. of air, the former is easily liquefied. If
the pressure be then raised to 150 or 200 atmospheres, the meniscus
of liquefied acid, before concave and well-defined, grows flat and in-
distinct, then it gradually becomes imperceptible, and the liquid at
length disappears altogether. The tube then appears as if filled with
homogeneous matter, wliich resists all further pressure as a liquid
would.
When the pressure is again slowly diminished, the liquid suddenly
reappears, at a pressure which is constant for given temperatures. A
thick cloud appears in the tube, spreads, and vanishes as the liquid
forms. The pressures at which the liquid carbonic anhydride re-
appears are at 55°, 130 atmospheres; at 10°, 124 atmospheres; at
13°, 120 atmospheres; at 18°, 113 atmospheres; at 19°, 110 atmo-
spheres. Carbonic anhydride gas compressed beyond 250 atmospheres
is not liquefied at 21°. It might be supposed that this disappearance
GENERAX, AND PHTSICAL CHEMISTRY. HOo
of the liquid is apparent only, in consequence of the refractive index
of compressed air increasing more rapidly than that of liquid carbonic
anhydride, so that at the point where the two indices become equal,
the surface of the liquid would cease to be visible. But, in that case,
the surface of separation should again become visible when the nres-
sure is further increased. This, however, does not occur, and the
author's conclusion is that under high pressures a gas and a liquid are
capable of solution in each other, so as to form a homogeneous
whole. R. R.
Note. — The recent experiments of Ramsay on the so-called critical
point of liquids (Proc. Hoy. Soc.) would seem to require some modifi-
cation of the above theory. — C. E. G.
Variation of the Tension of Vapour emitted above and
below the Point of Fusion. By P. de Moxdesie (Compt. rend.,
90, 11-58 — 1161). — The variations in the tension of the vapour of a
substance are so much greater above its point of fusion than below
that the two series of variations cannot be accurately represented by
the same curve. C. H. B.
Proportion of Carbonic Anhydride in the Air. By .J. Reiset
(Covipt. reiul, 90. 1144— 1148).— The mean of 91 day" and night
determinations made during the latter half of 1879 was 29v8 vols, of
carbonic anhydride in 10U,000 of country air. Between 9 a.m. and
4 P.M. the mean amount was 28"91 vols, in 100,000 ; durinof the niofht
30'84 in 100,000 ; i.e., the proportion of carbonic anhydride in the
atmosphere is greater during the night than in the daytime. In foggy
and hazy weather the mean amount was 31'66, with a maximum of
34"15 in a very dense fog. Details of the method of determination and
of the apparatus employed are given.
The proportion of aqueous vapour in the air varied from 4'21o
grams per cubic meter in November to 16"552 grams in August, the
mean being 10T35 grams (see also this Journal, 36, 744).
The author considers that no connection has yet been definitely
established between the variations in the proportion of carbonic
anhvdride in the air, and the mode of circulation of the latter.
C. H. B.
The Problem of Estimating the Number of Isomeric Paraffins
of the Formula C^Hs^ + o. By F. Heemanx (Ber., 13, 792;.— The
author gives no description of his method, but states that by a " more
concrete method " than Cayley's (On the analytical forms called
Trees. Report of British Association, 1875) he finds the possible
number of isomeric paraffins of the formula C10H06 to be 355.
G. T. A.
History of Periodic Atomicity. By L. Meter {Ber., 13,
259—265;.
606 ABSTRACTS OP CHEMICAL PAPERS.
Inorganic Chemistry.
Vapour-density of Iodine. By F. Meier and J. M. Crafts
(Ber., 13, 851 — 873). — The authors have repeated Victor Meyer's ex-
periments (Ber., 13, 399, and this vol., p. 433) on the density of iodine
A'apour, introducing slight modifications in the apparatus to increase
the accuracy of their results, and they find that the vapour-density of
iodine begins to be abnormal between 600° and 700°, and at a tem-
perature of 1390° it is 0'60 of the theoretical density.
The difference between the results of V. Meyer and those of Deville
and Troost (A^m. Ghim. Fhys., 59, 161) is partly due to the fact that
the latter authorities have taken the temperature of boiling zinc and
cadmium as 1040° and 860° instead of 940° and 746"3° respectivelv.
w. c. w.
Action of Potassium Iodide on Hydrogen Peroxide. By
E. ScHONE {Ber., 13, 627 — 629). — The separation of the small quantity
of free iodine which occurs on mixing pure hydrogen peroxide with
neutral potassium iodide is not due, as stated by Berthelot (Gompt.
rend., 90, 333), to the action of the carbonic acid in the air, or to
some constituent of the containing vessel, but to the fact that hydrogen
peroxide is decomposed by potassium iodide into water and oxygen, a
small quantity of free iodine and free alkali being liberated at the
same time (compare Annalen, 195, 228). T. C.
Decomposition of Hydrogen Peroxide in Presence of Alkalis
and Alkaline Earths. By E. Schone {Ber., 13, 623— 627).— The
author considers that Berthelot's theory {Gompt. rend., 90, 334) of the
decomposition of hydrogen peroxide in presence of alkalis or alka-
line earths is incomplete, since it does not account for the yellow
colour, which always accompanies the spontaneous decomposition
of the double compounds of hydrogen peroxide with the peroxides of
the alkalis and alkaline earths ; and that his own view {Annalen,
192, 257; 193, 241), according to which the formation of higher
oxides of the metal (tri-, teti-a-, or even pentoxides) plays an important
part in the decomposition of hydrogen peroxide in presence of the
alkalis and alkaline earths, is more in accordance with observation.
T. C.
Action of Sulphurous Anhydride on the Oxides of the
Alkaline Earth-metals. By K. Birnbadm and C. Wittich {Ber., 13,
651 — 653). — Barium oxide unites slowly with sulphurous anhydride
at 200°, and more rapidly at 230°, forming BaSOa. Strontium oxide
absorbs the gas less energetically than barium oxide, the reaction
commencing only at 230° ; the product is SrSOj. Galcium oxide (com-
pare Schott, Bingl. poltjt. J., 202, 52 ; and Ramcnelsberg, Pocjg. Ann.,
67, 249) does not absorb the gas below 400°, but at this temperature
combination takes place rapidly with the formation of a basic sulphite,
CaeSsOie. At 500° the gas is very rapidly absorbed, but the sulphite
tlien splits up into sulphate and sulphide. Magnesium oxide begins to
INORGANIC CHEMISTRY. 607
absorb the gas very slowly at 326°, forming MgSOs, but this is decora-
posed at a slightly higher temperature. T. C.
Persulphuric Acid, By Berthelot {Gompt. rend., 90, 269 — 275,
and o31 — 334). — The author describes in the first paper his recent
study of the formation by electrolysis of persulphuric acid, which
compound was discovered by himself in 1878. The most concentrated
solution of persulphuric acid he could obtain had 123 grams of SjOt in
1 litre, the liquid consisting in addition of 375 grams of sulphuric
acid and 850 grams of water. The method of operating was to pass
the current from 9 Bunsen cells, connected to form 3 elements,
through dilute sulphuric acid. The platinum electrodes were sepa-
rated by a porous partition, and measures were adopted to prevent the
temperature from rising. At a certain stage of concentration the
character of the reaction is modified, and instead of pure persulphuric
agid a combination of that substance with hydrogen peroxide is formed,
tending to the definite composition, S2O7.2H2O2. This compound,
the author considers, is analogous to the combination of barium and
hydrogen peroxides, BaOa.HoOo, discovered by Schone. S0O7.2H2O2
is almost entirely changed into persulj)huric acid when it is mixed
with an excess of monohydrated sulphuric acid. Persulpliuric acid in
solution slowly decomposes ; the excess of oxygen is gradually
liberated, but a certain quantity of hydrogen peroxide is at the same
time produced. The stability of the acid is increased by dilution.
In the second paper, the autltor gives the details of various thermic
determinations relating to the heat of formation of persulphuric acid
and other substances.
From these it appears that the formation of hydrogen peroxide, of
pei'sulphuric acid, and of ozone are endothermic, and form a graduated
series : —
Ozone, O2 + 0 = (Oz.) gives — 29'6 calories.
Persulphuric acid, S^Oe -(- O = (S2O7) absorbs 27'6 calories.
Oxygenated water, H2O -}- 0 = (H2O2) absorbs 21'6 calories.
These substances are transformable one into another, and they all
contain active oxygen, that is to say, oxygen which acts on oxidisable
bodies more readily than ordinary oxygen. This is explained by the
excess of energy which is stored up in them, as indicated by their
thermic relations. R. R.
Constitution of Selenious Acid. By A. Michaelis and B. Land-
MANN {Ber., 13, 656 — 657). — The fact that iodides of the alcohol
radicles act on sulphites with formation of sulphonic acids shows
that sulphurous acid may be considered as hydrogen sulphonic acid,
H.SO2OH. The following experiments have been made with the
object of determining whether selenious acid has a similar constitution.
Ethyl iodide acts on potassium selenite only at high temperatures,
forming free selenium, potassium iodide, and alcohol ; in a similar
manner by the use of benzyl chloride we obtain free selenium, potas-
sium chloride, benzaldehyde, and a little benzoic acid. Under these
circumstances, therefore, selenious acid acts as an oxidising agent.
608 ABSTRACTS OF CHEMICAL PAPERS.
Sodium etliylate and sulphui'ous chloride give S0(0Et)2, whilst ethyl
iodide and silver sulphite give Et.SOj-OEt; the corresponding com-
pounds of selenium, on the contraiy, give the same product in both
cases, viz., SeO(OEt)2, which is decomposed by water, forming selenious
acid. The above reactions show that selenious acid has a different
constitntion to sulphurous acid, being in fact a true dihydroxyl acid,
SeO(OH)3.
The ethoxylcJdoiide, SeO!Cl(OEt), is easily obtained by the action
of alcohol on selenious chloride. T. C.
Silicon Ethyl Series. By C. Friedel and A. Ladenburg (Ann.
Chim. Phys. [5], 19, 390 — 406). — The authors refer to former papers
on the organo-silicon compounds (Ann. Chim. Phys. [4], 9, 5 ; 19,
334; 23, 430; 27, 416-428).
In the preseijt paper they give the results of attempts to prepare
compounds containing as a nucleus 2 atoms of silicon ^Si^-Sizn, and
therefore analogous to ethane and its derivatives. The starting point
for the preparation of these compounds is silicon hexiodide, which the
authors have succeeded in preparing by heating silicon tetriodide with
finely divided silver (reduced by zinc from moist silver chloride), in
sealed tubes at 290 — 300° for several hours. The contents of the
tube are freed from unaltered tetriodide by repeated washing with
small portions of dry carbon bisulphide ; a larger quantity of hot
carbon bisulphide is then added, and the mixture filtered as rapidly as
possible out of contact with the moisture of the air. On cooling, the
solution deposits small colourless hexagonal prisms of SiJe, which
fume in moist air, and dissolve in potash with evolution of hydrogen.
Silicon hexiodide may be fused in a vacuum, but partially decomposes
at 250°. It cannot be distilled at atmospheric pressure or in a vacuum,
but on heating a portion sublimes, and the remainder decomposes into
the tetriodide and an orange substance which appears to be Silo.
Silicon hexahromide, SioBrg, is obtained by adding an equivalent of
bromine to a solution of the hexiodide in carbon bisulphide. It crys-
tallises in rhombic plates, presenting the optical phenomena of biaxial
crystals, and is tlierefore not isomorphous with the corresponding
iodide.
Silico-n he.rachloride, SioClg, is obtained by gently heating a mixture
of silicon hexiodide and mercuric chloride. The product is distilled
off, rectified over mercuric chloride, and purified by fractional distilla-
tion. It is a colourless liquid, distilling between 144° and 148°, and
crystallising about — 1° ; it fumes in the air, and is decomposed by
water, with formation of a product which in great part dissolves in the
acid liquid. All attempts of the authors to prepai'e this substance in
the dry way by the action of silicon, silver, zinc, sodium, and hydro-
gen on silicon tetrachloride at a high temperature, were unsuccess-
ful. MM. Troost and Hautefeuille, however, have recently prepared
SijClfi by the action of silicon tetrachloride on fused silicon, at a tem-
perature at which porcelain begins to soften.
Silico-oxalic hydrate, HoSiaO^. — When crystals of silicon hexahromide
are introduced into ice water, hydrogen is evolved, and a white sub-
stance deposited which, after drying in a vacuum and then at 100°,
INORGANIC CHEMISTRY. fi09
has a composition expressed by the formula H,>Si^04. Treated with
potash, it gives off hydrogen in theoretical propoi'tion, and when burnt
with oxygen and heated in the air it decomposes with incandescence,
leaving a residue of silica in the proportion required by the equation :
HoSi-.Oi + O = H3O + 2SiO,. The air-dried substance contains 10-4
per cent, water, the formula H^SioOj + 'iHoO requiring 12'8 per cent.
The authors explain the formation of silico-oxalic hydrate by suppos-
ing Si2(HO)6 to be first produced, and to become Si202(HO)2 by the
loss of 2H2O. Although this substance is the chemical analogue of
oxalic acid, it has no acid functions ; bases, even the most dilute,
decompose it with evolution of hydrogen, just as oxalic acid under
certain conditions is decomposed by potash.
Silico-oxalic hydrate may also be prepared by the action of silicon
hexiodide on absolute alcohol, the ethyl iodide, which is formed at the
same time, being removed by distillation.
Silicnn hexethide, Si2(C2H5)6. ^Silicon hexiodide is added in small
quantities to zinc ethyl in the proportion of Siole to 3ZnEt2. A brisk
reaction ensues, and a white substance is deposited. The product is
distilled, the distillate washed with water to remove zinc ethide,
agitated with concentrated sulphuric acid (to remove a substance
which appears to be oxide of silicon-triethyl), again washed with
water, dried, and submitted to fractional distillation. The distillate
boiling at 150 — 154" is silicon tetrethide, that coming over between
250° and 253^ is silicon hexethide, Si2(CoH5)6. Silicon hexethide is a
limpid, slightly oily liquid, with a faint odour resembling that of
silicon tetrethide. It buims with a bright flame, producing clouds of
silica. Two vapour-density determinations, made at about 300°, gave
the numbers 8"53 and 8"63, theory requiring 7-96. The excess was
probably due to the presence of the above-mentioned oxide of silicon-
triethyl. The density of the liquid silicon hexethide is 0-8510 at 0°,
0-8403 at 20°, compared with water at 0° and 20° respectively. This
compound may be regarded as a derivative of silico-ethane, Si2H6, just
as tetraphenylethane, C2H2(C6H5)4, is a derivative of ethane.
J. M. H. M.
Action of Certain Metals and Non-metals on Phosphorus
Oxychloride. The Existence of Leverrier's Phosphorus Sub-
oxide. By B. Reimtzee and H. Goldschmidt {Ber., 13, 845 — 851).
— When molecular silver is heated with phosphorus oxychloride in
sealed tubes at 250°, the following bodies are formed : phosphorus tri-
chloride and pentoxide, pyrophosphoryl chloride (P2O3CU), silver
chloride, and silver ortho- and pyro-phosphates.
With metallic copper, phosphorus oxychloride yields cuprous chlo-
ride and phosphide, also phosphoric anhydride and pyrophosphoryl
chloride. Under similar conditions, metallic mercury produces mer-
curic chloride, phosphide and phosphate, mercurous and phosphorous
chlorides, pyrophosphoryl chloride, and a small quantity of phosphoric
anhydride.
Sulphur and lead do not act on phosphorus oxychloride, and tin has
no action on it at 100°. In addition to phosphorus trichloride, zinc
metaphosphate and chloride, and small quantities of phosphoric anhy-
dride and pyrophosphoryl chloride, metallic zinc forms phosphorus
610 ABSTRACTS OF CHEMICAL PAPERS.
suboxide, P4O, described by Leverrier (Ann., 27, 167). This oxidei
tbe existence of wbicb was denied by Schrotter, is an orange-red
powder, wbicb reduces solutions containing silver, mercury, or gold,
and when boiled with potash blackens and evolves phosphoretted
hydrogen.
Mao-nesium and aluminium yield similar products to those obtained
in tbe case of zinc. By the action of iron on the oxychloride, ferrous
chloride and phosphate, and phosphorus trichloride and pentoxide are
produced.
A niodication of phosphorus suboxide, P4O, appears to be formed
by heating at 250° a mixture of phosphoriis and the oxychloride,
P4 + POCI3 = P4O + PCI3. It is a red substance, and differs
from the ordinary modification inasmuch as it is not attacked by
alkalis or by water, and does not reduce solutions of silver or gold.
With arsenic, phosphorus oxychloride yields the trichlorides of
arsenic and phosphorus, also phosphoric anhydride and pyrophospboryl
chloride.
The authors consider that the results of these experiments are
evidence in favour of the pentavalence of phosphorus, since isomeric
oxychlorides of phosphorus were not produced in any instance.
W. C. W.
Composition of Hydrated Barium Dioxide. By E. Schone
(Ber., 13, 803— 807).— Only one hydrate of barium dioxide, BaOz.SHoOo
can be obtained between 5° and 20°, either by spontaneous decomposi-
tion of the compound Ba02.H203 under water, or by addition of a
dilute solution of hydrogen peroxide to excess of barium hydrate.
G. T. A.
Dissociation of Barium Dioxide. By Boussingault (Ann. CUm.
Phys. [5], 19, 464 — 472). — In this paper Boussingault narrates the
series of attempts which he has made to devise a method of separating
tbe oxygen of the atmosphere economically on an industrial scale.
The method employed by him was the alternate peroxidation and
reduction of baryta at a dull red and a bright red heat respectively.
After a few heatings, it was found that the baryta almost loses its
power of absorbing oxygen. The author demonstrated that this loss of
activity is due to a change in tbe molecular state of the baryta induced
by the high temperature required for the decomposition of barium
dioxide under ordinary conditions. In fact, baryta obtained by very
strongly heating the nitrate will scarcely take up oxygen, and even
combines with water with extreme slowness. The experiments of Gay-
Lussac on the decomposition of calcium carbonate by heat, and the
subsequent researches of St. Claire Deville and Debray on dissociation,
suggested to the author that in a vacuum the decomposition of barium
dioxide might take place at a temperature low enough to have no
injurious influence on the power of baryta to absorb oxygen. This
was found to be the fact, barium dioxide dissociating at a low red heat
in a vacuum, whereas it requires a bright red or orange heat under
atmospheric pressure. The decomposition in a vacuum takes place at
about the same temperature (the melting point of zinc, 450" C.) as
the absorption of oxygen by baryta under atmospheric pressure. At
INORGANIC CHEMISTRY. 611
a low red heat the power of baryta to absorb oxygen is not at all
injured, and the alternate peroxidation and reduction may take place
an indefinite number of times. J. M. H, M.
Crystalline Form of Magnesium. By Des Cloizeaux (Compi.
rend., 90. 1101 — 1102). — The crystals obtained by Dumas by subli-
mation have the colour and lustre of silver, are malleable and sectile,
but have no cleavage. The faces are often curved and the edges
rounded. The usual form is a regular hexagonal prism, the basal
planes of which are less brilliant than the lateral faces. The prin-
cipal angle of the corresponding rhombohedron is 80° 3' 30", and is
therefore intermediate between that of zinc, the most acute of the
rhombohedral metals, and arsenic. C. H. B.
The New Metals of Gadolinite and of Samarskite. By M.
Delafoxtaine (Compf. rend.. 90, 221 — 223). — Discoveries of ten rare
earths have been announced by various chemists since the publication
in 1878 of papers on terbine by Marignac and by the author. The
latter believes that these alleged discoveries have really and definitely
added to the list of elements only three new ones, viz., ytterhium,
decipium, and philippium. Samarium is probably another real dis-
covery, but further proofs are needed. Mosandrum, liolmium, thulium.,
and the rest must be rejected, except possibly scandium, with which
the author disclaims any acquaintance. Holmium is, according to the
author, identical with philippium. R. R.
Vesbium and Norwegium. By C. Rammelsberg {Ber., 13, 250
— 251). — Scacchi (this vol., 445) has examined the green and yellow
incrustations found in the clefts of Vesuvian lavas, and has obtained
from them a red metallic acid, containing a new metal, vesbium. Its
reactions closely resemble those of molybdenum.
Dahll (^Zeit. d. Geol. Gesellschaft, 31, 480) claims to have dis-
covered a new metal (norwegium) in the red nickel-pyrites of Kragero
(this Journal, 36. 890). The metal is white and not very raalleal3!e ;
sp. gr., 9'44. It dissolves in nitric acid with blue colour, which be-
comes green on dilution. Its salts give a green precipitate with
alkalis, soluble in excess. Before the blowpipe it gives a yellow glass,
becoming blue on cooling ; with soda on charcoal, it gives a yellowish-
green incrustation. Ch. B.
Composition of Weldon-mud. By J. Post and G. Luxge
(Dingl. polyt. J., 236, 225 — 237). — In a paper recently published
(ibid., 235, 300) Lunge criticises Post's investigations as to the com-
position of WeldoD-mud. In reply. Post gives a detailed account of
his investigations which led him to afiirm that it is erroneous to
assume Weldon-mud to consist chiefly of a so-called calcium man-
ganite (Mn02)vCaO, since Weldon-mud itself, or when mixed even
with an unusually lai'ge percentage of " base," contains but little lime
(CaO). It is further shown that at the present time in the Weldon
process mud containing less than 0'5 of " base " to I'O of MnOo is found.
Lunge, in contradicting these statements, mentions that Post arrived
(512 ABSTRACTS OF CHEMICAL PAPERS.
at his conclusions by analysing three or four samples of but '•' slightly
washed " or " unwashed" mud ; whereas the analyses of " well washed "
mud and the conclusions drawn from the results seem to have been
entirely ignored by Post- These contradictory statements have given
rise to a large amount of correspondence between Lunge and Post,
and the present paper gives a full account of the same. D. B.
Borotungstates. By D. Klein (Bull. Soc. CMm. [2], 33. 466—
469)_ — Potassium borodiwdecitungstate, 2K20.12W03.B20:,.15H20, is
obtained in radiating masses, formed of acicular crystals, by boiling
together for 12 hours equal weights of tungstic hydi'ate and potassium
pentametaborate, K.H4.B50in.2H..O. It is slightly soluble in cold, very
soluble in hot water. At 175°, it loses all water of crystallisation, and
if heated more strongly, a small quantity of boric acid is volatilised. In
external appearance it resembles the metatungstate, K2O.4WO3.5H2O,
but is much less soluble in water.
Barium borodecitungstate, 2BaO.10WO3.B2O3.20HoO, is obtained by
adding a solution of 12 grams of barium chloride to a strong solution
of 35 grams of the preceding compound. It forms large brilliant
octohedrons, identical in appearance and crystalline form with those
of the metatungstate, but more stable. At 175° they lose all water of
crystallisation. The same compound is in all probability formed when
barium chloi'ide is added to the acidulated mother-liquors from the
treatment of sodium tungstate, with an excess of boric acid. From
this salt an acid was obtained, which, on concentration, crystallised in
quadratic octohedrons, the angles of which were truncated by the
faces of the primitive prism. C. H. B.
Red Antimony. By N. Teclu (Dingl pnljjt. J., 236, 336—340).
— As the opinions concerning the composition of red antimony still
differ in spite of the manifold investigations recently made, and
several new text-books class it among the oxysulphides, and others
among the trisulphides of antimony, the author thought it desirable
to undertake a series of careful analyses of this compound, so as to
enable him to decide this point, and also to determine whether the
]iroduct prepared according to Wagner's method from tartar emetic
differs in composition from that obtained from chloride of antimony.
It was found that red antimony in both cases consists merely of anti-
mony and sulphur, its composition being SbiSs. Its formation by
both methods may be illustrated by the following equations : —
(1.) 2C4H4KSb07 + 3S,03Na2 + H2O = Sb.Sa + SSOiNa, -f
2C4H5KO6.
(2.) 2SbCl3 + SSoOsNao + H2O = SboSs + 3S04Na.2 + 6HC1.
The formation of sulphurous acid, which is invariably observed
during the preparation of this compound, and the presence of free
sulphur in the product after extraction with carbon bisulphide, point
to the simultaneous result of a secondary process, which consists in
the decomposition of sodium thiosulphate by means of tartaric or
hydrochloric acid. D. B.
MIXERALOGICAL CHEMISTRY. 613
Action of Antimony Pentachloride on Phosphorus Tri-
chloride. By H. Kuhler {Ber., 13, 875 — 877).— When antimony
pentachloride is slowly added to phosphorus trichloride, dilutad with
five times its balk of chloroform, Weber's phosphorus antimony
decachloride {Pugg. Ann., 125, 78) is depositad as a white crystalline
powder, which fumes in the air and rapidly deliquesces.
PCls + 2SbCl, = SbCls.PCls + SbCla.
w. c. w.
Mineralogical Chemistry.
Crystal-tectonic of Silver. By A. Sadebbck Ualirh. f. Kin.,
1879, 85 — 86). — Notwithstanding the limited number of known forms,
silver exhibits great variety in its crystalline structure. There are
three crystal types, viz., the octohedral, the cubical, and a subtype,
the middle crystal. Twins according to the usual law of the regular
system. The author observed in regard to the tectonic properties, a
characteristic " shell-like structure," which is brought about by the
union of subindividuals in the octohedral and cubical faces. Silver
occurs also, like other precious metals, in " regular growths " (regel-
mdssigen VerwcicJisuyigeii) , which are dependent on the arrangement of
the crystals in certain directions, these directions being called by the
author the tectonic axes. The tectonic axes are all the four kinds of crys-
tallographical axes, viz., the fundamental axes, the prismatic axes, the
diagonals of the octohedi-al faces and the rhombohedral axes. As a
result of crystalline arrangement parallel to these directions, the
various serrated, rod-like and wire-like forms may be cited. If the
crystalline arrangement takes place parallel to various tectonic axes
Ipng in one plane, this plane becomes the tectonic plane and plate-
like formations are the final result.
In the case of native silver, cubical and octohedral faces appear as
tectonic planes. The tectonic axes are not necessarily formed of
similar axes, but can also be formed out of dissimilar axes. The
primary and the prismatic axes appear as the tectonic axes in the
cubical planes ; in the octohedral planes the tectonic axes are the pris-
matic axes and the diagonals. Finally, the formation can take place
parallel to various directions, resulting in skeleton growths. All the
specimens of silver examined were embedded in calcite and accom-
panied by fluorspar and barytes : hence the author concludes that they
were formed simultaneously in the wet way, more especially as the
reticulated growth of the sUver of Wittichen is intimately connected
"with the presence of barytes. C. A. B.
Artificial Production of Scorodite. By Yerneutl and Bour-
geois {Co nipt, rend., 90, 223 — 225). — To obtain scorodite, which is
regarded as a hydrated ferric arsenate having the formula —
Fe203As.05,4H20,
VOL. iXXVIII. 2 X
614 ABSTRACTS OF CHEMICAL PAPERS.
the anthors lieated iron wire in a sealed tube with a concentrated
solution of arsenic acid at 150'^ for several days. At the end of the
expei'iment the wire was found covered with fine crystals of scorodite
of a bluish-green colour, and identical in form with those of native
scorodite. K. R.
Felspar in the Basalt from the Hohen Ha gen near Gottingen,
and its Relation to the Felspar of Monte Gibele in the Island
of Pantellaria. By C. Klein (Jahrb.f. Min., 1879, 86— 87).— Haus-
mann first described the felspar from Hohen Hagen in 1849, but Klein
proved that the crystals were asymmetrical and not monosymmetrical.
A careful optical examination showed the felspar to be oligoclase, and
an analysis gave a further proof of the correctness of this conclusion,
the result being as follows, viz. : —
SiOa. Al.,03. FesOs. CaO. MgO. K.p. Nap.
64-33 21-97 0-45 2-07 013 495 6-99 = 100-89
An optical examination of the Monte Gibele felspar proved it to be
identical with that from Hohen Hagen. C. A. B.
The Mica Group. By C. Rammelsberg (Ann. Phys. Chem. [2],
9, 302 — 329). — This paper forms the second portion of the author's
monograph on the chemical constitution of the micas (this vol., 224).
The discussion of micas containing iron and magnesia is continued
under several sections.
Micas corresponding with the general formula —
M4Si04.3R"3Si04.R^''Si30i2, or MiR'eR^Si^O
28-
The specimens examined under this head are from Miask, Ilmenge-
birge ; Filipstad, Sweden ; New York ; Greenland ; Sterzing, Tyrol ;
Servance, the Vosges ; Persberg, Sweden; and Brevig, Norway.
Another section comprising micas of the general formula —
M4Si04.2R"2Si04.R^'2Si30,2, or M2R"2R^Si30i2, includes specimens
from Renchthal in the Black Forest; Lierwiese ; Hittero ; Portland,
Connecticut ; and Radauthal ; together with three varieties from
Freiberg.
To certain specimens from Brevig in Norway, and from Wiborg, in
Sweden, the general formula M4Si04.oR"2Si04.2R^2Si30i2, or
M..R"3R%Si302o, is assigned.
The formula .3M4Si04.3R"2Si04.4R^%Si30,2, or M6R"3R^'4Si9036, re-
presents specimens from St. Dennis, in Cornwall, and from Persberg,
in Sweden.
Micas of various composition, lithia-micas and baryta - micas,
from specified sources, are then discussed under these respective
heads. R. R.
Crystallisation of Cyanite. By M. Bauer (Jahrh.f. Min., 1879,
84 — 85). — The results of Bauer's researches are briefly as follows,
viz.: — (1.) Cyanite seldom exhibits an inclined laminated fracture
(blatterbruch). (2.) From the angles observed between these in-
MINERALOGICAL CHEMISTRY. 615
clined fractare-laminEe and certain faces (in conjunction with othei*
angles), the axial relations were ascertained, viz., brachjaxis, macro-
axis, vertical axis = 0-89912 : 1 : 0-69677. (3.) The twins parallel
to M are recognised by the re-entering angles observed on T, and the
differing position of the plane angle on M. (4.) The twins on which
T exhibits re-entering angles and not P are formed occasionally by a
revolution about the normal (in M) to the edge M : T, and not by a
revolution about the edge M : P. (5.) Many twins occur according
to the law, " the twin-axis the normal to M." (6.) Beer and
Pliicker first made it possible to distinguish the above-mentioned
twins by means of their optical properties. (7.) The plane of the
optical axes passes through the acute plane angles on M of 89° 45'.
(8.) The twin-plane of the penetration-twins has the symbol — a :
— — : c. (9.) There are twins whose twin-plane is a face of P, and
Li
the twin-axis the normal to P. (10.) The last-mentioned twins are
composite ones, parallel to M according to the second law given above,
so that a further twin-law may be stated, viz., twin-plane a face of P,
twin-axis a normal in P to the edge P : M. There were therefore six
different penetration-twins observed. (11.) For each of the three
twin-laws (having M as the twin-plane) there is a corresponding one
where the individuals are twinned parallel to a face of P. One law is
identical for P and M as twin-faces, and the number of twins parallel
to P and M is therefore five in all. (12.) The twins parallel to P ai*e
not the original twins, but were brought about by the action of pres-
sure, just as the twins of calcite according to the " first obtuser
rhombohedron." C. A. B.
Caucasian Minerals. By A. Frenzel {Jahrh.f. Min., 1878, 87 —
91). — liock-crystal from Kashek. Crystals mostly colourless and well
developed, the combinations observed being —
ooR.-R.R;ooB.R.-R.2P2;ooR.R.-R.2P2.6P4;
CO R . R . - R . 4R . 2P2 . 6Pf ;
dextrorotatory and laevorotatory. The crystals exhibit sometimes a
rhombic or monosymmetrical appearance, and are occasionally covered
with a soft black manganese ore or sometimes enclose chlorite.
Heliotrope is found as " pebble " in the valley of the Arpatschai,
north of Alexandropol in Armenia ; it has a fine dark leek-green colour,
is free from the red iron oxide spots, has a sp. gr. of 2-12 to 2 2 7,
and the following chemical composition, viz. : —
SiO.2. AI0O3. FeO. CaO. MgO. K^O. ISTaaO. UJD.
88-90 0-71 4-15 0-45 0-59 0-95 0-48 4-10 = 100-33
The basalts of Azkhur on the Upper Kur, between Bor.shom and
Achalzich, contain fibrous natrolite, transparent and opaque crystals
of analciine (202), transparent crystals of apophylUte (P . ooPoo), also
the variety of the same mineral called iclithjopjhthalm, in large foliated
masses of a flesh-red colour.
Magnetic-iron sand. — This is found in very large quantity on the
shores of the Caspian Sea, at various places near the Persian frontier,
2 a; 2
G16 ABSTRACTS OF CHEMICAL PAPERS.
more especially at Lenkoran. On Tscheleken, at various places,
deposits of iron salts are found, which exhibit the following character-
istics, viz. : —
1. A dirtv ochre-yellow earthy mass constituting a series of mounds
6 meters high at Sarakaja, about 1^ kilometer from the west coast.
The salt crops up to the surface, its colour increasing in intensity
with the depth. The Turcomans call the salt " Karabuja," and use it
for dyeing carpets. It is amorphous, and has the following composi-
tion : —
SO3. Fe.Oa. CaO. MgO. E.p. Xa^O. HoO. Eesidue (insol.).
30-30 19-00 18-60 0-20 0-35 2-29 12"86 16-50 = 100-00
The insoluble residue was a calcareous marl.
2. Five kilometers north-east of Sarakaja, there is another iron salt
deposit, the uppermost layer being ferrous sulphate about one foot in
thickness, whilst underneath this layer there is a large one of a beau-
tiful lemon to orange-yellow colour. The salt of the first layer has a
fine green colour and often encloses wedge-shaped masses of iron
pyrites. The composition of the green salt was
SO3. FeO. MgO. H2O.
29-10 25-75 0-30 44-85 = lOO'OO
3. JJrusite is the nam.e which Frenzel assigns to the yellow salt
above mentioned. Streak ochre-yellow. Sp. gr. 2*2-2. Hardness could
not be determined. Occurs in nodules, earthy or pulverulent. On
crushing a nodule very minute crystals are observed, which are rhom-
bic, the forms being ooPco . coPob . cxjP . Pcb . P . OP, but all the crystals
do not exhibit these forms in combination, OP being occasionally
absent, or sometimes it predominates at one end of the crystal and is
extremely secondary at the other, thus giving a hemimorphous habit
to the crystals. After deducting 3 per cent, of insoluble residue,
urusite was found to have the following composition, viz. : —
SO3. Fe.,03. ya.,0. H.,0.
4208 21-28 16-50 19-80 = 99-66
the formula deduced from this analysis being Fej032Xa204SOa + 8H0O.
4. North of Urus a salt occurs which resembles closely salt No. 1.
The pulverulent masses enclose nodules of the salt, pieces of clay and
fragments of gypsum. Sp. gr. 2-72. Chemical composition : —
SO3. FejOs. CaO. MgO. K.,0. Xa.O. H.,0. Residue (insol.).
29-62 39-70 470 0-20 0-74 3-28 10-96 10-80 = 100-00
C. A. B.
Ne-vsr Minerals from the Andesite of Mount Arany. By A.
KccH (Jahrh. f. Min., 1879, 83 — 84). — The author has already de-
scribed the minerals (pseudo-brookite and szaboite) found in the above
locality (Jahrb. f. Min., 1878, 652), but he did not give an exact
description of the rock in which they were found. He now states that
the rock is an augite-andesite identical in character with the augite-
andesite of Pachuca, in which G. v. Rath originally discovered tridy-
MDCERALOGIGAL CHEMISTIIT.
617
mite. Tr: _; :__.:r is present also in the augite-aiidesite of Mount Aranj.
Koch arrires at the following ooncliiBion from his examination of the
rock, riz., owing to the metamorphism exhibited, and the eommon
occurrence of tridvmite, it is highly probable that the original rock,
after its solidiiication. was exposed to the action of fmnaroles, result-
ing in the separation of silica and in making the Baolecnles of the
'• eroimd-mass '" ' ■':.- cansinLg more complete cry stalH^-
tion and a new f,_
:-aIs.
C. A. B.
Fermginous and Ni:ra:ed Mineral Waters, Bt E. Willm
(JBuJi. S-'-". Cj,ijjj. j_-j, 33. -io . — 4;-Sily. — inese springs are situated in
a TaHer oi the Verges between Saverne and Xiederbronn, at Beiperts-
wilira- or fiipj
Carbonic anhjdri ;
bonates)
Carbonic :-: " ■ r"
:ree)
Ferroas carbonate
Manganons „
Calciiua „
Magnesium „
Ferric phosphate . .
Potass: - . .
Silica
Potassium nitrate. .
Calcium 5 v : r . .
Magne -•'.:-- .,
Potass : ;. _ oride
Sodium „
Ma.gnesinm .,
Ore
r£r:in:c matter.
Sor... i_.
SoTJTPe.
SoTrree
SoTiree
SoTiree
Spacli.
Cffisar.
1V1a.deldne
ArthiiT.
0-15-52
0-14*01
— -
r 70-9 c.c.
0-09@S
0-0015
0-0009
0i>035
0-0320
0-0006
0-11550
0-05©2
0-0126
.-, -t - ^
0-0042
0-0107
0-0037
0-^3096
0-0113
trapses
0-1)035"^
0 0087
0-0140
o-ik:»76
— ~
0-0130
0-1297
O-O051
0-0lt4i
0-0228
0-0119
2 ' -
0-0106
0-0528
0-0043
0-0105
0-0203
2 "S
0-0326
0-0366
0^117
"I 2 ^
0-0048
0-0228
0-0(52
— — ^
00155
0-0145
0-0081^
^^^
0-3513
0 3572
r-----^---r-
U1070
0-3(«S8
0-35^
ij , _
Potassium is pipesent ": ' "' ^ '-r qnantitT than sodium: in :"' r
" source Cffi^r " potas? . , . .nstitntes one- third of the t-ZJ^
solid residue. The deposit left by tiie " source Spaeh," dried at 120",
had the composition SiOi, 24-75; FesOj, 56-62; FePO^, 8-99;
CaCOj, 0-55; MgCOs, 010; HjO, 909. ye manganese, arsenic, or
organic matter was present. C. H. B.
1)18 ABSTRACTS OF CHEfflCAL PAPERS.
Organic Chemistry.
Vapour-tension of the Halogen Derivatives of Ethane. By
W. SxAEDAL (Ber., 13, 839 — 841). -^The determination of the boiling
points of the chlorine substitution-products of ethane, at pressures
vai'jing from 400 to 1060 mm., yields results which show that the
increase of tension with the temperature depends not only on the
molecular weight, but also on the constitution of the compounds.
More heat is required to produce a given increase of tension in the
symmetrical than in the uusymuietrical derivatives. A comparison of
the bromine and chlorine substitution products shows that a bromine
derivative has the same increase of tension for 1°, which is possessed
by a compound containing, instead of 1 atom of bromine, 2 chlorine
atoms attached to the same cai'bon atom, e.g., ethyl bromide and
ethylidene chloride, ethylidene chlorobromide and trichlorethane.
w. c. w.
Preparation of Acetonitril. By E. DEMARgAT (Bull. Soc. Ohim.
[2], 33, 456 — 4-57). — When acetamide is distilled in a flask fitted with
a Le Bel-Henninger tube the distillate consists at first of acetonitril,
water, and ammonia, afterwards of acetonitril, water, and a small
quantity of acetic acid. Apparently the acetamide, when heated a few
degrees above its boiling point, splits up into acetonitril and water,
and the latter decomposes a small quantity of acetamide, giving am-
monia, which escapes, and acetic acid. When the quantity of acid in
the liquid reaches a certain amount this secondary reaction ceases.
This decomposition may be utilised for the preparation of acetonitril :
acetamide, is mixed with a small quantity of glacial acetic acid, and
boiled vigorously in a flask fitted with aLe Bel-Henninger tube having
four or five bulbs. The distillate is dried over potassium carbonate.
It is necessary to continue the boiling day and night for about a week,
in order to decompose four or five hundred grams of acetamide, but
the theoretical yield of the pure product is obtained. C. H, B.
Pure Methyl Cyanide. By A. Gautier (Bull. Soc. Chim. [2],
33, 615). — The author shows that the physical constants of methyl
cyanide from the light hydrocai-bons of coal, as given by Vincent and
Delachanal (ibid. [2], 33, 407, this vol., 624) are almost identi-
cal with those he gave for acetonitril twelve years ago (Ann. Chim.
Fhys. [4], 17, 103), when he showed the identity of Pelouze's methyl
cyanide and acetonitril. J. T.
Note on Platinum Thiocyanate. By G. Wyrouboff (Bidl. Soc.
Chun. [2], 33, 402 — 403). — -The compound which Marcano described
as a new platinum thiocyaiiate (ibid., 33, 250), and to which he
assigned the formula Pt(CNS)8, is really potassium thiocyanoplatinate,
K5Pt(CNS)f„ analysed some time ago by Buckton. The formula of
the crystal is K.Pt(CNS)6 + 2tt.O. Marcano's mistake arises from
ORGANIC CHEMISTRY. G19
relying on the estimation of water and metallic platinum. The sup-
posed, instance of octoatomic platinum therefore disappears.
J. M. H. M.
Ethylene lodopicrate. By L. W. Andrews (Ber., 13, 244 — 245).
— Ethylene iodide dissolved in chloroform acts at ordinary tempera-
tures on finely powdered silver picrate. At 70 — 80° the action is rapid.
The chloroform solution, freed from iodine by soda and dried, leaves
on spontaneous evaporation ethylene iodopicrate, C6Ho(N02)30.C2H4l.
By crystallisation from alcohol, it is obtained in colourless needles
(m. p. 69'5°), which become deep orange on exposure to light. It is
insoluble in water, sparingly soluble in alcohol or ether, soluble in
chloroform. Potassium cyanide gives with it a colouring-matter like
picrocyanine, and alcoholic ammonia converts it into a bandy yellow
crystalline substance, not yet examined.
Silver picrate (2 mols.), when heated with ethylene iodide (1 mol.)
and chloroform at 100° for six hours, gave the above iodopicrate,
resinous matter, and a substance (m. p. 78"') easily soluble in alcohol.
The latter is probably ethylene picrate, but has not vet been analysed.
Ch. B.
Carbohydrates from the Tubers of the Jerusalem Artichoke.
By E. DiECK and B. Tollexs (Anualen, 198, 228 — 255). — -The tubers
examined contained lajvulin and a dextrorotary sugar, but little or no
inuiin.
The authors find that the body described by Kopp (Aiinalen, 156,
181) as a sugar and named synauthrose, of the assigned formula
Ci2H220ii, is really analogous to dextrin, and has the composition
CsHioOj ; they propose to name it leevulin. It is optically inactive,
resembles the gums and dextrins in its properties, and enters into
alcoholic fermentation with yeast. Boiled with very dilute hydro-
chloric acid, it gives a sugar which reduces Fehling's solution, and
has a specific rotary power [ajo — —527°. Long heating with mode-
rately dilute sulphuric acid, converts Igevulin into IjBvulinic acid. The
expressed juice of the tubers gives afair yield of spirit on fermentation,
the liquid also containing mannitol, glycerol, and, on one occasion,
succinic acid. W. R. H.
Acetylisation of some Carbohydrates by Liebermann's Pro-
cess. By A. Herzfeld {Ber., 13, 205 — 268). — The acetyl in these
compounds is best estimated by Schiitzenberger's method. Five grams
of the body is heated in a Lintner's pressure tlask at 120 — 140'' with
20 c.c. of standard sulphuric acid (351 grams sulphuric acid of 1-831
sp. gr., = 75 per cent. SO:,, to 10 liters), and the solution titrated with
potash. Ko blackening occurs, and the results are accurate. It has
thus been found that Liebermann's pi'ocess always yields the highest
acetic derivatives.
Octaceh/l-gliicuce has been described by Eranchimont (Ber., 12,
1940). the author finds for it the m. p. 134° instead of 100". It
reduces Fehling's solution.
Odncefi/I-lactuse, doHuOnAcs, is almost insoluble in ether, but crys-
tallises from a mixture of alcohol and ethyl acetate ; it is soluble in
benzene and in acetic acid. It reduces Fehling's solution.
(■•,20 ABSTRACTS OF CHEMICAL PAPERS.
Odacetyl-maltose, CaHiiOnAcs (m. p. 152°), resembles the dextrose
compound, and crystallises in thin prisms.
Odaceti/l-saccharose (m. p. 78°) was obtained as a yellow resin,
easily soluble in alcohol and ether. It does not reduce Fehling's
solution ; for which reason, amongst others, the author regards it as
different from Schiitzenberger's octacetyl-diglucose.
Acetijl-maltodextrin (composition uncertain, m. p. 98°) is more
soluble than the maltose compounds, and is precipitated by water
from its solution in alcohol and ethylic acetate in white flocks.
Aceti/l-erythrodextrin and acetyl -acliroodextrin, C6H7(Ac)306 (m. p. of
both 180°), require prolonged boiling for their production. They are
insoluble in water (the sugar derivatives are somewhat soluble in hot
water), acetic acid, alcohol and ether, but dissolve in a hot mixture of
alcohol and ethylic acetate. From their solutions they separate as
white powders ; they do not reduce Fehling's solution. Ch. B.
Saccharin. By E. Peligot (Gompt. rend., 90, 1141 — 1143). —
Saccharin (this vol., 232), whether obtained from glucose prepared
from starch or from l^evulose, is dextrorotatory. Its rotatory power,
as determined by Laurent's polarimeter, is 93"5° ; that of ordinary
sugar, under the same conditions, being 67"" 18'. It is characterised
by its relative stability, and may be volatilised almost without decom-
position, does not ferment, and gives no reaction with Fehling's solu-
tion, even after prolonged boiling with dilute sulphuric acid. With
potassium and calcium hydrates, it forms compounds analogous to the
saccharates, and is converted by concentrated sulphuric acid into a
substance analogous to sulphosaccharic acid. When acted on by
potassium permanganate, it is slowly converted into water and potas-
sium carbonate, part of the manganese being precipitated as hydrated
dioxide. One gram of saccharin requires 4"6 grams of crystallised
permanganate for complete oxidation. Niti'ic acid is without action
unless highly concentrated, and it may therefore be purified by treat-
ment with this acid properly diluted. Saccharin is more readily ob-
tained from calcium Isevulosate than from inverted sugar or starch
glucose. It will probably be found in many commercial saccharine
products, and its presence will serve to explain the anomalous results
sometimes obtained with the saccharimeter. C. H. B.
Vapour-density of the Viscous Polymeride of Isobutalde-
hyde. By F. Urech (Ber., 13, 590— 594).— The vapour-density of
the viscous modification of isobutaldehyde (obtained by the action of
potassium carbonate on ordinary isobutaldehyde), as determined by
Naumann's method (viz., by distillation with aqueous vapour), is 211,
the calculated for (C4H8O) 3 = 216, whilst by Hofmann's method the
number 88'88 was obtained, CiHgO = 72. This shows that the mole-
cule (C4HbO);j undergoes dissociation on conversion into the gaseous
state, even under diminished pressure. T. C.
Derivatives of Isobutaldehyde. By A. Lipp (Ber., 13, 905 —
908). — When ammonia gas is passed into an ethereal solution of
isobutaldehyde, a compound having the composition C2tjH620N6 is pro-
ORGANIC CHEMISTRY. G'21
duced, thus: rCJisO + 6XH3 = (C4Hs);ON6H6 + 6H,0. This sub-
stance, which can also be prepared by pouring the aldehyde into an
excess of strong ammonia, forms glistening crystals belonging to the
hexagonal system. It melts at 3L° and evolves ammonia at 90° ; at
a higher temperature it yields a colourless liquid, having the com-
position CfeHisX.
By the action of a 30 per cent, solution of hydrocyanic acid on the am-
monia compound, amidoisovaleronitril and hydroxyisovaleronitril are
produced: (CiH8),OX6H6+7HCN'=6C4H8(NHo).CN + C4Hs(OH).CiN'.
Imidoisovaleronitril is formed at the same time by the decomposition
of the amidonitril. The crude product of the reaction is treated with
a 5 per cent, solution of hydrochloric acid and extracted with ether,
w^hich removes the imidovaleronitril and the hydroxynitril. After
the addition of ammonia to the residue, the amidoisovaleronitril can be
extracted with ether.
The ethereal solution is dried over calcium chloride and saturatedwith
dry hydrochloric acid gas, when amidoisovaleronitril hydrochloride is
deposited. The salt is very soluble in water and in absolute alcohol.
The free base is a yellow alkaline liquid, which splits up at the ordi-
nary temperature into ammonia and imidoisovaleronitril. The latter
compound can be separated from hydroxyisovaleronitril by the inso-
lubility of its hydrochloride in absolute ether. The hydrochloride is
decomposed by water.
By the action of ammonia on this salt, two isomeric imidonitrils
are formed, viz., a crystalline solid and an oily liquid.
Hydroxyisovaleronitril can be prepared by the direct union of
isobutaldehyde with dry hydrocyanic acid. It is a colourless oily
liquid, soluble in alcohol and ether. It is decomposed by heat into
hydrocyanic acid and the aldehyde. W. C. W.
Glyoxylic Acid. By C. Bottixger (Amuden, 198. 203).— After
giving a short historical sketch of the work done on the subject by
Debus, Church, Perkin, Duppa, and others, the author proceeds to
describe his own experiments. The glyoxylic acid used was prepared
by Debus's method.
A white pulverulent basic calcium salt was obtained by adding lime
water to a cold saturated solution of calcium glyoxylate, and this basic
salt is looked upon as the intermediate substance, from which calcium
glycolate and oxalate are formed on boding, as observed by Debus.
The normal calcium salt crystallised from cold dilute solutions was
found to contain 4H2O ; that crystallised from hot concentrated solu-
tions, 3H.0.
On treating syrupy glyoxylic acid with hydrocyanic acid and a
small quantity of hydrochloric acid, glycoUic, formic, and carbonic
acids were formed, together with ammonium chloride. The formation
of a double salt of calcium glycollate and oxalate was observed. No
oxalic acid was produced.
Sulphuretted hydrogen is readily absorbed by glyoxylic acid. On
exposure to the air for some days, a readily soluble crystalline sub-
stance was formed, to which the author assigns the formula C4H4SO5
as probable, although the analytical numbers do not agree with it.
G22 ABSTRACTS OF CHEMICAL PAPERS.
From the uncrjstal Usable residue, the calcium salts of two acids con-
tainins: sulphur were obtained, one of them being perhaps that of
thiodiglycollic acid, CiHiSOiCa, the other yielding an uncrystallisable
calcium salt. By the action of sulphuretted hydrogen in presence of
silver oxide, there were formed sulphoglycollic acid, sulphodiaflycollic
acid, and a sulphuretted oil of the formula ^(CoHsSsO). Oxalic acid
is formed at the same time in relatively large quantity.
By the action of alcoholic ammonia on an alcoholic solution of
glyoxylic acid, a white pulverulent precipitate, ammonium amido-
glyoxylate, was thrown down, the temperature being kept low during
the reaction. On boiling the aqueous solution, ammonia and carbonic
anhydride escape, and when the dark-coloured solution is evaporated,
a syrupy liquid is left, probably a condensation-product containing five
carbon atoms in the molecule. The residual alcohol solution from the
ammonium amidoglyoxylate, when left exposed to the air, deposited a
dark powder, which proved to be a fine red colouring-matter; its
analysis did not lead to decisive results.
Aniline acfs very energetically on glyoxylic acid, giving a preci-
pitate at first yellow, afterwards becoming deep yellowish-red. The
residue exhausted with ether alcohol is insoluble in water, slightly
soluble in alcohol, the solution dyeing silk of a pure yellow colour. It
is a mixture. By treatment with barium hydrate, a barium salt was
obtained, aniline being separated. It is in all probability barium
aniloglyoxylate. By boiling the original crude substance with water,
a residue was left, consisting of the anhydride of the acid. Boiled
"with barium hydrate, it yielded the impure barium salt.
The crude substance formed by the action of aniline on glyoxylic
acid, when distilled from a small retort, gave a crystalline sublimate of
carbanilide, together with aniline, carbonic oxide, carbonic anhydride,
water, and coloured vapours.
The author, in conclusion, sums up his results as follows: —
(1.) The transformation of glyoxylic acid into glycollic and oxalic
acids depends on the decomposition of a salt of definite composition.
(2.) With hydrocyanic acid and sulphuretted hydrogen, it behaves
similarly to its homologue, pyruvic acid.
(3.) Ammonia converts glyoxylic acid into amidoglyoxylic acid;
aniline into aniloglyoxylic acid.
(4.) Glyoxylic acid behaves likes an aldehyde.
(5.) Glyoxylic acid is sharply distinguished from pyruvic acid by
its slighter tendency to condensation, which is explained by the
absence of a hydrocarbon radicle (methyl), W. R. H.
New Synthesis of Carbon Acids. By A. Gruther, in conjunc-
tion with O. Frolich and A. Looss (AiiwiIph, 202, 288—331).—
Berthelot has shown {Gom.pt. rend., 41, 955) that formic acid can be
synthesised by the action of carbonic oxide on sodium hydrate,
and later {Ann. Chim. Phys. [3], 61, 463) that propionic acid can be
obtained, although in very small -quantity, by the action of carbonic
oxide on sodium ethylate in alcoholic solution at temperatures below
100°, a result confirmed by Hagemann (Ber., 4, 877 ; this Journal,
1872, 143). The author has reinvestigated the subject, employing
ORGANIC CHEMISTRY. 623
dry metallic alcoholates, and higher temperatures. Sodium ethjl-
ate heated to 190° in a current of carbonic oxide yielded (in
addition to the formate invariably obtained in all these reactions)
sodium propionate, and also a considerable quantity of acetate ; the
latter was probably formed by a secondary reaction, CoHsXaO +
2XaOH = CoHaOzNa + Na-^O + 4H, induced by the high temperature:
an experiment at 160' confirmed, this view, the proportion of acetate
being much reduced.
Sodium methylate heated at 100° in carbonic oxide yielded acetate
in small quantity. Sodium isoamylate heated with carbonic oxide at
210° gave no caproate, but the salts of formic and isovaleric acids, and
of a new acid, CjoHisOj. Further experiments made to elucidate the
formation of this acid showed that the necessary conditions were the
action of carbonic oxide on a mixt^ii'e of sodium isoamvlate and hydrate,
2C3HnOXa + 2XaOH + CO = C.oHiTNaOo + CHXab, + Xa^OV 6H;
or better still, on a mixture of sodium isoamylate and isovalerate,
CiHgO.Na -h CsHnOXa + CO = CioH.^XaO, + HCO.Xa + 2H.
The pure acid, CioHisO-,, is an oil of peculiar odour, of sp. gr. 0"961 at
12° : it boils at 268 — 270', and is probably amenyl valeric acid,
CiHs(CoH9).C00H. There are formed at the same time diamenyl-
valeric acid, C4H;(C5H9)2.COOH (b. p. 300—306^); a ketone (b. p.
208 — 209°) of quince-like odour, and sp. gr. 0-845 at 12°, probably
amylvalerone, CuHosO, and another liquid boiling between 279° and
285°, possibly butenylbutylvalerone, C17H32O.
A mixture of sodium ethylate and hydrate heated in carbonic oxide
at 205° yielded salts of the following acids, normal butyric, diethyl-
acetic, triethenylbutyric (CoHuO-, = C3H4(C2H3)3.COOH, distilling
between 240 — 260°) and mesitylenic, and also the following ketones :
propyl diethylketone, C3H7.CO.CHEt,, boiling between 180—190°,
and CisHyOa,' boiling between 280° and 300°, probably
CHEt.,.CO.C3H4(C2H3)3.
Sodium methylate and acetate heated in carbonic oxide at 200°
gave salts of propionic acid, and of an acid which is probably tetra-
or penta-methylated propionic acid. Sodium ethylate and isovalei'ate
under like conditions gave a salt of methylpropvl propionic acid,
CPrMeH.CHo.COOH (b. p. 220°), differing from "Crimshaw's iso-
oenanthylic acid (b. p. 210 — 213° Annalen, 166, 168 ; this Journal,
1873, 314), whilst its formation from an isovalerate precludes the
possibility of its being normal oenanthylic acid (b. p. 223 — 224°).
The other acids obtained were ethvl-diethenvlisovaleric acid,
C5H;Et(C2H3),Oo, distilling between 270° and 280°, C.sHaoO,, probably
ethyltriethenylisovaleric acid, distilling between 280° and 300°, and a
thick oily liquid distilling above 360°, of the formula C23H30O2 (?),
probably ethyloctaethenylisovaleric acid, also a small quantity of a
solid acid, apparently mesitylenic. The ketones obtained in this
reaction were,ethylisobutylketone, Et.CO.CH2.CHMe2 (b.p. 132 — 134");
CsHa^^O, boiling at 163—168° ; C^aHj^O or C^sHi^O, distilling between
200° and 210"; C>;H430 or C,tH«0, distilling between 240° and
20u".
A mixture of sodium acetate and ethylate heated with zinc-dust to
624 ABSTRACTS OF CHEMICAL PAPERS.
240 — 250°, gave the same acids as were obtained on heating acetate
and ethylate in carbonic oxide.
Sodium ethylate and hydrate heated at 160° in carbonic oxide gave
scarcely any ketones, a small quantity of butyrate, and much formate.
Sodium hydrate heated in carbonic oxide at 160° gave a very large
vield of formate,* and a small quantity of the salt of an acid richer in
carbon; heated in a mixture of carbonic oxide and ethylene, it gave in
addition to formate, a small quantity of a salt, whose sodium contents
vpas intermediate between that of acetate and propionate.
Sodium pheuylate did not react with carbonic oxide, nor sodium
isovalerate either with carbonic oxide or zinc- dust. A. J. G.
Compound of Titanium Tetrachloride with Acetic Chloride.
By A. Bertrand {Btdl. Soc. Ghim. [2], 33, 403— 405).— On mixing
titanium chloride with a.cetic chloride a precipitate is formed of
yellow octohedral crystals, soluble in excess of acetic chloride. The
crystals are rapidly decomposed by moist aii-, giving oft" thick fumes
of hydrochloric acid ; they are permanent in dry air and in dry
hydrochloric acid gas ; they melt at 25 — 30°, and recrystallise on
cooling. Distillation at atmospheric pressure resolves them into
titanium tetrachloride and acetic chloride. Carbon bisulphide dissolves
them. The results of analysis agree with the formula CaHaOCl.TiCli.
J. M. H. M.
New Mode of Forming Dimethacrylic Acid. By E. Duvillier
{Ann. Chim. Phys. [5], 19, 428 — 432). — When ethyl bromisovalerate
is treated with a solution of sodium ethylate in absolute alcohol, the
following reactions occur simultaneously : —
I. CMe^H.CHBr.COEt + EtONa^ NaBr+CMe2H.CH(0Et).C00Et.
Etlijlic etboxjisovalerate.
II. CMeoH.CHBr.COOEt -h EtONa = NaBr + EtOH +
CMeaiCH.COOEt.
Ethylic dimethacrylate.
After boiling for several hours with inverted condenser, the alco-
hol is distilled off, water added to the residue, the supernatant
liquid separated, dried, and distilled. The distillate passing over
between 155° and 190° is saponified with alcoholic potash ; the alpohol
removed by distillation ; excess of potash exactly neutralised by sul-
phuric acid ; the potash salts converted into zinc salts by means of zinc
sulphate ; and the solution evaporated to dryness on the water-bath.
The residue is treated with alcohol ; sulphuric acid added to the alco-
holic solution to remove the zinc ; the free acids dissolved by shaking
with ether ; and the ethereal solution evaporated ; — when dimethacrylic
acid separates in colourless transparent crystals, but slightly soluble in
water, very soluble in alcohol and ether. This dimethacrylic acid is
identical with the acid obtained by Neubauer by oxidising the valeric
acid from fermentation amyl alcohol {Annalen, 106, 6.3), and the acid
obtained by Miller by oxidising isobutylformic acid from isobutyl
cyanide {Ber., 11, 1526, 2216). Its formation by the reaction de-
* Comp. Merz and Tibiri(;a {Ber., 13, 23 ; this Journal, Abstr., 1880, 374).
ORGANIC CHEMISTRY. 625
scribed in tliis paper is analogous to tlie formation of crotonic acid by
the action of alcoholic potash on ethyl bromobntyrate (Hell and
Lauber). Uimethacrj-lic acid can now be prepared by three com-
pletely different synthetical methods, including that of Semliatzin and
Saytzeff (Annalen, 185, 157). J. M. H. M.
Tetrolic and Oxytetrolic Acids and their Homologues. By
E. De.makcat (Bull. Soc. ChiiH. [2], 33, -510 — 525). — Ethylic methyl-
acetoacetate, when acted on by bromine, gives the following reactions,
according to the amount of bromine employed : —
Me.CO.CHMe.COOEt + Br, = HBr + Me.CO.CBrMe.COOEt
CHa.CO.CHMe.COOEt + 2Br2 = 2HBr -h CHoBi'-CO.CBrMe.COOEt.
If the crude products are allowed to stand for some time, the hydro-
bromic acid present gives i-ise to the reactions —
Me.CO.CBrMe.COOEt + HBr = Me.CO.CHBrMe + CO, + EtBr
and CHoBr.CO.CBrMe.COOEt + HBr = CH^Br.CO.CHBrMe +
CO, + EtBr.
But if the products be treated at the proper time with alcoholic potash,
the following reaction takes place : —
Me.CO.CHBrMe + OH, = C^H^Oo + HBr + H^.
Other hydrogenised products corresponding with the hydra ted com-
pound, 3C4H1O2 + H3O, are formed simultaneously according to the
following reactions : —
Me.CO.CBrMe.COOEt + H5 + OH^ = EtOH + HBr +
Me.CH(OH).CMe(OH).COOH.
Dimethylglyceric acid.
Me.CO.CBrMe.COOEt + Ho = HBr + Me.CO.CHMe.COOEt.
But the methylacetoacetic acid thus regenerated is decomposed by
alcoholic potash, giving- rise to known products. From these equa-
tions it is seen that a tliird only of the brominated ether has to be
decomposed by hydrobromic acid. The dibrominated product under
the action of alcoholic potash gives analogous reactions —
CHoBr.CO.CHBrMe + 20Ho = C4H4O, + 2HBr + 2Ho.
Other acids are produced, some similar to those formed in the pre-
vious reactions, but they have not 3'et been sufficiently examined.
In the case of the homologous acetoacetic ethers, the reactions are
parallel at all points. The author has studied the ethyl salts of
methyl-, ethyl-, propyl-, isopropyl-, isobutyl-, and methylethyl-aceto-
acetic acid.
Tetrolic acid is obtained as follows : —
Ethylic methylacetoacetate with a little water is treated with bro-
mine added in small portions, the flask being kept cool (about 15°),
until a nearly equal molecular quantity of bromine has been added.
After allowing the liquid to stand for ten to eleven hours at 20°, two
026 ABSTRACTS OF CHEMICAL PAPERS.
to three times its volume of watei' is added, when a heavy oil separates
out. To this oil alcoholic potash is gradually added, the flask being
kept cool. Afterwards the alcohol is removed by a current of steam ;
acetone and other products going over at the same time. The acids
retained by the potash are set free by a slight excess of hydrochloric
acid. On cooling, much of the tetrolic acid separates out ; the rest is
removed by agitation with ether. In the case of the higher homo-
logups of tetrolic acid, after the addition of hydrochloric acid, the
liquid is distilled with 5 — 6 volumes of water until nothing but water
passes over. The acids are then extracted by means of ether. Oxy-
tetrolic acid and its homologues are prepared like the preceding.
Tetrolic acid is a white solid, crystallising in triclinic prisms (m. p.
189°), boiling with decomposition at about 2G0 — 280°. Heated in an
inert gas, it sublimes. Very soluble in boiling water, in alcohol, and
in ether. At 13"5", one of acid dissolves in 65" 7 parts of water.
Scarcely soluble in chloroform, cold or hot, but soluble in boiling chlo-
roform in presence of a little alcohol. Odour faint, like that of pro-
pionic acid. Taste and reactions acid ; and its salts crystallise readily.
Three types of salts are formed, one represented by the copper salt,
CUO.C4H4O2, a second by the barium salt, Ba0.2C4H403, and the third
and most common one, 2M2O.5C4HJO2. Anhydrous salts of ammonium,
silver, copper, potassium, and sodium, and hydrated salts of barium,
calcium, magnesium, and zinc are described. Ferric chloride gives
with the ammonium salt a violet to bright rose-coloured precipitate.
The acid and all its homologues are coloured an intense violet-red by
ferric chloride. Heated at 150° with water for some time, there is no
change. With dilute hydrochloric acid at the same temperature, a
black resin is produced with the odour of crotonic aldehyde. Heated
to the same temperature, or even lower, with potash and a little water
it yields formic and propionic acids, C4H4O2 + 2H2O = CH2O2 +
CaH602. Bi'omine yields an oily body which easily decomposes. Nitric
acid oxidises the acid completely, yielding small crops of crystallised
nitro-compounds, which may or may not be soluble in ether with a
beautiful blue colour. Potassium permanganate gives acetic acid and
carbonic anhydride. Sodium-amalgam, and zinc with acid appear to
have no action. Phosphorus pentachloride attacks the acid slowly in
the cold as follows : —
3C4H4O0 + K2O + 4PCI5 = 2HC1 + 4PCI3O + 3C4H4OCI0.
On washing well with water, the last compound is obtained as a
colourless oil boiling at 172° without change, unless boiled for a long
time ; its sp. gr. at 10'6° is 1'471. It is not sensibly attacked by alcohol
at 150°, or by water, potash, or ammonia at 100°. With chlorine, this
compound forms C4H4CI4O, a beautifully crystallised body, m. p. 49°,
which gradually decomposes ; with bromine this gives C4H4Cl2Br20,
which fuses at 66" and gives off bromine and hydrobromic acid.
J. T.
Hydroxyacrylic Acid. By P. Melikoff {Ber., 13, 271—274).—
When alcoholic potash is gradually added to a solution of monochloro-
lactic acid (prepared by direct addition of hypochlorous acid to acrylic
acid, Ber., 12, 2227), the mixture being kept cool, potassium chloride
ORGANIC CHEMISTRY. 627
is formed together -with the potnssium salt of hydroxyacrylic acid,
CsHaKOa.l^HvO. This potassium salt separates after the chloride in
globular or reniform groups of needles, which may be crystallised from
hot alcohol, but decompose at 80°. By double decomposition it yields
a silver salt, CsHaAgOs, which decomposes at 100°. The free acid may
be obtained by adding sulphuric acid to a solution of the potash salt
and shaking with ether. It is a volatile transparent and rather mobile
liquid, the vapour of which is highly irritating. Neither the acid nor
its salts gives a red colour with ferrous sulphate, as pyroracemic acid
does. When a solution of the calcium salt (obtained bv neutralising
the free acid with calcium carbonate and precipitating with alcohol) is
heated on the water-bath, water is assimilated and calcium glycerate,
CjHoCaOi.HjO, is formed. Glyceric acid is likewise produced by-
boiling an aqueous solution of the silver salt of liquid monochlorolactic
acid.
A mixture of hydroxyacrylic acid with fuming hydrochloric acid
becomes very hot, and on agitation with ether yields .solid chlorolactic
acid (m. p. 78 — 79°), crystallising in silky feathery needles. This is
identical with the acid prepared by Richter («/. pr. Chem., 20, 193),
by oxidising epichlorhydrin with nitric acid. It is not attacked by
fuming hydrochloric acid. On the other hand, monochlorolactic acid
from acrylic acid is liquid, and when heated at 100° with highly con-
centrated hydrochloric acid, yields dichloropropionic acid (m. p. 50°).
Ch. B.
Carbonyl Bromide. By A. Esimeelixg {Ber., 13, 873—875). —
Impure carbonyl bromide can be obtained in small quantities by gently
warming a mixture of sulphuric acid (50 parts), potassium chromate
(20 — 25 parts), and bromoform (5 to 10 parts). The operation is con-
ducted in a flask provided with an upright condenser to which a
U-tube, surrounded by a freezing mixture, is attached. After the free
bromine has been removed from the crude product by slow distillation
over metallic antimony, the carbonyl bromide is obtained as a colour-
less heavy liquid boiling between 12'' and 30°. W. C. W.
Syntheses by means of Ethyl Malonate. By M. Coxrad and
C. A. BisCHOFF {Ber., 13, 595 — 6Ul). — A continuation of the authors'
previous work on this subject (this Journal, 36, 7^)7 and 918), and for
the general methods of preparation of many of the following com-
pounds, the earlier communications must be consulted.
Ethylic isopropylmaloyiate, GHMe2.0H(COOEt)2, is a colourless
liquid (b. p. = 213°) ; its sp. gr. is 0-997 at 20° compared with water
at 1,5°.
Isopropylmalonic acid, CH]\Ie2.CH(COOH)2, crystallises in prisms
(m. p. = 8.3°) which decompose at 175 — 180° into carbonic anhydride
and isopropylacetic acid. CoHioOo (b. p. = 174°), identical with the
valerianic acid obtained by Erlenmeyer and Hell {Aunalen, 160, 264)
from isobutyl cyanide.
Ethylic ethylmethylmalonate, CMeEt(C00Et)2 (b. p. = 207°) ; sp.
gr. = 0-994 at 15°.
Ethijhnethyhnalonic a^id, CMeEt(C00H;2, crystallises in prisms
628 ABSTRACTS OF CHEMICAL PAPERS.
(m. p. = 118°) which decompose on heating into carbonic anhydride
Hud ethylmethylacetic acid, CsHmO,, which is an optically inactive
liquid (b. p. = 173°), and is identical with the ethylmethylacetic acid
obtained by Saur (Annalen, 188, 257) from ethyl acetoacetate, and
with that obtained by Schmidt and Berendes (Annalen, 191, 117) by
heating tiglic acid with hydriodic acid, and with that prepared by
Pagenstecher {Annalen, 195, 121) from bromhydrotiglic acid by the
action of sodium-amalgam, and also with the product obtained by
Bocking (Inauguraldiss : Wurzburg, 1879) by the action of hydriodic
acid on ethomethoxalic acid. A determination of the solubility of the
silver salt of this acid shows that the valerianic acid obtained from
commercial amylenes is not ethylmethylacetic acid, as stated by
Eltekolf {Ber., 10. 706). The authors confirm Erlenmeyer's supposi-
tion that the optically active valerianic acid from active amyl alcohol
is either a molecular compound or a mixture of isopropyl- and ethyl-
methyl acetic acid.
Ethylic isobntijlmalonate, C4H9.CH(COOEt)3 (b. p. = 225°, sp. gr.
= 0-983 at 15°).
Eihi/lic dioctyimalmiate, C{CJli-!)2(COO'Et)2, from octyl iodide (b. p.
221")," is a colourless oil (b. p. = 338°) ; its sp. gr. is 0-896 at 18°
compared with water at 15°.
Dioctylmalonic acid, C19H36O4, forms colourless crystals (m. p. 75°)
which are insoluble in water.
Dwctylacetic acid, C18H3BO2, is a white crystalline mass (m.p. = 39°,
b. p. = 300°), which is identical with an isostearic acid obtained by
Gutzeit from ethyldioctylacetoacetic acid.
Efhylic allylmalonate, C3H5.CH(COOEt)2, b. p. = 220°; sp.gr. =
1-018 at 16° (water at 15° = 1).
Alhjlmalonic acid, CeHgOi (m. p. = 103'^), belongs to the fumaric
series, and is isomeric with hydromuconic acid. Allylacetic acid,
CsHgOo (b. p. 184°), is identical with the acid obtained by Zeidler
{Annalen, 187, 30) from ethylacetoacetic acid.
mhi/lic diallylmalonate, C(C3H5)2(COOEt)2, b. p. = 240° ; sp. gr.
= 0-996 at 14° (water at 15° = 1).
Diallylmalonic acid, C9H12O4, crystallises in pinsms (m. p. 133°).
Dialhjlacelic acid, C^JS^yiOi (b. p. = 219°), from the preceding, is
identical with that described by Wolff (Ber., 10, 1956) and Reboul
{Gompt. rend., 84, 1233).
Ethylic henzylmethyhnalonate, CH2Ph.CMe(COOEt)4 (b. p. = 300°) ;
sp. gr. = 1-064 at 19° (water at 15° = 1). This acid can also be
obtained by the action of methyl iodide on ethylic benzylsodium-
malonate, or by the action of benzoic chloride on ethylic methyl-
sodiummalonate.
Benzylmethylmalonic acid, C11H10O4, consists of crystals, m. p. =
135°.
Benzylniethylacetic acid, C10H10O3 (m. p. = 37°, b. p. = 272°), is
identical with the substituted acetic acid obtained from ethylic benzyl-
methylacetoacetate (Ber., 11, 1056), also with the phenylbutyric acid
obtained by the addition of hydrogen to the phenylcrotonic acid, pre-
pared according to Perkin (this Journal, 31, 391) from benzaldehyde
and propionic anhydride, and also with that produced by the addition of
ORGANIC CHEMISTRY. ()29
hydrogen to the acid (Annalen, 193, 310) obtained by the action of
sodium on benzyl propionate.
Ethyl nitmsomalonate, 011(^0) (C00Et)2, is obtained by the action
of nitrous acid on an alcoliolic solution of eth^-l sodium malonate. It
is a vellow oil which is decomposed on distillation ; sp. gr. = 1"149
at lol
Nitrosomalonic acid, C3H3NO5, is obtained from the silver salt, and is
identical with the acid described by Baeyer {Annalen, 131, 292). A
crystalline potassium salt, C3HNO5K2 + ^HoO, was prepared. On dis-
tillation, this acid splits up into carbonic anhydride, water, and hydro-
cyanic acid.
Etlujl nitrosobenzijlmalonafe, C7H7.C(NO)(COOEt)2, is obtained by
the action of sodium ethylate and benzyl chloride on ethyl nitroso-
malonate. On saponification with, potash, it gives a crystalline potas-
sium salt which, on dry distillation, splits up into potassium cyanide
and carbonate and benzyl alcohol. The free acid underofoes a similar
decomposition on boiling with water.
Ethyl monochlormalonate, CHCl(C00Et)2, obtained by the action of
chlorine on ethyl malonate, is a colourless liquid (b. p. 221° ; sp. gr.
= 1"185 at 20° ; water at 15° = 1). On saponification with potash it
gives ovlj potassium tartronate, CH(0H)(C00K)2.
Tartronic acid, CH(0H)(C00H)2, obtained by decomposing the
calcium salt with oxalic acid ; melts at 182° with evolution of carbonic
anhydride, leaving a glycolide, the aqueous solution of which on boiling
with calcium carbonate, gave calcium glycollate.
The ethyl mono-substituted malonates, on treatment with, chlorine^
give monochlorinated compounds.
Ethyl monochlorisobutyhnalonate, C4H9.CCl(COOEt)2 (b. p. 245°,
sp. gr. = 1"094 at 15°). On saponification with potash, it gives
potassium isobutylhydroxymalonate, C4H9.C(OH)(COOK)2, the free acid
of which decomposes on beating at 150° into carbonic anhydride and
hydroxyisohvAylo.cetic acid, C4H9.CH(OH).COOH.
Ethyl acetyltetracarhonate, (COOEt)2CH.CH(COOEt)2, is obtained
by the double decomposition of ethyl chloromalonate and ethyl sodium
malonate. It crystallises in long brilliant white needles (m, p. 75" j
b. p. 305°, with slight decomposition). T. C.
Inversion of the Optical Rotation of Ordinary Malic Acid.
By G. H. Schneider {Her., 13, 620 — G23). — Ordinary malic acid has
generally been considered as laevorotatory; if, however, the degree of
concentration of a dilute aqueous solution of the acid, which is Isevo-
rotatory, be gradually increased, the specific rotation gradually
diminishes until the percentage of acid is 34' 24, when the optical
activity entirely disappears ; on further concentration the rotation
becomes positive. The following interpolation formula [aju = 5'891 —
0"089592 {'1 =^ P^^ cent, of water) shows that for pure anhydrous malic
acid [a]D = -}- 5-89.
Sodium malate behaves exactly like malic acid, the interpolation,
formula in this case being [aj^ = 15'202- 0-33222 + 0-00081 845^
from which it follows that for the anhydrous salt [ajp = -\- 15*2, and
that a solution containing 47'43 per cent, of the salt is inactive.. A.
VOL. XXXVIII. 2 ^
fi30 ABSTRACTS OF CHEMICAL PAPERS.
similar observation has been made in the case of tartaric acid (com-
pare Boit, Memoires de VAcad., 15, 208 — 211; Ann. Ghim. Phys. [3],
29, 351, 366 ; Arndtsen, ibid. [3], 54, 415). T. C.
Behaviour of Monochlorotetracrylic Acid on Fusion. By A.
Geuther (Ber., 13, 242).— Kahlbaum (Ber., 12, 2337) is mistaken in
attributing to the author the statement that this acid is decomposed
on fusion. It is partly decomposed by distillation. Ch. B.
Nitrosothioglycollic Acid. By R. Malt and R. Axdreasch
(Ber., 13, 60l—m7).--Nitrosothiog]yconic acid, COOH.CH(NO).SH,
is obtained, together with cyanamide and dicyandiamide, by boiling 10
grams nitrosothiohydantoin (ibid., 12, 967) with 60 grams of crystal-
lised barium hydrate and 400 c.c. water, the reaction being in all
respects analogous to that which occurs in the case of thiohydantoin
(this Journal, 36, 712). The free acid was obtained as a crystalline
mass, which is very easily soluble in ether, and is decomposed by
CH(NO)S
alcohol or water. The barium salt, | /Ba + H2O, is a crys-
coo ^
talline powder or nodular mass which is insoluble in alcohol, sparingly
soluble in cold water, but more easily in hot ; it dissolves at once in
dilute hydrochloric acid. It is gradually decomposed on heating above
100°. The other salts are mostly obtained by precipitation of the hot
aqueous solution of the barium salt. The lead salt is a yellowish-white
precipitate, which is insoluble in acetic acid and boiling water, and is
not blackened by alkalis, but dissolves in hot soda to a clear liquid.
The silver salt is a yellow precipitate, which rapidly blackens on ex-
posure to light, and when freshly prepared is insoluble in ammonia
and nitric acid. A dark violet colour is obtained when ferric chloride
is added to a dilute solution of the barium salt, and this on addition of
a drop of hydrochloric acid changes to a pure blue. On long standing,
or on boiling, the colour disappears, because in both cases the nitroso-
thioglycollic acid is destroyed. Strong hydrochloric or nitric acid or
stannous chloride produces this effect at once. This reaction is ex-
ceedingly sensitive and serves as a very ready method for detecting
the acid. The free acid gives the blue colour at once on addition of
ferric chloride. Nitrosothioglycollic acid, and acidified solutions of its
salts are easily decomposed on heating into water and carbonic and
sulphocyanic acids or their salts. The free acid is thus decomposed
even at the ordinary temperature. T. C.
Action of Zinc on Succinimide. By C. A. Bell (Ber., 13,
877 — 878). — Pyrrol is formed by the distillation of a mixture of succi-
nimide and zinc-dust, and also by passing a current of hydrogen and
succinimide vapour over platinum black at a temperature above the
boiling point of the imide. "When the vapour of ethyl succinimide is
passed over zinc-dust at 350°, ethylpyrrol, CiHjNEt, is produced.
w. c. w.
Contribution to a Knowledge of the Ureides. By J. M. A.
Keamps (Ber., 13, 788— 791).— E. Mulder having succeeded in obtain-
ORGANIC CHEMISTRY. 631
mg dibromothioliydaritoin (Ber., 8, 1263), the autlioi' was induced to
repeat the researches of Claus and NeuhofFer (Ber., 10, 825) on the
action of chlorine and bromine on thiohydantoin. A sti'eam of chlo-
rine was slowly passed into a solution of thiohjdantom in hydrochloric
acid, surrounded by a freezing mixture.
At the end of half an hour white flocculent crystals appeared, but
on continuing the stream of gas they disappeared again. By stopping
the gas at the proper moment, however, the crystals could be collected.
They were found to consist of imperfectly shaped needles, insoluble in
water, alcohol, and ether. They dissolve in alkalis with decomposi-
tion, and the solutions have a green fluorescence. They are also
decomposed on heating to 110 — 120''. Their composition is repre-
NH.CH.OH
sented by the formula, CS\ | + HoO.
^K'H.CO
When excess of bromine was added to a solution of thiohydantoin
under the same conditions as above, colourless crystals of dibromothio-
hydantoin were obtained. They are soluble in alcohol and ether, and
are decomposed by hot water. Oxalic acid was found in the mother-
liquor.
The author's method of obtaining thiohydantoic acid diifers some-
what from Mah^'s (Ber., 10, 1849), inasmuch as he allows the aqueous
solution of monochloracetic acid and thiocarbamide to stand in the cold
without neutralising the hydrochloric acid.
Action of MonocTiloracetijl-carhamide on Thiocarhamide. — When these
two bodies were dissolved in alcohol in equivalent quantities at 60 —
70", large quantities of a nearly white flocculent body were obtained
of the composition NH^.CS.NH.CHo.CO.NH.CO.NH, + HCl. This
body, is insoluble in alcohol and ether, and yields silky needles of
thiohydantoin on addition of ammonia to its aqueous solution.
Monochloracetyldimethylcarbamide and thiocarbamide when dis-
solved in alcohol at 70 — 80°, yield crystals of thiohydantoin hydro-
chloride, but in the cold, nodules made up of needles are formed, which
consist of XHo.CS.NH.CHo.CO.NMe.CO.NHMe + HCl.
These crystals are decomposed by water into thiohydantoin hydro-
chloride and dimethylcarbamide. G. T. A.
Orthocjrmene. By A. Claus and H. Hansex (Ber., 13, 897 —
899). — Orthocymene is formed by the action of sodium on a solution of
orthobromotoluene and propyl bromide in absolute ether. The mix-
ture is gently warmed, but when the reaction has commenced, it is
cooled down to 10° in order to avoid the formation of ditolyl. At a
temperature below 8", considerable quantities of dipropyl are formed.
Orthocymene is a colourless liquid (b. p. 181°). On treatment with
sulphuric acid it yields two sulphonic acids ; the formation of the
a-acid is favoured by a low, and that of the (B- by a higher temperature.
Both acids are very soluble in water, and are uncrystallisable. The
a-acid fonns a sparingly soluble barium salt, which crystallises in
glistening plates containing 1 mol. HnO. The copper salt crystallises
in dark-green needles containing 4HoO.
The potassium salt forms shining rhombic crystals.
2^2
.632 ABSTRACTS OF CHEMICAL PAPERS.
The /3-acid does not form crystalline salts. The /3-siilphomc chloride
is a syriipy liquid converted by ammonia into /3-orthocymenesulph-
amide, which is deposited from an ethereal solution in glistening plates,
and from an aqueous solution in brittle needle-shaped crystals.
w. c. w.
Metacymene. By A. Glaus and T. Stusser (Ber., 13, 899 —
901). — Metacymene prepared by the action of sodium at 0'' on an
ethereal solution of propyl bromide and metabromotoluene, is a colour-
less liquid which boils at 176° (sp. gr. 0"86.3 at 16°).
Two sulphonic acids are formed by treating metacymene with snl-
phuric acid.
The a-acid forms a sparingly soluble barium salt which crystallises
in small plates, containing 1 mol. HjO. The copper salt forms green
hexagonal plates containing 4 mols. H2O. The lead salt contains
.3 mols. HoO, and the calcium salt which crystallises in prisms 2 mols.
HoO. The potassium salt forms anhydrous needle-shaped crystals,
which dissolve freely in water.
Barium |3-cymenesulphonate crystallises in needles containing 1 mol.
H2O, which are freely soluble in hot water.
a-Metacymenesulphonic chloride prepared by heating the acid with
phosphorus pentachloride in sealed tubes at 140°, is deposited from an
ethereal solution in needle-shaped crystals (m. p. 175°). The corre-
sponding sulphamide does not crystallise. W. C. W.
Paracymene and Sulphuric Acid. By A. Glaus and G. Gratz
(Ber., 13, 901 — 902). — When paracymene is treated with sulphuric
acid at the ordinaiy temperature, two sulphonic acids are produced,
viz., the well-known a-paracymenesulphonic acid and a small quantity
of a second acid, which is distingtiished from the a-acid by the greater
solubility of its barium salt. W. G. W.
Oxidation of Dibromocymene. By A. Glaus and G. "Wimmel
(Ber., 13, 902 — 904). — On oxidation with a solution of chromic acid in
glacial acetic acid, dibromocymene yields a new acid, GioHioBr202, which
crystallises in glistening needles (m. p. 152°) soluble in alcohol and
ether. It forms crystalline salts, which dissolve freely in water. The
barium salt contains 3 mols. HoO. If a mixture of strong nitric acid
(1 part) and water (1-^ parts) is used instead of chromic acid in the
preparation of this substance, dibromoterephthalic acid and another acid
are also formed.
If the oxidation is continued until the dibromocymene is completely
destroyed, pui^e dibromoterephthalic acid, G8H4Br204, is obtained in
white plates (m. p. 320°) soluble in alcohol, ether, and glacial acetic
acid.
The salts of this acid are very soluble in water and do not crystallise
readily. W. G. W.
Compounds of Organic Bases with the Haloid Salts of Mer-
cury. By 0. Klein (Ber., 13, 834—835). — In addition to the bodies
previously described (Ber., 11, 743 and 1741 ; this Journal, Abst.,
1878, QQ7 : 1879, 231), the author has obtained compounds of aniline
ORGANIC CHEMISTRY. 633
and toluidine with mercuric bromide and iodide. HgBr, + 2XH2Ph
crystallises in white needles (m. p. 110'^) which are decomposed by
boiling water. Hgis + 2XHoPh (m. p. 60°) resembles the preceding
compound, but is decomposed by treatment with alcohol. Mercuric
bromide combines with 2 mols. paratoluidine, forming a substance
crystallising in plates (m. p. 120°) which are soluble in alcohol and
ether, but are decomposed by hot water. The corresponding orthoto-
luidine compound also crystallises in plates, which begin to decompose
at 60°, but melt at 103" if rapidly heated. The compounds of mercuric
iodide with para- and ortho-toluidine resemble the compound with
aniline. The former melts at 81°, the latter does not melt, but gives
off orthotoluidine at 40°. W. C. W.
Derivatives of Parabromaniline. By M. Dexnstedt (Ber., 13,
226 — 236). — The following compounds have been prepared and
examined : —
JBromophemjhirethane, CgHioNOoBr (m. p. 84 — 85^), is obtained by
the action of ethyl chlorocarbonate on bromaniHne dissolved in anhy-
drous ether. From dilute alcohol, it crystallises in white felted needles,
insoluble in water, easily soluble in alcohol and ether.
Bromophenylcyanate, CtH^NOBt, is obtained by distilling the fore-
going with phosphoric anhydride; m. p. 39° ; b. p. 226°. It is easily
soluble in ether.
Bromopheiiylmethylurethane, CyHsOoNBr, is prepared by evaporating
the methyl alcohol solution of the cyanate and crystallising from
alcohol. It forms white needles, readily soluble in alcohol and ether ;
m. p. 124".
Br&mophenyl dicyanate, CiiHoNoOoBro, a dimolecular compound of the
cyanate, analogous to Hofmann's phenyl dicyanate {Anyicden, Supp., 1,
57; and Ber., 4, 246), is obtained when the cyanate, melted on a
water-bath, is stirred with a glass rod moistened with triethylphos-
phine. After long boiling with absolute alcohol it dissolves, and on
cooling, white needles of etJujl dihromrrpheiiyl allophanate,
CO(XH.C6H,Br).N(C6H4Br).COOEt
(m. p. 153°), separate. The latter may be crystallised from anhydrous
ether.
Dibromophenylbiuref, NH(CO.NH.C6H4Br)2, is formed when the pul-
verised dicyanate is allowed to stand with alcoholic ammonia. It
begins to sublime (without melting) at 240°, and decomposes at 280°.
It is insoluble in water, sparingly soluble in alcohol and ether.
Bromophenylthiocarhimide, CSN.CeHiBr, has been prepared by Otto
{Ber., 2, 408) by distilling dibromophenylthiocarbamide with phos-
phoric anhydride. The amide is formed with extreme slowness when
bromaniline is boiled with an alcoholic solution of carbon bisulphide
in theoretical quantity. The process is much hastened by adding a
little moderately strong caustic soda solution (a few c.c. for 40 grams-
bromaniline). The amide separates partly after an hour's boiling, and
the reaction is completed in six or seven hours. The caustic soda
perhaps assists by inducing the following reactions : —
()34 ABSTRACTS OF CHEMICAL PAPERS.
CoH4Br.NH3 + CSo + NaOH = NaS.CS.NH.CeH.Br + HoO
NaS.CS.NKCeH.Br + CeH^Br.NH, = CS(NH.C6H,Br)o + NaHS,
NaSH + H2O = NaOH + H.S.
Monobromophe7iyUhiocarbamide, CTHvlS'oSBr, is formed by treating-
tlie thiocarbimide with aleobolic ammonia. It forms needles (m. p.
183°) insoluble in water, soluble in alcohol and ether.
Plienylhromo'phenylthiocarhamide, Ci3HnN2SBr, obtained by boiling
the thiocarbimide with alcoholic solution of aniline, forms colourless
needles (m. p. 158°), which are tolerably soluble in cold, very soluble
in hot alcohol or ether.
Hemithiohromophenyhir ethane, CgHiolS'OSBr, is formed by heating
the thiocarbimide with absolute alcohol at 120" for several hours.
Slender slightly yellow needles, insoluble in water, easily soluble in
alcohol and ether. M. p. 105°.
Thiohromophenyhorethane, C9HioS2NBr, is prepared by heating the
thiocarbamide with ethyl mercaptan at 140°. It is insoluble in water,
soluble in alcohol or ether. M. p. 89°.
Isocyanomonohromophenyl chloride, C;il4lSrBrCl2, analogous to Sell and
Zierold's isocyanophenyl chloride (Ber., 7, 1228), is obtained by acting
with chlorine on bromophenylthiocarbimide. It is a yellowish heavy
liquid (b. p. 255 — 256°). By the action of bromaniline, it yields the
hydrochloride of a base, CeHiBr.N '. C(NH.C6H4Br)2.HCl, isomeric with
tribromophenylguanidine. This salt is crystallisable from dilute
alcohol, is very soluble in alcohol and ether, and when treated with
ammonia yields the free base as an uncrystallisable gummy mass. The
jilatinochloride forms bright yellow plates.
Ethenyldihromrphenyldiamine, (C2H3)(C6H4Br)oHN2, is prepared by
acting with phosphoriis chloride on a mixture of bromaniline and
acetic acid, heating for some time at 160°, extracting with water,
and precipitating with ammonia. It is a white thick liquid. Only
the hydi'ochloride and platinochloride were analysed.
FormohromaniUde, CIIO.NH.C6H4Br (m. p. 119°) is obtained by
heating ethyl formate with bromaniline at 100°. It is insoluble in
cold water, with difficulty soluble in hot water, readily soluble in
alcohol or ether. It may also be prepared by the action of bromine
water on formanilide rubbed up with water. Measurements of the
crystals, which belong to the rhombic system, are given.
Thioformohromanilide, CHS.NH.C6H4Br, is prepared from the above
in the same way as thioformanilide from formanilide (Hofmann, Ber.,
11, 338). It is soluble in hot alcohol and ether, and melts with decom-
position at 189—190°,
Bromophenylglycocine, CIl2(NII,C6H4Br).COOH, is obtained by
warming an ethereal solution of 2 mols. bromaniline and 1 mol.
chloracetic acid. It is very unstable, and exceedingly soluble in
filcohol, ether, and hot water. With suitable precautions it may be
crystallised from the latter ; m. p. 98°. It forms a bright green
copper salt.
Dihroraophenyloxethylenecarhamide, the bromanilide of bromophenyl-
glycocine, C6H4Br.NH.CIIo.CO.NH.C6H4Br, is prepared by boiUng
bromaniline monochloracetate with excess of bromaniline {vide
ORGANIC CHEMISTRY. 635
Meyer, Ber., 8, 1152), or by adding 1 mol. chloracetic chloride to
an ethereal solutiou of 4 raols. bromaniline. It is soluble in alcohol
and ether, insoluble in cold, sparingly soluble in hot water. It sub-
limes at 145'', and melts between 154;° and Idl^.
Ethyl bromophenylamidoacetate^ CsHiBr.NH.CHo.COOEt (m. p. 95—
96'), is prepared by gently heating 1 mol. of ethyl niouochloracetate
with 2 m.ols. bromaniline. It is sparingly soluble in cold, easily
soluble in hot alcohol or ether, and is insoluble in water.
Ch. B.
Metatoluidine. By 0. Widmax (Ber., 13, 676— 678).— This com-
pound (b. p. Vj7 — 200") may be obtained in large quantity by the
action of phosphorus pentachloride on metanitrobenzaldehyde, the
resulting metanitrobenzal chloride being reduced with zinc and hydro-
chloric acid thus : —
C6H,(N"02).COH + PCI5 = C«H/XOo).CHCl, + POCI3;
CcH,(XO.).CHCL + 3Ho = CsH^CXHO-CHClo + 2HoO;
CsHiCXH.J.CHCl, + 2H, = C6H4(NH3).CH3.
Metanitrobenzal chloride, C6H4(iSrO>).CHCl2, crystalhses from alcobol
either in colourless thin four- or six-sided plates or in white needles
(m. p. 65°), which are easily soluble in boiling alcohol and in ether,
but insoluble in water. T. C
Dinitroparatoluidine. By F. Beilstein {Ber., 13, 242—244). —
Tiemann {B>ir., 3, '11^) states, and it is commonly believed that the
dinitroparatoluidine (m. p. 168°), which he obtained by reducing tri-
nitrotoluene, is identical with the base (m. p. 166°) which the author
and Kuhlberg {Annalen, 158, 341) obtained by nitrating parace-
toluide and saponifying. This is erroneous. On nitrating para-
toluidine, the first product is metanitroparatoluidine [CH3: NOo : NH3
= 1:8:4]. Since a second nitro- group entering the molecule
should take the para-position with respect to the first, dinitropara-
toluidine must have the constitution [CH3 : NO3 : NHo : NO2 =
1:3:4:5], and the nitrogenous groups must be neighbouring; but
on niti-ating [1:2:4] dinitrotoluene, a trinitrotoluene [1:2:4:6]
should be obtained for the same reason. And if, as in the case of
dinitrotoluene, reducing agents first attack the paranitro-group, the
dinitrotoluidine prepared from it must have the constitution
[CH3 : XO2 : NH. : XO2 =1:2:4: 6].
The nitrogen groups must be symmetrical.
Independently of these theoretical considerations, there is also experi-
mental evidence of the difference of the two compounds, although
their physical properties appear to be the same. The author finds
that they behave differently towards oxidising agents. Friederici has
shown {her., 11, 1976), and the author confirms his statements, that
Tiemann's dinitroparatoluidine is slowly converted by boiling chromic
mixture into dinitroparamidobenzoic (chrysajumic) acid. But sym-
metrical dinitroparatoluidine is much more energetically attacked by
chromic mixture, and does not yield a trace of chrysammic acid. The
036 ABSTRACTS OP CHEMICAL PAPERS.
product is an indifferent amorphons insoluble powder, probably an
azo-compound.
Symmetrical dinitrotoluidine is best prepared by gi-adually addin^^
the theoretically necessary quantity of a concentrated aqueous solu-
tion of ammonium hydrosulphide to 1 part of trinitrotoluene well
rubbed up with 2 parts of alcohol, allowing to stand, precipitatinjg
with water, and extracting repeatedly with boiling hydrochloric acid
(sp. gr. 1"05). The base is then precipitated by ammonia, dissolved
in chloroform, and crystallised from 60 per cent, acetic acid, or
from hydrochloric acid sp. gr. 1'055 (m. p. 166'5 — 168°). It is
soluble in alcohol, acetic acid, benzene, and chloroform, sparingly
soluble in boiling water, insoluble in light petroleum. Ch. B.
Condensation Products of Tertiary Aromatic Bases. By
0. Fischer (Ber., 13, 807 — 809). — Dimethyl^^aratoluidine has no
action on benzaldehyde in presence of zinc chloride even at 120 —
130°. Dimethylor^/wtoluidine yields a small quantity of a base, the
constitution of which has not been ascertained. Dimethylme^a-
toluidine acts with great energy, even at the temperature of the water-
bath, and yields a base which is analogous to tetramethyldiamido-
triphenylmethane. Neither of these bases affords a colouring matter
on oxidation. According to the author's experience, no -para substi-
tution product of dimethylaniline yields condensation products with
aldehydes, alcohols, &c., and the same seems to be the case with
dimethylparatoluidine.
Benzaldehyde and dimethylmetatoluidine in presence of zinc chlo-
ride yield a base C25H30N2, which crystallises in large prisms (m. p.
109°). It is soluble in mineral acids, but is reprecipitated by sodium
acetate. It is easily soluble in benzene, alcohol, and ether, but is in-
soluble in water. The platinochloride of this base consists of fine
golden-yellow crystals. No colouring matter was obtained on oxida-
tion of the base.
A new reaction of dimethylaniline is also described in the paper.
When benzoic anliydride is gently warmed with dimethylaniline in
presence of zinc chloride, a fine green colouring matter is obtained,
having the appearance of malachite. Gr. T. A.
A New Class of Ammonium Compounds. Part I. By P.
Griess (Ber., 13, 246 — 250). — By acting with methyl iodide in excess
ou the isomeric amidophenols, the author has obtained new bases, to
which he assigns the constitution CeHi^ |
^^NMe3
/O
Orthotrimethylphenolammonium, d^/ \ + HoO, is prepared bv
^NMea
mixing a cold methyl alcohol solution of orthamidophenol hydrochlo-
ride with three parts of methyl iodide, and adding concentrated
potash solution to strongly alkaline reaction. Potassic chloride sepa-
rates out, and on allowing the mixture to stand its reaction becomes
acid. More potash is then added, and this addition is repeated as long
as an acid reaction appears on standing. When the action is completed,
ORGANIC CHEMISTRY. 637
the alcohol is distilled off, the solution acidified with hjdriodic acid,
and the yellowish crystals of the hydi-iodide which separate are crys-
tallised from boiling water with addition of animal charcoal. The
crystals are then dissolved in water, decomposed by silver oxide or
carbonate, and the solution evaporated on the water- bath, when a
syrup remainij which solidifies on standing. The pressed and recrys-
tallised base forms white prisms, which are soluble in water and
alcohol, but insoluble in ether : by the latter the base may be sepa-
rated from its alcoholic solution. Its taste is intensely bitter. It is
not acted on by potash or ammonia, but combines with acids (except-
ing carbonic acid) to form two classes of salts. The iodide,
C^HiaNO.HI + H,0,
the constitution of which is possibly C6Hi(OH).NMe3l -|- HoO,
crystallises in white indistinct prisms, very soluble in hot water.
When ammonia is added to an aqueous solution of this salt, a
sparingly soluble hemi-iodide, (C9Hi3\U)2.HI, separates in needles.
From alcohol, it separates in thick prisms. The base also forms a
very soluble crystalline hydrochloride, CgHiaNO-HCl + 2H2O; a red-
dish-grey nitroprusside. (C9Hi3XO)2.H2FeCy5(NO) ; a yellowish-red
platinochloride, (CgHiaXO.HCljo.PtCli ; and a brown periodide, with
green reflection, which is insoluble in water.
Heat acts on the base as on the aromatic betaines. When distilled,
it passes into the isomeric orthodimeAhylamido-anisol, C6H4(OMe).XMe2,
a colourless strongly refracting basic oil, of peculiar odour and burning
biting taste. This forms a deliquescent crystalline hydrochloride, and
a sparingly soluble platinochloride. It resembles dimethylaniline,
and like that body is capable of conversion into colouring matters,
which the author is engaged in investijjatinof.
When orthotrimethylphenolammonium hydrochloride is distilled, it
breaks up into methyl chloride and orthodimethylamidophenol,
C6H4(OH).NMeo (m. p. 45°), The latter is crystalline, very sparingly
soluble in boiling Avater, easily in alcohol, ether, acetic acid, and
potash solution. Its taste, at first biting, is afterwards bitter. Ferric
chloride colours its solutions red-violet. The hydrochloride di-ies up
to a gum : from its solution, ammonia precipitates the base as an oil,
which solidifies to small white rhombic crystals.
Paratrimethylphenolammonium, CellX | + H,0, crystallises in
^NMea
clear six- or eight-sided tables. It strongly resembles its isomeride,
and on distillation yields paradimethyl-amidoanisol, C6H4(OMe).NMe2
(m. p. 48°), which crystallises from alcohol in white rhombic leaflets.
Attempts to obtain similar bases by means of ethyl iodide were
unsuccessful. Ch. B.
A New Class of Ammonium Compounds. Part II. By
P. Griess (Ber., 13, 047 — 650). — TrimtthijlnitropJienolammonium,
C6H3(I«{'02)\ I , is obtained by the action of methvl iodide on
^NMes
088 ABSTRACTS OF CHEMICAL PAPERS.
Laurent and Gerhardt's amidonitrophenol, the process being conducted
as previously described in the case of the other triphenylammonium
bases, except that the free base is best obtained from its salts by the
use of potash in place of oxide of silver. Trimethjluitrophenolammo-
uium crystallises from water in brilliant yellow needles or tables,
having a strongly bitter taste. It is only sparingly soluble in cold
water or alcohol, but more easily in these liquids when hot. It is in-
soluble in ether and in benzene. It has no action on vegetable colours.
Heated above 200°, it is decomposed, without previous fusion, into a
residue of carbon and a reddish volatile oil. It is a strong base.
Trlmethylnitruphenolammonmm iodide^ C9H13N2O3.HI.2H3O, crys-
tallises in white needles, which are moderately soluble in hot, but only
sparingly soluble in cold water. The hydrocJdo7^{de, C9H10N2O3.HCI.H0O,
crystallises in prisms, which behave towards solvents like the
hydriodide. The platino chloride, (C9H,2N203.HCl)2,PtCl4.6HoO, forms
bright yellow needles or rhombic plates, which are sparingly soluble
in boiling water, hardly at all in cold water, and almost insoluble in
alcohol. The periodate crystallises in fsmall brown needles.
Trimethylamidophenolammonmm hydrochloride,
^NMe3.2HCL4H30
is obtained by the reduction of the corresponding nitro-compound with
tin and hydrochloric acid. It crystallises in white plates, which are
easily soluble in water or alcohol, even when cold, also in ether. With
ferric chloride, it gives a deep violet colour. The platinochloride,
C„HuN,0.2HCl.PtCh + 2HoO, forms small rhombic or six-sided
prisms, which are only sparingly soluble in cold water, and are decom-
posed by boiling water.
Orthotrimethi/lardsolanimonuim iodide, C6H4(OMe).NMe3l, is obtained
by the action of methyl iodide on a solution of orthotrimethylphenol-
ammonium in methyl alcohol, to which a little potash has been added,
or by the action of methyl iodide on dimethylamido-anisol, thus : —
/^
CeH,/ I + Mel = C6H4(OMe).NMeJ.
\NMe3
C6H4(OMe).NMe3 + Mel = aH4(OMe).NMe3l.
It crystallises in long white needles, which are easily soluble in hot,
but only sparingly soluble in cold alcohol or water. The platino-
chloride, (Cii)Hi6NOCl)2 + PtCb, forms brilliant yellow plates or six-
sided tables, which are only very sparingly soluble in cold water. The
hydrate, C6H4(OMe).NMe3.0H (':'), is obtained by the action of silver
oxide on the iodide. It is strongly alkaline, and gradually decom-
poses on warming into orthodimethylamido-anisol and methyl alcohol.
Paratrimethylanisolammonimn iodide, C6H4(OMe).NMe3l, is obtained
like the ortho-compound, using para- instead of ortho-trimethylphenol-
ammonium. It crystallises in four- or six-sided plates. The platino-
chloride, C,nHiG(N0Cl)2 + PCI4, consists of small yellow six-sided
prisms. Both the above compounds behave towards solvents like the
ORGANIC CHEMISTRY. 639
corresponding ortho-compounds. The hydrate is similar to the ortho-
compounds, and on heating splits up into paradimethylamidoanisol and
methyl alcohol. T. C.
Formation of Diamines. By A. Bernthsen and F. Szymanski
{Ber., 13, 9 1 7 — 919) . — BenziiUdenemono'ph enyldiamine,
NHPh.CHPh.NH^,
is formed, together with several other bases, when an alcoholic solu-
tion of benzenylmonophenylamidine is treated with sodium amalgam.
The liquid is from time to time neutralised with strong acetic acid,
and the reduction is stopped as soon as the formation of ammonium
amalgam commences.
The bases are separated by I'ecrystallising their hydrochlorides,
when benzylidenemonophenyldiamine hydrochloride, C13HUN2.HCI, is
deposited in thick prisms (m. p. 284°) soluble in alcohol and water.
The platinochloride crystallises in long needles, and also in rhombic
plates.
The free base is insoluble in water, but dissolves freely in other sol-
vents. It melts at US'", and distils without decomposition. On reduc-
tion, it yields benzylaniline. W. C. W.
New Synthesis of Organic Bases containing Oxygen. By
W. Staedel and O. Siepek.maxn {Ber., 13, 841 — 844). — When brom-
acetylbenzene, Ph.CO.CH.;Br (1 mul.), is dissolved in dimethylaniline
(2 mols.), a reaction takes place, and the liquid solidities on cooling,
forming a crystalline product, soluble in hot alcohol. The alcoholic
solution deposits yellow prismatic crystals of the new base, CieHnNO.
CsHvOBr -t CsHuN = CeHi.NO + HBr.
Colourless crystals of the hydrobromide of another base can be
obtained from the mother-liquor. The base, CieHnNO, is insoluble in
water, but dissolves sparingly in alcohol and ether, and freely in
benzene and toluene. It melts with partial decomposition at 120".
The base is also soluble in dilute hydrochloric and sulphuric acids,
but is reprecipitated when these solutions are diluted with water. The
hydrochloric acid solution forms precipitates with picric, phospho-
molybdic, and tannic acids, also with potassium, mercuric iodide, and
with platinum and stannous chlorides.
The platinochloride, (Ci6Hi7NUHCl).;PtCl4, crystallises in plates.
Ferric chloride or dilute nitric acid readily oxidises the base. By the
action of methyl iodide the compound CieHivNO.Mel is obtained. It
is purified by digestion with ether, and recrystallisation of the inso-
luble pox'tion from water. By treatment with silver oxide, the iodine
is removed from this substance, and a strongly alkaline liquid is pro-
duced, which forms ci-ystalline salts.
Bromacetylbenzene also acts in a similar manner on dimethylmeta-
toluidine and on tetramethylmetaphenylenediamine.
The compound from dimethylaniline probably has the constitution
Ph.CO.CHo.CsHi.NMe. and the dimethylmetatoluidine derivative maj-
be represented as C6H3(Ph.CO.CH,Me)(NMe), = [5:1: 3].
w. c. w.
640 ABSTRACTS OF CHEMICAL PAPERS.
Synthesis of Leucaniline. By 0. Fischer and P. Greiff (Bcr.,
13, GG9 — G71). — Paranitrobenzalclehyde (m. p. 93°) is converted into
a yellow crystalline nitro-base when digested with aniline hydrochloride
and zinc chloride at 120°. This compound dissolves in acids, forming
colourless solutions, and on reduction, with zinc-dust and acetic acid
gives paraleucaniline. The paranitrobenzaldehyde employed in the
above reaction was prepared by the action of lead nitrate and nitric
acid on paranitrobenzyl chloride.
The following are good lecture experiments : — Rosaniline is obtained
when a hot alcoholic solution of chloranil is poured into a hot freshly
prepared solution of lencaniline in alcohol. Tetramethyldiamidotri-
phenylmethane gives benzaldehyde green under similar circum-
stances. Other leuco-bases also behave in a similar manner.
T. C.
Some Compounds of the Leuco-base from Cuminol and
Dimethylaniline. By J. Zieglek (Ber., 13, 786— 788).— The best
method of obtaining the base described by 0. Fischer (Ber., 12,
1688) is to digest cuminol and dimethylaniline for a day with zinc
chloride and a little water at 120°. The hydrocJiloride is obtained by
passing a stream of dry hydrochloric acid gas into a solution of
the base in anhydrous ether or light petroleum. A white crystalline
and extremely hygroscopic powder separates out. When dried over
sulphuric acid in a vacuum it consists of 0961133.1^2.21101.
The picrate, CseHsjNo + 2C6H2(N02).s.OH (m. p. 166°), is formed
when an alcoholic solution of the base is mixed with picric acid. It
consists of fine green crystals, which explode when heated to 220°.
The metlbiodide, O26H3..N0.2OH3I, obtained by heating the base for
a day at 116° with methyl iodide and methyl alcohol under pressure,
consists of snow-white crystals (m. p. 200°), easily soluble in hot
water.
The platinochloride, 0261132^2(1101)2 + PtOU, is a yellow crystalline
body, which is sparingly soluble in water, and still less so in alcohol
and ether.
When the base is mixed with strong nitric acid and the solution diluted
with water, a yellowish body is obtained, which on repeated crystal-
lisation from acetic acid yields bright yellow acicular crystals (m. p.
206°). Apparently it is a hexnitrotetramethyldiamidotriphenylme-
thane. The leuco-base yields colouring matters on oxidation, which
closely resemble the green from benzaldehyde. The picrate is most
easily purified. All the salts of the colouring matter are characterised
by a bright red metallic lusti'e. G. T. A.
Supplementary Notice on New Colouring Matters. By W.
V. Miller (Ber., 13, 803). — Oompounds similar to those described by
the author have been obtained by Oaro and Schraube, and also by
Griess (Annale7i, 137, 84), who assigned to them the type —
PhsN : N.OeHaCNHo).^ : N.OeHi.N : NPh.
G. T. A.
Homologues of Phosphenyl Chloride. By A. Michaelis and
0. Panek (Ber., 13, 653— 666).— PAostoZi/Z chloride, OtHvPOL. The
ORGANIC CHEMISTRY. 641
presence of a small quantity of "water is necessary in the formation
of this compound from a mixture of phosphorus trichloride, toluene,
and aluminium chloride (ibid., 12, 1009) ; the best yield (56 grams) is
obtained by taking the following proportions : — 150 grams toluene,
200 grams phospliorus trichloride, 30 grams aluminium chloride, and
1 c.c. water. Pure phostolyl chloride forms crystalline masses of long
needles (m. p. 20^, b. p. 245''). Tnlylphosphorous acid, C7H7PO2H2, is
obtained by decomposing phostolyl chloride with water ; it crystallises
from alcohol in monoclinic tables (m. p. 104°). Tolylplwspliinic acid,
C7H7PO3H2, crystallises in needles (m. p. 188°). Plwstobjl tetrachloride,
C-H7PCI4, is obtained by the direct combination of chlorine with phos-
tolyl chloride. On heating in sealed tubes at 200° it gives monochlor-
benzyl chloride, phosphorus trichloride, phostolyl chloride, and hydro-
chloric acid, 2C7H7PCI4 = C7HeClo -f C7H7PCI2 + PCI3 + 2HC1.
This does not decide whether phostolyl chloride is Ph.CHo.PCL, or
CeHiMe.PCla, although as the reaction only takes place at 200° it
appears more probable that the chlorine attacks the methyl radicle,
and that the compoand is a true phostolyl chloride.
FJiosxylochJoride, CsHaPClj, and the acids C8H9PO2H2 and CsHgPOgHj,
have also been prepared. T. C.
Bromonitro- and Bromamido-anisoil. By W. Staedel and
G. Damm {Ber., 13, 838 — 839). — Monobromoparanitranisoil,
C6H3Br(N02).OMe,
prepared by heating potassium monobromoparanitrophenate with
methyl iodide and methyl alcohol, crystallises in white needles (m. p.
106°), soluble in alcohol and ether. On reduction with tin and hydro-
chloric acid it yields vionohromoparanisidine hydrocMnride. The free
base, C6H3Br(NH2).OMe, is an oily liquid, insoluble in water, but dis-
solving freely in alcohol and ether. Its salts are crystalline.
Dibromnparanisidine, C6H2Br2(jS'H2).OMe, prepared by the reduc-
tion of dibromoparanitranisoil (m. p. 126°) is a white solid bodv,
soluble in alcohol, ether, and benzene. It combines with hydrochloric,
sulphuric, and oxalic acids, forming salts, which crystallise in white
needles. W. C. W.
Orthanisidine. By 0. MUlhauser (Ber., 13, 919— 924).— Or/A-
anisidine, XHo.C'eH^.OMe, prepared by the reduction of orthonitraniso'il
(b. p. 276"5") by ammonium sulphide, boils at 228°. The hydro-
chloride, hydrobromide, and acid sulphate, form colourless crystals,
soluble in water and alcohoj. The neutral sulphate has not yet been
obtained. Acetaniside, NHAc.C6H4.OMe, formed by the action of
acetic anhydride on anisidine, is a pearly, crystalline substance, solu-
ble in glacial acetic acid and in hot water. It melts at 79°, and boils
at 305°. "When water is added to a solution of this compound in
strong nitric acid, dinitr acetaniside, NHAc.C6H2(N02)2-OMe is pre-
cipitated. On recrystallisation from alcohol, it is obtained in yellow
crystals (m. p. 147°). DianisyJcarbamide and anisidine hydrochloride
are deposited when carbonyl chloride is passed through a solution of
anisidine in benzene. After removing the latter substance by treat-
fi42 ABSTRACTS OF CHEMICAL PAPERS.
raent with dilute hydrochloric acid, the carbamide is recrystallised
from alcohol. The crystals which are colourless melt at 174".
Monanisiiharhnmide, NH.,.CO.NH.C6H4.0Me, prepared by the action
of potassium cyanate on an aqueous solution of anisidine hydrochloi^ide.
forms colourless crystals (m. p. 146-5°), soluble in hot water and
alcohol.
Bianisyltliiocarlamkle, SC('NH.C6H4.0Me)2, produced by warming
anisidine and alcoholic potash with an excess of carbon bisulphide,
crystallises in white needles (m. p. 184-o°) soluble in hot alcohol.
Monanisyltliiocarhamide, NHo.CS.NH.CsHj.OMe, is precipitated on
warming a mixture of anisidine hydi-ochloride and potassium thio-
cyanate. It crystallises in needles, which melt at 152°.
On oxidation with chromic mixture, anisidine yields a substance
which forms yellow crystals (m. p. 138°) having a penetrating odour.
w. c. w.
Benzamidophenolsulphonic Acids and Amides of the Amido-
phenolsulphonic Acids. By J. Post and L. Holst {Ber., 13, 617 —
619). — The same hydrogen atom is replaced by the HSO3 group,
whether nitrophenol (ortbo- or para-) or the corresponding amido-
phenol is converted into the sulphonic compound. This can be best
shown in the case of the benzamidophenolsulphonic acids, as they
form well charactei'ised salts. These benzoic derivatives are obtained
in the ordinary way by the use of benzoic chloride. For the prepara-
tion of the anilides of the amidophenolsulphonic acids, the unstable
sulphochlorides are first obtained by the action of phosphorus penta-
chloride, and then converted into the more stable anilides by means
of aniline. The compounds (both in the ortho- and para-series)
derived from nitrophenol and from the corresponding amidophenol,
are in all cases identical. Sodium henzainidophenolsidplionate,
C6H3(OH)(NH.CO.aH0.SO3Na 4- 4^ aq.
crystallises in needles, which are easily soluble in water and alcohol.
Barium salt [C,.,H3(OH)(NH.CO.C6H5).S03]2Ba, crystallises in
brilliant, colourless spangles, which are sparingly soluble in alcohol
and water. Strontium salt crystallises with 4| aq. in colourless, scaly
crystals, which are very sparingly soluble in water and alcohol.
Calcium salt also crystallises with 4^ aq., and is similar to the stron-
tium salt. Anilide of amidophenolsulphonic add,
C«H3(0H) (NH2).S02NHPh,
forms colourless needles (m. p. 205°), which are easily soluble in
alcohol, glacial acetic acid, and benzene, but insoluble in ether and in
light petroleum. All the above compounds are derived from orthamido-
phenolsulphonic acid. The anilide of paramidophenolsulphonic acid,
C6H3(OH)NH2.S02NHPh, derived from paramidophenolsulphonic
acid, consists of colourless, compact crystals (m. p. 98°), which are
easily soluble in alcohol, glacial acetic acid, and benzene, but insoluble
in light petroleum and in ether. T. C.
a-Dinitrophenyl Ether. By C. Willgerodt {Ber., 13, 887).—
a-DiHitivphenyl etJier, OCCGHs.Nbs.ISrOi)^ [1 : 2 : 4] is prepared by
ORGA^^C CHEMISTRY. 643
heating equal parts of potassium a-dinitrophenate and a-dinitrocliloro-
benzene, in sealed tubes at 150 — 200°. The crude product is washed
with water, and boiled with alcohol to remove impurities. The pure
residue is a colourless, crystalline substance (m. p. 195°), soluble in
hot amyl alcohol, benzene, chloroform, and glacial acetic acid, but
insoluble in alcohol. Boih'ng potash converts it into potassium di-
nitrophenate. W. C. W.
Oxidation of Substituted Phenols. By C. Magatti {Ber., 13,
224 — '12.6). — lu his paper on the ethylenic ethers of pyrogallol (Ber.,
12, 1860) the author stated that by oxidising diphenol in solution in
glacial acetic acid, he had obtained a brown amorphous substance,
which dissolved with blue colour in concentrated sulphuric acid. This
substance he suspected to be the simplest analogue of cedriret ; but he
has not been able to obtain it in a form suitable for analysis. It is
not formed if the acetic acid solution is heated, nor if nitric acid is
used as the oxidant. An alcoholic solution of diphenol also gives a
violet precipitate, soluble with blue colour in sulphuric acid.
A better result is obtained by oxidising fetrabromodipJienol. To
prepare this body, bromine is added to diphenol dissolved in warm
acetic acid until the colour no longer disappears, and the mixture is
heated. Tetrabromodiphenol, Ci2H6Br402, then separates in felted
needles, whicli may be purified by repeated crystallisations from abso-
lute alcohol (m. p. 264°). It is insoluble in water, sparingly soluble
in alcohol, ether, and sulphuric acid, but is easily dissolved by alkalis.
By digestion with acetic anhydride and sodiurn acetate for two hours,
it is converted into a diacetyl derivative, Ci2H4Ac2Br402 (m. p. 245°).
Oxidising agents differ in their action on tetrabromodiphenol.
Potassium dichromate and nitric acid give red precipitates in the
acetic acid solution; potassium ferricyanide gives a bine, and bromine
water a dirty brown precipitate with its solution in. alkali. All
these precipitates are soluble in strong sulphuric acid with blue colour,
soon passing into brown ; but none could be obtained pure. When,
however, a little red fuming nitric acid is added to a solution of
3 grams of tetrabromodiphenol in 100 of acetic acid, and heated to
95°, the mixture becomes deep red, and on cooling deposits crystalline
scales, which are dark red-brown by transmitted light, deep steel-blue
by reflected light. This substance has the composition Ci2H4Br402. It is
insoluble in all the ordinary menstrua, and cannot be fused without
decomposition. Its solution in sulphuric acid is violet, and gives a
brick-red precipitate on the addition of water. Digestion with sul-
phurous acid reconverts it into tetrabromodiphenol. It has doubtless
a constitution analogous to that of cedriret, and may be named tetra-
bromodiphenolquinone.
CeH^BrjO C6H2(OMe)20
I I I I
C6H2Br20 C6H2(0Me)20
Tetrabromodiphenolquinone. Cedriret.
The compound obtained from triiodophenol by Kammerer and
Benziger {Ber., 11, 557) is possibly similarly constituted.
044 ABSTRACTS OF CHEMICAL PAPERS.
TetracMorodiphenol, C,2H4Cl40. (m. p. 233'), is easily prepared by
treatinc? diplienol, suspended in ninch acetic acid, with a stream of
chlorine. The diphenol is soon dissolved, and the chlorine compound
subsequently separates. After washing with acetic acid and crystalli-
sation from highly dilute alcohol, it forms transparent needles. Ti-eated
as above described with a little nitric acid, it yields tetrachlorodiphenol-
quinone, C12H4CI4O2, having all the characters of the bromine com-
pound, but giving a blood-red solution with sulphuric acid. This
solution becomes colourless when slowly heated to 100°, and deposits
a body which crystallises in needles. Ch. B.
Compounds of Benzotrichloride with Phenols and Tertiary
Aromatic Bases. By 0. Doebner (Ber., 13, 610 — 614). — The name
benzein is proposed for the class of compounds described in former com-
munications (ihid., 11, 1236; 12, 1462). — Besorcinolbenzein is obtained
by gently warming 1 mol. bcnzotiichloride with 2 mols. resorcinol,
finally on a paraffin-bath at 180 — 190°. The product is extracted with
water, to take up unchanged resorcinol, the residue dissolved in soda,
and then precipitated by acetic acid. The yellow crystalline product
thus obtained is recrystallised from a mixture of alcohol and glacial
acetic acid, from which resorcinolbenzein separates in large prisms.
These crystals appear yellow by transmitted, and violet-red by reflected
light; an analysis of the substance dried at 100° led to the formula
CssHsoOg. The compound, when precipitated from alkaline solution
by an acid, is easily soluble in alcohol, whilst the crystals obtained as
above described are only very sparingly soluble in this solvent, but
more easily on the addition of an acid. This solution has a yellowish-
red colour, and fluoresces like fluorescein. By quick cooling of the
acid alcoholic solution, the compound separates as concentric groups
of yellow needles, but by slow cooling the prisms above described
are obtained. It is insoluble in water, ether, and benzene. On heating
at 130° it loses water, and then has the composition CagHoeOr =
2(Ci9Hu04 + H2O) ; at temperatures above 200° further decomposi-
tion occurs.
TetraJiydroxTjtriphenylmethane, CHPh[C6H3(OH)2]2- — Resorcinol-
benzein, when acted on by reducing agents, undergoes a change simi-
lar to phenolbenzein, and gives tetrahydroxytriphenylmethane, which
crystallises from alcohol in colourless needles (m. p. = 171°). It is
sparingly soluble in water, easily soluble in alcohol, ether, and glacial
acetic acid. It dissolves in alkalis to a colourless solution, and is repre-
cipitated in the crystalline state on the addition of an acid ; on oxida-
tion or on heating, it is reconverted into resorcinolbenzein ; its alkaline
solution is coloured yellowish-brown by potassium ferricyanide.
Tetrabromoresorcinolbeiizdn, Ci9lIinBr4C)4, is obtained by passing bro-
mine vapour into an alcoholic solution of resorcinolbenzein, or better,
by adding the calculated amount of bromine dissolved in glacial
acetic acid. It forms a fiery red powder, which is insoluble in
water, and only very sparingly soluble in alcohol, glacial acetic
acid, and other solvents, and could not therefore be obtained in
the crystalline state. Its alkaline salts are sparingly soluble in
water, but easily in alcohol, yielding a pomegranate-red solution
ORGANIC CHEMISTRY. 645
similar to tbose of the eosin salts : this solution dyes silk and wool like
eosin : its spectrum also greatly resembles that of the latter body. An
attempt to obtain an acetyl compound of resorcinolbenzein was unsuc-
cessful. Resorcinolbenzein is not taken up by acids, or by alkaline
sulphites, in this respect differing from phenolbenze'in.
As in the case of phenol and resorcinol, 1 mol. of benzotrichloride
combines with 2 mols. of the other phenols, forming dyestuffs belontnncr
to the triphenylmethane group. Those with the cresols, pyrocatechol,
quinol, orcinul, and /3-naphthol are yellow or yellowish-red bodies ;
that with pyrogallol, on the other hand, is blue ; and. that with
a-naphthol green. The great similarity of the compounds of the
phenols with benzotrichloride on the one hand, and with phthalic acid
on the other, appears to show that the latter are like the former,
derivatives of triphenylmethane, thus : —
Ph.CHrCeHi.OH).,. OH CH(aH,.0H)2.
Dioiytriphenylmethane. Leucaurin.
COOH.aHi.CHCCeHi.OH),.
Phenolphthalein.
T. C.
A Product obtained by the Action of Aqua Regia on
Orcinol. By S. Reymanx (Ber., 13, 8u9— 811). — This body is the
chlorine substitution-product of Liebermann's colouring matter
CaiHi^XoOe, obtained by the action of nitrous acid on orcinol. It con-
sists of C21H17CIX2O6. Resorcinol, under similar conditions, yields
two bodies, of which one is probably analogous in composition to the
above, whilst the other contains no chlorine. The first one dissolves
in alkalis, with a ptire blue colour. G. T. A.
Oxidation of Benzoic and Acetic Carbinols. Bv A. Beeuer
and T. Zixcke (Ber., 13, eSo— 64=1) .—BenzmjlcarbinoJ, Ph.CO.CH,OH,
gives benzoic aldehyde and benzoic acid when oxidised with silver
solution (compare ibid., 10, 1486; this Journal, 1878, Abstr., 223).
Bv oxidation with copper sulphate and soda, however, it gives chietiv
mandelic acid, CPhH(OH).COOH (m. p. 115—118°), together with
small quantities of benzoylformic and beuzoic acids. The formation of
mandelic acid is represented as follows: — (1.) Ph.CO.CH>.OH =
Ph.COH + H.COH. (2.) Ph.COH + H.COH = Ph.CH(OH;.COH.
The mandelic aldehyde is then oxidised to the corresponding acid by
the copper sulphate. The melting point of methyl mandelate is 48",
and not 114°, as stated by Naquet and Louguinine {Annalen, 139,
301). For the determination of the products of oxidation of acetyl-
carbinol, the acetate or benzioate must be employed, as the acetvl-
carbinol itself cannot be obtained in the pure state.
Aeetylcarhinol acetate, Me.CO.CH^.OAc (b. p. = 172°), was pre-
pared by adding o parts of monochloracetoue gradually to a warm
solution of 8 parts of anhydrous potassium acetate in 20 parts of
alcohol. Ethyl acetate and a liquid boiling at 125 — 135"^ (mesityl
oxide ?) are also obtained at the same time. Aeetylcarhinol acetate
thu5 prepared agrees in every respect with that obtained by Henry
{Ber., 5, 966).
VOL. XXXVIII. 2 z
«)4G ABSTRACTS OF CHEMICAL PAPERS.
Acetylcarbinol hmzoate, Me.CO.CH2.OBz, was obtained like the
acetate. It is a slightly yellow aromatic liquid (b. p. = 189 — 190° at
50-60 mm. ; 200—201" at 80—90 mm.; and 263—264° at the ordi-
nary pressure, in the last case with slight decomposition), which on
long standing becomes crystalline, forming colourless needles (m. p.
24°). These are easily solul)le in ether, alcohol, &c. ; but only sparingly
soluble in cold water, more easily in hot.
Acetylcarbinol acetate on oxidation with soda and copper sulphate,
gives lactic acid, together with a small quantity of pyro tartaric acid.
It is probable that all compounds containing the group — CO.CH2.OH
will, under similar circumstances, give bodies with the group
-CH<.OH).COH. T. C.
Pinacones and Pinacolins. By W. Thorner and T. Zincke
(Ber., 13, 641 — 647). — A continuation of the authors' previous work
on this subject (Ber., 10, 1473; 11, 65, 1396, 1988; this Journal,
Abstr., 1878, 2-23, 425, 874 ; and 1879, 317). From their results, they
draw the following general conclusions : — All ketone-pinacones, when
exposed to a high temperature, split up into a ketone and an iso-
alcohol. With those pinacones containing a benzene radicle, this de-
composition takes place easily ; whereas in the case of those containing
paraffin radicles, it only occurs with considerable difficulty. To the
pinacones there correspond two kinds of pinacolins, of which the
one {/B) can be easily obtained ; whilst the other (a) is only obtained
with difficulty, and then only from those pinacones which contain a
benzene radicle. Both pinacolins can also be obtained dii'ectly from,
the ketones, although up to the present the a-pinacolin has only been
got from purely aromatic ketones; those on the other hand, which,
like acetophenol, contain also paraffin radicles, give only /3-pinacolins,
and that not directly in the case of those ketones which belong en-
tirely to the paraffin series. No pinacone is known which partakes at
the same time of the character of a true diatomic alcohol. T. C.
Crystalline Form of Benzyl Orthothioformate. By M.
Dennstedt (Ber., 13, 238 — 240). — This substance crystallises in the
rhombic system a : h : c = 0'9978 : 1 : 0*9900 ; observed forms, 100,
010, 001, Oil, 101, 021, 201. C. E. G.
Occurrence of Vanillin in Raw Sugars. By E. 0. v. Lippmann
(Ber., 13, 662— 665).— The author, like Scheibler (J5er., 13,335; this
vol., 467), finds that vanillin occurs in certain kinds of raw sugar.
T. C.
Dioxybenzophenone. By W. Staedel and E. Sauer (Ber., 13,
836). — (3-dluxyhenzo2)henone, CisHmOa, is prepared by the action of
dilute sulphuric acid and potassium nitrite on flavine obtained by the
reduction of dinitrobenzophenone (m. p. 148"'). It crystallises in
white needles (m. p. 161°), which are more soluble in water than the
crystals of a- dioxybenzophenone (Ber., 11, 746). The ethereal salt,
CisHhOsBz;. which is formed by the action of benzoic chloride on 8-
dioxybenzophenone, is deposited from an alcoholic solution in silky
leaves (m. p. 101°). The diacetic compound, dsHsOsAcj (m. p. 90°),
ORGANIC CHEMISTRY. 647
also crvstallises in plates. /3-dioxybenzophenone is decomposed by
fusion with, potash, forming phenol and paroxybenzoic acid.
W. C. W.
Nitrobenzoic Acids. By A, Claus (Ber., 13, 891— 896).— A
considerable quantity of Fittica's " lemon yellow " mononitrobenzoic
acid (Ber., 11, 1207, and this Journal, Abstr., 1878, 980) was pre-
pared, and was shown to pos.se.ss no constant melting point. By re-
peated fractional recrystallisation, it was separated into meta- and
ortho-nitrobenzoic acids, W. C. W.
Metaparadinitrobenzoic Acid by Nitration of Paranitro-
benzoic Acid. By A. Clals and ^y. Halberstadt (Ber., 13, 815 —
817). — By the action of a mixture of 1 part of fuming nitric acid and
2 parts of fuming sulphuric acid on paranitrobenzoic acid in a closed
tube, the authors obtained a mixture of ortho- and meta-paradinitro-
benzoic acids. The two acids can be separated with some dit!iculty by
means of the barium salts, that of the latter acid being more sparingly
soluble.
Metaparadinitrobenzoic acid melts at 161° (uncor.), is easily soluble
in ether,- alcohol, and hot water, but sparingly so in cold water. It
crystallises in small colourless stellate groups, which contain no water
of crystallisation. Its solution in hot water has an intensely bitter
taste. It sublimes unchanged, but explodes when heated on platinum
foil. The barium salt crystallises in white radiating masses, and con-
tains 4HoO. The calciuvi sait consists of small white plates, becoming
yellow at 130°, and losing 3 mols. HoO at 136". The potassium,
sodium, and rimmoniiim salts are very soluble, but have not been ob-
tained in the crystalline state.
By heating paranitTobenzoic acid in closed tubes with bromine and
water up to 20()°, the authors have obtained a brominated compound ;
but whether this is brominated nitrobenzoic acid is doubtful.
G. T. A.
Orthohydrazinbenzoic Acid. By E. Fischer (Ber., 13, 679 —
682). — This acid, together with a small quantity of orthodiazobenz-
imide (m. p. 144°, Zeits. f. Ghem., 1867, 164), is obtained from anthra-
nilic acid in a similar manner to phenylhydrazine. It crystallises
from hot water in fine needles, which are much less soluble in alcohol
and ether than in water. On oxidation, it behaves like the primary
hydrazines, and is completely decomposed with evolution of gas by
Febling's solution, and bv mercury and silver salts even in the cold.
The hydrochloride, C6H4(COOH).NH.NH3.HCl, crystallises from hot
water, in fine white needles, which are easily soluble in hot water, less
soluble in alcohol, and almost insoluble in ether. The salts of ortho-
hydrazinbenzoic acid are easily soluble, and its alkaline solution may
be boiled for some time without any marked decomposition.
CO
Hydrazinhenzoic anhydride, C6H4<^^tt^NH, is obtained by warm-
ing the acid with strong hydrochloric acid, or better by heating the
acid alone at 220 — 230° in an atmosphere of carbonic anhydride. It
separates from alcohol in colourless compact crystals, which are
sparingly soluble in water, alcohol, and ether. By careful heating, it
2 z 2
048 ABSTRACTS OF CHEMICAL PAPERS.
melts and sublimes in colourless needles, but is partially decomposed
wheu rapidly heated. It no longer has basic properties, but dissolves in
alkalis and decomposes carbonates. It is more stable towards oxidising
agents than the ordinary hydrazine bases, and is not acted on by Fehling's
solution or by mercuric salts. Silver nitrate throws down a white precipi-
tate of the silver salt, consisting of fine needles, which are decomposed
on boilino-. The anhydride reduces ammoniacal silver solutions.
T. C.
Anthranilic Acid from Orthonitrotoluene. By P. Greiff
(Ber., 13, 288 — 290). — The presence of the nitro-group in the ortho-
position in orthonitrotoluene appears to render the methyl-group less
susceptible of change. Thus Wachendorff {Annalen, 185, 259) found
that the latter was unaffected by chlorine or bromine even at a
high temperature, these elements attacking the benzene nucleus.
Amongst the products of the action of bromine, he noticed a body
soluble in alkalis, which he erroneously took to be dibromonitrotolueue.
On repeating Wachendorff's experiment, the author finds this body to
be parametahromortlioamidobeiizoic acid, C6H,;Br2(NH2).COOH, isomeric
with dibromanthranilic acid and with dibromnitrotoluene. A singular
interchange of hydrogen and oxygen between the methyl and nitro-
groups takes place during the reaction, which hence may be used for
preparing anthranilic acid. This is effected by allowing 2 mols. of
bromine to drop gradually into orthonitroluene heated at 170°.
Hydrobromic acid is rapidly given off, and so much heat developed
that external heating is unnecessary when the weight of substance
exceeds 200 grams. From the solid mass obtained on cooling, the
acid may be separated by sodium carbonate ; the yellowish-white mass
deposited on adding an acid may be converted into barium salt by boil-
ing with barium carbonate, and the acid precipitated from the filtered
solution, crystallised from alcohol (m. p. 225°). By treating its alka-
line solution with sodium amalgam in the cold, anthranilic (ortho-
amidobenzoic) acid is easily formed (m. p. 145°) : this yields salicylic
acid when treated with nitrous acid, and aniline when distilled with lime.
The brominated acid is probably identical with Hiibner's dibrom-
anthranilic acid (m. p. 225°) from dibromobenzoic acid ; an isomeride
(m. p. 19G°) has been similarly prepared by Hiibner {Ber., 10, 1706).
Wachendorff did not obtain acid bodies by brominating para- and
meta-nitrotulene.
In the above reaction, nitrobenzyl bromide is perhaps first formed :
the passage of this into anthranilic acid would then be analogous to
the conversion of benzyl chloride into benzoic acid by the action of
nitric acid. A similar oxidation of the methyl-group of toluidine
occurs in the so-called nitrofuchsine-melt ; and the formation of
chlorinated bases when certain nitro-compounda are reduced by tin
and hydrochloric acid, and that of dichloramidophenol by the action
of hydrochloric acid on nitrosophenol, are also cases in point.
Ch. B.
Aromatic Products of the Animal Body. By E. Baumann
{Ber., 13, 279 — 285). — Hydroparacoumaric acid being the first, and
tinder the conditions given by the author {Ber., 12, 1452), the final
ORGANIC CHEMISTRY. ()49
putrefaction product of tyrosine, putrefaction affords a convenient
method of preparing- it. 20 grains of tyrosine thus yield 12 grams of
hydroparacouniaric acid. Salkowski has shown {Ber., 13, 189) that
when it occurs amongst the decomposition-products of albamin, it is
also derived from previously-formed tyrosine.
The homologous parahydroxyphenylacetic acid is also generated
during the digestion of albumin, and may be detected in the uriiie by
evaporating 5 — 10 c.c. with hydrochloric acid to remove phenols, and
extracting with ether. With Millon's reagent the ethereal extract gives
the red colour characteristic of hydroxy-acids. The acid may be pre-
pared by evaporating 25 litres of urine to 1-^ litres, strongly acidifying
with acetic acid and shaking with ether, a little alcohol being added to
decompose the emulsion which frequently forms. The extract, freed
from acetic acid, is again dissolved in water and exhausted with ether.
The portion of this second exti'act, soluble in water, gives with basic
lead acetate a precipitate of lead parahydroxyphenylacetate, from
which the acid may be liberated by sulphuretted hydrogen, and puri-
fied by crystallisation from water and benzene (m. p. 148°). About
\ gram of crude acid is thus obtained. Hydroparacouniaric acid
(m. p. 126 — 127°) is occasionally obtained from the urine by the same
jjrocess : it separates more slowly and incompletely from hot benzene
than its homologue.
Parahydroxyphenylacetic acid might be supposed to owe its origin
to an amido-acid, CsH^XOa, homologous with tyrosine, especially since
Schutzenberger has detected numerous amido-acids of the fatty series
amongst the decomposition-products of albumin ; the author shows,
however, that tyrosine alone is produced when horn-clippings are
boiled with dilute sulphuric acid.
In order, if possible, to detect some of the transition-products
between hydroparacoumaric acid and phenol (Ber., 12, 1453), o grams
of the former were administered to a man in whose urine hydroxy-
acids and phenols were normally' present only- in minute quantities.
On subsequently- examining the urine, it was found that the greater
part of the acid had been destroyed ; a small part ('8 gram) was
obtained unchanged ; and a still smaller quantity had been converted
into a phenol, obtained as an ethereal sulphate. Parahy^droxyphenyl-
acetic acid could not be detected.
That portion of the ethereal extract from urine, obtained as above
described, which was spai-iugly soluble in water, contained oily acids
which reacted with nitric acid like indole, and on prolonged contact
with putrescent substance yielded a considerable amount of skatole,
but no indole. These nitrogenous acids dissolve in hydrochloric acid,
and are resinified when boiled with it. They are probably the sources
of skatole and indole in the urine, and in decomposed albumin ; since
after either has been boiled with hydrochloric acid and the precipitated
resins removed, the bases are no longer obtained by putrefaction : and
putrescent albumin, not so far decomposed as to contain indole after
being agitated with ether, does not yield indole on further putrefac-
tion ; whilst the ethereal extract, when neutralised with sodium
carbonate and diluted with water, yields that base on standing in the
incubator lor six days. Ch. B.
050 ABSTRACTS OF CHEMICAL PAPERS.
History of Phenylacetamide. By A. Bernthsen {Ber., 13, 817)
* — Referring to Reimer's paper in Ber., 13, 741, the author states that
phenylacetamide (alphatoluylamide) was prepared by Weddige
(Sta3del's Jahresb., 1873, 324), and by himself {Annalen, 184, 294 and
316) from benzyl cyanide, G. T. A.
Phlobaphene. By C. Bottingee (Annale?i, 202, 2G9— 287). —
Phlobaphene is identical with the red substance (oak red), obtained
by boiling quercitannic acid with dilute acids ; it has the formula
(CuHio06)...H20, and forms a reddish-brown powder insoluble in most
of the ordinary solvents, but soluble to a considerable extent in solu-
tion of quercitannic acid ; it is also soluble in aqueous alkalis, yielding
a reddish-brown liquid, which absorbs oxygen. Acetican hydride at
140° converts it into triacetylphlobaphene, CuHtOcAcs ; benzoic
chloride at 130° gives tribenzayl phlobaphene, CuHTOnBzs. On heating
with strong hydrochloric or hydriodic acid, fdilobaphene loses a mole-
cule of water and one of carbonic anhydride, and is converted into a
brilliant black powder. This substance appears to be closely related
to the body obtained by heating pyrogallol at 160 — 180° with strong
hydrochloric acid, which on analysis gives results agreeing with those
for a mixture of the two pyrogallol ethers, CsHeOs and C6H8O4, and
which also appears to be a tanning agent ; the leather it produces is
black. Schiif has shown (Annalen, 170, 43; this Journal, 1874, 270)
that tannin is the anhydride of carboxylpyrogallol, and from the
results given above phlobaphene may be regarded as the anhydride
of methylpjrogallol and carboxylpyrogallol —
C6H,(OH),<^(J^>C6H2Me.OH.
The author considers it probable that phlobaphene is the essential
tanning agent in oak bark. A. J. G.
Compounds of Phthalic Acid with Phenols. By A. Baeyer
(Annalen, 202, 36 — 140). — In a former communication (this Journal,
31, 196), the author has described several compounds belonging to
this category. In the introduction, a historical sketch is given of the
views held as regards the constitution of these compounds, which
finally led to the adoption of those given in this Journal (36, 636).
I. Triphenylmethane Grovp. — Derivatives of Diphenylphthalide. — Di-
r\ XT
pJieiiijlphthalicIe, Ph.C< q ^>C, was prepared according to Friedel
and Crafts' method (Gompt. rend., 11th June, 1877) ; it crystallises in
needles, m. p. 112°, and dissolves in concentrated sulphuric acid, form-
ing a greenish-yellow solution, becoming violet when heated.
Trij)henyJcarhinolorthocarbox)jlic acid, C(OH)Ph2.C6H4.COOH. — Its
potassium salt is formed by treating diphenyl phthalide with alcoholic
potash ; the free acid cannot be obtained as it is immediately resolved
into diphenylphthalide. It corresponds with the benzene-ortho-alco-
holic acid described by Hessert (ibid., 34, 419).
Triphenyhnethanecarbnxylic acid, CHPho.Ceili.COOH, is prepared by
reducing the sodium salt of the above acid with zinc-dust : its forma-
ORGAXIC CHEMISTRY. 6ol
tion is expressed as follows : C(OH)Ph2.C6Hi.COOH + H, =
CHPho.CeHi.COOH + HoO.
Acids precipitate it frora the solutions of its salts, and it crystallises
from alcohol in large needles (m. p. 155 — 157°). On exposure to the
air or by treatment with chromic acid, it is converted into diphenyl-
phthalide. Triphenylmethanecarboxylic acid is insoluble in water,
easily soluble in ether and glacial acetic acid, dilute alkalis and alka-
line carbonates dissolve it ; it is soluble in hot concentrated alkalis,
and on cooling the salt separates out. When heated with baryta, it
yields phenylmethane, which crystallises in needles (m. p. 92"o°),
and on oxidation yields triphenylcarbinol (m. p. 159°), which was
converted into rosaniline by E. and 0. Fischer's method (ibid., 34,
384).
II. Anthracene Derivatives of Diphenylplithalide. By A. Schellinger
{Annalen, 202, 54 — 65). — Phenijlanthranol, Ph.Cr ^C.OH, is
obtained by treating triphenylmethanecarboxylic acid with concentrated
sulphuric acid, phosphorus pentachloride, or phosphoric anhydride. It
crystallises from alcohol in yellow needles (m. p. 141 — ■144°); when
strongly heated a portion distils, whilst the greater portion carbonises.
Hot alcohol, light petroleum, and acetone dissolve it, forming yellow
solutions, froia which it separates on cooling. It is easily soluble in
ether, forming a greenish-yellow fluorescent solution. Cold dilute
alkalis or alkaline carbonates do not dissolve it, whereas on warming
they dissolve it, forming yellow solutions, from which acids separate
a yellow flocculent precipitate. Its composition and properties show
it to be a phenyl derivative of the anthranol described by Liebermann
and Topf (£'er., 9, 1201).
Moiiacetophenijlanthranol, C20II13.OAC, is prepared by heating phenyl-
authranol with acetic anhydride ; alcohol, ether, benzene, and acetone
dissolve it easily, forming blue fluorescent solutions. Concentrated
sulphuric acid decomposes it into its constituents, whereas it is but
slightly acted on by dilute alkalis or alkaline carbonates. From alco-
hol, it crystallises in tufts of yellow needles (m. p. 165 — 166°).
C TT
Phenyloxanthranol, Ph(OH)C<^p*'TT*>CO, is prepared by oxidising
phenylanthranol in glacial acetic acid solution with potassium di-
chromate. On diluting the solution with water, it separates as a white
curdy precipitate. It is insoluble in water, but alcohol and similar
solvents dissolve it easily ; water precipitates it from its alcoholic
solution in colourless shining leaflets. It crystallises from glacial
acetic acid in colourless, acute, rhombic plates, which redden on expo-
sure to the air, and melt at 208°. It dissolves in concentrated
sulphuric acid with an intense purple-red colour ; when heated, it
becomes blue, the solution producing a strong absorption-band between
the blue and green, and two weaker ones in the yellow. When heated
further, it becomes violet ; these colorations are probably due to the
formation of sulphonic acids. It is related to phenylanthranol in the
same way that anthraquiuol is to anthranol. A monacetoxyl derivative
652 ABSTRACTS OF CHEMICAL PAPERS.
seems to be produced when plienyloxanthranol is heated with acetic
anhydride in sealed tubes at 180°.
CeHi
FhenylantJiracene, PhC^^ 7CH, is prepared by heating phenyl-
CbHj
antbranol, diphenylphthalide, on triphenylmethanecarboxylic acid with
zinc-dust. Alcohol, ether, benzene, carbon bisulphide, and chloroform
dissolve it easily on warming, forming solutions having a blue fluores-
cence, and from which it separates in yellow leaflets (m. p. 152 — 153°)
on cooling. Concentrated sulphuric acid dissolves it forming a yellow
solution, which, on heating, becomes brown. When heated, phenyl-
anthracene distils. Like anthracene, it forms a compound with picric
acid, and on oxidation yields phenyloxanthranol.
Phenyl an th/racene di/iydride, C20H16, may be prepared by reducing
phenylanthracene with hydriodic acid, or by the action of the same
reagent on phenyloxanthranol at 150 — 170°, or on triphenylmethane-
carboxylic acid at 180 — 200°. The product of these reactions is
extracted by ether, shaken up with sulphurous acid, and the ethereal
solution evaporated. By dissolving the residue in alcohol and evapo-
rating, it is obtained as an oil, which solidifies to a crystalline mass
(m. p. 120 — 120'5°) ; it may be distilled without decomposition. Its
properties are similar to those of anthracene dihydride (Graebe and
Liebermann, Amialev, Supp. 7, 265), save that it forms a compound with
picric acid, which may be due to the presence of a little phenylanthi-a-
cene. It dissolves in the same solvents as phenylanthracene, the
solutions exhibiting a blue fluorescence. On oxidation it yields
phenyloxanthranol. By the further action of hydriodic acid, higher
hydrides are formed.
By treating the solution of phenyloxanthranol in concentrated
sulphuric acid with benzene, a compound, CoeHigO, is formed,
thus : — CooHuOj + CgHs = CoeHigOo + H2O. It crystallises from alco-
hol and benzene in colourless crystals. Phenol forms a similar com-
pound.
III. Conversion of Biplienylplitlmlide into PhenolphtJialem.— This
conversion was effected, as has been stated (this Journal, 36, 636),
by the replacement of the nitro-groups in dinitrodiphenylphthalide by
two hydroxyl groups.
Dinitrodiphenylphthalide, C2oHio(N02)302, is prepared by dissolving
the phthalide in concentrated nitric acid : water precipitates it from
this solution in amorphous flocks. It separates from hot methyl alco-
hol in the form of oily drops, which solidify and melt at 75—95°. It is
probably a mixture of isomeric nitro-derivatives. When heated with
concentrated sulphuric acid it yields a body resembling alizarin.
Diamidodiphenylphthalide, CM^ ! CO C(C6H,.NH;)2, is prepared
^0^
by the reduction of the nitro-derivative, and the free base precipitated
ironi its salts by sodium carbonate. It (crystallises from alcohol in
thick lustrous plates, melting at 179—180°. The alcoholic mother-
liquors on evaporation yield a small quantity of another body in the
form of crusts melting at 205". The chief product, viz., that meltino-
ORGANIC CHEMISTRY. . 053
at 170 — 180°, is easily soluble in alcohol and ether (in the crystalline
state less soluble than when amorphous) ; it is sparingly soluble in ben-
zene and water, and insoluble in light petroleum. When heated with
concentrated sulphuric acid, it gives anthraquinol. It dissolves in
glacial acetic acid with reddish -violet colour, but its solution in hydro-
chloric acid is colourless.
When heated with methyl alcohol and hydrochloric acid at 180°, it
gives a green colouring matter, apparently identical with that obtained
by 0. Fischer by the action of dimethylaniline on phthalyl chloride, and
is probably tetrametbyldiamidodiphenylplithalide, C3oHi202(NMe2)2.
Nitrous acid converts the diamidophthalide into phenolphthalein.
IV. Triphenylmetliane Derivatives of Phenolphthalein. — The method
of preparing phenolphthalein by the action of sulphuric acid on phenol
and phthalic anhydride has been already described (Ber., 9, 12.30) ;
it may also be prepared by heating 1^ parts of phthalic anhydride,
2 of phenol, and 2^ of tin chloride at 11-5 — 120 . The hot melt so
obtained is poured into water, and washed with hot water until all
phenol is removed. The residue is then ti'eated with soda, and the
phthale'iu precipitated from the violet solution by means of acetic acid
and a little hydrochloric acid ; it separates out as a yellowish-white
sandy powder, which is purihed by precipitating its alcoholic solution by
water, part separates out in a i-esinous form, after removal of which
the phthale'in separates out in large crystals. These crystals, which
may also be obtained by dissolving it in water or hydrochloric acid at
150 — 200", are lance-shaped, and the measurements show them to be
triclinic. Phthale'in is easily soluble in alcohol, methyl alcohol, or
glacial acetic acid, and crystallises from these solutions in scales.
Ether dissolves amorphous phthale'in easily, but when crystallised
it is only sparingly soluble. It melts at 25(3 — 253", forming a colour-
less liquid, which solidifies to a vitreous mass at 217 — 210°. By
stronger heat, it is decomposed, with liberation of phenol. Concen-
trated sulphuric acid dissolves it, forming a yellow-red solution, from
which it is precipitated by water. Heated with sulphuric acid at 100',
a sulphonic acid is produced, whereas at 200°, oxyanthraquinol is
formed. Nitric acid yields a nitro-derivative ; no dinitro-derivative
has been obtained.
Phenolphthalein forms unstable salts ; caustic alkalis and altaline
carbonates dissolve it, forming reddish-violet solutions, vvhich have an
absorption-spectrum between the green and yellow. These solutions
are decolorised by an excess of caustic alkali, and the colour restored
by addition of acid, showing that phenolphthale'in might be used in
alkalimetry. It is also dissolved by ammonia ; on boiling, the ammo-
nia is expelled and the phthale'in separates out. Alum and copper
salts precipitate unaltered phthale'in from its alkaline solutions. The
silver salt is obtained as a violet amorphous precipitate, which on
heating becomes crystalline and then decomposes.
DiacetoxylijhenoljjhtlLaleiii, CioHi20i(Ac).), has been already described
{loc. cit.).
The methyl salt of phenol2jhthale'in has been obtained by heating 1 part
of phthale'in, 0"5 of potash, and 3 of methyl iodide, with alcohol at.
lUO° ; it is a crystalline compound.
()54 ABSTRACTS OF CHEMICAL PAPERS.
Chloride of phenolphthale'in or dichlorodiphenyJphthaUde, C20H12O2CI0.
— To the description (loc. cit.) already given of this body is added
that when boiled with concentrated sulphuric acid, it yields a com-
pound, apparently a dichloro-anthraquinol, which when fused with
soda yields alizarin.
Dichlorodipheni/Jcnrhinoharhoxylic acid. — Its potassium compound is
produced by the action of alcoholic potash on dichlorodiphenyl-
phtbalide. The acid cannot be prepared, as the dichloi'ophthalide
separates out on acidifying ifs alkaline solution.
Phenolphthalein dissolves in concentrated sulphuric acid, and if the
sohition is heated on a water-batli, sulphonic acids are formed; when
heated strongly, decomposition takes place, phtbalic anhydride and
phenolsnlphonic acid being formed, which react at 200° to form oxy-
and erythroxy-anthraquinone.
Tefrab ram opli oioljjhf hale'in, C2()He,Br404. — The preparation of this body
lias already been described (loc. rdt.) ; it crystallises in short prisms,
melting at 220 — 230°. Its behaviour with caustic alkalis is similar to
that of pheuolphthalem ; it is, however, a stronger acid than this
body, and its solutions in alkalis have a deeper violet colour. Alum
and copper salts precipitate the bromophthale'in from its solutions in
alkalis ; lead salts give a white lead compound, and silver salts a
Ijluish-violet pi'ecipltate of a silver compound. It dissolves in concen-
trated sulphuric acid with a light red colour, and is reprecipitated by
water ; when strongly heated with sulphuric acid, it gives dibromoxy-
anthraquinone. Oxidising agents, such as nitric and chromic acids, form
violet solutions containing a quinone. By the action of nitrous acid,
part of the bromine is replaced by nitro-gi*oups._
DiacetotetrahromophenoJphthalein., C2oHJ3r404Ac2, obtained by the
action of acetic anhydride on tetrabromophthale'in, crystallises from
alcohol in globular crystalline masses (m. p. 13-1;°) ; when carefully
heated it may be distilled. With sulphuric acid, it behaves similarly
to the bromophthalein.
FhenolpJithalin, a dioxytriphenylmethanecarboxylic acid,
CHCCsHi.OHjj.CeHi.COOH,
is prepared from phenolphthalein in the same way as triphenyl-
methanecarboxylic acid is from diphenylphthalide. It crystallises
from water and alcohol in concentrically grouped needles (m. p. 225°),
which are more soluble in water than phthalein. It is unacted on by
zinc and soda, also by zinc and hydrochloric acid in presence of alco-
hol. Phosphorus and hydriodic acid yield resinous products, whereas
with sodium amalgam, in presence of an acid, it forms phenolphthalol.
The phthalin has marked acid properties ; it dissolves barium carbo-
nate, and gives colourless solutions with alkalis, which are coloured red
by potassium ferricyanide and permanganate, owing to the formation
of phthalein. The aqueous solutions of the phthalin give a colourless
flocculent precipitate with lead acetate ; its aramoniacal solution, freed
from excess of ammonia, gives a blue precipitate with copper salts,
and a white flocculent precipitate with silver nitrate, the latter is
soluble in excess of ammonia. With sulphuric acid, the phthalin
yields the following characteristic reaction ; it dissolves forming a
ORGANIC CHEMISTRY. 655
rpcldish-vellow solntion and on addition of water greenish-yellow flocks
of phthalidin separate out. The solution in sulphuric acid gives
a dark green when manganese dioxide is added to it, and the solu-
tion after dilating with water, yields phthalidein on extracting it with
ether.
DiacetophenolphthaUn, C24H00O6, crystallises from alcohol in colour-
less needles (m. p. 146°). Glacial acetic acid dissolves it largely ; it
is sparingly soluble in cold, more easily in warm alcohol.
Chloride of Phenol pJithaJ in, oi.-Dichlorotriphenylmet}ianecarhoxylic Acid,
CH(C6H4Cr)..C6H4.COOH.— This body cannot be prepared by the
direct action of phosphorus pentachloride on phenolphthalin, but is
obtained by reducing the chloride of the phthale'in with hydriodic
acid, or zinc-dust and soda. Prepared by the former method, and
crystallised from glacial acetic acid, it forms colourless crystals (m. p.
195°) ; whilst by the latter method, and crystallisation from alcohol,
it is obtained in fern-like masses of needles (m. p. 205—200°).
Alcohol, ether, and acetone dissolve it easily ; it ci'ystallises from alco-
hol in six-sided tablets. It dissolves easily in alkaline carbonates and
caustic alkalis, forming salts which are sparingly soluble in alkaline
solutions. Warm concentrated sulphuric acid dissolves it, forming
yellow solutions, which rapidly change to green, blue, and finally
violet. This latter colour is produced instantaneously on adding
potassium dichromate, and is due to the formation of dichlorophenyl-
anthranol.
Tetrabromphenolphthalin, CH(C6H.2Br2.0H)...C6H4.COOH, may be
prepared like the phthalin by reduction of the brominated phthalein,
or better still by treating the phthalin in acetic acid solution with
bromine. It crystallises in compact needles (m. p. 205°) ; is easily
soluble in alcohol, methyl alcohol, acetone, glacial acetic acid, carbon
bisulphide, and ether ; it is soluble in warm, and sparingly in cold
benzene, and also sparingly soluble in chloroform. It dissolves slowly
in concentrated sulphuric acid with reddish-yellow colour, which
becomes green owing to the formation of tetrabromophthalidin.
TJiacetyltetrahromophtlialin, CooHnBrjOiAco, crystallises in stellate-
grouped needles, melting at 165 — 166°.
Phenolphthalol, C04H1SO3, is prepared by reducing the phthalin with
sodium-amalgam and acetic acid until the solution, after acidifpng
with sulphuric acid, ceases to yield a fluorescent solution on extraction
with ether. It crystallises from dilute acetic acid in large prismatic
crystals, and from water, in which it is sparingly soluble, in lance-
shaped crystals. Alcohol, ether, and acetone dissolve it easily, whilst
it is insoluble in benzene or chloroform. It melts at 190°, and may be
distilled. Its alkaline solutions, which are colourless, are oxidised by
potassium ferricyanide, the phthalein being formed. Its formation
from the phthalin is expressed as follows : —
CH(C6Hi.OH)2.C6H,.COOH + 4H = CH(C6H4.0H).,.C6H4.CH2.0H
It is therefore an alcohol, and, like aromatic alcohols when treated
with concentrated sulphuric acid, it yields condensation-products. The
existence in it of three hydroxyl-groups is shown by the formation of
656 ABSTRACTS OF CHEMICAL PAPERS.
ji triacetyl derivative, CzoHigOjAca, a vitreous mass (m. p. 40°) capable
of beintJ- distilled. It is insoluble in water, bat soluble in alcohol,
ether, and benzene.
V. Phenylanthracetie-derivatives of Fhenolplithalein. — Phenolj^hthali-
dln, a.dloxyphenylav.thrmiol, C20H14O3. The production of this body has
already been described (Ber., 9, 1234). By long-continued action of
concentrated sulphuric acid, it is converted into sulphonic acids.
Heated with sulphuric acid at 120°, it forms a dark-green solution
wliich, on boiling, becomes red. Its formation is similar to that of
phenylanthranol from triphenylmethanecarboxylic acid, and to it is
Cell,
assisfned the constitutional formula: OH.C^- ^C.C6B4 0H.
CeHs.OH
TetrahromojyMhalidin, OH.C^^ ^C.CeHaBrj.OH. This body is
CeHBr^.OH
produced in a similar manner to the above (loc. cit.}. It dissolves in
potash solution with a yellow colour, and on warming, the potassium
salt separates out in green crystals. It is soluble in concentrated
sulphuric acid with a green colour, which changes to blue when heated
at 130 — 140°, owing to the formation of tetrabromophthalidein. This
latter body is also formed by the action of oxidising agents. Bromine
acts on it, forming a compound which is decomposed by water into
bromophtbalide'in.
JJiacetotetrahromopJifhalidin, CjoHiiBriOsAco, crystallises from gla-
cial acetic acid in long hair-like needles. It is easily soluble in chlo-
roform, benzene, and carbon bisulphide, forming a green fluorescent
solution ; water, alcohol, and glacial acetic acid dissolve it but
sparingly. It melts at 256° ; when heated above its melting point it
yields bi'omophenol.
Plienolphtlialidm GJdoride, a-Dicldoropliemjlantliranol, CnoHioCUO. —
It cannot be prepared by the action of phosphorus pentachloride on
the phthalidin, but is obtained by reducing the phthalidein chloride
with zinc and acetic acid, and is precipitated by water from the
filtered solution as a yellow powder; it melts at about 170°, and may
be distilled in small quantities. Alcohol and glacial acetic acid dis-
solve it sparingly, and it crystallises from these solutions in needles.
With ether or acetone, it forms a bluish-green fluorescent solution,
and it is easily soluble in benzene and carbon bisulphide. Concentrated
sulphuric acid dissolves it, forming a reddish-yellow solution, from
which water precipitates it. Bromine and oxidising agents convert it
into the phthalidein chloride.
FhenolhydrophthaUdin chloride, OH.HC<^^JJVi >CH.C6H4Cl, is
obtained by the reduction of an alcoholic solution of phthalidin chlo-
ride with sodium-amalgam. It is easily soluble in ether, acetone,
chloroform, and carbon bisulphide, sparingly in cold alcohol, methyl
alcohol, and glacial acetic acid, but more easily when warm. It melts
at 50% and may be sublimed. By the action of concentrated sulphuric
ORGAXIC CHElVnSTRY. 657
acid, it forms condensation-products, dissolving with a yellow, then
red coloration; from this solution, ether extracts a body differing from
the phthalidein chloride. Phenolhydrophthalidin is obtained by re-
ducing the phthalidein with zinc-dust and soda, or its alcoholic solution
by zinc and hydrochloric acid. It cannot be obtained in a crystalline
state ; concentrated sulphuric acid converts it into a red condensation-
product, and it is oxidised by potassium permanganate to the phthali-
dein. Bromine converts it into the tetrabromophthalide'in. Sodium-
amalgam and acetic acid reduce it to the phthalol.
Phenol phthalidein, tetrahromophthalidevn, and their derivatives have
already been described (ibid., 123o — 1288). These compounds which
are formed by the oxidation of the corresponding phthalidins, the
author regards as derived from phenyloxyanthranol : phenolphthali-
dein being dioxyphenyloxanthranol, having the formula —
oc<aH:fdH)>c(OH).c.H,.oH.
It contains tTiree hydroxyl-groups, one of which is, as in the case of
phenyloxanthranol, with difficulty acted upon by acetic anhydi'ide.
YI. Action of Ammonia on Phenolphthaleln and its Derivatives. By J.
B. Burkhardt"(yl?wa?ew. 202, 111— 135).— The results of the action of
ammonia on phenol phthale'in, viz., the formation of diimidophenol-
phthale'in, &c., have been described in this Journal (34, 866).
Ammonia has no action on phenolphtbalin ; the brominated deriva-
tive, it decomposes at 160 — 200°, forming bromophenol. It reacts
with the phthalidin, forming the phthalidein, which latter is reduced
by alcoholic ammonia, whereas by aqueous ammonia it is converted
into a brown insoluble body. The tetrabromophthalidin is decom-
posed by ammonia at 200° into bromophenol.
By the action of alcoholic or aqueous ammonia at 150 — 160° on the
phenol compounds of phenolphthalide'in (Ber'., 9, 1237), a body is
obtained crystallising from a mixture of acetone and water in pale
yellow needles (m. p. 260°), which are easily soluble in methyl and
ethyl alcohols, but sparingly soluble in chloroform, benzene, and carbon
bisulphide. It has no basic properties ; its solution in alkalis is colour-
less, whereas it dissolves in concentrated sulphuric acid with a blue
colour. Its composition appears to be C20H15NO3.
VII. Oxidation of Tetrabromophenolphthalein . By C. Schraube
(AnnaJen, 202, 121 — 126). — An account of the formation of the
C IT Br
bromoquinone to which the constitutional formula, <^p^ p. "t. ^^Ojjis
attributed, has already appeared in this Journal (34, 869).
YIII. Fusion of Phthale'in and Phthalidein Derivatives vntJi Potash.
By J. B. Burkhardt (Avnalen, 202, 126— 135).— Phenolphthalein
when fused with potash yields dioxybenzophcnone {ibid., 34, 886) ;
the phthalidin and phthalidein yield the same product. The phthalin
is acted on by potash at high temperatures only, and does not yield a
dioxybenzophcnone.
Tetrabromodioxybenzophenone, CO(C6H2Br2.0H)2, is obtained by
658 ABSTRACTS OF CHEMICAL PAPERS.
treating the alcoholic solution of dioxybenzophenone with bromine ; it
is insoluble in water, chloroform, and carbon bisulphide, and sparingly-
soluble in alcohol, glacial acetic acid, methyl alcohol, and ace+one. It
crystallises in long needles or prisms (m. p. 213 — 214°), and maybe
distilled without decomposition. Alkalis dissolve it, forming colour-
less solutions. When fused with potash it yields a phenol-like com-
pound, which is coloured green by ferric chloride ; the tetrabromo-
phthale'in yields the same body. The existence of two hydroxyl groups
in bromodioxyphenone is shown by the analysis of its acetyl-deriva-
tive and of its barium salt, obtained by treating its ammoniacal solution
with barium chloride.
Bioxyleiulujdrol. — This unstable body appears to be formed by the
reduction of an aqueous solution of dioxybenzaphenone by sodium
amalgam. Since it cannot be obtained in the pure state, the solution
after reduction is acidified and the product treated at once with acetic
anhydride. Thus a compound is obtained^ apparently tetracetodioxy-
benzhydrol, (C6H4.0Ac)oHC.CH(aH4.0Ac)2. It is insoluble in
water and light petroleum, easily soluble in hot alcohol and benzene.
When heated, it is decomposed. Its dark-red solution in concentrated
sulphuric acid exhibits thick absorption- bands between the blue and
green, and when heated assumes a brownish-red tint. It is decomposed
by boiling potash.
IX. Formation of Oxyaiitlirnquhwne from PhenolpJdhalein. — An ac-
count of this has been already given (Ber., 7, 968). Further, the
formation of dibromoxyanthraquinone from tetrabromopbenolphtha-
le'in, and its conversion into alizarin, has been described by the author
(ibid., 9, 1231). Dibromophenol, which is formed at the same time,
may be prepared by distilling the tetrabromophthalein with concen-
trated sulphuric acid, diluting the distillate with water, and extract-
ing with ether. The quinone is removed from the ethereal solution by
means of lead acetate, and thus a dibromophenol is obtained melting
at 65 — 56°, differing from 1.2.4 dibromophenol, which melts at 40°.
Fraude (this Journal, 36, 634) has shown that orthocresolphthalein
yields only a dibromo-dei-ivative ; from which the author concludes that
the methyl-gi'onp in orthocresolphthalein occupies the position which
the second bromine atom takes in tetrabromophenolphthalein. Again,
Fraude has obtained from orthocresolphthalein a brommethylhydroxy-
anthraquinone, yielding methylalizarin. Therefore the bromine atom
in this quinone is in juxtaposition to the hydroxyl-group, and hence
in tetrabromophenolphthalein both the bromine atoms are next to the
hydroxyl-groups. So dibromophenol had the constitution CeHaOH.Bro
[1.2. 6], and dibromhydroxyanthraquinone —
Br
CH C
/\ /\
HC C— CO— C COH
II II
HC C— CO— C CBr
\y \/
CH C
P. P. B.
I
ORGANIC CHEMISTRY. 659
Phenylthiocarbimide-glycollide. By C. Liebermaxx and M.
VoELTZKOW (Ber., 13, 270 — 27'J). — The experiments of Liebermanu
and Lange (Ber., 12, 1588) have shown that in thiohjdantoin and its
derivatives, which by decomposition easily yield thioglvcollic acid,
HS.CHo.COOH, the residue — CHo.COOH must be directly united
with the sulphur, and not with the nitrogen ; and also that in the con-
version of thiocarbamide into thiohydantoin, the sulphur plays the
same peculiar part that it does in the formation of the alkylated
thiamides of Wallach, Bernthsen, and others, and of Hofmann's
chlorinated thiocarbimide.
To ascertain whether this reaction of sulphur is genera), molecular
weights of chloracetic acid and phenylthiourethane were heated together
with a little absolute alcohol at 160 — 170'. The following reaction was
expected to occur : —
NHPh.CS.OEt + CH,Cl.COOH = XPh : C(0Et).S.CH2.C00H + HCI,
but instead of this product the authors obtained a compound derived
from it by elimination of alcohol, to which the constitution —
XPh : c<^Q^2>co,
must be assigned. This body is soluble in alcohol and insoluble in
cold water, but crystallises from boiling water in white plates (m. p.
148°). It is identical with the compound, CgHT^SOo, which Lange
obtained by the action of Hydrochloric acid on diphenylthiohydantoin.
On boiling with baryta- water, it is almost quantitatively decomposed
as follows : —
CH^NSOs + 2BaHoO. = S.CH^.COOBa + BaCOa + C6H;X -t H,0.
It may therefore be regarded as an addition-product of phenylthio-
carbimide with glycollide, and may be named phenylthiocarbimide-
glycolide. It cannot be directly formed from these bodies, but is very
easily produced when phenylthiocarbimide and chloracetic acid (or
ethyl chloracetate) are heated togetherwith a little alcohol at 160 — 170°.
In this reaction, however, phenylthioui-ethane may be formed as an
intermediate product : and in fact a different reaction appears to occur
when ether is substituted for the alcohol.
An isomeride of this body, acetoxythiocarbimide, has been obtained
by Hofmann. The two bodies have different characters : the con-
stitutional difference between them is shown by the action of alkalis,
whereby the latter is decomposed into oxythiocarbimide and acetic acid
(Ber., 12, 1126). Ch. B.
Isoindole. By W. Staedel and F. Kleinschmidt (Ber., 13, 836—
837). — The best yield of bromacetylbenzene, Ph.CO.CHzBr, is obtained
by allowing bromine to drop slowly into a solution of acetophenone
(m. p. 205°, not 16^ as generally stated) in carbon bisulphide. A rapid
current of carbonic anhydride is passed through the solution, d urine
the process, in order to carry off the hydrobromic acid which is
liberated. When the reaction is completed, the carbon bisulphide is
removed by evaporation, and after expelling the hydrobromic acid by
060 ABSTRACTS OF CHEMICAL PAPERS.
a stream of cai'bonic anhydride, the residue consists of crystals of pure
bromacetylbenzene (m. p. 50°). Isoindole is obtained in dark-red
crystals by the action of alcoholic ammonia on the preceding com-
pound at "the ordinary temperature. A vapour-density determination
at a temperature of 500° gave G'o instead of 4*05 for CgH^N.
w. c. w.
Carbazol. By C. Graebe (Annalen, 202, 19 — 23). — When crude
anthracene is purified by distillation over potash (Perkin, Journ. Soc.
Arts, 1879, 339), the residue consists chiefly of a compound of potas-
sium and carbazol, (C6H4)2NK, which is also obtained by heating car-
bazol and potash together at 220 — 240°. Water decomposes it into
potash and carbazol. Soda forms a similar compound ; the action is,
however, less complete. P. P. B.
Some Derivatives of Carbazol. By C. Graebe and B. v.
Adlerskron (Amiule)i, 202, 23 — 27). — Metlujlcarhazol, (Cr,H4);NMe,
is prepared by heating carbazol, potash, and methyliodide in sealed
tubes at 170 — 190°. It crystallises from hot alcohol in white lustrous
leaflets; from dilute solutions, it separates out in needles (m. p. 187°).
It is insoluble in water, sparingly in cold, and easily soluble in hot
alcohol. Ether dissolves it easily. It does not form salts, and with
concentrated sulphuric and nitric acids, yields the same coloration as
carbazol. With picric acid, it forms a compound, (C6H4)2NMe +
C6Ho(N02):iOH, crystallising in dark-red needles, easily soluble in
alcohol, and melting at 141°.
Ethijlcarbazol, (C6H4)2NEt, is prepared in a manner similar to the
methyl-derivative ; it crystallises from ether, in which it is easily
soluble, in leaflets (m. p. 67 — 68°); cold alcohol dissolves it sparingly,
hot alcohol more easily : it is insoluble in water. Its picric acid com-
pound forms light red needles (m. p. 97°) ; easily soluble in alcohol.
EthylcarbazuUne is prepared by the action of ethyl iodide on car-
bazolineand alcohol at 100° ; it cannot be prepared from ethylcarbazol,
since phosphorus and hydriodic acid by their action regenerate car-
bazol. Ethylcarbazoline iodide, CioH,4N.EtIII, crystallises in large
thick tables, easily soluble in_hot water.
Acetylcarbazolive, CnHuNAc, formed by heating carbazoline with
acetic anhydride at 100 — 120°, crystallises from alcohol in beautiful
white needles (m. p. 98°). Alcohol and ether dissolve it easily. Ferric
chloride and chromic acid attack it less easily than carbazol.
Tdranitrocarhazol, Ci2H5(N02)4N, is prepared by adding carbazol
to nitric acid and heating the mixture on the water-bath. It is in-
soluble in alcohol, ether, and benzene, but soluble in glacial acetic acid,
from which it crystallises in yellow crystals. It forms a. potassium
compound which is insoluble in water, and is decomposed by acids.
P. P. B.
Chloro-derivatives of Carbazol. By W. Ktvecht {Annalen, 202,
27 — 37). — Trichlorocarbazol, CioHcCIsN", is obtained bypassing chlorine
into a solution of cai'bazol in glacial acetic acid until it assumes a
green colour, and then precipitating it with water. It crystallises
from benzene in greenish needles (m. p. 180°) easily soluble in
benzene, ether, alcohol, and chloroform. It sublimes in needles, and
ORGANIC CHEMISTRY. 661
distils at a tempoi'ature near the boiliu^ point of snlpliur ; by long--
continued heating' near its boiling point, it is decomposed with,
generation of carbazol. Hydrochloric acid dissolves it with a green
colour, which is darkened on addition of niti'ic acid, and disappears
when warmed. With picric acid it forms an unstable compound,
crystallising in red needles (m. p. 100°).
Hexcklorocarbazol. CioHsCleN". — By the continued action of chlorine
CD a solution of carbazol in glacial acetic acid, the solution becomes
red, and the addition of water then precipitates this compound. It
crystallises from benzene in long yellow needles, melting at 225° with
decomposition. It is easily soluble in benzene, and less soluble in
alcohol and glacial acetic acid. It can neither be sublimed nor dis-
tilled. Concentrated sulphuric acid dissolves it, forming a green-
coloured solution in which traces of nitric acid produce a blue
coloration, changing to violet, red, and finally yellow.
Octochlorocarbazol, doClgNH, is formed by treating the hexachloro-
derivative with antimony perchloride ; it crystallises from benzene in
beautiful white needles (m. p. 275°). It is easily soluble in hot
benzene, and sparingly soluble in cold alcohol, ether, and glacial acetic
acid. When suspended in sulphuric acid and treated with nitric acid,
it yields a blue coloration, and finally a golden yellow.
The final product of the action of antimony perchloride on octo-
chlorocarbazol is perchlorobenzene. P. P. B.
Amidotriphenylmethane. By 0. Fischer and L. Eoser (Ber.,
13, 674 — 676). — The previously unknown modification of amidotri-
phenylmethane is obtained by digesting benzhydrol Avith aniline
hydrochloride and zinc chloride at 150°, thus: —
CHPho.OH + NH,Pli = H,0 + CHPh^.CeH^J^Ho..
It crystallises from ether and light petroleum in prisms or plates
(m. p. 84°), and forms a compound with benzene, C19H17N" -|- CgHfi ;
this crystallises in colourless needles which melt partially at 69""
with loss of benzene. The platinocMoride, Ci9HnX.HCl)2.PtCh, is a
yellow crystalline precipitate, which is only sparingly soluble in hot
water. The sulphate, chloride, and nitrate crystallise in pearly needles,
which are scarcely soluble in water or alcohol. The methiodide,
C20H24NI, obtained by heating the free base with methyl iodide and
methyl alcohol at 100°, crystallises in colourless plates (m. p. 184°),
and i(s identical with the compound obtained in a similar manner from
dimethylamidotriphenylmethaue. T. C.
Diamidotriphenylmethane. By 0. Fischer (Ber., 13, 6G5—
669). — In the author's first experiment {ibid., 12, 1693) only a small
quantity of this compound was obtained by the action of benzalde-
hyde on aniline hydrochloride, in presence of zinc chloride, the chief
product being a resinous mass. This latter consists essentially of a
compound of diamidotriphenylmethane with benzaldehyde, which, on
boiling with dilute sulphuric acid, splits up into the above consti-
tuents; the aldehyde distils ofP, whilst the diamido-compound crys-
VOL, XXXYIII. 3 a
.<3(i2 ABSTRACTS OF CHEMICAL PAPERS.
tallises out as the sulphate. An improved method, depending on this
fact, is described for obtaining the base in larger quantities.
Diamidotriphenylmethane forms a colourless compound with ben-
zene, C.gHisN., + C«H« (m. p._ 106°), wlucb, on heating to 110° or by
tbe action of acids, splits up into benzene and the free base. The ben-
zene compound is yerj soluble in light petroleum. The free base
crystallises in colourless nodules (m. p. 139"), which are easily soluble
in ether, alcohol, chloroform, and light petroleum. Tbe sulphate is
only sparingly soluble in absolute alcohol, and crystallises from dilute
alcohol in colourless needles. The 2)lat'7iorJiI or id e, Ci9HisN2.2HCl.PtCl4,
is easily soluble in water and in alcohol, but only sparingly soluble in
ether. The free base is converted into triphenylmethane when treated
according to E. and O. Fischer's method (Annalen, 194, 270), and by
the diazo-reaction it gives apparently dioxytriphenylmethane. On
oxidation, it gives a colouring mafcter, which is bluer than methyl
violet. The free base is identical with Bottinger's diamidotriphenyl-
methane (Ber., 11, 27(3, 840; ibid., 12, 975; this Journal (1878),
Abstr., 506, 723; (1879), Abstr., 716). His melting point (75°),
however, was incorrect, owing to the presence of impurities.
T. C.
A New Triamidotriphenylmethane (Pseudoleucaniline). By
0. Fischer and J. Ziegler (Ber., 13, 671 — 674). — Metanitrobenz-
aldehyde, when digested with aniline hydrochloride and zinc chloride
at 100°, is converted into a new nitro-base, which is purified by means
of its benzene compound, C19H17N3O2 + CeHg. The latter separates
from solution in benzene in the form of lemon-yellow crystalline
groups (m. p. 81^). It is nearly insoluble in water, very easily soluble
in ether and alcohol, less so in benzene, and only very sparingly
soluble in light petroleum. The free nitro-base, C19H17N3O2, is ob-
tained by heating its benzene derivative at 110 — 120°. It consists of
pale yellow crystals (m. p. 136°), and on heating with an excess of
methyl iodide and methyl alcohol at 110 — 115°, it gives the compound
C23H25N302.2Mel, which crystallises from alcohol in needles (m. p. 225°
with decomposition, the substance becoming green), and loses the
whole of its methyl iodide at 200°. The residue appears to be con-
verted into benzaldehyde green when oxidised with manganese
dioxide and sulphuric acid (compare Ber., 12, 802). The above
methiodide is identical with the corresponding' compound of meta-
uitrotetramethyldiamidotriphenylmethane.
The nitro-base previously described gives triamidotriphenylmethane
(pseudoleucaniline) when reduced with zinc-dust and hydrochloric
acid. The benzene compound of pseudoleucaniline (CigHig^s + CeHe)
crystallises from benzene in white needles (m. p. 145°, with the pre-
vious evolution of gas). Pseudoleucaniline is obtained from its com-
pound with benzene, by boiling with sulphuric acid u.ntil all the
benzene has gone off, and then precipitating with ammonia. It crys-
tallises from ether on addition of a' little light petroleum, in brilliant
colourless rosettes, which are very apt to retain ether. After drying
at 100°, it melts at 150°. It is easily soluble in alcohol, less so in
ether, and scai'cely at all in light petroleum. It forms a methiodide,
which appears to be a raonomethylated triamidotriphenylmethane,
ORGANIC CHEMISTRY. 663
and cannot be obtained in the crystalline form. On boatincf at 200°,
it loses its methyl iodide, and leaves a residue which, on oxidation,
gives a dark screen dye-stuff. The platinochloride of pseudoleucaniline,
(CigNigNs.SHCOe.oPtCU, is a yellow crystalline precipitate, which is
very easily soluble in water, less soluble in alcohol, and still less so
in ether.
Metanitrodiamidotriphenylmethane, on oxidation with hydi'ochloric
acid at 150°, gives a fused mass, containing two dye-stuffs, which are
easily separated by means of water. The more soluble is violet, and
the other, which is obtained in larger quantity, is green. Pseudo-
leucaniline, under similar circumstances, gives only a violet dye-stuff,
which is easily soluble in alcohol and in water. By this means
pseudoleucaniline is readily distiiKjuished from paraleucaniline.
T. C.
Probable Occurrence of Furfurane (Tetraphenol) and a
Homologous Compound in the Products of the Dry Distilla-
tion of Pine Wood. By A. Atxekbekg {Ber., 13, Sru— 883).— The
low boiling poi'tion of the wood oil obtained by the dry distillation of
resinous pine wood, appears to contain tetraphenol ; the fraction boiling
at 30° seems to be a mixture of tetraphenol and valerylene, but neither
of these bodies was obtained in a pure state.
Sylvane, C4H30.Me (b. p. 63°), a homologue of tetraphenol, is con-
tained in that portion of the distillate which passes over between 59°
and 65°. It is a colourless liquid (sp. gr. 0"887), which is easily con-
verted into a resinous tarry mass. On oxidation with potassium per-
manganate, it yields acetic acid. Hydrochloric acid converts sylvane
into the compound Ci5H,,0, (b. p. 235—245°). W. C. W.
Phenylnaphthylcarbazol. By C. Geaefe and W. Knecht
{Annalen, 202, 1 — 19). — In a former communication the authors have
given some account of this body and some of its derivatives (Ber., 12,
.341), and also of its synthesis from /3-phenylnaphthylamine (this vol.,
168). Later deteiWnations show its boiling point to be about 450°.
Phenylnaphtht/IcarbazoUne, CieHisN". — This base is prepared by the
action of phosphorus and hydriodic acid on phenylnaphthylcarbazol
in sealed tubes at 200°. It is liberated from its salts by means of
ammonia, and cry.stallises from, alcohol in needles. It is easily soluble
in alcohol and ether, and but sparingly soluble in water. Hydro-
chloric acid dissolves it, forming a salt, decomposed by boiling water.
Platinum chloride produces an orange-yellow precipitate, which, on
warming, turns red, and finally brown. On oxidation, phenylnaphthyl-
carbazoline yields phthalic acid.
Phenylnaphihylcarliazoline iodide, CirHisN.HI, is prepared by dis-
solving the base in hj-driodic acid. It crystallises in long colourless
needles, which are soluble in water and alcohol, and sparingly soluble
in ether. When oxidised by potassium dichromate and sulphuric acid,
phenylnaphthylcarbazol yields phthalic acid and two qninones, viz.,
CisHjOiN and CieHgO,; these may be separated by means of sodium
carbonate, which dissolves the latter. On adding an acid or by treat-
ment with carbonic acid it may be reprecipitated.
3 a ^
664 ABSTRACTS OF CHEMICAL PAPERS.
PhenylnapMhijlcarhazoqtiinone, Ci6H9(03)N. — This body is purified by
subliming the raw product, and crystallising it from glacial acetic
acid ; it sublimes in reddish-yellow needles, resembling alizarin, and
melts at .307°. It is soluble in hot glacial acetic acid, in acetic ether
and benzene, is sparingly soluble in alcohol, and insoluble in carbon
bisulphide. It is insoluble in. alkaline carbonates, but dissolves in
caustic alkalis, forming a dark-i'ed solution, from which acids repre-
cipitate it. These solutions, when treated with zinc-dust, turn brown,
and finally yellow ; the oxygen of the air produces the opposite effect.
This quinone is oxidised to phthalic acid by potassium permanganate,
and yields phenylnaphthylcarbazol when heated with zinc-dust.
Quinone of phenylenenaplithalene oxide, Ci6H80!(03). — This body crys-
tallises from benzene in reddish-yellow prisms ; it melts at a very high
temperature, and is at the same time decomposed. It is soluble in hot
glacial acetic acid and benzene, and sparingly soluble in alcohol.
Alkalis and alkaline carbonates dissolve it, forming dark-red solutions,
from which it is precipitated by carbonic acid in reddish-yellow
flocks. When heated with zinc-dust, a compound is obtained which
crystallises in yellow leaflets, melting at .300", and having the compo-
sition CieHioO. To this compound the authors attribute the constitution
ri XT
<Cn^ ij ^0) similar to that of diphenylene oxide. Unsuccessful attempts
were made to prepare it by heating /3-naphthol and phenol with lead
oxide ; a-naphthol and phenol, however, yield a compound melting at
150°. To phenylnaphthylcarbazol and its quinone the authors attri-
CeHi CeHi .
bute the formulae | ^NH and | /NH,
CoH/ CioH/O^)''^ P. P. B.
Synthesis of Naphthyldiphenylmethane. By Y. Hemilian
(Ber., 13, 678 — 679). — A claim to priority of discovery (Jour. Buss.
Ghem. Sac, 12 [2], 4) of the above hydrocarbon over Lehue (Ber., 13,
358 ; this vol., 478). T. C.
Colouring Matters attained by the Action of Naphthol on
Diazoazobenzene. By R. Nietzki (Ber., 13, 800 — 802).— The
author claims the discovery of the colouring matter known as Biebrich
scarlet, and denies the accuracy of tlie statements of W. v. Miller
(this vol., 559) as to its composition. He will contribute a paper on
the subject. G. T. A.
Rouge Fran9ais. By W. v. Miller (Ber., 13, 268— 271).— The
dye sold under this name is a mixture of the sodium salts of two acids,
naphthol-azobenzenesulphonic acid, S03H.C6H4N3.(^)CioH6.0H, and
naphthol-azonaphthaleuesulphonic acid, SO.H.CioHsNo.dSjCioHe.OH.
The first salt is yellow ; the second red. The barium salts of both
acids are sparingly soluble. The calcium salt of the yellow acid dis-
solves easily in hot water; that of the red with difficulty. The com-
mercial product is probably formed by acting with /S-naphthol on a
diazotized mixture of sulphanilic and naphthylaminesulphonic acids.
A mixture of 30 parts of yellow salt with 70 parts red dyes the same
shade as rouge fran^ais. Ch. B.
ORGANIC CHEMISTRY. {]ij5
Fluorescence in the Anthracene Series. By C. Liebermann
(llcr., 13, 'Jlo — 91G). — An examination of solutions of the anthra-
cene derivatives in indifferent solvents shows that the property of
tluoreseenee is exhibited by those substances in which the two benzene
CM
nuclei are united by a group having the constitution<^p,^r^ (where
M represents a monad element or group of elements), but not by those
CO
derivatives containing the double ketone group<^pj^>or the group
ph.c(OH) : CO. w. c. w.
Derivatives of the Quinone from the Hydrocarbon CisHjo;
Polymeric Quinones. iiy A. Breuer and T. Zincke (Ber., 13,
tioi — Go-J). — In a previous communication (ibid., 11, 1995; this
Journal, 36, 327), it has been shown that the quinone CieHioO-i gives
a hydi'oxyimidoquinone CieHgfOH) '. (O.NH) when treated with
ammonia. Corresponding derivatives have since been obtained by
using various amines in place of ammonia.
Methylamine derivative, Ci6H9(OH) '. (O.NMe) consists of dark red
leaflets (m. p. 170°), which are but sparingly soluble in cold alcohol,
more easily in hot, and easily soluble in benzene. It dissolves in con-
centrated sulphuric or hydrochloric acid with a dark red colour, and
is precipitated therefrom on addition of water. It gives the hydroxy-
qumoue and methylamine, when heated with fuming hydrochloric
acid at 140 — 150°. It is slowly attacked by aqueous, but more easily
by alcoholic potash, with formation of the hydroxyquinone.
Uthylamine derivative, Ci6H9(OH)SO '. (O.NEt) forms dark brown
needles (m. p. 130°), which are soluble in concentrated sulphuric acid,
without change.
Aniline derivative, Ci6H9(OH) '. (OX.Ph), consists of dark red
leaflets (m. p. 158°, which are only sparingly soluble in alcohol, but
more easily in benzene. It dissolves unchanged in concentrated sul-
phuric acid, with a deep violet colour. Fuming hydrochloric acid at
150° converts it into the hydroxyquinone and aniline.
Toluidine derivatives, Ci6Hc,(0H) '. (O.NC7H7). — The ortho- derivative
is a red body, crystallising in needles (m. p. lOS''), and the para-com-
pound, a brownish- violet body, also crystallising in needles (m. p. 155°).
The ortho-compound dissolves in strong sulphuric acid with a red, and
the para-compound with a violet colour.
Naphthylamine derivative, Ci6H9(OK) '. (O.NCioH;), crystallises in
brownish-red needles (m. p. 148°) which dissolve in strong sulphuric
acid, with a violet colour. Trimethylamine, formamide, and acetamide
have no action on the quinone, whilst dimethylaraine forms only resi-
nous products. All the above compounds, when treated with reducing
agents, give colourless products, the nature of which varies with the
reducing agents employed. Zinc and hydrochloric acid, as well as
zinc-dust and an alkali, give compounds which, could not be isolated,
but on exposure to air are reconverted into the original coloured sub-
stances. They are all easily reduced by ammonium sulphide, which,
when added in excess, throws down the reduction product. The aniline
derivative under these circumstances gives colourless crystals (m. p.
|>66 ABSTRACTS OF CHEMICAL PAPERS.
290°). Reduction with aqueous sulphurous acid gives the hydroxy-
quiuone, together with a black compound, the nature of which has not
yet been fully investigated. This body crystallises from benzene or
light petroleum in dark steel-blue needles (m. p. 186°), which dissolve
in alcohol with a yellow colour, and is reprecipitated therefrom
unchanged on addition of water. Long treatment with alcohol, how-
ever, converts it into hydroxyquinone. It does not contain nitrogen,
and analysis gave 7876 per cent. C, and 4*88 per cent. H. It is pro-
bably an anhydride of the hydroxyquinone [Ci6Hi9(OH)2]20.
The authors have shown (Ben, 11, 1403 ; this Journal, 1878 ; Abstr.,
889) that solutions of the quinone Ci6Hin02, exposed to sunlight, give
two sparingly soluble compounds. These were found to be poly-
meric modifications ; they are separated by treatment with chloroforin,
in which one is more soluble than the other.
The more soluble modification crystallises in small yellow rhombic
tables (m. p. 225 — 229°) which are but little soluble in most sol-
vents; they dissolve most easily in chloroform, and in hot glacial
acetic acid. It is not easily reconverted into the ordinary form by
heat. It is not attacked by chromic mixture, and only slowly by a
mixture of chromic and glacial acetic acids, giving thereby benzoic
acid ; by potassium permanganate, it is oxidised to benzoic and phthalic
acids. By the action of alcoholic potash, it gives an almost black
compound, which, on exposure to the air and washing with alcohol,
becomes yellow, the same change being more quickly produced by water
or by warming with alcohol. This compound crystallises from glacial
acetic acid in fine yellow needles (m. p. above 300°), which are but
little soluble in alcohol, benzene, or chloroform. Analysis gave the
numbers 79"23 per cent. C, and 4"65 per cent. H., and it has thei*e-
fore the same composition as the reduction product from the amine
derivatives of the quinone (vide supra), and is probably a polymeric
modification of the same. It dissolves in alcoholic but not in aqueous
potash ; it dissolves in strong sulphuric acid, with a brownish-green
colour, whilst its solution in strong nitric acid is almost colourless ;
water precipitates it unchanged from both solvents. It is apparently
converted into an acetyl derivative by ti-eatment with acetic chloride
or anhydride, showing that it probably contains hydroxyl groups.
The less soluble polymeric modification of the quinone consists of white
leaflets (m. p. 207°), which on heating are easily converted into the
ordinary quinone. It is not attacked either by potassium perman-
ganate or by chromic mixture ; on oxidation with chromic and glacial
acetic acids, however, it gives benzoic acid. It acts in an entirely
difi^erent manner to the more soluble modification, when treated with
alcoholic potash. The reaction, which is very complicated, appears to
give rise to a polymeric hydroxyquinone. T. C.
Chemistry of Bast Fibres.* By E. J. Bevan and C. F. Cross.
— The authors' investigations have been confined to jute and esparto,
the former as a peculiarly typical bast fibre, the latter as representing
monocotyledonous growth.
* A Paper read before the Owens College Chemical Society, 16th April. Pub-
lished by Palmer and Howe, Manchester. See also Chem. Netns, 42, 77.
ORGANIC CHEMISTRY. 667
The inorganic constituents of the normal jute fibre are —
(a.) Water of hydration, varying from 10 to 12 per cent, of its
weight, with the temperatui-e aud hygrometric state of the air. It is
to be regarded as» dependent both on the chemical nature and structure
of the fibre (chemical adhesion), although scarcely upon its external
structure (capillarity), as conjectured by Sir W. Thompson.
(b.) Ash, — The general features of the inorganic skeleton of this
fibre may be expressed by the following average percentage numbers :
— SiO., 30—35; Fe^Oa, 5—8 ; AI2O3, 5—6 ; MuoOa, 0-5— 0-9 ; CaO, 13—
16; K2O + NaoO, 5— 10; P2O5, 8—13 ; SO-,, 1—5.
(c.) Organic (considered with exclusion of a and 6). Combustions
of the fibre (purified by boiling in dilute ammonia ; the fibre thereby
sustains a loss of 1 per cent, of its weight, losing a resinous consti-
tuent, which causes the adhesion of portions of cortical parenchyma,
and the matting together of the fibres in the raw state), shoAved it to
have the following aggregate (average) composition : C, 46'5 ; H, 5'80.
Nitrogen is present only in minute quantity^ e,g^ in a fair specimen
(previou.sly boiled in dilute sodium carbonate) the quantity determined
was 0053 per cent. The proximate constituents of the fibre are,
cellulose, 70 per cent., as isolated by the ordinary methods, and inter-
cellular and encrusting substance, 30 per cent.
Hugo Miiller's method for the quantitative determination of cellulose
gives satisfactory results with this fibre ; identical results are obtained,
but in a very much shorter time, by substituting chlorine gas for the
bromine-water, the fibre being boiled previously to chlorination in a
weak alkaline solution. The action of the gas is to form a definite
compound with the aix)matic portion of the fibre, which is decomposed
on boiling with ammonia, with formation of soluble products. Pure
cellulose is obtained on once repeating this treatment, whilst if bro-
mine-water is used, several repetitions (5 — 6). are necessary. A modi-
fication of thi& method, involving points discussed in another connection,
consists in boiling the chlorinated fibre with a solution of sodium
sulphite (5 per cent.) for & few minutes, and subsequently with an
alkali (a solution of potash, 1 per cent., is a better solvent for the pro-
ducts of decomposition,^ and its use does not aif ect the yield of cellulose) ;
by the method thus modified pure cellulose is at once obtained. It is
a remarkable fact that the yield of cellulose is, in this case, 5 per cent,
higher than by either of the two previous methods. There is addi-
tional evidence to show that jute cellulose is a chemical aggregate,
and therefore to a certain extent defined by the process by which it is
obtained. The above-mentioned chlorine derivative is a definite com-
pound, CujHi^CliOg; it has been obtained and purified in different
ways, but with constant analytical I'esults. It is soluble in alcohol
and glacial acetic acid, and is precipitated from its solution on the
addition of water, in yellow flocks ; it dries to an amorphous yellowish
powder, which has an odour closely resembling that of tetrachloro-
quinone. It further resembles this compound in dissolving in ammo-
nia to a purple solution, changing to brown on standing. The
analogies of this body to the quinone derivatives are unmistakable ;.
the authors are therefore able to confirm Hugo Miiller's observation of
the presence of a body having the reaction of a quinone in the inter-
CM ABSTRACTS OF CHEMICAL PAPERS.
cellular substance of bast fibres. The most striking reaction of this
derivative is the development of a pure magenta purple colour, of
o-reat brilliancy when treated with a solution of sodium sulphite.
This is best seen in the freshly chlorinated fibre; all bast fibres
examined by the authors (flax, hemp, manilla, &c.) gave the same
coloratiun after chlorination. Upon the reactions of these bodies the
method for the isolation of cellulose proposed by the authors was
based, the chlorine body being converted by the sodium sulphite into
soluble (reduction) products. Being a recent observation it is still,
under investigation.
A similar derivative was obtained from esparto. The brown solu-
tion obtained by heating the substance under pressure with an alkaline
lye, yields a flocculent precipitate when neutralised. After purification
by twice dissolving in glacial acetic acid, and reprecipitating by water,
it has the aggregate composition CoiHj^Ob (it contains also 1"2 per
cent, nitrogen). This body on heating with hydrochloric acid and
potassium chlorate, yields the chlorine derivative, CjoHoaCUOio, which
is also to be regarded as formed from a complicated quinone.
The quinone of the jute fibre appears to be associated with a carbo-
hydrate. By the action of dilute sulphuric acid (5 per cent.) at 80°, a
soluble carbohydrate is formed, and is obtained after purification as a
brown, sticky, hygroscopic solid, having the composition C13H18O9.
As no other products are formed, the aromatic portion of the fibre
resisting the action of the acid, and the loss of weight (23 per cent, in
a certain case) falling to a large extent on the intercellular substance,
this, it must be inferred, contains a carbohydrate. The same conchi-
sion is arrived at by a study of the action of alkalis on the fibre,
and of a peculiar fermentation, which is induced under certain condi-
tions of moisture and high temperature, by which this portion under-
goes resolution. The carbohydrate associated with the quinone is
rather of the nature of cellulose than glucose ; the fact that by a
certain decomposition of the intercellular substance the yield of cellu-
lose is increased, goes to shovr that a portion of the " aggregate "
cellulose obtained is a product of such decomposition. The authors
therefore regard the intercellular substance of this bast fibre as a
" cellulide," or more specifically a celluloquinone. Upon this consti-
tuent depends the integrity and remarkable dyeing capacity of the
fibre ; jjari passu with its removal, these disappear, until in the iso-
lated cellulose there is obtained a mass of disintegrated cells, having
no afiinity for colouring matters.
By the action of nitric acid (5 per cent.) this celluloquinone is
eiitirely converted into soluble products. The aroAiatic portion of
these are more conveniently studied in the analogous esparto deriva-
tive. From the solution obtained by digesting the acid on the resi-
nous precipitate before described, a peculiar nitro-derivative was
obtained. Concordant analyses of this body, in the form both of its
barium and calcium compound, established the formula as
CsHsiNO^aM",.
In the free state it is a powerful acid ; it has an intensely bitter
taste, and dyes animal fibres a brilliant yellow. C. F. C.
ORGANIC CHEMISTRY. 669
Hydrocamphene. By J. Kachler and F. V. Spitzee (Ber., 13,
615 — 616). — The authors have previously shown (^Annalen, 200, 340)
that the unsaturated hydrocarbon camphene, CioHie, maybe considered
as the nucleus of all the compounds of the camphor group. Hycho-
camphene, CioHis, is obtained, together with camphene, by acting on a
benzene solution of borneol chloride, CioHnCl (or of camphor dichlo-
ride, CioHieCl)) with sodium. The mixture of the two hydrocarbons,
after saturation with hydrochloric acid (so as to convert the regene-
i-ated camphene into the chloride), is again treated with sodium, and
this operation repeated ten times. The product, which solidifies to a
crystalline mass, is finally purified by sublimation, when the hydro-
carbon is obtained as a hard brittle mass (m. p. 140°) resembling stearic
acid. It is easily soluble in ether, but less soluble in alcohol and
acetic acid, and sublimes even at the ordinary temperature. Hydro-
camphene is possibly identical with the hydrocarbon CioHig, obtained
by Montgolfier {Chen. Centr., 1879, 52), by the action of sodium on
the fused hydrochloride of turpentine oil. T. C.
Action of Sodium on Turpentine Hydrochloride. By E. A,
Letts (Ber., 13, 793 — 796). — When turpentine hydrochloride is fused
with sodium, and the product distilled after removal of the chlorine,
a tine white solid (m. p. 157°) is obtained as the chief product, but on
raising the temperature, a yellowish-white liquid (b. p. 326 — 330°)
passes over, which solidifies in feathery crystals, resembling sal-
ammoniac.
The first of these bodies melts at 94°, and is supposed by the author
to have the composition CioHn, and not that of a mixture of CioHig
and CioHis. The second body also melts at 94°, and consists of C20H34.
It is extraordinarily stable. The mother-liquor remaining after the
crystallisation of this body has the same boiling point and compositioji
as the crystals, so that there seem to be two modifications of a new
hydrocarbon, C2oHj4.
The so-called liquid turpentine hydrochloride, when acted on bv
sodium, yields a solid, which is identical with the second solid body
obtained above.
Montgolfier, who has repeated the author's experiments (Comjot. rend.,
87, 840 — 842) finds that the first described solid, with lower boiling
point, is a mixture of inactive camphene, CioHie, and camphene
hydride, CioHis, and has isolated the two bodies from the mixture. He
gives the melting point of camphene hydride as 120°. He has also
obtained the liquid hydrocarbon with higher boiling point, and names
it colophene hydride, CooHsi.
By the action of sodium on liquid turpentine hydrochloride, he
has obtained two liquids, CmHis, boiling at 165 — 166°, and C10H16,
boiling at 173°. He has also isolated small quantities of the solid
C10H18 from the product of the last reaction (compare Kachler and
Spitzter, preceding abstract). G. T. A.
Action of Ammonia on Ethyl Camphoronates. By E. Hjelt
{Ber., 13, 796 — 799). — There are two isomeric monethyl camphoro-
nates, one of which is a liquid, and the other a solid, consisting of
070 ABSTRACTS OF CHEMICAL PAPERS.
colourless tabular crystals (m. p. 67°). When acted on bj dry am-
monia gas, the former yields a monamide (m. p. 212"), C9H13NO4,
the latter an amido-amide (m. p. 144 — 145)°, C9H16N2O4. An amido-
acid could not be obtained from the amido-amide.
Ammonia acts also on diethyl camphoronate when the two are
heated in sealed tubes at 115 — 130°, with formation of an amido-
amide (m. p. 160°), 09^116X201, which yields an acid, CgHjaNOs
(m. p. 212°), but this does not exhibit the ordinary reactions of an
amido-acid. The author supposes that the formation of amido-amines
instead of diamines arises from the hydroxyl group being placed
bistween two carbon atoms, which are united with oxygen.
G. T. A.
Ethereal Oil from the Californian Bay Tree, By J. M.
Stillmax (Ber., 13, G29 — 031). — The leaves of the Califot'nian bay
tree {Onodaplme Califoniican} when distilled with steam yield nearly
3 per cent, of a clear, limpid, yellow oil, haying a pleasant aromatic
odour, but producing tears when strongly inhaled ; sp. gr. 0'94 at 11°.
By fractional distillation, it may be separated into terpiuol (CuiHi7)oO,
b. p. 167—168, and Umbellal, CJli.O, h. p. 215^216°. V. d. = 439,
calc. = 4-29.
TJmbellol is a colourless limpid liquid, having a pleasant odour,
but producing tears and headache when inhaled in larger quantity.
It is insoluble in water, and but slightly volatile therewith. It dis-
solves in concentrated sulphuric acid with a blood-i-ed colour, which
rapidly becomes black. It is strongly attacked by sodium or by con-
centrated nitric acid. T. C.
Abietic Acid. By W. Kelbe (Ber., 13, 888— 891).— Abietic acid,
C44H64O5, is obtained by adding common salt to the solution of soda
which has been used for the purpose of purifying crude iDsin oil. The
soap is dried at 70 — 80°, and extracted with ether to remove impu-
rities ; the residue dissolves in alcohol, and on eyaporation the alcoholic
solution deposits needle-shaped crystals of sodium abietate. On the
addition of hydrochloric acid to the aqueous solution of the sodium
salt, a white precipitate of abietic acid is pi-oduced, which melts to a
resinous mass if the mixture is boiled. The acid is soluble in ether,
benzene, alcohol, and glacial acetic acid, and is deposited from its solu-
tion in the latter solvent in triclinic plates (m. p. 165°). The pure
salts of abietic acid form gelatinous masses with ether, but do not dis-
solve in it. W. C. W.
Caryophyllin. By E. Hjelt (Ber., 13, 800).— Caryophyllin has
the same empirical formula as camphor, but Mylius (Ber., 6, 1053)
prefers to double its formula. On oxidation with concentrated nitric
acid it yields caryophyllic acid, C20H32O6. Heated with acetic acid at
100°, it gi%^es rise to an acetyl-derivative, which crystallises in the
monoclinic system, and melts at 184°. Two chlorine compounds are
formed by the action of phosphorus pentachloride, C40H63O3CI and
C40H153O2CI3. The author concludes that the formula of caryophyllin is
C40H64O4. Cymene has not yet been obtained from it. G. T. A.
ORGANIC CHEMISTRY. ()71
Caroba Leaves. By 0. Hesse {Annalen, 202, 150 — 151). —
TLese leaves, -wliieh were formerly (Ber., 10, 2164) supposed to be de-
rived from the tree yielding the Pereiro bark, belong to a Brazilian
tree, viz., Cybistas antisyj^hiUtica (Marlino), or Jacaranda procera
(Sprengel). Extracts from these, e.g., Key's Brazilian injection, are
supposed to have great efficacy in cases of syphilis. An investigation
of these extracts has shown that no alkaloids are present.
P. P. B.
Glycyrrhizin. By J. Habermann (Chem. Centr., 1880, 253 — 256,
267 — 271, 282 — 287). — The present paper gives in detail an account
of the author's further investigations on glycyrrhizin and its decom-
position products. He shows — -(1.) That glycyrrhizic acid on boiling*
with dilute sulphuric acid decomposes into parasaccharic acid and
glycyrrhetin. Sugar was not found among the decomposition pro-
ducts. (2.) That parasaccharic acid is distinguished from ordinary
saccharic acid by affording no crystallisable salt. (3.) That pui"e
glycyrrhetin is a crystalline, almost indifferent nitrogenous body,
which gives very characteristic products with bromine, nitric acid,
and acetic chloride, but does not yield parosybenzoic acid on being
fused with potash. (4.) That commercial ammoniacal glycyrrhizin,
besides containing glycyrrhizic acid, also contains (a) amorphous
glycyrrhizin bitter, and a nitrogenous compound of an intensely bitter
taste. It occurs in subordinate quantities only. (&.) Dark brown
glycyrrhizin resin, soluble in alcohol and in alkaline aqueous solu-
tions to yellow-coloured liquids, also fusible with caustic potash, and
yielding along with a resinous compound various volatile fatty acids
and paraoxybenzoic acid. J. T.
Hypochlorin and its Origin. By Prixgsheim {Clem. Centr.,
1880, 299—304, 316—319, 331— 334).— In an earlier paper {ibid.,
9 and 27), the author has made known the existence of hypochlorin.
By the action of dilute hydrochloric acid on chlorophyll globules, semi-
fluid masses of irregular form, reddish or brownish in colour, make
their appearance, and out of these obscurely crystalline forms separate.
These appearances show the presence of hypochlorin, and afford an
unfailing reaction for this new body. The properties of the new body
are difficult to investigate. The separated masses seem to consist of
an oily mother-substauce, which bears a closer analogy to ethereal oils
than to fatty ones. The masses are insoluble in water, in salt solu-
tions, in dilute mineral and organic acids, but are easily soluble in
ether, benzene, carbon bisulphide, and ethereal oils, and also with more
or less difficulty in alcohol, even when considerably diluted. The con-
stituents of hypochlorin have not yet been ascertained. By hypochlo-
rin the author means the crystalline forms above named. The hypo-
chlorin reaction may be obtained without hydrochloric acid. Green
textures preserved in glycerol or in calcium chloride solution show it
here and there after a time. Ti-eatment with warm or hot water in
some cases, and with steam, forms one of the easiest means of separa-
tion.
In sprouting angiosperms no trace of hypochlorin can be detected
until the plant has been exposed to light, and exposed longer than is
672 ABSTRACTS OF CHEMICAL PAPERS.
required to turn the plant greeu, whilst in gymnosperms which are
peculiar as forming clilorophyli colouring matters in the dark, hypo-
chlorin is also formed in plants grown in the dark. J. T.
Synthesis of Quinoline. By W. Koenigs (Ber., 13, 911—913).—
Quinoline is formed by the dry distillation of acroleinaniline, and may
be purified by Baeyer's method (Ber., 12, 460), viz., by treatment
with, potassium chromate aud sulplim-ic acid. The best method for
preparing quinoline is by acting on a mixture of nitrobenzene,
aniline, and glycerol with sulphuric acid. In this process it is pro-
bable that acroieinaniliue is formed as an intermediate product.
w. c. w.
Nicotine Derivatives. By A. Cahours and A. Etard (Gompt.
rend., 90, 275 — 28U). — When thiotetrapyridine, C2UH18N4S, obtained
bv the action of sulphur on nicotine {ibid., 88, 999, and this Journal,
38, 732), is boiled with dilute nitric acid, it gives nicotinic acid
(m. p. 228—229°).
Thiotetrapyridine when distilled with finely divided metallic copper
loses sulphur, and yields a base, isodijjyridine, CioHioNo, isomeric with
dipyridene, but differing greatly from it in its properties. It is also
produced in small quantity by the action of alcoholic potash on thio-
tetrapyridine at 2UU~^. Isodipyridene is a colourless oil (b. p. 274 —
275°), having an odour somewhat resembling that of certain mush-
rooms. It does not solidify at —20°, and its sp. gr. at IS'" is 1'1245.
It is insoluble in cold, and only sparingly soluble in boiling water, but
easily in alcohol or ether. It unites energetically with hydrochloric
acid, but the hydrochloride does not crystallise. The platinochloride,
(CioHioN2.HCl)2PtCl4 + 2H3O, crystallises in deep orange plates of
the colour of potassium dichromate. It is decomposed if boiled with
water.
It was thought probable that if nicotine were submitted to limited
oxidation it might yield isodipyi'idine, thus : C10H14N2 + O3 =
CioHioNo + 2H2O. For this purpose pure nicotine was dissolved
in dilute potash solution, and oxidised with potassium ferricyanide,
and the product distilled. The bases extracted from the distillate
by means of ether, when submitted to fractional distillation, were
found to consist of isodipyridine mixed with unaltered nicotine.
If nicotine in the state of vapour is passed over red-hot porcelain,
it is in part decomposed (about 20 per cent.), yielding a gaseous mix-
ture of hydrogen with paraffins and olefines, and a liquid product con-
taining pyridine, picoline, collidine, and new basic substances boiling
at temperatures above 250°. C. E. G.
Formation of Hypoxanthine from Albuminoids, By E.
Dkechsel (Ber., 13, 24U — 242). — Salomon, Krause, and Chittenden
are of opinion that the hypoxanthine observed in the solutions obtained
from certain albuminoids by digestion, incipient putrefaction, or the
action of dilute acids, does not exist as such in the albuminoids, but is a
decomposition product. Thus Salomon could not detect it by ammoniacal
silver nitrate in the aqueous extract, hot or cold, from well washed fibrin ;
and Chittenden did not observe it in the alcoholic extract, unless the
ORGANIC CHEMISTRY 673
alcohol had been boiled with the fibrin for twelve hours. The author
does not reg-ard these experiments as conclusive, for fibrin as usuallv
prepared must necessarily include other blood constituents, which
could only be removed with great difficulty ; and, on the other hand,
Salkowski has shown {Pflnger's Archiv., 4, 94) that the precipitation
of hypoxanthine by ammoniacal silver nitrate does not take place in
mixtures containing gelatin. The author has been unable by this
reagent to detect purposely added hypoxanthine in the liquid obtained
by heating fibrin with water in a digester. Again, there is no proof
that the small quantity of hypoxanthine detected by Chittenden in
the acid liquid obtained on boiling eggs with dilute acetic acid, and
considered by him to exist as such in the egg, was not formed from
the albumin dui'ing coagulation. The origin of hypoxanthine is there-
fore still uncertain. Ch. B.
Morphine Hydrochloride. By O. Hesse (Annalen, 202, 151 —
152). — By dissolving this body in methyl alcohol, and allowing it to
stand, crystalline grains separate, which increase in quantity after
some time, the quantity being also increased by warming. These
crystals are anhydrous morphine hydrochloride, C17H19NO3.HCI. It
is sparingly soluble in ethyl or methyl alcohols, from which it sepa-
i^ates as a shining crystalline powder, or in short four-sided rhombic
prisms. One part of it dissolves in 51 parts of methyl alcohol. From
water it crystallises in the ordinary hydrated form, which by solution
in absolute alcohol is partially converted into the anhydrous form.
P. P. B.
Action of Phosphorus Pentachloride and Oxychloride on
Cinchonine Hydrochloride. By W. Koenigs (Ber., 13, 285—
287). — The mode of union of the oxygen in cinchonine and quinine
is still unknown. According to Wright the acetyl and benzoyl
derivatives described by Schiitzenberger are really derived from the
isomeric bases cinchonicine and quinicine. Zoi'n (/. pr. Ghem., 8,
279), by the action of fuming hydrochloric acid at 140 — 150°, obtained
the chlorinated bases C20H03N2CI + H.,0 and CooHmNoOCI + HoO
from cinchonine and quinine respectively. These retain chlorine and
water with great obstinacy, and cannot be reconverted into the alka-
loids. Zorn regards them as formed by displacement of hydroxyl by
chlorine, whilst Hesse (Annalen, 174, 340), looks on them as addition
compounds. By a similar process, Skraup {Ber., 12, 1107) obtained
from cinchonine a brominated base, CigHjjNaOBr -f H2O, which parts
with its bromine when heated with silver oxide, forming a very
soluble and unstable base. Since cinchonine yields formic acid by
oxidation with pei'manganate, Skraup supposes that it contains the
group OCH3, and that the nascent methyl bromide formed from this
combines with the nitrogen to form the bromide of an ammonium
base. Finally, Wischnegi'adsky {Ber., 12, 1480) regards cinchonine
as a ketone, its reduction products, (Ci9H22N20)2H2 and C19H24N2O,
being related to it as pinacone and isopropylic alcohol are to acetone.
Neither phosphoric chloride nor oxychloride acts on cinchonine ;
but when 6 — 7 parts of oxychloride are gradually added to 1 part of
cinchonine hydrochloride (dried at 110°) mixed with 2 parts of phos-
(374 ABSTRACTS OF CHEMICAL PAPERS.
phoric chloride, tlie mass becomes warm, and hydrochloric acid is
evolved : the reaction having been completed by prolonged heating
at 80 — 100°, the cooled product is poured into ice-cold vpater. On
addino- ammonia to this solution, a resinous precipitate first falls, and
on continuing the addition a white crystalline mass slowly separates.
When crystallised from dilute alcohol, this forms broad needles (m. p.
52°), soluble in alcohol, ether, benzene, chloroform, and carbon bisul-
phide, sparingly so in boiling water. The results of analysis agree
best with the formula C19H21N2CI. The body is probably, therefore,
cinchonine, in which hydroxyl has been replaced by chlorine. Its
hydrochloric acid solution gives a crystalline pi'ecipitate with pla-
tinic chloride. Hot alcoholic potash or sodium amalgam at ordinary
temperatures remove chlorine from it, by which reaction it is distin-
guished from Zorn's chlorocinchonide, C00H25N2OCI, which is not so
affected. Ch. B.
Hyoscyamine. By A. Ladenburg (Ber., 13, 254 — 256). — When
hyoscyamine is digested at 60° with baryta- water, it is decomposed ;
on precipitating the baryta with carbonic anhj^dride, acidifying with
hydrochloric acid, and shaking with ether, hyoscinic acid (ra. p. 116 —
117°) is obtained. This acid is probably identical with tropic acid
from atropine (m. p. 117 — 118°), which it resembles in physical
properties. Like that acid, when heated with dilute potassium
permanganate solution, it gives an odour of bitter almond oil,
and yields benzoic acid on treatment with excess of the oxidant.
Moreover, when boiled for seven hours with twice its weight of
barium hydrate, it is converted into atropic acid, C9HSO2.
After removal of the hyoscinic acid and addition of potash, ether
extracts from the residue a base, hyoscine, having approximately the
composition C6Hi5lS'0.-^H20, which is that of a hydrated tropine
(Ki*aut, Amiale)!, 133). Dry tropine melts at 61"5 (Kraut) ; but the
author has frequently observed a melting point of 50° for it. Hyos-
cine prepared as above melts at 47 — 50°, b. p. 229°.
Its platinochloride has the composition (C6Hi5NOHCl)2.PtCl4. The
formula CeHigN^, assigned to it by Hohn and Reichardt, is therefore
incorrect. This salt, as well as the picrate and aurochloride, cannot
be distinguished from the corresponding salts of ti'opine.
Hyoscyamine and atropine are undoubtedly different, but wherein
the difference lies has yet to be discovered. Ch. B.
Hyoscyamine and Atropine. By A. Ladenburg (Ber., 13, 607 —
609). — The author has in a previous communication (see above) directed
attention to the great similarity between hyoscinic and tropic acids.
Subsequent measurements of the crystals of the platinochlorides of
hyoscine and tropine show that they are identical. Hyoscine,
CsHijNO, prepared from daturine, which the author has shown to be
identical with hyoscyamine, crystallises from toluene in large clear
crystals (m. p. 62°, b. p. 229°), which are so exceedingly hygroscopic
that even after but slight exposure to the air the meltiag point sinks
to 50°, which explains the earlier melting point found for this sub-
ORGANIC CHEinSTRY. 675
stance. On a strict comparison of hjoscine and tropins from atro-
pine no difference could be detected between them.
Hyo.scinic acid and byoscine respectively were treated with dilute
hydrochloric acid on a water-bath, the alkaloid so obtained precipi-
tated with potassium carbonate, dissolved in chloroform, and evapo-
rated ; the residue was then dissolved in dilute hydrochloric acid and
precipitated with gold chloride, when an aurochloride was obtained
identical in every respect with that from atropine. By this means
hyoscyamine is converted into atropine, and all doubt as to the identity
of their decomposition products is removed. Atropine and hyoscya-
mine are most pi'obably physical isomerides. T. C.
Duboisine. By A. Ladenberg (Be/-., 13, 2.57 — 2-58). — In compo-
sition and in analytical and physical characters, this alkaloid, ob-
tained from the Australian plant Buhoisia myoporoules, is identical
with hyoscyamine. Ch. B.
Tropidine. By A. Ladenbeeg (Ber., 13, 252 — 254).— Besides the
ways already mentioned (Ber., 12, 944), tropidine may also be formed
by heating tropine at 220° with an equal weight of sulphui-ic acid,
diluted with twice its volume of water. The greater part of the
tropine is thus converted into tropidine, the remainder being decom-
posed in a more complex way. The tropidine may be separated by
distillation with potash, and extracted from the distillate by ether.
The aqueous solution of the base so prepared is not rendered turbid
by a further addition of water, and its solution in hydrochloric acid
does not become coloured on evaporation. These appearances, for-
merly described as characteristic, were due to impurities.
The aurochloride and platinochloride of the base were analysed.
The latter (CsHi3N.HCl)2PtCl4, is dimorphous, crystallising in the
monoclinic and rhombic systems. Its crystallographic constants have
been accurately determined. Ch, B.
Pereiro Bark. By 0. Hesse (Annalen, 202, 141—149). — An
extract from this bark is used in Brazil as a febrifuge. The bark is
obtained, according to Peckolt, from Geissospermicm velosii, whilst
according to Baillon, it is from Geissospermum Iceve. Gros (E^epert.
Pharm., 76, 32) finds it to contain an alkaloid, which is styled
pereirine ; whilst Peretti (Jour. Chim. Med., 26, 162) concludes that
it contains other alkaloids. The author has obtained from this bark
two alkaloids, viz., geissospermine and pereirine. The alcoholic ex-
tract of the bark is treated with soda, and then extracted with ether.
The ethereal extract is subsequently treated with acetic acid, and the
dark-brown acetic acid solution is shaken up with ammonia and ether.
Geissopermine then separates out, and the pereirine remains dissolved
in the ether, and is obtained by evaporating the ethereal solution.
Geissospermine, 0191124X203 + II2O, crystallises from alcohol in small
white prisms, the ends of which are surmounted by domes. It dis-
solves easily in hot, and sparingly in cold alcohol, the solution havinsr
an alkaline reaction. It is insoluble in ether and water. It dissolves
easily in dilute acids, and is precipitated from these solutions bv
(57 fi ABSTRACTS OF CHEMICAL PAPERS.
alkalis. Concentrated nitric acid gives a purple-red coloration, whicli
when heated, becomes orange-yellow. Its solution in pure concen-
trated sulphuric acid is at first colourless ; it however becomes blue
very soon, and then the colour fades again ; in presence of molybdic
acid, the blue is prodiaced at once and is permanent. When heated
with soda lime, a body is formed, subliming in leaflets, easily soluble
in ether, and giving a blue coloration with sulphuric acid and molybdic
acid, but no coloration with nitric acid. It undergoes a change when
heated to 160".
Its hydrochloride is amorphous ; the platinochloride forms an amor-
phous, light yellow precipitate, which loses water at 130°, and then
has the composition (Ci9Ho4NoOnHCl)2PtCl4. The aurochloride is a
dirty brown amorphous body. Its oxalate crystallises from alcohol as
a white powder, consisting of microscopic needles. The sulphate
crystallises from alcohol in stellate grouped white needles, is easily
soluble in water and hot alcohol, sparingly in cold alcohol, and inso-
luble in ether. Dried at 100", it has the formula (C,9H24]S'202)2HoS04.
By means of the aqueous solution of the sulphate, the author has
tested the delicacy of its reactions with several bodies, and finds that
the alkaloid is most easily precipitated by ammonia and soda, whereas
the reaction with phospohotungstic acid is not very delicate.
Pereirine, C19H24N2O. — -This alkaloid, obtained as described above, is
purified by dissolving it in acetic acid and boiling with animal char-
coal ; from the yellow solution obtained, ammonia gives a white amor-
phous precipitate, which, when air-dried, is a greyish-white powder. It
is easily soluble in alcohol, ether, and chloroform ; also in dilute acids,
from which latter it is precipitated by alkalis. Concentrated sulphuric
acid dissolves it with a violet-red colour, and nitric acid with a purple-
red. It melts at 124" to a red mass. Its sulphate and hj^drochloride
are amorphous, and easily soluble in alcohol. Its platinochloride is
a yellowish - grev amorphous precipitate, having the composition
(C,9H24N20HCl)2PtCl4 + 4H,0. P. P. B.
Protein Compounds. By A. Stutzer (Ber., 13, 251).— In this
preliminary notice the author states that he has successfully applied
cupric hydrate, recommended by Ritthausen for the precipitation of
dissolved protein compounds, to the quantitative estimation of such
bodies, and their separation from other nitrogenous substances occurring
in plants, such as amygdalin, solanine, leucine, tyrosine, asparagine,
alkaloids, mustard-oils, nitrates, and ammonia salts.
Further, that protein bodies yield two classes of compounds when
acted on by acid gastric juice (pepsine and hydrochloric acid). On
the one hand there are formed the decomposition products already
known (peptones, acid albuminates, &c.) ; whilst on the other a per-
fectly definite part of the protein body is absolutely indigestible. This
contains nitrogen and phosphorus, and appears to be allied to nuclein.
. Ch. B.
Albuminoids of Various Oily Seeds. By H. Ritthausen
{Tfiilijcrs Arcltiv., 21, 81 — 104). — The author, referring to his pre-
vious investigation on the constitution of gliadin, 1864, and conglutin,
1868, and the large proportion of nitrogen they contain (18"06 per
PHYSIOLOGICAL CHEMISTRY. 677
cent, and 18'4 per cent, respectively) as compared with albumin,
remarks that since that time his results have been confirmed by others
and himself. He then gives the details of investigations on the seeds
oi Arachis hypogcea {earth-nut) , Helianthiis annuus (sunflower), Sesamum
indicum, cocoa-nut, Brassica napus (rape), and potatoes.
The methods used were three.
(1.) Extraction with water, to which a small quantity of potash was
added (4 grams in 2o litres), and subsequent precipitation by acetic or
sulphuric acid, washing with water, alcohol, and ether, and. drying
over sulphuric acid.
(2.) Extraction with dilute lime or baryta water.
(3.) Extraction with 10 per cent, sodium chloride solution (solutions
of XH4CI, KCl, CaCL, BaCU, MgCU appear to answer equally well).
From these experiments, the author concludes that the albuminoids
obtained by the use of either dilute potash, bai'vta, or lime water, pre-
sent no appreciable differences from those obtained by the solutions of
the various salts above mentioned, and he thinks that there is no
doubt that the hydrates of the alkalis and alkaline earths act on these
bodies like a base on an acid, forming compounds readily soluble in
water, and that they are precipitated unchanged by neutralisation with
an acid.
There appear to be two albuminoids ; one containing more than
18 per cent, of nitrogen and one less ; the former is found alone in
almonds, earth-nuts, para-nuts, pumpkin and sunflower seeds ; whilst
in castor-oil seeds, sesamum, and cocoa-nut, both occur, but not in
rape seeds.
The albuminoids rich in nitrogen, so far as investigated (with the
exception of gliadin and the albuminoids found in para-nuts), contain
less carbon than animal albumin and casein by 1'5 to 2 per cent. ;
gliadin and the albuminoids of para-nuts always 1 per cent. This,
with the fact that they contain more than 2 per cent, more nitrogen,
will serve to distinguish these bodies from animal albuminoids. The
sulphur varies considerably, e.g., from O'bo per cent, in earth-nuts to
1'3 per cent, in sesamum. Compare the difference between the con-
glutin of lupins, which contains 0'91 per cent, of sulphur, and that of
almonds, which contains 0'45 per cent. Lastly, he draws attention to
the close relation between the bodies obtained by the methods above
mentioned, and conglutin from lupines and from almonds.
W. N.
Physiological Chemistry.
Changes which Starch undergoes in the Animal Organism.*
By E. H. BiMMERMAXX (Fjiiiger's Archif., 20, 201— 210).— The author,
after referring to the statement of Musculus and Gruber, that starch
* Conf. MusciJus and O'SuUivan, Journ. Chem. Soc, 1872 — 76 ; T. H. Brown
and .J. Heron, Journ. Chem. Soc, Sept., 1879 ; Roberts, Lumleian Lectures, 1880 ;
Malj, Jahresbericht Thier. Chem., 1878, pp. 49 — 54.
VOL. XXXVIII. 3 h
(')78 ABSTRACTS OF CHEMICAL PAPERS.
by the action of diastase or acids, yields soluble starcb, maltose, grape-
sugar, and tbree forms of dextrin, named respectively a, (3, and 7
achroodextrin, which are variously affected by ferments, proceeds to
state that while maltose and grape-sugar are produced by the action
of saliva on starch, glycogen, whether obtained on a diet of grape-
sugar or albuminoids, when treated in the same manner, yields larger
quantities of maltose and grape-sugar, and a reducible dextrin.
Sachsse's method of estimating sugar by mercuric iodide was used, as
it was found difficult to determine the end of the reaction with Feh-
ling's solution. The substances wei^e injected into the jugular vein of
a rabbit, and the urine subsequently examined, with the following
results : —
Maltose is partly converted in the blood into grape-sugar, and
partly passes out unchanged. Soluble starch yields dextrin and grape-
sugar. Achroodextrin (a) suffers only partial change, grape-sugai-
and maltose being found in the urine, together with dextrin. Achroo-
dextrin {(3) yields a similar result. Achroodextrin (7) yielded no
sugar. Generally, the results tend to show that the changes which
starch undergoes in the body are similar to those which occur when
it is submitted to the action of diastase outside it. W. J^.
Chemistry of Vegetable Physiology and Agriculture.
Comparative Value of Soluble and Insoluble Phosphates.
By A. VoELCKER (Jour. Roy. Agri. 80c. , 1880, 152 — 159). — This is a
summary of the comparative results obtained in early field experiments
by applying bones and other pliosphates alone and after previous
treatment with sulphuric acid, showing the advantage of the latter
method. R. W.
Analyses of Manures and of Cattle Foods. By A. Voelckek
(Joiir. Boy. Agri. Soc, 1880, 311). — The guano from Pabillon de Pica
is richer in ammonia than that from Huanillos, which is again much
more valuable than that from Lobos de Afuera and Lobos de Tierra.
Three samples of commercial soot contained 2-35, 3-63, and 504 per
cent, of nitrogen ; the second was of about average quality. An un-
usually rich sample of bats' guano contained 8-92 per cent, of nitrogen,
and 5'02 per cent, of phosphoric acid.
Rice meal consists chiefly of the external layers of rice, which are
separated in dressing. The mean of five analyses was as follows: —
Water.
Albuminoids.
Fat.
Carbohydrates.
Fibre.
Ash.
11-46
]2-47
11-61
49-66
6-79
8-00
R. W
ANALYTICAL CHEMISTRY. 879
Analytical Chemistry.
Vapour-density Determinations in the Vapour of Phospho-
rus Pentasulphide. By W. Knecht (Anualeu, 202, 31^36). —
Graebe (Ber., 11, 1646), in using Meyer's method with Wood's metal,
calculated the sp. gr. of this alloy at 530^ (the boiling point of phos-
phorus pentasulphide as determined by Hittorf, Fogg. Ann., 126,
193), to be y"051. The author has determined the sp. gr. of the alloy
directly, and finds it to be 9'06 at 530^, and also that its coefficient of
expansion is constant between 100'' and 530°. Further, the alloy is
not attacked by phosphorus pentasulphide, and in using the latter the
vessels may be easily freed from it by cooling down to 100°, and then
suspending them for some time in a vessel containing boiling watei
The author has determined the vapour-densities of the following bodies
in the vapour of phosphorus pentasulphide, and finds their densitien
are such as required by theory, viz., tripheuylbenzene (lO'Sl), isodi-
naphthyl (8'865), dinaphthylketone (9'07), and tetraphenylethane
(11-65J. P. P. B.
Modification of Zulkowsky's Apparatus for the Volumetric
Estimation of Nitrogen. By E. LLjjwitj {Ber., 13, b83 — 8«5).
Determination of Nitrogen. By H. Schiff (Ber., 13, 885—887) .
— A simpler and more conv^euient form of the apparatus described by
Schwarz for estimating nitrogen by Dumas' method {Ber., 13, 771)
was invented by the author in 1868. W. C, W.
Estimation of Gold and Silver by Quartation with Cadmium.
By F. Kraus {Diugl. polyt. J., 236, 323— 326).— BaUing {Oestrei-
cMsche Zeitschr. f. Berg, und Huttemoesen, 1879, 597) describes a modi-
fication of Giiptner's method of separating gold by quartation with
zinc, in which cadmium is used instead of zinc, the fusion of the
metals being made ander a layer of potassium cyanide. The author
has subjected this method to a close investigation, and has more
especially compared it with the methods usually employed in mints for
the determination of alloys of gold and silver. His resiilts seem to
show that Balling's method is simpler and more readily carried out
than the cupellation method, and he strongly recommends chemists
and assayoi's to investigate it more minutely. Moreover, the circum-
stance that the silver can be determined by Volhard's method in the
decanted acid solution and in the washings, gives it an advantage
over the process by cupellation. D. B.
Detection of Water in Alcohol and Ether. By C. Mann
{Dingl. pohjt. J., 236, 430; and Cheni. Zeitung, 1880, 307).—
Mix 2 parts citric acid and 1 part of molybdic acid; heat until
incipient fusion, and warm with 40 parts of water. Filter-paper
dipped in this and dried at 100^ is blue. In alcohol or ether free from
G80 ABSTRACTS OF CHEMICAL PAPERS.
water, fclie colour remains unchanged, but if water be present the paper
will lose its colour, especially if warmed. J. T.
Analysis of Wine. By Y. Waetha (Ber., 13, 657— 662).— In
order to detect the presence of rosaniline compounds in red wine, the
three following tests must be employed : —
(1.) 20 c.c. of the wine are mixed with an excess of magnesium
oxide in a test-tube, and then a mixture of equal parts of colourless
amyl alcohol and ether, gradually added with frequent shaking. On
standing, the supernatant liquid becomes rose-coloured, even if the wine
contains only 1 mgrm. of rosaniline per litre. With strongly coloured
southern wines containing only a small quantity of rosaniline, the
colour is sometimes yellowish or a bright brown.
(2.) 20 c.c. of the wine are shaken with 10 c.c. of lead acetate
solution (officinal strength) and filtered into a dry test-tube. If a
moderate quantity of rosaniline be present, the filtrate is rose-coloured ;
whereas if there is only a small quantity of rosaniline or aniline-violet
the liquid is either coloui^less or only slightly yellow. In either case
1 c.c. of the above mixture of amyl alcohol and ether is added, the
liquid shaken, and allowed to stand ; the upper layer of liquid then
becomes rose-coloured if rosaniline be present.
(3.) Evaporation is unnecessary if tests (1) and (2) have indicated
the presence of a considerable quantity of the dye. If, however, this
is not the case, 150 — 200 c.c. of the wine are quickly evaporated over
a naked flame to one-fourth of their original bulk, and the hot liquid
poured into a stoppered glass cyHnder (previously cleansed with strong
nitric acid and water), and excess of ammonia added, and the liquid
carefully shaken with 30—40 c.c. of pure ether. The ethereal solu-
tion is then passed through a dry filter into a porcelain basin contain-
ing one or two threads (3 — 4 cm. long) of Berlin wool previously
washed and dried ; the ether is allowed to evaporate spontaneously in
a warm place, when the wool becomes dyed rose-coloured if rosaniline
be present. This is further confirmed by dividing one of the threads
into two parts, one of which is moistened with strong hydrochloric
acid, and the other with strong ammonia, when the colour must be
replaced in both cases by yellow if rosaniline, and by green if aniline-
violet be present. By this means "01 mgrm. of rosaniline can be
detected in 1 litre of wine.
Sulphurous acid is frequently used for bleaching the so-called
Schiller wines, a process which otherwise takes place only very slowly.
As sulphurous acid not only destroys the peculiar flavour of many
of these wines, but has also a deleterious physiological effect, it is
important to be able to detect the presence of this acid in such wines.
For this purpose 50 c.c. of the wine are gently distilled until about
2 c.c. have passed over. A few drops of a neutral solution of silver
nitrate are then added to the distillate which becomes opalescent if it
contains sulphurous acid. To prove the absence of a chloride, a little
nitric acid is added ; the liquid should become quite clear. The dis-
tillate also decolorises iodide of starch and potassium permanganate.
The latter reagents may also be used when a quantitative determina-
tion is required.
AN-VLYTICAL CHEinSTRY. 681
The author states that sulphurous acid present in wines only oxidises
very slowly, sometimes taking many years. T. C.
Estimation of Urea by Sodium Hypobromite. By C. Mehu
(Bull. Soc. Ckim. [2], 33, 410 — 415). — The recent experiments of Jay
{ihid. [2], 33, 102 and 105) have confirmed the author's statement,
that in presence of cane-sugar and glucose the quantity of nitrogen
evolved from urea by the action of sodium h3"pobromite, is increased
by 7 to 7 '7 per cent,, i.e., that approximately the theoretical yield of
nitrogen is obtained. Neither cane-sugar nor glucose by itself causes
any evolution of gas from sodium hypobromite ; on the other hand,
sodium hypobromite solution, soon after its preparation, becomes
saturated with free oxygen, and the addition of cane-sugar or glucose
prevents or greatly retards the evolution of this gas. The actual
observed deficiency of nitrogen when working with pure urea and
hypobromite varies from 8 per cent., which is the constant number
obtained under the most favourable conditions, to 15 per cent., when
very dilute solutions of urea are employed, and the temperature is
about 0" C. An addition of sugar to normal urine causes an increase
in the nitrogen evolved of 3 — 5 per cent., rarely more. The increase
is greater with urine containing little extractive matter, veiy slight
when the urine is charged with blood, pus, &c., or has begun to
putrefy. With diabetic urine containing not less than 60 grams of
glucose to 10 grams of urea, the yield of nitrogen is scarcely increased
by adding sugar. It has been long recognised that in working with
normal urine, the deficiency of nitrogen is less than it would be with
a solution containing the same quantity of pure urea. This com-
pensation, which it is not easy to estimate accurately, has been attri-
buted to nitrogen disengaged by the hypobromite from creatinine, uric
acid, and other nitrogenous substances. Considering that the weight
of uric acid present is rarely more than one-fiftieth that of the urea,
and that of the creatinine about one-sixty-fifth of the urea, and that
these compounds yield only one-half and two-thirds their nitrogen
by the action of sodium hypobromite, the author concludes that the
greater part of the compensation cannot be due to this source, but
thinks it probable that the extractive matter present acts like sugar
in increasing the yield of nitrogen from urea. To render the results
obtained with saccharine urine comparable with those obtained with
normal urine, the author recommends that in all cases cane-sugar be
added to the amount of ten times the weight of the urea present. The
difference between the actual and theoretical yield of nitrogen will
then not exceed 1 per cent. J. M. H. M.
Quantitative Estimation of Urea. By E. Pflugee (Pflilger's
Archil-., 21, 248 — 286). — In this paper the author, after discussing
various objections which have been made to Liebig's method, states that
he has found a possibility of error to the extent of 14 per cent., but
believes that the method yields good results if Liebig's directions
with certain modifications are carefully carried out. He first de-
scribes a method of preparing a pure urea from the commercial
article, and also a method of preparing a pure mercuric nitrate solu-
(582 ABSTRACTS OF CHEMICAL PAPERS.
tion. Ho then gives a number of experiments demonstrating tlic
accuracy of his solutions, and shows that the manner in which the
neutralisation is carried out affects the result very materially. For
neutralisation, he uses a soda solution, and remarks that when baryta-
water is used for neutralisation more mercury solution is required to
give the colour reaction than with soda.
If the mercury and soda solutions are run into the urea solution
alternately and in small quantities at a time, the reaction is reached
too soon, e.g., at 17*2 to 17-o c.c, instead of 20 c.c.
If the whole quantity of mercury solution required be added as
nearly as possible at once, very accurate results are obtained. The
time allowed to elapse between the adding of the mercury solution and
neutralisation is also important ; if too long, the reaction comes too
early. Experiments are given tending to show that mercuric nitrate
forms more than one compound with urea.
The author then describes his own method of carrying out Liebig's
process. The solutions required are the usual mercury solution and
a soda solution of known strength, the quantity of which required to
neutralise a known volume of the mercury solution has been accu-
rately ascertained.
For testing, he uses a plate of colourless glass on black cloth : the
mercury solution is then run in, and the sodium carbonate test applied
on the glass plate, the drops being stirred each time until the yellow
colour, which at first disappears on this treatment, becomes perma-
nent ; then neutralises.
The experiment is then to be repeated, the mercury solution being
run in quickly up to the point indicated by the trial experiment,
neutralised at once with the standard sodium solution and tested as
before.
The author's correction for concentration differs somewhat from
that given by Liebig. Fflilger's rule is : given the volume of urea
solution + the volume of soda solution necessary for neutralisation.
-j- the volume of any other fluid free from urea which was added and
call this Vi ; call the volume of mercury solution used Vo, then the
correction C is :
C = - (Vi - V,) X 0-08.
Examples ai'e given for solutions of urea of I percent., 0'5 per cent.,
0'3o per cent., 0'25 per cent., showing that this formula will hold so
long as the mixture is less than three times the volume of mercury
solution used.
Experiments are given on strong solutions with the same result.
The necessity of adding nearly all the mercui'y solution at once is again
dwelt upon, elaborate directions are then given for preparing the
mercury and soda solutions (sodium carbonate of 1"053 sp. gr. is
recommended), and in conclusion the author states that if the sul-
phates, phosphates, and chlorides be removed, and the precautions
stated are used, the method gives excellent results with urine.
W. N.
Commercial Valuation of Bituminous Rocks and Lime-
stones. By P. KiENLEN {Bi'M. Soc. Ghim. [2], 33, 459— 461).— A
ANALYTICAL CaE:\IISTl{Y. 683
stout glass tube, about 50 cm, long and 25 mm. diameter, is fitted at
one end with a cork, the other end is blown out to a bulb, below
which the tube is drawn out and furnished with a glass stopcock. The
bulb is packed with asbestos or glass wool well washed and ignited,
and 10 grams of the finely-powdered rock are introduced in alternate
layers with pounded glass, so that the tube is about two-thirds filled.
50 CO- of a mixture of equal volumes of carbon bisulphide and benzene
are now added, and the tube is allowed to stand for an hour, when
the strongly coloured liquid is drawn off and the treatment repeated
until the extract is no longer coloured. Three digestions in the cold
of one hour each are usually sufficient. The volatile liquid is carefully
distilled off in a weighed flask, the residue dried in a current of aii- at
the ordinary temperature and weighed. Some bituminous limestones
from Lobsann (Alsace) contained 12 — 16 per cent, of bituminous
matter, whilst some volcanic rocks from the Auvergne contained
nearly 24 per cent. Sulphur may be estimated by fusing the finely-
powdered rock in a porcelain crucible with 4 parts potassium nitrate,
4 parts sodium carbonate, and 2 parts sodium chloride, extracting
with water, acidifying with hydrochloric acid, and precipitating by
means of barium chloride. C. H. B.
Analysis of Heavy Mineral, Resin, and Fatty Oils, and of
Resin in Commercial Oils (Part I). By A. Kemoxt (Bull. Soc.
Chim. [2], 33, 401 — 4G6). — The oils used for lubrication, currying,
&c., may be divided into two classes : 1, non-saponifiable ; 2, saponifi-
able.
Non-saponifiahle. — Heavy Tnineral oils, consisting mainly of satu-
rated hydrocarbons, are not acted on by alkalis, and are but slightly
attacked by acids. They have an amber colour, are dichroic, appear-
ing bluish-green by reflected light, exert no action on polarised light,
and are very slightly soluble in alcohol : sp. gr. =^ 0"850 to 0'920.
When purified they have little or no smell at ordinary temperatures,
but on warming them a petroleum odour is readily perceived. At a high
temperature, the oil darkens and evolves vapours which burn with a
bright smokeless flame. When di.sti]led, very little passes over below
300°, the greater portion distilling between 300° and 360° : in the
case of very heavy oils, a considerable residue remains even at 360°.
Resin oils, obtained by distilling inferior kinds of resin with lime,
consist of hydrocarbons of the benzene and terebenthene series,
together with bodies allied to the phenols, and are slightl}^ attacked
by alkalis. N"itric acid is without action in the cold, but if warmed
a violent reaction ensues, nitrous fumes are evolved, and a semifluid
mass is formed, which, when washed with water and cooled, yields a
brittle solid, soluble in alcohol. With sulphuric acid, they are black-
ened at ordinary temperatures : when heated, sulphurous anhydride is
given off, but the oil never completely dissolves. These oils have a
characteristic odour, and are somewhat moi-e soluble in alcohol than
the preceding group: sp. gr. = 0'9G0to 0'990. They have a brownish-
yellow colour, are dichroic and generally possess a dextrorotatory
power of about + 30° ; in only one case out of fifteen was a Isevorota-
tory power of ocj =: — S° 24' observed. Stannic chloride produces a
()84 ABSTRACTS OF CHEMICAL PAPERS.
characteristic violet colour, whicli requires some time for its develop-
ment. When distilled, a portion passes over below 250°, a considerable
quantity below 300°, and almost the whole below 360°. The vapour
burns with a very smoky flame.
Saponifiahle. — Fatty acids, generally of the oleic series, are some-
times mixed with oils. They are usually liquid at ordinary tempera-
tures, have a characteristic odour which becomes more marked as the
temperature rises, have a faintly acid reaction, and are readily soluble
in solutions of soda, alkaline carbonates, borax, and sodium silicate.
Oleic acid is soluble in all proportions in alcohol, even if moderately
dilute : a large excess of the solvent causes a slight turbidity which,
if due to pure oleic acid, disappears on the addition of a few drops of
hydrochloric acid. When strongly heated, these acids give oif highly
inflammable acrid vapours, which burn with a slightly smoky flame.
Sp. gr. = 0-900— 0905.
Fatty oils, usually of animal origin, dissolve, after boiling for
some time, in alkaline solutions ; on the addition of an excess of
caustic soda, or better of common salt, the soap separates out com-
pletely. When heated at 100 — 110' with 7 or 8 per cent, of sulphuric
acid of 66° B. they are completely saponified : the fatty acid may be
isolated by washing with a large quantity of boiling water. They are
slightly soluble in cold, but dissolve completely in hot alcohol, and,
like the fatty acids, have no action on polarised light. Sp. gr. 0'910
— 0"945 according to orign.
Resi7i or Colophony, sp. gr. 1"070, derived from the cedar or pine, is
sometimes dissolved in oils in order to increase their density. It has
a brownish-yellow colour, and dissolves easily in moderately strong
alcohol ; the solution has a mean rotatory power of [a]j = -j- 15^.
Like the oils, it is readily soluble in carbon bisulphide, chloroform,
benzene, ether, and light peti^oleum. It is easily saponified by solu-
tions of alkalis, alkaline carbonates, and borax. Resin soap is not
completely precipitated by either caustic soda or common salt, about
20 per cent, remaining in solution. C. H. ]}.
Detection of Coal-Gas in Earth. By E. Komgs (Dingl. polyt. J.,
236, 430). — In some excavations at Crefeld the eai'th had an unmis-
takable odour of coal-gas. The author {Corr-blatt Ver. Anal. Chem.,
1880, 59), treated 6 litres with sulphuric acid, and passed steam into
the vessel. In the first distillate, naphthalene could be detected.
J. T.
685
General and Physical Chemistry.
Measurement of the Actinism of the Sun's Rays and of Day-
light. By R. A. Smith {Ghem. Neios, 41, 211— 212).— The process
depends on the fact that potassium iodide acidified with dilute nitric,
or preferably sulphuric acid, undergoes little or no change in the dai'k,
but on exposure to light gives off iodine, the amount of which may
be readily and exactly determined by thiosulphate. Potassium bro-
mide may be substituted for the iodine, but it is less delicate.
F. L. T.
Relative Intensity of the Spectral Lines of Gases. By J.
R. Capkon {Fhil. Mag. [5], 9, 32'J— ooO).— The author refers to
experiments described in his " Aurorse and their Spectra." Geissler
tubes containing various gases were gradually moved farther away
from the slit of the spectroscope, when it was found that the colours
of the spectrum disappeared in tlie order — red, yellow, violet, green.
Hence the brighter Hues of a spectrum may be seen singly as a matter
of intensity, independently of other causes, such as temperature or
pressure. C. H. B.
Bright-line Spectrum of Scandium. By R. Thalen (Compt.
rend., 91, 45 — 4yj. — The spectrum of scandium, as obtained by pass-
ing a powerful induction spark between aluminiuiu poles moistened
"with a solution of the chloride, is very complicated, and contains more
than a hundred lines. All the lines, which are very characteristic, are
fine, with the exception of some in the yellow and orange, and seven
strong lines in the blue-violet. A line at 4374 is slightly more re-
frangible than a prominent yttrium line, "with which it might be con-
founded. Some very faint bands, situated at 5900 — 5730, are probably
due to the oxides, as are possibly also the broad lines in the blue-violet
at 6193 — »6016. A table is given showing the "wave-lengths of the
lines in decimeters. The chloride was prepared partly by Nilson
from euxenite and partly by Cleve from gadolinite and keilhanite.
Both samples gave absolutely identical spectra. C. H. B.
Relations between the Physical Properties of Bodies and
their Chemical Constitution. By J. W. Bruhl {Ber., 13, 1119—
lloO). — The statement made in a previous communication (Ber., 12,
2135, this vol., 293) that variations in atomic refraction can occur in
the case of multivalent elements only, whilst those of univalent ele-
ments are constant in all cases, has been abundantly confirmed by a
large number of experimental determinations. The following are the
mean atomic refractions obtained : —
ra.0" (the oxygen doubly combined with the same
carbon-atom) ^3"4
TaO' (the oxygen united with the same carbon-a,tom.
by only one of its combining powers) =2*8
raH = 1-3 ; r,C' = S'O ; iaCl = 9-88
VOL. XXXYIII, 3 C
686 ABSTRACTS OF CHEMICAL PAPERS.
Or for a ray of infinite wave-lengtli Ai —
r^O" = 3-29 ; r^O' = 271 ; rjl = 1-29 ; r^C = 4-86.
T. C.
Determination of Chemical Affinity in Terms of Electro-
motive Force, Part II. By C. R. A. Wright and E. H. Rennie
(Phil. Mag. [5], 9, 331 — 347). — Decomposition of Water. — The current
from a Daniell battery was passed through a voltameter placed in a
calorimeter, and the average difference of potential between the plates
of the voltameter was determined by means of a quadrant electro-
meter. The E.M.F. representing the amount of work corresponding
to the sum of the chemical and physical changes was calculated from
the formula
= E -
haxJ
n
where « = eqiiivalent of the electrolyte, h = the heat developed in the
voltameter, and n = the amount of decomposition in grams. The
water- value of the calorimeter and the corrections for radiation were
determined with the greatest possible care.
In the case of water acidulated with 22 per cent. H2SO4 the mean
h
value of E a^J for 18 experiments, with varying battery power
and time, was 1'5000 X 10^ Corrections were introduced for the heat
absorbed by the vaporisation of the water carried away by the evolved
gases and the work necessary to separate the water decomposed from
the sulphuric acid.
A series of experiments made by the authors tends to show that the
value of J, as determined by Joule in 1867 by the electric current
method, is about 0'5 per cent, too low, owing to three sources of error,
viz., tlie higher mean temperature of the wire compared with that of
the calorimeter, the increased resistance of the wire caused by the
coating of varnish applied to it, the gi'eater heating of the B.A. unit-
coil, the wires of which were imbedded in solid paraffin, compared
with the experimental wire which was placed in water. The experi-
ments also show that where a current has to be passed through a wire
for any length of time an error will be caused by the increased resist-
ance of the wire due to its being heated to a temperature above that of
the medium in which it is placed. C. H. B.
Constant and Powerful Voltaic Pile. By E. Regnier (Covvpt.
re)id., 90, 15")0 — 1.5-53). — The zinc plate, which need not be amalga-
mated, is placed in a solution of caustic soda, and the copper plate in
a solution of copper sulphate, the two liquids being separated by a
diaphragm made of several thicknesses of parchment paper, which are
folded so as to form a rectangular inner cell. The resistance of the
solutions is diminished by the addition of suitable salts, so that the
total resistance of the cell is about 0'07-5 ohm. The E.M.F. varies
from 1'3 to 1'5 volt, according to the strength of the solutions. By
means of a current from a magneto-electric machine the various sub-
stances may be i^egenerated and used again in the cell. This indirect
■ GENERAL AND PHrSTCAL CHEMISTRY. 687
transmission of the electricity produced by machines may in some cases
be more advantageous than direct transmission. C. H. JB.
Determination of the Specific Electrical Resistance of Cer-
tain Copper-Tin Alloys. Jiy 0. J. LoiuiK {Fhll. Mag. [5], 8, 554—
558). — The following table gives the percentage composition, specific
resistance in square centimeters per second, and conductivity of a
centimeter cube in B.A. units of the six alloys examined.
Cu.
Sn.
Resistance.
ConductiTity,
A ....
19-2
80-8
12960
77100
B ....
61-8
38-2
109C0
91200
C ....
68-3
317
47660
21000
D ....
0-0
100-0
11830
84500
E ....
87-4
12G
17090
58500
F ....
90-.3
97
15270
65500
The curve representing these results agrees very well with the
induction balance curve obtained by W. C. Roberts (this vol.), but
does not so closely resemble the curve representing the conductivity
for heat of similar alloys as determined by Matthiessen. The abnormal
behaviour of the alloy C (SnCu^) is worthy of notice. C. H. B.
Analogy between the Conductivity for Heat and the Induc-
tion Balance Effect of Copper-Tin Alloys. By W. C. Roberts
{Phil. Mag. [5], 8, 551 — 553). — The curve representing the action of
copper-tin alloys on the induction balance, as determined by the
author, is very similar to that representing the conductivity for heat
of a similar set of alloys, as determined by Calvert and Johnson, the
critical points being practically the same on both curves. The alloys
occupying the critical points on the induction balance curve are re-
spectively SnCu4, a speculum metal, having a yellow-grey tint and
large conchoidal fracture, and SnCus, having a blue-grey colour and
coarse surface of interrupted crystalline plates. The two alloys pass
insensibly one into the other. C. H. B.
Freezing Mixtures formed by an Acid and a Hydrated Salt.
By Berthelot {Convpt. n//</., 90, 1191 — 1195). — The author agrees,
on the whole, with Ditte (this vol., p. 602), but points out that in the
case of hydrochloric acid and sodium sulphate the maximum thermal
effect would correspond with the formation of sodium-hydrogen sul-
phate and not sulphuric acid. Hydrated sodium sulphate may be
regarded as a system in equilibrium composed of the true hydrate, a
certain quantity of the anhydrous salt, and free water. When brought
in contact with a substance capable of acting on it, such as hydro-
chloric acid, the latter will first attack the anhydrous sulphate, since
no work is required to separate it from combined water. The removal
of the small quantity of the anhydrous salt destroys the equilibrium
of the system, a fresh quantity is produced, this is immediately acted
on by the acid, and so on until the decomposition is complete, since
none of the new products bring about special conditions of equilibrium
tending to limit the reaction. The liberated water assumes the liquid
3 c 2
GSS ABSTRACTS OF CHEMICAL PAPERS.
condition, thus causing an absorption of heat. In the case of equiva-
lent quantities of hydrochloric acid and sodium sulphate, the end pro-
ducts of the reaction cannot be simply sulphuric acid and sodium chlo-
ride, for these two substances react together, forming sodium hydrogen
sulphate and hydrochloric acid, corresponding -with the maximum
thermal effect ; and, if there were no decomposition of the products,
the reaction would cease, whatever the excess of hydrochloric acid.
But the presence of the solvent modifies the reaction, the sodium-
hydrogen sulphate is partially decomposed, and a system is formed
composed of this salt, the normal sulphate, free sulphuric acid, and
water. The sodium chloride produced causes further complications,
and the final result is a system composed of water, hydrochloric and
sulphuric acids, sodium chloride and sulphate, and sodium-hydrogen
sulphate. This system remains in equilibrium under certain limited
conditions only. If excess of hydrochloric acid is present, the
sodium chloride is thrown out of solution and the equilibrium of the
system is destroyed ; the anhydrous sulphate is acted on by the hydro-
chloric acid, more sodium chloride is produced, this is at once thrown
out of solution, and so on. The whole of the sodium chloride, is, how-
ever, only precipitated and the decomposition thus rendered complete,
when the excess of hydrochloric acid added is such that, with the water
set free, it forms a hydrate of the composition 2HC1.13 — IGHjO, in
which the salt is almost totally insoluble. This explanation holds
equally well for the reaction of other acids with other hydrated salts.
In all these cases there is first an exothermic action, in accordance
Avith the principle of maximum work. The changes which cause an
absorption of heat are dissociation of the hydrated salt; disaggrega-
tion by the solvent ; solution, which in certain cases plays only an inter-
mediate part ; and the liquefaction of the liberated water.
C. H. B.
Some General Relations between the Chemical Mass of the
Elements and the Heat of Formation of their Compounds. By
Berthelot {Compt. rend., 90, 1511 — 1515). — The law expressing the
work done by the union of two heterogeneous molecules in terms of
their mass, temperature, and distance, is not yet known, and possibly
its discovery implies that of the more general function, which includes
all simple bodies in one common equation and reduces their different
states to multiple forms of the same matter, differing in the mode of
grouping of its parts and the nature of their motions. The study of the
chemical and physical properties of the elements tends to show that
atoms have a complex structure, are endowed with a specific architec-
ture, and have complicated internal motions.
Multi'ple proportions. — When no change of physical state occurs the
heat developed by successive combinations of two elements or com-
pounds diminishes as one of the elements accumulates.
S gas + O, = SOo evolves + 35-8 x 2
SO2 + O = SO3 gas „ + 22-6
N2O2 + 0 = N0O3 „ -f 21-0
N.A + O = NA „ + 17-0
N.Oi + 0 = N,05 „ + 4-0
GENERAL AND PHYSICAL CHEMISTRY. 689
Hg, solid, 4- Bi- solid
HgBr + Br solid
evolves
+ 35-0
+ 17-6
Hg, solid + I
Hgl + I
+ 23-8
+ 11-2
Sn + Br, solid
SnBr2 + Bro
>>
5J
+ 68-8
+ 32-2
The greater part of the work is done in the first combination of
heterogeneous molecules. This does not, however, apply to endo-
thermic combinations, such as the formation of cyanogen, acetylene,
or nitrogen monoxide. As a rule, the greater the complexity of the
system formed the less its stability.
When a change of state accompanies the chemical change the heat
evolved is in many cases proportional to one of the elements and is inde-
pendent of the other. For example, the heat of formation of amalgams
rich in mercury is sensibly equal to the lieat of fusion of the mercury ;
it is almost the same for l3oth potassium and sodium. Again, the heat
of formation of KI3 from KI and gaseous iodine is equal to the heat of
vaporisation of the iodine; similar relations are approximately true in
the case of potassium tribromide and the alkaline polysulphides. The
heat of formation of complex from simple saline hydrates is approxi-
mately equal to the heat of solidification of the water.
Chemical Functions. — Carbon compounds having the same function
evolve the same amount of heat when undergoing the same transfor-
mation. For example, the union of H2 with a hydrocarbon of the
ethylene series develops heat = + 22 cals., the union of a gaseous haloid
acid with the same hydrocarbons gives + 15 cals., the combination of
0 with an aldehyde to form an acid gives + 73 cals. Isomerides of
the same function evolve very slight quantities of heat when under-
going reciprocal transformations ; if, however, the function changes a
considerable development of heat takes place. A relation which is
too well mai'ked to be accidental can be traced between the atomic
weights and the heat of formation of the binary compounds of nickel,
cobalt and iron, calcium and strontium, thallium and lead, platinum
and palladium, chlorine, bromine, and iodine. A large number of
elements, however, show very different relations. C. H. B.
Thermo- chemistry of the Oxides of Nitrogen. By J. Thomse.v
{Ber., 13, 1093 — 1095). — A comparison of the numbers obtained by
the author (ihid.,\3, 428) with those of Berthelot {Comjpt. rend., 90,
779). T. C.
Thermo-chemical Study of the Alkaline Polysulphides. By
P. Sabatier (Comjjt. rend., 90, 1557 — 15G0). — Potassium Foly sulphides.
— The tetrasulphide, K2S4.2H2O, is obtained in large red deliquescent
crystals by dissolving 3 atoms of sulphur in a solution of the mono-
sulphide. The solution of 1 equivalent in at least 250 HoO at 12'"'
caused absorption of heat =: —7h cals. The preceding compound
effloresces in a vacuum, leaving K2S4.H2O. The solution of 1 equivalent
in 100 parts H2O at 11'3'', caused absorption of heat = — 224 cals.
090 ABSTRACTS OF CHEMICAL PAPERS.
A red, translucent, anhydrous tetrasulphide, K2S4, is obtained by beat-
ing the monohydrate below a dull red heat in a current of hydrogen.
The solution of 1 equivalent in water at 15" 7° developed beat =
+ 1'2 cals. A dilute solution of the tetrasulphide was decomposed
by hydi-ochloric acid in presence of an excess of iodine dissolved in
potassium iodide, and the beat developed was measured, the necessary
corrections being introduced for the specific heat of the iodine solu-
tion, and the heat absorbed in its formation. The various calorimetric
determinations gave the following results : — •
Heat of Formation.
K3 + S4 solid = K2S4 dissolved, gave -f 117'8 cals.
Ko + S4 „ = K2S4 anhydrous ,, -f- 116'6 „
KnS dissolved -1- S3 solid = K2S4 dissolved „ -|- 5"2 ,,
KoS anhydrous 4- S3 ,, = K2S4 anhydrous ,, -f 12'4 ,,
Heat of Hydration.
K0S4 anhydrous + HoO = K.S4.H0O (solid water) evolves -1- 2-66 cals.
K.Si „ + 2H2O = K2S4.2K2O „ „ + 5-76 „
K2S4.H2O + H2O = K2S4.2H2O „ „ -f 3-10 „
Sodium PohjsidpMdes. — The tetrasulphide, ]S'a2S4, is obtained as a
red, translucent substance by cautiously fusing the monosulphide with
sulphur in an atmosphere of hydrogen. The solution of 1 equivalent
in 600 HoO at 16'5° developed heat = + 9"8 cals. The author was
unable to obtain the crystallised tetrasulphide described by Schone.
The various polysulphides were obtained in solution by dissolving as
much sulphur as possible (3"6 equivalents) in a solution of the mono-
sulphide, and then mixing this solution with the requisite proportion
of monosulphide. Calorimetric determinations, made in the same
way as in the case of the potassium compounds, gave the following
results : —
Heat of Formation from Fle^nents.
Naj + S4 solid = ]SraoS4 dissolved, gave + 108"2 cals.
Na2 -t- S3 „ = Na^Sa' „ „ + 106-4
Nao + S2 „ = Na2S2 „ „ + 104-6
ISTaa -1-84,, = Na2S4 anhydrous ,, + 98-4
Heat of Formation from the Monosulphide.
Na2S anhydrous -|- S3 solid = NaoS4 anhydrous, gave + 10-2 cals.
Na^S dissolved + S3 ,, = Na3S4 dissolved ,, + i'O ,,
NajS „ -r S2 ,, = Na2S3 „ „ 4- 3-2 „
NajS „ -f B „ = Na2S2 „ „ + 1-4 „
The solution of each successive equivalent of sulphur in the mono-
sulphide develops heat = 4- I'Scals. ; this value is the same in the
case of potassium. C. H. B.
Thermo-chemical Study of AmrDonium Polysulphides and
Hydrogen Persulphide. By P, Sabatier {Compt. rend., 91, 51 — 54).
GENERAL AND PHYSICAL CHEMISTRY. 691
Ammonium Sulphides.
Ks + Hs + S4, solid = FsH^Si solid, gives + 69-06 cals.
N2 + H, + S5 „ r= N,HsS5 „ „ + 69-46 „
K, + Hs + Ss „ = N,H,Se „ „ + 69-66 „
No + Hg + S4, solid = jS'oHgS4, dissolved, evolves + 60-8 ,,
The composition of each atom of sulphur above the tetrasulphide
causes no sensible evolution of heat.
, gas + HoS gas + S3, solid = ^211884 solid, gives + 40-0 cals.
+ S4, „ • = N.HsSs „ „ + 40-4 „
+ S:, „ = N^HsSs „ „ + 40-G „
Dry ammonia and dry hydrogen sulphide in presence of solid
sulphur combine to form a certain proportion of polysulphide.
IS'iHi.Ss was obtained in red crystals by the action of the mother-
liquor from the pentasulphide, on sulphur. Fritzsche assigned to it
the composition N2HSS7.
Hydrogen Persulphide. — Obtained by the action of hydrochloric acid
on calcium polysulphide. Its composition vai'ied between HoSe and
H2S10. This substance acts very slowly on a solution of iodine ; it was
therefore decomposed by means of solid hydrated sodium sulphide.
H2S gas + S„_i solid = H2S„ gave —5-30 cals.
H2 + S„, soHd = H3S„, absorbs —0-/0 cals.
C. H. B.
Behaviour of Carbonic Anhydride in relation to Pressure,
Volume, and Temperature. By R. Clausids {Ann. Flnjs. Chem.
[2], 9, 337 — 358). — The author discusses the several formulae which
have been proposed by Rankine, Hirn, Recknagel, and Van der Waals,
for expressing the relations between the pressure, temperature, and
volume of gases, which, like carbonic acid, depart from Marriotte's
law. He has himself investigated an expression for these relations,
and has arrived at this formula
T> T c
V - a. T(v + 3f
where _p represents the pressure, v the volume, and T the absolute
temperature, while R, c, a, and (3 are constants. Taking one atmo-
sphere as the unit of pressure, and the volume of the gas at 0° under
760 mm. as the unit of volume, the following are the values of the
constants of the formula for carbonic acid gas : — R = 0-003688 ; c =
20935; a = 0-000843; /3 = 0-000977. On comparing this formula
with the results obtained by Andrews in three recent and in three
older series of experiments on carbonic acid, the author finds the most
satisfactory agreement between the observed and the calculated values
of p, except only where the pressure amounts to 400 or 500 atmo-
spheres ; and, for reasons explained in the paper, he considers that the
divergences are more probably due to errors of experiment than to
failure of the formula. R. R.
692 ABSTRACTS OF CHEMICAL PAPERS.
Suggestion as to the Constitution of Chlorine, offered by the
Dynamical Theory of Gases. By A. W. Rucker {Fhil. Mag. [5],
9, 35 — 39).— The specific heats of a gas at constant volume (Cp) and
constant pressure (C|^), and the degrees of freedom (m) of the mole-
cules of which it is composed are connected together by the equations
(1) (a— C.)a = -0694; (2) % — + — ? — ; where e = a quan-
tity depending on the potential energy of the molecule. Kundfc and
Warburg find for mercury vapour -f- = 1'666, from which it would
follow that the atoms of mercury are smooth, rigid spheres. For 0,
C
N, H, CO, N"0, and air, -^ = 1'4, which agrees with the supposi-
tion that their molecules are surfaces of revolution, for which
Boltzmann and Bosanquet have pointed out that m = 5, e = 0.
Such a surface of revolution would be formed by two spheres rigidly
united, or, as is more probably the case, bound together by forces
which prevent the separation of their surfaces, while leaving them
otherwise free to move. The maximum number of desrrees of freedom
of a molecule composed of n smooth rigid spheres would be 3n, but
this value would generally be reduced by the forces acting between
the spheres ; «?. + e could not be greater, but might be less than 3n + e.
For a molecule composed of 2 atoms e = 0, but this value will probably
increase with the complexity of the molecule. Two tables are given,
C
the first showing the values of -^, m + e, and Sn for Hg, 0, I^, H,
air, and several compounds of C, H, 0, and S, and N ; the second
showing the values of the same quantities for certain compounds of
chlorine. In the first table on + e is always less than on, except in
the case of Hg, when the two quantities are equal ; in the second 7n + e
is greater than 3n for more than two-thirds of the compounds given.
This difference may be explained by supposing either that in the case of
chlorine e is abnormally large, which would agree with the supjiosition
that tlie ato7ns composing the molecule are less firmly united; or that n
has been taJcen too snudl, i.e., the Tnolecule of chlorine consists of more
than 2 atoms. In the last column of the second table are given the
values of 3/^ on the supposition that Cfs should be written for CI.
The differences between '6n and m -\- e are now of the same order and
sign as in Table I. Hydrochloric acid (m + e = 5), however, presents
a difficulty, since the degrees of freedom of a molecule composed of
four spheres would be greater than five, unless the spheres were
rigidly connected, with their centres in the same straight line. Bro-
mine, and raonobromethane, the only one of its compounds which has
been studied, show similar differences. These observations have a
special interest in connection with V. Meyer's researches on the
vapour-density of chlorine. ' C. H. B.
Relations between the Pressures, Temperatures, and
Densities of Saturated Vapours. By A. Winkelmann {Ann. Ghem.
Fhys., [2], 9, 358 — 393). — This paper is a continuation of a previous
GEXERAL AXD PHYSICAL CHEMISTRY. 693
communication, and in it the author discusses mathematically the
formulas which have been proposed for expressing the relations between
the pressure, temperature, and density of the vapours of ether, carbon
bisulphide, carbon chloride, acetone, and chloroform. He gives tables
in which the observed values in many series of experiments are com-
pared with values calculated from the formulae. R. R.
Heat of Vaporisation of Sulphuric Anhydride. By Ber-
THELOT (Compt. rend., 90, 1510 — 1511). — SO3 (/as + HoO + water =
SO4H2 dilute, evolves + 49*2 cais. ; the hydration of solid SO3
(80 grams) evolves + 37"4 cals., hence the vaporisation of SO3
(80 grams) at about 18'^ absorbs — 11"8 cals., a number which does
not differ greatly from that for the vaporisation of solid HoO (18 grams)
at 0°, 12-3 cals. C. H. B.
Solubility of Solids in Gases. By J. B. Hanxat and J. Hogarth
(Chem. News, 41, lU3). — The term "gas" is applied to a fluid at any
temperature above its critical point. Alcohol gas dissolves potassium
iodide, &c., and no deposition of solid occurs at temperatures much
above the critical point. The spectrum of cobaltous chloride dissolved
in alcohol gas at 320° is identical with that of the chloride at 15°.
The critical point of alcohol gas is 234"6°, at a pressure of 65 atmo-
spheres ; if the gas contain dissolved potassium iodide, the critical
point is 237° for 71"1 atmospheres pressure.
A simple and efficient modification of Andrews's apparatus is de-
scribed. M. M. P. M.
"Flashing" in Assays of Gold. By A. D. v. Riemsdijk (Chem.
Neics, 41, 126). — When a mixture of gold, copper, and silver in
certain proportions is cupelled with lead at a temperature above the
melting point of gold, the liquid metal on leaving the muffle cools
below redness, and then suddenly emits a clear greenish light.
Any means which prevents the complete fusion of the alloy of gold
and silver, or disturbs the equilibrium of the cooling mass, prevents
the phenomenon of "' flashing." The phenomenon is explained by the
author by supposing that the molten alloy is in a superf used state, and
that as it cools a limit of temperature is reached at which it suddenly
parts with its latent heat of fusion ; this evolution of heat is attended
with a fl.ash of light.
The paper contains details of the circumstances which prevent
flashing, and also deals with the j-jractical application of the plienomenon
in testing gold for metals of the platinum group, some of which do,
whilst others do not prevent flashing, and in other departments of
gold assaying. M. M. P. M.
Chemical Repulsion. By E. J. Mills {Chem. Neivs, 41, 40).
— A glass plate is covered with barium chloride solution, and another
plate, with a perforation at the centre, is pressed upon the first. When
only a thin film of the solution remains between the plates, a little
dilute sulphuric acid is introduced through the perforation. Barium
sulphate is formed, and slowly spreads between the plates. If the upper
694 ABSTRACTS OF CHEMICAL PAPERS.
plate have two circular perforations, and if sulphuric acid be intro-
duced at each, two circles of barium sulphate are formed, but the circles
exercise a visible retardation on each other at their neighbouring
edges.
If the perforations are equidistant from the centre of a square plate
and situated on the diagonal of the plate, the other diagonal is
eventually traced out in a line of no chemical action.
Various modifications of the experiment are described. The author
concludes tliat " chemical action can take place at a distance," and
that " two or more chemical actions, identical except in position, com-
pletely exclude one another." M. M. P. M.
Molecular Volumes of Solid Carbon Compounds. By H.
Schroder (Ber., 13, 1070 — 1070). — This is a continuation of the
author's previous papers (ibid., 12, 561, 1612 ; this Journal, Absts.
(1879), 610; (1880), 21.
Molee. wt. Sp. gr. Molec. Vol.
Carbon sesquichloride, aClf, 237-0 2-011 117-8
Phthalic acid, CgHoO^ 166-0 < -i .^qe 104-8
Quinone, CgHiOo 108*0 < I'^^g n'^.g
. .1 . p-u-n OAQ.n J l"438to 144-7 to
Anthraqumone, OuHgUo zOo 0 "^ -i .j^i q -i Ap.fi
Phenanthraquinone, CuHsOo 208-0 < -i.^^rvt- '\AQ^^
Metanitrochlorbenzene, CeHiNO.Cl 157-5 1-534 102-6
Thiocarbamide, CSN0H4 76-0 | |'t?n ko 1
' [ 1-450 52-4
Diethyl cai'bamide, C5H10N2O 116-0 < -■ r.^^o m -q
Guanidine carbonate, C3H12N6O3 .. 180-0 < -1.900 taka
Styracin, ChH.oO,, m. p. 40—41°]^.,,^; 1-154 228-8
(= 44^ Miiller) '^^^^v<^^ ^,-^^^ ^^^,^
Citraconic acid, CsHeOj 130-0 < -1 .^ j /^ oa.k
1-632 79-7
Itaconic acid, C5H6O4 ISO'O < -1 .e-ro
Pyrotartaric acid, CsHeOi 1320 | }
Uric acid, C5H4N4O3 168-0 |
Cyanuric acid, H3C3N3O3 + 2Aq . . 165-0 | |^^~
Camphoric acid, CicHieOj, m. p. =) onn n / I'l^S 167-5
177—178° I -uu u j -^.-^g^ -^gg.Q
Monobromcamphor, CiHoBrO, m.p.| .^o-, r, / 1-437 160-8
= 76° / -'"-^"^ 1 1-449 159-4
Benzoic acid, CH^O, 1220 | \f^^ ^"^ ^.^| *°
82-6
1-413 93-4
108 93-8
1-855 90-6
1-893 88-8
1-722 95-8
5 95-1
INORGANIC CHEinSTRY. 695
Molec. wt. Sp. gr. Molec. vol.
So|nmnitroprnsside, | ^gg. J ^^ }^|j
:sa,FeCaNeH,03 | ^ ^.gg^ -^.g.- (Dudley)
Mercuric cyanide, HgCy^ 2520 < i^.."^ , ^p.o
Silver cyanide, AgCy 1340 3-988 33-6
Pyrocatechuic acid, CHeOi.H.O . . 1720 | J.'?^^ *° JJJ'^ *°
Gallic acid, CtHsOs-H.O. 1880 | J.gg? JJJ;^
Morphine, CnHi.XC.H^O 3030 | \.f^^ ^f^.^
Codeine, CisH,iX03.H,0 317-0 { ^^ ^.^
Thebame, C^,K,,^0^ 3ir0 | \^^ ^J|^
Laudanine, C2oH,5N04 3480 | ^'.^;^? 273-3
Cryptopine, C21H23NO5 3690 1-351 2731
Papaverine, C^iH.iNO, 351-0 | ^Ij^^ *° ^f.^.^ *°
Narcotine, C3.H.^X0, 413-0 | J|^! ^° •^^^^;^ *°
Cases are mentioned confirming the former statement that carbon,
hydrogen, and oxygen always occupy the space of one stare.
T. C.
Inorganic Chemistry.
Density of Iodine Vapour. By L. Troost {Compt. rend., 91,
54 — -56). — The iodine vras volatilised in porcelain globes of 250 —
300 c.c. capacity, glazed inside and out, which were placed in a muffle
and heated in an oil furnace, the temperatures being determined by
means of the air thermometer previously described. Assuming that the
coefficient of expansion of iodine vapour is the same as that of air, the
following results were obtained : —
12.35-5°
5-82
1-241°
5-71
1250°
5-G5
Temperature .
Density
The density was also determined at the boiling point of sulphui*
under varying pressures, assuming that iodine vapour obeys Boyle's
law :-
Pressure 768*0 mm. 67*2 48-6
Density .... 8-70 8-20 7-75
The author considers that these results indicate, not dissociation or
48-57
34-52
7-35
096 ABSTRACTS OF CHEMICAL PAPERS.
an isomeric change, but that the coefficients of expansion and com-
pressibihty of iodine vapour vary respectively with the temperature
and pressure. C. H. B.
Density of Iodine Vapour. By V. Meter (Ber., 13, 1103 —
1116). — This is a reply to the remarks of Crafts and Meier (Ber.,
13, 851 ; this vol.), on the author's method (1) of determining the
temperature, and (2) of taking vapour-densities. In regard to the
former it is allowed that Crafts and Meier's objections are well founded,
for, since the measurement of the temperature of the furnace is taken
at a time very different from that at which the actual vapour-density
determination is made, it is impossible to ensure that the temperature
of the furnace remains constant throughout that length of time, and
consequently the results obtained in this way do not give the correct
relation between the temperature and the density. The author is at
present engaged in experiments with a view to ovei-come this objec-
tion.
With respect to the objections as to the modus operandi in taking
vapour-densities, it is shown by a number of special experiments that
they are entirely without foiandation, and that therefore the method
formerly described gives correct results, T. C.
Dissociation of Iodine Vapour. By A. Naumann {Ber., 13,
1050 — 1052). — On the assumption that the molecule I2 splits up into
two atoms (I + I), the author has constructed a table showing the
amount of dissociation which iodine undergoes as the temperature in-
creases. For this purpose the experimental numbers of Meier and
Crafts (ibid., 13, 851) are employed, and use is made of the formula
]3 = ^ — —^(Annalen, 1867, Suppl., 5, 345), in which d = the
normal density of the undecomposed gas, D the observed density, a
the number of atoms into which the molecule is decomposed, and p
the percentage amount of decomposition. Since a = 2, and d =
2 X 126-8 Q ^^ ,, . n 100(8-76 - D)
— — — - = 8-70, the above becomes J3 = ^^ — =- ^.
The table so constructed shows that the course of the dissociation of
iodine vapour is quite in accordance with the result required by the
mechanical theory of gases, viz., that the increments of decomposition
corresponding to equal differences of temperature increase gradually
from the temperature at which dissociation commences, up to that at
which 50 per cent, of the vapour is decomposed, and then decrease in
a similar manner up to that temperature at which dissociation is
complete.
Attention is drawn to the unusually large range of the temperature
of dissociation, viz., from about 600° to about 1800°. T. C.
Physical Constants of Hydrochloric Acid. By G. Ansdell
(Chem. News, 41, 75). — The gas was condensed in a Cailletet pump.
INORGANIC CHEiUSTRY.
697
Coefficient
Temperature.
Density.
Temperature.
of compression
0°
0-908
47-0°
0-001G6
7-5
0-873
41-6
0-00123
11-67
0-854
330
0-00096
15-85
0-835
22-9
0-000635
22-7
0-808
15-85
0-00062
33-0
0-748
10-5
0-00054
41-6
0-678
5-7
0-000397
47-8
0-619
Temp.
Yol. of
saturated
Tapour at point
of
liquefaction.
0-00°
4-00
137-
9-25
118-
13-8
103-
18 1
91-
22-0
81-
26 -75 .
69-
33-4
55-
39-4
44-
44-8
36-
48-0
31-
49-4
27-
50-56
25-
51-00
23-
31
96
50
77
19
69
75
85
34
33
64
70
96
Fractional vol.
of gas at point
of liquefaction
referred
to initial toI.
under one
atmosphere.
Volume
of
condensed
liquid.
38-89
1
45-75
1
53 19
1
61 17
1
70-06
1
82-94
1
105 -98
1
134 -33
1
168 -67
1
197 -60
1
224 -96
7
7
8
8
9
9
10
10
11
12
12
14
■35
•90
•35
-7.4
•10
-50
-12
•68
-96
-00
•92
•30
Rati •) of vol.
of liquid
to that of
gas.
18-18
15 05
12 -39
10-50
8-72
7-33
5-50
4-19
3-03
2^61
2-13
1-79
Pressure
in atmo-
spheres.
29-8
33 9
37 75
41 •SO
45-75
51-00
58-85
66-95
75-20
80-80
84^75
85-53
M. M. P. M.
Analyses of Air. By H. Macagxo (Chem. Keics, 41, 97).— The
analyses are of the air of Palermo. A marked deficiency of oxygen
is shown dnring the prevalence of the sirocco wind^( March 20th, 19-994,
and May 31st, 20-017 per cent, by volume).
The mean results are as follows : —
698 ABSTRACTS OF CHEMICAL PAPERS.
Fehruary to May.
Gram per 100 litres.
' ^
Organic Mean Eainfall
0 (yolume). CO;. HT^Oj. NH3. matter, temperature. in mm.
20717 0-033 0-000 0-008 0-102 14-2° 173-18
June to August.
20-920 0-039 traces 0-009 0-160 23-4 0-00
M. M. P. M.
Variations in the Composition of the Atmosphere, By P. v.
Jolly- and E. W. Moeley (Bled. Centr., 1880, 230— 231).— The first-
named author employs two methods for the estimation of atmospheric
oxygen and nitrogen ; the results of both fully correspond. First, the
weighing of a definite volume of air in conjunction with the estima-
tion of the sp. gr. of oxygen and nitrogen, and afterwards the direct
endiometric analysis of the air; the direction of the wind currents too
must be closely observed. The end result of the observations shows
that the oxygen of the atmosphere is subject to not inconsiderable
variations. In the year 1877 the amount of oxygen varied from 21-01
to 20-53 per cent, in the years 1875-76, 20-96 — 20-47 per cent. ; in
both years the liighest figures were obtained during north, and the
lowest during the prevalence of southerly winds, but it is not affirmed
that these directions of the air currents are always accompanied by or
are a cause of these phenomena. A change of wind, however, from
one to other of these directions is generally followed by a variation of
a half of a per cent, in the composition of the air, and a brisk rapidly
chano-inp- wind is the best condition for obtaining well mixed air.
Further observations are looked forward to to show that notwithstand-
ing the richer vegetation of the tropics, the process of oxidation is
more active there than that of reduction, whilst the reverse is taking
place in northern regions.
Morley, in the American Jour. Science, takes the foregoing expei'i-
raents into consideration, and says that if Jolly's results are trustworthy,
and show, by an examination of the air of the temperate zone, such
differences, after travelling thousands of miles and being blended with
the air of the intermediate countries, the actual difference when esti-
mated near the pole and the equator miist be gi'eat indeed, and greater
than there is any reason for supposing. He therefore thinks further
research necessary. According to a theory recently propounded by
Loomis, the sudden lowerings of temperature are not caused by the
passage of cold currents of air from higher to lower latitudes, but
rather by the vertical descent of masses of cold air from the upper
regions of the atmosphere to the lower. Morley says if this be the
case, it is easy to understand that during the lowering of the tempera-
ture the air in the vicinity of the earth's sui'face should contain less
than the average amount of oxygen, and that a sample of air taken
from such a descending mass is in reality a sample of the upper
stratum of the atmosphere before mixing with the underlying sti-ata,
and it is also possible that if that sample was part of a mass which had
long been in the higher regions, it might have lost some of the oxygen
IN ORGANIC CHEMISTRY. 699
which it contained when resting on the surface of the ocean. He also
directs attention to the fact that Jolly's analyses showed the following
quantities of oxygen :— 20-48— 20-50, 20-49—20-46, 20*56, and that in
Fehling's " Neues Handworterbuch der Chemie," an analysis of air
from the Bay of Bengal gives oxygen at 20-46, one from the neio-h-
bonrhood of Calcutta, 20-39, and from the vicinity of Algiers, 20-41.
So that from Ihis it is improbable that such great differences really
exist. J. F.
Variations in the Carbonic Anhydride of the Atmosphere.
By P. Hasselbarth and J. Fittbogen {Bied. Centr., 1880, 161 — 164).
— The experiments recorded in this paper were undertaken in conse-
quence of the considerable differences existing between the obserya-
tions of Saussure and Boussingault on the one hand, and Schulze
(at Rostock) on the other ; they were also intended to throw lio-ht on
the effect of local influences on such variations.
The following is the record of experiments : —
The average of 347 estimations made at the station of Dahme show
a mean of 3-24 vols, of carbonic anhydride in 10,000 of air, which
serves to confirm the assertion of Schulze that Saussure and Boussin-
gault's estimate of 4 to 4-15 was too high. Henneberg in estimations
made at Weende found an average of 3-2 per cent., which is confirma-
tory of those of the author. Both localities are about the same distance
from the sea.
At Rostock 1,600 estimations were made, the mean of which was
only 2-92 vols, in 10,000 of atmospheric air; the difference appears to
be caused by the situation of the place close to the sea, the water of
which possesses such power of absorption for carbonic anhydride. At
Dahme the figures varied monthly, and were lowest in December,
which the authors ascribe to the cold retarding the ordinary processes
of decay.
The figures also show an intimate connection with the direction and
strength of the wind, its direction having most influence. In Dahme
the west wind always caused an increase ; at Rostock there was an
increase during northprhj winds, and a diminution during south-
westerly. An increase in the force of the wind, no matter from what
direction, invariably decreases the amount of carbonic anhydride, and
after high winds or storms, it almost always increases ; when this
does not occur, it is due to maintenance of higher winds than usual or
a change in their direction.
Rain generally causes a depression ; a thaw causes a decrease, foo-
sometimes a small increase, sometimes a decrease.
A course of experiments made during the summers of 1876 — 1877
in Dahme on evaporation from plants shows a general decrease in
carbonic anhydride fi'om sunrise to mid-day, from thence to sunset a
regular increase. All experiments show a sudden decrease shortly
after sunrise, which is attributed to the action of the awakened and
refreshed plants. J. F.
Formation of Hydrogen Peroxide and Ozone by the Action of
Moist Phosphorus on Air. By A. R. Leeds {Ber., 13, 1066—1070).
700 ABSTRACTS OF CHEMICAL PAPERS.
—The former statement (Annalen, 200, 28G) that both hydrogen per-
oxide and ozone are produced by the action of moist phosphorus on air,
is confirmed. The dilute solution of these two bodies is not completely
decomposed even after long standing. When the current of ozonised
air is passed through a tube heated to different temperatures, the
amount of water produced by the decomposition of the hydrogen per-
oxide increases with the temperature,, whilst the quantity of ozone
regularly diminishes up to 200", when it disappears altogether ; if
after this point is reached, the aqueous solution of the gases is titrated
with a slightly acid (sulphuric) instead of a neutral solution of potas-
sium iodide, the latter undergoes slow decomposition, which is not due
to ozone, but to the action of ordinary oxygen. T. C.
An Experiment with Sulphur. By T. Gross (Chem. Centr., 1879,
785). — Tiie author doubts the elementary character of sulphur. By
heating a mixture of sulphur (commercial milk of sulphur)* and lin-
seed oil in an open basin, he obtained a black porous mass, which dis-
solved in concentrated sulphuric acid, after long-continued heating, to
form a syrupy liquid. After dilution, sulphuretted hydrogen was
passed into this liquid, and produced a light brown precipitate, soluble
in ammonium sulphide or in hot potash solution. When burnt in air,
this preci Imitate left a black residue, which was not acted on by in-
organic acids, was not attacked by oxygen even at a red heat, and was
but slowly and partially changed by chlorine with formation of a sub-
limate, which was reduced to the original black substance by the action
of hydrogen. M. M. P. M.
Crystallised Calcium Oxide. By A. Levallois and S. Meuniee
{Comjit. rend., 90, 150G — 15(38). — A crystalline mass, in some parts
white, in others slightly coloured, found on the lining of a continuous
lime-kiln which had been in almost uninterrupted operation at Cham-
pigny for 28 months, consisted partly of rounded grains, partly of
small distinct cubical crystals. These crystals, the angles of which
were in some cases slightly modified, were opalescent and had no
action on polarised light. When exposed to the air they slowly
absorbed a small quantity of water and carbonic anhydride, and when
placed in water were gradually dissolved. Dilute acids were almost
without action in the cold, but, if slightly warmed, the crystals were
rapidly dissolved with considerable evolution of heat, but no gas was
given oft'. Analysis gave the numbers CaO, 96'9 ; H20, 1*9 ; insoluble
matter, 0'8 =: 99"6 ; sp. gr., o"32. Probably the crystalline oxides of
the allied metals and magnesium may be formed in a similar way.
C. H. B.
Note. — Briigelmann (this Journal, 1878, Absts. 471 and 771) has
obtained crystals of lime, baryta, and strontia by strongly heating the
nitrates in covered crucibles. — C. H. B.
Reactions between Calcium Carbonate and Ammoniacal
Salts. By NiVET {Compt. rend., 90, 1216— 1218).— Calcium car-
* No attempt, seems to have been made bj the author to ascertain ■whether the
sulphur was pure or not.
INORGAVIC CHEMISTRY. 701
bonate when boiled with solutions of aniraoniacal compounds or
nitrogenous organic bodies, causes the evolution of ammonia equally as
well as magnesia. With solutions of ammonium salts, the evolution
of ammonia, probably as carbonate, takes place even at ordinary
temperatures. The ammonia naturally present in soils is probably
mainly in the form of carbonate ; that added as manure is generally
in the form of suljjhate. A calcareous soil very rich in humus, a very
clayey soil, a sandy soil, and Fontainebleau sand, when mixed with
water, ammonium chloride, and calcium carbonate, evolved respec-
tively in 28 days at a mean temperature of 23^, 0"00303 gram, O'OOSIO
gram, 0'01390 gram, and 0"02120 gram of ammonia. The volatilisa-
tion of ammonia is also effected by passing a current of air, free from
carbonic anhydride, through solutions of various ammonium salts, in
the presence of calcium carbonate. If, however, the air be replaced
by carbonic anhydride only, a mere trace of ammonia is given off.
Soils rich in organic matter also contain considerable quantities of
carbonic anhydride, which will tend, therefore, to prevent the diffusion
of the ammonia into the atmosphere. It would appear, then, that in
waters and in soils a double decomposition takes place between am-
moniacal salts and calcium carbonate, tending to cause a loss of
ammonia, which in the case of a soil will be greater the greater its
absorbent properties, and less the greater the amount of carbonic
anhydride in the gases in the soil. . . . C. H. B.
Characteristics of the Alkaline Earths and of Zinc Oxide.
By G. Beugelmaxn (Zeits. Anal. Chem., 1880, 283—290). — Calcium
oxide is obtained in the amorphous condition by ignition of the hy-
drate or carbonate, whilst from the nitrate it is obtained in cubes ; the
sp. gr. of both forms is 3'25.
Strontium oxide, from the oxide or carbonate, is amorphous and of
sp. gr. 4'51, that from the nitrate crystallises in cubes, and has a
sp. gr. of 4" 75. Barium oxide prepared from the hydrate forms micro-
scopic needles, which cannot belong to the regular svstem, as they
show chromatic polarisation ; the sp. gr. is •5"32 ; the nitrate on igni-
tion yields microscopic cubes of sp. gr. 5' 78. Magnesium oxide was
invariably obtained amorphous, and of sp. gr. 3'42. Zinc oxide from
the carbonate or hydrate is amorphous ; sp. gr. 5'47 ; that from the
nitrate forms microscopic hexagonal pyramids of sp. gr. 5 '78.
A. J. G.
Revision of the Atomic Weights and Quantivalence of
Aluminiiim, By J. W. Mallet (Ckem. News, 41, 212—213). — In
the determination of the atomic weight, vessels of platinum or hard
porcelain were used where possible instead of glass.
In the first series of experiments the aluminium oxide was deter-
mined, which resulted from the ignition of a known weight of ammo-
nium alum.
In the second series a solution of aluminium bromide was precipi-
tated by silver nitrate, and tlie ratio was obtained of the silver used to
form the silver nitrate, to the aluminium, bromide.
In the third series, pure aluminium (obtained by the reduction of the
bromide by sodium) was dissolved in a solution of pure soda, and the
VOL. XXXVIII. 3 d
702
ABSTRACTS OF CHEMICAL PAPERS.
hydrogen evolved was either measured directly or burnt to water, and
weighed as such.
In the following epitome of the results, A, B, C denote groups of
experiments under each series, the experiments of each group differing
only in the quantity of material operated on, while the different groups
differ in the different preparation used, or in some feature of the
method. Thus in Series I, A was made with alum, dried by exposure
to air for two hours ; B with alum dried by exposure for twenty-four
hours. In Series II, A, B, C were made with successive portions of a
distillate of aluminium bromide. In Series III, A was made by
estimating the hydrogen by volume, B by weighing the water formed
by its combustion. Only the number of experiments in each group,
the mean results from the group, and the probable error of the mean
are here given : —
Series I.
Number
Mean
Probable error. . . .
A.
5
27-040
± 0-073
Series II.
B.
5
27-096
± 0-0054
c.
ITumber
Mean
Probable error. . . .
3
27-034
+ 0-0049
Series III.
5
27-023
± 0-0052
3
27-018
± 0-0069
Number
Mean
Probable error. . . .
6
27-005
+ 0-0033
3
26-990
+ 0-0046
—
From the fact that crystallised ammonium alum gradually loses
water on exposure to air, least confidence is reposed in Series I, B,
most weight being attached to Series III, A, the resulting hydrogen
occupying a large volume, and direct comparison being made with it,
without the intervention of other atomic weights. The mean from
the thirty experiments, all included, is Al = 27-032, with a probable
error of + 0-0045. Excluding Series I, B, the mean of the remain-
ing twenty-five is Al = 27-019, with a probable error of +0-0030.
F. L. T.
Edible Earth from Japan. By E. G. Love (Chem. News, 41,
187 — 188). — The analysis of a specimen of this earth, from Toietonai
(Eat-Earth Valley), on the north coast of Yesso, and used by the
Ainos as food, gave the following results : —
INORGANIC CHEMISTRY. 703
Silicon oxide 67"19
Aluminium ,, 13"61
Iron 1-11
0-07
3-89
1-99
0-23
0-75
Sulphuric anhydride 0"19
Phosphoric ,, trace
Water and volatile matter 11 '02
Manganese
Calcium
Magnesium
Potassium
Sodium
100-05
It is of alight grey colour, and very fine in structure. This analysis
shows that the earth is essentially an aluminium silicate with silicon
anhydride, and is similar in composition to those eaten by the Javanese
and Laplanders. This clay is eaten as soup, being boiled with lily
roots in a small quantity of water, and afterwards strained.
F. L. T.
Retrogradation of Superphosphates containing Iron and
Aluminium. By C. F. Meter {Zeits. Anal. Ghem., 1880, 309—311).
— The previous conclusions of the author (ibid., 1880, 145) are in-
correct. Ferric sulphate acting on monocalcium phosphate yields
gypsum and an acid ferric phosphate, which in its turn acting on any
tricalcic phosphate present, forms insoluble ferric phosphate together
with equal quantities of mono- and di-calcic phosphates,
A. J. G.
Atomic Weight and Characteristic Salts of Ytterbium.
By L. F. NiLSON (Comj't. rend., 91, 56 — 59). — About 20 grams of pure
ytterbia were isolated from 6 kilos, of the crude earths obtained from
many kilos, of gadolinite and euxenite by the method already de-
scribed. The oxide was dissolved in acid, the solution treated with
hydrogen sulphide, and the ytterbium precipitated as oxalate, which
when heated gave the oxide in a perfectly pure condition. The mean
of seven concordant determinations of the atomic weight by convert-
ing the oxide into the anhydrous sulphate was 173'01.
The oxide, YbiOs, is a white infusible powder, sp. gr. 9'175, in-
soluble in water, easily soluble in hot dilute acids, but attacked with
difficulty, even by strong acids, in the cold. Its solutions have a sweet
astringent taste, are colourless, and give no absorption-spectrum. The
salts impart no colour to the Bunsen flame, but with the electric spark
the chloride gives a brilliant spectrum. The nitrate forms large
crystals, which melt in their water of crystallisation at 100°, and
decompose when heated with evolution of nitric acid and nitrous
fumes, and formation of insoluble basic nitrates. The sulphate,
Tb23S04.8H20, forms large brilliant prisms which do not alter when,
exposed to the air, but lose their water at 100°. It dissolves slowly
in boiling water, and is completely soluble in a saturated solution of
potassium sulphate. The anhydrous sulphate may be heated to a
high temperature without decomposition, but at a white heat is com-
3 (Z 2
704 ABSTRACTS OF CHEMICAL PAPERS.
pletely converted into oxide. The normal selenite is obtained as a
voluminous amorphous precipitate by mixing solutions of sodium
selenite and ytterbium sulphate. When treated with excess of
selenious acid it yields an insoluble crystalline acid selenite,
YbaSSeOa.H.SeOo.ffljO, which loses its water at 100°. The oxalate,
Yb23C2O4.10H2O, is formed as a voluminous precipitate of small fine
needles by the addition of oxalic acid to a solution of an ytterbium
salt ; this precipitate soon contracts, and assumes the form of short
thick prisms. It loses 7H;0 at 100°, and is but slightly soluble in
water and dilute acids.
That ytterbia is a sesquioxide is shown by the composition of the
sulphate, analogous to and isomorphous with those of yttrium and
didymium ; by the composition of the acid selenite, and by that of the
oxalate and forrnate, analogous respectively to the corresponding salts
of didymium and yttrium ; and, lastly, by the molecular heats and
volumes of the oxide and the anhydrous sulphate. C. H. B.
Action of Potassium Chlorate on Ferrous Iodide. By R. H.
Parker (Pharui. J. Trans. [3], 10, 850 — 851). — By mixing syrup of
iodide of iron and potassium chlorate together, and allowing the
mixture to stand, iodine separates out, and a red precipitate is formed,
which appears to be ferric oxide with 1 mol. of water, FeoOsHoO.
The reaction is accelerated by heating the mixture, and also by adding
excess of potassium chlorate. During the gradual precipitation in
the cold the iron remaining in solution exists in the ferrous state, but
when the action is complete the whole of the iron is precipitated.
The reaction may be expressed 2Fel3 + KCIO3 + H3O = FcoOs-HoO +
2l2 + KGl ; it is not quite certain what amount of potassium chloride
is formed, but the question is being investigated. L. T. O'S.
Composition and Analysis of Weldon Mud. By H. Luxge
(Chem. Neivs, 41, 129 and 141). — This paper is mainly devoted to a
criticism of a communication by Post in the Bericlite (12, 1454). The
author details experiments which prove that the results obtained by
acting on the " mud " with ferrous sulphate, and titrating residual
iron by permanganate, are identical with those obtained by Bunsen's
iodometi'ic method.
For estimating total manganese he gives the pj*eference to Weldon's
original method of boiling with bleaching powder, with subsequent
titration of the precipitate by iron and permanganate ; he shows that
the " mud " may be boiled directly with bleaching powder without
previous solution in acid.
His experiments also confirm Weldon's view of the composition of
the " mud," so iar as the existence of a " base " is concerned.
M. M. P. M.
Atomic Weight of Antimony. By J. P. Cooke {Chem. News, 41,
201 — 203). — In a previous paper (Proc. Am. Ac. Art. Sci., 2, 11)
reasons were given for preferring antimonious bromide as the body
for determining the atomic weight of antimony from, and 15 results
were given, with the mean value 120'00 varying between 119'4 and
120'4. These previous results were obtained from the gravimetric
IXORGANIC CHEMISTRY. 705
determination by silver in presence of tartaric acid, of the bromine in
antimonious bromide, purified by fractional distillation and crystal-
lisation from carbon bisulphide. An apparatus was also described for
subliming antimonious iodide. This has been applied to the subli-
mation of the bromide with excellent i-esults.
The process now adopted is a volumetric one. If the atomic weight
of antimony were 122"O0 it would require 179 grams of pure silver
to 2"0 grams of the bromide; if it were 12000 it would require
1"80 grams of silver to the same amount of bromide.
Vaiying weights (2 — 4 grams) of the bromide prepared by subli-
mation were taken, and slightly less than the com-esponding amounts
of pure silver were dissolved in nitric acid, evaporated to dryness,
and added to the tartaric acid solutions of the bromide. The excess
of silver required being run in from a burette, and measured with the
usual precautions. No indicator was used.
Five results obtained by this method are given, with the mean
value 120'01, and varying from 119"98 to 120'02. The atomic weights
of silver and bromine being taken as 108 and 80 respectively.
To check the work in two of the determinations the silver bromide
was collected, washed, and weighed, first after drying at 150° C, and
secondly after incipient fusion. The loss was one-tenth and two-
tenths of a milligra,m. at the second weigliing in the two cases.
These two determinations give the amount of bromine present from
the silver bromide found, and the corresponding values of Sb were
120-00 and 120-01. F. L. T.
Volatilising Point of Metallic Arsenic. By G. M. Conechy
{Chehi. New.i, 41, Ib'Jj. — On heating together metallic arsenic (in an
atnacsphere of hydrogen), argentic chloride, argentic phosphate, and
zinc iodide, gradually until the arsenic had yielded a distinct sublimate,
it was found that the zinc iodide, m. p. 446° (Carnelley), had com-
pletely melted, and the argentic chloride, m. p. 457° (Carnelley) had
agglomerated, and was on the point of melting. From this 449 — 450°
is considered to be the volatilising point, although different authors
give temperatures varying from 180° to a dull red heat.
F. L. T.
Preparation of Potassium-bismuth Iodide. By J. C. Thresh
{r/iarin. J. Traas. [3], 10, 041). — A solution of potassium bismuth
iodide may be readily prepared by mixing I'o parts potassium iodide
and 8 parts liq. bismuthi (B. P.) with 1-5 parts hydrochloric acid.
This solution forms a very delicate reagent for the alkaloids, producing
an orange-red precipitate. 1 part of strychnine in 500,000 parts of
water and 1 part of morphine in 20,000 parts of water, may be
detected by this means. L. T. O'S.
Reduction of Gold Chloride by Hydrogen in presence of
Platinum. By D. Tommasi {Chem. Netos, 41, 110). — Gold chloride is
not reduced to metallic gold by the action of hydrogen alone, nor by
the action of platinum alone ; but it is reduced by hydrogen in pre-
sence of platinum. The author thinks that hydrogen being absorbed
by the platinum disengages heat, and that this disengagement of heat
700 ABSTRACTS OF CHEMICAL PAPERS.
determines a reaction between the hydrogen and gold chloride. One
of the results (not, as supposed by Phipson, the cause) of this action is
the production of an electric current. M. M. P. M.
Action of Sulphuric Acid on Platinum. By Scheurer-Kestner
{Gompt. rend., 91, 5y — G'2). — The action of chamber vitriol on the
platinum retorts used in the process of concentration is due to the
presence of a very minute trace of oxides of nitrogen, which gives
scarcely any reaction with ferrous suljjhate, but may be detected by
means of the blue colour formed by diphenylamine. The solvent
action is greater the greater the concentration of the acid. The oxides
of nitrogen exist in the oil of vitriol in presence of selenium and sul-
])hurous anhydride, and are apparently in a state of stable combination,
since they are not expelled during the process of concentration, whereas
all the sulphurous anhydride is given off. A very minute trace of
nitrogen oxides, which appear to act as intermediate agents in the
oxidation of the platinum at the expense of the oxygen of the sulphuric
acid, is consequently sufficient to cause continuous solution of the
platinum so long as the oil of vitriol remains in contact with it. If,
however, the oil of vitriol be previously boiled with a little ammonium
sulphate, all the oxides of nitrogen are destroyed, and the action on
the platinum is prevented. Perfectly pure sulphuric acid does not
attack platinum even when heated with it in closed tubes at the
boiling point of sulphur. C H. B.
Compound Platinates and a New Platino-potassium Salt.
By L. Pitkin (Ghem. News, 41, 118). — If platinic chloride and
potassium bromide solutions containing these salts in the proportion of
PtCU to 2KBr are boiled together for some time, the salt 2KBr.PtCl4
is formed ; but if a considerable excess of potassium bromide is used,
even in presence of hydrochloric acid, or if the salt 2KCI.PtCl4 is
boiled with potassium bromide solution, the double bromide 2KBr.PtBr4
is produced. M. M. P. M.
Action of Acids on Alloys of Rhodium with Lead and Zinc.
By H. Debray {Gompt. rend., 90, 1195— 1199).— When 1 part of
rhodium is fused with 2 — 8 parts of lead in a carbon crucible the two
metals combine, with evolution of light and heat, to form a crystalline
alloy having the colour of bismuth. Dilute nitric acid removes the
excess of lead, and leaves a residue composed partly of small,
brilliant crystals of a definite alloy, Pb.Rha, insoluble in aqua regia,
and partly of a blackish powder lighter than the alloy, from which
it may be separated by levigation. The quantity of this powder
formed is greater, the larger the quantity of lead in the original
alloy. When the amount of lead exceeds 85 per cent, it constitutes
the whole of tlr) residue, in the form of blackish friable needles, with-
out metallic lustre. Examined under the microscope the surfaces of
the crystals are found to be rough, and corroded by the acid in which
they have been formed. The alloy dissolves readily in aqua regia, and
also in hot concentrated sulphuric acid with evolution of much sul-
phurous anhydride. On heating it, a small quantity of water is at first
MINERALOGICAL CHEMISTRY. 707
given off, but at about 400° the substance decomposes with, deflagration,
evolvino: nitroc'en and oxides of nitrogen, and leavinor a residue of
partially oxidised lead and rhodium. The composition of the substance
varies with the amount of rhodium in the original alloy, and the
duration of the action of the acid. Analyses gave Rh G3 — 66,
Pb 15 — 20, hygroscopic moisture 2 — 3, O + N 15 — 17 per cent. The
oxygen and nitrogen are in the proportion necessary to form nitric
acid. It cannot be regarded as a basic nitrate of rhodium and lead,
since the amount of oxygen is too small, and, moreover, potassium
hydrate is without action on it ; it is unlikely that it is analogous to
nitrated organic compounds.
The residues left when alloys of zinc with iridium, rutheniuni, and
rhodium respectively are treated with concentrated hj-drochloric acid,
have no metallic lustre, and are readily soluble in aqua regia. When
heated to about 400° they deflagrate violently without any appreciable
evolution of gas, and the products of the deflagration have a metallic
appearance, and are almost insoluble in aqua regia. It would appear
that these alloys can exist in two isomeric modifications, one of higher
energy than, and readily convertible into, the other. Nitric acid dis-
solves these residues with difficulty, but a considerable quantity of the
acid combines with the residue, owing probably to capillary affinity.
The resulting compounds, which can also be obtained by the direct
action of nitric acid on the original alloys, explode at about 400°,
evolving nitrogen and oxides of nitrogen, and leaving a residue of
partially oxidised metals. The lead-rhodium compound has probably
a similar constitution. C. H. B.
Mineralogical Chemistry.
Analyses of Two New Amalgams and a Specimen of Native
•Gold. By W. Flight (Phil. Mag. [5], 9, 14G— 147).— A specimen of
'■native silver" from Kongsberg had the composition Ag 75"900,
Hg 23'065, insol. 0*490 = 99*455, corresponding almost exactly with
the formula Ao-^Ho-. The amalg^am from Moschelladsberg has the
composition AgHg^. Another specimen from the same locality had
the composition Ag 92*454, Hg 7*195, Fe^Os 0*033, CaO 0*055,
AgCl 0*088, insol. 1*328=101*153, corresponding to Agi.Hg (Ag 92*84,
Hg 7*16). Both amalgams appear to be definite compounds. Silver,
even when fused at a bright red heat, retains mercury with great
tenacity.
A sample of washed native gold, in laminated grains and scales,
from Punta Arenas, in the Straits of Magellan, had the composition
Au 91-760, Ag 7-466, Cu 0*248, Fe^Oa 1-224 = 100*698.
C. H. B.
Artificial Formation of the Diamond. By J. B. Hanxay (Chem.
News, 41, 106, and Proc. Roy. Soc, 204, 1880).— According to the
author the alkali-metals decompose the hydrocarbons present in
parafl&n spirit at high temperatures and pressures with separation of
708 ABSTRACTS OF CHEMICAL PAPERS.
carbon. When nitrogenous compounds were present a portion of the
carbon was occasionally observed to separate in the form of diamond.
Very strong tubes must be employed ; the processes present great
difficulties.
The best results were obtained with a mixture of 90 per cent, recti-
fied bone-oil, 10 per cent, paraffin spirit, sufficient to three-fourths
fill an iron tube 20" x 4" X ^" bore, and 4 grams of litliium.
The tube was kept at red heat for 14 hours. The author is of
opinion that the diamond was produced in his experiments from the
decomposition of a nitrogen compound, and not directly from the
hydrocarbons. M. M. P. M.
Condition in which Sulphur exists in Coal. By W. Wallace
(Ghem. News, 41, 201). — It has been assumed that sulphur exists in
coal chiefly, if not entirely, as iron bisulphide. Crace-Calvert has
asserted that in some cases it is partly present as sulphates. The
author shows that in some coals the sulphur chiefly exists as an
organic compound. The following table shows the relative quantities
of total sulphur and that existing as pyrites, assuming all the iron
found in the ash to have been present as bisulphide : —
Total sulphur Sulphur as bisulphide
per cent. per cent.
Ell coal (Lanarkshire) 0-91 O'll
Main coal „ O'GO 0-42
Splint „ 0-46 0-14
Pyotshan „ 0-68 017
Soft coal from Fife 0-93 0-49
The estimations of sulphur were made by Pattinson's method, and
also by fusion with sodium carbonate and potassium nitrate. The
Ell coal was found by Crace-Calvert's method to be free from sulphates,
the others were not tested. F. L. T.
Existence of Zinc in all Primary Rocks, and in Sea Waters
of all Ages. By L. Dieulafait (Compt. rend., 90, 1573—1576). —
Zinc is found in all rocks of the primary formation. In the greater
number of the 714 specimens examined it could be detected in
50 grams, and in all cases in lOO grams of the rock. It could also be
detected in 50 grams of each of 155 specimens of non-fossiliferous,
lustrous palaeozoic schists, and in the same quantity of 579 specimens
from the lower fossiliferous deposits (siluriau, devonian, carboniferous,
and permian). In the case of sulphuretted schists, especially if contain-
ing coal, zinc could almost always be detected in 5 grams of the rock.
It was likewise found in 50 c.c. of the last mother-liquors of the
French salt-marshes. Taking into account only the quantity remain-
ing in solution in these mother-liquors the waters of the Mediterranean
contain at least 0-002 gram zinc per cubic meter. The muds of salt
marshes, of old estuaries, and of estuaries still communicating with
the sea, contain the same metal in such quantity that it can be readily
detected in 50 grams. It can also be detected in 50 grams, indeed
frequently in a much smaller quantity, of saline deposits, which the
MEsERALOGlCAL CHEMISTRY. 709
author considers to be of estuarine origin, and the specimens of
vrhich, 128 in number, were mainly taken from the upper trias, and
in a similar quantity of dolomitic rocks.
Blende is found in primary rocks, but especially at the point of
contact of these with sedimentary deposits ; the carbonate usually
occurs in the latter. The deposits of Belgium and of Vieille-MontaoTie
are in the carboniferous formation, those of Silesia are in the trias.
Now zinc is readily detected in carboniferous schists and in saline
deposits of the triassic period. Probably the zinc-compounds have
been extracted from the primary rocks by the action of sea-water, then
concentrated in estuarine deposits, afterwards redissolved by other
water, and transported in a more or less pure condition to the places
where they are now found. If the water contained no dissolved
oxygen the zinc would be deposited as sulphide, if it were freely
exposed to the air, as carbonate.
The author has, up to the present time, proved the existence in the
primary rocks of lithium, strontium, barium, zinc, manganese, and
copper, and has shown that these metals are concentrated in muddy
deposits, which are always sulphuretted. When water containino- dis-
solved oxygen or carbonic anhydride acts on the deposits, these sub-
stances undergo a series of changes terminating in the formation of
the most stable compound, which will be different in different cases :
for strontium, and especially barium, the sulphate ; for mansranese,
the dioxide ; for lead, the sulphide ; for zinc and copper, the sulphide
or carbonate, according to the quantity of air dissolved. These trans-
formations will not all take place with the same raj)idity, consequently
the different minerals will be separated, and deposited at different
points of the water's course. But the barium tends only to form the
sulphate. The formation of this compound will therefore be gradual
and continuous ; it will be deposited at all points in the course of the
water, consequently in company with all the various minerals, and also
filling the gaps between the different metalliferous deposits, as we
actually find it in lodes. It follows that all minerals having a barytic
gangue have been formed from the primary rocks by one series of
changes : hence they contain traces of rare metals, such as thallium,
indium, and gallium, which also exist in those rocks. According to
this view new metals should be sought for, not in mineral deposits
having a barytic gangue, but in such rocks as the cupriferous schists
of Mansfeld, Russia, and Bolivia, which have undergone but little
modification. C. H. B.
Presence of Iron in the Dust Showers of Sicily and Italy,
By Tacchixi {Corrqjt. rtncl., 90, loG8 — loG'Jj. — The dust showers
Avhich from time to time have fallen in Sicily and Italy contain
spherical grains of meteoric iron ; similar grains are found in the sand
of the Sahara. In all probability the sand rains of Italy and Sicily
are purely terrestrial phenomena, the sand being transported from the
desert by cyclones. C. H. B.
Formation of Sulphuretted Mineral Waters. By E. Pla\chdd
{Ckeiii,. Aeifs, 41, 'ZoOj. — Under the microscope the long delicate
710 ABSTRACTS OF CHEMICAL PAPERS.
threads usually supposed to be sulphur, found clinging to the stones
in the neighbourhood of sulphur-springs, were found by the author to
be composed of hollow cylindrical tubes matted together. Most of
these tubes were filled with spores, which, when liberated, moved about
with a rapid motion, finally came to rest, and developed hair-like pro-
cesses similar to those from which they had been discharged.
The author filled three flasks with a solution of calcium sulphate ;
into one he put dead organic matter, into the other two hair-weeds
from a sulphur-spring ; one of the latter was boiled to destroy any life
in it. All three flasks were then sealed hermetically, and left at
rest under similar conditions ; on opening it was found that only
the flask containing the living hair-weeds gave off sulphuretted
hydrogen. At the end of six months, however, the flask containing
the dead organic matter had a faint smell of sulphuretted hydrogen,
and hair-weeds were found in it on examination. Hence the author
concludes the hair-weeds are the cause and not the effect of sul-
phuretted mineral waters. F. L. T.
Organic Chemistry.
Transformation of Amylene and Valerylene into Cymene
and Hydrocarbons of the Benzene Series. By G. Bouchardat
{Compt. rend., 90, 1560 — 1563). — Pure amylene prepared from amylic
alcohol by the action of zinc chloride, was converted into the dibro-
mide, from which valerylene was obtained in the usual way, all the
intei'mediate products being carefully purified. The valerylene
(b. p. 45 — 50°) was converted into polymerides by heating at 250°.
That portion of the product boiling between 170 — 190°, consisting
mainly of divalerylene, was dissolved in twice its volume of carbon
bisulphide, and bromine, also dissolved in carbon bisulphide, was
added in the proportion of two equivalents to one of CioHig. After ex-
pulsion of the carbon bisulphide the bromides obtained were decom-
posed, partly by heat, and finally by an alcoholic solution of potash.
The purified product of this series of reactions, boiling at 170 — 190°, was
treated with sulphuric acid in order to destroy CloHie-hydrocarbons,
which had escaped the action of the bromine. On distilling the
portions not attacked by the sulphuric acid a hydrocarbon was
obtained, which had all the physical properties of cymene. This
liquid was treated with fuming sulphuric acid, neutralised with
baryta, and, after separation of the barium sulphate, evaporated to
drj'ness. The crystalline residue thus obtained consisted of barium
cymenesulphonate, and a salt corresponding in composition to barium
mesitylenesulpbonate, but anhydrous. Substances derived from
benzene have thus been obtained from amylic alcohol by successive
removals of hydrogen. The author attempted to convert diamylene
into cymene by the successive action of bromine and potash, but, like
]M. Tougolessoff, was unsuccessful. C. H. B.
ORGANIC CHEMISTRY. 711
Etherification of the Haloid Acids. By A. Villiees (Compt.
rend., 91, 62 — 64). — According to Berthelot the solutions of the
haloid acids may be regarded as solutions of the lower in the higher
hydrates. As the temperature rises these hydrates are dissociated, the
rate of dissociation being probably influenced by the presence of the
alcohol. A.S a consequence the degree of dilution necessary to prevent
etherification is increased, and the limit of etherification is also
raised.
In those cases where no water is present at the commencement of
the reaction, the limit of etherification, which is lower than for the
organic acids, cannot be due to the water produced, for its amount is
not sufficient to produce the observed effect. Probably the haloid
acids form with the alcohol compounds analogous to the hydrates, or
to the crystalline compounds of the same acids with dulcite. The
existence of such compounds is indicated, according to Berthelot, by
the heat evolved when a haloid acid is dissolved in alcohol, even under
conditions such that no etherification takes place. The etherification
is the result of equilibrium between the hydrates and the alcoholates.
C. H. B.
Etherification of Hydriodic and Hydrochloric Acids. By A.
ViLLiERS {Compt. rend., 1563 — 1566).- — Hydriodic acid acts more
i-apidly on alcohol than hydrobromic acid, and the percentage etherifi-
cation is higher, the limits being —
Ordinary temp. At 44^ At 100^
HI + 2C,HbO 71-4 — 94-2 p. c.
HI -h lOCsHsO .... 71-4 69 9 85-5 „
In the case of hydrobromic acid the limits are, at 44^, 59'5° ; and at
100°, 80"0 per cent, of the acid used. With a certain degree of dilu-
tion of the alcohol, which increases with rise of temperature, and is
greater for hydriodic than hydrobromic acid, all action ceases.
Hydrochloric acid is much slower in its action than the other haloid
acids or the organic acids, and the limits of etherification are much
lower. The rapidity of the action, however, increases rapidly with
rise of temperature, as does also the degree of dilution at which the
action ceases. At ordinary temperatures the degree of dilution neces-
sary to prevent etherification corresponds to HCl + 2H.0.
C. H. B.
Compounds of Alcohols with Baryta and Lime, and the
Products of their Decomposition. By A. Uestrem {Compt. rend.,
90, 1213 — 121.0). — When au alcohol is heated with caustic baryta or
lime in closed vessels at 150 — 175°, the two bodies combine. The
compound of ethyl alcohol with baryta decomposes at about 300°,
giving almost equal volumes of hydrogen and ethylene, together, in
all probability, with other products which, however, have not yet been
isolated. The corresponding compound of amyl alcohol yields hydro-
gen and amyleae. As a rule, the compound of the primary alcohols
with baryta, when decomposed by heat, yield almost equal volumes of
hydrogen and a hydrocarbon of CHo^ series corresponding with the
particular alcohol. The lime compounds when similarly decomposed,
712 ABSTRACTS OF CHEMICAL PAPERS.
yield hydrogen and a liquid lighter than water, having an aromatic
odour, ]3ut no volatile hydrocarbon is given oS".
When glycerol is made into a paste v^ith caustic baryta or quick
lime, and heated at about 50°, the mixture at firbt liquefies, then con-
tracts, and solidifies with considerable development of heat ; finally it
swells up, forming a granular powder. The compound thus obtained
decomposes on heating into water, hydrogen, carbonic anhydride,
and a liquid lighter than water, boiling between 76° and 210°.
This liquid unites with sodium, forming a gelatinous compound ; it
also combines with baryta and with bromine. When distilled with
phosphorus iodide it forms an iodide, wliich, when treated with silver
acetate, yields an ethereal acetate. It is probably an unsatui'ated alco-
hol. Analysis of the fraction boiling between 160 — 170° gave numbers
agreeing fairly well with the formula CioHnnO. The liquid is probably
a mixture of homologues of the formula C^HoaO, formed in accordance
with the equations : —
CsH.Oa = a.H^o
+ COo.
+ 2H,
2C3HSO3 = G^HsO
+ 2C0o
+ 3R, + H,0
SCsHsOs = C0H12O
+ SCO,
+ 4Ho + 2H2O
nCsHsOi = C2,iH4„0
+ ttCOa
+ (2?i + 2)H + n
- IHoO.
C. H. B
a-Nitrosopropionic Acid. By H. Gutknecht (Ber.,13, 1116 —
1119). — It has been previously shown (ibid., 12, 2290), that nitroso-
methylethylketone, Me.CH(NO).CO.Me, gives on reduction the base,
MeHC — CMe (m. p. = 88", b. p. = 189°; the melting point was
given as 80° in the paper referred to, which on treatment with
bromine-water gives a brom-derivative crystallising in brilliant orange-
red plates, which lose the whole of their bromine on exposure to the
air. The free base is not acted on by nitrous acid, nascent hydrogen,
acetic anhydride, or ethyl iodide.
Several derivatives of Meyer and Zublin's (ibid., 11, 692) a-nitroso-
propionic acid have been prepared, including the silver salt —
CHMe(NO).COOAg,
the potassium salt, CHMe(NO).COOK + H3O, the barium salt,
[CHMe(NO).COO],Ba,
and the copper salt, containing water of crystallisation, which it loses
at 110", and then has the composition [CHMe(NO).COO]o.Cu. In
solutions of nitrosopropionic acid ferric chloride produces a brown-red,
and cobalt nitrate a brown coloration. Nitrosopropionic acid, on
rediiction with tin and hydrochloric acid, gives alanine, and on oxida-
tion with potassium permanganate in alkaline solution, ethylniti"olic
acid. T. C.
Constitution of the Reduction-product of Succinic Chloride.
By A. Saitzeff {Ber., 13, 1061— 1062).— The reduction-product of
succinic chloride is not an aldehyde as previously stated, but the anhy-
dride of normal hydroxybutyric acid, and belongs to Fittig's series of
so-called lactones. T. C.
ORGANIC CHEMISTRY. 713
Amidolactic Acids. By E. Erlenmeter (Ber., 13, 1077 — 1079).
— The amitlolactie acid obtained by the action of ammonia on /3-chloro-
lactic acid is identical with the amido-acid of ]V[elikoif ({hid., 12,
2228), whilst Cramer's (/. pr. Chem., 96, 94) serine is isomeric with
amidohydroxypropionic acid. T. C.
Action of Phosphorus Pentachloride and of Zinc-Dust on
Succinimide. By A. Bernthsen (Ber., 13, 1047 — 1050).— With the
object of preparing piperidine, CH2<^ptt'ptt"/^NH, by the reduction
PIT C(^
of the imide of pyrotartaric acid, CHo^^pTx' p^-j^NH, the author has
made a preliminary investigation with the corresponding succinimide.
A dark green liquid is obtained by the action of phosphorus penta-
chloride on succinimide at a temperature not exceeding 50 — 55° ;
tliis liquid is separable by means of light petroleum into a crystalline
body and an oil. The former consists of flat prisms (m. p. 145 — 148°
with partial decomposition) ; on distillation hydrochloric acid is
evolved, biit a portion appears to pass over undecomposed. It con-
tains chlorine precipitable by silver nitrate ; on heatiug with soda
ammoniacal fumes are evolved, whilst on boiling with water and mer-
curic oxide, a microscopic crystalline precipitate is obtained, but no
succinimide mercuric chloride. A base substance, not pyrroline, is pro-
duced on heating with amorphous phosphorus and hydriodic acid.
Pyrroline is obtained when succinimide is distilled with zinc-dust in a
current of hvdrogen, confirming C. A. Bell's results (Be?-., 13, 877).
T. C.
Derivatives of the Toluidines. By J. Cosack (Ber., 13, 1088—
1092j. — Orthotdlijlcarbo.mide, CgHioN-O, Is obtained by the action of
potassium cyanate on orthotoluidine hydrochloride. It is easily soluble
in ether and alcohol, moderately soluble in hot, but insoluble in cold
water. It crystallises from alcohol in small plates (m. p. 185°).
Met atolylcarh amide, G^ii^^O, obtained like the ortho-compound,
crystallises from hot water in plates, and from alcohol in a mixture of
plates and needles (m. p. 142^).
Mefaditohjlcarbamide, C0(N}lC-:Ti-,)2, is prepared by heating moist
raetatolylurethane, or by heating toluidine wiih monotolylcarbamide
at 150 — 160°. It is insoluble in water, but moderately soluble in hot
alcohol, from which it crystallises in long needles (m. p. 217°).
MetatoJyhirelhane, OEt CO.NH.C7H7, is obtained by the action of
ethylchlorocarbonate on metatoluidine. It is an oil which does not
solidify at — 47°. It is easily soluble in ether and alcohol. When
distilled in the moist condition it gives ditolylarea, alcohol, and car-
bonic acid. The ortho-compound has been previously described (Ber.,
12, 1479), whilst the para-derivative was obtained by Hofmann (ibid.,
3, 653).
Orthotohjlgliicocine, C9H,iX02, was prepared by heating orthotolui-
dine chloracetate with water and toluidine. Its formation was not
accompanied by that of any dye-stuff as stated by Staats (Ber., 13,
1.37), nor did it form lance-shaped crystals, but leaflets (m. p. 14.3°).
Its copper salt, (C9HioN02)2Cu.2H20, crystallises in very small needles.
714 ABSTRACTS OF CHEMICAL PAPERS.
The metatolylglycocine could not be obtained by the reaction corre-
sponding to the alone.
Faraditolijlamine has been already obtained by Girard (Annalen,
140, 346), and also by Gerber (Ber., 6, 446). The author has pre-
pared the nieta- but not the ortho-compound by similar reactions.
Metaditohjlamine, NH (07117)2, is a thick bright yellow oil (b. p. =
319 — 320°), which on exposure to the air assumes a deep brown colour.
It is easily soluble in ether and alcohol, but only sparingly so in acids,
and is volatile with steam.
Nitroso-'paraditolylamine, N(C7H7)2NO, was obtained on adding
potassium nitrite in slight excess to a hydrochloric acid solution of
paraditolylamine. It crystallises in yellow needles (m. p. 103°).
Acetometaditolylamine, NAc(C7H7)2, prepared by the method of
Liebermann and Hormann (Annalen, 196, 319), is a thick oil, which
distils at 324° without decomposition under a pressure of 300 mm.,
and the distillate, which is the pure compound, solidifies to a mass
consisting of colourless tables (m. p. 43"). It is easily soluble in alco-
hol and ether, from which, however, it separates again in the liquid
state. T. C.
Tropeines. By A. Ladenbueg (Ber., 13, 1081 — 1088). — This is a
continuation of the author's previous paper (Ber., 13, 106).
HydroxyhenzoiiJlrope'ine, CJ5H19NO3, is obtained by evaporating equal
parts of tropine hydrochloride and hydroxybenzoic acid witli not too
dilute hydrochloric acid. It consists of thin leaflets (m. p. 226°),
which are very sparingly soluble in water, rather more soluble in
alcohol and ether, and easily soluble in acids and alkalis. The hydro-
chloride, CigHigNOsjHCl, crystallises in needles, which are easily
soluble in water and in alcohol. The sulphate,
(C,5H,9N03)3.HoS04.4H20,
was also prepared, and the platinocldoride, (Ci5H9N03.HCl)2PtCl4,
forms orange plates, which are soluble in hot water, but insoluble in
alcohol. The picrate, auro-chloride, and periodide are also described,
as well as the results obtained on the addition of various reagents to a
solution of the hydrochloride.
Parahydwxyhenzoyltropeme, obtained like the hydroxybenzoyl-com-
pound, crystallises in colourless rhombic plates (m. p. 227°), which
are easily soluble in alcohol, but only sparingly soluble in water, and
contain 2 mols. H2O, which they lose at 110°. The free base is solu-
ble in acids and in soda, but insoluble in ammonia. The nitrate,
C15H10NO3.HNO3, the platinocUoride, (Ci5Hi9N03.HCl)oPtCl4, which
crystallises from hot water in orange-coloured leaflets, and the picrate,
C15H19NO3.C6H3N3O7, were also prepared, and the behaviour of the
base towards various reagents described.
Orthohydroxyhenzoyltropeine has been previously described. Its
hydrochloride crystallises in plates or prisms which are not easily solu-
ble in water, whilst the aurochloride crystallises from hot water in
golden leaflets.
Bevzoyltropeine, C15II19NO2, is obtained like the preceding com-
pounds, except that a little benzoic acid is added from time to time.
ORGANIC CHEMISTRY. 715
It crystallises in silkj plates (m. p. 58°), containing 2 mols. H2O.
Dried over sulphuric acid it falls to powder and loses | mol. H.^O, and
the meltfag point is then 37°. It is a strong base, which dissolves
easily in acids. The nitrate, CisHjgNOa.HNOs, the picrate,
and the platmocldoride, (Ci5Hi9XO...HCl)2PtCl4.2H20, are described, as
are also the reactions with various reagfents.
PhthalyUropeine, C24H32N'204, is very difficult to obtain, and only the
platinochJoride, C24H32N204.2HCl.PtCl4, which crystallised in needles,
was prepared.
Atropijltrope'ine or anJiydrotrope'ine, C17H21NO2, is prepared like the
previous compound from atropic acid, tropine, and hydrochloric acid.
It could be obtained only in the form of an oil.
The aurochloride, CnHjiNOa.HCl.AuCls, crystallises in small needles.
Ginnoimjltropeine, C17H21XO2, was obtained from cinnamyl, tropine,
and hydrochloric acid ; it forms small leaflets (m. p. 70°), which are
easily soluble in alcohol and chloroform, but only sparingly soluble in
water ; it is a strong poison, but has at most only a slight mydriatic
action. The hydrochloride, platinochloride, and aurochloride are de-
scribed, and also the reactions with several reagents.
Oxytoluyltropeine or Homotropeine, C16H21NO3. — This base, previously
described, has not yet been obtained in the solid state. The hydrobromide
hydrochloride, and the sidphate have been prepared. As a mydriati-
cum (?) it is about as energetic as atropine, but its effects are developed
much more rapidly ; it is less poisonous than atropine. T. C.
New Azo-Colours. By J. H. Stebbings (Chem. Neivs, 41, 117).
— The compounds described are : —
Azobenzene-trinitro-hydroxybenzene, CeHs.N" ! N.C6H(N02)3.0H, crys-
tallises in brown prismatic needles, with metallic lustre, from an alco-
holic solution of picric acid, mixed with an aqueous solution of 1 mol.
of diazo-benzene nitrate. The crystals explode at 70°. They are
insoluble in cold, and sparingly soluble, with partial decomposition, in
boiling water.
Azobenzene-pyrogaUol, CeHs.X '. 'N.C6S.i(OK)3, obtained by the action
of diazo-benzene nitrate in aqueous solution or an alkaline solu-
tion of pyrogallol. The substance crystallises from glacial acetic acid
and nitro-benzene in dark red-brown needles. Alcoholic solutions dye
silk and wool gold colour.
Azobenzene-hjdroxycarboxyl-benze^ie, CgHs.N '. IS'.CgH3(0H).C00H,
an orange dye, obtained by the action of diazo-benzene nitrate on an
alkaline solution of salicylic acid.
Azobenzene-diamido-toluene nitrate, CgHs.lS' I N".C6Ho(N'H2)2.CH3, an
orange dye, obtained by acting on an aqueous solution of diazo-
benzene nitrate with a-dinitro-toluene (m. p. = 99°), filtering after
an hour, dissolving in water and decomposing by ammonia.
Diamido-azonaphthalene hydrocJi loride,
C.oHv.N : N.C,oH5(NH2)2.HCl,
a brown dye, obtained by the action of an aqueous solution of diazo-naph-
thalene hydrochloride on an alcoholic solution of diamido-naphthalene.
71G ABSTRACTS OF CHEMICAL PAPERS.
AzoheiiZPMe-cresnl-snlplmriG ncid, CrHs.N '. ]SrC6H2Me(HS03).OH, forms
hrown needles with metallic lustre : obtained by decomposing with
hydrochloric acid the product of the action of diazo-benzene nitrate on
an alkaline solution of cresol sulphonic acid. M. M. P. M.
Saliretone. By P. Giacosa (J. pr. Chem., 21, 221— 227).— A new
crystalline substance was obtained by heating saligenol and mannitol at
100° ; it did not appear to be a compound of saligeninol with mannitol,
but rather a new condensation-product of saligeninol itself. To this
body the author assigns the name saliretone. It was obtained in still
laro'er quantities on substituting for the mannitol its equivalent weight
in glycerol, and it was likewise obtained by heating saligeninol with
metbylol with a reversed condenser on the water-bath. The most
efficient method for preparing this new body is to heat equal weights
of saligenin and dry glycerol in sealed f tiles (on heating in open vessels
no saliretone, or but mere traces are obtained) for eight hours in boil-
ing water; the saligeninol melts, and the whole mass is converted to a
yellowish, homogeneous fluid. On adding water, a yellowish resinous
mass separates, partly soluble in water on boiling, from which the
saliretone crystallises out on cooling in rhombic plates and needles.
The product weighs only 2'5 per cent, of the weight of the saligenol
employed, the greater portion remaining unchanged. The saliretone
can be further purified by recrystallisation from hot water, or still
more readily by solution in very dilute cold potash solution, and pre-
cipitation by hydrochloric acid. Purified saliretone, CuHioOs, melts
at 121-5".
Saliretone gives no blue with ferric chloride ; its dry crystals, how-
ever, like salicin and its derivatives, give a fine red colour with con-
centrated sulphuric acid. The fixed alkalis dissolve it easily, but it is
reprecipitated in needles on addition of acids. Difficultly soluble in
ammonia, and precipitated on dilution. After being melted, saliretone
no longer crystallises ; heated above 140°, it suddenly evolves gas, a
distinct smell of salicylic aldehyde is observed, and a resinous body is
left. Resinous bodies were also obtained by prolonged boiling with
water, or by the action of chlorine or bromine.
Saliretone was heated at 13-5 — 140°, until the weight was constant,
the product extracted by ether evaporated, and the residue dissolved
in dilute jjotash. The resinous precipitate thrown down by hydro-
chloric acid, washed, and dried at 140°, gave numbers agreeing,
though not absolutelv, with Piria's saliretin, C7H6O (Ann. Chivi. Phys.
[2], 69, 318 ; and [3], 14, 268). P. L. T.
Formation of Hippuric and Benzoic Acids in the Animal
Organism during Fever. By T. Weyl and B. v. Anrep (Ber., 13,
1092 — 1093). — The normal urine of rabbits fed with milk and oats,
contains hippuric acid, and mostly also free benzoic acid ; during fever
the quantity of free benzoic acid increases, whilst that of the hippuric
acid diminishes ; this does not depend solely on the deficiency of
glycocoll. The absolute quantity of benzoic acid present during fever
is not greater than in the normal condition, but the form in which it
occurs is different.
ORGAXIC CHEMISTRY. 717
The normal urine of a dog fed with fatty and albuminous food
always contains hippuric acid, and mostly also small quantities of free
benzoic acid. During fever the hippui'ic acid diminishes. In a
healthy dog the greater part of the benzoic acid is converted into hip-
puric acid, whereas during fever the benzoic acid occurs in the free
state to a greater extent than under normal conditions. T. C.
Two NewDye-stufFs. ByL. Vignon and J. B. Boasson (Ber., 13,
1060 — 1001). — A claim to priority of discovery of Biebrich scarlet
over Miller {ihid., h^l) and Nietzki {ihkl., 13, 800). The authors
have also obtained an additional series of dye-stuffs, one of which has
been isolated in the pure state, and is prepared by the action of diazo-
amidoazobenzene on /3-naphtholsulphonic acid. It imparts to wool a
more beautiful and solid colour than cochineal, the shade being more
violet the higher the temperature at which the naphtholsulphonic acid
has been prepared. This dye-stuff was introduced into the trade some
months ago, under the name of Ponceau R.R. T. C.
Camphor Chlorides. By F. V. Spitzer {Ber., 13, 1046—1047).
— The nature of the products obtained by the action of phosphorus
pentachloride on camphor depends on the amount of phosphorus penta-
chloride employed, and on the temperature {Ber., 11, 1818; this Journal,
Abstr., 1879, 168). If the mixture is kept cool, the only product of
the reaction is camphor dichloride, C10H16CI3 (m. p. = 155°). The
author is unable to confirm Pfaundler's statement, that an isomeric
camphor chloride of lower melting point (70°) is obtained by the action
of 1 mol. camphor on 2 mols. of phosphorus pentachloride, or that
the chloride, CioHisCl (m. p. 60°) is obtained by heating equal mole-
cules of the same reagentfi together : for he finds that Pfaundler's
compounds are only mixtures, and that the chief product in every case
is the dichloride (m. p. 155°). When the reaction was carried out
with the application of heat, a body containing less chlorine than
CioHieClz was obtained, but the monochloride, C10H15CI, could not be
isolated. T. C.
Resins contained in Jalap. By A. F. Stevenson {Pharm. J.
Trans. [3], 10, 644 — 645). — Resin of jalap consists of a mixture of
convolvulin and jalapin. They may be separated by mixing the finely
powdered resin with pure sand, and extracting first with ether, which
dissolves the jalapin, and then with absolute alcohol, which dissolves
the convolvulin.
Jalapin, CsiHfeOie, obtained from the ethereal extract is a soft resin,
soluble in ether, light petroleum, carbon bisulphide, oil of turpentine,
chloroform, and hydrochloric acid.
Oonvolvulin, C31H50O16, is obtained as a hard resin, odourless and
tasteless, and insoluble in ether, light petroleum, carbon bisulphide,
benzene, oil of turpentine ; it is soluble in cbloroform, water, and
hydrochloric acid.
Sulphuric acid dissolves jalapin with a maroon colour, and convol-
vulin with a bright red. Both resins are soluble in potash and in
ammonia.
TOL. xx.'svni. 3 6
718 ABSTRACTS OF CHEMICAL PAPERS.
Potassium chromate, permanganate, nitrate, or chlorate gives with
jalapin an odour of rancid butter, and a brown colour ; with convol-
vulin the same odour and an olive-green colour. Manganese dioxide
gives with jalapin a dark-green colour, and with convolvulin a rose-
pink colour. L. T. O'S.
Thapsia Garganica. By C. Bi.anchet (Phami. J. Trans. [3], 10,
889 — ^\)0). — The bark of the root of the Thapsia garganica contains,
according to Martin, a rubefacient resin, tannin, starch, extractive
lime, ligneous matter, and " thapsic acid;" the latter the author believes
to be hydrochloric acid. The bark loses about 80 per cent, of its
. weight on drying, and whilst, when fresh, it yields 2 per cent, of
resin, when it has been dried and kept for one year it yields only
5*55 per cent., this is due to the oxidation of the resin. The results
of analysis are : —
Dried bark. Fresli bark.
Water — 8070
Starch 20-52 4-41
Gum and colouring matters 7*32 1'47
Resins 6-55 2-15
Matter soluble in alcohol and water .... 1"38 2'42
Elements not estimated 57-08 7*32
Inorganic constituents 8-18 1-55
100-03 100-02
These results do not agree with those of Beslier (Traite de Pharmacie,
2, 192), who obtained from the fresh root 2 per cent, of resin, and
from the dried root 15 per cent., while Nielli obtained 4-5 per cent, of
resin from the fresh root, and only 5 per cent, from the dried.
The resin is soluble in alcohol (90°), ether, and carbon bisulphide;
it is of a brown colour. When treated with boiling water it softens ;
it has an acid reaction.
The best method of extracting the resin from the bark is to treat it
with hot water, dry, and cut it, and treat with boiling alcohol (90°)
several times ; the extracts are evaporated, the residue treated with
cold alcohol (90°), and the solution alter filtration, is evapoi'ated
to the consistency of honey. The residue has an aromatic odour,
imparted to it by an essential oil, which is soluble in alcohol and
ether, to which it imparts a blue colour; it is separated from its ethereal
solution by shaking with water. The resin is very valuable as an
irritant.
A resin is also obtained from " cleka," or "false thapsia," of a
yellowish-brown colour, soluble in alcohol (90°), ether, and carbon
bisulphide ; it possesses no rubefacient properties. L. T. O'S.
Nigella Sativa. By H. G. Greenish (Phann. J. Trans. [3], 10,
909—913, and 1013— 1016).— The examinaiion of the seeds of the
l\igella sativa was undertaken to determine the relation between
their chemical constituents and those of the other members of the
subdivision HelleboraB on the one hand, and of the Pseonise on the other.
ORGANIC CHEMISTRY. 719
Previous examinations have been made by H. Reinsch (Jahrb. f.
Pharm., 4, 384), and Fliicki.^er (ibid. [3], 2, 161).
A dark brown solid fat is extracted from the seeds by lit^ht petro-
leum, and a yellow volatile oil is obtained by distillation with water.
The oil erives a red coloration when boiled with water, and a violet-
red on addition of an alkali. The aqueous extract of the seeds is of a
])rown colour, and contains a mucilage, which is insoluble in alcohol, but
soluble in hydrochloric acid. Alcohol extracts from the aqueous solu-
tion (1) a brown substance, soluble in alkalis, probably a decompo-
siiion-prodact of some tannin, and belonging to the class of phloba-
phenes ; (2) a pale yellow substance, soluble in benzene, ether, and
chloroform; and (3) an amorplious brown substance, giving an odour
of orcinol when boiled with hydrochloric acid. Water also extracts
from the seeds a sugar, a yellowish-brown amorphous mass, containing
l)ho.sphoric, hydrochloric, and sulphuric acid, and an albuminous
body.
The alcoholic extract of the seeds consists of two portions, an oil
containing a small quantity of white resin, and an amorphous mass,
the alcoholic solution of which, on fractional precipitation with water,
gave an oil coloured green by chlorophyll, a light-coloured pi'ecipitate,
and an amorphous powder, insoluble in water, benzene, carbon bisul-
])hide, and light petroleum ; it is soluble in alkalis, and sparingly
soluble in chloroform : from alcohol it crystallises in gvey, microscopic
prisms, melting at 205°. A few drops of the alcoholic solution added
to water pi-odnce a considerable frothing on shaking ; the alcoholic
solution gives with ferric chloride a yellowish-green coloration. Sul-
]ihuric acid gives a reddish coloration, changing to yellow rose-red,
and finally violet-red. Sulphuric acid and sugar give a violet-blue
colour. The author calls the substance melaidhin, its formula beinsr
C'aoHaaOT. When boiled with hydi-ochloric acid melauthin is decom-
posed into a sugar, and a substance sparingly soluble in water, melan-
thigenin, C14H23O2. It forms microscopic crystals, and gives coloor
reactions similar to melanthin.
Melanthin may be distinguished from saponin and digitonin by its
being sparingly soluble in water, and easily soluble in alcohol ; the
aqueous solution of digitonin, when boiled with dilute acid, also gives a
red coloration.
From parillin and parigenin melanthin may be recognised by being
more sparingly soluble in water, by its property of frothing, its reac-
tion with sulphuric acid, and by its rapid decomposition when boiled
with dilute acid.
Helleborein is more soluble in water than melanthin, and its decom-
position product, hellehoretin, dissolves in alcohol with a red colour,
and gives a brown coloration with sulphuric acid. Melauthin may be
distinguished from helleborin by being less soluble in chloroform, and
by the facility with which it is decomposed by dilute acids.
Caustic soda extracts from the seeds a black powder consisting of
an impure albuminoid ; the extract does not contain any alkah/id.
The solid fats contained in the seeds consist of myristic and stearic
acid.
A quantitative analvsis of the seeds is given. L. T. 0"S.
3 e -z
720 ABSTRACTS OF CHEMICAL PAPERS.
Emetine. By Podwtszotzky (Pharm. J. Trans. [3], 10, 642—643).
— Ipecacvianba is extracted with ether and light petroleum to remove
the oil, fat, and colouring matter. The latter forms a purple- red com-
pound with alkalis. From the barium compound an acid is obtained,
crystallising from chloroform in straw-coloured needles, and called
erythrocejTalem.
The residue left on extraction with ether is dried and treated two or
three times with alcohol (85°); the extract is evaporated to a syrup,
and a concentrated solution of ferric chloride added in quantity suffi-
cient to combine with all the tannin. To the solution excess of dry
sodium carbonate is added, until a chocolate colour is produced, and
the mass is extracted two or three times with hot light peti'oleum,
until all the emetine is dissolved. On cooling the concentrated solution,
emetine separates out as a white precipitate. It is precipitated from
more dilute solutions by blowing air through them ; a more expeditious
method for separating the alkaloid is to treat the powder with suffi-
cient hydrochloric acid to make a paste, add ferric chloride and
sodium carbonate, leave the mixture at rest, and exhaust it with ether.
The ethereal solution is shaken with water containing a small quantity
of an acid, which dissolves the alkaloid; and the aqueous solution is
treated with excess of soda, and boiled with petroleum spii'it, from
which the alkaloid is separated as before, and dried over sulphuric acid.
Emetine (m. p. 62 — 65") is soluble in ether, chloi^oform, ethyl
acetate, methyl, ethyl, and amyl alcohol, carbon bisulphide, oil of
turpentine, essential oils, fatty oils, fats, and oleic acid. It is very
sparingly soluble in water ; it has a bitter and somewhat astringent
taste, and is coloured yellow by exposure to sunlight. If a concentrated
solution of emetine in light petroleum is evaporated very slowly on
filter-paper, it forms acicular crystals round the edge ; its reaction is
strongly alkaline. Its salts are all soluble in water except the tannate,
an amorphous white powder.
When treated with concentrated sulphuric acid, emetine gives oxalic
acid ; heated at 150° with dilute sulphxiric acid under pressure, it was
converted into a blackish-brown substance.
A drop of sodium phosphomolybdate in sulphuric acid, brought into
contact with a particle of emetine, colours it brown, and on adding a
drop of concentrated hydrochloric acid, the colour is changed to indigo-
blue. L. T. O'S.
Preservation of Solutions of Palmelline. By T. L. Phipson
{Cliem. News, 41, 216). — It is found that ether, which has no solvent
action on palmelline and does not affect its composition nor coagulate
it, may be used with success to preserve the liquid for an indefinite
period. It has been found that salicylic acid partially destroys its
optical properties. F. L. T.
Taraxacum Root. By J. B. Baexes (Phann. J. Trans. [3], 10,
849). — Experiment proves that the alcoholic extract of taraxacum
root is superior to the extract of the pharmacopoeia. It is entirely
free from albumin and inulin, and on evaporation to dryness leaves a
bright yellow hygroscopic powder with an intensely bitter taste and
ORGANIC CHEMISTRY. 721
soluble in water. Cold water does not extract the bitter principle
from the root. By extracting the dried root with alcohol, and distilling
the solution, an oil is obtained, soluble in ether. On evaporatinp- the
ethereal solution, a tasteless green oil is obtained, L. T. O'S.
Yerba Mausa. By J. U. Lloyd (Pharm. J. Trans. [3], 10, 666
— 667). — This plant, the Anemopsis Californica, when bruised, exhales
a pungent, disagreeable odour. Its taste, which is derived from a
volatile oil, is aromatic and peppery. The oil is extracted by distillino-
the roots with water.
The essential oil is heavier than water, of a yellow colour, highly
refractive, and is soluble in alcohol, ether, carbon bisulphide, and chlo-
roform. When treated with sulphuric acid, it gives a dark red liquid,
soluble in alcohol and chloroform with a red colour, insoluble in ether.
When gently agitated with aqua regia it first gives a blue coloration,
and is afterwards decomposed, yielding a brown resinous mass.
Treated "with hydrochloric acid in the same manner it gives a deep
blue colour, which on standing changes to violet, purple, and finally
brown. By exhausting the root with alcohol, and evaporating the
extract, an oil and a gummy substance are obtained.
The oil is heavier than water ; its odour and taste are the same as
those of the root. It is soluble in ether, alcohol, chloroform, and car-
bon bisulphide ; from the last solution a red flocculent precipitate
separates out, the supernatant liquid ha'sang a light colour similar to
the essential oil. The precipitate is astringent and deliquescent.
The gummy substance purified from the oil by washing with carbon,
bisulphide is a brown granular substance (m. p. 125 — 150° F.) havino-
an astringent and peppery taste ; it is soluble in dilute alcohol and in
glycerol. By treating the dried gum with water, a flocculent residue
is obtained, soluble in glycerol and in alcohol, insoluble in chloroform,
ether, and carbon bisulphide ; it gives a black precipitate with ferrous
sulphate. The filtrate from the residue is colourless, astringent, gives
a black precipitate wdth ferrous sulphate, and with Fehling's solution
a heavy red precipitate. When the residue insoluble in water is tritu-
rated with ether and chloroform, a portion dissolves leaving an
astringent deliquescent substance, which appeai-s to be the same as the
substance which separates from the solution of the oil in carbon bi-
sulphide.
The residue from the alcoholic extract when treated with water and
acidulated water, yields astringent solution giving reactions with
Fehling's solution.
All attempts to extract any wax or resin have failed.
L. T. O'S.
• Tayuya. By D. Parodi {Pharm. J. Trans. [3], 10, 667—66Q).~
Tayuya {Trianosperma ficifolia) a plant of the family of the Cucurbi-
tacese, gave on analysis the following results : —
722 ARSTRACTS OF CHEMICAL PAPERS.
Water 11-75
Glucose 0-84
Crystelline substance soluble in- alcohol. .. . 0"24
Resin 1*17
Starch 17-23
Organic acids, woody fibre 57-39
Silica 1-02
Lime 4" 71
Magnesia 312
Iron and alumina 1-23
Potash and soda 1-30
100-00
Trianospermin, a crystalh'ne body, is obtained from the root by
treating the alcoholic extract with water, which precipitates the resin.
To the solution lead acetate is added, and the filtrate freed from excess
of lead by sulphuretted hydrogen, is again filtered and evaporated,
whereupon potash and soda salts crystallise out. Alcohol is added to
the mother-liquor to separate the gum, and the sugar by addition of
ether. The solution is evaporated to dryness, the residue dissolved in
water, and the solution precipitated with tannin. The precipitate is
mixed with magnesia, dried and exhausted with alcohol. On evapo-
rating the extract to the consistency of syrup, and shaking it with
ether, the trianospermin is dissolved, and crystallises out on leaving
the solution at rest. The solution separated from the ether contains
trianospermin and a bitter substance ; the former crystallises on addi-
tion of alcohol.
Trianospermina forms colourless and odourless needles, having a
pungent taste and alkaline reaction, and soluble in water, alcohol, and
ether. It volatilises when heated, and gives precipitates with lead
acetate and platinum tetrachloride. L. T. O'S.
Cholecamphoric Acid and its Relation to Cholanic Acid.
By P. Latschinoff {Ber., 13, 1052 — 1060). — Cholecamphoric acid
obtained by the oxidation of cholic acid (Ber., 12, 1627), has in
aqueous solution a specific rotatory power of l*]d = + 56° 10', the
amount of which is not influenced by the degree of concentration ; in
glacial acetic acid [ajn = 57° 50'. A table is given showing the solu-
bility of the acid in water and in alcohol of various strengths.
Cholecamphoric acid when treated with sulphuric or hydrochloric
acid, loses water and gives the cholanic acid obtained by Tappeiner
{Aimalen, 194, 216) from cholic acid thus : —
2CioHi«04 -= ConH2f,06 -f 2H2O.
This change is, however, accomplished more easily by means of
etherification either by the action of a current of hydrochloric acid
gas on the alcoholic solution of cholecamphoric acid, or by the action
of ethyl iodide on the lead salt in presence of alcohol. In both cases
the products are the same, viz., ethyl cholanate, tetrethylcholauic acid,
and free cholanic acid.
Ethyl cholanate, CjoHovEtOfi, is a substance resembling wax in appear-
ORGANIC CHEMISTRY. 72
o
ance (m. p. 50 — 60°). It is odourless when cold, but when warmed
smells like burning sealing wax.
Tetrethylcholanic acid, CwHsjEtiOio, crystallises on slow evaporation
in long needles (m. p. 130 — 131°), which are easily soluble in alcohol
or ether, but insoluble in water. Its salts are precipitated from
aqueous solution by means of common salt in the form of bulky
gelatinous precipitates. They are also precipitated by ammonia, and
excepting those of potassium and sodium, are only sparingly soluble in
water. The acid on saponification gives cholanic acid. In addition to
Tappeiner's description of this acid (loc. cit.}, which is in most respects
confirmed, the author makes the following remarks : — The iuipure
acid is easily soluble in ether, whereas the pure compound is only
sparingly soluble, although more so than cholecamphoric acid. The
barium salt separates from the boiling solution in the crystalline
and not in the amorphous state, and contains not 7 but 10 mols. HoO.
Cholanic acid when heated with nitric acid of sp. gr. 1'3.7 takes up the
elements of water,, and forms cholecamphoric acid, this transformation
taking place even more easily than the inverse reaction referred to
above. The choloidanic acid obtained by Tappeiner (Iog. cit.) by the
action of nitric acid on cholanic acid, is notbiug more than impure
cholecamphoric acid, and this is the sole product. This explains why
cholic acid when treated with nitric acid gives cholecamphoric acid,
whereas on oxidation with potassium permanganate it gives only
cholanic acid. The author considers that the formulae of cholanic and
cholecamphoric acids are CigHuOs and C1CH16O4 respectively, and not
the double of these. T. C.
Globulin-substances in Potatoes. By P. Zoller (Ber., 13,
1064 — lU65j. — Potato filaments contain a globulin-substance very
similar to myosin. Potato juice also contains albuminous substances
belonging to the class of globulins. These bodies are soluble in a
dilute solution of salt, but insoluble in a strong solution or in pure
water. This to a certain extent explains the influence of salt on the
growth of the plant, fur if salt be added to the soil, the aerial portion
of the plant is richer in nitrogen, and grows more rapidly, but at the
expense of the subterraneous portion. T. C.
Products of Action of Hydrochloric Acid on Albuminoids.
By J. HoRBAczEwsKi (Chem. Ct'utr., 1879, 778 — 781, and 792 — 797).
The various nitrogenous substances were digested, usually for 2 — 3
days, in flasks fitted with inverted condensers, with hydrochloric acid
(generally 1:1) and stannous chloride.
Horn yielded aspartic and glutamic acids, leucine, tyrosine, ammo-
nia, and sulphuretted hydrogen.
Human hair yielded the same products, but only about O'l per cent,
of aspartic acid.
Gelatin yielded glutamic acid, leucine, glycocine, ammonia, and sul-
phuretted hydrogen.
Hard skin of oxen and horses yielded the same products as gelatin
with traces of tyrosin. M. M. P. M.
724 ABSTRACTS OF CHEMICAL PAPERS.
Physiological Chemistry.
Feeding Experiments on Swine. By E. v. Wolff and others
(Bled. Centr., 1880, 183 — 191). — These experiments -were made with a
view of comparing the effects of food chiefly containing vegetable
albumin with that containing similar quantities of animal albuminoids.
The subjects of the experiments were pigs, a certain number of which
were fed on boiled mashed potatoes, together with split peas ; another
lot on flesh-meal and starchy food, a little linseed oil being added to the
food of the former lot in order to equalise the fat contained in the flesh-
meal. The chemical constituents of each class of food were as equally
balanced as possible. In the beginning, the amount of flesh-meal was
about one-half, increasing to three-fourths the total food, and finally
two of the animals were fed altogether upon it.
The observations were somewhat interfered with by the death of
two of the animals, and the necessity of substituting others for them.
The duration of the experiments was in both cases 182 days. During
this period the swine which received the flesh-meal gained on an
average per day per head 496 gi'ams, whilst those fed on peas, &c., in-
creased 466 grams ; the amount of food actually digested to produce
100 kilos, of live weight was in the first case 319 kilos., and in the
second 346 kilos., not a large difference, and which would be found
smaller if account were taken of several days on which those fed on
peas were not in good feeding order, which accident did not occur to
those on flesh-meal. In fact, the difference in that case is so slight,
that the authors consider the chief value of the flesh-meal consists in
its being an agreeable addition to more bulky fodder, enabling the
animals to get the same nourishment in less bulk, and that when fed
upon it, their appetite is more regular. The price of flesh-meal is an
important factor in the question for the px-actical farmer. (Compare
this vol., p. 415.) J. F.
Assimilation in Sheep of Various Ages. By H. Weisee and others
{BiecL Centr., 1880, 268 — 280). — The chief object was to ascertain the
difference in the assimilation with increasing age of the various minei'al
constituents of fodder. For this purpose two lambs of about four
months old were fed on meadow hay and split peas until they were
two years old. The results of the assimilation of the mineral as well
as of the organic constituents are given in an extensive series of tables,
from which it appears that lambs assimilate during the first year a toler-
ably constant amount of chlorine and soda, but a gradually increasing
amount of lime, magnesia, and phosphoric acid, whilst potash appears
to be assimilated in proportion to the growth of the wool. Of these the
potash, phosphoric acid, and the lime are the most requisite constituents.
At the age of two years a very small amount of mineral substances
is apparently requii'ed, of which the alkalis still predominate. The
absorption of phosphoric acid and lime has now almost ceased, whence
it may be assumed that at two years the bones are fully developed.
A. J. C.
PHYSIOLOGICAL CHEMISTRY. 725
Absorption of Lime Salts. By L. Perl {Bied. Centr., 1880,
308). — The amount of lime secreted in the urine of a dog weighing 22
kilos., to which 7'10 grams of calcium chloride had been given daily
with the food, was increased from 0"135 gram to 0*325 gram per day
and the chlorine by 6" 14 grams. These results were confirmed by
another series of experiments in which the greater part of the lime
introduced as calcium chloride was found in the feeces, but the whole
of the chlorine in the urine. The calcium chloride had probably been
decomposed by the alkaline secretion of the bowels into sodium chloride
and calcium carbonate. A. J. C.
Effect of Feeding- Cakes on Milk Production. By G. I.
Hengefeld (Bied. Centr., 1880, 233). — The author carried out his
experiments at the Royal Veterinary School in Holland upon five
cows, which for a while received 1 kilo, of maize cake in addition
to their ordinary fodder, and in the second period the same quantity
of linseed cake. There was no difference in the quantity of milk ; the
mean of six analyses showed the following variations in composition
percentages : —
"Water. Dry sub. Fat. Milk-sugar. Albumin.
Maize .... 86-3.5 13-65 4-40 4-13 5*12
Linseed 89-915 14*085 4-56 4-01 5*515
Both kinds of food produced milk of excellent quality, but the
author states that the milk, butter, and cheese, after the feeding
on maize, were cf a more agreeable flavour than after the other
fodder ; the same should hold true of the flesh of maize-fed sheep.
J. F.
Activity of Bees. By E. Erlenmbter and Planta-Reichenau (Bied.
Centr., 1880, 191 — 193). — This paper is a sequel to former reports on a
similar subject (see this vol., 415), being further experiments made to
ascertain whether the wax secreted by bees is derived from the sugar
and other hydrocarbons which are found in the nectar of the flowers, or
from such nitrogenous matters as exist in the pollen. A healthy swarm
was bought in February, well cared and fed, and at the beginning of
the experiments was in a very healthy condition. A determined
number of the bees were carefully weighed, and with the queen trans-
ferred to the experimental hive, which was furnished with all appli-
ances requisite for carrying out the experiments. The food was
weighed in tared capsules ; before the weighing of the swarm 50 of the
bees were killed with chloroform vapour, and used for fat and nitro-
gen determinations. Each experiment lasted four days and four
nights, and for a whole day the animals were confined to the hive.
The bees were first fed with a solution of sugai'-candy, and a remark-
able yield of wax was the result. The suggestion was made that the
albumin in their bodies contributed to it, but both the nitrogen and
the fat were the same before and after the experiment. A second trial
was made by feeding the bees on honey, but the quantity of wax pro-
duced was less. Further observations, extended over longer periods,
were made with a view to see what effect temperature would
have on the production of wax. The first, made during favourable
72G ABSTRACTS OF CHEMICAL PAPERS.
weather on sugar-cancly solution mixed with 1 per cent, of wheat flour,
gave very good results ; the second, carried on simultaneously on honey
and wheat flour, gave good, but still inferior results ; the third, with
th.e same food as the first, but in less favourable weather, gave a much
inferior yield ; in another experiment the small proportion of 0"22 per
cent, dry gelatin was added to the sugar solution with unsatisfactory
results, whilst a much larger proportion of gelatin, 1 ^ per cent., added
to honey produced a very large amount. When, however, the quan-
tity of gelatin was increased to 5 per cent., and when a mixture of 20
parts peptone and 20 parts honey w^as employed, the bees refused their
food altogether, and most of them died. A mixture was made of 1'18
parts glutinous peptone, 100 parts sugar, and 60 parts rose-water ; it
was all eaten, but neither honey nor wax produced ; the bodies of the
bees were distended, their honey-bags full, but their stomachs empty.
A mixture of 342 grams sugar-syrup and 28 grams egg-albumin was
also quickly consumed, but no honey or wax obtained; a similar mix-
ture of egg-yolk (24 to 414 sugar syrup) produced a small proportion
of wax only. As general results the authors believe that the food of
bees should not be highly nitrogenous, and that beeswax is formed from
non-nitrogenous substances, especially sugar.
Erlenmeyer is further of opinion that the fatty portions of the
bees' bodies are formed solely from hydrocarbons, the albuminoids
only playing the part of nourishment to the active organs, keeping
them in working order and supplying waste. J. F.
Extractives from Muscles. By B. Demant (GJiem. Centr., 1879,
790). — The amount of creatine (and creatinine) increases rapidly in
the muscles of pigeons kept without food. Xanthine and hypoxanthine
decrease regularly in the muscles of healthy pigeons, but increase
during long-continued inanition.. Lactic acid decreases during inani-
tion. M. M. P. M.
Chemistry of Vegetable Physiology and Agriculture.
Influence of the Galvanic Current on Bacteria. By F. Cohn
and B. Mendelshon {Bied. Centr., 1880, 226— 227).— The authors
carried out their experiments to verify the assertion of Schiei, that the
galvanic current prevented the development of bacteria.
The results were that a feeble current from one pair of elements had
no perceptible effect ; a current from two elements rendered the solu-
tion inactive at the positive pole ; a current from five continued for 2 fc
hours completely sterilised the whole solution, and deprived it of its
power to infect another solution. The solution at the positive pole was
first affected, with the stronger current the liquid became acid at the
positive and alkaline at the negative pole. The induction current had
no perceptible effect on the bacteria. J. F.
Effect of Putrefactive Changes on Bacteria. By Wernich
{Bied. Centr., 1880, 224 — 226). — In all solutions containing bacteria
VEGETABLE PHYSIOLOGY AXD AGRICULTURE. 727
a time arrives when they cease to propagate, and after a longer time
they lose their power to induce further life in fresh nutritive solutions.
This admitted fact leads to the belief that the putrefaction induced by
bacteria produces substances which are poisons to these organisms.
Experiments were made on meat-extracts of various ages with phenol,
skatole, indole, and otlier putrefaction-products, all of which were
found to exercise an injurious effect on bacteria ; moreover substances
most disposed to putrefaction were easily preserved from it by means
of any of them in fresh solutions which were purposely impregnated.
The addition of trifling quantities of these matters promptly caused
inactivity of tlie bacteria, and the author considers he has fully proved
the truth of Baumaun and Nencki's propositions on the subject.
The experiments in question lead to the solution of a highly inter-
esting problem in pathology. The author says that the same or similar
operations are carried out in the progress of septic diseases ; the sup-
position that the organisms which are the cause of infectious diseases
give rise to products which eventually cause their own distinction
is the only way in which the progress of these diseases can be pro-
perly comprehended. Many sicknesses, such as smallpox, measles,
scarlet and relapsing fevers, which are now generally ascribed to the
presence of bacteria, progress so peculiarly and take such a regular
course that one is forced to believe that, with, the cause of the malady,
its own distinctive poison is produced in the same manner as in the
experiments here noted. J. F.
Bacteria in the Atmosphere. By Miflet {Bled. Centr., 1880,
227 — 228). — The autlior reports the results of numei'ous experiments
on the germs of bacteria contained in the air, and draws the following
conclusions therefrom : —
That the air contains numerous fertile germs, which can be gathered
by the experimentalist and systematically propagated and classified ;
that not only does the air contain the fertile germs of well-known
species, such as micrococci and bacilli, but of other peculiar species
which are not classified ; but that on the other hand the germs of the
bacteria of ferments, the Bacterium termo, the ferment of putrefaction,
spirilli, &c., have not been recognised. Air drawn through soil has
sometimes shown the presence of bacteria germs ; but on the other
hand the air from the rooms of a crowded hospital for spotted typhus
fever was found to be quite free, probably in consequence of excellent
ventilation and disinfection. Air taken from above a sink was rich
in fruitful germs. J. F.
Atmospheric Bacteria. By P. Miguel (Compt. rend., 91, 64 —
Q7). — The number of bacteria present in the air is very small in
winter, increases in spring, is still higher in summer and autumn, and
decreases rapidly during hoar frosts ; during dry periods the number
of bacteria is high, that of mould-spores is low ; in wet periods, the
number of bacteria is very low, that of mould-spores is high. The
author has endeavoured to determine the number of bacteria in a given
volume of air, but with no definite results. On certain days during
the winter 200 litres of air produced no change in solutions very liable to
728 ABSTRACTS OF CHEMICAL PAPERS.
alteration ; in some cases air taken from quiet rooms was without
effect in quantities less than 30 litres ; in the case of air taken near
sewers 1 litre was sufficient. Comparing the amount of bacteria in
the air with the prevalence of zymotic diseases, the author concludes
that an increase in the amount of bacteria is apparently followed,
after an interval of eight days, by an increase of contagious and epi-
demic diseases, but the evidence is not sufficient to definitely settle the
question. Other experiments lead to the conclusion that the vapour
of water rising from the soil, from rivers, or from masses in full putre-
faction, is free from germs ; that the gases evolved from decaying
substances, and the air passed over putrid meats are free from germs,
provided that the putrefying substance is as moist as soil taken 0*3 m.
from the surface. The author has inoculated many living animals
with bacteria of various kinds, but without any physiological effijcts.
C. H. B.
A Digestive Ferment of the Juice of the Fig-tree. By
BoucHUT {Gompt. rend., 91, <67 — <6d). — The milky juice which is found
in small quantity in the common fig-tree, was collected in Provence
in the month of April. 5 grams of the partially coagulated substance,
consisting of a syrupy liquid, and a wliite, sticky, resinous, elastic,
aromatic coagulum were mixed with 60 grams distilled water, 10
grams of moist fibrin added, and the mixture kept at a temperature of
50°. In less than 24 hours the fibrin was completely digested, leaving
a small quantity of white, homogeneous residue. A further quantity
of 10 grams, then 12, then 15, in all 90 grams of fibrin were added in
the course of a month. Each successive quantity was completely
digested in 24 hours, and each left a white residue, the composition of
which has not been determined. The liquid showed no signs of fer-
mentation or putrefaction. C. H. B.
Chemical Changes in Nitrogenous Substances during Fer-
mentation. By.M. DelbriJck: and others {Bied. Centr., 1880, 217 —
222). — This is an endeavour to estimate quantitatively the amount of
yeast formed during fermentation by examination of the mash before
and the filtrate at the end of the process. The authors pi'oceed from
the standpoint that the mash is a solution of nutritive material, from
which the yeast-cells in their growth abstract the matter necessary for
their development, and that consequently the difi^erence in the amount
of this material found at two examinations is an exact measure of the
yeast produced, the chemical composition of the yeast itself remain-
ing constant. The sugar contained in the mash cannot be taken as a
standard, as it splits up into alcohol and carbonic anhydride, and these
(.lo not remain in the yeast. It is otherwise, however, with albumin-
ous matters, of which the yeast shows a percentage of 60 per cent, in
the dry substance, these can be taken as an exact measure of the yeast
production.
The difficulty of directly estimating albuminous bodies leads the
authors to measure them by means of one of their constituents, nitro-
gen, and they find the process exceedingly accurate : for example, in
one experiment they found for 100 parts of nitrogen, which was con-
tained in the sweet mash, undissolved in the ground malt 46"2 parts,
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 729
dissolved in the filtrate 53"8, total 100 parts ; and after fermentation
undissolved in the grains and yeast 64*8, dissolved in the filtrate 35"2,
total 100 parts, showing that 18'G parts of nitrogen had passed from the
soluble to the insoluble state. A series of experiments was made with
like results, and the authors formulate the following rule. The abso-
lute quantity of yeast pi'oduced in a mash is independent of the
dissolved sugar, but depends directly on the amount of soluble nitro-
genous matter. The authors discuss the supposition that a combination
of the alcohol with the acid might lead to production of albuminoids,
but dismiss it as untenable, having found that a quantity of about 1'2 per
cent, lactic acid caused very little separation of those substances.
To settle the question they took 100 c.c. of clear filtered sweet mash,
and mixed it with 15 c.c. of 90 per cent, alcohol, so that the mixture
contained about 12 per cent, of alcohol. jNIany hours' observation
failed to show any results which would tend to lessen the value of the
proposed mode of estimation. Another important point in regard to
fermentation which the authors propose to decide is the period at
which the yeast cells are formed, and they believe that in this matter
also the estimation of the soluble nitrogenous matter is a valuable
indicator, as shown by the following experiment : the mash was of
potatoes with 4 per cent, of barley malt, and they found that at the
beginning of the head fermentation 33 per cent, of the soluble had
become insoluble, at the end of the head fermentation 35"4 per cent.,
and at the complete termination of the fermentation 36 '1 per cent.,
the vast bulk of the yeast having been formed before the visible work-
ing commenced. Thev draw the conclusion that the formation of
yeast cells has practically no connection with the visible working of
the mash.
Another experiment had an unexpected result : the mash was the
same as in the former instance, but the temperature at which the
operation was carried out was 2" Reaumur lower. After the top fer-
mentation was over there was a considerable increase in the amount
of soluble nitrogenous matter existing in the filtrate, as much as 7'5
per cent, which had previously become insoluble reverting to the solu-
ble condition. The authors believe that if the temperature is too low
there is a decomposition of the yeast, but they have not fully investi-
gated this aspect of the subject. J. F.
Seed Production of Red Clover. By G. Haberlandt (Bled.
Centr., 1880, 19'j — 2ul). — Every farmer who raises red clover for the
sake of the seed is aware of the uncertainty of its produce. The
quality of the crop frequently suffers from the unequal ripening of
the seeds, and this in a far greater degree than is the case with
other field crops. Darwin's researches have shown clover to be
one of those plants whose fructification depends on the visits of insects.
The florets of any individual head of blossom are not all at one time in
a fit state to profit by the visit of those insects, the lower florets ex-
panding first, the upper later, and when these are in full bloom the
lower have decayed, or at least are on their way to decay ; when the
crown of the stalk has bloomed the florets are weakly and unattractive
to insects.
730 ABSTRACTS OF CHEMICAL PAPERS.
The author's researches confirm this view. A certain number of the
ripe flower-heads, all grown under precisely similar conditions, were
examined as to the proportion of fruitful and sterile florets, and it
■was found that in the upper portion the fruitful seeds predominated ;
whilst the reverse was the case in the under portion of the flower
head. Some seeds were barren in the upper florets, but they were
too few to affect the proportion.
Under favourable circumstances the greater pai*t of the florets would
be fructified, but those circumstances rarely occur, and for a rarely
successful crop of seed, a vigorous and quick bloom, and an active
visitation of insects is necessary ; whilst bad results are to be expected
i'rom dull rainy weather, which retards blossoming and is unfavourable
to insect life. The author suggests the encouragement of bees about
clover farms, but can propose no other remedy for the unequal bloom-
ing- of the flowers than a careful selection of the seed. J. F.
Germination of Beet Seeds. By P. Putte (Bied. Centr., 1880,
196 — 199). — The author's ol)ject in the experiments reported was to
ascertain the effect of steeping the seed of the sugar beet in manure
materials. During the previous year, he had made experiments with
potassium nitrate, which was employed to the amount of 2| times the
weight of the seeds, either in fine powder applied, or in the form of a
solution of the strength of 22° Baume. Seeds steeped for 24 hours
germinated easily and quickly ; on the appearance of the seedling
leaves they took a fine colour, and developed more strongly than seed
which had not been so treated. Superphosphate has been tried in
concentrated solution, but is unsuitable by reason of its acid and cor-
rosive nature, and the difficulty of drying the seeds sufficiently for the
sowing machine. If employed at all it should be in the form of dried
powder.
The germination of the beet seed, begins between 6 — 7° C. ; at this
temperature it takes about 20 days to appear above ground. At less
than 6° the growth is arrested, to recommence when the temperature
is raised ; it is, therefore, necessary to sow in April. In the begin-
ning of the month the midday heat alone is useful, and it does not
penetrate deep enough into the soil, hence the necessity of shallow
sowings of this seed. It also requires a large amount of moisture, and
if sown deep or too early the tender shoots are unable to pierce the
thick layer of earth which covers it.
The author has had good results in practice from 48 hours' steeping
in liquid stable manure, and drying sufficiently to sow. Instead, how-
ever, of spreading the seeds to dry they may be gathered in heaps and
allowed to heat sufficiently to start the germination; in 5 or 6 days
the radicula appears, and sowing should be immediately proceeded
with. In well prepared ground the growth proceeds without inter-
ruption, and in less than 14 days, if sown in the middle of April,
there is a well grown crop of seedling.
No better cultural instructions can be given for beets than those
which are followed successfully with potatoes. The choice of soil,
manures, and all conditions are similar, and for both a late vegetation
is undesirable, as it diminishes the time for coming to maturity, until
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
whicli, the full quantity of sugar is not obtainable. Sugar can be
found at all stages in the growth of the beet, but it is much less in the
growing plant than when the cells are fully formed and their produc-
tion has ceased. In the plains of Algeria the beet is indigenous and
an annual ; there is no repose in vegetation, no need for the plant to
store up sugar for future use ; this is pi'obably the cause of the small
yield of sugar in the beets of Spain, Southern France, and Italy. The
beet thrives best in countries where a hot summer is followed by sudden
and great cold, in such places it is biennial and accumulates a supply
of sugar for its future needs. Mild damp climates, with many wind
currents from the sea are unfavourable.
The author believes that the excellence of the roots grown in
Bohemia, Poland, and Russia is due rather to these conditions of
climate than to care in cultivation. J. F.
Quantities of Amides and Albuminoids in Green Plants :
Decomposition of Nitric Acid and Ammonia in Plants. By O.
Kellxer (CAem. Centr., 1879, 744—749; 761— 768).— The author's
results, which are arranged in the following table, show that green
plants contain notable quantities of nitrogen in the form of amido-
acids and acid amides.
The original paper contains a discussion of these results from the
point of view of physiological botany.
Experiments are also detailed which show that peas grown in sand
soaked with calcium nitr-ate, ammonium chloride, and ammonium
nitrate respectively, and watered with solution of the same salts, con-
tained from 5 to 7 per cent, of their total nitrogen in the form of
amido-acids and acid amides, and about 25 per cent, in the form of
albuminoid compounds.
I/ucemc.
4 cm. lugb, 2 leaves
12 „ 4 „
Same, before flowering
50 em. high before flowering .
50 — 60 cm. high, in flower. . .
lied Clover in Second Year
4 cm. high, 3 leaves
T „ 6 „
35 „ full bloom
Total
nitrogen
per cent.
922
•760
•570
•474
•008
5 200
3 -974
2 -244
Nitrogen not present
as albumino^ids.
Per cent.
133
042
1S3
721
0-729
1-958
0-975
Calculated
in percents
of total
nitrogen.
30
35
33
29
2i
•5
•5
•1
•1
•2
37-7
245
16-5
Nitrogen
as aniido-
coinpounds.
Per cent.
1025
0-613
0-687
0-370
732
ABSTRACTS OF CHEMICAL PAPERS.
Espareet.
4 cm. high, 4 leaves .
8 ,, 9 „ .
Mye.
8 cm. high, no internodes
35 „ 8 „
Avena elatior.
17 cm. liigh
55 „ seeding
Dactylis glomerata.
15 cm. liigh
45 „ seeding
Meadoto Plants.
1st cutting
2nd „ ; . .
3rd „
1st „
2nd „
3rd „
Meadow hay
„ over ripe . . . .
After hay
Total
nitrogen
per cent.
3-028
3-251
4-433
3-574
4-644
2-420
5 091
2-533
-01
-61
-14
•824
■787
-354
•736
•450
-269
•384
Nitrogen not present
as albuminoids.
Per cent.
0-811
©•857
1-701
0-901
1 -460
0-637
1-306
0-452
0-875
0-496
0-293
0-983
0-285
0-102
0-218
0-233
Calculated
in pereents
of total
nitrogen.
26-7
26-4
38-5
25-2
31-3
26-3
25-8
17-8
22^8
190
13
34
16
7
12
16
15
15
Nitrogen
as amide-
compounds.
Per cent.
1^245
9-758
0
-763
0
-415
0
•257
0
•892
0
239
0
033
0
175
0
187
0
349
0-
356
Tannin of Sumach Leaves.
63).
M. M. P. M.
Bj H. Macagno (Chem. Neivs, 41,
June 10th, 1879.
„ 16th
„ 27th
July 14th
„ 29th
Aug. 11th
Water.
Upper
sides.
Under
sides.
58-15
60-
57 12
63 •
52-47
63-
51-15
62 •
49-80
60-
48-15
61 •
•23
•40
•44
•24
•33
•80
Tannin.
Upper
sides.
24 93
24^92
25^82
24-75
23-80
21-91
Under
sides.
17-45
16-11
15 -27
10-81
9-44
8-77
Means.
"VYater.
59
60
57
56
55
54
-19
•30
-95
-69
■06
•97
Tannin.
21-19
20-51
20-54
17-78
16 62
15 34
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 733
The leaves wei'e taken at the dates given from the upper and under
sides of the branches respectively.
The larger quantity of tannin in the leaves from the upper side of
branches is noteworthy. M. M. P. M.
Oxalic Acid in Beet Leaves. By A. MiJLLER {Bied. Centr.,
1880, 236). — The results of the author's investigations show that the
fresh leaves of the sugar-beet contain 4 per cent, oxalic acid, of which
one-third is in a sokibie form. When it is considered how great are
the quantities of these leaves eaten by cattle in countries whore the
beetroot sugar industry is large, it behoves farmers to be on their
guard, as the acid induces inflammation of the mucous coats of the
stomach. The pickling of the leaves with chalk is likely to prevent
this unpleasantness, the soluble acid being converted into calcium
oxalate, which is insoluble in the weak acids of the stomach.
J. F.
Distribution of Potassium Nitrate in the Beet. By H.
Pellet {Bled. Centr., 1880, 235).— The roots experimented on were
grown in ridges after Champonnois' system. They were manured
with 40,000 kilos, of stable manure and 1,200 kilos, of chemical
manure per hectare; 80 cm. between the ridges, and 10 — 11 cm.
between each plant in the row. The following is the amount of potas-
sium nitrate : —
Fresh substance. Dry substance.
Stalk and leaf-ribs 0-846 8-46
Green matter of leaves 0148 1"10
Under normal conditions the roots contain less than the leaves, but
when the whole contents are under the average, the root proportion is
comparatively higher ; for example, the author found in one plant
fresh leaves, 0'76 ; roots, 0'48, whilst Pagnoul in others found in the
leaves 0-006 and 0-292 ; in the roots of the same plant 0-008 and 0-193.
The leaves which had fallen from a plant on 26th September were
rich in the salt, equal to 1 per cent, at the time of their falling off.
The amount of the salt varies also in different parts of the root, one
of 600 grams containing 11-58 per cent, sugar in the juice, gave in
the middle 0-23, in the crown 0-80, and in the point O'l 78 per cent, of
potassium nitrate, the sugar in the point was 3 per cent, more than in
the crown. J. F.
Effect of Cold on Cherry Laurel, By, Fluckiger (Pharm. J.
Trans. ['S'j, 10, 749). — Cherry laurel leaves when exposed to intense
cold, yield a small quantity of an essential oil differing from that
obtained from the living plant. The oil has an acid reaction, but no
traces of hydrocyanic, benzoic, or formic acid were found. The cause
of the acid reaction is not known. Crystals separate out from the oil
on standing (m. p. 60'). L. T. O'S.
Nutritive Value of Fruits. By J. Koxig (Bi'ed. Gentr., 1880,
239 — •240). — The following is a valuable contribution to our know-
VOL. XXXVIII. 3 f
734
ABSTRACTS OF CHEMICAL PAPERS.
ledge of the subject. An analysis of potatoes is added for the sake of
comparison : —
Soluble in water.
Insoluble.
Water.
Sugar.
Free
acid.
Albumin.
Protein
and ash.
Seed
husk.
Ash.
Apples
r Minimum .
Maximum .
[ Average . . .
81-29
87-31
83-58
5-49
10-36
7-73
0-39
1-61
0-84
0-19
0-50
0-39
5-17
1-37
3-46
1-98
0-17
0-46
0-31
Pears ■
'Minimum .
Maximum .
_ Average . . .
80-00
86-00
83-03
6-58
11-52
8-26
trace
0-58
0-20
0-21
0-50
0-36
3-54
3-52
5-12
4-30
0-20
0-38
0-31
Plums.
Average . . .
81-18
6-15
0-85
0-78
4-92
5-41
0-71
r Minimum .
Potatoes ■< Maximum .
|_ Average. . .
"Water.
68-29
82-88
75-77
Nitro-
genous
substances.
0-50
3-60
1-79
Oil.
0-05
0-80
0-16
Non-nitro-
genous
extract.
12-05
26-57
20-56
Cellulose.
0-27
1 -40
0-75
J. F.
Influence of Steaming on the Digestibility of Hay. By Hoen-
RERGER (Landw. Versuchs.-Staf., 24, 380 — 381). — These experiments
on feeding oxen with steamed hay have as yet yielded no favourable
result, the nitrogenous constituents of the steamed hay being present
in a less digestible form than in ordinary dry hay : only 68 per cent,
of the digestible nitrogenous constituents were assimilated (comp. this
vol., p. 498). J. K. C.
Beet Residues as Fodder. By H. Pellet and Ch. de Levandier
(Bied. Gentr., 1880, 280 — 284). — It is stated that the residue obtained
by the diffusion method of extracting the juice from beeti'oots is of
more value as a cattle fodder than either the residue obtained by
hydraulic pressure or by maceration. Analyses are given, and a
method is described for the proper preservation of the residues.
A. J. C.
Damage to Seed Peas by Weevil. By G. Marge (Bted. Gentr.,
1880, 201 — 203). — There are different opinions as to the value of peas
which have suffered from the attacks of this pest ; it is admitted that
they are unsuited for human food, but many persons think they can
be used as seed. To settle the question, the author examined two
sorts, which out of 13 grown for experimental piirposes, were found to
be considerably damaged. Of every 100 seeds it was found that 40 on
an average were injured. 100 sound peas weighed 21'20 grams, the
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 735
same number of damaged only 1630, or a- difference of 231 per cent.
Of 100 of the partially eaten peas 74^ had' the radioula and pluniula
both seriously damag-ed, and in 13 only were neither injured. In the
majority of cases the portion of seed which is considered the most
valuable, suffered. A chemical analys-is given in the paper verifies this
observation, and the author gives as his opinion that damaged peas
should not be used as seed. The prevention of tlie damage next en-
gaged the author's attention. The effect' of a high temperature and
of chemicals- in particular, was tried. The employment of heat is
not always possible ; malt kilns must be used, and they shrivel and
dry up the seed, make it look old and unsightly, and there is a danger
of killing it by careless manipulation. The employment of chemical
solutions has the advantage of killing the worm without the destruc-
tion of the seed, but is still injurious. The seeds swell up, and unless
they are sown at once, they must be spread out and dried ; they
become wrinkled, and lose their marketable appearance. Large space
is required, and in unfavourable weather consi-dei'able loss is sustained
by mildew. Another plan proposed is to leave the seeds over for a
second year, which certainly frees them from live insects, but then the
damage done is far greater. Amongst gaseous remedies carbon bisul-
phide vapour is the best and o-heapest, others, such as alcohol and
ether vapour, being effectual, but dangerous and expensive.
J. F.
Symphytum asperrimum as a Fodder. By E. Wildt and others
(Bkd. Centr., 1880, 2ii0 — 2'JS), — This plant, which belongs to the
family Boraginece, is shown to be of great value as a cattle fodder, and
as it grows rapidly and gives a large produce, it would repay extensive
cultivation. Wildt's analysis of the dried plant gave per cent. : pro-
tein substances, 22".37 ; fibre, 13"24 ; fat, 3'06; non-nitrogenuus
extractive matter, 43'04 ; ash, 18"29 ; phosphoric acid, 1'62 ; potash,
7'87 ; lime, 3/4. A previous analysis by Voelcker showed 23"37 per
cent, protein substance in the leaves, and 13'06 in the stem ; non-
nitrogenous matter, 54'49 and 72"49 ; ash, 17"74 and 14:45 in the
leaves and stem respectively. Its properties; and the method followed
in its cultivation, are also described. A. J. C.
Chemical Examination of Ligneous Papilionaceae. By P.
Fliche and L. Geas dtHiAV (Bied. Centr., IB^^O, 284 — 286), — Four species-
growing on a siliceous soil were examined, viz., Gytisus Lahurnum^ IJlex-
Europa'us,.8arothatinis vidgaris, and Robinia Pseudo-aiacia. The i^esiilts
indicate that plants of the same natural family growing on the same soil
differ considerably in the amount and in the distribution of starch and
in the amount of ash and nitrogen. The percentage composition of
the ash shows still greater variation. These differences increase or
decrease according as the relationship between the plants becomes
more or less distant. The soil is exhausted in an unequal degree by
different members of the same family.
Comparison is made between the mineral constituents which were
absorbed from the soil by each of the four kinds, not one of which
would repay cultivation. A. J. C.
8 /• 2
73(i ABSTRACTS OF CHEMICAL PAPERS.
Cultivation of Sugar-Beet. By A. Ladureau (Bied. Gentr., 1880,
286—288) and H. Champonnois (ibid., 288— 289).— The authors have
independently examined the two methods which are generally em-
ployed in the cultivation of the sugar-beet, but the resultsobtained are
somewhat contradictory as to whether ridge culture is the more ad-
vantageous. A. J. C.
Cultivation of the Yellow Lupine. By E. Wein (Bied. Gentr.,
1880, 261 — 265). — A confirmation for the most part of Lehmann's
results (this Journal, 1876, 1, 734), that this plant is able to thrive in
soils which are not supplied with nitrogenous manure, and that the
nitrogen when supplied should be in the form of nitrate (of soda).
Instead of fallowing the soil, it is stated that the same result may be
obtained with greater profit by cultivating the lupine. A. J. C.
Fallowing. By E. Wollnt (Bied. Gentr., 1880, 252— 258).— The
author has examined the influence of fallowing on (a) the tempera-
ture, (b) on the humidity, and (c) on the decomposition of the soil.
a. A soil in fallow is warmer in summer, but colder in winter,
whilst the variations in the temperature are considerably greater than
is the case in a soil which is covered with a plant surface.
Plants prevent the direct action of the sun's rays on the surface of
the soil, and consume a quantity of heat, which is thus lost to the soil,
in the process of transpiration and of nocturnal radiation. Moreover,
as the upper organs of perennial plants decay, they form a surface
cover to the soil, and in this way the cooling action of the air and of
radiation is diminished. On fallow land the reverse action occurs ;
there is unimpeded radiation, and the temperature of the surrounding
air is communicated to the surface of the soil and thence transmitted
to a lower stratum.
b. The amount of water in a cultivated soil in vegetation is always
less than is in the same land in a state of fallow. This law is good for
all kinds of soils in fallow, even after repeated harrowing, &c. The
reasons that are given in explanation of this rule are in accordance
with those which have been previously stated by the author (this
Journal, Abst., 1880, 498).
Experiments on grass and clover land and on quartz-sand, turf, and
clayey soils, show that with the same rainfall a considerably larger
quantity of water percolates thi-ough a soil in fallow than through a
.soil which is covered with a vegetating plant surface.
It is therefore apparent that fallowing plays an important part in
regulating the humidity of the soil, and in sustaining the crops in
seasons of drought. It also partly accounts for the favourable results
obtained by growing rape after a crop of close growing and desiccating
plants, such as clover and clover glass, especially if the land has been
harrowed and kept in fallow some time previously to sowing out, — and
of wheat after rape. In the latter case the soil has had time in the
interval — July to September — to re-absorb an amount of moistare
equal to that withdrawn from it by the previous crop.
c. The generally humid condition of fallow land, together with a
higher temperature, promotes the decomposition of humus substances,
VEGETABLE PHYSIOLOGY AXD AGRICULTURE. 787
and enriches the air of the soil in carbonic anhydride. It was found
by Pettenkofer'^ method that the amount of carbonic anhydride in the
air in the soil at a depth of 25 cm. on land in fallow was on an average
during May to Xovember, four times as great as that in grass land.
This excess in carbonic anhydride is favourable to the decomposi-
tion of the insoluble constituents of the soil, thus increasing the nutri-
tive value of tlie soil to plant-life. Whilst as a general rule it may be
stated that fallowing is advantageous to the soil, yet under some con-
ditions it may have the contrary effect. It is injurious for instance on
sandy soils, where the object should be to keep the soil as much as
possible under a plant surface in order to avoid a washing out of its
soluble constituents ; also on clayey soils in damp climates or with
much rainfall, as the excess of water being unable to drain off by per-
colation lies on the surface of the land. Winter fallowing on binding-
soils is of value in assisting the disintegration of the soil by a succes-
sive freezing and thawing of the enclosed particles of water ; in this
way the soil acquires a structure which could be given to it only by a
considerable expenditure of labour. A. J. C.
Behaviour of Natural Soils and of Plants Growing in them
towards Water. By G. Havexsteix {Bied. Centr., 188u, 24^:— 252).
Absorption of Ammonia by the Soil. By Orth (Landw.
Versuchs.-Stat., 24. 37(j — o79). — The absorption of ammonia by the
soil varies with the quantity of oxide of iron or humus present. If
sandy soils be mixed with loam or moor soil, the absorption of nitrogen
is proportionately increased, especially by the latter. J. K. C.
Influence of Forests on the Rainfall. By M. Fauteat {Died.
Centr., 1880. 241 — 244). — Forests, and pine forests more especially,
have the property of attracting aqueous vapour, so that the rainfall is
greater over a pine forest than over a contiguous area which is
unplanted. This conclusion is supported by the results of the hygro-
metric and rainfall determinations "which were obtained in the two
cases, under similar conditions as regards elevation. A. J. C.
Comparative Rainfall in Woods and Fields. By A. Matthieu
(Bied. Centr., 188U, 164 — 168). — This paper is an abstract of a report
made by tne President of the Administration of Forests in France, on
certain meteorolojjical observations made dui-ing eleven vears at the
three stations in the neighbourhood of Nancy, two of them situated in
the forest, and one in the open country, their object being to determine,
1st, the effect of wooded and open land on the quantity of water absorbed
by the soil; 2;id, the proportion according to which the leaves hinder
the rain reaching the soil ; 3rd, the evaporation on wooded and on open
ground ; 4th, the temperature of the air within and without the
wood. The averages of the eleven years' rainfall at the two fore.st
stations were as lOU and 97, and at the open station 81, from which it
would appear that the influence of forests is to increase the rainfall,
and that therefore forests are useful in feeding springs and streams
738 ABSTRACTS OF CHEMICAL PAPERS.
but these observations, taken in a b'mited district, are not accepted by
the author as conclusive without further consideration.
The amount of rain which reached the soil under the trees was
quite as much, indeed rather more than in the open ground.
The amount of evaporation varies with the temperature in the open
ground, but in the woods it remains tolerably constant ; the total evapo-
ration in the former was in the eleven years three times as great as in
the latter.
The temperature within the forest on an average of nine years was
half a degree Cent, below that of the open ground, but the variations
less in amount. J. F.
Injurious Effect of Peat Water on Meadows. By Klein {Bied.
Centr., 1880, 168 — 171). — This paper was called forth by an overflow
of black bog water in a certain district of East Prussia, and the investi-
gations which were then made as to the amount of damage caused by
the overflow. The floyal Commissioner collected a quantity of the
water, and sent some to different experimental stations, with a request
for analysis and experiment. It was found that the water contained
in solution 31'28 per 100,000 organic matter (humic acid) ; 17'69
mineral matter, lime, iron, &c., together with a very large propor-
tion of suspended matter, humic and geic salts, and finely divided
particles of humus, the organic matters being presumably those
injurious to vegetation, firstly, by giving opportunity for the for-
mation of the so-called bog stone or bog ore, and thereby diminish-
ing the space available for the roots of plants, and also by acting as a
reducing agent, and producing chemical combinations poisonous to vege-
tation.
When this water is taken from its collecting ground, where it has
not had access to the oxygen of the air, its chemical composition
undergoes alteration. Combinations of humus and iron dissolved in
the water are precipitated, and gradually ]Xjrmeate the soil, becoming
so intimately combined that hard stony masses are formed, which
after a- time experience further changes, rendering them fatal to vege-
tation ; the surface of the earth becomes hard and impervious to the
oxygen of the air, and the humus, withdrawing oxygen from the iron
compound, forms salts destructive to vegetable life. Particularly
unsuitable are such waters to clay with a marly subsoil, whilst strong
calcareous soils bear it better, because of the property which lime
possesses of decomposing humus. Upon meadows growing on the
latter kind of soil the effect is most injurious, and might result in
changing it to moorland. The result of the series of experiments is
decidedly against the employment of this water in any farming opera-
tions. J. F.
Manure Experiments with Rye, Wheat, and Oats. By A.
Pagel and H. Meter (Bied. Centr., 1880, 178— 182).— The reluctance
of small farmers to employ artificial manures is considerable, except in
the neighbourhood of large farms, where example leads to their pai'tial
use. The authors instituted the following experiments, believing that
strong efforts should be made to overcome this reluctance.
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 739
The first experiment was to ascertain iE it would pay better to
employ a large or a small quantity of manure ; four spaces of 140 square
meters were carefully tilled and prepared exactly in the same way, one
was manured with sheep's dung ; the other w4th 600 kilos, of bone-
meal ; the third with 300 kilos, bone-meal ; and the fourth, 400 kilos,
superphosphate.
The tabulated results show that the employment of the large quan-
tity of bone-meal yielded the largest crop, but the 300 kilos, plot paid
the best interest on the capital expended.
The second experiment was to ascertain if the employment of larger
or smaller quantities of superphosphate after the bone-meal of the
preceding year, paid better interest on the capital employed ; and at
the same time trials were made as to whether sodium nitrate when
used should be dug in or used as top dressing. The experiments prove
to the authors' satisfaction that the use of 400 kilos, of superphos-
phate per hectare is more profitable than 200 kilos., and that the
employment of sodium nitrate is more successful as top dressing
than when dug in or sown with the seed ; in the latter case a con-
siderable amount of nitrogen is lost by sinking into the ground before
the plants are ready to assimilate it.
The third series of experiments was made to verify the effects of
artificial manures used with stable dung. The same course of treat-
ment was pursued, and the conclusion arrived at was, that the use of
the artificial manure increased the produce considerably. J. I'.
Bone-meal as a Manure for Potatoes. By Meyer {Bied. Centr.,
1880, 2t)5 — 268). — Bone-meal manure increases the weight of the
produce, but it is uncertain whether its action is to increase the size
or the number of the tubers. It probably tends to develop the entire
plant. A. J. C.
Report by Dr. Petermann "On the Agricultural Value of
so-called ' Retrograde Phosphoric Acid,' and Discussion
thereon, at the Meeting of Directors of Agricultural Experi-
mental Stations, held at Karlsruhe, September 16 and 17,
1879. (Landiv. Versaclis.-SUd., 24, olU — 'Soti.) — It is the universal
opinion of French chemists, that the agricultural value of retro-
grade phosphoric acid is equal in all respects to that of the soluble
form ; accordingly, in analyses of superphosphate conducted in France,
the worth of the article is fixed by the sum of soluble and retrograde
phosphoric acid, the latter being estimated by means of its solubility in
citrate of ammonia. Experiments by Grandeau, Koeth, and others
point to this conclusion, which, however, has, up to the present time,
not been accepted by German chemists. The author has therefore
performed some experiments, with the view of ascertaining the relative
values of soluble and retrograde phosphoric acid in the most effective
manner possible. The plants made use of in his experiments were
peas and barley ; these were grown in pots containing known quanti-
ties of soil and manure, the latter consisting of soluble or retrograde
phosphoric acid, precipitated dicalcium phosphate, soluble, in ammo-
740
ABSTRACTS OF CHEMICAL PAPERS.
nium citrate, or rendered insoluble by heat, The following bable gives
the results of the experiments : —
I. Peas.
Straw and
Finiit. pods. Total.
Grains. Grains. Grains.
Pots I and II, without manure 46-24 2879 75-03
„ III and IV, soluble phosphoric acid 50-48 34-52 85-00
,, V and VI, retrograde phosphoric
acid 49-58 33-70 83-28
,, VII and VIIT, precipitated phos-
phate 54-20 32-00 86-20
,, IX and X, precipitated and heated
phosphate 47-11 27-97 75-05
Pots I and II. i
„ III and IV.
„ V and VI.
,, VII and VIII.
,, IX and X.
II. Parley.
Grains.
before 20-66
25-32
23-98
27-31
21-83
Straw and
chaff.
Grains.
45-32
50-60
48-98
56-21
46-45
Total.
Grains.
65-98
75-92
72-96
83-52
68-28
From the above results we see that in the case of the peas, retro-
grade phosphoric acid produced as great an increase of yield as the
soluble form, and that in the case of both peas and barley, precipitated
phosphate produced a greater yield than either, whereas phosphate,
insoluble in ammonium citrate, had hardly any effect. These experi-
ments then confirm the conclusion previously arrived at by the author,
that phosphate soluble in ammonium citi'ate is to be regarded as of
equal value with phosphate soluble in water. In the case, indeed, of
soils poor in lime, it is even more advantageous to use precipitated
than soluble phosphate, as Volcker's experiments show.
The author employs a combination of Joule's and Fresenius' methods
for the estimation of the retrograde phosphoric acid.
Dr. B'leischer communicated the results of experiments with phos-
phates in various conditions on moorland ; in the majority of cases
retrograde and insoluble phosphoric acid produced greater yields than
the soluble form, the reason of this lying in the poor absoi-ptive power
of such soils. He also deprecated the drawing of conclusions from
isolated experiments.
H. Albert gave an account of some experiments carried out by him-
self, in conjunction with Volbrecht, on the absorption of soluble and
insoluble phosphates by various kinds of soil. They found that when
soluble phosphate was introduced into sandy soil poor in lime, a quick
distribution of the phosphoric acid took place, so much so that the
greater part of it was soon out of reach of the plant ; in the case of
dicalcium phosphate this did not take place, and the effect of the phos-
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 741
phoric acid was visible for two or three years afterwards, the dicalcium
phosphate becoming' gradually insoluble in ammonium citrate.
After a somewhat lengthy discussion, a motion was carried to the
effect that while recognising the value of retrograde and precipitated
phosphoric acid when applied to certain kinds of soil, the meeting
does not consider the evidence laid before it as conclusive in establish-
ing the relative agricultural value of retrograde in contradistinction to
soluble phosphoric acid. J. K. C.
Nitrogen Manure for Oats. By E. Heidex (Bied. Gentr., 1 880,
259— 261).— Nitrogen in the form of nitrate— 50— 100 kilos, of Chili
saltpetre per hectare as a top manure — is more efficacious for oats
than in the form of ammonia. A. J. C.
Chili Saltpetre for Beets. By Pluchet (Bied. Centr., 1880,
259).
Manuring Beets with Sodium Nitrate. By M. Marcker {Bied.
Centr., 188U, 175 — 178). — A field was divided into six portions, the
seed and manure employed were, as far as possible, of the same
quality, and evenly divided. The ground was prepared exactly the
same in each portion : plots No. 2 and 5 had no manure. No. 1 received
25 kilos., No. 3 50 kilos.. No. 4 75 kilos.. No. 6 100 kilos, of sodium
nitrate. 50 kilos, of seed in No. 1 produced 45660 of roots ; No. 3
580-50; No. 4 600-87; No. 6 610-05.
A second series of experiments was made under similar conditions
for the purpose of comparing the amount of sugar in beets grown
with superphosphate and with sodium nitrate ; the results were
unfavourable to the nitrate, but not conclusive, and further investi-
gations are invited. The author dwells on the importance of an
extended series of such experiments, the great development of the
beet-sugar industry having caused the exhaustion of the soil in many
localities, so that a strongly nitrogenous manure is required.
Sodium nitrate fulfils many of the necessary conditions, but it has
not yet been decided whether it is advantageous or not to use it.
J. F.
Thirty-eighth Year of a Farm without Stable Manure.
By Stecher {Bu'd. Centr., ISSO, 172— 175;.— This is the third
decennial report of the farm of Wingendorf, conducted by the author
since 1840 on the principle of keeping no cattle and not using any
stable manure. Since last report the property had passed into the
hands of the Government, which on the representation of the leading-
agriculturists of the district, continued the experiment, under the care
of the author, and it was made auxiliary to the State farm of Brauns-
dorf for purposes of comparison ; the latter farm was considered very
fertile. This arrangement allowed the author to compare results very
closely, as the two farms were treated exactly alike except in the
matter of the manure.
In the five years, 1873 — 1877, the rye crop at Wingendorf exceeded
that at Braunsdorf by an average of 46^ kilos, per hectare, and the
oats 11-^ kilos, per hectare : the straw being as abundant in one as in
742 ABSTRACTS OF CHEMICAL PAPERS.
the other. Potatoes were not so successful, showing a deficiency of
46"47 hectolitres per hectare, whilst clover and flax have failed for
many years, on which account a longer interval between the culti-
vation of these crops has been decided on.
The climate, soil, and situation of the two stations are very similar,
yet at Wingendorf the crops of clover yielded scarcely 20 per
cent, of a full crop : the grasses sown with the clover suffered equally ;
the seeds germinated well enough, and promised a good crop in April,
but in May and June they failed.
An examination of the manures put on the farm showed that in the
ten years from 1858 — 1867, there were 7786"55 kilos., and fi'om
1868 — 1877 3580'57 kilos, more phosphoric acid put into the ground
than was taken out of it. The large quantity of this class of manure
was proved to have been unnecessary by the results of the last ten
years, when the yield was so satisfactory without farther additions of
phosphates.
During the first ten years 2861'25 kilos., and in the last943'3 kilos.,
more nitrogen was removed from the soil than had been added. The
author considers the excess was in part drawn from the atmosphere.
Of potash salts in both periods considerably more was taken ofi" the
farm, respectively, 4641*5 kilos, and 3837'5 kilos, than had been added
to it. Analysis showed, however, that the soil was very rich in
potassium. To secui'e its solubility a large quantity of lime manure
was required, which was very liberally used, the first ten years show-
ing an excess of 13,658'9 kilos., the second ten years 7898"35 kilos,
over and above the quantity of lime taken off the farm.
What has been the cause of the failure of the clover, what properties
are possessed by the stable manure, which is absent from the phosphoric,
nitrogenous, potash, and lime manures, the author cannot explain, the
condition and treatment of both farms being so exactly similar that no
practical farmer could discern any difference ; the only explanation
that can be given being a supposition that the farm has been attacked
with the clover sickness, which sometimes attends clover fields where
this crop is grown for the sake of seed only. J. F.
Beet-sugar Refuse as Manure. By E. y. Wolff (Bled. Gentr.,
1880, 171 — 172). — In the process of clarifying the syrup from the
sugar-beet with lime large quantities of slime separate ; it has
frequently been submitted to analysis, in order to determine its value
for manurial purposes ; it contains varying amounts of moisture, and
abol^t 1 — 2 per cent, phosphoric acid, with perhaps ^ of a per cent,
of nitrogen ; its principal value, however, is the lime, which is useful
by bringing into play the vegetable matters in the soil in the form of
humus, and also when the soil is inclined to be of a sour nature. The
phosphoric acid is about four times, and the nitrogen scarcely half as
much as in ordinary stable manure. The employment of this material
is only to be recommended in conjunction with stable manure in about
equal proportions ; it is a valuable ingredient in a compost ; its money
value being altogether dependent on the cost of carriage and similar
commercial considerations. J. F.
ANiVLYTICAL CHEMISTRY. 743
Analytical Chemistry.
Modification of V. Meyer's Vapour-density Apparatus. By
J. PiccAKD {Her., 13. Iu7l> — lU.su). — The olyect of this luoditication of
Meyer's vapour-deu.sity apparatu.s is to avoid tlie error due to the
rephicing of the cork after the tube ^containing the weighed quantity
of substance has been dropped in. For this purpose the headpiece,
above the evolution- tube, is so arranged that it may be bent down at
right angles, which is attained by having it in a separate piece, and
attached to the rest of the apparatus by a moveable joint of india-
I'ubber. In an actual experiment the headpiece is brought down to
the horizontal position, the tube containing the substance pushed into
a short distance, and the cork replaced. The apparatus is maintained
in this position till no more bubbles issue from the evolution-tube,
showing that the temperature is constant. When this is the case the
headpiece is brought back to the vertical, and the tube containing the
substance slides down into the bulb of the apparatus, and is there con-
verted into vapour. T. C.
New Form of Instrument for the Determination of Specific
Gravity. 13y F. P. Duxnixgtox (Chem. News, 41, 154— 155). This
instrument may be described as a Nicholson's hydrometer, with a
thick graduated stem, the graduations on the stem being in one-tenth
c.c. Instead of the upper pan of the Nicholson there is a graduated
tube for holding water or other liquid and the solid under examination.
The weight of the solid -or liquid under examination is obtained from
the increase of volume of water displaced by the .stem on placing the
substance in the upper tube. The volume of the substance if solid is
obtained from its displacement in the upper tube, or if liquid is read
directly. F. L. T.
New Method of taking the Specific Gravity of Liquids. By
H. SoMMERKOKN (Chem. Neivs, 41, 203). — The apparatus required is a
thin-sided glass tube, divided into millimeters, and of from 3 — 4 centi-
meters in diameter, and a thin circular plate of exactly the same
diameter held by a string. The tube is closed with the plate, and
the apparatus plunged into the liquid to be examined, pulling the
plate against the tube with the string. If it is plunged deep enough the
pressure causes the plate to adhere; on slowly raising it in a vertical
direction, the point is easily observed at which the plate, after merely
hovering, sinks. The depth of the tube in the liquid is now
read off.
Sp. gr. =
Weight of glass plate
Area of glass plate X depth of tube in liquid'
The weight and area being constant, the depth is the only variable
quantity. F. L. T.
744 ABSTRACTS OP CHEMICAL PAPERS.
Detection of Hydrochloric Acid by Sulphuric Acid and
Potassium Bichromate. By H. W. Wiley {Chem. Netvs, 41,
176 — 177). — Instead of distilling the mixture of the chromate, sul-
phuric acid, and suspected chloride in. a retort, they ai'e distilled from
a beaker, and the chlorochromic anhydride is condensed on the under
surface of another beaker suspended inside the first, and containing
ice or ice and salt. A stirring-rod moistened with the chlorochromic
anhydride is brought into contact with a drop of sulphuric acid and a
cr3-stal of strychnine, the colour test for strychnine being readily
jDroduced.
In many cases the author has not succeeded in obtaining any
chlorochromic anhydride when operating on mixtures of iodides and
chlorides. F. L. T.
Determination of Active Oxygen in Sarium or Hydrogen
Peroxide. By M. A. Bertrand (Chem. Neius, 41, 215). — Known
quantities of either substance are added to pure hydrochloric acid
(free from uncombined chlorine), excess of potassium iodide (free
from iodate) added, and the liberated iodine, after the addition of an
excess of hydrogen sodium cai'bonate, is titrated by thiosulohate.
F. L. T.
Estimation of Sulphur in Pyrites. By B. Deutecom (Zeits.
AnaL (J he III., 18S0, 31oj. — Estimation of sulphur in pyrites by oxi-
dation with nitric acid and pi-ecipitation as barium sulphate gives
unsatisfactory results. The author recommends fusing 1 gram of the
pyrites with 8 grams of a mixture of equal parts of potassium chlorate,
sodium carbonate, and sodium chloride, in a large covered porcelain
crucible. Yfhen cold the mass is extracted with water, and the
sulphuric acid estimated in the solution. The residue is quite free
from sulphur. A. J. Gr.
Alkalimetric Determination of Sulphates. By J. Grossmann
{(Utem. Neics, 41, 114). — The process is based on the following
reactions : —
Na^SOi + (x + l)BaHo03 + i/H,0 = 2NaOH + a-BaH^Oo +
BaSOi + ijB.oO.
2NaOH + a^BaHoO. + a;CO, = 2NaOH + a^BaCOs + ajH.O.
At present the author has applied the process only to the determina-
tion of sodium sulphate in salt cake. The sample is dissolved in
water ; excess of a cold saturated solution of baryta is added ; the
whole is made up to a detei'minate volume and filtered; carbonic
anhydride is passed through an aliquot portion of the filtrate; the
liquid holding the precipitated barium carbonate in suspension is
boiled, allowed to cool, made up to a fixed volume, and filtered ; and
alkali is determined in an aliquot portion by one-fourth normal acid.
The chief sources of error are : — (1) Presence of barium nitrate in
the baryta used; this converts some of the sodium sulphate into
nitrate, and thei'efore diminishes the amount of alkali found in the
last operation. If the solution of baryta be precipitated by carbonic
ANALYTICAL CHEMISTRY. 745
anhydride, and the barium remaining' in solution after filtration be
determined, an estimation is arrived at of the amount of barium
nitrate in the specimen of baryta used.
(2) Errors of measuring- vessels. The original contains an account
of a modification of Gavolovski's method {Ghem. Ce?itr., 1879, 236) for
correcting this error.
(3) Error due to the bulk of the precipitate in the measuring
flasks. Experiments must be made with the flasks, liquids, &c., em-
ployed by each analyst for the determination of the magnitude of this
error. In the author's determinations it was equal to about 0*4 per
cent, in the first result.
(4) Certain unavoidable losses. The author states these are about,
equal to 1'3 per cent. As yet he has been unable to find the cause of
those losses. M. M. P. M.
Separation of Silicic Anhydride in the Analysis of Lime-
stones. Iron Ores, and other Minerals. By H. Rocholl (Ghem.
News, 41, 234 — 235). — In the examination of many minerals for silicic
anhydride by evaporating to dryness with hydrochloric acid and ex-
tracting with hydrochloric acid and water the insoluble residue is
found to consist not only of silicic anhydride, but also of aluminium
silicate. This necessitates either fusion of the insoluble residue with
alkaline carbonates or in the absence of iron and certain rarer bodies ;
if absolute accuracy is not required it may be treated with hydrofluoric
and sulphuric acids and ignited and the difference assumed to be silicic
anhydride, the residue being aluminium oxide. To avoid this the
author, if the mineral is of a basic character, ignites it previously to
acting on it with hydrochloric acid, when be finds the insoluble residue
to be pure silicic anhydride. In the case of iron ores the sample, after
ignition has to be re-weighed and re-powdered, allowance of course
being made for loss on ignition ; when the ore contains more than 25
per cent, silicic anhydride it is necessary to add some ferric oxide before
ignition to insure accurate results.
The residtie may still contain barium salphate and titanic anhydride.
In the former case, after treatment witli hydrofluoric and sulphuric
acids and ignition, the loss is taken as silicic anhydride ; in the latter
case the titanic anhydride may be separated by known methods.
F. L. T.
Estimation of Nitrous Compounds in Manufacture of Sul-
phuric Acid. By J. Mactear (Ghem. News, 41, 16, 43, 52, and 67).
— The author describes a process for estimating " total acids " in the
gases aspirated from the leaden chambers and from the Gay-Lussac
towers. The gases are passed into a series of four tubes, three of which
contain standard soda-solution and the fourth water coloured by
litmus : bleaching of this litmus indicates escape of sulphurous or
nitrous acid. After aspiration of a measured volume of gases, the
residual alkali in the tubes is determined by standard acid, the liquid
is then diluted and sulphuric acid is determined in an aliquot portion.
The results are checked by a determination of the amount of am-
monia evolved from a portion of the liquid by which the gases have
746 ABSTRACTS OF CHEMICAL PAPERS.
been absorbed by the action of zinc and iron in presence of caustic
soda.
Details of the method adopted for the ammonia determinations are
given. Heating must be continued until the contents of the vessels
become past J ; alkali is sometimes carried over, it is therefore well,
after titrating the distillate, to add a known excess of standard soda :
boil until all ammonia is expelled, and titrate with standard acid.
The "permanganate method" is ci'iticised. Experiments are de-
scribed which show that " nitrous vitriol " may contain N2O5, N2O3,
NO, SO2, AsoOa, and AsoOj, and that therefore reduction of perman-
ganate may be caused by substances other than nitrous compounds.
M. M. P. M.
Direct Method of Testing Vitriol Exits for Nitrogen Com-
pounds, liy G. E. Davis (Chem. Nevs, 41, 188—189). — A knov/n
volume of the exit gases is drawn through, a measured quantity of
hydrogen peroxide and the necessary amount of water. The resulting
solution is made up to a definite volume and divided into three por-
tions. In one the total acidity is determined by pure sodium liydrate,
it is then acidified, and the sulphuric acid determined as barium salt.
In the second the hydrochloric acid is determined by a standard silver
solution after decomposing the excess of peroxide by potassium per-
manganate and neutralisation. The third portion is treated with a
little silver sulphate, neutralised, filtered, and evaporated on the water-
bath to about 1 c.c. When cooled a drop or two of sulphuric acid is
added to decompose carbonates, and the solution is then transferred to
Crum's nitrogen tube. Twice its volume of pure and concentrated
sulphuric acid is now added, and the whole shaken up with the mer-
cury ; the evolved nitric oxide is allowed to cool, and measured.
F. L. T.
New Blowpipe Test for Phosphoric Acid. By W. A. Ross
(Chein. Netvs, 41, 187). — The test is based on the well-known pi^operty
of pure tungstic acid to afford a bright blue bead in the reducing
flame of the blowpipe with pJwsphor-sfiM, but only a yellowish or
brownish bead wdth borax. The suspected phosphate is heated on a
potash bead with potassium pyrotungstate in the peroxidising pyro-
cone, when a blue colour is produced.. It has been suggested to the
autbor that this blue is due to a trace of manganese in his tungstic
acid, but he is of a different opinion, F. L. T.
Behaviour of Sulphuretted Hydrogen with Salts of the
Heavy Metals. By H. Delffs (Chem. News, 41, 279).— As the limit
between precipitable and non-precipitable metals is modified by the sub-
stitution of acetic for hydrochloric acid, so is it further modified by I'e-
placing acetic by formic acid. Zinc is precipitated, but cobalt, nickel,
iron, and manganese are not precipitated in the last case. Manganese is
not precipitated from propionic, butyric, and valerianic acid solutions.
On adding to a mixture of cobalt and nickel nitrates, sodium acetate,
insufficient for complete double decomposition, and treating with, sul-
phuretted hydrogen, we obtain either cobalt free from nickel as a pre-
cipitate, or nickel free from cobalt in solution, according to the amount
ANALYTICAL CHEMISTRY. 747
of sodium acetate added. This is a very convenient method for
obtaining either of these metals in a state of purity. F. L. T.
Electrolytic Determination of Metals, By L. Schicht (Chem.
News, 41, 280). — Uranium, fi'om alkaline solutions (containinof tar-
taric, citric, or acetic acids, or mixed with sugar) or from neutral solu-
tions, is separated only to a very small extent with a yellow colour ;
in presence of mineral acids it is not precipitated, hut is reduced from
uranic to uranous oxide.*
Thallium is not precipitated from acid solutions, but is completely
precipitated on the negative pole, with brisk disengagement of gas, from
ammoniacal solutions, blackish-brown thallium oxide, much resembling
lead peroxide, being deposited on positive pole ; imperfectly precipi-
tated from neutral solutions on account of the acid liberated. The
oxide dissolves in hydrochloric acid with evolution of chlorine.
Indium is completely precipitated as metal at the negative pole, both
from acid and alkaline solutions ; in the latter case the metal is very
bright and firm.
Vanadium. Xo precipitation, but merely reduction in alkaline or
acid solutions.
Palladium nitrate, acidified with nitric acid, is deposited at the nega-
tive pole as bronze-coloured coating, which becomes darker and finally
black. Some reddish oxide forms at positive pole. Alkaline solutions
behave similarly, but the composition is slower and more adhesive.
Molybdenum, from an ammoniacal solution of molybdic anhydride,
is completely and firnaly deposited at the negative pole as molybdous
oxide, as coloured rings which thicken and become black.
The first blue precipitate is molybdic molybdate, then follows
molybdic and molybdous oxides. In acid solutions there is no pre-
cipitation ; in ammonium molybdate acidified with molybdic anhy-
dride, there is incomplete precipitation.
Selenium is completely thrown down both from acid and alkaline
solutions. If the current be strong the deposit is pulverulent.
Tellurium behaves like selenium, but is deposited much more readily
in acid solutions with a blue-black colour, in alkaline solutions in a
very loose state at the positive pole, with strong disengagement of gas.
Gallium, like zinc, is thrown down completely at the negative pole
in a pure state. F. L. T.
Electrolytic Estimation of Silver. By H. Fresenius and F.
BERGMA^■x {Zeitt;. Anal. Chem., 1880, 324 — 327). — Luckow first pro-
posed to estimate silver electrolytically (Dingl. j)ohjt. J., 178, 43 ; see
also Ztits. Anal. Chem., 1880, 1 ; this vol., 282). The authors have rein-
vestigated his process, and recommend the following method of pro-
cedure, the battery and electrodes being the same as mentioned in
the Abstract. 200 c.c. of solution should be employed containing
0"03 — 0'04 gram of silver and 3 — 6 grams free nitric acid ; the elec-
trodes should be 1 cm. apart, and the strength of current capable of
evolving 150 c.c. of mixed gases from water per hour. The silver
* This agrees with C. Luckow (this vol., 282).
748 ABSTRACTS OF CHEMICAL PAPERS.
separates in compact metallic form on the negative pole, no silver
peroxide being deposited on the positive. A. J. G.
Estimation of Silver in Galena. By C. Balling (Chem. News,
41, 42). The ore (o — 5 grams) is fused vpith 3 or 4 parts of a flux
consisting of equal parts of soda and nitre. The mass is heated with
water and filtered ; the residue is evaporated to dryness with addition of
nitric acid, and treated with very dilute nitric acid, and the solution is
filtered ; when the filtrate is cold, ferric sulphate is added and the silver
determined by titration with ammonium thiocyanate.
M. M. P. M.
Actual State of the Determination of Zinc. By W. Alex-
ANDEOWICZ (Chem. Netvs, 41, 279). — In presence of sufficient acid, no
appreciable quantity of zinc is precipitated by sulphuretted hydrogen
fi"om solutions containing copper or arsenic. For great exactness a
double precipitation is recommended in pursuance of copper, although
in such a. case it is impossible to completely separate zinc and cad-
mium.
To separate iron and zinc, the mixture should be poured drop by
drop into ammonia, not vice versa. The zinc remains in solution ; the
precipitate is washed with dilute ammonia.
To separate manganese and zinc, acidify with acetic acid, and pre-
cipitate by sulphuretted hydrogen. All the manganese remains in
solution. F. L. T.
Estimation of Cadmium in Presence of Zinc : Separation
of Zinc, Cadmium, and Copper, By C. C. Hutchinson (Phil.
Mag. [5], 8, 433 — 438). — The separation of cadmium from zinc in an
acid solution by means of hydrogen sulphide is rarely complete, and
the methods based respectively on the insolubility of hydrated cad-
mium oxide in a solution of an alkaline tartrate, and the solubility of
zinc sulphide in solution of potassium cyanide, are also unsatisfactory.
Accurate results may be oljtained by the following method. The
hydrochloric acid solution of the two metals is evaporated to dryness
on a water-bath, the residue dissolved in water, and the solution, which
should be moderately dilute, is heated to boiling, and sodium carbonate
added in slight excess. After standing for some time the granular pre-
cipitate is filtei'ed off, transferred to a platinum dish, and mixed with
a considerable quantity of a saturated solution of ammouiuai sesquicar-
bonate. The mixture is well agitated, and left in a warm place for
about 6 hours : the whole of the zinc carbonate is then dissolved.
The insoluble cadmium carbonate is filtered off and converted into
oxide. The filtrate is evaporated to small bulk to expel excess of
ammonium carbonate, diluted, and the zinc is estimated by means of
standard sodium sulphide solution. In the separation of copper, cad-
mium, and zinc, the most accurate results are obtained by precipi-
tating the copper as cuprous thiocyanate, by means of potassium
thiocyanate in presence of sulphurous acid. The zinc and cadmium
in the filtrate may be separated by the preceding method.
C. H. B.
ANALYTICAL CHEMISTRY. 749
Volumetric Determination of Cerium. By F. Stolba. (Chem.
Neir,-<, 41, ol). — Cerium, when freed from lanthanum and didymium,
may be precipitated as oxalate, and determined by means of permanga-
nate solution. . M. M. P. M.
Estimation of Ferrous Iodide. By R. H. Parker (PJmrm. J.
Trans. [3], 10, 851 — 854). — The reaction -which takes place between
potassium chlorate and ferrous iodide may be used to determine the
strength of a syrup of iodide of iron.
Estimation of Iron. — 10 c.c. of the syrup are mixed with 30 c.c. of
water and boiled with 2 grams potassium chlorate and 60 c.c. standard
thiosulphate solution ; the solution is filtered, the precipitate washed
and dissolved in dilute hydrochloric acid, and the iron precipitated as
hydrate, and estimated as FcoOs.
Estimation of Iodine. — 5 c.c. of the syrup are distilled with 15 c.c.
water and 2 grams potassium chlorate, and the distillate collected in a
solution of potassium iodide (2 grams). When nearly all the iodine
has passed over, the receiver is changed, and the distillation continued
until a colourless distillate is obtained. The distillates are then mixed
and titrated with standard thiosulphate solution.
The direct estimation of the iodine by boiling the syrup with potas-
sium chlorate and a known excess of standard thiosulphate solution,
and estimating the amount of the latter used, did not yield trust-
worthy results, owing to the decomposition which a solution of sodium
tetrathionate undergoes when boiled.
By allowing iodine to stand in contact with excess of metallic iron,
bubbles of gas are evolved, and the solution appears to be deficient in
iron. Experiments were made with iron wire and reduced iron, when
it was found that the solution made with iron wire lost, after 9 hours'
standing, 4" 7 per cent., and after 7 days 5"5 per cent. The other solu-
tion lost in the first case 9'4 per cent., and the second 39'7. This
reaction requires further investigation. L. T. O'S.
Presence of Nitrogen in Iron and Steel. By A. H. Allen (Chem.
Netvs, 41, 231 — 234). — As tests for or modes of determining nitro-
gen in iron and steel the following principles have been utilised : —
1. Ignition with soda-lime or pota.sh- baryta, in order to produce
ammonia (Schafhiiutl, Marchand).
2. Heating to redness in a current of hydrogen to produce ammonia
(Fremy, Stuart and Baker).
3. Dissolving in an acid, and distilling off the resultant ammonia
after addition of an alkali (Boussingault, Bonis).
4. Ignition in a vacuum with cupric oxide, and measuring the
liberated nitrogen as gas (Schafhiiutl, Marchand).
5. Ignition with native mercuric sulphide and measuring as gas
(Boussingault) .
6. Ignition with potas.sium or sodium, forming a cyanide (Mar-
chand).
In 1865, Stahlschmidt prepared a definite nitride of the formula
K2Fe4, and concluded that nitride of iron existed in an irregular state
of distribution in commercial steel.
VOL. XXXVIII. 3 g
750 ABSTRACTS OF CHEMICAL PAPERS.
With a view to produce ammonia from the nitrogen in steel, and at
the same time avoid the difficulties attending the process of heating in
a current of hydrogen, the steel or iron under examination is heated
in a current of steam, the hydrogen being in a nascent state, and the
ammonia being produced in a neutral atmosphere, and at once re-
moved from the sphere of action before the high temperature has
decomposed it.
The apparatus employed consists of a piece of combustion tubing
(about 7 feet), bent about the centre at an obtuse angle, one limb being
encased in a Liebig's condenser, the other fitted to a retort containing
water, to which a few drops of hydrochloric acid and some steel
borings had been added ; in the tubulure of the retort is a cork with
a tube passing through, and with a clip at the outer side.
The limb of the combustion tube, in connection with the retort, con-
tains the metal to be operated on, retained in its proper position by
two platinum gauze plugs.
To perform an experiment, 50 to 200 grams of the steel borings are
placed in the limb adjoining the retort, the water in the retort is
boiled until steam blows out uncondensed at the other end ; water is
now passed through the Liebig's condenser, and the distillate is col-
lected and tested by Nessler until free from ammonia ; as soon as free
the limb containing the metal is raised to a red heat, a fresh quantity
of ammonia is now evolved which is estimated by Nessler. In all
cases the iron or steel, before being placed in the apparatus, was heated
to redness in a muffle. In addition to Nessler's test, the condensed
steam was proved to contain ammonia by the ordinary tests for that
body.
By arranging the apparatus as usual, and iilling the space between
the platinum plugs with haematite ore, passing steam, raising to a red
heat, reducing the haematite by means of hydrogen, and then pas-
sing steam again, it was shown that no ammonia was produced, i.e.,
that iron reduced by hydrogen was free from nitrogen. Some nitride
of iron, prepared by heating iron in ammonia, was placed in the appa-
ratus, and on passing steam, ammonia was given off even at 100°, the
amount being much greater on heating to redness. Dissolving the
steel in hydrochloric acid affords the most convenient and satisfactory
means of converting the contained nitrogen into ammonia. The
method of experimenting is to take I gram of the iron or steel, heat it
to redness in a muffle, and tip it into a flask containing ammonia-free
water; the flask is then connected with a globe-shaped separating
funnel with a tap in the stem, the funnel contains a number of
recently ignited glass beads ; the water in the flask is now boiled until
a current of steam issues from the mouth of the funnel, when the tap
is closed and the lamp removed. 20 c.c. of hydrochloric acid (sp. gr.
I'll) are now poured into the funnel, the mouth of which is closed by
a cork fitted with a glass tube that terminates under the surface of
mercury ; the acid is boiled until all air is expelled and is then run
into the flask, the contents of which, together with the rinsings of the
funnel when the steel is dissolved, ai^e washed into a retort, distilled
Avith quicklime, and the resulting ammonia determined by Nessler in
the usual manner. The greatest care was exercised to obtain all the
ANALYTICAL CHEMISTRY. 751
reagents employed free from ammonia, and blank experiments were
performed from time to time for verification, cori-ection being made for
the minnte proportion of ammonia found in this way.
It is found that the presence of air exerts no influence on the
amount of nitrogen found.
A table, with the results of some 20 specimens of iron and steel and
other metals, is given, in which the proportion of nitrogen varies from
0'0041 per cent, in spiegeleisen, to 00172 per cent, in steel from
Dannemora iron.
Xo nitrogen was present in the specimens of commercial aluminium,
zinc, and nickel examined by the solution method, and but very small
proportions were foixnd in magnesium and sodium. Hence iron is
exceptional in the proportion of nitrogen contained in it.
F. L. T.
Estimation of Total Carbon in Iron and Steel. By S. C.
JcTSCM (Chem. Xeics, 41, 17).— Weyl's method for solution of the
metal is recommended (Fogg., 114, 507). The decomposition cell is
made of a 5-oz. beaker containing hydrochloric acid (1 concentrated
acid to 3 water) : into this dips a beaker without a bottom, between
the beakers is placed tlie positive platinum electrode. The steel bar
to be dissolved is ofround brisrht, weiohed, covered with rubber sheet-
ing to within an inch of the lower end, with the exception of a part
where a binding screw is attached, and immersed in the acid. A single
Grove's cell is recommended to be used ; solution may be allowed to
proceed over night. The separated carbon is filtered through a glass
tube containing fine sand and glass wool covered at its lower end by
filter-paper, muslin, and wire-gauze ; the tube is inserted through a
cork into a bottle which communicates with an exhausting pump. J^o
carbon passes through this filter ; the filtration and washing, first with
water, then with caustic soda, and finally with water, is complete in
10 minutes.
The covering at the bottom of the filter is removed, a little glass
wool placed at the top of the carbon, and the whole contents of the
tube pushed out into an Ullgren's apparatus, wherein the carbon is
oxidised and weij^hed as carbonic anhydride. M. M. P. M.
Estimation of Carbon in Steel. By J. W. Westmoreland (Chem.
Neu:<, 41, 1.j2). — In reply to Sergius Kern (Chem. Neius, 40, 225) the
author states that the colour test for carbon gives results argreeing
with the combustion process, and gives data in support of his assertion.
It does not give good results with high or very low percentages of
carbon, but it is invaluable for estimations ranging from O'l to I'Oper
cent. F. L. T.
Electrolytic Estimation of Nickel and Cobalt. By H. Fre-
SENius and F. Bergmanx (Zeits. Anal. Chem., 1880, 314 — 324). — Very
accurate results are obtained by the electrolytic precipitation of nickel
and cobalt, either together or separately, from solutions which con-
tain in 200 c.c, 0"1 — 0"15 gram of metal as sulphate, 2'5 — 4 grams of
ammonia (NH3), and 6 — 9 grams of ammonium sulphate. The elec-
trodes of which the negative is a platinum cone, the positive a wire
3 g 2
752 ABSTRACTS OF CHEMICAL PAPERS.
spiral, are placed i — ^ cm. apart, and the current — best generated by
a Clamond's thermopile — should be of such strength as to yield by
decomposition of water 200 c.c. of mixed gases in an hour. The pre-
cipitation takes 5 — 6 hours. The completion of precipitation can be
ascertained by adding a few drops of solution of ammonium sulphocar-
bonate, which should only give an extremely faint tinge, rose colour
with nickel, wine yellow for cobalt. Deficiency of ammonia injures
the results, excess has no effect beyond increasing the time necessary for.
complete precipitation. Ammonium carbonate can be substituted for
the sulphate, but retards the operation ; ammonium chloride or
nitrate almost entirely prevents the precipitation. A. J. G.
Volumetric Estimation of Lead. By W. Diehl (Zeits. Anal.
Chem., 1880, 306 — 309). — The lead having been separated from the
other metals in the ore by precipitation as sulphate, is dissolved in
ammonium acetate, excess of ^^th normal solution of potassium dichro-
mate is then added, together with a few drops of acetic acid, and
the plumbic chromate filtered off, after standing for about half an
hour. The excess of dichromate in solution is then determined by
adding sulphuric acid, heating to boiling and titrating with standard
sodium thiosulphate ; 4 mols. of dichromate are reduced by 3 mols. of
thiosulphate. The results are accurate. A. J. G.
Detection and Estimation of Arsenic. By T. D. Boeke (Chem.
Neivs, 41, 177 — 178). — For the detection of arsenic the author prefers
Marsh's method, provided the organic matter be removed ; this may
be done by ignition with potassium nitrate and sodium carbonate, or
by heating with sulphuric and a little nitric acid until the mass
is wholly converted into a porous coal. The author prefers the latter
method.
For estimation in organic mixtures, the author digests with potas-
sium chlorate and hydrochloric acid, filtering off any insoluble residue ;
the solution after neutralisation with sodium carbonate and concentra-
tion is again acted on by potassium chlorate and hydrochloric acid,
saturated with ammonia, precipitated by " magnesia " mixture and
allowed to stand 24 hours ; the magnesia precipitate is dissolved in
dilute sulphuric acid, sulphuretted hydrogen passed, and the arsenic
weighed as arsenious sulphide. F. L. T.
Detection of Bismuth. By J. C. Thresh (Pharm. J. Trans. [3],
10, G41). — Minute traces of bismuth may easily be detected by adding
potassium iodide to the solution rendered slightly acid by hydrochloric
acid, when an orange to a yellow coloration is produced according to
the quantity of bismuth present ; 1 part of bismuth in a million gives
a decided yellow coloration. The presence of mercury, lead, and anti-
mony slightly interferes with the test. Mercuric iodide is, however,
soluble in excess of potassium iodide and lead iodide on warming the
solution ; in each case, bismuth being present, the coloi'ation is pro-
duced. In presence of antimony the potassium iodide must not be
added in excess, as large quantities of the reagent give a reddish-
yellow coloration with antimony itself. Bismuth does not give a
ANALYTICAL CHEMISTRY. 753
coloration -with potassium iodide in neutral or alkaline solutions ; if
sulpliuric acid is present in excess it is necessary first to neutralise the
acid with ammonia, and then acidify with hydrochloric acid, otherwise
a dark-brov/n precipitate is formed.
To detect bismuth by this method in a mixture of salts, dissolve in
hydrochloric acid the precipitate produced by adding ammonia to the
nitric acid solution of the sulphides insoluble in ammonium sulphide,
in one portion test for lead, and in the other for bismuth, with potas-
sium iodide. L. T. O'S.
Method for Estimating Bismuth Volumetrically. By M.
KuHARA {Chem. Neivs, 41, ISo — 154). — The method consists in preci-
pitating the bismuth from its nitric acid solution by adding disodiuni
arsenate of' known strength in slight excess, allowing to stand until
the reaction is completed ; making alkaline with ammonia, then acid
with acetic acid, and estimating the excess of arsenate by standard
uranium nitrate, using potassium ferrocyanide as indicator.
The disodium arsenate (about 21 grams per litre) was standardised
on known quantities of bismuth ; tlie strength of nranium nitrate that
gave the best results was 43'2 grams of the crystallised salt per litre ;
it was standardised on the disodium arsenate.
The average error of six results olitained by working on known
weights of bismuth is '3 per cent, on total quantity. F. L. T.
Modification of Dumas' Method for Estimating Nitrogen.
By K. ZcLKOWSKT (-Be/-., 13, 1096 — 1103). — Several improvements
in the author's {Annalen, 182, 296) modification of Dumas' method of
estimating nitrogen in carbon compounds is described, the more im-
portant of which are as follows : —
In the old form of apparatus, the potash-solution for absorbing the
carbonic acid was very apt to run back when the current of gas was
not evolved with sufficient regularity; this is now avoided by inserting
a Bunsen's valve between the combustion tube and the azotometer.
The frequent emptying and refilling of the measuring tube is also
rendered unnecessary by a different manipulation of the apparatus.
According to the old method of operating, the combustion tube, sealed
at one end. was first partially filled with sodium bicarbonate, for the
evolution of carbonic auhvdride, to drive out the air, and then with
the mixture of the substance with copper oxide. The result of this
was that fresh copper oxide had to be employed for each determina-
tion, thus requiring much time and material. In order to avoid this,
the operation is conducted like an ordinary combustion, the combus-
tion tube being open at both ends, and connected at the end removed
from the azotometer, with a separate tube containing tlie sodium bi-
carbonate for the evolution of carbonic anhydride. This arrangement
allows of the substance being placed in a boat as in an ordinary com-
bustion with, an open tube, and hence the same tube and the same lot
of oxide of copper may be used many times in succession without any
re-arrangement, except the reoxidation of the copper in a current of air,
and the reduction of the copper coil in a current of hydrogen. The
apparatus thus consists of three parts : (1) the carbonic anhydride
754 ABSTRACTS OF CHEMICAL PAPERS.
generator ; (2) tlie combustion tube ; (3) tlie azotometer. For tbe
modus operandi reference must be made to the original paper. By
tliis apparatus nitrogen determinations can be made with very great
exactness and in a. very sliort time, viz., 1 to 1^ hours. T. C.
Ah sir actor'' s Note. — The introduction of a separate tube for the gene-
ration of the carbonic anhydride, as well as several other important
improvements, has also been proposed by Groves (this Journal, 1880,
Trans., 500).— T. C.
Proximate Analysis of Plants. By H. B. Parsons (Pharm. J.
Trans. [3], 10, 793 — 797). — Estimatum of Moisture. — 2 grams of the
finely powdered specimen are dried at 100 — 120*^ ; the loss gives mois-
ture, and sometimes a little volatile oil. In some cases it is necessary
to dry at lower temperature, or in a current of hydrogen or carbonic
anhydride.
Eslihiation of Ash. — 2 grams are gently ignited at a faint red heat
until quite free from carbonaceous matter.
The residue is extracted with water, dilute hydrochloric acid, and
concentrated alkali in succession, and the residue in each case
weighed.
Total nitrogen is estimated by ignition with soda-lime. If the nitro-
genous matter present is albuminoid, its amount is obtained by multi-
plying the amount of nitrogen by G"25.
Benzene Extract. — 5 grams are digested with benzene (b. p. 80 —
85°) for six hours, whereby certain volatile oils, resins, camphors,
organic acids, wax, fats, oils, chlorophyll and other colouring matters,
alkaloids, and glucosides are extracted.
The solution is evaporated to dryness, and the weighed residue
ti'eated with water and again evaporated; the residue dried at 110°
and weighed : loss in weight gives volatile oils. If the presence of
volatile alkaloids is suspected, a few drops of hydrochloric acid are
added previous to evaporation. Treat the residue with warm water,
leave it to cool, and filter. In one half of the filtrate determine total
organic matter and ash ; in the other half test for alkaloids, glucosides,
and organic acids. Dissolve the residue in benzene, evaporate the solu-
tion to dryness, and extract the residue with hydrochloi"ic acid ; filter
and test for alkaloids and glucosides in the filtrate. Treat the residue
several times with a large excess of alcohol. Evaporate the solutions
and estimate the extracted matter, which usually consists of chloro-
phyll and one or more resins ; these may sometimes be separated by
light petroleum, naphtha, or chloroform. Animal charcoal removes
chlorophyll and some resins. Camphor, if present in the plant, will be
found for the most pai't in the alcoholic extract.
It is sometimes advisable to exhaust the plant with light petroleum
before proceeding with benzene. Where pure benzene cannot be ob-
tained, chloroform serves as the best substitute.
AhoholiG Extract. — The residue from the extraction with benzene is
dried at 100°, and digested for 14 hours with alcohol (80 per cent.).
The solution is concentrated and left at rest, and any crystals or pre-
cipitate which may form are separated. The solution is made up to a
ANALYTICAL CHEMISTRY.
755
definite volume, and in a measured portion the total organic matter
and ash determined. In another the total orsranic matter and ash
soluble in water are determined, and by difference, the same insoluble
in water.
The remaining solution is evaporated to dryness, and the residue
treated with several portions of absolute alcohol.
A. Soluble in Absolute Alcohol.
(fl.) Soluble in water.
Precipitated hy Subacetate of
Lead.
Tannin and most organic acids,
some extractives, and inorganic
acids. Weigh precipitate, ignite
and weigh : loss eqaal to organic
matter.
Not Frecijntated by Subacetate
of Lead.
Alkaloids, glucosides, extrac-
tives and colours.
Soluble in Dilute
Hydrochloric Acid.
Alkaloids, gluco-
sides, some extrac-
tives : determine in-
soluble portion.
{b.) Insoluble in water,
Soluble in Dilute
Ammonia.
Most acid resins,
some colours.
Precipitated by Subacetate of
Lead.
Some colours, extractives, al-
buminoids, organic and inorganic
acids. Weigh, ignite, and weigh
again. Loss gives organic mat-
ter.
Insoluble in Dilute
Ammonia.
Neutral resins, co-
lours, and albumi-
noids. Dissolve resi-
due in alcohol. Eva-
porate and weigh.
B. Lisoluble in Alcohol.
(c.) Soluble in Water.
Not Precipitated by Subacetate
of Lead.
Alkaloids, glucose, saccharose
extractives. Determine by dif-
ference. Separate lead from
solution, and determine saccha-
rose and glucose with Fehling's
solution.
(d.) Insoluble in Water
Soluble in Dilute Hydrochloric
Acid.
Some alkaloids and glucosides.
Determine by difference.
Lisoluble in Dilute Hydro-
chloric Acid.
A few resins, extractives, and
colours. Dissolve in alcohol.
Evaporate solution and weigh.
When the plant contains much tannin or sugar, the following
method for analysing the alcoholic extract should be adopted.
Dilute the extract to 200 c.c. with alcohol (80 percent.). In 20 c.c.
determine total organic matter and ash ; in 20 c.c. determine orgaiuc
756 ABSTRACTS OF CHEMICAL PAPERS.
matter and ash, soluble and insoluble in water. Evaporate the re-
maining 160 c.c. to dryness, heat the residue with water, filter and
make the filtrate up to 160 c.c.
The residue may contain resins, colours, and glucosides, which
may be removed by dilute ammonia ; alkaloids and some glucosides
soluble in dilute hydrochloric acid ; also insoluble albuminoids and
resins.
In 20 c.c. of the filtrate the tannin is determined by A. Carpeni's
method (Ghem. Neivs, July 9, 1875, p. 19). 20 c.c. are precipitated
with normal lead acetate. The precipitate, which may contain tan-
nin, gallic and other organic acids, inorganic acids, albuminoids, ex-
tractives, and some colours, is dried at 100 — 120° and weighed.
20 c.c. are precipitated with subacetate of lead, and the precipitate is
weighed. A greater number of acids, extractives, and colours are pre-
cipitated by this reagent than by the former. To the filtrate add
excess of hydrochloric acid, boil, and determine the glucose in the
solution.
Precipitate another 20 c.c. with subacetate from the filtrate, remove
the lead with sodium carbonate, and determine the glucose in the
solution. Any appreciable difl^erence between this result and the
former is due to the presence of glucosides or saccharose.
A further 20 c.c. is precipitated with subacetate of lead, and the
organic acids in the precipitate determined after the removal of the
lead by sulphuretted hydrogen. Add sulphuric acid to the filtrate and
an equal volume of alcohol, allow the solution to stand two hours,
filter, evaporate the filtrate to expel alcohol, and test the solution for
alkaloids, glucosides, sugars, and extractives.
Aqtieous Extract. — The residue from the alcoholic extract is ex-
hausted with cold watei\ When the plant contains much gummy
substance, this is best done by adding a measured volume of cold
water to the residue, and leaving it from six to twelve hours. Filter
through linen, and in a measured portion of the solution estimate
the total organic matter and ash. In the case of fruits and fleshy
roots, pectin bodies, organic acids, albuminous substances, colouring
matters and sometimes a body resembling dextrin are found in this
residue, but otherwise it generally consists of gum.
Acid Extract. — The residue insoluble in water is boiled for six
hours with 500 c.c. water and 5 c.c. sulphuric acid (sp. gr. 1"34). By
this means all the starch is converted into glucose, which is estimated
with Fehling's solution, the result multiplied by "9 equals starch and
its isomerides ; the insoluble residue is weighed.
Alkali Extract. — The residue is boiled with 500 c.c. of a 2 per cent,
solution of caustic soda. The extract usually contains albuminous
matter, modifications of pectic acid, Fremy's " cutose," humus, and
decomposition products.
The residue, which consists of cellulose, is bleached with chlorine
and caustic soda and weighed.
Benzene, alcohol, and water remove from most plants the substances
of the greatest chemical and medical interest, but in the case of grain
fodder and foods, the substances extracted by acids and alkalis have
great value. L. T. O'S.
ANALYTICAL CHEMISTRY.
757
Use of the Spectroscope in Discriminating Anthracenes,
By B. Nickels (Chem. Netvs, 41, 52 and 95). — Those substances asso-
ciated with commercial anthracene, which yield " amorplious par-
ticles " on oxidation, are characterised by showing absorption-bands
between F and G, and immediately to the left of G (D at the right
hand). Commercial anthracene may be tested by dissolving a few
decigrams in 6 c.c. benzene, and placing the solution between a lamp
and the slit of a direct vision spectroscope. Absence, or faintness of
absorption-bands, points to absence of impurities ; the comparative
purity of samples may be judged of from the depth and intensity of
the absorption bands. M. ]\[. P. M.
Estimation of Glycerol. By W. Lexz (Zeits. Anal. Chem., 1880,
297 — 305). — The author has determined the specific gravity of mix-
tures of glycerol and water, and their refractive indexes at 12'5 —
12'8°. In the folldwino: table the specific gravity is L:-iven : —
Anhydrous
Specific
Anliydrous
Specific
Anhydrous
Specific
glycerol,
weight at
glycerol,
weight at
glycerol.
weight at
per cent.
12—14°.
per cent.
12-14°.
per cent.
12—14°.
100
1 -2691
G7
1-1795
34
0880
99
1 -2664
66
1764
33
0852
98
1 -2637
65
1733
32
0825
97
1 -2610
64
1702
31
0798
96
1 -2584
63
1671
30
0771
95
1 -2557
62
1610
29
0744
94
1 -2531
61
1610
28
0716
93
1 -2.504
60
■1582
27
0689
92
1 -2478
59
1556
26
0663
91
1 -24.51
58
-1530
25
0635
90
1 -2425
57
1505
24
•0608
89
1 -2398
56
1480
23
0580
88
1 -2372
55
1455
22
0553
87
1 -2345
54
1430
21
0525
86
1 -2318
53
1403
20
0498
85
1 -2292
52
1375
19
0471
84
1 -2265
51
1348
18
0446
83
1 -2238
50
1320
17
0422
82
1 -2212
49
1293
16
0398
81
1 -2185
48
1265
15
0374
80
1-2159
47
12.38
14
0349
79
1-2122
46
1210
13
0332
78
1 -2106
45
11S3
12
0297
77
1 -2079
44
1155
11
0271
76
1 -2042
43
1127
10
0245
75
1-2016
42
1100
9
0221
74
1 -1999
41
1072
8
0196
73
1 1973
40
1045
7
0172
72
1 • 1945
39
1017
6
0147
71
1 -1918
38
0989
5
0123
70
1-1SS9
37
0962
4
0098
69
1 -18.58
36
0934
3
1 -0074
68
1-1826
35
0907
2
1-0049
67
1 -1795
34
0880
1
J_
0025
A. J. G.
758 ABSTRACTS OF CHEMICAL PAPERS.
Detection of Starch-sugar Mechanically Mixed with Refined
Cane-sugar. By P. Casamajor (Chem. Neivs, 41, 221 — 222).— The
processes given ai"e the sacchariinetric, before and after inversion ; the
reduction with Fehling's solution ; the solubility in cold water, the
starch-sugar dissolving but slowly, and appearing as white specks
like crushed wheat, and the taste ; in the last case comparison must
always be made with a sample of refined sugar. F. L. T.
Action of Bone-black on Sugar Solutions. By P. Casamajor
(Chem. News, 4:1, 66). — Dried, newly made bone-black, when kept in
contact with a solution of pure sugar, absorbs O'OOG per cent, (of its
own weight.) Filtration of sugar solutions through bone-black does
not therefore interfere with subsequent testing by the optical method.
M. M. P. M.
Behaviour of Various Sugars with Alkaline, Copper, and
Mercury Solutions. By F. Soxhlet (J. pr. Ghem. [2], 21, 227 —
317). — The preparation of the various sugars in a state of purity is
described at some length.
An abstract of a previous paper by Soxhlet has already been
given in this volume (p. 66). Soxhlet shows that the quantities of
copper reduced under like conditions by the various sugars from
Fehling's or Ldwe's solutions, differ among themselves, and that the
quantity for any individual sugar depends on the strength of the
solution, and the amoujit of copper present in excess. In no case does
one equivalent of a sugar reduce 10 equivalents of cupric oxide. He
prefers as before {loc. cit.) to keep his Fehling's test in two separate
solutions, only mixing immediately before use.
The reducing power of a sugar is voluraetrically determined in the
following manner : — Varying quantities of the copper solution were
heated to boiling in a dish, equal volumes of the solution of Rochelle
salt and sodium hydrate being previously added. Then 50 c.c. or
100 c.c. of the 1 per cent, or ^ per cent, sugar solutions respectively
were added, and the whole was boiled for two, four, or six minutes,
according to the variety of the sugar. The contents of the dish are
then thrown on a filter, the filtrate is acidified with acetic acid,
and potassium ferrocyanide at once added to ascertain the presence of
copper. This process is i-epeated until two quantities of the copper
solution, differing from each other by -^-^ c.c, give, the one a filtrate
containing copper, the other a filtrate free from copper. The mean of
these two readings is taken as the result.
The gravimetric method of determining the copper reduced by the
sugars acting on Fehling's or Lowe's solution is to boil a measured
quantity of the sugar- solution with an excess of the Fehling's or
Lowe's solution, and then to filter by means of gentle suction, through
a weighed tube filled with asbestos ; wash with hot water, then with
absolute alcohol, and finally ether. On passing hydrogen through the
heated tube, the cuprous oxide is reduced to the metallic state in two
or three minutes, and then weighed. The following are the chief
results: —
ANALYTICAL CIIEJnSTRT. 759
Dextrose. — Oo gram in 1 per cent, solution reduces 105"2 c.c. Fehling
(undiluted), or 101"1 c.c. Fehling (diluted with 4 volumes of water).
Ratio of reduction, 1 : 10-52—1 : 10-11.
Invert sugar {i.e., equal molecules of dextrose and levulose obtained
by the action of acids on cane-sugar). — 0-5 gram in 1 per cent, solution
reduces 101*2 c.c. Fehling (undiluted), or 9?'0 c.c. Fehling (diluted
with 4 volumes of water).
Ratio of reduction, 1 : 1012—1 : 9- 7.
In the case of dextrose and invert sugar, dilution of the solution
lowers, excess of copper raises, the reducing power.
Milh-snrjar. — 0"5 gram in 1 per cent, solution reduces 74 c.c.
Fehling.
Ratio of reduction, 1 : 7-4.
Dilution has no noteworthy influence on the reducing power.
Excess of copper raises it, but to a much slighter extent than with
dextrose or invert sugar.
Galactose. — 0-5 gram in 1 per cent, solution reduces 98 c.c. Fehling
(undiluted), or 94 c.c. Fehling (diluted with 4 volumes of water).
Ratio of reduction, 1 : 9-8 — 1 : 9-4.
Dilution lessens the reducing power to the same extent as with
dextrose and invert sugar. Excess of copper raises the reducing
power, but to a somewdiat slighter extent than with dextrose and
invert susrar.
Levulose (calculated from the results with dextrose and invert
sugar). — 0-5 gram in 1 per cent, solution, reduces 97-2 c.c. Fehling
(undiluted), or 93" c,c. Fehling (diluted with 4 volumes of water).
Ratio of dilution, 1 : 9-72—1 : 9-3.
Dilution and excess of copper act respectively as with dextrose and
invert sugar. The reducing power of levulose is probably equal to
that of galactose.
Inverted Mine-sugar. — Reducing power equal to that of invert sugar
(Rodewald).
Maltose. — O'S gram in 1 per cent, solution reduces 64-2 c.c. Fehling
(undiluted), or G7-5 c.c. Fehling (diluted with 4 volumes of water).
Ratio of reduction, 1 : 6-09 — 1 : 6*41.
Dilution raises the reducing power. Excess of copper has no effect
with undiluted Fehling, but in highly dilute solutions raises the
reducing power to a slight extent.
With the exception of the determination of sugar in diabetic urine
(where, owing to the constant formation of ammonia, some of the
cuprous oxide is dissolved and passes through the filter, and conse-
quently the end of the reaction must be decided, as usual, by the dis-
appearance of the blue colour), the following plan is adopted for the
estimation of the various sugars. The approximate strength of the
sugar solution is first determined in the usual manner, by the dis-
appearance of the blue, operating on 25 c.c. Fehling. The sugar solu-
tion is now diluted so as to contain 1 per cent, of the sugar, and the
determination is proceeded with as described above, operating on
50 c.c. Fehling, undiluted with water.
In the case of highly coloured fluids, the indication with potassium
ferrocyanide is difiicult to recognise, the reaction with sulphuretted
7G0 ABSTRACTS OF CHEMICAL PAPERS.
hjdi^ogen giving still worse results. In such cases the following device
is adopted : — The filtrate is boiled with a few drops of the sugar
solution in a beaker, allowed to settle, and then poured off ; on wiping
the bottom and sides of the beaker with a piece of white filter-paper,
it will be coloured red if any copper still remain in the solution.
The behaviour of the sugars with alkaline mercury solutions was
tested both with Knapp's solution (alkaline mercuric cyanide), and
Sachsse's solution (alkaline mercuric iodide in potassium iodide).
It is found as observed by Brumme (/. pr. Chem. [2], 21), that dif-
ferent results are obtained from Knapp's solutions, according as the
sugar solution is added gradually, or all at once ; when gradually
added more sugar being required ; with Sachsse's, however, the reverse
is the case.
To get comparable results the sugar must be added all at once, the
solution boiled for two or three minutes, and the liquid tested for mer-
cury, always using the same indicator ; in using the alkaline tin solution
as indicator, 0'200 — 0"202 gram of grape-sugar were always required
for 100 c.c. Knapp, in a large number of experiments. It is remark-
able that these two solutions, although containing almost exactly the
same amount of mercury, require very different quantities of sugar to
reduce equal volumes of them. This is shown to be due, to a great
extent, to the different amounts of alkali present in them.
The amounts of mercury solutions which 1 gram of sugar in 1 per
cent, solution reduces ai'e : —
Gi'ape-sugar 497'5 c.c. (Knapp), 302"5 c.c. (Sachsse).
Invert sugar 502-5 ,, 376'0 „
Levulose 508-5 „ 449'5 „
Milk-sugar 322-5 „ 214-5 „
Galactose 413-0 „ 226-0
Inverted milk-sugar, . 448-0 ,, 258-0 „
Maltose 317-5 „ 197-6
The various sugars have different reduciag powers for the alkaline
mercury solutions, and there is no definite relation between the
amounts of Knapp's and Sachsse's solutions required by them ; the
amount of Sachsse's solution, to which 100 c.c. Knapp's correspond,
varying from 54*7 c.c. in the case of galactose, to 748 c.c. in the case
of invert sugar.
Taking the reducing power of grape-sugar = 100, the reducing
powers of the other sugars are : —
Feliling (undiluted). Knapp. Sachsse.
Grape-sugar 100 100 100
Invert sugar 96-2 99-0 (100 ?) 124-5
Levulose "(?) 92-4 102-2(100?) 148-6
Milk-sugar 70-3 64*9 70-9
Galactose 93-2 83-0 74-8
Inverted milk-sugar . . 96-2 90-0 85-5
Maltose 61-0 63-8 65-0
The two mercury methods have no advantage in point of accuracy
AXALYTICAL ClIE:\nSTRY. 761
or convenience over Fehling's method, the lattei- having the preference
on account of the great certainty of the point at which the reduction
is finished.
The mercury methods are, however, of great importance, both for
the identification of a sugar and for the estimation of two sugars in
presence of each other, as ah-eady proposed by Sachsse. For instance,
for the estimation of grape and invert sugars in presence of each other,
"we have the two equations : ax -\- hy =■ ¥, ex -^ dy = S. Where —
a = number of 1 c.c. Fehling, reduced by 1 gram grape-su^ar.
t = ,, ,, ,, ,, invert sugar.
c =■ „ Sachsse „ „ grape-sugar.
d =^ „ ,, ,, ,, invert sugar.
F = „ Fehling, used for 1 voL sugar solution.
S = „ Sachsse ,, ,, ,,
X = amount of grape-sugar in grams in 1 vol. of the solution.
U = „ invert sugar ,, „
It need scarcely be mentioned that the above, together with all other
indirect methods, leaves room for increased accuracy ; but nevertheless
the combination of a mercury method with a copper method in the
determination of a sugar whose nature is not exactly known, crives
a more serviceable result than the hitherto adopted plan, by which a
solution that reduced 10 c.c. Fehling was said to contain "Go gram of
" sugar." F. L. T.
Cupric Test Pellets for Sugars. (Chem. News, 41, 63).— The
solid ingredients of the ordinary copper test for sugar have been com-
pressed into pellets by Dr. Pavy. When required for use a pellet is
dissolved in about 3 c.c. of rain water. M. M. P. M.
Report on the Methods of Estimating Cellulose and on their
Defects. By C. Keauch {Landiv. Versuchs.-Stat., 24, 295 — 20y). —
The so-called " non-nitrogenous extract," separated in the ordinary
course of analysis from cellulose by successive treatment with potash
and sulphuric acid, in reality contains a large amount of cellulose,
varying in quantity with the strength of the solution employed.
Although the practical value of the analysis is not influenced by this
result, since experiment shows that the sum of the digestible parts of
the so-called extract and of the cellulose is about equal to the quantity
set down as non-nitrogenous extract, an incorrect idea is nevertheless
given of the quality and constitution of the substance under investiga-
tion. Rye, hay, and clover hay, which had been freed from starch, fat,
and protein, were boiled with potash and sulphuric acid solutions, and
it was found that 80 per cent, of the total cellulose and fibre in the case
of rye, and 50 per cent, in the case of hay and dried clover, had gone
into solution ; the composition of the dissolved cellulose was not con-
stant, varying considerably in the case of hay and clover.
J. K. C.
Estimation of Fat in Milk. By P. Yieth (Bied. Centr., 1880,
302 — o03j. — The '• lactobutyrometer," it is suggested, will be found
to supply the want of a ready and accurate dairy method of estimating
the fat in milk (see also Bied. Centr., 1876, 231; 1877, 226; 1879,
7 1)2
ABSTRACTS OF CHEMICAL PAPERS.
770). The results obtained witli the creamometer are shown to be
too much influenced by temperature to be of any value.
A. J. C.
Saponification of Pats. By von der Becke {Zeits, Anal. Ghem.,
1880, 291 — 297). — The saponifying action of lead oxide, of potassium
hydrate, and of lime, is veiy different, the amounts of glycerol libe-
rated especially differing, as shown in the accompanying extract from
the author's table.
Percentage of Glycerol.
Butter.
Cacao
fat.
TaUow.
Grease.
Olive
oil.
Rapeseed
oil.
Linseed
oil.
Lead oxide
Potassium hydrate
Lime
7-98
10-59
7-99
0-23
5-99
2-19
0-13
7-84
2-43
6-6
8-27
9-27
3-76
6-41
4-2
4-58
4-4
6-2
A. J. G.
Estimation of Fat in Fodder. By P. Wagner (Landw.
Versuchs.-Stat., 24, 289 — 294). — Three or four hours' treatment with
ether is generally considered sufficient for the extraction of fat from
organic bodies. The time is, however, too shoi't, as the following
experiment shows. Palm cake was extracted with ether by S torch's
method : —
After 3 hours, was extracted 11*88 per cent of fat.
,, 3 hours further .... 0'54 ,,
„ 6 ,, .... O'o3 „
,, io ,, .... U 4/ ,,
10
0-01
Altogether, after 37 hours, 13'23 per cent, of fat was extracted.
The same sample yielded 12 per cent, of fat when allowed to stand
two days with ether in the cold.
It was found that treatment with small quantities of ether at a time
was not sufficient, even after 21 days' standing, to extract the whole of
the fat ; relatively large volumes of ether seem to be necessary to break
up the fat-cells.
The above experiments were carried on with a material containing
9 per cent, of water, the action of absolute ether on the dried substance
was then tried. The fodder was dried over a water-bath, and after
27 hours' treatment with absolute ether, yielded 10-54 per cent, of fat.
The same dried over sulphuric acid, and treated similarly, gave
10' 73 per cent., and when allowed to stand with absolute ether in the
cold, 10'4 per cent, was obtained ; common ether, on the other hand,
extracting 11-35 per cent. Undried material treated 27 hours with
absolute ether, yielded 10'74 per cent., and with common ether,
13-01 per cent, of fat. It seems, therefore, that water must be present
both in the material and in the ether, in order that the whole of the
fat may be extracted. J. K. C.
AX.VLYTICAL CHEMSTRY. 7G3
Detection of Wax. Bj E. Hirschsohn (Pharni. J. Trans. [3],
10, 74y — 7'51). — As the result of a series of experiments on different
kinds of wax, the author submits the following method for their
detection.
The wax is boiled with ten times its volume of chloroform, nntil it
is completely dissolved, and the solution is then cooled.
I. The solution remains clear after cooling.
(A.) Ether dissolves the wax completely.
(n.) Alcoholic ferric chloride gives a precipitate with alcoholic solu-
tion of wax, insoluble on boiling. Wax from Mijrica querci-
folia.
(6.) Ferric chloride gives black coloration. Wax from undetermined
species of Myrica.
(c.) Ferric chloride gives brown coloration. Wax from Myrica ceri-
fra. Wax from Orizaba.
(B.) "SYax only partly soluble in ether. Boil with ten times its
volume of alcoholic potash, and heat the soap with 100 volumes of
water.
(a.) Soap is soluble. Japanese wax.
(&.) Soap is partially soluble. Beeswax, African beeswax.
II. Wax deposited from chloroform solution on cooling.
(A.) Alcoholic lead acetate gives a cloudiness on standing with
alcoholic solution of wax. Wax from shellac.
(B.) Alcoholic lead acetate gives no cloudiness.
(a.) Ethereal solution of wax becomes cloudy on addition of alcohol.
Brazilian and Carnauha wax.
(i.) Ethereal solution remains clear. Bahia luax.
L. T. O'S.
Tests for Alkaloids. By T. Tattersall (Ghem. Neios, 41, 63). —
Beljyhinine. — Thoroughly mix a small quantity with 2 — 3 parts of
malic acid, add 6 drops pure concentrated sulphuric acid, and stir
with a small agate pestle ; an average red colour is produced, changing
to rose red, becoming dark rose, with a violet shade at the edges after
some hours, then bluish- violet, and finally "a dirty cobalt."
Mor-pldne. — Concentrated sulpliuric acid with a crystal of sodium
arsenate gives a dim violet colour, changing to sea-green, with escape
of acid vapour on heating. M. M. P. M.
Determination of the Alkaloids. By J. C. Thresh {Pharm. J.
Trans. [3], 10, 809 — 814). — A solution of potassium bismuth iodide
may be used to estimate volumetrically solutions of tl;ie alkaloids.
4"68 grams bismuth oxide are dissolved in 80 c.c. hydrochloric acid,
(B. P.) ; the solution is made up to 300 c.c. with water ; 20 grams of
potassium iodide are dissolved in 700 c.c. water : and the two solutions
are mixed. By this method a clear bright orange-coloured liquid is
obtained. The solution is added to the alkaloid solution from a
burette until a drop of the reagent ceases to give a distinct immediate
precipitate with a drop of the filtered solution. The results are not
affected by the presence of hydrochloric or nitric acid, but acetic acid
764
ABSTRACTS OF CHEMICAL PAPERS.
decolorises the bismutli solution ; tliis is pi^evented by adding a little
potassium iodide to the solution of the alkaloid. Different formula
for the precipitates were found for solutions containing varying
quantities of bismuth. With a solution of the above strength the
following formula? were obtained : —
For the cinchona alkaloids the ratio of bismuth to alkaloid is 3 : 2,
giving the formula 3(BiI..,).2(Alk.HI).
For the opium alkaloids the ratio is unity, giving the formula
(Bil3).(Alk.HI).
For strychnine the ratio is f formula 5(Bil3)6(OoiH32N^302HI).
„ brucine „ -^\ „ 9(Bil3)10(C,oHo6N.,O4HI).
„ atropine „ 1 „ (Bil3)(CnHo3NO,HI).
„ aconitine „ | „ 3(Bil3)2(C54H4„NO,HI).
„ emetine „ f „ 3(Bil3)2(C3oH«N208HI).
The method may be applied to the valuation of cinchona and various
oth.er barks, and of various preparations of the alkaloids. The
reaction is very delicate, the following quantities being readily
detected : —
Quinine 1 in 200,000
Strychnine
Cinchonidiue 1
Morphine.
Atropine .
Brucine .
Quinidine
Aconitine 1
Codeine ....
Apomorphine
Narcotine . .
Narceine ....
Beberine ....
Theine
Caffeine ....
, 250,000
, 125,000
, 20,000
, 25,000
, 40,000
, 150,000
, 40,000
, 17,500
, 12,500
, 50,000
, 20,000
, 6,000
, 4,000
, 3,000
In the case of the two last alkaloids the precipitate only forms after
standing. L. T. O'S.
Estimation of Amido-compounds. By Keen (Landw. Ver-
suchs.-Stat., 24, 305 — 373). — The apparatus used was a modification
of Sachsse's, its chief advantage lying in the shortness of time required
fur the absorption of the nitric oxide, and the small quantity of ferrous
sulphate necessary. During some experiments on asparagin it was
found that the presence of ammonia salts interferes with the accuracy
of the method, as they are partially decomposed by nitrous acid. It
was also observed that organic acids in a high state of dilution are
able to decompose amido-compounds, such as asparagin, with separation
of ammonia : hence the sap of vetches, hay, &c., alter being heated,
will be found to contain salts of ammonia. J. K. C.
Estimation of Albuminoids and Non-Albuminoidal Nitrogen-
compounds in various kinds of Fodder. By E. Schulze (Landw.
TECHNICAL CHEMISTRY. 765
Versuchs.-Stat., 24, 358 — 365). After giving a historical sketch of
the discoveiy in vegetable products of nitrogenous bodies different
from albumin, and included in the groups of amido-acids, acid
amides, and peptones, the author proceeds to say that the distribution
of the total nitrogen of a fodder under examination, amongst the
various groups may be ascertained with sufficient exactness. The
albumin is fifst removed by means of a lead salt, and then the peptones
are precipitated by phosphotungstic acid, the amido-compounds being
finally determined in the filtrate, according to Sachsse's method.
J. K. C.
Xanthic Acid as a Precipitant for Albumin. By P. Zoller
(Ber., 13, lUG2 — luG4). — Albumin, even when present in very minute
quantities, is precipitated in the form of flocks when a few drops of
potassium xanthate are added to the slightly acidified solution. It is
better to avoid shaking the liquid, and the precipitate must consist of
flocks, as xanthic acid itself renders the liquid turbid, and also precipi-
tates some other organic substances. It is better to place the mixture
in a glass dish, and allow the whole to remain at rest at a temperature
of 35—38°.
In consequence of its behaviour towards albuminous substances
xanthic acid acts as a powerful antiseptic; T. C.
Technical Chemistry.
Rapid Developer for Wet Plate Photographs, By J. M. Eder
{Dingl. polyt. J., 236, 406— 409).— The author mentions the different
developing solutions which have been proposed at various times. He
finds that ferrous sulphate with \ per cent, of salicylic acid, and a
trace of sulphurous acid dissolved in water, forms a rapid developer,
which has recently been introduced from Paris. J. T.
Industrial Utilisation of Solar Heat. By A. Mouchot {Gom.pt.
rend., 90, 1212 — 1213). — By means of large mirrors the author has
been able, even in the middle of winter, to utilise solar radiation for
many chemical operations, such as distillation of alcohol and various
essences, calcination of alum, preparation of benzoic acid, sublimation
of sulphur, distillation of sulphuric acid, and carbonisation of wood in
closed vessels. He has also succeeded in working a small horizontal
engine with 120 i^evolutions per minute, at a constant pressure of
3"5 atmospheres, and a pump yielding 6 litres of water per minute,
and capable of throwing a jet 12 meters.
The large solar receiver used was of the same dimensions, and con-
structed on the same plan as that of Tours. Neither strong winds,
nor passing clouds, exercised any appreciable effect on the working of
the apparatus. C. H. B.
VOL. XXXVIII. 3 h
7I)() ABSTRACTS OF CHEMICAL PAPERS.
Heating Powers of Coal-gas of Different Qualities. By
W. Wallace {Chem. News, 41, 41). — The beating powers were com-
pared by causing the gases burned nnder similar conditions to
raise the temperature of equal weights of water through the same
interval. The heating value of the gases examined rose or fell with
the lighting value. Comparing coal with gas the author says, "a
pennyworth of coal gives as much heat as a shilling's worth of gas.
M. M. P. M.
Examination of some County Dublin Waters. By J. Fletcher
(Chem. Neivs, 41, 62).
Before
After Oxygen
Chlorine.
boiling.
boiling, used.f
1-28
12°
8° 0-12
1-278
18
9 0-10
3-124
20
16 022
6-993
22
17 013
2-378
17
16 0-10
3-017
17
16 0-10
9-445
14
9 0-01
6-465
18
18 0-18
3-550
19
12 0-06
2-52
25
14 0-0
3-73
19
19 00
M
. M. P. M.
Total
solids.
Rathmines Township, untiltered 420
filtered.. 26-0
Howorth Churchyard, No. 1 . . 32-0
No. 2 . . 51-0
Forge Well 70-0
Bath Well 72-0
Malahide, Hotel 67-0
,, Strand Pump 900
Sti'eet Well 40-0
Dalkey, Tobermue Well 50-0
Lady Well 49-0
Action of Water on Zinc and Lead. By X. Rocques (Bull.
Soc. Cliim. [2], 33, 499 — 501). — Zinc tanks are often found to be
corroded, and a muddy deposit settles in the tank. The action is
partly chemical and partly physical. From numerous experiments
the author infers — (1) That zinc, lead, and copper are attacked
very slowly by ordinary water and saline solutions in general
(c4ilorides, bicarbonates). (2.) If several metals are present, the
action is much more rapid. (3.) Nitrogenous matters and ammonia
increase the efEect mainly by their action on the zinc. (4.) The
maximum effect occurs in presence of oxygen. This is particularly
the case at the surface of the reservoir, where the metal is in contact
with air and water by turns.
The muddy deposits consist mainly of silicates and carbonates,
with 5 per cent, of zinc oxide, and 2-01 of lead oxide in one case, and
in another case, where the tank had been empty for some time,
11-56 per cent, zinc oxide, and 5-85 of lead oxide. The water from the
tank was not examined. For waters charged with salts, sheet-iron
tanks should be used, or at least the purest zinc, and the presence of
other metals or of ammonia should be avoided.
Lead pipes gave analogous results. A white crystalline deposit
from tanks connected with attacked lead pipes was mainly calcium
* Resxilts are stated in grains per gallon ; hardness in measures of soap solution.
t The water was kept in contact with standard permanganate for three hours.
TECHNICAL CHEMSTRY. 7()7
carbonate, with 0"027 per cent, of lead carbonate. In boilers fed bj
these tubes, the lead amounted toO'98 per cent, with a trace of copper.
Iron tubes should be substituted. J. T.
Report on the Treatment of Sewage. By R. A. Smith (Chem.
News, 41, -50). — Analyses of effluent waters from sewage purified by
various methods are given. The best purifying result is gained by
irrigation when no overflowing is caused by excessively wet weather ;
precipitation by alum, or alum and iron salts, comes nest. In wet
weather this pi-ocess has the advantage of being nearly independent
of dilution ; precipitation by lime is not so eflicient as the other pro-
cesses. M. M. P. M.
Boric Acid as a Preservative. By H. Endemaxx (Chem. Neu-s,
41, 1.52 — 153). — Fresh beef, packed with 1 per cent, of boric acid and
a salt pickle of 50 per cent., remained sweet and wholesome for several
months, even above 26°. Beef, previously salted, could not be pre-
served by boric acid. Hence the salting had removed something
which was necessary for the preservation of the meat. This preserva-
tive action is found to be dne to acid phosphates.
Experiments, in which equivalent quantities of other inorganic acids
were substituted for boric acid, gave exactly the same results, the best
results being obtained by phosphoric acid and mixtures of phosphoric
and hydrochloric acids. F. L. T.
Ammonia from the Nitrogen of the Atmosphere and the
Hydrogen of Water. By Rickmax and Thompson (Ghem. News,
41, 155). — In all attempts to manufacture ammonia synthetically the
process has hitherto been to combine the nitrogen and hydrogen at a
low heat, and receive the ammonia in solution in water.
Rickman and Thompson produce ammonium chloride directly.
They use simply a closed brick furnace, having the ash-pit closed to
regulate the supply of air, the steam being produced by the waste
heat. The deoxidising material employed is the dust of steam-coal
(Is. 6(7. a ton at the pits), mixed with 5 — 8 per cent, of common salt,
no other fuel being used, except to start with. The common salt,
being decompo.'^^ed at a red heat in presence of nascent ammonia, form-
ing ammonium chloride.
At the pre.sent time, with the consumption of 20 to 28 lbs. of the
mixture of coal-dust and salt per hour, from 2 to 3 lbs. of ammonium
chloride are formed.
On p. 195 a writer (J. H.) suggests that most of the ammonia is
derived from the coal itself. F. L. T.
On Cement. By R. Dtckerhoff {Bingl.polyt. ,/., 236, 472 — 480).
— The author has made a series of useful experiments as to the profit-
able application of Portland cement to the preparation of mortar and
concrete. He investigated the degree of strength of the hydraulic
properties of various mortars, and the firmness of the latter both when
allowed to set in moist air, and when brought into water directly
3/^2
768
ABSTRACTS OF CHEMICAL PAPERS.
after mixing. The following table shows the results arrived at with
two cements : —
1—1
1 part cement, 3 parts sand. Firmness
of cubes. Kilos, per 1 sq. cm.
Jl
O
i-H
9
bD
w
Allowed to set in
the air.
Directly into water.
CD
O
a
Per cent,
sifted wi
meshes.
Standards
sq. cm.
C3
.4^
o
S
■ <u
O
24
houi-s.
1
week.
4
weeks.
24
hours.
1
week.
4
weeks.
min.
A ..
20
10-5
12-6
20 min.
11 0
38-2
79-5
0-75
12-8
30 1
B ..
600
5 0
17-8
12 hrs.
8-4
60-7
114-4
0-23
17-8
32 1
As to the practical value of the expeiiments, the author clearly indi-
cates that it is not profitable to throw concrete direct into water, since
the firmness of the mortar is influenced considerably in such a case.
Similar experiments were made with poor cement mortar, with and
without the addition of fat-lime, and also with mortar made up with
trass and hydraulic lime. It was found that the firmness is increased
considerably by adding fat-lime, both modes of *' setting " being
adopted, and that the cheaper kinds of cement and lime-mortar are
preferable to trass or hydraulic mortar. As to the best modes of pre-
paring concrete, economically a large amount of practical work appears
to have been undertaken by the author, who concludes that —
1. The firmness of concrete is influenced materially if, as is fre-
quently the case, pure cement is worked up with too large a proportion
ct flint, instead of replacing part of it by the corresponding quantity
of sand.
2. Concrete, made of cement mortar and flint in economically the
best proportion, has the same firmness as cement mortar, per sd, pro-
viding that both are "beaten down."
"S. A decrease in. the addition of flint beyond the proportion of
1 cement, 2 sand, and 5 flint, is not economical, since the firmness is
raised but slightly, whereas the cost of pre23aring the concrete is
increased considerably.
4. As when flint contains 35 per cent, of hollow spaces, at least
twice as much flint as sand may be used ; the following proportions
hold good in practice with such a flint. One part cement requires
twice as much flint as sand, so as to produce an economically prepared
concrete with a given mortar. The firmness of the concrete will then
be the same as that of the mortar used in its preparation. D. B.
Diffusive Properties of some Preparations of Iron. By T.
Redwood (Pharm. J. Trans., 10, 709 — 712). — The results of experi-
ments made on the diffusive power of some salts of iron show that
whilst the sulphates and chlorides undergo diffusion to a greater
TECHXICAL CHEMISTRY.
769
extent and with greater rapidity than the so-called preparations nsed in
pharmacy, nevertheless the latter, and especially those with citric acid,
are not deficient in diffusive power.
The experiments on dialysed iron tend to show that it cannot be
considered as an active and efficacious medicine. L. T. O'S.
Gases from Bessemer Converters. By A. Tamm (Ghem.. Centr.,
1879, 712). — The author's results are contained in the following
table :—
Time from
Composition o1
' gas in 100 parts by wei
ght.
Length of
operation
beginning
of operation
at which
in minutes.
gas was
coUected.
0.
CO..
CO.
H.
N.
(1) 6
11-2!
0-0
11-04
23-70
0-08
65-18
(2) 6
5 -H
0-39
6-44
25-49
0-09
67-59
(3) 7i
2 —3
0 00
9-93
26-18
0-07
63-82
(4) 7i
3i-4i
0-00
7-67
27-68
0-09
64-56
(0 6
3 —4
0-00
8-52
26-55
0-05
64-88
(6) e\
5i— 6
0 00
5 00
26-50
0-07
68-43
(7) ok
2!-3!
0 14
7o4
28-51
0-12
63-69
(8) 5#
4i-oi
0-20
5-59
22 -88
0-05
71 -28
Of 100
parts of air blown in
Percentage of
There was found in the
0 taken
0 given out
carbon in
There was 0
in form of air
escaping gases.
up
by slag.
by
the slag.
product
before addi-
and H.O.
tion of Mn.
C.
0.
(1) 23 -95
15-52
25-42
1-47
0-25
(2) 24 -01
14-41
22-32
1-69
—
0-25
(3) 23-87
16-76
26-70
—
2-83
0 06
(4) 24-04
16-60
25-45
—
1-41
0-06
(5) 23 -67
16-22
25-30
—
1-63
(6) 23 82
14-28
21-08
2-74
—
0-06
(7) 24-35
17-21
26-43
—
2-08
0-06
(8) 23 -62
12-21
20 13
3-49
—
0-06
M. M. P. M.
Some Remarks on Siemens-Martin Steel. By S. Kerx {Chem.
News, 41, -irS). — The author desires to give a short description of the
working process, and a full account of some charges. All the required
materials (pig-iron, steel scrap, and ladle scrap, about 8 tons alto-
gether), are charged at once, and no additional charges are made after
770 ABSTRACTS OF CHEMICAL PAPERS.
the metal has become molten, nnless, on testing a sample, it is shown
to be too hard. In such a case the metal is softened by adding
puddled blooms (15 lo 20cwts.), or, what is quicker and cheaper, good
magnetic iron ore (2 to 5 cwts.) in fine powder.
Before the casting, if soft steel is wanted, ^ to 1 cwt. of ferroman-
ganese is added, aud for harder steel (0'5 to 0'65 j^er cent, of carbon)
often 3 to 10 cwts. of spiegeleisen.
" The following charges give an idea of the mode of working : —
Hard Steel. — Charge: steel scrap, 120 cwts.; ladle scrap, 17 cwts. ;
pig-iron (with 12 per cent, manganese), 17 cwts. ; all charged at
once. Charging commenced 4.30 a.m., finished at 6 a.m. Melted and
one sample taken out 8.15 a.m. ; 17 cwts. puddled iron blooms charged
9 a.m. ; sample hammered well, cooled, bent double ; 15 cwts. pig-
iron, containing 9 per cent, of manganese ; charged 10.20 a.m., casting
took place at 11 a.m. Analysis of the steel : carbon, 0"67 ; manganese,
0'40 per cent.
Medium Steel. — Charge : steel scrap, 135 cwts. : ladle scrap, 23
cwts.; pig-iron (with 12 per cent, manganese), 10 cwts. Charging
commenced 1 p.m., finished 2'45 p.m. ; melted, 0"5 cwt. ferromanga-
nese added, and first test taken 7.40 p.m. The steel was hard. 2'5
cwts. of magnetic iron ore added at 7'55 a.m. Test taken 8.30 p.m. ;
sample bar bent nearly double, giving only a slight crack ; 0'5 cwt.
of feiTomanganese added ; casting, 9.15 p.m. Analysis of the steel :
carbon, 0'35 ; manganese, 018 per cent.
Soft Steel. — Charge: steel scrap, 113 cwts.; ladle scrap, 26 cwts. ;
pig-iron (with 12 per cent, manganese), 6"5 cwts. Charging com-
menced 11 a.m., finished 12.30 p.m. Melted, and first test 6 p.m. ;
2 cwts. ferromanganese added 6.30 p.m. ; test bar bent double after
being hardened ; -| cwt. ferromanganese added 7 p.m. ; casting, 7.15
p.m. Analj'sis of the steel : carbon, 0'16; manganese, 0'14 per cent.
The steel was prepared for boiler plates. F. L. T
Contributions to the Metallurgy and Docimacy of Nickel.
By E. DoNATH (Dlncjl. 2:,oltjt. J., 236, 326—336 and 480— 486).— The
author in the first portion of his paper gives a brief outline of the
history of nickel since its disco vei'y by Cronstedt in 1751, the parti-
culars of which are well known to chemists.
Schwedor has made a series of interestino- investigfations as to
the chemical changes which take place in the roasting of sulphu-
retted nickel ores. The action of carbon, carbonic oxide, and hydrogen
on the sulphide of the metals connected with the nickel roasting pro-
cess, has also been investigated, the following results being obtained.
The sulphides of iron and copper are not acted on by carbon, carbonic
oxide, and hydrogen ; the sulphides of nickel and cobalt, however,
lose a large portion of their sulphur when fused with carbon and
ignited in a current of hydrogen ; cai^bonic oxide, on the contrary, is
inactive. The sulphates of copper, nickel, and iron are reduced by
ignition with carbon, carbonic oxide, or hydrogen. Schweder has pre-
pared sulphide of nickel of the composition NiS by fusing nickel
together with sulphur. It is known that cupric sulphide is decom-
posed by iron, CujS + Fe = FeS + 2Cu ; nickel does not, however,
TECHNICAL CHEMISTRY. 771
decompose it, but nickel sulphide is decomposed by copper. Wagner's
proposed method of preparing a useful alloy of nickel and copper
from the refined ore by smelting with soda and saltpetre has also been
investigated by Schweder, who found that the most satisfactory result
was obtained when a mixture of NiS and 4CU2S was used.
Badoureau {Annalen, 1877, 12, 237) in giving a description of the
metallurgy of nickel, mentions that in Silesia ores and iron pyrites,
with V'li) — 1'49 per cent, nickel, are roasted, the product being sub-
sequently smelted with lime, clay, slag, and coke. The stone is then
broken up in small pieces, again roasted, and the roasted mass smelted
with quartz. A product is thus obtained, which after separating the
slag contains 28 — 32 per cent> nickel and cobalt, 48 — 52 per cent, iron
and copper, and 20 per cent, sulphur, and is worked up in Silesia. The
roasting processes, as carried out in a number of well known nickel
localities, are described more minutely in the present paper by Badou-
reau ; the principle, however, appears to be the same.
According to a recent analysis, emerald-green, transparent, and
strongly shining garnierite, freed from all gangue, consists of —
SiOj. AI2O3. FeO. MgO. GuO. NiO. H.O.
440 1-68 0-43 3-45 l-07 33-61 1034
Gard (ibid., 227, 109), Zuogk (ibid., 222, 94), and Boussingault
(Compt. rend., 86, 509), have investigated the behaviour of fused
nickel towards carbon and silicon, and show that after heating nickel
for some time in a cementation furnace a product is obtained which is
poor in carbon. Winkler describes the preparation of large castings
of nickel and cobalt and of ductile nickel. He succeeded in obtaining
the latter by removing carbon and silicon from nickel by means of
fusion with oxide of nickel. The metal shows a tendency to become
crystalline. Meiffrer prepares an alloy resembling silver, and capable
of resisting the action of sulphuretted hydrogen by first fusing together
a mixture of 65 parts iron, 4 parts tungsten, and granulating it ; and
a corresponding mixture, 23 parts nickel, with 5 aluminium, and
5 copper, adding a piece of sodium to avoid oxidation. The granu-
lated metals are then melted together.
Docimatical and Arialtjtical Mdliods of Estimating Nickel. — Badoureau
describes the methods generally used in Varallo, Scopello, and Dobsina
(Hungary). In Varallo, 2 gi'ams of the pulverised ore are dissolved
in aqua regia, the copper is precipitated with sulphuretted hydrogen,
and the filtrate evaporated to dryness ; the residue is dissolved in a
few drops of hydrochloric acid and precipitated with chloride of lime.
The whole is then dissolved in acetic acid, and the iron is thrown
down by boiling the solution. The filtrate is treated with sulphuric
acid, and the nickel and cobalt precipitated galvanically by means of
a Bunsen battery. In order to test the ores quantitatively, 5 grams of
the sample are fused with borax, soda, and metallic arsenic, and the
regulus is examined with the blowpipe in a borax bead.
In Scopello, the following blowpipe method is found to give results
within 0'5 per cent, of the truth. 0"1 gram of the pulverised oi-e is
fu.sed with an arseniferous flux consisting of a mixture of equal parts
772 ABSTRACTS OF CHEMICAL PAPERS.
arsenious acid, potassium cyanide, soda, fused borax, and charcoal.
The test is said to occupy only a short time. The final regulus ob-
tained represents 61'7 per cent, of a mixture of nickel and cobalt.
Schweder describes a modification of Plattner's method of estima-
ting nickel and cobalt in cases where the ores contain copper. He
determines the latter by electrolysis, and treats a second portion of the
sample according to Plattner's method, deducting from the arsenic
regains, arsenite of copper, as Cu^As, and determining the cobalt by
scorification.
Allen describes a method of estimating the New Caledonian ores
and others free from sulphur and arsenic. The ore is fused with
potassium bisulphate and saltpetre, and the fused mass dissolved and
the solution filtered. In the filtrate the iron, aluminium, and chro-
mium are precipitated with ammonium acetate, the precipitate is redis-
solved and reprecipitated. Both filtrates and their washings are
brought together, evaporated, and treated with sulphuretted hydrogen.
Magnesium is left in the solution ; nickel and cobalt, however, are
converted into insoluble sulphites, which are oxidised into the sul-
phates and subjected either to fusion or electrolysis.
The method proposed by Margaret Cheney and Ellen T. Richards
depends on the complete solubility of nickel phosphate in acetic acid
in presence of sodium phosphate, whereas ferric phosphate is insoluble
in the same reagent. Dirvell proposes a new method of separating
nickel and cobalt quantitatively, the results, however, are inaccurate.
D. B.
Lead Analyses. By E. Priwoznik (Dm<jl. polyt. J., 236, 439 ;
and Berg. u. hilttm. Jahrb., 1880, 41).— (1.) Refined soft lead,
Przibram ; and (2) lead from Kapnik, Hungary.
S. Cu. Bi. Ag. Fe. Zn. Sb. Pb. (by diff.)
(1) _ -00096 -00161 -0019 -00079 -001 -00277 99-99097
(2) -0028 -136 -0052 '0023 -001 — 1-606 98-2467
J. T.
Analyses of Some Hair-dyes. By J. F. Braga (Chem. Neios, 41,
278 — 279).— Hair-dyes are of two kinds, those to darken and those to
lighten the hair. The latter, in all instances, were found to be hydro-
gen peroxide, sold under various fancy names. The former were
preparations of lead, of which the thiosulphate is about the best. A
successful imitation of one was made by the author as follows : — •
Plumbic acetate 5'7 grams
Sodium thiosulphate 11-.5 grams
Glycerol 50-0 c.c.
Spirits of wine 100-0 c.c.
Distilled water 850'0 c.c.
The plumbic acetate was poured into a mixture of the other con-
stituents ; it should be kept in the dark.
Another was : —
Plumbic oxide 17-0 grams')
Glycerol 300-0 grams > To 1 litre.
Precipitated sulphur. . . . 17-0 gramsj
TECHNICAL CHEMISTRY.
773
A third was : —
Plumbic acetate 12' 5 grams')
Glycerol 12r)0 grams >To 1 litre.
Precipitated sulphur. . . . 100 grams J
The last mentioned was a very dilute solution of lead in potassium
hydrate. F. L. T.
Influence of Superfusion on the Molecular Arrangement of
Cupelled Gold. By A. D. v. Riemsdijk {Chem. Neivs, 41, 266—267).
The author refers to his research on "flashing" {Chem. News, 41,
126), and then remarks that a button of cupelled gold which has
flashed {i.e., has been in a state of superfusion) is malleable under the
hammer, but a button of cupelled gold which has been prevented from
flashing {e.g., by being placed in contact with a piece of solid gold
whilst still molten), is brittle under the hammer. The cause of this
non-malleability is attributed to a trace of lead or bismuth not re-
moved by cupellation. This last trace of lead or bismuth may be
removed by remelting in a new cupel, and treating with a small
quantity of crystallised cupric chloride. When the reaction is tinished,
the gold, although it solidifies without flashing, is soft and malleable.
The platinum metals prevent flashing and the consequent malleability
of the gold, but not to the same extent as lead or bismuth.
F. L. T.
Alcohol Tables. By S. Cohn^ {Chem. Netvs, 41, 57, and A. H.
Ajlu:^, ihid., 70). — To convert " overproof " and "underproof" into
alcohol per cent. : — Percentage of alcohol by weight = W ; density
= D ; percentage of alcohol by volume = V ; percentage of proof
spirit = P.
(1)
(2)
V = P X 0-5706
WD
V =
0-7y38
(3) P = V X 1-7525
(4) P = WD X 2-208.
M. M. P. M.
Speyer Beer. By Halenke {Bied. Centr., 1880, 300— 301).— Mean
results of analysis gave —
Summer Beer.
Specific
Alcohol.
Extract
Ash
p.c.
Water
p.c.
Original
concentra-
tion of the
wort,
p.c.
Degree of
gravity.
Weight
p.c.
Volume
p.c.
p.c.
fermenta-
tion.
1018 4-4
5-5 7 -30
0-25
88-74
15-30
55-2
Winter Beer.
1-018 I 3 9
4-9
6-92 0 •2c
89-18
14-37
52 0
A. J. C.
774 ABSTRACTS OF CHEMICAL PAPERS.
Carbonic Anhydride in Beer. By T. Langer and W. Schultze
(Bled. Gentr., 1880, 299 — 300). — The brown coloration of the potash
solution which occurs in the estimation of carbonic anhydride in beer
by Schwackhofer's method can be avoided by passing the gas first
through concentrated sulphuric acid. All the carbonic anhydride is
not expelled from the beer by five minutes' boiling, but it is necessary
to continue the boiling, finally aspirating l^ — 1^ volumes of air
through the apparatus until the potash-tube ceases to increase in
weight. Without these modifications Schwackhofer s method gives
results which are too high by 100 : 107'4.
The amount of carbonic anhydride in beer is diminished by about
O'Ol per cent, of the weight of the beer, if between the limits of 0°
and 5° the temperature of the beer during the after-fermentation
sinks or rises 1°. For example,
100 per cent. CO; at 0-4° = 96-4 per cent at 1-6°
93-7 „ 2-8
89-5 „ 4-0
85-8 „ 47
Consequently beer contains about one-seventh less carbonic anhydride
at a temperature of 4'7", than it does at 0'4°. About 0"046 per cent,
of carbonic anhydride escapes through the bung-holes of the vats of
stored beer, and this quantity;, apparently insignificant, is really of
importance if it be considered that in a tightlj^-closed vat of 36 lil.
the beer would be forced to dissolve about 9 hi. more of carbonic
anhydride. A. J. C.
Tartar and Tartaric Acid in Must and Wine. By E. Mach
and others {Bied. Gentr., 1880, 207— 211).— The different amounts of
tartar and free tartaric acid found in various samples of must led the
authors to experiment on the solubility of tartar in different fluids, the
results of which are detailed.
The quantity of tartar depends jiartly on the amount of alcohol in
the wine, the more alcoliol the less tartar. A large amount of free
tartaric acid, sugar, or glycerol also diminishes in a small degree the
quantity of tartar. The influence of malic acid is considerable, but
in a contrary direction ; and a wine containing much malic acid will
also contain larger quantities of tartar. The influence of temperature
ranks in importance next to that of the percentage of alcohol ; there
are complicated considerations involved, but a high temperature assists
the solution of tartar.
The authors recommend a low temperature during the pressure of
the grape, and give directions respecting the temperature of the
cellars, they asserting that in bottled wine the amount of crust will
vary according as it has been bottled in summer or winter. The
authors extended their enquiries to free tartaric acid in must wine,
and say that the presence of this acid is a proof that the wine has
been made from grapes more or less unripe ; that its disappearance
shows the wine to be ripe and matured, and assigns the acid taste of
wine which has really been made from ripe graj^es to the milder
tannic, malic, succinic, and acetic acids, and their experiments show
TECHNICAL CHEMISTRY. 115
that fine wines do not contain more than 02 to 0"3 per cent, of free
tartaric acid.
The absence of tartar and presence of free tartaric acid is an evidence
of a plaistered wine. J. F.
Free Tartaric Acid in Wine. By J. Nessler and H. 'Wachter
{BieiJ. Centr., l8«U, 3'Jl — oij2). — The presence of free tartaric acid in
wine does not necessarily show an impi'oper admixture of tartaric acid
to the wine. According to Mach and Rotondi the amount of free
tartaric acid in the grape increases in proportion to the degree of
unripeness, so that its absence from wine can only occur under certain
conditions of ripeness of the grapes employed. Ahhough unripe grapes
are frequently used in considerable quantity in wine making, yet if the
ripe grapes are in excess the potash salts in them are more than suffi-
cient to separate the free tartaric acid in the form of tartar, and thi.'^
explains the fact that Avine so made generally contains no free tartaric
acid. A wine may be suspected of having been sophisticated if with
a small amount of free acid an undue proportion of it is tartaric.
A. J. C.
Tannin in Wine. By I. Macagno (Blerl. Cent,:, 1880, 212—
214). — The author undertook these experiments to settle the question
as to the influence of tannin on the keeping qualities of wine. In the
first series on the influence of age on the contents in tannin was
examined, the specimens examined being wines of the same class : —
Alcohol,
Glycerol
Tannin
vol. per cent.
per liter.
per liter.
Wine of 1870. .
.. 120
6' 10 grams
0'84 gram
„ 1871..
.. 11-8
5-80 „
0-89 „
„ 1872. .
. . 12-0
5-81 „
0-85 „
„ 1873. .
.. 121
5-32 „
1-02 „
„ 1874. .
.. 11-9
4-88 .,
1-14 „
From these figures it is evident that with increase of age the tannin
decreases while the glycerol increa.ses. He finds also that the mellow-
ness of old wine is due rather to the amount of glycerol than the defi-
ciency in tannin, and that the amount of alcohol in the wine is of more
importance in view of keeping qualities than is the tannin.
Further experiments were made with samples carefully bottled, the
bottles well filled and closely corked, and kept for a year : —
p. Eesults.
mouldy, corrupt,
well preserved,
mouldy,
well preserved.
tolerably well-preserved sediment,
turbid, corrupt ; no mould,
completely decomposed bacteria,
perfectly clear and good.
Alcohol,
Tannir
vol. per cent.
gram lit
A..
6-2
2-03
B..
. 11-.5
1-83
C.
5-9
1-83
])..
. 12-4
0-92
E..
6-2
0-92
F ..
. 12-4
0-38
G..
6-3
0-38
H..
. 13-9
0-43
776 ABSTRACTS OF CHEMICAL PAPERS.
D and F with the same amount of alcohol, but different quantities
of tannin, seem to point to the latter as the preserving agent, but H,
with more alcohol and little tannin, was well kept ; it is probable that
it depends on the relative proportions of alcohol and tannin.
J. F.
Digestive Ferment produced during Panification. By
Scheurer-Kestner (Compt. rend., 90, 369 — 371). — The paper relates
to comestibles, made by combining meat with farinaceous products.
A mixture is made of 57 parts of flour, 5 parts of baker's yeast, and
30 parts of fresh beef, very finely minced. To this as much water is
added as will form a paste of convenient consistence, which is then
exposed for two or three hours to a moderate temperature. The
meat dissolves completely in the paste and disappears. The paste is
then baked like bread, and the product may be preserved for years
without change. It may be eaten, or used for the preparation of
soups, &c. R. El.
Malt Extract and Maltose in Beer Mash. By W. Schulze
(Bied. Gentr., 1880, 205 — 207). — The author examines the best con-
ditions for the production of those substances. The most favourable
temperature for promoting the saccharine fermentation is 60' C, and
recent investigations have shown that the production of these bodies
diminishes with increase of temperature ; for example, 100 parts of
extract mashed at —
62° yield maltose 78"64 per cent.
65 „ 70-28
70 „ 62-72
75 „ 59-93
With reference to the proper amount of mash water the author
differs from the conclusions of both Otto and Mulder in believing that
the yield of maltose is not injuriously affected by increased propor-
tions of water ; he has obtained the same results with a,mount of water
from 4 up to 8 of water to 1 of malt.
His next experiments were on the length of time to be given to the
mashing, and he finds that a slow working from the commencement to
the sugar temperature yields more extract and more maltose than rapid
working.
The circumstances which exert an influence on the extract and
maltose should regulate the conduct of the mash, and whether an
infusion or decoction should be employed. The decision of this ques-
tion has led to a great variety of experiments, the results of which
may be summed up that both methods possess advantages and dis-
advantages peculiar to themselves, which the brewer must choose
between, according to his requirements. J. F.
Moisture in Malting Barley. By W. Schulze (Pyied. Centr.,
1880, 204). — These moisture determinations were made of the raw
barley and kiln-dried malt in the grain, the steeped and green malt in
a broken state; the grain being cat lengthwise once and crosswise
TECHXIC.VL CHEinSTRY. 7(7
four times with a fine scissors, dried in watch glasses in an air-bath at
100° to lOo"", and afterwards in a desiccator.
The following is the mean of six experiments : —
Raw fcarlej, percentage moistare 14'9
Steeped malt 40"3
Green malt 399
Malt after eight hours on the upper floor of a double
kiln 65
After another eight hours on the lower floor, with the
plumula 1"7
Ditto, ditto, without 16
J. F.
Adulteration of Malt Combings. By W. Richter (Bied. Gentr.,
1880, 233 — '234:). — -In consequence of the death of 18 cows, after being
fed on malt combings, the author made an examination of the contents
of their stomachs and found them and the combings to contain large
quantities of earthy matter, chiefly loamy sand, and also injurious
quantities of vegetable and mineral matter, the nature of which was
not ascertained. J. F.
Improvements in Treatment of Yeast {Bied. Ceutr., 1880,
224). — This paper is an account of the process of Hassal and Hehner,
patented in England. The vessel containing the yeast is gradually
filled with water at the lowest possible temperature, in the propor-
tion of three volumes of water to one of yeast ; after brisk agitation
the mixture is left at rest 24 hours, the water is then drawn off, fresh
water put in, again agitated, milk of lime added gradually, and soda or
other alkaline solution until the reaction is only slightly acid ; 50 kilos,
of the yeast are then mixed with 42 grams of salicylic acid, the veast
is allowed to settle, and the supernatant fluid is not removed until the
yeast is required for use ; a mixture is then made of. either malt- flour
or wheat-flour with an equal quantity of sugar; this mixture is inti-
mately blended with the yeast in the proportion of 5 to 100 of the
latter ; the yeast quickly seizes upon the sugary and starcy mass and
becomes very active with abundant evolution of carbonic anhydride.
J. F.
Rye as a Material for pressed Yeast. By M. Delbruck {Bied.
Centr., 18^0, 222 — 223). — Rye varies considerably in its chemical com-
position, especially as regards the ingredients most valuable to the
maker of dried yeast — the protein matters. The writer recommends
analyses by competent chemists of the gi-ain produced in different
districts, which operations he shows can be completed in a short time
and the results communicated with speed to the buyer. In four
samples analysed by him he finds the proportions of starch and
Drote'in were —
Protein 73 77 12-0 8-5
Starch 61-1 62-1 59-0 61-6
He formulates the rule that the less suitable the grain is for flour
778 ABSTRACTS OF CHEMICAL PAPERS.
production the more valuable it becomes as a material for yeast manu-
facture. J. F.
Investigation of Lubricating Oils. By F. Fischer (Dinr/l.
jwlyt. /., 236, 487 — 406). — -The following oils have hitherto been used
most frequently for lubincating purposes : Olive oil ; rape oil frequently
mixed with rock oil ; vegetable and animal fats, to which graphite is
sometimes added ; rosin oil and paraffins. The consumption of rock
oil as a lubricant seems to be increasing daily. The American mineral
oils are very largely used, and are brought into commerce under the
name of vulcan oil, topaz oil, star oil, &c. Breyraann and Hiibeuer
in Hamburg offer for sale " valvoline," and in the south of Germany
oils known as emerald oil and opal oil, are mostly used.
A lubricant may be investigated in order to determine either the
addition of an inferior oil or the value of the oil for lubricating pur-
poses. To determine the presence of rosemary oil and oil of turpentine
in fatty oils, it is recommended by Burstyu (ibid., 214, 300) to shake
up the oil with alcohol; decant the latter, distil it and add water to
the distillate, a turbidity if formed indicating the presence of the
ethereal oil. Mineral oils may be deterraiiied in fatty oils by saponifi-
cation with soda and extraction with ether, the latter on evaporation
leavinsr the mineral oil in the residue. In order to determine the addi-
tion of fat in a mineral oil, it is heated with the requisite quantity of
soda, and alcohol is added until saponification is completed ; the alcohol
is then expelled by evaporation ; and the residue is taken up with water,
then filtered, and acidified slightly with dilute hydrochloric acid. The
fatty acids are separated, and the liquid gives on evaporation the cha-
racteristic reactions for glycerol. To distinguish drying oils from non-
drying ones, Poutet treats the oil with mercury dissolved in cold nitric
acid ; Boudet, Wimmer and Kopp with nitric acid containing nitrous
acid. Non-drying oils solidify by the conversion of the ole'in into an
ela'idin, whereas the drying oils remain unaltered.
In order to determine the addition of other oils besides those above
mentioned, it has been proposed to investigate the oil as to its density.
Various methods of determining the density of an oil are described in
the original, the particulars of which are known to chemists. This
applies also to the determinations of the melting point of solid fats
recommended by some chemists as forming a criterion whereby the
quality of solid fats niay be judged. As to the ciystallising or solidi-
fying point of a solid oil, it is mentioned that the determination of this
is useful only in special cases, and not for the detection of foreign
additions. The most important point is that of ascertaining the
amount of free acid present in lubricating oils, and of determining the
property of the oil as regards the reduction of friction. Apparatus
for the direct determination of the latter point are described by the
author, and in conclusion the following table is given, illustrating the
results of some investigations made by the author on a number of
oils : —
TECHNICAL CHEMISTRY.
770
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p— 4
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cp cp
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-2
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o '?< t^ :;
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1—1
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n —
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5
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r^ 1— 1 r-
•s
3ur[0
H^A.
§ 1
780 ABSTRACTS OF CHEMICAL PAPERS.
It is a remarkable coincidence that one liter of the water associated
with the oil as it comes from the well at Oedesse contains : .S'Oll
NaCl, 0-460 CaCOa, 0-289 MgCOj (present as bicarbonates). traces of
H2SO4, SiOs, and organic matter. The presence of sodium chloride in
the water points to large supplies of oil. D. B.
Composition of Skim-milk and Cream from De Laval's
Cream Separator. By A. Voelcker (Jour. Boij. Agri. Soc, 1880,
160). — The skim-milk obtained in three trials with the centrifugal
cream-separator contained only 0-22, 0-46, and 0-31 per cent, of fat.
Skim-milk obtained by the usual plan of setting in shallow pans,
generally contains at least 0-75 per cent, of fat. The cream from the
centrifugal separator had the following composition : —
Water.
Albuminoids.
Fat.
Sugar.
Ash.
66-12
2-69
27-69
3-03
0-47
Cream obtained by ordinary skimming seldom contains 25 per cent,
of fat. R. W.
Celluloid. (Chevi. Centr., 1880, 334—336; and Techniher, 1879,
74). — Pyroxylin obtained by treating cellulose with a concentrated
mixture of 5 parts sulphuric and 2 parts nitric acid, is well washed,
dried, and incorporated with about 50 per cent, of camphor, and heated
to about 150" C, under hydraulic pressure. A hard elastic mass is
produced, in which the greater part of the camphor added seems to
have become combined. J. T.
Researches on the Decomposition of Certain Explosives.
By Saerau and Vieille (Gompt. rend., 90, 1112 — 1113). — The authors
have previously investigated the nature of the decomposition of gun-
cotion and nitroglycerin in closed vessels under high pressures (this
Jcjurnal, 36, 991). Under ordinary pressures, when they do not
detonate, but the substance is simply inflamed by a fuse, the products
of the decomposition are very different. The following table gives
the composition of the gas produced by the combustion of 1 kilo, of
difi'erent explosives : —
Total,
CO.
CO2.
H.
N.
CH4.
liters.
237
104
45
33
7
565
NO.
Gun-cotton lo9
Gun-cotton, with 60 per
cent, potassium nitrate .71 58 57 3 7 0 196
Gun-cotton, with 60 per
cent, ammonium nitrate 122
Nitroarlvcerin 218
In every case, nitric oxide and carbonic oxide are produced in con-
siderable quantities. It is therefore necessary, in mining operations,
to take special care to ensure detonation. C. H. B.
65
103
12
112
0
414
162
58
7
6
1
452
781
General and Physical Chemistry.
Chemical Constitution of Organic Compounds in Relation
to their Refractive Power and Density. Part II. By J. W.
Bruhl (AnnaJeit, 203, 1 — 63). — The accompanying table contains
those results of the author's investio-ation on specific refraction which
have not already appeared (An7i., 200, 139, and this volume, 295).
Under A are found the coefficients of refraction for a ray of infinite
wave-length, calculated by Cauchy's formula. B shows the coefficient
A — 1
of dispersion, and — - — = the specific refraction. The determina-
a
I
tions were made at 20'^, the specific gravities were also taken at this
temperature, and compared with water at 4'
reduced to vacuo.
The weio-hing's were
Name.
Ethylene chloride
Ethvlidene eliloride
Acetic chloride
Chloral
Propyl alcohol
I?opropyl alcohol
Methaldehvde
Propyl bromide
Isopropyl bromide
Propionic chloride
Propyl iodide
Isopropyl iodide
Butyl alcohol (normal). . .
Trimethylcarbinol
Butaldehyde
Isobutaldehyde
Butyric acid
Isobutyrie acid
Butyric chloride
Isobutyrie chloride
Butyl chloral
Butyl iodide
Isobutyl iodide
Ethyl monochloracetate . .
Ethyl dichloracetate
Ethyl trichloracetate
Amyl alcohol
Ethyl carbonate
Valeric chloride
Ethyl a-chloropropionate. .
Ethyl dichloropropionate . .
Acetal
Paraldehyde
Ethvl acetoacetate ,
1
Sp. gr.
1
1
•2521
1
1743
1
•1051
1
■5121
0-
8044
0
•7887
0
•8604
1
3520
ll
3097
1
0(346
1
7427
1
7033
0
•8099
0
7864
0
•8170
0
7938
0
•9587
0
9490
1
0277
1
0174
1
3956
1
6166
1
6056
1
1585
1
2821
1
3826
0
8104
0
9762
0-
9887
1
0869
1
2461
0
8314
0
9943
1
0256
•41348
•40453
•37752
•44141
•37542
•36789
•34482
•41985
•41080
•39271
•48228
•47570
• 38887
•37759
■37368
■36258
•38713
•38259
•39978
•39558
•46111
•47857
•47477
•41145
•42621
•43734
•39655
•37569
•40322
•40704
•43542
•37217
•39528
•40725
•44888
•41837
■42440
•49883
•34630
•33624
•30239
■49280
•49581
•42809
•79954
•84042
•35.569
■35065
■36843
•36071
•37312
■35971
■42843
•42843
•49514
•75193
•73953
•39290
•42877
•46062
•37010
■33055
•42944
•39265
■43614
•33758
•33456
•42910
A-1
d •
0^3446
0^3445
0-3146
0 2919
0 ^4667
0^4 65
0 -4008
0 ^3105
0 ^3137
0 ^3689
0^2767
0 ^2793
0 ^4790
0^4802
0 -4574
0 ^4568
0 ^4038
0 4031
0 ^3890
0 ^3888
0 3304
0 ^2960
0-2957
0 3552
0^3324
0^3163
0 ^4893
0^3848
0 ^4078
0^3745
0-3491
0 ^4476
0 3976
0^3971
Molecular
refraction.
34
34
26
43
28
27
30
38
38
34
47
47
35
35
32
32
35
35
41
41
57
54
54
43
52
60
43
45
49
51
59
52
52
5]
12
10
82
06
00
99
46
20
58
12
05
48
45
53
93
89
54
48
43
41
99
47
41
51
19
57
06
41
14
12
75
82
48
62
VOL. XXXVIII.
782
ABSTRACTS OF CHEMICAL PAPERS.
Name.
Ethyl oxalate
Ethyl chlorobutyrate
Oenanthol
Methylhexylcarbinol.
Methylhexylketone . .
Trietiiyl citrate
Tetrethyl citrate . . . .
Methyl alcohol
Ethyl alcohol
Water
Formic acid
Acetic , ,
Propionic acid
Valerianic „
Caproic ,,
Oenanthylic acid. . . .
Methyl acetate
Ethyl formate
Ethyl acetate
Methyl butyrate . . .
Metliyl valerate
Ethyl butyrate
Amyl formate
Ethyl valerate
Amyl acetate
Amyl valerate
Aldehyde
Valeral
Acetone
Ethyl ether
Acetic anhydride . . .
Glycol
Ethylene diacetate. . .
Glycerol
Lactic acid
Phenol
Benzaldehyde
Salicylaldehyde
Methylsalicylic acid .
Methyl benzoate . . .
Ethyl benzoate
'P- gr-
•0793
•0517
•8495
■8193
■8185
•1369
•1022
7953
■8000
■2188
■0495
9946
•9298
■9237
■9160
•9039
■9064
■9007
■8' 62
■8795
■8892
•8802
■8661
■8561
1 •
■8568
■7799
-*■
■7984
■7920
■7157
■0816
•1072
•1561
•2590
•2403
■0702
•0455
■1671
•1801
•0862
•0473
A.
•39920
•41296
•41426
•41325
•40474
•43286
•43498
•32143
■35322
•32392
•36062
•36184
■37643
■39344
•40264
■41005
35156
■35038
■36293
■37879
■38420
•38580
■38741
■38659
■39312
•40089
■32229
•37749
■34888
•34368
■37982
•41651
■41010
■46118
. -42968
■52035
•50940
■52167
■50148
.■48961
•48051
B.
•38988
•40329
■39390
•39088
•39524
•43816
■46767
■27821
•31532
•30997
•37250
•34588
•35210
37751
•38754
•39557
•32702
•32836
•33405
•35077
•36715
•35310
•36682
•36214
•36882
•38320
•32161
•37283
•35612
•32067
•3fi614
•37852
•39725
•40728
•40794
•03925
•28201
•85280
•23687
•94663
•88444
A-1
d ■
■3699
3927
■4877
•5044
•4945
•3807
■3946
■4042
•4415
■3239
■2959
•3448
•3785
•4231
•4359
•4477
•3889
•3866
•4029
•4227
•4368
•4339
•4401
•4464
•4592
•4679
•4132
■4728
•4405
•4802
•3512
•3762
•3547
•3663
•3464
■4862
•4872
•4470
•4249
•4508
•4588
Molecular
refractio.i.
54
59
55
65
63
105
119
12
20
5
13
20
28
43
50
58
28
28
35
43
50
50
51
58
59
80
18
40
25
35
35
23
51
33
31
45
51
54
64
61
68
■00
•10
•59
•57
•29
•09
•97
■93
•31
•83
•61
•69
■01
•16
■56
■19
•78
•61
■46
■11
■67
■33
•06
■03
■70
■48
■18
■66
■55
•53
■82
•32
•79
•70
•18
•71
•65
•53
•59
•30
•82
The following conclusions have been deduced from these observa-
tions : —
1. The atomic refraction of oxygen is variable : in those compounds
in which the oxygen is attached to a cai^bon-atom by double linking,
the value is 3-29, but in hydroxyl and in all cases where the oxygen
is united to two other atoms, the atomic refraction is 2-71.
2. The atomic refraction of chlorine, bromine, and iodine, is in-
variable.
o. The influence of double linking of carbon with oxygen atoms is
totally different from that between carbon-atoms alone. In the latter
case the refractive and dispersive power is greatly increased, whilst
GENERAL AXD PHYSICAL CHEMISTRY. 783
tbe double linking of carbon with oxygen exerts only a slight influence
in this respect. W. C. W.
Atmospheric Electricity. By Mascart (Compt. rend., 91, 158 —
161). — The author's observations were made by means of a Thomp-
son's quadrant electronieter, the needle of which was arranged to
mechanically record its position. The paii's of quadrants were con-
nected with the poles of a battery, the intermediate part of which
communicated with the ground, while the needle was joined to a care-
fully insulated vessel, from wliieh issued a stream of water. The
results show that the potential of the atmosphere, always positive, is
much higher and more uniform in the night than in the day. The
minimum occurs at 3 p.m., and the maximum about 9 p.m., remaining
nearly constant until 8 a.m. R. R.
Alternating Currents, and the Electromotive Force of the
Electric Arc. By J. Joubeet {ComiA. rend., 91, 161 — 161:). — The
intensity of the alternating currents generated by a Siemens or a
Gramme machine, are represented by a curve which is almost exactly
a sinusoid, except that the maximum is slightly displaced in the direc-
tion of the motion. The whole curve shows, however, a retardation
of one-eighth of a period, and this the author attributes to the inductive
action of the current on itself.
The difference of the potential between the two carbons of the arc
rises in an inappreciable time from zero to 40 or 45 volts, and its fall
is rapid, but traceable. Not only does the difference of potential
remain constant during the whole period of a current of given mean
inteusit}-, but even when the mean intensity of the current varies
within wide limits. The author attributes to the carbons an in-
dependent electromotive force analogous to the polarisation of elec-
trodes, but offers no explanation on this point at present.
R. R.
A New Air Thermometer. By A. Witz {Compt. rend., 91, 164).
The author proposes to employ Leslie's differential air thermometer
for the determination of temperatures absolutely, by keeping one of
the bulbs at a fixed temperature. This is accompKshed by enclosing
in it a coiled platinum wire, through which the current of a constant
battery circulates until the circuit is broken by the movement of a
column of mercury dependent upon the expansion of alcohol deter-
mined by the temperature of the air-bulb. The oscillations of tem-
perature do not exceed O'l^, and with only a little attention to keep
in action two small Poggendorff cells, the author has kept the
bulb at a uniform temperature for an indefinite number of days. By
suppressing the thermoscopic bulb, the apparatus becomes a barometer,
and may be employed for automatically registering the atmospheric
pressure. The author proposes to call this instrument a thermobaro-
grapli. R. R.
Specific Heat and Expansion of the Solid Elements. By
H. F. WiEBE (Ber., 13, 1258 — 1263). — In certain groups of elements,
a simple relation exists (according to the author) between the pro-
3 i 2
784 ABSTRACTS OF CHEMICAL PAPERS.
du<!ts of the specific heat of the elements by their melting points cal-
culated from the absolute zero.
These numbers are, for Group I: Li 8-54, ISTa 2-55, K ]-56, Cu 914,
Ag 5-14, Au 3-14. II : Zn 2-33, Cd 1-33. Ill : Br 1-23, I 1-21, &c.
When a represents the cubical expansion of a solid element, a its
atomic weight, c its specific heat, and 'm ^ its melting point calcu-
1
lated from the absolute zero, then a. . a gives the constant 2"6 with a
c. m
possible error of + 0*04. The expansion of an element can be calcu-
1
lated approximately by means of the formula cc = -— . Only
2'b a . c .m
those elements which crystallise in the regular system follow this
rule. W. C. W.
Expansion and Molecular Volumes of Liquid Organic Com-
pounds. By H. F. WiEiiE (Ber., 13, 1263— 1265).— For the acids
and ethereal salts of the acetic acid series, the product of the molecular
weight of any of these bodies, by the mean coefficient of expansion,
multiplied by the absolute boiling point, and divided by the density at
0°, is equal to a constant (which varies from 3'1 to 3"8) multiplied by
Act
the number of atoms in the compound, — — - T = ?^ constant, e.g., for
formic acid, — =- T = 15-57 = 5 X 3'1.
a
The density of a liquid at its boiling point Sg can be calculated by
means of the formula c, = o(,, + i) . •-{■542- W. C. W.
Refrigerating Mixtures with two Crystallised Salts. By A.
DiTTE (Conipt. rend., 90, 1282— 1285).— The author has already
shown that the reduction of temperature which accompanies the mixing
of certain crystallised salts with concentrated acids, is to be attributed
to the liquefaction of the water which separates from the hydrated
salt. Such being the case, it ought to be possible to prepare refri-
gerating mixtures by means of two solid substances, one of which is a
strongly hydrated salt ; it would be necessary to effect a double de-
composition of such a nature that the heat produced was very small as
compared with the number of heat units absorbed in the liquefaction
of tlie water of crystallisation.
Ammonium nitrate and Sodi'wm sulphate. — Without reckoning the 10
molecules of water of the sulphate which take no part in the decom-
position, the heat-units before reaction will be 80'7 + (163'2 + 2'3)
= 246-2, and after reaction 157-2 + 88-9 = 246-1 : the double decom-
position will therefore be effected without sensible variation of heat,
but as the 10 molecules of water set free will require for liquefaction a
large number of units, it is certain that the reaction will be accom-
pauied by a very considerable reduction of temperature. A direct
experiment showed that the temperature was lowered about 20° ; the
solution of the new products in the water formed will also tend to re-
duce the temperature.
GEXERAL AXD PHYSICAL CHEMISTRY.
785
In like manner, a mixture of ammonium nitrate and crystallised
sodium phosphate, reacting on the same principles, effects a reduction
of about 18°, and ammonium nitrate or chloride with sodium carbo-
nate about 25°. Ammonium nitrate and dry potassium carbonate
also acts as a refrigerating mixture, but the cold produced in this
instance is due to the dissociation of the ammonium carbonate (Ber-
thelot). J. W.
Heat of Combustion of Sulphur. By J. Thomsen (Ber., 13,
959 — 961). — Favre and Silbermaun found the heat of combustion for
one atom of sulphur, burning to form sulphurous anhydride, to be
71040 c. (Ann. CMm. Phys. [3], 34, -148). Berthelot (Compt. rend.,
84, 674), however, finds it to be 69140 c., explaining the difference of
this result from that of Favre and Silbermann, by supposing that in the
former case a larger amount of sulphuric anhydride was formed than
in the latter. The author has determined this quantity, estimating
the amounts of sulphurous and sulphuric anhydrides formed, and
after deducting the heat necessary to oxidise the sulphurous anhydride
to sulphuric anhydride, finds that the heat of combustion of rhombic
sulphur when burning to form sulphurous anhydride, is 71080 c, and
of monoclinic sulphur 71720 c. ; a result agreeing with that of Favre
and Silbermann. P. P. B.
Thermochemical Investigation of the Theory of the Carbon
Compounds. By J. Thomsex {Ber., 13, 1321— 1334).— The author
has determined the heat of combustion and of formation of the oxides
of carbon and of several hydrocarbons.
Heat of formation.
''T — ' '^ — \
L uder constant For constant Tolume.
Heat of pressure. - — — '^ ^
combustion. Experiment. Calculated.
CHi 213530 20150 19570 19380
CHs 373330 26570 24510 24190
C.Hs 533500 30820 29950 29000
CoH, 334808 - 4160 - 4740 - 4950
CsHg 495200 + 760 - 400 - 140
CoH, 310570 -48290 -48290 -48660
C + 0.... — +28590 +28880 +28980
CO + 0. ... — -r6S370 +68080 —
C + O2.... — +96960 +96960 96860
The results in column five are calculated by means of the formula
(CbHobi) = — nd + mq + 2v, where 2v = the sum of the values of
the bonds uniting the carbon- atoms together.
d =: the heat of dissociation of an atom of carbon = 38900 + x,
and o = r + — .
4
r = 14570°. V = r -\-- -.v- = r + x-.v" = 0 -\- ^-x:
^* = _2r + 2.f, and CO = 67880. W. C. W
78(5 ABSTRACTS OF CHEMICAL PAPERS.
Heat of Combustion of the Principal Gaseous Hydrocarbons.
By Bekthelot {(Ju7iipt. rend., 90, 1240 — 1246). — In order to measure
the heat of combustion, the hydrocarbon was exploded with oxygen
in a small steel calorimeter, platinised on the interior. The numbers
represent the heat of combustion at constant pressure, calculated from
the determinations at constant volume : —
Heat of fonnation.
/■■~ ~ ^
Heat of com- From From amorphous
bustion. diamond. carbon.
Hydrogen 69*0 — —
Carbonic oxide (iS'S + 257 + 287
Cyanogen 2G2-5 - 74 5 - 68-5
Methane 213-5 + 18-5 + 21-5
Ethane 388-8 + 6-5 + 12-5
Ethylene 341-4 - 15-4 - 9*4
Acetylene 318-1 — 60-4 ~ 54-6
Methyl ether 344-2 + 50-8 + 56-8
Propane 553-5 + 4-5 +13-5
Propylene 507-3 — 18-3 — 9-3
Allylene 466-5 - 46-5 - 37-5
These numbers show that the heat of combustion of a hydrocarbon
is not always equal to that of its elements. The variation is least in
the case of the saturated hydrocarbons, C„H2k+ o, but the heat disen-
gaged in the formation of marsh-gas from its elements appears to be
greater than that of any of its homologues ; a character which is in
accordance with its relative stability. The difference in the cases of
ethane and propane is small and nearly identical, so that if this figure
remains constant for the higher homologues, we may conclude without
going beyond the limits of experimental error, that the heat of com-
bustion of the higher members of the series at least is nearly if not
exactly identical with that of their elements.
The heat of formation of the other hydrocarbons is negative, the
variation increasing according as the hydrocarbon is less hydrogenised ;
thus the addition of H2 to the formula of acetylene disengages + 45
units; to allylene, + 28-2 units, the special character of the homo-
logous series being more marked in its first term, agreeably with what
has been already mentioned in the case of marsh-gas. The addition
of H3 to the formula of ethylene disengages + 21-9 units; to pro-
pylene, -t- 22-8, or nearly the same figure. Between any two con-
secutive homologues, the differences of the heat of combustion are : in
the CHo,, + 2 series, 175-3 and 164-7; in the C„H3„ series, 165-9; in
the C^HsM _ 2 series, 148-4, the actual combustion of C (diamond)
-j- Ho being 163.
Although the calculation of the heats of formation of organic com-
pounds by means of their combustion equivalents is accurate in prin-
ciple, it must be employed with increasing reservation when the
relation of the heat of combustion to the molecular weight becomes
more and more considerable. Nothing can be deduced from a dif-
ference of from 3 to 4 units in the ethyl series ; from 5 to 6 units in
GENERAL AND PHrSTOAL CHEMISTRY. 787
the propyl series ; nor from 8 to 10 units in the amjl series, and so
on. J. W.
Heat Disengaged in the Combustion of some Isomeric Fatty
Alcohols, and of Oenanthal. By W. Louguinine {Compt. rend.,
90, I'll'J — ^1282). — The experiments of Berthelot on the formation of
isomerides hav'infr similar chemical functions, led him to conclude
that their formation is attended with a disengagement of neaily equal
amounts of heat : tlie experiments of the author confirm this view.
Thus the molecule of normal propyl alcohol (taken in grams) evolved
480'3 units; of isopropyl alcohol, 478'2 units; the heat of combustion
of the normal alcohol calculated theoretically by Favre and Silber-
mann, should be 481"2 units.
In like manner the molecule of isobutyl alcohol evolved 636' 7 units ;
the theoretical number calculated by Favre and Silbermann being
633'6 units.
Fermentation amyl alcohol, which is a mixture of several primary
alcohols, was compared against the tertiary alcohol, dimethyl-ethyl-
carbinol ; the former gave 703'6, and the latter 788'5 units. Favre and
Silbermann's calculation for an isoamyl alcohol is 788'3 units. From
these data it would follow that the different operations involved in the
transformation of a primary into a secondary or tertiary alcohol, produce
a calorific effect whose sum is equal to zero ; the conclusion, however,
holds good only on the supposition that the value of the total heats of
vaporisation of the different alcohols is in all cases the same.
The molecule of oenanthal (in grams) evolved 1062'o units of heat.
From Favres table the heat of combustion of oenanthylic alcohol
should be 37"0 units hisjher than that of its aldehyde, or 1099'6 units ;
this number is less than that which corresponds to the difference,
540 units, between isopropyl alcohol and acetone. J. W.
Thermo-chemistry of Ethylamine and of Trimethylamine.
By iiEETHELOT (Coiiqjt. rend., 91, 139 — 145). — The heat of combustion
of ethylamine, C2H7N, is 409" 7 uidts ; that of trimethylamine, C3H9N, is
592'0 units. The heat of solution in water of the gas is, for ethylamine,
12"91 units ; for trimethylamine, 12"90 units. Both bases have, therefore,
great affinity for water, and the heat developed in diluting solutions of
trimethylamine is double of that developed by equivalent solutions of
potash and soda. The heats of formation of tlie hydrochloride, ace-
tate, and sulphate of trimethylamine are respectively 8"9, 8'3, and
1<J'9 units, the substances being in solution ; the formation of the solid
hydrochloride from the gases gives 39'8 units. Hydrochloric acid in a
solution containing equivalent quantities of trimethylamine and am-
monia is nearly equally divided between the two bases. R. R.
788 ABSTRACTS OF CHEMICAL PAPERS.
Inorganic Chemistry.
Vapour-density of Iodine. By V. Meyer (Ber., 13, 1010—1011).
By employing a higher temperature than hitherto attained, the author
finds the vapour-density of iodine to be 4*55, agreeing very nearly with
the value for I, and not II2, as obtained at lower temperatures. The
author thinks that by using still higher temperatures the iodine vapour
may undergo a still further dissociation. P. P. B.
Vapour-density of Iodine. By J. M. Crafts (Ber., 13, 1316 —
1321).— A reply to Victor Meyer (Ber., 13, 1010 and 1103).
w. c. w.
Proportion of Carbonic Anhydride in the Air : Reply to a
Note by M. Reiset. By Marie Davy (Gompt rend., 90,1287—1289).
— Reiset considers in the first place, that the author's results cannot
be considered as accurate, because the daily volume of air used was
not corrected for temperature and pressure ; secondly, having made a
series of experiments near Dieppe, he concludes that the proportion of
carbonic anhydride in the atmosphere is practically invariable, in oppo-
sition to Marie Davy, who from experiments near Paris had found
that it did vary, and had endeavoured to predict meteorological pheno-
mena therefrom.
To this the author replies, that whereas in Reiset's experiments by
weight, it was necessary to correct for temperature and pressure, in
his own experiments by volume it was less important, since it only
afi^ected the third place of decimals, which was the limit of precision
to which the analyses could attain.
That to deduce a perfect uniformity of composition from two series
of experiments only made at an interval of six years is impossible, and
that had Reiset obtained varying results instead of identical ones, it
would have been equally impossible to infer a permanent change in the
proportion of carbonic anhydride in the air.
To the theory of uniformity of proportion, numerous well-authenti-
cated facts can be opposed. Truchot found 3"13 parts of carbonic
anhydride in 10,000 at Clermont Ferrctnd, at an altitude of 395 metres ;
2'03 parts at the summit of the Puy de Dome, 1,446 metres ; 1"72 parts at
the summit of the Pic de Sancy, 1,884 metres ; moreover, Regnaulthas
shown that the proportion of oxygen can in certain cases, especially in
warm climates, vary from 2,093 parts in 10,000 to 2,030 parts ; if all
the oxygen which has disappeared were to be replaced by carbonic
anhydride, the proportion of this latter would rise from 3"0 parts to
66"0 parts, a variation which no one presumes ever to have observed.
During two rainy years, when Paris was under the influence of an
equatorial current, a large proportion of carbonic anhydride was found.
A year later, when a different atmospheric circulation obtained, a much
smaller percentage of carbonic anhydride was present. Towards the
end of October, 1879, the proportion of carbonic anhydride had fallen
to a minimum ; it was therefore concluded that a dry period was im-
INORGANIC CHEMISTRY. 789
minent. This coincidence was realised, and althougli this is at present
almost the only meteorological phenomenon known to be in any way
connected with the carbonic anhydride in the atmosphere, the author
thinks the further prosecution of the subject is not unworthy of the
attention of meteorologists. J. W.
Crystallised Hydrofluosilicic Acid. By M. Kessleb {Compt.
rend., 90, 1285 — 1286). — In order to prepare a concentrated solution
of hydrofluosilicic acid, silicon fluoride was passed into hydrofluoric
acid. The process was very successful, and it was found that when
the hydrofluoric acid was concentrated there was no deposition of
sihca, or absorption of excess of gas. In operating in this manner,
the tube through which the silicon fluoride passed and the recipient
became filled with needle-shaped crystals, which on examination proved
to be a definite hydrate of hydrofluosilicic acid. They were free from
hydrofluoric acid, for their aqueous solution after precipitation by
excess of potassium chloride, did not corrode glass, neither did they
contain excess of silicon fluoride, for the potassium siUcofluoride so
formed after having been washed with dilute alcohol, left behind no
trace of silica in the ev^aporated washing waters.
The crystallised acid is colourless, very hard, and very deliquescent;
it fumes strongly in the air, and melts at about 19°. Heated beyond
this point it boils, but decomposes at the same time. Its composition,
which was not very definitely made out, appears to be nearly
SiF4.2HF + 2H2O, or a little less than 2-5 molecules of water to one
of acid.
The author proposes to see whether it is not possible to obtain a
similar hydrate of hydrofluoric acid, or compounds of silicon fluoride
with other hydracids, such as hydrobromic and hydriodic acids.
J. W.
Pentahydrated Calcium Carbonate. By E. Pfeiffer {Arch.
Pharm. [2], 15, 212 — 216). — This compound, already described in
Gmelin's Handbook from the observations of Pelouze and Salm-
Hurtsmar, Avas found by the author as a crystalline deposit in the
pumps and pipes which delivered water from a well. The water, after
depositing this salt, acquired a flat taste, and was almost free from
carbonic acid. When the water was taken fresh from the well, shaking
and stirring also caused it to deposit the above calcium salt. The solid
residue of the water rose considerably, and consisted largely of potash
when the deposit formed most largely. The author considers that
the salt was formed by potash-lye leaking into the water and removing
the carbonic acid from the water, the salt being then precipitated in
a hydrated condition because of the low temperature (10 — 12° C.) of
the water. It was kept under water unaltered at a temperature of
20° C, but at a slightly higher temperature the particles lost their
transparency and water of crystallisation. In the air, it crumbled to
powder and also lost its water. The crystals appeared to belong to
the rhombic system. F. C.
Formation and Constitution of Bleaching Powder. By G.
LuxGE and H. Schappi (Liiujl. jjolyt. J., 237, 63—73). — The subject
790 ABSTRACTS OF CHEMICAL PAPERS. ^
tas been mncli investigated, but there is still great difference of
opinion. The present investigation deals with four questions. In all
cases the solid substance is considered.
1. The Infltience of the Amount of Water present in the Lime on the
preparation of Bleaching Poivder. — A commercial lime of great purity-
was used, having the following composition : —
CaO 72-62
CO2 0-51
AI2O3 0-06
SiOo trace
HoO 27-80
100-99
The lime, AA^th variable amounts of water, exposed to dry chlorine,
gave as follows : —
Water per cent. —
6-5, 13-6, 17-6, 21-6, 24, 26, 27-8, 28-2, 30-1, 31-8.
Bleaching chlorine —
9-06, 32-86, 37-38, 38-82, 40-71, 40-89, 43-13, 40-36, 38-78, 36-85.
Other experiments with incompletely dried, less dry, more moist,
and still moister chlorine gave, for lime containing 24 per cent, of
water, the following amounts of bleaching chlorine, viz., 42-12, 41-76,
38' 24, and 37 per cent, respectively. Calcium hydrate dried at 100",
and containing 24 per cent, w'ater, gave with dry chlorine 39-3 per
cent., and with incompletely dried chlorine 41-59 per cent. ; whilst
undried hydrate with 25-3 per cent, of water gave 40-6 and 40-6 per cent,
with both classes of chlorine. Hence that perfectly dry hydrate does
not absorb chlorine (Graham, Tschigianjanz, &c.) is erroneous, as
Stahlschmidt and Kopf er had found previously ; and the absorption goes
on when a large excess of quicklime is present, in which case the dry-
ness is ensuT-ed ; further, the amount absorbed is greater than would
be the case if the quicklime acted as dead ballast only. The strongest
bleaching powder containing up to 43-42 per cent, of available chlorine
can be obtained with perfectly dry chlorine. This is produced when
the lime contains about 4 per cent, more water than is necessary to
form hydrate. When the chlorine contains moisture, the lime used
must contain correspondingly less water, so that the end-product may
be the same.
2. The hifiuence of Air on Bleaching Powder. — In moist air at about
80°, much oxygen is evolved ; the whole of the chlorine remains in
the residue partly as chloride and partly as chlorate, thus : CaOCl2 =
CaCl2 + 0 and GGaOGk = CaCClOajo + SCL.. In dry air at 100°, the
air coming away contained 0-87 per cent, of oxygen, due to the
bleaching powder, and 14'94 per cent, of chlorine ; the residue con-
tained 22-25 per cent, chlorine as chloride, 3-51 as chlorate, and 1-35
as available chlorine.
3. Bleaching Poivder vrith Carhonic Anhydride. — Here the authors
remark that the conclusion cannot be avoided that no formula of
bleaching powder can be correct in which calcium chloride appears,
INORGANIC CHEinSTRY. 791
since in the presence of a little moisture almost all the chlorine is ex-
pelled by carbonic anhydride. They condemn the formulae of Gay-
Lussac, Kolb, Stahlschmidt, and others as impossible, and support
Odling's CI — Ca — OCl as being sufficient to explain all observed ap-
pearances.
4. Behaviour of the Water contained in Bleaching Povjder. — The
authors conclude that the water expelled below 150° is either hygro-
scopic, or from a hydrate of CaOClo, or from both ; between 150° and
290° very little comes off, whilst the water expelled between 290° and
a red heat comes from free calcium hydrate. The strongest bleaching
powder contains very little water in excess of what is required for the
formation of CaOClo, H^O, and Ca(0H)2. Over sulphuric acid not
only is hygroscopic water removed, but also some from the compound
CaOCl2.H20, if such a compound exists. Analysis of a good labo-
ratory sample of bleaching powder gave : —
CaO 39-89
Available CI 43-13
CI as CaCla 0-29
HoO (mean of three determinations) 17'00
CO2 0-42
100-73
From which the following composition may be calculated : —
CaOClo 88-08
CaCOs 0-96
CaClo 0-45
Ca(dH;o 6-74
H2O (by difference) .... 3" 7 7
100-00
Actual determination of the water gave 0-66 per cent. more. The
small quantity of calcium hydrate need not be considered essential to
the formula of bleaching powder, but seems due to mechanical ad-
mixture. The circumstance that good bleaching powder rubbed up
with a little water swells up and evolves heat, can easily be explained
by the equation 2(Cl.Ca.0Cl) = ClO.Ca.OCl + CaClo. On diluting,
the resulting product is obtained as voluminous flocculent precipitate,
as if separated from combination. J. T.
Compound of Alumina -with Carbonic Anhydride and
Ammonia. By M. Barth (Annalen, 202, 372 — 375).— Various
statements have been made with regard to the composition of the pre-
cipitate produced in a solution of alum by ammoninm carbonate, by
Bley (/. 2>?'. Chem., 39, 1) ; Barratt (ibid., 82, 61) ; Parkmann (Hid.,
89, 116) ; Muspratt (A7malen, 72, 120); Langlois (Hid., 100, 374);
Wallace (Jahresb., 1858, 70) ; and Rose (Pogj. Ann., 91, 461). Bley
proved that it contained alumina, carbonic anhydride, and often am-
monia; Muspratt gave it the formula 3AI0O3.2CO2 + I6H2O ; while
Rose regarded it as AI0O3 -f- (N'H4)oO + 2C0o + 4HoO ; and Langlois
as 3(Aio03.C02) -i- 5(Alo03.8HoO). Recently Urbain and Renoul
792 ABSTRACTS OF CHEMICAL PAPERS.
(/. Pharm. Ghim. [4], 30, 3-iO) res^ard the precipitate formed in the
cold as COo + AlaO, + BHoO.
By adding a solution of pure alumina in hydrochloric acid to excess
of cold ammonium carbonate, the author obtained a precipitate
which, when washed with cold water and dried over oil of vitriol, con-
tained (in one case) AloO, = 37-44, CO2 = 177, NH3 = 4-92, and
H-O = 39'94 per cent. It was obviously a mixture of a double alu-
minium and ammonium carbonate, with either alumina or aluminium
carbonate. A carbonate without ammonia has not as yet been proved
to exist. Ch. B.
New Aluminium Sulphate. By P. Marguerite (Compt. rend.,
90, 1354 — •1357). — When ammonium alum is decomposed by heat,
anhydrous aluminium sulphate is first obtained. By pushing the de-
composition somewhat further, sulphuric acid is volatilised ; so that
by carefully regulating the heat, a residue can be finally obtained
almost entirely soluble in water, and consisting mainly of the ses-
qidhasic sulphate. This salt, which has not been before described, is
entirely dilierent in appearance from the ordinary sulphate. It crys-
tallises in rhombohedrons and not in nacreous scales ; its solubility in
water at 15° is about 45 per cent., but it can be separated from the
ordinary sulphate by fractional crystallisation. Analysis gave : —
A1..0.. SO,. Fe.Ov H.,0. Los
ss.
21-2 33-84 0-01 44-90 0-05 = 100
from which the formula AI2O3.2SO3.I2H2O or fAlA-SSOa.lSHoO is
deduced.
A list is given in the memoir of ten different aluminium sulphates
which are known at the present day. J. W.
Specific Heat and Atomic Weight of Glucinum. By L. F.
NiLSON and 0. Pettersson (Compt. rend., 91, 168 — 171). — The authors
have redetermined the equivalent of glucinum, using pure specimens
of glucina, the mean of four experiments being 4-542 (0 =8). If
glncina be GI2O3, this gives 13-65 as the atomic weight of glucinum.
They find also that the specific and atomic heats of glucinum increase
with the temperature like those of iron, but at 300" the atomic heat
of g-lucinum is not so g'reat as that of iron. Glucinum cannot there-
fore be compared with carbon, boron, and silicon, the specific heats of
which increase much more rapidly. The atomic heat of glucinum is
quite normal if the atomic weight be taken as 13-65. R. R.
Colloidal Ferric Hydrate. By L. Magnier de la Source (Compt.
rend., 90, 1352 — 1354). — Several specimens of dialysed iron were
analysed and found to vary in composition from 12Fe203.Fe2Cl6 to
SOPeaOs.FeoCle. The latter preparation, known in commerce as " fer
Bravais," was constant in composition, and was itlentical with the
basic oxychloride of iron, the formula of which was first accurately
ascertained by Grraham.
In order to find out whether this constancy of composition was
due to the impossibility of separating the whole of the ferric chloride
INORGANIC CHEMISTRY. 793
bj dialysis, a sample was diluted so as to contain 0"8 per cent, of ferric
oxide, and submitted to prolonged dialysis for three months. At the
beginnins: of the experiment, the composition of the liquor was
SOFeoOa.FeoClo; after one month, G4Fe303; after two months, 102Fe2O3 ;
after three months, llGFe-iOs to one molecule of Fe2Cl6 ; whilst traces
of chlorine still continued to pass through the diaphragm. The latter
was now in too small proportion to measure quantitatively, but it was
placed beyond doubt that the oxychloride of composition 116Fe203.Fe..Cl6,
still lost chlorine by dialysis.
The author thinks that these experiments are sufficient to prove that
ferric hydrate is, under certain conditions, soluble in water, and that
it is unnecessary, in order to explain such solubility, to imagine that
the hydrate is engaged in some more or less complex combination. In
support of this opinion, it may be mentioned that, from considerations
of an altogether different character, Debray has already arrived at the
same conclusion.
"When "fer bravais '' is evaporated to diyness and the residue
treated with water, the ferric chloride dissolves, but the ferric hydrate
remains insoluble; the hydrate, in solution, and dried at 100°, appears
to be the normal salt 2Fe303.3HnO, at least as far as theoretical calcu-
lation of the weight of residue from known quantities of solution
may be considered to support such a conclusion. J. W.
Action of Chlorine on Chromium Sesquioxide. By H.
Moi.ssAX {Cumpt. reiul., 90, 1357 — lotJO). — Strongly ignited chromium
sesquioxide submitted to the action of dry or moist chlorine at 440^ is
not attacked, but chromium sesquihydrate under similar circumstances
is readily attacked, and red vapours are produced, which condense to
chromium oxychloride, C2O2CI2.
It would appear that chromium sesquioxide, anhydrous but not
calcined, is attacked by chlorine at 440° with production of the ses-
quichloride and not of the oxychloride, but the action soon ceases,
owing to the superficial coating of sesquichloride preventing the fur-
ther action of chlorine ; the presence, however, of water either in the
current of chlorine or in the oxide brings about at this temperature
the decomposition of the sesquichloride, according to the foUowino*
equations : —
Cr.,03 + n£\ = Cr.Cls -I- O3 + («-6)Cl
CraCle + 2H2O + nCl = 2C2O2CI2 + 4HC1 + (/i-2)CL
If the passage of moist chlorine over the non-calcined sesquioxide
be stopped as soon as red vapours begin to be disengaged, and the
excess of chlorine be expelled by a current of carbonic anhydride, there
will be found to remain in the apparatus a lu'own powder, the com-
position of which is nearly that of the oxychloride of Moberg. It is
an intermediate substance less oxidised than the ordinary oxychloride
and decomposible by wa^^er. Chromium oxychloride also results from
the action of dry oxygen at 440° on the sesquichloride. With the
non-calcined sesquioxide, oxygen causes an increase in weifht, and a
blackish-grey substance is produced which seems to be the oxide
794 ABSTRACTS OF CHEMICAL PAPERS.
CrOa ; it evolves chlorine readily when treated with concentrated
hydrochloric acid. J. W.
Combinations of Uranium Oxyfluo- Compounds with.
Fluorides of the Alkali Metals. By A. Ditte (Gompt. rend., 91,
1G6 — 168). — The action of the neutral fluoride of an alkah'ne metal on
the green oxide of uranium gives rise to insoluble, anhydrous crystal-
line compounds, having the formula U3O2FI2.4MFI, Acid fluorides of
alkali metals, on the other hand, react to produce soluble hydrated
salts, having the composition U40Fl4.4MFl.a;H20. R. R.
Organic Chemistry.
Action of Ethyl Chloride on Ethylamines. By E. Duvillibe
and A. Buisine (Comjjt. rend., 91, 173—175). — When ethyl chloride
is heated at 100'' in a sealed tube with an alcoholic solution of the
ethylamines produced in the reaction between ethyl chloride and
ammonia, and the product is treated with soda in excess, four ethyl
bases are obtained, namely, triethylamine, diethylamine, monethyl-
amine, and tetrethylammouium hydrate. R. R.
Decomposition of Simple Organic Compounds by Zinc-dust.
By H. Jaijn (i'er., 13, 983— 990).— The alcohols from ethyl alcohol
upwards are decomposed by zinc-dust at 300 — 350° into hydrogen
and the olefine corresponding with the alcohol. Propyl and isopropyl
alcohol both yield a propylene whose dibromide boils at 142 — 143°.
Methyl alcohol holds an exceptional position ; it is decomposed into
carbonic oxide, hydrogen, and a small quantity of marsh-gas. Ethyl
alcohol undergoes a similar decomposition at a dull red heat, yielding
marsh-gas, carbonic oxide, and hydrogen. This decomposition of
methyl alcohol is, to some extent, to be accounted for by the consti-
tution of its molecule ; and, further, Berthelot {Gomjpt. rend., 54, 515)
has shown that with respect to heat of formation, methyl alcohol
holds an exceptional position as compared with its homologues.
P. P. B.
Combination of Allyl Alcohol with Ba,ryta. By C. Vincent
and Delachanal (Gompt. rend., 90, 1360— 1361).— When allyl
alcohol is dried over anhydrous baryta, as is generally recommended,
a very large loss of alcohol results ; it was thought probable, there-
fore, that some combination had taken place between the baryta and
the alcohol. The addition of baryta causes a very considerable
development of heat, the alcohol becomes yellow, and the liquid
portion when filtered from the excess of baryta and evaporated to
dryness leaves a mass of microscopic ciystals. From these crystals,
which contain 62 per cent, of baryta, the alcohol can be recovered by
distillation with water. The formula 2C:jH60,BaO requires 56'88 per
cent, of baryta, the excess of baryta found over that theoretically
ORGANIC CHEMISTRY. 795
required bein^ dne to the solubility of barium hydrate in tho solution
of the allylate. Allyl alcohol also dissolves barium allylate, and this
solution when evaporated over sulpliuric acid leaves an amorphous
mass, which dries with difBculty at the ordinary temperature. In a
vacuum at 100°, however, the allylate becomes perfectly dry, and has
then acquired the property of decomposing rapidly on a slight ele-
vation of temperature, leaving a pulverulent and very voluminous
carbonaceous residue. J. W.
Action of Bromine on Cane-sugar. By O. Geieshammer
(Arrh. PItarm. [8], 15, 193 — 210). — The author gives a short notice of
the researches on this subject of Hlasiwetz, Barth, and of Habermann,
and then states that he has found that bromine readily acts on a
■warm aqueous solution of cane-sugar. When 2 atoms of bromine
were added, the colour quickly vanished ; on further addition of
2 atoms, the colour disappeared after several weeks ; a fifth atom did
not disappear after long standing, but decomposition and blackening
took place, and w^as increased by heating the liquid. After the
reaction, the bromine was found to be entirely present as hydrobromic
acid, no bromo-derivative of sugar being formed. The hydrobromic
acid was removed by lead oxide, since' when silver oxide was used,
silver was reduced. After removal of the lead by sulphuretted
hydrogen and evaporation to one-half, the easily decomposed acid
liquid was saturated whilst warm with zinc carbonate, and the zinc-
salt was precipitated and well washed with strong alcohol. This salt
is easily soluble in water, and its solution when treated with sul-
phuretted hydrogen yields the uncrystallisable acid. The solution was
evaporated over calcium chloride, and the formula obtained for the
acid vras CeHioOv -f 2H2O ; 1 mol. of water can be expelled at 100°,
and the second at 125°. A column 200 mm. in length of a 1 per cent,
solution rotates the plane of polarisation 2° to the right in Mitscherlich's
apparatus. The aqueous solution when made alkaline separates no
cuprous oxide from Fehling's solution, thus differing from Hlasiwetz's
acid, which doubtless contained sugar. Analyses of the salts of
barium, calcium, zinc, silver, lead, potassium, and ammonium are
given ; no acid salts could be prepared. The name gluconic acid has
been retained by the author, although the acid is not identical with
that obtained by Hlasiwetz. The acid was separated directly from the
product of the action of bromine on cane-sugar without previous treat-
ment with lead oxide by warming with zinc carbonate until the liquid
was only feebly acid, evaporating to one-half, and .shaking with eight
times as much 90 per cent, alcohol : the precipitate when well washed
yielded pure gluconic acid. Carbonates and hydrates of the metals of
the alkalis and alkaline-earths caused decomposition, and did not
yield gluconates.
A study of the reaction quantitatively showed that if more than
2 atoms of bromine were employed, no increased oxidation occurred,
and the main reaction is therefore probably represented thus : CpH-«On
+ 2Br + 2H,0 = CeHioO, + CeH^oOe + 2HBr. The gluconic acid
and grape-sugar were obtained in nearly the proportions required by
this equation ; but a certain amount of the sugar was changed into a
706 ABSTRACTS OF CHEMICAL PAPERS.
ffum-like substance, whicli was convertible into grape-sugar by being
treated with dilute sulphuric acid. A fuller examination of this sugar
and gum is promised. F. C.
Presence in Soja Hispida of a Substance soluble in
Alcohol, and transformable into Glucose. By A. Levallois
{Compt. rend., 90, 1298). — The analysis of this seed by Pellet gave
3'1 per cent, of sugar starch and dextrin. The author's results are
different. He finds 9 — 11 per cent, of a substance soluble in
alcohol, which reduces Fehling's liquor only after some minutes'
boiling with water acidulated with sulphuric acid. It has consider-
able dextrorotatory power, which is brought back to nearly that of
glucose (dextrose?) by boiling with acidulated water. In its optical
characters it resembles dextrin, but seems to dift'er from it in the
rapidity with which it is converted into glucose. J. W.
Behaviour of the Ethyl-mercaptides of Mercury and Lead at
High Temperatures. ByR.OTTo(5er.,13,1289— 1290).— When mer-
curic ethylmercaptide (m. p. 7Q'^) is heated with alcohol at 180°, it splits
up into metallic mercury and ethyl disulphide, only traces of mercuric
sulphide being formed. A similar decomposition takes place when
the diy mercaptide is heated, but in this case a somewhat larger
quantity of mercuric sulphide is produced.
Lead ethylmercaptide melts at 150"^, and decomposes at 180°, form-
ing lead sulphide and ethyl sulphide. W. C. W.
Etherification of Sulphuric Acid. By A. Villiers {Compt.
rend., 91, 124 — 127). — Berthelot has already shown that in a mixture
of sulphuric acid and alcohol, the proportion of acid neutralised
tends towards a limit which it cannot pass, and that this limit be-
comes gradually lower under the influence of time and temperature,
owing to the formation of ordinary ether. The following table shows
the influence of time in the etherification of sulphuric acid (ethyl
hydrogen sulphate being formed) at 100° : —
Percentage of acid etherified.
I , ^ III
CoHeO. 2C2H6O. 4C2H6O.
Immediately 59-0 1\q 83-2
After 15 minutes 58-0 72-2 —
,, 2i hours 49-3 64-3 76-0
„ 26 „ 45-5 46-5 53-9
„ 69 „ 45-5 45-3 347
,,154 „ — 44-1 32-1
At the end of the experiment, the proportion of sulphuric acid which
remains in combination with the alcohol appears to correspond with a
certain composition of the original liquor. This retrograde action is
observable also at 100° with mixtures containing water ; as might be
expected, it is greater than when alcohol alone is used.
ORGANIC CHEMISTRY. 797
Percentage of acid etherified, H2SO4 + CoHgO +
UliO. HoO. 2HoO.
53-0 48-4 46-0
49-9 — —
427 39-3 34-1
38-2 357 28-0
37-0 33-8 27-5
The formation of ether and dimimtion in proportion of acid half
neutralised goes on even at much lower temperatures : thus at 44° —
Percentase of acid etherified.
Immediately . . . .
After 15 minutes
„ 2^ hours
„ 69
„ 154
C.HgO. CiHgO + iH.O. C0H5O + HoO.
Immediately 59-0 53-0 48-4
After 69 daVs 487 421 394
,,142 ,; 44-5 37-9 36-0
,,221 „ 44-5 37-4 336
These results show that the action tends towards a fixed limit at 44°,
and that the ultimate limits corresponding to the temperatures of 44^
and 100° are identical. The coefficient of etherification begins to
increase at first rapidly, and passes to a maximum, which corresponds
with a short period of unstable equilibrium ; it then steadily dimi-
nishes, and ultimately settles to a period of stable equilibrium, which
is independent of the temperatui'e. J. W.
Preparation of Neutral Ethyl Sulphate. By A. Yilliers
(Compt. rend., 90, 1291 — 1292). — This ether can be prepared by
distilling in a vacuum a mixture of sulphuric acid and alcohol.
200 grams of absolute alcohol distilled very slowly in this manner
with twice their volume of concentrated sulphuric acid, yielded from
25 to 30 grams of the neutral ether ; the end of the operation is in-
dicated by the frothing of the contents of the retort, and by an increase
of the internal pressure. The distillate separates into two layers, the
lower of which consists of the pure ether. There is no advantage in
using fuming sulphuric acid, or in substituting ordinary ether for
alcohol. The boiling point of ethyl sulphate under a pressure of
45 mm. is 120'5°, which falls regularly 25° as the pressure dimi-
nishes 5 mm. It solidifies at about — 24"5^, and when treated with
warm baryta-water it gives the theoretical quantity of barium ethyl
sulphate and alcohol. J. W.
Transformation of Methyl Thiocyanate at High Tempera-
tures. By A. W. H0FM.\NX (Ber., 13, 1349— 1352).— When methyl
thiocyanate is heated at 180 — 185° for six hours, it is converted partly
into a polymeric modification, CeHgNsSs, and partly into methyl thio-
carbimide. The two substances are separated by distillation, the
latter boiling at 118"^, the former remaining in the retort.
NziC^SMe
The polymeride, MeS — C^ x-N , forms colourless crystals,
^N— C-SMe
VOL. XXXVIII. 3 h
798 ABSTRACTS OF CHEMICAL PAPERS.
wliicli melt at 188", and sublime at a higher temperature. They are
insoluble in dilute acids and alkalis, but dissolve in hot glacial acetic
acid.
Hot hydrochloric acid splits up the compound into methyl mercaptan
and cyanic acid.
A crystalline base is obtained by acting on the new methyl thio-
cyanate with alcoholic ammonia at 150°. W. C. W.
Furfuraldehyde. By E. Fischer (Ber., 13, 1.3.34— 1340).— The
name furoin is given to a compound having the composition
C4H3O.C0H2O2 C4H3O, which bears the same relation to furfuraldehyde
that benzoin bears to benzaldehyde. This substance is prepared by
boiling 40 parts of furfuraldehyde with 30 of alcohol, 80 of water, and
4 parts of potassium cyanide for three-quarters of an hour. The
crystalline mass which is deposited on cooling is drained, washed first
with water, then with a small quantity of alcohol, and dried between
filter-paper. It is obtained nearly colourless by precipitation with
alcohol from its solution in hot toluene. Furoin forms slender
prisms (m. p. 13.5°) soluble in hot water and hot toluene. It also
dissolves in sulphuric acid with an intense bluish-green coloration.
The acetate, CioH704Ac, m. p. 75°, is with difficulty obtained in a pure
and colourless state. Furoin dissolves freely in aqueous or alcoholic
solutions of soda, forming a deep red liquid, which appears bluish-
green by transmitted light. On passing a rapid current of air
through the solution, oxidation takes place, the colour changes, and
crystals of furil, C4H3O.C2O2.C4H3O, are deposited. By recrystallisa-
tion from alcohol this compound is obtained in golden needles
(m. p. 162°), soluble in chloroform and in hot alcohol.
An unstable acid appears to be formed by the action of a concen-
trated potash solution on furil. When such a solution is neutralised
with sulphuric acid and extracted with ether, a thick oily liquid is
obtained, which dissolves in alkalis and in ether. It undergoes a rapid
spontaneous transformation into a black solid mass, insoluble in the
usual solvents. A chloroform solution of -furil is not attacked by bro-
mine or chlorine, but when the dry compound is brought in contact
with excess of pure bromine, an octobromide, CioH6Br804, is produced.
The bromide is soluble in hot chloroform, but is partially decomposed
by recrystallisation. The crystals change colour at 150°, and melt
with decomposition at 185°, bromine and hydrobromic acid being
evolved, whilst d'tbromofuril, CioH4Br204, remains. By dissolving the
residue in hot alcohol and boiling with animal charcoal, the dibromo-
furil is obtained in golden plates (m. p. 183°). The mother-liquor
contains a yellow crystalline compound (m. p. 110°), soluble in alcohol
and ether, whose composition has not been ascertained.
Benzofuroin, Ph.CO.CH(OH).C4H30 or Ph.CH(OH).CO.C4H30, is
produced when a mixture of furfuraldehyde (18 parts), benzaldehyde
(20), alcohol (60), water (80), and potassium cyanide (4), is boiled
for 15 minutes in a flask provided with an upright condenser.
After successive recrystallisations from hot water, benzene, and
alcohol, the pure compound is obtained in crystals melting at 138°.
ORGANIC CHEMISTRY. 799
In its properties it occupies an intermediate position between benzoin
and furoiu. W. C. W.
New Lactones. By R. Fittig (Ber., 13, 955— 956).— To the
class of bodies styled lactones (this vol., p. 378) the following have
been added. Lactone of normal caproic acid, CeHmOj, obtained by
boiling the bromocaproic acid from hydrosorbic acid with water ; it
is a liquid boiling at 220°. Lactone of normal valerianic acid,
C5H8O2, obtained by boiling the addition-compound of allyl acetic
and hydrobromic acid with water ; it is a liquid, and boils at 206 —
207°. A third lactone has been obtained by the dry distillation of
terpenylic acid, the homologne of terebic acid. This lactone is a
liquid, containing seven atoms of carlxjn, and boils at 203 — 204°.
The above lactones may be distilled without decomposition, are
volatile in steam, and dissolve in water, forming neutral solutions,
from which they may be separated by addition of alkaline carbonates
as oils. "When boiled with caustic alkalis they yield salts of the cor-
responding hydroxy-acids. P. P. B.
Double Salts of the Lower Members of the Acetic Acid
Series. By A. Frrz (Ber., 13, 1312— 1316).— The following- double
salts of propionic acid were prepared : —
Ba(C3H502)2 + 2Ca(C:,H502)2, regular octohedrons.
Sr(C3H502)2 + 2Ca(C3H50o)2, resembling the preceding compound
in appearance, but crystallising in a combination of the quadratic
pyramid and secondary prism 1:1: 0'9759.
Pb(C3H502)2 + 2Ca(C3H502)2 is isomorphous with the calcium
strontium double salt.
Ba(C3H502)2 + Mg(C3H502)2 + H3O crystallises in a combination
of the cube, dodecahedron, and tetrahedron.
Pb(C3H502)3 + Mg(C3H502)2 + HjO resembles the preceding salt.
Calcium barium butyrate crystallises in anhydrous regular octo-
hedrons.
Sodium formate acetate, !N'aC2H303 + NaCHOa + 2H.0, forms mono-
clinic crystals, a : b : c = 2-101 : 1 : 0-617; |S = 86° 21'.
Barium isobutyrate and acetate, (C4H702)2Ba + (C2H302)2Ba -f HjO,
resembles in crystalline form the double acetate and propionate of
barium. W. C. W.
Dichloracrylic Acid. By 0. Wallach (Annalen, 203, 83—
94). — In the preparation of dichloracrylic acid by the action of nascent
hydrogen on chloralide (Ber., 10, 567, and this Journal, 1877, ii, 591),
the formation of monochloracrylic acid can be avoided by stopping the
operation before the whole of the chloranilide is decomposed. The
acid CCLJCH.COOH melts at 76° and solidifies at 59°. By sud-
denly cooling the melted acid, it is converted into a modification melt-
ing at 63°. The addition of dilute sulphuric acid to an aqueous
solution of a pure dichloracrylate throws down needle-shaped crystals
of the free acid. From impure salts, the acid is precipitated as an
oily liquid.
Barium dichloracrylate, (CCI2 ! CH.COO)oBa + 2H.,0, crv.stallises in
3 k 2
800 ABSTRACTS OF CHEMICAL PAPERS.
six-sided plates, probably belonging' to tbe monoclinic system. The
calcium salt forms crystals resembling tbose of tlie barium salt, and
also crystallises in needles. The free acid is not attacked by water
at 200°, bnt is decomposed by boiling baryta water, with formation
of monochloracetylene. The reaction prolDably takes place in two
stages, chloropropiolic acid being first formed, which afterwards splits
up into spontaneously inflammable chloracetylene and carbonic anhy-
dride (Ber., 11, 751 ; 12, 57 ; and this Journal, Abst., 1878, 653 ; and
1879,453).
These reactions show that this acid is not identical with that ob-
tained by Bennett and Hill {Ber., 12, 655, and this Journal, 1879,
Abst., 616) from chloromucic acid.
/3-monochloracrylic acid is not decomposed by baryta-water at
130°. W. C. W.
Constitution of Liquid Chlorolactic Acid and of Oxyacrylic
Acid. By P. Melikoff {Ber., 13, 956— 958).— By treatment with
zinc and sulphuric acid, liquid chlorolactic acid yields propionic acid
and a lactic acid, which, when treated with hydriodic acid, gives crys-
talline /3-iodopropionic acid, m. p. 82'5°. The formation of the latter
shows liquid chlorolactic acid to be chlorhydracrylic acid, i.e., an
a- derivative.
The formation of oxyacrylic acid from a-chlorolactic acid is similar
to that of epichlorhydrin from dichloropropyl alcohol, thus : —
CH,(0H).CHC1.C00H + KHO = <(^^ >CH.COOK + 2H2O -|-
KCI.
Oxyacrylic acid, like epichlorhydrin, unites with hydrochloric acid,
yielding (S-chlorolactic acid, whilst the latter yields dichlorhydrin.
Oxyacrylic acid is the inner anhydride of glyceric acid, and there-
fore the author styles it glycidic acid. It unites with ammonia, form-
ing an amido-derivative. P. P. B.
/3-Bromolactic Acid. By P. Melikoff {Ber., 13, 958).— This
compound is obtained by the action of hydrobromic acid on glycidic
acid. After removal of hydrobromic acid and extraction with
ether, it is obtained in prismatic crystals, m. p. 89 — 90°. It is soluble
in ether and water in all proportions. P. P. B.
Amidolactic Acid. By P. Melikoff {Ber., 13, 1265— 1266).— In
support of the hypothesis that the formation of amidolactic acid by
the action of ammonia on ethyl chlorolactate takes place in two stages,
viz., that glycidic acid is first produced by the elimination of hydro-
chloric acid, and then converted into amidolactic acid by direct union
with ammonia, the author states that the /:J- amidolactic acid obtained
by the action of ammonia on glycidic acid at 120° is identical with the
acid derived from ethyl a- or /3-chlorolactate.
Serine from silk has the constitution of an a-amidolactic acid.
w. c. w.
ORGANIC CHEMISTRY. 801
Diethylidenelactamic Acid. Bj W. Heixtz (Annalen, 202,
375 — 37*)). — A claim lor priority.
Action of Iodine on the Silver Salts of Bibasic Acids. By
K. BiKxnAi'M and J. Gaieh {Ber., 13, 127u — 1-272). — On gently beat-
ing an intimate mixture of iodine and silver succinate, malate, fuma-
i*ate, or tartrate, the following changes occur : — The silver and iodine
combine, the acid splits up into anhydride and oxygen, and the nascent
oxygen attacks the anhydride, converting a portion of it into carbonic
oxide, carbonic anhydride, and water ; the remainder of the anhydride
unites with the water, forming an anhydro-acid. This reaction is in
certain respects analogous to the electrolytic decomposition of aqueous
solutions of these acids.
Silver oxalate is completely converted by the action of iodine into
silver iodide and carbonic anhydride. W. C. W.
Preparation of Malonic Acid. By E. BorEGOiN {Gompt. rend.,
90, 12^y — 12'Jl). — lOU grams of monoehloracetic acid are dissolved
in their own weight of water and saturated with potassium carbonate,
71 grams of powdered potassium cyanide are then added, and the
whole is carefully heated on a water-bath ; a brisk ebullition, attended
by considerable evolution of heat, ensues, but the liquid remains per-
fectly colourless. To this solution twice its volume of strong hydro-
chloric acid is added, the potassium chloi'ide which separates is re-
moved, and the whole is then saturated with hydrochloric acid gas ;
the potassium chloride and sal-ammoniac are again separated, washed
with hydrocliloric acid, and the liquid is evaporated nearly to dryness
on a water-bath ; the residue is exhausted with ether and the ethereal
solution distilled, when about 70 grams of perfectly pure malonic acid
are obtained. From the mother-liquors, by suitable treatment, about
20 grams more of the acid can be procured, which requires recrystal-
lisation from ether to purify it. Although a small quantity of acetic
acid is formed, according to the equation C3H4O4 = CO2 + C2H4O2,
the yield of malonic acid is almost theoretical. J. W.
Synthesis of Citric Acid. By E. Grimaux and P. Adam (Compt.
rend., 90, 1202 — 1255). — The artificial formation of citric acid was
realised in the following manner: — Symmetrical dichloracetone was
prepared by oxidation of the symmetrical dichlorhydrin of glycerol.
It was purified by combination with sodium hydrogen sulphite and
then heated in a water-bath with concentrated hydrocyanic acid. The
cyanodichloracetone, which is a crystalline body, was not isolated, but
treated directly with hydrochloric acid ; the product, when the reaction
was complete, was distilled in a vacuum and the residue taken up by
ether. On evaporation a thick syrup remained, which, after a few
days, solidified to a mass of crystals of dichloracetonic acid, —
0H.C(CH,C1)2.C00H.
These crystals were in the form of transparent laminae, fusible at 90
— 92° ; very soluble in alcohol, water, and ether ; not volatile without
decomposition, except at a very gentle heat, when partial sublimation
takes place.
802 ABSTRACTS OP CHEMICAL PAPERS.
The dicliloracetonic acid was saturated with sodium carbonate and
heated with two molecules of potassium cyanide in concentrated solu-
tion ; the sodium dicyanoacetate was not separated but saturated with
hydrochloric acid gas, and heated in a water-bath for 15 hours.
After volatilising the hydrochloric acid, the citric acid was extracted
from the residue by careful neutralisation and precipitation with milk
of lime. The insoluble lime salt was decomposed by sulphuric acid, and
the solution, after concentration in a vacuum, was left to spontaneous
evaporation.
The identity of the artificial product with the natural acid was
proved by analysis and by crystallographic comparison under the
microscope. Its melting point was 146 — 147°. J. W.
Electrolysis of Benzene. By A. Renard {Compt. rend., 91, 175
— 177). — The electrolysis of a mixture of benzene, alcohol, and dilute
sulphuric acid gives a crystalline product soluble in water, alcohol,
and ether. This substance the author names isobenzoglycol, and assigns
to it the formula C6H6(OH)3. Heated ina sealed tube with acetic acid
it yields isobenzoglycol diacetate, C6H6(OAc)2. It is insoluble in water,
but soluble in alcohol or ether (m. p. 121°, b. p. about 300°).
R. R.
Influence of Constituents of Wood Spirit on the Production
of Dimethylaniline. By G. Kramer and M. Grodzky (Ber., 13,
1005 — lOlO). — The most hurtful constituent of crude wood-spirit
is acetone ; it lessens not only the yield of volatile bases, such as
dimethylaniline, but also that of the non-volatile ammonium com-
pound. Further, the violet obtained by the oxidation of such bases is
not good. By using pure acetone alone, a base was obtained boiling
at 220 — 230°, which on oxidation yielded a blackish-green mass. The
base produced by this acid belongs to the acetonamine bases, and
has the composition MboC '. NPh. From this it is seen that 1 mol.
acetone uses 1 mol. aniline. The presence of about 10 per cent, of
water in pure methyl alcohol has very little influence on the yield of
methylated aniline. Every increase of the proportion of methyl alcohol
to aniline above the theoretical amount tends to decrease the yield of
dimethylaniline, but increases that of the non-volatile ammonium com-
pounds. Impure methyl alcohols yield smaller quantities of volatile
bases, and the tubes on opening show much higher pressure, owing to
the formation, in some cases, of methyl ether. A mixture of 4"8 c.c.
of ethyl with 30 c.c. methyl alcohol gave the same yield as pure
methyl alcohol. When the higher alcohols are used, they are partially
decomposed into water and the corresjjonding olefines.
P. P. B.
Aromatic Guanidine-compounds. By F. Berger (Ber., 13,
992 — 994). — Glijcolymotwphenylg'uanidine, C9H11N3O2, is obtained by
the action of an alcoholic solution of glycocine containing a little
ammonia on phenylcyauamide. The residue obtained on evaporating
the solution to dryness, is dissolved in hydrochloric acid and ammonia
added, when the above compound is precipitated in small, round,
yellow grains. It turns brown at 240°, and melts at 260° with decom-
position. By evaporation of its solution in hydrochloric acid, it is
ORGANIC CHEMISTRY. 803
decomposed, gljcocino being formed. Its tormation is expressed as
follows : —
CH2(NH2).COOH + CN.NHPh = COOH.CH..NH.C(NHPh) : NH
Attempts to prepare the isomeride phenylglycocyamine from, phenyl-
glycociue and cyanamide have proved unsuccessful.
The hydrochloride of ft-dlcyandiorihotohjlguanidine, CoaHioN^sCl +
H;.0, is obtaiued by boiling dicyandiorthotolylguanidine with aniline for
half an hour ; ammonia is then evolved, and when the product is poured
into hydrochloric acid, the above compound separates out. It is
sparingly soluble in hot alcohol, forming a dark red solution, from
which it separates on cooling in fine needles of a brownish-red colour
and violet lustre. P. P. B.
Creatine-compounds of the Aromatic Group. By P. Griess
(ifer.,13, 977 — 979).— 1. Ortltohenzylglycocyamidine,
This compound is obtained in a manner analogous to glycocyamidine,
viz., by the action of aqueous solutions of cyanamide on 1 : 2 amido-
benzoic acid, thus : —
NHo.C6H,.C00H + XH^.CN = C.H^NaO + HoO.
It is also formed when the compound doHioNoOa, described by the author
(Ber., 2, 417) as resulting from the action of cyanogen on an alcoholic
solution of 1 : 2 amidobenzoic acid, is treated with ammonia, thus :—
EtO.CN.CO .TTT pn
I I + NH3 = NH : C<^.5 J:^^ > + EtHO,
a,-Orthohenzylcreatinine,l^^'.C<^^yr p tt >, is obtained by acting
on an alkaline solution of orthobenzylglycocyamidine with methyl
alcohol and methyl iodide in the cold. It crystallises from water in
small shining needles, sparingly soluble in hot water and ether, but
easily in boiling alcohol. It has a bitter taste and neutral reaction ;
melts to a colourless oil and may be distilled ; alkalis do not act on
it. The hydrochloride, C3H9N3O.HCl.H2O, crystallises in narrow
leaflets, easily soluble in cold water. The platinochloride,
(CsHgNaO.HCO.PtCU + 2H2O,
crystallises from hot water in bright yellow needles, or in small
rhombic six-sided prisms.
iS-Orthobe/izylcreatinine, C9H9N3O, is obtained in a manner similar
to benzylglycocyamidine by acting on the compound CioHioN302 with
methylamine, in sealed tubes at 100°. It crystallises from water in
white needles. In many properties it resembles the a-derivative, but
differs from it in being soluble in alkaline solutions, and reprecipitated
from them by acetic acid. The hydrochloride, C9H9N3O.HCI, forms
small tables or prisms having yitreous lustre. It is decomposed by
804 ABSTRACTS OF CHEMICAL PAPERS.
pure water, and can only be crystallised from water containing hydro-
chloric acid. a-Benzylcreatinine has stronger basic properties than
the /3- derivative. The B-plaHnocldoride, (C9H9N30.HCl)2PtCl,, forms
pale yellow narrow leaflets, united into stellate groups. It is only
sparingly soluble in hot water. P. P. B.
Aromatic Amidoketones. By O. Doebner {Ber., 13, 1011 —
1014). — Benzoyl-piitlialylauUide, C21H13NO3, is obtained by heating
benzoic chloride with phthalylanilide and zinc chloride at 180°. The
product, after recrystallisation from glacial acetic acid, yields this com-
pound in large colourless needles (m. p. 183°). It is neither acted on
by acids nor by alkalis, is insoluble in water, and only sparingly
soluble in alcohol or ether. When boiled with alcoholic potash, it
yields phthalic acid and benzoylaniline.
Benzoylaniline, C6H5.CO.C6H4.NH2, crystallises from dilute alcohol
in colourless, shining leaflets (m. p. 124°). It is but sparingly soluble
in water, largely soluble in alcohol, ether, or glacial acetic acid. Hy-
drochloric acid dissolves it easily, forming a hydrochloride, from
which alkalis and ammonia precipitate the base. Its hydrochloride
crystallises from water in large crystals, the sulphate in needles which
are less easily soluble than the hydrochloride. The platinochloride
crystallises in yellow needles. P. P. B.
An Azobenzenesulphonic Acid. By Mahrenholtz and Gilbert
{Annalen, 202, 381 — 340). — This acid may be prepared from meta-
nitrobenzenesulphonic acid by two methods. In the first process,
sodivim amalgam in theoretical quantity is added to a concentrated
solution of potassium metanitrobenzenesulphonate. The action being
ended, the solntion is acidified with sulphuric acid, and the sodium sul-
phate removed by crystallisation, C^'aporation, and addition of alcohoh
Finally, the mother-liquor is treated with barium carbonate, and the
sparingly soluble barium azobenzenesulphonate collected.
A better process consists in adding to potassium metanitrobenzene-
sulphonate dissolved in six times its weight of cold water, half its
volume of zinc-dust, and caustic potash in excess. The mixture is
stirred and heated on the water-bath until hydrogen begins to escape,
then rapidly filtered to avoid formation of hydrazo-acid, and the zinc
precipitated by carbonic acid. Potassium azobenzenesulphonate may
be separated from the filtrate by crystallisation.
Azobevzenesulphonic acid, C6H4(S03H)N !]SrC6H4(S03H), separated
from its barium salt by sxilphuric acid, remains on evaporation of its
solution as a syrup, which crystallises on standing over sulphuric acid.
It is deliquescent, and very soluble in alcohol and ether. It yields
only neutral salts, of which those of ammonium, potassium, sodium,
barium, and calcium ai'e described : they are easily soluble in water,
with the exception of the barium salt.
Azobenzenesulphonic chloride, C12HSN2S2O4CI2, is easily formed by
warming the dry potassium salt with phosphoric chloride, washing
with water, drying, and exhausting with ether. It forms ruby-red
needles (m. p. 166°). The chloride dissolves easily in absolute alcohol,
and on concentrating the solution and allowing it to stand, golden-
ORGANIC CHEMISTRY. 805
yellow needles of etlujl azohenzene.fidphonafe, CnHgEtoNoSoOfi, separate,
(m. p. 10U°). These are scarcely soluble in water, but soluble in alcohol
aud ether.
AzobenzenesuIpJionaynide, Ci..HhN2S20i(NHo)2, is formed by treating
the chloride with strong ammonia, evaporating, and extracting the
residue with boiling alcohol, from which it separates in yellow needles
(ra. p. '295") or in crusts of radiating groups of prisms. It is sparingly
soluble in boiling water and alcohol. A body similarly constituted,
but having quite different properties, is obtained by warming a solution
of metaniti-obenzenesulphonamide in caustic soda with zinc-dust, and
precipitating with hydrocliloric acid. This body (m. p. 254°) is very
sparingly soluble in alcohol, ether, benzene, toluene, and acetic acid,
and crystalli.ses from hot alcohol in small reddish-yellow needles.
Paranitrobenzenesulphonamide (m. p. I'SV) on similar treatment
yields an azobenzenesulphouamide (m. p. 176^\ which is much more
soluble in alcohol and water, and crystallises in yellow tables.
Hi/drazobenzenesulp})0)dc acid, CioHioN-iSoOe-^HoO, is obtained from
the azo-compound by heating it with ferrous sulphate and caustic soda
in excess, by the prolonged action of sodium amalgam, by prolonged
boiling with zinc and caustic potash, but most easily by the action of
stannous chloride. A solution of the azo-acid becomes very hot when
mixed with stannous chloride, and after 48 hours the whole of the
hydrazo-acid crystallises out in colourless monoclinic prisms, with
many secondary faces. It is sparingly soluble in hot water, less so in
cold, and insoluble in alcohol or ether. It is not converted into the
amido-acid by digestion at a high temperature with stannous chloride
or with hydriodic acid. Potassium, barium, and lead salts have been
prepared.
An acid chloride could not be obtained by the action of phosphoric
chloride either on the acid or on its potassium salt. The amide,
CpH.oNjS.O^CNHa)^,
is apparently formed by heating the alcoholic solution of azobenzene-
sulphouamide (m. p. 295°) with stannous chloride. It separates from
the filtrate in white prisms. Ch. B.
Two Azobenzenedisulphonic Acids. By H. v. Reiche (Annalen,
203, ti4 — 72). — Two nitrubenzenedisulphonic acids were prepared
from benzenemetadisulphonic acid, and were puritied by the method
described by Heinzelmann (Annalen, 188, 157 — 16U, and this Journal,
1877, p. 771). In order to prepare the azo-derivatives, the barium
salts of these acids are boiled with concentrated baryta-water and
zinc-dust until a rapid evolution of hydrogen takes place, the mixture
is then filtered, and the barium and zinc precipitated by carbonic
acid. The filtrate deposits needle-shaped crystals of barmm azobenzene-
disiilphunate.
a-AzobemenedisulphoniG acid, (S03H)oC6H3.N '. N.C6H3(S03H)2, is a
dark syrupy liquid, forming soluble salts. It crystallises when left in a
vacuum over sulphuric acid, but speedily deliquesces on exposure to
the air. It is precipitated by alcohol from an aqueous solution as a
resinous mass. The potassium salt. CnHeKjNoSiOio + SHaO, foi'ms
806 ABSTRACTS OF CHEMICAL PAPERS.
microscopic prisms soluble in water, but insoluble in alcohol ; the
ammonium salt is a yellow crystalline mass, soluble in alcohol. The
barium, salt is deposited in white needles containing 5H2O, insoluble in
alcohol. The lead salt is precipitated from the aqueous solution by
alcohol as a crystalline powder.
cc-Hydrazobenzenedisulphonic acid —
(S03H),CGH3.T^H.I^H.CaH3(S03H)3,
prepared by the action of stannous chloride on azobenzenedisulphonic
acid, is a syrupy liquid which bears the closest resemblance to theazo-
acid. The potassium salt, Ci2HnK4N2S40ia.2H20, forms small plates ;
the acid potassium, salt, C12H10K0N2S4O12 + 2|-H20, crystallises in
reddish scales of a silky lustre. The barium salt, Ci2H8Ba)N2S40i2 +
7^}liO, forms efflorescent needles insoluble in alcohol, and the lead salt
crystallising with 4H2O is also efflorescent.
By the action of nitrous acid on the bydrazo-acid, benzenemetadisul-
phouic acid is produced.
The following salts of ^-azobenzenedisulplionic acid were prepared: —
C,2HoK4N2S40i2.3H20 and Ci2H6Pb2N2S40.2.:cH20 form red crystalline
crusts insoluble in alcohol ; the barium salt is deposited in yellowish-
red flat needles containing 4 mols. of water of cry.stallisation.
^-Azobenzenedisulphonic chloride, Ci2H6N2S408Cl4, crystallises from
ether in broad needles (m. p. 58°). By the action of ammonia on the
preceding compound the amide is obtained in white needle-shaped
crystals (m. p. 222°), which are sparingly soluble in warm alcohol.
^-Hydrazobenzenedisulpjhonic acid forms crystalline potassium and
barium salts. If the solution of the acid is half neutralised with
potash, and treated with nitrous acid, diazobenzenedisulphonic acid is
produced. W. C. W.
Two Azotoluenesulphonic Acids. By A. T. Neale {Annalen,
203, 73 — 83). — The potassium salt of azotoluenesulphonic acid,
(S03H)C6H3Me.N : N.CeHsMeCSOsH)-!- 7iH20[Me : N : S03H=1 : 2 : 4],
is obtained by boiling an aqueous solution of potassium orthonitro-
tolueneparasulphonate with potash and zinc-dust. When the hydro-
gen begins to escape in considerable quantities, the mixture is filtered,
in order to prevent the further reduction of the compound to
orthamidoparatoluenesulphonic acid. Potassium azotuluenesulphonate,
Ct4HijKoN3S206 + 2|^tl20, forms beautiful red prisms, which dissolve
freely in hot water, but require 100 parts of water at 18" to dissolve
2"56 parts of the anhydrous salt. From the potassium salt, the other
metallic azotolufenesulphonates can be prepared by double decomposi-
tion. The barium and lead salts crystallise in red-coloured prisms,
containing 4 mols. H2O. They are sparingly soluble in water. The
calcium salt forms freely soluble red crystals containing SHjO. The
free acid crystallises in long prisms of a pink colour, which decompose
at 180° without melting. The sulphonic chloride, Ci4Hi2N2S204C]2,
is deposited from a solution in hot benzene in red-coloured prisms
containing 2 mols, benzene, which escape on exposure to the air. The
chloride (m. p. 220"") is sparingly soluble in ether. Hydr azotoluene-
sulphonic acid, CuHieNoSoOe + 2^)3ioO, separates as a white, crystalline,
ORGANIC CHEMISTRY. 807
sparingly soluble ]~owdcr, when an aqueous solution of the azo-acid is
treated with stannous chloride. On exposure to the air, the acid
assumes a red colour, due to its oxidation to the azo-acid. The
h}'drazot()luenesnlphonat(<s arc freely soluble in water, the potassium
salt, CmHuKoXjS.;06, is anhydrous ; the barium salt ci'ystallises with
5 and the calcium salt with 3^ H^O. They are both efflorescent.
The crystals of lead hydrazotoluenesulphonate contain "Z^H-iO, and
resemble calcium oxalate in form.
2. Azotoluenesidphonic acid [Me : SO3H : X = 1 : 2 : 4], prepared
from potassium paranitrorthotoluenesulphonate forms brown-coloured
rhombohedrons containing 7^1120. The crystals are freely soluble
in water and alcohol ; they melt in their water of crystallisation at 100",
and the anhydrous acid decomposes at 190° without melting. The
following salts were prepared: CUH12K2N0S2O6 + oHoO, CuHiaCaXoSoOs
-h 3HaO, yellow crystals ; CuHi-.PbX.SoOs + 2H3O, dark-brown crys-
tals. These three salts are freely soluble in water; the barium salt
forms orange-coloured microscopic needles (containing 1 mol. H^O),
sparingly soluble in water. Azotoluenesidphonic chloride is deposited
from benzene in deep red-coloured crystals (m. p. 194-°). The amide
is a yellow crystalline compound (m. p. 207°), soluble in alcohol. The
hydrazo-acid has not yet been obtained. An attempt to prepare it by
the action of stannous chloride on the azo-acid yielded paramido-
tolueneorthosulphonic acid. W. C. W.
An Azoxybenzenesulphonic Acid. J3y C. Bruxnemaxx (Anna-
ten, 202, 3-iO — ooUj. — Of the three known nitrobenzenesulphonic
acids only the meta-compound has been reduced to azoxy-acid. This
may be effected, but not satisfactorily, by heating with alcoholic potash,
or with zinc and potash. The best process consists ia boiling the acid
for four to six hours with alcoholic potash under an excess pressure of
400 mm. of mercury. The aqueous solution of the product, when
saturated with carbonic anhydride and evaporated, deposits the potash
salt, which may be obtained in needles by crystallisation.
C6H4(S03H).N
Azoxyhenzenesulphonic acid, \ yO, is obtained by de-
C6H,(S03H).n/
composing its barium salt with dilute sulphuric acid. It forms
microscopic needles, which are very hygroscopic, and soluble in alcohol,
ether, and water (m. p. 125°). Only neutral salts could be obtained;
those of ammonium, potassium, barium, calcium, and lead are de-
scribed. The barium and lead salts are sparingly soluble in water,
the others easily soluble.
Azoxyhenzenesulphonic chloride, CiaHaXoSaOsCla, is easily produced by
warming the potassium salt with phosphoric chloride. It is easily
soluble in benzene and ether, and crystallises from toluene in
yellowish-red oblique rhombic prisms (m. p. 138°). On heating it
with water at 14U'' not only azoxy-, but also much hydrazo-benzene-
sulphonic acid is formed. Treated with strong ammonia it yields an
amide, CnHsXsSoOs (XH2)2, crystallising in yellow monoclinic prisms
(m. p. 273°), very sparingly soluble in hot water, more easily in
alcohol.
808 ABSTRACTS OF CHEMICAL PAPERS.
The free azoxy-acid is not acted on by dry bromine. Its solution is
unaffected by sulphurous acid or by nitrous acid, but hydrogen sulphide
passed into its amraoniacal solution reduces it to azo-acid. The same
reduction is effected by sodium amalgam, whilst acid stannous chloride
converts it into the hydrazo-acid.
The anthor confirms the statements of Mahrenholtz and Gilbert
with regard to hydrazobenzenesulphonic acid, and describes several
new salts of it. It cannot be reduced to amido-acid; and neither the
inverse change, nor the oxidation of azo- to azoxy-acid, can be effected
by potassium permanganate. Water has little action on it, even at
240°. Dilute hydrocidoric acid at 230° partly decomposes it into sul-
phuric acid and benzidine. In this reaction, benzidinesulphonic acid is
first formed, and may be detected by heating the hydrazo-acid with strong
hydrochloric acid at 140° for five hours, evaporating and boiling the
residue with barium carbonate, when brilliant tables of Griess's barium
benzidinesulphonate may be obtained (^Annalen, 154, 213). The re-
action may be thus formulated —
C,,H:oN2(S03H)2 + H,0 = C,,HuNo(S03H) + H2SO4.
When hydrazobenzenesulphonic acid is suspended in water, and
treated with nitrous acid, it yields a diazo-compound, CioHinN4S208.2H^O,
fully described by Baleutine. Boiling with water decomposes this
compound, thus —
Cio.HioNiSoOb + HoO = 2C6H6SO4 + 4N + 0,
the liberated oxygen oxidising a portion of the substance.
The phenolsulphonic acid formed yields a barium salt,
[C6H4(OH).S03]3a.2H,0,
and a potassium salt, C6H4(OH).S03K.liH20, the solutions of which
give a violet colour with ferric chloride. Treated with chromic
mixture, they evolve an odour of quinone : the acid is probably there-
fore a para-compound. Evaporation with strong nitric acid converts
the free acid into dlnitrop]ienoJsul]jhonic acid, which yields both a
neutral and an acid potassium salt. Ch. B.
Dibrom- and Tetrabrom-hydrazobenzenesulphonic Acids.
By O. JuRDAN (Annalen, 202, 3GU — 371). — Hydrazobenzenesulphonic
acid is not acted on by dry bromine ; but when the finely-po-n dered
acid is covered with at most twice its weight of water, and bn mine
gradually added until a little acid remains undissolved, a mixtrre of
tetrabrominated and dibrominated derivatives is obtained in solution.
On concentrating the filtered liquid and allowing it to stand, the tetra-
brominated acid separates, and may be purified by crystallisation from
boiling water with the aid of animal charcoal. The process is repeated
until the mother-liquor forms a brown syrup ; from this the dibromo-
acid may be extracted by evaporating to dryness, dissolving in water,
precipitating with basic lead acetate, and decomposing the precipitate
by hydrogen sulphide. By crystallisation from water with aid of
animal charcoal it may be obtained pure.
ORGANIC CHEMISTRY. 809
Tetrabromhydrazohenzenesulphonic acid,
C«H,Br,(S0,H).NH.NH.C6H,Bro.S0,H + 4HA
is obtained by very slow crystallisation in transparent, almost colour-
less, efflorescent tables. When rapidly deposited, the crystals are
needles with only 2 mols. of water. The acid is easily soluble in
■water, less so in alcohol and ether. It is decomposed by sunlight
and by heat. At 170°, the crystals become black and insoluble in the
usual solvents, in acids, or in alkalis. Tt yields a brown solution
with concenti"ated sulphuric acid, from which water separates brown
flocks. It forms both neutral and acid crystalline salts, of which
those with ammonium, potassium, barium, calcium, lead, and silver,
have been prepared, and are fully described. The acid silver salt,
CuHTBriNoSjOsAg, crystallises from water in oblique rhombic prisms ;
the neutral salt, Ci2H6Br4N2S206Ag2, is obtained by double decomposi
tion in microscopic tables, scarcely soluble in water. Hot dilute nitric
acid converts it almost completely into the acid salt. Its ammoniacal
solution yields on evaporation grey- coloured prisms,
C,2H3r4NoS206Ag(NHi) .
On warming the potassium salt with phosphoric chloride, a dirty
yellow mass is obtained, which dissolves in ether, but does not crj-stal-
lise from it. It is probably an acid chloride ; it melts with decom-
position above 210°.
On passing nitrons acid into a solution of the tetrabrominated acid,
yellow tabular crystals of a diazo-compound, CiiHeBrjXjSaOs, separate.
They are sparingly soluble in water or alcohol. The decomposition-
products with water and hydrobromic acid could not be obtained pure.
The tetrabrominated acid does not part with its bromine when
treated with sodium amalgam. Its silver salt is decomposed by water
at 200—210", thus—
Ci2H6Br,N2S20sAg2 -I- 2HoO = CioHioBr2X2S206 + 2AgBr + O2,
part of the substance being oxidised by the liberated oxygen.
Dibromhydrazobenzenesulphonic acid, Ci2HioBr2ls"2S206.H20, crystal-
lises in delicate colourless needles, which easily form a reddish solution
in water, but are only sparingly soluble in alcohol or ether. It forms
neutral and acid salts, of which those with potassium, barium, calcium,
lead, and silver are described. The silver salt,
forms dirty white prisms, easily soluble in water, and blackened by
light.
An acid chloride could not be obtained. The diazo-compound,
obtained in the usual way, forms yellow rhombic prisms, which defla-
grate at 90°.
The silver salt above mentioned is decomposed by water at 220°,
Yielding metallic silver, some silver bromide, and free acid.
Ch. B.
Diazo-compouad ot Hydrazobenzenesulphonic Acid. By
"W. Balentine (Annalen, 202, 35] — 360). — This diazo-compound,
CuHioXiSaOs -I- 2H2O, is prepared, either by passing nitrous acid into
810 ABSTRACTS OF CHEMICAL PAPERS.
water, holding in snspension the finely powdered acid, and precipitating
with alcohol, or better, by passing the gas into a cold solution of the
potassium salt of the acid. It is deposited from its warm aqueous solu-
tion in rhombic tables, or may be precipitated therefrom by alcohol in
the form of slender needles of a dirty white colour. It is tolerably
soluble in warm water, but with difficulty in cold water or alcohol. It
explodes at 93 — 94°, but slowly gives off nitrogen above 90°, leaving a
brown amorphous residue, CuHmSoOs, which is not taken up by the
usual solvents, but dissolves in alkaline solutions, without, however,
forming crystallisable compounds. When heated with absolute
alcohol under an excess pressure of 400 mm. of mercury no aldehyde
is produced, and the amorphous brown product of the action is quite
insoluble in alcohol, water, ether, or aniline, but soluble in alkalis,
forming sparingly soluble uncrystalli sable compounds. Analysis
yielded very discordant results.
If the solution obtained by passing nitrous acid into potassium
hydrazobenzenesulphonate until gas begins to be evolved is evaporated
to dryness, the residue yields by crystallisation acid potassium dinitro-
phenolsul]jJwnate, from which the free acid may be extracted by treat-
ing it with sulphuric acid, and digesting with alcohol and ether.
Dinitrophenolsulphonic acid, C6H2(lSr02)2(OH).S03H.3H20, forms
greenish oblique rhombic prisms, which dissolve easily in water, less
easily in alcohol and ether. It decomposes at 160°, and forms both
acid and neutral salts. The acid potassium salt is yellow, the neutral
red; both are readily soluble in water and weak alcohol. Ch. B.
Action of Sulphuric Acid on Aromatic Sulphydrates. By
R. Otto (-Be;-., 13, 1290 — 1292). — The author confirms the accuracy
of Stenhouse's observation (Annalen, 149, 247), that thiophenol is
converted into phenyl disulphide by the action of sulphuric acid. A
\ello wish- white compound insoluble in alcohol and ether is formed at
the same time.
Paratoluene and benzyl sulphydrates undergo analogous changes
when treated with sulphuric acid or sulphuric monochloride.
w. c. w.
Beckurts' Toluenemetasulphonic Acid. By R. Otto (Ber., 13,
1292 — 1294). — A chemical examination of a specimen of Beckurts'
toluenemetasulphonic acid (Ber., 10, 943; and this Journal, 1877,
2, 774) shows that this substance is a mixture of toluenepara- and
ortho-snlphonic acids. This result a2:rees with Fahlberg's statement
(Ber., 12, 1048; and this Journal, 1879, Abst., 804). W. C. W.
Constitution of the Sulphinic Acids. By R. Otto (Ber., 13,
1272 — 1283). — New Si/vtJie-^es of Su.Jpho)tes. — The sulphones can be
readily prepared by warming an alcoholic solution of a sodium sul-
phinite with an alcoholic bromide. When the reaction is complete,
the alcohol is distilled off and the residue poured into water.
EthyJphevyh?iJjj]/oiie, PhEtSOj, prepared by this process, crystallises
in monoclinic plates (m. p. 42°), and is identical with the sulphone
which Beckmann obtained (J. pr. Chem., 17, 458) by the oxidation of
ethyl-phenyl sulphide with potassium pei^manganate. It is easily pre-
ORGANIC CHEJnSTRY. 811
pared by adding potassium permanganate to a solution of ethjl-phenyl
sulphide in warm glacial acetic acid.
EthijlparatohjlsuJ phone, Et(CGHiMe)S02, crystallises in rhombic
plates (m. p. 56°) insoluble in cold water, but freely soluble in ether,
benzene, chloroform, and warm alcohol. This substance is also formed
by the oxidation of ethyl paratolyl sulphide, a colourless liquid (b. p.
220^, sp. gr. 1"0016 at 17"5°) insoluble in water, but miscible in all
proportions with alcohol, ether, benzene, and glacial acetic acid. Di-
henzyhiilplirnie, (CH^PlO^SOe, forms small colourless needles or prisms
(m. p. 150°) of a silky lustre. It is soluble in benzene, glacial acetic
acid, and hot alcohol, and is converted by oxidation into benzoic and
sulphuric acids.
Paratolylbeuzi/lsulphone, CH2Ph.SO:-.CfiH4Me, crystallises in silkv
white needles (m. p. 145°) soluble in alcohol, benzene, and glacial
acetic acid. D i ethyls ul pit one, EtoSOj, has been previously described.
The author confirms Beckmann's statement (loc. cit-) that this com-
pound is not attacked by nascent hydrogen. This observation is in
direct opposition to v. Oefele's {Ann., 132, 90). Ethylenediphenylsul-
phone, Ph.SO2.CH2.CH3.SO2.Ph, forms silky needles or plates (m. p.
179"5°) sparingly soluble in hot water, more soluble in hot alcohol,
benzene, and acetic acid. It also dissolves in a dilute solution of
potash, forming potas.sium benzenesulphinate. At 150° ethylidene
chloride acts on sodium paratoluenesulphinate, forming a compound
which crystallises from alcohol in needles (m. p. 200°).
The conversion of the sulphinic acids into sulphones favours the
hypothesis that these acids are hydrides and do not contain the
hydroxyl group, and also that the sulphur-atom acts as a hexad and
rCsH.5'
■ J O"
not as a tetrad, e.g., benzenesulphinic acid, S'"< q-/
W. C. w.
Benzyl Derivatives Containing Sulphur. By R. Otto and R.
LuDERS {Ber., 13, 12^3 — 1289). — Benzyl -hydrogen sulphide,
CeH^.CHo.SH, is not converted into the disulphide by the action of
bromine, but yields an oily liquid, which is transformed into benzyl
hydrogen sulphide by nascent hydrogen. Dibenzylsulphone —
(C6H4.CH2)2S02,
can be prepared by oxidising with potassium permanganate a hot
acetic acid solution of benzyl oxysulphide (m. p. 1.33°) obtained by
treating benzyl sulphide with cold nitric acid, sp. gr. 1'3. It is iden-
tical with the dibenzylsulphone resulting from the action of benzoic
chloride on sodium benzylsulphinate.
Benzyl thiohenzoate, Ph.C0S.CH2Ph, forijaed by heating benzyl
hydrogen sulphide and benzoic chloride at 120°, is deposited from an
alcoholic solution in colourless triclinic crystals, which dissolve freely
in hot acetic acid, benzene and ether.
This compound is decomposed by alcoholic potash into benzoic acid
and benzyl-hydrogen sulphide, and is oxidised by potassium perman-
ganate, forming benzoic and benzenesulphonic acids.
812 ABSTRACTS OF CHEMICAL PAPERS.
BenzylsidpTiomc chloride, C7H7.SO2CI, prepared by the action of
pTiospliorus peniachloride on potassium benzylsulphonate, crystallises
in yellowish-white silky needles or prisms (m. p. 93°) soluble in warm
benzene or ether. It is decomposed by hot water, yieldinor hydro-
chloric and benzylsulphonic acids. The sulphonamide, C7H7.SO2.NH2,
forms white silky needles (m. p. 102°).
The sulphonic chloride is converted into benzylsul phonic acid by
warming with zinc-dust and water, or by reducing the solution in
benzene to which a few drops of water have been added with sodium
amalgam. The sodium salt of the acid crystallises in silky plates.
The free acid is very unstable, and decomposes with evolution of sul-
phurous anhydride.
When potassium benzylsulphonate is fused with potash in a retort,
toluene and a small quantity of benzene distil over, together with a
white crystalline compound (m. p. 106 — 110^), which is soluble in
alcohol. W. C. W.
Synthesis of Ethereal Salts of Thiosulphonates. -By E. Otto
(i)e/'., 13, 1282 — 1283). — Etlail thiohenzenesulplLonate or ethyl phenyl-
disnlph oxide, PhSOo.SEt, is formed on warming an alcoholic solution
of ethyl bromide and potassium thiobenzenesulphonate (prepared by
Spring's method, Ber., 7, 1157), viz., by the action of potassium sul-
phide on benzenesulphonic chloride. Ethyl thiobenzenesulphonate is
not attacked by water at 120°, but is easily saponified by potash, and
decomposed by reducing agents. W. C. W.
Constitution of Tetranitrodiphenylcarbamide. By S. M.
LOSANITCH {Ber., 13, 1297). — The dinitraniline {Ber., 11, 1539, this
Journal, 1879, Abst., 67) which is formed by the action of water on
tetranitrodiphenyl-potassium carbamide obtained by treating tetrani-
trodiphenylcarbamide with alcoholic potash, can be easily converted
into a-dinitropheuol, which Salkowski {Ber., 7, 373) has shown to
have the constitution CfiH3(0H)(N0o)(N0,) = [1:2: 4].
Tetranitrodiphenylcarbamide must have a similar constitution.
w. c. w.
Diphenic Anhydride. By C. Graebe and C. Mensching {Ber., 13,
13u2 — 13u5). — Diphenic anhydride is formed together with di-
phenylene ketone by the action of one or two molecules of phosphorus
pentachloride on 1 mol. of diphenic acid. It is also formed together
with other products of decomposition by the distillation of diphenic
acid. The anhydride is, however, best prepared by dissolving the acid
in strong sulphuric acid at 120°, and pouring the liquid into water.
Long-continued boiling in water has no effect on the anhydride. It
decomposes at the temperature of boiling sulphur, splitting up into
diphenylene ketone and carbonic anhydride. A phthaleiin is formed
when the anhydride is heated with phenol and stannic chloride. It is
a red crystalline compound, dissolving in alkalis with a red colora-
tion. Diphenic anhydride also forms a compound with resorcinol.
A chloride, having the composition CosHiuCloO.^ (m. p. 128°), is ob-
tained by gently warming a mixture of diphenic anhydride and phos-
phorus pentachloride. W. C. W.
ORGA^^C CHEMISTRY. 813
Diamidotriphenylmethane. By C. Bottixger (Ber., 13, 958 —
959). — This is a personal explanation, replyins' to the remarks of
0. Fischer (Ber., 13, 665) upon the base, doHigNo (diamidotriphenyl-
methane). The author contends for the correctness of the melting
point as given by him (Ber., 12, 975). P. P. B.
Substitution of Phenyl. By V. Merz and W. Weith (Ber., 13,
1298 — 13U"2j. — Diphenvlamine is formed by heating aniline zinc chloride
with phenol at 250°, NH,Ph + Ph.OH = NHPh. + HoO.
By the action of ammonium-zinc chloride (1 part) on phenol
(2 parts) at 280° for eight hours, a mixture of aniline, diphenylamine,
and diphenyl ether is obtained.
Phenyl ^-naphthi/lamine is prepared by heating aniline and /3-naphthol
in molecular proportions with an excess of zinc chloride at 180° for six
hours. The crude product is extracted with hydrochloric acid and
with a hot solution of soda, and the residue is dried and distilled in
a vacuum. The pure amine crystallises in colourless needles (m. p.
108°) which dissolve freely in the usual solvents at their boiling points.
When 3-naphthol is heated at 200° with twice its weight of ammonium
zinc chloride, li-naphthylamine and iS-dinaphthijlamine are formed. The
product is extracted with hydrochloric acid to remove the ;3-naphthyl-
amine. and boiled with a solution of soda. On dissolvinsf the residue
in hot benzene, (3-dinaphthylamine is obtained in silver- white plates
(m. p. 170'5°), soluble in hot acetic acid. W. C. W.
Conversion of a-Naphthylamine into a-Naphthyl Methyl
Ether. By A. Hakizsch (Ber., 13, 1347— 1348).— A good yield of
a-naphthyl methyl ether, doHv.O^le, is obtained by the action of zinc
chloride on a mixture of methyl alcohol and naphthylamine at 200°.
The crude product is treated with hydrochloric acid and extracted
with a mixture of ether and benzene. On distilling the extract,
naphthyl-methyl ether passes over at 264° as a colourless oily liquid
miscible with alcohol, ether, and benzene. With picric acid it forms a
red crystalline compound.
The corresponding ethyl ether can only be obtained in small quanti-
ties by this process.
Dim ethylnaphthyl amine can be easily prepared by heating naphthyl-
amine hydrochloride with methyl alcohol at 180°. W. C. W.
Biebrich Scarlet. By W. v. Miller (Ber., 13, 980— 982).— The
author defends the view that this colouring matter contains the tri-
sulphonic acid of an azo-compound, Ph.N iN.CeHi.N I XCioHb.OH.
against the assertion of Nietzki (Ber., 13, 800), who contends that it
contains the mono- and di-sulphonic acids only. The author .supports
his position by the analysis of the sulphonic acids obtained by reducing
the scarlet, from which mixture amidobenzenedisulphonic acid has
been obtained, the formation of which can alone be explained by the
existence of a trisulphonic acid, thus : —
aH3(S03H)..N:>f.C6H3(S03H).N" :N.C,„H6.0H -f 8H =
C6H3(SO,H)o..NH2 + C6H,(S03H)(NH2)2 + CioH6(NK2).OH.
VOL. xxxvni. 3 I
814 ABSTRACTS OF CHEMICAL PAPERS.
The formation of a trisulphonic acid would depend on the conditions
of temperature in preparing the " acid-yellow " from amidazobenzene,
and it is easy to suppose that the temperature would rise sufficiently
to produce it. Further, by treating " acid-yellow " with (S-naphthol,
the author has obtained a colouring matter having all the properties
of Biebrich scarlet. P. P. B.
Constitution of Phenanthrene. By G. Schtjltz (Annalen, 203,
95 — 118). — In previous communications {Annalen, 196, 1 ; Ser., 11,
215; 12, 235; and this Journal, Abst., 1878, 511; 1879, 538 and
653), the author has shown, by a comparison of the crystalline form
(monoclinic tabular crystals) and melting point (73"5°) of the methyl
salts of diphenic acid from phenanthrene and from metanitrobenzoic
acid, that these two diphenic acids are identical. He has also pointed
out that the base melting at 157°, which Struve obtained together
with benzidine by distilling diamidodiphenic acid with lime or baryta
(Ber., 10, 75 ; this Journal, 1877, ii, 902) is diamidofluorene, and not
a diamidodiphenyl.
Diamidofluctrene is deposited from an alcoholic solution in grey
needles, soluble in hot water and in hydrochloric acid. With dilute
sulphuric acid, it yields a sparingly soluble salt. The crystals change
colour on exposure to the air, and are easily attacked by oxidising
agents.
Diacetamidofi'uorene, Ci3H8(NHAc)2, crystallises in white glistening
plates, which begin to decompose at 250°.
Mononitrodiplienylene hetone, \ y-CO , prepared by dissolving
CsHi
diphenylene ketone in cold fuming nitric acid, is insoluble in water,
but dissolves in hot alcohol, benzene, xylene, glacial acetic acid, or
amyl alcohol. It forms needle-shaped crystals or plates (m. p. 220°),
which sublime readily. By the action of warm nitric acid, it is con-
verted into the dinitro- derivative (m. p. 290°), which on reduction
with tin and hydrochloric acid yields a new base (m. p. 286°), freely
soluble in ethyl and amyl alcohols and in ethyl acetate.
(3-Dinitrodiph enic acid is formed, together with the a- modification,
when nitric acid acts on diphenic acid. The isomeric acids are sepa-
rated by means of the greater solubility of the barium salt of the
/3-acid. It can also be prepared by heating phenanthraquinone with
a mixture of strong sulphuric and nitric acids, and pouring the crude
product into water, when diniti-ophenanthraquinone is precipitated.
The mother-liquor deposits /3-dinitrodiphenic acid when left at rest.
The precipitate of dinitrophenanthraquinone is extracted with boiling
acetic acid, which leaves the ordinary modification undissolved. On
oxidising the acetic acid solution with chromic acid, a mixture of a-
and /3-dinitrodiphenic acids is obtained, which is separated by conver-
sion into the barium salts and fractional crystallisation.
^-DinitrodipJienic acid forms needle-shaped crystals (m. p. 297°),
insoluble in cold water, but soluble in alcohol. Its salts are freely
soluble in water. Barium j3-dinitrophenate crystallises with 4 mols.
HoO in large transparent triclinic prisms. The methyl salt crystallises
ORGANIC CHEMISTRY. 815
in pale yellow monoclinic plates (m. p. 131°), whilst meihyl x-dinitro-
phenate forms small yellow monoclinic prisms (m. p. 177°).
The author represents the constitution of diamidodiphenic acid and
the diphenyl-derivatives by the following formulas : —
Diamidodiphenic acid.
NH,.(COOH)C6H3.C6H3(COOH)NH2 [1:3:4:2:4]. .
a-Dinitrodiphenic acid.
(NOo)(COOH)C6H3.C6H3(COOH)(N02) [1:3:4:2:4].
Diphenic acid.
(COOH)H,C6.C6H4(COOH) [1:2: 2].
W. C. W.
A Bromo-derivative of Nicotine. By A. Cahours and A. Etard
(Conipt. revel., 90, 1315 — 1317). — One part of nicotine is dissolved in
50 parts of water, and 2 mols. of bromine added for every mol. of
nicotine. A yellow flocculent resinous-looking precipitate falls, which,
together with the mother-liquor, is heated gently to 65 — 70°, more
bromine being added if required. The whole is then filtered and
allowed to cool, when an abundant crystallisation of the bromo-deri-
vative takes place. The undissolved portion treated separately with
water at 70° yields a crystalline deposit similar to the preceding.
The crystals are in the form of red needles often more than 1 mm.
in length, and are similar in colour to potassium dichromate. They
are unalterable in the air, but are decomposed by water at a tem-
perature higher than 70°. When dissolved in concentrated hydro-
bromic acid, they assimilate a molecule of HBr, forming the hydro-
bromide of the original derivative.
Analysis showed that the formula of the bromo-derivati\« is
CioHuNoBri. Huber's pentabromide is therefore probably the hldro-
bromide above mentioned, but the formula given to it by Huberlpon-
tains 3 atoms less of hydrogen. '
The tetrabromo-nicotine is decomposed and destroyed by an aqueous
solution of potash. J. W.
Homatropine. By A. Ladenburg (Ber., 13, 1340). — On recry.stal-
lisation from absolute ether, homatropine is deposited in colourless
transparent prisms, which melt between 95"5° and 985°. The crys-
tals are hygroscopic, although they do not dissolve freely in water.
W. C. W.
Non-identity of the Soluble Albuminoids of Crystallin with
those of White of Egg and Serum. By A. Bechamp (Compt.
rend., 90, 1255 — 1258). — Many experimenters have examined this
subject, but the results of their work do not appear to agree either
among themselves or with those of the author. On the part of the
latter, long and careful experiments have led him to conclude — (1)
that the soluble portion of crystallin contains two distinct albumins
clearly separable the one from the other, thus confirming the orio-inal
observation of Fremy. (2) The substantial unity of the albuminoid
substances must be denied, and their specific plurality affirmed.
3 I z
816 ABSTRACTS OF CHEMICAL PAPERS.
The coagulating power of these bodies was regarded as a property
of only secondaiy importance; their purity was determined, by imme-
diate analysis and by their constant rotatory power, the latter pro-
perty especially being adopted as the best criterion of the purity of
these uncrystallisable substances. The following matters were isolated,
and characterised.
Solnhle Phncozyynase. — This substance remains dissolved, in water
after the solution has been precipitated by alcohol. Its aqueous
solution begins to coagulate about 55°, and becomes violet when
boiled for a few seconds with strong hydrochloric acid. It liquefies
starch-paste, converting it into dextrin and possibly into dextrose. Its
rotatory power for (a)j = 41° to the left.
Crystalhumin is precipitable from its solution by alcohol. Its
Ifevorotatory power in acetic solution for {ol)j = 80*3'', in ammoniacal
solution = 76"6°. Like phacozymase, it turns violet when boiled in
strong hydrochloric acid, but, unlike egg and serum albumin, its
combination with basic lead acetate is not decomposed by carbonic
anhydride.
The crude solution from crystallin has a rotatory power of 47"1°,
which is very nearly the mean of the numbers already given. The
insoluble portion of crystallin is in acetic solution lasvorotatory to the
extent 7G"3°. It is, however, a mixture, for when dissolved in dilute
hydrochloric acid it yields a precipitate on addition of ammonia,
and this when redissolved in acetic acid has a rotatory power of 80"2°,
the same as that of crystalhumin. This crystal fibrin is only slightly
and with difficulty coloured violet by boiling in strong hydrochloric
acid.
None of the above-mentioned rotatory powers are exactly identical
with those of the albumins obtained from white of Qgg, from blood-
serum.
or from casein. J. W.
Lecithin and Nuclein in Yeast. By 0. Loew {Pflug. Archiv.
Phys., 22, 62 — 68). — This paper is chiefly a criticism of Hoppe-
Seyler's w^ork on the subject, the author being of opinion that his
(Hoppe-Seyler's) method of preparation, estimation, &c., was unsatis-
factory. Great stress is laid on the readiness with which these bodies
are decomposed by acids and alkalis, and an experiment is detailed
showing that traces only of lecithin can be obtained from feebly acid
yeast. The variable proportion of phosphorus (2 — 9 per cent.) found
in nuclein from various sources, is, the author thinks, reason enough
to doubt their identity. W. N.
Carbonyl-hsemoglobin. By T. Weyl and B. v. Aneep (Ber.,
13, 1294 — 1296). — The compound of haemoglobin with oxygen is
rapidly converted into methsemoglobin by potassium permanganate
and other oxidising agents, whilst the compound with carbonic oxide is
only slowly attacked. On the addition of a few drops of ammonium,
sulphide to a solution of metha^moglobin, reduction takes place, and
the abscirption-bands characteristic of this body disappear. On passing
oxygen through the liquid, the oxygen-compound of haemoglobin is
formed if the blood originally contained oxygen, but if it contained
PHYSIOLOGICAL CHEMISTRY. 817
carbonic oxide, then carbonyl-hgemoglobin is produced. This shows
that oxygen-methfemoglobin is totally distinct from carbonyl-methsBmo-
globin, although they both exhibit the same spectrum.
Detection of Garhonic Oxide in Blood. — The blood must be preserved
in a cold dark room, out of contact with air. Carbonic oxide is absent
when ammonium sulj)hide or feri-ous ammonium tartrate does not
cause a reduction to haemoglobin. It is present when the addition of a
few drops of dilute (0'025 percent.) solution of potassium permanganate
leaves the blood red and clear, and does not produce methsemoglobin in
20 minutes. A similar quantity of the oxidising solution, added to
fresh blood shaken with air, should change the colour to yellow, and
produce a turbidity.
One per cent, solution" of catechol or quinol at 40° may be used
instead of potassium permanganate. W. C. W.
Physiological Chemistry.
Influence of Glycerol on the Decomposition of Proteids in
the Animal Body. By X. Tschirwinsky {Zeits. f. Biologie, 15,
252 — 260). — This paper is a sequel to the preceding, the chief dif-
ference in the experiments being that this observer allowed the dog no
fat, in order that the effect of the glycerol on the proteid metamor-
phosis might be the more evident, and used very much larger quan-
tities.
The general result was an increase in the quantity of urine, aud a
slight fall in the elimination of urea.
The effect of large doses of glycerol appears to be sometimes hasmo-
globinuria, and the urine frequently contains a substance which
reduces copper solution (Ustimowitsch P16sz),and which is not sugar.
Catillon finds that glycerol passes unchanged into the urine, when
4 — 6 grams are given for every kilogram of body Aveight. He estimates
it in the urine by evaporating at 100°, extracting with alcohol, and
evapoi'ating the alcoholic solution to a syrupy consistence ; in normal
urine, the relation of the weight of this residue to the urea is 15 : 1.
The author then describes a method of estimating glycerol, based on
the fact that it dissolves copper oxide in presence of excess of alkali,
and calculates that in his experiments glycerol in quantities varying
from 37 per cent, to 60 per cent, of the quantity given -were eliminated
unchanged with the urine. W. N.
Influence of Glycerol on Proteid Tissue Change. By L.
Lewix [Zeits. J. JJtuluijic, 15, 243 — 2-Jl).— Alter some preliminary
remarks on the chemical relations of glycerol, the author quotes
Lauder Lindsay, Benavente, Davasse, and others, as to the fattening
properties of glycerol. Catillon's experiments are discussed in some
detail as the first real attempt to settle the question as to whether
glycerol is a food or not.
818 ABSTRACTS OF CHEMICAL PAPERS.
Catillon foiind that guinea-pigs wliicli maintained tlieir weight on a
certain diet gained one-tifteenth to one-tenth when 1 gram of glycerol
was added." The same observer found that glycerol diminished the
amount of urea excreted in man : hence he came to the conclusion that
glycerol was a food in Voit's sense, "that it diminished the consump-
tion of albuminoids." The author admits that the increase of weight
after glycerol is well nigh proven, but remarks that excess of water
will produce the same effect, and further that Catillon's experiments
were on his own showing of doubtful value, since the diet was not
regulated.
Immanuel Munk experimented on a dog in nitrogenous equilibrium,
nnd found that doses up to 25 grams and 30 grams produced no appre-
ciable effect on the proteid metamorphosis, whilst a dose of 40 grams
caused diarrhoea.
The author made experiments on a dog, and the results are tabulated.
The first table shows that nitrogenous equilibrium was maintained
on a diet of 750 grams meat and 150 grams fat. The second table
shows the effect of glycerol, i.e., a slight increase in the urea eliminated,
the average daily excretion being in the first case 51"84 grams, and in
the second, 53"35 grams ; the reverse was the case in Catillon's experi-
ments.
The glycerol increases the amount of urine, and after discussing the
possibility that the effects produced may be due to this diuresis, the
author comes to the conclusion that glycerol exerts no influence on the
total of proteid metamorphosis, as fats and carbohydrates have been
shown to do, and which he illustrates by experiments on the same dog
in a somewhat striking manner.
Doses of 300 grams of glycerol were found to be poisonous, pro-
ducing tonic and clonic spasms, and incontinence of urine and
faeces.
Davasse, Bas Glycerin, iibers. von Zeisse, Wien, 1860, 15 ; Ebstein u.
Miiller, Bed., Klin. WocJtensclir., 1875, Ni\ 5 ; Schleich, Wurtemb.
Gorrespondblatt, 44, 1874, Nr. 34 ; Catillon, Etude des Proprie'tes
Physiologiqnes et Tlierapeutiques de la Glycerin; Arch. d. Physiol. Normale
et Patholog., 1877, Nos. 1, 2 ; Munk, Verhandl. der Physiol. Ges., zu
Berlin, 13th Dec, 1878; Ustimowdtsch, Pjiuger's Archiv., Bd. 13,
453 ; Schultzen, Berlin, Klin. Wochenschr., 1872, Nr. 35 ; Harnack,
Archiv. f. Klin. Med., 13, 6. W. N.
Influence of the Supply of Water, the Secretion of Sweat,
and Muscular Labour on the Elimination of Nitrogenised
Decomposition Products. By H. Oppenheim {Pjiuger's Archiv.
PInjsiol., 22, 40—41). — During a 35 days' experiment, in which he
was in a state of nitrogenous equilibrium, the author investigated the
effect of varying physical conditions on the elimination of urea, with
the following general results : —
(1.) Increased ingestion of water continued for some time produces
at first an increase in the elimination, which gradually diminishes,
until the quantity falls below normal, so that the average over the
period is very little affected.
(2.) Injection of pilocarpine produced no especial effect either on the
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 819
nitrogen of the nrine or feces, even when water was taken to make up
for the loss sustained by the increased secretion of sweat and saliva.
(3.) Muscular labour appears to increase the nitrogen eliminated
only when carried to the extent of producing dyspnoea, and this is due
not to increased muscular activity but to the new conditions which are
set up. W. N.
Chemistry of Vegetable Physiology and Agriculture.
Influence of Air on Fermentation. By E. C. Hansen {Bied.
Ceritr., 1880, 479 — 480). — By passing air through a fermenting mash,
the number of yeast cells is increased twice or three times as much as if
no air were bubbled through, and about twice the quantity of liquid
is fermented, thus showing that a constant supply of oxygen is very
favourable to fermentation. J. K. C.
Schizomycetic Fermentations. Part VI. By A. Fitz (Ber.^
13, 13U'J — 1312). — On fermentation, calcium lactate yields a trace of
alcohol, propionic acid, and a small quantity of succinic acid. In a
second experiment with a different kind of ferment, propionic and
normal valeric acids were formed, together with calcium carbonate
and a small quantity of ethyl alcohol. When Pasteur's butyi-ic acid
ferment is used, the chief product is butyric acid ; small quantities of
ethyl and butyl alcohol are also produced.
In the preparation of butyl alcohol from glycerol, the relative quan-
tities of ethyl and butyl alcohols vary with the nature of the ferment.
A small quantity of propyl alcohol is also obtained. In the fermenta-
tion of calcium gly cerate by means of a species of bacillus, the chief
product is formic acid, but a small quantity of methyl alcohol and acetic
acid is also produced. _ W. C. W.
Influence of Fermentation on the Nitrogenous Constituents
of Potato Mash. By P. Behrend and A. Morgex (Hied. Centr., 1880,
486 — 487). — During fermentation, the soluble acid amides become con-
verted into amido-acids with loss of ammonia, which goes to the
nourishment of the yeast ; it appears also that more albumin is present
in the fermented mash than in the unfermented, and this seems to
point to the conclusion that during the fermenting process albumin
has been built up from the amido-compounds through the agency of
the yeast. J. K. C
Influence of Boric Acid on Acetous Fermentation. By
A. Herzen (Bied. Centr., 1880, 487 — 48bj. — Boric acid appears to have
no influence on the conversion of sugar into alcohol, but if added to a
wine undergoing acetous fermentation, it entirely prevents further
decomposition. The circumstance that boric acid is not a poison for
most microscopic plants and for Mycoderma cerevisice, favours the
assumption that the decomposition of alcohol into acetic acid is a
820 ABSTRACTS OF CHEMICAL PAPERS.
purely cliemical process, whioh is in some way prevented by the pre-
sence of boric acid. In order to test the truth of this assumption,
into a flask A was poured 100 c.c. of distilled water, 10 per cent, pure
alcohol, and a drop from the surface of a fermenting wine, full of
Mycoderma aceti. Flask B contained 100 c.c. distilled water, 5 per cent,
pure acetic acid, and a drop of the same wine. Flask C received
100 c.c. distilled water, 5 per cent, pure acetic acid, 5 per cent, satu-
rated boric acid solution, and a drop of the decomposing wine. All
three were closed with cotton wool, and placed in a bath at 25° C. The
result was that after eight days there was nothing to be seen in the
liquid in flask A, a stiong development of mycoderma in flask B, and
a less strong in flask C. This experiment then shows that Mijcoderma
aceti lives at the cost of the acetic acid already formed, and not on the
alcohol ; that the appearance of mycoderma in wine is rather a con-
sequence than the cause of the chemical decomposition, and that boric
acid, if it retards the development of mycoderma, has not the power
to prevent it in solutions which contain acetic acid ready formed.
J. K. C.
Nutrition of the Drosera. By E. Regel (Bied. Centr., 1880,
482). — Contrary to Rees and Darwin, the author finds that these
plants thrive best when not treated with animal food, and is of opinion
that their sustenance is properly derived through the roots.
J. K. C.
Loss of Dried Substance in Plants during Ripening. By
Mari^-Davy and others {Bied. Centr., 1880, 440 — 441). — The authors
have observed this fact in connection with wheat, barley, sugar-canes,
&c., and concur in the opinion that during the ripening period the
plant expels through its roots a certain quantity of superfluous material.
J. K. C.
Chemical Changes in Frozen and Rotten Potatoes. By H.
CzuBATA (Bied. Centr., 1880, 472 — 474). — It appears that by freezing,
the amount of sugar in the tuber is doubled, starch undergoing a cor-
responding diminution, while part of the protein passes from the
coagulable to the soluble form. During the process of rotting, the
potato loses half its nitrogenous constituents and the whole of the
susrai'. J. K. C.
o
Digestibility and Nutritive Value of Acorns. By H. Weiske,
G. Kennepohl, and B. Schulze (Bied. Centr., 1880, 431 — 434). — As
fodder Por pigs, acorns have been found very beneficial. The object of
the authors was to ascertain their value as bye-fodder in conjunction
with hay in the case of sheep. Their experiments show that acorns
tend to lessen the digestibility of hay in the same manner as bean
and starch meal, whilst alone they have no special value and belong to
the class of foods poor in nitrogen, such as potatoes and turnips.
J. K. C.
Methods proposed for Cleansing Lupines. By E. Wildt
(Bied. Centr., 1880, 434 — 436). — The bitter taste and poisonous quali-
ties of lupines, due to the presence of alkaloids, prevent their use as
fodder. Several methods of removing these alkaloids have been sug-
VEGETABLE PHYSIOLOGY AXD AGRICULTURE. 821
gested: washing with dilute acid removes them entirely, but the
nutritive value of the plants is very much diminished by the process ;
washing with soda is not sutficient to remove the alkaloids, and the
same may be said of the use of water alone ; and up to the present no
satisfactoiy process has been discovered. J. K. C.
Cultivation of Beetroot. By L. Vilmorin {Bied. Centr., 1880,
43? — 43i>). — Experiments were made with the view of ascertaining
the effect of deep ploughing on the yield of beetroot crops. The
results showed that deep ploughing has a very favourable influence on
the quantity of the crop, but in order to ensure the best quality the
plants must be sown near together. J. K. C.
Permeability of Soil for Air. By F. Renk (Zeitschr. Biologie, 15,
205 — 242). — After discussing the importance of the question, the diffi-
culty of the inquiry from the very various considerations it involves ;
and referring to the work of other experimenters on the subject, the
author proceds to describe his method of experimenting. Munich
gravel was the material used, and this was divided first into sand and
gravel, and each further subdivided into coarse, medium, and fine
by sifting. Tin cylinders, closed at the end by wire gauze of various
fineness (the advantages of gauze over wool for this purpose are dwelt
upon) were used to contain the material. These cylinders measured
25 cm. to 45 cm. by 5 cm., and were fitted with arrangements for
passing the air through them. The size is insisted on, as a closer
resemblance to the natural state of things is thereby attained, because
the space between any given series of particles and the side of the
vessel is greater than the intervals between the particles themselves
when closely packed, and this error is the less the larger the contain-
ing vessel be, within limits. A gasometer was used for containing the
air and an ordinary good gas meter for measuring. Eacli experiment
lasted 1 minute, with very dense material 10 minutes. Two lengthy
tables of results are given : No. 1 showing the number of litres of air
passed per minute under various pressures given in mm. of water,
No. 2 shows the actual amount passed during fixed times and under
fixed pressures. Coarse sand and gravel show an exception to the
rule that the amount of air passed varies as the pressure.
From the first series of experiments, the author concludes that when
air under pressure streams through a porous material the volumes of
air passed through are proportional to the variations of pressure so
long as the rate of flow is not more than 0"062 meter per second ; if
this limit is passed, the volume of air increases in a smaller ratio than
the pressure, and the proportion diminishes, the greater the speed of
the stream of air.
The next point taken up is the effect of varying the thickness of the
layer of soil, and from his experiments the author concludes that when
air under equal pressures passes through layei's of homogeneous mate-
rials of different thicknesses the quantity passed through is propor-
tional to the thickness of the layers provided the rate of flow does not
exceed 0'062 meter per second ; at greater rates, it diminishes in
smaller proportion as the thickness of the layer diminishes.
822
ABSTRACTS OF CHEIvnCAL PAPERS.
Next the effect of varying porosity is considered. The difficulty of
determiniug porosity is discussed and author's method described,
which is as follows : — A cylinder of known volume is filled with the
material by shaking, pressing, and hammering, and then turning the
contents into a measuring glass half full of water and reading off the
amount of absorption which takes place. This part of the subject
requires consideration under two heads : — Istly, where the total
porosity of the specimens is equal, but the width of the pores is vari-
able ; and 2ndly, where the width of the pores is equal but the total
volumes variable.
The results are given in the following table, which shows the vary-
ing resistance to the passage of air very markedly : —
Table.
G-ravel.
Sand.
Medium.
Fine.
Coarse.
Medium.
Fine.
Number of experiments.
86
87
88
89
90
Yolume of cylinder ....
981
981
981
981
981
grams.
grams.
grams.
grams.
grams.
Weight of material ....
1638
1638
1638
1463
1463
per cent.
per cent.
per cent.
per cent.
per cent.
Estimated vol. of pores
37-9
37-9
37-9
55-5
55-5
Pressure in mm. of water
20
20
20
20
20
Air passed (liters) ....
15-54,
6-91
1-28
0 112
0 -00133
After referring to the results of other experimenters (Gueront, Compt.
rend., 75 ; Schiirmann and 0. E. Meyer) on the passage of gases
through capillary tubes and similar resistances, he concludes that
the width of the pores has an important influence on the total per-
meability of the soil, to this extent : that by comparison of two speci-
mens of soil of equal volume, but of which the individual particles
were of different sizes, the pore volume and transverse sections equal,
and under equal pressures, it was found that the quantity of air passed
through the one might be 20,000 times greater than the quantity passed
through the other in ^he same time.
When the pores are of equal size, but the total pore volume varies,
the quantity of air which passes varies as the area of section of the
containing vessels.
The details of further experiments with loosely packed and wet soils
are given, and the author then proceeds to summarise the results of
all the experiments as follows : — When air under pressure flows
through a soil, the quantity which passes through is directly pro-
portional to the pressure and inversely proportional to the thickness
of the stratum, provided only that the rate of flow does not exceed
0-0G2 meter per second. If this limit be passed, the proportion changes
and the volume of air passing through diminishes in a smaller ratio
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 823
as the pressure dimmisbes and the thickness of the stratum increases,
and vice versi.
Porosity, by which only one property of a body is understood, viz.,
the existence of spaces throughout its apparent mass, lias a double
influence. 1st, in different soils whose pores are of equal dimen-
sions, under equal pressure, the volume of air passed through is pro-
portional to the total pore volume ; and 2ndly, when the pores are of
different dimensions, but the total pore volume is the same, it is pos-
sible m extreme cases, that the quantity of air passing through one
sample may be 20,000 times greater than through another.
An alteration of these factors occurs when a soil is loosened, for
then not only the size of the individual spaces, but also their total
volume, is increased; with fine soils, i.e., soils with fine pores, a relatively
greater permeability results than with soils whose pores are larger.
The wetting of soils by rain has, according to the width of the
pores, a very different effect ; soils whose pores are large may be but
slightly affected, whereas soils with fine pores may be rendered prac-
tically impermeable.
When a soil freezes, its permeability is lowered, and this not only
in consequence of the expansion of the water by frost, but also and
chiefly because the water when frozen is no longer moveable in the
pores. W. N.
Influence of Shade on the Amount of Carbonic Anhydride
in the Air of the Soil. By E. Wollxy (Bied. C>uitr., 18Su, 4u2—
405). — Three zinc cylinders were filled to the height of half a meter
with damp sandy soil into which a glass tube was sunk for half the
depth in order to draw off the air: one cylinder was covered with
grass, another with straw, and the third was left open. Experiments
carried on during the warmer season of the year showed that during
this time the air of soil shaded by green plants contained much less
carbonic anhydride than when the soil was covered by dead plants or
left open, whereas the opposite is the case during the colder seasons.
The author has formerly proved that the air under growing plants
during warm weather is both colder and drier than that which is not
so shaded, and in this we have the reason why less carbonic anhydride
is present. The author finds the amount of carbonic anhydride to
diminish in proportion to the density of the green plants.
J. K. C.
Difference between Loam and Clay. {Bied. Cenir., 1880, 480 —
481). — By a process of elutriation, the very fine parts were separated
from the coarser and subjected to a quantitative analysis; it was
found that the chief difference between loam and clay consisted in the
fine portions of the latter containing 13 to 14 per cent, of calcium car-
bonate, of which the loam contained none, but was correspondingly
richer in silicates. J- K. C.
Permeation of Vegetable Matter by Water. By W. Rigler
(Bied. Centr., 1880, 4Ut) — 4u8). — A gentle stream of w^ater was allowed
to play on beach and pine litter and on sphagnum ; the amount of
water which trickled through was measured. It was found that a
824 ABSTRACTS OF CHEMICAL PAPERS.
downfall of 10 mm. of water was reduced on the first day to 8 by
beecli straw, to 8"8 by the pine, and to 4j'3 mm. by the sphagnum.
Perfectly dry straw does not absorb water very quickly, a certain pro-
portion of moisture being necessary to give the most favourable con-
ditions. J. K. C.
The Best Mode of Applying Artificial Manure to Potatoes.
By M. Marcker (Bied. Centr., IbSO, 409 — 418). — Experiments were
carried on for four years Avith several different kinds of potatoes, and
in soil of very varied quality, to ascertain what kinds of artificial
manures were most suitable and in what proportions they should be
used, whether alone or in combination with other kinds of dung.
When artificial manures were used alone, the best effect was produced
by a mixture of Chili saltpetre and Baker superphosphate in the pro-
portion of one of the former to two of the latter. The saltpetre by
itself was productive of very good results, but the use of superphos-
phate alone was found to be a failure. In combination, however,
with stable manure, each separately produced about the same effect,
but when used together in the same proportions as given before, their
influence on the crop was still more favourable. Salts of ammonia
were of no use, the nitrogen being apparently not absorbed until
oxidised to nitric acid. J. K. C
Analytical Chemistry.
Meyer's Vapour- density Determinations. By L. Meyer (Ber.,
13, 991 — 992). — The author describes an arrangement by which the
error described by V. Meyer (Ber., 13, 813 — 814) may be avoided,
which results from the introduction of air into the apparatus when
the bottle containing the substance is brought into the apparatus. The
arrangement consists in closing the apparatus by a caoutchouc stop-
pei*, in which fits a glass tube closed at the upper end and open at the
lower end ; into this the tube containing the substance under experi-
ment is introduced. It is held in its position by means of a piece of
ii'on wire passing through the caoutchouc stopper, and bent below so
as to form a support for the tube, whilst above it is bent at right
angles so to form a handle, by which at the desired time it may be
turned round. In this way the support can be removed from below
the tube, when it drops down into the heated part of the apparatus.
To avoid the water being carried over through the side tube whilst
the tube is falling, a small bulb is blown on the side tube.
P. P. B.
New Alkalimetrical Method for Estimating Phosphoric Acid.
By 0. ScHLiCKU-M (Arch. Pharm. [3], 15, 325 — 334). — When litmus is
used as an indicator during the addition of an alkaline hydrate to
phosphoric acid, the neutral point is reached as soon as the liydrogen
of the acid is half replaced by metal.
AX.yL,YTICAL CHEMISTRY. 825
If tincture of cochineal is employed, the yellow colour imparted to
it by the acid changes to violet-red when one-third of the hydrogen of
the acid is replaced by the metal, that is, when a monometallic phos-
phate is formed. Cochineal therefore serves to indicate the stage at
which phosphoric acid is one-third saturated ; the presence of other
acids does not interfere, since they are neutralised by the alkali before
the phosphoric acid : hence when phosphates are to be estimated,
normal nitric acid is added and titrated.
Phosphoric acid in the presence of magnesium sulphate can be pre-
cipitated as MgXH4P04 by addition of normal ammonia, and each
molecule of acid requires 3 mols. of ammonia for its complete precipi-
tation : 1 mol. of a monometallic phosphate similarly requires 2 mols.
ammonia. The end of the precipitation process can be judged by
litmus, which remains violet-red until a drop of ammonia in excess is
added, which turns it blue : if excess of ammonia has been added it
may be titrated back by standard acid after separating the precipitate.
When it is to be estimated by the following process, phosphoric acid
must be present either as free acid or as a monometallic salt : all
other phosphates may be converted into the monometallic salt by
addition of nitric or hydrochloric acid until cochineal tincture is
tui^ned yellow.
The process consists in adding sufficient magnesium sulphate and
some tincture of litmus, and then running in normal ammonium
hydrate until no further precipitate forms and the litmus changes from
violet-red to blue : towards the end of the reaction, the precipitate
settles very rapidly, and it is necessary to allow a few seconds between
each addition of ammonia to complete the change. As soon as the
addition of the last drop of ammonia has produced no change of colour
the volume of ammonia used is read off. To calculate the amount o£
phosphoric acid present, it is only necessary to multiply by the factor
0"093 one-third the number of cubic centimeters of ammonia solution
used if free phosphoric acid was being titrated, and one-half the
number of cubic centimeters if a monometallic phosphate was present.
Excess of ammonia may be titrated back with normal acid, after first
separating the liquid from the precipitate.
If calcium is present, it must either be removed or precipitated as
sulphate by heating nearly to boiling with sodium sulphate and allow-
ing it to stand for half an hour : the solution containing a little dis-
solved calcium sulphate may be poured off and mixed witli magnesium
sulphate and litmus, or the removal of the precipitate may be neglected.
It is, however, necessary that the calcium phosphate should first be
converted into the monocalcium jjhosphate by normal nitric acid and
cochineal, or by normal ammonia as the case may be, and the quantity
of either of these normal solutions employed measures the amount of
calcium present. F- C.
Action of Ammonium Citrate on Phosphates. By A. Grupe
and B. Tollexs (Her., 13, 12tJ7 — 127u_). — Dicalcium phosphate dis-
solves in an alkaline solution of ammonium citrate with the formation
of ammonium phosphate and calcium citrate, the latter being soluble
in an excess of the ammonium salt. Tricalcic phosphate is less solu-
826 ABSTRACTS OF CHEmCAL PAPERS.
ble tlian the diphosphate in ammonium citrate. In order to estimate
the phosphoric acid in this solution, three times the amount of magnesia
mixture required by theory should be added ; a larger excess is to be
avoided. The precipitate invariably contains lime, which can be re-
moved by dissolving the washed precipitate in hydrochloric acid and
reprecipiting with ammonia. W. C. W.
Valuation of Zinc and Zinc-dust. By F. Beilstein and L.
Jawein (Ber., 13, 947 — 951). — The samples of zinc or zinc-dust are
dissolved in hydrochloric acid, the hydrogen liberated is collected in
an apparatus from which it expels water, and from the weight of the
latter the hydrogen liberated is calculated. For a description of the
apparatus and the precautions necessary to obtain accurate results,
the original must be consulted. P. P. B.
Valuation of Copper for Roofing. By A. Muller (Ber., 13,
1014 — 1016). — The author proposes submitting for equal length of
time pieces of sheet copper of equal size, to the action of hydrochloric
acid fumes, then to a solution of hydrochloric acid of 15 — 20 per cent.,
and after exposure to the air, dipping them into nitric acid of about
10 per cent. N2O3. Different varieties of copper are variously attacked ;
and -when their surfaces are examined microscopically data are ob-
tained sufficient to form an opinion as to the suitability of the copper
for roofing. Some samples are attacked uniformly over the whole
surface, giving a roughened surface only, whilst others are corroded
deeply here and there ; the latter kinds would be unsuitable for roofing
purposes. P* P- B.
Quantitative Determination of Acetone in Methyl Alcohol.
By Gr. Kramer (Ber., 13, 1000— 1005).— The method consists in
weighing the iodoform obtained by shaking up 1 c.c. of the alcohol
with 10 c.c. of double normal soda solution and 5 c.c. of double normal
iodine solution. To remove the iodoform, 10 c.c. of ether free from
alcohol are shaken up with the mixture, and an aliquot part of the
ether drawn off and evaporated on a weighed watch-glass. The
increase of weight of the watch-glass gives the iodoform contained in
the ether, from which the amount of acetone may be calculated.
Ethyl alcohol, acetic acid, and propyl alcohol, when treated as above,
give no iodoform, whereas isopropyl alcohol yields iodoform. Alde-
hyde does not give the theoretical amount ; ketones containing methyl
groups, e.g., methyl ethyl ketone, methyl hexyl and methyl phenyl
ketones also yield iodoform, and an acid containing 1 atom of carbon
less than the ketone. P- P. B.
Estimation of Starch in Sausages. By H. Fricklinger (Arch.
Pharm. [.3], 15, 234 — 285). — The presence of starch, introduced into
meat sausages as bread or wheaten flour, is an adulteration. Its
amount has usually been determined by conversion into sugar by
digestion with dilute sulphuric acid, and then titrating the sugar with
copper solution : the starch is considered to be entirely converted
when iodine solution imparts no blue or violet coloration. The author
ANALYTICAL CHEMISTRY. 827
points out that the intermediate pi'oduct, dextrin, has no action on
starch, and hence the iodine reaction cannot be employed : he found
that from one-third to one- half of the starch is not found if the iodine
test is used. The following method is recommended : A known weight
of the sausage in thin slices is digested at 100° with water containing
5 per cent, of sulphuric acid, until a filtered portion of the liquid
yields no further precipitate with alcohol. The liquid is filtered, the
residue well washed, and after making the solution alkaline with soda,
the sugar is titrated with copper solution. F. C.
Comparative Examination of the most important kinds of
Commercial Gum Arabic. By E. :Maskvg (Arch. Fhann. [3], 15,
21 G — 231). — lo per cent, .solutions of the gums clarified by standing
were usually employed, but in some cases dilution down to 5 per cent,
was necessary, owing to the liquid being too tenacious: clarification
was seldom necessary. The following reagents were employed, and
the solubility of the precipitate in excess of the reagents was tested by
pouring 2 c.c. of the gum solution into a test-tube, adding to this first
an equal volume of the reagent, then an additional 2 volumes and
shaking well : —
1. The solubility was determined by pouring 25 c.c. of water upon
O'o gram of the gum, and constantly shaking for 24 hours in a closed
ve.ssel ; the residue removed by filtration was dried at 110° C.
2. The moisture was estimated by drying the gum at 110° C.
3. The ash was obtained from 2 to 5 grams of air-dried gum, and its
alkalinitv was titrated.
4. Potassium silicate solution, made by diluting 1 part of thick
water-glass with 20 parts of water, precipitated almost all the gum
solutions.
5. Potassium stannate, as 2 per cent, solution, also affected all the
gum solutions except one.
6. Lead acetate reacted, with one exception, on all the solutions.
7. Neutral aluminium sfulpliate in 10 per cent, solution only precipi-
tated two gum solutions : but the precipitate obtained from other
.samples, on the further addition of potassium hydrate (1"13 sp. gr.),
was examined as regards its solubility in excess of the caustic alkali.
8. Neutral copper acetate in cold saturated solution, neutrnl lead
acetate in 10 per cent, solution, smd ferric chloride solution of 1"2 sp. gr.
were indifferent to almost all the gum solutions.
The reaction of most gum solutions was feebly acid. Starch was
estimated microscopically in the deposit from the water solution by
moistening it with a 1 per cent, aqueous iodine solution.
The author concludes from the examination of a large number of
gums, the results of which are tabulated, that although different kinds
of gum show differences when thus tested, the source of the gum can
seldom be inferred from such an examination. The value of the jrum
is better judged from its solubility than from its colour: the percent-
age of ash seldom varies beyond narrow limits, but the alkalinity of
the ash is much more variable ; the alkalinity was usually entirelv or
mainly due to lime, and potash was seldom present in any quantity.
The ash was invariably soluble in dilute hydrochloric acid, aud any
828 ABSTRACTS OF CHEMICAL PAPERS.
quantity of insoluble residue would therefore indicate the presence of
sand or other insoluble substances. The differences in behaviour
shown by the different kinds of o'um towards the same reagent proba-
bly indicates the existence of different modifications of arabic acid.
F. C.
Observations on Milk. By B. Ohm (Arch. Pharm. [3], 15, 211).
— When powdered well -burnt gypsum is mixed with milk to a stiff
paste, tbe time required for its setting serves as a measure of the quality
of the milk and of the quantity of water added as an adulterant.
Milk of 1"030 sp. gr. at 15° C. was mixed with about 30 grams of
gypsum, and set in 10 hours ; after the addition of 25 per cent, of
water 2 hours only were required, with 50 per cent. 1^ hours, and with
75 per cent, only 40 miniites.
Milk skimmed after standing for 24 hours and of 1"033 sp. gr.,
when mixed with gypsum set in 4 hours, with 50 per cent, of water
it set in 1 hour, and with 75 per cent, in about half an hour.
If the milk is warmed it sets more rapidly. The mass after setting
can be used for further examination. F. C.
Taking Samples of Milk. By C. Werkowitsch and v. Klenze
(Bled. Centr., 1880, 469— 470).— The milk should be well stirred, and
a sample taken from the middle by inserting an inverted beaker in the
liquid, reversing and drawing it cut. J. K. C.
Analysis of Milk. By E. Maechand (Bied. Centr., 1880, 466—
468). — The great variations in the analyses of milk by different
chemists are due, according to the author, to the abnormal conditions
of the cow, the various times of milking, or defective methods of
analysis. Only in the case of the fat does the quantity show any
great variation (2"7 to 8"2 per cent.). To estimate the fat, milk is
treated with moderately dilute acetic acid, which dissolves the casein,
and allows the fat to be filtered off ; or the fat is dissolved out by
shaking with ether. J. K. C.
"O
Analysis of Milk. By H. Yogel (Bmgl.polyt. J., 237, 59—61).—
The author recommends weighing the milk in a closed tube, as an appre-
ciable error results fi'om weighing it in an open basin. To estimate
solid residue and fat, he uses a tinned-iron boat made to fit Soxhlet's
extraction apparatus, and stirs up the milk, after the addition of sand,
during evaporation. Feeding cattle with green fodder caused no ap-
preciable change in the composition of the milk. The author thinks
that the number, 9, fixed by English analysts as a minimum for
solids, not fat, is too high ; he would prefer 8. Judged by the former
standard, all the samples in his district would be condemned as
watered. J. T,
Analysis of Butter. By E. Meissl (Bled. Centr., 1880, 471—
472). — 5 grams of well- washed butter are dissolved in alcohol and
saponified with caustic potash. After the alcohol has been evaporated,
the soapy liquid is distilled with dilute sulphuric acid, and the distil-
late titrated with decinormal potash solution. The number of cubic
TECHNICAL CHEMISTRY. 831
taken that the volume of water to be purified should be made as small
as possible. No water containing' free acid or alkali should enter a
stream until it has been neutralised, as the salts are less injurious than
the free acid or alkali : it will generally, however, be found that the
stronger washing-waters may with advantage be kept and their con-
tents worked up.
Lime and chalk are the most generally useful precipitants and
purifiers : by their means not only may acid liquids be neutralised,
but many colours and albuminous substances may be rendered in-
soluble. Alum and other substances may sometimes be used with
lime. Lime in excess is mixed with the refuse in the first of the above-
mentioned tanks: after subsidence, the clear efiluent will still contain
dissolved lime, which is injurious to fish and must be separated by
exposure to the air in larger ponds. The lime sediments can be used
for manure.
In all cases the purified effluent water should enter the stream by
pipes which discharge it tipwards from near the bottom and middle of
the stream ; this secures rapid admixture with a large quantity of
stream-water.
Details are given of the number of works which discharged impure
waste water into running water in Saxony in the year 1877 : the
majority were colour-, bleach-, and woollen-works. Breweries seldom
offended ; the author finds that the brewery waste contains chiefly
albuminous bodies, which can be almost completely removed by lime.
F. C.
Occurrence of Free Sulphur in the Dry Distillation of Tar.
By A. Keulstadt (Ber., 13, L'i4-"> — 1347). — A deposit in the passage
connecting the condensers at a tar distillery with the chimney was
found to consist chiefly of sulphur, which probably owed its origin
to the mutual decomposition of sulphurous oxide and sulphuretted
hydrogen. W. C. W.
Magnesium and Calcium Compounds as Refractory and
Dephosphorising Materials. By K. Bischof {Dingl. polyt. J., 237,
51 — 59, 136 — 148). — The author mentions the various compounds
hitherto proposed for basic refractory bricks, linings, &c. He then
examines the behaviour of three of the best mixtures propo.sed by
S. G. Thomas.
{a.) . (6.) {c.)
Parts. Parts. Parts.
CaO, pure 85 CaO 80-0 58-5
Clay (Grunstadt).. 5 MeO 5-5 30-5
A1,0, 4-0 2-5
Fe oxide .... 1"5 I'o
SiO. 8-0 7-0
& is a mixture given for bricks ; c is the best mixture for the outer
lining of converters.
a at the fusing point of cast-iron formed a yellowish smooth mass
like sealing-wax, with compact fractui'e ; h gave a rough, bi'ownish,
somewhat gi-anular mass, with a cellular and cracky fracture ; c, like
832 ABSTRACTS OF CHEMICAL PAPERS.
b, but darker ; a bit dropped from its platinum support to a clay sup-
port beneath seemed fused to the latter. At the fusing point of cast-
steel, a was darker, h and c as above, but with lava-like fractures. At
the melting point of bar-iron, a formed a light yellow enamel ; h was
yellowish-brown, partly fused to a yellow enamel ; and c was brownish-
yellow, beginning to form an enamel, a, the most fusible, is also most
complex in composition ; most of its proximate components are also in
combination to begin with. With h and c the fusibility increases
with the increase in amount of SiOa. Replacing the CaO in a by 85
parts of MgO, a mixture decidedly more refractory resulted ; near the
fusing point of bar-iron it baked together only, whilst the former be-
came enamel-like. Other experiments confirmed the conclusion that
MgO with clay gives more refractory mixtures than CaO does. The
assertion that MgO bricks formed of these compounds must be burnt
at a tempei'ature near the fusing point of platinum must be taken as
a very rough approximation only, as they would be quite fluid at that
temperature.
The author also examined the behaviour of the proximate con-
stituents, magnesia, lime, alumina, iron oxide, silica, a,nd phosphoric
anhydride at different temperatures, to throw some light on the beha-
viour of the compounds. Chemically pure magnesia heated to nearlij
the melting point of platinum becomes compacted on the surface, but
is infusible, even when in contact with refractory clay ; at the melting
point of })latinum a test fused to a grey mass. Lime at the melting
point of bar-iron forms a skin ; near the melting point of platinum, it
melts when in contact with clay. Pure alumina is perfectly infusible
at the melting point of platinum. Pure iron oxide gives a fused pro-
duct on platinum at the melting point of bar-iron. Silica is more
fusible at the melting point of bar-iron than magnesia. It bears
heating to near the melting point of platinum on a clay support.
Phosphoric anhydride fuses at i\, comparatively low temperatui'e.
Compounds of magnesia and silica slowly inci'ease in fusibility with
the amount of silica until a great excess has been added. With equal
parts of each, perfect fusion takes place at the melting point of bar-
iron. Magnesia with j^hosphoric anhydride gives much more fusible
compounds than with silica, and the fusibility increases with the
amount of anhydride present. Magnesia and alumina compounds,
either on a platinum or on a clay support, remain almost unchanged at
the melting ]ioint of bar-iron. Magnesia and lime compounds at the
melting point of bar-iron do not fuse, but those with a preponderance
uf lime show signs of incipient fusion. All the mixtures of magnesia
with iron oxide were infusible at the melting point of silver ; but at the
melting point of bar-iron all fused. The fusibility increases with the
amount of oxide.
Lime and silica form very much more fusible compounds than the
corresponding magnesia and silica ones. The same may be said of lime
and phosphoric anhydride. Lime forms much more fusible compounds
with alumina than magnesia does. This appears even in compounds
containing as much as 3 to 1 of alumina to lime. Similai'ly lime
and iron oxide are more fusible than the magnesia mixture.
J. T.
TECHNICAL CHEMISTRY. 833
Enamelled Cast-iron Vessels. By W. Biksch (Dingl. jwh/f. J.,
237, 7.S). — After picklincr :ind cleaning the vessels, they are covered
with a ground made as follows : — Quartz, 50 ; fluorspar, 7'5 ; borax,
22' 0 are fnsed together. Of this, 16 parts, 6'5 to l"2-5 quartz, 4 to 65
of cla}', 0'5 borax, are ground in wet mill, with addition of 2"5 clay
and 066 borax. This is laid on and burnt, forming a yellowish-
brown mass. For the outer coating, 2'5 powdered fluorspar, 1 zinc
white, 4*75 tin oxide, 0"75 bone ash, and 0"03 to 005 smalt are well
mixed. Of this 9 kilos, are mixed with 16 of finely ground fluorspar,
9"o boi-ax, 3"25 soda, 1'25 — 1"5 nitre, and the whole fused together.
The product is powdered, and 30 kilos, of it wet ground with six cups
of about 140 c.c. of white clay aud 0'3 zinc oxide. This is laid on and
bui-nt. J. T.
Alcohol from Potatoes. (Bled. Centr., 1880, 485.)— Compara-
tive experiments on mashing potatoes with sulphuric acid and with
malt showed that the yield of alcohol obtained by means of the latter
was very little greater than that obtained by boiling with sulphuric
acid at the ordinary pressui'e. J. K. C.
Analyses of Tokay Wines. (Bled. Centr., 1880, 485.)— In six
samplCjS of Avine the percentage of alcohol varied from 7'8 to 17"6 ;
of .solids from 27*1 to 8*4 : and of sugar from 23"4 to 6-1.
J. K. C.
Analyses of Hamburg Beer. By Niederstadt {Bied. Centr.,
1880, 484). — As a mean of 28 s^amples, the percentage of alcohol w-as
found to be 4"3, and of extract 5*7. J. K. C.
Extraction of Malt. (Bied. Centr., 1880, 485.)— Several samples
of grains were analysed, and it was found that about 7 per cent, of the
extractive matter was still present in the grains. J. K. C.
Experiments on Various Kinds of Yeast. By A. Riebe (Bied.
Centr., 1880, 477 — 478). — These experiments were carried out in
mashes of molasses. Yeast was found to be most active when it had
previously been allowed to stand Avith potato mash. An attempt was
made to substitute fresh malt yeast for dry malt yeast, which, how-
ever, was not successful. J. K. C.
Estimation of th.e Value of Raw Material in the Prepa-
ration of Yeast, By Heixzelmaxx {Bied. Centr., 1880, 475 — 476j. —
The yeast-producing power of grain is not proportionate to the
quantity of nitrogen it contains, but to the amount of soluble pro-
tein. This is a very variable quantity, rye containing from 30 to 50
per cent., and maize only 10 per cent, of its protein soluble in water
at 65° C, which is the most suitable temperature for mashing the
grain. J. K. C.
Inversion of Beet-sugar for Wine. By W. Euglixg {Bied.
Centr., 1880, 486). — Sulphuric, phosphoi'ic, and tartaric acids were
used in the inversion of beet-sugar, sulphuric acid lieing the quickest.
8^4 ABSTRACTS OF CHEMICAL PAPERS.
and tartaric acid tlae slowest in its operation. The inverted sugar was
tlien used for tlie preparation of after-wine, being mixed witli pressed
grapes and allowed to ferment. The best wine was obtained from the
sugar inverted by means of phosphoric acid. J. K. C.
Sugar from the Stems of Maize and Sorgho. By P. Collier
(Bied. Gcntr., 1880, 461 — 462). — The author found that sugar could
easily be obtained, and in considei*able quantity, from, the sap of the
steuis of maize and sorgho, the sap yielding about 15 per cent, of
syrup. J. K. C.
Action of Lime on Solutions of Sugar. By F. Desor (Bied.
C'entr., liSSO, 4t)4 — 465). — If lime-water be added to a solution of
sugar, the rotatory power of the latter is diminished, although the
diminution does not seem to follow any law. Addition of acetic acid
restores the rotatory power. J. K. C.
Gypsum in the Manufacture of Sugar. By A. v. Wachtel
(Lied. Cent)-., 1880, 463). — The author attributes the presence of
alkaline sulphates found in sugar to the presence of gypsum in the
water used in susfar works. J. K. C.
•■&'
Certain Properties of Bone Charcoal. By H. Pellet (Bled.
Centr., 1880, 463 — 464). — Bone-black will absorb lime from sugar
solutions, and lime salts equally well if an alkali be present. Potash
salts are also easily absorbed, especially in the presence of lime.
J. K. C.
Influence of Steaming on Starch. By M. Stumpf (Bled. Centr.,
1880, 457 — 45*J). — A mixture of one part of starch to four of water,
when heated at 130" C. under pressure, becomes a homogeneous
liquid, the starch, however, partially sejiarating out on cooling. After
four hours' heating, the author found that 20 per cent, of the starch
had been converted into sugar. When only half the quantity of water
is used, three hours' heating at a temperature of 125° under a pres-
sure of 2^ atmospheres, is necessary to reduce the whole to a liquid.
When the temperature is raised to 140 — 150° over 70 per cent, of
the starch may be converted into sugar. J. K. C.
Notes on Milking. {Bied. Centr., 1880, 232— 233.)— C. J. Eisbein
advocates the use of a strict record of trial milkings,* as not only useful
to detect bad milkers amongst the cows, but as a guide to the results
of the fodder, and enabling the farmer to better estimate his profits.
B. Martiny and W. Fleischmann give examples of the great errors
which may occur by taking trial milkings from a single cow in a
herd, especially if the trials are only made monthly : trustworthy
estimates of the yield of single cows can only be had if the trials are
made weekly. J. F.
Experiments with Milk Cooling Apparatus. (Bied. Centr.,
* Such trial luilkiugs are always followed b}' aualyses.
TECHNICAL CHEMISTRY. 835
1880, 214 — 216.) — The ol)ject of the experiments was to determine
whether it is more profitable before churnirij? to put the milk fresh
from the cow into the ice-water of the Swart's system, or to cool it
previously in the Laurence cooling apparatus. The results show that
when the milk is cooled too much, the yield of cream diminishes.
However, if the milk is not cooled too much, and is placed in ice im-
mediately after a slight cooling, there is vei'y little appreciable loss.
It is, however, different if the milk is left at rest for a few minutes
before being transferred to ice, the decrease in fat being then in quite
regular proportion to the time allowed to elapse. It is possible, how-
ever, to recover the normal amount by rewarming the milk, and then
placing it quickly in ice. If the milk is retained at a proper tempera-
ture, the yield is not injuriously affected by allowing it to remain
45 minutes previous to placing it in ice.
The writer's theory is that the sudden cooling of the milk first
takes efPect on the serum, and the fat-globules, l)efbre they have time
to cool, float to the surface ; another theory is, however, proposed by a
writer in the Centralhlaft, that the cooling sets up a current, the motion
of which carries the fat to the surface. In any case the experiments
recorded are in favour of the Swart's plan. J. F.
Supposed Conversion of Albumin into Fat in the Ripening
of Roquefort Cheese. By X. Sii:r>i;K (,/. jji-. Chem. [2], 21, 2u3—
221). — Bloudcau finds that such a conversion takes place, Brassier
{Ann. Chim. PJnjs. [4], 5, 1865) and Alex. Miiller (Jahrs. f. Arjri. Ch.,
1870-72, 246) come to a contrary conclusion, and the results obtained
by the latter agree with those of the author. The author severely
criticises Blondeau's experiments.
The author's results of the analysis of (1.) Fresh cheese (not
salted). (2.) Cheese after remaining in the cellar; and (3.) Very
old cheese, are : —
(1.) (2.) (3.)
Moisture 49-66 36-93 23-54
Casein 1372 5-02 8-53
Soluble albumin 6-93 20-77 18-47
Fat 27-41 31-23 40-13
A.sh 1-74 4-78 6-27
99-46 98-73 96-94
The most remarkable change in the ageing of the cheese is the loss
of moisture. The increase in fat is only an apparent one, for calculat-
ing on the dry substance we have the following percentages for the
fat and the albumin (casein + soluble albumin) : —
Fat 53-91
Albumin 40-80
The moisture was determined by drying at 115 — 120°. Blondeau
merely dried over sulphuric acid. The fat was determined by extrac-
tion with alcohol and ether, the residue free from fat was dissolved
(2.)
(3.)
49-94
56-14
40-53
37-78
836 ABSTRACTS OF CHEMICAL PAPERS.
in potasli, leaving but little residue, and the filtrate precipitated by
dilute acetic acid. This precipitate washed, dried, and weighed is
called casein, the total albumin being calculated from the nitrogen
determination by combustion with cupric oxide. In the case of the old
cheese, under the heading " soluble albumin," the nitrogen from
which the " soluble albumin " is calculated exists in part as tyrosine,
amido-fatty acids, and ammonium salts. In the old cheese, by operat-
ing on half a kilogram, 1"4 per cent, ammonia, and 0'167 per cent,
tyrosine were obtained. F. L. T.
Examination of Dog Biscuit. By A. Mater (Bied. Ccntr.,
1880, 233). — A Liverpool firm having introduced this article into com-
merce, it has been analysed by the author, who found it to yield the
following percentage composition : —
Starch and
Moisture!
digestible matter.
Fat.
Albumin.
Cellulose, &e.
Ash.
18
45-5
•?>■^^
1(3-1
19-3
2-r.
The composition appears similar to that of rye bread, only the fat
and albuminoids appear to be derived from slaughter-house refu.se ; a
microscopical investigation does not show the presence of good meat.
J. F.
Tonga. By A. W. Gerrarb (Pharm. J. Trans. [3], 10, 849).—
Tonga, a drug obtained from the Fiji Islands, is a mixture of fibrous
material, probably a root, and the inner bark of some plants. The
bark consists of pectin, glucose, an essential oil and fat ; the root con-
tains a volatile alkaloid, probably the active principle, and potassium
chloride.
The drug is used as a remedy for neuralgia. L. T. O'S.
Deterioration of Library Bindings. By W. R. ISTichols (Ghem.
Neivs, 41, 64). — The author's results confirm the generally accepted
view that the deterioration of leather bindings is to be mainly traced
to the action of sulphuric acid produced by combustion of coal gas.
Morocco leather is but little affected ; Eussia and calf are much acted
on ; ordinary sheep-skin is also attacked. M. M. P. M.
Fruit of Adansonia Digitata. By F. L. Slocum (Pharm. J,
Trans. [3], 10, 81G). — The fruit of Adansonia digitata contains pectin,
grape-sugar, malic acid and potassium, but not a trace of tartaric
acid, consequently it is distinct from the " cream of tartar " fruit.
L. T. O'S.
837
General and Physical Chemistry.
New Methods in Actino-Chemistry. By A. R. Leeds (Chew.
Xeivs, 42, 4!i). — Tiie authm- contirms his results previously obtained
(Am. J. ScL, 1878 and 1879), and also the laws relating to the change
of the soluble iodides in presence of actinic rays and dilute acids.
The amount of iodine set free in presence of hydrochloric acid in
sunlight is greater by a definite ratio than that liberated by sulphuric
acid. L. T. O'S.
Photochemical Behaviour of Silver Bromide in presence of
Gelatin. Bv H. W. Vogel (B,!-., 13, 12(M— 1208).— Collodion plates
prepared with an excess of silver nitrate are more sensitive than those
prepared with an excess of potassium bromide. Gelatin plates made
with excess of silver nitrate are more sensitive than the others, but
are excluded from use by faultiness. The sensitiveness of collodion
plates may be increased by use of morphine, pyrogallol, &c. The
latter increases the sensitiveness of gelatin plates somewhat, but
morphine does not. Gelatin emulsion is made more sensitive by
adding excess of ammonia, which is not the case with collodion emul-
sion, and silver bromide collodion emulsion in presence of certain
chemicals can by addition of pigments be made more sensitive to
certain coloured rays (Ber., 9, 669). This is not the case with gela-
tin emulsions. Gelatin emulsions are made moi^e sensitive by continued
digestion, which is not the ca.se with collodion. The author shows that
these differences of behaviour of gelatin and collodion silver bromide
emulsions may be explained by the properties of gelatin by the action of
the different chemicals on it, and further by the different forms in
which silver bromide is precipitated in gelatin emulsions and in col-
lodion emulsions. In the former, it may be obtained in a more finely
divided state, and consequently more sensitive to light.
P. P. B.
Electric Conductivity of Carbon as affected by Temperature.
By W. Siemens (Ann. Phys. Chem. [2], 70, 560— 574).— Matthiessen
having stated that the electric conductivity of gas-retort carbon in-
creases with the temperature, whilst Beetz found no such increase with
artificial coke, and Auerbach has asserted (1879) that the resistance
of gas-retort coke, like that of metals, increases with the temperature,
the author has investigated the subject afresh. His experiments con-
firm Matthiessen's statement as to gas-retort coke, and they show that
artificial coke also follows the same law. He traces the contradictory
results of Beetz and of Auerbach to defective methods of connecting
the pieces of coke with the circuit wires. R. R.
Galvanic Polarisation. By "W. Beetz (Ann. Phjs. Chem. [2], 70,
348 — 371). — The views of polarisation entertained by several physi-
cists, and particukrly by Exner, are discussed in this paper. The
VOL. xsxviii. 3 n
838
ABSTRACTS OF CHEMICAL PAPERS.
author explaius the methods of measurement used by him in a
series of experiments, the results of which lead to the conclusion that
with a current of constant intensity and electromotive force, the
polarisation of the two platinum electrodes is exactly alike, and the
effect is the same whether the polarisation be caused by oxygen or by
hj'drogen. R- R-
Direct Transformation of Radiant Heat into Electricity.
By W. Hankel (Ann. Phys. Cheni., 70, 618— 631).— The paper
describes in detail the effects of radiant heat on a crystal of quartz
in producing electric phenomena distinct from the ordinary pyro-
electric manifestations hitherto recognised, although in some way
related to them. The heat rays were made to traverse the crystal in
the direction of the secondary axes, and the edges at which the rays
entered, and also the opposite edges, were found to give indications of
chano-es of positive or of negative electricity according to the crystallo-
graphic relations of the axes. The phenomena are discussed in con-
nection with the author's circular-uudulation theory of electricity.
R. R.
An Aluminium Battery. By F. Wohler (Liehig's Annalen, 204,
119 — 120). — Under certain conditions aluminium immersed in strong
nitric acid gives a tolerably strong current when brought into con-
tact with another piece of the same metal.
A o-lass vessel 4 to 6 inches high is filled with very dilute hydro-
chloric acid or caustic soda ; an inner porous vessel contains
concentrated nitric acid. In each vessel is placed a cylinder of alu-
minium provided with a pi'ojecting piece passing thi^ough holes in the
cover. To the projecting pieces are fastened short thick copper wires,
between which is stretched a thin piece of platinum wire. As soon as
the cylinders come in contact with the liquids, the platinum becomes
white hot. Gr- T. A.
Molecular Heats and Molecular Volumes of the rare Earths
and their Salts. By L. V. Nilson and O. Pettersson (Ber., 13,
1459 — 1465). — The specific weight and the specific heat of the follow-
inij oxides and salts were determined : —
Specific
weight.
S lecific
leat.
Molecular
heat.
Molecular
volume.
BcoO,
3-016
3-990
3-864
5-046
7-179
8-640
9-175
6-480
6 950
5-850
0
0
0
0
0
0
0
0
0
0
0
2471
1827
1530
1062
1026
0807
0650
0646
0749
0810
1076
18-61
18-78
20-81
19-54
23-29
22-17
24-70
25-45
24-42
27-62
13-13
24-97
A1..0,,
25-76
SoO-,
35-19
GaoO-,
yt.,0-j . • •
44-99
In.,Ov
38-28
Ti],- O,
43 -98
Yb,Ov
42-94
La.^O.,
50-31
Di.,03
49-47
ZrOo
20-86
GENERAL AND PHTSTCAL CHEMISTRY.
839
Si)ecifif
weight.
Specific
heat.
Molecular
heat.
Molecular
volume.
CeO.2 ....
ThO., ....
Be., (SO,) 3
AU(S04)3
80,(804)3
Cr.,(804)3
Feo (80^)3
Ga., (80^)3
y,(S0,)3
In2(SO,)3
Lao (804)3
Ce.,(S04),
Du(S04)3
Er.,(S04)3
yb.,(S04)3
Th.;(so4)3
Be.,(S04)3
Yt.(S04)3
La, (804)3
Ce,(S04)3
Di2(S04)3
Er,(S04)3
1211,0
8H.,6 . .
9HoO . .
5H.,0 . .
8H.,0 . .
8fT.,0..
Ybo(S04)3+ 8H,0
•739
0 0877
■8fil
0 0548
•U3
0^1978
710
0-1855
•579
0 1639
•012
0^1718
■097
©•1656
—
0 1460
•612
0 1319
•438
0-1290
•fiOO
0-1182
•912
0-1168
•735
0-1187
•678
0-1040
•793
0 1039
—
0 -0972
•713
—
•5-40
0 2257
•853
0^2083
•220
0 -1999
•878
0^1948
•ISO
0-1808
•286
0-1788
15 -04
14-47
62-37
63-59
62-42
67-41
66 24
61-90
61 -60
66-41
66-90
66-23
68-96
64-48
65-87
41-21
137 -91
151 -64
131 -33
141 -23
138 13
139-11
25-45
26-77
129 07
126 -50
145 80
130 ^27
12916
178 ^80
149 -77
157-22
144 -94
155 "55
168 • 57
167 15
310-17
240 -55
255 -17
204 -04
251-91
240 -25
236 -79
From these niimbers, it is seen that in a group of isomorphous com^
pounds the molecular heat increases, whilst the molecular volume
diminishes with the increasing atomic weights of the metals.
„ The magnetic properties of the oxides were examined by
Angstrom : —
Magnetic . . .
Diamagnetic.
CraO.,, FeaOs, Y.Os, DUO,, EraO,, Yb.Oa, CeO,.
Be,03, AI2O3, ScA, In.Oa, La^Oa, ZrO^, ThO^.
W. C. W.
Heat of Formation of Hydrocyanic Acid and Cyanides. By
Bekthelut (('umpt. rend., 91, 1\) — 83j. — Two reaciious were made
use of in order to determiue the heat of formation of hydrocyanic
acid; firstly, its transformation into formic acid aud ammonia:
secondly, the conversion of cyanogen chloride into carbonic anhydride,
hydrochloric acid, and ammonia. The heat of formation of ammonia
which is involved in these calculations was taken at + 35-15 units as
determined by Thomson ; Berthelot has, however, shown that this
number must be reduced to + 21-0 ; consequently the number origin-
ally obtained for hydrocyanic acid mu.st be reduced by 14-15. By the
first method, the heat absorbed, — 8*4 units, becomes therefore
— 22-55 units for the liquid acid, and — 2825 for the same in the
gaseous state. The second method gave — lU'l units; this will now
be — 24-25 and — 30'0 units respectively. As very many data are
required in these calculations, it was thought advisable to eliminate
altogether the heat of formation of ammonia, and to measure the
3 n 2
840 ABSTRACTS OF CHEMICAL PAPERS.
results, if possible, in a direct manner by exploding the gaseous acid
with oxygen.
For this purpose, 0"14 gram of the pure liquid acid was enclosed in
a thin glass bulb, and introduced into the steel calorimetric bomb
described in a previous communication. Tlie bomb having been filled
with oxygen was closed, and the bulb broken. The acid volatilised
rapidly at 18°, and the explosion was effected without difficulty. The
carbonic anhydride produced was subsequently pumped out of the
apparatus, and received in weighed potash bulbs, whereby a valuable
control was obtained over the accuracy of the combustion ; in this way
it was found that a trace of hydrocyanic acid, about one-hundredth
part, always escaped combustion ; this was determined for every ex-
periment in the potash after the latter had been weighed, and allowed
for in the succeeding calculations. The numbers obtained at constant
volume have been corrected to constant pressure.
One molecule of hydrocyanic acid in grams gave, from the initial
weight of acid, 158"4 units ; from the carbonic anhydride produced,
IGO'2 ; mean, 159'3 units. This number exceeds the heats of com-
bustion of the carbon and hydrogen contained in the acid : —
C (diamond) + O, = + 94-0
H., + 0 = HoO liquid = + 34-5
128-5
So that the formation of hydrocyanic acid from its elements gives
+ 128 — 159'3 =^ — 80'2 units, a number which is practically con-
cordant with those obtained by the indirect methods ; the mean of the
whole is — 29'5 units. A complete table accompanies this communi-
cation, showinor the heat disengfao-ed in the formation of a large
number of the haloid and metallic combinations of cyanogen.
J. W.
Thermochemical Research on Cyanogen and Hydrocyanic
Acid. By J. Thomsen (£er., 13, 1392—1394). The heat of forma-
tion of gaseous hydrocyanic acid, as deduced by Berthelot from the
heat evolved in the decomposition of hydrocyanic acid by strong
hydrochloric acid, is incorrect. Instead of — 9740 the true value is
— 28360. The results based on the former number are consequently in-
correct. The corrected values are —
Heat of Heat of
combustion. formation.
CoT^. 261290 -67370
CNH 159500 -28360
N + H., — 11340
C0N2 + H2. . . . — 10650
N" + C -I- H. . 1 for gaseous 10540
C2 + N. / carbon 10430
w. c. w.
Constitution of Isomeric Hydrocarbons. By J. Thomsen
(Ber., 13, 1388 — 1391). — ^The heat of foi-mation of a hydrocarbon can
be f^alculated from the following formula : — (C«H2,«) ^ — nd + 2mq
GENERAL A\D PHYSICAL CHEMISTRY. 841
+ xv' + yv" + zv'", when d = the heat of dissociation of carbon ;
2q = the heat developed by the combination of an atom of carbon with a
molecule of hydrogen, and' x, y, and z are the number of single, double,
and triple linkings.
Since the values of q, v and v" are nearly equal, they may be re-
presented by r = 14570 ; and r'" is so small that it may be neglected,
the following simplified formula maybe used: (C«H2;n)= — n. 38900 -f
(2w + a; + ?/) 14570, d being equal to 38900°.
The constitution of isomeric hydrocarbons may in many instances
be ascertained from their heat of formation, since a double linking of
two carbon atoms has a considerable influence on this value, e.g., the
heat of formation of propylene was found to be —400, which shows
that its constitution is HoC '. CH.CH3, and not H3C.C.CH3, since the
calculated heat of the former compound is— 150°, and that of the
latter + 14430°. W. C. W.
Variations in the Coefficient of Expansion of Glass. By J. M.
Crafts (Compt. rend., 91, 413 — 415). — Since the coefficient of glass
varies with the temperature, it is clear that the interval between any
two points on a thermometer varies and the graduation becomes incor-
rect. By heating a thermometer for some time to 335", and then
cooling it slowly, the coefficient of expansion is diminished, so that if
the zero point be raised t'^, then 100^ is raised 100 + t +t'.
By determining the coefficient of expansion of glass between 0° and
100° and 0° and 216-14° before and after heating to 335°, it is found
that—
Between 0° and 100° before heating to 335^ k = 0-00002784
after „ „ k = 0-000027405
„ 0° and 216-14° before „ „ Z; = 0-00002979
after „ „ 7c = 0-00002914
which would have increased about 0-28 the value of 100^ on the
scale.
From a number of observations made on ordinary French glass, the
value of k for different temperatures may be calculated from the for-
mula kt = a + ht -f ct-. It remains to be shown whether this formula
remains constant for the same kind of glass after long heating and
slow cooling, and also what effect the different degrees of tension pro-
duced by blowing the bulb has on the coefficient of expansion.
The author advocates the use of thermometers with limited scales
(such as from 200° to 300"") for high temperatures, instead of those
registering from 0° upwards. L- T. O S.
Meyer's Method of Determining Vapour-densities. By 0.
Peitersson and G. Ekstrand {Ber., 13, 1185— 1191).— The authors
have submitted this method to a comparison with that of Dumas,
determining the vapour-densities of pure benzene, formic and acetic
acids in steam, and in the vapours of toluene, turpentine, aniline, and
nitrobenzene.
From this examination, it is found that Meyer's method gives results
smaller than those obtained by Dumas, and further, there is less
842 ABSTRACTS OF CHEMICAL PAPERS.
concordance amongst the results with the former method than with the
latter.
The authors point out the following sources of error in Meyer's
method : —
(1.) The condensation of air on the surface of the vessel containing
the substance. To neutralise this, experiments were made with formic
acid sealed in a bulb, which was fastened on to a long glass rod pass-
ing through the caoutchouc stopper. The whole was then heated by
the vapour of liquid used, and when it attained a constant temperature
the bulb was broken by moving the glass rod. Still with this the
vapour-density was found to be lower than by Dumas' method.
(2.) The chief error is the condensation of air on the substance
itself ; this error cannot be corrected, and its influence will vary with
diiferent bodies. The cause of the difference between the results of the
two methods, in the case of formic and acetic acids and of benzene, is
due to the presence of air or nitrogen, for Playfair's and Naumann's
investigations have shown that in the presence of a permanent gas the
vapour-densities of these bodies approach the normal. The authors
show also that the influence of the condensed air is great in case of
solids at 220°, and must be still more so at higher temperatures.
P. P. B.
Critical Point of Mixed Vapours. By J. Dewak (Ghem. Neivs,
42, 15 — 1?). — Carbo)iic Anhydride and Carbon Bisulplude. — Carbonic
anhydride at 19° liquefies in presence of carbon bisulphide under a
pressure of 49 atmospheres, and the liquid floats on the surface of the
bisulphide. The same phenomenon was observed at —
35° at a pressure of 78 atmospheres
40 „ „ 85
58 „ „ 110
At 47°, and a pressure of 80 atmospheres, the layers of liquids were
not so definitely marked. On increasing the pressure to 110 atmo-
spheres, the upper layer of liquid almost entirely disappeared, and on
reducing the pressure to 80 atmospheres, the liquids mixed completely ;
a further reduction of 5 atmospheres caused them to separate. On
quickly reducing the pressure to 58 atmospheres, and gradually in-
creasing it to 85 atmospheres, the liquids again mixed.
Carbonic A)tJii/dride and Ckloroform. — At 18^ and a pressure of 25
atmospheres, carbonic anhydride liquefies, forming a layer on the sur-
face of the chloroform. On increasing the pressure to 50 atmospheres,
the two liquids mixed completely after standing for a few minutes. At
33° the liquid forms under a pressure of 35 atmospheres, and at a
pressure of 55 atmosphei-es the two liquids mix. At 55° the liquid
forms at a pressure of 50 atmospheres, and at &7'^ under a pressure of
85 atmospheres, the two liquids in each case dissolving each other
after standing for a few minutes.
Carbonic Anhydride and Benzene. — In presence of benzene, carbonic
anhydride at 18'' begins to liquefy under a pressure of 25 atmospheres,
and dissolves in the benzene, the solution becoming saturated, any
further quantity of condensed liquid floating on the surface ; but on
GENERAL AND PHl'SICAL CHEMISTRY. 843
allowing the two liquids to stand for about five minutes, tliey mix
completely. At 35", the gas liqueties under a pressure of 35 atmo-
spheres. At this temperature, liquid carbonic anhydride is only
sparingly soluble in benzene. At 52° the liquid formed under a pres-
sure of 60 atmospheres, and at 70° under 85 atmospheres.
Carhonic Anlujdride and Ether.— At 20° a pressure of 20 atmo-
spheres is required to liquefy carbonic anhydride in presence of ether.
The two liquids mix in all proportions. At 42° under a pressure of
55 atmospheres a distinct layer of carbonic anhydride is formed, and
appears to slowly dissolve in the ether. A distinct layer of liquid at
68° is formed under a pressure of 110 atmospheres.
Carhonic Anlujdride and Nitrous Oxide. — These two gases when
liquefied mix together in all proportions. On reducing the pressure,
one liquid evaporates before the other, and a distinct line of separa-
tion appears for a short time.
Carbonic Anhydride and Phosjihorus Trichloride. — At 16'2° and 42'95
atmospheres, the carbonic anhydride began to liquefy before the phos-
phorus trichloride, and when the latter appeared, a slight indistinct
layer of carbonic anhydride floated on its surface, but the two liquids
mixed together on standing for a few minutes. At 23°, and a pressure
of 46 "91 atmospheres, the same phenomenon was observed. At 30°,
and under a pressure of 49"94 atmospheres, the carbonic anhydride
began to liquefy ; it is not so soluble iu phosphorus trichloride at this
temperature as at lower temperatures.
At 33° carbonic anhydride liquefies under 5084 atmospheres
40 „ „ 56-88
50 „ „ 66-53
With smaller quantities of substances the following results were
obtained : —
At 10-5° 22-70 atmos.
16-5 24-70 „
22-8 .32-18 „
30-0 33-88 „
At 40^ 36-36 atmos.
50 49-67 „
70 76-61 „
Carbonic Anhjdride and Carbon Tetrachloride. — At 12-8° the carbonic
anhydride begins to liquefy, forming a distinct layer on the surface of
the chloride. The two liquids, however, dissolve each other after a
short time. At 21-4°, 30", 40°, 52°, and 58°, similar effects take
place.*
Carhonic Anhydride and Methyl Cldoride. — Two volumes of carbonic
anhydride and one volume of methyl chloride at 13-5° C. The methyl
chloride liquefies first, and at a pressure of 26 67 atmospheres, the
anhydride began to liquefy, and rapidly dissolves in the chloride at
20-05°. Liquid carbonic anhydride appears at 28-57 atmospheres.
Carhonic Anhydride and Acetylene. — Equal volumes of the two gases
were condensed, together, in which proportion they mix completely at
the following temperatures : —
* No details of the pressures required are given in this case.
844 ABSTRACTS OF CHEMICAL PAPERS.
At 13-5° the pressure was 25-23 atmospheres
21-0 „ „ 26-8
341
42-26
65-3
75-52
26-8
31-9
39-0
41-0
The last temperature is the critical point.
Garhonic Anhydride and Hydrochloric Acid. — The following are the
temperatures and pressures at which a mixture of equal volumes of
the two gases liquefy : —
At 0-0° 36 atmos.
5-0 39 „
8-0 43-8 „
10-1 48-2 „
At 18-5° 59 atmos.
34-0 83 „
35-5 90 „
Garhonic Anhydride and Bromine. — At 40° and a pressure of 60
atmospheres, two distinct layers of bromine and liquid carbonic anhy-
dride containing some bromine dissolved in it, appear; at 90 atmo-
spheres' pressure, the two liquids are miscible.
Garhonic Anhydride and. Camphor,— 'Vh.Q camphor was melted, and
allowed to adhere to the sides of the tube. At 12°, the camphor melts,
and on increasing the pressure, two distinct layers are formed, the
lower liquid being cloudy from dissolved camphor, the upper one
quite clear. The two layers are always present at all temperatures up
to 55°. The upper layer, however, diminishes with increase of tem-
perature. At 40°, a thin layer remains even at a pressure of 125
atmospheres. A further experiment gave the following results. At
15° the camphor melts at a pressure of 2?-? atmospheres ; by increasing
the pressure to 37 atmospheres, two distinct layers of liquid are
formed, which become homogeneous after a short time. At 35°, two
layers are formed under a pressure of 80 atmospheres. At 100 atmo-
spheres, the two liquids mix. At 45°, the same takes place under 100
atmospheres, and the two liquids disappear on increasing the pressure.
At 42-5°, the pressure being suddenly reduced, the camphor crystal-
lises, and on increasing the pressure to 27-6 atmospheres, the cam-
phor liquefies completely without further increase of pressure. At
60°, the lower layer of liquid remained at a pressure of 100° atmo-
spheres.
Garhonic Anhydride, Air, and Camphor. — A mixture of 4 volumes
carbonic anhydride and 1 volume air, was saturated with camphor-
vapour. On increasing the pressure at 25°, the camphor liquefied ; at
50°, a quantity of liquid formed under a pressure of 65 atmospheres ;
on increasing the temperature to 60°, the pressure remaining the same,
crystals of camphor separated out on the tube above the liquid ; they
disappeared on increasing the pressure to 70 atmospheres. At 65°, on
reducing the pressure from 70 to 65 atmospheres, camphor crystals
again separate out, and redissolve on increasing the pressure to 73
atmospheres. On decreasing the temperature to 16°, camphor sepa-
rated out from the liquid, and dissolved again on increasing the
pressure, although it could not be separated again by reducing the
GENERAL AND PHYSICAL CHEMISTRY. 845
pressure. These effects may be due to supersaturation, and the effect
of pressure on adding solubility when contraction takes place during
solution.
It appears from the above experiments that carbonic anhydride in
presence of various substances acts at high pressures as though it pro-
duced unstable compounds, which are decomposed and reproduced
according to the conditions of temperature and pressure of the
medium. L. T. O'S.
Lowering of the Freezing Point of Water by Pressure. By
J. Dewar (Chem. News, 42, 1 — 2). — To test the accuracy of the pres-
sure gauge of Cailletet's pump and the constancy of thermal junctions
under pressure, experiments were made on the influence of pressure on
the freezing point of water.
In the experiments, a movement of the galvanometer to the negative
side showed a cooling effect of the junction inside the bottle. Two
thermal junctions were used, consisting of iron-copper wire insulated
by marine glue, the junction being covered with a thin layer of gutta-
percha. One junction was placed inside the bottle to show the influ-
ence of pressure under different circumstances, the other was kept out-
side at zero.
Series I. — One junction was fixed in a brass flange frozen in a test-
tube containing boiled water placed in an iron bottle and surrounded
with water at 0^ ; the bottle was also packed with ice. The pressure
was raised in different experiments from 300 to 700 atmospheres in
steps of 25 atmospheres at a time. The mean deflection obtained for
25 atmospheres was 19" 7 on the scale (1 division = xi2° C.) or
0"18° C, which gives a reduction of 0'00027° for 1 atmosphere
pressure.
Series II. — The junction was placed in a quill open at both ends
and surrounded with water at 0° ; the iron bottle was packed as in
Series I. The total deflection obtained for 200 atmospheres was
4 divisions ^ ~° C. This result is in accordance with Joule's ex-
periments on tiie compression of water.
Stries III. — The junction was surrounded with a mixture of water
and ice and the iron bottle packed as before. In this case similar
results were obtained to those in Series I, a mean deflection of 19"4
divisions for every 25 atmospheres.
Series IV. — In these experiments, the junction was surrounded with
brine and placed in the bottle, which was packed with ice and salt to
reduce the temperature to — 2U°. The junction outside was also placed
in ice and salt. A heating effect was produced which decreased as the
pressure increased, the total increase in temperature being ^V" C. for
200 atmospheres' pressure.
Series V. — The junction, frozen in a block of ice, was placed in the
bottle and surrounded with brine at — 20°; the bottle was packed
with ice and salt. A slight heating effect was produced, 1^ divisions
of the scale for 200 atmospheres.
Series VI. — These experiments were similar to Series I, excepting that
mercury instead of water surrounded the junction in the test-tube.
The results obtained were exactly the same as those above mentioned.
846 ABSTRACTS OF CHEMICAL PAPERS.
but owing to tlie heating of the mercury by compression the experi-
ments could not be continued for long, since the ice rapidly melted.
Series VII. — Since the junction appeared to be afFected by continual
subjection to pressure, and in some cases worked somewhat irregularly,
both junctions, insulated by marine glue, were placed in the flange;
one was frozen inside the test-tube and the other remained outside and
placed in the bottle, and both subjected to pressure. Exactly the same
results were detained as when one junction was place outside the
bottle, but still after repeating the experiment two or three times
irregularities occurred. To prevent the junction being subjected to
pressure, an iron tube closed at the bottom, about a quarter of an
inch internal diameter and long enough to reach to the centre of the
bottle, was soldered into the flange ; a few drops of alcohol were placed
in the tube and the junction was lowered into it from outside, the por-
tion of the tube in the bottle was frozen into a test-tube and thus sus-
tained the pi'essure, any alteration in temperature being conveyed
through the iron to the junction. In this case also the results cor-
responded with those previously obtained.
These results prove that those deduced from the observed differences
of volume of ice and water and the latent heat of fluidity under one
atmosphere pressure are correct. It may therefore be assumed that
TV
= constant where V is the difference of volume and L the latent
heat of fluidity. If V is assumed to be approximately constant, then
T X L is the latent heat of ice diminished as the freezing point is
diminished by pressure. L. T. O'S.
Oven for Heating Sealed Tnbes. By L. v. Babo (Ber., 13,
12iy — 1223). — The autlior describes a new form of such oven pos-
sessing many advantages, and in which by the circulation in it of
the heated gases from the source of heat an equable temperature is
obtained. Further, an arrangement is described by which the amount
of gas burnt is regulated so as to obtain a constant temperature. For
details the orisrinal must be consulted. P. P. B.
Lecture Experiments. By M. Rosenfeld (Ber., 13, 1475 —
147/).-— 1. Change of temperature produced when salts dissolve.
2. Absorption of ammonia and hydrochloric acid by water.
3. Crystallisation of sulphur and of mercuric iodide from solution
in acetic anhydride. W. C. W.
Inorganic Chemistry.
Vapour-density of Iodine, &c. By Berthelot (Compt. rend., 91,
77 — 78). — This paper is merely a statement of the author's opinion
that inasmuch as V. Meyer and others have shown that iodine and the
other halogens at high temperatures and low pressures do not obey
the laws of Mariotte and Gay-Lussac, as established upon three ele-
INORGANIC CHEMSTRY. 847
mentary gases only, and as the diminntion of density in the case of
iodine is moreover pi'ogressive, no correct conclusion can be drawn
with respect to variation in the number of molecules. He thinks that
one law only remains universally applicable to the elements, namely,
the invariability of their relative combining weights, that is to say, the
notion of equivalents. J. W.
Ozone. By P. Hautkfeuille and J. CnA?PUis {Comitt. rend., 91,
228 — 200). — The tension of the transformation of oxygen into ozone
is dependent on both the temperature and pressure. This tension
increases rapidly as the temperature decreases, being at — 23° nearly
double what it is at 2u°. For temperatures above 0", the proportion
of ozone produced is greatest when the pressure is above Oo atmo-
sphere. By raising the temperature, the rate at which the ozone is
formed is lessened, and it is also more difficult to complete the reac-
tion, especially if the gas is rarefied ; and it may be that this maximum
is consequent on the slowness with which the transformation takes
place.
The proportion of ozone to the total volume of gas is not influenced
by pressures below certain limits (about 180 mm.). This transforma-
tion of oxygen under the influence of the electric spark is analogous
to the dissociation of compound gases, which at certain temperatures
is limited by tension proportional to the total pressure. In the case of
hydriodic acid, the proportion of free iodine and hydrogen increases as
the pressure diminishes, and in the case of the formation of ozone, the
proportion of the oxygen in relation to the ozone also increases as the
temperature diminishes. L. T. O'S.
Formation of Hydrogen Peroxide and Ozone. By A. R.
Leeds {Ckem. Nevjs, 42, 17 — 19;. — The author proves that both
hydrogen peroxide and ozone are formed by the action of air on moist
phosphorus. On heating the ozonised air, the quantity of water formed
by the decomposition of the hydrogen peroxide increases regularly,
whilst that of the ozone decreases, until at a temperature of 20U° both
are completely decomposed.
That ozune and hydrogen peroxide in the dilute state can exist
together without much loss is also proved, and it is shown that the
proportion the two gases bear to one another is 3 to 1.
Oxygen from which all traces of ozone and hydrogen peroxide have
been removed by strong heating oxidises an acid solution of potassium
iodide, it is therefore necessary that the reagent used for the detection
of ozone should be perfectly neutral. L. T. O'S.
Vapour-densities of Selenium and Tellurium. By H. St.
Claiee Deville and Teoost {Compt. rend., 91, S3 — bb). — Recent ex-
perimental research having reopened questions respecting the vapour-
densities of selenium and tellurium, it is thought advisable by the
authors to give full details of their work in connection with this sub-
ject. The analyses were executed 2U years ago, and at the time of
publication a summary only was given. For obvious reasons these
details cannot be wholly reproduced in abstract.
848
ABSTRACTS OF CHEMICAL PAPERS.
In comparing at a very higli temperature the vapours of iodine and
selenium, the increase in weight of the flask in the case of selenium
was 0"014 gram, in the case of iodine O'Oll gram. It was then re-
marked that " there is a manifest error in the weight of iodine remain-
ing in the flask, for with the number O'Oll gram a temperature of
nearly 2,000° would be attained;" to this is now added, " owing to
the recent experiments of Victor Meyer, that which appeared erroneous
in 1860 may now be considered as correct."
The vapour-density of selenium was also taken in a porcelain globe
and compared with that of air contained and heated in a similar
apparatus. The calculated temperature being 1,420^, the theoretical
density became 5"54 ; the density actually found was 5'68.
Operating in a similar manner with tellurium, the results of its
vapour-density determination were, at a temperature of 1,439^, theory
8'93, experiment 9*0 ; at a tempei-ature of 1,390'', theory 8*93, experi-
ment 9-08. J. W.
Ammonia in Air and Water. By A. Lifivr (Com.pt. rend., 91,
94 — 97). — liain Water. — Although individual analyses of rain water
collected from different quarters of Paris show varying proportions of
ammoniacal nitrogen, the mean monthly and yearly results are
sensibly identical. The quantity of nitrogen decreases pretty regu-
larly in passing from the cold to the warm season of the year,
generally reaching its minimum in July ; the mean result for that
month in 1879 was 0'93 mgrm. per litre of water, and the mean for
the year, with four recording stations, 1'17 mgrms.
In the latter months 1,he drinking water of Paris also shows a
minimum of ammoniacal nitrogen, 0'21 mgrm. per litre ; the maximum
0'27 mgrm. occurring in December ; the small difference between these
numbers shows the great uniformity of the Paris water supply.
The yearly means in 1879 — 1880 were —
Vaune 0'21 mgrm.
Dhuis 0-24 „
Marne 0-24
mgrm.
Ourcq 0-22
Seine 0-22
(Sewage) .... 20"00 mgrms.
Summing up the results of four years analyses of rain water col-
lected at the Observatory of Montsouris we have —
September
Mean
Nitrogen per
to August.
Rain gauge.
per litre.
square metre.
1875—1876
541'5 mm.
1-98 mgrm.
1074-78 mgrm.
1876 1877
601-7 „
1-54 „
929-65 „
1877—1878
600-1 „
1-91 „
1149-40 „
1878—1879
65.5-3 „
1-20 „
787-32 „
Air. — Contrary to what has been observed in the case of rain
water, ammonia was most abundant in the air during the hot season.
Thus in 1878 — 1879 the total weight in winter corresponding to
153 days' analyses was 257-6 mgrms., giving as a mean 1-68 mgrms.
per 100 cm. ; in summer the total weight was 269-7 mgrms. for
129 days, or 2-09 mgrms. for 100 em.
IXORGAXIC CHEMISTRY. 849
The same volume of air collected in the Paris sewers gave from
4"6 to 9"4 msrrms. of ammoniacal iiitrogfen.
These numbers differ from those obtained by Griiger, Kemp, and
Fresenius, but accord very well with those of Ville and Schloesing.
J. W.
Chemical Composition of certain Hydrated Oxides. By
J. M. V. Bemmklx {JJer., 13, 1460 — 14G'J). — An examination of the
hydrated oxides of silicon, manganese, and tin, shows that the com-
position of these bodies varies with the molecular condition of the
oxide, and also with the temperature and the amount of moisture in
the atmosphere. The hydrates have a definite dissociations-tension,
which varies with the temperature and humidity of the atmosphere.
w. c. w.
Isomeric Modification of Aluminium Hydrate. By D. Tom-
MASi {Comjjt. rend., 91, "iolj. — By allowing ordinary aluminium
hydrate, precipitated by ammonia from a solution of alum, to stand
with water for about three months, it undergroes a molecular chanare.
It is only very sparingly soluble in acids and alkalis. In acetic acid
it is insoluble. It has the same formula as the normal hydrate, but it
does not combine with aluminium chloride to form an oxychloride.
The author proposes to call it aluminium hydrate d to distinguish it from
the normal hydrate a, gibbsite /3, and the colloid hydrate of Graham, 7.
L. T. O'S.
Potassium and Sodium Aluminates. By A. B. Prescott (Ghem.
Nevjs, 42, 29). — Potassium Aluminate. — On treating a decinormal
solution and a deci-l|-normal solution of potassium alum respectively
with normal and decinormal .solutions of caustic potash until the pre-
cipitate formed was just dissolved, it was found that in every case the
proportion of potassium to aluminium in the soluble aluminate is re-
presented by the formula K2ALO4, or AI2 < (Trr\\ , the equation being
K,AL(S04 + 8KH0 = K.,AloOi + 4K,S0i -f- 4H,6.
The quantity of potassium sulphate solution present for one part of
soluble potassium aluminate in the different degrees of dilution is as
follows : —
With AI2 deci-l^-normal and K normal .... 79 parts solution.
„ AI2 decinormal and K normal 91 ,,
„ AL deci-l|^-normal and K decinormal 445 ,,
,, AI2 decinormal and K decinormal. . . . 456 ,,
The same compound is obtained by saturating caustic potash wnth
aluminium hydrate, evaporating to dryness, and extracting the excess
of alkali by alcohol (Pogg. Ann., 7, 723).
Fremy (Ann. Chhn. 'Phijs. [3], 12, 362 ; Compt. rend., 15, 1106)
obtained it in a crystalline form by fusing the residue ; he also states
that K2AI2O4 is decomposed by much water, aluminium hydrate being
precipitated, and Al2(KO)6 is probably left in solution.
Sodium Aluminate. — Similar experiments were made with alum and
caustic soda with similar results, the formula for the compound being
850 ABSTRACTS OF CHEMICAL PAPERS.
AlA /-vr n^ ' formed according to the equation K2Al2(S04)4 +
8NaH0'=: NaoAl,04 + K0SO4 + SNaoSOi + 4H2O. The greatest
dilution was 1 part of aluminate in 546 parts solution, and the least
1 part in 95 parts. Tissier {Gompt. rend., 48, 627, and .Tahr. Chem.,
1859, 143) obtained four different compounds, N'a2Al304, Na6Al409,
Na4Al,05, and N-acALOc L. T. O'S.
Atomic Weight of Glucinum. By L. F. Nilson and 0. Pkt-
TERSSON {-Ber., 13, 1451 — 1459). — The authors have determined the
atomic weight of glucinum by the analysis of the sulphate, and
obtain the value 13"65 as the mean of four experiments. The specific
heat of tlie metal increases with the temperature. Between 0° and
100°, specific heat = 0-4246, atomic heat = 579. Between 0" and 300°,
specific heat = 0'5060, and the atomic heat = 6"90.
In reply to L. Meyer's statement (Ber., 6, 576) that the atomic
heat of oxygen calculated from the molecular heat of glucina, G2O3,
is too low, viz., 2'47, the authors point out that this number closely
agrees with that deduced from the specific heats of the other metals of
this group,
At. heat of O. At. heat of O.
GoOs 2-34 GaoOs 2-88
Ai.,0, 2-35 In^Oa 3-08
SC2O3 2-67 W. C. W.
Atomic Weight and Characteristic Salts of Scandium. By
L. F. NiLSON (Cumpt. rend., 91, 118—121, and Ber., 13, 1439-1450).
— The scandia used in these experiments was principally extracted
from euxenite, but some residues from gadolinite and keilhauite were
also at the disposal of the author.
The new earth may be separated from ytterbia by taking advantage
of the fact that the nitrate decomposes more easily by heat than that
of vtterbium, and that scandium sulphate produces in a saturated
solution of potassium sulphate an insoluble double salt. This double
salt nevertheless contains a little ytterbium sulphate, which may be
finally removed by converting them into nitrates, and submitting the
latter to partial decomposition by heat ; the ytterbium nitrate can
then be washed out.
The sample of scandia used for determining the atomic weight was
prepared by dissolving the pure sulphate in water with addition of a
little nitric acid, and precipitating it as oxalate ; the oxalate when
calcined yields scandia perfectly pure. A specimen prepared in this
manner was examined spectroscopically by Thalen, who was unable to
detect the presence of any foreign substance.
The atomic weight was found by weighing the oxide, converting it
into sulphate, and weighing the sulphate produced. If the oxide be
ScoOa, then the mean of four experiments gives 44'03 as the atomic
weight of scandium.
Scandia, ScjOij, is a light, infusible, white powder resembling mag-
nesia. It dissolves easily in boiling nitric and hydrochloric acids, but
scarcely at all in the cold. It is not volatile, and gives no coloration
INORGANIC CHEMSTRY. 851
to iame, although a very brilliant spectrum may be obtained by the
electric spark from the chloride.
The nitrate crystallises from a strong solution in small prisms ; when
strongly ignited, it is converted into oxide, but on treating this with
water, a very basic nitrate generally dissolves, forming an opaque
milky solution, which never becomes clear ; this reaction is very
characteristic of scandium.
The sulphate, 800(804)3 + 6H0O, may be prepared as before men-
tioned ; it is unalterable in the air, but loses 4 mols. of water at 100°,
and the anhydrous salt is produced on gentle ignition ; when strongly
heated, it loses sulphuric acid and forms scandia.
The do2tble sulphate, K.S04.8c2(804)3 + aiHsO, forms small prisms
grouped in a peculiar manner, which gives them a characteristic ap-
pearance. It is very slightly soluble in water, and quite insoluble in a
saturated solution of potassium sulphate.
The selenite and oxalate may be made by precipitation with the
corresponding sodium salts ; both are insoluble.
The composition of the earth, 8C0O3, is proved by the following
facts : —
1. 8candia is found in minerals associated with other rare earths of
the formula R2O3.
2. Solutions of scandium and ytterbium salts behave in the same
manner with oxalic acid.
3. There is great analogy between the behaviour of the nitrates of
these two metals at high temperatures.
4. The composition of the double salt with potash shows that
scandium belongs to the group of metals obtainable from gadolinite
and cerite, all these metals giving salts of the same typical composi-
tion.
5. The insolubility of the same salt in a solution of potassium sul-
phate singles out scandium in particular as a member of the cerite
group.
6. In the composition of the selenites, this earth presents great
analogy on the one side to Y0O3, ErjOj, Yb.;03, and on the other to
AI2O3, In.Os, Ceo03, La203, which furnish analogous acid salts.
7. The atomic weight, 44, is the number which Mendelejeff predicted
for the undiscovered element elcaboron.
8. The specific heat and molecular volume of the earth and of the
sulphates place scandia as intermediate between glucina and yttiia.
J. W.
Cerium Tungstate. By A. Cossa and M. Zecchini (Gazzetta, 10,
225 — 232). — The cerium tungstate was prepared by gradually adding
a solution of pure cerium sulphate to a cold aqueous solution of normal
sodium tungstate, keeping the latter in slight excess ; if the tungstate
be added to the solution of cerium sulphate, the precipitate will be
contaminated with the sparingly soluble sodium cerium sulphate.
The yellowish flocculent precipitate dried at 100° has the composi-
tion CeWOi + HjO, but loses its water on ignition, and fuses at a
very high temperature, but more readily than scheelite. On cooling,
it forms a sulphur-yellow crystalline mass, with conchoidal fracture ;
sp. gr. = 6"514 at 12°; specific heat as determined by Naccari, 0'0821.
852 ABSTRACTS OF CHExMICAL PAPERS.
That of scheelite is 0-1005 (Kaccari) or 0-0967 (Kopp). Taking Ce
as 92 tliis gives
Mol. weight. Sp. heat.
CeWO, 340 X 0-0821 = 27-91
CaWOi 288 x 0-1005 = 28-94
CaW04 288 x 0-0967 = 27-84
so that it would seem probable the cerium in cerium tungstate is
bivalent like calcium. C. E. G.
Zinc Oxide in Alkaline Solutions. By A. B. Prescott (Ghem.
Neivs, 42, oO). — By treating a normal solution of zinc sulphate with
a normal potash solution, it is found that at 17° C. 8 c.c. of
the alkaline solution are required to redissolve the precipitate, and
that 4 c.c. of a seminormal sulphuric acid solution can be added to the
mixture before reprecipitation takes place. It therefore appears that
the compound KsOZnO is formed according to the equation, ZnS04-|-
4K0H = KoOZnO + KoSOi + 2H,0. This compound has previously
been obtained in the crystalline state by Laux {Annalen, 9, 165), and
Fremy (Co^npt. rend., 15, 1106). The solution with excess of alkali
is reprecipitated by excess of water. Decinormal potash solution
would not dissolve the precipitate. The weakest solution capable of
16-5
dissolving the precipitate is — — • x normal. At a temperature of 50°,
the solubility of the precipitate is greatly diminished.
Caustic soda forms a similar compound, Na^OZnO, which is more
soluble in the alkali, requiring only an excess of 3 c.c. ; at 50°, the
solubility of the precipitate is also diminished.
Ammonia also forms a compound with zinc oxide. 1 c.c. of zinc
sulphate requires 5 c.c. of normal ammonia solution, and the reaction
takes place according to the equation 2ZnS04 + IONH4HO =
3(NH4)22ZnO + 2(NH4)2S04 + 5HoO. The precipitate forms again
on diluting the solution with water. Malajjuti (Cunipt. rend., 62,
413) obtained a crystalline zinc ammonium oxide having the composi-
tion NH3.Zn0.3H20[NH4HO.Zn(OH)o.HoO], or Zn(OH)(NH,)..3HoO.
Weyl (Jahresb., 1864, 165, and Fogg. Ann., 123, 353) obtained the
compound (NH3)aZnO. The author considers the compound obtained
fNHa
. . ZnO j ^
by himself to have the constitution | <( -vrxT^
ZnO ^^^
NH3
NH3 L. T. O'S.
Silver- ammonium Oxide. By A. B. Prescott {Cliem,. News,
42, 31). — The compound formed when ammonia is added to silver
nitrate in sufficient quantity to dissolve the precipitate first produced,
NH Ao- 1
may be represented by the formula, ]sttt\^ \ 0, the reaction being
2AgN03 -f 4NH4OH = (NH3Ag)oO -f 2NH4NO3 + 3H,0.
L. T. O'S.
INORGANIC CHEMISTRY. 853
Two New Basic Copper Chromates. Non-existence of
Potassium Copper Chromate. By M. Rosenfeld (Ber., 13, 1469
— 1475). — Tlie preripitiite wliicli is formod when potassium chromate
is added to a snlutiou of copper suljthate, has the composition
Cr0..3CnO ^ 2H.,0.
Although tlie colour of the substance varies with the temperature
and concentration of the solutions, its composition is constant. Tlie
same salt is formed by disfestins^ freshly precipitated copper hydroxide
with a solution of potassium dichromate, but in this case it is mixed
with crystals of potassium dichromate.
No change takes place when solutions of potassium dichromate and
copper sulphate are mixed toorether, but if sufficient potash is added
to convert the dichromate into neutral chromate, then CrOa.SCuO +
2H2O is formed. If a larcrer quantity of potash is used, a yellow or a
green precipitate will be thrown down. The former has the composi-
tion 2CrO:,.7CuO + oHjO, the cjreen salt which changes to brown on
drying has the formula CrO^./'CuO + 5H,0. W. C. W.
Fluorine Compounds of Uranium. By A. Ditte (Compt. rend.,
91, 115 — 118). — When the s'reen oxide of uranium, UaOj*, is treated
with hot concentrated hydrofluoric acid, it is rapidly attacked, with
production of a vellow solution and an insoluble fine green powder.
On evaporation the solution yields yellow transparent crystals which,
when dried at VKf, have the formula U..P:i.4HF.
This fluohydrate, heated in a closed crucible, first melts, and then
evolves fumes of hydrofluoric acid ; if air has access, the fluoride is
completely decomposed, and uranium protoxide is produced. The
green substance before mentioned is insoluble in water, and very little
soluble even on heating in dilute aeidi?, other than sulphuric acid and
aqua regia. It is an oxyfluoride to which analysis assigned the
formula IJ.O3F.
The author regards the green oxide as capable of separating und( r
favourable conditions according to the equation 2Ua04 = 2U2O3 -f
U2O3 ; in presence of hydrofluoric acid, the sesquioxide dissolves with
formation of flaohydrate, whilst the protoxide behaving like an ele-
mentary body combines with the halogen of the acid, and liberates
hydrogen. This reaction was verified by treating a known weight of
the green oxide with hydrofluoric acid, and weighing the products of
the reaction.
Uranyl fluoride. U2O2F, melts and decomposes at a bright red heat,
giving off vapours which conden.se tx) yellowish-white transparent
needles, and leaving behind brilliant black crystals of uranium prot-
oxide. The reaction appears to be as follows: — 2U-.0,iF = U2OF2 -h
U2O2 + 0. ^
The oxyfluoride, U2OF2, is very soluble in water; it melts and
volatilises at a red heat, but in presence of air it is decomposed with
formation of protoxide.
When uranyl fluoride is heated to redness in a current of hydrogen,
it evolves hydrofluoric acid, and is ultimately converted into crystalline
* U = 120.
VOL. xxxviii. 3 0
854 ABSTRACTS OF CHEMICAL PAPERS.
protoxide; but as long as the reaction is incomplete and the salt
retains fluorine, it yields a sublimate of oxyfluoride, U3OF2, if strongly
heated in a close vessel. J. W.
Chemistry of the Platinum Metals. By T. Wilm (Ber., 13,
11'JS — 1204). — According- to v. Schneider (Armalen, Sup., 5, 261),
pure palladium may be obtained from, the filtrate of platinum-ammo-
nium chloride, by precipitating the metals with zinc and dissolving
out tiie copper and palladium by nitric acid. The palladium is then
separated by treatment with mercury, whereby an amalgam is obtained,
"which on distillation leaves pure palladium. The author finds, how-
ever, that all the platinum metals when precipitated by zinc are soluble
in nitric acid, also that it is not possible to remove palladium alone by
shaking the solution with mercury, as the latter precipitates all plati-
num metals. A solution of platinum chloride may be decomposec^ by
shaking with mercury, and a dark grey amalgam obtained. Furthei',
the amalgam of platinum metals cannot be freed from mercury by dis-
tillation and ignition. By treating such an ignited residue with
hydrochloric acid, and precipitation with ammonium chloride, a com-
pound, PdCl2,5NH4,ClHgvCl2, has been obtained ; it crystallises in beau-
tiful concentrically gi'ouped needles ; on ignition in hydrogen, it yields
a residue of mercury and palladium. From the residue insoluble in
hydrochloric acid, by dissolving in aqua regia and removing the pla-
tinum by ammonium chloride, a filtrate was obtained, which by treat-
ment with salt, and ammonium chloride and alcohol, yielded palladium
ammonium chloride. This the author finds has the composition
PdCl2,2NH4Cl, and does not contain water of crystallisation. On
ignition it leaves a residue of spongy palladium, Avhich exhibits the
absorption of hydrogen in a very marked manner. P. P. B.
Mineralogical Chemistry.
Hemihedry of the Diamond. By K. Martin (Jahrh. f. Min.,
1879, 156). — The author examined the fine collection of diamonds
in the Leyden Museum, and found one specimen which in his opinion
proved the hemihedry of the diamond. The crystal in question was
apparently a fine triakisoctohedron 5 mm. in size, the faces being
strongly striated and rounded off. Upon these faces the faces of
the octohedron appeared to exist, but they exhibited alternately such
a difierence in size that the author concluded that the faces were
those of the positiv^e and negative tetrahedi^on, consequently the pre-
dominating form ("grundform ") must be considered to be built up of
the positive and negative deltoid-dodecahedron. The question to be
answered was this : " Were the segments in the opposite lying octants
of the octohedron dependent on each other in their growth ? " It was
evident that in the growth of each of the four segments (correspond-
ing in position to a tetrahedron) there was a dependence. From this
MINERALOGICAL CHEMISTRY. 855
the author concludes tbat, tbe crystal exhibited the following forms in
,. ,. v>0 -ntO 0 -O
combination: — . -^- ■ j ■ -^ ■ C. A. B.
Two Regular Intergrowths of Different Minerals. By A.
Sadebeck {Jahrb. f. 2Iui., 1879, 154 — 155). — (1.) Arsenical pyrites
intergrcnvn with Iron pyrites. — Some fine crystals of arsenical pyrites
from Freiberg Avere found to be covered by numerous crystals of iron
])yrites. The arsenical pyrites exhibited the usual forms, the crystals
being built up of numerous subindividoals in hypoparallel position,
the axis parallel to which they arrange themselves being the vertical
axis. The iron pyrites crystals are cubes characterised by the absence
of the usual striation, the faces however appearing drusy, owing to the
occurrence of numerous subindividuals also in hypoparallel position.
These subindividuals do not exhibit sharply defined outlines, their
faces and edges being more or less rounded or bent. The iron pyrites
cubes occur in the arsenical pyrites crystals in such a manner that one
of the crystallographical axes of the former coincides with the vertical
axis of the latter, whilst the prismatic axes of both crystals also coin-
cide. This peculiar law w'as first discovered by the author in the case
of a similar intergrowth of iron pyrites with marcasite in some speci-
mens of the last-named mineral from Tavistock. The occurrence of
a similar intergrowth of the two isomorphous minerals (marcasite and
arsenical pyrites) with iron pyrites, seems to show that the isomor-
phism is not due to form alone, but also to the molecular structure, as
both minerals apparently exert an equal molecular attraction upon the
iron-pyrites.
(2.) Copper pyrites intergrown with FaJilerz. — The author observed a
very peculiar and interesting intergrowth of the above-mentioned
minerals on some specimens from Kapuik, the crystallographical axis
of the two minerals coinciding, so that the positive tetrahedron of the
fahlerz lies in the same position as the negative tetrahedron (sphenoid)
of the copper-pyrites, and vice versa. The edges of the two tetra-
hedrons intersect at right angles, so that the individuals occupy the
same position as two regular tetrahedrons, twinned according to the
law, " the twin-axis a prismatic axis." The copper pyrites tetra-
hedrons predominate, the combination being the positive tetrahedron
(sphenoid) Avith modified .solid angles, with occasionally the " first
acuter " pyramid. The fahlei-z crystals (exhibiting the combination
positive tetrahedron, triakistetrahedron and rhombic dodecahedron)
project from the faces of the copper pyrites tetrahedron. There is of
course no real twin-formation in the above case, as the minerals are
different and also the crystal-systems. C. A. B.
Microscopical Observations of the Growth and Resolution
of the Alums in Solution of Isormorphous Substances. By F.
Klocke (Jahrb. f. Min., 1879, 81 — 82). — There is nothing of impor-
tance in this paper to add to the author's previous observations
{Jahrb. f. Mia., 1878, 958—959; this Journal, 36, 439).
C. A. B.
3 0 2
P = 48° 62'
ooP ;
: ooP.= 124° 20'
P5 = 48° 50'
Pcb ;
: Pco = 124' 37'
856 ABSTRACTS OP CHEMICAL PAPERS.
Feuerblende (Rittingerite) from Chanarcillo. By A. Schrauf
(Jahrb. f. Mln., 1879, 144). — The author observes that the rittingerite
of Joachimsthal described by him (Sitzungsber. d. Wiener Akad., April
11th, 1872) seems to be identical with the mineral from Chaiiarcillo.
The axial ratios are the same, and there is an analogous dvelopmeut
of the forms. The following measurements will make this more ap-
parent : —
Rittingerite OP
Min. from Chanarcillo ooPoo
The OP of Schrauf corresponds with the coPcb of Streng. Schrauf
states that the results of his examinations of true feuerblende agree
with those of Miller. C. A. JB.
Manganese- Garnet. By Heddle (Jahrb. f. Min., 1879, 83). —
Crystals of this garnet are found in various localities in Scotland, but
particularly fine ones are found at Glen Skiag, in Ross, accompanied
by mu.scovite crystals, tourmaline, and more rarely by zircon and apa-
tite. The garnets are trapezohedrons, exhibiting two colours, the first
being light red and often one inch in diameter, the second are brown
and sometimes five inches in diameter. An analysis showed the two
varieties to have the following composition, viz. : —
Light red garnet —
SiOo. AloOs. FeoOs. FeO. MnO. CaO. MgO. HjO.
35-99 16-221 8-G38 2327 15-24 0-403 0-471 0-249 = 100-482
Brown garnet —
36-076 18-957 7-033 21-56 13-615 0-904 1769 0*325 = 100-239
Similar garnets are -at Struay Bridge and also at Ben Resipol,
in Argyllshire. C. A. B.
Desmine (Stillbite), By A. v. Lasaulx (Jahrb. f. Min., 1879, 82,
83). — The author examined crystallographically and optically some
desmine crystals from various localities, and concluded from the
results obtained that desmine crystallises in the mono-symmetrical
system, being isomoi'phous with harmotome and phillipsite. The
axial relations were a : b : c = 0-70325 : 1 : 1-119395 P = ooP; ooPob.
= OP; OP. = +Poo; cxjPoo = coPoo; ooP = Pco. There are no simple
crystals of desmine, but only twins, according to the same laws as
those of harmatome and phillipsite. C. A. B.
Analyses of Minerals and Rocks. By A. Hilger (.Tahrb. f.
Mill., 1«79, 127—132). — Porphynj from the Paper Mill near Weilburg,
No.ssau. —Thifi rock was found to have a sp. gr. of 2-79 and the follow-
ing composition, viz. : —
SiOo. AI..O3. Fe.Oa. CaO. MgO. Na,0. K-.O. CO.,. HjO.
61-12 16-96 6-23 1-13 0-85 4-37 4-63 2-78 1-36 = 9933
There were traces also of manganese and sulphuric acid. The pre-
MINERALOGICAL CHEMISTRY. 857
sence of carbonic anhydride is due to infiltration of calcium carbonate
and ferrous carbonate, both of these substances being derived from
the neighbouring rock. The manganese was present as manganoso-
manganic oxide.
Diorite from Diez in the RiqihacTithal, Nassau. — This rock is interpo-
lated in great masses in the lower Devonian orthocerasic slates. An
analysis was made of it with the following results, viz. :—
(a.) Soluble in hydrochloric acid —
SiO.2. FcjOa. Al-Ps. CaO.. P2O5.
0-84 6-83 1-47 269 O-'OOI = (with traces of alkalis) 11-83
(6.) Insoluble in hydrochloric acid —
SiO.,. CaO. ¥eX>3. Al.Oa. MgO. Xa^O. K^O.
6-44 0-51 4-90- 1073 07 3u0 OSo = 8713
98-96
The amount of FeO was found to be 5'76 per cent., and that of the
FejOa 423 per cent.
Diallagite and Bronzite from Dun Mountain, near Nelson, New Zea-
land.— Both these minerals occur intermixed in large foliated masses,
penetrating olivine and serpentine.
Bronzite. — Sp. gr. = 2*58. Its chemical composition was found to
be as follows, viz. : —
SiOo. AI2O3. CaO. MgO. Kp. Na;0. FeO. H2O.
41-82 6-*28 3-52 26-80 0-82 0-66 8-57 1103 = 99-50
There were traces also of Cr-Os and P2O5.
Diallagite. — Sp. gr. = 3- 19. Its chemical composition was found to
be as follows, viz. : —
SiOj. CaO. MgO. AI0O3. FeO. H.p.
.52-23 20-15 16-85 471 3-48 2-53 = 99-95
The bronzite is much decomposed, notwithstanding its fresh appear-
ance, whilst the diallagite is not so much decomposed.
Finito'id, from Gleichlinger Fels in the Fichtelgebirge, occurs in
light greyish-green masses in the decomposed granite, being a product
of the decomposition of orthoclase. Sp. gr. 2-81 ; chemical composi-
tion as follows, viz. : —
SiOj. Al.,03. CaO. MgO. KjO. Na.,0. Fe,P:,. P2O5, HoO.
45 29-96 1-44 1-15 10-13 2-15 3-16 032 6-24 = 99-79
Zinc-blende occurs in the keuper-sandstone (Lettenhohlen sandstein)
of Rothenburg in foliated nodules. Its chemical composition was as
follows, viz. : —
Insoluble
Zn. S. FejOs^ Cu. Tl. matter.
62-37 30-69 1-33 traces traces 564 = 100*03
Calamine (Smithsonite) is found as a light-grey crust, accompanied
8,58 ABSTRACTS OF CHEMICAL PAPERS.
by iron pyrites and spathic iron and quartz at Eras, Nassau. Cliemical
composition as follows, viz. : —
Insoluble
ZnO. COo. FeoOj. S. matter.
52-42 28-31 4-DO 1-30 1217 = 99-10
The sulphur is combined with iron, forming 2-44 per cent, of iron-
pyrites, the remaining iron being in the form of ferric oxide.
Mixture of cinnabar, metacAnnaharite, and stibUte, from Huitzucs, in
Mexico. Sp. gr. = 4-66. This mixture was analysed and found to
have the following composition, viz. : —
Insoluble
Hg. S. Sb. O. H.O. matter.
15-79 2-54 59-66 15-06 2-29 2-51 := 98-45
There is little doubt that the antimony really exists in the form of
stiblite in this mixture, as the following shows, viz. :—
18 = 0-12 = 1
122 = 0-49 = 4
16 = 0-97 = 8
Delfs (/. pr. Ghem., 40, 318), and Schnabel (Pogg. Ann., 105,
146), found the formula of stiblite to be HaSboOs or SboOj.H^O.
On igniting the mineral until the weight was constant, there was a loss
of 22-15 per cent., a result which diifers little from the percentage of
mercury, sulphur, and water added together. The residue contained
59-24 per cent, of antimony.
Pyromorphite from Dernbach, near Montahaur, Nassau. — Crystals ex-
hibiting the following forms in combination, viz. : — coP, OP, and P,
were found imbedded in pyrolusite. On analysis their chemical com-
position was found to be as follows, viz. : —
H,0 .
. = 2-29 per cent.
Sb ...
. = 59-66 „
0 ...
. = 15-66
Insoluble in
Pb.
Ca.
CI.
PO4.
nitric acid.
75-070
0-300
2-133
21-267
0-313 = 99-083
Fluorine was not detected. C. A. B.
Heat of the Comstock Lode. By J. A. Church {Ghem. New.^,
42, 42—43 and 52— 53).— J. A. Phillips {Quart. Jour. Geol. Soc,
August, 1879) maintains that the heat evolved by the kaolinisation of
the felspar rocks is not sufficient to raise the temperature of the Com-
stock Mine to 85°. In reply, the author upholds his theory, and points
out that the amount of alkalis which enter into solution affords no
measure of the quantity of rock which is undergoing the pi'ocess, for
there is a large amount of aqueous vapour which pervades the lode
and enters into chemical combination with the kaolinised rock, evolv-
ino- large quantities of heat without dissolving any of the alkalis, &c.
There are moreover gaseous currents, the result of kaolinisation per-
meating the rocks, which carry the heat with them and distribute it
throughout the whole mass.
G. F. Barker maintains that the heat is produced by the movement
MIXER.VLOGICAL CHEMISTRY. 859
of the rocks, but this movement is caused by the swelling of the rocks
when their conditions have been altered artificially by excavation.
There is no indication of any natural movement at a depth of 2,OuO
feet sufficient to produce the requisite amount of heat. The first
thousand feet — although the principal zone of oxidation and solution —
does not exhibit any unusual increase of temperature, the increase
being about 3"o° for every hundred feet. L. T. O'S.
Two remarkable Meteors observed in Sweden. By A. E.
NoBDEXSKlOLD {Jahrh. f. Min., 1879, 77 — 81). — A meteor fell on the
18th of March, 1877, and was seen over the greater part of Sweden,
exploding over Wernern Lake^ which at the time was covered with
ice. Some account of it is given by eye witnesses in Verb. d. Geol.
Ver. in Stockholm, bd. 4, 73 — 75. Another meteor fell on the 28th of
June, 1873, at Stiilldalen in the middle of the day, whilst the sun was
shining brilliantly. It was seen for a distance of about -450 kilo-
meters. From the observations of several scientific men, the author
is of opinion that the principal part of the cosmical substance of the
meteorite consisted of a combustible substance, which left no residue
behind, and the burning of this sub.stance produced the brilliant light
observed. The burning nucleus had a diameter of about 150 to 400
meters, and some observere were certain that the meteor consisted of
two or more "fire-balls" following each other. It exploded at a
height of about 38 kilometers, and 11 stones were collected, weighing
in the aggregate about 35 kilograms. The ground-mass of the
meteorite consists of a grey and a black shining substance, both con-
taining numerous black shining faces, grains, and microscopical
crystals of olivine disseminated throughout, also nickel-iron in grains
and reticulated veins. The presence of magnetic iron pyrites was
made apparent on a polished surface, whilst chondrodite was observed
in thin sections, the resemblance -of the meteorite to the Orvinio
meteorite of Tschermak being xevj striking under the microscope. An
analysis of the meteorite by Lindstrom showed it to have the following
composition, viz. : —
SiOs.
I .. 35-71
II .. 38-32
Na.,0. E"..0. Fe. ]S'i. Co. P. vS. CI.
I . . 0-G2 015 21-10 1-Gl 0-17 O'Ol 2-27 0-0-4=100-00
PA-
AI2O3.
A2G3.
FeO.
MnO.
NiO.
CaO.
MgO.
0-30
2-li
0-40
10-29
•0-25
0-20
1-61
23-16
0-31
215
9-75
1-00
0-42
1-84
25-01
II . . Xot determined 17-48 1-02 — 251 — = 99-81
The first gives the composition of the grey ground-mass, the second
that of the black ground-mass; sp. gr. at 23° = 3-733. Nordenskiold
assigns the following constitution to the meteorite from Stalldalen,
\'iz. : —
860
ABSTRACTS OF CHEMICAL PAPERS.
r.
Magnetic iron pyrites . . 5"74
Nickel iron . . ." 19-42
Soluble silicates 33-46'
Insoluble silicates 40-69
Chrome-iron 0'59
99-90
II.
6-36
14-65
78-99
100-00
The grey ground-mass becomes black on being heated either in the
reducing or oxidising flame, and the author considers it probable that
those stones -which exhibit a grey colour have not been exposed to so
high a temperature as the darker ones. Nordenskiold recalculated
the analyses of all the meteorites which most nearly approach the
Stalldalen meteorite in chemical composition, and found (on express-
ing the constituents in the elementary form) that they were identical
in composition, a fact which the following table will serve to illus-
trate, viz. : — ■
Locality.
Analyst.
Si.
Mg.
Fe.
Ni.
Co.
Mn.
Erxleben
Stromeyer ....
A. Kuhlberg . .
26-11
26-70
21-79
23-61
44-29
42-90
2-43
2-68
—
0-83
Lixna
0-66
Blansko
Berzelius ....
Bukeisen ....
26-91
26-12
23-22
21-52
43-12
47-82
1-59
2-75
0-09
0-56
Ohaba
9 18
Pdlistfer
Grewingk and
Schmidt
28-02
22-09
42-99
2-99
—
0-01
Dundrum
Haughton ....
27-55
20-45
44-74
1-58
—
0-44
Hessle (large stone)
Lindstrom ....
26-26
21-28
43-57
3-29
0-03
0-50
„ (small stone)
]S^ordeuski6ld. .
26-43
23-07
41-37
3-30
trace
trace
Orvinio (chondritic
L. Sipocz
26-09
21-28
43-29
3-16
—
—
ground-mass)
Ditto (black ground-
L. Sipocz ....
26-65
20-18
42-55
4-71
—
—
mass)
Stalldalen (grey
Lindstrom ....
25-66
21-41
44-83
2-73
0-26
0-29
ground-mass)
Locality.
Analyst.
€a.
Al.
Na.
K.
Cr.
Sn.
Erxleben
Lixna
Blansko
Stromeyer ....
A. Kuhlberg . .
BerzeUus ....
Bukeisen ....
G-rewingk and
Schmidt
Haughton ....
Lindstrom ....
Js^ordenskiold, .
L. Sipocz ....
L. Sipocz ....
Lindstrom ....
2-13
trace
1-02
0-53
2-09
1-97
2-28
2-46
2-56
1-77
1-31
2-12
1-85
0-23
2-07
0-70
1-94
1-27
1-75
1-91
1-74
0-85
0-83
0-85
trace
0-25
0-26
0-50
0-42
0-26
0-53
1-07
0 08
0-49
0-42
0-12
Ohaba
1-12
0-39 0-31
Pillistfer
0-14
Dundrum
Hessle (large stone)
„ (small stone)
Orrinio (chondritic
ground-mass)
Ditto (black ground-
mass
Stalldalen (grey
ground-mass)
0-72
1-05
1-78
1-59
1-10
0-71
0-66
0-38
0-34
0-18
0-03
0-01
ORGAXIC CHEMISTRY. 861
From the above table, it appears that a remarkable resemblance
exists in the chemical composition of tlie meteorites, consequently it is
highly probable that they had a common origin, having been origin-
ally either completely metallic or completely oxidised, their present
composition being due to subsequent oxidation or reduction. Nor-
denskiold is of opinion that other similar groups of meteorites may
be arranged. C. A. B.
Organic Chemistry.
Aluminium Iodine Reaction. By J. H. Gladstone and A.
Tribe (Chem. Neiu-i, 42, 2 — 3). — Water, alcohol, and ether, although
not acted on by either aluminium or iodine, are readily attacked when
these bodies act conjointly on them. Water at finst forms a definite
hydrate with aluminium iodide, but in presence of excess of the metal
it is decomposed, hydrogen being evolved and aluminium hydrate
formed.
Alcohol is similarly decomposed by aluminium and its iodide, with for-
mation of aluminium ethylate and aluminium iodoethylate, hydrogen
being evolved at the same time. Ether is attacked only by a mixture
of iodine and aluminium, ethyl iodide and aluminium iodoethylate being
formed. Similar reactions take place with amyl ether and ethyl and
amyl acetates. Z-inc and iron cannot be substituted for aluminium,
but the chloride or bromide may be used instead of the iodide.
To decompose the alcohol, a .small quantity of iodine (which is
capable of decomposing a large quantity of the alcohol) is dissolved in
it, the required excess of aluminium added, and the mixture is heated.
Hydrogen is then evolved, and the reaction continues until all the
aluminium is dissolved. By this means the ethylate, normal propyl-
ate, isobutylate, amylate, benzylate, phenylate, cresylate, and thy-
raolate f)f aluminium have been obtained. Of these the first four may
be distilled in a vacuum, but the other undergoes decomposition when
distilled.
Methyl alcohol is not decomposed by a mixture of aluminium and its
iodide, but in presence of free iodine, hydrogen is slowly evolved. An
aluminium-platinum C(^uple may be substituted for the metal.
Fseudopropyl alcoJiol is attacked under any circumstances.
Ceti/l alcohol is slowly decomposed below 200", above which tempera-
ture a secondary reaction sets in, cetyl iodide and aluminium hydrate
being formed.
Allyl alcohol is at first decompo.sed in a similar manner to the alco-
hols of the series C„H2„+i.0H, but afterwards a portion of the hydrogen
set free acts on the excess of alcohol, forming propylene and water.
Ethylene alcohol is only very slightly acted on by the reagent.
Propenyl alcohol is decomposed above 140°, with the formation of
allyl iodide, aluminium hydrate, and free iodine ; but when excess of
862 ABSTRACTS OF CHEMICAL PAPERS.
aluminiiim is present, no iodine is set free. No hydrogen is liberated.
Hydrogen is not liberated from aldehyde.
It is seen, therefore, that aluminium is substituted for the basic
hydrogen of water in monohydric alcohols, pseudopropyl alcohol being
excepted ; whilst in the di- and tri-hydric alcohols, aluminium is not
substituted for the hydrogen, as is also the case with aldehyde. In
the case of the ethers and of glycerol, the iodides of the positive radi-
cals are formed.
The aluminium alcohols are solids, melting to clear liquids and
remaining fluid at temperatures far below their melting points ; those
of the fatty series are capable of distillation. They are more or less
soluble in alcohol, ether, and benzene, and are decomposed by water
into the alcohol and aluminitam hydrate. Their specific gravities at 4°
are : ethylate, 1"147 ; propylate, 1'026 ; butylate, 0'988 ; amy late,
0'980 ; phenylate, 1"25 ; cresylate, 1"166 ; and thymolate, 1'04.
They are decomposed by heat, being resolved into the alcohol, and
its olefine and alumina, and at the same time into alumina and the
ether. Aluminium ethylate is decomposed mainly according to the first
reaction : (C2H50)6Al2 = AI3O5 + 3C2H4 + SCaHsO, where as
the phenylate yields chiefly the ether (C6HaO)6Al2 = AljOj +
3(C6H5)20 : other reactions take place, yielding new compounds not
yet investigated. The thyroolate is decomposed into alumina, propy-
lene, and bodies of the cresyl group, one of which is obtained in pearly
plates by sublimation or crystallisation from alcohol ; it appears to be
an ether having the formula CuHijQ, but is under investigation.
The reaction which takes place in the above decomposition is proba-
bly as follows : first, the aluminium iodide decomposes the alcohol
with liberation of hydriodic acid, which is decomposed by the metallic
aluminium present with evolution of hydrogen, and the iodide formed
acts on a further quantity of alcohol, setting free more hydriodic
acid, and so the reaction continues until all the metallic aluminium is
dissolved, according to the equations — ■
(1) 6(C„H2„_,.OH) + AloJa = A\,(C,;R,u-nO)e + 6HI; and
(2) 6HI + Alo = AlJe + SHj.
L. T. O'S.
Action of Bromine on Dichlorhydrin and Propylphycite.
By A. Claus and R. Lindhokst (Ber., 13, 1209— ] 212).— When
dichlorhydrin is heated with bromine (3 mols.) and water in sealed
tubes at 110 — 120° until the colour of the bromine disappears, dibromo-
dichloracetone is formed in the following way: CsHeCUO +3Br2 —
CaHoBroCUO + 4HBr.
Dibromodichloracetone forms a hydrate with water, which on cooling
may be obtained in well-formed crystals ; these lose their water when
kept over sulphuric acid. The anhydrous substance crystallises in
bundles of leaflets, which may be melted by the warmth of the hand.
It may be distilled in a vacuum without decomposition.
If, after the formation of the above compound, the heating is con-
tinued, then trihroniomonocliloracetone, C3H2Br3C10, is obtained in the
form of prismatic needles ; these after being separated mechanically
from the dibromodichloracetone and recrystallised, melt at about 50°.
ORGANIC CHEMISTRY. 803
By continaed heating, it was formerly supposed (Lindliorst, Dissert.,
Freiburg, 1877) that a tetrabroniaeetoue was formed; further investi-
gation has, liowever, shown that it is a condensation product.
Dibromodichloracetone is easily decomposed by baryta-water in the
cold, giving a yellow precipitate, which by the action of hydrochloric
acid, gives formic and glycollic acids, the products of decomposition of
the acid existing in the yellow precipitate as a barium salt. This
decomposition shows the constitution of dibromochloracetone to be
CH,Cl.CO.CBr,Cl.
The authors conclude that when bromine acts on dichlorhydrin,
acetone is first formed, and that the hypothetical bromodichlorbydrin,
from which propylphycite is obtained, does not exist. P. P. B.
Fermentation of Glucose. By L. Boittroux (Compt. rend., 91,
23ti — -oti). — In a previous paper (this Journal, 36, 566) the author
states that by sowing the ferment Mijcodenna aceti in a solution of
glucose, lactic acid is produced; on further examination of the acid,
however, he finds that in all its reactions it corresponds to the gluconic
acid of Hlasiwetz and Haberraann {Annalen, 155, 123) ; its formula is
identical, CeHpO;, but its calcium salt contains 1 instead of 2 mols.
H,0.
This reaction is not fermentation properly so called, but merely
oxidation, since every molecule of glucose absorbs 1 atom of oxygen.
L. T. O'S.
Fermentation of Glucose. By Maumen^ {Compt. rend., 91,
331). — The author states that in his Traite theoretiqne et pratique de la
fabrication du siicre, he shows that the gluconic acid of Boutroux (pre-
vious Abstract) is produced by the oxidation of glucose by copper
acetate, mercuric oxide, &c. From his experiments, he finds that the
acid contains a molecule of oxygen more than Boutroux gives iu his
formula. He has not published his results. L. T. O'S.
Chemistry of Sugar {Dinrjl. pohjt. J., 237, 146— 153).— Horsin-
Deon examined palm-sugar from Calcutta with the following
results : —
Cane-sugar 87'97
Reducing sugar 1'71
Gum 4-88
Water and volatile constituent 1"88
Ash 0-50
Mannite, and loss 3'OG
The sugar was fermenting.
Liebermann and Horman have examined the glucoside from Persian
berries, and represent its decomposition thus : —
CisHseOo, + 5H,0 = 2C,,H,o05 + 4C6Hu06.
Xanthorhamnin. Khamnetin. Sugar.
They succeeded in obtaining beautiful crystals of the sugar, which
analysis showed to be identical with isodulcite. Its rotatory power is
given by —
[a]D = + 8-Or
o
\'70
o
864 ABSTRACTS OF CHEMICAL PAPERS.
Hom'g and Rosenfeld have obtained a compound of grape-sugar and
sodium, CeHiiNaOe, by decomposing an alcoholic sugar solution with
alcoholic sodium.
E. Demole has effected a partial synthesis of milk-sugar. Milk-
sugar was decomposed into galactose and lactoglucose by means of
dilute acid, and the mixture was treated at the boiling point with
acetic anhydride. The resulting ether was saponified with baryta ;
the product after repeated crystallisation from alcohol agreed with
milk-sugar in all its properties. An analogous experiment with cane-
sugar did not succeed.
V. Lippmann has investigated the inversion of cane-sugar by means
of carbonic anhydride, and has found that with dry gas and sugar no
inversion takes place. A sugar solution of + 100° saturated with
carbonic anhydride showed after 150 days a rotation of — 44'2° ; the
inversion was thus complete. The inverting power of carbonic anhy
dride is considerably increased by strong pressure. A solution of 100
saturated with the gas under pressure and heated, is completely in-
verted in 20 to 30 minutes.
By the action of zinc chloride on fused sugar, the author obtained a
liquid which by fractional distillation yielded aldehyde, acetone,
nietacetone, formic acid, acetic acid, furfurol,. and apparently mesetyl
oxide. Besides these, carbonic anhydride, carbonic oxide, hydrocar-
bon, ethylene and propylene were observed. In the neck of the retort
small, pure white, hard crystals were found, which had a melting
point of 150°, and which by analysis agreed with hexmethylbenzene,
C6(CH3)6.
Durin has found that in a solution of cane-sugar containing invert
sugar, no inversion of the cane-sugar takes place at a temperature of
70^ to 75'', when the alkalinity is maintained about that of '001 of
CaO. When heated to from 75° to 114°, the solution becomes faintly
acid, and the inversion begins and goes on until completed. If the
solution is maintained alkaline, no inversion takes place. The presence
of invert sugar is not necessary, the inversion taking place without it
on formation of the acid.
Wachtel finds that the arable acid of the beet is not separated by
lime and filtration, but forms an arabate which must be found in the
molasses.
F. Weyer has found tricarballylic acid in the residue of Robert's
apparatus, and has obtained it pure by Lippmann 's process. The
same author has obtained vanillin from many i-avv siagars by agitating
an acid solution of the sugar with ether.
Lippmann finds the composition of tribasic calcium saccharate
to be —
CuHooOn + 3CaO + SHoO. J. T.
Decomposition-products of Sugar. By E. Reichardt and
others {Bied. Gentr., 1880, 559). — By the action of bromine on cane-
sugar, one-third is converted into gluconic acid, one-third into glucose,
and the remainder into gura. By allowing a thin stream of melted
sugar to fall on heated chloride of zinc, Lippmann observed that a
very violent reaction set in, aldehyde, acetic acid, furfurol and other
ORGAXic CH e:\iistry. 865
products being formed, together with hexmethylbenzeiie, a body
having a melting point of 150°, and boiling point of 258—260^.
J. K. C.
Saculmic Acid (Gazzetta, 10, 240 — 245), and Saculmin
{ibi'L, 355 — 3C)1). By F. Sestini. — This acid is obtained by treatiuo"
crude saculmin (this vol., p. 538) with a cohl dilute solution of
potash or soda, filtering and precipitating; the precipitate is washed
and dried over sulphuric acid, it then forms lustrous black frao-nients,
sparingly soluble in water, easily in dilute alcohol, bat almost insoluble
in absolute alcohol. It may be purified by fractionally precipitatino- its
alcoholic solution with ether. Its solutions are precif)itated by baryta,
by hydrochloric acid, or by sodium chloride. When heated to 100°, it
is altered, and is no longer completely soluble in dilute alcohol or in
potash solution. The results of the analy.ses correspond with the
formula CiiH,n04, so that its formation may be represented by
Ci,H240.o = C„H,o04 + H.COOH + 6H,0. The silver compound ob-
tained on adding silver nitrate to an alcoholic solution of saculmic
acid exactly neutralised with potash, had the formula CiiH9Ao-04.
Barium saculmate, Co-jHigBaOH + H2O, was thrown down as a brown
precipitate on adding baryta- water to a solution of saculmic acid.
Saculmin. — The residue left after the crude saculmin had been
treated with cold potash solution, as above mentioned, is partly
soluble in hot 5 per cent, potash solution ; this portion the author calls
saculmous acid, and the insoluble residue saculmin. Analysis shows
that saculmous acid contains more carbon and less hydrogen than sac-
ulmic acid. Saculmin after treatment with dilute hydrochloric acid
has the composition C44H38O15, and may be regarded as an anhydride
derived from 4 mols. sacculmic acid, CnH,n04, by elimination of 1 mol.
H2O. It has a strong affinity for bases, taking up potash and baryta
from their solutions ; these combinations are not decomposed even by
prolonged washing with distilled water. C. E. G.
Action of Glycerol on Starch. By K. Zulkowski {Ber., 13,
1395 — 1398). — Since glycerol at 190" is capable of dissolving (} per
cent, of powdered starch and converting it into the soluble modifica-
tion, soluble starch may be easily prepared by heating potato starch
with glycerol at 180 — 190° for half an hour (if rice or wheat starch is
used, the conversion takes place much more slowly). The solution is
allowed to cool down to 120", when it is poured into three times its
volume of strong alcohol.
The precipitated starch is washed with alcohol first by decantation
and then on a cotton filter with the aid of a filter-pump until it is free
from glycerol. It may be further purified by solution in warm water,
and reprecipitation by alcohol.
This soluble starch appears to be identical with Maschke's prepara-
tion (Gnielin Kraut, 4, 540), since its solution is powerfully dextro-
gyrate, and the substance lo.ses its solubility when dried.
The concentrated aqueous solution slowly deposits insoluble starch.
Dilute solutions are precipitated by lime and baryta- water, and are
coloured blue by iodine. W. C. W.
866 ABSTRACTS OF CHEMICAL PAPERS.
Nature of the Sugar in the Liver. By J. Seegen and
F. Kratschmer {Fflugers ArcMv., 22, 206— 214).— The object of
this paper is to combat the assertion of Musculus and Mering (Zeitsch.
f. Physiol. Ghem., 2) that maltose is found in the liver. A prelimi-
nary experiment is described, in which the extract obtained, when
examined by fermentation, reduction, and the polariscope, gave evi-
dence only of the presence of grape-sugar.
The method of extracting the sugar by fractional precipitation as
■used by Musculus and Mering is described at length, and the results
of experiments by this method are given ; no evidence of any other
sucar than grape-sugar could be obtained. Then follow the details
of experiments with cold liver extract. The first series yielded the
same result as before. A second and third series gave such a high
specific rotation that the presence of maltose was suspected. The
authors, however, give a different explanation of this high specific
rotation. The figures were obtained from the liquids which had been
fermented, and the results of experiments are given which show that
dextrin in the presence of grape-sugar and yeast readily ferments,
and that a body is formed having a very high specific rotation, which
reduces copper solutions energetically. A large number of experi-
ments were also made by dialysis. The dialysate was examined by
fermentation, reduction of copper solution, and the polariscope, and
ao-ain after treatment with hydrochloric acid : all the results tend to
show that grape-sugar alone was present, and to tiiis view the authors
therefore adhere. W. N.
Maltodextrin. By A. Herzfeld {Bled. Gentr., 1880, 347—350). —
Experiments on the saccharification of starch by means of diastase
having raised some doubts respecting the formulee of the products
formed, the author instituted those mentioned in the present article in
order to obtain further information on the subject. The results of his
labours show that saccharification of starch by diastase always pro-
duces dextrin through the series of amylo-, erythro-, and achroo-
dextrin ; at the same time a part of the achroodextrin is transformed
into maltodextrin and maltose. This transformation takes place
within certain limits. The absence of a sufiicient quantity of sugar
arrests the process, which is however resumed when the fermentation
is allowed to proceed in the produced sugar. The temperature must
be under 65° ; if higher, and up to 80°, the diastase operates only
as far as the erythro- and malto-dextrin stage, it being uncertain if
achroodextrin and maltose will be produced. These conclusions
coincide with those of Payen, by whom, however, maltodextrin was
only considered a transition product.
The view of Musculus, that the starch molecule splits up into sugar
on the one side and dextrin on the other, finds further refutation in
these experiments, for, as shown by Boudonneau, both maltose and
maltodextrin are produced by the action of diastase on dextrin quite
free from starch. The theory must therefore be set aside until some
satisfactory evidence is bi'ought in its favour. J. F.
Preparation of Laurie, Myristic, Palmitic, and Stearic Alde-
hydes. By F. KrAfft (Ber., 13, 1413 — 1418). — Laurie aldehyde,
ORGANIC CHEMISTRY. 867
C13H04O, is prepared bj subjecting to dry distillation under a pres-
sure of 15 — 25 mm. a mixture of calcium or bai'ium formate (3 parts)
and laurate (2 parts), to whicb a small quantity of calcium carbonate
has been added to diminish the fusibility. If the distillation is not
carried on too far, the distillate can be easily purified by rectifica-
tion under diminished pressure, after it has been freed from oily
impurities by lying on porous plates. After recrystallisation from
ether it form.s glistening plates, which melt at 44'5° and boil at 143"^
under 22 mm. pressure.
Myristic aldehyde, CuHosO, obtained by a similar process, melts at
52"5°, and boils at 1G9^ under 22 mm. pressure.
Palmitic aldehi/de, CisHajO, crystallises in pearly plates, which melt
at 58'5° and boil at 193^ under 22 mm. pressure. The body pre-
Wously known as cetyl aldehyde appears to be merely impui-e cetyl
alcohol.
Stearic aldehyde, CibHacO, melts at G3"5° and boils at 213° under
22 mm. pressure, and at 261° under 100 mm. pressure. It crystallises
in plates, which exhibit a bluisb lustre. W. C. W.
Monobromacetone and the Alcohol of Acetone. By A. Em-
WERLING and R. Wagner {Annalen, 204, 27 — 49). — The main object
of the authors was to obtain from acetone a body which they name
acetol, CH3.CO.CH2.OH, by the action of silver oxide or an alkaline
carbonate on monobromacetone. The monobromacetone was prepared
by acting on 100 grams of acetone with 138 grams of bromine. At
first one drop of bromine was added to start the reaction, and then
the rest was drawn through in the form of vapour mixed with air by
means of an aspirator. The next step was to replace the bromine by
the OH group, by acting on the monobromacetone with silver oxide
and water. A volatile oil was thus obtained, which has a strong re-
ducincr action on Felilinof's solution, and which the authors believe to
be acetol ; but they failed to separate it from the water with which it
was combined. In the attempts to effect the dehydration of acetol,
small quantities of an oily liquid with high boiling point, of the for-
mula C3H8O2 + ajHzO, were obtained, and also a second one having
the composition CaHgO, but which is not identical with acetone or
other known compounds. The first of these is probably propylene
glycol, which on further dehydration is converted into CsHeO. In
the preparation of acetol an acid was also obtained, which has a com-
position answering to the formula C^HigO;.
Action of Potassium Carbonate on an Aqueous Solution of Monobrom-
acetone.— 100 grams of monobromacetone were heated at 65° for a day
and a half with 70 grams of potassium carbonate dissolved in 100
grams of water. On filtering and distilling, a liquid of strongly re-
ducing power was obtained. A part of this was submitted in sealed
tubes to the action of freezing mixtures, and this yielded a stronger
solution of acetol, which again became more concentrated when dis-
tilled at 60° to 60° in a vacuum. The sti-ongest solution of acetol
which the authors succeeded in obtaining was estimated to contain
not more than 11 per cent.
The experiments have shown that acetol is very soluble in water,
8(38 ABSTRACTS OF CHEMICAL PAPERS.
to which it imparts a pleasant odour and a nnt-Kke taste. It boils at
above 100°, and is volatile in steam. Its specific gravity is greater
than that of water. When distilled, it yields a liquid containing more
■water and a residue richer in acetol. When a frozen solution thaws,
the portion which first liquefies contains more acetol than the rest.
Evaporated over sulphuric acid it leaves no residue. Solutions of
acetol reduce alkaline solutions of copper oxide with separation of the
red suboxide: they also reduce ammoniacal solutions of silver and
bismuth oxides on boiling. The solution of pure acetol has a neutral
reaction, but on boiling with water an acid body is formed. Strong
dehydrating agents, such as copper sulphate and calcium chloride,
destroy acetol. Bases such as lime and baryta, and also potassium
carbonate, decompose it with formation of an acid, especially on
warming. On oxidation with potassium dichromate and dilute sul-
phuric acid, it yields acetic and carbonic acids. Gr. T. A.
Action of Ethylamine and Diethylamine on Acetone. By
0. Eppingeu (^4H«a/e??, 204, 50 — G7). — By the action of ammonia on
acetone, Heintz obtained a number of compounds, the most important
of which were diacetonamine, triacetonamine, and dehydrotriaceton-
amine (this Journal, 1874, 1081; and 1875, 351). It seemed probable,
therefore, that similar reactions would take place between amines and
acetone.
Ethylamine and diethylamine were not found to behave towards
acetone in a manner analogous to ammonia, for ethylamine alone
forms a base, and one only, ethyldiacetonamine, corresponding with
diacetonamine, whilst ethyltriacetonamine and its de hydro-compound
either do not exist at all, or could not be obtained by the aathor's
methods.
Diethylamine acts towards acetone in a manner analogous neither to
ammonia nor to dimethylamine. In fact it seems that the capacity of
actincr with the amines on acetone decreases as their number of carbon
atoms increases. Phenylamine, for instance, was found by Pauly
(Annalen, 187, 198) to have no action on acetone. G. T. A.
Vapour-densities of Anhydrous and Hydrated Formic and
Acetic Acids. By 0. Petterson and G. Ekstrand (Ber., 13, 1191 —
1X95. — In this investigation the authors have used a method similar
in principle to that of Dumas, but combining the accuracy of Bansen's
thermostatic method.
A vessel, A, made from thin glass tubing, closed at one end, and
having a thin glass tube sealed to the other, is weighed filled with
air, and then with the vapour of the body experimented on. Its capa-
city is ascertained by weighing it, filled up to a mark on the narrow
tube, with water free from air. It is then filled with dry air and
weighed, and thus the weight of water and its volume found. The
narrow tube is drawn out into a capillary above the mark. A similar
apparatus. A,, is made, and used as a tare for A. Both are filled
with dry air, brought on to the pans of a balance, and equilibrium
carefully established. A is then suspended in a tube containing the
liquid, at the temperature of the vapour of which the determination is
ORGANIC CHEMISTRY.
869
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VOL. XXXYIII.
3 V
870 ABSTRACTS OF CHEMICAL PAPERS.
to be made. In this it is heated for some minutes, and then sealed.
It is finally weighed, after washing with alcohol, drying, and cooling,
using A as tare. The end of the capillary of A is then cut off, and
the liquid introduced into it. It is then heated as above, and soon
becomes filled with the vapour of the liquid, some of which con-
denses in the capillary ; to remove this a cylindrical piece of platinum
foil attached to a copper wire, is heated and passed over the capillary.
When all is vaporised the capillary is sealed, and the tube, when cold,
is washed with alcohol, dried, and weighed. In this manner, the
weights of the volumes of air and vapour filling A at a certain tem-
perature are obtained, from which the vapour-density may be calcu-
lated. Further, the temperature of observation may be calculated
from the weight of air in A at that temperature.
The tables (p. 869) contain the results of observations made with
acetic and formic acids, containing varying amounts of water. These
show that in case of formic acid addition of water increases the boiling
point, whilst with acetic acid the opposite takes place ; also that water
decreases the vapour-density of these acids. P. P. B.
Butyl and Isobutyl Hippurates. By G-. Campani and D. Bizzarri
(Gazzetta, 10, 257—260).
Isobufyl hippurate, C0Ph.NH.CHo.C00(CHo..CHMe2), prepared by
the action of isobutyl iodide on silver hippurate, crystallises in minute
transparent, rhombic prisms (m. p. 45 — 46°), having an odour of aniseed,
and a persistent bitter taste. It is insoluble in water, but soluble in
alcohol, ether, benzene, and chloroform.
Normal butyl hippuraie, COPh.NH.CH,.COO(CHo)3.CH3, prepared
in the same way, ci-ystallises with greater difliculty than its isomeride.
It forms quadratic prisms (m. p. 40 — 41°), resembling the isobutyl
compound in odour and taste, and also in its solubility. It is saponified
by the action of potash.
The author draws attention to the fact that, like many other
ethereal salts of carbosylic acids, the melting point becomes lower as
the alcoholic radicle becomes more complex.
Melting point.
Methyl hippurate 80-5°
Ethyl „ 60-5
Isobutyl ., 45'5
Butyl ,, 40-5
Isoamyl „ 27"5
C. E. G.
Action of Potash on Ethyl Isochlorobutyrate. By A. Testa
{Gazzetta, 10, 877— 383).— Balbiano (this Journal, 36, 615) found that
wl'en ethyl isochlorobutyrate was decomposed with baryta in dilute solu-
tions, hydroxybntyric acid was formed as the principal product of the
reaction, but at the same time a secondary reaction gave rise to di-
butyllactic acid, and a small quantity of another acid which combined
readily with bromine, peihaps methacrylic acid. The author's experi-
ments were made with the object of ascertaining the nature of the
second acid.
Ethyl isochlorobutyrate (4 parts) is allowed to drop slowly into a
ORGANIC CHEMISTRY. 871
boiling solntion of potash (6 parts), in water (1 part). The product
is then diluted with water, and after being boiled to expel the alcohol
produced by the saponification, is treated with dilute sulphuric acid in
slight excess, and agitated with ether. A dense white gelatinous pre-
cipitate, consisting of dibutyllactic acid, and a polymeride of metha-
crylic acid, is thus produced (see next abstract). This precipitate is
filtered off, and the ethereal solution distilled to dryness, Avhen a dense
oily liquid is obtained, liolding a little dibutyllactic acid in suspension;
this may be separated by diluting with ether and filtering. After
removal of the ether, the acids are neutralised with zinc oxide, and
the sparingly soluble zinc hydroxybutyrate sepai'ated by crystallisation.
The more soluble zinc salt is decomposed by sulphuretted hydrogen,
the liberated acids neutralised with silver oxide, and the silver salts
separated by fractional crystallisation from their solutions in water
and alcohol. In this way the silver salts of etJioxi/isubuti/ric acid,
CMe2(0Et).C00H, and metlmGnjlic add, CH, ! CMe.COOH, can be
isolated. The formation of these two acids may be represented by the
following equations : —
CH^.CMeCl.COOEt + 2KH0 = CH.: CMe.COOK + KCl + EtHO
+ H^O.
CMeoCl.COOEt + 2KH0 = CMeo(OEt).COOK + KCl + HoO.
C. E. G.
Dibutyllactic Acid and a Polymeride of Methacrylic Acid.
By L. Balbiaxo and A. Testa (Gazzdta, 10, 373 — 377). — When ethyl
isochlorobutyrate is saponified by boiling with aqueous potash-solution,
and the liquid is acidified with sulphuric acid, and agitated with ether,
a gelatinous white precipitate is produced, wdiich consists of dibutyl-
lactic acid, and a polymeride of methacrylic acid. To separate these,
the precipitate, after being well washed with ether, is treated with hot
water; the polymeride of methacrylic acid dissolves readily, whilst the
dibutyllactic acid remains behind ; by reprecipitating the solution with
ether and again dissolving in warm water, repeating the operation
once or twice, the polymeride may be obtained in a comparatively pure
state ; the dibutyllactic acid, however, obstinately retains traces of the
])olymeride. Both these substances closely resemble one another in
physical characters, being amorphous, and when dry transparent and
gelatinous, like isinglass.
Dihutylladic acid, COOH.CMeo.O.CMej.COOH, is not sensibly
attacked by hot nitric acid, but is readily decomposed when fused
with potash ; the reaction has not been examined by the author further
than to note that much potassium carbonate is produced.
The polymeride of methacrylic acid differs from that described by
Engelhorn and Fittig, particularly in its reaction when fus'.'d with
potash. The modification described by the author is readily decom-
posed under these circumstances, whilst Engelhorn and Fittig's is
attacked with difficulty. C. E. G.
Octylic Aceto-acetate and its Derivatives. By M. Guthzeit
(Annalen, 204, 1 — 14). — Etliyloctylacetoacetate, CuHosOa, or
CH,.C0.CH(C8Hn).C00Et, is prepared by acting on ethyl aceto-
3_p :i
872 ABSTRACTS OF CHEMICAL PAPERS.
sodacetate with octyl iodide. It is a colourless oil (b. p. 280 — 282°,
uncorr.), which refracts light strongly, and has a sp. gr. of 0*9304
(at IS'S*^, compared with water at 17'5°). On saponification it yields
octylacetone (normal methyl nonylketone), and octylacetic acid
(caproic acid).
Etliyllc diocfy lacetoacetate, C02H40O3, obtained by acting on ethyl
acetosodacetate with octyl iodide, is a light colourless oil (b. p. 340 —
342°, uncorr.).
On saponification, it yields dioctylacetone and dioctylacetic acid,
which is isomeric with stearic acid. Dioctylic or isostearic acid,
Ci9H3602, differs from stearic acid in its melting point, 38'5° ; that of
stearic acid, according to Heintz (Annalen, 84, 299), being 69'1 —
69*2°. When slowly crystallised from alcohol, it consists of fine,
colourless, transparent plates. The sodium salt can be obtained as a
white powder, which, when moistened, swells up to a gelatinous mass,
easily soluble in water. The barium salt, (Ci8H3502)2Ba, crystallises
from alcohol in snow-white, matted needles, which in presence of
moisture form a viscous mass. The silver salt, Ci8H3502Ag, is inso-
luble in water, and becomes blackened on exposure to light. The ethyl
salt, CnHas.COOEt, prepared by saturating an alcoholic solution of the
acid with hydrochloric acid gas, and adding water, is a colourless oil,
which could not be crystallised by cooling to 0°. G. T. A.
Two New Sjntlieses of Methyl-ethyl-hydroxyacetic Acid.
By E. BoCKiNG (Annalen, 204, 14— 26).— (1.) From methyl-ethyl-
ketone, by heating it with an aqueous solution of hydrocyanic acid
and hydrochloric acid, and extracting with ether, or better, by adding
a little more than the calculated quantity of potassium cyanide, then
a molecule of fuming hydrochloric acid, drop by drop, and finally,
after addition of the same quantity of hydrochloric acid, heating on
the water-bath.
Another method is to heat the ketone for a day with anhydrous
hydrocyanic acid in a closed tube, at 70 — 80°.
Methyl-etliyl-hydroxyacetic acid, CoHmOs, or CEtMe(OH).COOH,
is very soluble, has a sour taste and reaction, and sublimes at 90° in
fine, colourless, stellate groups of needles, which, when thrown into
water, rotate rapidly during solution. The acid agrees in the above
properties with the ethomethoxalic acid of Frankland and Duppa
(Annalen, 135, 36), but differs in melting point — 63°, instead of 6Q°.
The silver salt, CsHgOsAg, agrees in properties with the corresponding
compound of Frankland and Duppa. The barium salt, (C5H903)2Ba,
consists of colourless, soluble, silky masses. The zinc salt forms a
bulky, white, crystalline precipitate. Methyl-ethyl-hydroxyacetic acid,
when heated with fuming hydriodic acid, is deconiposed with difficulty,
yielding methylethylacetic acid.
(2.) From methylethylacetic acid, by converting it into a-bromo-
raethylethylacetic acid, and heating the ethyl salt of the latter with
sodium carbonate. G. T. A.
Suberic Acid produced by Oxidation. By F. Gantter and
C. Hell (Ber., 13, 1165 — 1170). — This acid was prepared by oxidising
ORGANIC CHEMISTRY.
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ABSTRACTS OF CHEMICAL PAPERS.
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ORGANIC CHEMISTRY. 875
palm oil with nitric acid ; the product, after being repeatedly melted,
was extracted with ether, as long as the portions sparingly soluble in
ether, after crystallising from water, exhibited the melting point, 135°.
This portion was then dissolved in ammonia, and fractionated by pre-
cipitating with calcium chloride. The second fraction yielded an acid
(m. p. 139°), which, after crystallisation from strong nitric acid, and
then from water, exhibited the melting point, 140°, viz., that of pure
suberic acid. From solutions containing sodium chloride, it crystallises
in feathery crystals, resembling those of ammonium chloride. It
distils about 300°, without decomposition, and is not volatilised by
steam. 100 pts. of water dissolve 0"142 of the acid at 15'5°. The fol-
lowing salts have been prepared (see table, pp. 873 and 874).
Etbyl suberate is obtained by digesting 15 grams of suberic acid
and 25 grams of alcohol, with 25 grams of concentrated sulphuric acid ;
it boils at 280 — 282^, is decomposed by boiling with soda, but only
partially by aqueous ammonia. P. P. B.
Trioxymaleic Acid. By S. Tanatar (Ber., 13, 1382—1388).—
Trioxymaleic acid is prepared by oxidising a cold dilute solution of
potassium maleate with a dilute solution of potassium permanganate.
When the operation is finished, the" manganese oxide is removed by
filtration, and the filtrate is acidified with acetic acid and concentrated
by evaporation. The solution is then boiled with calcium acetate and
filtered. As the filtrate cools, rhombic prisms of calcium trioxymaleate
are deposited, but several days are required for the complete separa-
tion of these crystals. A further yield of this salt may frequently be
obtained by treating the residue, consisting chiefly of calcium oxalate,
with boiling water. In order to prepare the free acid, calcium trioxy-
maleate is converted into the potassium salt by boiling with a solution
of potash ; and the lead salt obtained from the potassium salt by
double decomposition is subjected to the action of sulphuretted hydro-
gen. Trioxymaleic acid is a thick colourless liquid which is converted
at 110° into a brittle amorphous mass i-esembling glass in appearance.
The dried acid dissolves freely in water and sparingly in alcohol. It
melts at 110° and begins to decompose at 180°. This acid forms two
uncrystallisable potassium salts, which are very soluble in -water. Cad-
mium and barium trioxymaleates crystallise in rhombic prisms, freely
soluble in hot water. The zinc salt, C4H.Zn07 + 2H,0, forms trans-
parent, lustrous, rhombic prisms, which are sparingly soluble. Silver
trioxymaleate is amorphous. Diethyl trioj'y maleate, CJl.FAoO-„ is a
colourless liquid of the consistency of honey. It is soluble in alco-
hol, ether, and water. The diacetic derivative of this ethereal salt,
CiEtsAcsOT, is a thick liquid which solidifies to a crystalline mass
composed of silky needles (m. p. 48 ) Avhen kept for several weeks.
The presence of two hydro xyl groups in this acid is evidence in
favour of Fittig's views of the constitution of fumaric and maleic acids.
C00H.C(0H)2.C0.C00H. COOH.CH^.C.COOH.
Trioxymaleic acid. Maleic acid.
COOH.CH : CH.COOH.
Fumaric acid.
w. c. w.
870
ABSTRACTS OF CHEMICAL PAPERS.
Preparation of the Ethereal Salts of Tartaric and Racemic
Acids. Bj R. Ancshutz and A. Pictet (-Ber.,13, 1175—1178 and 1538).
The cliiet' difficulty in obtaining these ethers by the ordinary method is
due to the fact that water decomposes them. The authors recomtaend
treating the sohition of the acid in alcohol with hydrochloric acid
gas in the cold. The saturated solution is allowed to stand and then
treated with a stream of dry air, and the alcohol and aqueous hydro-
chloric acid are removed by heating the solution under reduced
pressure on the water-bath. The product so obtained is again treated
in a manner similar to the free acid, and then after drying in the man-
ner described is distilled under reduced pressure. By this method the
following ethers have been prepared : —
Dimethijl dextrotarfrate, C2H2(OH)2(COOMe)2, is a viscous, odour-
less, strongly-refractive liquid ; has a sweet taste. After some time
it suddenly assumes the solid state, forming a crystalline mass melting
at 48". The solid ether is easily soluble in alcohol, chloroform, and
benzene, from which it may be obtained in well-formed crystals. Its
sp. gr. at 15° is 1'3403, it boils at 163° under 23 mm. pressure, and at
280° under atmospheric pressure.
Diethyl dextrotartrate, C2H2(OH)2(COOEt)2, is a colourless, viscous
liquid. Its sp. gr. is 1'2097 at 14°, it boils at 162° under 19 mm.
pressure, and at 280° under ordinary pressure.
Dlproiryl dextrotartrate, C2Ho(OH)2(COOPr)2, is a colourless liquid,
more mobile than the ethyl salt. Its sp. gr. is 1"1392 at 17°, it boils
at 181° under 23 mm. pressure, and at 3U3" under ordinary pressure.
A column 220 mm. long, with a Wild's polaristrobometer, gave the
following results, the temperature being about 18° : —
Dimethyl ether
Dietliyl
Dipropyl „
Angle of
rotation.
+ 5-40
+ 19 -88
+ 30 -30
[a]i,.
+ 1-83
+ 7-47
+ 12 09
M.
+ 3-26
+ 15-39
+ 28 -29
Difference.
} 12-13
} 12 -90
The difference between the molecular rotatory power of the dimethyl
and diethyl ethers is seen to be the same as that between the diethyl and
dipropyl ethers.
Dimethyl-racemafe forms a white crystalline mass, crystallising from
alcohol in monoclinic crystals resembling angite ; it melts at 85° and
boils at 282° under ordinary pressure. Its alcoholic solution is opti-
cally inactive.
TJiacetoxyl-dextrotartaric anhydride, C2H2(OAc)2C203, melts at 125
— 129^ (Perkin, 126°). Its benzene solution rotates strongly to the
right. The aqueous or alcoholic solution of its syrupy acid hydrate is
Isevogyrate, as are also the barium and sodiumsalts.
Dihenzoyl-dextrotartaric anhydride, C2H2(OBz)2C203, forms small,
Avhite needles, easily soluble in alcohol, chloroform, and benzene. It
melts at 174°. Alkalis and ammonia dissolve it, but it is insoluble in
Avater,
ORGANIC CHEMISTRY. 877
Diaceti/l-racemic anhydride, C2Hi(OAc)..C203, melts at 122 — 125°.
It is optically inactive, as also is its aqueous solution. P. P. B.
Citric Acid. By G. Anpreoni (Ber., 13, 1394— 1395).— By treat-
ing ethyl bromacetate with the product of the action of sodium on an
ethereal solution of trietliyl malate and distilling the mixture in a
vacuum, a noncrystallisable syruj)y liquid is obtained which the author
believes to be ethylcitric acid. W. C. W.
Propylneurine. By U. G. Morley (Compt. rend., 91, 333—334).
— By heating propylene chlorhydrin with trimethylamine at 100° in
.sealed tubes propyleneneurino chloride, CsHsCHO^.NMeaCI, is ob-
tained. It forms colourless, transparent crystals, is very hygroscopic,
and acquires a brown colour on exposure to light. Its platinochloride
crystallises in plates, insoluble in alcohol and ether, but soluble in
water. By treating the chloride with moist silver oxide, a syrupy
basic liquid is obtained, most probably the free base.
By heating propylene chlorhydrin Avith dimethylamine at 100°
for some time a neutral liquid is obtained which vields a crystalline
jjlatinochloride of the formula (C3H70H.NMe),.2HCl.PtCl4.
L. T. O'S.
Synthesis of Thiohydantoin. By R. Andreasch (Ber., 13, 1421 —
1423). — Thiohydantoin thioglycollate is formed when an aqueous solu-
tion of cyanamide and thioglycolic acid is evaporated to dryness.
CoH.SOo + CN.NHo = CaHiNjSO + H,0.
Thiogljeollic acid. Thiohydantoin.
The residue is dissolved in water and the thiohydantoin precipitated
by ammonia. W. C. W.
Carbamideacetosulphonic Acid, a New Derivative of Thio-
hydantoin. By K. AxDREAscu (Bi ,-., 13, 1423 — 14:27).— Butusaium
carhariiideucdosulphfmate, NH2.CO.NH.CO.CH2.SO3K, is formed by
adding potassium chlorate in small quantities to 5 grams of thiohy-
dantoin and 50 c.c. of hydrochloric acid (sp. gr. 1 08). The mixture
is gently warmed to start the reaction, but if the evolution of chlorine
takes place too rapidly, the temperature must be lowered ; 4"2 grams
of potassium chlorate are required for 5 grams of thiohydantoin.
When the reaction is complete, the potassium salt slowly separates as
a crystalline meal, which is freed as much as possible from the mother-
liquor, washed with alcohol, and crystallised from warm water. It
forms monoclinic plates, which require for solution 58"6 parts of water
at 22° and 4-3 at 100°.
Potassium carbamideacetosulphonate is decomposed by nitrous acid
with the formation of acid potassium acetosulphonate and carbonic
anhydride, C3H5KX2SO5 + N2O3 = CoH^KSOj + CO^ + 2N2 + H,0.
W. C. W.
Synthesis of Meta-isopropyltoluene. By A. Ziegler and W.
Kelbe {Ber., 13, 1399 — 14u2). — The meta-isopropyltoluene, which is
formed by treating a mixture of 500 grams of toluene and 100 grams
878 ABSTRACTS OF CHEMICAL P.VPERS.
of isopropyl iodide with 40 grams of aluminium chloride, is identical
with the cymene obtained from resin oil {Ber., 13, 1157).
w. c. w.
A New Cymene from Light Resin Oil. By W. Kelbe (Ber.,
13, 1157 — 1160). — Light resin oil when treated with soda is separated
into two portions, one containing the salts of acids belong to the fatty
series, and the other consisting of several hydrocarbons. On distilla-
tion, the latter gave a fraction boiling at 170 — 178°, and consisting of
the new cymene. When it is heated with strong sulphuric acid, two
sulphonic acids are produced, which may be separated by taking ad-
vantage of the difference in solubility of their barium salts in alcohol.
Barium «,-cymene-sulphonate, (CioHi3S03)oBa + H2O, crystallising
in shining leaflets, is the less soluble salt ; by treatment with phos-
phorus pentachloride and ammonia, ic yields a sulphamide crystallising
from water in leaflets (m. p. 73°).
Barimn ^-cymene-salphonafe is obtained from the filtrate from
the above as an ill-defined crystalline mass. It separates as a crys-
talline powder from absolute alcohol in which it is easily soluble.
!3-Cijme7ie-sulphainide crystallises from water in large, flexible, glis-
tening leaflets, resembling naphthalene.
The cymene obtained from barium a-cymene-sulphonate by heating
it at 200° with hydrochloric acid, is a colourless, strongly refractive
liquid, having an odour like cymene, and boiling at 178 — 175°. On
oxidation it yields isophthalic acid, and since its /3-sulphonic acid
differs from that of metacymene, the author regards it as meta-isopro-
pyltoluene. P. P. B.
Action of Bromine on Toluene and its Derivatives. By C.
L. Jackson and A. W. Field {Ber., 13, 1215 — 1216). — The authors
have determined the amount of benzyl compounds formed by the action
of bromine on toluene, parachlorotoluene, parabromo- and orthobromo-
toluene, at temperatures vai-ying from 80° to a little above the boiling
point of these compounds. These experiments show that at higher
temperatures benzyl compounds are formed, and at lower substituted
toluenes, as pointed out by Beilstein. The benzyl compounds form
the chief product at temperatures near the boiling point of toluene ;
above this there is a slight increase for every increment of tempera-
tare, but the greatest increase takes place between 100° and 111°.
Toluene takes up bromine more easily than its substituted derivatives ;
in the case of the monobromotoluenes the para-compound when treated
with bromine forms benzyl derivatives more quickly than the meta,
and this latter more quickly than the ortho. Finally, the authors
find that the presence of iodine in toluene does not prevent the forma-
tion of benzyl bromide at high temperatures. P. P. B.
Parachlorobenzyl Compounds. By C. L. Jackson and J. White
{Ber., 13, 1217 — 1218). — In a former communication one of the
authors has shown the necepsity of a revision of these compounds
which have been studied by the following : — Bohler (Annalen, 154,
56), Vogt and Henninger {iUd., 165, 372), Pauly {ibid., 167, 187),
ORGANIC CHEMISTRY. 879
Beilstein (ilnd., 116, 336), Neahof {ibid., 147, 339), and mquet {ihid.,
Suppl., 2, 24-9).
ParachJoroheuzyl bromide (m. p. 48'5°), treated with sodium sul-
phite, yields a sulphonic acid crystallising in quadrangular leaflets
(m. p. about 108°), which are very unstable, and its chloride melts at
85'o°. Sodium and potassium parachlorobenzylsulphonate crystallise
without water, the barium salt with 2H20, the calcium salt with 7 and
2HoO, the copper salt with 2H2O, the lead salt with 1 mol. HjO,
and the basic lead salt contains PbOoS/iHjO.
Parachlorobenzyl sidphide, (C6H4C1.CH->)>S, melts at 42°, the di-
sulphide, (C6H4C1.CH,)2S., at 59°: the mercaptan, C6H4C1.CH,.SH, at
19°(?); the sulphone, (C6H4Cl.CH2)oSO,, at 165°; and the disulphide
dioxide, (CeHaCl.CH.jS.O., at about 120°. The parachlorobenzyl
ether, C6H4Cl.CH2.OEt, is an oil. P. P. B.
Orthobromobenzyl Compounds. By C. L. Jacksox and J. P.
"White (Ber., 13, 1218 — 1219). — Orthobromobenzyl bromide,
C6H4Br.CH2Br, obtained by the action of bromine on boiling bromo-
toluene, is purified by distilling in hydrobromic acid vapour; it
crystallises in broad tablets (m. p. 30°). From this the following
derivatives have been obtained : —
The alcohol, CeHiBr.CHo.OH, in white flat needles (m. p. 80°).
Tlie cyanide, a dark coloured oil, which yields, when saponified,
orthobromophenylacetic acid, C6H4Br.CH2.COOH. It crystallises in
shining scales, or flat needles (m. p. 102'5 — 103°).* Its calcium salt
crj-stallises in radiating anhydrous needles; the barium salt is un-
crystallisable.
The thiocyanate, C6H4Br.CH2SCN, is an oil.
The primary ami)ie, C6H4Br.CH2.NH2, is an oil; its carbonate melts
at 95°, and its chloride at 208°.
The secondary amine, (C6H4Br.CH2)2NH, melts at 36°, and its chlo-
ride at 166°.
The tertiary base, (C6H4Br.CH2)3N', melts at 121"5°, and its salts are
ill defined. P. P. B.
"• Tetrabromodibenzyleneparadimethylphenylamine. By G.
Mazzara (Gazzetta, 10, 370 — 372). — Dibenzyleueparadimethylphenyl-
amine, prepared according to Schifp's method by the action of benz-
aldehyde on paratoluidine, is dissolved in carbon bisulphide, and a
bisulphide solution of bromine is gradually added, taking care to
keep the mixture cold. The canary-yellow precipitate which is pro-
duced is washed first with l)isulphide and then with ether. The
tetrabromo-derivative, (CHPh)2(NC6H2Br2Me)2, thus obtained de-
composes rapidly in contact with the air, and when heated it melts
at 160 — 165° with decomposition. It is very soluble in alcohol, and
the solution when boiled undergoes decomposition. On cooling, long
silky needles of a dibromotoluidine (m. p. 73°) are deposited, whilst
the solution contains benzaldehyde. C. E. Gr.
* The Abstractor has shown that this acid is obtained by brominating phenyl-
acetic acid, and found its melting point to be 103 — 104° (this Journal, Trans.,
1880, 95).
880 ABSTRACTS OF CHEMICAL PAPERS.
Action of Benzotrichloride on Primary Amines. By J. H.
Stebbins {Chem. News, 24, 7). — By allowing benzotrichloride and
paratoluidine to react on one another in equal molecular proportions,
a violent action takes place, hydrochloric acid being evolved, and a
white granular mass obtained soluble in alcohol, crystallising from
the solution in needles (m. p. 115°) on slow cooling, and in rhombic
prisms on rapid cooling. The crystals sublime at a temperature a
little above their melting point; they are sparingly soluble in water
and hydrochloric acid, but soluble in acetic acid. Sulphuric acid
dissolves it with evolution of hydrochloric acid ; by adding water to
the solution, a precipitate is formed. By oxidation, a substance is
obtained crystallising from alcohol in yellow needles. The author is
continuing the research to ascertain the constitution of the body.
L. T. O'S.
Substituted Azobenzenes. By A. Calm and K. Heumann (Ber.,
13, 1180 — 1185). — ParadicJiJorhydrazobcnzene (m. p. 122°), prepared
by the action of zinc-dust and aqueous soda on parachloronitrobenzene,
when heated with moderately concentrated hydrochloric acid, yields
faradichlorazohenzene, m, p. 183" {Ber., 8, 912), a.nd parachloraniline,
thus : —
CeH^Cl.NH _ CfiH^ClN
2 I ~ II + 2C6H1CI.NH2.
CeHiCl.NH CeH^ClN
Baradihromoliyd.razohenzene (m. p. 130°) is decomposed in a similar
manner, forming paradlhromazohenzene (m, p. 205°), and parahrom-
aniline (m. p. G3°).
Paradichlorazuhenzene-inmiosulplionic acid, Ci2H7Cl2(S03H)N2, is ob-
tained by heating paradichlorazobenzene with fuming sulphuric acid
at 140 — 160°. It crystallises from hot water in fine reddish-yellow
needles, which are soluble in cold water, but more easily in hot water
and alcohol. Its sodiiim salt crystallises in shining golden leaflets.
By reason of the insolubility of its salts, it decomposes chlorides and
nitrates, but is precipitated from the solutions of its salts by hydro-
chloric and sulphuric acids.
Mononitrodicldorazohenzene, Ci2H7Cl2(NOo)N2, is obtained by treating
nitroparachlorazoxybenzene, m. p. 154° {Ber., 5, 912), with alcoholic
ammonixim sulphide. It crystallises in pale yellow needles, is
sparingly soluble in alcohol, and melts at 210^. The possibility of its
being a hydrazo-derivative is excluded by its high melting point.
Attempts to prepare it by nitrating dichlorazobeuzene resulted in the
formation of mononitroparadichloi'azoxy benzene (m. p. 133 — 134°).
P. P. B.
Colouring Matters produced by the Action of Diazo-com-
pounds on Phenols. By J. H. Stkbbins {Chem. News, 42, 44). —
Azoheuzene-t rin.it ro-oxijhenzene, prepared by the action of diazobenzene
nitrate on trinitrophenol, explodes violently on heating.
Azohenzene-'pyrogallol, prepared by the action of azobenzene nitrate
on pyrogallol, crystallises in red-brown needles, sparingly soluble in
alcohol.
Parazo-suljL)Jwxyl-ienzene-]pJi,loroglucinol is obtained by acting on
ORGANIC CHEMISTRY. 881
diazosulphanilic acid with phloroglucinol. It forms a soda salt, readily
soluble in water, and an acid baiinm salt which is sparingly soluble in
water.
Azobenzene-sitlphocresol, obtained by the action of cresolsulphonic
acid on diazobenzene nitrate, crystallises in red-brown needles, soluble
in alcohol, and sparingly soluble in hot water.
I)initro-oxij-azohemene-orthoxijsulphoxyhenzene, obtained from diazo-
dinitrophenol and phenol-ortho-sulphacid, crystallises in yellow-brown
needles, having a metallic lustre, and sparingly soluble in hot and cold
water.
Azonaphthalene-sulphoxyl-oiihomtroxyl-benzene crystallises in red-
brown microscopic needles, soluble in water; it is prepared by the
action of diazonaphthionic acid on orthonitrophenol.
Parazo-suJjjIiOxylbeiizeiie-betaoxydisiiIphoxi/hiajiht/Kilene, obtained by
treating diazosulphanilic acid with naphthalenedisulphonic acid, crystal-
lises in orange-coloured leaflets, with a beetle-green lustre ; it is solu-
ble in water, and forms a lead salt, a yellow powder soluble in water.
Azobenzene-disulplionaphtluil is prepared by treating the sodium salt of
/3-naphtlioldisulpbonic acid with diazobenzene nitrate ; its soda salt is
very soluble in water, and the barium salt only sparingly soluble.
Parazotoluene-^-nfqjIitJtol-disuIphonic acid is prepared by acting on
diazotoluene nitrate with /3-naphtholdisulphonic acid ; it crystallises
in red laminae, soluble in water, and dyes a scarlet colour. Its soda
salt is very soluble in water ; and its barium salt sparingly soluble.
The ortho- and meta-compounds have been prepared ; the former
gives a more yellow, and the latter a redder shade than the para-com-
pound.
Parazosulplioxyl-naplithalene-resorcinol, obtained by the action of
diazonaphthionic acid on resorciuol, forms dark-brown needles, very
soluble in water.
Parazodibromo-sulpTioxylhenzene-IB-napht'halein, obtained by treating
paradiazodibromo-benzene-sulphonic acid with ^-naphthol, is soluble
in water. L. T. O'S.
Colouring Matters from Phenols. By R. Meldola (Chem.
News, 42, 3'J). — When nitroso-dimethylaniline acts on phenols (not
containing the methyl-group) the oxygen of the nitroso-group directly
attacks the hydrogen of the aromatic nucleus, thus :
NMe..C6H4.XO + CoHv.OH = NMe..C6H4N : CoHs-HO + H,0.
The compounds formed are crystalline violet colouring matters, form-
ing readily oxidisablo leuco-bases. 0. N. Witt (this Journal, 35, 356)
describes the action of nitroso-dimethylaniline on meta-toluene-
diamine, in which the oxygen of the nitroso-group attacks the hydro-
gen of the alcohol radical —
NMe2.C6Hi.NO.(CH3)XC6H3(NH2), = OMe^-CeH^N I CH.CoH3(XH2)2
-I- H2O.
L. T. O'S.
Amarine. By A. Claus and K. Elbs (Ber., 13, 1418—1421).—
An ethereal solution containing amarine and methyl iodide in their
882 ABSTRACTS OF CHEMICAL PAPERS.
molecular proportions, deposits in the course of a few days crystals of
amarine metliiodide.
Amarine benzoclaloride can be obtained by a similar reaction. These
bodies are soluble in hot alcohol ; they are not attacked by ammonia,
but are converted by alcoholic potash into methylamarine (ra, p. 175°)
and benzylamarine respectively.
Methylamarine metliiodide, formed by the action of methyl iodide on
a boiling alcoholic solution of amarine, crystallises in brilliant pyra-
mids (m. p. 246"), which are soluble in alcohol. This substance is not
acted on by ammonia, but is decomposed by alcoholic potash, forming
dimethylamarme, a base crystallising in mcmoclinic prisms (m. p. 146°).
The salts of dimethylamarine are, with the exception of the acetate,
sparingly soluble in water. The iodide ob<^ained by the union of
hydriodic acid with the base is not identical with methylamarine
methiodide, since it is readily decomposed by ammonia. By boiling
an alcoholic solution of dimethylamarine with benzyl chloride, the
chlorides of two new bases are obtained. The chlorides can be
separated by the difference of their solubility in water. The sparingly
soluble chloride yields a crystalhne base, which melts at 204°; the
soluble chloride gives a base, which melts at 158°.
Analogous results are obtained if ethyl bromide is substituted for
benzyl chloride,
Bevzi/Jamarme henzyl cldnrlde is soluble in alcohol ; it begins to melt
at 40°, and is completely liquefied at 75°. It is not attacked by ammo-
nia, but is converted by alcoholic potash into dibenzylamarine. This
base is deposited from its alcoholic solution in white needles (m. p.
146°). The hydrochloi-ide of dibenzylamarine is quite distinct from
benzylamarine benzyl chloride, since it is readily decomposed by am-
monia. W. C. W.
Paraethylmethylphenol. By G. Mazzara {Gnzzetta, 10, 256 —
257). — Paraethyltoluene (b. p. 162°), prepared by the action of sodium
on a mixture of ethyl iodide and pure parabromtoluene, was con-
verted into the sulphonic acid by heating it on the water-bath for
several hours with twice its weight of a mixture of ordinary and
fuming sulphuric acid. The barium salt obtained from the crude acid
was converted into the potassium salt, and then fused with twice its
weio-ht of potash. The phenol extracted from the product in the usual
way by acidifying with hydrochloric acid and agitating with ether, boiled
constantly at 215° after rectification. Pure paraethylmethylphenol,
CgHsMeEt.OH, is a colourless oil which does not solidify in a freezing
mixture of ice and salt ; is but sparingly soluble in water, and gives a
blue colour with ferric chloride. C. E. G.
Cumophenols. By P. Spica (Gazzetta, 10, 246— 253).— This
paper contains further researches on the phenols obtained from the
two cumenesulphonic acids, produced by the action of sulphuric acid
on cumene (this vol., 166). When the crystalline para-cumophenol
is gently heated with monochloracetic acid, — soda-solution being added
from time to time, — and the product decomposed by hydrochloric acid,
an acid is produced, which may be purified by crystallisation first from
URGAXIC CHEMISTRY. 883
alcohol, and then from water. It forms long silky needles (m. p. 81°),
having the composition of cumophenolglycollic acid —
C6H,(C3H0O.CH,.COOH.
The hari'nm salt, (CiiHi303)2Ba + 2HjO, crystallises with diflSculty in
long prisms. The lead salt, (CnHiaO.O.Pb + 2H.0, forms micaceous
scales, only sparingly soluble in cold, but readily in hot water or
boiling alcohol. The s^ilver salt, CnHiaOsAg, is obtained as a white
floccnlent precipitate, on adding silver nitrate to an aqueous solution
of the acid which has been partially neutralised with ammonia ; under
the microscope, it is seen to consist of slender needles.
The liquid orthocumophenol, which boils at 213 — 215°, and not at
218^ as previously stated, yields an oily acid when treated with raono-
chloracetic acid in the manner above described. It was converted
into a barium salt, and the barium salt analysed, but the results
obtained did not correspond with those required by a cumophenol-
glycollic acid.
The reactions of the two acids with various reagents is given in a
tabular form. C. E. G.
A New Cumophenol. By M. Fileti (Gazzetia, 10, 279—280).—
This is a preliminary notice on a new cumophenol, prepared by the
action of nitrous acid on the cumidine from amidocumic acid. It boils
at about 214^, under a pressure of 753 3 mm., and solidifies to a crys-
talline ma.ss (m. p. 8 — 10°) at a low temperature. Its methyl ether
boils at 198 — 199° under a pressure of 751 mm. This would seem to be
the third of the possible cumophenols, the (1 : 4), and (1 : 2) com-
pounds having been previously described by Paterno and Spica and
by Spica.
The author also notices that when amidocumic acid is distilled with
baryta, besides cumidine, a small quantity of a white crystalline sub-
stance (m. p. 88 — 89°) is formed. It is insoluble in acids, and contains
nitrosren. C. E. G.
^o"-
Derivatives of Natural and Synthetical Thymol. By E.
Pateexu and F. Canzoneui {Gazzetta, 10, 233 — 23'J;. — In a former
paper (this vol., p. 246), the authors discussed the action of dilute
nitric acid on the ethers of thymol and camphothymol (carvacrol), the
former yielding methoxynitrotoluic acid and ethoxynitrotoluic jy^id ;
whilst the synthetical camphothymol gave methoxy- and ethoxy-tere-
phthalic acids. In order to elucidate this reaction more fully, the
authors have studied the action of dilute nitric acid on the methyl
ethers of the two nitrothymols.«. ..
Action of Nitric Acid on the Methyl Ether of Nitrothymol. — The nitro-
thymol was prepared by oxidising nitrosothymol with potassium ferri-
cyanide, and after recrystallisation from dilute alcohol, it melted at
138 — 139°. It was converted into the methyl ether by digestion
with methyl iodide, and a solution of potash in methyl alcohol ; the
crude product obtained by precipitation with water was then boiled
with dilute nitric acid (1 acid to 4 of water) for five days. The crys-
talline precipitate after purification melted at 175°, and was shown to
884 ABSTRACTS OF CHEMICAL PAPERS.
be metlioxynitrotoluic acid, C6H2Me(N02)(OMe).COOH, by the
results of the analyses of the acid and of its barium salt. This con-
firms the authors' opinion that in the action of dilute nitric acid on the
ethers of thymol, a nitro-derivative is first produced which is then
oxidised to the nitrotolnic acid .
Action of Nitric Acid on the Methyl Uther of Nitrocarvacrol. — The nitro-
derivative was prepared in a manner similar to that above described,
but the yield was considerably smaller, much resinous matter being
formed. The product obtained by boiling the nitrothymol with dilute
nitric acid crystallised in small prismatic needles (m. p. 145 — 146°),
easily soluble in alcohol, ether, benzene, and chloroform. On analysis
it was found to be methoxypropylnitrobenzoic acid —
CeH^CCsH,) (NO2) (OMe).COOH,
which was confirmed by an analysis of the barium salt ; the latter
forms fine lustrous prisms of a pale yellow colour.
The authors consider that the difference in behaviour of the two
nitrothymol derivatives is due to the different relative positions of the
NOo and CsH, groups.
The methyl ether of thymol was submitted to the action of bromine,
by passing air saturated with its vapour over the ether in the propor-
tions of 2 Br to 1 mol. of the ether, and the product, after being
washed with water and potash solution, was fractionally distilled, when
the greater portion passed over between 263° and 205°. On analysis,
however, it was found to contain somewhat more bromine than that
required by the formula of the monobromo-derivative, so that it pro-
bably consisted of the methyl ether of monoiromothymol —
C6HoBrMe(C3H;).OMe,
mixed with a small portion of the dibromo-derivative. When sub-
mitted to the oxidising action of dilute nitric acid, it yielded a product
which was separated by fractional crystallisation into various portions
melting at different temperatures from 140° to 245°. The fraction
melting at 193 — 194° had the composition of methoxydibromo-
toluic acid, C6HBrMe(0Me).C00H ; it crystallises from benzene in
transparent needles, and from dilute alcohol in silky scales. It is very
soluble in ether or alcohol, but almost insoluble in water. The
fractions more soluble in water seemed to contain methoxynitrotoluic
acid.
It is possible to explain the formation of these two acids on the
supposition that in the monobromo-derivative the bromine has entered
by substitution into the C3H7 group. Under these circumstances, a
portion of the compound might be converted into methoxynitrotoluic
acid, whilst the bromine, liberated by the oxidation of the CsHoBr
group, would enter into the reaction to give rise to the dibrominated
derivative. C. E. G.
Amidophenyl Mercaptans or Thiohydranilines. By A. W.
HOFMANN {Ber., 13, 1223—1240). — This consists of a continuation of
the investigation, some account of which has already appeared (this
vol., 386 — 387). In a foot-note the author states that 1 part of
ORGANIC CHEMISTKT. 885
sulphur and 3 parts of phenylbenzamide give the best yield of ben-
zenylamidophenyl mercaptan, and that by action of concentrated
nitric and sulphuric acids this body is converted into a mononitro-
derivative (m. p. 188°), which yields an amido-derivative on re-
duction.
Methenylamidoplienyl mercaptan may be obtained by heating form-
anilide with sulphur, thus : CsHs.NH.CHO + S = CeH/ >CH +
HoO. This represents but a small portion of the decomposition, some
of the formanilide yielding aniline and carbonic oxide (this Journal [2],
1, 72) ; further, sulphuretted hydrogen and thioanilide are formed.
Ethenyl-, propionyl-, and iientenyl-ainidophenyl mercaptans are ob-
tained by the action of sulphur at high temperatures on the anilides
of acetic, propionic, and valerianic acids. The yield of these bases
is comparatively small, other reactions taking place.
Benzenylamidophenyl mercapAan is also obtained in small quantities
by heating phenylacetanilide with sulphur. Phenylacetanilide is ob-
tained by boiling aniline with phenylacetic acid. It crystallises in
shining flat needles (m. p. 117°).
Oxalic acid Derivative of Amidophenyl Mercaptan, CuHsNoS^. —
When acetanilide is heated to boiling with sulphur for some time,
sulphuretted hydrogen and carbonic anhydride are foi'med, and acetic
acid, acetanilide, aniline, and the above ethenyl-base distil over. The
evolution of sulphuretted hydrogen diminishes after some time, and a
sublimate is formed in the retort. If the crystalline residue in the
retort, after extraction with alcohol to remove aniline, &c., be sub-
limed in a current of air, the oxalic acid derivative of amidophenyl
mercaptan is obtained in large yellow needles. It is insoluble in the
ordinary solvents. It crystallises from hot toluene in microscopic
prisms. It is very sparingly soluble in hot alcohol, and its alcoholic
solutions have a bitter taste. It melts at about 300°, and may be dis-
tilled without decomposition. That its constitution is
is shown by its being resolved into amidophenyl mercaptan and oxalic
acid by heating with potash at 200° ; and further, its decomposition
into ethenylamidophenyl mercaptan and aniline sulphydrate by hy-
driodic acid and phosphorus at 150°, thus —
(1) CeH / >C-Cf >C6H, + 3H, = CeH/ >C.CH3 +
NHo.CcH,.SH.
(2) NH^.CsH^.SH + Ho = NHo.CeHs + H.S.
That the above is the constitution of this compound is further
shown by its production in the following cases : —
(1.) When oxalic acid and amidophenyl mercaptan react in pre-
sence of phosphorous trichloride.
VOL. XXXVIII. 3 q
886 ABSTRACTS OF CHEMICAL PAPERS.
(2.) By the action of amidoplienyl mercaptan on crystalline ethyl
oxalate.
(3.) By passing cyanogen into an alcoholic solution of amidophenyl
mercaptan, thus —
2C6H, I ^^' + CN.CN = C6H4<( ^C-C^ ^CsH^ + 2NH3.
So
(4.) By the action of the methenyl base on its chloro- derivative,
thus —
Xv /^X X\ /^V
CsH/ >CH + €eH/ >CC1 = CeH/ >C-Cf NCeH^ + HCl.
\g/ \g/ \g/ \g/
(5.) By the action of zinc on the chloromethenyl base.
Finally it is obtained by acting on the methenyl base vrith acetic
chloride or benzoic chloride in sealed tubes at 150°.
A partial explanation of its formation from acetanilide is obtained
by supposing that a thioacetanilide, S(C6H4.NHAc)2 or C16H16K3O2S,
is first formed, and this when decomposed by sulphur gives the fol-
lowing products : —
CieHieNjO.S + 4S = CuH8N.,So + aHA + 3H,S.
As a means of preparing orthamidophenyl mercaptan, the author
recommends the prepai-ation of this oxalic acid derivative from acet-
anilide, and its decomposition with potash at 200°.
Derivatives of Amidophemjl Merca/ptan. — (1.) Succinyl derivative,
CieHijNoSz, is obtained by action of the mercaptan on succinamide ;
the latter is dissolved with liberation of ammonia. It crystallises
from alcohol in beautiful colourless needles (m. p. 137°). It forms a
hydrochloride crystallising in lemon-yellow needles, which are decom-
posed by water. The platinochloride forms sparingly soluble crystal-
line scales. The am-ochloride, Ci6Hi..N'2S2.HCl.AuCl3, crystallises in
yellow needles.
Potash resolves this succinyl derivative into amidophenyl mer-
captan and succinic acid ; phosphorus and hydriodic acid resolve it
apparently into the tetrenyl base and aniline, thus —
(CfiH/ >C)2(CH2), + 4Ho = CoH/ >C.CHo.CHoMe +
NH,Ph + H.S.
(2.) The plithahjl derivative, (CgHi^ >C)2 ' CeHi, is obtained by
the action of phthalic anhydride or chloride on amidophenyl mer-
captan. It cr3^stalHses from concentrated alcoholic solutions in thick
prisms, and from dilute in fine needles. It is soluble in ether, but
insoluble in water, and melts at 112°. It is a feeble base. Its hydro-
chloride and platinochloride are both decomposed by water.
ORGANIC CHEMISTRY. 887
(3.) GhjcoUyl derivative, CeHZ ^C.CHo.OH, is obtained from
amidophenyl mercaptan and chloracetic acid. It crystallises from hot
alcohol in lon<>' fine brittle needles (m. p. 176°). It is insoluble in
water and hydrochloric acid, but dissolves in concenti-ated sulphuric
acid, and is reprecipitated from this solution by water. The influence
of the hydroxyl group is shown by its solubility in alkalis, from
which solutions it is reprecipitated by acids.
N
(4.) Phenylacetic derivative, CeHj/ ^C.CH.Ph. Its hydrochlo-
ride is obtained by acting on amidophenyl mercaptan with phenyl-
acetic chloride. This salt crystallises from hydrochloric acid in light
yellow, stellate, grouped needles. It is easily decomposed by water or
alkalis, yielding the base as an oily liquid, insoluble in water, but
soluble in alcohol and ether. The platinochloride,
(CuHnNS.HCOaPtCli + 5H2O,
crystallises in yeUow needles.
/^\
(5.) The Girmamyl derivative, C^B./ >C.CH : CHPh, is obtained
by heating clnnamic acid with amidophenyl mercaptan. It crystallises
from alcohol in thick strongly refractive prisms, melting at 115". It is
a feeble base ; forms a hydrochloride and platinochloride. Similarly to
the above derivative, it is resolved by potash into the mercaptan and
cinnamic acid.
Amidophenyl mercaptan reacts with aldehydes, yielding interesting
results ; e.g., with acetaldehyde the ethenyl base has been obtained,
thus —
N"
CsH^jg^' + 2CH3.CHO = C,B.,<^ ^CMe + CHoO + H^O.
Benzaldehyde yields the benzenyl base, and salicaldehyde yields a
salicyl derivative, C^H/ ^C.CeH^.OH. This compound crystallises
from alcohol in beautiful shining needles (m. p. 129°). It forms salts
with acids, and is also soluble in alkalis, owing to the presence of the
phenol group. Potash resolves it into the mercaptan and salicylic
acid. This compound has been obtained by Schuhwirth by the action
of sulphur on phenylsalicylamide.
Amidophenyl mercaptan reacts with hydrocyanic acid, yielding
methenylamidophenyl mercaptan, and similarly with acetonitril and
benzonitril it yields the ethenyl and benzenyl base respectively, the
reaction in the last two cases requiring a higher temperature than in
the first. P. P. B.
3 g 2
888 ABSTRACTS OF CHEMICAL PAPERS.
Chlorinated Quinones. By S. Levy and Gr. Schultz (Ber., 13,
1427 — 1430). — MonocMoroqidnol forms a diacetic compound,
CsHaCKOAc)^,
which crystallises in transparent prisms (m. p. 72°). The dibenzoic
derivative, C6H3Cl(OBz)2, crystallises in long needles (m. p. 130°),
soluble in xylene, ether, benzene, chloroform, hot alcohol, and strong
sulphuric acid. Heated with phthalic anhydride and strong sulphuric
acid, nionochloroquinol yields a chlorinated quinizarine, which dissolves
in a solution of soda with a blue colour. An aqueous solution of
monochloroquinol is converted by oxidation with chromic acid into
monochloroquinone and a small quantity of a-dichloroquinone. The
monochloroquinone, after repeated recrystallisation from alcohol, forms
thick rhombic prisms of a yellow colour, which melt at 57°. It dis-
solves in concentrated hydrochloric acid, forming a mixture of a-di-
and tri-chloroquinols. The former compound (m. p. 164°) yields on
oxidation a-dichloroquinone (m. p. 154°), which is converted by strong
hvdrochloric acid into a mixtui*e of trichloroquinol, C6HCl3(OH)2, and
tetrachloroquinol.
When /3-dichloroquinone (prepared by the action of nitric acid on
trichlorophenol) is treated with strong hydrochloric acid, the same
results are obtained. From neither a- nor /3-dichloroquinone can
a chlorinated quinizarine be derived. The benzoic derivative of
trichloroquinol crystallises in colourless needles (m. p. 174°), sparingly
soluble in cold alcohol.
Trichloroquinone is changed into tetrachloroquinol by boiling with
strong hydrochloric acid. This substance forms a benzoic derivative
(m. p. 230°), which is sparingly soluble in alcohol and freely soluble
in benzene.
TetracJiloroqwinone, C6CI4O0, forms yellow plates belonging to the
monoclinic system. The reduction of tetrachloroquinone by strong
hydi'ochloric acid to tetrachloroquinol shows that intermediate pro-
ducts of the composition C6Cl4(OCl)(OH) do not exist.
The preceding experiments show that, starting from monochloro-
quinol, it is possible to proceed step by step to the formation of tetra-
chloroquinol. W. C. W.
Thymolglycollic Acids. By P. Spica (Gazzetta, 10, 340—349).—
In this paper two thymolglycollic acids are described, obtained from
natural thymol and camphothymol (carvacrol) respectively.
The derivative from natural thymol was prepared by fusing a mix-
ture of 12 parts of thymol with 7'5 of monochloracetic acid, and then
gradually adding the *nixture to 50 of soda solution of sp. gr. 1'35.
The product forms two layers, which mix on adding an equal volume
of water : the unaltered thymol is removed by adding a slight excess
of hydrochloric acid, neutralising with ammonium carbonate, and
agitating several times with ether. The thymoglycollic acid is then
precipitated by an acid, and purified by crystallisation from dilute
alcohol. The yield is theoretical for the amount of thymol acted on.
Pure thymoglycollic acid, C6H3Me(C3H7)O.CH2.COOil, forms fine
prisms (m. p. 147 — 148°), sparingly soluble in water, but easily in
ORGANIC CHEMISTRY. 889
alcohol or ether. The barium salt, (Ci2Hi503)2Ba.2H20, crystallises
with difficulty; it loses the 2HoO at 120—130°. The lead salt,
(Ci2Hi503)2Pb, is obtained as a white amorphous precipitate on adding
lead acetate to a solution of the acid previously neutralised with
ammonia. The silver salt, Ci2Hi503Ag, forms microscopic prisms,
almost insoluble in boiling water. Ethyl thymoglijcullate, dsHisO-jEt,
prepared by saturating an alcoholic solution of the acid with dry
hydrochloric acid, is a limpid, almost colourless liquid (b. p. 290"),
having an odour resembling that of ethyl oxalate. It does not solidify
in a mixture of ice and salt, but when allowed, to stand some days it
deposits a colourless substance (m. p. 110"), possibly a polymeric
modification of the ether. When treated with aqueous ammonia, the
ethyl salt yields thymolgl ycollamide, a substance crystallising in prisms
(m. p. 96 — 97°), sparingly soluble in cold water, but readily in hot.
Camphothymol (carvacrol, b. p. 233 — 235°) when treated with
monoehloracetic acid and soda in the manner above described, yielded
a mixture of three acids ; one, melting at about 110^, formed but in
very minute quantity, another, melting at 126 — 127°, and a third,
carvacrolglt/collic acid ; this is the principal product of the reaction,
the others owing their origin to impurities in the carvacrol employed,
or to a secondary action. These acids were first separated by frac-
tional crystallisation, and the carvacrolglycollic acid was finally puri-
fied by converting it into the barium salt and repeatedly crystallising
the latter. Pure carvacrolglycollic acid crystallises in coloui-less
needles (m. p. 149°), very sparingly soluble in cold water, but readily
in alcohol or ether. The barium salt, (Ci2Hi503)nBa + 4H2O, is more
soluble in hot water than in cold. The lead salt, (Ci2Hi503)2Pb is
thrown down as a gummy precipitate, but crystallises from alcohol in
tufts of microscopic needles. The silver salt, Ci2Hi30jAg, forms
microscopic needles. Ethyl carvacrolglycollate is an oil (b. p. 289°),
which solidifies at a low temperature. The amide, which closely re-
sembles its isomeride, melts at 67 — 68°.
The acid of melting point 126 — 127° forms crystalline nodules
l)uilt up of microscopic needles. It is more soluble in water than the
carvacrolglycollic acid, and is also distinguished from the latter inas-
much as it gives an orange-yellow precipitate with ferric chloride,
whilst carvacrolglycollic acid solution merely becomes turbid. The
silver salt is amorphous, and the results of its analysis, as well as of
that of the acid itself, corresponds with a thymolcarboxylic acid.
The author draws attention to the fact that although the fusion
points of the two isomeric glycollic acids, and also the boiling points
of their ethereal salts, are very close, there is a difference of about 30°
in the melting points of the amides. C. E. G.
Constitution of a-Toluenedisulphonic Acid. By P. Classen
and H. Berg {Ber., 13, 1170 — 1171;. — The constitution of a-toluene-
disulphonic acid, which has been investigated by Blomstrand (Ber., 4,
717) and Hakansson (Ber., 5, 1084), is shown to be orthoparatoluene-
disulphonic acid, since it is formed both from para- and from ortho-
toluenesulphonic acid by the action of fuming sulphuric acid.
P. P. B.
890 ABSTRACTS OF CHEMICAL PAPERS.
Cymenesulphonic Acids. By P. Spica (Gazzetta, 10, 254 —
255). — This is mainly a claim of priority in respect of a paper by
Clans (Ber., 13, 901). — The author has repeated his former experi-
ments (Gaz. 9, 397) on the action of sulphuric acid on cymene,
and finds that two sulphonic acids are really produced, the barium
salts of which crystallise with 3H2O and 4H3O respectively. The sul-
phonic chlorides have also been prepared, as well as the amides. In
conclusion, the author observes, "As is usual in Germany, Claus
makes no mention of the researches on cymene published in Italy."
C. E. G.
Nitro-derivatives of Diphenyl-mono- and Di-sulphonic
Acids. By S. Gabriel and A. K. Dambergis (Ber., 13, 1408 — 1412).
— Cojyper nitrodiphenylstdplionate is prepared by pouring a solution
of paranitrodiphenyl in warm strong sulphuric acid into cold water,
and adding copper sulphate to the mixture. The copper salt is
deposited in small rhombohedral crystals, which have the composition
[Ci2H8(N03)S03], Cu + 4HoO.
Sodium mtrodiphenylsulphonate, Ci2H8(N02).S03Na, is obtained in an-
hydrous lustrous plates by boiling the copper salt with soda. The barium-
salt forms glistening white needles, containing 4 molecules of water.
Nitrodiphe^iylsidphonic chloride, Ci2H6(N02).S02Cl, is deposited
from a glacial acetic acid solution in needles (m. p. 178°). It can be
prepared by the action of phosphorus pentachloride on the sodium
salt, or more readily by dissolving diphenylmonosnlphonic chloride in
fuming nitric acid. The formation of the chloride by these two
methods indicates that the sulphonic acid is a dipara-derivative, viz.,
paranitrodiphenylparasulphonic acid.
Nitrodiphenylsiilphamide, prepared by digesting the chloride with
alcoholic ammonia, melts at 228°.
Paramidodiphenyl-parasulpjiihydrate hydrocMoride,
SH.C6H4.C6H4.NH2.HCI,
is formed when hydrochloric acid is added to the solution in soda of
the yellow precipitate produced by the addition of water to the pro-
duct of the action of tin and hydrochloric acid on the nitrosulphonic
chloride. It crystallises in lustrous plates, which are decomposed by
water, forming an amorphous mass. On the addition of potassium
monochloracetate to a solution of the hydrochloride in an alkali,
potassium amidodiphenylthiacetate is precipitated. The free acid
forms granular or tabular crystals, which dissolve sparingly in water,
and melt above 200°.
Nitro-derivatives of diphenyldisulphonic chloride are obtained by
adding 10 parts of strong sulphuric acid to a solution of 1 part of the
sulphonic chloride in 10 parts of fuming nitric acid. If the tempe-
rature is not allowed to reach 60°, the only mononitro- derivative
(m. p. 130°) is formed ; if the mixture is heated at 90 — 95°, the dinitro-
prodnct (m. p. 166°) is obtained. The solution is poured into water,
and the precipitate dried and recrystallised from glacial acetic acid.
The crystalline double salt, which is formed by the reduction of the
mononitro-derivative with tin and hydrochloric acid, is decomposed
ORGAXIC CHEMISTRY. 891
by boiling water with the production of amido-diphenyl disulphhydratc,
HS.C6H4.aH3.(NH,).SH (m. p. 153°). W. C. W.
Phenanthrene Derivatives. By R. Anschutz and I. v. Siemenski
(JBer., 13, 117y — 1180). — When broraophenauthrene is heated on the
water-bath with strong sulpharic acid, a bromosulphonic acid is ob-
tained, which is soluble in water. On adding potash, ■potassium
bromophetianthrenemonosidphonate, CuHsBr.SO^K, separates as a white
precipitate; it crystallises from hot water in small white needles.
Fusion Avith potash yields no hydroxyl compound.
Silver l)romophena)t.threnemon(jsulphonate, CuHsBr.SOsAg, is obtained
by adding silver nitrate to a hot aqueous solution of the potassium
compound. On cooling, it separates out in greyish-white shining
needles. These derivatives are decomposed by strong nitric acid with
great difficulty.
Barium hromopTienanthrenemonosuJpTumate, (CuH8Br.S03)aBa, forms
a white amorphous precipitate, insoluble in water. The free acid is
obtained with difficulty in. a pure state ; other isomerides are simul-
taneously formed.
From the diazo-compound of sulphanilic acid and phenanthrol (Rehs,
this Journal, 34, 7&), a red colouring matter belonging to the tropaeoline
C6H3(OH)CO
class has been obtained. Further phenanthrenequinone, | | ,
C6H4 CO
obtained from phenanthrol, has marked colouring properties. It is
soluble in a hot solution of sodium hydrogen sulphite, from which
acids precipitate it as a red amorphous powder. Alkalis dissolve it,
forming carmine-red solutions ; heated above 200°, it decomposes par-
tially, but may be sublimed, and is obtained in the form of red needles
resembling alizarin. P. P. B.
Bromonitro-, Nitro-, and Amido- camphor. By R. Schiff {Ber.^
13, 1402 — 1406; also Gazzetta, 10, 317 and 362). — Brornonitro-camphor,
CioHuBrNOs, is formed together with camphoric acid by heating
bromo-camphor with nitric acid for several hours. It is a white crys-
talline body (m. p. 105°), almost insoluble in cold alcohol. If the pre-
ceding compound is dissolved in alcoholic potash, the alcohol removed
by evaporation, and dilute sulphuric acid added to the aqueous solu-
tion of the residue, nitro-camphor, CioHu(OH.)N02, separates as an
oily liquid, which slowly solidities. The crude product can be purified
by solution in ammonia and reprecipitation by acids. The pure sub-
stance melts at 83"" ; its aqueous solution is coloured red by ferric
chloride, and forms a crystalline nitroso-derivative with potassium
nitrite. Nitro-camphor is converted into camphoric acid by nitric
acid, and into camphoric anhydride by nitrosulphuric acid. Heated
in a current of steam, in the absence of air, it is decomposed, yielding
camphoric acid, camphoric anhydride, and ammonia. Nitro-camphor
can also be prepared by the action of zinc and dilute sulphuric acid
on an ethereal solution of bromonitro-camphor.
"When' a solution of nitro-camphor in potash is treated with sodium
amalgam, amido-camphor, CioHu(OH).NH2, is formed This powerful
892 ABSTRACTS OF CHEMICAL PAPERS.
base distils without decomposition at 246"4°, and solidifies on cooling
to a wax-like mass. It forms a hydrochloride, crystallising in needles,
and a crystalline platinochloride (CioHnNO.HCljoPtCU, which is
soluble in hot alcohol. The aqueous solution reduces metallic salts,
and resembles hydroxylamine in many of its reactions.
A crystalline oxy camphor (m. p. 155°) is formed, when the aqueous
solution is treated with nitrous acid. It is volatile in a current of
steam, and is soluble in alkalis.
Amido-camphor hydrochloride is decomposed by distillation in a
current of steam into dicamphorilimide, C20H31NO2, which is found, in
the distillate, and campliimide, which is contained in the residue. The
former of these compounds crystallises in yellow needles (m. p. 160"),
which are insoluble in acids : on adding potash to the residue
camphimide is obtained as an oily liquid, which rapidly solidifies.
This base appears to have the constitution C8Hu<r | ^NH.
W. C. W.
Constitution of Bromo- camphor. By R. Schiff {Ber., 13,
1406 — 1407; also Gazzetta, 10, 332). — The conversion of bromo-
camphor into camphor and of nitrobromo- camphor into nitro-camphor
by the action of nascent hydrogen or of alcoholic potash, seems to
indicate that bromo-camphor contains the group ^C.OBr.
The formation of sodium camphor, when a solution of bromo-
camphor in toluene is treated with metallic sodium, is also evidence
in favour of this view.
Sodium camphor is converted into ordinary camphor by the action
of water. W. C. W.
Action of Zinc Chloride on Bromo-camphor. By R. Schiff
(Ber., 13, 1407 — 1408; also Gazzetta, 10, 317). — By heating a mixture
of zinc chloride and bromo-camphor at 150 — 160° until the evolution
of hydrobromic acid ceases and then distilling the residue, hexhydro-
paraxylene, CgHie, and liquid thymol, CioHuO, are obtained.
Hexhydroxylene boils at 137'6° (corr.), and has the sp. gr. 0"7956
at 4°. The trinitroparaxylene derived from it melts at 127°.
The thymol (sp. gr. I'OlOl at 4°, b. p. 232°) appears to be identical
with the thymol Kekule (Ber., 6, 934) obtained by the action of
iodine on camphor. W. C. W.
Camphocarbonic Acid. By J. Kachlee and T. V. Spitzer (Ber.,
13, 1412 — 1413). — CauqtJiocarhuxylic acid, CuHieOs, is deposited on re-
crystallisation from warm water in colourless needles, which melt at
124°, but begin to decompose below 100°. By treating the ethereal
solution of the acid with metallic sodium, a non-hygroscopic sodium
compound, CosHsiNaOe, is produced, from which the corresponding
barium salt, Co2H3(,BaOG, can be prepared.
By the action of phosphorus pentachloride on camphocarboxylic acid,
a chloride crystallising in prisms (m. p. 44°) is obtained. A crys-
talline compound is also formed by treating a solution of the acid in
chloroform with phosphoric anhydi-ide. W. C. W.
ORGANIC CHEMISTRY. 893
Preparation of Camphoric Acid and Camphoric Anhydride.
By P. ^LvLSSEN {Gazzetta, 10, libU— libl). — Instead of acting directly
on camphor with nitric acid, the mixture of cam])hor and borneol ob-
tained as a residue in preparing borneol by Baubigny's method may
be employed. Camphor is dissolved in any convenient hydrocarbon
boiling above 100^, and sodium is introduced into the hot solution in
small pieces at a time, until it no longer dissolves. When cold, the
pasty mass is agitated with water, and the oily layer separated and dis-
tilled. The residue in the retort may be used for the preparation of
camphoric acid. For this purpose, 300 grams are boiled with 800 of
nitric acid and 200 of water for three days. The crude acid which
separates in the crystalline state may be purified by dissolving it in
potash, filtering, and precipitating with an acid. The yield is about
80 per cent., whilst camphor never gives more than 50 per cent, of its
weight.
To prepare camphoric anhydride, the camphoric acid is boiled with
acetic anhydride and dry sodium acetate in molecular proportions.
When cold, the product is extracted with cold water, and the residue
crystallised from boiling alcohol. In this way, almost the whole of
the camphoric acid is obtained as pure anhydride (m. p. 217°).
C. E. G.
Products of the Distillation of Colophony. By A. Renard
{Compt. rtiul., 91, 41U— 421J. — By subjecting colophony to several
fractional distillations, and removing acids from the distillates by
washing them with alkalis, a hydrocarbon (b. p. 103 — lOO"") is ob-
tained, for which the author suggests the name heptene. It is purified
by washing with caustic soda, drying first over calcium chloride, and
then over sodium, and finally distilling over sodium in a current of
carbonic anhydride. Its analysis and vapour-density correspond with
the formula C7H12. It is a mobile colourless liquid, soluble in alcohol
and ether, sp. gr. = 0'8031 at 20° ; it has a peculiar odour, and is
without action on polarised light. It absorbs oxygen from the air,
evolving carbonic anhydride.
When treated with chlorine, it forms a resinous mass, with evolution
of hydrochloric acid. Bromine acts on the hydrocarbon with great
violence. If. however, it is dropped slowly into the cooled hydrocarbon,
and the mixture containing excess of bromine be allowed to stand in the
shade for two or three days, a thick liquid is obtained, which, after
washing with alkalis, yields a yellow oil. By extracting the oil with
ether and allowing the ethereal solution to stand, crystals of a hexa-
bromo-compound, CTHoBrg, separate out (m. p. 134'') ; it decomposes
at 150°.
By allowing the above mixture of hydrocarbon and bromine to stand
for 8 — 10 days in the sunlight, an isomeride of the above compound
is obtained ; a thick, oily brown liquid, decomposing at 150°.
A dibromide, C-iVLxJivi, is obtained by dropping a solution of the
hydrocarbon in ether into a cooled solution of bromine in ether,
keeping the bromine in excess. On allowing the solution to evaporate
spontaneously, white crystals are formed, which are very unstable,
decomposing a few minutes after their formation.
Nitric acid (sp. gr. 1"15) acts on the heptene at 80°, forming acetic,
894 ABSTRACTS OF CHEMICAL PAPERS.
formic, oxalic, and succinic acids, with, evolution of carbonic oxide
and carbonic anhydride. Fuming nitric acid acts with great violence
on the hydrocarbon. Gaseous hydrochloric acid forms a green liquid
with heptene, but no hydrochloride is formed. An aqueous solution
of the gas is without action.
By treating the cooled hydrocarbon with concentrated or fuming
sulphuric acid, an oily liquid is obtained, consisting of a mixture of
unaltered heptene and diheptene, CuHai (b. p. 235 — 240°). Diheptene
is readily oxidised, absorbing oxygen eight or ten times more quickly
than heptene. It has no action on polarised light. A sulphonic acid
is also formed, which yields a very soluble barium salt.
Heptene unites with the elements of water, forming a crystalline
hydrate. L. T. O'S.
Chlorophyll from Eucalyptus Globulus. By E. Schunck
(Chem, JSle^vs., 31, .3'2). — The peculiar appearance presented by the
leaves of the Eucalyphis globulus is due to an exceedingly thin cover-
ing of fatty matter, such as is seen on fresh plums and other fruit.
The ethereal solution of this fat leaves a semicrystalline residue which
melts much below 100° ; it is partially soluble in alkalis, and, there-
fore, most probably contains some fatty acid. The ethereal or alcoholic
extract of the leaves containing chlorophyll, when kept tightly corked
and in the dark, assumes a yellowish tint, and shows absorption- bands
corresponding with those of " acid chlorophyll." The extract of green
grass does not behave in a similar manner, but, on exposure to the
action of sunlight, it gradually loses its colour and becomes pale yel-
low. The alcoholic extract of eucalyptus leaves also becomes paler on
exposure to light. The change which takes place is attributed to the
action of the essential oil contained in the extract on the oxygen of
the air forming ozone, which acts on the alcoholic extract of the
chlorophyll. Extract of orange leaves when kept in the dark remains
unchanged. After insolation, it slightly differed from an extract of
grass made at the same time and exposed to sunlight along with it.
The bands I and IVa absent in the grass-spectrum were present in
that of the orange extract. L. T. O'S.
Crystallised Chlorophyll. By Hoppe-Setler (Bied. Centr., 1880,
375 — 376). — Leaves of grass after being treated with ether until the
wax was completely remoVed, were boiled with alcohol, which dis-
solved two colouring matters ; both of these crystallised out during
cooling. The first is red in transmitted light, and is evidently iden-
tical with the substance to which Bougarel gives the name of ery-
throphyll. After this substance has been removed by filtration, the
filtrate concentrated, and the residue washed repeatedly with water,
dissolved in ether, and left to evaporate, reappear on the sides and
bottom, of the vessel ; they are granular crystals, brown in transmitted,
green in reflected light. These crystals may be purified by repeated
washings in cold and solution in warm alcohol and in ether.
The author gives this substance the name of chlorophyllan ; it has
the consistence of soft wax ; in a fairly dry condition, it melts at 110°.
The crystals are sparingly soluble in cold alcohol, but dissolve readily
ORGANIC CHEMISTRY. 895
in ether or chloroform. The solution shows the flaorcscence of alco-
holic or ethereal extracts of green plants, and a similar hut not
precisely identical spectrum, which leads the author to the conclusion
that chlorophjllan does not exist as such in the plant, but is formed
during the treatment ; the percentage composition is given as C, 73*4 ;
H, 9-7; N, 5-62; 0,957; P, 137; Mg, 0-34 ; the phosphorus and
magnesium are not considered as impurities, but appear to be normal
constituents of the substance. Further experiments are promised.
J. F.
Behaviour of the Cinchona Alkaloids with Potassium Per-
manganate. By S. HooGEWERFF and W. A. v. Dokp (Ltebig's Annalen,
204, 84 — 118). — Quinine, cinchonine, quiuidine, and cinchonidine,
when oxidised by permanganate, yield tricarbopyridinic acid together
with ammonia, oxalic and carbonic acids, and some other products
which need further examination. A dicarboxylic acid identical with
Weidel's cinchomeronic acid is easily obtained from the tricarboxylic
acid. A monocai'boxylic acid has also been prepai^ed but not fully
investigated.
Preparation of Tricarhojiyn'dwic Acid. — The alkaloids or their sul-
phates are mixed with potash solution and heated to boiling in a flask
in a calcium chloride bath. The permanganate is added in small
quantities until the red colour imparted by it remains permanent
after an hour's boiling.
After addition of nitric acid and concentration of the solution the
potassium is removed by crystallisation as potassium nitrate.
Barium nitrate is then added as long as a precipitate is formed. This
precipitate, consisting of barium oxalate and tricarbopyridinate, is
decomposed by sulphuric acid.
Tricarbopyridinic acid forms transparent tabular crystals, which
appear greenish by reflected light, and exhibit a strong play of colours
under polarisation. It is moderately soluble in alcohol and very spar-
ingly so in ether and benzene, but dissolves readily in boiling water. It
gives a faint red colour with feiroiis salts. It gives up its water of crys-
tallisation between 100" and 120° without decomposition, but becomes
blackened at 190°, and melts at 244—250°. The aqueous solution gives
an amorphous precipitate with barium acetate ; with calcium acetate, a
warty crystalline mass of needles; with silver nitrate, an amorphous
precipitate which becomes crystalline after a time, and is not much
altered by exposure to light ; with copper acetate, a bright blue
amorphous precipitate ; with lead acetate (and also the basic acetate),
white amorphous precipitates. No red fumes are evolved when the
acid is boiled with concentrated nitric acid. It is readily acted on by
permanganate in acid, but not in alkaline solutions. It consists in the
anhydrous state of CnHsNOe, and is tribasic. It crystallises from
aqueous solutions with 1^ mol. of water. The neutral potassium salt,
CsH.KaNOs + 3H3O, forms brilliant plates which exhibit a flne play of
colour in polarised light. The neutral barium salt when prepared by
addition of barium acetate to a .solution neutralised with ammonia,
consists (if precipitated in the cold) of C^HiBaaNOe + 811.0, and
loses 7HoO at 100°, and all its water at 280—300°. If the barium acetate
896 ABSTRACTS OF CHEmCAL PAPERS.
is added to an acid solution, another salt containing, when dried in
air, only 6H0O is obtained, in addition to the one just described. The
calcium salt contains 7H2O. The normal silver salt CsHoAgaNOs +
2HoO, consists of an amorphous precipitate which loses part of its
water over sulphuric acid, and is not much altered by exposure to
light. It is obtained by adding silver nitrate to a solution of the acid
neutralised by ammonia. If the aqueous solution of the acid is mixed
with silver nitrate, a precipitate is thrown down which is at first
amorphous, afterwards crystalline, and which consists of CsHsAgaNOe
+ H2O. Another silver salt, CsHiAgNOs + CgHsISrOe, crystal-
lising with 2^ HoO, may be obtained by dissolving the neutral
silver salt in warm dilute nitric acid and concentrating the
solution.
Ginchomeronic acid may be obtained by heating tricarbopyridinic
acid to 180 — 190°, when decomposition takes place in accordance with
the equation, CsHsNOe = C7H5NO1 + CO3. This acid is identical
with the one Weidel and Schmidt (A-moale^i, 173, 96) obtained by
direct oxidation of quinine, ciuchonine, and cinchonidine. It is
sparingly soluble in ordinary solvents. It gives no colour when mixed
with ferrous sulphate. It contains no water of crystallisation, and
melts at 250° with evolution of carbonic anhydride, but without being
blackened. When distilled with excess of calcium hydrate, the dis-
tillate smells strongly of pyridine. The normal barium salt,
CvHsBaNOi, forms tufts of needles which are sparingly soluble. The
normal calcium salt crystallises in large prisms, and is more easily
soluble than the barium salt ; when dried in air, it retains 3|-Il20.
The normal silver salt, C7H3Ag2N04, is anhydrous, and not much
altered by exposure to light. The acid silver salt, C7H4AgN04, is
obtained by dissolving the acid in boiling water with addition of a
few drops of nitric acid, and adding silver nitrate. It is crystalline
and anhydrous. The normal copper salt, C7H3Cu]Sr04 + 4H2O, forms
dark blue sparingly soluble crystals. It loses its water of crystallisa-
tion at 180°,
Ginchomeronic acid splits up on heating into pyrocinchomeronic acid
(Ber., 13, 61) and nicotinic acid, whilst carbonic anhydride is
evolved.
The action of permanganate on the four cinchona alkaloids seems
to be as follows: — In the first stage, the molecules containing two
nitrogen atoms are split into two groups containing one atom of
nitrogen in each. In the second stage, the nitrogen of one of these
groups is evolved as ammonia, while from the other several bodies
containing nitrogen are obtained, among the rest, tricai-bopyridinic
acid.
The authors do not agree with Weidel and Herzig's supposition that
cinchomeronic acid is constituted (according to Korner's pyridine and
quinoline formula) as 1 . 2 . 3, the nitrogen having the place 1 ; but
they assign this constitution to their quinolic acid obtained by the
action of permanganate on quinoline, and which they consider to be
the normal oxidation product of this body. (Compare Jour. Chem.
Soc, Trans., 1878, 102, and 1879, 189). G. T. A.
ORGANIC CHEMISTRY. 897
Bromine Derivatives of Nicotine. By R. Laiblin (Ber., 13,
1212 — 121-1). — By the action of bromine and Avater on nicotine in
sealed tubes at 120 — 150°, the author has obtained a crystalHne com-
pound similar to that obtained by Cahours and Etard, which is pro-
bably CioHi.BroNo + HBr. On treatment with potash, it yields
nicotine.
Bromonicotine, CioHioNoBrs. — For the preparation of this compound
the author recommends the following method, instead of Huber's
(Amialen, 131, 257), which does not yield very good results. To
50 grams of bromine and 30 grams of water are added a solution of
16 grams of nicotine in 20 grams of water in small quantities at a
time, the temperature not being allowed to rise above 50 — 60°. The
"whole is warmed on a water-bath until the oil so formed is dissolved,
and then 60 — 70 grams of water are added ; on cooling a crystalline
body separates out, probably the compound CinHi2BroN2.2IIBr. This
is decomposed by aqueous ammonia, and yields bromonicotine. The
author is at present engaged in the study of the oxidation-products of
this body. P. p. B.
Compounds belonging to the Creatine and Creatinine
Groups. Bj E. Duvillier {Gompt. rend., 91, 171 — 173). —
a-ni/droxyhutyrocyamine, NH2.CO.NH.CO.CH(N"Ho).CH2Me, a homo-
logue of glycocyamine, may be prepared by adding cyanamide to a
cold saturated solution of amido-a-butyric acid, then a few drops of
ammonia, and allowing the mixture to stand. After about a month,
the crystals of the new compound are collected, washed with alcohol,
and purified by crystallisation from w'ater containing a little ammonia.
It forms long slender needles, sparingly soluble in cold water, but
easily in dilute acids, almost insoluble in alcohol or ether.
a-Hydroxyhutyrocyamidine, NH '. C ! N.CO.CH(NH2).CH2Me, is
easily prepared by boiling the corresponding cyamine with dilute sul-
phuric acid : the sulphuric acid is then removed by treatment with
barium carbonate, the solution evaporated to dryness, and the new
cyamidine dissolved out of the residue by alcohol. It crystallises from
water in long transparent needles of the formula CsHgNsO -|- H^O,
"which lose their water of crystallisation at 150°.
Isohydroxyvalerocyamme, CRH13N3O2, forms short prismatic crystals
resembling the corresponding butyric compound in properties. It is
prepared in a similar manner, and when boiled with sulphuric acid is
converted into the isohydroxyvalerocyamidine, CeHuNsO -t- ^HaO.
Strecker and Erlenmeyer regard the creatines and creatinines as
substituted guanidines ; but the author considers that they are ureides
of amido-acids, and represents their constitution by the formula given
above. C. E. G.
Hypoxanthine from Albuminoid Bodies. By G. S.\lomox
{Ber., 13, 1160 — 1163). — The author, whilst replying to the criticism
of Drechsel {Ber., 13, 210) on a former communication (this Journal,
36, 176), adds the following as a further proof of the production of
hypoxanthine from albuminoid bodies. When fibrin is treated with
pepsine and hydrochloric acid and the syntonine is removed, a solu-
898 ABSTRACTS OF CHEMICAL PAPERS.
tion is obtained which gives no precipitate with aramoniacal silver
solution ; if, however, a milligram of pure hypoxanthiue be added, an
immediate precipitate is obtained, thus proving that hypoxanthiue
does not occur ready formed in the fibrin. P. P. B.
The Form in which the Cinchona Alkaloids occur in the
Bark. By J. E. de Veij (Arch. Pharm. [3], 16, 34— 39).— On
evaporation, the aqueous extract of Chichona succirubra yields a white
solid, of which about 40 per cent, is soluble in alcohol. This alcoholic
solution has an acid reaction and is leevoratory. Reagents show the
presence of quinic and quinotannic acids, and lime. The insoluble por-
tion likewise consists of the same three compounds, but seeing that
quino-tannic acid is generally readily soluble in alcohol, it is here pro-
bably in some new combination. The solubility of quinine in water,
when the bark is macerated in water, is due to the presence of this
acid reacting compound. E. W. P.
Alkaloids from the Decomposition of Albumin. By F. Selmi
{Ber., 13, 206, and Bled. Gentr., 1880, 560).— The author describes the
apparatus employed, tabulates the volatile bye-products, and gives the
reactions of the new bodies formed and of their combinations with
hydrochloric and hydriodic acids. The hydrochlorides have a poisonous
action on frogs similar to curare. J. K. C.
Researches on the Alkaloids of Jaborandi Leaves. By E.
Hamack and H. Meyer (Annalen, 204, 67 — 84). — In addition to
pilocarpine, the authoi's have obtained a second alkaloid from the
leaves of jaborandi {Filocarpus pennatifolius), for which they propose
the name of " jaborine." The separation of the two alkaloids depends
on the facts that free jaborine is more easily soluble in ether and more
sparingly soluble in water than pilocarpine, and its platinochloride
more soluble in alcohol than that of the latter alkaloid ; also that the
compounds of jaborine do not crystallise.
The presence of minute quantities of jaborine in pilocarpine is most
easily detected by its action on a frog's heart, since jaborine exactly
i-esembles atropine in this respect.
Erom analyses of pilocarpine aurochloride and platinochloride the
authors assign to the free base the composition indicated by the for-
mula CuHieNoOo.
A curious fact was observed with regard to its aurochloride. When
pilocarpine chloride is mixed with gold chloride, a crystalline precipi-
tate is obtained consisting of CuHiglSrsOo.HCl + AuClg. If this is
dissolved in alcohol and boiled for a time, a crystalline salt having the
composition CuHieNsOo + AuClg, separates on cooling.
The authors are inclined to class pilocarpine among tertiary dia-
mines. Since the physiological action of pilocarpine is analogous to
that of nicotine, experiments (which proved unsuccessful) were made
to ascertain if there were any relation between its composition and
that of nicotine, CioHuOa. Pilocarpine might, for example, be re-
garded as a methyl substitution-product of nicotine, thus : —
CioHa(CH3)(HO)2N2 = CuHieN^O^.
ORGANIC CHEMISTRT. 899
This view is supported by the fact that jaborandi leaves yield
pyridine bases among other products of their decomposition, and nico-
tine does the same.
Trimethylamine is formed daring tlie dry distillation of pure pilo-
carpine with excess of alkali, but no coniine. Also when crude pilocar-
pine was distilled alone no coniine could be detected, but when dis-
tilled at IGO' with excess of alkali small quantities of a body identical
with coniine are formed, as stated by Poehl (Ber., 12, 2185), due
probably to some prodncts of decomposition, possibly of jaborine.
Preparation of Jaborine. — The crude product (commercial prepara-
tion of pilocarpine, &c.) dissolved in alcohol is submitted to fractional
precipitation with an alcoholic solution of platinum chloride. The
first part of the precipitate which forms a hard mass, insoluble in
water, is removed ; the decanted hquid is again precipitated and
filtered, and the solution then fully precipitated. After filtration from
the precipitate, the jaborine platinochloride separates from the alcoholic
solution. This salt, together with the third precipitate, is extracted
with hot water and the filtrate concentrated by evaporation over sul-
phuric acid in a vacuum. Jaborine platinochloride is a bright yellow
powder or a dark-red amorphous crumbling mass. The deeper colour
is due to impurities, which can be partly removed by washing with
alcohol. Another method of obtaiuing tolerably pure jaborine is to
mix the aqueous solution of the crude substance with hydrochloric
acid, filter, and add mercuric chloride until a precipitate forms. On
shaking and filtering, a bright yellow liquid is obtained: sulphuretted
hydrogen is added to remove the mercury, and the concentrated liquid
is mixed with soda solution and shaken up with ether. On evapora-
tion, jaborine is left as a clear colourless amorphous body. Jaborine is
a very strong base, which differs from pilocarpine, especially in its
sparing solubility in water and more ready solubility in ether. Its salts
are soluble in water and alcohol, and do not crystallise. Free jaborine
volatilises with diflBculty at high temperatures. It probably belongs
to the tertiary amines. The composition of jaborine is either identical
with that of pilocarpine, or their empirical formulae are closely related.
It is probably contained in small quantities, together with pilocarpine
in the leaves of the plant.
Compare Kingzett (this Journal, 1867, 2, 366). G. T. A.
Alkaloid in Aethusa Cynapium. By W. Beekhardt (Arch.
Pharrn. [3], 16, 117). — When the seeds of common fool's parsley
are distilled with milk of lime, a reddish-yellow oil passes over. This
oil has a strongly alkaline reaction and a very powerful penetratino-
odour. It appears to contain nitrogen. This alkaloid seems to have
been first noticed by Ficinus (ibid., 24, 257; see also Watts' Diet.,
Cvnapine), but he describes it as a crystalline solid, while Walz
(Xeu. Jahrb. Pharm., 11, 351), on the other hand speaks of it as an
oil. E. W. P.
Chemistry of the Yew. By D. Amato and A. Capparelli
(Gazzetta, 10, 349 — 355). — The green needles of the yew (Tazus
haccata) were exhausted successively with ether, alcohol, distilled
900 ABSTRACTS OF CHEMICAL PAPERS.
•water, and finally with dilute sulphuric acid, and each extract care-
fully examined. The extract left on evaporation of the ethereal solu-
tion was mixed with dilute sulphuric acid (1 : 20) and distilled in a
current of steam, when an essential oil passed over resembling that of
wild fennel in odour. The hot acid solution separated from the
insoluble residue in the retort, deposited an amorphous powder on
standing, and the filtrate from this when treated with excess of
baryta and agitated with ether yielded an alkaloid. A colourless
non-nitrogenous crystalline substance was extracted from the insoluble
residue above-mentioned by treating it with alcohol and small quan-
tities of animal charcoal. Its purification is a matter of considerable
difficulty, and requires careful attention to details given in. the original
paper.
The alkaloid is a colourless, crystalline, nitrogenous substance,
having a musty odour, sparingly soluble in water, but easily in
alcohol or ether. Dense white fumes are produced when a rod
dipped in dilute hydrochloric acid is held near it. It gives a
canary-yellow precipitate with phospho-molybdic acid, and with
tannin a white precipitate, which becomes crystalline on standing.
Picric acid gives a yellow precipitate, and iodised potassium iodide
reddish-brown crystals.
The non-nitrogenous crystalline substance forms stellate groups of
needles (m. p. 86 — 87''), easily soluble in boiling alcohol, but only
sparingly in. the cold.
The solution obtained by exhausting the yew needles with alcohol
after they had been extracted with ether was found to contain the
same substances as the ethereal solution. From the aqueous and acid
extracts, oxalic acid and email quantities of the alkaloid were obtained.
C. E. G.
Milk Albumin and Curd Formation. By G. Muzzo and C.
Menozzi (Bied. Centr., 1880, 364— 366).— The object of the author
was to determine whether the albumin of milk was of the same com-
position as egg albumin. The albumin of milk was obtained by coagu-
lating the casein, when the albumin remained in the whey. According
to the method of Hoppe-Seyler, it is obtained by separating the casein
with acetic acid and carbonic anhydride, boiling the residue, and filter-
ing off'; but the author says he obtains better results by evaporating
the filtrate from the precipitated casein. After adding sodium or
magnesiuna sulphate, by the Hoppe-Seyler method, 100 grams of
milk yielded 0"5 gram, and by his own method he obtained 0"572 —
0"604 grams of albumin. The analysis of this albumin, as compared
with that of blood, shows the following percentage composition,
proving both bodies to be nearly identical.
Carbon. Hydrogen. Nitrogen. Sodium. Oxygen.
Milk albumin. .. . 53-74 6-95 15-52 1-55 22-24
Blood albumin .. 53-5 7-0 15-5 1-6 22-4
The authors proceed to consider the behaviour of the albumin during
precipitation at different temperatures, and they find that in milk
deprived of its casein by the addition of acetic or lactic acid (0-50 —
0-75 gram to 100 grams of milk), the slightest warming causes a pre-
ORGANIC CHEMISTRY. 901
cipitate in the clear whey ; it takes place at so low a temperature as
3 — 4° C. On heating' it to 40° a further precipitation takes ])lace ; aorain
at 59-68^ ; at 72° ; and finally at 100°. When the milk is boiled previous
to bein^ treaied either with rennet or acid, the precipitate is greater
than when it is not boiled and no albumin separates ; but the total
obtained in that case is simply the sum of the albumin and casein.
J. F.
Peptone. By C. A. Pekelharing {Pfliiger's Archiv., 22, 185—206).
The researches of Plosz, Maly, and Adamkiewicz, the author admits,
point to the conclusion that albuminoids, although changed by the
digestive fluids into peptones, resume after absorption their original
properties, and further, that peptone may be substituted for albu-
minoids, as a fi od not only without harm, but with positive advantage
to the animal. But it is obvious from the methods of preparation of
peptone adopted by the.se observers, that the word " peptone " has not
the clear and definite meaning usually attributed to it. The method
used in all these cases was the digestion of fibrin by gastric juice. But
the times deemed sufficient by each observer for complete conversion
vary widely. Plosz, 2 — 3 wrecks ; Maly, 2 — 8 days ; Adamkiewicz,
2 — 5 hours. Despite these diiferences, the conclusions arrived at agree
in. the main, viz., that peptone can replace proteids as food, and that
animals so fed will not only maintain, but increase their weight.
After examining these results more in detail, the author remarks on
the importance of experimenting with a substance of constant com-
position, and proceeds to describe his method of preparing pure peptone,
which depends on a property described by Place and Huizinga ("Onder-
zoekingeu gedaau in het. physiologisch laboratorium der Leid.sche
Hoogeschooi," 1870, and " Maandblad voon Naturwetenschappen,''
1873, p. 29), viz., that in the cold a solution of peptone, having an acid
reaction, is precipitated by neutral sails, the precipitate redissolving
on warming.
Fibrin from bullock's blood and egg-albumin was used, and was
digested with 0'2 per cent, hydrochloric acid, and pepsin (either com-
mercial or prepared by extracting pig's or dog's gastric mucous mem-
brane in glycerol) for 2 — 5 hours at 40° C. The solution was then
neutralised until the reaction was very feebly acid, heated to boiling,
and filtered hot. The filtrate after cooling, usually opale.scent or dis-
tinctly cloudy, was evaporated a little, made .strongly acid with acetic
acid, and saturated with sodium chloride. The somewhat abundant
flocculent precipitate so produced was filtered off, after 8 — 12 hours.
The fluid, which filters readily, passes perfectly clear through the paper,
and the precipitate dissolves very readily in distilled water on warm-
ing, still not without a .slight flocculent cloudiness, due to albumin
which has not been completely precipitated by boiling in a feebly acid
solution, but when precipitated by sodium chloride and acetic acid, is
not soluble on heating. If the precipitate is dissolved in a sufficiency
of water, the fluid, when separated from the albuminoid precipitate, is
perfectly clear; if, however, the distilled water be spared, with the
idea of avoiding a large mass of fluid, the precipitate will return on
cooling. The solution is then to be dialysed, in order to get rid of the
acetic acid and sodium chloride ; in one day, a precipitate of peptone
VOL. xxxviii. 3 r
902 ABSTRACTS OF CHEMICAL PAPERS.
is formed, which continually increases as the dialysis is pushed, and
which on warming, or the addition of small quantities of acid, alkali
or salts, is completely dissolved. After three or four days' dialysis,
the fluid is nearly free from .salts, and the precipitate may be removed
from the dialyser, boiled in water, and the resulting solution, which is
not quite clear, filtered hot. The filtrate is a pure peptone solution,
and will yield a heavy precipitate on cooling. It is to be concentrated at
a gentle heat, and finally dried in a vacuum over sulphuric acid.
When dry, peptone so prepared is a pure white powder, and is not
hygroscopic. It has the following properties : —
Heated over a flame, it does not melt, but forms strong tenacious
bubbles. The ash is small ; the substance heated at 105" gave
0'4 per cent, and 0'47 per cent. ash.
The powder is only partially soluble in oold water, but dissolves
completely on warming, separating again as the solution cools. The
solution has a perfectly neutral reaction.
Addition of a small quantity of sodium chloride will prevent pre-
cipitation on cooling ; added in excess, however, it causes a slight
turbidity in the cold, which disappears on warming.
Very small quantities of acids or alkalis will cause solution in the
cold. Peptone is precipitated from the alkaline solution by sodium
chloride in excess ; this does not occur, however, if the peptone is
warmed in the acid solution, provided the acid is not present in too
small quantity, and has acted thoroughly (this is best effected by
warming) ; saturation with sodium chloride to the extent of 4 per cent,
gives a precipitate, which completely disappears on heating. The
same takes place if more salt is added. When 16 per cent, of salt has
been exceeded, complete solution only occurs when the peptone solution
is somewhat dilute. Peptone is precipitated from the feebly acid or alka-
line solution by neutralisation ; if, however, too much acid or alkali has
been used for solution, sufficient salt may be formed to hinder precipita-
tion. Strong nitric acid gives a precipitate, which vanishes on heating,
before the yellow coloration appears, and returns on cooling. Silver
nitrate added to a solution of peptone which is cooling, and therefore
is becoming cloudy, increases the cloudiness. The precipitate dis-
appears almost entirely on cooling ; a slight opalescence, due to sodium
chloride, alone x'emaining. The precipitate produced by silver nitrate
is soluble in acetic acid.
Absolute alcohol precipitates peptone in neutral, but not in acid or
alkaline solution. Potassium ferrocyanide and acetic acid give a
voluminous precipitate, soluble on heating.
Basic lead acetate, with ammonia, tannic, and phosphomolybdic acids,
give precipitates which are not soluble on heating.
The precipitate yielded by Millon's reagent dissolves with a red
colour, if only small quantities of the mercury solution are used. More
of the reagent gives a red precipitate, permanent on heating ; cupric
sulphate, ferric acetate, ferric sulphate, lead acetate, and basic lead
acetate do not precipitate the peptone solution, unless sodium chloride
or potassic acetate is present.
The author then proceeds to say that from these reactions no
albumin can be present. Peptones from fibrin or albumin or other
PHYSIOLOGICAL CHEMISTRY. 903
sources resemble one another in all their chemical properties. All are
laevorotatory, but there is some difference in the degree of rotation,
albumin peptone having the least, and casein peptone the greatest,
effect on polarised light.
No elementary analysis was made by the autlior. The question
whether peptone is isomeric with albumin, or differs from it by one or
more molecules of water, is then raised, and the experiments of
Huizinga and others on the subject criticised at great length. With
the view of showing that these observers did not use a pure material,
Meissner's peptones are examined with the same conclusion.
W. N.
Physiological Chemistry.
Respiration under Reduced Pressure. By J. Setschenow
(Pjiiiijer's An-ldv., 22, 251 — 'ICA). — The entry of oxygen and nitrogen
into the blood under normal circumstances has been fairly well inves-
tigated, and Paul Bert has made some researches on the effects of com-
pressed air ; less is known of the effect of rarefaction, the chief
authorities on the subject being L. Meyer, Fernet, and J. Worm-
!Miiller. The author points out differences between figures given by
the latter and some results obtained by Paul Bert, as to the relations
of the oxygen in the blood to the pressure ; he then refers to the death
of the aeronauts Sivel and Croce-Spinelli, at a height at which
the barometer registered only one-third of an atmosphere, and describes
a series of experiments with oxygen and nitrogen. The results with the
former confirm those of ^leyer, Fernet, and Worm-Miiller. Nitrogen
was found to behave to blood as to water under varying pressures, and
he concludes that a pressure much below half an atmosphere cannot
be borne without danger to life. W. N.
r>
Hydrolytic Ferments of the Pancreas and Small Intestines.
By H. T. Brown- and J. Hekox {Chem. News, 42, o.)— (i7).— The
authors confirm the results of Musculns and De Mering (Bull. Soc.
Chim., 31, 105) on the hydrolytic action of the pancreatic secretion.
They find that starch is converted into maltose and dextrose, the latter
being a product of the action of the secretion on the maltose. Its
action, however, differs from that of malt extract on stai'ch, since in
the latter case maltose is the final product.
The pancreatic secretion has no action on cane-sugar, if organic life
be excluded ; but if the digestion be continued sufficiently long to
develop bacteria, evolution of gas takes place.
Extracts of the small intestines of a fasting animal have little or no
hydrolytic action on starch or cane-sugar; but in the case of an animal
killed during the process of digestion, the extract has a somewha t greater
action. The intestine itself possesses far more pronounced hydrolytic
action than its extract ; different portions of the intestine act differ-
ently on cane-sugar.
•^ 3 r 2
904
ABSTRACTS OF CHEMICAL PAPERS.
The portion of duodenum below the pylorus, containing Brunner's
fflands, acts after digestion for 16 hours in the cold, and 5 hours at
45°. The duodenum below Brunner's glands, acts after digestion for
16 hours in the cold. The jejunum without Peyer's patches, and the
ileum, acts after 3^ hours' digestion at 40°, Peyer's patches act after
11 hours' digestion, at 40°.
"Portion of the small intestines act on starch in a manner similar to
the pancreatic secretion ; maltose is first formed, and the final product
is dextrose into which the former is ra]")idly converted. The small
intestine acts more rapidly and completely on maltose tlian on cane-
sugar, in which case the action ceases when 25 per cent, of the total
quant ty of cane-sugar has been inverted, whilst in the former case
the action is continiious.
The actions of the pancreas and small intestine on starch are
mutually dependent on each other, for whereas the pancreatic secre-
tion rapidly converts starch into maltose, it only very slowly and
partiallv converts maltose into dextrose ; this conversion is, however,
readily efi^ected by the small intestine.
The variability of the hydrolytic action of the different portions of
the intestines is dependent on the frequency of either the Lieberkiihn
or B runner glands, but appears to be correlative with the distribution
of Peyer's glands. L. T. O'S.
Nutritive Value of Fluid Meat. By M. Rubner (Zeits. f.
Biologie, 15, 484 — 492).— The general properties of the so-called fluid
meat having been described, the author gives tables of analysis, com-
paring it with meat and meat extract ; 12'61 per cent, of NaCl was
found : —
Water • •
Dry substance
N in 100 pts. dry substance.
Alcohol extract
Ash
Organic matter
N" in 100 pts. organic matter
Fluid
meat.
20-79
79-21
10 -Sfi
43-30
18-64
81-36
12-73
Fluid meat
after
removal of
NaCl.
11-86
49-54
6-90
93-10
12-73
Meat.
75
24
14
6
5
94
-90
-10
-10
-66
-39
-61
14-91
Meat
extract.
21
78
10
70
22
77
13
•70
■30
-25
•39
-36
•64
•21
The inorganic constituents of 100 parts of the dry substance, after
removal of the NaCl as compared with meat, was found to be as
follows : —
PHYSIOLOGICAL CHEMISTRY. 905
Fluid meat.
NaCi i-emoved. Meat.
SiOj 0-U51 0-4:^2
F0O3 0-021 0-053
CaO 0-026 0-093
MgO 0-162 0-178
PO5 0-715 1-852
SO3 preformed 0-112 —
SO3 in the ash 1-758 2-250
The quantity of peptone present is important. This was estimated
by Schmidt's method (Du Bois, Archiv., 1879, 8, 39), and the general
results are contained in the following table : —
100 parts fluid meat contain —
Water 20-8
Dry residue 79*2
Ash 14-8 with 10-0 NaCl
Organic matter 64-4
Peptone 23-8
Extractives 40-6
As a result of his investigations, tlie author concludes that fluid
meat is very like meat extract plus peptone, and after mentioning the
peptone preparations of Sanders-Ezn, Adamkiewicz, and Leube and
Kosenthal, he points out that the cost of sufficient fluid meat, as a sub-
stitute for the ordinary proteid of an average man for one day, would
not be less than 10s., and expresses the opinion that the peptone is
the really important element ; it can never come into general use as a
food stuff at the price, and will not supersede Liebig's extract for other
purposes. W. N.
The Proteid required by the Average Workman. By H. C.
Bowie {Zeits. Biolo(/ie, 15, 459 — 484). — The author criticises at great
length the objections raised by G. R. Beneke to the standard diet for
a man doing moderate work, suggested by Voit (118 grams albumi-
noids, 56 grams fat, 500 grams carbohydrates per diem). This being
in his (Beneke's) opinion too much. W, N.
Influence of Lactic Acid in Fodder. By Siedamgrotzky and V.
HoFMEiSTKR {Bied. Ceidr., 1880, 373 — 374). — Experiments were under-
taken to discover the effects of lactic acid on the bones of animals, and
they are of a certain importance in view of the frequent employment of
factory residues rich in starch as fodder, such substances being easy of
decomposition in the intestinal canal and forming lactic and other
acids there ; the subjects of experiment were goats and slieep, and it
was .shown that the presence of the acid exerts a solvent effect on the
boues, more especially on those of young and growing animals ; with
sucking animals the efiects cannot be estimated, as they could not be
prevailed on to eat the food; the lime and phosphates were principally
attacked, the magnesia untouched, but rhachitis and osteomalacic
were not induced by the use of this food. J. F.
Formation of Sugar in the Liver. By J. Seegex and F.
Kratschmer (Pdugers Archiv., 22, 214 — 239). — The authors have
90() ABSTRACTS OF CHEMICAL PAPERS.
already endeavoured to show that the liver-sugar is grape-sugar,
whilst the sugar which is formed by the action of all diastatic fer-
ments, diastase, ptyalin, paucreatic ferment, &c., on starch or glycogen
differs from grape-sugar in its reducing power and specific rotation ;
probably the sugars so produced are all identical with maltose
(Dubrunfaut, O'Sullivan, Schultze). There are, however, slight
differences according to the method of preparation, and the question
is : Is the sugar obtained from the dead liver a ferment sugar, or true
grape-sugar ?
The sugar found in the liver closely resembles that produced by the
action of acids on glycogen : hence the existence of acid in the liver is
of importance. A series of experiments are given, which show that
side by side with the increase of sugar in the liver after death there is
an increase in the acidity.
The action of the acids extracted from the liver on glycogen were
next investigated. The liver was prepared by the Liebig-Scherer
method. A strong glycogen solution heated with lactic acid was not
affected, but when the two were placed together in a seated tube and
heated at 100" C. for 24 hours, sugar was produced. The method of
treating the liver, preparing the extract, and surmounting the difficul-
ties of the sugar and glycogen estimation, are then described at length.
The possibility that the sugar and glycogen formation was not the
same in all parts of the liver was next investigated ; Wittich's experi-
ments are referred to (Centralblatt med. Wiss, 1875, No. 8). Analyses
of a whole liver, divided into 4 parts, are given ; and the authors con-
clude that the formation is regular and equal in all parts of the organ.
Dogs were used for the experiments, being poisoned by potassium
cyanide, and the livers excised whilst the heart was still beating ; they
were then cut into small pieces, and treated by the method described, at
intervals varying from two minutes to six days after excision. Five dogs
were used, and were fed (a) on bread, (/3) on flesh, and (7) starved.
The percentage of sugar found in the liver two or three minutes
after excision was 0"46 to 0"55 in all cases, i.e., the nature of the diet
does not appear to affect the quantity found so shortly after death.
The percentage of sugar rises slowly for some time after death, most
rapidly during the first hour or two. In the starved animal there was
no further increase after the first 24 hours.
The estimation of the total sugar plus the sugar obtained by the
acids on the glycogen in sealed tubes, gave remarkable results. If the
sugar arises entirely from the conversion of glycogen, the quantity
found by this method should be the same for all the pieces ; but this
is not tlie case, and therefore the authors argue from this, and the fact
that in their experiments the rise in the sugar did not correspond to the
fall in the glycogen, but was greater than could be accounted for in
this way, that there must be some source of sugar in the liver other
than glycogen. The experiments show further a steady rise in the
acidity of the liver after death.
Experiments on rabbits yielded somewhat different results. The
quantity of glycogen found was so much greater than in the dogs that
the experiment was repeated four times, under the impression that
some mistake had been made, but always with the same result, the
PHYSIOLOGICAL CHEMISTRY. 907
quantity of glycogen amounting to more than twice as much as was
found in the dogs' liver. Experiments an cats yielded much the same
results as those on dogs.
The authors sum up their results as follows : —
(1.) In all the animals experimented on, the liver, when taken out
with all possible speed, was always found to contain from U'5 to 0"6 per
cent, of sugar.
(2.) That the liver-sugar is not entirely derived from glycogen, but
has some other source.
(3.) That not only the liver-sugar, but any carbohydrate which by
heating with acids can be converted into sugar (glycogen or dextrin)
can be formed afresh in the dead liver.
(4.) The liver glycogen experiences a considerable diminution about
48 hours after death.
(5.) An energetic ti-ansformation of glycogen^, immediately after
death, occurs only in rabbits. W. N.
Some Ingredients of Normal Urine. By C. SciiiAPPARELLr and
G. Peroxi (Gazzetta, 10, o'JU— :3'J2j.— xLs it is well known that lithium,
caesium, and rubidium are almost always associated with the alkaline
metals, and that in some minerals, and in bones and plants, cerium,
lanthanum, and didymium are associated with calcium, the authors
have examined human urine to see if the same association of metals
occurred in it ; 600 kilos, of urine were evaporated, and the incinerated
residue carefully analysed. Rubidium and ctesium were found, and
lithium in smaller quantity; also cerium, lanthanum, and didymium,
with a trace of manganese. The authors consider that in normal urine
copper only occurs in infinitesimal quantity. C. E. G.
Influence of Borax on the Decomposition of Albumin in the
Organism. By J\I. Gruber {IJied. Centr., 1«80, SOU— 510).— Experi-
ments on animals showed that the quantity of urine secreted increased
with the amount of borax given with the food, and the decomposition
of albumin was consequently increased. Borax does not seem to affect
the digestion or injure the appetite. J. K. C.
Influence of Fodder on the Secretion of Milk. By W.
Fleischmann {Bled. Centr., 1880, 510 — 515). — A herd of cows nearly
at the end of the milking period, having been for some time pi'evious
supplied with an insufficient quantity of fodder, were allowed a larger
amount, the result being that the quantity of milk yielded by them
was also increased, but not to such an extent as to repay the extra
cost. In the case, however, of another herd, all of which were at the
beginning of the lactation period, an increase of the quantity of fodder
(previously insufficient) was attended with a corresponding increase in
the quantity of milk more than sufficient to repay for the added cost of
food ; the quality of the milk was also greatly improved.
J. K. C.
Influence of Arsenic on Animals, By C. Gies {Bied. Centr.,
1880, 372 — 373). — The author experimented with rabbits, cocks, and
swine, constantly increasing quantities of arsenic acid being mixed
with their food for nearly four mouths ; all the animals became fatter,
908 ABSTRACTS OF CHEMICAL PAPERS.
the growth of bone in the younger animals was constant, and in
cases where under normal conditions there would have been a spongy
growth, these animals had compact bone substance. Stall fed animals
showed the phenomenon very markedly, the arsenic was freely elimi-
nated through the skin and lungs ; full-grown animals showed a pro-
nounced thickening of the corticalis diaphysis, and a fatty condition
of the muscles of the heart, the liver, kidneys, and spleen ; when the
doses were further increased, symptoms of chronic poisoning ap-
peared. J. F.
Chemistry of Vegetable Physiology and Agriculture.
Influence of Oxygen on Fermentation. By A. Matfe (Ber.,
13, 11G3 — 1164). — When the fermenting liquids contain only sugar
and yeast cells, the author finds that oxygen aids fermentation, inas-
much as it favours the gi'owth of the yeast plant. When yeast cells
lose their power on account of the concentration of the sugar solutions,
it is restoi'ed by adding some sodio-potassic tartrate. This observa-
tion, the author considers, throws some light on the fact that artificial
fermentation mixtures work more slowly than in the preparation of
wine, &c. Also that the experiments on the influence of oxygen need
to be repeated with the addition of organic acids.
P. P. B.
Lower Organisms in the Air. By E. C. Hansen (Bled. Centr.,
1880, 5iG — 547). — Flasks partly filled with boiled beer- wort were
placed under different fruit trees in summer, and were found to attract
very different organisms, even when placed near to one another: some
kinds of spores were found to frequent one place and some another.
J. K. C.
Action of Light and Darkness on Tannin Solutions. By
A. R. Leeds (Chcm. Neics, 42, 44). — A standard solution of ammo-
nium chloride under the influence of fungoid growth does not undergo
any change on exposure either to light or to darkness when oxygen is
excluded, whether chloroform is present or not.
Tannin solutions containing saproligneous growths, to which
oxygen is freely admitted, undergo a slight change when exposed to
diffused light, and in darkness change takes place to a great extent,
with a large development of fungi. Chloroform slightly retards the
development of the fungus. The circumstances therefore most favour-
able to preservation of standard solutions are exposure to light, with
exclusion of oxygen and germs of fungoid growth. L. T. O'S.
Gelatinous Matter in Beets. By P. v. Tieghem (Bled. Centr.,
1880, 337 — 339). — This paper is a review of Scheibler's discovery of
this remarkable substance, which he has named from its properties
" frogspawn." He considered it to be the protoplasm of the beet, out of
which a new carbohydrate, " dextran," has been separated. Borscow,
on the other hand, takes a different view, and asserts that this gela-
tinous matter has neither the physical properties nor chemical com-
VEGETABLE PHYSIOLOGY AND AGRICULTURE. 909
position of protoplasm, particularly because of its non- nitrogenous
character. He considers it to be a substance of a pectose nature,
having its origin in the cells of the beet. Another observer shares
the error, and Duriu also asserts that the substance is nou-nitrogenous.
He calls it " cell matter," and thinks it is produced by spontaneous
fermentation of the cane-sugar in the root.
Previous to those observers, however, two French chemists, Jubert
and Mendis, had arrived at sounder conclusions on the subject, and
expressed their conviction that this beet-jelly was a plant of a distinct
character. The author confirms this view, and names the plant
Leuccmostoc mesenteroides, and describes it as being produced in the
juice during the manufacture of sugai', with the aid of the dissolved
oxygen ; he finds that it inverts the sugar and nourishes itself upon
it, being a powerful medium of inversion. It is on that account a
dreaded enemy of the sugar industry, and every possible means should
be taken for its destruction. J. F.
Fermentation Theory of Nitrification. By J. H. Stoker
(Bied. Centr., 1880, 388 — o8'J). — The author offers these experiments
as a confirmation of Schlosing's theory of nitriticatiou. Eleven flasks,
well corked, with inlet and outlet tubes, were connected in series,
some of them containing peat, viz.. No. 8, peat with ammonium chlo-
ride, No. 9, peat with oxide of iron, No. 10, peat with both ammonium
chloride and oxide of iron, the others different combinations of am-
monia, clear water, &c. Oxidising agents were drawn through the
series by an aspirator for eleven days. Those flasks w-hich contained
peat were the only ones which yielded nitrogen reactions. The same
experiments were repeated with peat which bad previously been
treated with warm acids, the results in this case being negative,
farther confirming Schlosing's theory that the ferments in the peat
were desti-oyed by the acid. J. F.
Influence of Atmospheric Electricity on the Growth of
Plants. By C. Naldin {Lud. Centr., Ibfii), SS6 — 'S'67). — Grandcau
by his experiments showed that the blooming and fruiting of plants
was retarded or accelerated by the fact of atmospheric electricity
being allowed access or not to certain plants.
The author of this paper does not exactly contradict Grandeau's
conclusions as far as the plants which he (Grandeau) experimented
on, but the results of the later experiments are calculated to throw
doubts on the general application of any rules as yet discovered.
Naudin's observations wei'e made at Antibes, in the south of France,
whilst Grandeau's were made at Nancy, in the north-east. The field
was quite open, no high object in the neighbourhood. The apparatus
for keeping of}' electricity was an iron cage, which let in less light
than Grandeau's arrangement. The plants were French beans, lettuce,
and tomatoes, some of which were planted under the cage and some
outside, but the other conditions were exactly similar. As already
indicated, the results of the crop were that the plants which were
sheltered from atmospheric electricity were in every respect superior
to those grown in the open.
910 ABSTRACTS OF CHEMICAL PAPERS.
The author thinks that the injurious effect of trees on vegetation is not
due to their effect in keeping away electricity, but finds a ready solu-
tion in their shadow, and the exhaustion and drying up of the soil by
their extended roots. On the other hand, many plants seek and thrive
best in the shade of trees. The question of the effect of atmospheric
electricity is still in a very unsettled state, and probably varies with the
species of plant, the climate, &c., and while our experience is so
limited the promnlgation of generalities on the subject should be
avoided. J. F.
Energy of Assimilation in Plants. By C. A. Weber {Bied.
Centr., 1880, 378). — The green leaves of the higher orders of plants
by their activity in assimilation produce their combustible consti-
tuents. These, minus the ash, are generally taken as the measure-
ment of the energy ; but the experiments made by the author lead
him to believe that there is a considerable difference between the
powers of assimilation in different species of plants. Those actually
experimented on were Tropceolum majus, Phaseolus onultiflorus, Ricinus
communis, and Heliantlins animus. J. F.
Formation of Chlorophyll in the Dark. By C. Flahault
(Bled. Centr., 1880, 556 — 557).- — The author suggests that the chloro-
phyll in the young shoots of certain plants which have grown in the
dark was already formed in the seed while still connected with the
plant. J. K. C.
Chlorophyll in Epidermis of Foliage of Phanerogams.
By A. Stohk {Bled. Ceidr., 1880, 376). — Chlorophyll was found in the
epidermis of the leaves of 94 out of 102 specimens of dicotyledons
and broad-leafed Gymnosperms, but was not detected in the narrow-
leafed species, or in monocotyledons. It was found chiefly in the
cells of the under leaves, the leaf-stalks and the stems ; that which
existed in the cells of the upper surface of the leaves had been decom-
posed by the action of intense light. It was formed by the aggrega-
tion of green protoplasmic matter to the starch corpuscles ; the starch
was modified afterwards, but the chlorophyll showed no assimilation
energy. J. F.
Influence of Annual Temperature on Change of Colour
in Leaves. By H. Hcfmann {Bied. Cejitr., 1880, 378— 379).— If a
thermometer be freely exposed to sunlight, and the readings above
0° C. added together from the 1st of January to the day in autumn
when the turn of the leaf is general, and the same practice pursued
for several years, a curve can be constructed which will show consider-
able variations. If then another curve is constructed below it, com-
posed of the various days on which the change of colour became
general, there wall be found a correspondence which cannot be acci-
dental, but which, on the contrary, has been confirmed by so many
observations, that the author does not hesitate to formulate it as the
expression of a law. The tempei'atures of January and February, the
time of rest for plants, cannot exercise any influence, neither is it
probable that of April or May does so, when the leaves first appear,
VEGETABLE PHYSIOLOGY AND AGRICULTURE. Oil
and as there is no regular interval of time between the budding of
the leaves and their turn, the few weeks immediately previous to that
period are the most important. The more cloudy the autumn, and
the lower the sum of the temperature of the last month of it, the
longer the leaves remain green. The author draws attention to
similar results to be observed with plants grown in shade, although
their behaviour under such conditions is not so regular. J. F.
Breathing of Plants and Animals. By J. Jamieson (Bied.
Gent)-., IbbU, oT-i). — Thu author, in a memorial submitted to the Royal
Society of Victoria, traces certain resemblances between the breathing
of plants and of animals, and says that in the same manner as the in-
haled oxygen combines with the hsemoglobulin of the blood of animals
and forms more active combinations of the character of ozone, so does
it combine with some fluid in plants, which fluid has not yet been
identified, but that the presence of ozone in the ripe fruit can be de-
tected by any of the ordinary tests, such as guaiacum or iodide of
starch. J. F.
Intramolecular Respiration of Plants. By J. Wortmaxx
(Bied. Cent)-., 1880, 55-4 — 5o5). — From experiments made with young
shoots of Vicia faba and Fhaseolus rmdtijlorus, the author concludes
that the carbonic anhydride given off by plants is referable to intra-
molecular action alone, and is independent of atmospheric oxygen,
that the albumin converts the carbohydrates into alcohol with evolu-
tion of carbonic anhydride ; the alcohol by means of atmospheric
oxygen is converted into acetic acid, and by consolidation and re-
arrangement of the molecules of the latter, carboliydrates are again
formed. J. K. C.
Influence of Continuous Sunlight on Plants. By Schubeler
(Bied. Gentr., 1880, 521 — 523). — The results of the transporting of
southern plants to arctic regions, where they enjoy a lengthened
period of unbroken sunlight, are that the development of the pig-
ments and aroma of the plants and fruit is greatly increased, whilst
the sweetness of the latter is much dimiuished. The ripening process
is also quickened. J. K. C.
Functions of Vegetable Ducts. By J. Buhm (Bied. Gentr.,
1880, o2tJ — o2'J). — Tlie author, after stating that the original function
of the ducts in growing plants is for the conveyance of sap, and
not of air, and that as the tubes become older, air finds an entrance,
proceeds at some length to give the conditions under which the
passage of water through the ducts occurs. J. K. C.
Influence of Salts on the Absorption of Water by Roots.
By J. VE-SyUE (Bitd. Ceutr., IbbU, ijob). — Under normal conditions
plants absorb moisture more quickly from distilled water than from
saline solutions ; but after being for some time in the former, they
absorb water more rapidly from salt solutions, and vice versa.
J. K. C.
912' ABSTRACTS OF CHEMCAL PAPERS.
Quantity and Distribution of Water in Trees. By N. Gelez-
NOVV (Bied. Centr., 1880, 379). — The author's experiments were made
on trees 11 to 85 years old of the s-pecies Acer plafano'ides, Betula alba,
and Populus tremula ; he fonnd that the amount of moisture increases
from the bottoms to the tops both of stems and branches, the extreme
points, however, being drier than the part immediately below, and the
extreme base somewhat damper than the portion immediately above
it. In the bark, this law is observed even more strictly than in the
wood, the author havinof found no variations from the before-men-
tioned rule. T-he relative moisture of bark and wood varies very
much in ditferent trees ; the loood, of the fir is damper than the barJc ;
with the maple, the reverse is the case. The wood of the fir contains
more moisture than that of any of the other trees examined, containing
in winter 64'5 per cent., in spring and autumn 63 per cent., in summer
60 per cent. ; maple in spring 44'4 per cent., in winter 37"1 per cent.
The birch similarly shows less moisture in winter than in summer,
advancing from 46'4 per cent, to 71"8 per cent, in the month of May.
J. F.
Sap of Trees and Specific Gravity of their Wood. By
XoRDLiNGER (Bied. Geutr., 1880, 379 — 381). — The presumption that
the dryness or heavy rainfall of the preceding winter has an effect
on the quantity of sap in trees has been found to be erroneous. The
author has constructed a graphic curve which shows a regular propor-
tion, irrespective of rainfall or weather, all the trees observed show-
ing a decided falling ofi: in quantity at the end of the year, changing
to an increase as the winter passed away, and continuing into the
summer.
The minimum quantities of sap contained in different trees does not
appear to vary in proportion to their specific gravities, the beech with
one-third greater sp. gr. (dry) than the hazel shows the same minimum
contents of sap, and the denser mulberry contains moi-e tha,n the hazel.
The maximum sap-content, however, is different, being higher in the
soft and porous than in the hard and denser kinds ; trees with needle
foliage showed the least variation in both their maxima and minima.
The differences of dry and green weight of the various woods ex-
amined is less during the course of the year than the variations of
sap-contents. The author has constructed graphic curves showing
these variations. J. F.
Relation between the Starch, Phosphoric Acid, and Mineral
Constituents of the Potato. By H. Pellet {Gompt. rend., 90,
13(31 — 13t)3). — The results of the analyses of H. Joulie, which were
undertaken with an entirely different object, having been placed at
the disposal of the author, have been recalculated by him so as to
exhibit, firstly, the relation existing between the starch and mineral
constituents of the potato tuber, and secondly, the unvarying composi-
tion of the whole vegetable when the constituents are referred to 100
kilos, of starch.
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
913
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914 ABSTRACTS OF CHEMICAL PAPERS.
From these tables it will be seen —
1. That there is a constant relation between the total phosphoric
acid derived from the whole plant and the starch.
2. That there is also a relation between the starch and the total
mineral constituents, the silica being deducted.
3. That there are great differences in the proportions of the prin-
cipal alkalis, potash and lime, when calculated to 100 kilos, of
starch, but that there is an equivalent substitution for these alkalis, so
that the quantity of sulphuric acid necessary to saturate all the bases
is sensibly the same.
4. That these relations exist in different sorts of potatoes grown on
different soils and in different years,
5. That the silica and nitrogen vary between considerable limits, as
has already been shown in the case of beetroot.
Another variety of potato, called " chardon," gave likewise I'l
kilos, of phosphoric acid per 100 kilos, of starch, whilst the
"rose hative'' yielded 0'989 kilo, of phosphoric acid; the ash of
the former, without the silica, was 8"22 kilos., and that of the
latter 7 kilos.
The interesting point in connection with these analyses is that the
relation, I'l kilos, of phosphoric acid to 100 kilos, of starch, is
sensibly identical with the relation between the phosphoric acid and
sugar in the sugar-beet. J. W.
Calcium Oxalate in Plants. By B. J. van der Ploeg (Bied.
Cevtr., 1880, 5o6). — In the leaves of many plants the lime increases in
the ash with the age of the leaf from 6 to 9 per cent., but is unaccom-
panied by a proportionate increase of oxalic acid, and appears to have
no connection with the amount of the latter substance present.
J. K. C.
Presence of Alcohols and Hydrocarbonss in Plants. By
GuTZEiT (Bied. Centr., 1880, 377). — The author discovered ethjd and
methyl alcohols in the distillates from the fruits of the Heradeum
gi'ganteum, Pastinata sativa, and Antliriscus Cerefolium, and also ethyl
iDutyrate in the lowest boiling fraction of the heracleum oil. He dis-
misses as unfounded the supposition that these have been formed during
the process, biit believes they exist in a free state in the plants. The
author also proves the existence of a hydrocarbon of the general formula
C„H2«, and has discovered a new body which he calk heraclin. This
substance does not contain nitrogen, is devoid of smell and taste, and
is of the empirical formula C32H22O10 ; melts at 185'') and crystallises
out of an alcoholic solution in star-shaped groups of silky needles,
which are at first white, but become yellow on exposure to light.
Heraclin is indifferent to litmus, insoluble in water, but easily soluble
in chloroform, with difficulty in cold ether, carbon bisulphide, and alco-
hol. Concentrated sulphuric acid yields a deep gold-coloured solution,
from which it separates on the addition of water. Heraclin, as also the
hydrocarbon above mentioned, is found in the fruits of R. giganteum,
H. spondijliuin, and Pastinaca sativa. Further experiments are promised,
to show whether it varies in quantity with the ripeness of the fruit
and also with the quantities of alcohol present. J. F.
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
915
Composition of the Ashes of the Trunk. Leaves, and Fruit
of the Orange and the Mandarin Orange. By L. Kicciardi
(Gnizzttta, 10, 205—279).
Analyses of the Ash of Certain Spice Seeds. By C. Edzardi
(Bied. Cent,:, 1880, 382— 383).
Amount of ash in air-dried "1
substance J
Potash
Soda
Lime
Magnesia
Oxide of iron
Phosphoric anhydride
Sulphuric „
Silicic ,,
Chlorine
Coriander,
per cent.
4-76
35
1
22
12
1
18
6
1
2
•16
•28
■10
•21
•18
•55
•54
•03
•51
Fennel,
per cent.
7 •eg
31
2
19
14
2
16
9
0
3
•96
•38
54
•03
•12
•47
■98
•87
•41
Dill, Carraway,
per cent. per cent.
6-31
5-
31 61
26-
2 11
Q-
26 51
18 •
7 45
8^
196
Z-
17 32
24 •
6 72
5
2-50
4-
4-88
3
31
54
04
27
57
29
39
98
10
The composition and quantities of ash resemble those of the seeds
of the esparset, fodder beet, sugar beet, &c. J. F.
Sweet Potato. By H. Endemann and G. A. Prochazka {Chem.
News, 42, 8). — The sweet potato rot is produced by the parasite
Mucor mncedo. The myceUum of the parasite travels to a certain
distance into the interior of the plant -where it disappears, and the
potato is rapidly destroyed by Bacteria. Aspergillus niger produces a
similar result, but is not so rapid in its action. Aspergilhis glaucus
and PenicilUum, glaucum do not produce sweet potato rot. From the
authors' researches, it appears that cane-sugar is produced, although
Ledour states tliat the sugar formed is glucose. L. T. O'S.
Influence of the Manure on Potato Disease, and the Starch in
the Potato. By M. Marcker {Bied. Cenfr., 1880, 50l—5o4).— Experi-
ments carried on with the view of ascertaining the influence of dif-
ferent kinds of manure on potato disease, showed that in the c-ases
under investigation Chili saltpetre especially favoured the spread of
the disease. This, however, might perhaps be better accounted for
by the different depths and different soils in which the potatoes were
placed, as experiments of a few years back showed that with the same
manure the perceatago of diseased potatoes varied from 4 to 17.
As regards the quantity of starch in potatoes, this was found to be
very little affected by any of the manures employed, and vai^ied more
with the sort of potato under investigation. J. K. C.
Influence of Ethyl Iodide on Germination. By C. Radcteau
(Bied. Cent/-., 1880, 375). — The iutluence of this compound is to pre-
916 ABSTRACTS OF CHEMICAL PAPERS.
vent germination. A quantity of the seeds of the watercress sown on
a sponge in damp sand in a vessel supplied with clean pure water ger-
minated in two days, but ceased growing when ethyl iodide in water
was put into the bottom of the vessel. The behaviour of the sub-
stance with plants is similar to ether, chloroform, and ethyl bromide ;
it acts on the animal organism in the same manner as chloroform.
J. F.
Analyses of Norwegian Hay. By W. Dirks (Bied. Gentr., 1880,
331 — 332). — -A report of the examination of certain samples of forest
hay from different districts in Norway. One of the samples was from
a person who had fed cattle upon it with the simple addition of straw,
and found his herd subject to weakness of the bones. The- composi-
tion of the different samples showed, in comparison with ordinary
meadow hay, an abnormal proportion of silica, with only about one-
third of the avei'age quantity of lime and phosphoric acid generally
found in good fodder. Should cows be fed solely upon this hay, there
would be barely enough phosphoric acid for their daily needs. If they
should be heavy milkers or with calf, the quantity would be insuffi-
cient, and the result would be a weakening of the bones and liability
to fracture. The addition of bone meal or fish guano to the hay is
recommended, or the employment of some other highly concentrated
fodder. J- F.
Digestibility of Oat-straw, Hay, and Pea Holms. By E.
Wolff and others (Bled. Gentr., 1880, 328 — 330). — The consumption
of different kinds of straw by sheep has been little investigated, and
the question presents difficulties, owing to the different quantities
given to the animals. The oat-straw used in the experiment was fully
ripe, rather sti'ong and coarse ; the pea holms contained some leaves
and half-formed pods, and was consequently proportionately more
tasty and nourishing. ; the meadow hay was of an ordinary and average
character. The animals were two wethers of the bastard Wurtemberg
breed, 10 months old. The consumption and the digestibility of the
pea holms was far better than that of the oat-straw, and as a food
fully equal in every respect to good average meadow hay, young
growing sheep could supply the requirements of their growth on the
former, but the meadow hay alone was not sufficient nourishment as a
constant food. It is, however, probable that older animals might have
consumed positively and relatively larger quantities with advantage;
the oat-fetravv also was of a coarse nature. J. F.
Disease in Sheep caused by Lupines. By F. Krocker {Bied.
Gentr., 1880, 617 — 52U). — -A large flock of sheep were fed with lupines,
of which the seed contained 1 per cent, of alkaloids. In less than
three weeks more than half of them died. The lupibe hay was covered
with a kind of fungus, but whether this had anything to do with its
poisonous effects wa.s not. ascertained. J. K. C.
Disease in Sheep caused by Lupine. By J. Kuhn (Bied.
Gentr., 1880, 560 — 562). — As the injurious action of lupine seeds can
be prevented by steaming, the author suggests that experiments be
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
1>17
instituted to find whether this result may be obtained by the over-
heating of lupine hay during its preparation. J. K. C.
Composition of Two Varieties of Turnips. By G. Jaxecek
(Bied. Centr., 1880, 632— 630).— Two kinds of turnips, "golden
tankard" and " mammoth red long," were analysed; the former pro-
duced diarrlia?a when given as fodder, and tlie cause of this was ex-
plained by the chemical constitution of the ash, which was found to
contain more soluble nitrates and sulphates than the former.
J. K. C.
Value of Acorns as Fodder. By H. Czctbata {Bied. Centr.,
1880, 327 — 328). — The author's experiments with Quercus pedunculata
and Q. cerris shows that the kernel of the acorn is a valuable food
when supplemented by starchy material ; nearly half the husks consists
of cellulose. He states also that the kernels of various species of oak
differ considerably in the proportion of their constituents.
The chemical analyses of the two above-named varieties will give a
fair idea of the general composition of the kernels : —
Soluhle Constituents — per cent.
Other or-
Sugar. Dextrin. ProteTn.
Ash.
ganic matter
Quer.
ped. . .
.. 3-31 0-0 1-21
270
11-82
Quer.
cerris . .
.. 671 472 0-62
Insoluhle Constituents — jyer cent
1-99
7-97
Cellulose. Oil. Ash. Protein.
Stareli.
Other organic
matter.
Quer.
ped. .
1-96 6-03 0-10 4-82
64-48
501
Qner.
cerris .
2-51 11-52 0-20 3-52
58-64
1-60
J. F.
Cultivation of Sugar-beets. By A. Ladueeau (Bied. Centr.,
1880, 321 — 3-itj). — This paper is a report of experiments made at the
Agricultural Experimental Station of the Department du Nord in the
year 1878, on the culture of the sugar-beet. The experiments were
divided into four sections : firstly, as to the effect of increased quan-
tities of suitable manures ; secondly, a comparison of the effects of
twenty different manures ; thirdly, the sowing of sprouted or un-
sprouted seeds ; fourthly, on the advantages of ridge culture. The
first experiment was made with a mixture of manures which the
author had previously found to be eflBcacious ; it contained nitrogen in
three forms, "viz., in combination with organic substances, 2-60 per
cent. ; in the form of ammonia, 3-00 per cent. ; as nitric acid, 2-26 per
cent. ; available phosphoric acid, 7 per cent. ; potash, 5 per cent. ;
100 kilos, of this manure cost 30 francs, and the quantities employed
were 350, 700, 1,050, 1,400, 1,750 kilos, per hectare; one plot re-
mained unmanured. The seeds were of two sorts ; one the so-called
Betterave de Pologne, and the other the acclimatised White Silesian.
The field was a clayey soil ; the seed sown on 30th April ; the manure
spread out some time previously. In one portion it was ploughed in,
while in the other it was laid in the furrow.
VOL. XXXYIII. 3 s
918 ABSTRACTS OF CHEMICAL PAPERS.
The results were tabulated, and the following conclusions drawn hy
the author : — The weight of the crop increases proportionally to the
manure employed. The ploughing in of the manure invariably pro-
duced better crops than when left in the fum'ows.
At an examination made 1st September of roots taken from plots
treated with the larger quantities of manure, the juice was thinner
and poorer in sugar ; but after that, the differences equalised them-
selves. The actual qiiantity of sugar yielded increased with the in-
crease of manure. With similar quantities of manure, the red-topped
beet produced heavier roots and more sugar, but the juice of the white
Silesian was richer in sugar. With both kinds of seed the results of
the experiments were very satisfactory, there being an increase in the
crop more than sufficient to compensate for the exjDense incurred.
The manner of distributing the manure has also a considerable effect
on the form of the roots. The plants grown on the plot which had
been ploughed in were regularly formed ; only 35 per cent, with side
roots or any ii'regiilarities, whilst GO per cent, of the roots from the
other plots were irregular, foi'ked, and side-rooted.
The experiments on the effect of different manures were made on
soil of a medium quality; a cold, damp, clay field, poor in lime.
Sowings made 1st June; digging out on 5th October; on 1st Sep-
tember an examination of the roots was fairly made. In respect of
weight, the later drawn roots had the advantage over the earlier ; the
easily decomposed salts were assimilated in the earlier portion of the
time. During the last month of the period, very little change took
place in the quantity of juice or its sugar contents.
There were 25 sorts of manure tried, and the author, as in the
former case, summarises the results of his tables thus : — The addition
of precipitated phosphate to stable manure gave no remarkable results.
Superphosphate was better, bat not more than lime alone, which goes
to prove that the soil was deficient in lime rather than in phosphoric
acid. Wool waste and rags gave their best results when mixed with
caustic solutions and rendered soluble ; the addition of lime increased
the amount of the crop considerably ; phosphoric acid and potassium
superphosphate had a similar effect. The best results were, however,
obtained when chemical manures were ploughed in together with
lime; lime in combination with roasted leather also produced good
results. Slaked lime in powder is more efficacious than unslaked in
lumps. Sodium nitrate, particularly mixed with lime, gave higher
results than ammonium sulphate.
These experiments are considered as proving conclusively the ad-
vantage of employing manure containing nitrogen in the three forms
already referred to, with the addition of available phosphoric acid and
potash.
The employment of seeds sprouted, according to Deromo's method,
w^as the subject of the next experiment. The seeds, after being
steeped, are allowed to heat spontaneously until the germination is
started. So prepared, they appear above ground in four or five days
at latest, and grow very regulai'ly ; the start which they get saves
them from the insects to which they are liable to become a prey when
ten ler. A bottom layer of chemical manure under the seeds about
VEGETABLE PHYSIOLOGY AND AGRICULTURE.
019
^ to 1^ cm. deep helps tlieir progress. Ladureau's experiments with
nine different sorts of manure bears out Derome's conclusions as to
the decided advantage of sowing the sprouted seeds. J. F.
Potato Culture. By P. Wagner and W. Rohn (Bied. Cenfr.,
1880, 3o9 — 341). — The design of the authors was, bj an extensive
series of experiments with different varieties of the root, to discover
the particular kind most suitable to the soil and climate of their
province ; for this purpose they selected 75 different kinds of potato,
and, having carefully cultivated them, give the results in gross weight
and perceutage of starch, of which the following are those obtained
with a few of the most prolific sorts. The thii-d column shows the
relative yield as compared with the average of the whole 75 taken as
100. The morgen equals 0"25 hectare, the centner 50 kilos : —
Comparative
Yield.
Sorts.
Centner per
morgen.
Eed Aldekerte
136 -8
W^hite Bavarian
123-6
Patterson's Eleorancy
140-0
RieHfcer's Iinncrator
241 1
Patteraon's Blue Iri^h
125 1
Irlachin
161 -0
Eichter's Snowroste
159-5
Eavlv Vermont
132 -4
Violet Victoria
165-6
153
138
156
269
140
180
178
148
184
The astonishing results of Richter's imperator strike the eye at
once, and every one who has cultivated it agrees that it is of a very
hardy nature ; it is also a handsome, smooth potato, and the stillk
strong and straight. The authors recommend this variety most
strongly to the attention of farmers ; the other sorts mentioned are
also commended. J. F.
. Damage to Pea and Bean Seeds by Weevil. By E. Wollny
and others (Bied. Centr., 188U, 341 — o-i3). — The authors refer to pre-
vious experiments by G. Marck, alreadj^ noticed (this vol., p. 734),
in which he says that the larvae of this beetle generally destroy both
plumula and radicula ; and they say that such destruction is quite
exceptional, but that beans suffer less than peas. The result of twenty
experiments prove the damaged seeds to be slower in their germina-
tion, and the young plants weaker than those from untouched seeds.
The yield from the sound seeds was also greater than from the un-
sound.
It is recommended to suspend the cultivation of these crops for
several years when the weevils appear to have made their home in any
part of the farm. The means recommended for destruction of the
pest is the use of carbon bisulphide vapour in close vessels, where they
perish in less than ten minutes.
3 s 2
920 ABSTRACTS OF CHEMICAL PAPERS.
Further examinations of the seeds showed that 100 contained 190 —
200 larvfe, some of them having as many as six in the one seed.
J. F.
Cultivation of Beet Seeds. By K. Muller (Bled. Centr., 1880,
381). — This is a report of comparative trials of the quaHties of
certain beet seeds raised by Simon Legrand, a famous French seed
grower. The experiments were made against certain favourite local
sorts ; they resulted entirely in favour of M. Legrand's seeds, but the
details are not of general interest. J. F.
Analysis of Beet Seed. By H. Pellet and M. Liebschdtz
(Compt. rend., 90, 1363 — 1365). — Four sorts of seeds were taken for
examination :—(l.) Red-crowned white sugar-beet. (2.) Improved
white " vilmorin." (3.) Green-crowned beet. (4.) Red variety.
100 seeds weighed 2"083 grams. The seeds were rubbed between two
wire sieves so as to separate the exterior portion called dentelle or
envelope, from the interior portion or nucleus, in order that both
might be analysed separately. 100 grams of seed yielded 14"87 grams
of envelope and 85*13 grams of nucleus (vide Table, p. 921).
The quantity of mineral matter contained in the envelope is nearly
three times as great as that in the nucleus, whilst the latter is richer
in fatty substances and starch.
The authors propose to keep some seeds for three or four years in
order to ascertain whether the oxidation of the fatty matter is the
cause of its non-germination, it having been stated by Ladureau, more
especially in connection with oleaginous seeds, that this is the cause of
the non-g'ermination of old seeds. J. W.
t)^
Investigation of the Composition of Soil from a Graveyard.
By E. Reichakdt (Arch. Phann. [3], 15, 421— 426).— The graveyard
from which the samples were taken had been unused for thirty years,
and they were taken in two series from depths of (1) 2 raetres ;
(2) 1^ metre ; (3) 1 metre ; (4) 0*5 metre below the surface ; (5) the
surface. In none of them could ammonia be detected, and they lost
when ignited quantities varying from 5"1 — 8" 7 per cent, of their
weight ; part of this loss must be due to carbonic anhydride, as the
soil consisted principally of dolomitic chalk. Ignited with soda-lime,
the samples from the surface yielded larger quantities (0'28) of nitro-
gen than the samples from 2 metres (0'14). Also when ignited in
closed tubes it was found that all samples yielded water, ammonia, and
animal oil, but that this was yielded in larger quantities by the surface
than by the lower soil. E. W. P.
Influence of the Soil on the Tannin of Oak-bark. By M.
Fleischer (Bied. Centr., 1880, 489 — 491). — In order to compare the
quantity of tannin in the bark of oak trees grown on sandy soil and
moorland, samples of the bark of ten twelve-year old trees grown on
each, of the two kinds of soil were taken and analysed ; bark of oak
from sandy soil was found to contain 4"3 per cent., and that from
moorland 5" 7 per cent, of tannin. J. K. C.
VEGETABLE PHYSIOLOGY AXD AGRICULTLTIE.
921
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922 ABSTRACTS OF CHEMICAL PAPERS.
Ash of Beet. By H. Pellet (Bied. Centr., 1880, 529— 532).— For
every 100 kilos, of sugar in beet about 1.3 or 14 kilos, of ash, con-
sisting chiefly of alkaline and earthy phosphates, are taken up from
the soil. J. K. C.
Experiments on the Growth of Hyacinths. By A. E. v.
RoGEN (Bied. Centr., 1880, 381).
Sowing Broadcast or in Drills. By Paetow (Bied. Centr., 1880,
374 — 375). — Two plots of ground were well tilled 12 inches deep, and
one of them sown broadcast with rape ; the other plot was sown in
drills, the former very thinly; frost came on in May which did this
plot some slight damage, the stalks in the drills were stronger, and,
consequently, did not suffer so much ; the yield per 100 square ruthen
was —
The portion sown in drills 251 kilos.
Broadcast 207 „
Surplus in favour of drill culture. . 42
J. F.
Manuring Experiments. By P. Wagner and G. Drechsler
(Bied. Centr., 1880, 491 — 499). — Manuring experiments carried out by
difierent individuals have yielded such varying and often conflicting
results, that it has been proposed to allow a working error of + 5 per
cent, in each experiment ; if this, however, were fully carried out, the
variety and conflicting nature of the results would be very largely
increased, instead of diminished. The only method of obtaining
genuine comparative results is to take great care that the conditions
of each experiment should vary as little as possible. Wagner makes
use of small plots of land, from 1 to 2 meters square, separated by
walls of cement, containing soil which has been made as uniform as
possible in quality by careful mixing, and six plots, at some distance
f roiin each other, are selected for each kind of manure to be operated
on. By this means the experimental error may be reduced to 1 per
cent. Drechsler recommends that, as soils are nowhere uniform,
experLTXbents with the various crops to be raised should first be carried
on without any manure, in order to ascertain the capabilities of the
soil of the various plots used, and to make allowance for these in inter-
preting the results of manuring experiments. J. K. C.
Manxtring Experiments with Wheat. By P. Genay (Bied.
■Centr., 1880, 372). — The following experiments on the effect of dif-
ferent manures on wheat are of interest ; but the author expressly
.says that the results are only of decisive value for his own land. The
ground had not been manured for the previous three years.
ANALYTICAL CHEIMISTRY.
023
Amount
applied per
hectare.
Crop. Q-ain over uumauured.
Name of manure.
Grain.
Straw. Grain.
Straw.
Chili saltpetre
Poudrette
200 kilos....
25 hliters. . .
1000 kilos. . .
600 kilos. . .
100 kilos. . .
15 hliters...
33 „ . .
kilos.
2150
2000
1950
1900
1900
1850
1800
IGOO
kilos. 1 kilos.
5040 550
4960 400
4800 350
4720 300
kilos.
1160
1040
Malt combings
Poppy cake
710
880
Chili saltpetre
Poudrette
4560
4720
4960
3880
300
250
200
640
840
Do
1040
TJnmanured
J. F.
Manuring Experiments on Moorland. By Waldxer and
Stacbesand {Bied. Centi:, 1880, 499 — 500). — Bone-meal and potash
salts were employed as the manures. Two plots of moorland, one
uncultivated and the other reclaimed, were separated each into two
parts, over one of which sand was strewn to the depth of 2 cm., and
planted with potatoes. The yield was not satisfactory in any case, but
the plots which had been covered, with sand produced much more
than the uncovered soil, especially where potash salts were employed
as manure. J- K. C.
Manuring Experiments with Beet-sugar. By M. Marcker
(Bied. Gentr., 1880, 505—509). — In some cases Chili saltpetre gave
better results when applied in autumn, and in others when used in
spring; in combination with superphosphate, the best yield was obtained
when the crops were manured in spring, whereas sulphate of ammonia
applied in autumn always produced a better effect than in spring,
although in neither case was the yield equal to that obtained by the
use of Chili saltpetre in the early part of the year. The quality of
the produce was very little influenced by the use of any manure except
phosphate, the latter raising the percentage of sugar in the sap from
11-8 to 12-5, the results being most favourable when the phosphate
was applied in spring. J. K. C.
Analytical Chemistry.
Method for Determining the Temporary Hardness of Water.
By V. WAPaHA {Ber., 13, 1195— 119.^).— lU c.c._ of tlie water_ are
introduced into a cylinder graduated in cubic centimeters ; to this is
924 ABSTRACTS OF CHEMICAL PAPERS.
added a piece of filter paper, which has been saturated with the extract
of Campeachy wood and di-ied. To the water thus coloured, centinormal
hydrochloric acid is added, until it becomes orange, and is then well
shaken ; the greater portion of carbonic acid is evolved, and the solu-
tion becomes red ; acid is added, and the shaking repeated until the
liquid assumes a bright oi-ange yellow. The amount of hydrochloric
acid added may be read off on the cylinder, and may either be calcu~
lated as calcium carbonate, or in degrees of alkalinity, which the
author proposes should be done, since the alkalinity of a water depends
not only on carbonates of calcium and magnesium, but also on alkaline
carbonates and silicates. Every cubic centimeter of centinormal
hydrochloric acid is taken as a degree of alkalinity. In some good
waters, the author finds this to vary from 3 — 6°, whereas in bad waters
it rises to 15°. This method is specially adapted for travellers, as it
requires the use of very little apparatus.
When water is heated under pressure, its alkalinity decreases with
increase of pressure. P. P. B.
Estimation of Retrograde Phosphoric Acid as Ammoniiini
Citrate. By A. Konig (Bied. Centr., 1880, 552 — 553). — By using quan-
tities of the same material, varying from 0"6 to 2 grams, the percentage
of phosphate dissolved in ammonium citrate was found to vary as much
as 7 or 8 per cent., according to the proportions taken ; results, there-
fore, obtained by this method can only be even comparative when the
sam^'quantity of material is used. J. K. C.
Standard Soda Solution. By H. Endemann and G. A. Peochazea
(C7iem. News, 42, 8). — The authors confirm the statement of Gerres-
heim (Annalen, 1879) regarding the basic properties of Millon's base,
obtained by the action of ammonia on mercuric oxide. Soda solution
containing chlorine, sulphuric, silicic, and cai"bonic acid, may be freed
from these impurities by shaking with the base. A chemically pure
standard soda solution may also be prepared by this means.
L. T. O'S.
Detection of Copper. By H. Endemann and G. A. Prochazka
■■{Chem. News, 42, 8). — ^On evaporating a solution of cupric bromide,
its colour changes from blue to reddish-brown, and finally to black,
the anhydrous bromide being formed. By adding concentrated hydro-
bromic acid to a dilute copper solution, a dark brownish-red or a violet
colour is at once produced. O'OOl mgrm. of copper may readily be
detected by this means. L. T. O'S.
A Lecture Experiment. (Ghcm. Neivs, 42, 27). — By means of
Holman's lantern for the oxyhydrogen blowpipe, which may be used
either as a vertical lantern, a projecting microscope, or a megascope,
the cupellation of gold or silver may be effectively illustrated.
The cupel is held by means of a thick copper wire in the focus of
the light from the condensing lenses of the lantern ; its image is
projected on the screen, and it is brought to incandescence by means
ANALYTICAL CHEMISTRY. i)25
of the oxyhydrogen blowpipe. The weighed quantity of alloy, enclosed
in sheet lead, is dropped into the cupel, whereby it is melted, and the
lead as it is oxidised is absorbed by the cupel, forming a dark ring in
the bottom. As the precious metal becomes exposed to view, a sheet
of light passes over the surface, and finally, when all the lead is
absorbed, the purified metal becomes visible as a brilliant globule.
L, T. O'S.
Detection of Cotton-seed Oil in Olive Oil. By B. Nickells
(Cheiii. Xea:<, 42, -7 ). — Olive or Gallipoli oil gives an absorption-
spectrum showing a cutting out of the blue and violet rays, a fine line
in the green, and a distinct deep band in the red. Cotton seed oil gives
the same result in the blue, but the green and red are continuous. By
comparing the spectrum of the suspected oil with that of a standard
thickness of olive oil, any difference in the intensities of the band in
the green and red portions of the spectrum will indicate adulteration
of the oil. L. T. O'S.
Stall Sampling in Milk Analysis. By P. Du Rot and Kiechner
(^Bitd. Ctntr., IbbO, oo- — 3-j-ij. — The authors propose that when a
suspected sample shows on the lactodensimeter an abnormally low
degree, that a proper officer should milk the cows in the stall within
one day at latest from the time of confiscating the original sample, the
analysis of the second being made in exactly the same manner as the
first sample.
This recommendation is based on the consideration that milk expe-
riences very little alteration during 2-t hours, either as regards specific
gravity or composition, in support of which the authors give some com-
prehensive tables. From these tables, it may be seen that old milking
cows yield a higher percentage of total solids and of fat than fresh
milkers. The older milkers gave with two exceptions 13, 14, and even
16 per cent, total solids, and 4 to 5 per cent, butter ; the young milkers
giving seldom over 13 per cent, solids, and the butter ranged between
2-848 and 4'573 per cent. The milk of a herd when mixed together
varies but little from day to day ^ but when a single cow is in question,
there maybe palpable differences between the morning and evening milk-
ings, and the authors caution analysts against too speedy a condemna-
tion on insufficient data. Tollens, commenting on this paper, recom-
mends that analysts should cease to certify that milk is adulterated
\vith such and such a percentage of water, but to fix a standard suffi-
ciently high to condemn all milk below that, and have it sold at a low
price, whilst milk which reached or pas.sed the standard should be
designated good, particularly good, nursery milk, &c., &c. : that in
fact the quality should rule the price in the same way as choice joints
of meat are charged a higher price than those Avhich are coarser.
J. F.
Milk Analysis. By Behrexd and others (Bied. Cevtr.^ 1880, 351
— 352).— The three data in milk analysis which are generally deter-
mined experimentally — fat, total solids, and sp. gr., are interdependent,
and the authors formulate a method of deducing one of them when
926 ABSTRACTS OF CHEMICAL PAPERS.
the other two are known. The fat being determined by the lacto-
butyrometer, and the sp. gr. in the usual manner, the authors, by
means of vohiminous tables which they have compiled, determine the
"solids not fat," and adding thereto the fat obtain the " total solids."
They have submitted their tables to proof by analysing a number of
samples and comparing the results with those shown in the tables, the
difference being very small, not 0*38 per cent. Clansnitzer and Mayer
determine the sp. gr. and obtain the total solids by evaporating 0"5 c.c.
in a platinum capsule at 110'^ in a drying chamber with glass doors
and cover, and obtain the fat by the following formula: —
S — 1
X = t X 0789 -
0-00475'
X being the fat sought, t the total solids found, S = sp. gr. of the
milk : for example —
12-70 X 0-789 - .I'O^SS - 1 ^ g.-^g ^^^ sought.
One of the authors made an attempt to estimate the water in milk
by means of common salt, the principle being the same as that employed
in beer analysis, where the poorer the beer in alcohol, the more salt it
will take up. This succeeded with the milk to a certain extent, but
eventually it became so thick that the sp. gr. could not be taken, and
the attempt was abandoned as unsuccessful. J. F.
Condensed Milk. By E. Wein (Bied. Centr., 1880, 362).— Experi-
ments have shown the author that the fat in condensed milk cannot be
estimated in the usual manner by evaporation with sand and treat-
ment in an ether apparatus, as the large quantity of sugar present
causes the formation of hard lumps which the ether cannot penetrate.
The method he piirsues is to place 5 grams of the milk in a dish
and treat it with continually renewed quantities of ether until it is all
washed through a filter into a flask ; sea-sand is added, and the lumps
which form constantly broken up, and the operation repeated until all
the fat is completely exhausted ; the ether evaporated, the fat redis-
.solved, the ether again evaporated, and the fat weighed. For the nitro-
gen determination, the author adds gypsum, dries on the water-bath, and
proceeds according to the soda-lime process : if the milk be dried in
Holfmeister's dishes, care must be taken not to employ too great heat
as a small loss of nitrogen occurs, 0-2 per cent. Some samples of con-
densed milk made in a certain factory, examined according to this
method, gave results very close to those obtained with normal milk.
J. F.
On Blood Stains. By D. Vitalt (Gazzetfa, 10, 213—225, and
261 — 264). — The author points out that the blue colour produced
when a mixture of turpentine and alcoholic solution of guaiacum is
agitated with blood, is an effect of oxidation, and may readily be pro-
duced by many other substances, especially if copper or iron salts are
present. It is necessary therefore to use this test with great caution :
the suspected fluids should first be agitated with a small quantity of
tincture of guaiacum and allowed to stand some hours, when it will
AN.VLYTICAL CITEMISTRY. 927
remain colourless if no substance is present capable by itself of colour-
ing tlie cruaiacum. If, however, blood is present, a blue colour will be
produced on adding turpentine to the mixture and agitating. If the
stains have dried, they should be dissolved off with a little dilute
solution of potash free from nitrites, and the liquid neutralised with
acetic acid previous to adding the tincture of guaiacum. The author
has observed that the guaiacum, when precipitated from its alcoholic
solution by water in presence of haemoglobin, carries down the whole
of the latter, so that the test becomes one of extreme delicacy, the
reaction being quite distinct with a solution containing one part of
dried blood in one hundred millions, especially if it is gently heated.
The precipitated resin, however, is in so fine a state of division that
it is very difficult to collect it, and it is better to agitate with ether or
amylic alcohol. With the former, the blue colour is produced at once
in the cold without the addition of turpentine; with the latter, heat
must be applied. It was found that the colour reaction Avas obtained
even with dilute blood which had been allowed to stand two months
in an open vessel and had become putrid. C. E. G.
Colouring-matter of Grapes and Bilberries and the Artificial
Colouring of Red Wines. By A. Ande^e (Arch. Pharm. [3], 16,
90 — 112). — The results of the author's researches on wine prepared
by himself from Bordeaux grapes are (I) the colouring-matter does
not vary with the different grapes, and this colouring-matter is re-
moved from the skins during fermentation by the tannin acid, the
colour being blue or red according to the amount of acid present.
(2) The blue colouring-matter is unaltered in its composition by fer-
mentation ; but a wine by keeping becomes paler in colour because of
the precipitation of the colouring-matter caused by the decomposition
of the tannin which holds this substance in solution. (3) The tint
is no criterion whereby to judge of the presence of fermented bilberry
juice, the test being solely dependent on the amount of acid present,
for as wine becomes brown by age, so does bilberry juice. It has been
stated that an unadulterated wine will not produce a coloured foam,
but this is incorrect, as all young wines when shaken do produce a
coloured foam, a foam dependent for its quantity on the amount of
tannin present, but for its permanency on the alcohol, and dis-
appearing more quickly the more highly alcoholic the wine.
Reactions with wine should be carried out in a shallow white
porcelain basin, 5 — 10 grams only of the wine being employed,
and the resulting colours observed by reflected light ; and then if
the reactions are different from what was expected, the difference
is due, not to the colouring-matter, but to the substances which
are present in the wine in varying proportions. In & series of experi-
ments it is shown that ammonia changes the colouring-matter of
wine or bilberries, which is naturally of a rose or lilac tint, to a blue,
which with excess of ammonia becomes colourless ; an intermediate
tint of green may also be observed ; this green colouration may some-
times amount to a precipitate, which seems to be a compound of
ammonia and the colouring substance. In the case of an old wine, the
green precipitation occurs immediately on addition of the ammonia,
928 ABSTRACTS OF CHEMICAL PAPERS.
but rapidly diapges to a brown ; this reaction is exactly the same as
that which occurs when the bilberry colouring-matter is substituted
for the wine. Ammonium, sodium, and potassium hydrates and car-
bonates react in a similar way, no difference between the two colouring
materials being observable.
Upon one test, great reliance has heretofore been placed, because of the
great delicacy which it possesses for the detection of minute traces of
bilberry colouring-matter. When burnt magnesia is worked up into
paste with water, placed in a shallow basin, and then wine poured on
the surface of the magnesia, the magnesia is tinted blue-grey or blue-
green (according as the wine is coloured blue or green by ammonia),
which tint rapidly cha.nges to a grey-brown or brown ; whereas with
bilberry the colour is blue, and with mallow green. The author has
found that all commercial wines are identical as regards the above
reaction, but finds that with wine which he has himself prepared, the
colours produced are identical with that of the bilberry ; hence he
concludes that this test must no longer be considered to be of value.
Several other tests are tried, and the conclusion drawn is, that, cceteris
IJdrihus, there is no distinction between the colouring-matters in either
the grape or the bilberry, but that often a distinction has been appa-
rently discovered which, on careful examination, may be shown to be
due to other substances present in the bilberry extract, as for example,
the precipitate formed by lead acetate in a wine is finely divided,
whereas when bilberry juice is employed the pi-ecipitate is coarse ;
but if the alcoholic extract of the berries is used, the two precipi-
tates are identical in appearance ; the difference is shown to be due to
the pectin in the aqueous extract. The final result then of the in-
vestigation is, that the two colouring-matters are identical. They
have been prepared by treating the lead precipitate with sulphuretted
hydrogen, and then digesting the mass with alcohol and acetic acid ;
as long as acid is present, the solution is red, but when all acid has
been evaporated, the solid is of an indigo-blue. It is completely
insoluble in alcohol and ether, but only when all acid is absent.
E. W. P.
Determination of Wine- extract. By E. A. Geete {Ber., 13,
1171 — 1175). — For this purpose the author proposes to evaporate
10 c.c. of the wine with 10 — 20 e.c. of titrated baryta-solution ; the
residue obtained is heated at 110" until its weight is constant. The
residue consists of the barium salts of the acids present and of a
molecular compound of barium oxide and extract constituents and of
barium carbonate. To ascertain the amount of baryta used to form
salts, 10 c.c. of the wine are titrated with baryta-solution : for every
molecule of Ba(0H)2 used, Ba 4- H., must be deducted from the
weighed residue. The amount of barium oxide is determined by dis-
solving the residue in water and titrating with sulphuric acid. The
sum of the c.c. of baryta corresponding with this, and those needed
to neutralise the acids, when deducted from the number of c.c. taken,
give the number of c.c. of baryta which have been changed into
carbonate. The sum of the weights of barium carbonate, oxide, and
Ba -\- Ho, when deducted from the weight of total residue, gives the
weight of extract required. P. P. B.
TECIIXICAL CHEMISTRY. 929
Malt Examination. By J. S. Lipps (Bied. Centr., 1880, 383). —
This paper describes the behaviour of a certain reagent employed by
the author in malt examinations. He describes it as a basic lead
acetate, ^Yhich is not to be confounded with " Goulard's solution ;"
but there are no details as to its preparation, although some de-
scription of its reactions is afforded. The principal advantage in its
employment appears to be that when added to a cold solution contain-
ing dextrin and starch, the latter is precipitated, and when the solution
is boiled, the former thus affording an easy means for separating and
estimating the two. J. F.
Detection of Oiled Wheat. By C. Himlt (Bied. Centr., 1880,
38y). — The author has devised a simple method of detecting this
sophistication, which appears preferable to others commonly employed.
A sample of the suspected wheat is shaken up in a perfectly clean
flask with some of the bronze powder ordinarily used in printing
illustrated tickets, &c., and it is then emptied on a clean dry filter-
paper, and rubbed with it ; the oiled grain will hold the powder and
present a fine gilt appearance ; if the grain has not been oiled, the
bronze-powder will not adhere. J. F.
Technical Chemistry.
Silver Bromide Gelatin Emulsion. By T. Schnauss (Arch.
Pharm. [3], 16, 113 — 116). — A short history of the introduction of
the emulsion process for photography occupies the first portion of the
article, and is followed by the following receipt, which is used with
success at the observatory in Potsdam: — In an opaque flask TO gram
of ammonium bromide is dissolved in 40 c.c. of distilled water, and
to this is added 46 grams of Nelson's gelatin ; after an hour the flask
is placed in warm water so as to melt the mass, and 2-52 grams of
silver nitrate dissolved in 17 c.c. of distilled water are added, and the
whole well shaken. To attain the highest sensitiveness, the emulsion
is kept at a temperature of 30"" for several days ; afterwards nothing
more is required than to wash the emulsion free from ammonium
bromide and nitrate. When thoroughly wa.shed the emulsion is
melted, poured on to horizontal glass plates, and dried over calcium
chloride or sulphuric acid ; when dried, the plates are piled one on the
other, but kept separate by pieces of tissue-paper ; naturally all these
operations must be conducted in non-actinic light. The " developer "
employed is either "pyro " containing ammonium bromide, and made
alkaline by ammonia, or a concentrated solution of ferrous oxalate
dissolved in potassium oxalate. Fi- '' • P-
Disinfection and Preservation of Animal Matters, such as
Blood, for Agricultural Purposes. By E. Vautelex {Cumjjt.rend.,
90, 1365J. — The process cousibts in the use of the following sub-
930 ABSTRACTS OF CHEMICAL PAPERS.
stances in proper proportions : — (1) Aluminium sulphate. (2) Sul-
phuric acid. (3) Nitric acid. By the addition of sulphuric acid to
aluminium sulphate, an acid sulphate is formed ; this salt, less soluble
than the neutral one, when added to blood causes its rapid coagulation.
Nitric acid may be used with similar effect. No details are given.
J. W.
Purification of Water from Sugar Works. By W. Knauer and
others (Bied. Centr., 1880, 537 — 539). — After filtration through a
sieve, Knauer recommends heating the water by means of steam to
80°, treating with milk of lime, and then with manganese chloride ;
after the deposits have settled, the water is cooled and allowed to run
oiT through a sieve. This method was investigated by a commission,
but was not considered satisfactory. Tolke limits the comsumption
of water, and then drains it off through soil. J. K. C.
Malleable Nickel. By J. Garnier {Compt. rend., 90, 331—333).
— By adding to pure nickel, which after fusion is brittle, some sub-
stance which will readily combine with the oxygen absorbed by the
molten metal whilst cooling, and which will diffuse through the
whole mass, it may be made perfectly malleable. Phosphorus is best
adapted for this purpose, 0*3 per cent, being sufficient to render the
nickel soft and malleable, a greater quantity of phosphorus makes the
metal harder and less malleable. Tlie phosphorus is added in the
form of phosphide of nickel, containing about 6 per cent, of phos-
phorus. It is prepared by fusing a mixture of calcium phosphate,
silica, charcoal, and nickel. Nickel containing 0"25 per cent, of phos-
phorus may easily be rolled into leaves 0"5 mm. thick. L. T. O'S.
Mercuric Oxide in Grey Powder. By D. Lindo (Chem. News,
42, 67). — Grey powder, after keeping for some time, is found to con-
tain large quantities of mercuric oxide, and therefore becomes unsuit-
able for medicinal purposes. L. T. O'S.
Strong's Water Gas System. By G. S. Dwight (Chem. News,
42, 27 — 29). — This system consists in raising coke to incandescence
and causing the products of combustion to superheat a given quantity
of steam, which is brought into contact with coal-dust, and then led
.back to the coke. In this way it is possible to utilise all the heat
evolved in the combustion of coal, to within 10 or 12 per cent, of
the theoretical value.
Experimental and numerical details are given in the paper.
L. T. O'S.
Vaseline. By H. Werner (Arch. Pharm. [3], 16, 45). — Three
samples of vaseline of German, Austrian, and American origin were
examined, and appeared to behave differently when mixed with balsam
of Peru, although of the same general appearance. The German and
Viennese samples mixed completely to half their weight in the balsam,
whereas the American sample mixed completely with its own weight
of the balsam, and did not sepai*ate even on standing for a considerable
time. E. W. P.
TECHNICAL CHEMISTRY. 931
Purification of Spirit. By J. E. Berliex (Bied. Centr., 1880,
543 — S-i-i). — A small quantity of solution of silver nitrate removes all
unpleasant aroma from the crudest spirit of commerce. J. K. C.
Fermentation of Molasses. By M. Fiedler (Bied. Centr., 1880,
645 — 545). — Molasses which had been kept a long while and was in
a condition highly unfavourable to fermentation, was subjected to
two different methods of treatment ; in one case the molasses was
diluted and boiled with a small quantity of sulphuric acid, again
diluted and allowed to ferment, the yield of alcohol being 84 per cent,
of the theoretical amount : in the second experiment the molasses was
carefully neutralised with chalk, diluted, and then allowed to ferment,
90 per cent, of the theoretical yield being obtained. J. K. C.
Fermentation of Beet-root Sap obtained by Diffusion. By
A. MiLLor and Maqui:nne (Bied. Centr., l6bU, 5tju;.— An inflammable
gas is given off by this sap after fermenting for some time; this the
authors have explained by showing that butyric fermentation sets in,
causing hydrogen to be evolved. J. K. C.
Aeration of Must. By E. Rotondi (Bied. Centr., 1880, 545—546).
— By passing air through must, the ferment is more thoroughly mixed
with the liquid, and the decomposition of sugar and albumin Ijecomes
more rapid. Wines which have been prepared in this manner a^-e
more quickly, and are less liable to decomposition than other wines.
J. K. C.
Direct Decomposition of Sugar-lime. By M. Pauly (Bied.
Centr., 1880, 559 — 5(30). — The author decomposes sugar-lime by means
of carbonic anhydride, and obtains 96 per cent, of the calculated
• amount of sugar. J. K. C.
New Clarifier for Beer. By Y. Griesmeyer (Bied. Centr., 1880,
386). — The liaja clarata has been recommended as a clarifier in
breweries by Griesmeyer, and a great reduction in its price has brought
it into considerable prominence recently. A brewer named Kubiek,
in Ossegg, has made a series of experiments on its use, which he has
])ublished in several technical journals. He finds it a specific against
muddiness in the yeast, that it causes a separation of the yeast at the
top instead of the bottom of the cask, and that it is forced from the
bung, requiring some little attention in this regard. J. F.
Sap-quotient of Beet. By F. Sachs (Bied. Centr., 1880, 534—
536). — The sap-quotient is defined as the number obtained by dividing
the percentage of sugar in the root by the percentage in the liquid
pressed out at the first pressing. In the author's experiment, the number
was 0-94. J. K. C.
Preparation of Sugar from Sap of Beetroot. By K. Lowig
(Bied. Centr., 1880,533 — 534). — The colouring-matter is separated by
the addition of gelatinous alumina and gently warming : the sugar
is obtained from the filtrate by crystallisation. J. K. C.
932 ABSTRACTS OF CHEMICAL PAPERS.
Sorghum Saccharatum. By A. v. Wachtel (Bied. Centr., 1880,
344 — 345). — This plant is extensively cnltivated in certain parts of
the United States for the manufacture of cane-sugar. It grows to a
height of 12 — 14 feet in those regions, yields about 19,500 kilos, per
Prussian morgen (0'2o ha.), and contains 10 per cent, of sugar. In
the year 1850, an attempt was made to obtain spirit from it at Konig-
saal, and an excellent rum was produced. In 1879 an attempt at
cultivation was made at Czako^yitz, in Bohemia, with American seed,
and the plants were submitted to the author. They only attained a
height of 5^ to 6 feet. The yield of cane-sugar was 15"3 per cent.,
and inverted sugar 0'85 per cent. The quantity of juice was small,
and the waste about three times as great as from sugar-beets ; the sap,
however, appeared tolerably clear ; the watery extract at 50° when
concentrated produces a considerable crop of crystals, which became
tolerably bright when washed with water. J. F.
Sugar in Raisins. By Haas {Bied. Centr., 1880, 386). — This paper
gives an estimation of the contents in sugar of different sorts of
raisins, varying from 14"5 to 61 "75 per cent., and the observer
cautions purchasers against buying on mere appearance when such
material differences exist. J. F.
Production of Sugar from Starch. By Rohr {Bied. Centr.,
1880, 547— 548).— Temperatures varying from 40° to 52° R. have
been recommended as the best for the production of sugar from
potato-mash, and the time allowed from twenty minutes to two hours.
The author finds that at any temperature between the above limits
the conversion of starch into sugar is complete, and proposes as the
most convenient digestion at a temperature of 44 — 46° R. for 1;^ to 1^
hours. J. K. C.
Preservation of Butter. By H. Bat {Bied. Centr., 1880, 388).—
The experiments here recorded were made by Manetti, and show that
butter thoroughly washed until the wash- water runs away perfectly
clear, keeps sweet nearly twice as long as that which has been washed
a shorter time and then packed. The addition of one-thousandth part of
common salt preserves butter ten days, two-thousandths twenty days,
and three-thousandths thirty days. The smaller quantity leaves a
scarcely perceptible taste. The addition of one- to two-thousandths
of borax preserves the butter 15 to 20 days. The flavour, however, is
unpleasant. J. F.
Whole Milk Butter Compared with Cream Butter. By
M. ScHRODT and P. \)\] Koi {Bled. Cent)-., 1880, 363). — The author
took equal quantities of the same milk, allowed them to cream ; one
of them he skimmed after 36 hours and churned the cream ; the
other portion he allowed to stand for 34 hours, when it became
slightly acid. He churned the whole of it without skimming. The
cream churned in 25 — 55 minutes ; the whole milk took 35 — 65
minutes. The butter was weighed after the first kneadingr, unsalted,
and the quantity of milk required to make a kilogram of butter calcu-
TECHNICAL CHEMISTRY. 933
lated. The following are the averages of ten experiments in each
case: whole milk, 2876; cream, 30-35 of milk. The larger yield of
the former is attributed to the presence of greater quantities of casein,
milk-sugar, and water than in the cream butter, which naturally
deteriorates its keeping qualities. J. F.
Experiments with Laval's Separator. By IST. Engstrom {Bled.
Cefntr., 1880, 360 — 361). — In these experiments, the author was able
to obtain 20 per cent, of cream, and compared with the Swarfs
method tried on milk of the same cows, the average surplus was
.5-15 per cent., and even much more was obtained in certain localities.
A prejudice exists against the butter made by this method as not being
good for keeping, but the handling of the butter appears to have a
great deal to do with it. When it comes from the separator the
author puts the cream into ice- water, where it is left for 6 — -10 hours;
it has then a clean fresh taste. It is warmed to 13° C, acidified, and in
twelve hours churned at a temperature of 11°. By this method a
butter is obtained which the most experienced butter dealers have
classed in the first rank.
The refuse which collects in the outer division of the apparatus con-
.sists principally of organic matter free from fat. On being micro-
scopically examined, it was found to contain, besides nucleiu, portions
of epidermic scales, a few fat globules, threads, &c. J. F.
A New Skimming Process. By A. Mayer and F. Clausxitzer
(Bied. Centr., 1880, 358 — 359). — The authors treat the milk with a
small quantity of soda-solution, and find that it preserves the milk
from decomposition from three to five days, and further, that it
assists the sepai-ation of the cream, and leaves less fat in the skim-
milk than the ordinary treatment. 1'3 to 1'5 grams of Na20 to the
kilogram of milk gives the best results ; a larger quantity makes the
casein so thick that creaming ceases. The quantity of cream taken
off by this method being larger, the percentage of fat in it is naturally
smaller than when a lesser quantity is removed ; but the authors rely
on the small quantity of fat left in the skim-milk as a proof of the
completeness of the process.
An experiment was then made as to the quantity and quality of
the cream so separated. Two of Swarts's apparatus were prepared ; in
one was placed 15 litres of milk without soda, in the other the same
quantity with 0T4 per cent, of iSra20. After four days they were both
skimmed, with the result that the portion treated with soda gave
669 grams of butter, and that without the soda 627 grams. The
original percentage of fat in the milk was 2"32 ; the percentage ob-
tained by the soda process was 1'83, and by the ordinary means 1"67.
The butter was washed and worked. No disagreeable taste was per-
ceived. It was kept in a cellar for several weeks, and was perfectly
fresh at the end of that time. The skim-milk is, however, unfit for
human food, owing to the strong taste of soda ; after neutralisation,
however, it can be used for pig-feeding. The reason of the process
the authors are unable to give, but they think that the coating of
VOL. xxxvrii. 3 t
034 ABSTRACTS OF CHEMICAL PAPERS.
serum is attacked hj tlie alkali, and the fat globules are liberated
more freely. J- F.
Experiments with Skimming by the Schwartz and Holstein
Systems. By M. Schrodt and C. Du Roi (Bied. Centr., 1880, 356—
357). — Complaints are common of so-called "lazy milk," in which
the cream does not separate well, and although good, does not yield
its butter freely. The time of these complaints is generally about the
period when the cows are put out first on the meadows, and it occurred
to the authors that the sudden change from the dry hard feeding of
the stalls to the tender soft grass had something to do with the cause
of the complaint. They therefore caused a herd to be fed in the stalls
with green food previous to being out at grass, commencing with small
quantities of green fodder, and increasing it until they had nothing
else. The experiment lasted 14 days, and at its end the cows were
put out to grass, but there were no complaints of lazy milk.
The milk was divided into two portions, and separated by the
Sch warts and Holstein methods. By the foi'mer it required 30' 72
kilos, of milk to produce 1 kilo, of butter; by the Holstein method it
only required 27'95 kilos, to yield the same quantity.
The meadowing of the cows had a great effect on the yield of
butter, and while at grass the two systems gave almost identical
rasults. J- F-
Composition of Curds. By M. Rubnee (Zeits. f. Biologie, 15,
496).
Wafer in 100 parts 3973
Solids , 60-27
Casein „ 24-84
Fats „ 7-33
5»
Ash „ 4-02
Milk-sugar, &c., in 100 parts .... 3-54
The quantity of water varies 2 or 3 per cent, in different samples.
W. N.
Examination of Danish Export Cheese. By V. Storch (Bied.
Centr. ,1880, 366 — 370) . — This paper is an exhaustive report of numerous
experiments on the composition of Danish cheese, and is accompanied
by various tables. The first question examined was the effect of
leaving the milk a longer or shorter time before skimming or curding,
and he found that practically the amount of cheese obtained varied
very little, except in those intended to contain the fat of the milk.
In such cases prompt treatment is the most desirable, but in cheese
which is made from skimmed milk the difference arising from delay
is extremely small. The water in skim-milk cheese varies consider-
ably, from 58-65 to 69 31 per cent. The author believes that it exists
in combination with the casein as a hydrate.
The temperature at which the operations should be conducted is
an important point. At a low temperature a fatter cheese is ob-
tained than at a higher, and a low temperature yields a cheese with
TECHNICAL CHEMISTRY. 985
a larfjcr proportion of water. The cutting and stirrino;' of the curd
should also be performed as soon as possible after the addition of the
rennet, and when the milk begins to curd. The loss of weight
which cheese experiences when stored is loss of water. The decom-
position into ammonium compounds takes place only on the surface.
The insoluble combinations are removed bj the brushing, scraping,
&c., to which the goods are often subjected.
Microscopically examined, cheese consists of a mass of casein con-
fining innumerable fat globules, giving to it the appearance of a fine
network, fat or creamy cheeses owing their softness in the mouth to
the thinness of the cells which confine the globules. A good method
of observing this structure is to stain a piece with methylaniline, the
casein taking the colour, whilst the fat globules do not. J. F.
Cleansing Lupines. By 0. Kellner (Bied. Centr., 1880, 515 —
617). — After steeping for 36 hours in cold water, the seeds are sub-
jected to the action of steam for one hour, and then transferred to
vats and washed with cold water, the latter being changed four times
in 40 hours. By this means the alkaloids are removed with very little
loss of protein, the greatest loss occurring in the non-albuminous
parts of the seed. J. K. C.
Weighting of Silk. By E. Koxigs (Blngl. pohjt. J., 237, 73—
76). — The author examined a sample of black French silk from a
consignment which spontaneously ignited on board a Bremen steamer.
Treating with cold soda-lye and hot oxalic acid does not give con-
cordant results as to the amount of weighting ; also, the amount of
ash bears no definite relation to the adulteration. Undyed raw silk
gave I'l per cent, ash, scoured silk 0'77, and weighted silk 14. The
relation borne by ash to the various substances employed was deter-
mined, and by calculation the amount of admixture was ascertained.
Analyses (a) of the warp, and (h) of the weft, gave as follows : —
(«) (b)
Moisture 10-84 10-89
Prussian blue 7-40 3-15
Gum 3-00 —
Fat trace 2-48
Catechu-tannate of tin 3-33 —
Tin ferrocyanide — 0*70
Ash 10-04 12-74
After taking from the ash, a, the tin oxide found, 1*8 per cent., iron
oxide 4-9, corresponding to the Prussian blue, and 04 of ash due to
the silk itself, there remains 2-94 per cent, iron oxide, corresponding
to 21-17 percent, catechu-tannate of iron, and only 54-26 percent,
of raw silk. This corresponds to 6014 per cent, of scoured silk, after
adding 5-88 of moisture ; and 100 lbs. of raw silk give 152-32 of warp.
Similarly b gives 9-35 per cent, of iron oxide in excess, corresponding
to 47-68 per cent, of iron tannate, which gives 35-10 per cent, of raw
silk. Adding 3-82 of moisture, this equals 38-92 of normal silk, which
o
936 ABSTRACTS OP CHEMICAL PAPERS.
with 64-9 — 3-82 equals 61-08, or 157 per cent, of loading. The
weighting of the weft is usually attained by the use of iron pyrolig-
nite and catechu or chestnut extract, then potassium ferrocyanide and
a little tin salt, and finally a tolerable amount of fat. Experiments
showed that tannin compounds with some iron salts give bodies which
easily take fire like tinder. On the contraiy, tannin compounds pro-
duced with iron acetate are difficult to ignite, so that if the iron pyro-
lignite could be replaced by acetate the danger of spontaneous
combustion would be removed. J. T.
"Mogdad" Coffee. By J. Moeller (Dingl. pohjt. J., 237, 61—
68). — The author describes microscopically a sample of so-called
"Mogdad" coffee, seeds of Cassia occldentalis, L. It can be detected
by means of the microscope when added to coffee. J. J. Pohl gives
the following analysis of the seeds : —
Cellulose 21-21
Fatty oil 2-55
Mucilage 36-60
Tannic acid (green with Fe) 5-23
Inorganic salts 4-.33
Nitrogenous organic matter (and loss). . . . 15-13
Non-nitrogenous organic matter 3-86
Caffeine 0*00
Water 11-09
100-00
J. T.
Wild and Cultivated Raspberries. By E. Reichaedt (Arch-
Pharm. [3], 15, 324 — 325). — -A comparison of the fruit in a fresh
condition showed that from the cultivated berries 90-4 per cent, of
juice could be expressed, and only 81-64 from the wild ones.
Amongst other results given in the paper, it is stated that the amount
of acid was about equal in both, that the cultivated contained 4-45
per cent, of sugar and tlie wild only 2-80, and whilst the wild con-
tained 2-80 per cent, of carbohydrates convertible by acids into sugar,
the percentage in the cultivated was only 0-45. Cellulose was present
in the wild berries to the extent of 4-15, and in the cultivated it
amounted only to 2-26.
The comparison in the above particulars is evidently favourable to
the cultivated fruit, aiid in respect of aromatic principles the advan-
taji'e seems to lie in the same direction. F. C.
~o--
INDEX OF AUTHORS' NAMES.
ABSTRACTS. 1880.
A.
Abney, "W. W., acceleration of oxirla-
tion causerl by the less refrangible end
of the spectrum, 429.
• photograph of the ultra-red portion
of the solar spectrum, 429.
production of photographs exhibit-
ing natural colours, 72.
Adam. SeeGrrimaux.
Adamec, J., and E. Klose, new me-
thod of estimating the air-space in
seeds and fruits, 189.
Adamkiewicz, A., interchange of
material in the animal organism, 56o.
Adler, A., products from brown-coal
tar, and some derivatives of chrvsene,
263.
Adlerskron. See G-raebe.
A dor, E., isophthalophenone, 470.
A dor, E., and F. Meier, xyhc acid, its
preparation and derivative's, 252.
Alexandrowicz, W., actual state of
the determination of zinc, 748.
Allary, E., titration of iodine by
stable standard solutions. 28.5.
Allen, A. H., analytical examination of
tinctures. 194.
■ examination of coffee, 353.
presence of nitrogen in iron and
steel, 749.
Allen. See also Cohne.
Almen, A., chalybeate springs of Carl-
stad, 20.
Amato, D., and A. Capparelli, che-
mistry of the yew, 899.
Amato, D., and P. Figuera, gasome-
tric methods, 345.
Amnion, Gr., absorptive power of soil
constituents for gases, 134.
Andrcae, H., nitro-orth- and nitropar-
azophenetols, 466.
Andreasch, K., carbamidacetosul-
phonic acid, 877.
characteristic reaction of thiogly-
collic acid, 236.
VOL. xxxvni.
Andreasch, R., decomposition of thio-
hydantoTn by barium hydrate, 236.
synthesis of thiohydantoin, 877.
Andreasch. See also M a 1 y .
Andree, A., colouring matter of grapes
and bilberries, and the artificial
colouring of red wines, 927.
Andreoni, G., citric acid, 877.
Andrews, L. W., ethylene iodo-
picratc, 619.
V. Anrep. SeeWeyl.
Anschiitz, R., tetrabromethanes, 98.
Anschiitz, R., and A. Pictet, prepa-
ration of tlie ethereal salts of tartaric
and racemic acids, 876.
Anschiit z, R., and I. v. Siemenski,
phcnanthrene derivatives, 891.
Ansdell, Gr., physical constants of
liquid iiydrochloric acid, 696.
Arm 8 by, H. P., estimation of albumin,
829.
Armstrong, H. E., action of iodine on
oil of turpentine, 125.
Aronstein, L.,and J. M. A. K ramps,
action of ethyl iodide on ethyl iodace-
tate, 541.
Atterberg, A., probable occurrence of
furfurane (tetraphenol) and a homo-
logous compound in the products of
the dry distillation of pine wood, 663.
Austin, A., diamylbenzene, 107.
B.
Babo, L. T., oven for heating sealed
tubes, 846.
Baeyer, A., action of potassium pyro-
sulphate on indigo white, 46.
compounds of phthalic acid with
phenols, 650.
Baeyer, A., and O. R. Jackson, syn-
thesis of the homologues of hydrocar-
bostyril and quinoline, 406.
synthesis of methylketole,
an isomende of skatole, 395.
3 u
038
INDEX OP AUTHORS.
Balbiano, L., amides and anilides of
l3-hjdroxy butyric acid, 461.
■ some derivatives of /i-chlorobutyric
acid, 54.1.
Balbiano, L., and A. Testa, dibutyl-
lactic acid and a polymeride o£ meth-
acrjli(; acid, 871.
Balentine, W., diazo-eornpomid of
liydrazobenzeuesulphonic acid, 809.
Balling, C, estimation of silver in
galena, 748.
Ballo, M., constitution of cainphor
compounds, 50.
Balsohn, M., synthesis of ethylben-
zene from ether and benzene, 463.
Balsohn. • See also Friedel.
Bandrovrski, E., acetylenedicarboxy-
lic acid, 160.
Baranetzky, J., starch-altering fer-
ments in plants, 331.
Bar bier, P., action of acetic anhy-
dride on phenol aldehydes, 318.
action of acetic anhydride on some
aromatic aldehydes, 468.
Barbieri. SeeSchulze.
Barisch, F., monobroraocinnamic
acids and phenylfumaric acid, 42.
Barnes, J. B., taraxacum root, 720.
Barral, J. A., nitrates in sugar-beets,
495.
Barth, M., compound of alumina with
carbonic anhydride and ammonia,
791.
Bartlett, H. C, presence of arsenic in
the atmosphere, 585.
Baswitz, M., diastase, 132.
Battandier, estimation of glucose,
512.
Baudrimo-nt, A., I'esearches on beet-
root, 495.
Baudrimont, E., action of potassium
permanganate on potassium cyanide,
307.
Bauer, E., on frothy fermentation,
518.
Bauer, M., crystallisation of cyanite,
614.
Baiimann, 'E., aromatic products of
the animal body, 648.
formation of hydroparacoumaric
acid from tyrosine, 254.
Baumann, E., and F. Tiemann, po-
tassium liydrindigotin sulphate aiid
potassium indoxylsulphate, 475.
Baumgartner, specific heat of water,
601.
Baur. See Meyer.
Bay, H., preservation of butter, 932.
Bechamp, A., non-identity of the
soluble albuminoids of e-rystallin
with those of wliiteof egg and serum,
815.
Bechamp, J., presence of alcohol in
animal tissues during life and after
death, 174.
Bee hi, Gr. v., solubilities of some con-
stituents of coal-tar, 258.
von der Becke, saponification of fats,
762.
Becker. See Michaelis.
Beetz, W., galvanic polarisation, 837.
Behrend, P., action of sulphonic mo-
nochloride on alcohols, 310.
Behrend, P., and A. Morgen,
changes effect'ed by fermewlation in
the nitrogenous constituents of sweet
mash, 357.
growth of beets, 502.
— influence jof fermentation on
the nitrogenous constituents of potato
mash, 819.
Behrend, P., and- others, estimation of
starch in potatoes, 513.
- — — milk analysis, 925.
Beilstein, F., dinitroparatoluidine,
635.
■Beilstein, F., and L. Jawcin, di-
rect separation of manganese from
iron, 61.
new method of separating
manganese and iron, 289.
valuation of zinc and zinc
dust, 826.
Beilstein, F., and A. .Kurbatow,
dinitrobenzoio acid, 471.
dinitronaphthalene, 477.
Bell, C. A., action of zinc on succini-
mide, 630.
Bell, J. C, iodic acid as a test for mor-
phine, 68.
Belli. SeeWallach.
Belohoubek, A., preparation of pro-
pylene glycol from glycerol, 232.
Bemmelen, J. M. v., chemical compo-
sition of certain hydrated oxides,
849.
condition of -alkaline phosphates in
aqueous solutions, 2.
Benedikt, R., bromoxyl derivatives of
benzene. 246.
Beran. See Wurster.
Berg. See Claesson.
Berger, F.^ aromatic guanidine com-
pounds, 802.
oi'tliotoluidine guanidines and their
cyanogen derivatives, 244.
Bergmann. See Fresenius.
Berkhardt, N,, alkalo'id in AeLhusa
cy napium, 899.
Berlien, J, E., purification of spirit,
931.
Bernthsen, A., action of phosphorus
pentachloride and of zinc-dust on suc-
cinimido, 713.
INDEX OF AUTHORS.
939
Bernthsen, A., history of plienylaeet-
amide, 650.
Bernthsen, A., and F. Szvmanski,
formation of diamines, 639.
Ber.sch, W., enamelled east-iron ves-
sels, 8.33.
Berth elot, action of hvdroj^en per-
oxide on silver oxide and metallie sil-
ver, 441.
elieuiical constitution of amalgams
of the alkali metals, 1 .
chemical stability of matter in
sonorous vibration, 437.
compounds of hydrogen peroxide,
602.
copper hydride, 299.
copper hydride : a reply to Wurtz,
299.
decomposition of hydrogen selenide
by mercury, 150.
decomposition of potassium per-
manganate by hydrogen peroxide, 444.
— freezing mixtures formed by an
acid and a hydrated salt, 687.
heat of combustion of the prin-
cipal gaseous hydrocarbons, 786.
— heat of formation of ammonia,
207.
heat of formation of chloral hy-
drate, 293.
heat of formation of gaseous chlo-
ral hydrate, 434.
— heat of formation of hydrocyanic
acid and cyanides, 839.
heat of formation of the oxides of
nitrogen, 522.
heat of vaporisation of sulphuric
anhydride, 693.
oxidation of gold by galvanic ac-
tion, 158.
persulphuric acid, 607.
relation between the heat de-
veloped on solution and that deve-
loped on dilution with complex sol-
vents, 208.
remarks on Cochin's note relating
to alcoholic fermentation, 276.
remarks on the saccliaroses, 233.
silver sesquioxide, 441.
some relations between the chemi-
cal mass of the elements and the heat
of foi-mation of their compounds,
•688.
thermo-chemistry of cuprous chlor-
ide, 208.
thermo-chemistry of ethylamine
and of t'.imethylamine, 787.
— — vapour-density of iodine, &c., 846.
Berthold. See Reinke.
Bertoni, Gr., conversion of hydroxyl-
amine into nitrous and nitric acids,
298.
Bertoni, G., preparation of hydroxy 1-
amine, 297.
Bertrand, A., action of titanium te-
traehlaride, stannic chloride, and
antimony penfacldoride on acetic acid
and acetic anhydride, 460.
compound of titanium tetrachlo-
ride with acetic chloride, 624.
Bertrand, M., determination of active
oxygen in barium or hydrogen per-
oxide, 7 14.
Bielefeldt, M., derivatives of isodu-
rene, 37.
Bilek, F., manuring experiments, 345.
Bimmermann, E. II., changes which
starch undergoes in the animal organ-
ism, 677.
Bindschedler, R., manufacture of
resorcinol and colouring-matters de-
rived from it, 426.
safranine, 391.
Binz, C, and H. Schultz, chemical
cause of the toxicological action of
arsenic, 174.
Birnbaum, K., a new salt of an iridi-
amnionium, 13.
peculiar changes of gas-pipes, 198.
Birnbaum, K., and J. Gaier, action
of iodine on the silver salts of bibasic
acids, 801.
Birnbaum, K., and M. Mahu, beha-
viour of calcium oxide to carbouio
anliydride, 5.
Birnbaum, K., and C. Wittich, ac-
tion of sulphurous anhydride on the
alkaline earths, 606.
Bischof, K., magnesium and calcium
compovmds as ret'rai-tory and dephos-
phorising materials, 831.
Bischof. See also Conrad, Lieber-
mann, and VVeyl.
Bischoff, H., colouring-matter of the
C'aryophyllac, a>, 413.
Bittmann, C, estimation of sugar in
beetjuicCj 144.
Bizio, G., distribution of copper in the
animal kingdom, 565.
Bizzarri. SeeCampani.
Blair, T., separation of phosphorus
from iron, 74.
Blanchet, C, Thapsia garganiea,
718.
Blankenhorn, A., raising vines from
seed, 418.
Blankenhorn, A., and others, prepa-
ration of wine, 200.
Bleunard, A., constitution of stag's
horn, 271.
products of the decomposition of
prote'ids, 482.
Blom strand, C. "W., titanites from
Smiiland, 15.
3 M 2
940
INDEX OF AUTHORS.
Elunt, T. P., effect of light on chemi-
cal compounds, 521.
Ely t hi A. W., determination of specific
gravity, 572.
Boasson. See Vignan.
Bodenbender, N., manuring of beet-
root, 137.
Bodenbender, H., and Ihlee, com-
position of ash of two kinds of beet
seed, 496.
Bode wig, C, Fittica's nitrobenzoic
acids, 251.
Bocker. See Oser.
Booking, E., two new syntheses of
methyl-ethyl-hydroxyacetic acid, 872.
Bohm, J., functions of vegetable ducts,
911.
Boeke, T. D., detection and estimation
of arsenic, 752.
Bottinger, C, decomposition of mes-
oxalic acid by sulphuretted hydrogen,
237.
diamidotri'phenylmethane, 813.
glyoxylic acid, 621.
new method of preparing thiodi-
lactic acid, 238.
phlobaphene, 650.
Boisbaudran, L. de, researches on
erbia, 6.
le Bon. See Cyon.
Borodin, J., distribution and functions
of asparagine in the vegetable king-
dom, 58.
Bouchardat, G., action of haloid acids
on isoprene. Formation of caout-
chouc, 323.
transformation of amylene and
valerylene into cymene and hydrocar-
bons of the benzene series, 710.
Bouchut, E., digestive ferment of the
juice of the fig tree, 728.
enumeration of fat globules in
milk as a test, 191.
B our cart, R., action of ammonia on
anthraquinonesulphonic acids, 263.
Bourgeois. SeeVerneuil.
Bourgoin, E., electrolysis of malonic
acid, 462.
• preparation of malonic acid, 801.
Boiissingault, dissociation of barium
dioxide, 610.
Boutroux, L., fermentation of glucose,
863.
B o V e t, V. , antiseptic action of pyrogallol,
73.
Bowie, H. C, the prote'id required by
the average workman, 905.
Boymond, sodium h_y|:)ophosplute, 367.
Braga, J. F., analyses of some hair
dyes, 772.
Brauner, B., action of silver cyanate
on isobuLyl iodide, 228.
Brauner, B., constitutional changes in
the molecule of the isobutyl group,
229.
Bredt, J., and R. Fittig, pvroterebic
acid, 315.
Breiholz, H., amount of oil in grass
seeds, and its relation to their germina-
tion, 342.
Bremer, G. J. W., inactive malic acid,
462.
Brenken, O., examination of mineral
oils, 589.
Brenning, manuring of oats, 508.
Br eon, R., separation of minerals of
greater density than quartz by means
of fused mixtures of lead and ^nc
chlorides, 511.
Breslauer, M., epichlorhydrin deriva-
tives, 29.
Bretet, H., extracts of narcotic plants,
425.
Breuer, A., and T. Zincke, coni-
pounds obtained from hydro- and iso-
hydro-benzoTn by the action of dilute
sulphuric acid, 116.
— derivatives of the quinone
from the hydrocarbon Cigll,^i, 665.
oxidation of benzoic and
acetic carbinols, 645.
Brieger, L., skatole, 258.
Briem, H., manuring of beet, 185.
Briem. See also Feltz.
Broockmann, K., and K. PolsLorf f,
methylmorphine hydroxide, 408.
Schiitzenberger's oxymor-
phine, 408.
Brown, H. T., and J. Heron, hydro-
lytic ferments of the pancreas and
small intestine, 903.
Briigelmann, characteristics of the
alkaline earths, and of zinc oxide, 701.
Briihl, J. W., cliemical constitution of
organic compounds in relation to th(!ir
refractive power and density. Part II,
295, 781.
relations between the physical pro-
perties of bodies and their chemical
constitution, 293, 685.
Brunnemann, C, an azoxybenzene-
sulphonic acid, 807.
Brunner, analysis of mineral super-
phosphates and of " phosphate pre-
cipite," 576.
Bruylants, G., a new method for pre-
paring hydriodic acid and liydro-
bromic acid, 89.
essence of lavender and spike, 50.
■ essence of maijorani, 50.
Bruisine. See Duvillier.
Bucking, H., crystal forms of epidote,
534.
Bullock, C, Veratrum viride, 170.
INDEX OF AUTHORS.
941
V. Bulow, experiments with artificial
manures, 506.
B urgerstein, A., influenee of nutritive
material on the transpiration of jjlants,
335.
B urgo'in, E., solubiUty of benzoic and
. salicylic acids, 471.
Butlerow, A., isobutylene, 230.
Byk, S., desulphui-ation of guanidine
thiocyanate, 311.
Cahours, A., and E. Demar^ay, the
acids whicli are formed by tlie distil-
lation of the crude fatty acids in a
current of superheated steam, 540.
Cahours, A., and A. Etard, a bromo-
derivative of nicotine, 815.
nicotine derivatives, 672.
Cailletet, L., compression of gaseous
mixtures, 604.
Calm, A., and K. Heumann, substi-
tuted azobenzenes, 880.
Campani, Gr., andD.Bizzarri, butyl
and isobutyl hippurates, 870.
Cannizzaro, S., analysis of four
waters for Turin, 591.
Canto, E. da, influence of smoke on
the development of blossom, 177.
Cantoni, Gr., influence of manures on
the combustibiUty of tobacco, 417.
Canzoneri. See Paterno.
Capparelli. See Amato.
Capron, J. B., relative intensity of the
spectral lines of gases, 685.
Carl, F., changes of ammonium is-
ethionate at high temperatures, 28.
Carnelley, T., Mendelejefl's periodic
law and the magnetic properties of the
elements, 206,
vapour-density of stannous chlo-
ride, 219.
Caro. See Graebe.
Cars ten, H. J., manuring of oats on
fen lands, 185.
Casamajor, P., action of bone black
on sufjar solutions, 758.
detection of starch-sugar mechani-
cally mixed with refined cane-sugar,
758.
rapid estimation of pure sugar in
raw and refined commercial sugars, 64.
Cazeneuve, P., lactic fermentation,
513.
oxidation of formic acid and
oxalic acid by ammouiacal cupric
oxide, 235.
transformation of acetic acid into
gly collie acid by cupric oxide, 32.
Cech, C. O., wild Croatian hops, 428.
Chappnis. See Ilautefeuille.
Christy, S. B., genesis of cinnabar
deposits, 221.
ChroustchofF, P., thermic study of
succinic acid. 151.
Church, J. A., heat of the Comstock
lode, 858.
Church. See also Wagner.
Ciamician, G. L., action of zinc-dust
on resins, 126.
products of thff distillation of gum
ammoniac with zinc-dust, 39.
spectroscopic researches, 361.
Ciamician. See also Weidel.
Cienkowski, L., organisms in beet-
sap, 334.
Claassen, T. E., phytolaccin, 412.
Claesson, P., sulphates of mono- and
poly-hydric alcohols and carbohy-
drates, 28.
Claesson, P., and H. Berg, constitu-
tion of a-toluenedisulphonic acid,
889.
Claesson, P., and K. Wallin, toluene-
monosulplionic acid, 255.
C la is en, L., test for phenylglyoxylic
acid, 67.
Claisen, L., and C. M. Thompson,
metamidophenylglyoxylic acid, 253.
Claus, A., nitrobenzoic acids, 647.
Claus, A., and C. Cratz, paracymene
and sulphuric acid, 632.
Claus, A., and K. Elbs, amarine, 881.
Claus, A., and W. Halbe rstadt,
nietaparadinitrobenzoic acid by
nitration of paranitrobenzoic acid,
647.
Claus, A., and II. Hansen, orthocy-
mene, 631.
Claus, A., and R. Lindhorst, action
of bromine on dichlorhydriu and pro-
pylphycite, 862.
Claus, A., and T. Stiisser, raetacy-
mene, 632.
Claus, A., and C. Winnel, oxidation
of dibromocymene, 632.
Clausius, R., behaviour of carbonic
anhydride in relation to pressure,
volume, and temperature, 691.
Clermont, P. de, and J. Frommel,
observations on sidphur baths, 196.
Cl^ve, P. T., derivatives of ij-dichloro-
naphtlialcne, — o-nitronaplithalene-
sulphonic acid, 47.
erbium, 157.
scandium, 7.
two new elements in erbia, 7.
Coale. See Remsen.
Cochin, D., alcoholic fermentation,
276, 277.
Cohn, F., and B. Mendelsohn, m-
942
INDEX OF AUTHORS.
fluence of the galvanic current on
bacteria, 726.
Cohne, S., and A. H. Allen, alcohol
tables, 773.
Collier, P., sugar from the stems of
maize and sorgho, 834.
Cols on, A., estimation of sulphur in
natural sulphides, 139.
Conechy, E. G. M., volatilising point
of arsenic, 705 .
Conen, J., derivatives of triethjl citrate,
36.
Conrad, P., constitution of antimonic
acid, 94.
Conrad, M., and C. A.tBischoff, syn-
thesis by means of ethyl malonate,
627.
Contamine. See Corenwinder.
Cooke, J. P., atomic weight of anti-
mony, 300, 704.
Cooper. See Wanklyn.
Coppola, M., artificial production of
oligist, 223.
Sfereocaulon T'esuvianum, 382.
Corenwinder, B., and Gr. Conta-
mine, analysis of parsnips, 342.
influence of the leaves on
the production of sugar in the beet,
336.
new process of analysing com-
mercial potash, 286.
Cornstock, W. J., analysis of tetra-
hedrite from Huallanca, Peru, 220.
analyses of some American tanta-
lates, 531.
cliemical composition of the pitch-
blende from Branchville, Conn., U.S.,
530.
Cor nil, A., ultra-violet limit of the
spectrum at various heights, 201.
Co sack, J., carbamides derived from
the isomeric toluidines, 245.
derivatives of the toluidines, 713.
Cossa, A., and M. Zecchini, cerium
tungstate, 851.
Councler, C, fluoboric ethylene, 230.
Crafts, J. M., density of chlorine at
high temperatures, 431.
density of some gases at a high
temperature, 434.
vapour-density of iodine, 788.
variations in the coeiKcient of ex-
pansion ot glass, 841.
Crafts, J. M., and F. Meier, density
of iodine at high temperatures, 433.
method of measuring high
temperatures, 509.
Cratz. SeeClaus; also Meier.
Crookes, W. G., and others, butter
adulteration. 423.
Cross, C. F., ehemistrv of bast fibre,
667.
Cyon, C. de, and Gr. le Bon, physiolo-
gical activity of borax, 415.
Czubata, H., chemical changes in
frozen and rotten potatoes, 820.
value of acorns as fodder, 917.
D.
Dahll, T., norwegium, 93.
Uambergis. See Grabriel.
Damm. See Staedel.
Dana, J. D., some points in lithology.
II. Composition of the capillary vol-
canic glass of Kilauea, Hawaii, 536.
Dancsi, L., action of potassium dichro-
mate on acetic acid, 160.
Danesi. See also Funaro.
D'Arsonval, a new voltaic condenser,
521.
Daubree, a meteorite which fell on
January 31, 1879, at la Bocasse, Com-
mune of Dun-le-Poelier (Indre), 226.
examination of the volcanic dust
whicli fell at Dominica, January 4,
1880, and of the water which accom-
panied it, 453.
Davis, Gr. E., direct method of testing
vitriol exits for nitrogen compounds,
746.
Davy, E.W., nitrification, 279.
Davy, M., proportion of carbonic anhy-
dride in the air, 788.
Davy, M., and otliers, loss of dried sub-
stance in plants during ripening, 820.
Daw, F. R. W., cmpieetite. 222.
Deb ray, H., action of acids on alloys
of rJiodium with lead and zinc, 706.
Debray. See also Delville.
Debrun, E., an electro-capillary ther-
mometer, 205.
D e f r e s n c, T., ptyalin and diastase, 330.
Degener, P., action of fused alkalis on
aromatic sulphonic acids, 320.
De he rain. P., and Nan tier, devclo}!-
ment of oats, 336.
Dehmel, B., estimation of albuminoids
in vegetable substances, 352.
■ occurrence of a reducing substance
in the urine of herbivorous animals,
332.
Dehmel. See also Weisk e.
Deimst, Liebermann.
Deininger, J., new plant for fodder,
183.
Delachanal. See Yincent.
Dehifontaine, M., the new metals of
gadolinite and of samarskite, 611.
De la Motte, H., action of phosphorus
pentachloride and hydriodic acid on
saccljaric acid, 36.
De la Rue, W., and H. Muller, eh;--
INDEX OF AUTHORS.
94r>
trie discharge of tbe chloride of eilTer
battery, 203.
Delbriick, M., rye as a material for
yeast, 777.
Delbriick, M.j and others, chemical
changes in nitrogenous substances
during fermentation, 728.
surface fermentation of
potato mash, — souring of yeast, 518.
Deles 86, explosion in a coal mine due
to carbonic anhydride, 220.
Dclffs, H., behaviour of sulphuretted
hydrogen with salts of the heavy
metals, 746.
Deraant, B., extractives from muscle,
726.
Demar^ay, E., preparation of ace-
tonitril, 618i
tetrolic and. oxytetrolic acids and
their homologues, 625.
Demar^ay. See also Cahours.
Demel, W., arsenates of zinc and cad-
mium, 217.
. Roussin's salt, 218.
Demole, E., constitution of dibrom-
othylene, 158.
partial synthesis of milk-sugar and
a contribution to the syntiiesis of
cane-sugar, 29.
Dennstedt, M., derivatives of para-
bromaniline, 633.
crystalline fomi of benzyl ortho-
thioformate, 646.
Den z el, J., halogen derivatives of
ethane and ethylene, 228.
Deon, P. H., neutral and inverted
sugar, 100, 458.
sygar from the date palm, 100.
Derome, P., separation of phosphoric
acid from h'cn and alumina, 286.
Desbarres, L., passage of nutritive
material in plants, 4i)3.
Des Cloizeaux, crystalline form of
magnesium, 611.
Desor, F., action of lime on solution
of sugar, 834.
Destrem, A., compounds of alcohols
with baryta and lime, and the pro-
ducts of their decomposition, 711.
Detmer, W., passage of plant mate-
rial in seedlings, 335.
Deutecom, B., estimation of sulphur
in pyrites, 744.
Deutsch. See Gabriel.
Deville, H. St. Claire, motion pro-
duced by the diffusion of gases and
liquids, 293.
the temperature of decomposition
of vapours, 209.
Deville, H. St. Claire, and II.
Debray, artificial laurite and platini-
ferous iron, 222.
Deville; H. St. Claire, and L.
T roost, determination of high tem-
peratures, 521, 526.
vapour-densities of selenium
and tellurium, 847.
De war, J., critical point of mixed va-
pours, 842.
formation of hydrocyanic acid in
the electric are, 23.
loweriug of the freezing point of
water by pressure, 845.
Dewey, F. P., Clarke's method for the
separation of tin from arsenic and
antimony, 289.
Dieck, E., and B. Tollens, carbohy-
drates from tlie tubers of Jerusalem
artichoke, 619.
Dichl, W., volumetric estimation of
lead, 752.
Dieulafait, L., existence of zinc in all
primary rocks and in sea waters of all
ages, 708.
normal presence of coyipcr in the
plants which grow on primordial
rocks, 494*
occurrence of lithium in rocks, sea
water, mineral waters, and saline de-
posits, 17.
Dircks, W., analyses of Norwegian
hay, 916.
DirvcU, v., new method of separating
nickel from cobalt, 287.
Ditto, A., action of tlie hydr.icids on
the sulphates of mereury, 12.
action of metallic nitrates on nitric
acid, 153, 154.
combinations of uranium oxyfluo-
corapounds witJi liuoridcs of the
alkali metals, 794.
fluorine compounds of uranium.
853.
— freezing mixtures of an acid and a
hydrated salt, 602.
— freezing mixtures with two crys-
tallised salts, 784.
Dittmann. See Wolff.
Doebner, O., aromatic amido-kctones,
804.
compounds of benzoirichloridc
with phenols and tertiary aromatic
bases, 239, 644.
Domoyko, pliosphatcs and boro phos-
phates of magnesia and lime in the
guano deposit of Mejiilones, 446.
Donath, E., chemical technological
notes, 516.
contributions to the metallurgy
and docJmasy of nickel, 770.
decomposition of arsenic and anti-
mony comjjounds, 348.
estimation of cobalt and nickel,
287.
944
INDEX OF AUTHORS.
Donath, E., method for the detection
and estimation of iodine in presence
of chlorine and bromine, 285.
V. Dorp. See Hoogewerff.
Dotto-Scribani, F., economical pro-
cess for preparing bibasic quinine
citrate, 126.
Dragendorff, formation of resin and
chemistry of ethereal oils, 125.
mannitol as a bje-prodiict in the
formation of lactic acid from cane-
sugar, 100.
Draper, J. C, dark lines in the solar
spectrum on the less refrangible side
of a, 201.
Drechsel, E., carbamido-palladious
chloiide, 161.
cyanamide, 307.
formation of hypoxanthine from
albuminoids, 672.
galvanic experiments (platinum
bases) , 300.
Drechsler, Gr., Chili potash-saltpetre,
507.
Dl-echsler. See also Wagner.
D wight, G. S., Strong's water-gas
system, 930.
Dyckerhoff, E.., on cement, 767.
Diinkelberg, feeding horses with flesh-
meal, 57.
Dunnington, F. P., new form of in-
strument for the determination of
specific gravity, 743.
Du Roi, P., and Kirchner, stall
sampling in milk analysis, 925.
Du Roi. See also Kirchner and
Schrodt.
J)uvillier, E., amido-acids from
a-bromocaproic acid, 543.
compounds belonging to tire crea-
tine and creatinine groups, 897.
new mode of forming dimethacry-
lic acid, 624.
Duvillier, E., and A. Buisine, action
of ethyl chloride on etbylamine, 794.
commercial trimethylamine,
159.
formation of tetramethvl-
ammonium nitrate, 545.
E.
Eckstrand, A. Gr., nitro naphthoic
acids, 261.
Eckstrand. See also Petterson.
Eder, J. M., a new chemical photome-
ter, 361.
Eder, J. M., composition of pyroxylin,
372.
estimation of ferrous oxide in pre-
sence of organic acids or sugar, 583.
potassio-ferrous oxalate and its
use for developing photographic bro-
mide of silver plates, 590.
- rapid developer for wet plate pho-
tographs, 765.
reducing properties of potassium
ferrous oxalate, 544.
Edzardi, C, analyses of the ash of
certain spice seeds, 915.
Elirhard, A. C, Fhytolacca decandra,
412.
Ehrhard. See also Fischer.
Eichler, E., octyl derivatives, 229.
Eisenberg, L. J., action of ferro- and
ferri-cyanic acids on amides, 231.
Eisfeld. See Wichelhaus.
Elbs. See CI a us.
Elder. See Rodwull.
Emmerich, R., influence of impure
water on health, 488.
Emmerling, A., carbonyl bromide,
627.
formation of vegetablealbumin, 341.
Emmerling, A., and R. Wagner,
clover sickness, 505.
monobromacetone and tlie
alcohol of acetone, 867.
Emmerling, O., abietic acid, 264.
Eudemann, H., boric acid as a preser-
vative, 767.
Endemanu, H., and Gr. A. Pro-
chazka, detection of copper, 924.
standard soda solution, 924.
sweet potatoes, 915. .
En gel, Gr., aetioii of infusorial earth on
•colouring matters, 427.
Engel, R., and de Gi-irard, method of
producing acetal, 458.
Engelhorn, F., methacrylic acid, 378.
Engstrom, N., experiments witli La-
val's separator, 933.
Eppinger, O., action of ethylamine
and diethylamine on acetone, 868.
Erlenmeyer, E., amidolactic acids,
713.
constitution of pheuyl-halogen pro-
pionic acid, 42.
oxvpropionic acid (oxyacrylic acid),
544. '
phenylbromolactic acid, 471.
phenyl-lactic acids, 471.
synthesis of substituted guani-
dines, 243.
Erlenmeyer, E., and A. v. Planta-
Reichenau, activity of bees, 415,
, 725.
Etard, A., synthesis of aromatic alde-
hydes : cuminaldehyde, 467.
IXDEX OF AUTHORS.
945
Etard. See also Caliours.
Kugling, \\'., inversion of beet-sugar
for wine, 833.
Eugling anil others, machines for milk
churning, 357.
F.
Far sky, F., growth of plants in arti-
ficial solutions, 337.
Fa u Connie r. A., estimation of urea,
513.
Fautrat, M., influence of forests on
rainfall, 737.
Fehlau, (lesh-meal as fodder for milch
cows, 501.
Feltz, E., and H. Briem, proportion
of sugar to the weight of beetroot -s
519.
Feuerbein, C, aromatic thiocarbu-
mides, 44.
Fiedler, M., fermentation of molasses,
931.
Field. See Jackson.
Figuera. See Aniato.
Fiieti, M., a new cumoplienol, 883.
Fileti, M., and A. Riccini, decompo-
sition of ethvlamine hydrochloride by
heat, 30.
Fischer, E., a new series of dye-stuffs,
474.
furfuraldehyde, 798.
hydrazines of the fatty series,
234.'
orthohydrazinbenzoic acid, 647.
phenanthrenedisulphonic acid and
its derivatives, 478.
Fischer, E. and O., dye-stuffs of the
rosaniline group, 390.
Fischer, E., and W. Ehrhard, ethyl
derivatives of phenylhydrazine, 242.
Fischer, F., adulteration and examina-
tion of food and drink, 422.
apparatus for estimating oxygen in
the atmosphere, 137.
apparatus for measuring the heat
of combustion, 1.
burning of fuel in house stoves,
145.
— evolution of carbonic oside from
red-hot iron stoves, 592.
investigation of lubricating oils,
778.
Fischer, O., condensation products of
aldehydes with primary aromatic
bases, 39.
condensation products of tertiary
aromatic bases, 40, 636.
diamidotriphenylmethane, 661.
Fischer. O., and P. Grieff, synthesis
of leucaniline, 640.
Fischer, O., and L. Roser, amidotri-
phenylmethane, 661.
Fischer, O., and J. Zicgler, a new
triamidotriplieuyl methane, 662.
Fittbogen. See Ilasselbaut.
Fit tig, R., new lactones, 799.
polymerised non- sat a rated acids,
120.
Fit tig, R., and H. Liepmann, fluor-
anthene, a new hydrocarbon fironi
coal tar, 400.
Fittig, R., and others, unsaturated
monobasic acids with six atoms of
carbon, 375.
Fittig. See also Bredt.
Fitz, A., doable salts of the lower
members of the acetic acid series, 799.
normal propyl alcohol from glyce-
rol, 372.
schizomycetic fermentations. Part
VT, 819.
Flahault, C, formation of chlorophyll
in the dark, 910.
Flawitzky, F., changes produced by
hydration and dehydration in the
liBvorotary terpene from French tur-
pentine oil, 402.
hydration of terpenes, 264.
laivorotary terebenthcne from
French turpentine oil, 559.
Fleischer, M., influence of the seed on
the tannin of oak bark, 920.
Fleischmann, AV., influence of fodder
on the secretion of milk, 907.
Fleischmann, W., and P. Vieth,
milk secretion, 330.
observations on the milk of a
large herd of cows, 487.
Fletcher, F. W., citrate of iron and
quinine, 68.
Fletcher, J., examination of some
County Dublin waters, 766.
water of the River Vartry, 21.
Flicke, P., and L. Grandeau, chemi-
cal examination of ligneous Papilio-
nacea?, 735.
Fliiiht, W., analyses of two new amal-
gams, and of a specimen of native
gold, 707.
Fliickiger, effect of cold on cherry
laurel, 733.
Ftirster, M., ethyl derivatives of or-
thoamidophenetol and orthamido-
phenol, 463.
Forcrand, ethyl nitracetate, 32.
Fouque, F., and A.M. Levy, artificial
production of felspars containing
barium, strontium, and lead, 419.
artificial production of a
leucitophyr, identical with the crys-
946
INDEX OF AUTHORS.
talline layas of Vesuvius and Somma,
448.
Franchimont, A. P. N., cellulose, 159.
glucose, 159.
preparation of ethereal acetates,
104.
tuniein, 233.
Frank land, E., dry fog, 439.
Fraude, Gt., aspidospermine, 54.
perchloric acid a^ a test for alka-
loids, 69.
Freda, P., artificial tannin, 122.
French, A., lead fume, and a new pro-
cess of fume condensing, 146.
Fresenius, H., and F. Bergmann,
electrolytic esiimation of ni(,'kel and
cobalt, 751.
electrolytic estimation of
silver, 747.
Freuzel, A., Caucasian minerals, 615.
Freyberg, E., resiiirative power of
naarsh and water plants, 335.
Freytag, B., some derivatives of pro-
pionic acid, 312.
Fricklinger, H., estimation of starch
in sausages, 826.
Friedburg, mill waste for manure, 60.
Friedel. C, and M. Balsohn, action
of bromine on diphenylmethane, 558.
conversion of bromostyrolene
into methylphenyl ketone, 469.
limited oxidation of ethvl-
benzene, 469.
Friedel, C, and A. Ladenburg,
silicon ethyl series, 608.
Friedlander. See Tiemann.
Fritz sc he, P., phenoxyacetic acid,
318.
Frolich. See Gevither.
Frommel. See Clermont.
Fruhiing. SeeSciiulze.
Funaro, A., formation of fatty matter
and ripening of the olive, 568.
salts obtained from the mother-
liquox-s of the Voltera brine springs,
146.
Funaro, A., and L. Danesi, succinin,
463.
v. Funke. See Wolff.
G.
Gabriel, S., action of hydrocyanic acid
on diazo-compounds, 41.
derivatives of tbiacetic acid, 33.
Gabriel, S., and A. K. Dambergis,
nitro-derivatives of diphenylmono-
and di-sulphonic acids, 890.
Gabriel, S., and A. Deutsch, sulphur
derivatives of diphenyl, 476.
Gaier. SeeBirnbaum.
Galimberti. See Eotondi.
Galloway, W., influence of coal-dust
in colliery explosions, 439.
Gantter, F., and C. Hell, suberic acid
produced by oxidation, 872.
Garnier, J., malleable nickel, 930.
Gauthier, A., presence of copper in
food, 490.
Gautier, A., chlorophyll, 266.
pure methyl cyanide, 618.
Gaw alow ski. A., determination of sap
in beet, 829.
estimation of carbonic anhydride
in gases, 573.
Gay, J., absorption of nitrogen dioxide
bv ferrous salts, 9.
Gay on, W., inactive giucose or neutral
sugar, 458.
Geleznow, JN"., quantity and distribu-
tion of water in trees, 912.
Gen ay, P., manure experiments with
wheat, -922.
Genth, F. A., uranium minerals from
N. CaroUna, 96.
Gerichten, E. v., Cv>nstitution of
phthahc chloride, 473.
Gerrard, A. W., tonga, 836.
Geu>ther, A., action of carbonic oxidt-
on alkaline hydi'ates at high tempera-
tures, 459.
behaviour of monochlorotetracry-
lic acid on fusion, 630.
Geuther, A., O. Frolich, and A.
Loos, new synthesis of carbon acids,
622.
Ghizzoni. See Rotondi.
Giacosa. P., saliretone, 716.
Gies, C, influence of arsenic on ani-
mals, 907.
Giglioli, I., resistance of seeds to tlie
prolonged action of chemical agents,
280.
Gilbert. See Mahrenholtz.
Gintl, W. F., water of the Ferdinands-
brunnquelle, Marieubad, Bohemia,
306.
Girard. See Engel.
Giunti, M., distribution of copper hi
the animal kingdom, 275.
Gladstone, J. H., and A. Tribe,
aluminium iodine reaction, 861.
Godef roy, J., and others, permanent
pasture a substitute for clover, 499. *
Godlewski, E., causes of the change
in the form of etiolated plants, 177.
Goes, B., diphenyldiimidonaphthol,
399.
Goessmann, C. A., amount of sugar
in sorghum, maize, and melons, 594.
manuring of sugar-beet in Ame-
rica, 418.
INDEX OK AUTHORS.
947
Goldschmidt. Sec Reinitzer.
Gorceix, niarlitc from Brazil, 4-17.
Gore, G., thermo-electric properties of
liquids, 431.
Gounard, F., associated minerals con-
tained in certain trachytes from the
ravine of Riveiiu Grande, 2v!5.
Graebe, C, carbazol. fifiO.
constitution of alizarin-blue, 262.
occurrence of paraleucaniline in
the manufacture of rosaniline, lf52.
Graebe, C, and B. Adlerskron.
some derivative? of carbazol, 660.
Graebe, C, andH. Caro, acridine, 398.
Graebe, C, and W. Knecht, phenyl-
naphthylcarbazol, 168, 663.
Graebe, C, and C. Mensching, di-
phenic anhydride, 812.
Grandeau, L., compcsition of maize,
183.
See also Flicke.
v., Baptisia tinctoria,
Grandeau.
Greene, F.
411.
Greene, W
dride, 550.
dioxymethjlene
H., aceto-benzoic anhy-
prf>paration of
methylene cliloride, 307-
preparation of bromobenzene and
iodobenzencs, 316.
synthesis of saligenol, 318.
Greene, W. H., and A. J. Parker,
note on hyraceum, 172.
Greenish, H. G., 2\igella saliva,
718.
G re iff. P., some new colouring-mat-
ters, 41.
anthranilie acid from orthonitro-
toluene, 648.
Grete, E. A., determination of wine-
extract, 928.
Grieff. See also Fischer.
Griesmeyer, V., new clarifier for beer.
931.
Griess, P., action of cyanogen com-
pounds on diazobenzene, 316.
action of methyl iodide on a*para-
ginc, 315.
a new clas.s of ammonium com-
pounds, 636, 637.
creatine compounds of the aroma-
tic group, 803.
triniefrhylparamidobenzenesulpho-
nic acid, 322.
Griesshammer, O., action of bromine
on cane-sugar, 795.
Grimaux, E., new derivative of the
parabanic series, 105.
Grimaux, E., and P. Adam, action of
bromine on dichlorhydrin, 99.
action of bromine on epi-
chlorhydrin, 457.
synthesis of citric acid, 801
Grodzky. See Kramer.
Gross, T., an experimeut with sulphur,
700.
Grossmann, J., alkalimetric determi-
nation of sulphates, 744.
<• -oth. P., cobalt glance, 13.
^ cobalt speis, 13.
manganite, 14.
G ruber, M., influence of borax on the
decomposition of albumin in the
organism, 907.
Grupe, A., and B. Tollens, action of
ammonium citrate on phosphates,
825.
Guaresci, I., podophyllin, 479.
Giimbel, C. W., manganese nodules
from the bed of the Pacific Ocean, 10.
Gunning, J. \V., vital power of schizo-
niycctes in absence of oxygen, 277.
Gurnaud, M., light, shade, and soil
studied in their influence on the
growth of forest trees, 566.
Gustavson, G., reactions due to the
presence of aluminium bromide and
chloride, 370.
Guthzeit, M., octylic acetoacetate and
its derivatives, 871.
Gutkneckt, H., a-nitroso-propionic
acid, 711.
Outzeit, presence of alcohols and
paraffins in plants, 914.
Gutzkow, F., preparation of soda from
the sulphate by means of lime and
sulphur, 592.
H.
Haas, sugar in raisins, 932.
Haberlandt, F., the mo3t advan-
tageous method of sowing corn, 181.
Haberlandt, (Jr., relation of the colour
of clover seed to its value, 134.
seed production of red clover, 729.
Habermann, J., glycyrrhizin, 671.
llager, H., speeilic gravities of fats,
resins, &c., 70-
Jlalberstadt. See Glaus.
Haleuke, Speyer beer, 773.
Hall, L. B., and I. Remsen, oxidation-
products of cymenesulphonamide, 257.
Hall. ScePeckham.
Hammarsten, 0., fibrinogen, 172.
casein, and on the action of rennet,
171.
Hammer, apparatus for quick fermen-
tation, 518.
Hammerl, H., action of water on
silicon and boron fluorides ; solution
of cyanogen in water, 435.
948
INDEX OF AUTHORS.
Hammerl, H., specific heat of con-
centmted solutions of hydrochloric
acid, 207.
specific heats of solutions of potash
and soda, 435.
Ham pel, L., amount of dew on plants,
493.
Hampel. See also Hess.
Han am an n, J., composition of Bohe-
mian beer-wort determined by che-
mico-optieal processes, 181).
manuring of beetroot, 509.
natural phosphates and their Talue
in agriculture, 506.
planting of sugar-beets, 502.
- — — relation of yield of beet to rain
and sunAine, 178.
Hank el, W., direct transformation of
radiant heat into electricity, 838.
Han nay, J. B., artificial formation of
the diamond, 7u7.
Hannay. J. B., and J. Hogarth, solu-
bility of soiids in gases, 210, 693.
Han riot, action of sodium on epi-
chlorhydriu, 457.
constitution of epichlorhydriu, 457.
Hansen. See Claus.
Hantzsch, A., conversion of a-napli-
thylamine into o-naphthylmethyl
etiier, 813.
Hardtung. See Post.
Hardy. See Reguault.
Harnack, E., and H. Meyer, re-
searches on the alkaloids of Jaborandi
leares, 898.
Hartdegen, A., production of the red
colour in salting meat, 80.
Hartley, W. N., and A. K. Hunting-
ton, absorption of the ultra-violet
rays by the spectra of organic sub-
stances, 430.
examination of essential oils,
201.
Harz, C O., certain sorts of vegetable
marrow, 184.
comparative investigation of hops,
417.
Hasenclever, R., effect of acid gases
on vegetation, 496.
H ass el bout. P., and J. Fit t bo gen,
variations in the carbonic anhydride
of the atmospliere, 699.
Hassell, A. v., direct determination
of soda in potashes, 580.
H ass en cam JO, H., a new method of
preparing methyl violet, 75.
Has well, A. E., Volhard's perman-
ganate method of titrating manga-
nese, 585.
Hausen, K. C, influence of air on fer-
mentation, 819.
• lower organisms in the air, 908.
Hautefeuille, P., a new property of
vanadates, 527.
new silicates of aluminium and
lithium, 447.
production of ampliigene, 449.
simultaneous reproduction of
quartz and orthoclase, 531.
two new silicotitanates of sodium,
531.
Hautefeuille, P., and J. Chappuis,
ozone, 847.
Havenstein, Gr., behaviour of natural
soils and of plants growing in them
towards water, 737.
Hazard, J., formation of soils by wea-
thering, 449.
Heckel, E., influence of salicylic acid
and other bodies on germination,
335.
Heddle, manganese-garnet, 856.
Hehner, O., mineral constituents of
cinnamon and cassia, 360.
Heiden, E., nitrogen manure for oats,
741.
Heine, K., sulphoisophthalic acid and
the corresponding hydroxyisophthalic
acid, 549.
Heiutz, W., diethylidenelactamidic
acid, 801.
products of the oxidation of tri-
acetonamine, 101.
triacetonamine chromates, 101.
■ urea platinochloride, 104.
Heinzelmann, estimation of the
value of raw material in the prepara-
tion of yeast, 833.
Heinzerling, C, mineral tanning, 427.
Hell, C, rate of substitution of bro-
mine in the acetic acid series, 539.
Hell, C, and O. Miilhauser, acids of
the formula C8H13O4 derived from
bromobntyric acid, 542.
• action of finely divided silve
on ethyl monobromobutyrate, 542.
Hell. See also Grantter.
Hemilian, V., synthesis of naphthyl-
diphenylmethane, 664.
Hengefeld, G-. I., effect of feeding
cakes on milk-production, 725.
Henry, L., dry distillation of sodium
trichloracetate, 236.
on the addition of oxygen to un-
saturated compounds, 231.
spontaneous oxidation of nitro-
laetic acid, 237.
Hensgen, C, potassium and ammo-
nium ferric chromates, 10.
Henshaw. SeeStorer.
Hermann, F., the problem of estima-
ting the number of isomeric paraiEiis
of the formula C„U2„+2, 605.
Heron. See Brown.
INDEX OF AUTHORS.
949
Hertz. See Hiinefeld.
Herzen, A., influence of boric acid on
acetous fermentatioTi, 819.
Herzfeld, A., acetylisation of some
earboh-vdrates. 619.
• action of diastase on starch-paste,
310.
malto-dextrin, 866.
Hess and L. Hampel, eflfect of mn-
nures on growth of larches and pines,
509.
Hesse, O., amidomethylene pvrot-a-
techols. 24S.
Californian orcella weed, 255.
caroba leaves, 671.
r'nchona barks. 328.
morphine hydrochloride, 673.
pereiro bart. 675.
quinamine, 270.
quinic acid, quinone, and allied
compounds, 317.
Hesse. See also Jobst.
Hesz, J. J., electro brass plating, 42-5.
Heubel, E.. action of dehydrating
agents on the crystaUine lens of the
eye, 333.
Heumann,K., idtramarine compounds,
217. 367.
Heumann. See also Calm.
Hilger, A., analyses of minerals and
rocks. 856.
• mineral constituents of the Ries-
ling grape, 342.
Him lev, C, detection of oiled wheat,
929.
Hinteregger, F., diffusion experi-
ments with acid solutions of mixtures
of salts, 89.
Hirsch, B., Balsamnm antarthritieum
hidirnm. 168.
Hirsch sohn, E., detection of wax,
763.
Hirschwald, J., crystal system of
lencite, 16.
Hjelt. E., action of ammonia on ethyl
camphoronates, 669.
• carrophyllin, 670.
Hjortdahl.T., piperidine salts, qui-
nine sulphate and selenate, 54.
Horler, H., petroleum, 199.
Hofferichter, P., synthesis of ketonic
acids, 35.
Hoffn:ann, H., influence of annual
temperature on change of colour in
leaves, 910.
Hoffmeister, W., nutritive value of
the Elodea canadenaia, 500.
Hofmann, A. W., a series of aromatic
bases isomerides of the thiocar! :i-
mides, 387.
action of sulphur on phenylben-
zamide, 886.
Hofmann, A. "W., amidophenylmer-
captans or thiohydranilines, 884.
methvlpvrogallol and the forma-
tion of pittacal, 2 18.
pittacal and eupitonic acid, 164.
transformation of methyl thio-
cyanale at high temperatures, 797.
TTofmeister. See Siedam grotzky.
H ngarth. See Hannay and Mills.
I Holdefleiss, F., amount of albumi-
i noids in potatoes, 568.
some analyses of starchmakers'
residue, 595.
Hoist. See Post.
Homeyer. See Liebermann.
Hoogewerff, S., and W. A. v. Dorp,
behaviour of the cinchona alkaloids
with potassium permanganate, 895.
pyridenetricarbox\lic acid
from cinchona alkaloids, 406.
pyridiuccarboxylic acids, 405.
Hoppe-Seyler, F., active condition
of oxygen induced by nascent hydro-
gen, 3.
chlorophyll, 53.
crystallised chlorophyll, 894.
Horbacze wski, products of the action
of hydi'ochloric acid on albuminoids,
723.
Horn, W. J., phosphoric acid, 367.
Hornberger, influence of steaming on
the digestibility of hay, 734.
Hornberger. See also Prehn.
Houdart and T. Petit, valuation of
wine, 421.
Houzeau, A., valuation of pyrites by
the gravimetric method, 583.
Howard, D., notes on cinchona bark,
177.
Hiibner, H., and E. Lellraann, di-
iodopropyl alcohol and moniodallyl
alcohol, 538.
Hiibner, H., and A. Stromeyer,
nitration of paranitrobenzoic acid,
549.
Ilunefeld, E. Reichardt, and
Hertz, formation of nitric acid in
the soil, 59.
Huntington. See Hartley.
Hussak. E., basaltic lavas of the
Eifel, 19.
Hutchinson, C. C, estimation of cad-
mium in presence of zinc : separation
of zinc, cadmium, and copper, 748.
I.
I bled, D., method of selecting beet for
seed, 13 1.
Ihlee. See Bodenbenuer.
950
INDEK OF AUTHORS.
Ingenhoes, P. H. B., existence of
double Exalts in solution, 32.
Irby, crystallography of calcite, 530.
Jackson, C. L., relative displaceability
of bromine in the monobromobenzyl
bromides, 161.
Jackson, C. L., and A. W. Pi eld,
action of bromine on toluene and its
derivatives, 878.
Jackson, C. L., and J. F. White,
orthobroraobenzyl compounds, 879.
parachlorobenzyl compounds,
878.
synthesis of anthracene, 262.
Jackson. See also Baeyer.
Jacobsen, O., behaviour of cymene in
the animal organism, 38.
Jahn, H., action of phosphonium iodide
on carbon bisulphide, 370.
decomposition of simple organic
compounds by zinc-dust, 794.
Jahns, E., ethereal oil of Origanum
hirtum, 112.
Jamieson, J., breathing of plants and
animals, 911.
Jamieson, T., influence of soluble and
insoluble phosphates as manure for
turnips, 186.
Janecek, Gr., composition of two varie-
ties of turnips, 917-
Janke, L., analysis of milk, 514.
Janovsky, J. V., niobite from the
Isergebirge, 369.
some chemical constants, 365.
Javpein. See Beilstein.
Jay, estimation of urea in urine, 513.
J ens sen, C, manuring experiments
with oats, 136.
Jewett, J., influence of acetic acid on
the separation of iron as basic acetate
from manganese, zinc, cobalt, and
nickel, 289.
Jobst, J., and O. Hesse, coto-barks,
and their characteristic ingredients,
325.
Jorgensen, S.M., contributions to the
chemistry of the chromammonium
compounds, 10.
Jolly, L., combinations of phosphoric
acid in the nervous substance,
274.
distribution of phosphates in the
muscli's and tendons, 275.
Jolly, P. v., variation in the composi-
tion of the atmosphere, 85.
Jolly, P. v.,audE. W. Morley, varia-
tions in the composition of the atmo-
sphere, 698.
Jordan, O., dibrom- and tetrabrom-
hydrazobenzene sulphonic acids, 808.
Joubert, J., alternating currents and
the electromotive force of the electric
arc, 783.
Joulie, H., and others, reduction of
superphosphates, and the behaviour of
phosphoric acid in soils, 571.
Joulin, L., researches on diS'usion,
526.
Jour dan, F., synthesis of normal
nonylie acid, and of an isomeride of
palmitic acid, 313.
Julian, A. A., composition of cymato-
lite from Goshen, Mass., 225.
Jungfleiscli, preparation of acetylene,
456.
Jutsum, S. C, estimation of total car-
bon in iron and steel, 751.
K.
Kachler, J., adipic acid from camphor,
559.
Kachler, J., and F. V. Spitzer, cam-
phocarbonic acid, 892.
hydrocamphene, 669.
relations of the camphenes
obtained from borneol and from cam-
phor, 324.
Kade, R., action of chloride on di-
benzyl, 46.
Kamenski. SeeWallach.
Kapusstin, M., estimation of carbonic
acid in the air, 420.
Karetnikoff, /S-chlorobutyraldehyde,
235.
Kehlstadt, A., occurrence of free sul-
phur in the dry distillation of tar, 831.
Kelbe, W., a new cymene from light
resin oil, 878.
abietic acid, 670.
Kelbe. See also Ziegler.
Kellermann. See Raumer.
Kellner, C, formation of fat in ripen-
ing cheese, 594.
Kellner, O.. albumin and amido-com-
pounds in plants, 279.
cleansing of lupines, 935.
estimation of non-albuminous
nitrogen-compounds in plants, 513.
muscular activity and waste of
tissue, 486.
quantitative estimation of digested
protein, 563.
quantities of amides and albumi-
noids in green plants : decomposition
of nitric acid and ammonia in plants,
731.
— spent hops as fodder, 344.
INDEX OF AL'TIIORS.
9')!
Keniieclr, Cr. W., coca, 1(59.
Kern, S., Bessemer steel plates, 356.
estimation of amido-compounds,
764.
— estimation of carbon in cast steel,
289.
— some analyses of iron, 73.
some remarks on Siemens-Martin
steel, 769.
Kerr, J., electro-optic observations on
various liquids, 599.
Kessler, F., atomic weight of antimony,
299.
pentathionic acid, 298.
Kessler, M., crystallised hydrofluo-
silicic acid, 789.
Kienlen, P., commercial valuation of
bituminous rocks and limestones, 682.
Kinch, E., agricultural chemistry in
Japan, 134.
Kingzetf, C. T., atmospheric oxidation
of turpentine, 51.
is ozone produced during the
atmospheric oxidation of phosphorus ?
3.
Kirchhoff, a manuring experiment,
923.
Kirehner, W. J., and P. du Roi,
influence of ground nuts on the pro-
duction of milk, 487.
Kirehner, W., and others, experiments
on creaming, 75.
Kirehner. See also Du Roi.
Kjeldalil, J., diastase, 562.
Klebs, E., preservation of milk, 148.
Klein, injurious effect of peat water on
meadows, 738.
reaction of tungstates in presence
of mannitol, 30.
Klein, C, felspar in the basalt from
the Hohen Hagen, near Gottiugen,
614.
Klein, D., borotungstates, 612.
Klein, J., constitution of deoxaiic acid,
36.
Klein, O., compounds of organic bases
with the haloid salts of mercury, 632.
Kleinsehmidt. See Staedel.
Klenze. See Werko witch.
Klocke, B. F., sensitiveness of alum-
crystals to variations in the strength
of their mother-liquors, 529.
microscopical observations, of the
growth and re-solution of the alums
in solution of isomorphous substances,
855.
Klose. See Adamec.
Knapp, ultramarine, 155.
Knauer, W., and others, purification of
water from sugar works, 930.
Knecht, W., chloro-derivatives of car-
bazol, 660.
Knecht, W., vaponr-density determi-
nations in tlie vapours of phosplioru.s
pentasulphide, 679.
Knecht. See also Graebe.
Knop, W., albuminoids, 562.
Koch, A., a colouring matter contain-
ing sulphur from paraphenylenedia-
mine, 110.
new minerals from the andesite of
Mount Arany, 616.
Kohler, H., action of antimony penta-
diloride on phosphorus trichloride,
613.
chloro-derivatives of amines, 233.
etliylamine, 159.
synthesis of phosphenyl sulpho-
chloride, 558.
T<^ '<"> II i g. A., estimation of retrograde
I'li'isphorie acid by ammonium citrate,
924.
Konig, J., adulteration of rye bran
with rice husks, 200.
analyses of marl, 60.
estimation of oxygen dissolved in
wat r, 421.
injurious effect of industrial efflu-
ent water and of gases on soils and
plants, 497.
nutritive value of fruits, 733.
Koenigs, W., action of phosphorus pen-
tachloride and oxycliloride on cincho-
nine hydrochloride. 673.
conversion of piperidine into pyri-
dene, 404.
synthesis of quinoline, 672.
Konigs, E., detection of coal-gas in
earth, 684.
• weighting of silk, 935.
Koth, U. v., determination of the che-
mical peculiarities of soils and manures
requi?ite for them, and on the action
of soluble and reduced phosphates,
418.
Kolbe, H., basicity of dithionic acid, 5.
destructive action of wood on sali-
cylic acid, 520.
Koninck, T., action of fused alkaline
carbonates on platinum, 581.
Kramer, Gr., quantitative determina-
tion of acetone in methyl alcohol, 826.
Kramer, G., and M. Grodzky. influ-
ence of constituents of wood spirit on
the production of dimethyianiline,
802.
Krafft, F., lauric acid and its conver-
sion into unclecylic acid, 34.
preparation of lauric, myristic,
palmitic, and stearic aldehydes. 866.
tridecylic, pentadccylic, and mar-
garic acids, 34.
Kramjjs, J. M. A., contribution to a,
knowledge of the ureides, 630.
952
INDEX OF AUTHORS.
Kramps. See also Aronstein.
Kratschmer. See Seegen.
Krauch, C, report on the methods of
estimating cellulose, and on their de-
fects, 761.
unorganised ferments in plants,
175.
woodv fibre estimation and its de-
fects, 588.
Kraus, C, influence of light on the
growth of plants, 57.
Kraus, F., determination of gold and
silver by quartation with cadmium,
679.
Kraut, bclladonnine. 410.
filter-paper and filtering, 573.
Krelage. See Rojen.
Krestownikoff, /S - chloropropalde-
hyde, 234.
Krestownikoff. See also Markow-
n i k o f f .
Kretschy, M., kynuric acid, 44.
Kreusler, M., method for the continu-
ous measurement of the intensity of
dayligiit and its application 1o physio-
logico-botanical investigations, 188.
Kreusler, U., estimation of nitrogen
in albuminoids, 350.
Kreusler, U., and others, digestibility
of steamed hay, 498.
Krieger-Pelf t, J., application of pota-
toes and undried malt in the prepara-
tion of yeast, 200.
Krocker, adulteration of bone-meal,
354.
Krocker, F., disease in sheep caused
by lupines, 916.
Kli ii n, disease in sheep caused by lupines,
916.
Kuhara, M., method for estimating
bismuth volumetrically, 753.
Kuhlmann, F., explosion of a plati-
num still used for concentrating sul-
phuric acid, 517.
Kurbatow. See Beilstein.
L.
Laar, C, sulphanilic acid, 820.
La Coste, W., and A. Michaelis,
aromatic arsenic compounds, 396.
Ladenburg, A., alkaloids of bella-
donna, datura, jusquiame and du-
boisia, 5G1.
■ artificial alkaloids, 420.
duboisine, 675.
lioniatropino, 815.
hyoscyamiue, 674.
Ladenbvirg, A., hyoscyamine and atro-
pine, 674.
tropemes, 714.
tropidine, 675.
Ladenburg, A., and Gr. Meyer, datu-
rine, 482.
Ladenburg. A., and S. Kiigheimcr,
artificial formation of tropic acid,
472.
Ladenburg. See also Friedel.
Ladureau, A., cultivation of sugar-
beet, 736, 917.
Laiblin, R., bromo-derivatives of nico-
tine, 897.
Lamek, J., and C. Portele, experi-
ments with various sorts of beet, 59.
Landmann. See Michaelis.
LandolphjF., analysis of organic com-
pounds containing fluorine and boron,
61.
anethol-derivatives, 384.
two new hvdrofluofeoric acids and
ethylenefluoboric acid,, 28.
Lange. See Liebermann.
Langer, T., carbonic acide in beer,
774.
Lassaulx, A. v., de?mine, 856.
■ the eruptive rocks in the Saar and
Moselle districts, 537.
Latschinoff, P., cholecamphoric acid
and its relation to cholamic acid, 722.
oxidation of cbolic acid, 562.
oxidation- products of cholic acid,
56.
Laubenheimer. SeeWitt.
Lauche, njanures for cabbages and
fruit-trees, 506.
Lauenstein, depreciation of barley by
overgrowth, 179.
La Valle, G., crystallographie constants
of some benzene derivatives, 384.
Leclerc, M., and M. Moreau, experi-
ments with manures, 570.
Leeds, A. R., action of light and dark-
ness on tarmin solutions, 908.
action of ozone on the colouring
matter of plants, 58.
bleaching sugar syrups by ozone.
74.
— formation of hydrogen peroxide
and ozone, 847.
— formation of hydrogen peroxide
and ozone by the action of moist
phosphorus on air, 699.
— influence of volume and tempera-
ture in the preparation of ozone : a
new ozonizer, 90.
new methods in actino-chemistry,
837.
— non-production of ozone in the
crystallisation of iodic acid, 213.
oxidation of carbonic oxide by
IXDEX OF AUTHORS.
953
moist air in presence of phosphorus
at the ordinary temperature, 237.
Leeds, A. E., reduction of carbonic an-
hydride by phosphorus at ordinary
temperatures, 237, 298.
• solubility of ozone in water, 213.
Lef ort, J., use of femithson's pile for
the detection of mercury in mineral
■waters, 510.
Lehmann. See Wein.
Lehne, A., condensation of benzhydrol
and naphthalene, 478.
Lelellier, A., oxidation of alcohol by
an ammoniacal solution of cupric
oxide, 310.
Lellmann. SeeHiibner.
Lemberg, J., decomposition of sili-
cates, 503.
Lenz. W., estimation of glycerol, 757.
Lepel, F., adulteration of wine, 191.
■ behaviour of fruit-juices with re-
agents, 354.
Letts, E. A., action of sodium on tur-
pentine hydrochloride, 669.
■ phthale'in of hsematoxylin, 54.
Leuckart, E., ethylcarbamide and
some of its derivatives, 383.
Levallois, A., presence in the Soja
hispida of a substance transformable
into glucose, 796.
Levallois, A., and S. Meunie r, crys-
taUised calcium oxide, 700.
L6vT, A., ammonia in air and water,
848.
Levy, L., sketch of the origin of the
mineral waters of Savoy, 453.
Levy, S., and G. Schultz, chlorinated
quinonea, 888.
Levy. See also FouquS.
Lewin, L., influence of glycerol on
proteid tissue change, 817.
Lewis. See Storer.
Lewkowitsch, J., preparation of ni-
tro-fatty acids, 33.
Lieben, A., analyses of four waters for
Turin, 591.
Lieberman, C, and M. Yoeltzkow,
phenylthiocarbimide glycoUide, 659.
Liebermann, C, fluorescence in the
anthracene series, 665.
Liebermann, C, and A. Bischof,
the third anthracenecarboxyhc acid,
399.
Liebermann, C, and J. Dehnst,
decomposition of oxyanthraquinone,
49.
Liebermann, C, and J. Homeyer,
peculiar formation of tolane tetra-
chloride, 259.
Liebermann, C, and A. Lange, for-
mulae of thiohydantoms, 44.
Liebig, M., introduction of nitric acid
VOL. XXXVIII.
into the sulphuric acid chambers
along with the steam, 196.
Liebmann, A., synthesis of cumeue,
384.
Liebmann. See also Wallach.
Liebsehutz. See Pellet.
Liepmann. See Fittig.
Lindhorst. See Claus.
Lin do, D., mercuric oxide in grey
powder, 930.
Lindstrom, G., thaumasite, 16.
Lionet, A., purification of hydrogen, 2.
Lipp, A., derivatives of isobutaldehyde,
620.
Lipmann, E. O. v., occurrence of tri-
carballylic and aconitic acids in beet-
juice, 36.
occurrence of vanillin in raw su-
gars, 646.
sugar from poioulin, 29.
Lipmann, E., and W. Strecker, ni-
trocuminaldehyde and its derivatives,
251.
Lipps, J. S., malt examination, 929.
Lloyd, J. U., berberine salts, 169.
Yerha mausa, 721.
Lockyer, J. N., existence of carbon in
the coronal atmosphere of the sun,
429.
experiments tending to show the
non-elementary character of phospho-
rus, 4.
Lodge, 0. J., determination of the
specific electrical resistance of certaia
copper-tin alloys, 687.
Loew, O., lecithin and nuclein in yeast,
816.
source of hippuric acid in the urine
of herbivora, 173.
synthesis of formic acid, 460.
Loew. See also Nageli.
Lowig, K., preparation of sugar from
sap of beetroot, 931.
Loir, a double function of monobasic
acids, 31.
Lommel, E., dichroic fluorescence of
magnesium platino-cyanide, 598.
Loos. See Geuthcr.
Losanitch, S. M., constitution of te-
tranitrodi phenyl carbamide, 812.
Lossen, F., guanidine, an oxidation
product of albumin, 413.
Louguinine, W., heat disengaged in
the combustion of some isomeric alco-
hols, 787.
heats of combustion of glycerol.
and of ethylenic glycol, 604.
Love, E. G., edible earth from Japan,
702.
Luckow, C, apphcation of the gal-
vanic current to analytical chemistry,
282.
3 X
954
INDEX OF AUTHORS.
Luclwig, E., modification of Zulkow-
sky's apparatus for the volumetric
estimation of nitrogen, 679.
Liiders. See Otto.
Lunge, G-., composition and analysis
of the binoxide of manganese re-
covered in the Weldon process, 528.
researches on nitrous acid and ni-
trogen tetroxide, 91.
researches on nitrous anhydride
and nitrogen tetroxide, 440.
Lunge, G-., and H. Schappi, forma-
tion and constitution of bleaching
powder, 789.
Lunge, H., composition and analysis of
Weldon mud, 704.
Lunge. See also Post.
Lux, F., volumetric analysis of red lead,
585.
Lytc, F. M., blow-pipe assay of silver
"lead, 585.
M.
Macagno, H., analyses of air, 697.
tannin of sumach leaves, 732.
Maccagno, I., tannin in wine, 775.
Mach, E., and others, tartar and tar-
taric acid in must and wine, 774.
M act ear, J., estimation of nitrous
compounds in the manufacture of sul-
phuric acid, 745.
Marcker, M., density of the mash,
517.
influence of the manure on potato
disease and starch in potatoes, 915.
manuring beets with sodium ni-
trate, 741.
manuring experiment with sugar-
beet, 923.
the best mode of applying arti-
ficial maniu'e to potatoes, 824.
Marcker, M., and E. We in, spent
hops as a fodder for cattle, 502.
Magatti, C, oxidation of substituted
phenols, 613.
ethylene ether of pyrogaUol, 250.
Magnier de la Source, L., colloidal
ferric hydrate, 792.
Mahrenholtz and Gilbert, an azo-
benzenesulphonic acid, 804.
Mahu. See Birnbaura.
Maissen, P., preparation of campho-
ric acid and camphoric anhydride,
893.
the meteorite of Albarello, 369.
Mallet, J. W., revision of the atomic
■ weight and quantivalence of alumi-
nium, 701.
Maltschewsky, aniline dithionate,
240.
Maly, E., and R. Andr easch, nitroso-
thioglycollic acid, 630.
Mann, C, detection of water in alcohol
and ether, 679.
Manoury's method of desugarising
molasses, 357.
Maquenne. See Millot.
Marcet, W., function of respiration at
different altitudes, 483.
March and, C, abnormal composition
of human milk, 332.
analysis of milk, 828.
Marchetti, C, some naphthol deriva-
tives, 260.
Marck, Gr., damage to seed peas by
weevil, 734.
Marguerite, P., new aluminium sul-
phate, 792.
Marie-Davy, carbonic acid in the air,
334.
Markl, A., composition of grains from
malt, 148.
Markownikoff and Krestowni-
koff, homoitaconic acid, 238.
Marquardt, F. W., malt combings a
source of yeast, 518.
Martin, K., hemihedry of the diamond,
854.
Mascart, atmospheric electricity, 783.
Masing, E., comparative examination
of the most important kinds of com-
mercial gum arable, 827.
Masino, F., compounds of the myris-
tic series, 460.
Masino, See also Schiff.
Matthieu, A., comparative rainfall on
woods and fields, 737.
Maumen6, E. J., compounds of hy-
dracids with ammonia, 4.
fermentation of glucose, 863.
oxygen acids of sulphur, 5.
Maumene, Gail, and Co., patent pro-
cess for preparing inverted sugar,
425.
Maxwell, T., paranitrophenylacetic
acid, 119.
Mayer, A., combustibility of, and
amount of chlorine in manured to-
bacco, 417.
examination of dog biscuit, 836.
influence of oxygen on fermenta-
tion, 908.
Mayer, A., and F. Clausnitzer, a
new skimming process, 933.
Mazzara, G., hydroxyazobenzene and
paramethyl-hydroxyazobenzene, 163.
metamidocinnamic acid, 163.
paracthylmethyl-phenol, 882.
tetrabromodibenzylparadimethyl-
phenylamine, 879.
IXDEX OF AUTHORS.
955
Mazzara, G., tolylphenol, 161.
Medicus, L., and S. Scherer, testiug
butter, 587.
Mehu, C, estimation af urea bj sodium
bypobromite, 681.
Meier, F., and J. M. Crafts, vapour-
density of iodine, 606.
Meier. See also Ador and Crafts.
Meissl, E., analysis of butter, 828.
Meldola, R., action of nitrosodimcthyl-
aniline on pbenols wbicb do not con-
tain tbe metbyl groups, 162.
coloiu'ing matters from pbenols,
881.
di- and tri-derivatives of naphtba-
lene, 260.
Melikoff, P., action of bypocblorous
aeid on acrylic acid, 160.
amidolactic acid, 800.
/3-bromolactic acid, 800.
constitution of liquid chlorolactic
acid and of oxyacrylic acid, 800.
bydroxyacrylie acid, 626.
Mendelsobn. See Colin.
Menozzi. SeeMuzzo.
Mensebing, C, nitration of salicyl-
anilide, 556.
Mensebing. See also G-raebe.
Menscbutkin, N., etberification of
unsaturated monobasic acids, 375.
structure of sorbic and bydrosorbic
acids, 382.
Merling, Gr., litbium pbospbates, 581.
Merz, v., and J. Tibiriga, syntbetical
formation of formic acid, 374.
Merz, v., and W. Weith, substitution
fn tbe pbenyl group, 813.
Merz, v., and Gr. Zetter, resorcinol
and orcinol derivatives, 113.
Meunier, S., artificial production of
spinel and corundum, 447.
Meunier. See also Lev all ois.
Meyer, bone-meal as a maniu'C for
potatoes, 739.
Meyer, 0. F., contribution to the
knowledge of reduced pbospboric acid,
574.
retrogradation of superpbosphates
containing iron and aluminium, 703.
Meyer, E. v., cyanetbine, 31.
Meyer, L., history of periodic atomi-
city, 605.
Meyer's vapour-density determina-
tions, 824.
Meyer, R., behaviour of bsematoxybn
on destructive distillation, 248.
Meyer, R., and A. Baur, hydro^yla-
tion by direct oxidation, 165.
Meyer, V., behaviour of iodine at high
temperatures, 433.
calorimetrical temperature deter-
minations, 434.
Meyer, V., density of iodine vapour,
696.
■ observations on vapour-densities,
433.
vapour-density of iodine, 788.
vapour-densities of the alkali-
metals, 434.
Meyer. V. and C, behaviour of chlo-
rine at higli temperatures, 214.
Meyer, V., and H. Zublin, behaviour
of chlorine at liigb temperatures,
432.
density of bromine at high
temperatures, 432.
determination of the density
of vapours wliich attack porcelain at a
red lieat, 149.
platinic bromide, 445.
volatile metalhc cUorides,
604.
Meyer. See also Harnack, Laden-
burg, Pagel, Micbeler, and Rei-
necke.
Micbaelis, A., and P. Becker, mono-
phenylboron chloride, 395.
Micbaelis, A., and B. Landmann,
constitution of selenious acid, 607.
Micbaelis, A., and C. Panek, homo-
logues of phospbenyl chloride, 640.
Micbaelis. See also La Costc.
Michler, W., and K. Meyer, action
of sulphonic chloride on amines, 108.
Michler, W., and F. Sale the, action
of sulphonic chlorides on amines, 108.
M if let, bacteria in tlie atmosphere,
727.
Miller, O., products of the dry distil-
lation of calcium piitlialute, 255.
Miller, W. v., a new colouring-matter,
559.
Biebrich scarlet, 813.
hydroxetbylmetliylacctic acid, 34.
bvdroxyisobutylformic acid, 34.
hydroxyvaleric acids and angelic
acid, 314.
rouge Fran^ais, 664.
— — supplementary notice on new
colouring-matters, 640.
Millot, A., dicalcium phospliate, 442.
synthesis of ulmic substances, 482.
Millot, A., and Maquenne, fermen-
tation of beetroot sap obtained by
difl'usion, 931.
fermentations produced in
preparing syrups from beet-juice by
diffusion, 519.
Mills, E. J., chemical repulsion, 693.
Mills, E. J., and J. Hogarth, re-
searches on cbemi-al equivalence.
Part II, hydrogen chloride and sul-
phate, 438.
researches on lactin, 458.
3 a; 2
956
IISTDEX OF AUTHORS.
Mills, E. J., and T. W. Walton, re-
searches on chemical equivalence.
Part I, sodium and potassium sul-
phates, 437.
Mi quel, P., atmospheric bacteria, 727.
Bacillus urea, 133.
fermentation accompanied by for-
mation of hydrogen sulphide, 132.
Mixter, W. G., ethyhdenamine silver
sulpliate, 234.
Moeller, J., free carbonic anhydride in
soils, 505.
linaloes wood, 428.
" mogdad " coffee, 936.
prima vera- wood, 596.
Mohr, C, volumetric determination of
phosphoric aeid by means of uranium
in the presence of iron, 575.
Moissan, H., absorption of oxygen and
expiration of carbonic anhydride by-
plants, 416.
action of chlorine on chromium
sesquioxide, 793.
sulphides and selenides of chro-
mium, 527.
Monde sir, P. de, comparison of the
curves of the tensions of satiu'ated
vapours, 435.
variation in the tension of vapour
emitted above and below the point of
fusinn, 605.
Morawski, T., glycerin cement, 428.
Moreaii. See Leclerc.
Morgen. SeeBehrend.
Moritz, J., mode of action of sulphur
as a remedy against vine disease,
281.
Morley, E. W., possible cause of varia-
tion of the proportion of oxygen in
the air, 90.
Morley, H. F., action of nitrous acid
on mono- and di-ethyleuediphenyldi-
amine, 112.
Morley, H. G-., propylneurine, 877.
Morley. See also Jolly and Wurs-
ter.
Moser, J., composition of the kernels
and husks of the seed of Gleditschia
glabra, 133.
feeding value of some manufactu-
rers' waste, 183.
manuring of sugar-beet, 185.
on various manures, 344.
Mo ser, J., and others, analyses of sugar,
519.
Moser, J., and E. Soxhlet, analyses
of milk, 520.
Mouchot, A., industrial utilisation of
solar heat, 765.
Muck, E., determination of ash in coal,
590.
■ removal of large quantities of
sodium chloride in mineral analyses,
580.
Miilhauser, O., orthanisidine, 641.
M ii 1 h a u s e r. See also Hell.
Miiller, A., oxalic a«id in beet leaves,
733.
— ^— valuation of copper for roofing,
826.
water analysis, 139.
Miiller, K., cultivation of beet seeds.
920.
Miiller. See also De la Hue and
Peters.
Miiller-Erzbach, W., luminosity of
phosphorus, 298.
reduction of metallic oxides by
hydrogen, 298.
Miiller-Thurgau, H., locality of al-
bumin secretion in plants, 492.
Muntz. See Schloessing.
Musso, Gr., and F. Schmidt, presence
of sulphuric acid in milk, 423.
Muzzo, Gr., and C. Menozzi, milk
albumin and curd formation, 900.
Mylius, E., opium testing, 829.
N.
Naccari. A., and S. Pagliani, absorp-
tion of gases by liquids, 525.
Nageli, C. v., and O. Loew, formation
of fat in the growtli of fungi, 337.
Nantier. SeeDeherain.
Natanson, S., Fittica's fourth nitro-
phenol, 463.
Nan din, C, influence of atmospheric
electricity on the growth of plants,
909.
Naumann, A., dissociation of iodine
vapoiu', 696.
relation between molecular weight
and density of gases, 525.
Nay lor, W. A. H., volumetric estima-
tion of arsenic acid, 421.
Neale, A. T., two azotoluenesulphonie
acids, 806.
Negri, A. de, improvement of Italian
tobacco by permeating the leaves with
the juice of exotic tobacco, 200.
Negvi, A. and G. de, colouring-matter
of anguria and colycynth, 267.
Nencki, M., empirical formula of
skatole, 167.
Nencki. M., and F. S chaffer, chemi-
cal composition of bacteria, 176.
Ner linger, T., employment of peat as
manure, 506.
Nessler. J., determination of wine ex-
tract, 515.
INDEX OF AUTHORS.
957
Jfessler, J., foreign colouring-matters
in red wine, 191.
liquid for the preservation of bo-
tanical specimens, 596.
Nessler, J., and H. Wachter, free
tartaric acid in wine, 775.
Ney, 0., influence of light on beer, 200.
Niaudet, A., new galvanic couple, 149.
Nichols, W. R., deteiioration of
library bindings, 836.
Nickels, B., detection of cotton-seed
oil in oliye oil, 925.
•^-^ use of the polariscope in testing
crude anthraquinoue for anthracene,
292.
use of the spectroscope in discrimi-
nating anthracenes, 757.
Niederstadt, analysis of beer, 833.
Niederstadt, B. C, guano from the
island of Ichaboe, 506.
• on explosives for blasting, especially
nitroglycerol, 595.
Nietzki, R., colouring matters obtained
by the action of naphthol on diazo-
azobenzene, 66-4.
formula of quinhydrone, 247.
toljlenediamines, 162.
xylene derivatives, 552.
Nilson, L. F., atomic weight and
characteristic salts of scandium, 850.
atomic weight and characteristic
salts of ytterbium, 703.
Nilson, L. F., and O. Pettersson,
atomic weight of glucinum, 850.
molecular heats and molecu-
lar volumes of the rare earths and
their salts, 838.
specific heat and atomic
weight of glucinum, 792.
Nivet, reactions between calcium car-
bonate and ammoniacal salts, 700.
Nordlingcr, sap of trees and sijecific
gravity of their wood, 912.
Nolte, R., estimation of chlorine in
grain and in forage, 285.
Nolting. See Reverdin.
Nordenskiold, A. E., two remarkable
meteors observed in Sweden, 859.
Nordstrom, T.,vanadite, 15.
Nowak. SeeSeegen.
0.
Oberlin and Schlagenhauf f en, al-
kaloids of Alstonia convstricta, 127.
Ogier, J., a new hvdride of silicon,
298.
combinations of phosphine with the
haloid acids, 150.
Oglialoro, A., paramethoxyphenyl-
cinnamic acid and methoxvstilbeue,
253.
synthesis of phenylcoumai'in, 164.
Ohl, W., electrolytic estimation of co-
balt, nickel, and copper, 583.
Ohm, B., obsei-vations on milk, 828.
OlJI^euheim, H., influence of the
supply of water, the secretion of sweat
and muscular labour on the elimina-
tion of nitrogenous decomposition-pro-
ducts, 818.
Orth, absorption of ammonia by the
soil, 737.
Oser, J., and F. Bocker, condensation-
products of gallic acid, 394.
Ossikovszky, J., constitution of tyrosin
and skatole, 473.
formation of cinnamic aldehyde
during fibrin-pancreas digestion, 469.
Ost, H., formation of parahydroxyben-
zoic acid from sodium phenate, 43.
Otto, R., action of sulphuric acid on
aromatic sulphydrates, 810.
Beckurts' toluenemetasulphonic
acid, 810.
behaviour of mercury and lead
ethyl mercaptides at high tempera-
tures, 796.
constitution of the sulphinic acids,
810.
synthesis of ethereal salts of thio-
sulphonates, 812.
Otto, R., and R. Liiders, benzyl de-
rivatives contairung sulphur, 811.
P.
Pabst, J. A., preparation of ethyl ace-
tate, 541.
Paetow, sowing broadcast or in drills,
922.
Pagel, A., and H. Meyer, manure ex-
periments with rye, wheat, and oats,
738.
Pag Hani. See Naccari.
Pagnoul, A., formation of nitrates in
sugar-beets, 494.
Panebianco, R., crystalline form of
nitrosothymol, lapachic acid and cu-
mic acid, 548.
crystalline form of some aromatic
compounds, 105.
Panek. See Michaelis.
Papasogli, G-., detection of cobalt and
nickel in presence of each other,
286.
958
INDEX OF AUTHORS.
Parker, R. H., action of potassium
chlorate on ferrous iodide, 704.
estimation of ferrous iodide, 749.
Parker. See also G-reene.
Parodi, D., tayuja, 721.
Parsons, H. P., proximate analysis of
plants, 754.
Pasqualini, A., effect of gypsum on
the quantity and quality of clover
crops, 185.
Pas savant, S. C, nitrites from hydro-
cyanic acid and aldehyde ammonia,
313.
Paternb, E., chemical constituents of
Stereocaulon vesuviannm, 551.
lapachic acid, 267.
Patern6, E., and F. Canzoneri, deri-
vatives of natural and synthetical
thymol, 883.
products of the oxidation of
the ethers of thymol, 246.
Patern6, E., and P. Spica, cymene
from cumic alcohol, 106.
cymenecarboxylic acid, 163.
Pauchon, E., tension of the vapour of
saline solutions, 211.
Paulsen, W., action of different
manures on the yield of potatoes, 187.
Pauly, M., direct decomposition of
sugar-lime, 931.
Pavy, F. W., physiology of sugar in re-
lation to the blood, 486.
volumetric estimation of sugar by
an ammoniacal copper test, giving re-
duction witliout precipitation, 512.
Pawel, 0., Roussin's salt, 217, 218.
Pawlowski, B., the speed of reactions,
438.
Paykiill, S. E,., zirconium deriva-
tives, 6.
Peckham, S. F., and C. W. Hall,
lintonite and other forms of thomson-
ite, 535.
Peckmann, H. v., constitution of an-
thraquinone, 323.
Peckolt, J., Carica papaya and papay-
alin, 128.
Pedler, A., and others, cobra poison,
490.
Peirce, B. O., emission spectra of
haloid mercury compounds, 81.
Peirce. See also Smith.
Pekelharing, C. A., peptone, 901.
Peligot, E., compound of levulose with
lime, 539.
• saccharin, 620.
some properties of glucose, 232.
Pellegrini, N., analysis of chrysocolla
from Chile, 97.
physico-chemical analyses of clay
soils, 511.
Pellet, H., ash of beet, 922.
Pellet, H., beet residues as fodder, 73 1.
certain properties of bone char-
coal, 834.
distribiition of potassium nitrate in
the beet, 733.
estimation of organic nitrogen in
natural waters, 62.
existence of ammonia in vegetables,
568.
relation between the starch, phos-
phoric acid, and mineral constituents
of the potato, 912.
relation between the sugar and
mineral and nitrogenous matters in
normal beetroot and in beetroot run
to seed, 569.
Pellet, H., and M. Liebschutz,
analysis of beet seed, 920.
Penfield, S. L., chemical composition
of amblygonite, 530.
composition of amblygonite, 96.
Perger, H. R. v., amidanthraquinone
from anthraquinonesulphonic acid,
49.
Perl, L., absorption of lime salts, 725.
Peroni. See Schiapparelli.
Personne, M., constitution and pro-
perties of dialysed iron, 356.
Petermann, A., composition of fowl's
dung, 345.
germinating power of beetroot
seeds, 177.
Norwegian phosphorite, 356.
on Belgian phosphorites, 198.
report on the agricultural value of
the so-called retrograde phosphoric
acid, 739.
Petermann, A., and others, agricul-
tural value of reduced and insoluble
phosphates, 571.
Peters, P., and K. Miiller, analysis of
a calculus from a horse, 174.
Petit, A., testing of j^epsin, 424.
Petit. See also Houdart.
Pettersson, O., and G. Ectstrand,
Meyer's method of determining va-
pour-densities, 841.
vapour-densities of anhydrous
and hydrated formic and acetic acids,
868.
Pettersson. See also Nilson.
Pfeiffer, E., pentahydrated calcium
carbonate, 789.
Pfliiger, E., quantitative estimation of
urea, 681.
Philipp, J., solidifying point of bro-
mine, 215.
Philipp, J., and P. Schwebel, tung-
sten bronze, 157.
Phipson, T. L., characin, 53.
notes on some analyses of waters,
62.
INDEX OF AUTHORS.
959
Phipson, T. L., palmellin and characiu
extracted from algae by water, 325.
preservation of solutions of palmel-
lin, 720.
Picard, J., modification of V.Meyer's
vapour- density apparatus, 743.
Piccini, A., testing for nitric acid in
presence of nitrous acid, 139.
Pictet. See Anchiitz.
Pinner, A., allyl cyanide and the pro-
ducts of its saponification, 99.
Pitkin, L., compound platinates and a
new platino-potaasium salt, 706.
Piutti, A., action of phosphorous pen-
tachloride on molybdic anhydride,
219.
Planchud, E., formation of sulphuret-
ted mineral waters, 709.
Planta- Reichenau. See Erlen-
nieyer.
Pluchet, Chili saltpetre for beets, 741.
Podwyszotzky, emetine, 720.
Poleck, T., water of the Oberbrunnen,
Flinsberg, Silesia, 226.
Polls, A., cubic alum and chrome alum,
444.
PoUacci, E., new method of ascertain-
ing the ripeness of grapes, 352.
Polstorff, K., action of benzoic chlo-
ride on morphine, 407.
action of potassium ferricyanide on
methylmorphine iodide, 409.
action of potassium ferricyanide on
morphine, 408.
Polstorff. Seealso Broockmann.
Pooley, T. A., analysis and composition
of English beers, 353.
Portele, C, researches on the ripening
of grapes and fruits, 178.
ripening of grapes, 336.
Portele. See also Lamek.
Posen, E., phenylactimide, 322.
Post, J., action of sulphuric acid on
phosphates, especially calcium phos-
phate, in connection with the mauu-
lacture of superphosphates, 425.
composition of the Weklon "man-
ganese mud" and some similar com-
pounds, 219, 368.
influence of nitro- and amido-
gi'oups on a sulphonic group entering
the benzene molecule, 238.
• spontaneous oxidation of manganese
oxide with reference to the manganese
recovery process, 73, 368.
Post, J., and E. Hardtung, sulphonic
acids from isomeric nitramido- and
dianiido-benzenes, 394.
Post, J., and L. Hoist, benzamido-
phenolsulpbonic acid, 642.
Post, J., and G-. Lunge, composition
of Weldon mud, 611.
Potilitzin, A., limits and velocities of
chemical reactions, 365.
mutual replacement of the halo-
gens, 365.
Pott, R., growth of legumes, 567.
Praetorius-Seidler, G., cvanimide,
370.
Precht, H., estimation of potassium as
platinochloride, 577.
volumetric estimation of sulphates,
576.
Prehn, A., and R. Hornberger, esti-
mation of the WUl and Yarrentrap
method of nitrogen determination,
348.
Preis, K., and B. Rayman, certain
dichromates, 444.
Preis. See also Rayman.
Prendel, R., the meteorite of Yavi-
lovka, 20.
Prescott, A. B., morphiometric pro-
cesses for opium, 191.
potassium and sodium aluminates,
84y.
silver ammonium oxide, 852.
valuation of tincture of opium, 193.
zinc oxide in alkaUne solution.
852.
Preusse, C, supposed presence of pyro-
catechol in plants, 417.
Preusse. See also Tiemann.
Pringsheim, chlorophyll, 560.
hypochlorin and its origin, 671.
Priwoznik, E., lead analyses, 772.
Prochazka. SeeEndemann.
Proctor, B. S., smoke of an electric
lamp, 81.
Prunier, adulteration of coffee with
chicory, 514.
Putte, P., germination of beet seeds,
730.
R.
Rabuteau, C, rnflu nee of ethyl iodide
on germination, 915.
Rammelsberg, C, vesbium and norwc-
gium, fill.
the mica group, 224, 614.
Raoult, F. M., freezing point of alco-
hohc liquids, 523.
Rath, G. v., crystal system of cyanite,
534.
pseudomorphs of calcite after ara-
gonite, 15.
Raumer, E. v., and C. Kellerinann,
lime in plant Hfe, 568.
960
INDEX OF AUTHORS.
Rajmann, B., and K. Preis, action
of iodine on aromatic compounds with.
long side chains, 463.
Raymaun. See also Preis.
Redwood, T., diffusire properties of
some preparations of iron, 768.
Re gel, E., on two varieties of the
Drosera, 820.
Regnault, J., andE. Hardy, action of
bleaching powder on propyl, butyl,
and amyl alcohol, 456.
Regnier, E., constant and powerful
voltaic pile, 686.
Reichardt, E., action of water on lead
piping, 198.
■ investigation of the composition of
soil from a graveyard, 920.
purification of refuse water, 830.
wild and cultivated raspberries.
936.
Reichardt, E., and others, decom-
position-products of sugar, 864.
Reichardt. See also Hiinefeld.
Reichc, H. v., two azobenzenedisulpho-
nic acids, 805.
Reichl, C, new class of phenol colours,
426.
Reineckc, and G. Meyer, estimation
of the decolorising power of animal
charcoal, 422.
Reinitzer, B., and H. Goldschmidt,
action of certain metals and non-
metals on phosphorus oxychloride,
609.
Reinke, J., and G. Berthold, dry
and wet rot in potatoes, 416.
Reiset, J., proportion of carbonic an-
hydride in the air, 605.
Remont, A., analysis of heavy mineral,
resin, and fatty oils, and of resin in
commercial oils. Part I, 683.
Remont. See also Riche.
Remsen, I., oxidation of sulphamine-
metatoluic acid, 473.
Remsen, I., and R. D. Coale, anhycb'o-
sidphonamideisophthalic acid, 258.
Remsen. See also Hall.
Renard, A., electrolysis of benzene,
802.
electrolysis of terebenthene, 479.
■ oxidation of alcohols by electro-
lysis, 24.
products of the distillation of colo-
pliony, 893.
Renk, F., permeability of soil for ah*
821.
Renner. See Zulkowski.
Rennie. See Wright.
Reverdin, F., and E. Nolting, the
a- and /3-positions in naphthalene,
379.
Reymann, S., a product obtained by
the action of aqua regia on orcinol,
645.
Reynaud, H., estimation of glycerol in
wine, 512.
Rhalis, M., orthobromobenzoic acid,
118.
Rieciardi, L., composition of the ashes
of the trunk, leaves, and fruit of the
orange and mandarin orange, 915.
Riccini. See Fileti.
Richard, A., bases of the pyridene
series, 480.
Riche, A., waters of Bourboule,
455.
Riche, A., and A. Remont, Bassia
longifolia, 519.
Richter, V. v., action of nitric acid
on epiclilorhydrin, 32.
synthesis of the closed benzene
ring, 37.
Richter, W., adulteration of malt
combings, 777.
Rickmann and Thomson, ammonia
from the nitrogen of the atmosphere
and the hydrogen of water, 767.
Ridolfi, L., manuring of field beans,
569.
Riebe, A., experiments on various
kinds of yeast, 833.
Riedel, C, constitution of nitrosodi-
methylmetatoluidine, 386.
Riedel. See also Wurster.
Riegler, W., permeation of vegetable
matter by water, 823.
Riemsdijk, A. D. v., flashing in assays
of gold, 693.
influence of superfusion on the
molecular arrangement of cupelled
gold, 773.
Riess, E. R., composition of eclogite,
16.
Rilliet. See Soret.
Rimpau, W., fertihsation of rye, 493.
R i 1 1 e r, cotton seed cake as fodder, 500.
Ritthausen, H., albuminoids of
various oily seeds, 676.
Rjabinin, methyl and ethyl ethers of
diallylcarbinol, 372.
Roberts, W. B., action of lime on
silica in mortar, 216.
Roberts, W. C, analogy between the
conductivity for heat and the induc-
tion balance efleet of copper-tin alloys,
687.
Roc ho 11, H., separation of silicic anhy-
dride in the analysis of limestone,
iron ores, and other minerals, 745.
Roeques, X., action of water on zinc
and lead, 766.
Rodiczky, E. t., culture of the lentil
vetch, 500.
Rodwell, G. F., and H. M. Elder,
IXDEX OF AUTHORS.
961
effect of heat^ on mercury dioxide,
443.
R 6 h r, production of sugar from starch,
932.
Roemer. See Schunck.
Rosch. See Wein.
Rossler, C, use of copper phosphide
in the refining of copper, 197.
volumetric estimation of man-
ganese and cobalt, 347.
Rogalski, analyses of chlorophyll, 561.
Rogen, A. E. y., experiments on the
growth of hyacinths, 922.
Rogen, A. E. v., and Krelage, mineral
constituents of hyacinths, 58.
Rohn. See Wagner.
Rosenberg, J. O., nitrosothioferrates, 9.
Rosenfeld, M., lecture experiments,
846.
two new basic copper chromates,
853.
Rosenstiehl, A., constitution of rosa-
nihne salts, 553.
Rosenthal, I., specific heat of animal
tissues, 483.
Roser. See Fischer and Wurster.
Rosieki, J., resorcinol-isosuccinein,
385.
Ross, W. A., new blowpipe test for
phosphoric acid, 746.
Rossetti, F., thermal absorption and
emission of flames and tlie tempera-
ture of the electric arc, 206.
Roster, G-., lithobilic acid, 270.
lithofellic acid and some litho-
fellates, 131.
new method of determining the
fusing points of organic substances,
419.
Rother, R., calcium phosphite, 5.
Rotondi, E., aeration of must, 931.
ash of different parts of the vine,
133.
Rotondi, E., and A. G-alimberti,
action of various manures on the com-
position of the must, 507.
composition of leaves of dis-
eased vines, 416.
composition of must at dif-
ferent stages of ripeness of the grape,
425.
Rotondi, E., and A. Ghizzoni, re-
searches on the bleeding of vines, 133.
Rubner, M., absorption of various
elementary materials in the human
intestinal canal, 563.
composition of curds, 934.
nutritive value of fluid meat, 904.
Rudneff, W., amines containing ter-
tiary radicles, 545.
thiocarbimides with tertiary
radicles, 548.
Rudorff, F., estimation of aqueous
vapour in the atmosphere, 420.
Rudolph, C, action of ferric chloride
on orthamidobenzene, 162.
action of nascent hydrogen on
orthonitrobenzaldehyde, 469.
Riicker, A. W., suggestion as to the
constitution of chlorine offered by the
dynamical theory of gases, 692.
Riigheimer. See Ladenburg.
s.
Saarbach, L., action of phenols on
halogen-substituted fatty acids, 392.
Saare. See Weigelt.
Sabatier, P., thenuochemical study of
ammonium polysulphide and hydrogen
persulphide, 690.
thermochemical study of sulphides
of the earth metals, 523.
thermochemical study of the alka-
line polysulphides, 689.
Sachs, F., sap-quotient of beet, 931.
Sadebeck, A., crystal-tectonic of sil-
ver, 613.
two regular intergrowths of differ-
ent minerals, 855.
Salethe. See Michler.
Salkowski, bf., arsenates of zinc and
cadmium, 216.
parahydroxyphenylacetic acid, 252.
Salkowski, E. and H., putrefaction-
products of albumin, 413.
Salomon, F., determination of the acid
in sugar of lead and in lead vinegar,
189.
Salomon, G-., hvpoxanthine from albu-
minoid bodies, 897.
S a m e k, cacao rind as fodder for calves,
502.
Santos, J. R., volcanic ash from Coto-
paxi, 97.
Sarauvv, bromine derivatives of qui-
none, 385.
Sarrau and Vieille, researches on the
decomposition of certain explosives,
780.
Sauer. See Staedel.
Saytzef f. A., constitution of the reduc-
tion product of succinic chloride, 712.
Scacchi, A., examination of the yellow
incrustation on the Vesuvian lava of
1631 ; vesbium, 445.
Schiippi. See Lunge.
S chaffer. See Nencki.
Scharff, F., step-like and skeleton
growth of some regular crystals, 529.
Scheibe. See Wurste-r.
9G2
INDEX OF AUTHORS.
Scheiblev, C, occurrence of Tanillin
m certain kinds of raw beetroot sugar,
467.
Sell ei bier, C, and others, Scheibler's
new process for the determination of
sugar in beet, 587.
Schenk-Bauliof, proper tliickness and
depth to sow corn, 181.
Scherer. See Medicus.
Scheurfir-Kestner, action of sul-
phuric acid on platinupi, 706.
■ digestive ferment produced during
panification, 776.
Schiapjiarelli, C, and G. Peroni,
some ingredients of normal urine,
907.
Schicht, L., electrolytic determination
of metals, 747.
Schiff, H., colouring matters from fur-
furaldehyde, 391.
— constitution of ellagic acid, 43.
' determination of niti'ogen, 679.
digallic acid, 551.
estimation of acetyl by means of
magnesia, 67.
■ formation of complex glucosides,
126.
Schiff, H., and F. Masino, the iso-
meric nitrosalicylic acid, 121.
Schiff, R., action of zinc chloride on
bromo-camphor, 892.
bromo-, nitro-, and amido-camphor,
891.
constitution of bromo-camphor,
892.
piperidine, 127.
Schiff, R., and S. Speciale, action of
potassium cyanide on ammoniacal
derivatives of chloral, 102.
S c h i r o k o f f, ,8-dipropyl- and /S-diethy-
lenelactic acid ; oxidation of allyl-
dimethyl carbinol and diallvl carbinol,
382.
S c h i s c h k o f f, L., chemical composition
of milk, 273.
Schlagenhauffen. See Oberlin.
Schleirmacher, A., condensation of a
liquid at the wet surface of a solid,
363.
Schlickum, C, new alkalimetrical
method for estimating phosphoric
acid, 824.
Schloessing, V., and A. Muntz,
nitrification, 277.
Schmidt, A., digestion of albuminoids,
484.
Schmidt, E., daturine, 481.
Schmidt, F., and others, determination
of the fat in milk by the lactobutyro-
meter, 352,
Schmidt, G-., relative space occupied
by gases, 87.
Schmidt, H., preparation of glyceryl
triacetate, 312.
Schmidt. See also Musso.
Schmitz, A., physiological influence of
adulterated wine, 174.
Schnauss, T., silver bromide gelatin
emulsion, 929.
Schneider, Gr. H., inversion of ordi-
nary malic acid, 629.
Schneider, R., behaviour of bismuth
containing arsenic towards nitric acid,
and the preparation of basic bismuth
nitrate free from arsenic, 219.
Sclinorrenpfeil, F., results with stall
feeding of sheep, 503.
Schobig. See Wurster.
Scliof fel, R., estimation of chromium
and tungsten in steel and in their
alloys with iron, 288.
Sell one, E., action of potassium iodide
on hydrogen peroxide, 606.
composition of hjdrated barium
dioxide, 610.
— decomposition of hydrogen perox-
ide in presence of alkalis and alkaline
earths, 606.
Schorlemmer, C, normal paraffins,
158.
Schrauf, A., feuerblende from Chanar-
cillo, 856.
Sohreib, H., orthochlorubenzpara-
toluide and its derivatives, 557.
Schreiner, L., action of ethyl chloro-
carbonate on amines, 311.
Schrodt, M., and P. du Roi, experi-
ments with skimming by the Schwartz
and Holstein systems, 934.
whole milk butter compared
with cream-butter, 932. ,
S c h r o d t. See also W e i s k e.
Schroder, H., molecular volumes of
solid carbon compounds, 694,
specific gravities of solid organic
compounds, 21.
Schroder, -T., amount of nitrogen in
forest trees and in the under litter of
leaves, 506.
constitution of frozen beech-leaves,
416.
course of the nitrogen and mineral
constituents in the development of the
early shoots, 335.
injury to vegetation caused by acid
gases, 496.
mineral constituents of fir and
birch, 343.
Schr otter, H., bases from fusel oil,
234.
Schubse, E., estimation of non-albu-
minoid nitrogen in fodder, 588.
Schubeler, influence of continuous
sunlight on plants, 911.
INDEX OF AUTHORS.
963
Schiitzenbcrger, P., silicon nitride,
153.
Schultz, A., antiseptic action of sali-
cylic acid, 515.
Schultz, Gr., constitution of phenan-
threne, 814.
Schultz, H. C. E., E. Wildt, and
others, poisoning of sheep by lupines,
57.
Schultz. See also LcTv.
Schultze, "VV., testing malt, 71.
Schulz, H. C, alkaloid of Lupinus
luteus, 416.
Schulz. See H. Schulze.
Schulze, E., decomposition of albu-
minoids in plants, 493.
■ estimation of albuminoids and non-
albuminoid nitrogen compounds in
Tarious kinds of fodder, 764.
Schulze, E., and J. Barbieri, decom-
position of albuminoids in pumpkin
sprouts, 180.
leucine and tyrosine in pota-
toes, 342.
■ suint, 520.
Schulze, r., estimation of sugar-beet
and the amount of sugar the roots
contain, 586.
Schulze, H., lecture experiment, 366.
oxidation of haloid salts, 436.
Schulze, H., R. Friihling, and J.
Schulz, quality of milk, 352.
Schulze, W., malt extract and maltose
in beer-mash, 776.
— — moisture in malting barley, 776.
Schulze. See also Wallach.
S c h u n c k, E., chlorophyll from Eucalyp-
tus globulus, 894.
Schunck, E., and H. Roemer, detec-
tion of alizarin, iso- and flavo-purpurin,
and the estimation of alizarin, 424.
Schuster, A., specti-a of metalloids;
spectrum of oxygen, 430.
Schutz. See Binz.
Schwarz, A. v., peaty soils, 182.
Schwarz, H., homofluorescein, a new
colouring-matter from orcinol, 551.
Schwebel. See Philipp.
Sch werin-Putzar, manuring experi-
ments with superphosphate and Chili
saltpetre, 507.
Seegen, J., and F. Kratschmer, for-
mation of sugar in the hver, 905.
nature of the sugar in the
liver, 866.
Seegen, J., and J. ISTowak, gaseous
nitrogen, a product of the decomposi-
tion of albuminoids in the body,
272.
Seelheim, F., volatility of platinum in
chlorine, 94.
Seidel, O., salts of plumbic acid, 94.
Selini, F., alkaloids from the decom-
position of albumin, 898.
Sella, Q., crystalline form of Sardinia7i
anglesite, 96.
Selmi, A., and others, lupine seeds as a
manure, 507.
Semljani^in, allylmethylpropyl car-
binol, 372.
Sendtner. See Wurster.
Sestini, F., estimation of albuminoids
in fodders, 190.
physico-chemical analysis of clay
soils, 511.
saculraic acid and saculmin, 865.
some neutral ammonium salts,
citrate, phosphate, and photosanto-
nate, 104.
— — ulmic compounds formed from
sugar by the action of acids, 538.
Setschenow, J., respiration under re-
duced pressures, 903.
Shull, D. F., Erijthroxi/lon coca, 411.
Sieber, X., antiseptic action of acids, 72.
supposed conversion of albumin
into fat in the ripening of Roquefort
cheese, 835,
Siebold, L., specific gravity of liquids,
61.
■ testing drugs, 71.
Siedamgrotzky and Y. Hofmeis-
ter, influence of lactic acid in fodder,
905.
Siemens, W., electric conductivity of
carbon as affected by temperature, 837.
Siemenski. See Anschiitz.
Siepermann. See Staedel.
Siewert, estimation of starch in pota-
toes, 512.
Silva, R. D., synthesis of diphcnylpro-
pane ; new method of forming di-
benzyl, 259
Simon, S. E., combinations of lithium
and magnesium chloride with alcohols,
310.
Simpson, M., action of acetic chloride
on valeraldeliyde, 459.
compound of calcium iodide with
silver iodide, 442.
direct formation of the chlorobro-
mides of the olefines and other un-
saturated compounds, 456.
Singer, M., bleaching of jute, 200.
Si vers, M. v., nitrogen in turf, 344.
Sjogren, A., occurrence of manganese
in Nordmark's mine, Werraland, 15.
Sjogren, H., bismuth minerals from
Xorberg's mine, Wermland, 14.
Skraup, Z. H., constitution of cincho-
nine and cinchonidine, 409.
homocinchonidine, 270.
Sloan, B. E., rock salt from Saltvtlle,
95.
964
INDEX OF AUTHORS.
SI 0 cum, F. L., fruit of Adansonia
digitata, 836.
Smith, E. C, magnetite, 95.
Smith, E. F., a new base, 387.
Smith, E. F.,ancl G. R. Peiree, nitra-
tion of metachlorosalicjlic acid, 392.
Smitli, R. A., measurement of the
actinism of the sun's rajs and of dav-
lio;ht, 685.
• report on the treatment of sewaee,
767. ^
S m i t h , W. , synthesis of phenylnapbtha-
lene, 125, 261.
Smorawski, S., fusion of rhamnetin
with potash, 53.
Sommerkorn, H., determination of
the specific gravity of liquids, 419.
new method of taking the specific
gravity of liquids, 743.
Soret, J. L., spectra of the earths of
the yttria-group, 7.
Soret, J. L., and A. Rilliet, ultra-
Tiolet absoqjtion spectra of ethereal
salts of nitric and nitrous acids,
202.
Sorokin, W., constitution of diallvl,
370. ^
formation of /3-methyloxyglutaric
acid from diallylmethylcaVbinol, 383.
Southby, E. K., examination of the
effect of hard and soft water on the
br.wing of beer, 593.
South worth, R. J., relation of the
volumes of solutions of hydrated salts
to their composition, 212.
Soxhlet, F., behaviour of various sugars
with alkaline copper and mercury
solutions, 758.
Soxhlet, F., and others, behaviour of
various sugars with Fehling's solution,
65.
Soxhlet. See also Moser.
Soyka, J., rapidity of germ diffusion in
the air, 515.
Speciale, S., the lavas of the volcanos
of Ernici in the Valle del Sacco
(Rome), 226.
Speciale. See also Schiff.
S peer, relation of the grasses of mea-
dows and pastures, 498.
Spica, P., amines con-esponding with
a-toluic alcohol, 241.
cumenesulphonic acid and a new
cumol, 166.
cymenesulphonic acids, 890.
cumophenols, 882.
— ^~ process for simultaneously detect-
ing nitrogen, sulphur, and cliloriue in
organic compounds, 348.
Saturej a Juliana, 128.
thymoglycollic acids, 888.
Spica. See also Paternd.
Spitzer, F. V., camphor chlorides, 717.
Spitzer. See also Kachler.
Spring, W., new basic salts of mercuric
sulphide, 157.
non-existence of pentathionic acid.
215,367.
Staats, G., ortho- and para-toluidine
derivatives, 386.
Staedel, W., vapour-tension of the
halogen derivatives of ethane, 618.
Staedel, W., and G. Damm, bromo-
nitro- and broraamido-anisoil, 641.
Staedel, W., and F. Kleinschmidt,
isoindole, 659.
Staedel, W., and E. Sauer, dioxy-
benzophenone, 646.
Staedel, W., and O. Siepermann,
new synthesis of organic bases con-
taining oxygen, 639.
Stammer, R., valuation of raw sugar,
520. °
Stammer. See also Wichelhaus.
Staubesand. See Waldner.
Stebbins, F., some azo-derivatives,
389.
Stebbins, J. H., action of benzotrichlo-
ride on ])rimary amines, 880.
■ colouring matters produced by the
action of diazo-compounds on phenols,
880.
new azo-colours, 715.
S tec her, thirty-eighth year of a farm
without stable manure, 741.
Stefan, J., diffusion of hquids, 364.
Stein, G., the acid of Drosera inter-
media, 36.
Stevenson, A. F., resins contained in
jalap, 717.
Stillman, J. M., ethereal oil from the
Californian bay-tree, 670.
Stiutzing, R., carbonic anhydride from
muscle, 330.
Stock, W. F. K., behaviour of copper
ammonium chloride with ferrous sul-
phide, 12.
Stohr, A., chlorophyll in the epidermis
of foliage of phanerogams, 910.
Stolba, F., volumetric determination
of cerium, 749.
S torch, v., examination of Danish
export cheese, 934.
Storer, F. H., and J. A. Henshaw,
the shells of crabs, oysters, mussels,
dkc, as manure, 60.
Storer, F. II., and S. Lewis, calcium
carbonate in water filtered tlirough
dry soil, 59.
Storer, J. U., fermentation theory of
nitrification, 909.
Strecker. See Lippmann.
Strenz, A., mineralogical notes on the
ores of Chanarcillo, North Chili, 301.
INDEX OF AUTHORS.
965
Strieker. See Wallach.
Stromeyer. See Hiibner.
Striiver, J., polysynthetieal twin-
crystals of oriental spineUe, 14.
Stiirtz, B., pliosphorescence, 598.
Stiisser. See Glaus.
Stumpf, M., influence of steaming on
starch, 834.
Stutzer, A., protein compounds, 676.
Suida, W., action of oxalic acid on
cai'bazol, 245.
Szymanski. SeeBernthsen.
Tacchini, presence of iron in the dust
showers of Sicily and Italy, 709.
Tamm, A., gases from the Bessemer
converters, 769.
Tanatar, S., maleic acid fi*om dichlor-
acetic acid, 35.
maleic and malic acids from
a-dibromopropionic acid, 374.
preparation of pure dioxyfumaric
acid, 383.
trioxymaleic acid, 875.
Tanret, C, alkaloids of the pomegra-
nate, 481.
Tappeiner, H., oxidation of cholic
acid, 55.
Tatarinoff, P., action of cyanamide
on dimethylamine hydrochloride, 233.
Tatlock, E. E., nitric nitrogen in
guano, 68.
Tattersall, T., tests for alkaloids, 763.
Tawildaroff, some reactions of acro-
lein and glycerol, 235.
Teclu, N., red antimony, 612.
Terrell, A., and A. Wolff, resin from
rose-wood, 559.
Testa, A., action of potash on ethyl
isochlorobutyrate, 870.
Testa. See also Balbiano.
Thaer, A., manuring experiments on
wheat and rye, 508.
Thalen, E.,"^ bright-line spectrum of
scandium, 685.
Than, C. t., action of phenol vapour on
organic matter at high temperatures,
72.
six lecture experiments, 212.
Thdrner, W., new organic acid in
Agaricus integer, 4A>.
on the quinone occurring in Aga-
ricus atraiome}2fosus, 47.
Thorner, W., and T. Zincke, pina-
cones and pinacolins, 646.
Thompson. See Claisen and Kick-
man.
Thoms, Gr., analyses of feeding stuffs,
343.
analysis of concretions taken from
an abscess in the jawbone of a horse,
333,
ash analyses, 343.
Thomson, G. C., decomposition of the
substitution-products of the lower
fatty acids by water, 379.
Thoms en, J., allotrojDic modifications
of hydrogen, 89.
constitution of isomeric hydrocar-
bons, 840.
heat of combustion of sulphur, 785.
heat of formation of ammonia, of
the oxides of nitrogen, and of the
nitrates, 603.
heat of formation of cuprous chlo-
ride, 361.
heat of formation of cyanogen, 361.
on the carbonates, 361.
thermochemical investigation of
the oxides and acids of nitrogen, 81.
thermochemical investigation of
the theorv of the carbon compounds,
785.
thermochemical research on the
carbonates, 82.
thermochemical researches, 363.
thermochemical researches on
cyanogen and hydrocyanic acid, 840.
thermochemistry of the oxides of
nitrogen, 689.
Thresh, J. C., detection of bismuth,
752.
determination of the alkaloids,
763.
preparation of potassium bismutJi
iodide, 705.
soluble essence of ginger, 359.
Tibiri(;a. See Merz.
Tieghem, P. v., gelatinous matter in
beets, 908.
the butvric ferment in the carboni-
ferous period, 334.
Tiemann, F., and L. Friedlander,
aromatic amido-acids, 473.
Tiemann, F., and C. Preusse, me-
thods for indicating the presence of
organic matter in water, 290.
quantitative estimation of
oxygen dissolved in water, 137.
Tiemann. See also Baumann.
Tollens. See Di eek and G-rupe.
Tomlinson, C, supersaturated sahne
solutions, 438.
Tommasi, D., isomeric modification of
aluminium hydrate, 849.
non-existence of nascent hydrogen,
2.
reduction of gold chloride by hy-
drogen in presence of platinum, 705.
966
IXDEX OF AUTHORS.
Trachsel, E., extension of Dietrich's
table for the calculation of nitrogen,
346.
Tribe. See Gladstone.
Tripke, P., note on the Silesian basalts
and their mineral constituents, 19.
T roost, L., density of iodine vapour,
695.
Troost. See also Devi lie.
T s c h a p 1 o \v i t z, F., determination of
dry substances by the use of alcohol,
351.
ripening of apples after gathering,
179.
Tsehelzaff, determination of nitrogen
in explosive ethereal nitrates, 355.
Tschermak, G., the meteorite of
Grrosnaja, 20.
the micas, 532.
Tscherniak, J., spontaneous decompo-
sition of dichlorethylamine, 311.
Tschirwinsky, N., influence of gly-
cerol on the decomposition of prote'ids
in the animal body, 817.
Tugolessoff, the hydrocarbon CjoHig
from diamyleue, 231.
u.
L'lbricht, K., must and wine analysis,
586.
Parkes' method of estimating cop-
per, 510.
seeds of the corn-cockle as fodder
and as distillery material, 501 .
Ullik, F., application of natural pro-
ducts as manures, 417.
Urech, F., action of certain reagents
on paraisobutaldehyde, 103.
action of potassium carbonate on
isobutaldehyde, 103.
action of potassium carbonate on
isobutyl alcohol, 538.
polymerides of isobutaldehyde,
104.
— reactions of acetone with potassium
cyanide, thiocyanate, and aqueous
hydi'ochloric acid, 545.
— - vapour-density of the viscous po-
lymeride of isobutaldehyde, 620.
V.
Vander Ploeg, B. J., calcium oxalate
in plants, 914.
Vangel, B., action of dehydrating sub-
stances on organic acids, 459.
Varenne, L., passive state of iron,
211.
Vautelet, E., disinfection and preser-
vation of animal matters, such as
blood, for agricultural purposes, 929.
Venables, F. P., hvingstonite, 95.
mul ual relations of potassium and
sodium alums in aqueous solutions,
83.
tungsten manganese bronze, 199.
Yerneuil and Bourgeois, artificial
jiroduction of seorodite, 613.
Vesque, J., influence of salts on the
absorption of water by roots, 911.
Vibraus, O., manuring of beetroot,
137.
Vieille. See Sarrau.
Yieth, P., estimation of fat in milk,
761.
Vieth. See also Fleischmanir.
Vignan, L., and J. B. Boasson, two
new dye-stuffs, 717.
Villiers, A., crystallised oxalic acid,
544.
etherification of hydriodic and hy-
drochloric acids, 711.
etherification of sulphuric acid,
796.
prejiaration of neutral ethyl sul-
phate, 797.
Viliuorin, L., cultivation of beetroot,
821.
Vincent, C, calcination of beetroot
molasses, 233.
Vincent, C, and Delachanal, com-
bination of allyl alcohol with baryta,
794.
some properties of mixtures
of methyl cyanide with ethyl and
methyl alcohols, 524.
Vines, S. H., chemical composition of
ale urone- grains, 483.
VioUc, J., specific heats and melting
points of the refractory metals, 149.
Vitali, D., on blood stains, 926.
Voelcker, A., analyses of manures and
of cattle foods, 678.
bat-guano from various sources,
345.
comparative value of soluble and
insoluble phosphates^ 678.
four-yearly rotation of crops, 185.
Voeltzkow. See Li ebermann.
Vogel, H., analysis of milk, 828.
Vogel, H. W., new hydrogen lines, and
the dissociation of calcium, 597.
■- photochemical behaviour of silver
bromide in presence of gelatin, 837.
Volhard, J., estimation and separation
of manganese, 141.
Volta, A., action of ozone on some
noble metals, 205.
IXDEX OF AUTHORS.
967
Vorster, F., preparation of phospho-
rite, 356.
Vortmann, G-., detection and estima-
tion of chlorine in presence of iodine
and bromine, 509.
Vrij, J. E. de, the form in which the
cinchona alkaloids occur in the bark,
898.
Vulpius, detection of paralbumin, 829.
w.
Wachtel, A. v., adulteration of bone
meal with phosphorite, 516.
—— gypsum in the manufacture of
sugar, 834.
■ Sorghum saccharatum, 932.
Wachter. SeeNessler.
Wagner, A., formation of nitric oxide
by ignition of nitre, 574.
reduction of carbonic anhydride
to carbonic oxide by red-hot stannous
oxide, 574.
Wagner, P., beetroot, 495.
estimation of fat in fodder, 762.
■ influence of the physical condition
of superphosphate on its value, 60.
Wagner, P., and Gr. Drechsler,
manuring experiments, 922.
Wagner, P., and W. Rohn, experi-
ments on the manuring of barley, 13.).
■ on the quantities of acid and
sugar in grapes cut at various stages
of their growth, 179.
potato culture, 919.
Wagner, R., estimation of proteins in
fodder, 588.
dephosphorisation of pig-iron, 593.
Wagner. See also Emmerling.
Waldner and Staubesand, manur-
ing experiments on moorland, 923.
Wallach, O., dichloraerylic acid, 799.
remarks on the preceding papers,
548.
thiamides, 556.
Wallach, O., and L. Belli, conversion
of azoxybenzene into oxyazobenzene,
556.
Wallach, 0., and I. Kamenski, for-
mation of bases from acid amides,
547.
Wallach, 0., and A. Liebmann,
action of alcohols and phenols on
amide chlorides, 557.
Wallach, C, and E. Schulze, bases
of the oxalic acid series, 547.
Wallach, O., and G. Strieker, oxal-
ethyliue and chloroxalallyliue, 546.
Wallace, W., a peculiar water, 591.
condition in which sulphur exists
in coal, 708.
heating powers of coal-gas of dif-
ferent qualities, 766.
Wallin. See Claesson.
Walton. See Mills.
Wanklyn, J. A., and W. J. Cooper,
products of the oxidation of wool:
cyanopropionic acid, 460.
Wartha, V., analysis of wine, 680.
method for dctcrmininjj the tem-
porary hardness of water, 923.
Weber, C. A., energy of assimilation in
plants, 910.
Weber, R., analyses of soils from the
Bunter sandstone formation, 281.
Weddige, A., ethylene derivatives of
phenyl and salicylic acid, 316.
We id el, H., compounds from animal
tar, 267.
Weidel, H., and G. L. Ciamician,
compounds in animal tar, 403.
Weigelt, C, injury to fishes by waste
liquids, 490.
influence of varying pressures on
grape must and wine, 358.
picking of grapes, 517.
Weigelt, C, and O. Saare, clearing
action of Spanish earth, 517.
time of first drawing of wine,
517. ^
Weigert, L., detection of salicylic
acid in wine and in fruit juices, 352.
We in, E., condensed milk, 926.
cultivation of the yellow lupine,
736.
superphosphate from pure trical-
cium phosphate, 141.
Wein, E., L. Rosch, and J. Leh-
mann, analysis of superphosphates,
140.
Wein. See also Maercker.
Weisbach, A., sulphides of silver, 14.
Weiske, H., assimilation in sheep of
various ages, 724.
digestive power of geese for fibrin,
330.
influence of shearing on yield of
milk, 487.
Weiske, H., and others, composition of
red clover and maize, 499.
digestibility and nutritive
power of caroba beans, 563.
• digestibility and nutritive
value of acorns, 820.
digestibility and nutritive
value of the soja bean, 501.
nutritive value of asparagine,
330, 485.
spent hops as fodder, 502.
Weiske, H. M. Schrodt, and B.
^68
INDEX OF AUTHORS.
Dehmel, influence of fodder on the
quantity and quality of milk fat,
184.
Weith. SeeMerz.
Werkowitsch, C, and t. Zlenze,
taking samples of milk, 828.
Werner, H., vaseline, 930.
Wernich, effect of putrefactire changes
on bacteria, 726.
estimation of
Westmoreland, W.,
carbon in steel, 751.
Wetzig, B., recent improTements in the
iodine industry, 195.
Weyl, T.,andB. v. Anrep, formation of
hippuric acid in the animal organism
during fever, 716.
carbonvl-hBemoglobin, 816.
Weyl, T., and Bischoff, gluten, 482.
Wli i t e. See Jackson.
Whitney, H. C, apiol, 412.
Wichelhaus, H., formula of quin-
hvdrone, 41.
Wichelhaus, H., K. Eisf eld, and X.
Stammer, experiments with Scheib-
ler's method of analysing raw sugar,
144.
Widmann, O., action of chlorine on
chloronaphtlialene ; nitro - derivatives
of a- and /3-dicliloronaphthalene, 47.
action of chlorine on naphthalene
a-sulpbonic chloride ; X-trichloronaph-
thalene, 167.
dichloronaphthalene-a-sulphonic
acid, 168.
metatoluidine, 635.
Wiebe, H. F., absolute expansion of
liquid and sohd bodies, 88.
expansion and molecular volumes
of Uquid organic compounds, 784.
specific heat and expansion of the
solid elements, 783.
Wiedemann, E., phosphorescence pro-
duced by electrical discharges, 204.
Wigner. "G. W., analysis of various
tinned foods, 594.
coefficient of expansion of butter,
lard, fats, &c., 70.
determination of carbonic acid in
carbonates, 316.
Koettetorfer's process for butter
analysis, 69.
Wign'er, Gt. W., and A. Church,
analysis of two ancient samples of
butter, 357.
Wildt, E., methods proposed for
cleansing lupines, 820.
Wildt, E., and others, Symphytum as-
perrimum as a fodder, 735.
Wildt. See alBO Schultz.
Wiley, H. W., detection of hydrochlo-
ric acid by sidphuvic acid and potas-
sium dichromate, 744.
Will, H., and A. Laubenheimer,
the glucoside from white mustard
seed, 265.
Willgerodt, C, a-dinitrophenyl ether,
642.
Willm, E., composition of the waters
of Cransac (Aveyron), 454.
^ ferruginous and nitrated mineral
waters, 617.
minei-al waters of Bussang (Vosges),
455.
Willm, T., estimation of chromium,
188.
chemistry of the platinum metals,
854.
Willotte, H., law of Dulong and
Petit applied to perfect gases, 83.
Wimmel. See Claus.
Winkel, experiments on churning,
75.
Winkelmann, A., relations between
the pressures, temperatures, and den-
sities of saturated vapours, 692.
Winogradoff, W., action of alumi-
nium chloride on acetic chloride,
236.
Wisclmegradsky, collidine from
aldehyde, 54.
Wisclmegradsky, A., some deriva-
tives of cinchonine, 269.
Witt elsh ofer. P., analysis of mate-
rials used for fodder, 183.
Wittich. See Birnbaum.
Witz, A., a new air thermometer, 783.
Wohler, F., an aluminium battery,
838.
Wolff, E. v., beet-sugar refuse as
manure, 742.
fattening animals, 173.
Wolff, E. v., W. v. Funke, and G.
D i 1 1 m a n n, feeding experiments with
pigs, 415.
Wolff, E. v., and others, assimilation
of ordinary horse fodder, 173.
digestibility of oatstraw, hay,
and pea-haulms, 916.
digestion in sheep, 484.
digestion of food by the horse
when at work, 414.
feeding experiments on swine,
724.
■ niitritive value of grass at
various stages of growth, 329.
Wolff, J., aniline blacks, 76.
separation of fats from soaps, 587.
transfen-ing Lightfoot-black from
one fibre to another, 75.
Wolff. See also Terreil.
Wolffhiigel, G., amount of carbonic
anhydride in shingle, 181.
Wolfram, G-., preparation of perbromic
acid, 91.
INDEX OF AUTHORS.
9(39
Wo liny, E., estimation of the value of
grain, 594.
■ fallowing, 736.
grass mowing, 498.
influence of shade on the amount
of carbonic anhydride in the air of the
soil, 823.
result of drying seeds, 493.
Wollny, E., and others, damage to
pea and bean seeds by weevil, 919.
Wortmann, J., intramolecular re-
spiration of plants, 911.
Wright, C. R. A., and E. H. Rennie;
determination of chemical affinity in
terms of electromotive force, 686.
Wroblewsky, separation of ortho-
xylene from its isomerides, 240.
Wiist, comparison of various milk
coolers, 357.
Wurm, E., formation of vinegar by
bacteria, 334.
Wurster, C., colouring matters ob-
tained by the oxidation of di- and
tetra - methylparaphenylenediamiue,
111.
Wurster, C, and A. Reran, action of
nitric acid on tribromobenzene, 106.
parabromodimethylaniline,
108.
Wurster, C, and H. F. Morley, te-
tramethylmetaphenylenediamine, 111.
Wurster, C, and C. Riedel, di-
methylmetatoluidine ' derivatives, 109.
Wurster, C, and L. Roser, ferro-and
ferricyanides of certain tertiary bases,
98.
Wurster, C, and A. Scheibe, bromo-
dimethylaniline, 107.
Wurster, C, and E. Schobig, action
of oxidising agents on tetramethyl-
paraphenylenediaraine, 111.
Wurster, C, and R. Sendtner, di-
methylparaphenylenediamine deri-
vatives, 110.
Wurtz, A., copper hydride, 299.
heat of formation of chloral
hydrate, 293, 604.
reply to Berthelot on the heat of
formation of chloral hydrate, 435.
temperature of the decomposition
of vapours, 293.
Wyroubof f, G., note on platinum thio-
cyanate, 618.
Y.
Young, W. C, oxidation of sulphur in.
gas on combustion, 355.
z.
Zander, O., amidobenzenedisulphonic
acids, 122.
Zecchini. See Cossa.
Zetter. See Merz.
Ziegler, J., some compoimds of the
leuco-base fromcuminol and dimethyl-
aniline, 640.
Ziegler, A., and W. Kelbe, synthesis
of metisopropyltohiene, 877.
Ziegler. See also Fischer.
Zimmermann, C, separation of the
heavy metals of the ammonium sul-
phide group, 188.
Zimmermann, J., phenylbetaine or
dimethylphenylglycocol, 162.
Zincke, T., action of ammonia and
amines on quinones, 48.
compounds of the hydrobenzo'iu
and stilbene series, 114.
physical isomerism with special
reference to hydro- and isohydro-ben-
zoin, 118.
Zincke. See also Breuer and
Thorner.
Zoebl, A., sulphurous acid as a remedy
for bunt in wheat, 572.
ZoUer, P., globulin-substance in pota-
toes, 722.
xanthic acid as a precipitant for
albumin, 765.
Zorn, W., new method of forming
hyponitrites and hydi-oxylamine, 4.
Zublin. See Meyer.
Zulkowski, C, and Q-. Renner, com-
position of diastase and beet mucilage,
561.
Zulkowski, K., action of glycerol on
starch, 865.
modification of Dumas' method
for estimating nitrogen, 753.
VOL. XXXVIII.
V
INDEX OF SUBJECTS.
ABSTRACTS. 1880.
A.
Abietic acid, 264, 670.
Absorption of food, 414.
of gases by liquids, 525.
of oxygen and expiration of car-
bonic anhydride, by plants, 41€.
of the ultra-violet rays of the
spectrum by organic substances, 430.
Absorptive power of soil-constituents for
gases, 134.
Aeetal, method of producing, 458.
Acetaldehyde-amiuouia and hydrocyanic
acid, nitrils from, 313.
Acetamide, cldor-, action of potassium
«yanide on, 103.
dichlor-, 102.
Acelanilide, brom-, crystalline form ^of,
105.
monochlor-, 547.
trichlor-, action
pentachloride on, 547.
Acetaniside, 641.
dinitro-, 641.
of phosphorus
of
of
phosphorus
phosphorus
Acetethylamide, action
pentachloride on, 547.
dichlor-, action
pentachloride on, 547.
trichlor-, 547.
trichlor-, action of phosphorus
pentachloride on, 547-
Acetic acid, action of potassium dichro-
niate on, 160.
action of titanium tetrachlo-
ride, stannic chloride, and .antimony
pentachloride on, 460.
electrolysis of, 27.
influence of, on the sej)aration
of iron as basic acetate from manga-
nese, zinc, cobalt, and nickel, 289.
. transformation of, into gly-
collic acid, 32.
anhydrous
and
hydrated,
vapour-density of, 868.
chlor-, decomposition of, hy
water, 379.
dichlor-, maleic acid from, 35.
monochlor-, action of euge-
Acetic acid series, rate of substitution by
bromine in, 539.
series, double salts of the
lower members of, 799.
Acetic anhydride, action of titanium
tetrachloride, stannic chloride, and
antimony pentachloride on, 460.
Acetic chloride, action of aluminium
chloride on, 236.
compound of titanium tetra-
chloride with, 624.
Acetmethylauilide, 548.
Acetobenzoic anhydride, action of chlo-
rine and hydrochloric acid on, 550.
Acetol, 867.
Acetoluides, crystalline form of, 106.
Acetone, action of ethylamine and di-
ethvlamine on, 868.
alcohol of, 867.
quantitative estimation of, in
methyl alcohol, 826.
reaction of, with potassium cya-
nide, thiocyanate and aqueous hydro-
chloric ticid, 545.
chlorotribrom-, 457.
cyanodichlor-, 801.
dibromo-dichlor-, 862.
monobrom-, 867.
action of potassium carbonate
on, 867.
tribromomonocldor-, 862.
nol, thymol, and orcinol on, 393.
Acetonic acid, 104.
Acetonitrile, preparation of, 618.
Acetonylcarbamic acid, 545.
Acetonylcarbaminate, 545.
Acetonylsulphocarbaminate, 545.
Acetorthohomoparoxybenzaldehyde,387.
Aceto-salicylol, 318.
Acetyl, estimation of, by means of mag-
nesia, 67.
Acetyl-achroodextrin, 620.
Acetylbenzene, brom-, action of, on
diinethylaniline, dimethylmetatolui-
dine, and tetramethylmetaphenylene-
diamiue, 639.
preparation of, 659.
Acetylbenzoic anhydride, 31.
Acetylcarbazoline, 660.
Acetylcarbinol acetate, oxidation of, 616.
INDEX OF SUBJECTS.
i)7l
Acfitylcarbinol acetate, preparation of,
645.
benzoate, preparation of, 646.
Acetylene, preparation of, 456.
monochlor-, 800.
tetrabromide, 98.
Acetyleuedicarboxylic acid, 160.
dibrom-, 160.
Acetyl-erythrodextrin, 620.
Acetylhydrocotoin, 328.
Aeetyl-nialto-dextrin, 620.
Acetyl-paraoxybenzaldehyde, 468.
Acetylphenylcoumaric acid, 164.
Achroodextrin, changes which it under-
goes in the animal organism, 678.
Acid amides, formation of bases from,
547.
anhydrides, behaviour of, with
haloid salts in absence of oxygen,
437.
in sugar of lead and in lead vine-
gar, estimation of, 189.
Acids, action of, on alloys of rhodium
with lead and zinc, 706.
antiseptic action of, 72.
free mineral or organic, test for,
517.
• monobasic, double function of, 31.
of nitrogen, relations of, to sul-
phuric acid, 91.
of the formula C8H14O4, derived
from broniobutyric acid, 543.
organic, action of dehydrating sub-
stances on, 459.
• polymerised non-saturated, 120,
which are formed by the distilla-
tion of the crude fatty acids in a cur-
rent of superheated steam, 540,
Acouitic acid, occxirrence of, in beet-
juice, 36.
Acorns, digestibilitv and nutritive value
of, 820. " *
• value of, as fodder, 917.
Acridine, 398.
action of oxidising agents on, 398.
Acridinic acid and its salts, 398.
Acrole'in, some reactions of, 235.
Acryhc acid, action of hypochlorous acid
on, 160.
dichlor-, and its salts, 799.
/3-monochlor-, 800.
Actinism of the sun's rays and of day-
light, measurement of, 685.
Actnio-chemistry, new methods in, 837.
A.danson,ia digitata, fruit of, 836.
Adipic acid, 36.
from camphor, 559.
Aethusa ciinapium, alkaloid in, 899.
Agaricus atrotomentosus, quinone occur-
ring in, 47.
integer, new organic acid occur-
ring in, 44.
Aglaite, 225.
Agricultural chemistry in Japan, 133.
Air, a possible cause of variation of tte
proportion of oxygen in, 90.
ammonia in, 848.
carbonic anhydride in, 334, 788.
formation of hydrogen peroxide
and ozone by the action of moist phos-
phorus on, 699.
• influence of, on fermentation, 819.
lower organisms in, 908.
of Palermo, analyses of, 697.
rapidity of germ-diffusion in, 515.
variation in the composition of,
85.
Air-space, new method for estimating,
in seeds and fruits, 189.
Air-thermometer, a new, 783.
Alanine, 712.
/3- Alanine hydrochloride, 33.
Albumin, action of bromine on, 562.
action of potassium permanganate
on, 413.
alkaloids from the decomposition
of, 898,
estimation of, 829.
in plants, 279.
influence of borax on tlie decom-
position of, in the organism, 907.
putrefaction-products of, 413.
secretion, locaUtv of, in plants,
492.
supposed conversion of, into fat in
the ripening of Koquefort cheese, 835.
— vegetable, formation of, 341.
xanthio acid as a precipitant, for,
765.
Albuminates, estimation of nitrogen in,
350.
Albuminoid, a new, 177.
in whey, a new, 274.
nitrogen, estimation of, in fodders,
190.
Albuminoids, 562.
amount of, in potatoes, 568.
decomposition of, in plants, 493.
digestion of, 484.
estimation of, in various kinds of
fodder, 764.
estimation of, in vegetable sub-
stances, 352.
formation of hypoxanthine from,
672.
gaseous nitrogen a product of the
decomposition of, in the body, 272.
in pumpkin sprouts, decomposition
of, 180.
— of crystaUin, soluble, 815.
— of various oily seeds, 676.
— products of the action of hydro-
chloric acid on, 723.
— quantities of, in green plants, 731.
3 V 2
972
INDEX OF SUBJECTS.
Alcohol, detection of water in, 679.
from potatoes, 833.
oxidation of, by an ammoniacal
solution of cupric oxide, 310.
• presence of, in animal tissues dur-
ing life and after death, 174.
tables, for converting " over-
proof" and "underproof" into alco-
hol per cent., 773.
Alcoholates, dry metallic, action of car-
bonic oxide on, 622.
Alcoholic fermentation, 276, 277.
liquids, freezing point of, 523.
Alcohols, action of barvta and lime on,
711.
action of hydrogen peroxide on,
• action of ozone on, 27.
— — action of sulphuric monochloride
on, 310.
combinations of lithium and mag-
nesium chlorides with, 310.
— — decomposition of, by zinc-dust,
794.
isomeric fatty, heat of combustion
of some, 787.
oxidation of, by electrolysis, 24.
28.
poly-
presence of, in plants, 914.
—— sulphates of mono- and
hydric, 28.
Aldehyde, colhdine from, 54.
Aldehydes, aromatic, action of acetic
anhydride on, 468.
synthesis of, 467.
condensation-products of, with
primary aromatic bases, 39.
— phenolic, action of acetic
anhy-
dride on, 318.
Aleurone grains, chemical composition
of, 483.
Alimentary raaterials, various, absorp-
tion of, in tlje humaii intestinal canal,
563.
Alizarin, detection and estimation of,
424.
Alizarin-blue, constitution of, 262.
Alkali-metals, ehemioal constitution of
amalgams of, 1.
vapour-densities of, 434.
Alkaline earth-metals, at^ion of sul-
phurous anhvdride on the oxides of,
606.
Alkaline earths, characteristics of, 701.
liydrates, action of carbonic oxide
on, at high temperatures, 459.
phosphates, condition of, in aque-
ous solution, 2.
Alkaloid in Aethusa ci/Hapi'H.m,BQ9.
of Zfupiiious luteus, 416.
of the yew, 900.
Alkaloids, a delicate test for, 705.
artificial, 410.
Alkaloids, cinchona, behaviour of, with
potassium permanganate, 895.
estimation of, 763.
from the decomposition of albumin,
898.
in lupines, 57, 416.
of Afsfonia consfricta, 127.
of belladonna, datura, jusquiame,
and duboisia, 561.
of jaborandi leaves, researches on,
898.
of the pomegranate, 481.
perchloric acid as a test for, 69.
relation between the bases of the
oxalic series and some of the, 548.
tests for, 69, 763.
Alloy of nickel and copper, 771.
resembling silver, preparation of,
771.
Alloys, copper-tin, analogy between the
conductivity for heat and the induc-
tion balance effect of, 687.
estimation of the specific
electrical resistance of, 687.
of rhodium with lead and zinc,
action of acids on, 706.
of zinc with iridium-, ruthenium,
and rhodium, action of acids on,
707.
Allyl alcohol, combination of, with
baryta, 794.
moniodo-, 538.
bromodichloride, 4.56.
chlorodibromide, 456.
cyanide and the products of its
saponification, 99.
formation of crotonic acid
from, 99.
Allvldimethyl carbinol, oxidation of,
382.
AUylmalonic acid, 628.
Allyln\ethylpropyl carbinol, 372.
Alshedite, 15.
Alstonia constricta, alkaloids of, 127.
Alstonicine, 128.
Alstonine, 127.
Alum, action of ammonium carbonate
on, 791.
ammonium, decomposition of, by
heat, 792.
cubic, 444.
crystals, sensitiveness of, to varia-
tions in the strength of their mother-
liquors, 528.
potassium and sodium, mutual re-
lations of, in aqueous solution, 83.
Alumina, action of ammonium carbonate
on, 792.
Aluminium, revision of the atomic
weights and quantivalence of, 7'H .
separation of phosphoric acid from,
286.
INDEX OF SUBJECTS.
973
Aluminium alcohols, 861, 862.
battery, 838.
bromide, reactions clue to the pre-
sence of, 370.
chloride, reactions due to the pre-
sence of, 370.
hydrate, isomeric modifications of,
849.
iodine reaction, 861.
sulphate, new, 792.
sulphide, heat of formation of, 523.
and hthium, new silicates of, 447.
Alums, microscopical observations on the
growth and resolution of, in solutions
of isomorphous substances, 855.
Amalgams of the alkali-metals, chemical
constitution of, 1.
two new, 707.
Amarine, 881.
methiodide, 881.
Amblygonite, composition of, 96, 530.
Amides, quantities of, in green plants,
731.
Amido-acetic hydrochloride, 33.
Amido-acids, aromatic, 473.
Amido-azoxyleue, 552.
Auiido-compounds, estimation of, 764.
in plants, 279.
Amidodimethylacetic acid (amidovaleric
acid) , 101.
Amidodimethylpropionic acid (amido-
butyric acid), 101.
Amido-groups, influence of, on a sul-
phonic group entering the benzene
molecule, 238.
Amidoketones, aromatic, 804.
Ainidomercaptans from nitrobenzenesul-
phonic acids, 389.
Amidomethylene-catechols, 248.
Amidomethylenecatechol hydrochloride,
248.
Amido-oxyanthraquinone, 263.
Amidophenols, isomeric, action of methyl
iodide on, 636.
a-Amidopropiouitril, 313.
Amines, action of ethyl chlorocarbonate
on, 311.
action of ferro- and ferri-cyauic
acids on, 231.
action of sulphonic chlorides on,
108.
ciiloro-derivatives of, 233.
corresponding with a-toluic alcohol,
241.
Ammeline-argentic oxide, 311.
Ammehne niti-ate, 311.
Ammonia, absorption of, by the soil, 737.
compounds of hydracids with, 4.
decomposition of, in plants, 731.
existence of, in vegetables, 568.
— from the nitrogen of the atmo-
sphere and the hydrogen of water, 767.
Ammonia, heat of formation of, 207,
603.
in air and water, 848.
Ampaoniacal salts and calcium carbonate,
reactions between, 700.
Ammonium citrate, 104.
cyanide, heat of formation of, 151.
di-isethionate, 29.
ferric chromates, 10.
ferrid-thioglycollate, 236.
isethionate, changes of, at high
temperatures, 28.
nitrosoferrothioferrate, 9.
phosphate, 104.
photosantonate, 104.
polvsulphides, thermo - chemical
study of, 690.
salts, heat of formation of, 523.
sidpliides, heat of formation of,
151, 691.
thiocyanate, extraction of, from gas
liquors, 358.
Amphigene, production of, 449.
Amyl alcohol, action of bleaching powder
on, 456.
fermentation, heat of com-
bustion of, 787.
thiocyanopropionate, 312.
Amylene, brom-, 376.
transformation of, into cyinene
and hydrocarbons of the benzene
series, 710.
Analytical chemistry, application of the
galvanic current in, 282.
Anemopsis californica, 721.
Anethol, action of alcoholic potash on,
385.
camphor, or anethol tetrahydride,
385.
dihydride, 385.
hexbydride, 385.
monochlor-, action of alcoholic
potash on, 385.
tetrahydride, or anethol camphor,
385.
Angelic acids, 314.
Anglesite, Sardinian, crystalline form of,
96.
Anguria, colouring-matter of, 267.
Anliydrosulphonauiidoisophthalic acid,
258.
Anhvdrosulphonamidoterephthahc acid,
257.
Anhydrotropine, 715.
Aniline, compounds of, with mercuric
bromide and iodide, 632.
dinitro-, 812.
dithionate, 240.
ferrocyanide, 231.
parabroni-, 880.
parachlor-, 880.
■ blacks, 76.
974
INDEX OF SUBJECTS.
/S-Anilobutyric acid, 462, 542.
anilide of, 542.
Animal body, aromatic products
of,
648.
834.
charcoal, certain properties of,
estimation of the decolorising
jiower of, 422.
kingdom, distribution of copper in,
565.
matters, snch as blood, disinfection
and preservation of, for agricultural
purposes, 929.
— organism, behaviour of cymene in,
38.
changes which starch under-
goes in, 677.
formation of hippuric and
benzoic acids in, during fever, 716.
interchange of material
565.
— tar, compounds from, 267.
compounds in, 403.
— tissues, presence of alcohols
during life and after death, 174.
specific heat of, 483.
m.
Animals, breathing of, 911.
fattening of, 173.
influence of arsenic on, 907.
occurrence of a reducing substance
in the urine of, 332.
Anisidine, oxidation of, 642.
Aniso'i'l, bromaraido-, 641.
monobromoparanitro-, 641.
Anomite, 532.
Anthracene series, fluorescence in, 665.
synthesis of, 262.
Anthracenecarboxylic acid and its salts,
399.
Anthracenes, use of the spectroscope in
discriminating, 757.
Anthranilic acid from orthonitrotoluene,
648.
Anthraquinoline, 262.
Anthraquinone, amido-, acetoxy-deriva-
tive of, 49.
from anthraquinone-monosul-
phonie acid, 49.
constitution of, 323.
crude, use of the polariscope in
testing for anthracene, 292.
hydroxy-, decomposition
potash, 49.
orthobrom-, 323.
of, by
Anthraquinonesulphonic acids, action of
ammonia on, 263.
Antimonic acid, constitution of, 94.
Antimony, atomic weight of, 299, 300,
704.
compounds, decomposition of, 348.
pentachloride, action of, on phos-
phorus trichloride, 613.
Antimony, red, 612.
and arsenic, Clarke's method for
the separation of tin from, 289.
Antiseptic action of acids, 72.
of pyrogallol, 73.
Apiin, 413.
Apiol, 412.
Apparatus for measuring the heat of
combustion, 1.
Apples, ripening of, after gathering,
179.
Aqueous vapour, estimation of, in the
atmosphere, 420.
Aragonite, pseudomorphs of calcite
after, 15.
Aromatic compounds with long side-
chains, action of iodine on, 463.
Arsenates of certain metals, 217.
of zinc and cadmium, 216, 217.
Arsenic, chemical cause of the toxicolo-
gical action of, 174.
detection and estimation of, 752,
influence of, on animals, 907.
metallic, volatilising point of, 705.
presence of, in the atmosphere,
585.
acid, volumetric estimation of,
421.
compounds, aromatic, 396.
decomposition of, 348.
and antimony, Clarke's method for
the separation of tin from, 289.
Arsenical-pyrites intergrown with iron-
pyrites, 855.
Ash analyses, 343.
of beet, 922.
of beet seed, composition of, 496.
of certain spice seeds, analyses of,
915.
of different parts of the vine,
133.
volcanic, from Cotopaxi, 97.
Ashes of the trunk, leaves, and fruit of
the orange and the Mandarin orange,
composition of, 915.
Asparagine, action of methyl iodide on,
315.
distribution and functions of, in
the vegetable kingdom, 58.
nutritive value of, 330, 485.
Aspidospermine and its salts, 54.
Atmosphere, apparatus for estimating
oxygen in, 137.
■ estimation of aqueous vapour in.
420.
estimation of carbonic acid in the,
420.
presence of arsenic in, 585.
proportion of carbonic anhydride
in, 605.
— variations in the carbonic anhy-
dride of, 699.
IXDEX OF SUBJECTS.
975
Atmosphere, variations in the composi-
tion of, 698.
Atomic heat of glucimim, 850.
of oxygen, 850.
Atomicity, periodic, history of, 605.
Atropine, 481, 674.
artificial, 410.
light, 561.
Atropyltropeine, 715.
Azobenzene, paradibrom-, 880.
paradichlor-, 880.
mononitrodichlor-, 880.
Azobenzene-cresol-sulphonic acid, 716.
Azobenzene-diamidotoluene nitrate, 715.
Azobenzene-disulphonaphthol, 881.
Azobenzenedisulphonic acids and their
salts, 805, 806.
;8-Azobenzenedisulphonic chloride, 806.
Azobenzene - hydroxy carboxylbenzene,
715.
Azobenzenemonosulphonic acid, para-
dichlor-, 880.
Azobenzene-pyrogallol, 390, 715, 880.
Azobenzene-sulphocresol, 881.
Azobenzenesulphonamide, 805.
Azobenzenesnlphonic acid and its salts,
804.
chloride, 804.
Azobenzene - trinitro - hydroxybenzene,
715.
Azobenzene - trinitro - oxybenzene, 389,
880.
Azo-colours, new, 359, 715.
Azo-derivatives, some, 389.
Azonaphthalene-sulphoxyl-orthonitr-
oxyl-benzene, 881.
Azophenetol, dinitro-, 466.
Azophenyldisulphonic acid, potassium
salt of, 322.
Azophenylethyl, 243.
Azotoluenesulphonamide, 807.
Azotohienesulphonic acids and their
salts, 806, 807. '
chlorides, 806, 807.
Azoxybenzene, conversion of, into oxy-
azobenzene, 556.
mononitroparadichlor-, 880.
Azoxybenzcnesulphonamide, 807.
Azoxybenzenesxilphonic acid and its
salts, 807.
chloride, 807.
B.
Bacillus ami/lobacter (butyric ferment)
in the carboniferous period, 334.
ttrecB, 133.
Bacteria, chemical composition of, in
putrefying liquids, 176.
Bacteria, effect of putrefactive changes
on, 726.
formation of vinegar by, 334.
in the atmosphere, 727.
• influence of the galvanic current
on, 726.
Balsamum antarthriticutn' indicu^ru, 168.
Baptisia tinctoria, 411.
Barium allylate, 794.
borodecitungstate, 612.
cholate, 55.
clirysoquinonedisulphate, 264.
dicliromate, preparation of, 441.
dioxide, dissociation of, 610.
hydrated, composition of,
610.
formionitrate, 32.
isobutyratw and acetate, 799.
oxide, action of sulphurous anhy-
dride on, 606.
— • peroxide, estimation of active
oxvKcn in, 744.
— platinochloride, solubility of, ia
alcohol, 578.
thioglycoUate, 236, 237.
Barks, cinchona and other, valuation of,
764.
Barley, depreciation of, by overgrowth,
179.
malting, moisture in, 776.
manuring of, 135.
Basaltic lavas of the Eifel, 19.
Basalts of Azkhur on the Upper Kur,
615.
Silesian, and their mineral- consti-
tuents, 19.
Base, a new, 387.
fi'om chlorophenylthiocarbimidc,
388.
Bases, aromatic, a series of, isomeric
with the thiocarbimides, 387.
formation of, from acid amides,
547.
from fusel oil, 234.
of the oxalic acid series, 547.
primary aromatic, condensation-
products of aldehydes with, 39.
Bas.s'ia loiifj-lfol im, 519.
Bast fibre, chemistry of, 666.
derivative from, 667.
Bat-guano from various sources, 345.
Bav-tree, Califomian, ethereal oil from,
670.
Beech-leaves, frozen, constitution of,
416.
Beer, carbonic anhydride in, 774.
effect of hard and soft water on
the brewing of, 593.
Hamburg, analyses of, 833.
influence of liglit on, 200.
new clarifier for, 931.
Speyer, analysis of, 773.
976
INDEX OF SUBJECTS.
■Beer-mash, malt extract and maltose in,
776.
Beer-wort, Bohemian, composition of,
determined by chemico-optical pro-
cesses, 189.
Beers, English, analysis and composition
of, 353.
Bees, activity of, 415, 725.
Beet, ash of, 922.
cultivation of, 736, 917.
distribution of potassium nitrate
in, 733.
— — estimation of sap in, 829.
examination of, and the amount of
•sugar tlie roots contain, 586.
experiments with various sorts of,
59.
influence of the leaves on the pro-
duction of sugar in, 336.
manuring of, 185, 418.
method of selecting, for seeding,
134.
relation of yield of, to rain and
sunshine, 178.
sap-quotient of, 931.
Beet-juice, estimation of sugar in, 144.
fermentation produced in pre-
paring syrups from, by diffusion.
519, 931.
occurrence of tricarballylic
and aconitic acids in, 36.
Beet leaves, oxalic acid in, 733.
Beet mucilage, composition of, 561.
Beet residues as fodder, 734.
Beetroot, cultivation of, 821.
examination of, 495.
growth of, 502.
manuring of, 137, 509, 741.
nitrates in, 494, 495.
normal relation between the sugar
and mineral and nitrogenous matters
in, 569.
planting of, 502.
researclies on, 495.
run to seed, relation between the
sugar and mineral and nitrogenous
matters in, 569.
molasses, trimethylamine from,
233.
• gelatinous matter in, 908.
Beetroots, proportion of sugar to the
weight of, 519.
Beet sap, organisms in, 334.
Beet seeds, composition of ash of, 496.
cultivation and analysis of.
920.
germination of, 177, 730.
Beet-sugar, inversion of, for wine, 833.
• manuring experiments with.
refuse as manure, 742.
Belladonna, alkaloids of, 561.
BeUadonnine, 410.
Benzal chloride, metanitro-, 635.
Benzaldehyde, action of, on dimethyl-
toluidines, 636.
— — metanitro-, action of aniline hydro-
chloride and zinc chloride on, 662.
paranitro-, action of a mixture of
aniline hydrochloride and zinc chloride
on, 640.
orthonitro-, action of nascent
hydrogen on, 469.
green, constitution of, 40.
Benzamidoparatoluide, orthochloro-,
557.
orthochloro-, action of benzoic
chloride on, 557.
Benzamidophenolsulphonic acids and
their salts, 642.
Benzanilidimide chloride, action of
phenol on, 558.
Benzaurin, 239.
Benzene, bromacetyl-, preparation of,
659.
bromo-, preparation of, 316.
bromoxyl derivatives of, 246.
derivatives, crystalline forms of,
105.
diamido-, sulphonic acids from,
394.
dinitroiodo-, crystallographic con-
stant of, 384.
dinitrobromo-, 106.
electrolysis of, 802.
iodo", preparation of, 316.
mononitrotribromo-, 106.
nitramido-, sulphonic acids from,
394.
— nitrometadiiodo-, crystallographic
constant of, 384.
nitro-orthometatribromo-, crystallo-
graphic constant of, 384.
orthodiamido-, action of ferric
chloride on, 162.
tribromo-, action of nitric acid on,
106.
Benzene molecule, influence of nitro-
and amido-groups on a sulphonic
group entering the, 238.
Benzene ring, closed, synthesis of, 37.
Benzenedisulphonamide, bromo-, 123,
125.
Benzenesulphonamide, meta- and para-
nitro-, action of zinc-dust on, 805.
Benzenedisulphonic acid, action of fused
alkalis on, 320.
■ bromo-, 123, 124.
diazobromo-, 123.
dibromamido-, 123.
paramidobromo-, and its salts,
123.
Benzenedisulphonic acids, amido-, and
their salts, 122.,
INDEX OF SUBJECTS.
977
Benzenedisulphonic acids, di- aud tri-
bromo-, 124.
ortho- and met-amido-, and
their salts, 124.
chloride, bromo-, 123, 124.
Benzenemetadisulphonic acid, 806.
Benzeuesulphonic acid, metadiamido-,
and its salts, 395.
metanitramido-, and its salts,
395.
394.
394.
a- and /S- nitro-, 239.
orthodiamido-, and its salts,
orthonitramido-, and its salts,
acids, nitro-, amido-mercaptans
from, 389.
Benzenylamidophenyl mercaptan, 885.
Benzhjdrol and naphthalene, conden-
sation of, 478.
Benzidine, 80!S.
Benzmetamidoparatoluide, auhydro-
orthochloro-, 557.
Benzmetanitroparatoluide, orthochloro-,
557.
Benzofuro'in, 798.
Benzoic acid, formation of, in the animal
organism during fever, 716.
solubilitj of, 471.
dinitro", 471.
nietamido-, action of, on
hehcin, 126.
metaparadinitro-, and its
salts, 647.
nitro-amido-, 119.
nitro-orthobromo-, 119.
orthobromo-, and its salts, 118.
— ■ parametabromortlioamido-,
648.
paranitro-, action of bromine
paranitro-, nitration of, 549.
paraorthodinitro-, prepai'ation
of, 549.
— acids, nitro-, 647.
nitro-, Fittica's, 251.
chloride, metanitro-, 253.
cvanide, metanitro-, 253.
on, 647.
Benzophenone, dihvdroxj-, 240.
Benzotrichloride, compounds of, ■with
phenol and tertiary ai'omatic bases,
239.
Benzoyl carbiuol, oxidation of, 645.
Benzoyl cyanide, ortlionitro-, test lor, 68.
Benzoyl-acetic anhydride, 31.
BenzoylanUine, 804.
Benzoylphthalylanihde, 804.
Benzoyltrope'ine, and its salts, 714.
Benzparatoluide, di- and trinitro-ortho-
chloro-, 557.
orthochloro-, and its derivatives,
557.
Benzyl bromide, parachloro-, 879.
bromides, monobromo-, relative
displaceability of bromine in, 161.
compounds, ortliobromo-, 879.
parachloro-, 879.
derivatives containing sulphur,
811.
811.
mercaptan, action of bromine on,
810.
action of sulphuric acid on.
orthothioformate, crystalline form
of, 646.
— sulphides, parachloro-, 879.
thiobenzoate, 811.
Benzylamarine benzyl chloride, 882.
Benzylamidophenyl mercaptan, 386.
Benzyhdenemonophenyldiamine, 639.
BenzylmethyJacetic acid, 628.
Benzylmethylmalonic acid, 628.
Benz^lsuljjhonauiide, 812.
Benzylsulplionic acid, parachloro-, and
its salts, 879.
chloride, 812.
Benzyltliiacetamide, 34.
Benzylthiacetic acid, 34.
Berberine, preparation of, 169.
salts, 169.
Bessemer converters, gases from, 769.
steel plates, 356.
Biebrich scarlet, 559, 813.
Bilberries, colouring-niatter of, 927.
Birch, mineral constituents of, 343.
Bismuth containing arsenic, behaviour
of, towards nitric acid, 219.
detection of, 752.
method for estimating, volumetri-
cally, 753.
minerals from Wermland, 14.
nitrate, basic, preparation of, free
from arsenic, 219.
Bituminous rocks, commercial valuation
of, 682.
Bleaching sugar syrups by ozone, 74.
Bleaching powder, action of, on propyl,
butyl, and amyl alcohols, 456.
formation aud constitution
of, 789.
Bleeding of vines, researches on, 133.
Blood, detection of carbonic oxide in,
817.
disinfection and preservation of,
for agricultural purposes, 929.
pliysiology of sugar in relation to,
486.
Blood-stains, 926.
Blossoms, influence of smoke on the de-
velopment of, 177.
Blowpipe assay of silver lead, 585.
Bodies, relations between the physical
properties of, and their chemical con-
stitution, 685.
978
INDEX OF SUBJECTS.
Bone-black, action of, on sugar solutions,
758.
■ certain properties of, 834.
Bone-meal, adulteration of, 354.
adulteration of, with phos-
phorite, 516.
as a manure for potatoes.
739.
Borax, influence of, on the decomposi-
tion of albumin in the organism, 907.
physiological action of, Ho.
Boric acid as a preservative, 767.
inflvience of, on acetous fer-
mentation, 819.
Bomeol and camphor, relations of the
camphcnes obtained from, 324.
Boron, analysis of organic compounds
containing, 61.
quantivalence of, 395.
fluoride, action of water on, 435.
Borophosphate of magnesium and cal-
cium, analysis of, 447.
Borotungstates, 612.
Botanical preparations, liquid for the
preservation of, 596.
Brasilin, 248.
Breathing of plants and animals, 911.
Brine-springs of Volteri-a, salts obtained
from the mother-liquors of, 146.
Broniamylene, 376.
Bromethylpara- and ortho-nitrophenol,
316.
Bromine, density of, at high tempera-
tures, 432.
rate of substitution by, in the
acetic acid series, 539.
• relative displaceability of, in the
monobromobenzyl bromides, 161.
solidifying point of, 215.
/3-Broniisobutyric acid, 379.
^-Bromostyrene, 43.
Bronze, tungsten-manganese, 199.
Bronzite from Dun Mountain, near
Nelson, New Zealand, 857.
Bunt in wlie.it, suli)hurou3 acid as a
remedy for, 572.
Butter, adultonition of, 423,
analysis of, 69, 828.
analvsis of two ancient samples of,
357.
coefficients of expansion of, 70.
preservation of, 932.
testing, 587.
Butterine, coefficients of expansion of,
70.
Butyl alcohol, action of bleaching pow-
der on, 456.
preparation of, from glycerol,
819.
cyanate, tertiary, 228.
hippurate, normal, 870.
Butylamylamine, 546.
/3-Butylhydrophenylbetame, 542.
Butyraldehyde, /3-chloro-, 235.
Butyramide, /3-amido, 461, 541.
^-Biityi'anilbetaine, 462.
Butyranilide, /S-amido-, hydrochloride
of, 462.
Butyric acid, amido- (amidodimethyl-
propionic acid), 101.
/3-amido, 541.
bromo-, acids of the formula
CsHhOj, derived from, 543.
a-bromo-, decomposition of,
by water, 380.
calcium and barium double
salt of, 799.
;8-chloro-, some derivatives of.
541.
j8-monochloro-, 99.
— ferment {Bacillus amtflohacter) in
the carboniferous period, 334.
c.
Cabbages, manures for, 506.
Cacao rind as fodder for calves, 502.
Cadmium, arsenates of, 216, 217.
estimation of, in presence of zinc,
748.
zinc, and copper, separation of,
748.
Calamine, analysis of, 857.
Calcite, crystallography of, 530.
pseudomorphs of, after aragonite,
15.
Calcium, dissociation of, 597.
spectrum of, 361.
carbonate in water filtered through
dry soil, 59.
pentahydrated, 789.
and ammoniacal salts, re-
actions between, 700.
cyamide, formation of, from melam,
308.
glycerate, fermentation of, 819.
iodide with silver iodide, com-
pound of, 442.
lactate, fermentation of, 819.
levulosate, 539.
oxalate in plants, 914.
oxide, action of sulphurous anhy-
dride on, 606.
behaviour of, with carbonic
anhydride, 5.
crystallised, 700.
— phosphates, action of ammonium
citrate on, 825.
phosphite, 5.
phthalate, products of the dry dis-
tillation of, 255.
INDEX OF SUBJECTS.
979
Calcium, platinocUoride, solubility of, in
alcohol, 579.
saccharate, tribasic, 864.
and magnesium compounds as re-
fractory and dephosphorising ma-
terials, 831.
Calculus from a horse, analysis of, 174.
Calico-printing, use of thiocyanates in,
358.
Calorimetrical temperature - determi-
nations, 434.
Calves, cacao rind as fodder for, 502.
Camphene, inactive, 669.
hydride, 669.
Camphenes obtained from borneol and
from camphor, relations of, 324.
Camphimide, 892.
Campho-carbonic acid, 892.
Camphor, action of phosphorus penta-
chloride on, 717.
oxidation of, 559.
amido-, 891.
bromo-, action of zinc chloride on.
892.
constitution of, 892.
Camphor, bromonitro-, 891.
chlorides, 717.
-compounds, constitution of, 50.
nitro-, 891.
and borneol, relations of the cam-
phenes obtained from, 324.
Camphoric acid, preparation of, 893.
anhydride, preparation of, 893.
Camphothymol, ethyl ether of, 247.
Camphrene, constitution of, 50.
Cane-sugar, action of bromine on, 795,
864.
mannitol as a bye-product in
the formation of lact ic acid from, 100.
refined, detection of starch-
sugar mechanically mixed with, 758.
synthesis of, 29.
Caoutchouc, formation of, 323.
Caproic acid, 872.
a- bromo-, ami do-acids from,
dibromo-, 377.
dibromo-, action of water on,
isodibromo-, 377.
isodibromo- action of water
543.
377.
on, 377.
moniodo-, 377.
monobromo-, 377.
normal, lactone of, 799.
• tetrabromo-, action of water
on, 378.
Carbamide, dibromophenyloxethylene-,
634.
diorthotolyl-, 245.
ethyl-, and some of its derivatives,
383.
Carbamide, metaditolyl-, 245, 713.
mono- and di-anisyl-, 641, 642.
• mono- and di-plienylethyl-, 242.
para- and meta-tolyl-, 245.
tetranitro - diphenyl-, constitution
of, 812.
tolyl-
ortho-, and meta-, 713.
Carbamide-acetosulphonic acid, a new
derivative of thiohydanto'in, 877.
Carbamides derived from the isomeric
toluidines, 245.
Carbamido-palladious chloride or palla-
doso-uramonium chloride, 161.
Carbanilide, 622.
Carbazol, 660.
action of oxalic acid on, 245.
hexchloro-, 661.
octochloro-, 661.
action of antimony perchlo-
ride on, 661.
tetranitro-, 660.
trichloro-, 660.
compound
of, with
picric
of the
acid, 661.
Carbohydrates from the tubers
Jerusalem artichoke, 619.
sulphates of, 28.
table of the absorption of, in tlio
human intestinal canal, 564.
Carbon, electric conductivity of, as af-
fected by temperature, 837.
estimation of, in cast-steel, 289.
existence of, in the coronal atmo-
sphere of the sun, 429.
total, estimation of, in iron and
steel, 751.
bisulphide, action of pliosphonium
iodide on, 370.
compounds, solid, molecular vo-
lumes and specific gravities of, 694.
thermo-chemical investigation
of the theory of, 785.
dioxide, reduction of, by phos-
phorus at the ordinary temperature,
237.
monoxide, oxidation of, by moist
air in presence of phospliorus, 237. '
Carbonates, determination of carbonic
acid in, 346.
heat of formation of, 82, 361.
Carbonic anhydride, determination of, in
carbonates, 346.
estimation of, in the air,
420.
in the air, 334.
absorption of oxymn and ex-
piration of, by plants, 416.
behaviour of calcium oxide
with, 5.
behaviour of, in relation to
pressure, volume, and temperature,
691.
980
IJ^DEX OF SUBJECTS.
Carbonic anhydride, density of, at a liigli
teinperatnre, 434.
estimation of, in gases, 573.
■ free, in soils, 505.
from muscle, 330.
beat of neutralisation of, 362.
• proportion of, in tlie ail',
605, 788.
reduction of, by phosphorus
at ordinary temperatures, 298.
variations in, of the atmo-
sphere, 699.
reduction of, to carbonic
oxide by red-hot stannous oxide, 574.
Carbonic oxide, action of, on alkaline
hydrates at high temperatui-es, 459.
action of, on dry metallic
alcoholates, 622.
detection of, in blood, 817.
evolution of, from red-hot
u'on stoves, 592.
reduction of carbonic anhy-
dride to, by red-hot stannous oxide,
574.
Carboniferous period, butyric ferment
{Bast 1 1 us amiilobacter) in, 334.
Carbonyl bromide, 627.
-haemoglobin, 8i6.
Carica fat acid, 12;).
Carica papaya, 128.
Caricin, 129.
Caroba beans, digestibility and nutrient
power of, 563.
leaves, 671.
Carvacrol, 112.
nitro-, action of nitric acid on the
methyl ether of, 88 k
Carvacrolglycollamide, 889.
Carvacrolglycolhc acid and its salts,
889.
Carvacrolsulphonic acid and its salts,
112.
Carvophyllacese, colouring matter
413.
Caryophyllic acid, 670.
Caryophllin, 67U.
• acetyl-derivative of, 670.
chlorine-compounds of, 670.
Casein, 171.
action of rennet on, 172.
Cassia, mineral constituents of, 360.
Cast-steel, estimation of carbon in, 280.
Catechol, supposed presence of, in plants,
417.
Cattle foods, analyses of, 678.
Caucasian minerals, 615.
Cellulide ill bast fibre, 608.
CdUuloTd, 780.
Cellulocpiinone from bast fibre, 668.
Cellulose, action of a mixture of acetic
anhydride and eulphmic acid on,
159.
of,
Cellulose, digestive povrer of geese for,
330.
methods of estimating, 761.
nitro-derivatives of, 372.
estmiation of nitrogen in, 374.
Cement, 198, 767.
glycerina-, 428.
Cerium, volumetric estimation of, 749.
tungstate, 851.
Chalybeate springs of Carlstad, 20.
Characin, 53.
extracted from algse by water,
325.
Charcoal, condensation of gases by, 526.
Cheese, Danish export, examination of,
934.
ripening, formation of fat in, 594.
Roquefort, supposed conversion of
albumin into fat in the ripening of,
835.
Cliemical affinity, estimation of, in terms
of electromotive force. Part II, 686.
compounds, effect of light on, 521.
constants, some, 365.
equivalence, researches on. Part I,
socUum and potassium sulphates, 437.
researches on. Part II, hydro-
gen chloride and sulphate, 438.
reactions, Umits and velocities of,
365.
repulsion, 693.
teclinological notes, 516.
Cherry laurel, effect of cold on, 733.
Chicory, estimation of, in coffee, 514.
ChiU potash saltpetre, 507.
saltpetre for beets, 741.
manure experiments with,
507.
Chloral, action of potassium cyanide on
ammoniacal derivatives of, 102.
hydrate, decomposition of, 293.
dissociation of, 209.
heat of formation of, 293,
604.
on the heat of formation of
gaseous, 434, 435.
Chloralbenzamide, action of potassium
cyanide on, 103.
Cldorides, volatile metallic, 604.
Chlorine, behaviour of, at high tem-
peratures, 214, 432.
density of, at high temperatm-es,
431.
detection and estimation of, in
presence of iodine and bromine, 509.
estimation of, in grains and forage,
285.
estimation of, in must and wine,
586.
in carbon compounds, easy process
detecting, 348.
suggestion as to the constitution of,
INDEX OF SLTBJECTS.
981
offered by the dyiiaTTiical theory of
gases, 692.
Chlorophyll, 53, 266, 560.
analyses of, 561.
crystallised, 894.
from Eiicah/pfus qlohuhm, 894.
formation of, in the dark, 910.
in epidermis of foliage of phanero-
gams, 910.
Chlorophyllan, 53, 267, 894.
Chloropurpiireo-chromium salts, 10.
Chloroxalallyline, 546. 547.
Cholanie acid, 722, 723.
relation of, to cholecamphoric
acid, 722.
Cholecamphoric acid, 56.
and its relation to cholanie
acid, 722.
Cholic acid, oxidation of. 55, 562, 722.
oxidation-products of, 56.
Choloidanic acid, 723.
Choloidic acid, 56.
Chromammonium compomids, 10.
Chrome alum, 444.
Chromium, estimation of, 188. ,
estimation of, in steel, and in their
alloys with iron, 288.
monoselenide, 527.
monosulphide, 527.
oxy chloride, 793.
sequichloride, 793.
sesquioxide, action of chlorine on,
793.
• sesquiselenide, 527.
sesquisulphide, 527.
Chrysene, deriTatives of, 263.
tribromodinitro-, 263.
Chrysocolla from Chili, analyses of, 97.
Chrysoquinone, dibromo-, 263.
~ dinitro-, 263.
Churning, experiments on, 75.
Cinchomeronic acid and its salts, 896.
Cmchona alkaloids, behaviour of, -with
potassium permanganate, 895.
the form in which they occur
in the bark, 898.
bark, 177, 328.
analysis of, 190.
coto, 325.
Cinchonic acid, constitution of, 410.
oxidation of, 409.
Cinchonidine, constitution of, 409.
oxidation of, 409.
Cinchonine, constitution of, 409.
some derivatives of, 269.
hydrochloride, action of phosphorus
pent'acliloride, and oxvchloride on,
673.
Cinnabar deposits, genesis of. 221.
Cinnamic acid, naetamido-, 163.
— metamido, hydrochloride, 163.
polymerised, 121.
Cinnamic acids, monobromo-, 43.
aldehyde, formation of, during
fibrin-pancreas digestion, 469.
Cinnamon, mineral constituents of, 360.
Cinnamyltropeine and its salts, 715.
Citrate of iron and quinine, analysis of,
68.
Citric acid, 877.
synthes^is of, 801.
Clai-ifier for beer, new, 931.
Clarke's method for the separation of
tin from arsenic and antimony, 289.
Clay and loam, diU'erence between, 823.
Clav-soils, physico-chemical analysis of,
511.
Clays, contributions to our knowledge of,
155.
Clearing action of Spanish earth, 517.
Cleka or false thapsia, resin from,
718.
Clover, permanent pasture a substitute
for, 499.
red, composition of, 499.
crops, effect of gypsum on the
quantity and quality of, 185.
Clover-seed, relation of the colour of, to
its value, 134.
Clover-sickness, 505.
Coal, condition in which sulphur exists
in, 708.
estimation of ash in, 590.
Coal-dust, influence of, in colliery ex-
plosions, 439.
Coal-gas, detection of, in earth, 684.
of different qualities, heating
powers of, 766.
Coal mines, explosion in, due to carbonic
anhydride, 220.
Coal-tar, brown, products from, 263.
solubility of some constituents
of, 258.
colours, new, 358.
Cobalt, electrolytic estimation of, 583,
751.
estimation of, 287.
new method of separating nickel
from, 287.
volumetric estimation of, 347.
and nickel, detection of, in pre-
sence of each other, 286.
separation of iron from, 189.
Cobalt-glance, 13.
Cobalt-speiss, 13.
Cobra poison, 490.
Cobric acid, 491.
Coca, 169.
Cocaine, 169, 411.
Coffee, adulteration of, with chicory,
514.
examination of, 353.
" Mogdad," 936.
Cold, effect of, on cherry laurel, 733.
982
INDEX OF SUBJECTS.
Collidine, 480.
from aldehyde, 54.
Colliery explosions, influence of coal-
dust, in, 439.
Colophene hydride, 669.
Colophony in commercial oils, analysis
of, 684.
products of the distillation of, 893.
Colouring matter, blue, from the action
of paratoluenesulphonic chloride on
dimethylaniline, 108.
obtained by the action of
sodium nitrite on tetramethylpara-
phenylenediamine, 111.
containing sulphur from para-
phenylenediamine, 110.
from diamidotriphenybne-
thane, 662.
from the action of ammonia
on glyoxylic acid, 622.
green, from dimethylaniline,
636.
267.
814.
new, 559.
new, from orcinol, 551.
of anguria and colycynth,
of grapes and bilberries, 927.
of the Caryophyllaceae, 413.
scarlet, from " acid-yellow,"
Colouring matters, action of infusorial
earth on, 427-
derived from resorcinol, manu-
facture of, 426.
foreign, in rod wine, 191.
from furfuraldehyde, 391.
from phenols, 881.
new coal-tar, 595.
new, supplementary notice
on, 640.
■ obtained by the action of
naphthol on diazoazobenzene, 664.
obtained by the oxidation of
di- and tetra-methylparaphcnylene-
dianiine, 111.
of plants, action of ozone on
the, 58.
produced by the action of
diazo-compounds on phenols, 880.
some new, 41, 551, 559.
Colours, phenol-, new class of, 426.
Colycynth, colouring matter of, 267.
Comstock lode, heat of, 858.
CoDcretions taken from an abscess in
the jawbone of a horse, analysis of,
333.
Condensed milk, 926.
Confectionery, adulteration of, 422.
ConvolTulin,717.
Copper, acetylenedicarboxylate, 160.
ammonium chloride, behaviour of,
with ferrous sulphide, 12.
Copper chromates, basic, 853.
detection of, 924.
distribution of, in the animal king^
dom, 275, 565.
electrolytic estimation of, 583.
for roofing, valuation of, 826.
hydride, 299.
normal presence of, in the plants
wliich grow on the primordial rocks,
494.
— Parkes's method for estimating,
510.
phosphide, use of, in the refining
of copper, 197.
— presence of, in food, 490.
use of copper phosphide in the
refining of, 197.
cadmium, and zinc, separation of,
748.
Copper-pyrites intergrown with falilerz,
855.
Copper tin alloys, analogy between the
conductivity for heat and the induc-
tion balance effect of, 687.
■ estimation of the specific elec-
trical resistance of, 687.
Corn, most advantageous method of
sowing, 181.
Corundum, artificial production of,
447.
Cossaite, 533.
Coto-barks and their characteristic in-
gredients, 325.
Cotogenin, 326.
Cotoin, 326.
tribromo-, 326.
Cotone, dinitro-, 327.
Cotton-seed cake as fodder, 500.
oil, detection of, in olive oil,
925.
Cows, milch, flesh-meal as fodder for,
501.
"Craie grise," 198.
Cream, composition of, from De Laval's
cream separator, 780.
butter, whole-milk buttercompared
with, 932.
Creaming, experiments on, 75.
Creatine compounds of the aromatic
groujj, 803.
■ group, compounds belonging to,
897.
Creatinine group, compounds belonging
to, 897.
Cresol, nitroso-, 109.
trinitro-, 109.
Crops, four-yearly rotation of, 185.
Crotonic acid, formation of, from allyl
cyanide, 99.
Crystalbumin, 816.
Ci-ystalfibrin, 816.
Crystallin, non-identity of the soluble
INDEX OF SUBJECTS.
98a
albuminoids of, with those of white of
egg and serum, 815.
Crystallographic constants of some ben-
zene derivatives, 384.
Crystals, step -like and skeleton-growth
of, 529.
Cumene, synthesis of, 384.
Cumenesulphamides, 166.
Cumenesulphonic acids, 166.
Cumic acid, crystaUine form of, 549.
Cumic alcohol, cymene from, 106.
Cumidic acid, 479.
Cuminaldehyde, 251, 467.
nitro-, and its derivatives, 251.
oxidation of, 251.
reduction of, 251.
Cuminic acid, nitro-, 251.
Cuminol and dimethylaniline, some
compounds of the leuco-base from,
640.
Cuminuric acid, and its salts, 38.
Cumol, a new, 166, 167.
Cumopheuolglycollic acid and its salts,
883.
Cumophenols, 882, 883.
Cumyl chloride, 107.
Cupric oxide, oxidising action of, 32.
Cuprous chloride (sic), heat of forma-
tion of, 36L
thermo-chemistry of, 208.
Curd formation, 900.
Curds, composition of, 934.
Cuscamidine, 329.
Cuscamine and its salts, 329.
Cyanamide, action of formic and other
acids on, 371.
action of hydroxylamine hydro-
chloride on, 370.
action of, on dimethylamine hydro-
chloride, 233.
action of phenol on, 370, 371.
constitution of, 309.
preparation of, 307.
Cyaoethine, 31.
Cyanides, heat of formation of, 839.
Cyanite, crystallisation of, 614.
crystal-system of, 534.
Cyanogen, amount of heat evolved on
solution of, in water, 435.
heat of combustion of, 840.
heat of formation of, 361, 840.
Cyanomelamidine, 311.
Cyanopropionic acid and its salts, 460.
Cymatohte from Groschen (Mass.), com-
position of, 225.
Cymene, action of iodine on, 463.
behaviour of, in the animal organ-
ism, 38.
from cumic alcohol, 106.
new, from hght resin oil, 878.
transformation of amylene and
valerylene into, 710.
Cymene, dibromo-, oxidation of, 632.
Cymenecarboxylic acid, 163.
Cymenesulphouamide, lu7, 878.
oxidation-products of, 257.
Cymenesulpaonic acids, 878, 890.
D.
Date-palm, sugar from, 100.
Datura, alkaloids of, 561.
Daturine, 481, 482.
Davlight, measurement of the actinism
of, 685.
method for the continuous mea-
surement of the intensity of, and of
its application to physiological and
botanical researches, 188.
Delphinine, test for, 7fi3.
Densitv of bromine at high temperatures,
432.'
of chlorine at high temperatures,
431.
of iodine at high temperatures,
432, 433.
some gases at a high temperature,
434.
of vapours which attack porcelain
at a red heat, estimation of, 149.
and refractive power, chemical
constitution of organic compounds in
relation to their, 295.
Deoxalic acid, 36.
Dephosphorising materials, magnesium
and calcium compounds as, 831.
Desmine, 856.
Dew, amount of, on plants, 493.
Dextran, 908.
Dextrosechloride - tetrasulphonic acid,
28.
Diacetamidofluorene, 814.
Diacetonamine, products of oxidation
of, 101.
Diaceto-phenolphthalin, 655.
Diaceto-tetrabroujophenolphthalein,
654.
Diaceto-tetrabromophthalidin, 656.
Diacetoxyldestrotartaric anhydride, 876.
Diacetoxyl-phenolphthalein, 653.
Diacetylquinol, 317.
dinitro-, 317.
Diacetylracemic anhydride, 877.
Diacet'yltetrabromophthalin, 655.
Diallagite from Dun Mountain, near
Nelson, New Zealand, analysis of, 857.
Diallyl, constitution of, 370.
Diallvlcarbinol, methyl and ethyl ethers
of,'372.
oxidation of, 382.
Diallybnalonic acid, 628.
984
INDEX OF SUBJECTS.
DiallylmethTlcarbinol, formation of
fi-methTloxyglutaric acid from, 383.
Diallvloxamicle tetrabromide, 547.
Dialysed iron, constitution and proper-
ties of, 356.
Diamido-azonapbthalene bydrocbloride,
715.
Diamidotripbenylmetbane, 39.
Diammonium pentanitro - diaz o - amido-
monoxyhomofluorescein, 552.
Diamond, artificial formation of, 707.
■ bemibedry of, 854.
Diamylbenzcne. 107.
Diamrlene, hydrocarbon, CioHig, from,
231.
Diastase, 132, 562.
action of, on starcb, 132.
• action of, on starcb in presence of
bvdrocbloric acid or pure gastric juice,
330.
action of, on starch-paste, 310.
composition of, 176, 561.
Diazoazobenzene, colouring matters ob-
tained by the action of napbthol on,
664.
Diazobenzene, action of cyanogen com-
pounds on, 316.
Diazobenzenedisulphonic acid, 806.
Diazobenzene nitrate, bromo-, action of
potassium cyanogen on, 41.
sulphate or nitrate, action of po-
tassium cyanide on, 41.
Diazo-compounds, action of hydrocyanic
acid on, 41.
Diazobvdroazobenzencsulphonic acid,
808. '
Diazoparabenzenedisulphonic acid and
its salts, 122.
Dibenzyl, new method of forming, 259.
Dibenzoyldextrotartaric anhydride, 876.
Dibenzoyleupittonic acid, 165.
Dibenzoylhydrocotone, 327.
dibrorao-, 327.
tetrabromo-, 327.
Dibenzyl, action of chlorine on, 46.
paradichloro-, 46.
Dibenzylamarine, 882.
Dibenzylsulphone, 811.
Dibutylamine, 546.
Dibutyllactic acid, 871.
Dicamphorilimide, 892.
Dicalcium phosphate, 442.
Dicarbopyridenic acid, 269.
Dichloracetonic acid, 801.
Dichlorethylamine, spontaneous decom-
position of, 311.
Dichlorhvdrin, action of bromine on, 99,
862.
Dicotom, 326.
Dicyanamide, 237.
Diethylaeetic acid ? 376.
Diethyl dextrotartrate, 876.
Dietlivlenediphenyldiamine, diuitroso-,
112.
Dipthylenediphenylenetetramine, 112.
^-Diethyl-ethylenelactic acid, 382.
Diethylic ethylenesalicylate, 316.
Diethylidenelactamic or a-imidopro-
pionic acid, 313, 801.
D ietb y 1 pheny Itetrazone, 243 .
Diethylsulphone, 811.
Difi'usion experiments with acid • solu-
tions of mixtures of salts, 89.
researches on, 526.
Difurfurotolylenediamine, 391.
Digallic acid, action of sulphuretted
hydrogen on, 551.
Digestion in sheep, 484.
of albuminoids, 484.
of food by the horse when at work,
414.
Diglucose, 30.
Diglycid, 29.
Diheptene, 894.
Diheptylacetic acid, 314.
Dihydrobenzophenone, 240.
Diimidonaphthol hydrochloride, action
of ortlio- and para-toluidine on, 399.
Dimethacrylic acid, new mode of form-
ing, 624.
Dimethoxyl - tetrethoxyl - pararosaniline,
250.
Dimethyl amidoethylformate, 312.
dextrotartrate, 876.
racemate, 876.
Dimetbylacetic acid, amido- (amido-
Taleric acid), 101.
Dimethylacrylic acid, 315.
Dimethylamarine, 882.
Dimethylamine hydrochloride, action of
cyanamide on, 233.
Dimethylaniline, action of benzoic anhy-
dride on, 636.
action of bromacetylbenzene on,
639.
— action of a-naphthalenesulphonie
chloride on, 108.
action of paratoluenesulphonic
chloride on, 108.
— bromo-, 107.
— ferro- and ferri-cyanides of, 98.
nitroso-, 99.
action of, on phenols which
do not contain the methyl group, 162.
— parabromo-, 108.
pentanitro-, 108.
— preparation of, 802.
and cuminol, some compounds of
the leuco-base from, 640.
— and dimethylphenylenediamine,
oxidation of a mixture of, 391.
Dimetbylaniline-pbthale'in, 41.
Dimethyl-dikatabutylethylene, 231.
Dimethylethylcarbamine, 546.
1
INDEX OF SUBJECTS.
y85
Dimethyl-etliyl-carbinol, heat of com-
bustion of, 787.
Dimethylguanidine, 233.
Dimethylic methylpyrogallate, 249.
Dimethylmetatoluidine, action of bro-
macetylbenzene on, 639.
bromo-, 109.
derivatiTes, 109.
dinitro-, 109.
nitro-, 109.'
nitroso-, constitution of, 386.
hydrochloride of, 109.
Dimethylnaphthylamine, 813.
Dimethylparaphenylenediamine, action
of bromine on, 110.
ethoxamate, action of nitrous acid
on, 110.
colouring matters obtained by the
oxidation of, 111.
derivatives, 110.
Dimethylphenylenediamine and dime-
thylaniline, oxidation of a mixture of,
391.
Dimethylphenylglycocine or phenyl-
betaine, 162.
Dimethylpropionic acid, amido- (ami-
dobutyric acid), 101.
Dimethylpyrroline, 401.
Dimethylsulphanilic acid, salts of, 321.
Dimethyltoluidines, ferro- and ferri-
cyanides of, 98.
Dimethyltolylenediamine, 109.
oxidation of, 386.
Diinethyltriamidobenzene, 110.
/3-Dinaphthylamine, 813.
Dinaphthylketone, vapom'-density of,
679.
Dioctyl, 229.
Dioctylacetic acid and its salts, 628,
872.
Dioctylacetone, 872.
Dicotylmalonic acid, 628.
Diorcoxydiacetic acid and its salts, 393.
acids, mononitro-, two isomeric,
394.
Diorite from Diez in the Eupbachthal,
Nassau, analysis of, 857.
Diorthotolylguanidine, ^-dicyano-, hy-
drochloride of, 803.
Dioxethylmethylene, 307.
Dioxybenzhvdrol, 658.
Dioxybenzophenone and some of its salts,
646.
Dioxybenzophenone, tetrabromo-, 657.
Dioxyfumaric acid, pure, preparation
of, 383.
o-Dioxyphenylanthranol, 656.
Dioxytriphenylmethane-carboxylic acid,
654.
Diphenic acid, /3-dinitro-, and its salts,
814.
anhydride, 812.
VOL. XXXVIII.
Diphenic anhydride, compound of, with
resorcinol, 812.
phthalein of, 812.
chloride, 812.
Diphenol, oxidation of, 250.
tetrabromo-, oxidation of, 643.
preparation of, 613.
tetracbloro-, preparation of, 644.
Diphenolquinone, tetrabromo-, 643.
tetracbloro-, 644.
Diphenyl, 262.
amido-disulphydrate, 891.
disulphydrate, 477.
disulphide. 476.
Diphenyl-paramido-parasulphydrate hy-
drochloride of, 890.
sulphide, 476.
sulphocyauide, 477.
sulphur-derivatives of, 476.
Diphenylaldehyde, 118.
Diphenylamine, 813.
Diphenylamine blue, 75.
Diphenylarsinic acid and its salts, 397.
Diphenylarsenious clilorido, 396.
Diphenylcarbinol, 559.
ethyl and amyl ethers of, 558,
559.
Diphenylcarbinolcarboxylic acid, di-
chloro-, 654.
Diphenyldibromomethane, 558.
Diphenyldiimidonaphthol, 399.
Diphenyldimetliylamiflosulplione, 108.
Diphenyldisulpliacetic acid, 477.
Diphenyldisulphamide, 477.
Diphenyldisulphonic chloride, 477.
Diphenylcthane, 260.
Diphenylethylamine, 242.
hydrochloride, 241.
Diphenylethylene, imsymmetrical, 158.
Diphenyl mereaptan, 476.
Diphenylmethane, action of bromine on,
558.
tetramethyldiamido-, 40.
Diphenylmethyl acetate, 559.
Diphenylmonobromomethane, 558.
action of water on, 559.
Diphenylmonosulphacetic acid, 477.
Diphenylmonosulphamide, 476.
Diphonylmonosidphinic acid, 477.
Diphenylmono- and di-sulphonic acids,
nitro-derivatives of, 890.
Diphenylmonosulplionic chloride, 476.
Diphenylphtlialide, 650.
anthracene derivatives of, 651.
conversion of, intophenolphthalein,
652.
derivatives of, 650.
diamido-, 652.
dichloro-, or chloride of phenol -
phthalein, 654.
dinitro-, 652.
Diphenylpropane, synthesis of, 259.
3 z
986
INDEX OF SUBJECTS.
Diphenrlsulphone, 476.
Diphenyltliiacetic acid, amido-, 890.
DiphenTltliiohTdantoin, formula of, 45.
Diplienjlene ketone, 812.
dinitro-, reduction of, 814.
mono- and di-nitro-, 814.
Diplienyleneketone-earboxjlic acid, 401.
nitro-, 401.
Dipropionylquinol, 317.
Dipropyl dextrotartrate, 876.
jS-Dipropyl-ethylenelactic acid, 382.
Distillery material, seeds of tlie corn
cockle as, 501.
Dispersion, table of the coefficients of, of
organic compounds, 781.
Distyrene, 121.
Disiilplianilic acid and its salts, 122.
Dithionic acid, basicity of, 5.
Ditolylamine, acetometa-, 714.
nitro-para-, 714.
para- and meta-, 714.
Dog biscuit, examination of, 836.
Double salts, existence of, in solution,
32.
Drink, adulteration and examination of,
422.
Drosera, nutrition of, 820.
Drosera intermedia, acid of, 36.
Drugs, testing, 71.
Dry matter, increase of, in several agri-
cultural plants during growth, 416.
Dualin. 596.
Dubuisia, alkaloid of, 561.
Duboisine, 675.
Dust showers of Sicily and Italy, pre-
sence of iron in, 709.
Dye-stuffs, a new series of, 474.
of the rosaniline group, 390.
two, from metanitrodiamido-
triphenylmethane, 663.
two new, 717.
Electric arc, formation of hydrocyanic
acid in, 23.
temperature of, 206.
discharge of the chloride of silver
Earth, detection of coal-gas in, 684.
Earthenware goods, contributions to our
knowledge of, 155.
Eartlis of the yttria-group, spectra of, 7.
rare, magnetic properties of the
oxides of, 839.
and their salts, molecular
heats and molecular volumes of, 838.
Eclogite, composition of, 16.
Edible earth from Japan, analysis of,
702.
Effluent water, industrial, injurious
eflect of, on soils and ])lants, 497.
Ekabor, or ekaboron, 8, 851.
Electric arc, alternating currents, and
the electromotive force of, 783.
battery, 203.
lamp, smoke of, 81.
Electrical discharges, phosphorescence
produced by, 204.
■ resistance of certain copper-tin
alloys, estimation of, 687.
Electricity, atmospheric, 783.
influence of, on the growth of
plants, 909.
direct transformation of radiant
heat into, 838.
Electro-brass plating, 425.
Electro-capillary thermometer, 205.
Electrolysis, oxidation of alcohols by, 24.
Electro-optic observations on various
liquids, 599.
Elements, magnetic properties of, and
Mendelejeff's periodic law, 206.
solid, specific heat and expansion
of, 783.
some general relations between the
chemical mass of, and the heat of for-
mation of their compounds, 688.
EUagenc, 394.
Ellagic acid, constitution of, 43.
Elodea canadensis, nutritive value of,
500.
Emetine, 720.
Emplectite, 222.
Enamelled cast-iron vessels, 833.
Eperna falcata, 168.
Epicblorhydrin, action of bromine on,
457.
action of nitric acid on, 32.
action of sodium on, 457.
constitution of, 457.
derivatives, 29.
Epicyanhydrin, 544.
Epidote, crystal forms of, 534.
Epihvdriu acetate, 29.
'alcoliol, 29.
Erbia, researches on, 6.
two new elements in, 7.
Erbium, 157.
Eruptive rocks in the Saar and Moselle
districts, 537.
Erythrocepalein, 720.
Erythrophyll, 53.
Erythroxyanthraquinone, 654.
Erythroxyline, 169.
Erifthroxylon coca, 411.
Esparto fibre, chemistry of, 666.
Essential oil of Yerha mausa, 721.
oils, examination of, 201.
hmited oxidation of, 51.
Ethane, halogen derivatives of, 228.
vapour-tensions of the halogen
derivatives of, 618.
INDEX OF SUBJECTS.
987
Ethane, cMorpentabrom-, 228.
a-dichlorotetrabrom-, 228.
hexbrom-, 228.
pentabrom-, 228.
■ tetrabrom-, 228.
Ethanes, tetrabrom-, 98.
Etbenylamidophenyl mercaptan, 389,
885.
Ethenyldibromophenyldiamine, 634.
Ether, detection of water in, 679.
Ethereal acetates, preparation of, 104.
nitrates, explosive, estimation of
nitrogen in, 355.
oil from the Californiau bay tree,
670.
• from paracoto bark, 328.
— — Origanum hirtum, 112.
oils, chemistry of, 125.
salts of nitric and nitrous acids,
ultra-violet absorption spectra of, 202.
Ethoxybutyric acid, 99.
Ethoxyisobutyric acid, 871.
Ethoxynitrotoluic acid, 247.
Ethoxyplienylacetic acid, 252.
Ethoxyterephthahc acid, 247.
Ethoxytoluic acid, 247.
Ethyl acetate, preparation of, 541.
acetyltetracarbonate, 629.
• alcohol, some properties of mix-
tures of, veith methyl cyanide, 524.
allylmalonate, 628.
amidoethylformate, 312.
azobenzenesulphonate, 805.
benzylmethyhnalonate, 628.
bromophenylamidoacetate, 635.
camphoronates, action of ammonia
on, 669.
carvacrolglycoUate, 889.
cholanate, 722.
/3-ehlorbutyrate, action of aniline
on, 462.
chlorocarbonate, action of, on the
amines, 311.
deoxalate, 37.
derivatives of phenylhydrazine,242.
diallylmalonate, 628.
dibromophenylallophanate, 633.
diheptylacetoacetate, 314.
• dinitrophthalate, 478.
dioctylacetoacetate, 872.
dioctylmalonate, 628.
diphenylmonosulphonate, 477.
ethylmethylmalonate, 627.
heptylacetoacetate, 313.
iodide, influence of, on germination,
915.
iodoacetate, action of ethyl iodide
on, 541.
isobutylmalonate, 628.
isochlorobutyrate. action of potash
on, 870.
isopropylmalonate, 627.
Ethylmerca^jtides of mercury and lead,
behaviour of, at high temperatui'es,
796.
Ethyl metadinitrobenzoate, 471.
monobrom-a-naphtholate, 260.
monobromobuty rate, action of finely
divided silver on, 542.
monoclilorisobutylmalonate, 629.
monochlormalonate, 629.
nitracetate, preparation of, 32, 3^.
nitro-oi'thobromobenzoate, 119.
nitropropionate, preparation of,
33.
nitrosobenzylmalonate, 629.
nitrosomalonate, 629.
octylacetoacetate, 871.
orthobromobenzoate, 119.
paranitrophenylacetate, 120;
phenyldisiilphoxide, 812.
■ racemate, 37.
suberates, two isomeric, 542.
sulphate, 28.
neutral, preparation of, 797.
thiobenzenesulphonate,. 812.
thiocyanopropionare, 312.
thymoglycollate, 889.
Ethylallophanic acid, ether of, 384.
Ethyl-amido-a-caproic acid, 543.
Ethylamine, 159.
action of mercuric cliloride on,
159.
thermo-chemistry of, 787.
camph orate, action of phosphorus
pentacldoride on, 548.
— dichlor-, 233.
■ spontaneous decomposition of.
311.
hydrochloride, decomposition of,
by heat, 30.
Ethylamines, action of ethyl chloride on,
794.
Ethylbenzene, limited oxidation of, 469.
synthesis of, 463.
Ethylcarbazol, 660.
compound of, with picric acid, 660.
Etliylcarbazohne, 660.
iodide, 660.
Ethylchloroquinoline, 407.
Ethylcitrie acid, 877.
Ethylcrotonic acid, 375.
broni-, 375.
dibrom-, 376.
Ethyleumols, 167.
Ethyl diacetonamine, 868.
Ethylene chlorobromide, direct forma-
tion of, 456.
chlorotribrom-, 228.
derivatives of phenol and salicylic
acid, 316.
dibrom-, constitution of, 158.
fluobor-, 230.
halogen derivatives of, 228.
3^2
988
INDEX OF SUBJECTS.
Ethylene, iodide, 541.
iodopicrate, 619.
— — nitrodibrom-, 114.
perchlor-, action of oxygen on the
oxy-derivativo8 of, 231.
Ethylenedipara- and ortho-nitrophenol,
316.
Ethylenediphenyldiamiiie, preparation
of, 112.
Ethylenediplicnyldiamines, action of
nitrous acid on, 112.
Ethylenediphenyldinitrosaniine, 112.
Ethylenediphcnylsulphone, Sll.
Ethylenedisahcjlic acid, 317.
Ethylenefluoboric acid, 28.
Ethylenic glycol, heat of combustion of,
66l.
Ethylhydrocarbostyril, 406.
Etliylidenaanine silver sulpliate, 234.
Ethylidene bromiodide, 456.
chloriodide, 456.
monetliylate, 24.
Ethylmetliylacetic acid, 628.
Ethyhiiethylnialonic acid, 627.
Ethylnitroiic acid, 712.
Etliylparatolylsulphone, 811.
Ethylplienol, ortho-, 39.
Ethvlphenylhydraziuc, symmetrical,
243.
Ethyl])henylsulphone, 810.
Ethvljiropylene, 376.
Etliylpyriflenc, 269.
Etliylpyrrol, formation of, from ethyl
snccinimide, 630.
j3-Ethylquinolinc, 407.
Eucalyptus globulus, chlorophyll from,
894'.
Eugenol, action of, on monochloracetic
acid, 393.
Eugenoxyacetic acid, 393.
Eupittone, 249.
Eupittonic acid, 16t, 249.
dibenzoyl-, 165.
liomologiie of, 250.
Expansion of butter, lard, fats, &c., co-
efficients of, 70.
of liquid and solid bodies, 88.
of liquid carbon compounds, 784.
of tlie solid elements, 783.
Explosion in a coal mine due to car-
bonic anhydride, 220.
Explosives, researches on the decompo-
sition of, 780.
for blasting, especially nitroglyce-
rine, 595.
Eye, action of dchydi-ating agents on the
crystalline lens of, 333.
Fai-m without stable manure, tliirty-
eighth year of, 741.
Fat, amount of, in milk, 330.
estimation of, in fodder, 762.
in milk, 761, 828.
fornuition of, in the growth of
fungi, 337.
supposed conversion of albumin
into, in the ripening of Roquefort
cheese, 835.
table of the absorption of, in the
human intestinal canal, 564.
Fats, coefficients of expansion of, 70.
saponification of, 762.
separation of, from soaps, 587.
specific gravities of, 70.
various, amount of glycerol libe-
rated on saponification of, 762.
Fattening of animals, 173.
Fatty acids, action of phenols on halo-
gen-derivatives of, 392.
crude, the acids which are
formed by the distillation of, in a
current of supei'heated steam, 540.
lower, decomposition of the
substitution-products of, by water,
379.
— nitrated, preparation of, 33.
sa[)onifiable, analysis of, 684.
F.
Fallowing, 736.
oils, analysis of, 684.
Feeding experiments with pigs, 415,
724.
value of some manufacturers' waste,
183.
Feeding-cakes, effect of, on milk j^roduc-
tion, 725.
Feeding stuffs, analyses of, 343.
Felspars containing barium, strontium,
and lead, artificial production of,
449.
Felspar in the basalt from the Hohen
Hagen, near Gottingen, 614.
" Fer Bravais," 792.
Ferment, digestive, produced during
panification, 776.
Fermentation, acetous, influence of boric
acid on, 819.
accompanied by formation of hy-
drogen sulphide, 132.
alcoholic, 276, 277.
amount of yeast formed during.
728.
changes effected by, in the nitro-
genous constituents of sweet mash,
357.
chemical changes in nitrogenous
substances during, 728.
frothy, 518.
influence of air on, 819.
influence of, on the nitrogenous
constituents of potato mash, 819.
— influence of oxygen on, 908.
rXDEX OF SUBJECTS.
089
Fermentation, la?tic, 513.
of beet-root sap obtained by dif-
fusion, 931.
■ of glucose, 863.
of molasses, 931.
quick, apparatus for, 518.
schizomycetic, 819.
surface-, of potato mash, 518.
theory of nitrification, 909.
produced in preparing syrups from
beet-juice by diffusion, 519.
Fermented liquors, table of the points
of congelation of various, 524.
Ferments, hydrolytic, of the pancreas
and small intestine, 903.
starch-altering, in plants, 334.
unorganised, in plants, 175.
Ferric hydrate, colloidal, 792.
Ferrous iodide, action of potassium
chlorate on, 704.
estimation of, 749.
— oxide, estimation of, in presence of
organic acids or sugar, 583.
salts, absorption of nitrogen di-
oxide by, 9.
siilphide, behariour of copper-
ammonium chloride with, 12.
Feuerblende, 304.
(Rittingerite) from Chanarcillo,
856.
Fibrinogen, 172.
Fibrin-pancreas digestion, formation of
cinnamic aldehyde during, 469.
Field beans, manuring of, 569.
Fig-tree, a digestive ferment of the juice
of, 728.
Filtering and filter-paper, 573.
Filter-paper and filtermg, 573.
Fir, mineral constituents of, 343.
Fishes, injury to, by waste liquids, 490.
Flames, thermal absorption and emission
of, 206.
" Flashing " in assays of gold, 693.
Flaro-purpurin, detection of, 424.
Flax seed capsules and stems, ash ana-
lyses of, 343.
Flesh-meal as fodder for milch cows,
501.
Flour, adulteration of, 422.
Fluid meat, nutritive value of, 904.
Fluoborethylene, 230.
Fluorantliene, a new hydrocarbon from
coal-tar, 400.
Fluorene, preparation of, from fluorenic
acid, 402.
diamido-, 814.
Fluorenic acid and its salts, 401.
Fluorescence in the anthracene series,
665.
Fluorine, analysis of organic compounds
containing:, 61.
- — compounds of uranium, 853.
Fodder, analvsis of materials used for,
183.
beet residues as, 734.
cotton-seed cake as, 500.
estimation of albuminoids andnon-
albuminoidal nitrogen-compounds in
various kinds of, 761.
estimation of fat in, 762.
estimation of proteids in, 588.
for calves, cacao rind as, 502.
for cattle, spent hops as, 502.
for mdch cows, flesh-meal as, 501.
influence of lactic acid in, 905.
influence of, on the quantity and
quality of mUk-fat, 184.
influence of, on the secretion of
milk, 907.
new plant for, 183.
seeds of the corn cockle as, 501.
spent hops as, 344.
Symphytum asperrimum. as,. 735.
value of acorns as, 917.
Fog, dry, 439.
Food, absorption of, 414.
adulteration and examination of,-
422.
presence of copper in, 490.
Foods, tinned, analysis of various, 594.
Forage, estimation of chlorine in, 285.
Forest trees, amount of niti'ogen in,
506.
Forests, influence of, on the rainfall,
737.
Formic acid, anhydrous and hydrated,.
vapour-density of, 868.
■ • electrolysis of, 27.
oxidation of, by ammoniacal
cupric oxide, 235.
synthesis of, 460.
svnthetical formation of, 374.
^y
Formobromanilide, 634.
Fowl's dung, composition of, 345.
Freezing mixtures, 602, 687.
point of water, lowering of,
'pressure, 845.
Fruit juices, detection of salicylic acid
in, 352.
of different ages, behaviour
of, with reagents, 354.
Fruit trees, manures for, 506.
Fruits, new method of estimating the
air space in, 189.
nutritive value of, 733.
ripening of, 178.
Fuel, burning of, in liouse stoves, 145..
Fumaric acid, action of iodine on the
silver salt of, 801.
Fume condensing, new process of, 146.
Fungi, formation of fat in the growth
of, 337.
Furfuraldehyde, 798.
colouring-matters from, ?91.
990
IM)EX OF SUBJECTS.
Furfuramidobenzoic acid, 392.
Furfurane or tetraphenol, 663.
Furfurobenzidine, 892.
Furil, 798.
action of potash on, 798.
dibromo-, 798.
octobi'oniide, 798.
Furoin, 798.
Fusel oil, bases from, 234.
Fusing points of organic substances, new
method of determining, 419.
G.
Gadolinite, the new metals of, 611.
Gralena, estimation of silver in, 748.
Galenobismuthite, 14.
Galeopsis tetrahit, ash analysis of the
hay of, 343.
Gallic acid, condensation-products of,
394.
Galvanic couple, new, 149.
current, application of, in analy-
tical chemistry, 282.
experiments (platinum bases),
300.
polarisation, 837.
Garnierite, analysis of, 771.
Gas from the Lago di Naftia, or Lago
dei Palici, near Etna, analysis of, 345.
oxidation of sulphur in, on com-
bustion, 355.
Gas-liquors, extraction of ammonium
thiocyanate from, 358.
Gas-pipes, peculiar changes in, 198.
Gaseous mixtures, compression of, 604.
Gases, absorption of, by liquids, 525.
absorption of, by wood charcoal,
and charcoal saturated with hquid,
526.
action of, on seeds, 280.
acid, efFect of, on vegetation, 496,
497.
estimation of carbonic anhydride
in, 573.
evolved in the manufacture of std-
phuric acid, estimation and testing of,
745, 746.
from Bessemer converters, 769.
injurious efPect of, on soils, 497.
liquefaction of, a lecture experi-
ment, 366.
■ motion produced by the diffusion
of, 293.
perfect, law of Didong and Petit
applied to, 83.
relation between molecular weight
and density of, 525.
relative intensity of the spectral
lines of, 685.
Gases, relative space occupied by, 87.
solubility of solids in, 210,'693.
Gasometric methods, 345.
Geese, digestive power of, for cellulose,
330.
Geissospermine, and its salts, 675.
Gelatin, action of hydrochloric acid on,
723.
emulsion, 929.
Germ-diffusion, rapidity of, in the air,
515.
Germination, influence of ethyl iodide
on, 915.
influence of salicylic acid and other
bodies on, 335.
Ginger, preparation of soluble essence
of, 359.
Glass, mirror, composition of various
kinds of, 516.
use of heavy spar in the manufac-
ture of, 516.
variations in the coefficient
of
ex-
pansion of, 841.
Gleditschia glabra, composition of the
kernels and husks of the seed of, 133.
Globulin-substances in potatoes, 723.
Glucinum, atomic weight of, 850.
specific and atomic heat of, 850.
specific heat and atomic weight of,
792.
Gluconic acid, and its salts, 795, 863,
864.
Glucose, 158.
electrolysis of, 27.
estimation of, 512.
fermentation of, 863.
inactive, 458.
some properties of, 232.
Glucoside from white mustard-seed,
265.
Glucosides, complex, formation of, 126.
Gluten, 482.
Glycereincs, 426.
Glycerin. See Glycerol.
Glycerina cement, 428.
Glycerol, action of baryta on, 712.
amount of, liberated on the saponi-
fication of fats, 762.
• electrolysis of, 25.
estimation of, 757, 817.
estimation of, in wine, 512.
heat of combustion of, 604.
influence of, on proteid tissue
change, 817.
influence of, on the decomposition
of proteids in the animal body, 817.
— normal propyl alcohol from, 372.
— refractive indexes of, 757.
some reactions of, 235.
table of specific gi-avities of, 757.
Glyceryl triacetate, preparation of, 312.
Glycidic acid, or oxyacrylic acid, 800.
INDEX OF SUBJECTS.
991
Glycogen, action of the acids of the liver
■ on, 906.
Grlycol, electrolysis of, 26.
GlycoUic acid, preparation of, 379.
transformation of acetic acid
into, 32.
Glycolymonophenylguanidiae, 802.
Glycyrrhetin, 671.
Glycyrrhizic acid, action of dilute sul-
phuric acid on, 671.
Glycyrrhizio, 671.
commercial ammoniacal, 671.
GlyoxyUc acid, 621.
■ action of alcoholic ammonia
on, 622.
action of aniline on, 622.
action of sulphuretted hydro-
gen on, 621.
Gold, cupelled, influence of superfusion
on the molecular arrangement of, 773.
• " flashing" in assays of, 693.
estimation of, by quartatiou with
cadmium, 679.
— native, 707.
— • oxidation of.
by galvanic action,
158.
chloride, reduction of, by hydrogen
in presence of platinum, 705.
Grain, estimation of the value of, 594.
Grains, estimation of chlorine in, 285.
from malt, composition of, 148.
Grape, Riseling, mineral constituents of,
342.
Grape-must, influence of varying pres-
sures on, 358.
Grapes, colouring matter of, 927.
new method of ascertaining the
ripeness of, 352.
picking of, 517.
quantities of acid and sugar in, cut
at various stages of their growth, 179.
ripening of, 178, 336.
Grass mowing, 498.
nutritive value of, at various stages
of growth, 329.
Grass-seeds, amount of oil in, and its re-
lation to their germination, 342.
Grasses of meadows and pastures, rela-
tion of, 498.
Grey powder, mercuric oxide in, 930.
Groenhartin, 267.
Ground-nuts, influence of, on tlie pro-
duction of milk, 487.
Guanidine,an oxidation-product of albu-
min, 413.
dicyanodiorthotolyl-, 244.
a-dicvanotriorthotolyl-, 244.
dimethyl-, 233.
di- and tri-orthotolyl, 244.
di- and tri-orthotolyloxalyl-, 24 1.
thiocyanate, desulphuration of,
311.
Guanidine compounds, aromatic, 802.
Guanidines, orthotoluidine-, and their
cyanogen derivatives, 244.
substituted, synthesis of, 243.
" Guano cristalizado," 446.
deposit of Mejillones, phosphates
and boro- phosphates of magnesium
and lime in, 446.
en roche, 446.
from the Island of Ichaboe, 506.
nitric nitrogen in, 68.
Gum ammoniac, action of zinc-dust on,
126.
products of distillation of,
with zinc-dust, 39.
Gum arable, commercial, comparative
examination of the most important
kinds of, 827.
Gunimite, 96.
Gypsum, effect of, on the quantity and
quahty of clover crops, 185.
in the manufactui'e of sugar,
834.
H.
Hsematoxylin, behaviour of, on destruc-
tive distillation, 248.
Hsematoxylin-phthalem, 54.
Haemoglobin and its compound with
oxygen, 816.
Hsemoglobinuria, 817.
Hair, human, action of hydrochloric
acid on, 723.
Hair-dyes, analyses of some, 772.
Halogens, atomic refraction of, 782.
mutual replacement of, 365.
Haloid acids, action of, on the sulphates
of mercury, 12.
■ ether ification of, 711.
salts, behaviour of acid anhydrides
with, in absence of oxygen, 437.
oxidation of, 436.
Hay, digestibdity of, 916.
influence of steaming on the diges-
tibihty of, 734.
Norwegian, analyses of, 916.
steamed, digestibility of, 498.
Heat, analogy between the conductivity
for, and the induction balance effect
of copper-tin alloys, 687.
decomposition of ethylamine hydro-
chloride by, 30.
developed on solution and that de-
veloped on dilution with complex
solvents, relation between, 208.
difference between the evolution of.
during formation of sulphates or ni-
trates, and of carbonates, 362.
992
INDEX OF SUBJECTS.
Heat of combustion, apparatus for mea-
suring, 1.
of cyanogen and liydrocyanic
acid, 840.
of glycerol, and of ethylenic
glycol, GOi.
of some isomeric fatty alcohols
and of oenanthol, 787.
of sulpliur, 785.
of tlie oxides of carbon, 785.
of the principal gaseous hy-
drocarbons, 786.
Heat of decomposition of certain com-
pounds of liydrogeu peroxide, (502.
Heat of formation of a livdrocarbon.
840.
aluminium sulphide, 523.
ammonia, 207, 603.
ammonium cvanide and sid-
phide
435.
151.
— ammonium salts, 523.
— ammonium sulpliides, 691.
— anliydrous nitrates, 82.
— anhydrous sulpliates, 82.
— carbonates, 82, 361.
— cldoral hydrate, 293, 604.
— cuprous chloride {sic), 361.
— cyanogen, 361, 841.
— gaseous chloral hydrate, 434,
839, 840.
hydrocyanic acid and cyanides,
hydrogen persulphide, 691.
magnesium sulpliide, 523.
nitrates, 522, 603.
oxides of nitrogen, and of the
nitrates, 82, 603.
oxides and acids of nitro-
gen, 82.
ride, 89.
oxides of carbon and several
hydrocarbons, 785.
— ■ oxides of nitrogen, 82, 522,
603.
phos])hine, 151.
pliospliine compounds, 150.
potassium cldorate and chlo-
potassium polysulphides, 690.
salts of succinic acid, 151.
sdicon sulpliide, 523.
their compounds, relations be-
tween the chemical mass of the ele-
ments, and, 688.
hydration of potassium polysul-
phides, 690.
neutralisation of carbonic anhy-
dride, 362.
the Comstock lode, 858.
vaporisation of sulphm-ie anhy-
dride, 693.
Heat, solar, industrial utihsation of,
765.
Heayy metals, behaviour of sulphuretted
hydrogen with the salts of, 746.
' of the ammonium sulphide
group, separation of, 188.
spar, use of, in the manufacture of
glass, 516.
Helleburetin, 719.
Helicin, action of metamidobenzoic acid
on, 126.
Heliotrope, 615.
Heptene, 893.
Heptylacetic acid, 314.
Heraclin, 914.
Hexane, chlorination of, 158.
Hexbromoplicnoquinone, 246.
Hcxenic acid, 376.
Uexhydroparaxylene, 892.
Hexmethylbenzene, 864.
Hexniti'omonoxy - homofluorescein ni-
trate, 552.
High temperatures, determination of,
509, 521, 526.
Hippuric acid, formation of, in the ani-
mal organism during fever, 716.
source of, in the urine of
herbivora, 173.
Holmia, 7.
Holmiura, 7.
Homatropine, 815.
or oxvtoluyltropeine, 410.
aurochloride, 410.
picrate, 410.
Homocinchonidine, 270.
Homoeosin, tetra- and Jiexa-bromo-,
552.
tri-iodo-, 552.
Homofluorescein, a new colouring mat-
ter from orcinol and its salts, 551.
hexanitro-, 552.
Homofluoreseeincyamic acid, hexanitro-,
552.
Homoitaconic acid, 238.
Hoinopyrroline, 404.
Houiotropei'ne and its salts, 715.
Hops, conipai'ative iuvestigatioxi of,
417.
spent, as fodder, 344, 502.
wild Croatian, 428.
Horn, action of h3drocldoric acid on,
723.
Horse, digestion of food by, when at
work, 414.
beans, growth of, 567.
fodder, ordinary, assimilation of,
173.
Horses, feeding of, with fleshmeal, 57.
House stoves, burning of fuel in, 145.
Human liair, action of hydrochloric acid
on, 723.
Hyacinths, experiments on the growth
of, 'J22.
mineral constituents in, 58.
EvTDEX OF SUBJECTS.
993
Hydraeids, compounds of, with ammo-
nia, 4.
Hydracrjlic acid, chlor-, or liquid cliloro-
lactic acid, 800.
Hvdrastine, 170.
Hjdrazinbenzoic anhydride, 647.
Hydrazines o£ the fatty series, 234.
Hydrazobenzenedisulphonic acids and
their salts, 806.
Hydrazobenzenesulphonamide, 805.
Hydrazobenzonesulphonic acid and its
salts, 808.
diazo-compound of, 809.
dibromo-diazo-compound of,
809.
tetrabromo-diazo-compound
of, 809.
acids, di- aud tetra-brom and their
salts, 808, 809.
Hydrazophenetol, dinitro-, 466.
Hydrazo-phenylethyl, symmetrical, 243.
Hydrazotoluenesulphonic acid, 806.
Hydrindigotin-sulphuric acid, 475.
Hydriodic acid, etherification of, 711.
— — - new method for preparing,
89.
Hydrobenzom, compounds obtained
from, by the action of dilute sul-
phuric acid, 116.
anhydride, 117.
• chloride, 118.
dichlorides, 115, 117.
oxidation of, 117.
reduction of, 118.
Hydrobenzoins, compounds of, 114.
physi(tal isomerism of, 118.
Hydrobromic acid, new method for pre-
paring, 89.
Hydrocamphene, 669.
Hydrocarbon, C'loHig, 404.
CiflHig, from diamylene, 231.
Ci,Hi8, 404.
CigHi-i, derivatiTcs of the quinone
from, 665.
Hydrocarbons, heat of formation of,
840.
gaseous, heat of combustion of the
prmcipal, 786.
isomeric, constitution of, 840.
showing the absorption-bauds of
cymene, examination of, 202.
-— transmitting continuous spectra,
examination of, 201.
Hydrocarbostyril, synthesis of the ho-
mologues of, 406.
Hydrochloric acid, chemical equivalent
of, 438.
density of, at a high tempera-
ture, 434.
detection of, by sulphuric
acid and potassium dichroraate, 744.
^ etherification of, 711.
Hydrochloric acid, physical constants
of, 696.
specific heat of concentrated
solutions of, 207.
Hypochlorin, 560.
and its origin, 671.
Hydrocynnamylacrylic acid, 407.
Hydrocotoin, 327.
^— dibrom-, 328.
monobrom-, 328.
Hydrocotone, 327.
Hydrocyanaldine, 313.
Hydrocyanic acid, action of, on diazo-
compounds, 41.
formation of, in the electric
arc, 23.
— — - heat of combustion and for-
mation of, 840.
■ ■ heat of formation of, 839.
and acetaldehyde ammonia,
nitrils from, 313.
Hydroethylcrotonic acid, 376.
Hydroriuoboric acids, two new, 28.
Hvdrofluorosihcihc acid, crystallised,
"789.
Hydrogen, allotropic modifications of,
89.
nascent, non-existence of, 2.
• ^purification of, 2.
chloride, chemical equivalent of,
438.
ethyl sulphate, electrolysis of, 25.
lines, new, 597.
methyl sulphate, electrolysis of,
peroxide, action of, on silver oxide
and metallic silver, 441.
— action of, on the alcohols,
25.
606.
action of potassium iodide on,
compounds of, 602.
decomposition of, in presence
of alkalis and alkaline earths, 606.
estimation of active oxygen
in, 744.
formation of, 847.
formation of, by the action of
moist phospliorus on air, 699.
thermic relations of certain
combinations of, with alkahs, 602.
sulphate, chemical equivalent of,
438.
sulphide, fermentation accom-
panied by formation of, 132.
Hydrolytic ferments of the pancreas and
small intestine, 903.
Hydroparacoumaric acid, formation of,
from tyrosine, 254.
— preparation of, by putrefac-
tion of tyrosine, 649.
Hydroquinone. See Quinol.
994
INDEX OF SUBJECTS.
Hydrosorbic acid, 377.
monobromo-, 377.
structare uf, 382.
Hydroxethylmethjlacetic acid, 34.
Hydroxyacrylic acid, 626.
Hydroxyauthraquinoiie, dibrom-, consti-
tution of, 658.
Hydroxyazobenzene or phenyldiazoben-
zene, 163.
Hydroxybenzoic acid, para-, formation
of, from sodium plienate, 43.
Hydroxybenzoyltropeine, and its salts,
714.
/S-Hydroxybutyric acid, amides and ani-
lidcs of, 461.
Hydroxy butyric anhydride, normal, 712.
o-Hydroxybutyrocyamidine, 897.
a-Hydroxybutyrocyamine, 897.
Hydroxycaproic acid, 377.
a-Hydroxycthylmethylacetic acid, 315.
Hydroxy liirfuraniline, 391.
Hydroxyhydrosorbic acid, 378.
Hydroxyisobutylacetic acid, 629.
Hydroxyisobutylformic acid, 35.
Hydroxyisocaproic acid, internal anhy-
dride "of, 378.
y-Hydroxyisophthalic acid and its salts,
549.
y-Uydroxyisophthalic acids, three iso-
meric, table of properties of, 550.
Hrdroxyisovalerouitrd, 621.
Hydroxylamine, conversion of, into
nitrous and nitric acids, 298.
new metliod of forming, 4.
preparation of, 297.
Hydroxylation by direct oxidation, 165.
Hydroxyphenylacetic acid, ortlio-, and
its salts, 266.
Hydroxysuberic acid, 543.
Hydroxy valeric acids, 3 14.
Hygrine, 169.
Hyoscine, 674.
Hyoscinic acid, 674.
Hyoscyamiue, 411, 561, 674.
Hypouitrites, new method of forming, 4.
Hypoxanthine, formation of, from albu-
minoids, 672, 897.
Hyraceum, 172.
I.
Imide chlorides, action of alcohols and
phenols on, 557.
Imido-dimethylaceto - dimethylpropionic
acid, 102.
a-Imidopropionic or diethylidene-lacta-
mic acid, 313.
a-Imidopropionitril, 313.
Indican from urine, 46.
Indigo-white, action of potassium pyro-
sulphate on, 46.
Indoxylsulphuric acid, 475.
ludulin, manufacture of, 77.
Infusorial earth, action of, on colouring-
matters, 427.
Intestinal canal, human, absorption of
various alimentary materials in, 563.
Intestine, small, hydrolytic ferments of,
903.
Iodic acid as a test for morphine, 68.
non-production of ozone in
the crystallisation of, 213.
Iodine, behaviour of, at high tempera-
tures, 433.
density of, at higli temperatures,
432, 433.
method for the detection and
estimation of, in presence of chlorine
and bromine, 285.
titration of, by stable standard so-
lutions, 285.
vapour-density of, 606, 788, 846.
industry, recent improvements in,
195.
vapour-density of, 695, 696.
dissociation of, 696.
Ipecacuaniia, 720.
Iridammoniura, new salt of an, 13.
Iron, dialysed, 769, 792.
constitution and properties
of, 356.
dh-ect separation from manganese,
61.
estimation of total carbon in, 751.
influence of acetic acid on the
separation of, as basic acetate from
manganese, zinc, cobalt, and nickel,
289.
— passive state of, 211.
— presence of, in the dust-showers of
Sicily and Italy, 709.
— presence of nitrogen in, 749.
separation of, from manganese.
143.
separation of, from nickel and
cobalt, 189.
— ■ separation of, from uranium, 189.
separation of phosphoric acid from.
286.
— some analyses of, 73.
— dinitrosulphide, 217, 218.
nitrosulphocarbonate, 218.
and manganese, new method
separating, 2s9.
and phosphorus, separation
74.
of
of,
Iron-magnesia-micas, 225.
Iron micas, 225.
Iron ores, separation of siUcic anhydride
in the analysis of, 745.
pyrites, magnetic, crystals of, 306.
stoves, red-hot, evolution of car-
bonic oxide from, 592.
IXDEX OF SUBJECTS.
995
Isatropic acid, action of chromic acid on,
120.
action of sulphuric acid on,
120.
■ destructiye distillation of,
121.
polymeride of, 121.
Iserino from the Isergebirge, 369.
Iserite from the Isergebirge, 369.
Isoamyl alcohol, heat of combustion of,
787.
Isobenzogljcol, 802.
diacetate, 802.
Isobutaldehyde, action of ammonia on,
620.
action of potassium carbonate on,
103, 538.
polymerides of, 104.
vapour-density of the viscous poly-
meride of, 620.
Isobutyl alcohol, heat of combustion of,
787.
cyanate, 228.
group, constitutional changes in
the molecule of, 229.
hippurate, 870.
iodide, action of silver cyanate on.
228.
Isobutylhydroxymalonic acid, 629.
Isobutyric acid, a-brom-, decomposition
of, by water, 380.
iS-brom-, 379.
Isocaproic acid, brom-, 378.
Isodinaphthyl, 262.
vapour-density of, 679.
Isodiphenic acid, and its methyl and
ethyl salts, 401.
Isodipyridena, 672.
Isodurene, 37.
derivatives of, 37.
monqbrom-, 38.
Isodureuesulphonic acid and its salts, 37.
Isoduric acids, a- and ^-, 38.
Isohydrobenzoin, compounds obtained
from, by the action of dilute sulphuric
acid, 116.
oxidation of, 115.
anhydride, 117.
oxidation of, 117.
reduction of, 118.
(/3-hydrobenzoin) dichloride, 115.
Isohydroxyvaleroeyamidine, 897.
Isohydroxyvalerocyamine, 897.
Isoindole, preparation of, 659.
vapour-density of, 660.
Isomerism, physical, of hydro- and iso-
hydro-benzoin, 118.
Iso-pelletierine, 481.
Isophthalophenone and its salts, 470.
rediiction of, 471.
a- and /3-diamido-, 471.
a- and jd-dinitro-, 470.
Isoprene, action of haloid acids on, 323.
bromides, 323.
chlorides, 323.
iodides, 323.
Isopropyl alcoliol, heat of combustion
of, 787.
Iso]jropylbenzoic acid, crystalline form
of, 549.
Isopropylmalonic acid, 627.
Isopropylphenols, 167.
Isopurpurin, detection of, 424.
Isoterpene, lajvoratory, 403.
dichlorhydrate, 403.
Isotributylene, 230.
oxidation of, 230.
Isotrichlorhydria, 234.
Isovaleronitril, aniido-, 621.
J.
Jaborandi leaves, alkaloids of, 898.
Jaborine, 898.
Jalap, resins contained in, 717.
Jalapin, 717.
Jerusalem artichoke, carbohydrates from
the tubers of, 619.
Jervine, 170.
Jusquiame, alkaloids of, 561.
Jute, bleaching of, 200.
fibre, cliemistry of, 666.
K.
Karabuja, 616.
Ketonic acids, synthesis of, 35.
Kieselguhr, composition of, 595.
Koettstorfer's process for butter ana-
lysis, 69.
Kynuric acid, 44.
Lactic acid, amido-, 800.
jS-bromo-, 800.
chloro-, 627.
/j-cliloro-, 5-4-1-.
influence of, in fodder, 905.
liquid chloro-, constitution of,
800.
mannitol as bye-product in
the formation of, from cane-sugar, 100.
nionochloro-, 32, 160.
nitro-, spontaneous oxidation
of, 237.
acids, amido-, 713.
fermentation, 513.
996
INDEX OF SUBJECTS.
Lactin, researches on, 458.
Lactobutyrometer, estimation of the fat
in milk bv, 352.
Lactones, 378, 799.
Laevulin, 619.
Lapacliic acid, 267.
crystalline form of, 548.
Larches, efiect of manures on growth of,
509.
Lard, coefficients of expansion of, 70.
Laurie acid, 34.
ketone from, 34.
Laurie aldehyde, preparation of, 866.
Laurite, artificial, 222.
Laval's separator, experiments with,
933.
Lavas, basaltic, of the Eifel, 19.
of the volcanos of Ernici in the
Yalle del Sacco (Home), 226.
Lavender, essence of, 50.
Law of Dulong and Petit applied to per-
fect gases, 83.
Lead, action of water on, 766.
analyses, 772.
volumetric estimation of, 752.
acetate, estimation of the acid in,
189.
ethyl mercaptide, behaviour of
high temperatures, 796.
fume, 146.
piping, action of water on, 198.
vinegar, estimation of the acid in
at
189.
Leaves, amount of nitrogen in the under
htter of, 506.
influence of annual temperature on
change of colour in, 910.
influence of, on the production of
Light, influence of, on beer, 200.
on the growth of forest trees,
sugar in the beet, 336.
Lecithin in yeast, 816.
Lecture experiments, 212, 846, 924.
Legumes, growth of, 567.
Ljntil vetch, culture of, 500.
Ijepidolite (litliia-mica), 533.
Lepidomelanc, 533.
LeucauQine, synthesis of, 640.
Leucine in potatoes, 342.
Leucite, crystal-system of, 16.
incipient crystalline forms of, 448.
Leucitophyr, ariificial production of,
identical with the crystalline lavas of
Vesuvius and Somma, 448.
Leuco-base from cuminol and dimethyl-
aniline, some compounds of, 6i0.
Leuconostoc mesenieroides, 909.
Leucotin, 326.
dibromo-, 326.
tetrabromo-, 326.
Levulose, compound of, with lime, 539.
Library bindings, deterioration of, 836.
Light, efPect of, on chemical compounds,
521.
566.
57.
on the growth of plants,
Lightfoot black, 76.
• transferring, from one fibre
to another, 75.
Ligneous Papilionacese, chemical ex-
amination of, 735.
Lime, action of, on silica in mortar,
216.
on solutions of sugar, 834.
in plant-life, 568.
and phosphates and boro-phos-
phates in the guano deposit of Mejil-
lones, 446.
salts, absorption of, by the animal
system, 725.
Limestones, separation of silicic anhy-
dride in the analysis of, 745.
Linaloes-wood, 428.
Lintonite and other forms of thomsonite,
535.
Liquid, condensation of, at the wet sur-
face of a solid, 363.
for the preservation of botanical
preparations, 596.
bodies, absolute expansion of, 88.
Liquids, action of, on seeds, 280.
determination of the specific
gravity of, 419.
difiusion of, 364.
electro-optic observations on, 599.
motion produced by the diffusion
of, 293.
new metliod of taking the specific
gravity of. 743.
putrefying, chemical composition of
bacteria in, 176.
specific gravity of, 61.
thermo-electric properties of,
431.
Lithia-micas, 224.
Lithium, estimation of, as orthophos-
phate, 581.
occurrence of, in rocks, sea-water,
&c., 17.
chloride, combinations of, with
alcohols, 310.
phosphates, 581.
idtramarine, preparation of, 367.
and aluminium, new silicates of,
447.
Lithobilic acid, 270.
Lithofellates, 131.
Litliofellic acid, 131.
Litliofracteur, 596.
Lithology, some points in. II. Compo-
sition of the capillary volcanic glass of
Kilanea, Hawaii, called Pele's hair,
536.
INDEX OF SUBJECTS.
997
Liver, action of the acids of, on glycogen,
906.
formation of sugar in, 905.
nature of the sugar in, 866.
Livingstonite, 95.
Loam and clay, difference between,
823.
Lupine, yeUow, cultivation of, 736.
seeds, as a manure, 507-
Lupines, alkaloids in, 57, 416.
cleansing, 820, 935.
poisoning of sheep by, 57, 916.
Lupiiius luteus, alkaloid of, 416.
M.
Magnesia-iron-micas, 225.
Magnesia-mieas, 225.
Magnesium chloride, combinations of,
with alcohols, 810.
crystaUine form of, 611.
oxide, action of sulphurous anhy-
dride on, 606.
phosphates and boro-phosphates in
the guano deposit of Mejilloues, 4-16.
platinochloride, solubdity of, in
alcohol, 578.
platinocyanide, dichroic fluores-
cence, 598.
sulphide, heat of formation of,
523.
and calcium compounds as refrac-
tory and dephosphorising materials,
831.
Magnetic iron pyrites, crystals of, 306.
sand, 615.
Magnetic properties of the elements,
and MendelejefE's periochc law,
206.
Magnetite, 95.
Maize, amount of sugar in, 594.
composition of, 183, 499.
sugar from the stems of, 834.
Malachite green, constitution of,
555.
Maleic acid from a-dibromopropionic
acid, 374.
from dichloracetic acid, 35.
Malic acid, from a-dibromopropionic
acid, 374.
inactive, 462.
action of iodine on the silver
salt of, 801.
ordinary, inversion of the
optical rotation of, 629.
Malonic acid, electrolysis of, 462.
nitroso-, 629.
preparation of, 801.
Malt examination, 922,
Malt, extraction of, 833.
testing, 71.
undried, application of, in the pre-
paration of yeast, 200.
combings a source of yeast, 518.
• adulteration of, 777.
extract in beer mash, 776.
Malto-dextrin, 311, 866.
Maltose, changes which it undergoes in
the animal organism, 678.
in beer mash, 776.
Mamao wax, 129.
Mandarin orange, composition of tlie
ashes of the trunk, leaves, and fruit
of, 915.
MandeUc acid, 645.
Manganese, chemical composition of the
hydrated oxides of, 849.
direct separation of, from iron,
61.
141.
estimation and separation of.
— occurrence of, in Nordmark's mine,
Wermland, 15.
precijjitation of, by oxidising
agents, 143.
separation of iron from, 143.
Yolhard's permanganate method of
titrating, 585.
— volumetric estimation of, 347.
binoxide, composition and analysis
of, recovered in the Weldon process,
528.
oxides, spont.'ineous oxidation of,
with reference to manganese-recovery
process, 368.
garnet, 856.
— -nodules from tlie bed of Pacific
Ocean, 16.
-recovery process, spontaneous oxi-
dation of manganese oxides witli re-
ference to, 73, 368.
and iron, new method of separat-
ing, 289.
Manganite, 14.
Manganous acid, Gorgeu's, 219.
oxides, spontaneous oxidation of,
with reference to the manganese-
recovery process, 73, 368.
Mannitol'as bye-product in the forma-
tion of lactic acid from cane-sugar,
100.
electrolysis of, 26.
Manoury's method of desugarising mo-
lasses, 357.
Manufacturers' waste, feeding value of
some, 183.
Manure, artificial, best mode of apply-
ing, to potatoes, 824.
beet-sugar refuse as, 742.
experiments with rye, wheat, and
oats, 738.
998
INDEX OF SUBJECTS.
Manure experiments vritli superphos-
phate and Chili saltpetre, 507.
influence of, on potato disease,
and starch in potato, 915.
lupine seeds as a, 507-
mill waste for, 60.
shells of ci-aijs, oysters, mussels,
&c., as, 60.
use of peat as, 506.
Manures, analyses of. 678.
application of natural products as,
417.
different, action of, on the yield of
potatoes, 187.
■ effect of, on growth of larches and
pines, 509.
experiments with, 506, 570.
for cabbages and fruit trees, 506.
influence of, on the combustibility
of tobacco, 417.
various, 344.
various, action of, on the composi-
tion of must, 507.
Manuring experiments, 345, 922, 923.
on wheat and rye, 508.
• with oats, 136.
of barley, 135.
of beetroot, 137.
of field beans, 569.
Margaric acid, 34.
Margiirite, 533.
Marjoram, essence of, 50.
Marl, analyses of, 60.
Martite from Brazil, 447.
Mash, density of, 517.
sweet, changes effected by fermen-
tation on the nitrogenous constituents
of, 357.
Matter, chemical stability of, in sonorous
vibration, 437.
Meadows, injurious effect of peat water
on, 738.
Meat, boric acid as a preservative for,
767.
production of the red colour in
salting, 80.
Melanthigenin, 719.
Melanthiu, 719.
Melons, amount of sugar in, 594.
Melting points of the refractory metals,
149.
Mendelejeif's periodic law and the mag-
netic properties of the elements, 206.
Mercaptans, amido-, from nitrobenzene-
sulphonic acids, 389.
Mercuric dioctyl, 229.
iodide, coefficients of expansion of,
443.
octyl chloride, 229.
octyl hydrate, 229.
octyl iodide, 229.
sulphates, thiobasic, 157.
Mercuric sulphide, new basic salts of,
157.
Mercury, action of the haloid acids on
the sulphates of, 12.
use of Smithson's pile for the de-
tection of, in mineral waters, 510.
compounds, haloid, emission spec-
tra of, 81.
di-iodide, eff'ect of heat on, 443.
ethyl mereaptide, behaviour of, at
high temperatures, 796.
Mesoxalic acid, decomposition of, by
sulphuretted hydrogen, 237.
Metabenzenedisulphonic acid and its
salts, 123.
Metacymene, 632.
a-Metacymenesulphamide, 632.
Metacymenesulphonic acids and their
salts, 632.
a-Metacymene s\ilphonic chloride, 632.
Metadihydroethylbenzene, 404.
Metadiliydromethyleyraene, 404.
Metaisatamide, 253.
Metaisatic acid (metamidophenylgly-
oxylic acid), 253, 254.
Metallic chlorides, volatile, 604.
nitrates, action of, on nitric acid,
153.
oxides, reduction of, by hydrogen,
298.
Metalloids, spectra of, 430.
Metals, action of ozone on some, 205.
electrolytic estimation of, 747.
of gadolinite and of samarskite,
new, 611.
• refractory, specific heats and melt-
ing points of, 149.
various, electrolytic quantitative
separation and estimation of, 282.
Metamethylbenzaldehyde, 468.
Metamethylethylbenzene, 126.
Metatoluidine, 635.
estimation of, in crude toluidine,
110.
Meteorite of Albarello, 369.
of Grosnaja, 20.
of Vavilovka, 20.
which fell at la Becasse, 226.
Meteors, two remarkable, observed in
Sweden, 859.
Methacrylic acid, 378, 871.
polymeride of, 871.
polymerised, 120, 379.
Methane, new synthesis of, 370.
Methenvlamidophenyl mercaptan, 389,
885, 887.
Methoxydibromotoluic acid, 884.
/3-Methoxyglutaric acid, 372.
Metlioxynitrotoluic acid, 246, 884.
Metlioxypropylnitrobenzoic acid, 884.
MethoxVstilbene, 253.
Methoxyterephthalic acid, 247.
IXDEX OF SUBJECTS.
999
Methyl acetate, preparation of, 541.
alcohol, quantitative estimation of
acetone in, 826.
some properties of mixtures
of, with methyl cyanide, 524.
cyanide, pure, physical constants
of, 618.
some properties of mixtures
of, vrith ethyl and metlivl alcohols,
524.
a-dinitrophenate, 815.
eupittonate, 165.
mandelate, melting point of, 645.
a-naphtholate, 261.
(S-naphtholate, 261.
orthobromobenzoate, 119.
paranitrophenylacetate, 120.
sulphate, preparation of, 28.
thiocyanate, polymeric, 797.
polymeric, action of alcohohc
ammonia on, 798.
Methylamarine mefhiodide, 882.
Methylamido-a-caproic acid, 543.
Methylamidoethyl formate, 311.
MethylanHine, monobromo-, 107.
Methylcarbazol, 660.
compound of, ■with picric acid,
660.
Methyl-dikatabutylacetic acid, 231.
Methylene chloride, preparation of, 307.
Methylethylhydroxyacetic acid, two
new syntheses of, 872.
Methylisothiacetanilide, 557.
Methylketole, an isomeride of skatole,
synthesis of, 395.
Methylmorphine hydroxide, preparation
of, 408.
iodide, action of potassium ferri-
cyanide on, 409.
Methyl a-naphthyl ether, 261.
^-naphthyl ether, 261.
Methylnonyl-ketone, normal, 872.
Methyloctyl-ketone, 314.
Methyloxydimorphine hydroxide, 409.
iodide, basic, 409.
sulphate, neutral, 409.
/S-Methyloxyglutaric acid, formation of,
from diallylmethylcarbinol, 383.
Methylpelletierine, 481.
Methylphenylketone, conversion of bro-
mostyrolene into, 469.
/S-MethVlpropylethylactic acid, 372.
Methylpyrosallol, 248, 249.
Methylquinhydrone, formula of, 318.
Methylthiocarbimide, 797.
MethVlumbeUic acid, crystalline form
of, '106.
Methyl-violet, new method of preparing,
75.
Metisopropyltoluene, synthesis of, 877.
Mica group, 224, 614.
Micas, 532.
Milk, adulteration of, 423, 828.
amount of fat in, 330.
analyses of, 520.
analysis of, 514, 828, 925.
chemical composition of, 273.
condensed, 926.
enumeration of the fat globules as
a test for, 191.
estimation of fat in, 352, 761.
human, abnormal composition of,
332.
— influence of fodder on the secretion
of, 907.
influence of ground nuts on the
production of, 487.
— influence of shearing on yield of,
487.
— lazy, 934.
— observations on, 828.
of a large herd of cows, obser-
vations on, 487.
— presence of sulphuric acid in.
423.
preservation of, 148.
quaUty of, 352.
taking samples of, 828, 925.
albumin, 900.
butter, whole, compared with
cream butter, 932.
churning, machines for, 357.
coolers, various, comparison of, 357.
cooling apparatus, experiments
with, 834.
fat, influence
of fodder on the
quantity and quality of, 184.
— production, eliect of feeding-cakes
on, 725.
— secretion, 330.
Milk-sugar, partial synthesis of, 29.
ililking, notes on, 834.
Mill waste for manure, 60.
Mineral analysis, removal of large
quantities of sodiiun chloride in, 580.
constituents, course of, in the
development of tlie early slioocs, 335.
of fir and birch, 343.
of Silesian basalts, 19.
. of the Eiesling grape, 342.
containing cinnabar, metacinna-
barite, and stiblite, analysis of, 858.
oils, examination of, 589.
heavy, analysis of, non-sapo-
nifiable, 683.
— superphosphates, analysis of, 576.
— tanning, 427.
waters, ferruginous and nitrated.
617.
of, 455.
of Bourboule, 455.
of Bussang (Vosges), analysis
of Cransac (Aveyron), com-
position of, 454.
1000
INDEX OF SUBJECTS.
Mineral waters of Savoy, sketch of the
origin of, with some analyses, 453.
sulphuretted, formation of,
709.
use of Smithson's pile for
the detection of mercury in, 510.
Mineralogif-al notes on the ores of
Chanarcillo, North Chili, 301.
Minerals, bismuth, from Wermland, 14.
different, two regular intergrowtlis
of, 855.
in certain trachytes from
the
ravine of Riveau Grande, at Mont
Dore, 225.
— new, from tbe andesite of Mount
Arany, 616.
of greater density than quartz,
separation of, by means of fused
mixtures of lead and zinc chlorides,
511.
separation of silicic anhydride in
the analysis of, 745.
" Mogdad '" coffee, 936.
Molasses, fermentation of, 931.
Manoury's method of desugarising,
357.
Molecular heats of the rare earths and
their salts, 838.
refraction of carbon compounds,
table of, 781.
volumes of liquid carbon com-
pounds, 784.
of solid carbon compounds.
21, 694.
of the rare earths and their
salts, 838.
Molybdenum pentachloride, 220.
Molybdic anhydride, action of phos-
phorus pentachloride on, 219.
Monaceto-phenylanthranol, 651.
Monethylene pyrogaUate and its deri-
vatives, 250.
Monethyloxamide, 547.
Monobasic acids, double function of, 31.
unsaturated, etherification of,
375.
Monocarbopyridenic (nicotinic) acid,
269.
Monomethylanilinenitrosamine, mono-
bromo-, 107.
Monophenylarsinic acid and its salts,
396.
Monophenylboric acid, 396.
Monophenylboron chloride, 395.
tetrachloride, 396.
Monophenylethylamine, 242.
hydrochloride, 241.
Monophenylguanidine, 44.
Monothiobasic trimercuric siilphate, 157.
Monotolylarsenious oxides, 397.
Monotolvlarsinic acids and their salts,
397.
Moorland, manuring experiments on,
923.
Morphine, action of atmospheric oxygen
on, in ammoniacal solution, 408.
action of benzoic chloride on, 407.
action of potassium ferricyanide
on, 408.
• action of potassium permanganate
on, 408.
iodic acid as a test for, 68.
test for, 763.
hydrochloride, 673.
tribenzoyl-, 407.
Morphiometric processes for opium,
191.
IMortar, action of Hme on silica in, 216.
Motion produced by the diffusion of
gases and liquids, 293.
Mucic acid, chloro-, 36.
Muscle, carbonic anhydride from, 330.
distribution of phosphates in, 275.
extractives from, 726.
Muscovite, 533.
IMuscular activity and waste, 486.
Muscular labour, influence of, on the
elimination of nitrogenised decompo-
sition products, 818.
Must, action of various manures on the
composition of, 507.
aeration of, 931.
analysis of, 586.
composition of, at different stages
of ripeness of the grape, 425.
tartar and tartaric acid in, 774.
Mustard-seed, white, glucoside from,
265.
Mycoderina aceti, growth of, 819.
Mycoprotei'n, 177.
Myristamide, 460.
Myristanilide, 460.
Myristic acid, 34.
— aldehyde, preparation of, 867.
series, compounds of, 460.
Myristolic acid, 460.
N.
Naphthalene, a- and j8-positions in, 399.
chloro-, action of chlorine on, 47.
o^-dibromo-, 260.
«- and /3-dichloro-, nitro-deriva-
tives of, 47.
J/-(lichloro-, derivatives of, 47.
dinitro-, oxidation of, 477.
-y-trichloro-, 167, 168.
Naphthalene-a-sulphonic acid, dichloro-,
and its salts, 168.
chloride, action of chlorine
on, 167.
dichloro-, 168.
INDEX OF SUBJECTS.
1001
Naphthalene-a-sulphonic cbloride, tetra-
chloride of, 167.
Naphthalenesulphonic acid, a-bromo-,
260.
^-niti'o-, derivatives of, 47.
Naphthalene and benzh} drol, condensa-
tion of, 478.
Naphthaquinone, methyldihydroxy-, 48.
Naphthoic acids, nitro-, 261.
Naphthol-derivatives, 260.
a-Naphthol and phenol, action of lead
oxide on, 664.
^-Naphthol, /iJ-naphthylamine from,
813.
Naphtholazobenzenesidphonic acid, salts
of, 664.
Naphtholazonaphthalene, sulphonic salts
of, 664.
^-Naphtholsulphonic acid, action of di-
azoamidoazobenzene on, 717.
Naphthoquinol, 49.
Naphthoqxunone, action of aniline on,
48.
action of ammonia on, 48.
action of paratoluidine and of di-
phenylamine on, 49.
a-Naphthylamine, conversion of, into
a-naphthyl-methyl ether, 813.
Naphthylamine, a/3-dibromo-, 260.
/3-Naphthylamine, 813.
a-NaphthyldimethylomidophenylsuI-
phone, 108.
Naphthyldiphenylmethane, 478.
synthesis of, 6G4.
a-Naphthylmethyl ether, compound of
with picric acid, 813.
conversion of a-naphthyl-
amine into, 813.
a-Naphthylphenyl carbinol, 478.
«-Naphthylphenylketone, incomplete re-
duction of, 478.
Narcotic plants, extracts of, 425.
Natural products, application of, as
manures, 417.
Nepheline, incipient ciystalline forms of,
448.
Nervous substance, combinations of
phosphoric acid in, 274.
Nickel, electrolytic estimation of, 583,
751.
estimation of, 287.
from cobalt, new method of sepa-
rating, 287.
malleable, 930.
metallui'gy of, 770.
methods of estimating, 771.
preparation of, 593.
ore of New Caledonia, composition
of, 593.
and cobalt, detection of, in pre-
sence of each other, 286.
separation of iron from, 189.
VOL. XXXVIII.
Nicotine, bromo-, 897.
derivatives, 672.
tetrabromo-, 815.
Nicotinic aoid, 268.
Nlgella sativa, examination of the seeds
of, 718.
Nigrosin, manufacture of, 78.
Niobite from the Isergebirge, 369.
Nitrates, heat of formation of, 522.
in sugar beets, 494, 495.
metallic, action of, on nitric acid,
153, 154.
heat of formation of, 603.
Nitre, formation of nitric oxide by
igjiition of, 574.
Nitric acid, action of metallic nitrates
on, 153, 154.
decomposition of, in plants,
731.
estimation of, 574.
formation of, in the soil, 59.
heat of formation of, 603.
• introduction of, into the sul-
phuric acid chamber along with the
steam, 196.
testing for, in presence of
nitrous acid, 139.
oxide, formation of, by ignition of
nitre, 574.
Nitrification, 277, 279.
fermentation theory of, 909.
Nitrils from hydrocyanic acid and ac6t-
aldehydeammonia, 313.
Nitrogen, albuminoid, estimation of, in
fodders, 190.
amount of, in forest trees, and in
the under litter of leaves, 506.
course of, in the development of
the early shoots, 335.
determination, examination of the
Will-Varrentrap metliod, 348.
dioxide, absorption of, by fen-ous
salts, 9.
— estimation of, 679.
— estimation of, in albuminates, 350.
— estimation of, in explosive ethereal
nitrates, 355.
— extension of Dietrich's table for
the calculation of, 346.
gaseous, a product of the decompo-
sition of albuminoids in the body,
272.
— heat of formation of the oxides of,
522.
— in turf, 344.
in organic compounds, easy pro-
cess for detecting, 348.
— manure for oats, 741.
— modification of Dumas' method for
estimating, 753.
Zulkowsky's apparatus for tlic
volumetric estimation of, 679.
4 '.4
1002
INDEX OF SUBJECTS.
Nitrogen, nitric, in guano, 68.
non-albuminoid, estimation of, in
fodder, 588.
organic, estimation of, in natural
waters, 62.
oxides, lieat of formation of,
603.
thermo-ehemistry of, 689.
presence of, in iron and steel, 749.
table of the absorption of, in the
human intestinal canal, 565.
— tests for, and estimation of, in iron
and steel, 749.
— thermochemical
investigation of
the oxides and acids of, 81.
Nitrogen-compounds, non-albuminoidal,
estimation of, in various kinds of fod-
der, 764.
non-albuminous, estimation
of, in plants, 513.
tetroxide, researches on, 91, 440.
Nitrogenised decomposition products,
influence of the supply of water, the
secretion of sweat, and muscular la-
bour on the chmination of, 818.
Nitrogenous constituents of sweet mash,
changes effected by fermentation in,
357.
substances, chemical changes in,
during fermentation, 728.
Nitro-groups, influence of, on a sulphonic
group entering the benzene molecule,
238.
Nitrolactic acid, spontaneous oxidation
of, 237.
Nitro-octane, 229.
NitrosofeiTous potassium sulphide, 10.
Nitroso-sodio-ferrous sulphide, 218.
Nitrosothioferratcs, 9.
Nitrous acid, heat of formation of, 603.
researches on, 91.
anhydride, researches on, 440.
compounds, estimation of, in the
manufacture of sulphuric acid, 745.
Nonoic acid, normal, synthesis of, 313.
phosphorite, 356.
Norwegium, 93, 611.
Nuclein in yeast, 816.
0.
Oak-bark, influence of soil on the tannin
of, 920.
Oats, development of, 336.
manuring experiments with, 136,
738.
manuring of, 508.
on fen lands, 185.
nitrogen manure lor, 741.
Oat-straw, digestibility of, 916.
Oetacetyl diglucose, 159.
Octacetyl-glucose, 619.
Oetacetyl- lactose, 619.
Octacetyl-maltose, 620.
Octacetyl-saccharose, 620.
Octane, nitro-, 229.
Octyl acetoacetate and its derivatives,
871.
cyanide, 230.
derivatives, 229.
nitrite, 229, 230.
Octyl-acetic acid, 872.
Octyl-acetone, 872.
Octylamine, 229.
Octylnitrolic acid, 229.
Oenanthal, heat of combustion of, 787.
Oil, amount of, in gi-ass-seeds, and its
relation to their germination, 342.
of marjoram, Cretan, 112.
of Orif/anmn creticum, 113.
of turpentine, action of iodine on,
125.
Oils, commercial, analysis of resin in,
684.
essential, examination of, 201.
heavy mineral, resin, and fatty,
analysis of, 683.
lubricating, investigation of, 778.
mineral, examination of, 589.
transmitting continuous spectra,
examination of, 201.
Ok'fines and other unsaturated com-
pounds, direct formation of the
chlorobromides of, 456.
Oligist, artificial production of, 223.
Olive, fonnation of fatty matter and
ripening of, 568.
oil, detection of cotton seed oil in,
925.
Opium, morphiometric processes for,
191.
tincture of, valuation of, 193.
testing, 829.
Orange, composition of the ashes of
trunk, leaves, and fruit of, 915.
Orcella weed, Californian, 255.
Orciuol, action of, on monocliloracetic
acid, 393.
a new colouring matter from, 551.
a product obtained by the action of
aqua regia on, 645.
trinitro-, 113.
Ores of Chanarcillo, North Chili, minera-
logical notes on, 301.
Organic acid, new, occurring in .^^oWcms
integer, 44.
acids, action of dehydrating sub-
stances on, 459.
bases containing oxygen, synthesis
of, 639.
— bodies, relation between the phy-
IXDEX OF SUBJECTS.
1003
sical properties of, and their chemical
constitution, 293.
Organic compounds, chemical constitu-
tion of, in relation to their refractive
power and density. Part II, 781.
containing fluorine and boron,
analysis of, 61.
liquid, expansion and mole-
cular Tolumes of, 784.
detecting nitrogen, sulphur,
and chlorine in, 348.
solid, molecular volumes and
specific gravities of, 21.
matter in water, methods for in-
dicating the presence of, 290.
Organisms in beet sap, 334.
lower, in the air, 908.
Orthamidophenylbenzoic acid, internal
anhydride of, 246.
Ortlianisidine, 641.
Orthobenzylcreatinine, 803.
Orthobenzylglycocyamidine, 803.
Orthoclase and quartz, simultaneous re-
production of, 532.
Orthocymene, 631.
/3-Orthocymenesulphamide, 632.
Orthocvmenesulphonic acids and their
sa]ts,"^631.
Orthodiamidobenzene, action of ferric
chloride on, 162.
Orthodimethylamido-anisol, 637.
Orthodimethylamido-phenol, 637.
Ortho-ethylphenol, 39, 126.
Ortho-hydrazinbenzoic acid, 647.
Ortho-hydroxybenzoyltropeine, 714.
Ortho-hvdroxyphenylacetic acid and its
salts, 266.
Orthotoluidine derivatives, 386.
Orthotolylglycocine, 387.
Orthotolylurethane, 245.
Orthotrimethvlanisolammonium iodide,
638.
Orthotrimethylphenolammonium and its
salts, 636.
Orthoxylene, separation of, from its iso-
merides, 240.
Oven for heating sealed tubes, 846.
Oxalamyline, chlor-, 547.
Oxalethyline and its salts, 546.
action of bromine on, 547.
action of methyl iodide on, 547-
Oxalic acid, action of iodine on the
silver salt of, 801.
crystallised, 544.
electrolysis of, 27.
in beet leaves, 733.
oxidation of, by ammoniacal
cupric oxide, 235.
series, bases of, 547.
Oxalovinyl chloride, dichloro-derivative
of, 232.
Oxalpropyline, chlor-, 547-
Oxalyl-biuretic acid, amide of, 105.
Oxamethane chloride, reactions of, 557.
Oxamide, monethyl-, 547.
Oxethylbenzenedisulphonamide, 124.
Oxethylbenzenedisulphonic acid and its
salts, 124.
chloride, 124.
Oxidation, acceleration of, caused by
the less refrangible end of the spec-
trum, 429.
Oxides, metallic, reduction of, by hydro-
gen, 298.
Oxyacrylic acid (oxypropionic acid),
544.
constitution of, 800.
Oxyanthraquinonc, 654.
formation of, from phenolphtha-
lein, 658.
dibrom-, 654.
formation of, from tetra-
bromophenolphthale'in, 658.
Oxyazobenzene, conversion of azoxyben-
zene into, 556.
Oxyazobenzene-orthoxysulphoxyben-
zene, dinitro-, 881.
Oxycamphor, 892.
Oxycaproic acid, an, 312.
Oxydimorphine and salts, 408.
Oxyfluorescein hexamido-, hydrochloride
of, 552.
Oxygen, absorption of, and expiration of
carbonic anhydride by plants, 416.
active condition of, induced by
nascent hydrogen, 3.
active, estimation of, in bariiim or
hydrogen peroxide, 744.
apparatus for estimating, in the
atmosphere, 137.
— atomic heat of, 850.
— atomic refraction of, 782.
- — • behaviour of, to haloid salts in
presence of acid anhydrides, 436.
— dissolved in water, quantitative
estimation of, 137.
— estimation of, dissolved in water,
421.
— in the air, a possible cause of vari-
ation of the proportion of, 90.
— influence of, on fermentation.
908.
spectrum of, 430.
Oxygen-acids of sulphur, 5.
Oxyleucotin, 327.
dibrom-, 327.
tetrabrom-, 327.
Oxymercurethylaniine chloride, 159.
Oxymoi-phine, Schiitzenberger's, 408.
a-Oxyparatoluic acid, 257.
Oxypropionic acid (oxyacrylic acid),
514.
Oxysorbic acid, 268.
Oxysorbinic acid, 268.
i a 2
1004
INDEX OF SUBJECTS.
Oxytetrolic acid and its liomologues,
625.
Oxytoluic aldehyde, liquid and solid,
acetyl derivatives of, 468.
Oxytoluyltropeine or homatropine, 410.
and its salts, 715.
aurochloride, 410.
picrate, 410.
Ozone, 847.
action of, on some noble metals,
205.
— action of, on the alcohols, 27.
- — action of, on the colouring matters
of plants, 58.
— bleaching sugar syrups by, 74.
— formation of, 847.
formation of, by the action of
moist phosphorus on air, 699.
— influence of volume and tempera-
ture in the preparation of, 90.
non-production of, in the crystalli-
sation of iodic acid, 213.
— production of, during the atmo-
spheric oxidation of phospliorus ? 3.
solubility of, in water, 213.
Ozoniser, a new, 90.
Palladium, compound of, with ammonia
and mercury, 854.
preparation of, 854.
ammonium clilonde, 854.
Pallndoso-uranionium chloride or car-
bamido-pidladious chloride, 161.
Palmeliin extracted from algffi by water,
325.
preservation of solutions of, 720.
Palmitic acid, synthesis of an isomeride
of, 313.
aldehyde, preparation of, 867.
Pancreas, hydrolytic ferments of, 903.
Panification, digestive ferment produced
during, 776.
Papaya oil, 129.
Papayatiu, 128.
Papayotin, 129, 130.
Papayic acid, 129.
PapilioiuicetE, ligneous, chemical exami-
nation of, 735.
Para-anisidine, dibromo-, 641.
hydrochloride, monobromo-,
641.
Parabanic series, new derivative of,
105.
Paracotenes, 328.
Paracoto-bark, 325.
ethereal oil from, 328.
Paracotoic acid, 326.
Paracotoin, 326.
Paracotoin, action of bromine on, 326.
Paracotols, 328.
Paracresoldiazobenzene or paramethyl-
hydroxyazobenzene, 163.
Paracymenesulphonic acids, 632.
Paradiamidotoluene, 162.
Paradimethylamido-anisol, 639.
Para-ethylmethylphenol, 882.
Paraffins, isomeric, of the formula
C„Ho„+2, problem of estimating the
number of, 605.
normal, 158.
presence of, in plants, 914.
Paragonite, 533.
Parahydrocyanaldine, 313.
Parahydroxy benzoic acid, 240.
Pai*ahydroxybenzoyltropeine and its
salts, 714.
Parahydroxyphenylacetic acid and its
salts, 252, 255.
preparation of, from urine,
6W.
Paralbumin, detection of, 829.
Paraleucaniline, constitution of, 553.
nonomethylated, 390.
occurrence of, in tlie manufacture
of rosaniline, 162.
Paramethoxyphenylcinnamic acid, 253.
Paramethylhydroxyazobenzene or para-
cresoldiazobenzene, 163.
Parapapayotin, 130.
Paraphenylenediamine, colouring matter
containing sulphur from, 110.
Para,rosaniline, constitution of, 553.
Parasaccharic acid, 671.
Paratoluene sulphydrate, action of sul-
phuric acid on, 810.
Paratoluidine, action of benzotrichloride
on, 880.
derivatives, 386.
dinitro-, 635.
Paratolylbenzylsulplione, 811.
Paratrimethylanisolammonium iodide,
638.
Paratrimethylphenolammonium, 637.
Paraxylenc, trinitro-, 892.
Paraxylenediamine, 553.
Pai-azodibromosulphoxylbeuzene/S-naph-
thalein, 881.
Parazosulphoxylbenzene - /3-oxydisul -
phoxylnaphthalcue, 188.
Parazosulphoxylbenzene - phloroglucinol,
880.
Parazosulphoxylnaphthalene-resorcinol,
881.
Parazotoluene - /3 - uaphtho - disulphonic
acid, 881.
Parisobutaldehyde, action of certain re-
agents on, 103.
Parkes's method of estimating copper,
510.
I Parsnips, analysis of, 342.
1
INDEX OF SUBJECTS.
1005
for
on
Passive state of iron, 211.
Pasture, permanent, a substitute
clover, 499.
Pea haulms, digestibility of, 916.
Peat, use of, as manure, 506.
Peat water, injurious effect of,
meadows, 738.
Peaty soils, 182.
Pele's hair, composition of, 536.
Pelletierine, 481.
Pentadecoic acid, 34.
Pentathionic acid, 298.
non-existence of, 215, 367.
Pentenylamidophenvl mercaptan, 389.
885.
Pepsin, testing of, 424.
Peptone, 901.
— pure, preparation of, 901.
Perbroniic acid, preparation of, 91.
Perchloric acid as a test for alkaloids,
69.
Pereirine, 676.
Pereiro bark, 675.
Periodic atomicity, history of, 605.
law, Mendelejeff's, and the magne-
tic properties of the elements, 206.
Persulphuric acid, 607.
Petroleum, 199.
Phacozymase, soluble, 816.
Phanerogams, chlorophyll in the epider-
mis of foliage of, 910.
Phenanthraquinone, action of ammonia
on, 48.
action of methylamine on, 48.
dinitro-, 814.
from phenanthrol, 891.
Phenanthrene, constitution of, 814.
Phenanthrenedisulphonic acid, action of
phenols on, 474.
and its derivatives, 478.
bromO", salts of, 891.
Phenanthrenequinonimide, 48.
Phenanthrenesulphein-resorcin, 474.
Phenetol, diethylorthamido-. and its
salts, 465.
dinitro-, 467.
monethylnitro-orthamidonitroso-,
464.
monethylorthamido-, and its salts,
464.
nitramido-, 466.
orthamido-, ethyl-derivatives of.
463.
preparation of, 463.
Phenol, action of ammonium zinc
ride on, 813.
action of
chlo-
its vapour on orgamc
matter at high temperatures, 72.
compounds of benzotrichloride
with, 239.
— influence of, on germination, 335.
— dibromo-, 658.
Phenol, ethylene derivatives of, 316.
monethylorthamido-, and its salts,
464.
mononitrochloro-, crystaUographic
constant of, 384.
nitro-, Fittica's fourth, 463.
orthamido-, ethyl-derivatives of, 463.
orthamidonitroso-, 465.
tetrabromo-, 246.
tribromo-, bromide of, 246.
colours, new class of, 426.
and a-naphtliol, action of lead
oxide on, 664.
Phenolic aldehydes, action of acetic
anhydride on, 318.
PhenolaniUne, a-monochlorodinitro-, •
392.
Phenoldiazobenzene or hydroxyazoben-
zene, 163.
Phenolglycereiin, 426.
Phenolhydrophthalidin, 657.
chloride, 656.
Phenolorthosulphonic acid, action of
fused alkalis on, 320.
Phenolplithalein and its derivatives, ac-
tion of ammonia on, 657.
chloride of, or dichlorodiphenyl-
phthahde, 654.
conversion of phenylphthaUde into,
652.
formation
of oxyanthraquinone
from, 658.
fusion of, with potash, 657.
methyl salt of, 653.
phenylanthracene derivatives of,
656.
preparation of, 653.
triphenThnethane derivatives of,
653.
diimido-, 657.
tetrabromo-, 654.
. action of oxidising agents on,
654.
formation of dibromoxyan-
thraquinone from, 658.
oxidation of, 657.
Phenolphthaleinsulphonic acids, 653,
654.
Phenolphthalidein, action of ammonia
on the phenol compounds of, 657.
and its derivatives, 657.
fusion of, with potash, 657.
Phenolphthahdin, 656.
action of ammonia on, 657.
fusion of with potash, 657.
chloride, 656.
tetrabromo-, action of ammonia on,
657.
Phenolphthalin, 654.
action of ammonia on, 657-
chloride of, 655.
fusion of, with potash, 657.
lOOfi
INDEX OF SUBJECTS.
Phenolphthalin, tetrabromo-, 655.
Phenolphthalol, 655.
triacetyl derivatiTe of, 656.
Phenols, action of nitrosj-dimethylani-
line on, 881.
actioTi of, on halogen-derivatiTCS of
fatty acids, 392.
compounds of plithalic acid Tvitli,
650.
araido-, isomeric, action of methyl
iodide on, 636.
— - dinitrochloro-, two isomeric, 392.
Phenolsulphonic acid, 808.
dinitro-, 808.
• and its acid potassium salt, 810.
amido-, amides of, 612.
Phenoquinone, 318.
formula of, 247.
Phenoxyacctamidc, 319.
Phenoxyacotanilidc, 319.
Phenoxyacetie acid and its salts, 318.
monobromo-, 320.
orthonitro-, 319.
paranitro, 319.
Phcnoxyaectonitril, 319.
Phenoxyaci'tothianiide, 319.
Phenoxypropionic acid and its salts,
393.
■ monobrom-, 393.
Phenyl, substitution of, 813.
amido-bisulpliide, 386.
hydrocldoride, 386.
bromo-cyanate, 633.
bromo-dicyanate, 633.
chloride, isocyanomonobromo-, 631.
Phenyl ether, a-dinitro-, 612.
Phenylacotamide (a-toluylamide), his-
tory of, 650. ,
Phenylacetic acid, paramido-, 252.
paranit-o- and its salts, 119.
Phcnylaniidoacetic acid, 473.
Pheuylanthracene, 652.
derivatives of phcnolphthalein,
656.
dihydride, 652.
Phenylanthranol, 651.
o-dichloro-, 656.
Phenvlbenzamide, action of sulphur on,
386.
PhenylbctaTne or demethylphenylgly-
cocine, 1G2.
chlorethide, 162.
hydrochloride, 162.
Phenylbiurei, dibromo-, 633.
Phenylbroniolactic acid, 472.
Phenylcoumaric acid, acetyl-, 164.
Phenylcouniarin, action of sodium amal-
gam on, 164.
synthesis of, 164.
Phenylcyanamide, 44.
Phenylenedioxyaeetic acid, 33.
dibromo-, 33
Phenylenedithiacetic acid, 33.
Phenylenenaphthalene oxide, quinone
of, 664.
Phcnylethylpropionic acid, 406.
Pheuylfumaric acid, 43.
Phenylglycocine, bromo-, 634.
Phenylglyoxylic acid, test for, 67.
metamido-, (metaisatic acid),
253, 254.
Phenvlhalogenpropionic acids, constitu-
tion of, 42.
Phenvlhydrazine, ethyl-deriratives of,
242.
oxidation of, by mercuric oxide,
243.
Phenyl-a-hydroxypropionic acid, 471.
Phenyllactic acid, 471.
acids, constitution of, 42.
PhenyUactimide, 322.
Phenyl mercaptan, amido-, 386.
amido-, action of aldehydes
on, 887.
amido-, action of hydrocyanic
acid on, 887.
amido- oxaUc derivative of.
885.
886.
orthamido-, preparation of.
mercaptans, amido-, derivatives of,
886.
Phenylmethyliirethane, bromo-, 633.
Phenyluaphthalene, synthesis of, 125,
261.
Phenyl-/3-naphthylamine, 813.
Phenylnaphtliyliarbazol, 168, 663.
oxidation of, 663.
PiicDylnaphthylcarbazoline, 663.
iodide, 663.
Phenaphthylcarbazoquinone, 664.
Phenyloxanthranol, 651.
action of benzene on, 652.
Phenylvaleric acid, nitro-, reduction of,
407.
normal, 407.
Phenylthiocarbimide-glycoUide, 659.
Phcnylthiourethane, 6o9.
Phcnyluretliane, bi'omo-, 633.
Philippia, 7.
Phlobaphene, 650.
action of hydrochloric or hydriodic
acid on, 650.
Phlogopite, 533.
Phosphanilidesulphonic acid, dibromo-,
ethyl salt of, 321.
ethvl and methyl salts of, 321.
chloride, 321. '
PlK:spliate precipite, analysis of, 576.
Phosphates, action of ammonium citrate
on, 825.
action of sulphuric acid on, 425.
alkaline, condition of, in aqueous
solution, 2.
IXDEX OF SUBJECTS.
1007
Phosphates, comparatire value of solu-
ble and insoluble, 678.
distribution of, in the muscles and
tendons, 275.
influence of soluble and insoluble,
as manure for turnips, 186.
natural, and their value in agricul-
ture, 506.
— reduced and insoluble, agricultural
value of, 571.
soluble and reduced, action of, on
sods, 418.
Phosphenjl chloride, homologues of,
640.
sulphochloride, synthesis of, 558.
Phosphine, heat of formation of, 151.
Phosphonium iodide, action of, on car-
bon bisulphide, 370.
Phosphorescence, 598.
produced by electrical discharges,
204.
Phosphoric acid, behaviour of, in soils,
571.
combinations of, in the ner-
vous substance, 274.
• new alkalimetrical method
for estimating, 824.
— . new blowpipe, test for, 746.
— ■ preparation of, 367.
" reduced," contribution to
the knowledge of, 574.
retrograde, 739.
estimation of, as ammonium
citrate, 924.
separation of, from iron and
aluminium, 286.
volumetric estimation of, by
means of lU'anium in the presence of
iron, 575.
acids, ortho- and pyro-, separation
of, 574.
Phosphorite, Norwegian, 356.
preparation, 356.
Phosphorites, Belgian, 198,
Phosphoi-us, experiments tending to
show the non-elementary character of,
4.
luminosity of, 298.
antimony decachloride, Weber's,
613.
oxychloride, action of certain
metals and non-metals on, 609.
pentachloride, action of, on molyb-
dic anhydride, 219.
suboxide, Leverrier's, existence of.
609.
trichloride, action of antimony
pentachloride on, 613.
and iron, separation of, 74,
PhosphuranyUte, 97.
Phostolyl chloride, 640.
tetrachloride, 641.
Phosxyloehloride, 641.
Photographs exhibiting natural colours,
pi'oduction of, 72.
wet plate, rapid developer for, 765.
Photometer, chemical, a new, 361.
Phthalein derivatives, fusion of, with
potash, 657.
of haematoxyUn, 54.
PhthaUc acid, compounds of, with
phenols, 650.
dinitro-, and its salts, 478.
■ chloride, 473.
Phthahde, action of phosphorus penta-
chloride on, 473.
Phthahdein, 655.
bromo-, 656.
chloride, 656.
derivatives, fusion of, with potash,
657.
tetrabromo-, 656.
and its derivatives, 657.
Phthalidin, tetrabromo-, 655, 656.
Phthalylpiperide, 127.
Phthalyltropeine, 411, 715.
Phyllocyanic acid, Fremy's, 266.
Pliylloxanthin, 266.
Physico-chemical analysis of clay soils,
511.
Phytolacca decandra, 412.
Phytolaccin, 412.
Picoline, a- and /3-, 269.
PicoUnic acid, 268.
Picropharmacohte, 216.
Pig-iron, dephosphorisation of, 593.
Pilocarpine, 898.
Pinacohns, 646.
Pinacones, 646.
Pines, eiiect of manures on growth of,
509.
Pinitoid from Gleichlinger Fels, in the
Fichtelgebirge, analysis of, 857.
Piperidine, 127.
conversion of, into pyridine, 404.
salts, 54.
Piperine or piperonyl-piperidine, 405.
Piperonyl-piperidine or piperine, 405.
Pitchblende (uraninite) from Branch-
vUle, Conn., U.S., chemical composi-
tion of, 530.
Pittacal, formation of, 248.
acid, 164.
Plant life, lime in, 56S.
Plant material, passage of, in seedhngs,
335.
Plants, absorption of oxygen and ex-
piration of carbonic anhydride by,
416. .
albumin and amido-compounds m,
279.
. amount of dew on, 493.
breathing of, 911.
calciimi oxalate in, 914.
]008
INDEX OF SUBJECTS.
Plants, decomposition of albuminoids in,
493.
decomposition of nitric acid and
ammonia in, 731.
energj of assimilation in, PIO.
estimation of non-albiiminous ni-
trogen-compounds in, 513.
• etiolated, causes of the change in
the form of, 177.
growing in natural soils, beharioxir
of, towards water, 737.
growth of, in artificial solutions,
337.
increase of dry matter in, during
growth, 416.
intluence of atmospheric electricity
on the growth of, 90'J.
influence of light on the growth of,
57, 911.
influence of nutritive material on
the transpiration of, 335.
injurious effect of industrial effluent
water on, 497.
intramolecular respiration of, 911.
locality of albumin secretion in,
492.
— loss of dried substance in, during
ripening, 820.
marsh and water, resiiirative power
of, 335.
— narcotic, extracts of, 425.
passage of nutritive maleiial in,
493.
-^— presence of alcohols and parafllns
in, 914.
proximate analysis of, 754.
quantities of amides and albumi-
noKls in, 731.
starch-altering ferments in, 334.
iinorganised ferments in, 175.
which grow on primordial rocks,
presence of copper in, 494.
Platinates, compound, 706.
Platinic bromide, preparation of, 445.
chloride, preparation, for the esti-
mation of potassium, 577.
Platiniferous iron, 222.
Platinochlorides of the alkali and alka-
line earth metals, solubility of, in alco-
hol, 578.
Platino-potassium salt, a new, 706.
Platinum, action of fused alkaline carbo-
nates on, 581.
' action of sulphuric acid on, 706.
volatility of, in chlorine, 94.
bases, 300.
metals, chemisti-y of, 854.
still, explosion of, used for concen-
trating sulphuric acid, 517-
sulphide, 223.
thiocyanate, 618.
I'lumbic acid, salts of, 94.
Podophyllin, 479.
Polariscope, use of, in testing crude an-
thraquinone for anthracene, 292.
Poly erase, 15.
Pomegranate, alkaloids of, 481.
"Ponceau, K. K.," 717.
PopuHn, sugar from, 29.
Porosity of soils, estimation of, 822.
Porphyi-y from the paper mill, near
AVcilburg, Nassau, analysis of, 856.
Potash, commercial, new process for
analysing, 286.
specific heats of solutions of, 435.
Potash-micas, 224.
Potashes, direct estimation of soda in,
580.
Potassium, estimation of, as platino-
chloride, 577.
operations in estimating, 579.
acetate, action of potassium di-
chromate on, 160.
aluuiinate, 849.
azophenyldisulphonate, 322.
benzcnesulphinate, 811.
benzylsulphonate, fusion of, with
potash, 812.
— bismuth iodide, preparation of,
705.
— boroduodecitungstate, 612.
chloride, heat of formation of, 89.
chlorate, heat of formation of, 89.
copper chromate, non-existence of,
853.
cyanide, action of potassium per-
manganate on, 307.
ferric chromates, 10.
ferrous oxalate, and its use for
developing photographic bromide of
silver plates, 590.
reducing properties of.
54i.
— hydrindigotin-sulphate, 475.
— iodide, action of, on hydrogen per-
oxide, 606.
— indoxyl-sulphate, 475.
nitrate, distribution of, in the beet.
733.
nitrophenylsulphate, crystalline
form of, 106.
pcrchlorate, reduction of, 2.
permanganate, decomposition of,
by hydrogen peroxide, 444.
platinochloride, solubility of, in
alcohol, 578.
plumbate, 94.
polysulphides, heat of formation
and hydration of, 689, 690.
pyrosuiphate, action of, on indigo-
■white, 46.
sulphate, chemical equivalent of,
437.
tetrathionate, 215.
I
INDEX OF SUBJECTS.
1009
Potato, influence of manure on starch
in, 915.
relation between the starch, phos-
phoric acid, and mineral constituents
of, 912.
blossom, influence of, on the amount
of produce, 502.
— culture, 919.
— disease, influence of manure on, 915.
mash, influence of fermentation on
the nitrogenous constituents of, 819.
surface fermentation of, 518.
rot, sweet, 915.
Potatoes, action of different manures on
the yield of, 187.
alcoliol from, 833.
amount of albuminoids in, 568.
analysis of, 734.
application of, in the preparation
of yeast, 200.
best mode of applying artificial
manures to, 824.
— bone-meal as a manure for, 739.
dry and wet rot in, 416.
— estimation of starch in, 512, 513.
— frozen and rotten, chemical changes
in, 820.
— globulin-substances in, 723.
leucine and tyrosine in, 342.
Pressures, varying, influence of, on grape-
must and wine, 358.
Primavera-wood, 596.
Propaldehyde, /3-chloro-, 234.
Pro^Jenylamidophenyl mercaptan, 389.
Propenylbenzenesulphamide, 166.
Propionic acid, double salts of, 799.
some derivatives of, 312.
a-bromo-, decomposition of,
by water, 380.
a-dibromo-, maleic and malic
acids from, 374.
/3-iodo-, 800.
decomposition of.
water, 380.
a-monochloro-.
action of
phenol on, 393.
^-nitro-, preparation of, 33.
a-nitroso-. and its salts, 712.
Propionitril, a-amido-, 313.
■ ■ a-imido-, 313.
Propionylamidophenyl mercaptan, 885.
Propyl alcohol, action of bleaching
powder on, 456.
normal, from glycerol, 372.
heat of combustion of,
787.
diiodo-, 538.
■ action of potash on,
538.
amidoethyl formate, 312.
Propviene clilorobromide, direct forma-
tion of, 456.
Propylene chlorhydrin, action of di-
metbylamine on, 877.
Propylene glycol, preparation of, from
glycerol, 232.
Propyleneneurine chloride, 877.
Propylneurine, 877.
Propvlphyeite, action of bromine on,
862.
Propylpyrogallol, 249.
Proteid required by the average work-
man, 905.
tissue change, influence of glycerol
on, 817.
Proteids, estimation of, in fodder, 588.
influence of glycerol on the decom-
position of, in the animal body, 817.
products of the decomposition of,
482.
Protem, digested, quantitative estima-
tion of, 563.
compounds, 676.
Proustite, 302.
PseudoleucaniUne (triamidotriphenyl-
methane), a new, 662.
compound of, with benzene, 662.
Pseudopelletierine, 481.
Ptyalin, 562.
action of, on starch, in presence of
gastric juice, 330.
Pumpkin, certain sorts of, 184.
sf)routs, decomposition of albumi-
noids in, 180.
Pyi-argjrite, 304.
Pyridine, conversion of piperidine into,
"404.
series, bases of, 480.
Pyridinecarboxylic acids, 410.
and their salts, 405.
Pvridinetricarboiylic acid from cinchona
'alkaloids, 406.
Pyrites, estimation of sulphur in, 744.
valuation of, by the gravivolumetric
method, 583.
Pvrochlolesteric acid, preparation of,
'56.
Pyrocinchomeronic acid, 406.
Pyrocinchonic acid, 406.
Pyrogallol, antiseptic action of, 73.
benzoyl derivatives of the dimethyl
ethers of' 249.
ethylene ether of, and its deriva-
tives, 250.
Pyromorphite from Dernbach, near
Montabaur, ?fassau, 858.
Pyroterebic acid, 315.
— ^ action of hydrobromic acid
on, 378.
Pyroxyhn, composition of, 372.
Pyrrol, formation of, from succinimide,
"630.
Pvrroline, 713.
boiling point of, 404.
1010
IXDEX OF SUBJECTS.
Q.
Quartz and orthoclasc, simxiltaneous re-
production of, 532.
Quinamine, 270.
Quinhvdrone, 318.
formula of, H, 247.
Quinic acid, and allied compounds, 317.
Quinine citrate, bibasic, economical pro-
cess for preparing, 126.
selcnatc, 54.
sulphate, 54.
Quinol, or b vdroquinone, 317.
nionobromo-, 42.
Quinol gljcere'in, 427.
Quinoline, 44.
oxidation of, 409.
preparation of, 072.
synthesis of, 672.
■ synthesis of the homologues of,
406.
Quinolinecarboxylic acid, 398.
Quinolinemonocarboxylic acid, oxidation
of, 409.
Quinols, chlorinated, 888.
Quinone and allied compounds, 317.
brouiine-derivatives from, 385.
from the hydrocarbon CieHjo, deri-
vatives of, 665.
occurring in Agaricus atrotomen-
tosus, 47.
bronio-, 657.
bromotrihydroxy-, 114.
triaeetoxy-, 114.
trihydroxy-, 114.
Quinones, action of ammonia and amines
on, 48.
chlorinated, 888.
polymeric, 665.
R.
Eacemic acid, preparation of the ethereal
salts of, 876.
Radiant heat, direct transformation of,
into electricity, 838.
Rainfall, comparative, in woods and
fields, 737.
influence of forests on, 737.
Rain water, ammonia in, 848.
Raisins, sugar in, 932.
Raspberries, wild and cultivated, 936.
Reactions, speed of, 438.
Red antimony, 612.
clover seed, production of, 729.
colour, production of, in salting
meat, 80.
lead, volumetric analysis of, 585.
Refraction, table of coefficients of, of
carbon compounds, 781.
Refractive power and density, cbemical
constitution of carbon compounds in
relation to theii", 295.
Refractory materials, magnesium and
calcium compounds as, 831.
Refuse water, purification of, 830.
Refrigerating mixtures, 784.
Rennet, action of, on casein, 172.
Resin from rosewood, 559.
from Teratrum vin'de, saponifiea-
tion of, 171.
formation of, 125.
in commercial oils, analysis of,
684.
oils, analysis of, 683.
Resins, specific gravities of, 70.
Resoquinone, 247.
Resorcinol, or resorcin, manufacture of,
and colouring matters derived from it,
426.
products obtained by tlie action of
aqua regia on, 645.
pentabromo-, 246.
trinitro-, 113.
Resorcinolbenzein, 644.
tetrabromo-, 644.
Resoreinoi-isosuceinein, 885.
Resorcinol-succinein, 248.
Respiration, function of, at various
altitudes on the Island and Peak of
Teneriffe, 483.
under reduced pressure, 903.
Rhamnetin, fusion of, with potash, 53.
Rhexite, 595.
Rhodium with lead and zinc, action of
acids on alloys of, 706.
Rice husks, adulteration of rye bran
with, 200.
Rice meal, analysis of, 678.
Rittingcrite (feuerblende) from Cha-
narcillo, 856.
River Yartry, water of, 21.
Rock crystal from Kasbek, 615.
salt from Saltville, 95.
Rocks, bituminous, commercial valua-
tion of, 682.
eruptive, in the Saar and Moselle
districts, 537.
— primary, existence
708.
of zinc in,
Roots, influence of salts on the absorp-
tion of water by, 911.
Rosaniline, detection of, in red wine,
680.
group, dye-stufFs of, 390.
occurrence of paraleucandine in
the manufacture of, 162.
constitution of, 553.
Rosewood, resin from, 559.
Rouge Francjais, 664.
Roussin's salt, 217, 218.
Rubidine, 267.
INDEX OF SUBJECTS.
lOU
Rye as a material for pressed Teast,
777.
fertilisation of, 493.
manuring experiments with, 508,
738.
— bran, adulteration of, "with rice
husks, 200.
s.
Saccharic acid, action of phosphorus
pentachloride and hydriodic acid on,
36.
Saccharin, 232, 233, 620.
Saccharosis, remarks on, 233.
Saculmic acid, 538, 865.
Saculmin, 538, 865.
Saculmous acid, 865.
Safranine, 391.
Salicaklehjde, action of acetic anhydride
on, 318.
Salicylanilide, a-nitro-, 556.
Salicylic acid, antiseptic action of, 515.
destructive action of wood
on, 520.
detection of, in wine and in
fruit juices, 352.
■ ethylene deriratiTes of, 316.
solubility of, 471.
and other bodies, influence
of, on germination, 335.
metachloro-, nitration of,
392.
nitrochloro-, and its salts,
392.
acids, isomeric nitro-, 121.
Salicylorthonitranilide, 556.
action of nascent hydrogen on,
556.
Salicyltropeine, 410.
Saligeuol, action of mannitol and of
glycerol on, 7 1 6.
synthesis of, 318.
Sahne solutions, supersaturated, action
of oils on, 438.
. tension of the yapours of,
211.
Saliretone, 716.
Saltpetre, Chih, manure experiments
with, 507.
potash, 507.
Salts, double, existence of, in solution,
32.
halo'id, oxidation of, 436.
hydrated, relation of the volumes
of solutions of, to their water of com-
position, 212.
influence of, on the absoi'ption of
water by roots, 911.
obtained from the mother-hquors
of the brine springs of Volterra,
146.
Samarskite, the new metals of, 611.
^ap, estimation of, in beet, 829.
of beetroot, pi'eparation of sugar
from, 931.
of trees and specific gravity of
their wood, 912.
Sap-quotient of beet, 931.
Sausages, adulteration of, 422.
estimation of starch in, 826.
Satureja Juliana, 128.
Scandia, 7, 850.
ScaucUum, 7.
atomic weight and characteristic
salts of, 850.
— — bright-Une spectrum of, 685.
salts of, 8.
hydrate, 8.
oxide, 8.
Schizomycetes, vital power of, in ab-
sence of oxygen, 277.
Schizomycetic fermentations, 819.
Scorodite, artificial jjroduction of, 613.
Sea waters, existence of zinc in, of all
ages, 708.
Seed of GleditscMa glabra, composi-
tion of the kernels and husks of,
133.
production of red clover, 729.
peas, damage to, by weevil, 734,
919.
prevention of the damage to,
by weevil, 734.
Seedlings, passage of plant-material in,
335.
Seeds, new method of estimating the air
space in, 189.
of earth-nut, sunflower, cocoa-nut,
rape, and potatoes, investigation of,
677.
of the corn-cockle as fodder and
distillery material, 501.
oily, "albuminoids of various, 676.
• pea and beau, damage to, by
weevU, 919.
resistance of, to the prolonged ac-
tion of chemical agents, 280
result of drying, 493
Selenious acid, constitution of, 607.
Selenium, vapour-density of, 847.
ethoxylchloride, 608.
Seleniuretted hydrogen, decomposition
of, by mercury, 150.
Serine, Cramer's, 713.
from silk, constitution of, 800.
Serum, non-identity of the albuminoids
of crystallin with, 815.
Sewage, report on the treatment of, 767.
Shade, influence of, on the amount of
carbonic anhydride in the air of the
son, 823.
1012
INDEX OF SUBJECTS.
Shade, influence of, on the gi-owth of
forest trees, 566.
Shearing, influence of, on yield of mUk,
487.
Sheep, assimilation in, of all ages,
724.
digestion by, 484.
■ poisoning of, by lupines, 57, 916.
results with stall-feeding of, 503.
Shells of crabs, oysters, mussels, &c., as
• manure, 60.
Shingle, amount of carbonic anhydride
in, 181.
Silber-kies (sulphide of silver), 14.
Silesian basalts and their mineral con-
stituents, 19.
Silica in mortar, action of lime on,
216.
Silicates, decomposition of, 503.
Silicic anhydride, separation of, in the
analysis of limestones, iron ores, &c.,
745.
Silico-oxalic hydrate, preparation of,
608.
Silicon, chemical composition of tlie hy-
dratod oxides of, 849.
ethyl series, 608.
fluoride, action of water on, 435.
hexbromide, preparation of, 608.
hexcliloride, preparation of, 608.
liexethidc, preparation of, 609.
hexiodide, preparation of, 608.
nitride, 153.
sulphide, Iicat of formation of, 523.
trihydride, 298.
Silk, weighting of, 935.
Silver, crystal tectonic of, 613.
electrolytic estimation of, 747.
■ estimation of, by quartation with
cadmium, 679.
estimation of, in galena, 748.
metallic, action of, on hydrogen
oxide, 441.
ammonium oxide, 852.
bromide gelatin emulsion, 929.
photochemical behaviour of,
in presence of gelatin, 837.
chloride battery, electric discharge
of, 203.
iodide with calcium iodide, com-
pound of, 442.
lead, blowpipe assay of, 585.
oxide, action of hydrogen peroxide
on, 441 .
sesquioxide, 441, 442.
sulphide (silber-kies), 14.
ultramarine, 217.
Sinalbin, 265.
thiocarbimide, 265.
Sinapin, 265.
cyanide, 265.
sulphate, 265.
Skatole, 258.
constitution of, 473.
empirical formula of, 167.
Skim-milk, composition of, from De
Laval's cream separator, 780.
Skimming by the Schwartz's and Hol-
stein systems, experiments with, 934.
process, new, 933.
Skin, action of hydrochloric acid on,
723.
Smithsonite, analysis of, 857.
Smithson's pile, use of, for the detection
of mercury in mineral waters, 510.
Smoke, influence of, on the development
of blossoms, 177.
of an electric lamp, 81.
Soaps, separation of fats from, 587.
Soda, direct estimation of, in potashes,
580.
preparation of, from the sulphate
by means of lime and sulphur, 592.
specific heats of solutions of, 435.
Soda-lyes, crude, mode of desulphuri-
sing, obtained in the Le Blanc pro-
cess, 592.
Soda-micas, 224.
Sodium aluminate, 849.
camphor, 892.
chloride, removal of large quanti-
ties of, in mineral analyses, 580.
formate acetate, 799.
livpophosphite, pure, preparation
of, 367.
paratoluenesulphinate, action of
ethylidene chloride on, 811.
— phenate, formation of parahydroxy-
benzoic acid from, 43.
platinochloride, solubility of, in
alcohol, 578.
polysulphides, heat of formation
of, from their elements and the mono-
sulphide, 690.
— • silicotitanates, two new, 531.
sulphate, chemical equivalent of.
437.
— thiacetanilide, reactions of, 556.
trichloracetate, dry distillation of.
236.
SDil, absorption of ammonia by, 737.
estimation of the porosity of,
822.
from a graveyard, investigation of
the composition of, 920.
formation of nitric acid in, 59.
influence of, on the growth of
forest trees, 566.
influence of, on the tannin of oak-
bark, 920.
influence of shade on the amount
of carbonic anhydride in the air of,
823.
permeability of, for air, 821.
IXDEX OF SUBJECTS.
1013
Soil-constituents, absorptive power of,
for gases .134.
action of soluble and reduced
phosphates on, 418.
Soils, analysis of, from the Bunter sand-
stone formation, 281.
• behaviour of phosphoric acid in,
571.
determination of the chemical pe-
cuUarities of, and manures requisite
for them, 418.
free carbonic anhydride in, 505.
fonnation of, by weathering, 449.
injurious effect of industrial ef-
fluent water and of gases on, 497.
natural, behaviour of, towards
water, 737.
peaty, 182.
Soja bean, digestibility and nutritive
value of, 501.
Soja hispida, presence in, of a substance
soluble in alcohol, and transformable
into glucose, 796.
Solar heat, industrial utilisation of, 765.
spectrum, dark lines in, on the less
refrangible side of Gr, 201.
photograph of the ultra-red
portion of, 429.
Solid bodies, absolute expansion of, 88.
SoUds, solubihty of, in gases, 210, 693.
Solutions, action of, on seeds, 281.
Sonorous vibration, chemical stability of
matter in, 43.
Sorbic acid, 377.
structiire of, 382.
Sorgho, sugar from the stems of, 834.
Sorghum, amount of sugar in, 594.
Sorghum saccharatum, 932.
Sowing broadcast or in drills, 922.
Spanish earth, clearing action of, 517.
Specific gravity, new form of instrument
for the determination of, 743.
of carbon compounds, deter-
mination of, 572.
of liquids, determination of,
61, 419, 743.
gravities of fats, resins, &c., 70.
of soKd carbon compounds.
21, 694, 781.
Specific heat of animal tissues, 483.
of cerium tungstate, 852.
. of concentrated solutions
of
hydrochloric acid, 207.
of glucinum, 792, 850.
of the solid elements, 783.
of water, 601.
heats of solutions of potash and
soda, 435
of the rare earths and their
salts, 838.
Specific refraction of organic com-
pounds, table of, 781.
Specific weights of the rare earths and
their salts, 838.
Spectra, emission, of lialoid mercury
compounds, 81.
of calcium and strontium, 361.
of metalloids, 430.
of the earths of the yttria-group, 7.
Spectral lines of gases, relative intensity
of, 685.
Spectroscope, use of, in discriminating
anthracenes, 757.
Spectrum, acceleration of oxidation
caused by the less refrangible end of,
429.
briglit-line, of scandium, 685.
of oxygen, 430.
solar, dark lines in, on the less re-
frangible side of Gr, 201.
ultra-violet Umit of, at various
of the refractory metals,
149.
heights, 201.
Spever beer, analysis of, 773.
>pice seeds, certain, analyses of the ash
of, 915.
Spike, essence of, 50, 51.
SpineUe, artificial production of, 447.
oriental, j)olysynthetical twin-crys-
tals of, 14.
red and blue, composition of, 369.
Spirit, purification of, 931.
Stag's horn, constitution of, 271.
Stall-feeding of sheep, results with, 503.
Stall sampling in milk analysis, 925.
Standard soda solution, 924.
Stannous chloride, vapour-density of,
219.
Starch, action of diastase on, 132.
action of diastase on, in presence of
hvdrocliloric acid or pure gastric
juice, 330.
action of glycerol on, 865.
action of ptyalin on, in presence of
gastric juice, 330.
changes which it undergoes in the
animal organism, 677.
estimation of, in potatoes, 512, 513.
estimation of, in sausages, 826.
in potato, influence of manure on,
915.
influence of steaming on, 834.
production of sugar from, 932.
— saccharification of, 866.
soluble, 865.
Starchmaker's residues, some analyses
of, 595.
Starch-paste, action of diastase on, 310.
Starch-sugar, detection of, when me-
chanically mixed with refined cane-
sugar, 758.
Steaming, influence of, on the digestibi-
lity of hay, 734.
1014
INDEX OF SUBJECTS.
Stearic aldehyde, preparation of, 867-
Steel, estimation of chromium and tung-
sten in, 288.
estimation of total carbon in, 751.
presence of nitrogen in, 749.
Siemens-Martin, 769.
Stereocatdon resuvianum, chemical con-
stituents of, ool.
composition of the ash of,
382.
crystalline body from, 382.
Stilbene, compounds of. Hi.
Stilbophenol, 253.
StUlbite, 856.
Strong's water gas system, 930.
Strontium, spectrum of, 361.
dichromate, preparation of, 4-1-1.
action of suljihurous anhydride on,
606.
platinochloride, solubiUty of, in
alcohol, 579.
Styrene, /3-bromo-, 43.
Styrolene, bromo-, conTcrsion of, into
mcthylpbenylketoiie, 469.
Suberic acid i)roduced by oxidation, and
its salts, 872.
Substances, dry, determination of, by the
use of alcohol, 351.
showing strong bands of absorption
in tlie spectrum, 202.
Succinic acid, action of iodine on the
silver salt of, 801.
heat of formation of salts of,
151.
394.
dibromo-, action of phenol on,
chloride, constitution of the reduc-
tion-product of, 712.
Succininiidc, action of phosphorus penta-
chloride, and of zinc dust on, 713.
action of zinc on, 630.
Succinin, 163.
Sugar,
action of lime on solutions of,
834.
— amount of, in sorghum, maize, and
melons, 594.
amount of, in the roots of sugar-
beet, 586.
— analysis of, 519.
chemistry of, 863.
— decomposition-products of, 864.
— estimation of, in beet juice, 144.
formation of, in the liver, 905.
from populin, 29.
from the date-palm, 100.
from the stems of maize and sorgho,
834.
— gypsum in the manufacture of,
834.
— in raisins, 932.
in the liver, nnture of, 866.
inactive and inverted, 100, 458.
Sugar, inverted, patent process for pre-
parinu, 425.
neutral and inverted, 100, 458.
phvsiology of, in relation to the
blood," 486. '
preparation of, from sap of beet-
root, 931.
production of, from starch, 932.
proportion of, to the weight of
beetroots, 519.
quantity of, in grapes cut at
various stages of their growth, 179.
— rapid estimation of, in raw and
refined commercial sugars, 64.
— raw, experiments with Scheibler's
method of analysing, 14-t.
— raw, valuation of, 520.
Scheibler's new process for the
estimation of, in beet, 587.
— - idmic compounds formed from, by
the action of acids, 538.
— volumetric estiniation of, bv an
ammoiiiacal copper test, giving reduc-
tion witliout precipitation, 512.
volunictrical estimation of the re-
ducing power of, 758.
Sugar beet. See Beet,
Sugar lime, direct decomposition of, 931.
Sugar solutions, action of bone-black on,
758.
Sugar syrups, bleaching of, by ozone,
74.
Sugars, cupric test pellets for, 761.
raw, occurrence of vanillin in, 646.
various, behaviour of, with alka-
line, copper, and mercury solutions,
758.
various, behaviour of, with Feh-
ling's solution, 66.
various, reducing power of, 759.
Suint, 520.
Sulphaminemetatoluic acid, oxidation of,
473.
Sulphanilic acid, and its salts, 239, 320.
Sulphates, alkalimetric estimation of,
744.
anhydrous, heat of formation of,
82.
of mono- and poly-hydric alcohols
and carbohydrates, 28.
volumetric estimation of, 576.
Sulphinic acids, constitution of, 810.
Sulplionamidoparatoluic acid, 257.
Sulphones, new synthesis of, 810.
Sulphonic acids, action of fused alkalis
on, 320.
from isomeric nitramido- and
diamido-benzenes, 394.
Sulphonic group, influence of nitro- and
amido-groups on a, entering the ben-
zene molecule, 238.
Sulphontcrephthalic acid, 257.
INDEX OF SUBJECTS.
1015
Sulphur, an experiment with, 700.
condition in which it exists in coal,
708.
estimation of, in natural sulphides,
139.
estimation of, in pyrites, 744.
free, occurrence of, in the dry dis-
tillation of tar, 831.
heat of combustion of, 785
organic compounds, easy process
for detecting, 348.
— — mode of action of, as a remedy
against vine-disease, 281.
oxidation of, in gas when burnt,
355.
—— oxygen-acids of, 5.
Sulphur-baths, observations on, 196.
Sulphuretted hydrogen, behaviour of,
■with the salts of the heavv metals,
746.
Sulphuric acid, chemical equivalent of,
438.
— — chamber, introduction of
nitric acid into, along with the steam,
196.
estimation of, in must and
wine, 586.
■ estimation of nitrous com-
pounds in the manufacture of, 745.
etherification of, 796.
presence of, in milk, 423.
Sulphuric anhydride, heat of vaporisation
693.
monochloride, action of, on alco-
hols, 310.
Sulphurous acid, detection of, in wine,
680.
anhydi-ide, action of, on the oxides
of the alkahne earth-metals, 606.
Sumach leaves, tannin of, 732.
Sun, existence of carbon in the coronal
atmosphere of, 429.
Sunlight, continuous, influence of, on
plants, 911.
Sun's ravs, measurement of the actinism
of, 685.
Superphosphate, influence of the physi-
cal condition of, on its value, 60.
manure experiments with, 507.
action of sulphuric acid on phos-
phates, in connection with the manu-
facture of, 425.
analysis of, 140.
containing iron and aluminium,
retrogradation of, 703.
from pure tricalcium phosphate.
141.
mineral, analysis of, 576.
reduction of, 571.
Sweat, influence of the secretion of, on
the elimination of niti-ogenised decom-
position-products, 818.
Sweet potato-rot, 915.
Swine, feeding experiments on, 724.
Sylvane, 663.
action of hydrochloric acid on,
663.
Symphytum asperrimum as a fodder,
735.
Synanthrose, 619.
Syinips, fermentations produced in pre-
paring, from beet juice by diffusion,
519.
T.
Ta'iguic acid, 267.
Tannin, artificial, 122.
in wine, 775.
of oak-bark, influence of soil on
920.
of sumach leaves, 732.
solutions, action of light and dark-
ness on, 908.
Tanning, mineral, 427.
Tantalates, American, analysis of some,
531.
Tar, animal, compounds from, 267.
occurrence of free sulphur in the
dry distillation of, 831.
Taraxacum root, 720.
Tartar in must and wine, 774.
Tartaric acid, action of iodine on the
silver salt of, 801.
preparation of the ethereal
salts of, 876.
Tartronic acid, 629.
Tayuya, 721.
Tellurium, vapour- density of, 847.
Temperature, influence of, in the pre-
paration of ozone, 90.
of decomposition of vapours, 209,
293.
determinations, calorimetrical, 434.
Tendons, distribution of phosphates in,
275.
Teneriffe, the function of respiration at
various attitxides on the Island and
Peak of, 483.
Tensions of saturated vapours, compari-
son of the curves of, 435.
Terebenthene, electrolysis of, 479.
leevorotary, action of alcohol and
sulpliuric acid on, 559.
• laivorotary, from French tiupentine
oil, 559.
monohydrate, 479.
hydrate, 559.
Terephthahc acid, dibromo-, and its
salts, 632.
Terpene, Isevorotary, from French tur-
pentine oil, changes produced by hy-
dration and dehydi'ation in, 402.
1016
INDEX OF SUBJECTS.
Terpene, dihydrochloridc, 403.
hydrate, laevorotary, 402.
monochlorhydrate, 403.
Terpenes, hydration of, 264.
Tertiary aromatic bases, compounds of
benzotrichloride witli, 239.
bases, ferro- and ferri- cyanides of
certain, 98.
butyl cyanate, 228.
Tetrabromodibenzylene - paradimethyl-
phenylamine, 879.
Tetracetodioxybenzliydrol, 658.
Tetracetylquinide, 317.
Tetracrylic acid, monochloro-, behaviour
of, on fusion, 630.
Tetrahedrite from Huallanca, Peru,
220.
Tetrahydroxytriphcnylmethane, 61-t.
Tetramethylammonium nitrate, forma-
tion of, 545.
Tetramethyldiamidodiphenylmethane,
108.
Tetramcthyldiamidotriphenylmethane,
40.
Tetramethylmetaphenylenediamine, a. -
tion of bromucctylbcuzene on, 639.
and its sjilts, 111.
Tetramethylparaplicnylenediamine, ac-
tion of oxidir^inj; agents on. 111.
colourini; matters obtained by the
oxidation of, 111.
Tctramethylphcnylcncdiamine ferrocya-
nides, 99.
Tetramethyltolylcncdiamine, 109.
Tetraphent)!, or furfurane, 663.
Tetraphenylethane, Tapour-density of,
679.
Tetraphenylethylene, 558.
Tetrathionic acid, 215.
Tetrethvlcholanic acid, 723.
Tetrethyl citrate, 36.
Tetrolic acid, action of phosphorus
pentachloride on, 626.
and its homologucs, 625.
Thapsia, false, or ckka, resin from,
718.
Thapsia garganica, 718.
Thapsic acid, 718.
Thaumasite, 16.
Thcniial absorption of flames, 206.
Thermobarograph, 783.
Thermochemical researches, 363.
Thermochemistry of cuprous chloride,
208.
Thermoelectric properties of liquids,
431.
Thermometer electro-capillary, 205.
Thiacetic acid, derivatives of, 33.
Thiacctomethylanilide, 557.
Thiacetotoluidides, two isomeric, melting
points of, 557.
Thiamides, 556.
Thioearbamide, action of monochlor-
acetylcarbamide on, 631.
action of monochloi-acetyldimethyl-
carbamide on, 631.
di-isobutyl-, 548.
dinaphthyl-, 245.
diorthoto'lyl-, 244.
lactyl-, 312.
• mono- and di-anisyl-,642.
monobromophenyl-, 634.
monophenyl-, action of alcoholic
ammonia on, 44.
phenylbromophenyl-, 634.
propionyl-, 312.
tertiary amyl-, 548.
tertiary butyl-, 518.
tolyl-, ortho- and para-, 386.
tolylethyl-, ortho- and para-, 387.
tolylphenyl-, ortho- and para-,
:is7.
Tliiocarbamides, aromatic, 4-k
Thiocarbimide, acetoxy-, 659.
acetoxyphenyl-, 388.
amidophenyl-, 388.
bromophenyl-, 633.
chloronitrophenyl-, 387.
anilidophenyl-, 388.
chlorophenyl-, 387.
base from, 388.
et]ioxvi)henyl-, 388.
phcnyl-i.hcnyl-, 389.
tertiary amyl-, 548.
Thiocarbimides, a series
bases ij^omeric with, 387.
chlorophenyl-, 388.
Thiocyanates, use of, in calico printing,
358'.
Thiodiglycollic ncid, 236.
Thiodilactic acid, new method of prepar-
ing, 238.
Tliioformobromanilide, 634.
ThioglycoUic acid, characteristic reaction
of, 236.
nitroso-, and its salts, 630.
Thiohydantoin, action of chlorine and
bromine on, 631.
decomposition of, by barium hy-
drate, 236.
dibromo-, 631.
formula of, 45.
synthesis of, 877.
Thiohydauto'ins, formula? of, 44.
Thiophenol, action of sulphuric acid on,
810.
Thiosulphonates, synthesis of ethereal
salts of, 812.
Thiotetrapyridine, action of dilute nitric
acid on, 672.
distillation of, with metallic copper,
672.
Thomsonite, liutonite, and other forms
of, 535.
of aromatic
INDEX OF SUBJECTS.
1017
Thymol, nitro-, action of nitric acid on
the metliyl ether of, 883.
action of, on monochloracetic acid,
393.
— influence of, on germination, 335.
— liquid, 892.
ethers of, products of the oxidation
of the, 246.
monobromo-, methyl ether of, 884.
nitroso-, crystalHne form of, 548.
Thymolcarboxyhc acid, 889.
Thymolglycollamide, 889.
Thymolglycollic acids and their salts,
888.
Thvmoxyacetic acid, 393.
Thulia, 7.
Thulium, 7.
Tin, chemical composition of the hy-
drated oxides of, 849.
Clarke's method for the separation
of, from arsenic and antimony, 289.
Tinctiu-es, analytical examination of,
194.
Tinning solution, 425.
Titanates from Smaland, 15.
Titaniferous iron ore, 15.
Titanium tetrachloride, compound of,
with acetic chloride, 624.
Tobacco, influence of manures on the
combustibility of, 417.
Italian, improvement of, 200.
manured, amount of chlorine in,
417.
combustibility of, 417.
Tokay wines, analysis of, 833.
Tolane, oxidation of, 259.
dibromide, 259.
tetrachloride, peculiar formation
of, 259,
Toluene, a new base obtained by the
perchlorination of, 387.
and its derivatives, action of bro-
mine on, 878.
orthonitro-, anthi-anilic acid from,
648.
paradiamido-, 162.
a-Toluenedisulphonic acid, oonsdtution
of, 889.
Toluenedithiaoetic acid, 33.
Toluenemetasulphonic acid, Beckurt's,
810.
Toluenemonosulphonic acids, 256.
a-Toluic alcohol, amines corresponding
with, 211.
Toluidine, carbamides derived from, 245.
compounds of, with mercuric bro-
mide and iodide, 632.
ci-ude, estimation of metatoluidine
in, 110.
— dibromo-, 879.
dinitro-, symmetrical, preparation
of, 636.
VOL. XXXVIII.
Touhdine, nitro-, crystalline fonn of,
105.
Toluidines, dimethyl-, action of benz-
aldehyde on, 636.
Toluquinone, trihydroxy-, 114.
a-Toluylamide (phenylacetamide), his-
tory of, 650.
Tolyl chloride, 161.
Tolyldimethylaniidophenylsulphone,108.
Tolylenediamines, 162.
Tolvlglycocine, 713.
Tolylplienol, 161.
Tolylphosphinic acid, 641.
Tolyphosphorous acid, 641.
Torylurethane, 713.
Tonga, 836.
Trachytes, minerals contained in certain,
from the ravine of Eiveau Grande, at
Mont Dore, 225.
Transpiration of plants, influence of
nutritive material on, 335.
Trap of West Rock, New Haven, Conn.,
U.S., composition of, 536.
Ti-ees, light, shade, and soil, studied in
their influence on the growth of, 566.
■ quantity and distribution of water
in, 912.
sap of, and specific gravity of their
wood, 912.
Trope'ines, 714.
Triacetonamine, products of oxidation
of, 101.
chromates, 101.
Triacetyl-cotoin, 326.
Triacetyl-phlobaphene, 650.
TTiallylamine, 99.
Trianosp erma fie i folia, 721 .
Trianospermin, 722.
Tribenzoylmorphine, 407.
Tribenzoylphlobaphene, 650.
Tricaleium phosphate, pm-e, superphos-
phates from, 141.
Tricarballylic acid, 864.
occuri'ence of, in beet juice,
36.
Tricai'bopyridenic acid and its salts, 895.
Trichloracetic cjanide, 35.
action of hydrochloric acid
on, 35.
Trichloracetylcarboxylic acid, 35.
Ti-idecylic acid, 34.
Triethyl citrate and its derivatives, 36.
Tri-isobutylene, 230.
oxidation of, 230.
Trimellitic acid, 265.
anhydride, 265.
Trimethvlamido-phenolammonium chlo-
ride, 638.
Trimethylamine, commercial, 159.
from beet-root molasses, 233.
thermochemistry of, 787.
Trimethylcarbamine and its salts, 545.
4 b
1018
INDEX OF SUBJECTS.
TrimefhTlmetaphenTlenediamine, trini-
tro-, in.
Trimethvlnitrophenolanimoniuni, 637.
iodide and its salts, 638.
Trimetlivlparamidobenzenesulplioiiic
acid, 322.
TrimethTlparaphenylenediamine, 111.
Trimethvlparaphenylenediaminenitrosa-
mine, nitro-. 111.
Trimethyltriainidobenzene, 111.
diacetyl-dcrivative of, 111.
Trinitrazox^iihenetol. 467.
Trioxymaleic acid and its salts, 875.
Trioxymethylene, 25.
Triphenvlarsine, 397.
sulphide, 397.
Triphenylbenzene, vapour-density of,
679.
Triphcnylcarbinol, tetraniethTldiamido-,
40.
Triphenvlcarbinolorthocarboxylic acid,
650.
Triphenyletliylnniine, 242.
hydrochloride, 241.
Triphenylmethane, araido- and its salts,
661.
deriratiyes of phenolphthalein,653.
dianiido-, 39, 661, 813.
dianiido-, and its salts, 661.
diamido-, compound of, with ben-
zene, 662.
dianiido-, oxidation of, 662.
metanitro-diamido-, oxidation of,
663.
tetramethyldiamido-, 40.
tetrjimcthyldianiidopropyl-, 40.
triamido- (pseudolcucaniline), a
new, 662.
Triphenylmethanecarboxylic acid, 650.
a-dichloro-, 655.
Trisulphodiphcnyl hyponitrite, 477.
Trithiobasic mercuric sulphate, 157.
Tropic acid, artificial formation of,
472.
chloro-, 472.
Tropidin e675.
platinoch loride, 675.
Tubes, sealed, oven for heating, 846.
Tungstates, reaction of, in presence
of
mannitol, 30.
Tungsten, cst'mation of, in steel, and in
their alloys with iron, 288.
Tungsten-bronze, 157.
Tungsten-manganese bronze, 199.
Tunicin, 233.
Turf, nitrogen in, 344.
Turnips, composition of two varieties of,
917.
influence of soluble and insoluble
phosphates as manure for, 186.
Turpentine, atmospheric oxidation of,
51.
Turpentine, hydrochloride, action of
sodium on, 669.
Tyrosine, constitution of, 473.
formation of hydroparacoumaric
acid from, 254.
in potatoes, 342.
u.
Ulmic compounds formed from sugar
by tlie action of acids, 538.
synthesis of, 482.
Ultramarine, 155.
compounds, 217, 367.
green, action of silver nitrate on,
368.
silver-, decomposition of, 367.
Ultra-violet absorption spectra of ethe-
real salts of nitric and nitrous acids,
202.
rays of the spectra, absorption
of, bv organic substances, 430.
Umbeliol, 670.
Undecylic acid, conversion of lauric acid
into, 34.
Unsaturated compounds, addition of
oxygen to, 231.
Uraninite (pitchblende) from Branch-
ville, Conn., U.S., chemical composi-
tion of, 530.
Uranium, fluorine compounds of, 853.
minerals from North Carolina, 90.
oxide, precipitation of, by ammo-
nia, 189.
oxyfluo-eompounds, combination
of, with fluorides of the alkali metals,
794.
separation of iron from, 189.
Uranotil, 96.
Urea, estimation of, 513.
estimation of, by sodium hypo-
bromite, 681.
estimation of, in urine, 513.
pure, preparation of, 681.
quantitative estimation of, 681.
platinoehloride, 104.
Ureides, contribution to the knowledge
_ of. 631.
Urethane, hemithiobromophenyl-, 634.
metatolvl-, 713.
orthotoiyl-, 245.
thiobromophenyl-, 634.
Urine, estimation of urea in, 513.
indican from, 46.
normal, some ingredients of, 907.
of herbivora, source of hippuric
acid on, 173.
of herbivorous animals, occurrence
of a reducing substance in, 332.
Urusite, 616.
INDEX OF SUBJECTS.
1019
Valeraldeliyde, action of acetic chlo-
ride on, 459.
Yaleric acid from active amyl alcohol,
628.
normal, lactone of, 799.
amido-, (amidodimetliylacetic
acid), 101.
Valervlene, transformation of, into cy-
mene and hydrocarbons of the ben-
zene series, 710.
Vanadates, a new property of, 527.
Vanadinite, 15.
Vanillin from sugar, 864.
occurrence of, in certain kinds of
raw sugar, 467, 646.
Vapour, rariatiou of the tension of,
emitted above and below the point
of fusion, 605.
Vapour-densities, Meyer's method of
determining, 841.
modification of Meyer's ap-
paratus for the determination of,
431.
observations on, 433.
of anhydrous and hydrated
formic and acetic acids, 868.
of selenium and tellurium,
847.
of the alkaU-metals, 434.
Vapour-density apparatus, V. Meyer's
modification of, 743.
determinations in the vapour
of phosphorus pentasulphide, 679.
determinations, Mever's, 824.
of iodine, 606, 788,'816.
of isoindole, 660.
of stannous chloride, 219.
of the viscous polymeride of
isobutaldehyde, 620.
Vapour-tension of the halogen-deriva-
tives of ethane, 618.
Vapours, mixed, critical point of, 842.
of saUne solutions, tension of,
211.
satm-ated, comparison of the curves
of the tension of, 435.
saturated, relations between the
pressures, temperatures, and densities
of, 692.
temperature of decomposition of.
209, 293.
Vaseline, 930.
Vegetable ducts, functions of, 911.
matter, permeation of, by water,
823.
substances, estimation of albumi-
noids in, 352.
Vegetables, existence of ammonia in,
568.
Vegetation, effect of acid gases on, 496,
497.
Veratrum viride, 170.
Vesbine, 445.
Vesbium, 445, 611.
Vetch, common, grt)wth of, 567.
Vine, ash of different parts of, 133.
Vine disease, mode of action of sulphur
as a remedy against, 281.
Vmegar, formation of, by bacteria,
334.
Vines, diseased, composition of leaves of,
416.
raising of, fi-om seed, 418.
researches on the bleeding of,
133.
Vitriol exits, direct method cf testing,
for nitrogen compounds, 746.
Volcanic ash from Cotopaxi, 97.
dust which fell January 4th, 1880,
at Dominica, 453.
glass, capillary, of Kilauea, Hawaii,
called Pele's hair, composition of,
536.
Volcanos of Ernici in the Valle del Sacco
(Rome), lavas of, 226.
Volliard's permanganate method of ti-
trating manganese, 585.
Voltaic condenser, a new, 521.
pile, constant and powerful, 686.
Volume, influence of, in the preparation
of ozone, 90.
Volumes of solutions of hydrated salts,
relation of, to their water of compo-
sition, 212.
w.
Waste hqnids, injury to fishes by, 490.
Water, a peculiar, 591.
action of, on lead piping. 198.
action of, on silicon and boron
fluorides, 435.
action of, on zinc and lead, 766.
analysis, 139.
decomposition of, 686.
detection of, in alcohol and ether.
679.
estimation of oxygen dissolved in,
421.
filtered through dry soil, calcium
carbonate in, 59.
fi'om sugar works, purification of,
930.
hard and soft, effect of, on the
brewing of beer, 593.
impure, influence of, on the health,
488.
industrial effluent, injurious effect
of, on soils and plants, 497.
influence of the supply of, on the
eUmination of nitrogenised decompo-
sition products, 818.
4: h 2
]020
INDEX OF SUBJECTS.
Water, lowering of the freezing point
of, by pressure, 845.
method for delcrmining the tem-
))orarj hardness of, 923.
methods for indicating the pre-
sence of organic matter in, 290.
of the Ferdinandsbrunnquelle at
Marienbad, Bohemia. 306.
of tlie Obcrbruimen, Flinsberg,
Silesia, 226.
of tlie River Vartry, 21.
refuse-, purification of, 830.
specific heat of, 601.
which accompanied the volcanic
dust wliich fell January 4th, 1880, at
Duuiinica, 453.
"VVater-gaa syetera. Strong's, 930.
Waters, estimation of organic nitrogen
in, 62.
four, for Turin, analyst's of, 591.
notes on sonu- analyst's of, 62.
of County Dublin, 766.
Wax, detection of, 763.
Weldon manganese " mud " and some
similar coin|>uund8, ctjmposition of,
219, 368, 611,704.
process, coujjwsition and analysis
of the binoxide of nmnganese re-
covered in, 528.
Wheat, manuring experiments with,
5U8, 738, 922.
oiled, detection of, 929.
Whey, a new albuminoid in, 274.
White of egc, non-ith-ntity of the albu-
minoTds of crystallin with, HI 5.
Wine, adulterated, physioloi'i. hI influ-
ence of, 174.
adulteration of, 191.
analysis, 586, «J8(.).
detection of siilicylic acid in,
352.
— detection of sulphurous acid in,
680.
— estimation of glycerol in, 512.
foreign colouring matters in.
191.
680.
free tartaric acid in, 775.
inversion of beet-sugar for, 833.
preparation of, 2(M).
red, detection of rosaniline in.
tannin in, 775.
tartar and tartaric acid in, 774.
time of first drawing of, 517.
valuation of, 421.
Wine-extract, estimation of, 515, 928.
Wines, red, artificial colouring of,
927.
Tokay, analyses of, 833.
Wood, destructive action of, on salicvlic
acid, 520.
Wood's metal, specific gravity of, 679.
Woody fibre estimation, 588.
Wool, products of the oxidation of,
460.
Xanthic acid as a precipitant for albu'
min, 765.
Xylene derivatives, 552.
Xylic aeid, its preijaration and deriva-
tives, 252.
Xylophosphinie acid, 641.
Xylophosphorvuis acid, 6-H.
Xyioquinol, 5.'>3.
chloro-, 553.
Xyloijuinone, 5.')3.
XvUlamide. 252.
X'vlV 2.'.2.
X"\r\ hli-, 2."j2.
Y.
Yeast, amount of, forineil during fer-
mentation. 728.
a))plii-ation of potatoes and un-
dried nialt in tin- ])re|>aratiun of,
2rK>.
e?«timation of the value of raw
mat<-riiil in tlie prcjmmtion of, 833.
experiment!* i>n varit)us kinds of,
833.
improvements in treatment of,
777.
lecithin and nuclein in, 816.
malt ••ombini;!! a source of, 518.
pressed, rve as a material for,
777.
souring of, 518.
Yerba mauxa, essentir.l oil of, 721.
Yew, rheinistry of, 899.
Ytterbia, 704.'
Ytterbium, atomic weight and chanu-
teristic salts of, 703.
Yttria-group, spectra of the earths
of, 7.
z.
Zinc, action of water on, 766.
actual state of the estimation of,
7 IS.
arsenates of, 216, 217.
ixistcnce of, in all primary rock^
and in sea waters of all ages, 708.
tinning, 425.
valuation of, 826.
INDEX OF SUBJECTS.
1021
Zinc, with iridium, nifhenium, and rho-
dium, action of acids on alloys of,
707. ^
ammonium oxide, 852.
cadmium, and copper, separation
of, 748. "^^ ^
oxide, characteristics of, 701.
in alkaline solutions, 852.
Zinc, potassium oxide, 852.
sodium oxide, 852.
Zinc-blende from Eothenburg, analysis
of, 857.
Zinc-dust, valuation of, 826.
Zinnwaldite, 533.
Zircon from the Isergebirge, 369.
Zirconium derivatives, 6.
ERRATA.
Page
69
110
182
248
249
330
465
855
858
860
Line
22 for criticised read confirmed.
25 „ but „ and that.
13 and 14 from bottom, /or dimethyl-j9-phenylenediamine ethoxamate
read ethjUc dimethjl-^j-phenyleuediamine-oxamate.
In the table at bottom of the page, cols. 3 and 4 give sp. heat of equal
weights of the soil, cols. 5 and 6 that of equal vols.
13 from bottom, dele " Acid."
16 from top, ./or dimethyl methylpyrogallate read dimethjlic methjl-
pyrogailate.
8 In this abstract /or "fibrin" read "fibre" or "cellulose."
5 Jbr hypochlorous* read hydrochloric.
18 „ iodide „ chloride.
2 from top, /or — ; — read — — .
1
8
21
22
dele " and."
for " Huitzucs" read "Huitzuc."
„ 9-18 read 018.
„ 2-99 „ 2-92.
This error occurs in the original paper.
HAEBISOjr A2J» SONS, PEINTEES IN OEDINAEY TO HER MAJESTY, ST. MAETIX S LANE.
V
QO Chemical Society, London
1 Journal
C6
V.3S
co"n.3
Applied Sci.
3enals
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