摘要:

J O U R N A LTHE CHEMICAL SOCIETY.H. E. ARMSTRONG, Ph.D., F.R.S.A. DUPRB, Ph.D., F.R.S.C. GRAHAM, D.Sc.F. R. JAPP, M.A., Ph.D.HERBERT MCLEOD, F.RS.r. P. BEDSON, nsaH. BAKER.D. BENDIX.C. H. BOTBAMLEY.B. BRAUNER, Ph.D.B. H. BROUGH.T. CARNELLEY, D.Sc.C. F. CROSS.J. I(. CROW, D.Sc.JOSEPH FLETCHER.A. J. GREENAWAY.OTTO HEHNER.HUGO MULLER, Ph.D., F.R.S.W. H. PEBKIN, Ph.D., F.R.S..W. J. RUSSELL, Ph.D., F.R.S.E. SCHUNCK, Ph.D., F.R.S.J. MILLBE THOMSON.&bit:rrr :HENRY WATTS, B.A., F.R.S.D. A. LOUIS.A. I(. MILLER, Ph.D:J. M. H. MUNRO, D.Sc;D. PAGE,.M.D.E. W. PREVOST, Ph.D.E. H. RENNIE, M.A., D!So;R. ROUTLEDGE, B.Sc.L. T. THORNE, Ph.D.V. H. VELEP, M.A.JOHN I. WATTS.W. U. WILLIAMS.Vol. XLIV.I 8 8 3. ABSTRACTS.LONDON:J. VAN VOORST, 1, P A T E R N O S T E R ROW.1883LONDON :H 4RIlISON AND SONS, PRINTERS IR’ OLLDINABY TO &EX MAJESTY, ST.XSXTIN’S LANEC O N T E N T S .PAPERS READ BEFORE TEE CHEMICAL SOCIETY :-General and Physical Chemistry.LIVEING ((3. D.) and J. DEWAR. Spectrum of Carbon . . . .LIVEIN~ (G. D.) and J. DEWAR. Disanpearance of some Spectral Lines, andthe Variation of Metallic Spectra due to Mixed Vapours . . .TOMMASI (D.). Action of Light on Silver Bromide . . . . .HOLZER (A.). Sources of Error in PoIarising . . . . . .JOUBERT (J.). Method of Determining the Ohm . . . . . .BICHAT (E.) and R. BLONDLOT. Oscillations of the Plane of Polarisation byElectric Discharges . . . . . . . . . . .TOMMASI (D.). Zinc-carbon Couples in Electrolysis , .. . .JAMIN and 8. MANEUVRIER. .SPOTTISWOODE (W.) and J. F. MOULTON. Movement of Gas in " VacuumDischarges " . . . . . . . . . . . .VIOLLE (J.). Apparatus for the Determination of Specific Heats byCooling . . . . . . . . . . . . .THOULET and LAGARDE. Specific Heats of Small Quantities of Snb-stances , . . . . . . . . . . . .BRRTHELOT and OQIER. Specific Heat of Gaseous Acetic Acid . . .HILL (S. A.). The Constituent of the Atmosphere which absorbs RadiantHeat . . . . . . . . . . . . .RAOULT (F. M.). Law of Freezing of Aqueous Solutions of Carbon Com-pounds . . . . . . . . . . . . .TOMMASI (D.). Nascent Hydrogen . . . . . . . .BERTHELOT. Reciprocal Displacement of the Halogens . . . .BERTHELOT. Perchloric Acid . . .. . . . . .BERTHELOT. Berthollet's Laws, and the Combinations of Mercuric Oxidewith Acids . . . . . . . . . . . .BERTHELOT and TLOSTAY. Double Salts formed by Fusion . . . .DITTE (A.). Decompositions of Salts by Fused Substances . . . .ALEXEJEFF (W.) . Mutual Solution of Liquids . . . . . .DIXON (H. B.). Velocity of Explosion of a Mixture of Carbonic Oxide andOxygen with Varying Quantities of Aqueous Vapour . I . .DIXON (H. B,). Influence of Aqueous Vapour on the Explosion of CarbonicOxide and Oxygen . . . . . . . . . . .LOSSEN (W.). Specific Volumes of Liquids . . . . . . .ZANDER (A.). Specific Volumes of Ally1 and Propyl Compounds . . .LSNOLEY. Observations on the Solar Spectrum . . . . . .EGOROFF. Absorption Spectrum of the Earth's Atmosphere .. .DE CHARDONNET. Reflection of Actinic Rays : Influence of the ReflectingSurface . . . . . . . . . . . . .MONCKHOVEN (D. T.). Widening of the Lines in the Hydrogen Spectrum .LIVEING (a. D.) and J. DEWAR. Spectrum of Water . . . ' . .MONCKHOVEN (D. v.). Influence of Temperature on the Spectra of Nm-Metals . . . . . . . . . . . .SORET (J. L.j and E. SARASIN. Circular Polarisation of Quartz . . .GOOSSENS (B. J.). .ELSTER (J.) and H. GERTEL. Electricity of Flame . . . . .The Reaction Current of the Electric ArcThe Metallic Galvanic Circuit of Ayrton and Perrya 2PAGE12334444566G77788101111111212231313713713813914014014'011 114iv CONTENTS .TOMMASI (D.). Electrolysis of Hydrochlorichid . .. . .DESAINS (P.). Distribution of Heat in the Ultra-red Region of the SolarSpectrum . . . . . . . . . . . .TOMMASI (D.). Laws of Thermal Consta>nts of Substitution . . . .CRAFTS (J . M.). Comparison of Mercurial Thermometers with the HydrogenThermometer . . . . . . . . . . . .HANNAY (J . B.). Limit of the Liquid State . . . . . .SPRING (W.). Expansion of Isomorphous Salts . . . . . .KLEIN (D.). Modification of the Usual Statement of the Law of Iso-BRUGELMANN (G.). Observations on Crystallisation . . . . .BBUOELMANN (G.). Experiments on Crystallisation exemplifying Berthollet’sLaw of Affinity . . . . . . . . . . .MALLARD and LE CHATELIER . Nature of the Vibratory Movements whichaccompany the Propap tion of Flame in Mixtures of Combustible GasesBERTHELOT .The Light emitted by Comets . . . . . .JANSSEN (J.). Telluric Rays. and the Spectrum of Water Vapour . .LIVEING (G . D.) and J . O E W ~ R . Spectra of Carbon and its Compounds .LIVEING (G . D.) and J . DEWAR . The Ultra-violet Spectra of Elements .LIVEING (G . D.) and J . DEWAR . An Arrangement of the Electric Arc forHARTLEY (W . N.). Reversal of Metallic Lines in Over-exposed Photographsof Spectra . . . . . . . . . . . .HARTLEY (W . N.). Researches on Spectrum Photography . . . .GOLDSTEIN (E.). Electric Discharge in Rarefied Gases . . . .DIVERS (E.). The Leclanche Cell and the Reactions of Manganese Oxideswith Ammonium Chloride . . . . . . . . .BRARD . Currents Produced by Fused Nitrates in Contact with IncandescentCarbon . .. . . . . . . . . . .Specific Heat and Heat of Transforma-tion of Silver Iodide and its Alloys with Cuprous and Lend Iodides .Direct Determination of the Heat of Combination of cer-tain Gases . . . . . . . . . . .RIVI~RE ((3.). Law of Cooling . . . . . . . . .morphism . . . . . . . . . . . .the Study of Radiation of Vapours . . . . . . .NASINI (R.). Atomic Refraction of Sulphur . . . . . .Determination of High Temperatures . . . . . . . .BELLATI (H.) and R . ROMANESE .RAABE (F . W.).BERTBELOT . Lead Iodides . . . . . . . . . .BEBTEELOT . Ethylene Oxide . . . . . . . . .ANSDELL (G.). Critical Point of Mixed Gases . . . . . .RAOUST (F . 11.). Law of Freezing of Solvents . . . . . .PAWLEWSKI (B.).Critical Temperatures of Alkyl Salts . . . .BLASERNA (P.) and S . CANNIZZARO .GAL (H.) .EITTLE~ (E.).Report on a Memoir by R . Schiff ‘‘ OnPassage of Alcoholic Liquids through Porous Vessels . . .Electromot>ive Force of a Daniell’s Element . . . .the Molecular Volumes of Liquids ” . . . . . . .HOFMANN (A . W.). Lecture Experiments . . . . . . .STXEINTZ (F.). Galvanic Polarisation . . . . . . . .HAGA (H.) . Amalgamation Currents . . . . . . . .ELSTER (J.) and H . GEITEL . Electricity of Flame . . . . .HANIEEL (W . G.).BRAUN (F.).EOHLRAUSCH (W.) .WACHTER (F.).STRECKER (K.).JAROLIMEK (A.).Actino-electric and Piezo-electric Properties of Quartz,and their Relation to the Pyro-electric . . . . . . .Electrical Energy and Chemical Action .. . . .Specific Conductivity of Sulphuric and Pyrosulphuric .Particles of Matter in the Electric Spark . . . .Specific Heat of Gaseous Compounds of Chlorine, Bro-Relation between Pressure and Temperature in the Satu-Acids, and the Specific Gravity of Concentrated Sulphuric Acid .RIESS (P.). Electric Shadows . . . . . . . . .mine, and Iodine with one another and with Hydrogen . . . .rated Vapours of Water and Carbonic Anhydride . . . . .PAGE1421431431441441451461471471481482612612612622622632632642662722’132742742742752752762772782792792’7940941041241241241341341541641741COSTENTS .WROBLEWSKI (S . v.). Absorption of Gases by Liqnids under HighPressure .. . . . . . . . . . . .ENELAAR (J . E.). Osmosis of Salts . . . . . . . .SCHRODER (H.). Constitutionof Liquid Compounds . . . . .TAYLOR (I.). Rupert’s Drops . . . . . . . . .PFAUNDLER (L.) . Explosion of a Tube containing Liquid Carbonic Anliy-dride . . . . . . . . . . . . .LAGARDE (H.). Photometric Intensity of the Lines of the Hydrogen Spec-trum . . . . . . . . . . . . .HAGENBACH (E.). Stokes’s Law of Fluorescence . . . . . .SCHRODER (H.) . Dependence of Molecular Refraction of Liquid Carbon . . . . . .SIEMENS (W.). Luminosity of Flame . . . . . . . .BARTOLI (A) . Constitution of Electrolytes . . . . . . .BARTOLI (A.) and G . PAPASOQLI . Electrolj-sis of Water and of Solutionsof Boric Acid . . . . . . . . . . . .SEMMOLA (E.).New Experiment in Electrolysis . . . . . .HANKEL (W . G.). Thermoelectric Properties of Minerals . . . .NEESEN (F.). Specific Heat of Water . . . . . . . .VIEILLE . lliIeasurement of Pressures developed in Closed Vessels by theExplosion of Gaseous Mixtures . . . . . . . .MALLARD and LE CLIATELIER . Momentary Pressures produced during theCombustion of Gaseous Mixtures . . . . . . . .THOMSEN (J.). Thernochemical Investigation of the Chlorides of Iodine .THOMSEN (J.). Thermochemical Investigation on the Chlorides of Sulphur,Selenium, and Tellurium . . . . . . .THOXSEN (J.). Method of Estimating the Heat of Formation of D i f f i h l yCombustible Volatile Carbon Compounds . . . . . .THOMSEN (J.). Heat of Formation of the Chlorides of Phosphorus andArsenic .. . . . . . . . . .THOMSEN (J.). Heat of Formation of the Chlorides and Oxides of’ilnti:mony and Bismuth . . . . . . . . . . . .THOMSEN (J.). Heat of Formation of Carbon Tetrachloride and EthylenePerchloride . . . . . . . . . . . .NIES (F.) and A . WINKELMANN . .SCHULLER (*4.). Distillation in a Vacuum . . . . . . .GERNEZ (D.). Velocity of Solidification of Bodies in a State of Super-fusion . . . . . . . . . . . . .LARGER (C.) and V . MEYER . Dissociation of Chlorine and Bromine . .WIEDEMANN (E.) . Dissociation-heat of the Water-molecule and the Elec-tric Luminosity of Gases . . . . . . . . .ISAMBERT . Ammonium and HSdrogen Sulphide . . . . . .SCHIFF (R.). Constant of Capillarity of Liquids at their Boiling Points .MENSCHUTKIN .Mutual Displacements of Bases of Neutral Salts in Homo-geneous Systems . . . . . . . . . . .GOODWIN (W . L.). Nature of Solution . . . . . . .LIVEIXG (G . D.) and J . DEWAR . Origin of the Hydrocarbon FlameOGIER (J.). Sulphuric Monochloride . . . . . . . .BERTRELOT . Heat. of Formation of Chromic Acid . . . . .FORCRANY (DE) . Heat of Formation of Solid Glycollates . . . .ISAMBERT (F.). Vapour of Carbaniide . . . . . . . .PICKERING (S . IT.). Supereaturation . . . . . . . .TIMIRIAZEFF (C.). Chlorophyll and the Distribution of Energy in the PolarHITTORF (W.). Luminosity of Flame . . . . . . . .FROMME (C.) . Electric Researches . . . . . . . .TROUT% . Modification of the Bichromate Battery . . . . .Compounds on their Chemical ConstitutionVolume-change of Metals on FusionGAL (H.).Passage of Alcoholic Liquids through Membranes . . .Spectrum . . . . . . . . . . . .Spectrum . . . . . . . . . . . .1-PAGE41842042242242253753753853954054054u540541542542543543543544544514545545546516547548549549550550641642642644645645697697697700REYNIER (E.), Observations on TrouvB’s Paper-on the Bicliroinatc Battery 70vi CONTENTS .HERZ (H.), Electric Discharges . . . . . . . . .FOUSSEREAU (G.). Influence of Temper on the Electrical Resistance of GlassMEYER (I€.). Electric Resistance of Psilomelane . . . . . .BAUR (C.). Radiation of Rock-salt at Various Temperatures . . .CEAPPUIS (P.). Evolution of Heat in the Absorption of Gases by Solide andLiquids .. . . . . . . . . . . .WIEDEMANN (E.). Thermochemical Researches . . . . . .BERTHELOT . Alkaline Sulphites . . . . . . . . .BRRTHELOT . Pyrosulphites . . . . . . . . . .BERTHELOT . Alkaline Thiosulphates . . . . . . . .BERT HELOT^^^ VIEILLE . Nitrogen Selenide . . . . . .BERTHELOT . Chromates . . . . . . . . . .TOMMASI (D.). Heat of Formation of Blycollates . . . . .DE FORCRAND . Heat of Formation of Glycollates . . . . .MENSCHUTKIN (N.). Mutual Displacement of Bases of Neutral Salts inTRATJBE (M.). A Correction . . . . . . . . .WESENDONCK (K.). Spectra of Carbon Compounds . . . . .BECQUEREL (H.) . Observations of Infra-red Spectra by Meaw of Phospho-rescence . . . . . . . . .. . . .VOGEL (H . W.). Lockyer's Dissociation Theory . . . . . .RIEDEMANN (E.) . Molecular Refraction . . . . . . .DUFET (H.). Variation of tlie Indices of Refraction of Water and Quartzwith the Temperature . . . . . . . . . .LOMMEL (E.) . Fluorescence of Iodine Vapour . . . . . .RADZISZEWSKI (B.). Theory of Phosphorescence . . . . .DVORAK (V.). Researches in Statical Electricity . . . . . .CLAUSITJS (R.). The Units of Electricity and Magnetism . . . .BRAUN (F.). Electromotive Force of certain Galvanic Combinations . .TROUVB . .KONIG (A.). Substitution of Hydrogen Peroxide for Nitric Acid in GalvanicBatteries . . . . . . . . . . . .Homogeneous Systems . . . . . . . . . .Reply to the Observations of Reynier on Bichromate BatteriesBARKER (G .I?.). Secondary Batteries . . . . . . .FROMME (C.). Electric Researches . . . . . . . .EDLUND (E.). Researches on the Heat-changes at the Poles of a Volta-PROBEXT (I.) and A . W . SOWARD . Effect df Absorbed Gases on the'Elec:meter . . . . . . . . .trical Conductivity of Carbon . . . . . . . .BRAUP; (J.). Unipolar Conductivity of Solid Bodies . . . . .STEPHAN ((3.). Fluidity and Galvanic Conductivity . . . . .HOADLEY (J . C.). Platinum-water Pyrometer . . . . . .VIOLLE (J.). Radiation from Silver at the Solidifying Point . . .VIEILLE . Specific Heats of Gases at IIigh Temperatures . . . .MEYER (I,.). Basis of 'I'hermo-chemistry . . . . . . .DE PORCRAND . Neutralisation of Glycollic Acid by Bases . . . .DE FORCRAND . Salts of Glycollic Acid .. . . . . .TOMMASI (D.). Heat of Combination of Glycollates . . . . .ISAMBERT . Ammonium Hpdrosulphide and Cyanide . . . . .BERTHELOT and VIEILLE . Wave of Explosion . . . . . .GEIJTHER (A) . Affinity-values of Carbon . . . . . . .ments in Various Allotropic ModificationsWIEDEMANN (I?,.). Constitution of Hydrated Salts . . . . .of the Solar Spectrum . . . . . . . . . .Rays by Yarious Substances . . . . . . . . .KOFILRAUSCH (W.). Electrical Conductivity of Silver Halofd Salts . .BERTHELOT . Some Relations between Temperatures of Combustion, SpecificHeats, Dissociation, and Pressure of Explosive Mixtures . . .MULLER-ERZBACH (W.) . Specific Gravity and Chemical Affinities of Ele- . . . . . .ABNEY (W . W.) and R . FESTING .LIVEING (G .D.) and J . DEWAR .Atmospheric Absorption of the Infra-redNote on the Absorption of Ultra-violetPAGE700701701702702704704705707707707708708'708709761761762762762763763763764'7 6476576576576676776976976976976977177177177377477577577577777977978083V83CONTENTS . viiLIVEING (Gt . D.) and J . DEWAE . Reversal of Hydrogen Lines . . .LIVEING (Gt . U.) and J . DEWAR . Order of Reversibility of LithiumLines . . . . . . . . . . . . .FRANELAND (E.) . Chemistry of Storage Batteries . . . . .Scrivanow's Chloride of Silver Element . . . . . . . .PREECE (W . H.). Effects of Temperature on the Electromotive Force andResistance of Batteries . . . . .. . . . .BIDWELL (S.). Electric Resistance of Carbon Contacts . . . .CRAFTS (J . M.). Thermometric Measurements . . . . . .MALLARD and LE CHATELIER . Combustion of Gaseous Mixtures . . .BUTLEROW (A.). Notice on the Atomic Weights . . . . . .ST . MARTIN (L . Gt . DE) . Special Form of Gasometer . . . . .OBERBECK (A.). Electro-dynamic Interferenceof Alternating Currents .GOUY . Distort>ion of Polarised Electrodes . . . . . . .FRIEDEL (C.) and J . CURIE . Pyroelectricity of QuartzVIEILLE . Specific Heats of Gases at High Temperatures . . . .JANIX (J.). Critical Point of Gases . . . . . . . .MEYER (L.). Air-baths . . . . . . . . . .QUINCKE (G.) . Electric Researches . . . . . . . .WITKOWSEI (A.). Theory of Galvanic Circuits . . . . . .HELLMANN (H.).Difference of Positive and Negative Discharge . . .HERZ (H.). Researches on the Glow Discharge . . . . . .PAWLEWSKI (P.), Determination of Vapour-density . . . . .rated Vapours . . . . . . . . . . .. . . .SCHWARZ (H.). Modification of V . Meyer's Vapour-deneity Apparatus .HANKEL (W.). Observations on Thermo- and Actinclelectricity of Quartz .JAROLIMEK (A.). Relation between the Tenbion and Temperature of Satu-RAOULT (F . M.). Congelation of Aqueous Solutions of Organic Bodies .KANONNIKOFF (J.). Refractive Power of Organic Compounds in Solution .BRAUNS (R.). Cause of the Anomalous Double Refraction of certain SaltsCrystallising in the Regular @stem . . . . . . .KRUSS (G.) and S . (ECONOMIDES . Relation between the Composition ofOrganic Compounds and their Absorption Spectra .. . . .MULLER.ERZBACH . Relation of the Heat of Combustion of Isomeric Or-ganic Compounds to their Densities . . . . . . .SCHIFF (R.). Molecular Volume of Liquid Substances . . . .KROUCHKOLL . variation of the Constant of Capillarity of the Surfaces,Water.Ether, and Water-Carbon-bisulphide under the Action of Electro-motive Force . . . . . . . . . . . .Experiments on the Diffusion of some Organic andAffinity and its Relation to Atomic . . . . .JAHN (H.). Electrolytic Researcbes . . . . . . . .SCEEFFER (J . D . R.).DONATH (E.) and J . MAYRHOFER .Inorganic Compounds . . . . . . . . . .Volume, Atomic Weight, and Specific GravityPAGE83883983084Q84084'.84284484684'789789789'7898898899900945948949949950951951952104110411041104210441044104'710471048Inorganic Chemistry .COJIBES .On the Supposed Compound NH. . . . . . . . 14SCHETZENBERGER (P.) and A . COLSON . Silicon . . . . . . 15SABATIER (P.). Compounds of Silicon with Sulphur . . . . . 15COLSON (A.). Combination of Tetratomic Elements . . . . . 15KIENLEN (P.). Extraction of Selenium from a Waste Product . . . 16TROOST (L.). Boiling Point of Selenium . . . . . . . 17NICOL (W . W . J.).tions . . . . . l ?KRAUT (K.). " Ciloridk of Lime'" and" Chloride of Lithia" 17LUNGE (G.) a n d R . SCHOCH . CalciumHypoiodite . . . . . 17C ~ V E (P . T.). Didymium . . . . . . . . . . 18XRAUNEX (B.). Didymium . . . . . . . .. . 18Coefficient of Expansion of Sodium Sulphate Solu-. . viii CONTENTS .DEVILLE (H . SAINTE-CLAIRE) and H . DEBRAY . Explosive Alloys of Zincwith certain Platinum Metals . . . . . . . . .TOMMASI (D.). Action of Aluminium on Cupric Chloride . . . .TOMMASI (D.). Stability of Cupric Hydroxide . . . . . .ETARD (A.) . Transformations of Cuproso-cqric Sulphites . . . .BOISBAUDRAN (L . DE) . Separation of Gallium . . . . . .BAUBIQNY (H.). Action of Ammonium Sulphide on Stannous Sulphide .PRUD’HOMME (M.) and F . BIN.DER . Clwomic Acid and Chromates . .ELEIN (D.). New Class of Borotungstates . . . . . . .TOMMASI (D.) and G . PELLIZZARI . Change which Perric Hydrate undergoesafter a Time . . . . . . . . . . . .TOMMASI (D.). Ferric Hydrates .. . . . . . . .BAUBIGNY (H.). Action of Hydrogen Sulphide on Solutions of NormalNickel Sulphate . . . . . . . . . . .BAUBIQNY (H.). Action of Hydrogen Sulphide on Nickel Sulphabe inAcetic Acid Solution . . . . . . . . . .BAUBIGNY (IT.). Action of Heat a n an Acid Solution of Nickel SulphateVORTIMANN (G.). Cobaltamine Compounds . . . . . . .GERDES (B.). Electrolysis of Ammonium Carbamate and Carbonate . .DRECHSEL (E.) . Ammonioplatinum-diammonium Compounds . . .LIDOFF ( A ) and W . TICHOMIROFF . Action of the Galranic Current onChlorat es . . . . . . . . . . . .TRAUBE (M.). Oxidation of Carbonic Oxide by Palladium Hydride andOxygen . . . . . . . . . . . . .ANAGAT (E . H.). Compressibility of Nitrogen . . . . . .FILHOL (E.) and SENDERENS .Neutral Phosphates of the Aikalis . .MALLET (J . W.). Properties of Pure Aluminium . . . . .GRANDEAU (H.). Decomposition of Phosphates by Potassium Sulphabe atHigh Temperatures . . . . . . . . . .NILSON (L . F.). Determination of the Equivalent of Thorium . . .MOISSAN (H.). Chromous Sulphate . . . . . . . .in Presence of Hydrogen Sulphide . . . . . . . .VORTMANN (G.). Cobalt Sulphate . . . . . . . .THENARD (P.). BlackPhoephorus . . . . . . .WEBER (A.). Calcium Chloride . . . . . . . . .NILSON (L . F.). Metallic Thorium . . . . . . . .KRAUT (K.). Magnesia alba . . . . . . . . .BOISBAUDRAN (L . DE) . Separation of Gallium . . . . . .BOISBAUDRAN~(L . DE) . Separation of Gallillm . . . . . .DITTE (A.). Compounds of Tin Disulphide and Diselenide .. . .PEHRMANN (A.). Preparation of Lead Dioxide . . . . . .MESCHTCHERSKY (I.). Barium Compounds of Bismuth Peroxide . .PARMENTIER (F.). A Hydrate of Molybdic Acid . . . . .WAUNER (A.). Oxygen prepared from Potassium Chlorate . . . .KAPPEL (S.). Formation of Ozone and Hydrogen Peroxide . . .MULDER (E.) and H . G . L . VAN DER MEULEN . Ozone in Presence of Plati-num-black . . . . . . . . . . . .VOGLER (C . A.). Variation of the Amount of Oxygen in the Atmosphere .COOK (E . H.). Carbonic Anhydride in the Atmosphere . . . .KAPPEL (S.). Nitrification in Presence of Copper and other Metals . .RIBAN (J.). Conversion of Tricalcium Phosphate into Chlorine CompoundsSCHERTEL (A.). Volume-weight of Sulphuric Acid . . . . .TRAIJBE (M.).Activity of Oxygen . . . . . . . .of Phosphorus . . . . . , . . . . .PILLITZ (W.). Argentous Oxide . . . . . . . . .BECKMAN (E.). Barium Aluminetes . . . . . . . .v . BEMIMBLEN (J . M.). Beryllium Hydroxides . . . . . .CLEVE (P . T.). Atomic Weight of Yttrium . . . . . .with Sulphur . . . . . . . . SC EWARZ (H.). Lecture Experiment illustrating the Combination of Zinc19191920212222222324242425252525272814915015915015115115115115215215315315615615715815828128228228428428628’728828828929129229228OOSTESTS .BOISBAUDRAN (L . DE) . Separation of Gallium . . . . . .DITTE (A.) Stannous Oxide and some of its Compounds . . . .WELLER (A.). A Higher Oxide of Titanium .. . . . .SCHULZE (H.). Arsenious Sulphide in Aqueous Solution . . . .DITTE (A.). Formation of Crystallised Uranates in the Dry Way . .PAVEL (0.). Nitroso-sulphides and Nitroso-cyanides . . . . .DEBRAY (H.). Artificial Production of Iridosmin . . . . .TRAUBE (M.). Action of Platinum and Palladium on Carbonic Oxide andHydrogen . . . . . . . . . . . .BERTHELOT and J . OGIER . . . .VERNEUIL . Nitrogen Selenide . . . . . . . . .OGIER (J.). Pyrosulphuric Chloride . . . . . . . .BARLOW (W . H.). Mechanical Properties of Aluminium . . . .PEMBERTON (H.). Potash Alum from Felspar . . . . . .RAMMELSBERG (C.). Double Chloride of Potassium and Thallium . .RAMMELSBERG (C.). Thallium and Lithium Phosphates . . . .REIS (K.) and B . RAYMAN .. . .AUSTIN (P . I'.). .WIESNEB . Uranyl-potassium Chromate . . . . . . .BERTHELOT . Natural Formation of Manganese Dioxide, and some Reactionsof Peroxides . . . . . . . . . . . .DITTE (A) . Crystallisation of Chlorine Hydrate . . . . . .BASAROFP (A.). Oxidation of Sulphur in the Air . . . . .BERTHELOT . Reactions between Sulphur, Sulphur Oxides, Carbon, andCarbon Oxides . . . . . . . . . . .KONOVALOFF (D.). Pyrosulphuryl Chloride . . . . . .NILSOX (L . F.). Crystalline Form, Specific Heat, and Atomicity ofThorium . . . . . . . . . . . . .CLEVE (P . T.). Atomic Weight of Lanthanum . . . . . .ENGEL (R.). Allotropic Arsenic . . . . . . . . .PFORDTEN (0 . v.3. Reduct. ion of Tungsten Compounds . . . .JORGENSEN (8 . M.). .MAQEENNE .Ammonio-cobalt Compounds . . . . . . .GORGEE (A.). Manganese Sulphite . . . . . . . .BLOMSTRAND (C . W.). Oxy-acids of Chlorine . . . . . .MEYER (V.) . Hydroxylamine Hydrochloride . . . . . .ISAMBERT (F.). Dissociat#ion of Phosphine Hydrobromide . . . .OGIER (J.). Pyrosulphuric Chloride . . . . . . . .RAMMELSBERG (C.). Potassium Sesquicnrboiiate . . . . . .DENSTAN (W . R.) and F . RANSOM . Constitution of Liquor soda chlorat@DUNSTAN (W . R.) and F . RANSOM . Action of Chlorine on Solution ofSodium Carbonate . . . . . . . . . . .DITTE (A.). Produetion of Brom-apatites and Bromo-wagnerites . .BECKMANN (E.). Basic Halogen-salts of Barium . . . . .BECKMAA-N (E.) . Barium Aluminates . . . . . . . .NILSON (L . F.). . . . .SPRING (W.). Formation of Arsenides by Pressure .. . . .KNORRE (G . v.). Tungstex Compounds . . . . . . .JANNETAZ (E.). A Phosphide of Nickel . . . . . . .CRAFTS (J . M.). . . .JACOBSEN (0.). Phosphorescence of Sulphur . . . . . .FILEOL (E.) and SENDERENS . . . .BILLITZ (G.) and K . HEUMANN . New Modes of Formation of Pyrosulphuric . . . . . . .HEUMANN (K.) and P . XOCHLIN . Pyrosulphuric Chloride . . . .HAUTEFEUILLE and MARGOTTET . Crystallised Phosphates . . . .SCHULTEN (A . DE). Barium Potassium Phosphate and Barium SodiumPhosnhate . . . . . . . . . . . .Researches on the HyponitritesCompounds of Tin with BrominePreparation of Stannic Oxide from Sodium Stannate .VOGLER (C . A.). Variation in the Amount' of Oxygen in the Air . . .Chemistry of the Chromammonium Compounds .Specific Heat and Valency of ThoriumDensity of Clilorine at High TemperaturesAction of Sulphur on OxidesChloride and of Chlorosulphonic AcidLANDRINI(E.).Action of Different Tarieties of Silica on Lime-water . . .ixPAGE2932942952952962972984324224234234244244244'3442442 5425425550551551551553553553554554554557558645646646R44364664764764. 864964964965065065171 071071071071071171171x CONTENTS .LE CHATELIER (H.). The Setting of Piaster of Paris . . . . .DEBRAY (H.). Preparation of Cerium Oxide . . . . . .ANDRE ((3.). Ammoniobromides and Oxybromides of Zinc . . . .1)ELACHARLONNY ( P . M.). Aluminium Sulphate . . . .. .GUCKELBERBER (G.). Ultramarine . . . . . . . .BOISBAUDRAN (L . DE) . Separation of Gallium . . . . . .DITTE (A.). Crystallised Stannates . . . . . . . .ANURB (G.). Double Chlorides of Lead and Ammonium and Oxycliloridesof Lead . . . . . . . . . . . . .TAQUET (C.). Chromic Selenite . . . . . . . . .MAUYENB (E.). Chlorine Hydrates . . . . . . . .WROBLEWSKI (S.) and K . OLSZEWSKI . Liquefaction of Oxygen and Nitro-HECXANN (K.) and P . KOCHLIN . Action of Heat on Sulphuric Monochlo-ride and Dichloride . . . . . . . . . .KONOWALOFF (D.). Pyrosulphuric Chloride . . . . . .HAUTEFEUILLE (P.) and J . MARGOTTET . Combination of Phosphoric Acidwith Silica . . . . . . . . . . . .HAUTEFEUILLE (P.) and J . MARBOTTET . Phosphates . . . . .FILHOL (E.) and SENDERENS .Action of Sulphur on Alkaline Phospha'es .DITTE (A.). Bromapatites and Brornowagnerites . . . . . .DITTE (A.). Iodo-apatites . . . . . . . . . .SCHULZE (H.). Antimonious Sulphide in Aqueous Solution . . .DITTE (A.). Production of Crystallised Vanadates in the Dry Way . .FREIH (0.). Reduction of' Tungsten Compounds . . . . . .KLEIN 0.). Borotungstates . . . . . . . . . .HOPPE-SEYLER (F.). Activity of Oxygen in Presence of Nascent HydrogenSpecific Gravities of Solutions of Ammonia and Ammonium Carbonate . .SCHEURER-KESTNER (A.). Formation of Nitrous Acid in the Evaporation ofWater . . . . . . . . . . . . .WALLROTH (I( . A.). Action of Microcosmic Salt on various Oxides . .Specific Gravity of Sulphuric Acid . . . . . . . .CLEVE (P .T.). Atomic Weight of Didymium . . . . . .PICICERING (S . U.). Basic Sulphates of Copper . . . . . .CROSS (C . F.). Rehydration of Ferric Oxide . . . . . .SCHOTTLANDER (P.) . Gold Compounds . . . . . . .GORBEU (A) . Double Sulphites of Manganese and the Alkalis . . .gen ; Solidification of Carbon Bisulphide and of Alcohol . . .BORNTRAGER (H.). Preptration of Selenium on a Large Scale . . .DEWAR (J.) and A . SCOTT . Atomic Weight of Manganese . . . .TRAUBE (M.). Action of Nascent Hydrogen on Oxygen Gas . . .KONOWALOW (D.) . Pyrosulphuric Chloride . . . . . . . CROSS (C.) and A . HIGGIN . Decomposition of Water by Metalloi'ds . .ISAYBERT . Phosphorus Sesquisulphidc . . . . . . .ENBEL (R.). Analogy between the Allotropic Modifications of Phosphorusand Arsenic .. . . . . . . . . . .FLUCICIGER (F . A.). Potassium Carbonate . . . . . . .REYCHLER (A.). Silver Nitrate and Ammonia . . . . . .SPRING (W.). Formation of Sulphides by Pressure . . . . .SPRING (W.). ColloYdal Copper Sulphide . . . . . . .BOISBAUDRAN (L . DE) . Iridium and Potassium Sulphate . . . .BOISBAUDRAN (L . DE) . Reactions of Iridium . . . . . .ANDRB (G.). Double Salts of Lead . . . . . . . .KLINGER (H.). Basic Double Salts . . . . . . . .WROBLEWSEI (S.) and K . OLSZEWSKT . Liquefaction of Nitrogen and . ofCarbonic Oxide . . . . . . . . . . .LTJNGE (G.) and P . NAEF . Bleaching-powder and Analogous Compounds .THALBN (T.) . Spectral Researches on Scandium, Ytterbium, Erbium, andThulium . . . . . . .. . . . . .SCHRAMM (J.). Position of Thallium in the Chemical Svstem and its Pre-PAGE71271371371471471571671771771878078178178278278878378378478478478578684884985085085185 285285385385385690090090090190190.2902903904904904905505952953954sence ih 8ylvin . . . . . . . . . . . . 95CONTENTS . xiWILM (F.). Preliminary Notice . . . . . . . . .HOPPE-SEYLER (F.). Activity of OxSgen . . . . . . .LADENBURG (A.) . Lecture Experiments . . . . . . .TYNDALL (J.) . Unobserved Resemblance between Carbonic Anhydride andCarbon Bisulphide . . . . . . . . . . .SCHELZE (H.) . Phosphorus 8ubsulphide . . . . . . .WENZELL (W . T.). Preparation of Phosphoric Acid by the Oxidation of .. . . .IIEUMANN (K.) and P . KOECHLIN . Thionyl Chloride and PyrosulphurylChloride . . . . . . . . . . . .WITTJEN (B.) and H . PRECHT . Blue Rock'Salt . . . . . .PHILIP (J.). Silver Hypophosphate . . . . . . . .LONGI (A.). Iodide of Argentammonium . . . . . . .MAUMENB (E . J.). Hydrates of Baryta . . . . . . .BALLO (M.). Platinised Magnesium as a Reducing Agent . . . .BAILEY (E.). Dried Alum . . . . . . . . . .DEMAR~AY [E.). Thorium Sulphate . . . . . . . .DEBRAY . Solubility of Cupric Sulphide in Alkaline Thiomolybdates . .WRIGHT (L . T.) . ColloYdal Copper Sulphide . . . . . .THOMSEN (J.). Hydrogen Gold Chloride . . . . . . .BOISBAUDRAN (L . DE) . Separation of Gallium . . . . . .PICCINI (A.). Oxidation of Titanic Acid .. . . . . .BONGARIL (J.). Atomic Weight. of Antimony . . . . . .WITX (T.). Chemistry of the Platinum Metals . . . . . .BOISBAUDRAN (L . DE) . Violet Iridium Sulphate . . . . . .JOEBENSEN (5 . M.). Contributions to the Chemistry of RhodammoniumCompounds . . . . . . . . . . . .ISAYBERT . Phosphorus Sulphides . . . . . . . .Phosphorus with Air in Presence of MoistureLESCCEUR (H.). Hydrates of Baryta . . . . . . . .Mirteralogical Chemistry .PAGE (W . T.). Metallic Iron accompanying Native Gold in MontgomeryCo., Virginia . . . . . . . . . . . .BRANDL (J.) . .NOELLNER (A.). Some Artificial Products from Cryolite . . . .NORDSTR~M (T.). The Pyrolusite Mines of Bolet . . . . .BOURGEOIS (L.). Artificial Production of Witherite, Strontianite.andCalcite . . . . . . . . . . . . .BRUN (A.) . Mineralogical Notes . . . . . . . . .DES CLOIZEAFX and DAMOUR . Chalcomenite. a New Mineral Species (Sele-nite of' Copper) . . . . . . . . . . .SEAMON (W . H.). Fergusonite from Brindletown. Burke Co., N . Carolina .SEAMON (W . H.). Analysis of a Niobate which has been improperly calledEuxenite. from Mitchell Co., N . CarolinaMANN (P.). Rutile as a Product of the Decomposition of Titanite . .SCHULTEN (A . DE) . Artificial Production of a Crystallised HydratedSilicate . . . . . . . . . . . . .SANDBEEGER (F.). Rutile in Phlogopite . . . . . . .MUSGRAVE (R . N.). Analysis of Beautifully Crystallised Albite fromAmelia Co . . . . . . . . . . . . .SCHUBERT (B.) . Occurrence of Minerals a t Jordansmiihl.in Silesia . .Waltherite from JDachimsthal . . . . . .GONNARD (F.). The Granites on the Banks of the Sabne . . . .RICCIARDI (L.). Composition of Various Layers of a Lava-current fromEtna . . . . . . . . . . . . .Chemical Composition of Minerals of the Cryolite Group. . . . . .SCHULTEN (A . DE) . Artificial Analcime . . . . . . .BECKE (F.). Euclase from the Alps . . . . . . . .BERTRAND (C.).PAGE9541048104810491049104910501051105110621052105210521053105310531054105416541054105510561057105710582929303131313132323333343434343536363xii CONTENTS.PAGEMEUNIER (S.) . Lithological Determination of the Meteorite of Esther-ville, Emmet Co., Iowa .. . . . . , . . . 37SEAMON (W. H.). Supposed Meteorite found in Augusta Co., Virginia . 37PEBAL (L.). Mechanical Separation of Minerals . . . . . . 158GOLDSCHMIDT (V.).Iodides to Mineralogical and Petrographical Researches . . . 159SEAMON (W. H.). Native Palladium Gold from Taguaril, Brazil . , 160SEAMON (W. H.).the Native Platinum of Columbia . . . . . . . 160PINARD (G.) .White Sand accompanying the same . . . . . . , 160DEMEL (IT.). Dopplerite from Aussee . . . . . . . 160PAGE (W. T.).Mine, Colorado . . . . . . . . . . . 161SILLIYAN (B.).Durango, Mexico, and Iron Ores of Sinaloa . . . . . . 162DARTON (N. H.). New Locality for Hapesine . . . . . . 162PENFIELD (S. L.).of Monazite . . . . . . . . . . . . 162MASSIE (F. A.). Colourless Mimetite from the Richmond Mine .. . 163HIDDEN (W. E.). Notes on some N. Carolina Minerals . . . . 163ALLEN (C. L.). Composition of Two Specimens of Jade . . . . 163SEAMON (W. H.) . Analysis of a Mineral Allied to Orthite . . . 164CROSS (W.) and W. F. HISLEBRAND.in the Basalt of Table Mountain, near Golden, Colorado . . . 164S Z A B ~ (J.). Garnet and Cordierite in the Trachytes of Hungary . . . 166HARADA (T.). The Lugano Eruptive District . . . . . . 167GRODDECK (A. T.). Sericite Rocks occurring in Ore Deposits . . . 168SOMMERLAD (H.). Basalt Rocks containing Hornblende . . . . 169PLIGHT (W.). Examination of certain Meteorites . . . . . 169BOUSSINGAULT. Deposits of Mmganese on the Surfaces of Rocks . . 170THRESH (J. C.). The Orchard Alum Spring .. . . . . 171POTILITZIN (A.) . Analysis of Waters accompanying Petroleum and ofthose Ejected by Mud-Volcanoes . . . . . . . . 1’71GUYOT (P.). Analysisofthe Coal of the Muaraze . . . . . 299NILSON (L. F.). The Thorite of Arendal . . . . . . . 299JANNETTAZ (E.).Schistose Rocks by means of their Thermic Properties . . . . 300DIEULAFAIT.of Contrexeville and Schinznach (Switzerland) . . . . . 301SCHLAGDENHAUFFEN (M.). 3G2SCHLAGDENHAUFFEN (M.) .taining Calcium Sulphate . . . . . . . . . 302JOLY (N.). Glairin or Baregin . . . , . . . . . 302NORDSTROM (T.), Silver Amalgam from the Sala Mines . . . . 426COLLIER (P.). A Remarkable Platinum Nugget . . . . . . 426LEWIS (H. C.).Scranton, Pa. . . . . . . . . . . . . 427SCHARIZER (R.).Idrialite . . . . . . . . . . 427FRIEDEL (C.) and M. BALSOBN. Artificial Production of Mellite . . . 427KLEIN (C.). Cryolite, Pachnolite, and Thomsenolite . . . . . 427D’ARCHIARDI (A.). Minerals found near Massa, in the Apuanian Alps . 428BRUN (A.). Galena with Octohedral Cleavage . . . . . . 428RUMPF (J.). Analysis of Miargyrite from Pribram . . . . . 428KONIG (G. A.). Alaskaite, a new Bismuth Mineral . . , . . 429ZECCHINI (M.). Compact Magnetic Iron Ore from Cogne, Valley ofAosta . . . . . . . . . . . . . 429TORNEBOHM (A. E.). Occurrence of Iron Ores a t Taberg, in Smaaland . 429DE GEER (G.). A Manganese Mineral from Upsala . . . . . 429HINTZE (C.). Paeudomorphic Senarmontite Crystals . . . . . 430Application of a Solution of Potassium and MercuryAlloys of Gold, Silver, &c., found in Grains along witbOn a Bed of Coal Discovered in Algiers, and on the Layers ofNew Sulphide received as Tstrahedrite from Great EasternMartite of the Cerro de Mercado, or Iron Mountain ofOccurrence and Composition of some American VarietiesMinerals, mainly Zeolites, occurringStudy of “ Longrain,” and Measure of the Foliation inLithium, Strontiuni, and Boric Acid in the Mineral WatersPresence of Arsenic in the Waters of BarBges .Origin of Arsenic and Lithium in Waters con-Subetance Resembling Dopplerite from a Peat Bog neaCONTENTS .xiiiARZRTJNI (A.). Artificial and Natural Gaylussite . . . . .VENATOR (E.). Strontianite in Westphalia . . . . . . .SILLIMAN (B.). Turquoise from New Mexico .. . . . .GROTH (P.).FRIEDEL (C.) and others .FRIEDEL (C.) and E . SARASIN . Artificial Production of Phosgenite . .Netural Barium Nitrate . . . . . . . .SCHOBER ( J . B.). Examination of the Ores from Amberg, and of theaccompanying Phosphates . . . . . . . . .GONNARD (F.). Existence of Apatite in the Pegmatite of Lyons . .WEISBACH (A.). Mineralogical Notes . . . . . . . .JANNRTTAZ (E.) and L . MICHEL . Relation between the Chemical Composi-tion and Optical Characters in the Group of Pyromorphites and Mimet-esites . . . . . . . . . . . . .ARZRUNI (A.). Dietrichite . . . . . . . . . .Composition of Dawsonite . . . . .BAERWALD (C.). Thenardite from Aguas Blancas . . . . .LINDGREN (W.). Arsenates from Laangban . . . . . .HALLOCK (E .D.). Analysis of Columbite . . . . . . .MALLET ( J . W.). Crystalline Form of Sipjlite . . . . . .KOCH (S.). Wulfenite . . . . . . . . . . .HIDDEN (W . E.). .SCHMIDT (A.) . Pseudobrookite . . . . . . . . .FISCHER (H.). Tin Ores, Aventurine Glass, and Green Aventurine QuartzSJOGREN (H.) . Composition of Minerals of the Chondrodite Group . .Anatase and Xenotime from Burke Co., N . Carolinafrom Asia, and Krokydolite Quartz from Greeiilandv . RATH (G.). Iron Glance and Augite frorn AscensionJANNETTAZ (E.) and L . MICHEL . Nephrite or Jade of Siberia. . . .. . . . . . .ARZRVNI (A.). Jadeite Axe from Rabber, Hanover . . . . .LUDWIG (E.). Danburite from the Scopi, in Graubundten . . . .HAINES (R.). Helvite from Virginia . . . . .. . .LACROIX (A.). Melanite from LantgnO (Rh6ne) . . . . .ERDMANN (E.). Change of Colour in Felspar under the Influence ofLight . . . . . . . . . . . . .BAMBERGER (E.). Bechi’s so-called Picranalcime from Xonte Catini Mine,Monte Caporciano . . . . . . . . . . .BRUSH (G . J.) and E . S . DANA . Spodumene and the Products of its Altera-tion . . . . . . . . . . . . .SMITH (J . L.) and others . Hiddenite, an Emerald-green Variety ofSpodumene . . . . . . . . . . . .SIPOCZ (L.). dnalyses of Scapolite . . . . . . . .HEDDLE (M . F.). New Face on Stilhite (Desmin) . . . . .DOELTER (G.). Crystalline Form of Iodocrase (Vesuvian) . . . .BADTLER (B.). Minerals from Fritz Island, Pennsylvania . . . .CORSI (A.) and E . BECHI . Prehnite from Tuscany, &c .. . . .BECHI (E.). Prelinite and Laumontite from Monte Catini] . . . .TRECHMAXN (C . 0.). Epistilbite . . . . . . . . .JANNASCH (P.). Epistilbite and Heulandite . . . . . . .BERTRAND (E.) and DAMOTJR . .BARET . Chlorophyllite from Loquidy, near Nantes . . . . .LUDWIG (E.). Chemical Composition of Epidote . . . . .BECKE . Hornblende and Anthrophyllite after Olirine . . . . .GONNARD (F.). Gedrite in the Gneiss of Beaunan, near Lyons . . .STARKL (G.). Bole from Steinkirchen, near Budweis, in Bohemia . .STARKL (G.). Poljhydrite from St . Cristoph Mine, Breitenbrunn, inSaxony . . . . . . . . . . . . .COSSA (A.) and A . ARZRTJNI . Chromic Tourmalin, and the Deposits ofChrome-iron Ore in the Urals . . . . . . . .BAUER (M.). Dioptase from the Corderillas of Chili .. . . .Cossil (A.). Chemical and Microscopical Researches on Italian Rooks andMinerals . . . . . . . . . . . . .SONDBN (K.). Analysis of Petalite fromuto . . % . . .Zinc Aluminite, a New Mineral SpeciesPAGE43043043143143 143143243 24324334334344344.3443543543 543543543643643643743743’:4384384384384404404414414414424424424434434434444444444.404414444.4444644xiv COSTEXTS,.WORTSCHACH (G.). The Granite Hills of Konigshain. in Oberlausitz. withv . UNGERN-STERNBERG (T.) . The Rapakiwi Granite. from Finland . .#ENITZ (E.). Phyllite from Rimogens. in the Ardennes . . . .MICHEL-L~VY (A.). Micaceous Porphyrite of Morvan . .. . .STEIN (G . E.). The Melaphyres of the Little Carpathians . . . .#UMBEL (C . W.). The so-called Andesites of South and Central America .KUHN (J.). Examination of Ophites from the Pyrenees . . . .TECKLENBURG . The Clay Ironstone of Rheinhesse . . . . .CRONQUIST (A . W.). The Lake Deposits of Kolsnaren, Viren. and Hiigsjon.Sodermanland. Sweden . . . . . . . . . .FOUQU~ (F.) and MICHEL.LI$VY . .DAUBR~E (A.). Meteorite of Louans (Indre-et-Loire) . . . . .CRONQUIST (A . W.). Analysis of a Spring Water from Rindo. near Stock-holm . . . . . . . . . . . . .TLES (M . W.) . Occurrence of Smaltite in ColoradoDERBY (0 . A.). Brazilian Specimens of Martite . . . . . .CLASSEN (E.). Analysis of a Variety of Siderite . . . . . .HAUTEFEUILLE (P.) and J .MARQOTTET . .WIIK (F . J.). Relation between the Optical Properties and Chemical Com-BOURGEOIS (L.). Artificial Production of Wollastonite and Meionite . .WIIK (F . J.). The so-called Ersbyite from Pargas . . . . .WIIK (F . J.). Emerald from Paavo. in Finland . . . . . .HARRINGTON (B . J.). Diorites of Montreal . . . . . . .Monazite and Zircon from the Quarries of Nil.St . Vincent .ILES (M . W.) . Vanadium in the Leadville OresMACPHERSON (J.) . Occurrence of Aerinite . . . . . . .HUSSAK (E.). Serpentine from the Alps . . . . . . .DANA (J . D.). Metamorphism of Massive Crystalline Rocks . . .COLEMAN (A . P.), The Melaphpes of Lower Silesia . . . . .DAMOUR (A.). Aluminium Borate from Siberia . . . . . .BROGGER (W . C.). The Silurian Rocks of Christiania .. . .especial regard to the Minerals found therein . . . . . .Artificial Formation of Various Rocks. . . . .Silica and Lithium Silicates .position of Pyroxene and Amphibole . . . . . . .RENARD (A.). . . . . . .POLECK (T.). Analysis of a Mineral Spring at Salzbrunn . . . .STELZNER (A.) . Melilite and Melilite Basalts . . . .DOLTER (C.). The Volcanic Rocks of the Cape Verde'Islands . . .WILLIAMS (G . H.).DIEULAFAIT .BOLTON (H . C.).BUTTGENBACX .The Eruptive Rocks near Tryberg in the Black Forest ..Application of Organic Acids to the Examination ofMinerals . . . . . . . . . . . . .Separation of Minerals according to the Degree of CohesionAn Ammonio-phosphatic Deposit in the Vicinity ofCape Town . . . .. . . . . . . .Manganese in Sea-water and in Certain Marine DepositsGRIFFITHS (A . B.). Analysis of some Minerals . . . . . .WILM (T.). Magnetic Property of Platinum Ore . . . . .GORGEU (A.). Artificial Hausmannite . . . . . . . .KOSMANN . Minerals from Upper Silrsia . . . . . . .COSSA (A.) . Hieratite. a New Mineral Species . . . . . .SCHRAUF (A.). The So-called Liebigite from Joachimsthal . . . .DANOUR (A.). Rhodizite . . . . . . . . . .SCHRAUF (A.) and others . Danburite from Switzerland . . . .Table Mountain. Colorado . . . . . . . . .SPEZIA ((3.). Beryl from Craveggia. Piedmont . . . . . .WILL (W.) and K . ALBRECHT Diabase from WeilburgGRIPPITHS (A . B.).CROSS (C . W.) and W . F . HILLEBRAND . Minerals. mainly Zeolites. fromRENARD (A.).FOKTAINE (W .F.).Garnet and Amphibole Rocks of the Bastogne Region . .Notes on the Occurrence of certain Minerals in AmeliaCo .. Virginia . . . . . . . . . . . .. . . . .SPEZIA (G.)." The Gneiss of Beura . . . . . . . .LORENZEN (J.) . Minerals in the Sodalite Syenite of South Greenland . . 960PAGE44644744744744744841.844844844844944955955955955956056056156156156156256356256256356371971972072372372585'785885885985985995595595595695695695895895995996COXTENTS . xvROHRBACH (C.). Application of a Solution of Barium and Mercury Iodideto Petrographical Purposes . . . . . . . . .BERTRAND (E.). Optical Properties of Nocerine . . . . . .BODEWIG (C.).Analyses of Magnetic Pyrites . . . . . .LUEDECKE (0.). Tinder Ore from the Harz . . . . . . .FRIEDEL (C.). Brucite from Cogne . . . . . . . .WEISBACH (A.) . Brucite . . . . . . . . . .PRINZ (W.). The Inclusions in Sapphire, Ruby, and Spinel . . .Artificial Production of Barytes, Celestine, and Anhy-drite . . . . . . . . . . . . .BERTRAND (E.). Optical Properties of Cobalt Carbonate . . . .New Locality for Hayesine. and its Novel Occurrence .Two New Minerals. Monetite and Monite. with a Noticeof Pyroclasite . . . . . . . . . . . .Analysis of a Pyromorphite from Zahringen. in Baden .BAERWALD (C.) . Analysis of Crocoisite . . . . . . .HIDDEN (W . E.). Notes on some North Carolina Minerals . . . .SCACCHI (A.). New Sublimates from the Crater of Vesuvius .. .Calculation of Analyses of Augites and Amphiboles fromFinland . . . . . . . . . . . . .Formation of Bauxite and of Pisolitic Iron Ore . . .Note on some Interesting MineralsGORGEU (A.).HARTON (N . H.).SHEPARD (C . U.).BAERWALD (C.).KENNGOTT (A.).MEUNIER (S.).CROSS (W.) and W . F . HILLEBRAND .occurring near Pike's Peak. Colorado . . . . . . .CLAASSEN (E.). aineralogical Notes . . . . . . . .DAMOUR (A.). Chemical Composition of a Green Mica from Syssert . .CATHREIN (A.). Saussurite . . . . . . . . . .KRENNER . Jadeite . . . . . . . . . . .DES CLOIZEAUX and JANNETTAZ . .Idocrase from Kedab6k in the CaucasusJANNASCH (P.) . .JANNETTAZ . Analysis of a Green Pyroxene from the Diamond Mines of theCape .. . . . . . . . . .NICOLAJEW (D . P.j. Chemical Composition of Walujewite . . . .BECK (W . v.) and J . W . v . MUSCHKETOW . Nephrite . . . . .CATHREIN (A.). Chemical Composition of Diallage . . . . .EENNBOTT (A.). Analyses of Humite . . . . . . . .GEINITZ (El . E.). Pseudomorph of Nacrite after Fluorspar . . . .SCHEERER . Analysis of the Mansfeld Copper Slate . . . . .TELLER (P.) and C . v . JOHN . .LE CONTE (J.) and W . B . RISING . Metalliferous Vein Formation a t SulphurBank . . . . . . . . . . . . .HAUER (F . v.) and others . . . . .GALLIA (5.) and A . BREZINA . The Meteorites of Alfianello . . . .TERREIL (A.). Mineral Water a t Montrond (Loire) . . . . .Nepheline in the Oligoclase of DQniseKORN (0.). . . . . .Discovery of Fluorine in the Idocrase from Vesuvius .Dioritic Rocks of Rlausen in the Tyrol .The Klausenburg MeteoritePAGE10601060106110611061106110621062106210621063106310631C631064106510651065106610661066106610671067106710671068106510681068106!j106910691070107010711071Organic Chemistry .MAQUENNE (L.).Action of Ozone on Hydrocarbons . . . .PHILLIPPS (S . J.). Conversion of Maltose into Glucose . . .SOXHLET (F.) and A . BEHR . Manufacture of Starch-sugar . . .WAAGE (A.). Action of Ammonia on Propaldehyde . . . .EMMERT (A.) and R . FRIEDRICH . y-Diethylbutyrolactone . . .ZATZEK (E.). Bees' Wax . . . . . . . .MEYER (V.) and E . J . CONSTAM .CERESOLE (M.). Acetoacetic Acids . . . . .. .NOELTING (E.) . Dissociation of Trichlorornethyl Sulphochloride . .HABERMANN (J.) and M . HONIG . Action of Cupric Hydroxide on SugarsCHANLAROFF (M.). Action of Thiacetic Acid on Ethyl Thiocyanate .Azaurolic AcidsSaccharin and Lactic Acid from Sugars. . . .CUISINIER (L.) and H . KILIANI .. 37 . 38 . 58 . 3x . 39 . 39 . 39 . 31, . 3!) . 4:t . 41 . 4xvi CONTENTS .FRUHLING (J.). y-Hydroxybutyric Acid . . . . . . .OBACH (EL) . Purification of Carbon Bisulphide . . . . . .ILOSVAY . Physical Properties of Carbon Oxysulphide . . . . .CLAUS (A.). Dibromosuccinic Acid and Diamidoauccinic Acid . . .LE BEL (J . A.). Geometrical Formulae of Maleic Acid and Fumaric Acids .CONRAD (M.) and M . GUTEZEIT . Et'hylic Methenyltricarboxylate andEthylio Acetomalonate .. . . . . . . . .BISCEOFF (C . A.). Ethylic Ethenyltricarboxylate . . . . .BWCHOFF (C . A.). Ethylic Monochlorethenyltricarboxylate . . . .BISCHOFF (C . A.). Ethereal Salts of Propenyltricarboxylic Acid . . .?VALTZ (G.) . Ethylic Propyl- and Isopropyl-ethenyltricarboxylates . .BISCHOFF (C . A.). Ethylic Isallylenetetracarboxylate . . . . .CONRAD (M.) and C . A . BISCHOFF . Tetrethylic Acetylenetetracarboxylate .GUTHZEIT (M.) . Diethylic Acetylenetetracarboxylate . . . . .CONRAD (M.) and M . GUTHZEIT . Tetrethylic Dicarbontetracarboxylate .HILL (H . B.) and C . R . SANGER . Action of Potassium Nitrite on Muco-bromic Acid . . . . . . . . . . . .SPRING (W.) and E . LECIROS . Alkylthiosulphuric Acids . . . .WALLACH (0.). .SCICHILONE (S.) and A .DENARO . Mannitiiie, a new Alkaloxd from Man-nitol . . . . . . . . . . . . .LADENBURQ (A.) . Benzene Formulze . . . . . . . .MEYER (R.). Benzene Formule . . . . . . . . .JACOBSEN (0.). Isodurene, Isodurylic Acids, and the Third Trimethyl-benzene . . . . . . . . . . . . .DUMXEICRER (0 . v.). Action of Aluminium Chloride on the MomhalogenDerivatives of Benzene . . . . . . . . . .NOELTINQ (E.). Rosaniline Derivatives . . . . . . .LIPPMANN (E.) and F . FLEISSNER . Azyliiies . . . . . .MICHAELIS (A.) and L . CZIMATIS . Triniethylphosphorbenzobeta'ine . .MEYER (L.). Formation and Decomposition of Acetanilide . . . .GRIESS (P.). Constitution af the Azimido-compounds . . . . .CZIMATIS (L.). Mixed Aromatic Tertiary Phosphines .. . . .MEUNIER (J.) . Action of Potassium Carbonate on BenzyZ and BenzyleneChloride . . . . . . . . . . . . .NOLTINO (E.) and E . v . SALIS . Nitro-derivatives of the Cresols . . .BARTH (L.) and J . SCHREDER . Fusion of Orcinol and Gallic Acid withSoda . . . . . . . . . . . . .Action of Phosphorus Pentachloride on Acid Amides .E HRLICH (A.) . Metat oluidine . . . . . . . . .LIEBMANN (A.). Isobutyl- and Amyl-phenols . . . . . .SCHIFF (H.). Methylarbutin . . . . . . . . .SCHUBERT (S.). Di-isobutylquinol . . . . . . . .of Quinone with Nitranililies . . . . . . . . . HEBERAND (A.).ETTI (C.).PAAL ((2.).Compounds of Benzo- and Tolu-quinol with Amines, andCompounds of Vanillin with Pyrogallol and with Phloroglucol .Action of Acetic Chloride on Benzaldehyde in presence of Zinc-dust .. . . . . . . . . . . .ROMBURGH (P . v.). .ROMBURQH (P . v.). Action of Benzoic Anhydride on MonochloracetoneMETER (R.) and E . MULLER . . . . .NOELTINQ (E.) and H . BOURCHART . Action of Sulphuric Acid on Proto-catechuic Acid . . . . . . . . . . . .~ T I L L O T (A.). Oxidation-products obtained from Carbon by Electrolysis .GABRIEL (S) . Orthamidobenzaldehyde . . . . . . .and on Pyruvyl Benzoate . . . . . . . . .GABRIEL (S.). Phenylacetic Acid . . . . . . . . .KORNER (G.). Caffeic Acid from Cuprea Bark . . . . . .CANZONERI (F.). Dibromonaphthalene from P-Naphthol . . . .Action of Benzoic Anhydride on Epichlorhydrin .Synthesis of Cumic AcidH i j ~ ~ a (M.) and F . BERQER . Action of Chloroform on Naphthalene inpresence of Aluminium Chloride .. . . . . . .PAGE42434343444445454546464646464747485051515253545465655656575859595960606161626262636364656566676CONTENTS . xviiWORMS (R.). Constitution of Nitronaphthols . . . . . .PABST (M . A.). Indophenol . . . . . . . . . .ELSBACH (L.), a-Naphthaquinone-ethylanilide . . . . . .BERNTHSEN ( A . ) and E . BENDER . Derivatives of Gtyrolene . . . .ROEMER (H.). New Nitro- and Amido-anthraquinones . . . .on Dinitroanthraquinone . . . . . . . . . .LIEBERMANN (C.) and A . HAGEX .BRUNCK (H.) and C . GRAEBE . Soluble Alizarin-blue . . . . .TILDEN (W . A.). Hydrocarbons of the Foi.rnula (C5H8),, .. . .CHAPOTEAUT (P.). Essence of Sandal Wood . . . . . .BORNSTEIN (E.). Methylanthraquinone and some of its Derivatives . .LIEBBRMANN (C.) and A . EAGEN . Action of Concentrated Sulphuric AcidDerivatives of Anthrol Salts . . .SCHULER (G.) . Dihydroxyanthracene from a- Anthraquinone . sulphonicAcid (Flavol) . . . . . . . . . . . .MICHAEL (A.). Synthesis of Salicin, and of Anhydrosalicylic Glucoside .CANNIZZARO (C.) and G . CARNELUTTI . Santonous and Isosantonous Acids .SPICA (G.). Psoromic Acid, a new Acid extracted from Psoroma crassurn .OUDEMANS (A . C.). Laws of the Variation of the Specific Rotatory Powerof Alkalo’ids under the Influence of AcidsCIAMICIAN (G . L.) and M . DENNSTEDT . Action of Nascent Hydrogen onYyrroline . .. . . . . . . . . .HaNTzscn (A.). Synthesis of Pyridine-derivatives from Ethyl AcetoacetateSKRA-UP (Z . H.) and Gt . VORTMANN . Dipyridyl-derivatives . . . .HOOGEWERPF (S.) and W . A . v . DORP . The Quinoline of Coal.tar, audof the Cinchona Alkalo‘ids, and its Oxidation by Potassium Perman-ganate . . . . . . . . . . . . .. . . . . .and Aldehydammonia . . . . . . . . . .CONINCK (0 . DE) . Quinoline from Cinchonine . . . . . .La COSTE (W.). Nitro- and Amido-bromoquinoline . . . . .FISCHER (0.). Hydroxyquinolines . . . . . . . .SKRAUP ( 8 . H.). Synthetic Researches in the Quinoline SeriesRHOUSSOPOULOS (A.). Quinoline-derivatives . . . . . .HESSE (0.). Hydrocinchonidine . . . . . . . . .GOLDSCHMIDT (H.). Strychnine . . . . . . . . .. . .LA COSTE (W.).Bromoquinolinesulphonic Acids . . . . . .TANRET . Caffeine . . . . . . . . . . . .ROSER (W.). Xeronic and Pyrocinchonic Acids . . . . . .SCICHILONE (S.) and v . MAGNANIMI . Distillation of Strychnine with Zinc-dust . . . . . . . . . . . . .BAIJMERT (G.). Action of Dehydrating Agents on Lupinine . . .PHIPSON (T . L.). Colouring Matter (Ruberine) and Alkalold (Agarjthrine)GAUTIER (A.) and A . ~ T A R D . . . .GAUTIER (A.). Formation of Alkalo’ids from Normal Human Fluids . .HUPPE (F.) . .MAYER (A.) and others . The Temperature most favourable to the actionof Invertin . . . . . . . . . . . .BAUER (E.). .KUTSCHEROFF (M . G.). Action of Hydrocarbons of the Acetylene Series onMercuric Salts . . . . . . . . . . .ARONSTEIN (L.).Transformation of Propyl Bromide into Isopropyl Bromide,under t. he Influence of HeatHENRY (L.). a-Monochlorallylic Alcohol and its Derivatives . . .URECH (F.). Strobometric Determination of the Rate of Inversion of Cane-sugar, and Transition of the Birotation of Milk-sugar tto its NormalRotation . . . . . . . . . . . .HESSE (0.). Anhydrous Grape-sugar from Aqueous Solution . . .BAUBIGNY . Transformation of Amides into Amines . . . . . .VOL . XLIV . bin Agaricus ruter . . . . . . . . . . .NENCKI (M.) and N . SIEBER . Urorose’in . . . . . . .Bases Formed by PutrefactionBehaviour of Unorganised Ferments a t High TemperaturesInfluence of Invertin on the Fermentation of Cane-sugar. . . . . . . . .BERTHELOT . Ethylene Oxide . . . . .. . . .PAGE69ti97070707172737474$5767677808182828588899091929696979798999910010010010110110110130117217217317417417517xviii COXTESTS .LOVISE (E.). .BREDT (J.). Action of Nitric Acid on Fatty Acids containing the Isopropyl-group . . . . . . . . . . . . .COURTONNE (H.). Solidification of different Mixtures of Naphthalene andStearic Acid . . . . . . . . . . . .WILLQERODT (C.) . Conversion of Acetone-chloroform into Hydroxyiso-butyric Acid . . . . . . . . . . . .WILLGERODT (C.). Bye-products in the Preparation of Acetone-chloro-form . . . . . . . . . . . . .COXRAD (M.). Halogen Substitution-compounde of Ethyl Acetoacetate .LIPPMANN (E.). Addition of Bromine to Ethyl Acetoacetate .. .MENSCHUTKIN (N.). Decomposition of Tertiary Amy1 Acetate by Heat .LJVBAVIN (N.). Action of Ammonium Cyanate on Glyoxal . . .SELL (W . T.). Series of Salts containing Chromium and Urea . . .HORBACZEWSKI (J.). Synthesis of Uric Acid . . . . . .UARNER (I?.). Crystallographic Examination of a- and P-Dinitroparaxylene~ T A R D (A.) . Benz-jdeneorthotolglamine and Methylphenanthridine . .SAMOXOFF (N.) . Azoxylene . . . . . . . . . .MOLTCHANOFPSEY (N.). Elinger’s Method of preparing Azoxybenzene .Action of Anhydrous Aluminium Chloride on Acetone .and of Dinitroparaxylene (m . p . 93”) . . . . . . .GRI ESS (P.) . Diazo-compounds . . . . . . . . .LIPPMANN (E.) and F . FLEISNER . Azylines . . . . . .LELLXANN (E.) .Phenjlenethiwarbamides . . . . . . .SCHULTE (C.). Yhenylarsine Sulphides . . . . . . .Phenylcacod yl . . . . . . . . . . .BAMBBERGER (E.). Formation of Phenylxanthamide . . . . .MICHAELIS (A.) and L . GLEICHMANN . Aromatic Isophosphines . . .MICHAELIS (A.) and C . SCHULTE . Arsenobenzene, Ardenonaphthalene, andFBIEDLANDEB (P.) and R . HENRIQUES . Reduction of Orthonitrobenz-aldehyde . . . . . . . . . . . .TIEMANN (F.) and R . LUDWIG . Metahydroxybenzaldehjde and some of itsDerivatives . . . . . . . . . . . .VOSWINCKEL (H.). New Deriratives of Salicjlaldehjde . . . .WEQSCHEIDER (R.). Isovanillin . . . . . . . . .GEVEKOHT (H.). Preparation of the Three Isomeric Kitracetophenones .TRAUBE (J.). Action of Cjanogen Chloride on Amido-acids .. .TRAUBE (J.) . Contributions to the Knowledge of Meta-uramidobenzoic Acidand Carbamidodibenzoic Acid . . . . . . . .LIPPMANN (E.) . Diamidocumic Acid . . . . . . . .Constitution of the Halogen Cinnamio Acids . . . .GABRIEL (S.). Hydrocinrramic and Cinnamic Acids . . . . .ERLENMEYER (E.). Derivatives of Cinnamic Acids . . . . .YLGCHL (J.).BAEYER (A.) and F . BLOEM . Orthamidophenylpropiolic Acid and itsDerivatives . . . . . . . . . . .TIEMANN (F.) and R . KRAAZ . Derivatives of Homoferulic Acid . . .‘IIEMANN (F.) and K . PIEST . Phtnylljhenamidoacetic Acid and its Amideand Nitrile . . . . . . . . . . . .TIEMANN (F.). a-Phenamidoisobutyric Acid and its dniide and Nitrile .TIEMANN (F.) and R . STEPHAN . Nitriles of a.Pheuaiiiido., a-Paratolu-amido., and a-Orthotoluamidopropionic Acids and their Ainides andNitriles .. . . . . . . . . . . .. . . .Isatin . . . . . . .CLAUS (A.) . Amarine . . . . . . . . . . .FRIEDLANDER (P.) and A . WEINBERQ . Constitution of Carbostyril andHydrocarbostjril . . . . . . . . . . .WIDMAN (0.). a - and r . L , ichloroiiaphthalenes . . . . . .TIEMANN (F.) and W . WILL .BAEPER (A.) and d . ~ECONOXIEES .BECKER (P.). Metniiitrodipheny1met;hane . . . . . . .Constitution of BzculetinTIEMANN (F.) and R . KRAAZ . Constitution of Eugenol. . . .SGHWARZ (H.). a., P., and y-Pyrocresoles . . . . . . .PAGE17’617617617717717717717817817817917917918018018018418518518518618718718818919019119219419419419519619619819819919919920320120220320420480COXTENTS .xixWALDER (H.). 13-Difiaphthol . . . . . . . . .ZINCPE (T.) and F . BRAUNS . Action of Amines on QuinoiicYATERN~ (E.) . Lapachic Acid . . . . . . . . .CAZENEUVE (P.). A New Monochlorocampl~or . . . . . .mocamphors . . . . . . . . . . . .from /3-Dibromocamphor . . . . . . . . .MAUMEN~ (E . J.). (Enocyanin . . . . . . . . .. . .SWARTS (T.).KACHLER (J.) and B . V . SPITZER .Contributions to the History of the Isomerism of the Dibro-Action of Nitric Acid on OxycamphorEyKNaN (J . F.).GINTL (W.) and F . REINITZER .The Poisonous Constituent of Andromedajaponica . .Constituents of the Leaves of Fraxinusexcelsior . . . . . . . . . . . . .Hydrates of Pyridic Bases derived from Cincho-nine .. . . . . . . . . . . .SPIEOEL (A.). Euxanthic Acid . . . . . . . . .SCHOTTEN (C.). Conine . . . . . . . . . .HOFMANN (A . W.). Conhydrine . . . . . . . . .DUTILLIEB (E.). Compounds of the Creatinine Group . . . .GERICHTEN (E . v.) and H . SCHROTTER . MorphineWEIDEL (H.) and K . HAZARA .LEXTRRIT . Strychnine Sulphate . . . . . . . . .CONIXCK (W . 0 . DE) .. . . . .Cinchonine . . . . . . .BAUMERT (G.) . Preparation of Lupinine H-drochloride from LupinineResidiies . . . . . . . . . . . . .GAUTIER (A.) and A . GTARD. Putrid Fermentation, and the AlkaloYdsInvertin . . . . . . . . . .STAEDEL (W.). Relation between Boiling Points and Specific Volumes .ROYBUROH (P . v.). Conversion of Orgauic Chlorides into Iodides by meansof Calcium Iodide .. . . . . . . . . .Produced by it . . . . . . . . . . .KJEDAHL (M . J.).BERTHELOT . Decomposition of Cyanogen . . . . . . .MUL~ER (E.). Properties of Normal Cyanic Acid . . . . .Cyanetholine . . . . . . . . . . . .BERTHELOT . Ethyl Peroxide . . . . . . . . .FAUCONNIEFZ (A.). Second Anhydride of Mannitol . . . . .PFEIFFER (‘I’.) and others . Formulaof Starch . . . . . .MULDEFZ (E.) . A Reaction of the Compounds of Normal Cyanuric Acid andURECH (F.). Influence of Mass and Time on the Inverbion of Sugar . .REBOUL (E.) . Action of TriethFlamine on Symmetrical Trichlorliydrin andon the two Dichloropropylenes . . . . . . . .HADZISZEWSEI (B.). Glyoxaline and it. s Homologues . . . . .MENSCHUTKIN (N.).Decomposition of l’ei*tiarp Amy1 Acetate by Heat .HILL (H . B.) and C . F . MABERY . .HILL (H . B.). Constitution of the Substitilted Acrylic and Propionic AcidsMELVILLE (W . H.). Crystalline Form of Tribrornacrylic Acid . . .MELIKOFF (P.). Addition of Hypochlorouv Acid to /3-Crotonic Acid . .MATTHEWS (A . E.) and W . R . HODGKINSON . Ethyl Acetoacetate . .CONRAD (M.) and M . GUTHZEIT . Action of Chloroform on Sodium Ethyl:malonate . . . . . . . . . . . .MULDER (E.) and (3 . HAMBURGER . Action of Sodium Ethylate on the SodiumCIAMICIAN (G . L.), and M . DENNSTEDT . .BAUDROWSKI (E.). AcetylenedicarboxJlic Acid . . . . . .CONRAD (M.) and M . GDTHZEIT . Derivatives of Barbituric Acid . .SCHULZE (E.). Extraction of Asparagine from Liquids .. . .HEPP (P.). Trinitro-derivatives of Benzene and Toluene . . . .HEPP (P.). Addition-products of Nitro-derivatives with Hidrocarbom .ASCHENBRANDT (H.). Paradiethylbenzene . . . . . . .Tetra-substituted Propionic Acids .KLEPL (A.). Preparation of Rfethj-1 Chlorocarbonate . . .Salt of Symmetric Dibromosuccinic Acid . . . . . .Derivatives of Citraconic AcidBAUDROWSKI (E.). Propargylic Acid . . . . . . . .MEYER (V.). Benzene from various Sources . . . . . .t 2PAGE208209210214214215215215216219220220220220221222223224224225302. 303’30330430530530530630730’73083093(’93103 1031131131131131231231331431431531531531 xx CONTENTS .SPICA (P.).Camphor-cymene and the so-called Second Sulphonic Acid ofParacymene . . . . . . . . . . . .KORNER (H.). Paradipropylbenzene . . . . . . . .LOUISE (E.). A New Hydrocarbon . . . . . . . .STAEDEL (W.). The History of the Metanitrils . . . . . .HINSBERG (0.). Oxalic Acid Derivatives of Metanitroparatoluidine and3-4 Diamidotoluene . . . . . . . . . .HOFMANN (A . W.). Crystalline Cuniidine . . . . . . .I h L M A N N (E.). The Three lsolveric Phenylenediamines . . . .JANOVSKY (H.). Substitution-products of Azobenzene . . . .TOBIAS (G.). Formation of Anilides . . . . . . . .TOBIAS ((3.). Formanilide and its Homologues . . . . . .MENSCHUTKIN (N.). Decomposition of Acetanilide by Water . . .MICHAELIS (A.) and A . REESE . Aromatic Arsenic and Antimony Com-HENRIQUBS (R.).New Nitro-derivatives of Phenol . . . . .WALLACH (0.). Conversion of Tolylenediamine into an Amidocresol andWIDMAN (0.). Synthesis of Indole from Cuminol . . . . .CANZONERI (F.) and P . SPICA . .FRIEDLANDER (P.). Orthamidobenzaldehyde . . . . . .MOHLAU (R.). Bromacetophenone . . . . . . . .MOHLAU (R.) . Action of Bromacetophenone on Phenol . . . .GISSMANN (R.). Oxidation of Durene by Chromic Acid . DinitrodurylicAcid . . . . . . . . . . . . .SCHIFF (H.) . Protocatechutannic Acid and Anhydrides of Aromatic Hydr-SCIFHILONE (S.). Allyloxybenzoic Acids . . . . . . .CURTIUS ('I.). Synthesis of some Acids analogous in constitution to Hip-puric Acid . . . . . . . . . . . .WEDDIBE (A.). Tribasic Nitrophenyl Orthoformate .. . . .CALM (A.) . Paradichlorazobenzene-monosulphonic Acid . . . .BAEYER (A.) and V . DREWSEN . Preparation of Indigo-blue from Orthoni-pounds . . . . . . . . . . . . .y-Orcinol . . . . . . . . . . .Brominated Derivatives of ToluquinoneMOELAU (R.). Acetophenoneanilide . . . . . . . .oxycarboxylic Acids . . . . . . . . . .BAEYER (A.). Benzoylttcetic Acid . . . . . . . .TIEMANN (F.) . Triphenyl Orthoformate . . . . . . .trobenzaldehFde . . . . . . . . . . ."OHLAU (R.). I)iphenyldiisoindole . . . . . . . .NOHLAU (R.). Azo-colouring Substances from Diphenyldiisoindole . .LELLMANN (E.). Derivatives of Diphenyl . . . . . . .LELLMANN (E.). A Case of Physical Isomerism . . . . . .NERZ (v.) and w . WEITH . . . .MARCHETTI (C.). Picrates of a- and p-Naphthol . .. . .AGRESTINI (A.). Derivatives of Naphthalene Hexhydride . . . .BEILSTEIN (F.) and E . WIEGCAND . . . . .HJELT (E.) and U . COLLAN . Ledum Camphor . . . . . .EIJKM~N (J . F.). Poisonous Principle of Andromeda japonica . . .ERDMANN (E.) and G . SCHULTZ . Hsemdtoxjlin and Hmnatei'n . . .CIAMICIAN ((3 . L.) and M . DENNSTEDT . Compounds of the Pyrroline SeriesFRIEDLANDER (P.). Substitut.io n.derivatives of Quinoline . . . .MEYER (E . v.). . . . .SCHWEBEL (P.). Specific Rotatory Power of Ssltrs of Nicotine . . .PISCHER (E.). Cafleine, Theobromine, Xanthine, and Guanine . . .OUDEMANS (A . C.). Specific Rotatory Power oE Apocinchonine and Hydro-RI~HAUSEN (H.). Behaviom of Conglutin from Lupines towards SalineSolutions .. . . . . . . . . . .RITTMESEX (H.). Albuminoids in Peach-kernels and SesamB-cake . .Nitro-derivatives of NaphthaleneSome Ethereal OilsSCHIFF (H.). Glucosides . . . . . . . . . .Cyanethine and Bases derived from i tGRIMAUX (E.). Home Derivativesof Morphine . . . . . .chlorapocinclionine under the Influence of Acids . . . . .PAQE3203213233233233243243243253253%32732732932933033133233233233333533533633734034034134134234234334334334434534634634734a3493503513 5233435435835936036CONTENTS . XXlROMBURGH (P . v.). Isomeric Monochlorallyl Iodides . . . . .NIEDERIST ((3.). Trimethylene Glycol and Trimethylene Bases . . .FBANCHIMONT (A . P . N.).Action of Anhydrides on Aldehydes, Ketones.and Oxides . . . . . . . . . . .FRANCHIMONT (A . P . N.). Paraldehyde . . . . . . .FITTIG (R.). Non-saturated Acids (Part TI) . . . . . .GFOTTSTEIN (L.). Two New Caprolactones . . . . . . .WOLFF (L.). 8-Lactone of Normal Caproic Acid . . . . . .YOUNG (S.). Hepto- and Octo-lartones . . . . . . .HJELT (E.) . Lactones from Allylmalonic, Diallylmalonic, and DiallylaceticAcids . . . . . . . . . . . . .YOUNG (S.). Peculiar Decomposition of the Ethereal Salts of SubstitutedAcetoacetic Acids . . . . . . . . . . .MAQUENNE . Decomposition of Formic Acid by the Silent Discharge . .MULDER (E.). Synthesis of Optically Active Carbon Compounds . . .BEER (A.). Itamalic, Paraconic, and Aconic Acids . . . . .ROTHER (R.).Ferrous Citrate and its Double and Secondary Salts . .SPICA (P ) . A Metacymene and a New Isomeride of Thymol . . .PIEPER (R.) . Four Metameric Benzanisethyl-hydroxylamine~ . . .MAZZARA (G.). Isopropyl., Di.isopropyl., and Dipropyl-metacresols . .HERZIG (J.). Action of Nitrous Acid on Guaiacol . . . . .NIETZKI (R.). Quinones and Quinols . . . . . . . .BARTH (L.) and J . SCHREDER . Action of Melting Potassium Hydroxide onBenzoic Acid . . . . . . . . . . . .SUSSENOUTH (H.). Monobromopseudocumic Acid and Dibromomesif ylenicAcid . . . . . . . . . . . . .. . .HERZIG (J.). Guaiaconic and Guaiaretic Acids . . . . . .BROUN (P . H.). Ethoxymetatoluic Acid . . . . . . .EBERT ((3.). Coumarin . . . . . . . . . .PENFIELU (S . L.). Phmylhornoparaconic Acid .. . . . .FITTIG (R.) and G . EBERT . Coumarilic Acid . . . . . .ERDMANN (E.). Action of Sulphuric Acid on Cinnamic Acid . . .LANDSBERG (M.). Imicles of Bibasic Acids . . . . . . .RODATZ (P.). Constitution of some Azobenzenedisulphonic Acids . .RODATZ (P.). Brominated Azobenzenedisulphonic Acids . . . .SHENSTONE (W . A.). Jafferabad Aloes . . . . . . .JACKSON (C . L.) and A . E . MENKE .FRABK (A . B.). Hppochlorin and its Formation . . . . . .MEPER (A.). Nature of Pringsheim’s Hypochlorin Crptals . . .WEIDEL (H.) and M . RUSSO . Researches on Pyridine . . . . .BAUMHAUER (H.) . The Trapezohedral Hemihedry of Strychnine Sulpbate .BURI (E.). Hydropiperic and Piperhydronic Acids . . . . .MAYEE (A.). Action of Invertin .. . . . . . . .MARKOWNIKOFF (W.) and W . OGLOBLIN . Chlorination of Hydrocarbonsfrom Caucasian Petroleum . . . . . . . . .LOSANITSCH (S . M.) . Formation of Dibromodinitromethane and of VillierdTetranitroethylene Bromide . . . . . . . . .GUSTAVSON (G.). Conversion of the Propyl- into the Isopropyl-group .BERTHELOT . Direct Combination of Hydrogen with Ethylene . . .PAWLESKI (B.). St(abi1ity of Trimethyl Carbinol . . . . . .KILIANI (H.). Saccharin and Saccharic Acid . . . . . .MEYER ((3.). Aldehyde-ammonium Bases . . . . . . .FITTIG (R.) and H . W . JAYNE . Phenylhydroxypivalic AcidJAYNE (H . W.). Phenplbutyrolactone and Phenylparaconic Acid . .JACESON (C . L.) and A . E . MBNKE . Certain Substances obtained froniTurmeric . . . . . . .. . . . .Turmeric Oil: Turmerol . . .WORM-MULLER and J . OTTO . Schwarz’s Process for preparing Pure Grape-sugar . . . . . . . . . . . . .Some Oxides of the Ethylene Series and their Action onWater . . . . . . . . . . . . . ELTEKOFF (A.).PAGE44945045245345445445545545645645’76’74574 584594604634644654684 94704714714714 724-7347447447547747848048048245348348348548548656456456558556556556556656xxii CONTENTS .TCHERNIAC (J.) and T . H . NORTON . Thiocyanopropimine . . . .MEYER (V.) . Isonitroso-compounds . . . . . . . .PETRACZEE (J.). Aldoximes . . . . . . . . . .LIEBEN (A.) and S . ZEISEL . Condensation-products of Aldehydes and theirDerivatives .. . . . . . . . . . .MEYEB (V.) and M . CERESOLE . Constitution of Nitroso.compounds . .TREADWELL (F . P.) and B . WESTENBERQEB . . . .SCHRAMM (C.). Isonitroso-ketones . . . . . . . .PROPPER (M.). Action of Nitric Acid on Ethyl Acetoacetate and Chlor-acetoacetate . . . . . . . . . . . .KOLIIE (C.). Brom-addition-derivatives of the Crotonic Acids and of Meth-acrylic Acid . . . . . . . . . . . .NOACK (E.). New Method for Preparing Carbonic Oxide . . . .BALLO (M.). Carbonic Hydroxide . . . . . . . .OSTWALD (W.). Action of Acids on Acetaniide . . . . . .GUSTATSON (G.). Action of Aluminium Chloride and Bromide on Hydro-carbons . . . . . . . . . . . . .NOYES (W . A.). Oxidation of the Nitrotoluenes by Potassium Ferri-cpnide . . . . . . . .. . . . .ROBINET (C.) . Derivatives of Mesitylene . . . . . . .LOUISE (E.). Benzoylmesit ylene . . . . . . . . .WALLACH (0.). Metanitrils . . . . . . . . . .REINHARDT (H.) and W. STAEDEL . Methylation and Ethylation of Anilineand Toluidine . . . . . . . . . . . .STAEDEL (W.). Hydrobromides and Hydriodides of Aromatic Bases . .BERNTHSEN (A.). Nitrotoluidines from Liquid Dinitrotoluene . . .WELLER (A.). Ethylnitraniline . . . . . . . . .BAUR (H . v.) and VC'. STAEDEL . Dimethylxylidines, Dimethylmetachlor-aniline, and Dimethylnietamidopheneto'il . . . . . .BERNTHSEN (A.) . Preparation of the Base Cl9EIlBN from Benzoyldiphenyl-amine . . . . . . . . . . . . .JANNY (A.). Acetoximes . . . . . . . . . .GABRIEL (S.). So-called Nitrosomethglbenzene Compounds .. . .WELLER (A.). Phenacy etliylanilide . . . . . . . .LOSANITSCH (S . M.). Action of Iodine on Mono- and Di-nitrodiphenyl-thiocarbamide . . . . . . . . . . .GIRARD (C.) and A . PABST . Azo-derivatives . . . . . .WALLACH (0.) and E . SCFIULZE . Azo- and Diazo-derivatives of Phenylene-diamine . . . . . . . . . . . . .WALLACH (0.). New Azo- and Diazo-compounds . . . . .Nitroso-ketonesJANNY (A.). Acetoximes . . . . . . . . . .BORN (R.) and K . HEUMANR . Parazophmol . . . . . .KLEPL (A.). Compound of Phenol with Carbonic Anhydride . . .HOLZER (A.). Compound of Phenol with Sulphurous Anhydride . . .TIEMANN (F.) and R . LUDWIQ . Isomeric Nitroberizaldehydes . . .STAEDEL (W.) and others . New Ethereal-derivatives of Phenols .. .SCHULZE (E.). Appendix to the Paper on Cholesterin . . . .STAEDEL (W.) . Bromucetophenone and dcetophenone-deriratives . .FISCHER (E.) and I3 . KUZEL . Ethylic Orthonitrocinnamylacetoacetate .FISCBER (E.) and H . KTJZEL . Ethylic Orthonitrocinnamylacetoacetate (Pt . 11)HENTSCREL (W.). Conversion of Phenyl Ethers of Carbonic Acid intoSalicylic Acid . . . . . . . . . . . .JACOBSEN (0.) and H . MEYER . Sulphamic and Hydroxy-acids fromPseudocumene . . . . . . . . . . .SCHRAMM (C.). Acetoximic Acids . . . . . . . .BARTOLI (A.) and G . PAPASOGLI . Electrolysis of Hydrofluoric Acid and ofBARTOLI (A.) and G . PAPASOQLI . Electrolysis, with Carbon Electrodes, of .JACOBSEN (0.) and H . LEDDERBOGE . Amidometaxglenesulphonic Acid .Potassium Antimonate, with Carbon Electrodes .. . . .Solutions of Binary Compounds and of various Acids and Salts .PAGE5685695695705725725735735735745745755775775-7757757757857857957957958058058158158258258358358358458458558558658658658755858858959059059259CONTENTS . xxiiiEHRLICH (A.). Glycocines. Glycocine Ethers. and Oxet hylenecarbamidesof the Toluyl and Xjlgl Series . . . . . . . .BENZ (G.). Primary and Secondary Naphthylamines . . . . .FITTIQ (It.) and H . ERDMANN . Synthesis of a-NaphtholBOES~NECK (P.). a-Naphthoic Cyanide and its Derivatives . . . .ARKELL (K . E.). a-Chloronaphthylsulphonic Acid . . . . .ALEN (J . E.). Nitronaphthalenedisulphonic Arids . . .. .anthraquinone . . . . . . . . . . . .CAZENEUVE (P.). Physical Isomerism of Monochloro-camphor . . .RENARD (A.). Products of the Distillation of Colophony . . . .. . . .JAPP (F . R.). Addition oQ Acetone under the Influence of Caustic Alkalis .LIEBERNANN (C.). Action of Concentrated Sulphuric Acid on Dinitro-WURTZ (A.). Madder Colours . . . . . . . . .CIAMICIAN (a . L.) and M . DENNSTEDT . Action of Cyanogen Chloride onPotassium-pyrroline . . . . . . . . . .RHOUSSOPOULOS (0.). Action of Chloroform and Iodoform on Quinoline .BESTHORN (E.) and 0 . FISCHER . .SALOMON (G.). Paraxanthine, a New Constituent of Human Urine . .HESSE (0.). Cuprea Bark . . . . . . . . . .HESSE (0.). Hydroconquinine andconquinine . . . . . .DOEBNER (0.) and W .v . MILLER . Quinaldine . . . . . .Formation of Peptone and its Conversion into AlbumindidSubstances . . . . . . . . . . . .SCHORLEMMEB (C.) and T . E . THORPE . Normal Paraffins . . . .DURIN (E.). Hydrocarbons from Peat . . . . . . .HERZFELD (A.). Maltose and Isomeric Gluconic Acids . . . .MEYER (E . v.). Cyanmethine . . . . . . . . .TCRERNIAC (J.) and R . HELLON . Thiocyanacetone . . . . .JAHN (H.). New Method for Preparing Carbonic Oxide . . . .A New Class of Colourinp-matters .POEHL (A.).GAL (H.). Action of Zinc-ethyl on Amines and Phosphines . . .LANDOLF (F.). Decomposition of a-Fluoboracetone by Water . . .LEms (A . R.). Insoluble Residue from the Distillation of Castor-oil . .DCISBERO (C.). Addition of Bromine to Ethyl Acetoacetate .. .HJELT (E.). Allylsuccinic and Carbocaprolactonic Acids . . . .MEhNEL (E.). Meconic Acid and some of its Derivatives . . . .FREYDL (J.). Dry Distillation of Tartaric and Citric Acids with Excess ofLime . . . . . . . . . . . . .RESINSKI (F.). Biuret Dicyanamide . . . . . . . .SCHULZE (E.) and E . BOSSHARD . Glutamine . . . . . .of Organic Oxysulphides . . . . . . . . .DAPERT (F . W.). Amylbenzene . . . . . . . . .thy lamine . . . . . . . . . . . .SPRING (W.) and C . WINSSINQER . Action of Chlorine on Sulpho-derivativesLEEDS (A . K.) . CEnanthal.aniline, CEnanthal.xylidine, and Enanthal-naph-SILBERSTEIN (H.). Diazo-derivatives of Symmetrical Tribromaniline . .STAEDEL (W.). Substitution-products of Ethereal Derivatives of Phenols .STAEDEL (W.).Bromonitro- and Bromamido-aniso'ils and -phenetoils . .GOLDSCHMIEDT (G.) . Products of the Distillation of Calcium Parahydroxy-benzoate . . . . . . . . . . .G-OLDSCHMIEDT (G.) . Products of the Distillation of Salicylic Anhydrides .LEEDS (A . R.). Acrole'inure'ide and Condensed Urei'des . . . .ANDREASCH (R.). Oxidation of the Bases obtaiued by the Action of HalogenTREADWELL (F . P.) and V . MEYER . Molecular Weight of Isoindole . .WALDER (H.). a-p-Hydroxynaphthobenzoic Acid . . . . .LACHOWICZ (B.). Action of the Chlorides of Phosphorus on Phenanthra-STAEDEL (w.). Niti*OCreSOlS . . . . . . . . .KLEPL (A.). Hydroxybenzoic Acid . . . . . . . .Compounds on Tliiocarbamide . . . . . . . .quinone . . . . . . . . . . . . .CAZENEUVE (P.) .Cliloronitro-camphor . . . . . . .PAQR5935945955955955965!1659769369859969960060060160160260260365165365265365365465565565565665665665866865865966965966066ii66266266466c664t1646616656666%66x xiv CONTENTS.TRAUB (M. C). Action of Phthalic Anhydride on Quinoline . . .GRINAUX (E.) . Phenolquinoline , . . . . . . .LEEDS (A. R.). Cryptidilie . . . . . . . . .GRIESS (P.). Creatine-compounds of the Aromatic Group . . . .HANRTOT. Strychnine-derivatives . . . . . . . .LADENBURG (A.). Constitution of Atropine . . . . . .ZEISEL (S.). Colchicine and Colchice'ino . . . . . . .MALY (R.) and F. EMICH. Behariour o f the Bile Acids with Albumin andPeptones : Antiseptic Action of tho Bile Acids .. . . .KRETSCHY (M.). Oxidation of Kynurins and Kynurenic Acid . . .JOHNSON (G. S.). Action of Potash on Albumin . . , . .BACHMANN (A.). Aldehydetbyl Chloride and Behaviour of Acetals withAlcohols at a High Temperatlure . . . . . . . .ISAMBE~T. Vapour-tensions of Ethylarnine and Diethylamine Hydrosul-phides . . . . . . . . , . . . .NAGELI (E.). The Hydroxylaniine Reaction . . . . . .RADZISZEWSKI (B.). Synthesis of Oxctline Bases . . . , .CLERMONT (A.). Preparation of Ethers of Trichloracetic Acid . . .POETSCH (W.). Action of Carbonic Oxide on a Mixture of Sodium Acetateand Sodium Tsopent~late . . . . . . . . .FITTIG (R.) and F. ROEDER. A Non-saturated Acid Isomeric with ItaconicAcid . . .. . . . . . . . . .PAWLOW (W.). Tetric Acid . . . . . . . . .FITTIG (R ). Action of Water on Lactones . . . . . . .FITTIQ (R.). Conversion of Unsaturated Acids into the Isomeric Lactones .PINNER (A.). Conversion of Nitrils into h i d e s . Action of Hydrocpuic.NIETZKI (R.). Colouring Matters of the Safranine Series . . . .F ~ R E (A.). Mononitroresorcinol . . . . . . . .COLSON (A.) . An Aromatic Tribromhydrin . . . . . . .KALCKHOPF (F.) . Arnidophenols . . . . . . . . .NOACK (E.). Phenyl Salts of Phosphorous Acid . . . . . .LEWINSTEIN (I.). B-Naphtholtrisulphonic Acid . . . . . .ROEME R (H.) . Dinitroanthraquinone and Diorthamidoanthraquinone : aNew Method of preparing Anthrarufin . . . . . . .KELBE (W.) and J. LWOFF. Occurrence of Methyl Alcohol in the Productsof the Dry Distillation of Colophony .. . . . . .CONINCK (0. DE). Bases of the Pyridine and Quinoline Series . . .CONINCK (0. DE). Isomerism in the Pyridine Series . . . . .ARNOLD (C.). Poisonous Principles contained in certain Lupines . .KOHXLEIN (B.). Pr2paration of Paraffins . . . . . . .HENRY (L.). " Reaction Aptitudes " of the Halogens in Mixed Halo'id EthersBLOXAN (C. L.). Reconversion of Nitroglycerol into Glycerol . . .LAATSCH (H.) . Ethglidene Oxychloride . . . . . . .HOFMANN (A. W.). .PTSCHER (E.). Triacetonamine . . . . . . . . .GRODZKI (M.). Test for Acetal . . . . . . . . .>[EYER (V.) and A. MULLER. Constitution of Nitrosomalonic Acid . .OBT (H.). Derivatives of Meconic Acid containing Nitrogen, and their Con-version into Pyridine .. . . . . . . . .KELRE (W.). Oxidising Action of Dilute Nitric Acid on Metaisobutyl-toluene . . . . . . . . . . . . .GATTERMANN (L.). Symmetrical Tribromaniline . . , . . .Z~MMERMANN (J.) and M. KNYRIM. Action of Ethyl Chioracetate onPrimary Diamines . . . . . . . . . . .LELLMANN (E.). Cyanic Acid Derivatives of Three Isomeric Phenylene-Ziamines . . . . . . . . . . . . .REISENEGGER (H.). Compounds of the Hjdrazines with the Ketones. .RITTHAUSEN (H.). Legurnin . . . . . . . .Acid and Ethylene Cyanide on Hydrochloric Acid and Alcohol .Action of Bromiue on Amines in Alkaline SolutionsKOCHLIN. Gallo-cyanins . . . . . . . . .PAQE66766866966966967067 267367467467572672772872872972973073073073073 1731733734734735737737'738738740740'7877877887887897907 907907917967967 96c c49179879CONTEXTS .xxvBAHRMANN (R.), Amarine and Furfurine . . . . . . .BOTTCHER (W.). Anhydro-compnunds . . . . . . .and Benzenesulphonparatolnide . . . . . . . .STEUDEMANN (H.). Metanitrophenylthiocarbimide . . . . .PFAFF (F.). Reduction of Substituted Phenols . . . . . .HENRY (L.). Phenol-derivatives . . . . . . . . .BENEUIKT (R.). Nitro-derivatives of Resorcinol . . . . . .WITTENBERG (M.) and V . MEYER . Benzil . . . . . . .JOKJRDAN (E'.). Decomposition of Benzil by Potassium Cyanide . . .Action of Acetic Chloride on Benzaldehyde in presence of Zinc-dust . . . . . . . . .. . . .FISCHER (E.) and H . KOCH . Ethylic Phthalylacetoacetate . . . .KELBE (W.). Displacement of the Srilphonic Group by Chlorine . . .KELBE (W.). Barium Paratoluenesulphonate . . . . . .ethylene and Benzene . . . . . . . . . .MELDOLA (R.). Rosaniline Colouring-matters . . . . . .BOESSNECK (P.). Derivatives of a-Naphthoic Acid . . . . .PECHMANN (H . v.). Synthesis of Dihydronaphthoic Acid . . . .BARBIER (P.). Liquid Terebenthene Hydrochloride . . . . .NAKJDIN (L.). Essence of Aagelica Root . . . . . . .REKJTER (A) . Action of Zinc Chloride on Camphor . . . . .LA COSTE (W.). Nitroquinolines . . . . . . . . .FISCHER (E.) and H . KUZEL . Quinazole-compounds . . . . .HOFMANN (A . W.). Piperidine and Pyridine . . . . . .SCHOTTEN (C.). Oxidation o€ Piprridine .. . . . . .LELLMANN (E.). Nitro- and Amido-derivatives of BenzenesulplionanilideMBRZ (V.). Conversion of Phenols into Sitrils and Carbosylic Acids . .PAAL (C.).ANSCHUTZ (R.) . Action of Aluminium Bromide on Symmetrical Dibrom-ANSCIIUTZ (R.) and F . ELTZBACHER . New Synthesis of Anthracene . .MEYER (A.). Gentianose . . . . . . . . . .JACOBSEN (E.) and C . L . REIMER . Action of Phthalic Anhydride on Quino-line . . . . . . . . . . . . . .PLOSCZ (P.). New Crystalline Colouring Matter in Urine . . . .HOPPE-SEYLER (F.). Metahzmoglobin . . . . . . .KLINKENBERG (W.) and A . STUTZER . Nuclei'n . . . . . .LEGLER (E.). A New Product of the Slow Combustion of Ether . . .MAQ~ENNE (L.). Action of Carbonic Oxide on Steam . . .. .DOEBNER (A.) . Compounds of Benzotrichloride with Phenols and Phenyl-ainines . . . . . . . . . . . . .STAEDEL (W.). Action of Nitric Acid on Phenols . . . . .STAEDEL (W.). Nitrophenols and Nitrocresols . . . . . .STAEDEL (W.). Ethyl Amido-cresols . . . . . . . .JANO \-SKY (J . V.) . Nitro- and Amido-derivatives of Azobenzene . .LIPPMANN (E.) and F . FLEISSNER . dzylines . . . . . .GOLDSCHMIEDT (G.). Pyrenequinone . . . . . . . .LIEBEN (A.) and L . HAITINGER . Chelidonic Acid . . . . .Preparation of Methyl- and Ethyl-derivatives of Hydroxyquinolinetetra-FCHMIDT (E.). Action of Hydrochloric Acid on Xanthine . . . .SCHMIDT (E.) and H . PRESSLER . Theobromine . . . . . .SCHMIDT (E.). Occurrenceof Caffe'ine in Cacao . . . . . .SCHMIDT (E.).Action of Hydrocliloric Acid on Caffe'ine . . . .HAMMARSTEN (O.).- Metalbumin and Paralbumin . . . . .HELL (C.) and F . URECH . Carbon Thiobromides . . . . .HELL (C.) and F . URECH . Formation of a New Colouring Matter by theAction of Heat on Carbotrit. hiohexbromide . . . . . .BAMBEROER (E.). Dicyandiamide, I . . . . . . . . .LE BEL (J . A.). .LIEBERMANN (C.) aud C . PAAL . Allylamine-derivatives . . . .LADENBURG (A) . Imines . . . . . . . . . .hydride . . . . . . . . . . . . .Formation of Amy1 Alcohol in Alcoholic FermentationPAGE79980080080180280280280380380580580680680780780780780880980980981081081181281281381381481481486086086186186486686786886987087187187287387387490790790790890891xxvi CONTEN LS .WALLACH (0.).Oxaline and Glyoxalines . . . . . . .BISCHOFF (C . A.). Synthesis of Ketonic Acids (11) . . . . . .ANDREASCH (R.). Potassium Ethylene-disulphonate . . . . .HILL (H . B.). Substituted Pyromucic Acids . . . . . .LIPPMANN (E . 0.). . . .GAL (H.), Metallic Derivatives of Amides : Method of Distinguishingbetween Monamides and Diamides . . . . . . . .CERESOLE (M.). Violuric Acid . . . . . . . . .TRZCINSKI (W.). Action of Dibromobarbituric Acid on Thiocarbamide andThiocyanates . . . . . . . . . . . .CHANCEL (G.) . Alkyl-nitrous Acids . . . . . . . .PIERSON (A.) and K . HEUMANN . Action of Ethyldichloramine on AromaticAmines and on Hydrazobenzene . . . . . . ..KELBE (W.). Action of Acid Amines on Aromatic Amines . . . .GABRIEL (S.). Nitrobenzaldoxime . . . . . . . .BERNTHSEN (A.). Methylene-blue . . . . . . . .TPPKE ( P . G . W.). Nitro-derivatives of Reeorcinol . . . . .PFAFP (F.). A New Homologue of Resorcinol . . . . . .CLAUS (A.). Sulphonic Acids of Paracymene . . . . . .FRIEDLAEDER (P.) and J . MARLY . Isoindole . . . . . .BISCHOFF (C . A.). Action of the Alkgl-derivatives of the Halogen-substi-tuted Fatty Acids on Aniline . . . . . . . . .GABRIEL (S.). Aromatic Nitroso-compounds . . . . . .KLINGER (H.). Isobenzil . . . . . . . . . .CLATTS (A.) and H . LIPPE . Oxidation of Pentachlorontlphthalene . .HOLM (J.). Fluorene Derivatives . . . . . . . . .JACOBSEN (E.) and C . L . REIMER . Coal-tar Quinoline .. . . .WURTZ (A.). Quarternary Base derived from Hydroxyquinoline . . .FISCEER (0.) and C . RIENERSCHMID . .KOSSEL (A.). Xanthine and Hypoxanthine . . . . . . .HANRIOT and BLAREZ . Solubility of Strychnine in Acids . . . .BRIEGER (L.). Putrefaction Alkaloi’ds . . . . . . . .SALKOWSKI (E . and H.). Basic Products of Putrefaction . . . .BBCHAMP (A.). Zymase of Human Milk . . . . . . .POEHL (A.). Peptone . . . . . . . . . . .DE FORCRAND . Compounds of Hydrogen Sulphide withEthers . . .KACELER (J.) and F . V . SPITZER . Bromodinitromethme . . . .KILIANI (H.). Saccharone and Saccharin . . . . . . .LIEBEN (A.) and S . ZEISEL . condensation-products of Aldehydes andtheir Derivatives . . . . . . . . . . .NATTERER (K.) . ay.Dichlorocrotonaldehyde, a Condensation-product ofMonochloraldehyde . .. . . . . . . .ELSASSER (E.). Specific Volumes of the Alkyl Salts of Fatty Acids . .Occurrence of a New Acid in Beet-juicePp-idenemonosulphonic Acid .WISLICENUS (J.). Methyl 6-Butyl Ketone and its Derivatives . . .FRIEDRICH (R.). Monohalogen-derivatives of Crotonic Acids . . .MELIKOFF (P.). Derivatives of the Isomeric Crotonic Acids . . .BAUER (A.). New Acids of the Series C,H2,_40, . . . . .HJELT (E.). Dicarbocaprolaetouic Acid . . . . . . .BEILSTEIN (P.) and E . WIEGAND . Alkyldphamic Acids . . . .ENGELCKE (J.). Dialkyldisulphoisethionic Acids . . . . .NISHACK . Methylsulphonic Acid . . . . . . . . .EMICXI (F.). Biguanide . . . . . . . . . .REIBENSCHUH (A . F.). Methylgusnide and its Compounds .. .EMICH (F.), Ethylbiguanide and its Compounds . . . . .SPINDLER (P.). Nitration of Benzene-derivatives . . . . .SCRRAMM (J.). Action of Bromine on Sromatic Hydrocarbons . . .OEUTHER (A.). Constitution of the Compounds of the Sulphonates withAlkyl Sulphates . Constitution and Dimorphism of Sulphates . .WISPEK (Y.) and R . ZUBER . Action of Ally1 Chloride ou Benzene in thePresence of Aluminium Chloride . . . . . . . .PAG E910912912912933913913913914915915916916917918918918919919920921921923,92392392492492492592692696196196296396496696796896997097097197297297397397497497597797CONTENTS . sxriiDAFEBT ( F . W.). Researches on Periodides .. . . . .REKOUF (E.). Derivatives of Triphenjlmethane . . . . . .METER (R.) and H . KREIS . Hydroxyazo-compounds . . . . .CLAUEI (A.) andK . ELBS . Amarirte . . . . . . . .MARTINI (A.) and A . WEBER .MEYER ( R ) . Hydroxylation by Direct Oxidation . . . . .h ydrox ybenzene . . . . . . . . . . .HAITINGEB (L.). Action of Sulphur on Sodium Phenate . . . .Similarity of the Boiling Points of the CorrespondingKetones, Ethereal Salts, and ChloranhydridesSTAEDEL (W.). Aromatic Ketones . . . . . . . .ERLEXMETER (E.) and A . LIPP . Cinnamlc Acid DerivativesERLENMEYER (E.) and A . LIPP . Synthesis of TyrosineLIPP (A.). Phenylglyceric Acid . . . . . . . . .ETTI (C.).WEGSCHEIDER (R.). Derivatives of Opianic Acid . . . . .BAUER (A.). Pimelic Acid .. . . . . . . . .THOMPSON (C . M.). Metazophenyl-glpoxylic Acid . . . . .PIUTTI (A.). Phthalamidobenzoic Acid . . . . . . .PATERNO (C.). Cgmene-sulphonic Acids . . . . . . .STENGEL (F.). Dialkyldisulphobenzoates . . . . . . .ELBS (K.). Syntheses with Chloropicrin . . . . . . .PASTROVICH (P.). Reichenbach’s Picamar . . . . . . .Silicates of the Phenols . . . .PLOCHL (J.) and F . BLUMLEIN . Constitution of Benzoyl-carbinol . .BENEUIKT (R.). Chloroxy- and Bromoxt -derivatives of Benzene . .BARTR (L.) and J . SCHREDER . Hydroxyqulnol, the Third Isomerlc Tri-SCHRODER (H.). . . . . .. . .. . . .Tannins of Oak-bark . . . . . . . . .DUTT (U . K.). a-Naphthonitrilsulphonic Acid. . . . . . .GOLDSCHMIEDT (G.) and R .WEGSCHNEIDER . Pyrene-derivatives . .PASTROVICH (P ) . Ccerulignol : Reichenbach’s Oxidieing Principle . .KACHLER (J.) and F. V . SPITZER . Action of Sodium on Camphor . .KACHLER (J.) and F . V . SYITZER . Mode of Formation of the Isomericnibromocamphors . . . . . . . . . . .KACHLER (J.) and F . V . SPITZER . Reaction of the two Isomeric Dibromo-camphors with Nitric Acid . . . . . . . . .KACHLER (J.) and F . V. SPITZER . Hydroxycainphor from P-Dibromo-CLAUS (A.) and F . TOSSE . Addition-products of Quinoline . . . .UAUS (A.) and F . QLYCKHERR . Oxidation of Quinoline Benzyl Cblo-ride . . . . . . . . . . . . .SKRAUP (2 . A.) and A . COBENZL . . . .MALY (R.) and R . ANDREASCH . Caffeine and ‘Iheobromine . . . .WOOD (C . H.) and E . L .BARRET . Notes on Cinchona Alkaloyds . . .BRUCKER (E.). .MEYER (R.). Hydroxjlation by Direct Oxidation . . . . .BEILSTEIN (F.) and E . WIEQAND . Caucasian Ozokerite . . . .REFORMATSKY (S.) . Hydrocarbon, Cl0HlS, prepared from 6113.1 DipropylCarbinol . . . . . . . . . . . . .NIKOLSKY (W.) and A . SAYTZEFF . Hydrocarbon, C1ZH20, prepared fromAllyl Dimethyl Carbinol . . . . . . . . . .STEINER (A.). Conversion of Fulminates into Hydroxylamine . . .SCHULZE (J.). Preparation of Ammonium Thiocyanate . . . .FRENTZEL (J.). Normal Primary Hexyl Alcohol . . . . . .KRAFFT (F.) . Preparation of .Normal Primary Decyl, Dodecyl, Tetradecyl,Hexadecyl, and Octodecyl Alcoho!s . . . . . . .DIEFF (W.). Bye-product of the Preparation of Allyl Dimethyl Car-binol .. . . . . . . . . . . .LADENBURG (A.). Preparation of Chlorhydrins . . . . . .URECH (F.). Effect of Temperature and Concentration of Acid on the . . . . . . . .camphor . . . . . . . . . . . .n- and 8-NaplithaquinolineAlkophyr, and the True and So-called Biuret ReactionMEYER (V.) and E . NAGELI . Oxoctenol . . . . . . .Rate of Inversion of SaccharosePAGE9i898198298298398398398498798399099099 299499499499699899899999999910001001l(101100-k10051006100710081008100810091010101610181019107210’731073107410741074l G i 51075107610‘761077107xxviii CONTENTS .TAPPEINER (H.). Fermentation of Cellulose . . . . . .LIEBERMANN (C.) and C . SCHEIBLER . Reduction of Saccharin .. .MEYER (G.). Some Anomalous Reactions . . . . . . .COMBES (A.). Base derived from Crotonaldehyde . . . . .WILLGERODT (C.). Acetone-chloroform . . . . . . .YINNER (A.). Condensation of Acetone . . . . . . .SCHBAMM (J.). Action of Sodium on Methyl Ethyl Ketone . . . .SCHRAMM (J.). Diethyl Ketone . . . . . . . . .CLARK (W . I.). Ethyl Acetate . . . . . . . . .HANTZSCH (A.) . .CONRAD (M.) and M . GUTHZEIT . Halogen-substituted Ethyl Aceto-acetates . . . . . . . . . . . . .HANTZSCH (A.) . Condensation-products of Ethyl Acetoacetate . . .PERKIN, Junr . (W . H.). Action of Trimetliylene Bromide on Ethyl Aceto-acetate, Benzoylacetate and Ethyl Malonate . . . . . .HERRMANN (I?.). Constitution of Ethyl Succino-succinate .. . .FITTIG (R.). So-called Tetric, Pentic, and Hexic Acids . . . .DE FORCRAND . Formation of nisodium Glycollate . . . . .PHILIPP (J.). Basic Potassium Beryllium Oxalate . . . . .THOXPSON (C.). Lithium Citrate . . . . . . . .LIEBERMANN (C.) and A . HAGEN . Action of Sulphuric Acid on Di- andTri- Ally lamine . . . . . . . . . . .RADZISZEWSKI (B.). New Glyoxalines . . . . . . . .SCHULZE (J.). Preparation of Acetamide and other Amides of the AceticSeries . . . . . . . . . . . . .PINNER (A.). Derivatives of Ethyloximide and Ethyl-succinimide . .PINNER (A.). Conversion of Nitrils into ImidesMEYER (G.). Aldehydammonium Bases . . . . . . .BAMBERGER (E.) . Dicyanodiamide . . . . . . . .MEYER (V.). Coal-tar Toluene . . . . . . . . .ABELLI (M.).Chlorides of Ortho- and Meta-nitrobenzyl . . . .DAFERT (LV.). Derivatives of Diethyl-toluene . . . . . .ROBINET and COLSON . Mesitylene . . . . . . . .WISPEK (P.) . Derivatives of Mesitylene . . . . . . .LIEBERKANN (C.). Decomposition of Rosaniline by Water . . . .Action of Aldehyde Ammonia on Methyl AcetoacetateBANBERGER (E.). Melanuric Acid . . . . . . . .CURTIUS (‘J?.). Glycocine . . . . . . . . . .. . . . . .MEYER (V.). Thiophene, a Substance contained in Coal-tar Benzene . .(XALLE (K.). Tetrethylbenzene and Hexethylbenzene . . . . .CLAUS (A.) and I€ . BECKER . Trinitrotoluene and Liquid Dinitrotoluene .WALLACH (0.) and M . WUSTEN . Reaction of Aromatic Amines with LacticAcid . . . . . . . . . . . . .FISCFIER 0 . and L . GERMAN .The Violet-derivatires of Triphenylmethane .WICIIELHAUS (H.). Dye-stuff from Dimethylaniline and Cliloranil . .BERNTHSEN (A.). Formation of Nitril Bases from Organic Acids andAmines . . . . . . . . . . . . .PINNER (A.). Action of Acetic Anhydride on the Amidines . . .LIPPMANN (E.) and F . FLEISSNER . Azylines . . . . . .JAVOKSEY (J . V.). Amidazobenzeneparasulphonic Acid . . . .ORIESS (P.) . Diazo-derivatives . . . . . . . . .ERLENMEYER (E.).LACH (B.). Aldoximes . . . . . . . . . . .JANOVSKY (J . V.) . Substitution-products of Azobenzeneparasulphonic AcidConstitution of the Nitrosamines . . . . .Paranitrobenzaldoxiine and Amidobenz-aldehyde . . . . . . . . . . . . GABRIEL (S.) and M . HERZBERQ .GABRIEL (S.) . MetamidobenzaldoximeRICHTER (V.) v Cinnoline-derivativesEHRLICH (A.).OrthotoluyihydantoSn . . . . . . .MAINZER (K.). Products of the Decomposition of Mixed Aromatic Thio-carbarnides by Acids . . . . . . . . . .. . . . . . .. . . . . . . .PAGE1077107810781079107910791079108010801082108210831083108410851085108510861086108610861087108810881089109010901091109 11092109210031093109510951096109710971098109910991100110111011102110311041104110511051106110COXTEN TS . xxixPAGEASCHAN (0.). Action of Phenylthiocarbamide on Amido-acids . . . 1107HENTSCHEL (W.). Diphenylcarbamide and Triphenylguanidine . . . 1107HEIM (R.). Phenolic Phosphates . . . . . . . . 1108chlorites on Phenol .. . . . . . . . . 1108SCHALL (C.). Action of Iodine on Sodium Phenate . . . . . 1109~ C H A L L (C.). Diiodophenol . . . . . . . . . . 1109SCHOFF (F.). Reduction of Monobromorthonitrophenol . . . . 1109KALCGHOFF (F . A.). Amidophenols . . . . . . . . 1109HEIM (R.). Conversion of Phenols into Nitrils and Acids . . . . 1111RICHTER (A . K.). Thymol-derivatives . . . . . . . . 1112KOLBE (H.). Preparation of Phenetoil . . . . . . . 1113BOTTCHER (W.). Molecular Transformations . . . . . . 1113HAZURA (K.). Nitroresocinolsulphonic Acid . . . . . . 1114SEYDA (A.). Sulphonic Acids of Quinol . . . . . . . 1115LEVY (S.). Chlorine and Bromine-derivatives of Quinone . . . . 1117ZINCEE (T.). Action of Amines on Quinones . . . . . . 1117BENEDIKT (R.) and M .v . SCHMIDT . Halogen Derivatives . . . . 1118GOLDSCRMIDT (H.) and V . MEYER . Benzil . . . . . . 1120CHANDELON (T.). Chlorophenols obtained by the Action of Alkaline Hypo-HANTZSCH (A.). Reaction of Ethyl Acetoacetate with Orthamidophenol . 1111CLAUS (A.) and P . RIEYANN . Dichloroparacresol and Dichlororthocresol . 1111BAEYER (A.) and P . BECEER . Paranitrobenzaldehyde and Acetone . . 1120JACOBSEN (0.) and F . WIERSS . Derivatives of Orthotoluic Acid . . 1121GABRIEL (S.) and 0 . RORGMAKN . 1121SCHULZE (E.) and J . B ARBIERI .by the Action of Stannous Chloride on Albuminoids . . . . 1122SCHULZE (E.) and J . BARBIERI .valeric Acid from Lupine-shoots . . . . . . . . 1122FITTIQ (R.). Pcrkin’s Reaction . . . . . . . . . 1122GABRIEL (S.) and M .HERZBEBG . Derivatives of Cinnamic and Hydro-cinnamic Acids . . . . . . . . . . . 1123JACOBSEN (0.1. Hydroxytoluic and Hydroxyphthalic Acids . . . 1124LEWKOWITSCE (J.) Lsevorotatory Mandelic Acid . . . . . 1124LEWKOWITSCH (J.). Separation of Inactive Mandelic Acid into TwoOptically Active Isomerides . . . . . . . . . 1124BALBIANO (L.). Dry Distillation of Sodium Dibromanisate . . . . 1125NAPOLITANO (M.). Derivatives of Paracresolglycollic Acid . . . . 1126DRECHSEL (E.). Action of Phthalic Anhydride on Amido-acids . . . 1126CLAUS (A.) and G . HEMMANN . Azophthalic Acid . . . . . 1126GABRIEL (S.). Constitution of Phthalylacetic Acid . . . . . 1127BOTTINQER (C.). Anilpyrmvic Acid . . . . . . . . 1128HINSBERG [O.). Derivatives of Anhydroamidotolyloxamic Acid .. . 1129CLAUS (A.) . Cymenesulphonic Acids . . . . . . . . 1129MULLER (A.). Isonitroso-acids . . . . . . . . . 1129KOLBE iH.). Isatin . . . . . . . . . . . 1130BAEYER (A. ) :tnd W . COMSTOCK . Oxindole and Isatoxime . . . . 1130BAEYER (A.). Nitrosoxindole and Nitrosindoxyl . . . . . . 1131FISCHER (0 ) and L . GERMAN . New Synthesis of Skatole . . . . 1132ANSCHUTZ (R.) and F . ELTZBACHEB .phenylethane . . . . . . . . . . . . 1132FISCHER (E.) and H . KUZEL . Ethylhydrocarbazostyril . . . . 1132BERNTHSEN (A.) and F . BENDER . Sjnthesis of Acridines . . . . 1133FISCHER (0.). Acridine . . . . . . . . . . 1134BERNTHSEN (A.) and F . BENDER . Acridine . . . . . . 1134BOESSNECK (P.). Methylnaphthalene . . .. . . . . 1135ZINCKE (T.). Phenylhgdrazine-derivatives of the Quinones . . . . 1135LANDSHOFF (L.). ~-Napthylamineeulphonw Acid . . . . . 1135LIMPACH ( L ) . Naphtholtrisulphonic Acid . . . . . . . 1136KAUFFMANN (G.). P-Naphthacoumarin . . . . . . . 1136HENZOLD (0.). New Method of Forming Anthracene . . . . . 1137Benzyl Derivatives . . . . .Formation of Phenylamidopropionic AcidYhenylamido-propionic and Phenylamido-Synthesis of Unsymmetrical Tet.r aXYX COSTESTS .ROENEB (H.). Reciuction in the Anthracene Series . . . . .ROEMER (H.) and W . LINE . Ainidoniethylanthranol . . . . .ROEXER (H.) and W . LINE . Nitro., Amido., and Hydroxy-methylanthra-quinone . . . . . . . . . . . . .BOLLERT (L4.). Derivatives of Anthramine . . . . . . .MEISSEN (P.).Addition-products of some Terpmes . . . . .SCHIFF (H.) . Aldehydic Kature of Oxidation-products of Terebene . .NAYLOR (W . A . H.). Bitter Principle of Hymenodktyon excelsum . .GANTTER (I?.). Colouring-matter of' Wine . . . . . . .SCHMIEDEBERG (0.). Active Principle of the Root of Apocynum canna-binzirn . . . . . . . . . . . . .CIAMICIAN (G . L.) and M . DENNSTEDT . Action of Nascent Hydrogen . onPyrroline . . . . . . . . . . . .HOFFMANN (L.) and W . KONIQS . Tetrahydroquinoline . . . .FISCHER (0.) Derivatives of Hydroxyquinoline . . . . . .RIEMERSCHMIED (C.). ,t? .Hydroxyquinoline . . . . . . .FRIEDLANDER (P.) and C . F . GOHRING . Preparation of Substituted Quino-lines . . . . . . . . . . . . .DREWSEN (V . B.). a-Methvlquinoline .. . . . . . .DOEBKER (0.) and W . v . MILLER . Phenvlquinoline . . . . .SPALTEHOLZ (W.). Colouring-matters from Coal-tar Qninoline . . .LADENBURG (A.). Syntheses in the Pgridine Series . . . . .LADENBURG (A ) . Synthesis of Ethplpyridine . . . . . .RIEDEL (C.). Quinoline- and Pyridine-carboxylic Acids . . . .FISCHER (E.) . Triacetondkamine . . . . . . . .DUVILLIER (E.). Compounds of the Creatinine-group . . . . .LADENBURG (A.). Hgdrotropidiiie . . . . . . . .HAY (M.). New Alkaloyd in Cannabis indica or Indian HempLUXARDO (0.1. Existence of a Basic Substance in Maize . . . .GUARESCHI (J.) and A . Mosso .POEHL (h.). Putrefaction Alkalo'ids . . . . . . . .BRIEGER (L.). Putrefaction Alkalo'ids . . . . . . . .~ A L K O WSKI (E . and H.) .Putrefaction AlkaloYdsRHOUSSOPOULOS (A.). Methylenediquinoil Hydrochloride . . . .SCHIFF (R.) and J . PULITI . Introduction of Hydrocarbon Radicle3 into thePgridine-group . . . . . . . . . . .LADENBURG ( t i . ) , Action of Methyl Alcohol on Piperidine Hydrochloride .. . .Ptomaines . . . . . . .. . . . . .MCMUNN (C . A ) . Colouring-matter of Bile of Invertebrates and Verte-brates, and unusual Urine Pigments . . . . . . .Physiological Cl&e?nistry .KONIQ (J.). Nutritive Value of Skim Milk . . . . . . .RITTHAUSEN . Skim Milk as Food . . . . . . . .FINDEISEN . Feeding Horses with Flesh Meal . . . . . .KELLNER (0.). Researches on the Digestibility of Purified Lupine Seeds bythe Horse, and Observations on the Working Power of the Horse whenThe Gastric Juice .. . . . . . .Decomposition of Hydrogen Peroxide by certain OrganisedBodies . . . . . . . . . . . .Minrozymas, the Cause of the Decomposition of HydrogenAction of Hgclrogen Peroxide on the Red Colouring MatterFed with Lupines and Oats . . . . . . . . .C~IAPOTEAUT (J.).BBCHAMP (A.) .BBCHAMP ( i j .B~CHAMP (A.).Peroxide by Animal Tissues . . . . . . . . .of the Blood and on HematosinCROFT (Ii . IT.). Rattlesnake Poison . . . . . . . .RBCHAMP (A.) . Spontaneous Fermentation of Animal Matters . .. . . . . . . .MARCUS and 0 . DE CONINCE . Plipsiological Action of a-Collidine . .WEISEE (H.) and others . . Effect of Food on Sheep of Different BreedsPAGE1137113711381139114011411141114111411142114311461147114811491149115011501151115111511152115311531154115511551156115611571159115911591021021021021031031031031b410422623COSTESTS. sssiPAOY2272272272272272283613613624864874874884886U3606608609675675675677678'7407427437457458158158158 1581581581681 6817818818818818818818818819875875876PFEIFFER (T.).Artificial and Natural Digestion of pitrogenous Matter .POWER (.J. B.). Excretion of Nitrogen from the Skin . . . . .ERLENMEYER. Milking of Cows Twice or Thrice Daily . . . .MUSORAVE (R. N.). Nitrites in Human Saliva . . . . . .Lupine Sickness in Sheep . . . . . . BECHAMP (A.)..HARMUTII and others.SCHMIEDEBERG ((3.). Oxidations and Syntheses in the Animal Organism .SCHMIEDEBERG (0.). Decomposition and Synthesis in the Animal OrganismBROCKHAUS. Experimmts on the Poisonous Action of Potato Uraidy .BINZ (C.). Behariour of Ozonz with Blood . . . . . . .HOFFXANN (M.). Digestibility of C'asei'n from Warmed XilL . . .The Digestire Fluids aiitl Digcstion ofthe Horse . . . . . . . . . . . .CHATIN (I$.). Hygienic Action of Maize as Fodder . . . . .Alkalinity and Disstatic Action ofHuman Saliva . . . . . . . . . . .KUCKEIN (F.). Tisuue-waste in the Fowl during Starvation. . . .Decrease in Weight of Individual Organs in ChildrenDying from Atrophy . . . . . . . . . .HASEBROCK (K.). Coagulatiolz of the Blood . . . . ..Evolution of Oxygen from Hydrogen Peroxide by PibrinELLENBERGER and HOFXEISTEI~.CHITTENDEN (R. H.) and J. S. ELY.OHLMULLER (W.).WEISKE (H.). Occurrence of Crystals of Ammonium Magnesium Phosphatein Urine. . . . . . . . . . . . .REISET (J.). Exhalation of Nitrogen Gas during the Respiration ofA niin als . . . . . . . . . . . . .PAUL (G. A.) Feeding Calves with Skim-milk . . . . . .HOFXEISTER (F.). Distribution of Peptone in the Animal Body. . .HOFYEISTER (F.). The Proportion of Peptone in the Gastric MucousMembrane . . . . . . . . . . . .HUFNER (G.). On the Oxygen Pressure a t which, a t a Temperature of 3 5 O ,the Oxgh~moglobin of the 1)og begins to give up its Oxygen . .LEBEDEFF (A.). Nutrition by P a t . . . . . . . .REISET (J.). Blue Milk .. . . . . . . . .Micro-organisms . . . . . . . . . . .FORT (J. A.). Physiological Action of Coffee . . . . . .BLAKE (J.). Relative Toxic Power of Metallic Salts . . . . .KIETZ (A.). Researches on Digestiou in the Stoinacli . . . . .WASSILIEFF (N. P.). Influence of Calomel on Fermentation and the Life ofEYINQXR (L.). .KONIGSBERG (P.). Digestibility of Meat . . . . . . .HOFFMANN (M.). Digestibility of Casei'n from Heated Milk . . .LANGLEY (J. N.). Decomposition of Digestive Ferments . . . .LANGSDORFF (K. v.). Fattening of Calves . . . . . . .XUHN (G.) and others. Digestibility of Meadow Hay and VC'lieat Brantreated with Hot and Cold Water . . . . . . . .ELLENBERGER Results of the Suppression of Perspiration of Animals. .SEEGEN (J.). .. . .STUMPF. Alteration in the Secretion of Milk under the Influence ofZWEIFEL. Behaviour of Blood when T)eprived of Oxygen . . . .ROHRMANN (F.). Observations on a Dog with Biliary Fistula . . .BLENDERUAXX (C.). Formation and Decomposition of Tyrosine. . .Reurtion of the Living Mucus Lining of the Stomach.Feeding of Cattle with Dry Fodder . . . . . . .Peptone the Source of Sugar in the LiverDrugs . . . . . . . . . . . . .ERMAN. Adipocere . . . . . . . . . . .ANACKER. Poisoning of Cattle by Earth-nut Cake . . . . .WALLACE (W.). Insensibility arising from a Deficiency of Oxygen in theAir . . . . . . . . . . . . .BRUNTOX (T. L.) and T. CASH. Action of Calcium, Barium, and PotassiumSalts on Muscle . . . . . . . . . . .ABELES (MJ.Secretion cf the Kidney fed with Defibrinated Blood . .GARROD (A. B.). Formation of Uric Acid in the Animal Economy . xxxii COXTENTS .BLENDERMANN (H.). Forniation and Decomposition of Tyrosine in theBotly . . . . . . . . . . . . .HORBACZEWSKI (J.). Behaviour of Elastin in Peptic Digestion . . .CRAMER (T.). Vegetarianism from a Phjsiological Standpoint . . .TAPPEINEE (H.). Comparative Investigations of Intestinal Gases . . .POUCHET (A . G . ) . Sugar from the Lungs of Phthisical Patients . . .LAWES (J . B.) and J . H . GILBERT . Composition of the Ash of the EntireAnimals. and of Certain Separate Parts of some of the Animals, used asHuman Food . . . . . . . . . . . .BISCHOFF (C.). Distribution of Poisons in the Human Organism in CasesBELL (J.).Chemistry of Food . . . . . . . . .PAVY (F . W.). Physiology of Carbohydrates in the Animal System . .RCJNEBERG (J . W.). Filtration of Albumin Solutions through AnimalMembranes . . . . . . . . . . . .TER.GRIQORIANTZ . Hemialbumosuria . . . . . . . .LEHMANN (V.). Further Contributions to t. he Distribution and Eliminationof Lead . . . . . . . . . . . . .of Poisoning . . . . . . . . . . . .JAKSCH (R . v.). Acetonuria . . . . . . . . .Chemistry of Vegetable Physiology and Agriculture .HAYDUCK (M.). Influence of Alcohol on the Development of Yeast . .ENGELMANN (T . W.). Elimination of Oxygen froni Plant-cells . . .WILSON (W . P.) . Elimination of Carbonic Anhydride by Plants in AbsenceDETMER (W.). Action of various Gases, especially Nitrous Oxide, on Plant-Cells .. . . . . . . . . . . .DPEBRATN (P . P.). Influence of the Electric Light on the Development ofPlants . . . . . . . . . . . . .BATJER (E.). Nature and Formation of Dextran . . . . . .of Oxygen . . . . . . . . . . . .NACHBAUR (K.). Embryos of Ungerminated Rye . . . . .CRIPER (W . R.). Analyses of Indian WoodKNOP (W.). Percentage of Ash in the Sugar-cane . . . . .THUMEN (F . v.) and others . Vine Diseases. and Remedies . . . .KUHN (J.) and H . JOULIE . Diseases of Sugar-beetPETERMANN (A.). Composition of Fodders . . . . . . .Composition of Malt from 1877 Barley . . . . . . . .RENOUARD (A.). Cotton Cake . . . . . . . . .EONIG (J.). Cultivation of Lupines . . . . . . . .LEYDHECKER (A.) and others . Potato Culture .. . . . .RIMPAU (W.) and others . Sugar-beet CultureLADUREAU (A.). Cultivation of the Sugar-beet . . . . . .WARINGTON (R.) . Nitrification in Soils . . . . . . .MARI&.~AVY . Nitrification in the SoilSALFELD (A.) . Comparative Manuring Experiments . . . . .WAGNER (P.).F;DT,ER . Manuring Potatoes with Potassium Nitrate . . . . .LECOUTEUX (E.). Composition of Pig Dung . . . . . .Analysis of Mud from the Mouth of the EiderGUILLAUME (L.), Mineral Phosphates on Arable Soil . . . . .. . . . . .DIXON (W . A.). Inorganic Constituents of some Epiphytic Ferns . .DANGER (L.) and others . Parasitic Diseases of Plants. and their Prevention. . . . .. . . . . . DEECHSLEE . Specific Gravity of Cereal Grains. . . . . .. . . . . ..Influence of the State of Division of Manures on theirAction . . . . . . . . . . . . .. . . . . .. . . . . . . . KERN (E.).]ETARD (A.) and L . OLIVIER .D~HBRAIN and MAQUENNE . Reduction of Nitrates in the SoilA New Milk FermentReduction of Snlphates by Living Orga-nisms . . . . . . . . . . . . .. . .PAQX87692792892892910191020116011601160116111621163104105105105105105107107108110110110111111111111111114114114Ilk11511611611711711711722922DBH~RAIN and MAQUENNE . Reduction of Nitrates in Arable Soil . .GAYON and DUPETIT . Fermentation of Nitrates . . . . . .RICCIARDI (L.). Composition of the Banana at Different Stages ofPHILLIPS (F . C.). Absorption of Metallic Oxides by Plants .. . .Maturity . . . . . . . . . . . .SIEWERT (M.). Oxalic Acid in Potatoes and in Malt . . . . .merce compared with that in the Seeds . . . . . . .KUTZLEB (V.). Researches on the Causes of Clover Sickness . . .LAPITTE (P . DE) and others . On Phylloxera . . . . . .JENSEN (J . L.). Cure for Potato Disease . . . . . . .RINICKER and DOSSEXEL . Hailstorms and their Origin . . . .KINCH (E.). Soja-bean . . . . . . . . . .LEPLAY (H ) . White Sugar-beet of Silesia . . . . . . .FEEMSTER (J . H.). Averagc Amount of Caffeine in the Guarena of Com-JIUNTZ (A.) and E . AUBIN . Atmospheric Nitrification . . . . .PITTBOGEN (J.) and others . Cultivation of Various Crops . . . .TOBISCR .STUMPF . Amount of Gluten in Wheat .. . . . . . .BOHMER (C.) . Albumino'id and Non-dbumino'id Nitrogen-compounds ofHENSEN (N.). Fertility of L Soil as Dependent on the Action of Worms .WOLLNY (E.). Effect on the Fertiiity of the Soil Produced by Covering itBESELER . Manuring Sugar-beet with Dung . . . . . . .MARCKER (M.). Manuring Alpine Meadows . . . . . .DELACHARLONNP (P . M.). Transformation of Blood into a Solid InodorouiManure . . . . . . . . . . . . .MARPMANN (G.). Schizomycetic Fermentation . . . . . .MARPMANN ((3.). Progress in the Knowledge of Bacteria . . .MARCANO (V.). Direct Fermentation of Starch . . . . . .MORI (A.). The First Product of Plant-Assimilation . . . . .VRIES (H . DE) . . . . . . .LEPLAY (H.). Chemistry of the Maize Plant . . . . . .LEPLAY (H.).Chemistry of White Silesian Beetroot . . . . .GRUNING (W.). Chemistry of the Nympheaeese . . . . .ROMANIS (R.). Analysis of Tobacco Ash . . . . . . .DUQAST (M.). Composition of Different Varieties of Fodder-cabbage . .D ~ H ~ R A I N (P . P.). Loss and Gain of Nitrogen in Arable Land under theInfluence of different Systenis of Cultivation . . . . . .GRIFFITHB (A . 3.). Analysis of a new Guano from Australia . . .Utilisation in Agricultuye of the Slag from the Basic DephosphorisingProcess . . . . . . . . . . . . .KRETZSCHMAR (L.). The Test for Life . . . . . . .HOPPE-SEYLER (I?.). Influence of Oxygen on Permentation . . ~DETMER (W.). Contributions to the Dissociation Hypothesis .WILL (H.).IAIEBENBERGT (A . v.). .HORNBERGER (R.) and E .v . RAUNEE . Researches on the Growth of theMaize Plant . . . . . . . . . . . .DSHPRAIN (P . P.) and MEYER . . . . .RBYNOLDG (J . E.). Comparative Effect of Two Metameric Bodies on theGrowth of Nicotiana lortgijlora . . . . . . . .GRIPPITHS (A . B.). Growth of Plants under Special Conditions . . .FABSKY . Chlorine as a Plant-food . . . . . . . .i%lULLER (H.) . Contributions to the Knowledge of the Interchange of. . . . . . .GODLEWSKI (33.1. Respiration of Plants . . . . . . .JANDOUS (A.). Composition of Ivy Berries . . . . . . .XANQON (H.). The Ice Plant (~eseiiabl.iant6einunl crystallinuin) . IInfluence Exerted by the Weight of Potato " Sets" . . .certain Vegetables . . . . . . . . . . .with Farmyard Manure . . . . . . . . . .LENN$ (A.).Employment of Peat as Litter . . . .Function of Resins in PlantsEffect of Steeping and Drying on the Germination of SeedsPart played by Lime in the Germination of SeedsDevelopment of WheatMaterial in Amylaceous Plant OrgansPAGB2292302312312322322332332332332342352352352362362362372372382382382393633 643653653653663683693723735733753754894894894904904914934954 964974974913499490CONTENTS . xxxiiiVOL . XLIV . xxxiv CONTENTS .BILLWILLEE (R.). Influence of Fallen Snow on the Temperature of theAir . . . . . . . . . . . . . .WOLLNY (E.). Influence of the State of Aggregation on the Temperature ofand Moisture in a Soil . . . . . . . . . .TEUCHERT .Irrigation of Meadows by Waste Water from Beet-sugarFactories . . . . . . . . . . . .PETERMANN (A.). Manurial Value of “ Dissolved Wool ” . . . .GUILLAUNE (L.) . Chemical Manures and Farmyard Manure . . .DBHBRAIN (P . P.) and MAQUENNE . .PETERMANN (A.). Analysis of Materials used in the Preparation of Com-posts . . . . . . . . . . . . .RIFFARD ((3.)- Artificial Manuring of Sugar-canes . . . . .MAYER (A.) and F . CLAUSNITZER . . . . .GAYON (U.) and G . DUPETIT . Reduction of Nitrates and Nitrites . .DBEBRAIN (P . P.) and L . MAQUENNE . Butyric Terments in Arable Soils .PLAUCTIUD . Reduction of Sulphates by “ Sulfuraires, ” and Formation ofNatural Mineral Sulphides . . . . . . . . .WEYE (T.). Influence of Chemical Agents on the Assimilative Capacity ofGreen Plants .. . . . . . . . . . .ENGELMANN (T . W.). Assimilation by Hzcmatococcus . . . .BORGMANN (E.), Presence of Formic and Acetic Acid in Plants . . .LIPPMANN (E . 0 . v.). Occurrence of Coniferin in the Woody Structure ofthe Beetroot . . . . . . . . . . . .DUPETIT ((3.). Poisonous Principle of Edible Mushrooms . . . .NIESSING (C.) and others . Diseases of Plants and their Prevention . .KRAUCH (C.). Poisoning of Plants . . . . . . . .STREBEL and others . Cultivation of Cereals . . . . . .DOHN (W.) and F . NOBBE . Cultivation and Feeding Value oi’ some Varietiesof Vetches . . . . . . . . . . . .WEISKE (H.) and others . Comparative Feeding Value of Symphytumasperrimurn . . . . . . . . . . . .BEIBEL (P.) and others .. . . .CORENWINDER (B.). Biological Researches on the Beetroot . . . .KOHNE and others . Employment of Dried Potatoes . . . . .FINKHAUSER . Comparative Meteorological Observations in Forests . .WOLLNY (E.). Influence of Climate and Weather on the Amount of Car-STELLWAAG (A.). Rise of Temperature induced in Soila by the CondensationSTUTZER (A.) and W . KLINGENBERGF . Decomposition of NitrogenousAnimal Manures . . . . . . . . . . .Reduction of Nitrates in the Soil .Analysis of Gas-limeGRBGOIRE (T.). Cultivation of Bombo . . . . . . .Removal of the Leaves of Rootsbonic Anhydride in Air . . . . . . . . . .of Liquid and Gaseous Water and of Gases . . . . . .MASURE (F.). Evaporation of Water from the Soil . . . . .REINDBRS ((3.).Manuring Experiments in Holland . . . . .MUEL (M . E.). Manuring of Forest Trees . . . . . . .CAYON and others . A Denitrifying Ferment in Soils . . . . .~ T A R D (A.) and others . Reduction of Sulphates by AlgseHECKEL (E.). The Ice-plant (Mesembrialzthernzcrn crystallilzurn) . . .CARRIERES (E . A.) and others . Pbylloxera and Means for its Destruction .SCHULZE (F.) and others . Cultivation of Potatoes . . . . .MORGEN (A.) . .HEINRICH (R.). Influence of the Percentage of Moisture in Peaty Soils onVegetation . . . . . . . . . . . .DUMAS (L.) . Retentive Capacity for Plant-food posseased by Soils . .MARCPER (M.) . Manuring with Splphuric Acid . . . . . .JORDAN (W . H.). Action of Manures on the Quantity and Quality of aWheat Crop . . . .. . . . . . . .KONIG (A.) and others . Researches on the Behaviour of Insoluble Phos-phateo in Peaty Soils and in Dilute Solvents . . . . . .COCHIN (D.). Action of Air on Yeast . . . . . . . .. . . .Feeding Value of Fresh and Dried Diffusion-residue .PAGE50050050050050150350450650660961061061161161161161161261261261261361361361361461461461561561561761’767968068068068068068168168168168174CONTENTS. xxxvPAGELEPLAY (H.). Chemistry of the Maize-plant . . . . . .BARTHBLEMY (A.). Respiration of Aquatic and Submerged Aero-aquaticPlants . . . . . . . . . . . . .ELINKENBERG (W.). Proportion of Nitrogen in the Form of Amides, Albu-min, and Nucle'in in different Feeding-stuffs .. . . . .DBHBRAIN (P. P.). Loss and Gain of Nitrogen in Arable Land . . .LOEW (0.). Chemical Character of Living Protoplasm . . . .REINKE (J.) . Autoxidation of Plant-cells . . . . . . .ENGELMANN (T. W.). Colour and Assimilation . . . . . .BOHM (J.). Formation of Starch from Sugar . . . . . .WALTHER (F.). .WOLDE (W.). Rice and Earth-nut Meal as Food for Milch Cows . .ULLIK (F.). .HOPEE-SEYLER (F.). Fermentation of Cellulose . . . . . .WAGNER (F.). Intluence of Organic Manures on the Temperature of theS o i l . . . . . . . . . . . . .FLEISCHER (M.) and R. KISSLINQ. Application of Insoluble Phosphates toSoils . . . . . . . . . . . .WARDEN (C. J. H.). Ash of Pistia Stratiotes or " P6n6 S i t " .TSCHUSCHKE (A.). Manuring of Sugar-beet .. . . . . .REINEE (J.). Easily Oxidisable Constituents of Plants . . . .AMTHON (C.). Studies on Ripe Grapes . . . . . . .VIBRANS. Influence of Manuring on the Composition of Potatoea . .WORTMANN (J.). Diastatic Ferment of Bacteria . . . . . .BOUSSINGAULT. Cultivation of the Cacao Tree . . . .MEISSL (E.) and F, BOCHER.HECKEL and SCHLAQDENHAUFFEN. Chemistry of Globularia . . .KUHN (J.). Phoma Qentiana : a newly-observed Parasitic Fungus . .KERN. Artificial Digestion of Meadow-hay . . . . . . .MARCKER (M.). Decomposition of Diffusion-residues from Beetroot . .KOETH (D. v.), Culture of Various Descriptions of Sugar-beet . . .SUTTON (F,). Hay and Ensilage from a Poor Quality of Grass . . .ERAUCH ((3.). Effect of Water containing Zinc Sulphate and Common Salton Soils and Plants .. . . . . . . . . .GASPARIN (P. DE). Submersion of Vineyards . . . . . .HOWARD (J. E.). '?f€e,t of 'Altiiude on the Alkaloids of the Bark oi Ci.n:chona succirubra . . . . . . . . . . .PAUL (B. H.). Cinchona Bark gi'own in Jamaica . . . . .MCCALLUM (H.). Seeds of Camellia oleifera . . . . . .STUTZEH. (A.). Occurrence of Nuclejin in Moulds and in Yeast . . .Experiments on the Value of Vdrious Fodders for CowsNitrogenous Constituents of Malt, Wort, Beer, and Bread. .Constituents of the Beans of Soja hispidaATTFIELD (J.). . . . . . .Analytical Chemistry.CROVA (A.). A New Condensation Hygrometer . . . . . .VORTMANN (U.). Direct Estimation of Chlorine in Presence of Bromineand Iodine .. . . . . . . . . . .MUNTZ (A.) and E. AUBIN. Estimation of Carbonic Anhydride in theAtmosphere . . . . . . . . . . .PFORDTEN (0. v. D.). Estimation of Phosphoric Acid. . . . .CRAIG (G. E.). Estimation of Sulphur in Iron and Steel . . . .LEDEBUR (A.). Estimation of Oxygen and Carbon in Iron . . . .MILLOT (A.). Electrolytic Estimation of Zinc . . . . . .PFORDTEN (0. v. D.). Reduction of Molybdenum Compounds .KRAUCH (C.).DAVID (J.). Estimation of Glycerol in Fatty Matters . . . . .WILEY (H. W.). Estimation of Dextrose, Maltose, and Dextrin, in Starch-sugar . , . . . . . . . . . . .MARECK (G.]. Diffusion of Sugar in Beet . . . . . . .Otto's Method for the Estimation of Fuse1 Oil in Brandy7477477487498198198198208208208218218218228228238808818829309331024102510251025102510261026102711641164111651165116611661181191211211211 2 112212212312312312xxxvi CONTEXTS.SALOMON (F.).Estimation of R8ice Starch . . , , . . .CHANDELON (T.). Volumetrical Estimation of Phenol , .TOLLENS (B.). Ammoniacal Silver Solution as a Test for FormaldehydeSCEEPPER (H. Y. DE) and A. GEIBEL. Examination of F a t , , . .HAITINGER (L.). Occurrence of Organic Bases in Commercial Amy1Alcohol . . . . . . . . . . . . .LAAR (C.). .MIXTER (W. G.). Sauer's Method of Estimating Sulphur . . . .PICKERING (S.). Testing for Barium or Sulphuric Acid . . . .SCHULZE (B.). Estimation of Sulphuric Acid in Presence of AlkalineChlorides .. . . . . . . . . . .GLADDING (T. S.). Estimation of Phosphoric Acid as Magnesium Ppro-phosphate , . . . . . . . . . . .MAPER (L.) and E. V. SCHMID. Estimation of Phosphoric Acid . . .GUYOT-DANNECY. Analysis of Potassium Thiocarbonate . . . .BRITTON (B.). Normal Solutions for the Volumetric Estimation of Iron .FOHR (K. F.). Sources of Error in Estimating Iron in Ores by the StannousChloride Method . . . . . . . . . . .DIEHL (W.). Volumetric Estimation of Peroxides . . , . .LEDEBUHR (A). .JUPTNER (H. V.). Haswell's Method for the Volumetric Eatinistion ofMercury . . . . . . . . . . . , .PATROUILLARD (C.). Use of Oxalic Acid as a Test fbr Arsenites in Alka-line Salts . . . . . . . . . . . .LUSTGARTEN (S,). Detection of lodoform, Naphthol, and Chloroform .ALLIHN (F.).Reducing Power of Grape-sugar for Alkaline Copper Soh-tions . . . . . . . . . . . .MACH (E.) and C. PORTELE. Amount of Ex'tract in Tyrolese Wines . .REMONT (A.). Rapid Method of Estimating Salicylic Acid in Wines . .DIRCES (V.). Occurrence of Myronic Acid, and Estimation of Xustard Oilin the Seeds of Cruciferac andin Oil-cakes . . . . . .EMMERICH (R.). Estimation of Milk F a t . . . . . . ,BASTELAER (A. v.). Analysis of Butter . . . . . . .MUNIER (J.). Butter Testing . . . . . . . . .GABEL (U.). Margarimeter of Lcune and Harbulet . . . . .GARNIER (L.). Albumin from Urine coagulated by Nitric Acid and solublein Alcohol . . . . . . . . . . . .LOGES (G.). Estimation of Humus in Soils, . . . . . .TSCHIRCH (A.).Microchemical Reaction Methods . . . . .HARCOURT (A. Y,). An Instrument for Correcting Gaseous Volume . .GEPPERT (J.). Improvements in Gas Analysis Apparatus . . . .ARNOLD (C.). Estimation of Organic Nitrogen . . . . . .MULDER (E.) and H. J. HAMBURGER. Estimation of the Halogens in CarbonCompounds . . . . . . . . . . . .KXOP (W.). Analysis of Silicates. . . . . . . . .BROOCEMANN (K.). Estimation of Phosphoric Acid and of Manganese .KRATSCHMER and SZTANKOVANSZKY. Volumetric Estimation of PhosphoricAcid . . . . . . . . . . . . .TOBIAS (G.). .Testing Silver Nitrate . . . . . . . . . . .WIEGAND (E.). Estimation of Titanic Acid in Presence of Iron . . .WELLER (A.). Detection and Estimation of Titanium. . . . .HAGER (H.). Detection of Arsenic Microscopically .. . . .LENZ (W.). Examination of Bismuth Subnitrate. . . . . .TICITBORNE (C. R.). New Form of Apparatus for Estimating Ammonia inPotable Waters . . . . . . . . . . .KNUBLAUCH (0.). Determination of Sulphur in Coal-gas . . . .DROWN (T. M.). Suhhur in Coal . . . . . . . .Use of Diphenylamine and Aniline in Qua!itative AnalysisA Colour Method for the Estimation of Manganese .SOLTHIEN. Separation of Silver from Allojs . . . . .Behariour of Alkaline Phosphates to T-arious Indicators .PAGE12412412512512723923924024024024124124124 2242242242243243243244245245245246246247247247247376378378378370379380380380381381381381382382382383STODDBI~D (J.+.). Ffashing Point of Petroleum . . . . . . 38CONTENTS. xxxviiLIEBERMANN (L.). Detection of Sulphurous Acid in Wine . . . .SCHMITT (C.) and C. HIBPE. Estimation of Fixed Organic Acids in Wine .WOLFF (C. IT.). Detection of Rosaniline Hydrochloride in Wine b r Meansof Stearin . . . . . . . . . . . .AMTHOR ((3.). Glycerol in Beer . . . . . . . . .BACRMEYER (W.). Test for Organic Acids in Phenol . . . . .URBCH (F.). Rapidity of Separation of Cuprous Oxide by the Action ofInvert-sugar on Fehling’s Solution . . . . . . . .MEISSL (E.). Detection of Benzoic and Boric Acids in Milk . . .BACHMEYER (W.). Test for Sodium Carbonate in Milk . . . .GELIS (A. and T.). Sulpliocarbometer. . . . . . . .ARBOLD (B.). New Colour Reactioiis of the Alkalo‘ids .. . . .MEYER (H.) . Quactitative Estimation of Cinchona Alkalo‘ids . . .GAWALOVSKI (A.). Estimation of Tannin . . . . . . .SIMAND (F.). Estimation of Tannin . . . . . . . .WITTMACK. Detection of Adulterations of Flour with Rye-meal . . .GRATZEL (A.). Creasote from Beechwood Tar . . . . . .RERTHELOT. Properties of Chlorinated Organic Gases and Vspours . .BEANLEY (E.). .CASAMA JOR (P.) . Asbestos Pi1 ters . . . . . . . .MACALUSO (D.) and G. GRIMALDI. Influence of Hygroscopic Condensationin Glass Vessels on the Determination of the Density of AqueousVapour . . . . . . . . . . . . .HARVEY (J. W. C.). A Modified Process for the Estimation of Chlorine inBleaching Powder . . . . . . . . . . .TOPSOE (H.). Estirnatioii of Chlorides, Bromides, and Iodides, in Presenceof Sulphuretted Hydrogen .. . . . . . . .SOND$N (K.). Modifbation of Scheibler’s Azotorneter . . . . .BOEHMER (C.). Estimation of Nitric Oxide and Nitric Acid . . .OLLECH (H. v.). Estimation of ‘‘ Half Soluble ” Phosphoric Acid . .SIDERSEY (D.). Separation of Strontium and Calcium . . . .RANSOM (F.). Detection of Strontium. . . . . . . .Weil’s Method for the Determination of Copper, Iron, and Antimony . .WERNER (H.). The Thiocyanate Reaction for Iron . . . . .TAMM (A.). Analpis of Iron . . . . . . . . .AUSTIN (P. T.) and G. B. IIURFF. Reduction of Ferric Salts . . .CRAIG (G.). Estimation of Sulphur in Iron and Steel. . . . .ROCHOLL (H.), Estiniation of Sulphur in Pig-iron . . . . .HARVEY (J. W.C.). Volumetric Estimation of Manganese Dioxide . .HALBERSTADT (1V.j. Sepsration of Vanadic Acid from Metals . . .NAYLOR (W. A. H.) and J. 0. BRAITHWAITE. Test, for Arsenic . . .HITCHCOCK (R.). .MARSH (C. W.). Ammonia Process for Water Analysis . . . .DAVY (E. W.). Determination of Nitrites . . . . . . .STAPLETON (a.). Yrepuration of Alkaline Potassium Permsnganate Solutionfor Water Analysis. . . . . . . . . . .TICHBORNE (C. R. U.). Preparation of a Volumetric Solution for Determin-ing the Hardness of Water . . . . . . . . .VOGEL (A.). Estimation of the Fertility of a Soil . . . . .STODDARD (J. T.). Determination of the Flashing-point of Petroleum .GALLOWAY (R.). Estimation of Coke and Volatile Products in Coal . .XESSLER (J.) and M. BARTH.EYtimation of Alcoliolic Liquors . . .BORGNANN (E.). .FRESENIUS (R.) and E. BORQMAXN. Analyses of Pure Wines . . .DEGENER (P.) and F. ALLIHN. Estimation of Sugar by Alkaline CopperSolutions . . . . . . . . . . . .ARBOS (J.). Pyrole’in . . . . . . . . . . .YPEIFFEB (E.). Milk Analysis . . . . . . . . .SCHXITT (E.). Adulteration of Butter . . . . . . .RBMOST (A.). Es‘iniation of Salicylic Acid in Milk and Butter . . .Estimation of Haemoglobin in Blood by Optical MeansExamination of Water and Air for Sanitary PurposesRelation between the Glycerol and Alcohol in Winec 2PAGE384384384385385385355385386386388391391392393394.39450650750750550850850850350!450351051051251251251 36135135145 1451551651651751751751851851851951952158152xxxviii CONTENTS.COPPOLA (F.).Genesis of Ptomai‘nes . . . . . . .JOFFRE (J.). .MEYER (V.). Vapour-density Determination . . . . .OSTWALD (W.). Manufacture and Correction of Burettes . . .LOEWE (J.). Storage of Oxygen i n Zinc Gasholders . . . .UASPARIN (P. DE). .Estimation of Phosphoric Acid in Manures . . . . . ,WARTHA (V.). Estimation of Sulphurous Acid in Wine . . .OBTH (A,). Mechanical acd Chemical Analysis of’ Soils . . .VORTMANN (G.). Separation of Nickel from Cobalt . . . .GRIGOREFF (P.). Analysis of some Moscow Waters . . . .WOLFF (C. H.). Examination of Molasses for Dextrin Syrup . .FRANCEE (G.). Estimation of Starch in Grain . . . ..New Method of Detecting Dyes in Yarns or TissuesEstimation of Phosphoric Acid in Arable SoilsCOPPOLA (F.): Qenesis of Ptomai’nes . . . . . . .THOMAS (C.). Examination of Wine Coloured by Aromatic SulphonicDerivatives . . . . . . . . . . . .FLEMING (H.) . Glycerylphosphoric Acid . . . . . . .THOMSON (R. T.). Litmus, Methyl-orange, Phenacetolin, and Phenol-SHEPHERD (H. H. B.). Determination of Nitrogen in Mixtures containingNitrogenous Organic Matter, Ammoniacal Salts, and Nitrates . .HARTEY (J. W. C.). Volumetric Estimation of Chromic Acid in Chromatesand Dichromates . . . . . . . . . . .LEHMANN (v.). Methods of Detecting Lead., Silver, and Mercury in theDESPRAX (P.). Ready Method of Estimating the Alkalinity of Limed Bset-syrupDUNETAN (W: R.) and F.W. SHORT. Assay of Nux Vomica . . .BENEDIET (R.). Tests for Resorcinol Dyes . .. . . . . .TAUBER (E.). Estimation of Phosphorus by the Molybdate Method . .Essmina tion of B utter . . - . . . . . . . .MEYER (L.). Recognition of Suinh in Suet and other Fats . . . .Examination of Oil-cakes . . . . . . . . . .MEYEIG (R.). Microscopic Investigation of Dyed C&ton Fabrics . . .ETARD and C. RICHET. Estimation of the Redwcing Power of Urine and ofthe Extractive Matter whieh it contains . . . . . . .TAYLOR (J.) . Preparation of Hydrogen Sulphide from Cod-gas . . .THOMSON (R. T.). Litmus, Methyl-orange, Phenacetolin, and Phenol-phthale’in as Indicators . . . . . . . . . .THOMSON (R. T.). Use of Rosolic Acid as Indicator ; Additional Notes onPhenol-phthale’in and Methyl-orange .. . . . . .LUNGE (G.). Determination of Caustic Alkalis in presence of the Carbo-nates . . . . . . . . . . . . .MACARTHUR (R.). Determination of Zinc as Sulphide. . . . .JACKSON (E.). A New Test for Titanium and the Formation of a NewOxide of the Metal. . . . . . . . . . .MCCAY (L. W.). Water Analysis. . . . . . . . .BORGMANN (E.). Sulphuric Acid in Sherry . . . . . . .WORM-MULLER. Estimation of Sugar in Urine . . . . . .LOEW (0.) and T. BOCEORNY. Employment of Magenta with SulphurousAnhydride as a Microchemical Test for Aldehyde . . . . .PENZOLDT (F.) and E. FISCHER. New Reaction for Aldehydes . . .LOGES (G.). Estimation of Humus in Soils . . . . . . .Estimation of Iron and Steel . . ’ .. . . . . .Determination and Investigation of Drinking Water . . . . .CASAMAJOR (P.). Detection of Anhydrous Glucose mixed with RefinedCane- sugar . . . . . . . . . . . .UAUMANN (X.). Detection and Estimation of Phenols and Hydroxy-acids inthe Urine . . . . . . .HASLAM (A. B.). Detection of Albumin in Urinephthaleh as Indicators . . . . . . . . .Body in Cases of Poisoning . . . . . . . .. . . . . * . . . . . .625683682685686687689689689750750’75075175175182482482’782882882882982982982982983088 2883884885885PAGE. 522 . 523 . 618 . 619 . 619 . 619 . 620 . 621 . 621 . 621 . 622 . 624 . 624 . 62COXTENTS. xxxixDetection of Rice-meal in Buckwheat Flour . . . . . . .CLASSEN (A.) and 0.BAUER. Use of Hydrogen Peroxide in AnalyticalChemistry . . . . . . . . . . . .KITICSAN (S.). Distillation of Wine . . . . . . . .MUNTZ (A.). Estimation of Carbon Bisulphide in Thiocarbonates . .CLAUS (A.). .BULKOWSKY (K.). Examination of Fats . . . . . . .GROUVEN (H.). Nitrogen Estimation, a Method of General Application .KONIG (J.). Comparative Estimation of Nitrogen in Guano . . ,GRETE (E. A.). Nitrogen-estimation in Saltpetre by Potassium Xanthate .GRETE (E. A.). Phosphoric Acid Determination . . . . . .GISEFIUS (P.). bpecific Gravity of Minerals and their Mechanical Separa-tion . . . . . . . . . . . . .STEAD (J. E.). ANew Form of Chromgmeter . . . . . . . . .THOMAS (N. W.) and E. F. SMITH. .MCCAY (L. W.). .LEGLER (L.).Estimation of Methaldehyde . . . . . . .ZULKOWSKY (K.). Analysis of Fats . . . . . . . .SCHEIBE (E.). Separation of Morphine in Chemico-legdl Investigations .BLOXAM (C. L.), Detection of Urea in an Aqueous Solution . . .DRECHSEL (E.). Experiments on the Small Scale i n Sealed Tubes . .WIELAND (J.). Alkalimetric Indicators . . . . . . .BARNES (J. B.). Separation of Chlorine, Bromine, and Iodine . . .MILLER (0.). Detection of Free Sulphuric Acid in Presence of AluminiumSulphate . . . . . . . . . . . .ERUTWIG (J.) and A. COCHETEUX. Estimation of Iron by means of Per-manganate Solution . . . . . . . . . .STORCH (L.). Precipitation of Iron by Hydrogen Sulphide . . . .STORCH (L.). Solubility of Metallic Sulphides in Thio-acids . . .PASCHKIS (H.).Detection of Mercury in Animal Tissues . . . .MALLET (J. W.). Determination of Organic Matter in Potable Water. .LONGI (A.). Testing for Hydrocyanic, Hydrochloric, Hydrobromic, Hydr-iodic, Chloric, Bromic, Iodic, Hydroferrocyanic, and HydroferricyanicAcids . . . . . . . . . . . . .BOECHERS (W.) . Method of Determining Hydrochloric, HFdrocyanic, andThiocyanic Acid3 simultaneously present . . . . . .CRIPPS (R. A.). Estimation of Hydrocyanic Acid . . . . .STBUVE (H.). Milk . . . . . . . . . . .COWNLEY (A. J.). Ether-test for Quinine . . . . . . .BLOXAM (C. L.). Use of Bromine in testing for Alkalo’ids . . . .JACKSON (H.). Bromine as a Test for Strychnine . . . . .DUNSTAN (W. R.) and F. W. SHORT. Analysis of NUX Vomica . . .JOHNSON (G.) ..STRUVE (H.). Dialysis of Putrescible Substances. . . . . .DBECHSEL (E.). Use of Phosphoric Acid in Pettenkofer’s Reaction for BileAcids . . . . . . . . . . . . .Occurrence and Estimation of Free Tartaric Acid in WineNew Method of Estimating Carbon in Iron and Steel.Electrolysis of Bismuth SolutionsNew Volumetric Method for the Eatimation of ArsenicPicric Acid as a Test for Albumin and Sugar in UrinePAGE885934934935935936105810301031103110311032103410341035103610361167116711671( 13611681168116911691169117111721173117411741174117511751175117611771177Technica 1 Chemistry.GALLOWAY (W.). Influence of Coal-dust in Colliery Explosions . . . 127ROMANIS (R.). Water of Rangoon .. . , . . . . 128ALLEN (A. H.). Action of Water on Lead . . . . . . . 128ROBINET (E.) and H. PELLET. Antiseptic Action of Salicylic Acid . . 128BEAME (C.). Certain Properties of Hydrogen Cyanide . . . . 1’29Boiler Explosions . . . . . . . . . . . . 129SCHAEPPI (H.). Recovery of Sulphur by Mond’s Process . . . . 129ABRAHAM (K.). The Currents of the Gases in Sulphuric Acid Chambers . 12XI COXTESTS .PAGEWACHTEL ((3.).ture of Sulphuric Acid . . . . . . . . . . 130FAHLBERG (C.).from h o n . . . . . . . . . . . . 130~ORSCHELT (0.). Japanese soils: a Natural Cement . . . . . 131On Cement and its Application . . . . . . . . . 131Iron Industry . . . . . . . . . . . . 132Utilisation for Agricultural Purposes of the Basic Slag obtained in theDephosphorising Process .. . . . . . . . 133HAMPE . Desilvering of Lead . . . . . . . . . 134HUNTINGTON (A . K.). Reactions of the Mexican Amalgamation Process . 134BLAS and MIEST . Extraction of the Precious Metals from all kinds ofOres by Electrolysis . . . . . . . . . . 134MORITZ (J.). Freezing of Wine . . . . . . . . . 135BAUER (A . H.). Preservation of Beer . . . . . . . . 136%m-. grains . . . . . . . . . . . . . 136GXIESSMAYER (V.). Loss of Sugar by Long Steaming of the “ Mash” . . 136P . MERING . Does Potato-sugar contain any Deleterious Matter ? . . . 136SCHOTT and others . Purificttion of Sugar-beet Juice . . . . . 136Absorption and Utilisation of the Siilphurous Anhydride contained inFurnace Gases . . . . . . . . . .. 248MAYER (A.). Antiseptics . . . . . . . . . . 249KOCH (R.). Disinfectants . . . . . . . . . . 249T R ~ E . Prevention of Explosions in Boilers by Means of Sheet Zinc . . 250GUYOT (P.). Industrial Value of Crude Alunite . . . . . . 250GutLkoff’s Process for the Separation of Gold in California . . . . 251BLAREZ . Deplaslering of Wines . . . . . . . . . 252KOTTMAN (G.). Application of Strontium Chloride in Purifying Syrups . 252SCHEIBLER ((2.).Hydroxide . . . . . . . . . . . . 252Preparation of Brown and White Cellulose . . . . . . . 253Preparation of the Homologues of Phenol, Pu’aphthol, and Resorcinol . . 253FLEISCHMANN (W.) and R . SACHTLEREN . Beclier’s Creaming Process . . 253FLEISCHMANN (W.) and R . SACHTLEBEN . Jscobsen’s Testing Churn .. 253GABEL (U.). On Creaming . . . . . . . . . . 253BUSSE . Preservation of Milk . . . . . . . . . 254FLEISCHMANN (W.). Preserved Milk, &c . . . . . . . . 254H A a E M A n ” (W.). Preservation of Butter . . . . . . . 254SCRAAT, (E.). Injurious Action of a Cupriferous Oil used in Turkey-redKOECRLIN (M . H.j. Fixation of Artificial Colouring Matters by Means ofUtilisation of the Nitrogen Compounds from the Manufac-Preparation from Bauxite of Aluminium Sulphate freeRecorery of Sugar from Molasses by means of StrontiumBARFF and others . Preservation of Milk, &c . . . . . . . 253DIETZELL (B.). Preservation of Milk . . . . . . . . 254SCHRODT (M.) and others . On Milk . . . . . . . . 254VIETH (P.) and others . Cheese, Oleomargarin.cheese, &c .. . . . 256Dyeing . . . . . . . . . . . . 256Metallic Mordants . . . . . . . . . . . 256Preparation of Aluminium Thiocyanate . . . . . . . . 256SCIXMID (13.). Application of Baejer’s Artificial Indigo . . . . 257DEBUS (H.). Chemical Theory of Gunpowder . . . . . . 258Cause of the Acid Reaction of some Kinds of PaperMULLER (A.). Cleaning of Glass Laboratory Vessels . . . . . 395OBERNETTER (J . B.). Silver Bromide Gelatin-emulsion . . . . 395XOLBE (11.). Antiseptic Properties of Carbonic Anhydride . . . . 395Rinidor, a 1)isinfectant . . . . . . . . . . 396IVAN (A.). Bauxite . . . . . . . . . . . 397GUYOT (P.). Calcination of Alunite . . . . . . . . 397PUSCHER (C.). Weather-proofcement Work . . . . . . 398FISCIIER (F.), Application of Electricity in Metallurgy .. . . 398. . . HAERLING . 2f‘OHARNACK (E.). Carlsbad Saits . . . . . . . . . 396WAGENER (G.). Glass Enamels, Porcelain, Stoneware, and Refractory Clay . 39CONTENTS . sliLUBISCH ('I.). Toughened Glass . . . . . . . . .ARNOLD (H.). Bromine Amalgamation Process . . . . . .KOSMANN . Roasting of Zinc-blende . . . . . . . .from Sulphides by Air-blast . . . . . . . . .Separation of Copper from L e d by Refining in FreibergImprovements in the Manufacture of IronIron Industry . . . . . . . . . . . . .DELAFOND . Bteel from Pig-iron containing Phosphorus . . . .Galranising and Nickeling of Iron in Cleveland. Ohio . . . . .PAS CHER (C.) . Argentine . . . . . . . . . .Pliy lloxera . . . . . . . . . . . .New Dyes .. . . . . . . . . . .NIEDERSTADT . Meat Extract from South America . . . . .LOWE (J.) .Roessler's Method for the Separation of Gold, Silver. Lead. and Copper. . . .Modification of the Hunt-Douglas Process for the Extraction of Copper . .. . . . . . .Influence of Charcoal on the Amount of Phosphorus in Pig-iron . . .WASUM . Influence of Sulphur and Copper on the working of Steel . .LIEBER (K.). Application of Aluminium Palmitate . . . . .SESTINI (F.). Preparation of Thiocarbonates for the Destruction ofFLUCKI~ER (F . A.) and W . v . MILLER . American Storm . . . .MALENFANT . Alteration of Syrup of Tolu . . . . . . .Adulteration of Cochineal . . . . . . . .BAUDET . Prevention of Boiler Incrustation . . . . . . .RAYDT (W.).Liquid Carbonic Anhydride as a Fire Extinguidicr . .LIDOFF (A.). Analysis of Petroleum Coke . . . . . . .FLETCHER (T.). Flnmeless Combustion . . . . . . .PFAUNDLER (L.). Explosion of a Zinc Gasometer containing Oxygen .Improvements in the Preparation of Alkalis . . . . . . .BRIGORJEFF (P.). New Mineral Manure Deposits . . . . .DEXARCHI (L.) and 0 . FODERA . Production of Pozzolana . . . .MICHAELIS (W.). Portland'Cement and its Adulteration . . . .PUSCHER (E.). Process for Rendering Cement and Lime less subject toAtmospheric Influences . . . . . . . . . .EGLESTON (T'.). Tellurium in Copper . . . . . . . .R e m o d of Fixed Glass Stoppers . . . . . . . . .LUNGE (G.). Recent Progress in the Soda Industry . . . . .English Cement . . . . .. . . . .Novelties in the Iron IndustryTungsten Steel . . . . . . . . . . . .. . . . . . . . .RINMAN (L.). Composition of Firwood Charcoal . . . . . .NAWRATIL (A.). Examination of Galician Petroleum . . . . .New Source of Benzene, Naphthalene. and Anthracene . . . . .FRIEDBURG (L . H.). Carbon Bisulphide . . . . . . .DEYUCB (D.). Presermtion of Wine by Salicylic Acid . . . .LANGER (T.). Amount of Carbonic Acid in Beer . . . . .GRIESSMAYER . The Ferment of Chica Beer . . . . . .SCHEIBLER (C.). The Strontia Process for the Separation of Sugar fromMolasses . . . . . . . . . . . . .MELDOLA (R.). Action of Dibromonaphthol on Amines . . . .Cement for Conduct-pipes . . . . . . . . . .BORGMANN . Photo-electric Battery . . . . . . . .FISCHER (F.).Flameless Combustion . . . . . . . .PISCHER (F.). Practical Application of Thermo-electricity . . . .RRARD . Fuel to Produce Electricity . . . . . . . .WELDON (W.). Manufacture of Sodium Sulphide . . . . .SEGER (H.). Analgsis of Clay from Lothain . . . . . .LAXDRIN (E.). Analysis of Puzzuolanas and Estimation of their Compara-tive Values . . . . . . . . . . . .STOLTLER (L.). Crystalsin Cementation Steel . . . . . .Presence of Gold in German Standard Silver Coins . . . . .PAGE3993993994004004004024024034034044044q0540540540640640740740840840840852352452452452852952053053053053153153353353353453553553553553653653662562562662662762762862962xlii CONTENTS .THAN (C .v.). Examination of Illuminating Gas . . . . . .Manufacture of Spirit from Wheat . . . . . . . .Simultaneous Employment of Potatoes and Grain in Spirit Factories . .SALZER (L.). Purification of Alcohol prepared from Molasses or Beetroot .WACHTER (H.) . Analysis of Markgrafler of different Districts andVintages . . . . . . . . . . . .HEYNINBER . A New Alcohol in Wine . . . . . . . .DETWER (W.). Influence of Foreign Matter in the Conversion of Starch byDiastase . . . . . . . . . . . . .On Malt . . . . . . . . . . . . .BOCKMANN (F.). Manufacture of Sorgho- and Imphy-sugar in the UnitedStates . . . . . . . . . . . . .LOEW (0.) and others . . . .SCHATZ (F.). Oiling and the Operations connected therewith in Turkey-redProcess for Preparing Crocin-scarlet and Crocin-yellow . . . . .Alizarin- blue . . . . . . . . . . . . .New Coal-tar Colours . . . . . . . . . . .TCEERNIAC (J.) and others. Manufacture of Thiocyanates . . . .Dressing for Driving-bands . . . . . . . . . .HALLBERG (C . S.). Ergot . . . . . . . . . .KONIQ (J.). Purification of Contaminated Waters . . . . .BOUSSINQAULT . Bronze Implements used by the Mirlers of Peru . .KUSTEL . Roasting of Gold Telluride . . . . . . . .WEHMER (J.). Preparation of Pressed Yeast . . . . . .UEGENER (P.). Influence of Chlorides of the Alkalis and Alkaline Earths .New Process for the Extraction of Fish-oil . . . . . . .GIBBONS (W.). Cranium Oleate . . . . . . . . .WEIDMANN (M.). Composition and Ripening of Emmenthal Cheese . .PAUL (B . H.). Liquid Extract of Cinchona . . . . . . .CROSS (C . F.), Technical Aspects of Lignification . . . . .KOECHLIN (H.) . Indophenol . . . . . . . . .BURQW (F.) . New Probess for Preparing Press-cake from Maize, &c . . .Preservation of Diffusion Residues from the Beet-sugar Manufacture . .FLEICHTINQER . Cause of the Acid Reaction exhibited by some kinds ofChanges occurring in Preserved MilkDyeing . . . . . . . . . . . . .on the Precipitation of Lime Saccharate from Warm Solutions .Paper . . . . . . . . . . . . .CROS (C.) and A . VERGERAUD . A New Photographic PaperPreparation and Purification of Carbon for Blectric LightingVariation of the Amount of Ammonia in Rain-water . .Preparation and Testing of CementHydraulic Silica and its Functions in Hydraulic Cements .LE CH~TELIER (H,) . Hydraulic Silica . . . . . . . ..Plastering of Wines ; Rapid Estimation of Cream of TartarInfluence of Barley on the Fermentation ProcessDefecation of Beet-juice with Strontium Saccharate . . . .LITACHE (A.). Action of Certain Metals on Oils . . . . . .Investigations on Milk . . . . . . . . . . .FLEISCHXANN (W.) and A . MORQEN . Scherff's Preserved Xilk . . .Preservation of Milk . . . . . . . . . . .Preparation of Blue and Violet Dye-stuffsARCHBOLD (G.). A New Method vf Manufacturing Paper-pulp . . .Waterproof Paint for Stones, &c . . . . . . . . . .Compound, " Pouzzo-Portland " . . . . . . . .LE CHALELIER (H.) . Hardening of Cements . . . . . .STEAD (J . E.). Chemistry of the Bessemer ConverterGUBDERMANN . Purification of Molasses . . . . . . .. . .JACQUELAIN .HOUZEAU (A.).LANDRIN (E.).GRUNER .PICHARD (P.) .. . . . . . . .Relative Oxidisability of Cast and Malleable Iron and Steel. . . . . .. . . . . . .HAERLING .LANDRIN (E.).Cause of the Acid Reaction exhibited by some Kinds of PaperAction of Water on the Lime of Theil . Existence of a New. . . . .PAGE62963063063063163163163163363463563563563663964064069169169169269269269269269369469569569569675 275275375375475575575575675s756767757758759759759'76083083183283CONTENTS .PELLET (H.) and A . DUBAELE . Manufacture of Sugar without Bone-charcoal. Sand. or Sulphurous Anhydride . . . . .' ~ R ~ V E S I . Prevention of Boiler Explosi&s . . . . . .'FOBIN (T . W.). Explosive and Dangerous Dusts . . . . .PEMBERTON (H.). Working of Sulphuric Acid Chambers . . .SCHEURER-KESTNER (A.). Notes on the Soda Industry . . .MAYER (L.) and 0 . WAGNER . Analjsis of BauxiteClay and Earthenware Goods . . . . . . . .FISCHER (F.). Contribution to a Knowledge of Sewer Gases . .. . . .Process for Preparing Dichromates . . . . . . .Scale of Hardness of Metals . . * . . . . .Extraction of Lead from Ores occurring in the Upper Hartz . . .Process for Preparing Litharge and Red Lead . . . . .Italian Red Wines . . . . . . . . .PANPE (F.). Contribution to the Problem of Frothy Fermentation .WINTHER (A.). Process for Preparing Orcinol . . . . .IilAUBER and A . ~TEINHEIL . . . . .Mordants used for Fixing Artificial Colouring-matters . . . .Novelties in Dyeing and Calico-printing . . . . . .1:tilisation of Battery Residues . . . . . . . .]'reparation of Terra-cotta Lumber . . . . . . .Polychrome Varnish for White Metal . . . . . . .Spontaneous Combustion of Coal . . . . . . . .11 dultcrated Soaps . . . . . . . . . . .Use of soap in DyeingFroYcess for Preparing Printing Ink . . . . . . .YOGEL (H . W.). Modification of Silver Bromide and Chloride . .ZWEIPEL (P.). Scientific Basis of Antisepsis, and Origin of Septic Paison .KESSLER (L.) . Hardening of Soft Calcareous Rocks by means of Fhosili-cates of Insoluble Bases . . . . . . . . . .DELATTRE . Treatment of the Washings from Wool . . . . .BOUSSINGAULT . Mineral Combustibles . . . . . . . .FISCHER (F.). Investigation on Boiler Fires . . . . . .Process for Preparing Weatherproof Wall Paintings . . . . .STANFORD (E . C . C.). New Substance obtained from some of the commonerKERN (S.). Russian Basic Steel . . . . . . . . .WALLACE (W.). Decay of Building Stones . . . . . . .MULLER (A.). Utilisation of Butter-milk in Bread-making . . . .HALL (F . P.). Action of Certain Vegetable Acids on Lead and Tin . .TAPPEINER (H.). Marsh-gas Fermentation in the Mud of Ditches, Swamps,and Sewers . . . . . . . . . . . .ROHART . New Properties of Ferric Sulphate . . . . . .FORSTER (J.). Employment of Boric Acid for Preserving Food . . .FRIEDBURG (L . H.). Manufacture of Tartaric Acid . . . . .ATWATER (W . 0.). Chemistry of Fish . . . . . . .MOUSSETTE . Fermentation of Bread . . . . . . . .CHICANDARD (G.). Fermentation of Bread . . . . . . .Species of Marine Alge . . . . . . . . . .xliiiPAGE835835836886887A8 788888889089689189189889289289389389489489589689689689693693794094094194294294310361036103710381177117811781178117911791179PORRO (B.). it&an Petroleume . . . . . . . . . 118

ISSN:0368-1769    

DOI:10.1039/CA88344FP001

出版商:RSC    

年代:1883

数据来源: RSC

摘要:

14 ABSTRACTS 011’ CHEMICAL PAPERS.In o r g a n i c C h e mi s try.On the Supposed Compound NH,. By COMBES (Cornpt. rend.,94, 1717).-Reference is made to a communication from Mnumene(Cornpt. re.nd., ISSS), in which he claims to have produced a new sub-stance, N&, by the reactmion of potassium permanganate on am-monium oxalate. As the existence of NH, or rather of N2H1, is theo-retically probable, the author has repeaked the experiments, with thefollowing results :-The carbonate mentioned by Maumene, treatedwith hydrochloric acid and p l a h u m chloride, givcs a crystallineprecipitate identical in form with ammonium platinochloride, andcontaining 1.9 per cent. of hydrogen (NH,Cl,PtCld = 1.8 per cent. H),whilst Maurnen6 obtained only 1.35. The aqueous solution of thesupposed new body, saturated with hydrochloric acid, Fields crystalsidentical in form with ammonium chloride, and this is confirmed bythe analytical results.The reaction, therefore, yields only ammoniaand carbonic acid. R. RINORGANIC CHERIISTRT. 15Silicon. By P. SCH~~TZENBERGER and A . COLSON (C’owpf. Tend., 94,1710--1713).--Platinum foil, heated to a reddish-white heat amidst amass of lamp-black, is found to contain silicon, which must have beencarried through the lamp-black from the crucible. Other experimentsdetailed in the paper show that the silicon reaches the platinum in thevaporous form, and that nitrogen, and probably also oxygen, play apart in the transference of the silicon, a s well as in the formation of thecarbo-silicic compounds which the authors have previously described.R.R.Compounds of Silicon with Sulphur. By P. SABATIER (BuZl.Xoc. Chirn. [2], 38, 153--154).-When dry hydrogen sulphide ispassed over crystalline silicon a t a red heat, a violent reaction occurs,and at t>he cooled part of the tube a ring of a reddish substance is ob-tained, in which fine white needles of silicon disulphide, SiS,, are found.Beyond the ring, the tube is covered with an orange-yellow powder,which is given off in fumes during the course of the reaction. TheVellow and brown substances seem to be identical with those obtainedby Colson (vide following Abstract). The latter has a variable composi-tion, and is probably a mixture of the disulphide with amorphous siliconor a subsulphide ; on treatment with water, if, gives off hydrogen sul-phide and leaves a brown residue.In the tube, there is alwayspresent a deposit of crystalline silicon, which the author explainsby supposing the formation a t the high temperature of a volatile sub-sulphide, which a t the lower temperature is decomposed into disulphideand silicon. The yellow substance seems to consist for the greaterpart of the disulphide contaminated with a certain quantity of thesubsulphide, to which the author attributes a probable formula Si,S4.V. H. V.Combination of Tetratomic Elements. By A. COLSON (Bu77.Xoc. Chirn. [2], 38, 56-60, and Conzpt. rend., 94, 1526--1528).-1fa current of ethylene or hydrogen saturated with benzene is passedover silicon contained in a porcelain tube surrounded by a clay jacket-ing tube which is heated in a reverberatory furnace, a carbosilicide ofthe formula SiCO, is obtained ; the necessary oxygen is derived fromthe silica of the tube.This compound is a whitish powder, and is unat-tacked by acids, chlorine, or oxygen a t a red heat. It is decomposedby fused potash, or a mixture of litharge and lead chromate. On sub-stituting carbonic anhydride for ethylene, a compound of the formulaSi,C,30 is formed, with liberation of carbonic oxide. The authorexplains the fact that an oxygen-containing compound like carbonicanhydride yields a less oxygenated product than ethylene, by suppos-ing a. simultaneous loss of oxygen of the silica and carbonic anhydride,analogous to the simultaneous loss of hydrogen when benzene andmethane are passed through a red-hot tube.On heating pulveriseilsilicon in a carbon crucible surrounded by a t.itaniferous (carbon andrutile) jacket, and heated to a white heat, a compound of formulzSi2C30, was obtained.If vapour of carbon bisulphide is passed over silicon a t a whiteheat, two componncls arc formed, the one a yellow volatile compoundof the formula SiS, the other a yellowish substance of probable conipo16 ABSTRACTS OF CHEMICAL PAPERS.sition SiSO. Both these substances are decomposed by water or dilutealkalis, with evolution of hydrogen. If the contents of the tnbz arefurther heated with a boiling soliition of potash to remove the excessof silicon and its sulphur compounds, and then digested for some timewith warm hydrofluoric acid, a greenish powder of the compositionSi4C4S is obtained: when heated in a current of oxygen this doesnot alter in weight, but is converted into an oxygen&gd compound,Si4C402.- I The author draws attention to the fact that the analogy of sulphurand oxygen does not hold good. a t high temperatures, for CO, yieldsSi4C402, but CS2 yields SiS and Si4C4S. V. H. V.Extraction of Selenium from a Waste Product. By P.KIENLEN (Bull. SOC. Chinz. [2], 3 7, 440-443).-The selenious anhy-dride produced by the combustion of seleniferous pyrites is reducedby sulphurous anhydride in the Glover tower to the state of selenium,which partly dissolves in the acid, partly remains in suspension.At aworks where pyrites from Sain Bel, near Lyons, are used, the amountof selenium present in the acid is often sufficient to impart to it adistinct blood-red tint.The amount of selenium in the sulphuric acid may be estimated bydiluting a considerable quantity of the acid with three times its bulkof water, and leaving it, in a warm place for a long time. The clearliquid is then decanted or siphoned off, the selenium collected on aweighed filter, washed, and dried a t 100". Glover tower acid of sp. gr.1.606 was found to cont'ain 28.3 mgrms. of selenium per litre, or 17.6mgrms. per 1000 grams, whilst chamber acid of sp. gr. 1-532 con-tained 34.2 mgrms. per litre, or 22.3 mgrms. per 1000 grams.When the sulphuric acid containing selenium is used for the manu-facture of salt-cake, the selenium volatilises along with the hydro-chloric acid, and is deposited in the first condensers, sometimes insuch quantity that it imparts a red fluorescence to the acid.It is thedeposit in these condensers which constitutes the new source of sele-nium. This deposit forms a brick-red mud, which becomes black ondrying. When dried a t 100" it contains from 41 to 45 per cent. ofselenium. The selenium is estimated by suspending 20 grams of thedried mud in water in a flask with a long neck, adding soda tofeeble alkaline reaction, and then adding bromine drop by drop withcontinual agitation. After some time the liquid is filtered, the filtratemixed with the washings, boiled with a little hydrochloric acid, andthe selenium precipitated by sulphurous acid.I n order to extract selenium from the deposit, it is suspended inwater, and treated with a current of chlorine in large Woolf's bottles.The selenium is converted into tetrachloride, and this is decomposedby the water, yielding selenious acid, which is partially oxidised toselenic acid.As fioon as the brick-red tint in the first vessel has dis-nppeared, the vessel is removed, and the second vessel put in its place,another vessel containing fresh mud being put on at the end. Thedark-coloured liquid thus obtained contains selenious, selenic, andhydrochloric acids. It is filtered through cloth, and boiled withexcess of hydrochloric acid, which reduces the selenic acid to seleINORGANIC CHEMISTRY.17nious acid, then diluted to its original volume, and the selenium pre-cipitated by adding sodium hydrogen sulphite until the liquid smellsstrongly of sulphurous anhydride. The selenium is deposited in largered flakes, which agglomerate t,o a pitchy mass with a bronze lustre.The liquid is boiled by passing in steam, when the precipitate rapidlyagglomerates and contracts, forming a spongy steel-grey mass, whichis then washed, dried, fused in a clay muffle, and cooled under wateror in glass moulds. By this method large quantitie8 of selenium canbe easily and rapidly obtained in a state of considerable purity.C. H. B.Boiling Point of Selenium. By L. TROOST (Compt. rend., 94,1508-1 510).-The author finds that the boiling point of seleniumnnder 760 mm.pressure is 665", and he suggests the use of boilingselenium as a means of maintaining a constant temperature for thedetermination of vapour-densities, &c. R. R.Coefficient of Expansion of Sodium Sulphate Solutions.By W. W. J. NICOL (Ber., 15, 1931--1932j.-On the assumption thatin sodium sulphate solutions the salt is in the anhydrous conditionabove 33-34', and hydrated below Chis temperature, the authorthought i t probable that a solution of this salt would show a suddenlyincreased or diminished coefficient of expansion a t about this tempera-ture. He has examined solutions of different strengths between 20"and 40', and has found that the coefficient of expansion gradually in-creases with rise of temperature up to 34-36', when it suddenlydiminishes.It increases again with further rise of temperature.A. K. M.Chloride of Lime '' and Chloride of Lithia." By K. KRAUT(AnnuZen, 214, 254-36O).-When chlorine is passed over moistlithia, a mixture of lithium chloride and hypochlorite is produced, buthalf of the lithia present takes no part in the reaction-4LiOH + 2C1 = LiOCl + LiCl + H20 + 2LiOH.When exposed to the action of carbonic acid, the hypochlorite is de-composed, and the hypochlorous acid which is set free acts on thechloride, and chlorine is evolved. A similar reaction takes placewhen a mixture of basic calcium chloride and calcium hypochlorite issubmitted t o the action of carbonic acid.As it mould not be possible for a monad metal, such as lithium, toform a compound having a composition analogous to ClCaOCl, theauthor concludes that Odling's formula, for bleaching powder is incor-rect.w. c. w.Calcium Hypoiodite. By 0. LUNGE and R. SCHOCH (Bw., 15,1883- 1888) .-The bypoiodites are generally stated to be highly un-sfable compounds, of which, however, little is known, as they have notbeen isolated.By the action of iodine on lime suspended in water (several hoursbeing allowed to complete the reaction), the authors have obtained acolourless solution, which has an odour of iodoform, and gives theVOL. XLIV. 1s ABSTRACTS OF CHEMICAL PAPERS.following reactions :-Addition of acid produces immediate separationof iodine ; solution of starch gives no coloration ; hydrogen peroxidein acid solution produces turbidity and abundant evolution of oxygen ;cobaltous nitrate gives a green-coloured precipitate ; coal-tar coloursare not affected, whilst cochineal, logwood, litmus, &c..are bleached,From these results, and more especially from the bleaching power ofthe solution, the authors conclude that by the action of iodine on limeat the ordinary temperature the compound CaOI, = Ca(OT), + CaIzis produced, besides calcium iodide and iodate. From quantitativeexperiments on the bleaching power of this iodide of lime, they showthab it is much more stable than the alkaline hypoiodites are generallysupposed to be. It decomposes slowlyin the dark, more rapidly whenexposed to sunlight, and by boiling for many hours is decomposed onlyto the extent of one-half.A. K. M.Didymium. By P. T. C L ~ E (Compt. rend., 94, 1528-1530)-The author has for several years suspected the presence of a newelement accompanying didy mium, and he has recently by fractionalprecipitation and decomposition separated a portion, the spectrum ofwhich, besides the known lines of didymium and lanthanum, gave newlines, and amongst these a very strong one of wave-length = 4333.5.This line was previously observed by Thalhn in 1868, in a mixture oflanthanum and didymium, but was absent from the spectra of samplesof lanthanum and of didymium prepared by the author in 1874.The atomic weight of the first fraction precipitated by potassiumsulphate was 146; that of the last fraction, 142. Without namingtbe new element, the author proposes to designate it by the symbolDip’.The author intends to continue his researches on didymium.R.RDidymium. By B. BRAUNER (Compt. rend., 94,1718-1719).-1nthis paper the author does not claim priority over ClBve (precedingAbstract), but merely asserts that his observations are independent,and were announced in the Anzeiger dei. Acnd. Wissenschaft in W i e n of6th October, 1881, and 9th June, 1882. He found that lanthanumsulphnte may by repeated crystallisations be divided into two frac-tions, the more basic having an atomic weight = 138.3, and the lessbasic = 140.2. By repeatedly treating didymium free from oxide oflanthanum with ammonium nitrate, the author obhined an earthhaving the atomic wclight, of 140.6, the atomic weight of the remainingdidymium being 142.5 ; but by repeated precipitations n product wasobtained with an atomic weight of 146.6.In the spark spectra of thedifferent fractions, raye were found belonging to none of the knowncerite metals. These phenomena are doubtless due to the fourthelement designated Dip by ClBve. The author succeeded in sepa-rating another earhh of a higher atomic weight than 145.4. Ordinarydidymium appears to be a mixture of a t least three elements. Oneis true didymiuni (Di = 145.4) ; another (the Dip of ClBve) is a morebasic metal, and has an atomic weight of about 141; the tbird, of ELhigher atomic weight, is less basic than didymium. R. RISORGANIC CHEMISTRY. 19Explosive Alloys of Zinc with Certain Platinum Metals.By H.SAINTE-CLAIRE DEVTLLE and H. DEBRAY (Comnpt. rend., 94,1557-1560) .-Oxide of iridium is projected into fused zinc, themass is kept in fusion for six hours, and the cooled ingot treated withhydrochloric acid to remove the excess of zinc, &c. When thegraphite-like residue, washed and dried at lOU", is heated to 300" itinstantly takes fire, almost explosively, giving off fumes of zinc and ofosmic acid. This deflagration occurs also in a vacuum, but naturally,without production of zinc oxide or of osmic acid. At 300", there istherefore a change of state attended by great development of heat,which in the air occasions combustion. This phenomenon is somarked that by its means 1 or 2 per cent. of iridium may be detectedin platinum.Ruthenium and rhodium produce similar effects.R. R.Action of Aluminium on Cupric Chloride. By D. TOIIIIASI(BUZZ. SOC. C'him. [a], 37, 4&3-445).-Aluminium acts rapidly, evena t ordinary temperatures, on a solution of cupric chloride, with libera-tion of hydrogen and copper, and formation of an aluminium oxychlo-ride, the composition of which depends on the concentration of thecopper solution. With a 31.25 per cent. solution of cupric chloride,the aluminium oxychloride had the composition 2A12H606,3A12C16,and with a 7-81 per cent. solution, the composition Al~H,0s,4Al,Cl,.These oxychlorides are easily- decomposed and will not crystallise :Tbey are not true compounds, but variable mixtures of aluminiumchloride and oxychloride.The action of metallic aluminium on theseoxychlorides yields as a final product the compoundTo obtain this compound, a 31.25 per cent. solution of cupric chlorideis treated with alnminium until all the copper is precipitated ; theliquid is filtered, the filtrate heated, and aluminium added in succes-sive small quantities unbil it ceases to dissolve, water being added fromtime to time to make up for loss by evaporation; The clear liquid isthen evaporated to a syrup, and finally dried a t 40-50". In this waythe oxychloride is obtained in white flakes resembling those of potas-sium boro-tartrate. A solution of this oxychloride, like that of ferricoxychloride, is precipitated by sulphuric acid and by certain salts, suchas the sulphates of sodium, ammonium, potassium, magnesium, zinc,copper, and iron ; but it is not precipitated, evec on boiling, by thechlorides of potassium, ammonium, sodium, copper, or barium, bypotassium iodide, potassium bromide, ammonium nitrate, o r potassiumnitrate.The aluminium hydroxide thrown down is but slightlysoluble in sulphuric acid, and appears to be an isomeric modification,AIZCl,,GAI~H,O6 + I2Hz0.probably the modification 6, described by the author (Conzpt. yenti.,1880). C. H. F.Stability of Cupric Hydroxide. By D. TOMMASI (UZCZZ. SOC.Chim. [el, 37, 197-202).--Cupric hydroxide, perfectly free fromoxide, can be obtained only by using very dilute solutions of coppersulphate and sodium hydroxide, the precipitation being effected a t 0".The author has determined the influence of the presence of variousc 20 ABSTRACTS OF CHEMICAL PA4PERS.salts on the dehydration O F the cnpric hydroxide. In contact withdistilled water at 6-8", cu pric hydroxide undergoes sensible dehydra-tion after 120 hours.A sensible amount of dehydration takes placein 24 hours in presence of sodium hydroxide, and is greater the moredilute the soda solution. It is most marked with a 0.2 per cent. solu-tion, but with a 10 per cent. solution the hydroxide remains blue, evenafter 48 hours; it becomes black, however, after 96 hours. Inpresence of sodium acetate, carbonate, or sulphate, dehydration takesplace more slowly, and, in presence of calcium chloride, sugar, man-ganese sulphate, or potassium chlorate, no dehydration is perceptible,even after a long time.Halojid salts of the alkalis appear to formsmall quantities of oxyhdoid copper compounds. The presence ofsmall quantities of certain substances a1 together prevents the dehydra-tion of the copper hydroxide; the presence of 0.3 per cent. man-ganese snlphate, for example, prevents dehydration, even at 100".Cupric hydroxide added to a solution of nickel sulphate is convertedinto an apple-green precipitate which contains both copper and nickel,probably in the form of a double basic sulphate. No copper passesinto solution. When the hydroxide is added to a solution of leadnitrate, the copper displaces a portion of the lead, which is precipitatedas hydroxide, whilst the copper passes into solution.The influence of different salts on the temperature of dehydrationis shown by the following table :-Salt.Na2C03........KC1.. ........NaHO ........NaC2H302 ....NazSOa ......NaHO ........NaHO. .......KBr ..........KClO s . . . . . . . .KI ..........HZO ..........Strength ofsolution.5 per cent.10 ,,10 9,10 9,ITemperature ofdehydration.50"71747778798384858586 ........ .. .. No dehydration, ...... even at 100".C. H. B.Transformations of Cuprosocupric Sulphites. By A. ~ T A R D(Compt. rend., 94, 1475--1477).-The formula for the precipitat,e,obtained by the addition of an insufficient quantity of sulphurous acidor sodium hydrogen sulphite to a solution of cupric acetate, was givenby Pkan as SO~Cuz,S03Cu,5Hz0. The author's analyses of this saltlead him to assign to it the composition S8027Cu"lo(Cu2) + 26H,O,wit.h the following rational formula :-after a type already adopted by him, and he proposes to call the sub-stance acid cuproso-cupric octosulphite........... CaCl, 10MnS04.. 10Sugar 10S8032C~'Z,~u''z~C~''~(HB)H1 + 21H20INORGANIC CEEMISTRY. 2.1By the action of sulphuroun acid, the abwe salt is transformed intoChevreul’s salt, SO3Cu2SO3,’LH20, and by the action of sodiumhydrogen sulphite into a yellow salt already described by the authoras acid octosulphite of cz~proswz, cupricum, and sodium (ibid., 94,1422).The reaction is represented thus :-Ss03~Cu’zCu‘’2Cu’’8( He) He,21H20 + S80zrNasH8 = S20sH8 +8H2 0 + SSeparation of Gallium.By L. DE BOISBATJDRAN (Compt. rend.,94, 1439-1442 ; 1625-1629) .-Separ ation from Gluciwm.-T hegallium is precipitated by potassium fersocyanide from a solutioncontaining hydrochloric .acid in large excess, or it may be throwndown along with arsenious sulphide.Xeparatioiz from Cerium, Lant haw urn, Didy mium, Xamar him, Ytt r izcm,Holmium, and Thu/ium.-These earths may be precipitated by potas-sium hydroxide i n considerable excess a t the boiling temperature, andthe gallium separated from the alkaline solution by means of cuprichydroxide or by addition of ammonia and long boiling after previousneutralisattion with hydrochloric acid. Gallium may also be separatedfrom the above-named metals by precipitating it with potassium ferro-cyanide from solutions containing excess of hydrochloric acid.Gal-lium is carried down when arsenious acid is precipitated by hydrogensulphide.Separation, from Iron.-This is effected by a boiling solution of potas-sium hydroxide, but as the iron oxide carries down with it a littlegallium, it must be re-dissolved and re-precipitated four or five times.When the quantity of iron present is relatively large, it is preferableto reduce the ferric salt with metallic copper, add a small excess ofcuprous oxide, and, after repeating this operation three or four times,to pass hydrogen sulphide through the last strongly acid hydrochloricacid solution. The remainder of the iron is then eliminated by twoor three treatments with boiling potassium hydroxide.Separation f ronz Thorium.-The methods with potassium hydroxide,with potassinm ferrocyanide, and with arsenious sulphide are allapplicable in this case.h’eparutioiz f rona Zirconium.-This may be effected either by boilingwith potassium hydroxide or by arsenious sulphide, but not by potas-sium ferrocyanide, because the latter precipitates very acid and dilutesolutions of zirconium.Separation from 1Manganese.-For this nine processes are giacn.That by potassium hydroxide is applicable, but it must be severaltimes repeated, and has no advantages in the presence of much man-ganese.Barium carbonate or calcium carbonate separates gallium i nthe cold after some hours, leaving manganous chloride in solution.Very good separations may be obtained by arsenious sulphide, also bycupric hydroxide used hot.The reaction with potassium ferrocyanidemay be used, but with special modifications, of which it long anddetailed account is given in the paper.Separation fq-orn Zinc.-The method with copper hydroxide com-pletely separates gallium from zinc. Barium or calcium carbonate32 C u’* C: u’’~ CU”~ ( Naa ) Hz , S 0 ,4Hz4, 5 H20.R. R22 ABSTRACTS OF CHEMICAL PAPERS.precipitates gallium, but considerable quantities of zinc are carrieddown with it. R. R.Action of Ammonium Sulphide on Stannous Sulphide. ByH. BAUBIGNY (Compt. rerid., 94, 1473--1475).-Stannous sulphide isquite insoluble in pure normal ammonium sulphide. If air has access,however, the oxygen decomposes the ammonium sulphide with forma-tion of sulphur ; this unites with a portion of the stannous sdphideand transforms it into stannic sulphide which is soluble in the liquid.Sulphide of ammonium or of the alkaline metals is employed inanalysis to dissolve and separate stannous sulphide, but these reagentsact as solvents only when they contain sulphur in excess, and arewithout action when reduced to the state of normal sulphides.Thissource of uncertainty would be avoided if the ammonium sulphideused in analysis were always fully sulphurised by previously dissolvingin it a sufficient quantity of sulphur.By M. PRUDHOMME and F.BINDER (BUZZ. SOL Chim. [2], 37, 194--196).-When barium chlorideis added to a solution of potassium dichromate, normal bariumchromate is precipitated, and potassium chloride and chromic acidremain in solution, thus : K2Cr207 + BaCI, = BaCrOa + 2KC1 + GO3.'l'his reaction furnishes additional evidence in favour of the view thatpotassium dichromate is a molecular combination of the normalchromate with an easily displaceable molecule of chromic anhydride,,z view also supported by the fact that many dichromates (NH4, K, Ca,kc.), can be prepared by tho direct action of chromic anhydride on amolecule of the corresponding normal chromate.By treating di-chromates with alkalis, alkaline earths, or the corresponding car-bonates, double chromates are freqaently formed. Zinc, aluminium,cupric, and chromic hydroxides, when heated with potassium dichro-mate, form normal potassium chromate and a chromate of the parti-cular base.I n this way, certain chromates, e.g., ZnCr04, can be pre-pared, which were formerly obtained only by the action of chromicacid on the carbonate or oxide. This method of preparation explainsthe formation of chromium chromate when potassium dichromate is'treated with hydrogen sulphide or sodium thiosulphate. Chromichydroxide is first formed, and is then acted on by the excesR of di-chromate. When a strong solution of potassium dichromate is addedt o a solution of sodium hydrogen sulphite of 30" B., a green solution isobtained, which rapidly solidifies, owing t o the formation of greenchromic oxide. If the dichromate is in excess, brown chromiumchromate is formed.R. R.Chmmic Acid and Chromates.C. H.B.Chromous Sulphate. By H. MOISSAN (BUZZ. Xoc. Chim. [3], 37,2136--298).-The greater part of this paper has already appeared intlie Conzpt. rend. (Abstr., 1881, p. 684). Chromous sulphate does notdecompose water a t 100". 12.35 grams of the salt dissolve in 100 C.C.of water at 0", but it is only slightly soluble in alcohol. With potas-sium or sodium hydroxide, a solution of chromous sulphate gives ablack precipitate, insoluble in excess ; with ammonia, a black precipiINORGANIC CHEMISTRY. 23tate, soluble in excess, forming a blue solution; with alkaline carbo-nates, a reddish precipitate ; with potassium chromate, a maroonprecipitate ; cupric salts, a brick-red precipitate ; ammonium molyb-date, a dark maroon precipitate ; gold chloride, a deposit of metallicgold ; hydrogen sulphide, no precipitate ; alkaline hydrosulphides, ablack precipitate.When moist chromous carbonate or acetate is treated with a largeexcess of concentrated sulphuric acid, the hydrate CrSO, + 3H,O isobtained in white crystals, more stable when exposed to air than thehydrate CrS04 + 7H,O.I n contact with a small quantity of water,it passes into the normal hydrate Cr,S04 + 7H20. C. H. B.New Class of Borotungstates. By D. KLEIN (Bull. HOG. Chim.[2], 3 7, 202--208).-The disodium salt previously described (Bull.SOC. Chiin., 35, 14) may be a boroduodecitungstate, or a boro-quatuordecitungstate, or a boroyuindecitungstate. The analyticalresults agree equally well with all three formule,The bariunz salt is obtained in white crystals by adding a boilingsaturated solution of barium chloride in excess to a warm saturatedsolution of the sodium salt.If the mixed solutions are allowed toboil, the small quantity of hydrochloric acid which is set free preci-pitates tungstic acid. Too frequent crystallisation from water alsodecomposes the salt, pTobably with separation of metatungstic acidand formation of a basic salt. The addition of a few drops of hydro-chloric acid appears to prevent t'his decomposition. The amount ofwater of crystallisation in the salt appears to be very variable, andthe salt is in all probability efflorescent. When dried a t 160°, thecomposition of the salt agrees more closely with the formula14WO,,R2O3,3Ba0,5K2O than with 15WO3,B2O3,3Ba0,5Hz0,The potassium salt is obtained in slender needles, closely resem-bling dipotassium tungstoborate, by decomposing the barium salt withpotassium sulphate.It has the composition 14WOy,Bz0,,3K,0,Hz0 +The silver saZt is obtained by adding silver sulphate to a solution ofthe barium salt. It is a white crystalline powder, almost insoluble incold, and very slightly soluble in hot water. It cannot be completdxdried without partial decomposition, but appears to have the compo-sition 14W03,B203,3Agz0,Hz0 + 7H20.When a limited quantity of barium chloride is added to the solutionwhich yields the sodium salt on acidification, and the precipitate fil-tered off, the filtrate deposits small granular crystals, very slightlysoluble in cold, more soluble in hot water.They have the composition14W03,B,0a, (3&Ba0,1&Na20),6H,0 + 29H20. This complicated doublesalt resembles the double paratungstates obtained by Marignac. Thecorresponding strontiumcompound, 14Wo3,B2O~, (3$3r0.lhN~0),6HzO + 29.8,0, is obtained in a similar manner by mixing saturated solu-tions of strontium chloride and the sodium salt. All these salts forma new group of boroquatiiordecituiz~states. The barium-sodium andstrontium-sodium compounds are possibly not true double salts, butmolecular combinations of the two salts. The author was unable toobtain the tetrapotassium or pentapotassium salts. When potassium21HZO23 ABSTRACTS OF CHEMICAL PAPERS.carbonate is added to tripotassium boroquatuordecitungstate, potas-sium tungstoborate and a precipitate of potassium parat ungs tate areformed.C. H. B.Change which Ferric Hydrate undergoes after a Time. ByD. TONMASI and G. PELLIZZARI (Bull. Soc. Chim. [2], 37, 196--197).-Ferric hydrate kept under water for a year loses its gelatinousstructure, and changes in colour from brown to yellowish-red. About30 per cent. passes into a modification insoluble in dilute acids, andabout 0.3 per cent. is converted into a soluble modification identicalwith Graham's colloidal hydrate. The change is very slightly, if atall, affected by light. C. H. B.Ferric Hydrates. By n. TOMMASI (Bull. XOC. Chim. [Zj, 38, 152-153).-The author separates the ferric hydrates into two isomericclasses, the a or red series, and the /3 or yellow series, the main pointsof difference between which are given in the table below :-Yellow o r @-series.I Red or a-series.Obtained by precipitating aferric salt with alkalis.a-Fe203,2H20 begins to be de-a-Fe20s,H,0 dehydrated at 92".a-Fe203 is brown.Sp. gr. of Fe203 = 5.11.The hydrates dissolve in diluteThe hydrates are dehydratedhydrated at 50".acids.on boiling with water.Obtained by oxidation of ferroushydrate, ferroso-ferric hydrate,or ferrous carbonate./3-Fe203,2H20 begins to be dehy-drated at 105".p-Fe,03,H20 dehydrated at 150".p-Pe,03 is red or yellowish-red.Sp. gr. of %'c?203 = 3-95.The hydrates are sparingly solu-ble in concentrated acids.The hydrates, even on long boil-ing, retain a molecule ofwater, which can easily be re-moved by a concentrated soh-tion of calcium chloride.The hydrates of the a-series may not only be distinguished, butseparated from the hydrates of the @-series ; for the former are solublein ferric chloride and are reprecipitated by the addition of sodium sul-phate or sulphuric acid, whereas the latter are quite insoluble in theAction of Hydrogen Sulphide on Solutions of NormalNickel Sulphate.By H. BAUBIGNY (Compt. rend., 94, 1473-1475).-The experiments described in this paper show that the pre-cipitation of nickel from a solution of the normal sulphate by hydro-gen sulphide _depends on the tension of the gas. The quantity ofsulphide thrown down in a given time is greater as the liquid is richerin hydrogen sulphide, and the effect of heating at 100" in closedvessels is that the same limits of precipitation are obtained in a fewhours which at the ordinary temperature would require as manyweeks.same reagent.v. H. vINORGANIC CHEMISTRY. 25The pi*ecipitation of the nickel ia complete when the solution doesnot contain more than 1 gram of sulphate in the litre.The limit of precipitation does not depend entirely on the degree ofacidity acquired by the liquid, but varies according to other circum-stances.The action of heat on a solution of neutral nickel sulphate in thepresence of hydrogen sulphate furnishes an exact method of separatingnickel from manganese, aluminium, &c., whose salts are not decom-posed by hydrogen sulphide, but not from iron.R. R.Action of Hydrogen Sulphide on Nickel Sulphate in AceticAcid Solution. By H. BAUBIGNY (Compt. rend., 94, 1715-1717).-The action of hydrogen sulphide on nickel sulphate in solution is re-tarded or entirely prevented if a sufficient quantity of acetic acid isadded in proportion to the quantity of nickel salt present. At thetemperature of loo", however, and in a closed vessel, acetic acidhas no power to retard the action of hydrogen sulphide on dissolvednickel sulphate, the reaction taking place as with an aqueous solutionof the neutral sulphate. It. R.Action of Heat on an Acid Solution of Nickel Sulphate inPresence of Hydrogen Sulphide. By H. BAUBIGNY (Comnpt. rend.,94, 1595--1598).-The experiments detailed in this paper lead to theconclusions that-1.In acid solutious of nickel sulphate, as in neutral solutions,when the ratio of the weights of the acid and the metal remainsconstant, the precipitation of the nickel by hydrogen sulphide is moreoomplete as the solution is more dilute.2. Whatever the ratio of tlie volumes of gas and of liquid, theamount of nickel precipitated increases with the time. R. R.Cobalt Sulphate. By G. VORTMANN (Ber., 15, 1888-1889).-On adding concentrated sulphuric acid to an aqueous solution of ncobadt salt, and then evaporating, cobalt sulphate containing 1 mol. ofwater of crystallisation is produced. The same compound is alsoformed on treating purpureocobaltic chloride with a small quantity ofwater and strong sulphuric acid until dissolved, and then heating to220".It forms a crystalline peach-coloured powder, sparingly solublein cold water, being less soluble than the anhydrous salt. A low redheat is required to drive off the water. In contact with moist air, itabsorbs water very slowly.Cobaltarnine Compounds. (Part 111.) By G. VORTMANN (Ber.,15, 1890-1903) .--Octcwtine Compouwds.-IInstead of preparing thesecompounds from tthe carbonate, as described in his first paper (Ber., 10,154), the author heats the decamine-purpureo chloride for some timeon a water-bath with dilute ammonia and solid ammonium carbonate.On evaporating the solution it assumes the dark cherry-red colour ofthe octamine carbonate. If any luteo-chloride should be present, itwill separate out on cooling, and can be filtered off.Octamine-roseo-oobaltic chloride, Co,(NH&( 2Hz0) Cls + 4H20, generally crystallisesA. K. M26 ABSTRACTS OF CHEMICAL PAPERS.(as previously shown by the author) with 2 mols. H20, but by addingconcentrated hydrochloric acid to the cold solution above-mentioned,it is obtained with 4H20. With mercuric chloride, the compoundCoz(NH3),(2H,O) C1,,6HgCI2 + ~ H z O is precipitated of a pale-redcolour. Heated to 100" it loses 3H20. Octamine-purpureocobalticchloride also forms a double salt with mercuric chloride ; this whentreated with concentrated hydrochloric acid and evaporated on a water-bath yields greyish-violet crystals of Co,(NH,),C1,,SHgCl2 + H,O, buton further concentration, green crystals of the praseo double salt,CO,(NH,),C&,H~CI,, are obtained.This compound is sparinglysoluble in cold water ; hot water con-ierts it into octamine-purpureo-cobdtic chloride. On adding praseocobaltic chlornitrate to acidu-lated mercuric chloride solution, a green precipitate ofis produced. Octamine-cobaltic nitrate, prepared by adding nitricacid to a solution of the corresponding carbonate, forms a crys-talline precipitate of the formula Co~(NH3),(NO3),2HzO. It hasalso been obtained with 1 and with 6 mols. H20, also anhydrous.Octamine-cobaZtic chromate, Co2(NH3),(2H,0) (CrO& + 2H20, is pre-pared by the action of potassium dichromate on the octamine-pur-pureo chloride, sulphate, or nitrate, and may be purified by crystal-lisation from a weak acetic acid solution : it forms bronze-colouredplates.If normal potassium chromate is employed, the compound ob-tained is olive-green, and contains 8 mols. H20. Solutions of bothcompounds in strong acetic acid when evaporated yield an orange-red body of the formula Co,(NH3),(2HzO)(Cr04j2,Crz07 + H20. Aplatinnchloride has been prepared, but its formula is not established.The acid carbonate, to which the author previously gave the formula,Coz03(NH3),,4C0, + 2H20, contains 3H20, 2 mols. of which aredriven off a t 100". Praseocobaltic chlornitrate, COz( NH3),(N03),C1, +2H20, is precipitated on adding dilute nitric acid or potassium nitratesolution to solution of praseocobaltic chloride. With potassium dichro-mate the latter gives a yellowish-green precipitate of the chlorochro-mate, CO,(NH,),(C~,O~)C~~ + H,O.Hexamine Compounds.-To an ammoniacal solution of octamine-cobnltic chloride, ammoni urn carbonate is added, and the solutionevaporated to dryness.On redissolving and repeating the same treat-ment, the residue consists of cobalt hydroxide and hexaminecobalticcarbonate, and from this 0the.r hexamine salts are obtained by theaction of acids. Hexamine-cobaltic chloride is a green compound, ofthe formula CO,(NH~)~C~, + 2H20. It dissolves in cold water to abluish-violet solution, which changes to violet-red on warming ; fromthis solution concentrated hydrochloric acid precipitates octamine-purpureocobaltic chloride. Hexamine-cobaltic sulphate was obtainedas an oil, which after frequent treatment with alcohol gradually be-came crystalline.It forms a red powder, easily soluble i n water. Itsformula is CO,(NH,)~(SO~), + 6H20. The nitrate, CO,(NH,),(NO~)~ + 8H20, is a dark cherry-red deliquescent body. The carbonate,Co,( NH&( OH),( GO3), + 3H20, is formed in preparing the octnrnine-cmbonate, and is precipitabed by alcohol as an oil, which afterCog (NH,)sC16,2HgC1INORGANIC CHEMISTRY. 27repeated solution, precipitation, and treatment with alcohol, becomescrystalline.Heptaqnine Compounds.-The author has in a previous paper given amethod for the preparation of melanocobaltic chloride. In order toconfirm the formula which he gave for Rose's " black salt,"COz(NH,)s(NH,Cl) C Lhe has prepared other derivatives, which he finds to be of analogouscomposition.ikIelanocobaltic ch.Zorockromate,Co,(NH,),(NHzC1) C&,Cr207 + HzO,by precipitating the melanochloride with potassium dicliromate.With platinum chloride, the melanochloride gives a brownish-blackprecipitate of Go2( NH3)6 (NH,C1) C I,, P t C1,. 0 n heating melanocobalticchloride solution, i t becomes red ; with platinum chloride this redsolution gives a reddish-brown precipitate, which (air-dried) has theformula Coz (NH,),( NH2C 1 j CI, (OH),,PtCI,. With mercuric chloride,pale-red needles of Coz(NH,),(NHzCl) CIz( OH),,3HgCIZ + HzO, areprecipi tnted. With picric acid, melanocobaltic chloride gives a brownprecipitate, which explodes violently on heating. A. K. M.Electrolysis of Ammonium Carbamate and Carbonate withAlternating Currents and Platinum Electrodes. By B.GERDES(J. pr. Chem. [2], 26, 257-276).-Dnrechsel has observed (J. pr.Chem. [2], 22, 476) that on electrolysing solutions of ammoniumcarbamate and carbonate with a1 ternating currents, the platinumelectrodes become strongly corroded, with formation of soluble andinsoluble platinum bases, of urea, and of an oily substance soluble inammonia. The author has isolated and studied the platinum basesreferred to. He used platinum electrodes two inches by one inch, abattery of 6 6 Grove's cells, and alternated the current about, 10times in each second, the duration of each experiment being 10-12hours, and the solution being kept cool. After that time a thickyellowish or white precipitate had formed, the solution being colour-less, and the electrodes much attacked.Besides ammonium nitrite and nitrate, urea, and a fatty substance,the filtrate was found to contain a soluble platinum salt thrown downas a blue or green precipitate by hydrochloric acid, and crystallising inneedles.It was not, however, obtained in quantity suficient to allowof detailed investigation.The white precipitate contains most of the platinurn dissolved offthe electrodes. It is a carbonate insoluble in cold water, but on heat-ing dissolves sparingly, forming an a1 kaline solution. After havingbeen dried over sulphuric acid, it does not lose weight a t 110", but athigher temperatures it first becomes yellow and then suddenly decom-poses, with evolution of ammonia and water, leaving metallic platinumin a very fine state of division.Its composition corresponds wellwith the formula PtN,H&,O,. The carbonate dissolves in dilutesoda, and is precipitated without alteration from its solution by car-bonic anhydride. When dissolved in hydrochloric acid and precipi-tated by sodium carbonate in sufficiently dilute solutions sniall wellformed octohedrons separate28 ABSTRACTS OF CHEMICAL PAPERS.The chZoride, P t ( NH,) &I4, is easily obtained in small rhombohedronsor in needles; i t dissolves readily in hot water, and with gold orplatinum chloride gives precipitates resembling ammonium platino-chloride. The nitrate, Pt (NH,)6(NOs)4, is readily soluble iu water,.arid crystallises in needles. The sulphate is practically insoluble inwater, even calcium sulphate solution giving an immediate precipitatewith solutions of the soluble salts. It could only be obtained in theamorphous condition.Other compounds have been prepared, buthave not been analysed. C hromates produce a yellow, hydrofluosilicicacid a white precipitate. The free base has not yet been isolated in astate of purity.If during the action of the electric current the solution of carbonateor carbamate is not artificially cooled, the temperature of the fluidrises to 40-50", and no precipitate of the carbonate just describedis obtained, but on cooling, long prismatic highly refractive crystalsseparate from the solution. These likewise consist of a carbonate,PhN,C4OI4H,,. Their solution gives with nitric acid a colourless pre-cipitate, which gradually changes into bright blue octohedrons ofplatodianzntoniunz nit rate, Pt (NH,), (NO,),.The author believes the formation of the several platinum bases totake place as follows :-Electrolysis a t first takes place in the ordinarymanner, (NHJ2C03, splitting up into 2NH4 and GO,, the former com-bining in the nascent state with the negative electrode, formingPtH,(NH3),. The current alternating, the negative pole becomespositive, and C03 is added to the compound formed, yielding H, +Pt { ",$>CO, that is to say, platosammonium carbonate, which saltdirectly combines with NH3, yielding plntodiammonium carbonate,P t { ~ ~ : ~ ~ " , > C O . To the latter, on further alternation of cnrreut,~ -I -HNH3 NH NH.0 2NH4 are added, giving H-H,>Pt<NH::NH:o >CO, from which in- -a similar manner the insoluble carbonate-Ammonioplatinum Diammonium Compounds. By E. D RECH-SEL (J. pr. Chem. [2], 26, 277--281).--In an appendix to the previouspaper, the author points out the strikitig similarity of the reactions ofthe platinum base described by Gerdes with those of barium com-pounds, the solutions being precipitated by sodium carbonate, potas-sium dichromate, sodium phosphate, sulphuric acid, calcium sulphate,hydrofluosilicic acid, and alkaline oxalates, hyposulphates and ferro-cyanides. By the reagents named in fact the platinum compoundcannot be distinguished from baryta. Hydric sulphide and ammoniumsulphide produce precipitates only after some time. The ammonio-platinum diammonium compounds stand therefore in the same relationto the alkaline earths as ammonium does to the alkalis. 0. H

ISSN:0368-1769    

DOI:10.1039/CA8834400014

出版商:RSC    

年代:1883

数据来源: RSC

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MINERALOGICAL CHEMISTRY. 29M i n e r a l 0 g i c a l Chemistry.Metallic Iron accompanying Native Gold in MontgomeryCo., Virginia, and in Burke Co., N. Carolina. By W. T. PAGE(Chem. News, 46, 205).-The grains of iron removed by a magnetfrom gold, obtained by alluvial washing in the bed of Brush Creek,have a sp. gr. 7.20, and consist of-Fe. c u . S. Quartz.97-12 0.04 1.47 0.82 = 99.45.C, P, Ni, Co, Sn, and Mn absent. This iron is shown not to be derivedfrom tools employed by workers, but is a case of the occurrence ofnative iron with gold. Similar specimens from Carolina had a sp. gr. =7.57, and consisted of-Fe. co. 8n. Quartz.99.77 trace trace (?) 0.25 = 100.02.E. W. P.Chemical Composition of Minerals of the Cryolite-group.By J. BEANDL (Jahrb. f.Mila., 1882, 2, Ref., 201-203).A l . . ...... 13.01 13.606 13.04 13.00 13-26Ca ........ - 18.83 17.22 17.21 17-22Mg ...... - - 0.39 0.20Na ....... 32.41 11.73 10.02 10.49 10.43F ........ 54-29 55.69 50.65 50.62 30.61H,O ...... - - 8.48 8.33 8.42a. 6. cl. c2. c3.-99.71 99.856a.Al.. ........ 22.14Ca.. ........ 1.53Mg ........ 3.56Na ......... 5.50F ........... 57.12HzO ........ 10.0099.80 99.85 99-94e l . e2. f.17.66 17.64 23.37- - 16.19- 0.1124-97 25.00 0.3357.30 57.30 35.01- 12.41-~99.85 99.93 99.94 87.4212-58100*00Loss reckoned as oxygen.. ......a. Cryolite, representing the formula AlF, + 3NaF. b. Pachnolite,Pachnolite contains no water, and thus differsc 1, 2, and 3, are analyses of thomsenolite, agree-d.Ralstonite,e 1, 2, are analysee of chiolite fromAll?, + CaF, + NaF.from thomsenolite.ing with the formula, AIF, + CaF, + NaF + H,O.4A1F3 + 3Na (MgCa)F + 3H2030 ABSTRACTS OF CHEMICAL PAPERS.Miask. They represent the formula 3A1F, + 5NaF. f is an ana.lysisof prosopite from Altenberg in Saxony. It proves that this mineralis free from silicon. Supposing that the oxygen is combined withaluminium, so that the aluminium is partly combined with fluorine andpartly with oxygen, the analysis gives the following results :-Ca. Mg. Na. Al. A1203. F. H20.16.19 0.11 0.33 9.82 26.55 35.01 12.41Taking for granted that fluorine and hydroxyl can replace eachother, the formula for pros0pit.e should be Ca(Mg,Na)Al,(F,OH),.This mineral does not yield up its water a t 260".B. H. B.Some Artificial Products from Cryolite. By NOELLLNER ( J a h ~ b .f. illin., 1882, 2, Ref., 200--201).-1n order to determine, experi-mentally, if the minerals cryst'allised out in the cavities of cryolitehave originated from the action of salt solutions, the author digestedfor three months a t 100" about 12 grams finely powdered cryolite witha saturated solution of barium chloride. Saturated solutions of stron-tium nitrate, calcium chloride, and magnesium chloride, were alsoemployed. Cryolite was also treated with the same solutions forsix days in closed tubes a t a temperature of 180-190". The productsthus obtained mere then dried and andlysed? giving the followingresults :-Products of the reaction,7 r--A--1. Cryolite + BaCl?.. . . A14BaANa4Fs2. Cryolite + SrNzO, . . A14Sr4Na4FZ( A1,Sr5NaZF2, + 4H203, Cryolite + CaCl,.. . . Al,Ca4Na4F24 Al,Ca5NazF24 + 4H204. Cryolite + MgCl,. . . Al4Mg4Na4FZ4 A14RIg5Na,F,4 + 4H20The product No. 3a was further treated with MgCl, a t 180Oforsix days, and the product had the composition A1,Ca4Nlg,Na6Fd, + 8H,O.I n the same way the Droduct No. 4a. was heated a t 180" for six davsMaterial. a. A t 180" 6. At 100" after(Cryolite = Al,Na,F,,. after 6 days. 3 months.A14Ba5NazF24 + IT,Owith CaCl,, andu yieldid a body of the composition A1,Mg,Ca,Na,F48 $8Hf,0.From these experiments the author deduces :-(l), that cryolite isdecomposed by solutions of salts of the alkaline earths ; (Z), that thealkaline earths displace the sodium which goes into solution ; (3), thatthe degree of change effected is dependent on the time, the tempera-ture, and the proportion of the salt in the solution ; (4), that the perfectdisplacement of the sodium did not occur, but that it would probablybe effected after tlie lapfie of sufficient time. (5.) That the substitutedcalcium or magnesium can be partially replaced by magnesium orcalcium.(6.) That in all these reactions water is taken u p ; theamount being dependent on the nature of the incoming elements.(7.) That the products obtaiiied artificially closely resemble the naturalminerals crystallised out in the cavities of cryolite, and that thetheory of their formation by the same chemical process is highlyprobable.B. H. BMISERALOGICAL CHEMISTRY. 31The Pgrolusite Mines of Bolet. By T. Nomsmofir (Juhrb. $~Min., 1882, 2, Ref., 195).-At Bolet, in Sweden, pyrolusite occurs insufficient quantity to be worked. The veins and pockets are found a tthe contact of finely grariiilar gneiss and mica-slates with granitic gneiss,which is a variety of Orebro granite. The carities were first filledwith mica and chlorite, which was then partially replaced by pyrolusite.The latter is, in places, accompanied by heavy spar, calcspar, quartz,felspar, vanadinite, fluorspar, and calcspar coloured black by fine needlesof pyrolusite. B. H. B.Artificial Production of Witherite, Strontianite, and Cal-cite. By L. BOURGEOIS (Bull. Xoc. Chim. [2j, 37, 447-448).-Ifsmall quantities of precipitated barium, strontium, or cltlciurri car-bonate are thrown into a, fused mixture of potassium and sodiumchlorides in equivalent proportions, no carbonic anhydride is given off,but the carbonates assume a dist,inct crystalline form, identical in eachcase with that of the corresponding mineral.Barium carbonate formshexagonal plates, sometimes elongated in it direction parallel with thefaces of the prism. Strontium carbonate forms elongated primis, andcalcium carbonate usually forms agglomerations of crystals resemblingsnow crystals. C. H. B.Mineralogical Notes. By A. BRUN (Jahrb. f. Min., 1882, 2,Ref., 198) .--(a) Xtypticite from ChiZi.-The empirical formula of thissalt, Fe203,2S03 + 10H20, should be H4Fe,S2OI1 + 8Aq, as the wateris given up at 80-180", with the exception of the last 8 per cent.,which is only driven off at a dull red heat together with the sulphuricacid.On dissolving it in boiling water, brown basic iron snlphate isprecipitated .(b.) Dolomite fronz Teruel in Xpain.-This is shown by the micro-scope to be composed of grey and brown zones; the latter beingcoloured by numerous opaque granules (magnetic iron ore). Theanalysis gave 2.63 per cent. FeOj and traces of- MnO.(c.) Minerals of the Miage Glacier, $1. Blanc.--In the moraine ofthe " Glacie_r_ de Miage," crystals of quartz htlxle-been found, on whichonly R(1011) is developed, without -R(O111). The author alsofound galena, albite (complicated crystals), orthoclase (simple com-binations), various micas, chlorite, asbestlos, and small crystals ofberyl.B. H. B.Chalcomenite, a New Mineral Species (Selenite of Copper).By DES CLOIZEAUX and DAMOUR (Jc1hrb.f. Min., 1882, 2, Ref., 204).-For some time the existence has been known of selenium-lead,selenium-silver-copper-lead, and selenium-copper-lead ores at the Cerrode Cachenta, about 50 miles south-west of Mendoza in the Argen-tine Republic. Accompanying these ores, Des Cloiseaux found somevery small crystals of a violet-blue colour, which he called chalcomenite.The system of this new mineral is monoclinic ; the axes have the pro-portion a : b : c = 0.722187 : 1 : 0.246037. L3 = 89" 9'. Chalcomenitehas the formula CuSe03 + 2H20 ; and is therefore a representativeof a group, the selenious acid salts, up to the present time unknown innature. When heated in a, tube closed at one end, the mineral give32 ABSTRACTS OF CIIEMICAL PAPERS.up first water, which is acid, then selenious acid, and finally melts to abrown mass.Heated on charcoal before the blowpipe, it melts to ablack slag, gives off selenium vapours, and colours the flame dark blue.I n a bead of microcosmic salt, it is quickly dissolved, and gives agreenish-blue glass, which becomes red in the reducing flame, especi-ally after the addition of tin. The mineral is soluble in the ordinaryacids. A drop of the solution in sulphuric acid, placed on a brightplate of copper, gives a black stain which cannot be removed by wash-ing, and the mineral can thus be distinguished from the phosphatesand arsenates of copper.The analysis gave thefollowing result :-Its sp. gr. is 3.76.SeO. CUO. E20. Total.48.12 35.40 15-30 98.82At the request of Des Cloizeaux, Friedel and Sarasin prepared chal-comenite artificially. They employed for the purpose a neutral solutionof potassium selenide, and to this they added copper sulphate, when awhite smorphous precipitate was formed, which became converted intoa blue crystalline powder. Seen under the microscope this was foundt o be a mass of small rectangular pyramids, which might be rhombicor monoclinic. The analysis gave results corresponding with theformula of chalcomenite. B. H. B.Fergusonite from Brindletown, Burke Co.,’ N. Carolina, ByW. H. SEAMON (C’hem. News, 46, 205).-The crystals are small, oftetragonal habit, reddish-brown, and give a yellow-brown streak.Lustre between vitreous and resinous, brittle, fracture conchoidal.Hardness = 6.Sp. gr. 5.6.Nb,O,. Ta,O,. WO,,SnOs. UrO2. Y203, &c. Ce203. Di2O3,%O3.43.78 4.08 0.76 5.81 37.21 0.66 3-491.81 0.65 1-62FeO. CaO. H2O.Counting the water as basic, the above figures lead to the orthonio-bate formula M”NbO4. E. W. P.Analysis of a Niobate which has been improperly calledEuxenite from Mitchell Co., N. Carolina. By W. H. SEAMOM(Chem. News, 46, 205).-This mineral, formerly described by J. L.Smith, in no way agrees with the mineral of that name from Norway ;it is reddish-brown in colour, with lustre between resinous andadamantine. Hardness = 5.5. Sp.gr. 4.33. Freed from mica andcrust the mineral contains :-Kb205. W03Sn02. Ur02. Y203. Ce203. Di2O3L%O,. FeO. CaO. H,O.47.09 0.40 15.15 13.46 1.40 4.00 7.09 1.53 9.55but very little of any oxide of the erbium or ytterbium class could bedetected by the spectroscope ; the orthoniobate formula is thereforeM”,Nb,O,, in which about one-eighth of the hydrogen of the water iMIXERALOGICAL CHEMISTRY. 33basic, the actiial distribution of the elements being (33”‘ + ++M” + :$M”’ + +8M’”’)Nb20e ; euxenite, besides containing much titanicoxide, is a metaniobate. E. W. P.Rutile, as a Product of the Decomposition of Titanite. ByP. MANN (Jahrb. f. Min., 1882, 2, Briefw., 200-201).-111 somefoyaites from the Serro de Monchique, the titanite (sphene) was com-pletely decomposed, and the author found in the decomposed massnumerous bright yellow crystals which, by the help of the microscope,he proved to consist of rutile.The lime had probably been extracted by the action of water andconverted into carbonate of lime, whilst the titanic acid, mixedperhaps with some amorphous silica, formed the decomposed crust.B.H. B.Artificial Production of a Crystallised Hydrated Silicate.By A. DE SCHULTEN (BUZZ. SOC. Chim. [2], 37, 449--457).-Whenlime-water is added to a concentrated solution of potassium silicateuntil a slight precipitate is formed, and the mixture is then heated i nsealed tubes at 180-200” for 24 hours, the gelatinous mass whichforms on cooling encloses a small quantity of some substance crystnl-lised in prismatic needles.If the tube is heated for several days withoccasional agitation, tthe gelatinous matter gradually disappears, andthe quantity of the crystals increases. By repeated levigation, theplates of silica can be removed, and the prismatic crystals are thenobtained, mixed only with a small quantity of hexagonal plates : thequantity of hexagonal plates increases, and that of the needles dimi-nishes if the lime-water is added in too small quantity ; if, however,too much lime-water is added, no crystals are formed at all. Theprismatic crystals are white, have a Cacreous lustre, melt before theblowpipe, and are decomposed by hydrochloric acid with separationof gelatinous silica which retains the form of the original crystals.They have the composition :-Si02.A1203. CaO. Na20. E20. H,O.64.2 0.7 14-7 3.3 2.2 14.5 = 99.6,which corresponds with the formula (R,,N~,Ca)0,3Si0,,2H20, theratios between K20,Na20 and CaO being 1 : 2 : 10. The soda isderived from the glass tubes, and the presence of alumina is due to t,hepresence of the hexagonal plates, which probably consist of Zezyne,formed by the action of potassium silicate on the aluminous glass.When dried in a water-bath, the crystals lose4to 5 per cent. of water.S o natural zeolite has the composition of these artificial crystals.Okenite consists of calcium silicate, and contains SiO,, 56.60 ; CaO,Examined by polarised light, between crossed nicols, the crystalsexhibit brilliant colours which are extinguished longitudinally.Thegreatest axis of elasticity corresponds with the direction of elongation.If sodium silicate is used instead of potassium silicate, a compoLuldis obtained which has a very similar composition.VOL. XLIV. d26.42; HzO, 16.98.C. H. I(34 ABSTRAUTS OF CHEMICAL PAPERS.Artificial Analcime. By A. DE SCHULTEN (BUZZ. SOC. Chim. [2],37, 448449).-When solutions of sodium silicate and sodium alu-minate are mixed in such proportions that the silica and the aluminaare in the same ratio as in analcime, a suitable quantity of lime-wateradded, and the liquid heated in a closed copper tube at 180" for 18hours, crystals are obtained which have a composition identical withthat of natural analcime. The lime-water simply facilitates crystallisa-tion.If it is not added, isolated crystals are rarely obtained; thecryskals separate out in spherical aggregations with rough surfaces.The crystals are sometimes cubical trapezohedrons, sometimes hexa-hedrons. Apparently the trapezohedrons are formed when the solu-fions are concentrated and strongly alkaline, and the hesahedronsunder the reverse conditions. Unlike the artificial analcime obtainedin glass tubes (Abstr., 1881, p. 25), the crystals have no action onpolarised light, even when a quartz plate cut parallel with the axis isinterposed. The optical properties of natural analcime are similar t othose of crystals of the quadratic system ; the optical properties of theartificial variety previously obtained (Zoc. cit.) are those of the hexa-gonal system.The optical behaviour of the new crystals is identicalwith that of crystals of the cubic system. It is evident therefore, thatthe axes of elasticity of the crystals of analcime undergo slightchanges sufficient to modify their optical properties, but not sufficientto alter the external forms of the crystals from those of the cubicsystem. C. H. B.By SANDBERGER (Jahrb. f. Min., 1882, 2,Briefw., 192-193) .-The author received a crystal of phlogopite,about a pound in weight, from Ontkrio, in Canada. I n it he dis-covered, by means of a lens, numerous colourless crystalline needles,which he proved by analysis to consist of pure titanic acid. This is,without doubt, the best material to illustrate the separating out oftitanic acid from a decomposing mica.Rutile in Phlogopite.B.H. B.Analysis of beautifully Crystallised Albite from Amelia Co.By R. N. MUSGRAVE (Chew. News, 46, 204).-This mineral occurs inmasses of clear colourless flattened crystals, having a hardness = 6 ;sp. gr. = 2.605 ; and a composition of-SiO2. AW,. Na,O. E,O .68.44 19-35 11.67 0.43 = 99.89.E. W. P.Euclase from the Alps. By F. BECKE (Ja,hrb. f. Min., 1882, 2,Ref., 209).-Sinall pale yellow crystals, which proved to be euclase,have been found in the Alps, toget'lier with pericline. The crystalswere about 0.5 mm. long. The following combination is tolerablygeneral : mpm, mF2, mg20, 2gm, cmP, 3gm, -P. Theaccompany-ing minerals are pericline and ankerite as theoldest, also rock crystali n long prisms.The euclase appears to have been formed at the sametinie as the rock crystal, as do also little globules of helminth.B. H. BMINERALOOlCAL CHEMISTRY. 35Occurrence of Minerals at Jordansmuhl, in Silesia. By B.SCHUBERT (Jahvb. f. Min., 1882, 2, Ref., 193--195).-This paperdescribes the following minerals and rocks found in the serpentine bedat Jordansmuhl.Prehnite occurs partly in crystals, partly in crystalline aggregates.It is rose-red, orange-yel_low, or "greenish, rare5 cologrless. - The-fol-lowing faces occui': mPm, mPm, OP, wP, Pm, aPm, SPm, $Pm,P, 2P. The analysis yielded :-Si02. Al,O,. Fe20,. CaO. MgO. H20.4412 26-00 0.61 25.26 traces 4.90approximating to the prehnite formula EI&a4A14Si602, = +(- 2Ca2Si0,.A14S13012White garnet, for which the formula is calculated t o be Ca,A1,Si3012.Chronziunz garnet forms an emerald-green coating over prehnite.Garnet rock, of a white colour, has the following composition :-Si02. Al,O,.Fe,03. CaO. H,O. Total.38.91 24.29 0.70 37.07 0.45 101.42From this the formula of the lime-alumina-garnet may be calculated.A second piece of rock gave-SiO,. A1,0,. CaO. MgO. H20. Total.43.94 21.79 34.19 1.54 0.60 102.06From this is calculated the formula Ca,A12Si301z + SiO,.By the help of the microscope, the rock was proved to consist ofA third rock of a dirty pink colour lime-alumina-garnet and quartz.gave-Si02. &03. Fe20,. CaO. MgO. H,O. Total.36-84 31.53 2.78 25.53 192 2-51 101.11It contained diaspore, and probably some quartz.nation of the forms aP, mPm, P, Pm, OP.cavities of the white garnet rock ; the analysis gave-Vesuvia,n, characterised by its fine blood-red colour and the conibi-It occurs in drusySO2.A1203. Fe203. CaO. MgO. HdO. Total.37.51 21-24 0.69 35.45 2.11 2.77 99.77Diaspore occurs in compact garnet ; analysis gave-A1303. H20.82-66 17.44Natrolite, in drusy cavities of the garnet rock in radiabed apb ogre-gates, in the combination wP, P.d 36 ABSTRACTS OF CHEBIICAL PAPERS.Mangartese-ore.-Pseudomorphs, apparently pyrolusite after calcite,consisting ofMnO2. MnO. SiO2. H20. Fe203. MgO. Total.62.92 4.80 8.00 18.79 2.77 4.41 101-69Quartz Rock.-This rock was ricb in quartz, of a rose-red colour,and occurred in great beds. It gave on analysis :-Si02.A&03. Fe,03. CaO. H20. MgO. Total.69.48 19.21 0.34 10.29 0.34 trace 99.613It probably consists of a mixture of quartz and a lime felspar.02aZ, of a bright green colour, gave on analysis :-SiOP 8120% Fe203. FeO. CaO. MgO. H,O. Total.81.43 4-11 1.04 0.83 8.06 4.65 0.80 100.92SeTentine, containing magnetic iron ore, gave on analysis :-SiO,. A1%03. Fe203. MgO. H20. Total.42.21 9.59 1.40 34.88 13-28 101.36B. H. B.Waltherite from Joachirnsthal. By C. BERTRAND (Jahrb. f.Min., 1882, 2, Ref., 195--197).-Vogl described, under the name ofwaltherite, a mineral from Joachimsthal, occurring in thin prisms ofa brown and green colour. This is now proved to consist of twodistinct minerals. The brown jibrow mineral cleaves easily.It isrhombic; mP = 116". The cleavage is in the direction of OP, mP,and mP&.The green mineral, on the other hand, is not so distinctly fibrous,and does not cleave so easily as the brown. The system could not bedetermined, on account of the smallness of the crystals.The Granites on the Banks of the Sa6ne. By F. GONNARD(Juhrb. f. Xin., 1882, 2, Ref., 199).-During the construction of awater reservoir near Lyons, a bed of pegmatite was laid bare, in whichthe following accessory minerals were found :-Almandine, combinations mO, 202 of 15-20 mm.diameter. The smaller crystals were partly opaque and partly trans-lucent, of a fine red colour, and simple (202).B. H. B.(1.) Garnet.(2.) Small columnar crystals of black tourmaline.(3.) Pinite. Only one crystal was found, 10 mm.long and 4 i mm.(4.) A mineral belonging to the Cordierite group, very similar to(5.) A yellowish-grey mica, of silky lustre, and easily scratcheddiameter, enclosed in the quartz of the pegmatite.the chlorophyllite of Haddam.with the nail ; it appears to be related to sericite. B. H. B.Chemical Composition of Various Layers of a Lava Currentfrom Etna. By L. RICCIARDI (Compt. rend., 94, 1657--1659).-Theresults given in this paper go t o prove that samples of lava taken fromone current at various depths on the same vertical plane differ onlORGAN10 CHEMISTRY. 37in the greater or lesser quantity of protoxide and peroxide of iron theycontain, the quantity of the latter being great'er where the parts havebeen in contact with aqueous vapour or the atmosphere. The lavasbelonging to one and the same eruption, however, if collected atdifferent points, may differ in their chemical and mineralogical compo-sition. R. R.Lithological Determination of the Meteorite of Estherville,Emrnet Go., Iowa (10th May, 1879). By S. MEUNIER (Compt.rend., 94, 1659--1661).-The Emmet meteorite belongs to the typedesignated logronite by the author in 1870. The chief minerals itcontains are olivine, bronzite, peckltanzite (Lawrence Smith), pyrrhotin.e,schreibersite, ferric oxide, and nickeliferous iron.Supposed Meteorite found in Augusta Co., Virginia. ByW. H. SEAMON (Chem. News, 46, 204).-The mass of metallic iron,which weighed 1-25 kilos., and was covered with a crust 13 mm. deep,was at first supposed to be a meteorite, but the analyses show that it isnot so.Pe. Mu. C. S. P. SiO2. Al,O,. CaO. Oandloss.R. R.90.45 G.10 0.13 0.15 0-37 4.18 0.49 2.16 1.91Sp. gr. = 5.76 ; Ni and Co absent ; SiO, soluble in sodium carbonate.Widmanstatt figures not produced by treatment with acids.E. w. P

ISSN:0368-1769    

DOI:10.1039/CA8834400029

出版商:RSC    

年代:1883

数据来源: RSC

摘要:

ORGAN10 CHEMISTRY. 370 r g an i c C hem i s t riy.Action of Ozone on Hydrocarbons. By L. MAQUENXE (Bull.Soc. Chim. [ 21, 3 7, 298-300) .-Coal-gas,. purified by being passedthrough sulphuric acid and potash, is oxidised by ozone, with forma-tion of formic acid, together with small quantities o€ methaldehydeand a substance which reduces cupropotassic tartrate,. probably me-thylenitan. A small quantity of an amber liquid, which sometimesexplodes violently, is also formed ; it is possibly eit'her oxybenzeneor a nitrogen compound. Nitrogen tetroxide also combines readilywith hydrocarbons. A sensible quantity of nitrobenzene is quicklyformed when benzene mixed with sulphuric acid is exposed to theaction of ozonised air. Pure methane is not affected by ozone, but ifa mixture of methane and oxygen is subjected to the silent discharge,formic acid and methaldehyde are formed.These results confirmBerthelot's view of the experiments of MM. Thenard (Compt. rend.,1873). The products obtained by the action of the silent discharge ona mixture of carbonic anhydride and methane are undoubtedly formedby the oxidation of the latter, and the sugar produced is methylenitan,C7Hl4Os. The same substance is formed by the a.ction of hydrogen oncarbonic oxide38 ABSTRACTS OF CHEMICAL PAPERS.These facts possibly explain the formation of carbohydrates inplants. Methane may occupy an intermediate position between thecarbohydrates and the mixture CO + H2, produced in the chlorophyllcells under the influence of light; by simple oxidation, it yieldsmethylene oxides and sugars ; by polymerisation analogous to thatwhich takes place under the influence of the silent discharge, it yieldsthe complex hydrocarbons and various products so common in thevegetable kingdom.C. H. €3.Dissociation of Trichloromethyl Sulphochloride. By E.NOELTING (Bull. SOC. Chinz. [2], 37, 392--394).-Trichlo~omethyl sul-phochloride, CCl,.SO,Cl, was heated in sealed tubes for eight or tenhours a t a temperature between 170" and 200". A t 170" some un-altered compound remains, but at 200" it is completely decomposedinto sulphurous anhydride, carbon tetrachloride, carbon oxychloride,and thionyl chloride, thus : CCl,.S02C1 = CClp + SO, and CC13.S02C1= coc1, + soc1,. C. H. B.Action of Cupric Hydroxide on Sugars.By J. HABERMANNand M. HONIG (Monatsh,. Chem., 3, 651-667).-By the action ofcupric hydroxide in neutral solution on cane-sugar, inverted sugar,grape-sugar, and fruit-sugar, there were obtained in each case car-bonic anhydride, formic acid, glycollic acid, and a mixture of acidswhose uncrystallisable calcium salts gave an amount of calcium inter-mediate between that required for erythroglucic and glyceric acids.I n the experiments made in alkaline solution (with baryta-water) thesame products were observed, but were obtained in shorter time andin increased amount: in one experiment, in which a solut'ion ofgrape-sugar was heated with soda and copper hydroxide, gluconicacid was obtained. Although the products were the same with eachof these sugars, t,here were great differences in the course of the reac-tions. I n the case of cane-sugar, the reduction commenced only aftersome hours' boiling, apparently not until the sugar had been inverted.With inverted sugar, reduction of the copper oxide commenced shortlyafter the boiling point was reached.With grape-sugar in neutralsolution the reduction was rather slow, whilst in alkaline solution itstarted with the iiitroduction of the copper oxide into the warmliquid. With fruit-sugar the reduction was much quicker than withgrape-sugar.I n conclusion, the authors give reasons for doubting the accuracyof the statements of Reichardt (Annulen, 127, 297), that gum andgummic acid, and of Claus (ibid., 147, 114), that tartronic acid areamongst the products of the oxidation of sugar with copper oxide.A.J. G.Conversion of Maltose into Glucose. By S. J. PHILLIPPS(Bied. Centr., 1882, 710) .-Maltose yields glucose under the influenceof ferments ; artificial gastric juice produces no change. Maltoseappears in the intestinal canal after feeding with starchy matters.Maltose appears in the urine if i t has been previously injected into a,vein ; subcut,aneous injection of maltose results in the conversion of ORGANIC CHEMISTRY e 39portion of it into glucose.the mesenteries contains glucose only.Manufacture of Starch-sugar.After feeding with starch, the blood ofBy F. SOXHLET and A. BEHR(Bied. Ceiztr., 1882, 698 ; compare Abstr., 1882, 1274).-From con-centrated grape-syrup at 30-35", Behr has obtained crystallisedanhydrous grape-sugar by the introduction of st crystal of the same.The sweetness of grape- as compared with that of cane-sugar is1 : 1Q.Action of Ammonia on Propaldehyde.By A. WAAGE (Monatsh.Chem., 3, 693-695).-By the action of ammonia gas on propalde-hyde, cooled by a mixture of ice and salt, a small quantity of a solidproduct, C,H,O,NH,, and an oil were obtained. The oil appears tobe a mixture, and on exposure to an atmosphere contaiuing carbonicacid, long colourless tabular crystals separate, of the formulaCl5HZ9N3 (m. p. 74"), soluble in ether and alcohol, but insbluble inwater. What part the carbonic acid plays in the formation of thesecrystals could not be ascertained.By heating the crude product of this reaction for some days a t200" in sealed tubes, a dark-brown liquid is obtained ; and when thisis distilled, and the fraction 170-210" dissolved in hydrochloric acid,separated fkom resinous and oily matters, and distilled with potash,a colourless base, C9HI3N, is obtained, boiling at 193-195" (corr.),probably parvoline.A. J. G.r-Diethylbutyrolactone. By A. ENMERT and R. FRIEDRICH (Ber.,15, 1851--1852).--From succinic chloride and zinc-ethyl, Wischin(dnndew, 143, 262) obtained ethylene diethyl diketone, which decom-posed on distillation. On repeating his experiments, a body of acidreaction was obtained which boiled at 230-235" without decom-position, and on analysis gave numbers corresponding with a mixtureof nearly equal parts of ydiethylbutyrolactone and ydiethyloxy-butyric acid.The latter was converted into the lactone by standingover solid potassium carbonate ; the liquid then boiled a t 228-2:%3".The barium and calcium salts were prepared, both soluble in alcoholand in water.On attempting to convert the acid into lactone by means of phos-phoric anhydride, a hydrocarbon (C8H1I)% distilled over at 270".E. W. P.E. W. P.J. K. C .Bees' Wax. By E. ZATZEK (Monatsh. Chern., 3, 677-679).-Schalfeef has stated (this Jouriial, 1877, i, 454) that Brodie's ceroticacid is in reality a mixture of acids, into which it may be resolved byfractional precipitation with lead acetate. The author has repeatedthese experiments, but entirely fails to confirm Schalfeef's results.The first fraction which, according to Schalfeef, should contain anacid C3&HS8O2, gave nnmbers perfectly agreeing with those required for(:erotic acid (C27H5402).By 14.CHANLAROFF (Ber., 15, 1987-1989) .-On heating these substancesA.J. G.Action of Thiacetic Acid on Ethyl Thiocyanate40 ABSTRACTS OF CHEMICAL PAPERS.together for 10-1 5 minutes, they combine, forming ethy lic acety ldz'thio-cnrbamnte, CS( SEt) .NHrc ; it crystallises in brilliant yellow needles,melt,ing at 122-123", and is readily soluble in alcohol, ether, and hotvater. On being heated, it decomposes into its original constituents.When boiled with baryta-water, it yields mercaptan and barium thio-cyanate and acetate; with dilute hydrochloric acid, it gives ethylicdithiocarbamate, mercaptan, carbon oxysulphide, acetic acid, andammonium chloride.A. J. G.Azaurolic Acids. By V. MEPER and E. J. CONSTAM (Annalen,214, 328-353).-The ethylnitrolic acid used in the preparation ofethylazaurolic acid is best obtained by the following process :-6 C.C.nitroethane are brought into a vessel containing small pieces of ice,25 C.C. of potash solution (= 6.7 grams KOH) are added, and the mix-ture is shaken until the nitroethane is dissolved. The liquid, havingbeen tra.nsferred to a beaker containing ice, is mixed with 15 C.C. ofsodium nitrite solution (15 C.C. = 8 grams NaN02). Dilute sulphnricacid is now added until the red colour of the mixture changes to paleyellow, when the solution is rendered alkaline by the addition ofrotash.The liquid is three times alternately acidified and made alka-line. It is finally acidified with sulphuric acid, and three times ex-tracted with one-sixth of its volume of ether. The nitrolic acid isdeposited on evaporating the ether.I n order to prepare ethylazaurolic ctcid, 45 grams of 5 per cent.sodium amalgam are added to 2 grams of ethylnitrolic acid, suspendedin 10 C.C. of water. The vessel in which the operatiou is conducted issurrounded by ice and salt, so as to keep the temperature about zero.The alkaline liquid is separated from the metallic mercury and acidifiedwii h dilute snlphuric acid, whereupon ethylazaurolic acid is depositedin needle-shaped crystals, which are purified by recrystallisation fromboiling alcohol.The pure acid forms orange-coloured prisms, sparinglysoluble in water and in ether. It melts a t 142" with detonation, formingleucazone, nitrous oxide, and water. On oxidation with chromic acidmixture, it is converted into acetic and carbonic acids. An ammo-niacal solution of ethylazaurolic acid gives a brown precipitate withsilver nitrate, and yellow precipitates with lead and zinc salts. Ethyl-azaurolic acid is decomposed by warm dilute hydrochloric acid intoethylleucazone and hydroxylamine : to separate these bodies, thehydrochlorides are converted into sulphates by treatment with silversulphate, and on addiag a large quantity of alcohol to a cold concen-trated aqueous solution of the sulphates, hydroxyiamine sulphate isprecipitated, and on evaporating the alcoholic filtrate, ethylleucazonesiilphate is deposited in colourless prisms, melting a t 161.5".Bydouble decomposition with bnryta-water, the sulphate is convertedinto the free base C4K,N30, which crystallises in white needles, meltinga t 158", and soluble in alcohol and in water. The aqueous solutiongives a reddish-brown coloration with ferric chloride. The bariumsalt, (C4H6N,0)2Ba, is a colourless hygroscopic powder. On theaddition of silver nitrate to a solution of leucazone, leucazone silvernitrate, C4H7NS0,AgN03, is deposited as a white crystalline preci-pitate. Ethylleucazone is also produced by the action of stronORGANIC CHEXISTE1Y. 41ammonia or of sodium amalgam on ethyl azaurolic acid.Theconstitution of azaurolic acid may perhaps be represented byCMe(N0) : N.NE.CMe(NOH), or more probably by the formulaCHMe(NO).N : N.CHMe.NO.Propylazaurolic m i d , CsH6N20, prepared from propylnitrolic acid,forms pink crystals, soluble in ether and in alcohol. It melts at 127.5"to a colourless liquid, which does not solidify on cooling.iKethyZa.zauroZic acid has not yet been obtained in the pure state. w. c. w.Acetoacetic Acids. By M. CERESOLE (Ber., 15, 18'71-1878).--These acids were isolated by saponification with potash, and treatmentwikh sulphuric acid. The ethyl salt of the acid required is shaken upwith a slight excess of a 24 per cent. aqueous solution of potash untilthe ether is dissolved. The mixture is then left for 24 hours in thecold, acidified with sulphuric acid, and shaken with ether.Theethereal solution is carefully evaporated and the mixture of the newacid and unchanged salt treated with barium carbonate and water, theacid going into solution as barium salt, whilst the unaltered ethyl saltis removed by ether. The free acid is obtained from the barium saltby treatment with sulphuric acid, shaking with ether, evaporatingthe ethereal solution, and drying over sulphuric acid.Acetoacetic Acid.-The free acid is a hygroscopic and very acidliquid, miscible with water in all proportions, and decomposing rapidlybelow 100" into carbonic anhydride and acetone. The silver andcopper salts are less stable than the barium salt, which is very deli-quescent, but stable in dilute solutious ; on evaporation, i t undergoespartial decomposition into acetone, barium carbonate, and carbonicacid ; on boiling its aqueous solution, it was found that 1 molecule ofcarbonic anhydride was given off for each molecule of barium carbo-nate thrown down, The dried barium salt was analysed volumetricallywith satisfactory results, the admixed barium carbonate being esti-mated and allowed for.By dry distillation, it yields barium carbonateand acetone.Moxometliy lacetoacetic acid, prepared in the same way as acetoaceticacid, is a viscid liquid of similar properties. On boiling, i t decom-poses into carbonic anhydride and ethyl methyl ketone. The bariumsalt is very soluble, and gives no precipitate with silver nitrate ; bydry distillation it yields ethyl methyl ketone.Nitrous acid convertsthe acid into nitrosomethyl acetone, melting a t 74".Dimethy Zacetoacetic acid, dried over sulphuric acid, forms colourlesscrystals of agreeably acid smell, which are however undergoing con-tinual decomposition, and deliquesce a t once in the air. The bariumsalt can also be obtained crystalline, and possesses similar propertiesto those of the other two acids. On dry distillation, it yields the cor-responding ketone.Benaylacetoacetic acid is an acid and aromatic oil, sparingly solublein water, and easily decomposable. Its barium salt is soluble, but notdeliquescent, an d yields benzyl acetone on dry distillation. Concen-trated solutions give a precipitate with silver nitrate. With nitrousacid, nitrosobenzyl-acetone was obtained in white needles melting a42 ABSTRACTS OF CBEMICAL PAPERS.80-81". The barium salts of all the acetoacetic acids give violet orbrown colorations with ferric chloride.The above acids were obtained from the corresponding ethyl salts bysaponification, without any separation of ketone or acid. Their mostprominent characteristic is their instability, and in this they agreewith other ketone acids in which the carbonyl and carboxyl groups areonly separated by one methylene or substituted methylene.Where,however, separation is effected by several methylene groups or by anaromatic residue, the ketone acids appear to be stable, as in the caseof la3vulic or benzoylbenzoic acids.Formation of Saccharin and Lactic Acid from Sugars.ByL. CUISINIER and H. KILIANI (Bied. Centr., 1862, 703--705).-1fmaltose is treated with lime, a solution is obtained which after con-centration yields coloured crystals of the composition C12H20010Ca0 +H20 (14.07 per cent. CaO). This salt has been termed maltate of lime,and is soluble in 100 parts hot water; from it, oxalic acid separates" maltic " acid, C6H100j, which melts a t 95" and resembles saccharin ;a 10 per cent. solution of the crystals has a dextrorotatory power of[a]= = + 63", which is reduced by dilute acids, but raised t o + 73.3"by concentrated acetic acid. I\ilaltic acid is readily soluble in water,glycerol, methyl, and ethyl alcohol, reduces alkaline copper solutions,and does not ferment. The s&lts are laevorotatory, and so is the freeacid when first separated, but after being kept, and more rapidly whenheated with an acid, it changes into a dextrorotatory modification ; itis therefore analogous to saccharin, and the name maltosaccknrin isproposed for1 it, in contradistinction to glucosaccharin.Maltate of lime has also been obtained from lactose.In anothercommunization, it is stated that glucose loses its rotatory power whenin contact with alkalis in the cold, but not its reducing action oncopper solutions j in the presence of alkalis, oxygen is absorbed frornthe air.Kiliani prepares lactic acid from inverted sugar by the followinqprocess: 500 grams of cane-sugar are heated for t,hree hours at 50'in a stoppered flask with 250 C.C.water and 10 of acid (3 partsH,SO, with 4 parts H,O) ; after cooling, 400 C.C. of soda solution(1 NaHO in 1 H,O) are added in small portions, the whole being keptcool, but afterwards the mixture is to be heated to 70" until it onlycolours Fehling's solution green, then sulphuric acid is added in quan-tity equivalent to the soda present, and the freed lactic acid is sepa-rated by 93 per cent. alcohol, and converted into the zinc salt. Saccharinis also formed at. the same time; it is converted by silver oxide andwater into glycollic acid, together with a small quantity of formic andEtcetic acids. E. W. P.J. K. C.pi-Hydroxybutyric Acid. By J. FR~~HLING (Monatsh. Chem., 3,696-704).-Trimethylene glycol (100 parts) mas heated with hydro-bromic acid (70 parts) a t 100" for five hours.The resulting trimethylenehromhydrin, CH,Br. CH,.CH,.OH, forms a colourless liquid distillingbetween 98" and 112" under a pressure of 185" mm. Its sp. gr. at20" is 1.5374. On treatment with potassium cyanide, it gives thORGANIC CHEMISTRT. 43corresponding cyanhydrin, which by the action of moderately concen-trated hydrochloric acid or of potash is converted into yhydroxybutyricw i d , thus completely confirming Saytzeff's formula,CH,(OH) .CH,.COOH,for this acid. A. J. G.Purification of Carbon Bisulphide. By E. OHACH (J. pr. Chem.[2], 26, 281--307).-The author finds that potassium permanganateis without action on pure carbon bisulphide or on the odorous im-purities present in the commercial article, hydric sulphide excepted.Under the influence of daylight the pure bisulphide however yieldssome sulphuretted hydrogen, which is oxidised by permanganate, freesulphur passing into solution.I n the case of impure bisulphide, treat-ment with permanganate causes a rise in the amount of dissolved solidmatters, chiefly sulphur.Effectual purification is obtained by first filtering the bisulphidethrough a dry paper filter to separate water and dirt, distilling fromcalcined lime, treatment of the distillate with about 5 grams per litreof dry powdered permanganate, then with metallic. mercury until allfree sulphur has combined, and lastly with mercuric sulphate. Thebisulphide is then redistilled from calcium chloride, and must be keptin the dark.0. H.Physical Properties of Carbon Oxysulphide. By ILOSVAY( B u l l , Xoc. Cl~irn. [ a ] , 37, 294--296).-Carbon oxysulphide can befreed from carbon bisulphide by passing the gas over a column ofwood charcoal. The mean coefficient of expansion of the gas between0" and 100" at constant volume is 0.0037317 ; at constant pressure,0.003i908. The pressure necessary to liquefy the gas a t differenttemperatures is given in the following table. The critical point is105".Temperature : 0" 3.8" l0.Y 12.0" 17.0" 39.8' 41.2" 630' 69.0" 746" 85.0".Press. in atmos. : 12.5 15.0 1'7.5 19.6 21.5 44.0 45.0 59.0 65.0 '74'0 80.Liquid carbon oxysulphide is colourless, mobile, and highly refrac-tive. It dissolves sulphur, and mixes with alcohol or ether, but notwith water or glycerol.If the pressure is suddenly released, solidflakes are deposited, and persist for some time. These experimentsshow that the physical and chemical properties of carbon oxysulphideare intermediate between those of carbon bisulphide and carbondioxide, and also afford further evidence that the coefficient ofexpansion of an easily liquefiable gas is greater than that of a gasdifficult to liquefy.Carbon oxysulphide, mixed however with mercaptan, carbondioxide, hydrogen sulphide, &c., can be obtained by the action ofsulphuric acid on potassium ethyl-thiocarbonate, C0,SKEt.C. H. B.Dibromosuccinic Acid and Diamidosuccinic Acid. By A.CLAUS (Ber., 15, 1844-1851) .-In t,he preparation of diethyl dibro-mosuccinate by Kekul6's method, after separation of the etherea44 ABSTRACTS OF CHEMICAL PAPERS.salt by adding water and evaporating the solution, a crystalline sub-stance is left, which is the monoethylic salt of dibromo-succinic acid(m.p. 275'). Potassium and sodium ethyl-dibromosuccinates wereformed by mixing alcoholic solutions of the alkalis with the acid, ascrystalline groups, easily soluble in water: the silver salt is a whitecrystalline precipitate. With ammonia, the ammonium salt of di-bromosuccinamic acid is obtained, but an attempt to isolate the acidfailed. Methyldibromosuccinic acid is prepared in the same way asthe ethyl compound. Its sodium and ethyl salts (m. p. 62.5") wereobtained in the usual way.When ethyl dibromosuccinate is treated with sodium and ethylbromide, only diethyl and black products are obtained ; if, however,the sodium is replaced by zinc, the ethyl bromide is not attacked, anddistils over unchanged, while one or two atoms of zinc enter into com-bination with the acid, without removing the bromine, and syrupyliquids are formed containing varying percentages of zinc.Heatedwith ethyl bromide in sealed tubes at above 150", fumaric acid andzinc bromide are the chief products.According to Lehrfeld, the amide of ethyl imidosuccinate is formedby the action of ammonia gas on an alcoholic solution of ethyl dibro-mosuccinate. The author, however, on repeating tho experimezltcould obtain nothing beyond ethyl diamidosuccinate. Lindner, bytreating free dibromosuccinic acid with ammonia, claims to have pre-pared the diamido-acid, which he states is insoluble in water, alcohol,and ether.This body the author was also unable to prepare, and heis of the opinion that Lindner worked with impure materials, andthat the body he describes was perhaps produced from the glass ofthe sealed tube.As regards bromamidosuccinic acid, traces of the diamido-acid arealways formed, whether excess of ammonia or of dibromosuccinic acidbe present. The pure acid can only be obtained by fractional precipi-tation of the silver salt, the middle fractions consisting of pure silverbromamidosuccinate. J. K. C.Geometrical Formulae of Maleic and Fumaric Acids deducedfrom their Products of Oxidation. By J. A. LE BEL (Bull. XOC.Chim.[ 21, 37, 300-302).-By oxidation, fumaric acid yields racemicacid, and maleic acid yields mesotartaric acid. The only suppositionwhich agrees with these and other known properties of the two acidsis that the four hydrogen-atoms are in the same plane as the carbon-atoms and form a rectangle. I n maleic acid, the rectangle is symme-trical about a plane perpendicular to the rectangle and bisecting it.The COOH-groups are a t opposite ends of one side of the rectangle,and the H-atoms at opposite ends of the other side. I n fumaric acid,the rectangle is symmetrical about its central point, the COOH-groupsbeing one a t each end of one diagonal, and the H-atoms one a t eachend of the other diagonal. It follows from these structures thatmaleic acid can yield only mesotartaric acid, whilst fumaric acid canyield only racemic acid.C. H. B.Ethylic Methenyltricarboxylate and Ethylic AcetomalonateORGANIC C€EMISTRY. 45By M. CONRAD and M. GUTHZEIT (Annalen, 214, 31--38).-Eth?jZicrnethenyltrica.rboxylate, CH( COOEt),, prepared by warming a mixtureof ethyl chlorocarbonate, benzene, and e thy1 sodium malonate, crys-tallises in needles or prisms which melt at 29", and boil a t 253". Itssp. gr. at 19" is 1.10 compared with water a t 15". The crystals aresoluble in ether and alcohol. On saponification, i t yields malonic acid.Methenyltricarboxylic acid could not be isolated.Ethylic acetowtalonate described by Ehrlich (Ber., 7,892) decomposeson saponification, forming alcohol, acetone, carbonic and acetic acids.w. c. w.Ethylic Ethenyltricarboxylate. By C. A. BISCHOFF (Annalen,214, 38-44) .-The preparation of the ethylic salt of ethenyltricar-boxylic acid has been described by Pull (Ber., 14, 752). This com-pound is a colourless liquid (b. p. 278") soluble in alcohol and ether.I t s sp. gr. at 17" is 1.1089 compared with water a t 15". It is readilysaponified by a solution of soda, and on decomposing the sodium salt,ethenyltricarboxylic acid, COOH.CHz.CH(COOH), is obtained in pris-matic crystals soluble in alcohol, ether, and water.The acid melts at 159", decomposing into carbonic and succinicacids. Barium tri-ethenylcarboxylate crystallises in white prismssparingly soluble in hot water. The zinc salt contains 2 mols. HzO.It is less soluble in hot than in cold water.w. c. w.Ethylic Monochlorethenyltricarboxglate. By C. A. BTSCHOFF(AnnuZen., 214,44- 53) .-When a current of chlorine is passed throughwarm ethylic ethenyltricarboxylate, the monochlorinated derivative,CC1( COO E t). CH,.COOEt,is produced. This substance is purified by distillation under reducedpressure. It boils at 205-215" under 160 mm. pressure. Continuedboiling with dilute hydrochloric acid splits up the ethereal salt intocarbonic and fumaric acids. On saponification with an aqueous solu-tion of potash, it yields malic acid (m. p. 130-135"), which appears tobe identical with the malic acid which Loydl ( d i d . , 192, 80) obtainedfrom fumaric acid. Treatment with alcoholic potash converts ethylicmonochlorethenyltricarboxylate into ethoxyethenyltricarboxylic acid. w.c. w.Ethereal Salts of Propenyltricarboxylic Acid. By C. A.BISCHOFF (Annalen, 214, 53-58) .-Eth ylic propeny ltricarboxylate,CHMe(CO0Et) .CH(COOEt),, prepared by the action of ethyl a-bro-mnpropionate on an alcoholic solution of the sodium compound ofethyl malonate, is a colourless oil (b. p. 270") miscible with alcoholand ether. Its sp. gr. at 16" is 1.092. Diethylir, monomethyl propenyl-tricarboxy lat e, C 0 OE t. CH (CO OE t) . CHMe. CO OMe, is obtained whenmethylic a-chloropropionate is substituted for ethyl bromopropionatein the above reaction. This liquid boils at 267". It is soluble in alcoholand ether. Its sp. gr. is 1.079 at 15" compared with water at 4".Yropenyltricarbo~~lic acid melts at 146", splitting up into carbonic andpyrotartaric acids and alcohol.The barium salt, Ba,(C6H,0,), issparingly soluble in water. w. c. w46 ABSTRACTS OF CHEMICAL PAPERS.Ethylic Propyl- and Isopropyl-ethenyltricarboxylates. ByG. WALTZ (Armalen, 214, 58-61) .-Ethylic propzJlethenyltricarboxy7-ate, CPr( COOEt),.CH2.COOEt, prepared by the action of sodiumethylate and propyl iodide on ethylic ethenyltricarboxylate, is acolourless oil miscible with ether and alcohol. J t boils a t 280" withpartial decomposition. The free acid,C Pr (C 0 OH) 2. CH,. c) 0 0 H,forms lustrous needles (m. p. 148') soluble in water, ether, andalcohol. A solution of ammonium propylethenyl tricarboxylate gives acrystalline precipitate with barium, silver, and lead salts.Zinc, cal-cium, iron, and copper are precipitated from hot solutions. The acidbegins to decompose at its melting point, yielding carbonic, propyl-succinic, and traces of butyric acids.Theneutral solution gives a white crystalline precipitate with silver andlead salts.Ethylic iso~ropylet?~e~zylt,.ical.boz?/Znte was not obtained in a state ofpurity. The impure compound decomposes a t 180" forming isopropyl-Its sp. gr. a t 13" = 1.052.Propylsuccinic acid, CHPr(COOH).CH,.COOH, melts a t 91".succinic acid (m. p. 114"). w. c. w.Ethylic Isallylenetetracarboxylate. By C. A. BISCHOFF(Annalen, 214, 61-67) .-The preparation and properties of isallylene-tetracarboxylic acid, (COOH.CH,),C(COOH),, and of its ethyl salthave already been described by the author (Abstr., 1881, 156).Thefollowing salts were prepared :-C,TI,Ag40,, somewhat soluble in hotwater: C,H,Pb,Os + H,O and C7H,,Zn208 are crystalline salts. Tbetricurbullyllic acid, obtained by heating issllylenetetracarboxylic acid,is identical with the acid described by Miehle (Annalen, 190, 325). w. c. w.By M. CONRAD and C, Tetrethylic Acetylenetetracarboxylate.A. BISCHOFF (AnnaZen, 214, 68-72).-The ethereal salt,(COOE t),CH. CH( COOE t) 2,formed by the action of ethyl monochloromalonate on ethyl sodiummalonate, crystallises in needles (m. p. 76") soluble in alcohol, ether,and benzene. It boils at 303" with partial decomposition. Whenheated with hydrochloric acid or with alkalis, it splits up into alcohol,carbonic and ethen yltricarboxylic acids.w. c. w.Diethylic Acetylenetetracarboxylate. By M. GUTHZEIT (A%-nalen, 214, 72-75) .-When an alcoholic solution of tetrethylicacetylenetetraca,rboxylate is treated with potash a t 0", the diethyl salt,COOEt.CH(COOH).CH(COOH).COOEt + +H,O,is deposited. This substance forms deliquescent plates soluble inalcohol and ether. It melts a t 132" with decomposition, and at 180"it splits up into carbonic and succinic anhydrides and ethyl succinate.By IT. CONRAD and If.GUTH ZEIT (Amalen, 2 14, 76 -80) .-Te tre thylic dicarbonte tracar-w. c. w.Tetrethylic DicarbontetracarboxylateORGANIC CHEMISTRY. 47boxylate, (COOEt),C : C (COOEt),, prepared by warming an alcoholics~lutiori of sodium ethylate with ethyl chloromalonate, crystallises inmonoclinic plates soluble in ether and in boiling alcohol.It melts at58" and boils at 325-328" with partial decomposition. On saponifyingit with potash solution, the potassium salt, C6H2O8K3, is obtained inmonoclinic prisms, The lead, zinc, and calcium (C608Ca2 + 7H,O)salts are crystalline ; the silver salt, Ag4CsOe, explodes when heated.The free acid is an unstable compound.Action of Potassium Nitrite on Mucobrornic Acid. By H.B. HILL and C. R. SANGER (Ber., l5,1906--1910).-The reaction tookplace in alcoholic solution ; on gently warming it, carbonic anhydridewas given off, and a reddish-yellow potassium salt, K2C3HN307, sepa-rated out in small flat needles. This salt is easily soluble in cold water,sparingly in dilute alcohol.When dry, it explodes on warming orwhen struck, also on moistening it with concentrated mineral acids, Itis decomposed by water at 40", but can be crystallised unchanged fromdilute potash. When heated with strong potash, a new and very un-stable compound is obtained, the composition of which has not yet beendetermined. By the action of bromine on KzC3HN307 suspended incarbon bisulphide, the compound C3HBr,N,0, was produced. It c r ptallises like ammonium chloride, and is easily soluble in carbon bisul-phide, sparingly in cold chloroform. On heating K,C3HN30, withwater or dilute alcohol to 40-60", an evolution of carbonic anhydride,hydrocyanic acid, and nitrous acid takes place, and, on evaporatingthe solution, crystals of the composition KC3H2N04,H20 were ob-tained which lost their water over sulphuric acid.This salt explodeson heating.From sodium nitrite and mucobromic acid, the corresponding sodiumsalt, NazC3HN307, could not be obtained, but, on heating the solutionto 40--CiO0, the compound NaC3H,N04,H,0 was formed and crystal-lised out on cooling. The calcium salt, Ca( C3H,NO4),,4H,O, crystal-lises in sparingly soluble prisms. Salts of barium, lead, copper, andsilver have also been prepared. Attempts to prepare the free acidhave as yet been unsuccessfnl.The action of potassium nitrite on ethyl mucobromate was found todiffer from its action on the free acid, a compound of the formulaAlkylthiosulphuric Acids. By W. SPRING and E. LEGROS (Ber.,15, 1938-1940) .--The sodium salts of ethyl- and methyl-thiosul-phuric acids, prepared by digesting equivalent quantities of' the alco-holic iodides with sodium thiosulphate, have already been described(Ber., 7, 646 and 1162; also Ber., 15, 946).The authors have con-tinued their experiments, and have succeeded in preparing sodiumsalts of propyl-, primary isobutyl-, and amyl-thiosnlphuric acids. Allthree crystallise well, and are soluble in water and in alcohol. Whendecomposed, they yield disulphides of the radicles, sodium sulphateand sulphurous anhydride. Attempts to make alkylthiosulphates con-taining other radicles have been unsuccessful. With allyl and iso-propyl iodides, the authors obtained allyl and isopropyl bisulphides,It decomposes below 100".w. c. w.It is easily soluble in water, sparingly in alcohol.KC6H6llu'O6 being formed. a. K. M48 ABSTRACTS OF CHEMICAL PAPERS.together with sodium suiphate and sulphurous acid. Chloroform,ethylidene dichloride, and some other similarly constituted bodies alsoyielded negative results.The conclusions drawn by the authors are that the only alkyl-thiosulphates which can exist are those in which the nlkyl-group isprimary and saturated, and that they are the more easily formed thesimpler the organic radicle. It also seems that compounds do notexist in which more than one S,O,Na group is joined to one carbon-atom.Propyl bisulphide, ( C3H7),S2 (normal and iso-) , bntyl bisulphide,(CaH,),S2, and amyl bisulphidc, (C5Hll)2S2, which were obtained incourse of the research, are liquids having the characteristic odourand other properties belonging to this class of compounds.Action of Phosphorus Pentachloride on Acid Amides.Part 11.By 0. WALLACH (Annalen, 214, 193--327).-Action of Phos-phorus Pentachloride on the Amides of Monobasic Acids in which oneHydrogen-atom of the NH, group has been replaced by a HydrocarbonRadicle.-The imidochloride, CMeCl : NC6H4Me, obtained by the actionof phosphorus pentachloride on acetoparatoluidide, and the amines de-rived from this compound, have already been described (this Journal,1877, i, 91). Analogous products can be prepared from acetortho-toluide. On carefully heating the imidochloride obtained in this way,a base, C,,H,ClN, (m. p. 52"), is formed.Orthotolylacetnmidie,NHC7H7.CMe : NC7H7, melts a t 69" ; the corresponding para-com-pound melts at 120", and the mixed orthopars-amidine melts a t 142".The imidochloride of benzoylbenzyl sulphamide, CPhCl : NS02Ph(Abstr., 1878, 669) melts a t 80°, and a t a higher temperature decom-poses into benzonitrile and benzenesulphonic chloride, instead of yield-ing a new base. By the action of aniline on the chloride, phenybdplao-phenyl benzamidine, NHPh.CPh NS02Ph, is produced. This amidinecrystallises in plates (m. p. 139"), soluble in alcohol and benzene. Ondistillation it decomposes into diphenylamine, benzonitrile, and phenylsulphide.To ly bu~ho~henylbei~znmidiize, C6H4Me.NH. CPh : NS02Ph, formsmonoclinic crystals (m. p. 145"), soluble in alcohol and benzene.Ondistillation, tolylphenylamine is produced.Benzeneszdphodiphenylamine, PhS02.NPh2, prepared by heating amixture of benzene sulphochloride and diphenylamine at ZOO", crystal-lises in silky needles (m. p. 1 2 4 O ) , soluble in alcohol, ether, and ben-zene. Benzene sulphanilide, PhS02.NHPh, €orms octahedra, whichmelt at 102". It is completely decomposed by heating a t 220" withlead dioxide.The products of the action of phosphorus pentachloride on mono-and tri-chloracetanilide, and on mono-, di-, and tri-chloracetethyl-nmide, have been previously described by Kamenski (Abstr., 1880.The amidine, C4H30.C(NHEt) : NEt, prepared by distilling ethyl-amine pyromucamide, C,H,O.CONHEt, with phosphorus penta-chloride (Abstr., 1881, 714), boils a t 240".It forms a crystallineplatinochloride. When phosphorus pentachloride and formanilide areA. K. M.54.7)ORGANIC CHEXIISTRY. 49brought together, carbonic oxide and hydrochloric acid are evolved,leaving a mixture of phosphorus oxychloride and diphenyl-formami-dine, NHPh.CH : NPh, melting at 137".II. Action of Phosphorus Pentachloride o n those Amides of Mono-basic Acids ~ V L which the Hydrogen of t h e NH,-group has beelk cona-p l e t d y replaced by ITydrocarbon Ihdicles.--No new bases were obtainedby treating acetodidhylamide, MeCONEt, (b. p. '185") or diphenylbcnzamide, PhCONPh, (m. p. 176") with phosphorus pentachloride.Diphen,ylacetamide, MeCONPh, (m. p. lolo), yields a base which wasnot obtained in a state of purity.MeCONMePh,a base is derived which probably has the composition C,,H,,C1N2.Acetopiperidide when treated with phosphorus pentachloride yiddsthe chloride CMeC12.NC5Hlo.The following reaction takes place whenphosphorus pentachloride acts on diethylformamide :-From acetometkyZanilide,HCONEt, + PCI, = POCI, + CHCl,.NEt,, and2CHCl,.NEt, = C,,H,,CNZ + 3HC1.111. Action of Phosphorii 8 Pentachloride onl the A m i d e s of DibasicAcids.-CCanz~horet72ylimidet~yli~~aid~n~, C14H21N20, prepared by heatinget hylsmine camphorde with phosphorus pentachloride (Abstr., 1881,284), is decomposed 'by 'hydrochloric acid a t 200" into ethylaminehydrochloride and camphoric ethylimide.This decomposition may be represented by-co + H,O = C,H,d<CO>NEt + NH,Et.CSH1d.C : NEtI 1CO--NEtCamphor ethylimidethylimidine can be prepared synthetically bytreating the product of the action of phosphoric chloride on cam-phor ethylimide with ethylamine (Abstr., 1881, 28s).IV.Action of Phosphorus Pentachloride oic the Amides of OxnlicAcid.-An account of the substituted oxamides and formamides hasbeen previously published {Ber., 14, 735-751 ; this Journal, Abstr.,1881, 717). Chloroxalethyline and many of its derivatives have alsobeen described (Abstr., 1880, 546-547). By the action of bromineon a solution of chloroxalethyline in chloroform, cl~loroxaZethy linehydrobronzide, c6H,C1N2,HBr, and dibrol-nide, C6H9ClN,,Br2, are pro-duced. The crystals of the hydrobromide are colourless; those ofthe dibromide have a deep red colour.A mixture of bromoclz7or-ozalethy liiie hydrobyomide, C6H8C1BrN2,HBr, and bronaocl~loroxalethyli~aedibronzide, C6H8ClBrN2,Br,, is formed when bromine acts on a solutionof chloroxalethyline dibromide in chloroform. Bromochloroxalethylinedibromide crystallises in red needles or prisms melting at 113". It issoluble in alcohol and ether, and sparingly soluble in chloroform. Thehydrobromide forms bright red monoclinic prisms (m. p. 133"), whichdissolve freely in chloroform. Both the hydrobromide and the dibro-mide are decomposed by hot water, yielding 6 i - ~ ~ z o c l ~ l o r o ~ a l e t l ~ ~ ~ l i ~ C6H8BrC1N2. From this solution, the flee base is obtained by addingVOL. XLIV. 50 ABSTRACTS OF CHEMICAL PAPERS.an alkali to the solution, and extracting the mixture with chloroform.On evaporating the extract, the base remains as an oily liquid, whichslowly solidifies to a crystalline mass.CeH,BrCIN2,HCl,and the nitrate form prisms containing water of crystallisation.ylatir~ochZoride, (C6HBBrCl~,,HCl),,Pt~~~, and the silver saZt,can be recrystallised from alcohol.Chloroxalethyline is decomposed by dilute sulphixric acid a t 240°,with formation of ammonia and ethylamine.On oxidation withchromic acid, ethyloxamide, oxnlic and (probably) ethyloxamic acidsare produced. When a mixture of chloroxalethyline and lime is dis-tilled, pyrroline, ammonium chloride, and para-oxrcZmethy Zine, C,H,N2,are formed.DioxaZetly Zin e, ClzHl9N4, qrepared by the action of sodium on chlor-oxalethyline, is an oily liquid which boils above 300".On distilla-tion with lime, oxalethyline yields pyrroline, hydrocpanic acid, para-oxalmethyline, and animonium chloride. When oxalethyline isheated with dilute sulphuric acid a t 240", it yields ethylamine, andon oxidation with potassium permanganate it splits up into ammonia,acetic and oxalic acids.The derivatives of oxalmethyline and propyline have been pre-viously described (Abstr., 1881, 572).Chloroxalanzyliiie, C12HzlC1N2, prepared by the action of phosphoricchloride on di-amyloxaniide (m. p. l28"), is a liquid boiling a t 267-270". The hydrochloride and platino-chloride are crystalline.Oxalmethyline has been shown to be identical with methy Z-g ZyoaaZine,NH : C<C,">N (Abstr., 1882, SZl), but oxalethyline and oxalpropy-line are not iden tical with propyl- and amyl-glyoxalines.The hydrcchZoricZe,The( CeH, B rCl'N2) 2, AgN03,This base crystallises in silky needles, melting at, 136".It is not miscible with water.CHThe constitutional formulE of these two oxalines is either-CH,.CH, CHMe\---C@ - CH/C H,.CH, CMe,CH : N'NH: C/ \N or NH:C( \N\- CHfl'WH~ or NH:C/ \N. NH: C<w. c. w.Mannitine, a New Alkaloid obtained from Mannitol: By S.FCICHILONE and A. I~ENARO (Gnzzefta, 12, 416-424) .-This base,C6HRKz, is formed by distilling mannite with ammonium chloride, thereaction, which takes place according to the equation, CsH,(OH), +2(NH3,HCl) = 2HC1 + 6H,O + C6H8N2, being analogous to that ofsal-ammoniac on ethyl alcohol, by which Berthelot obtained et>h;pl-amine (-47172.ClLim. Plrys. [ 3 ] , 38, 63), and to that of the samesalt on glycerol, by which Etard obtained glycoline, C,,H,oNORGANIC CHEJIISTRY. 51(Abstr., 1881, 708). The distillate is a red-br<)wn liquid, having astrong but pleasant odour, and containing a few drops of oil, thequantity of which is increased on adding strong potash-ley ; and onagitating the liquid several times with ether, separating the etherealsolution by a tap-funnel, and distilling it, the mannitine remains inthe form of a brown strong-smelling oil soluble in hydrochloric acid,and precipitated therefrom by potash. It was purified by cmvertin?it into hydrochloride, and decomposing that salt with potash, and thengave by analysis 66.77 per cent.C, 6-32 H, and 25.84 N, agreeingnearly with the formula C6H8N2, which requires 66.67 C, 7.40 H, and2.5.93 N. Its vapour-density, determined by V. Meyer’s method, is3.82 (air = l), the formula requiriug 3-74. Mannitine boils withoutalteration at 170” (bar. 760 mm.). It dissolves in alcohol, in ether,and to a perceptible amount in water ; it has a very bitter taste, andexhibits the following reactions : with sodium phosphomolybdute, im-mediate orange-yellow precipitate, soluble in ammonia ; with potassio-nzercuric iodide, reddish-yellow amorphous precipitate ; with iodisedpotassium iodide, reddish-yellow, insoluble in dilute hydrochloric acid ;with mercuric iodide, flesh-coloured precipitate soluble in ammoniumchloride ; with Fruhde’s reagent, indistinct yellow coloration ; withnuric chloride, black precipitate.Benzene Formulae.By A. LADEVBURG (Ber., 15, 1782-1783).-Ac2ording t o Claus, the best expression of the atomic relationship inbenzene is shown by the appended figure.H. W.Clam meets the objection raised by the author, that when theatomic linking only is taken into considerntion, the combinations 1 : 2,1 : 4, and 1 : 6, are equal, by quoting another of his statements, thatthe geometrical relationships of a formula must represent correspond-ing relative attractions of the atoms, and that therefore 1 : 4, as repre-senting a diagonal, cannot be equal to 1 : 2, which expresses a side.To this the author replies that such an assumption necessitates thehypothesis that one of the combining affinities of the caybon-atomis different from the rest, As such a hypothesis is opposed to allknown facts, he considers the above graphic formula untenable.J.K. C.Benzene Formulae. By B. METER (Bey., 15, 1833--1828).--Theso-called “ diagonal ” formula, defended by Claus, has been repre-sented by the author as only allowing the pcssibility of two isomericbisubstitution products : this statement being denied by Claus, theauthor proceecls to explain his reasons. I n the prism formula, t h epositions represented by the two kinds of sides, differ from oneanother in other respects than in their functions as sides of trianglesor quadrilaterals. For example, the two carbon-atoms 1 arid 3, besidese 52 ABSTRACTS OF CHEVICAL PAPERS.being in direct combination, are also bound indirectly through 5,whilst 1 and 4 are indirectly bound by two atoms, 3 and 6 or 5 and 2.--I \ ( 1;In other words, the difference of the positions (1, 3) and (1, 4) isnot a geometrical one only, but expresses also a difference in theatomic linking.On the other hand, in the diagonal formula-4the indirect communication between (1, 2) is exactly -the same asbetween (1, 4), for instance, (1, 6. 3, 2) and C1, 6, 3, 4), &c.To this Claus answers that the diagonal linkings have a, differentvalue from the ordinary or side bonds, but this assumption the authorregai-ds as arbitrary and as introducing a new definition into thescience. The objection to the prism formula', that it does not expressthe well-known tendency of ortho-compounds to form " inner snhy-drides," becomes groundless, .when it is recollected that a similarobjection was raised against the formulae of quinones.Claus considers that it is more than probable that the formula ofnaphthalene is unsymmetrical, as it mould be if represented by thediagonal formula.If such were the case, however, there would existfour isomeric mono-derivatives, whilst, as yet only two have been dis-covered. Molecules like those of benzene and naphthalene, wbichpossess such an extraordinary degree of stability, must exhibit a verystable equilibrium in the position of the various component atoms,and this nould be best attained by a symmetrical structure.Isodurene, Isodurylic Acida, and 'the Third Trimethyl ben-zene. By 0.JACOBSEK (Bey., 15,1853-1858).-Isodurene is obtainedby the action of methyl chloride and aluminium chloride on niesitylerie(b. p. 195"). Dibromisodurene (m. p. 203") is formed from this bytreating it with excess of bromine in presence of iodine : it crystal-lises from hot alcohol in long needles. The dinitro-compound crystal-lises from the same solvent in colourless prisms melting a t 156". Thesulphonic acid was obtained in fine plates, and its barium and sodiumsalts prepared : the corresponding amide (m. p. l l 8 O ) may be obtainedin thin needles from its aqueous solution, by the usual method. Ryfusing sodium isodurenesulphonate with potash, isodurenol is obtainedas a crystalline mass melting a t 108".Isodurylic Acids.-Isodurene is boiled for some time with dilutenitric acid, and after removal of the nitro-compounds the liquid issteam-distilled.From the misture of the three acids, the a-acid maybe separated as crystalline barium salt, the other two acids being leftJ. K. C ORG-WIG CHEMISTRY. 53in the iincrystallisable mother-liquor : in its properties it agrees withBielefeldt's description. The remaining acids are precipitated byhjdrochloric acid, and separated by crystallisation from petroleum.The less soluble, termed /3-isodarylic acid, is obtained in hardshining prisms, melting at; 151': its calcium salt crystallises fromwater in a mass consisting of fine needles. Onrevaporating the petro-leum solution, e/-isodurylic acid (m.p. 84-85') is left behind incrystalline crusts, and may be purified from adhering p-acid by takingadvantage of the greater solubility of its calcium salt. It is preci-pitated from the latter in flakes, and crystallises from alcohol andwater in needles. The barium and potassium salts are uncrystallisable.By the oxidation of isodurenesulphonamide with potassium perman-ganate, sulphaminisodurylic. acids are formed, corresponding to theabove @- and y-acids.The three isodurylic acids were distilled with lime in order to ascer-tain their constitution. a-Isodurylic acid' yields the third trimethyl-benzene called by the author hemellithene .- i t is therefore representedas C6H&Ie3COOH [COOH : Me : Me : Ne = 1 : 3 : 4: 51.From the@-acid [COOH : Me : Me : Me = 1 : 2 : 4 : 61 pure mesitylerie was ob-tained, and pseudocumene from the y-acid, [COOH : Me : Me : Me =1 : 3 : 5 : 61. Hemellithene, C6H,Me, [Me : Me : Me = 1 : 2 : 31, was ob-tained pure from its sulphamide by heating it' with hydrochloric acida t 200". It boils at 168-170". Tribromh'emellithene crystallisesfrom alcohol in fine needles, melting a t 245". ~emeZZithenesuZpho?ticacid crystallises well in six-sided plates, and its amide in short trans-parent prisms, melting a t 196". Coal-tar cumene does not containhemellithene. J. K. C.Action of Aluminium Chloride on the Monohalogen Deriva-tives of Benzene. By 0. v. DUMREICHER (Bey., 15, 1866-1870).-Chlorobenzene is not acted on even when boiled for several dajs withaluminium chloride ; with bromobenzene, however, a lively r e d i o nsets in above loo", hydrochloric and hydrobromic acids are evolved inlarge quantities, and after eight or ten hours a blaok mass is formed.When this is steam-distilled, and the oil fractioned, pure benzene, andtwo dibromobenzenes, para and liquid, together with unaltered bromo-benzene, are obtained, the benzene and dibromobenzene being formedin equal molecular weights.Iodobenzene reacts with aluminium chloride at 80", the liquid be-coming violet from separation of iodine.No hydriodic acid is givenoff, the products of the reaction being benzene and diiodobenzene,with large quantities of iodine. The benzene formed is very large incomparison with the diiodobenzene, and the latter consists chiefly ofthe para-compound.It appears that the hydriodic acid formeddecomposes a t once with iodobenzene into free iodine and 'benzene.The author explains the action of aluminium chloride ou bromo-benzene by the following equations :-(1.) A12C16 + C6H,Br = BrCl + AI,CI,.C6H5.(2.) C6H5Br + BrCl = C6H4Br2 + HCl.(3.) AI,C&,(C&&) + HC1 = Al,Cl, + C6H6. J. K. C54 ABSTRACTS OF CHEJIICAL PAPERS.Metatoluidine. By A. EHRLICH (Ber., 15, 2009--2012).-Thegreater portion of this paper describes improvements in the details ofthe methods for the preparation of metatoluidine proposed by Beil-stein and Kuhlberg and by 0. Widman.~ ~ e t a t o l u y l g l y r o c i n e is obtained as a non-crystalline mass by theaction of 2 mols. metatoluidine in ethereal solution on 1 mol.mono-cliloi~acetic acid. The copper saZt, (CgHloN02)2Cu,2H20, forms brilliantgrass-green plates. Ethy ZmetatoZuy Zg ZZlcoaine, CH, (NH. C7H7). CO OE t(ethyl metatoluylamidoacetate), is obtained by the action of metato-luidine on ethyl chloracetate ; it crystallises in flat plates meltirlg at68", and is readily soluble in alcohol and ether, but only sparingly inhot water. By the action of ammonia in alcoholic solution, it isconverted into the amide of toluylglycocine cry stallising in longspear-shaped needles. A. J. G.37, 390--392).-The introduction of the NO,-group into the halogen-derivatives of the hydrocarbons of the benzene series renders thehalogen more easily displaoeable.Ammonia, for example, has noaction on monochlorobenzene, but yields dinitraniline by its action onmonochlorodinitrobenzene. The chloro- deriva ti ves of the benzeneseries are without action on rosaniline, but the chloronitro-derivativesform substitution-products which give various shades of brown andmaroon. The author has obtained such compounds by acting 011rosaniline with [ 1 : 2 : 41 chlorodinitrobenzene ehlorotrinitrobenzene,and a mixture of chloronitronaphthalenes obtained by treating mono-cliloronnphthalene with a mixture of nitric and sulphuric acids.1 mol. rosaniline is heated with 1 mol. of the chloronitro-derivative,e.g., chlorodinitrobenzene, and some glacial acetic acid in an oil-bath a t180-2200" for five or six hours.When cold, the product is extractedwith very dilute acid to remove unaltered rosaniline, then dried andtreated with benzene to remove excess of the chloride and resinouscompounds. The residue consists of the hydrochloride of the newbase, mixed with carbonaceous products. The hydrochloride and thesulphate are insoluble in water, but soluble in alcohol ; the acetate issoluble both in water and in alcohol. The hydrochloride is extractedfrom the residue by means of alcohol, and the solution mixed withsodium hydroxide, which precipitates the base in the form of a paste.The base is dissolved in dilute acetic acid, and can then be used fordyeing. On silk, it yields a very fast violet garnet colour, approachingmaroon. The dried base forms an amorphous black powder ; the saltsare green, with metallic lustre, but are not crystalline.The new colouring matter formed from chlcrodinitrobenzene is inall probability dinitrophenyl-rosaniline formed in accordance with theequation C20H19N3,H20 + CsH3C1(N0,), = CZoH~,N,.C6H,(NO,),,HCl +H20.Attempts to introduce two or three dinitrophenyl-groups wereunsiiccessful. Any excess of chlorodinitrobenzene always remainedunaltered. No satisfactory results were obtained by heating neutralor alkaline alcoholic solutions in sealed tubes. It is worthy of notethat the introduction of two nit'roxyl-groups changes the colour ofmonophenylrosaniline from violet to maroon.Rosaniline-derivatives. By E. N o E r m N G (BUZZ. XOC. Cl~im.. [2]ORGAXIC CHEMISTRY.55Phenylrosaniline is converted into a sulphonic acid by the action ofDinitrophenylrosaniline is carbonised withoutThe sulphonic acid may, however, beIt formsNitronaphthylrosaniline has a much more violet colour than thestrong sulphuric acid.formation of sulphonic acid.obtained by the action of chlorosulphonic acid S0,HCl.salts which yield colours very similar to those of the original base.nitrophenyl-derivative. C. H. B.Azylines. By E. LIPPNANN and I?. FLEISSNBR (Honatsh. Chenz., 3,705--714).--The authors apply the berm uzylirces to a series of basesobtained by the action of nitric oxide on tertiary amines, and in whichthe tetravalent-group >N-N< is contained in union with benzenenuclei. At present, tertiary azylines of the aromatic series alone havebeen obtained.These compounds are crystalline, and of red colour ;dissolve in hydrochloric acid to fine purple liquids, and in acetic acid t ogreen solutions, from which they are reprecipitated in the amorphousform on adding water. They yield crystalline compounds with thechlorides of platinum, iron, gold, &c. The picrates are crystallineand sparingly soluble. When heated with alcoholic iodides a t loo",the azylines form ammonium compounds. With nitrous acid, nitroso-compount 1s are formed ; as these give Liebennann's colour-reactionwith phenol and sulphuric acid, the tertiary nature of the compoundsis rendered highly probable. If treated with stannous chloride or withhy driodic acid and phosphorus, the azylines yield unstable hydro-corn-pounds, from which crystalline platinochlorides can be prepared.Yiil-zethylu?zili,Leazylitie, NMe2.C6H, : N.N C6H3.NMe2 (m.p. 266'),has been already described. (Abstr., 1881, 161, the formula, C9H,,N-,there ascribed to it being due to an error in analysis). Its formationis represented by the equation 2CBH1,N + ZNO = dH,O + CI6Hl8Ni.On oxidation, i t yields oxalic acid and carbonic anhydride. The picrateis obtained as an alcoholate, CisHl8N4,C6H3(NO2),O 4- C2H60, inbrilliant leaf-green needles.Diethllln?LiLineazyZirLe, C2,H2,N4 (m. p. 170"), forms red needles solublein chloroform and hot alcohol, sparingly soluble in cold alcohol. Thepicrate, C,0H26N4.2[ C6H,(N02)sO], crystallises in yellow needles.Ui~.l.opyla?Lili?Lea~~line, C2iH3iN,, crystallises in red tables of therhombic system, melting at 90".The crystals were measured byScrauf, and gave axial relations a : b : c = 1 : 0.629 : 0.913. Themost important, faces are 101 : 100: 110 : 001.DibutyZ~nill?zeazyZine, C2sH12N4, crystallises in needles melting at1%".Dia~nnyZarLili?zeazyZ,ine, C3,H54N, (m. p. l l S O ) , forms red spear-shapedcrystals, soluble in hot alcohol. It dissolves in concentrated hydro-chloric acid, butl is decomposed on boiiing. A. J. G.Trimethylphosphobenzobetai'ne. By A. MICHAELIS and L.CZIMATIS (Bey., 15, 2018--202O). - Trimethylphosphobenzobeta'ine isobtained as chloride by the oxidation of paratolyltrimethylphospho-nium chloride with potassium permanganate a t a temperature of 55".The chloride forms short, thick, brilliant, colourless prisms of th56 ABSTRACTS OF CHEMICAL PAPERS.formula C6H4(COOH),PMe,Cl ; it is insoluble in ether, soluble in hotalcohol, and very soluble in water.Theplatinochlokle is obtaiiied as a light yellow crystalline precipitate.The free betuzne, C6H4<'pMe~>0,3H,O, is obtained by neutralisationof a solution of the chloride ; it crystallises in rhombohedrons, andeffloresces readily. It does not give salts with bases, but with acids itgives well characterised compounds. The acetate crystallises inslender needles of nacreous lustre, the nitrate in needles. Withexcess of dilute snlphurio acid, it gives an acid salt also crystallisingin needles. On heating the chloride with potash, it is decomposedaccording to the equation-It is decomposed by heat.coC6H4(COOB[).PMe3Cl + KOH = C6H,.COOH + PMe30 + KCI,By the action of potassium permanganate, on the addition-productof ethylene bromide and dimethyltolylphosphine, a compound,C6H4 (c 00 H) .PMeZO,is obtained; it crystallises in colourless prisms of faint acid taste,melts at 243",.and can be ,sublimed with but little decomposition.A. J. G.Formation and Decomposition of Acetanilide. By L. MEYER(Ber., 15, 1977-1978) .-With regard to the formation of acetanilide,the results obtained a t 130" by Steudel in the author's laboratoryagree with those of Menschutkin ; a t 155" a complete reaction nevertakes place., but in the reverse reaction an important difference occurs.According to Menschutkin, the incompleteness of the reaction is duet o the resulting water reacting on the acetanilide and partially decom-posing i t ; but on heating acetanilide with water at 130" for sometime, no traee of an mid reaction could be obtained, so that theincompleteness of the reaction cannot be due to that cause.A. J.(3.Constitution of the Aximido-compounds. By P. GRIESS (Eer.,15, 18Z3--1882).-Under the above definition, the author includesthose bodies which have so far been obtained only by the action ofnitrous acid on aromatic orthodiamido-compounds, the first of whichwas prepared by Hofmann from orthodiamidonitrobenzene. Amongstothers, two have been obtained by the author from 6- and ydiamido-benzoic acids. Two different views of the constitution of thesebodies have been proposed, the one by KeknlB, and the other byLadenburg. According to the former, Hofmam's compound would be,NH.represented by NO,.C N /VN, while Ladenburg assigns the for-5(-N-Nmula N0,.C6H3(NH2)' 11 .'NThe author's investigations, however, lead him to represent thORGANIC CHEMISTRY.57Nabove compound thus : N02.C&&( 1 )NH, and he bases his view on'Nthe following facts :- a- and 6-nitrouramido-benzoic acids,B. 6.COOH (1) (1)N02.CsH3 NH.CO.NH, (3) (4)when heated to boiling with concentrated potash-solution, are bothconverted into p-azimidobenzoic acid with formation of ammonia andcarbonic anhydride.According to RekulB's view, two isomeric acids would be formed ;whilst, if Ladenburg's view were correct, the production of an azimido-benzoic acid would in this case be impossible.When the above fi- and &acids are treated with tin and dilutehydrochloric acid, they: are converted ints the corresponding diamido-acids, which by nitrous acid are converted into the same azimido-uramidobenzoic acid, a fact which only admits of explanation whenthe formula proposed by the author is employed.In the same manner, y-nitrouramidobenzoio acid can be convert'edinto azimido-compounds5 the and s-acids, however, react in atotally different way.Mixed Aromatic Tertiary Phosphines.By L. CZIMATIS (Ber.,15, 2014-2018) .-These compounds were preplared from the homo-logues of phosphenyl chloride by the action of the zinc alkyls.Parndinzethylto7y~hos~hine, C6H4Me.P&fe2, is a colourless liquid ofdisagreeable odour ; it boils a t 210", and does not, solidify a t - 10" ;i t has basic properties, and dissolves in acids ; the chloride yields ajellow flocculent precipitate with platinum chloride. It does notoxidise on exposure to air, but is.converted by mercuric oxide intodirnefI~y1toly~hosphine oxide, C6H4i!de.P1\/Ie0., forming a thick oilyliquid. With mercuric chloride, this yields the double salt,C6H&le.Plk!e20,HgC12,H20,crystallising in slender silky needles, melting a t 156".Methyl iodideuiiites violently with dimethyltolylphosphine, .yielding the phos-phonium iodide, C6H4Me.Ph!fe31 ; it crystallises in colourless needlesmelting at 255", readily soluble in water and hot alcohol, sparingly incold alcohol, insoluble in ether.With mercuric chloride it gives anunstable double salt crystallising in needles. The hydroxide is obtainedby t,he action of silver oxide and water as a strongly basic deliquescentmass ; on treatment with hydrochloric acid and platinum chloride, t,heplatinochloride, ( C6H,D/Ie.PMe3CI)2,PtC14, is obtained in orange-yellowplates melting a t 250".C6H4Me.PMe313,olitained by the action of iodine on the iodide, cryst~tllises in steel-blue rhombs, soluble in alcohol, and sparingly in benzene and ether.Dimethy1to)ylphosphine combines wikh benzyl chloride to an uncrys-(NH, (4) (3)J. K. C.Trimethyltolylphosphonium periodide58 ABSTRACTS OF CHEMICAL PAPERS.talline mass ; the platinochloride, ( C,H,nle.PMe,.C1CiH.I)2,PtC14, meltsat 226".Pu~ad~ethyltol~~hosp7z~ne, CfiH4Me.PEt,, boils at 240", and resemblesthe preceding compound.The methiodid e crystallises in colourlessneedles melting a t 137'" ; the platinochloride in clear yellow plates.Dim ethy ZLy ZyZphosphine, C6H3Me2.PMe2, is a colourless liquid boilinga t 230".DiethyZlryly~~hosphin,e, C,H,Me,.PEt,, is a thickish liquid of faintcolour, boiling a t 260'. The methiodide (m. p. go"), and ethiodide(m. p. 136"), form white crystalline powders, readily soluble in waterand hot alcohol, insoluble in ether. Methyldiethylphosphoniumplatinochloride crystallises in cadmium-yellow rhombic plates, meltingat 202".A comparison of the boiling points of the phosphines shows a riseof 20" for the entry of a methyl-group ifito the aromatic nucleus, whilstthe difference of boiling points of the members of the series is 30".B.p. B. p. Diff.C6H5.PMe, ........ 190" CfiH,Me.PMe, .... 210" 20"C6H5.PEt, ........ 220 C6H4Me.PEt2 .... 240 20B. p. Diff.C6H,Me,.PMe2 .......... 230" 20"C6&jh!fe2.PEt2.. .......... 260 20Dimeth ylphenylphosphine and carbon bisulphide, when mixed inethereal solution, give a compound of the formula C6H,.PMe,,CS,,crystallising in glistening red scales, soluble in carbon bisulphide, in-soluble in ether. It melts in open tubes, with dissociiLtion, at 97" ; inclosed tubes at 101". It has basic: properties, is dissolved by diluteacids, and reprecipitated by soda.( C6H5.PMe?? H C1, C S,) 2, Pt C14,is obtained as an amorphous pale yellow precipitate ; on exposure toair, it loses carbon bisulphide, and is converted into dimethylphos-phonium platinochloride.When the original compound is treated withdry hydrochloric acid or methyl iodide, it is decomposed, carbon bisul-phide being eliminated and phosphonium compounds formed. Waterdecomposes the compound slowly a t ordinary temperatures ; rapidlyon heating.Dimethyltolylphosphine unites with carbon bisulphide, formingclear red plates of the formula C6H4MePMe2,CS2, melting at 110" inan open tube, a t 116" in closed tubes. It closely resembles the pre-ceding compound ; the platinochloride, however, is more stable whenexposed to the air.DimethylxylylphospEiine and carbon bisulphide form the compoundCfiH,Me2.PMe,,CS2 ; it ciytallises in clear red plates, and melts a t115" in open, and a t 121" in closed tubes.Diethylphenylphosphine unites slowly with carbon bisulphide,forming a red crystalline product which could not be obtained in astate of sufficient purity for analysis.Action of Potassium Carbonate on the Chlorides of Benzyland Benzylene.By J. MEUNIER (Bull. Xoc. Chim. [ 2 ] , 38, 159-The platinochloride,A. J. GORGXXlC CHI"M1YTRP. 59160). - By heating ethylene bromide with an aqueous solution ofpotassium carbonate, Zeller and Hufner have obtained glycol directly(this Journal, 1876, ii, 64) ; the author has studied an analogousreaction with benzyl and benzylene chlorides. I n the case of benzylchloride the corresponding or benzylic alcohol mas obtained, but withbenzylene chloride benzaldehyde was formed, the yield being two-thirds of that required by theorj-.By A.LIEBXANN (Ber., 15,1990-1992).-Isobutylphenyl ethyl oxide boils a t 241-242" uncorr. (not234-236", as given in the author's previous communications, Abstr.,1882, 171, 727). By treatment with nitric acid, it yields the ?litm-ether as an oil volatile with water vapour, boiling with decomposi-tion at about 300", and yielding the nmido-ether on reduction. AnlyZ-yhenyl ethy2 om'de boils iat 259-261", and yields mononitro- andamido-compounds like the above.Nitro-derivatives of the Cresols. By E. NOLTING and E. v.SALTS (Ber., 15, 18,58-1865) .-Dinritl.o-~arucl.esoZ.-The ethylic etherof this body is prepared by treating the silver salt suspended in alcoholwith ethyl bromide or iodide; it melts a t 73".The correspondingdiamido-salt, of which only the hydrochloride was prepared, shows thecharacteristic reactions of metadiamides.Dinitro-orthocresol, CGHzMe(N02)2.0H [NO, : NO, = 4 : 61, agreesin all its properties with that obtained by Picard from saffron sub-stitute. The barium salt crystallisesin shining yellow needles, easily.soluble in hot water. The hIdro-chloride of the diamido-compound decomposes in the air, and must beevaporated in a stream of sulphuretted hydrogen.!fii.nitro-cresoZ, obtained from coal-tar cresol, is identical with thatprepared from meta-cresol : it, separates from water in slenderyellowish-white needles melting a t 106".Like picric acid, i t formsmolecular compounds with hydrocarbons. Its composition is repre-sented by the formula-V. H. V.Isobutyl- and Amyl-phenols.A. J. G.The ethylic ether melts at 46".[NOz: OH :NO,: Me: NO, = 1 : 2 : 3 : 4 : 51.The ethyl ether is easily converted into trinitro-toluidine by treat-ment with ammonia ; no separation of a nitro-group occurs as wouldbe the case if two of these groups were in the ortho-position to eachother. The ethylic ether may be prepared by treating the silver saltwith ethyl bromide, and forms thick white needles, melting a t 72".Trinitro-metatoluidine forms small crystals melting a t 126", verysoluble in alcohol and ether, and having weak acid characteristics.Heated with alkaline solutions, it is coovered into trinitro-cresol.J.K. C.Fusion of Orcinol and Gallic Acid with Soda. Bg L. BARTHand J. SCHREDER (Nonutsh. Ckem., 3, 645-650). - Orcinol, whenfused with sodium hydroxide, yields resorcinol (15-16 per cent.),phloroglucol (about 1.5 per cent.), pyrocatechol (1-1.5 per cent.),and a new body, C13H,,0A (about 5 per cent.). This latter is, in allprobability, tetral?,~droz2/di~lienZll?nethane, CHz[ C6H3(OH),]z, it formslong, satiny, snow-white needles, readily soluble in alcohol and ether 60 ABSTRACTS OF CHENICAL PAPERS,it. commences to decompose at 260". It gives no coloration withferric chloride. I n this reaction, it would appear that the methyl-groupis first oxidised, and then split off, so that resorcinol is formed, whichby fiirther oxidation yields phloroglucol : a very large proportion ofthe orcinol however is completely oxidised.The substance, C13H1204,is an intermediate product, and the catechol is due to a secondaryreaction. In accordance with this view, when the heating is continuedfurther, little but phloroglucol is obtained.By the action of fused soda on gallic acid, .phloroglucol is formedin small quantity (0-6-0.8 per cent.) in addition to pyrogallol andhexhydroxydiphenyl (Abstr., 1879, 926).Catechol is acted on by soda a t a high temperature only, and is thencompletely oxidised. Quinol also is but slowly attacked by soda;the products of the reaction have not yet been obtained in the purestate. A. J. G.By H. SCHIFF (Bey., 15, 1841--1844).-Thisbody has already been prepared by Michael from methylqiiinol andacetochlorhydrose ; it was thought advisable to prepare it by anothermethod, and to compare the substances obtained.Equal volumes ofa methyl alcohol solutions of methyl iodide and potassium hydroxide,were gradually added to a solution of arbutin in the same medium,the mixture being boiled after each addition : after concentration andcooling, the methylarbutin. which separated was purified by repeatedcrystallisation from water; it was found to differ in two points fromMichael's preparation : it melted a t 175-176" (168-169" Michael),and contained 1 rnol. H20 instead of half a molecule. Mixed witharbutin (m. p. 187") it melted a t a much lower temperature.Fromconcentrated solutions containing potassium iodide it can be recrys-tallised free from water. It is soluble in water especially wheu hot,and in alcohol, but only sparingly in ether. Commercial arbutin con-tains about 30 per cent. metJiylarbutin, identical with that obtainedby the author. Whether the latter is the same as that prepared byMichael is still open to question.By S. SCHURERT~ (Monatsh. Chel-ra., 3, 680-687).-Di-isobutylquinol (paradi-isobutoxybenzene), CGH,( C4H,0),, isprepared by heating together quinol, potassium isobutyl sulphate, andpotassium hydroxide, in sealed tubes, for 4-5 hours at 150". It formsa colourless leafy crystalline mass of fatty lustre, is insolnble in water,more soluble in benzene and light petroleum, readily solable inalcohol and in hot glacial acetic acid.By theaction of chlorine, it yields chloranil, dichlorodi- isobufylquiiaol, crystal-lisirig in colourless rhombic plates, and tetl.achlorodi-isohut~lzz~~~~~Z,forming long, colourless, interlaced needles, of silky lustre. The onlybromine-derivative obtained was dib,.omodi-isobutylyui7iol, crystallisingin colourless quadratic plates. Tetranitrodi-isob uty Zpuinol cryetallisesin long thin needles, sparingly soluble in water, readily soluble inalcohol, ether, and hot glacial acetic acid.Compounds of Benzo- and Toln-quinol with Amines and ofQuinone with Nitranilines. By A. HEBERAND (Ber., 15, 1973-Methylarbutin.J. K. C.Di-isobutylquinol.It boils a t about 262".A. J. GORGASIC CHEJIISTRT.611!)76) .-Occasionally, in the preparation of quinonedianilide, a com-pound of quinol and aniline, C6H,(OH)2,(C6H5NHz)2, is found in themother-liquor. It forms large micaeous plates, melting a t 89-90",and is readily soluble in hot water and in alcohol. In aqueous solution,i t is readily oxidised to quinonedianilide. It is decomposed when boiledwith benzene, and quinol crystallises out, but the same substance canbe prepared by boiling quinol and aniline in aqueous solution. Thecorresponding paratohidine compound, c6&(oH)z, (C,H,.NH2)z (m. p.95-98") , prepared directly from quinol, resembles the aniline com-pound. Orthotoluidine and naphthylamine compounds could not beobtained in the pure state.Attempts were made to prepare similar compounds with phenol,resorcinol, antl pyrogallol, but without success. With toluquinol, ananiline compound, mystallising in white Eeedles, melting at 82-85',and a paratohidine compound, crystallising in nacreous plates, melt-ing a t go", were obtained.Quinune and Pa?.anitraniZiize.-On mixing hot alcoholic solutions ofthese bodies and cooling, large dark-red crystals (m.p, 115-120')separate, which by heating or by boiling with water are resolved intotheir constituents. The composition of this substance varied in dif-ferent preparations from-C6H407 C:,Ha(NOz) NHz, to 2CsH4OZ73'(NO2. C,H,.NH,).I n acetic acid solution, or by long boiling with alcohol, the course ofthe reaction is different, quinonedinitranilide ,being formed in smallbrown needles, together with a substance of wid nature, crystallisingin red-violet plates, melting at 183".Quinone and O1.t~onitraniZL'ne.-Solutions of these substances, whenmixed, yield large red crystals melting at 94-97"; with excess ofnitraniline, a new body of the formula c 6 ~ , 0 2 , 2 ( N ~ , .c , H ~ . ~ H ? ) , isobtained. When boiled with glacial acetic acid, it yielded the corre-sponding dinitmnilide, crystallising in brownish-red needles. Meta-nitraniline and quinone yield nothing but puinunedinzetan,it~aiziZide,forming yellowish-brown needles.With orthonitraniline toluquinone gives an addition-product (m. p.31") resembling those already described. A. J. G.Compounds of Vanillin with Pyrogallol and with Phloro-glucinol.By C. ETTI (Munatsh. Chem., 3, 637-644).--Singer hasrecently shown (Abstr., 1882, 1122) that the deep red coloration im-parted to pine wood by phloroglucol in presence of hydrochloric acid,is due to a compound formed with the vanillin which is present in thewood. The author has further investigated this compound, and alsothe analogous one of pyrogallol with vanillin.PyroyaZZovaniZZei??, C20H,R08, is prepared by mixing vanillin and pyro-gallol with alcohol and an excess of concentrated hydrochloric acid ;it forms colourless crystals destitute of odour, insoluble in water,sparingly soluble in ether, readily soluble in strong alcohol, By longstanding over sulphuric acid, or by drying at 110", 2 mols. of the sub-stance lose 1 mol. of water, yielding the body C40H30015. Whencrystallised from solutions containing free hydrochloric acid, pyro62 ABSTRACTS OF CHEMICAL PAPERS.gallovanillejin is obtained in fine violet-blue crystals, which containhowever, a trace of hydrochloric acid.PhZoruylZuci~zol.c;.anil Zein, prepared in a manner similar to the above,forms yellowish-white crystals, and behaves towards solvents likep,rro,nallovanillejin.It loses water more readily with formation of thehrownish-red compound, C40H14015. Crystallised from hydrochlorica cicl solutions, the characteristic fiery-red compound is obtained, buta s in the previous case the amount of chlorine contained is too smallto estimate. The formation of these vanilleins is expressed by theequation-COH.CGH3(OH).0Me + 2C6H,(OH), =~H[c~H~(oH)~]~.c6H3(ofT) .OMe + H20,and they must be regarded as derivatives of triphenylmethane.On rubbing together resorcinol with vanillin and hydrochloric acid,a deep bluish-violet coloration is produced ; but the colour vanishesafter a time ; the addition of water causes the precipitation of a whitecrystalline powder. A.J. G.Action of Acetic Chloride on Benzaldehyde in presence ofZinc-dust. By C. PAAL (Ber., 15, 1818--1820).-When acetic chlo-ride is dropped into an ethereal solution of benzaldehgde in whichzinc-dust is suspended, a violent reaction takes place ; zinc chloride isformed, and the ethereal solution, after being washed with water andevaporated, deposits a yellow crystalline mass from which alcoholextracts a substance crystallisirig in white needles of the formulaCeH80,, melting at 125-1 28".Heated with amorphous phosphorusand hgdriodic acid, i t yields dibenzyl, and, when distilled with zinc-dust, i t gives rise to stilbene : these decompositions, however, throwno light on its constitution. A reaction similar to the above occurswhen ethaldehyde is treated with acetic chloride.Orthamidobenzaldehyde. By S. GABRIEL (Bey., 15, 2004-2006).-The author has already shown, in conjunction with R. Meyer(Abstr., 1882, 188) , that nitrosomethylorthonitrobenzene yields ortho-nitrobenzaldehyde on oxidatlion, and (Abstr., 1882, 1070) that the cor-responding meta-compounds give similar results ; as this appears to bea general reaction for nitrosomethyl compounds, he has applied i t tonitrosomethylorthamidobenzene. The oxidation was effected by adightly insufficient quantity of ferric chloride ; during the reaction,some salicylic aldehyde distils.The contents of the retort are madealkaline and distilled, when o?.tharnidoheizza7del~~ae is obtained as anoil, solidifying to a crystalline mass on cooling ; i t melts a t the tempe-rature of the hand. In an exsiccator over sulphnric acid, i t appears todecompose, the walls being covered with a crystalline deposit, whilstthe other (greater) part of the substance is converted into a yellowbody not meltiiig a t 100".Action of Benzoic Anhydride on Epichlorhydrin. By P.VAX ROXBURGH ( R e c . 7'r.a~. Chim., I, 46--52).*-When these two bodies* Recueil des Travaux Cliimiques des Pap-Bas : par W.A. van Dorp, A. P. N.Franchimont, S. Hoogewertf, E. Xulder, et A. C. Oudemans, Jr. Leide. 1882.J. K. C.A. J. GORGANIC CHEMISTRY. 63in molecular proportion are heated together in sealed tubes at about190" for seven to ten hours, and the product is left a t rest for sometime, the whole concretes to a mass of small crystals soaked in a thickliquid. By solution in ether and spontaneous evaporation, colourlesscrystals (m. p. 70") are obtained containing a small quantity of chlo-rine, and by recrystallising these from alcohol crystals are formed freefrom chlorine, and melting at 74". These crystals have the composi-tion Cl2Hl0O3, or rather C21H2006, and are resolved by saponificationwith alcoholic potash into benzoic acid and glycerol.The compoundis tberefore t r i b e n z o i c i n , formed according to the equationCH,: CHO.CH,Cl + 2BY20 = E C l + O&.CH(CH2.0&)2*;and, as thus prepared, it is identical in its properties with that whichis obtained by heating glycerol with benzoic acid or benzoic anhydride.I t s formation in the manner above described is accompanied by that ofa liquid, which the author regards as probably consisting of a mixtureof mono- and di-benzoicin. H. W.Epichlorhydrin. Tribenzokin..Action of Benzoic Anhydride on Monochloracetone and onPyruvyl Benzoate. By P. VAN ROMBURGH ( R e c . Trav. Chim., 1, 53-54).-Monochloracetone and benzoic anhydride, heated together forthree honrs in a sealed tube a t 180°, formed a black solid substancecontaining benzoic acid, and having a faint odour of benzoic chloride.By heating monochloracetone with potassium benzoate in alcoholicsolution for 12 hours, then filtering and expelling the alcohol by eva-poration, a liquid is obtained which, when distilled a t 245" under apressure of 380 mm., yields a yellow distillate solidifying when sur-rounded by ice; and 011 pressing the solid mass between bibulouspaper to remove oily products, then dissolving it in ether and evapo-rating, p y r u vyl benzoate, CI0H1003 = COMe.CH,.OE, is obtainedin splendid colourless crystals which melt at the heat of tlie hand (25")and have a density of 1.143 at.25'. Their alcoholic solution has noaction on polarised light.Pyruvyl benzoate, like monochloracetone,reduces potxssio-cupric sulphnte, even at ordinary temperatures.Heated with benzoic anhydride i n a sealed tube a t 180", it graduallyblackens and yields a sublimate of benzoic acid.H. W.Synthesis of Cumic Acid. By R,. METER and E. M ~ L L E R (Bey.,15, 1903-1906) .-The authors have repeated their synthesis of cumicacid (Ber., 15, 496) on a larger scale with the view of examining thecause of discrepancy between the melting point ( 1 l O O ) of their syn-thesised acid and that (116") of ordinary cumic acid. The ciwneneW a s prepared by the action of isopropyl bromide on benzene in thepresence of aluminium bromide, then converted into parabromocumene,and this, after careful purification, WRS submitted to the action ofsodium and moist carbonic anhydride.The acid obtained in this waydiffered from that previously prepared in having the correct meltingpoint (116--117"), and it agreed in all respects with ordinary cumicacid. Since both the para-propylbeuzoic acids have now been madesynthetically by similar reactions, there can be no further doubt o64 ABSTRACTS OF CHEMICAL PAPERS.their constitution-cumic acid containing the isopropyl group, and itsisomeride, normal propyl.An attempt to prepare propylbenzoic acid by the action of sodiumamalgam on para-propylbenzene and chlorocarbonic ether did not yieldvery definite results, for although a small quantity of propylbenzoicacid appeared to be formed, the chief product of the reaction was anew bojy of the formula HgJC6H,.C3H;)2 [Hg : C,H, = 1 : 41 (m.p.logo). A. I(. M.Phenylacetic Acid. By S. GABRIEL (Ber., 15,1992-2003).-Bythe action of fuming nitric acid on bromacetamidobenzyl cyanide(m. p. 12 7-129'), acetanzidobromn?iitrobe.lzzyl cyapbide,CsH2(CH2.CN)(N02)(NH&)Br = [l : 3 : 4 : 51,is obtained in slender pale-yellow needles melting a t 190-1 91", andspa,ringly soltible in cold water, more readily in alcohol and glacialacetic acid. When boiled with hydrochloric acid, it yields arnidobromo-nitro$hen,yZace€ic acid,C~H2(N02)(NH2)Br(CHz.COOH) = [3 : 4 : 5 : 13,crystallising in long golden-yellow needles melting a t 191-192", aridsparingly soldble in cold water, readily in hot alcohol, moderatelysoldble in chloroform and benzene. By reduction with tin and hydro-chloric acid, it is reduced to the diarnide-acid,C6H2Br (N13,)2.CH2.000H.This forms groups of long colourless needles, which darken a t 190'and melt with intumescence to a black mass a t 19'Fj--2OO0.Theresults of the reduction show €hat the nitro-group must have enteredthe benzene nucleus a t the 3-position, as in the case of the otherpossibilities [ 2 or 61, an inner anhydride, bromamiao-oxindole,NH2C6HdBr<NH CH2 >CO,would be produced, on reduction.Metanitroparamidophenylacetic acid (m. p. 143.5-144'5") giveson reduction the diamido-acid, c6H3(XH2) (NH,) (CH,.COOH) =[3 : 4 : 13, crystallising with 1 mol. H20 in short hard compact formsshowing numerous faces, sparingly soluble in hot alcohol.By the action of amyl nitrite and hydrochloric acid on the abovemetanitro-acid (m.p. 191-192"), a large yield of a substance givingdiazo-reactions was obtained, buit no formula could be deduced fromits analysis, the fact that it contains chlorine and brominein no simpleratio to one another pointing to a mixture of substances. On gentlyheating it with alcohol, a crystalline mass is obtained which, on beingmixed with soda and distilled with steam, gives an oil solidifying aftera time t o a mass of crystals insoluble in soda, whilst the residue in theretort, after acidification and renewed distillation with steam, yieldscolourless crystals (m. p. 108-109") soluble in water. The results ofanalysis showed these to be a mixture of dihalogen nitrosomethyl-benzenes, C,H3X2.CH2N0 (X, = ClZ or Br, or BrC1). The crystalsinsoluble in soda first obtained (broad flat needles melting a t 65-65.5") gave results agreeing with a mixture of dihalogen benzaldehjde,and on oxidation yielded a mixture of dihalogen cinnamic acids.A.J. GORGANIC CHEMISTRY. 63Action of Sulphuric Acid on Protocatechuic Acid. Bg E.NOELTING and R. BOURCHABT (Bull. 8oc. Chim. [2], 37, 394-397).-1 gram protocatechuic acid is heated with 2 grams of benzoic acid and50 grams of sulphuric acid of 66" B. a t 140-145" for eight hours, andthe product is poured into water, which throws down a deep brownflocculent precipitate ; this is collected, dissolved in dilute soda solu-tion, and precipitated by hydrochloric acid, this treatment beingrepeated several times.The clear brown flocculent substance thusobtained produces with mordants almost the same shades as alizarin,but is distinguished from the latter by the reddish-brown colour of itsalkaline solution and by its a~sorp~ion-spectrurn. The yield is verysmall, whatever the proportion of sulphuric acid, the time of heating,and the temperature. The benzoic acid appears to play no part in thereaction, for, when protocatechuic acid is heated alone at 140-145"with 20-25 times its weight of sulphuric acid, the same product isobtained, although in this case also the yield is very small.The substance thus formed yields an orange-yellow alcoholic solu-tion, which becomes violet with a yellowish fluorescence on addition ofpotash, After some time, the compound is precipitated in red flocks.Alcoholic lend acetate throws down a floccnlent brown precipitate :calcium chloride and ba,riunL chloride produce a violet fluorescence inthe yellow solution, and after some time a precipitate is formed ; ,ferricchloride gives a blackish-brown, ammonia a violet-brown, and alum areddish precipitate.I t s solution in dilute ammonia is brownish-red,approaching violet. In this solution calcium and barium chloridesproduce a brown, lead acetate a reddish-brown, and absolute alcohol aviolet-brown precipitate. Its solution in dilute potash gives, withabsolute alcohol, a reddish precipitate, with alum a reddish-lake, andwith ferric chloride a blackish-green lake. The substance is dissolvedby strong sulphuric acid, with formation of a brownish-violet solutionwhich, when poured into water, yields a yellow solution and a slightprecipitate. It also dissolves in glacial acetic acid, forming an orangesolution.The properties of this substance agree with those of rufiopitbe,CeH,(OH),< c0>CG€12( OH),, obtained by Anderson ( Annalen, 98,51) by the action of concentrated sulphuric aci3 011 opianic acid a t180", and described by Liebermaim and Chonjnacki (Am~alen, 162,321).By analogy from the behavioiir of other hydroxyl-derivativesof benzoic acid, protocatechuic acid ought to form a colouring matteraccording to the equationIt cannot be sublimed without decomposition.coThis reaction is more complicated in the case of opianic acid; butsince in both compounds the hydroxpl-groups occupy the same posi-tions with respect to the carboxgl-groups, it is highly probable thatthey will yield identical condensation-products when acted on bysulphuric acid.C. H. 13.Oxidation-products of Carbon obtained by Electrolysis.By A. MILLOT (Bull. SOC. Chiha. [2), 37, 337-339).--The gas-VOL. XIJV. Gci ABSTRACTS OF CHEMICAL PAPERS.carbon electrodes (Abstr., 1880, 482) are much more rapidly attackedin alkaline solutions than in pure or acidulated water. The dark solu-tion obtained by the electrolysis of a 5 per cent. solution of ammonia,with gas-carbon electrodes becomes acid on evaporation. It containsammonium nitrate and an acid which may be isolated by evaporatingalmost to dryness, heating the precipitated black matter with alcohol,and evaporating the alcoholic solution, when crystals of the ammo-nium salt of the acid, mixed with ammonium nitrate, separate out.The crystals are dissolved in water and mixed with lead nitratewhich produces a crystalline precipitate.This precipitate is sus-pended in water, treated with hydrogen sulphide, the solution filteredfrom lead sulphide and evaporated, when the acid separates out inneedles. I t s composition will be determined when a-sufficient quantityhas been obtained.The black matter precipitated by the addition of an acid to the solu-tion obtained by the electrolysis of a 2 per cent. solution of potassiumhydroxide has the composition 0 37.72 ; C, 58-65 ; H, 3.27 ; N, 0.56.The whole of the nitrogen was evidently not removed from the carbonelectrodes, although the latter were treated withchlorine for 150 hours.The black substance is soluble in boiling water even after being drieda t lc)Oo, bnt is precipitated by ebullition in contact with air.It isinsoluble in alcohol, ether, benzene, and chloroform. When anaqueous solution of the black substance is treated with a current ofair, it absorbs a considerable quantity of nitrogen, which however isagain partially removed by continued passage of the air, the substancea t the same time being oxidised and destroyed.By G. K~RNER ( P l ~ m . J.Trans. [3], 13, 246). - The bark emplojed differs from ordinarycinchona bark, in that its aqueous solution becomes reddish-violet onthe addition of potash, and, moreover, it yields caffeic acid when em-ployed for the manufacture of sulphate of quinine ; ’ the caffeic acid isfound in the mother-liquors as quinine caffeate.The author hasobtained the acid from the bsrk by the following process, the yieldbeing about 0.5 per cent; :--The powdered bark is first extracted withether and then thoroughly with boiling alcohol. The latter extract isevaporated to dryness and the residue treated with 24 times its weightof boiling water and its own weight of potash; the whole is thenboiled for three hours, -supersaturated with dilute sulphuric acid, fil-tered hot, and extracted with ether. This extract is concentrateduntil crystals form. The crystals are well washed with small quantitiesof ether, and are purified by boiling with animal charcoal and recrys-tallising.They form brilliant hard yellowish tables, with 4.8 per cent.water of crystallisation. From acetic acid they separate in crusts ofopaque nodules, which decompose without melting a t 212”, and havetbe formula C,H,O, + +H20, and they give the characteristic reac-tions of caffeic acid. Dimethylcaffeic acid and methylic dimethyl-caffeate were prepared from the acid and identified.The presence of this acid furnishes an additional proof of the re-lationship existing between the coffee and cinchona plants.C. H. B.Caffeic Acid from Cuprea Bark.D. A. LORGANIC CHEJIISTRY. 67Dibromonaphthalene from ,%Naphthol. By P. CANZONERI(Gazzetta,, 12, 424-431) .-When 10 g. of the monobromonaphtholwhich A.J . Smith obtained by the action of bromine on naphthol(this Journal, 1879, Trans., 789) is mixed in a retort with 15 g. phos-phorus tribromide, no action takes place in the cold ; but on graduallyheating the mixture to a temperature above its meltinq point, anaction commences, attended with rapid evolution of hydrogen bromide.This, however, ceases in a few minutes, and if the mixture be thengradually heated, the action mcommences less energetically, the con-tents of the retort at the same time distilling over. This distillation,if carried on to a red heat, yields :-(1) A quantity of unaltered phos-phorous bromide ; (2) an oil having a faint yellow colour ; (3) a thickyellow oil, solidifying in bhe neck of the receiver. In the retort thereremains a considerable quantity of charcoal.The second fraction, which constitutes by far the larger fraction ofthe product, solidifies either at once or after renewed distiIIation (atabout 300") to a mass of hard transparent crystals melting at 67-68'.The substance thus obtained is a dibromonaphthalene, C10H6Br2, a,ndwhen recrystallised from a small quantity of alcohol, forms largemonoclinic prisms, cleaving easily parallel to the base OP, less easilyparallel to MP.It is but slightly refractive, and exhibits only a faintcoloration in polarised light.This dibromonaphthalene does not dissolve in nitric acid of sp. gr.1-40, but funiing nitric acid dissolves it, especially if the mixture begently heated and immediately afterwards cooled.On subsequentlyadding water, a yellow disagreeably-smelling oil separates, which soonsolidifies, and is best purified by dissolving it in a small quantity ofalcohol and precipitating with water, whereupon it separates in yel-lowish-white flocks, apparently made up of slender needles. Thesecrystals, after drying, melted a t 100-105", and gave by analysis 4'7.50per cent. bromine, the formula CI,HsBr2(N02) requiring 48.34. Thesubstance is probably a new nitrodibromonaphthalene isomeric withthat (m. p. 116.5") which Jolin obtained (Bull. SOC. Chim. [2j, 28,515) by the action of nitric acid on the P-dibromonaphthalene, whichmelts a t 81".The third portion of the above-mentioned distillate, the quantity ofwhich was relatively very small, consisted of opaque yellow scalesimpregnated with a yellow oil difficult to separate ; but by crystallisa-tion from dilute acetic acid and afterwards from alcohol, the substancewas obtained in white silvery scales, melting at 55-60", and givingby analysis numbers agreeing nearly with the formula of rnonobromc/-naphthalene, C10H7Br. As only two such compounds are possible, andone of them (a) is liquid, the compound obtained in the manner justdescribed must be the /3-modification which was obtained by Lieber-mann and Palm (Annalen, 183, 267) from p-naphthylamina, anddescribed as crystallising in lamina?, having the same appearance, butmelting a t 68" ; the difference in the melting points perhaps arisingfrom the circumstance that the author's determinations were madewith a very small quantity of material.The formation of this mono-bromonaphthalene may perhaps be ascribed either to the action of thephosphorous bromide on small quantities of @-naphthol contained inf 68 ABSTRACTS OF CHEMICAL PAPERS.the bromonaphthol, or to decomposition of the dibromonaphthalene a tthe high temperature of the reaction.From the perfect agreement in melting point between the dibromo-naphthalene above described and that recently isolated by Guareschi(Abstr., 1882, 734), from Glaser's impure product (melting a t 76"),the autlhor infers the identity of the bodies obtained in these severalways, and thence deduces the constitutional formula of the dibromo-naphthalene in question. This body in fact, having been obtained byGlaser from a-bromonaphthalene, must have one of its bromine-atomsin the a-position, b u t since it is also producible from monobrom-6-naphthol, it must have the other in the @-position, and consequentlymust be an a-/3-dihromonaphthalene.Now of the ten possible dibromo-naphthalenes, four only have the a-@-structure, viz. : [I : 21, [l : 31,[l, 2'1, [l : 3'1. Moreover, A. J. Smith (Zoc. cit.), by oxidising mono-brom-@-naphthol with permanganate, obtained phthalic acid or anhy-dride, and thence inferred that in this brom-p-naphthol the hydroxyl-and the bromine-atom must be found in the same benzene-ring. Thesame conclusion may be extended to the dibromonaplithalene derivedtherefrom : consequently, the two bromine-atoms of this latter cannotbe in the positions 1 : 2' or 1 : 3', and must therefore have the posi-tion 1 : 2 or 1 : 3.Now, Meldola in a recent memoir (Rer., 12, 1962)describes a dibromonaphthalene melting at 64"-obtained by theaction of nitrous acid on dibromonapht hylamine-to which he assignsthe formula [l : 31 ; and since there appears to be no reason for sup-posing that this product is identical with the above-described dibromo-naphthalene melting a t 67-68', the author infers that the latter mustbe represented by t,ie formula [l : 21.Appenclim.-The author has likewise obtained an acetyl-derivativeand a nitroso-derivative of bromo-&naphthol. The former is a densefaintly yellow liquid, decomposed by distillation under ordinarypressures, but passing over undecomposed at about 215" under apressure of 20 mm.By bromine in acetic acid solution, it is con-verted into a brominated derivative, which is resinified by boiling withpotash.The nitross-derivatire sepat-ates from solution in ether in unstablegreen crystals, melting a t 61-65". H. W.Action of Chloroform on Naphthalene in presence ofAluminium Chloride. By M. BONIG and 2'. BERGER (Mo?zmh.Chem., 3, C68-672).-This reaction has been already investigated byScliwartz (Abstr., 1881, 912), who could not obtain any definite pro-ducts frcm it. A pitch-like mass is obtained, from which solventsfail to extract any well-characterised substance. The crude product isdissolved in benzene, filtered, the benzene distilled off, and the residueafter being heated a t 230" for some time to remove unaltered naphtha-lene, is distilled in a vacuum.The distillation begins far above 360°,and wm carried on to redness. By a long series of crystallisations, asubstance was obtained from the distillate, forming plates of a paleyellow colour (m. p. 189-190°, uncorr.), whose formula would appearto be a multiple of C,,H,, ( ClSH8<, 3). It is possible that this hydro-carbon may be identical with Zeidler's synanthrene ( l h ? z a l e ? ~ , 191ORGANIC CHEMISTRY. 69298). Two substances, melting respectively a t 170-175" and at 215",were also obtained and are being investigated.Constitution of Nitronaphthols. By R. WORMS (Bey., 15,lS13--1818).-Two nitronaphthols from a-naphthol are known : inone the nitro-group occupies the para- or a-position; in the other oneof the @-positions, but it is not known which.An anhydro-base froma-naphthol is also known, but the corresponding nitro-compound hasnot been isolated, and it appeared interesting to, compare it with theother known nitro-a-naphthols. For this purpose benz-a-naphthalidewas converted in small quantities into the corresponding nitro-com-pounds. On cooling, the para-compound crystallises out, and the fil-tered liquid is tjhrown into water to precipitate the ortho-compound.It crystallises from alcohol in yellow needles, melting a t 174". Onboiling it with potash and adding an acid, orthonitro-a-naphthol isobtained in yellow cryst,als, melting a t 128". It is identical with the/3-nitro-a-naphthol obtained by Liebermann and Dittler (AnnaZen,183, 228). That the nitro-group occupies the ortho-position withrespect to the hydroxyl is shown by the fact that the correspondingnitrosonaphthol is easily converted into an anhydro-base.To this end,P-nitroso-a-naphthol benzoate was first prepared by treating the cor-responding sodium-nitrosonaphthol with benzoic chloride in the cold.The benzoate (m. p. 162"), purified by crystallisation from chloroform,is treated with tin and hydrochloric acid, when a violent reaction setsA. J. G.n vin, and the anhydro-base, benzenyl-P-amido-a-naphthol, CIoH,/ 'CPE, \N/is obtained in small needles (m. p. 122"), wh,ich may be purified bysublimation.It appeared also of interest to ascertain whether an anhydro-basecould be produced from the a-nitroso-/&naphthol of Stenhouse andGroves (AtinnZen, 189, 153), in .which the nitroso-group and thehydroxyl have been shown to stand relatively in the ortho-position.The same process was used as above, the sodium salt and then thebenzoate (ni.p. 114") being first prepared, and the latier reduced withtin and hydrochloric acid. Renzenyl-a-amido-@-naph tho1 was thusobtained in colourless prisms melting a t 120°, and soluble in waterand alcohol ; it may be purified by sublimatiov.The formation of anhydro-bases in the naphthalene series seemsthus t o be a property of the ortho-position. It is also noteworthy thatorthonitro-a-naphthol can be separated by steam from the solid para-compound, just in the same way as in the case of the two nitrophenolfi.J.I(. C.Indophenol. By M. A. PABST (BUZZ. SOC. Chinz. [2], 38, 160-162) .-Meldola, and Koechlin and Witt have obtained colouringmatters by the action of nitrosodimethyl- or nitrosodiethyl-aniline onphenols or naphthols. One of t,hese substances, indophenol, is manu-factured by the oxidation of sodium a-naphthol a n d amidomethyl-aniline with potassium dichromate or sodium hypochlorite. It givesa blue dye on reduction, like indigo, and can be fixed on fabrics b70 ABSTRACTS OF CHEMICAL PAPERS.stannous oxide. It is more stable than indigo to light and soap, andis less costly, but is destroyed by concentrated mineral acids. Thecolour varies from a violet to a greenish-blue, according to the par-ticular phenol employed.Koechlin, by the action of nitrosodimethylaniline on tannin, gallicacid, and the catechins, obtained a violet dye, galbcyanine ; it formsbeautiful crystalline salts, and can be fixed on cotton by chromiumsesquioxide.These colouring matters are prepared in France by Durand andHuguenin, and it seems probable that from their cheapness andstability they will replace alizarin for violet, and indigo for bluetints.'V. H. V.a-Naphthaquinone-ethylanilide. By L. ELSBACH (Ber., 15,1810--1813).-Two parts of a-naphthaquinone are heated in a flaskwith five parts of glacial acetic acid and three parts ethylaniline ; thereaction proceeds by itself when the mixture has begun to boil. Oncooling, the mass is extracted with alcohol, and by repeated crystalli-sations the pure a-naphthaquinone-ethylanilide,is obtained in dark violet needles, melting at 155".When boiled withstrong caustic soda, it is conver.ted into a reduction product and a re-sinous mass. It is a feeble base, and combines readily with acids toform salts, which are easily decomposed.During its formation by the above reaction, a yellowish-green bye-product is formed, which amounts to one-fifth of the yield. Afterboiling it with alcohol and ether, it was analysed, and found to con-tain no nitrogen, numbers being obtained corresponding with theformula C20H1004. Zinc andhydrochloric acid reduce it, forming a green fluorescent solution. I na11 probability, therefore, it appears to be the a-product correspondingwith the p-dinaphthadiquinone discovered by Stenhonse and Groves.J.K. C.Derivatives of Styrolene. By A. BERNTHSEN and F. BENDER(Ber., 15, 1982-1986). -In addition to the method already described(Abstr., 1882, 20l), paramidostyrolene, CsH,(NH,)C,H,, can be pre-pared by heating paranitrocinnamic acid in a paraffin-bath until themass is in quiet fusion. The melting point is difficult to determine ;softening occurs a t 76", complete fusion at 81".Parahydroxystyrolene appears to be obtained in small quantity bydistilling barium paracoumarate mixed with sand, and forms a nearlyc~lourless oil, of phenol-like odour, sparingly soluble in water. Thesolution is precipitated by bromine.Styrolene unites directly with hydrobromic acid, yielding a brom-ethylbenzene. This is a, pale-yellow liquid, of odour resembling thatot benzyl chloride, sp. gr.1.3108 a t 23". When heated, it is decom-posed into hydrobromic acid and styroleue. It is probable that it hasthe constitution CH2Ph.CH2Br.Methylanthraquinone and some of its Derivatives. By E.U~~KNSTEIN (Ber., 15, 1820--182S).--The substance bearing this name,(/3) NXtPh.CloHt,: 0 2 (a),It is soluble only in fuming nitric acid.A. J. GORGANIC CHEMISTRY. 71and sold commercially, was examined for the purpose of identification.After repeated crystallisations from alcohol, it melted at 175-176O,and gat-e on analysis numbers corresponding with the formula ofmethylanthraquinone. Reduced with zinc aud ammonia, and boiledwith xylene, greenish-yellow crystals of rnethylanthracene were ob-tained and analysed.After repeated crystallisation, it melted a t 203".By oxidation wikh chromic acid, anthraquinonecarboxylic acid wasformed, and a dibrominated product was also prepared, melting a t148". Attempts to prepare a definite methylhydroanthranol havehitherto been unsuccessful. J. K. C.New Nitro- and Amido-anthraquinones, and New Methodof Preparing Erythroxyanthraqginone. By H. ROEMER (Ber.,15, 1786--1794).--Nitro- and amido-anthraquinones have been ob-tained by Bottger and Petersen (Ber., 6, 16), and an isomeric amido-compound by von Perger (Bey., 12, 1566). Other experimentershave failed to obtain a nitro-compound by Bottger and Petersen'smethod, and have recommended another, viz., to treat dibromanthra-cene with fuming nitric acid.The author was also forced to haverecourse to this process, but on repeating his experiments could obtainno product of settled composition. Another method was thereforetried, and with success. Anthraquinone dissolved in sulphuric acidwas treated with the requisite quantity of nitric acid ; crystals wereformed, and after two days the whole was poured into a large quantityof water. The white precipitate thus obtained could be separated intothree bodies by crystallisation from alcohol. The body of mediumsolubility attracted attention at once by the beauty and size of itscrystals.The following method was found to give the largest yield:-10 grams of anthraquinone dissolved in sulphuric acid were treated with4.5 grams of nitric acid (sp.gr. 1*48), and left foil two days. The crudeproduct after being washed with water was extracted with ether, theextract distilled until crystals began to form, and after cooling, thefiltered liquid was found to contain the body most soluble in alcohol,whilst the crystals contained the wished-for product, purifiable byrecry stallisation. For larger quantities,. the crude product can besimply extracted by repeated small quantities of hot alcohol : after thesecond extraction the body is obtained almost pure. The pure pro-duct on analysis gave numbers closely agreeing with the formula fornitranthraquinone. That it is not a mixture of anthraquinone andits dinitro-compound is proved by its behaviour with ammonium sul-phide, the latter converting it into a body soluble in cold stronghydrochloric acid, in which anthraquinone is insoluble, even aftertreatment with ammonium sulphide.Nitrmthrayz&mne sublimes in yellow crystals (m.p. 220°), inso-luble in water, sparingly soluble in alcohol, ether, and glacial aceticacid, and crystallising therefrom in brilliant prismatic needles, butmore soluble (with yellow colour) in benzene, chloroform, and con-centrated sulphuric acid. Its solution in the latter becomes red whenheated, and on being thrown into water gives a reddish-violet preci-pitate, which yields a purple solution in alcohol, showing two dar72 ABSTRACTS OF CHEMICAL PAPERS.bands. It thus exhibits decided differences from the body describedby Bottger and Petersen, which become more striking when the amido-compound is examined.Orthami&on.nthra.qrui.1Lone is easily obtained in a pure state by dis-solving the above nitro-compound in alcohol, precipitating withwater, and adding an alkaline solution of stannous oxide.A cleargreen solution is at once obtained, which after twelve hours' standingbecomes reddish-ydlow, and depasits. the amido-compound in beautifulred needles, purified by washing with water. Andysis shows them toconsist of amidoanthraquinone (m. p. 241'). It, sublimes withoutcharring in deep-red needles, insoluble in water, but giving reddish-Fellow solutions with alcohol, ether, benzene, chloroform, glacialacetic, sulphuric, and hjdrochloric acids.From its hot saturatedsolution in the last, the hydrochloride separates out on cooling in whiteneedles. I t s acetyl-compound is obtained by boiling it with aceticanhydride and sodium acetate, and may be separated by adding water.It crystallises from alcohol in mange-red needles melting at 202", or39" lower than Perger's acetyl-compound, exactly the same differencebeing observed between the two * amidoanthraquinones. Perger'sdescription and.results were also confirmed by the anthor, and as hisamidoanthraquinone is a metn-compound, it seemed probable that thebodies obtained by the author belonged to the ortho-series, an assump-tion which was eonfirmed by their conversion into erythro-oxyanthra-quinone in the following way :-The amidonnthraquinone was dis-solved in glaeial acetic acid, a little concentrated snlphuric acid added,and then potassium nitrite until the solution had become yellow.After standing a short time water was added, the mixture boileduntil yellow flakes separated, increasing in quaiitity as the aceticacid evaporated.Crystallisation from alcohol then yields a t onceorange-yellow feathery crystals melting .at 191", and agreeing inevery other characteristic with epythroxyanthraquinone. The nitro-and amido-anthraquinones obtained by the author belong therefore tothe ort h 0- series. J. K. C.Action of Concentrated Sulphuric kcid on Dinitroanthraqui-none. By C. LIEBERMANN and A. HAGEN (Bey., 15,1801-1806).-Bythe action of hot concentrated sulphuric acid on dinitroanthraquinone,a dye-stuff is formed (Be?.., 3, 905), which has not received a thoroughinvestigation. To obtain it, the anthraquinone is heated with 15 timesits weight of sulphuric acid at 2@0', and the cooled *mixture pouredinto water. A brown%precipitate is thrown down,[ dissolving in alkaliswith violet colour,; after being-throwu down again by hydrochloricacid, it is purified by boiling with hryta-water, in which it partlydissolves.The substame is again precipitated by acid from the solu-tion, washed, and transferred in the pasty condition into cold bargta-water. After standing, the filtered liquid is again treated with acid,the precipitate washed, and crystallised repeatedly from alcohol. Onanalysis, numbers were obtained corresponding with the formulaC28H18N207.Ou heating it with hydrochloric acid, a colouring matter is obtainedfree from nitrogen.With nitrous acid, however, it splits up intORGANIC CHE MISTRP. 73erythroxyanthraquinone and purpurosantbin. 'It appears thereforeprobable that the dye-stuff in question consists of a mixture of theamides of these two bodies. The action of sulphuric acid on dinitro-nnthraquinones is first an oxidation, sulp hnrous and phthalic acidsbeing formed : the sulphurous acid then reduces the nitro-groups,forming amides, and this part of the process can be greatly accele-rated by introducing sulphurous anhydride or zinc. The amido-groups are then partially attacked by sulphuric acid and convertedinto hydroxyls. A complicated mixture of substances is thus formed,of which the substance investigated by the authors fornis but a smctllpart. J.I(. C.Derivatives of Arithrol Salts. By C. LIEBERMANN and A. HAGEN(Ber., 15, 1794--1800).--In a former communication (Ber., 15, l427),the authors have given thernameo of ethyl dinitroanthrolate to the bodyobtained by the action of nitric acid on ethyl anthrolate. Furtherexperimmts have, however, shown that this view is not correct, bothit's reduction and oxidation products pointing to another formula.Boiled with glacial acetic acid, tin, and hydrochloric acid, ethyl mon-amidoanthrolate is formed, and, the other half of the nitrogen is foundin solution as ammonia. One only, therefore, of the nitro-groupspossesses the ordinary characteristics of aromatic nitro-groups, andthe other is in reality a nitroso-group, The body in question is there-fore termed by the authors the nitroso-anthrone of ethyl mononitro->CsH,(NO,). fIl3t.nnthrolate, CsH,<rH(NQ) co -\ I By oxidation with boiling acetic and chromic acids, the correspond-ing nitroxyanthraquinone ethylate is obtained in colourless needlesmelting a t 243"; and this when boiled with glacial acetic acid andgranulated tin until the solution becomes red, yields amidoxyanthra-quinone ethylate in red crystals melting a t 182". Contrary to theauthor's expectation, the ethyl-group in t,he above compounds could notbe eliminated by boiling with alkalis or acids, or with alcoholic potash :by fusion with potash, they are, however, decomposed in a more corn-phcat'ed way.The reactions of the hydroxyanthraquinone salts weretherefore studied in order to throw light on this curious behaviour.Ethyl anthrolate was oxidised in acetic acid with excess of chromicacid, hydroxyanthraquinone ethylate being formed (m. p. 1 3 5 O ) , verysoluble in alcohol. This is also proof against all alkaline solutions, andis only gradually attacked by fused potash and converted into alizarin.The ethyl ether of anthraflavol was also found to exhibit this stability,which appears to be characteristic of the hydroxyanthraquinones. Adecomposing agent was, however, found in hot concentrated sulphuricacid. On heating it solution of the ether in this acid to ZOO", it turnsbrown, and on cooling and adding water, hydroxyanthraquinone isthrown down (m.p. 301"). A similar reaction takes place with theethers of anthraflavol. Amidoanthraquinone ethylate was thereforetreated in the same way, and was found to be converted into alizarin-amide, easily recognised by its r( actions.The constitutional formula of the nitroso-anthrone of ethyl nitro-anthrolate is therefore74 ABSTRACTS OF CHEMICAL PAPERS.CJ34<,H~N0)>C,W2<~~~ -co- [NO,: OEt = 1 : 21.J. K. C.Dihydroxyanthracene from a - AnthraquinonedisulphonicAcid (Flavol). By G. SCH~LER (Bw., 15, 1807--1810).-Commercialsodium a-anthraquinonedisulphonate was redaced with zinc-dust andammonia to obtain the sodium salt of flavanthracenedisulphonic acid,which forms yellowish-grey crystals, dissolving in water with intenseblue fluorescence. The thallium and barium salts are whitre andcrystalline, those of silver and lead are yellowish precipitates.Sodiumarzthrosulplio.lzate, C,aH,(OH) .SO,Na, is obtained by fusing the cor-responding disulphonate with potash until the mass has becomethin : when cold, it is treated with acid filtered and alcohol added ;the precipitated salt is recrystallised from water, to which it communi-cates a greenish fluorescence; precipitates are formed with the heavyand earth metals.PZuvoZ, C,4H8(OH)2, is formed when the fusion with potash is con-tinued until the mass becomes intensely black, and gives off a tarryodour. By decomposing the product with acid, and repeatedly re-crystallking the insoluble portion from alcohol, flavol is obtained as abright yellow crystalline powder (m.p. 260-270"), soluble in alkaliswith yellow colour and very fine green fluorescence, Diacetylflavol,prepared in the usual way, crystallises in white plakes, melting a t254-255". The diethylic ether, obtained by saturating an alcoholicsolution of flavol with hydrochloric acid, melts a t 229" after beingpurified by crystallisation from glacial acetic acid.Flavol differs from the other known dihydroxyanthracenes in thestrong fluorescence of its alkaline solutions and in the higher meltingpoints of its salts.Soluble Alizarin Blue. By €3. BRUNCK and C. GRAEBE (Ber., 15,1783-1 786) .-Alizarin blue being but sparingly soluble, and there-fore difficult to fix on the fibre, has not been as extensively appliedas was to be expected from its otherwise valuable properties.Inorder to convert it into a more soluble form, experiments weremade by Brunck, ending in the issue of a patent, from which themethod of obtaining the soluble blue may be briefly extracted asfollows : -Alizarin blue in a fine state of division, and in the form ofa paste containing 10-12 per cent. blue, is stirred up with 25--30percent. of a solution of sodium hydrogen sulphite (sp. gr. 1-25), and themixture left for 8-10 days. lt is then filtered, unchanged blue beingleft behind, and the soluble blue separated from the filtrate in reddish-brown crystals by addition of common salt, or evaporation a t a lowtemperature. The dry powder can be heated to 150" without under-going change, but its aqueous solution begins to decompose at 60", aridon boiling, the blue separates out.In the cold a solution of chromicacetate produces no change, but a t 60-70°, the blue chromium lakeis thrown down. This fact is made use of in printing; the solubleblue and chromic acetnte mixed with starch are printed on the fabric,and the latter steamed for 10 or 20 minutes and then washed.After makirig due allowance €or the sodium chloride present, anJ. K. CORGANIC CHEAWSTRP. 75analysis of the commercial article gave numbers corresponding withthe formula C,,H,N04 + 2HNaS03.Neither alizarin nor the purpurins possess the property of combin-ing with alkaline bisulphites ; quinoline, however, forms very solublecrystalline compounds, whose aqueous solutions decompose in the sameway as those of soluble alizarin blue.It appears therefore probablethat the capacity for combining with biaulphites rests in both cases withthe nitrogen-group. J. K. C.Hydrocarbons of the Formula (C5He)%. By W. A. TILDEN(Chem. News, 46, 120--121).-The author has already suggest,ed(Trans,, 1878, 85-88> that the liquid terpenes and citrenes (CloH16)are not correctly represented as dihydrides of cymene. He now findsthat the hydrocarbons of the formula C5H8 appear to supply importantevidence in connection with this question. The author has furtherexamined isoprene, the most interesting of these hydrocarbons, andobserves that it boils at 35" (not 38"), has the vapour-density for C5H,,that it forms a tetrabromide, C5H8Br4, an oily yellowish liquid- whichcannot be distilled without decomposition, and remains liquid at - 18",and moreover he confirms Bourchardat's statement that when heatedfor some time a t 280" it forms &-isoprene, CIoH,, (b.p. 174-176"),apparently identical with terpilene from turpentine, yielding the samehydrochloride, and being converted by the action of dilute acids intoterpin, CIOHZ2O3, having the same crystalline form as the terpin from tur-pentine. It likewise resembles turpentine in its behaviour with sulphuricacid. Hence it seemed to the author that isoprene might be oht,ainedby depolymerising turpentine. When turpentine is passed through ared-hot iron tube, among the other products a substance is found(b.p. about 37', vap.-den. 35", C5H8 requires 34")) having the samecomposition and some of the properties of isoprene. A litre ofturpentine yields about 20 C.C. of the fraction (37-40"). Rebonl'svalerylene from amylene dibromide, and Hofmann's pipcrylene (Abstr.,1881, 571), are both isomerides of isoprene. Valerylene differs frompiperylene by not forming a tekabromide and from isoprene by form-ing a ketone when digested with mercuric bromide and water ; isopreneis unaffected. Theoretically there are eight compounds of the formulaC5&, all open chains ; of these, three are acetylenes, forming copperand silver derivatives, thus differing from the above isomerides. Asvalerylene is easily converted into a ketone, it would probably be cor-rectly represented as a dimethylallene, either CHMe : C : CHMe orChile, C CH2; and as isoprene does not undergo this change theauthor is inclined to regard it, as P-methyl-crotonylene,-CH, CMe.CH CH,.It would be difficult to explain how such a substance could be poly-merised into a methylpropylbenzene, therefore the author is of opinionthat terpene may be more correctly represented either by the formulaCH, CH.CMe : CH.CH CHP@ or thus:-CH, : CPrp.CH : CH.CMe : CH2.He also feels disposed to look on isoprene as the first term of a seriessomewhat analogous t0 the olefines, COHB, C,,H16, C15H24) &c.Colo76 ABSTRACTS OF CHEMICAL PAPERS.phene from turpentine, seems to be a saturated hydrocarbon of thisform.The absorption spectrum of isoprene a t the ultra-red endhas, according to Abney, the characteristics of that of an aromaticbody. At the other end, according to Hartley, it resembles that ofaustralene, the main constitutent of common turpentine.D. A. L.rend., 89,1117-1120: this Journal, Abstr., 1880, 323).-D. A. L.Note. -Bourchardat has described two bromides of isoprene (Compt.Essence of Sandal1 Wood. By P. CHAPOTEAUT (Bull. XOC. Chim.[2], 37, 303-305) .-!Essence of sandal wood, obtaining by distillingthe wood with water, is a somewhat thick liquid of sp. gr. 0.943 a t15", and boiling between 300" and 340". Tt consists almost entirelyof two oxygenated bodies, the more abundant of which is C,5Hz40 (b. p.300") ; and the other, C&Z,O (b.p. 310"). 'When treated with phos-phoric anhydride essence of sandal wood yields two hydrocarbons,C15H2, (b. p. 248'), and CI5Hz4 (b. p. 260'). Oil of cedar, whenpuritied from oxygen compounds, has the composition C15H22, and boilsa t the same temperature as the hydroc~rbon from essence of sandalwood. The two products are probably identical. The hydrocarbon,C15H2,, is either isomeric or idelltical with oil of copaiba.When slowly distilled, essence of sandal wood yields products boilingbelow 250" and above 350°, together with water arid hydrogen, but thedecomposition is not complete. If the essence is heated in sealedtubes a t 310", it splits up in accordance with the equations 4Cl5H,O=C2,H3,0 $- C&6203 + 2H2, and GOH,,O3 = C4,H6,OZ + &O.Thecompound, C,o€€300, boils at 240°, and when treated with phosphoricanhydride yields a cymene boiling a t 175-180'. The product,C10H6203, is a thick liquid, boiling at about 340", and the third body,C,oH,,Oz boils at 350", and has the consistence of honey. The essence,C15H260, apparently splits up in a similar manner.When heated a t 150" under pressure for seven or eight hours withhalf its weight of glacial acetic acid, essence of sandal wood yields twoproducts, CMH4,0 (b. p. 280-285"), formedfrom 2C!,H,,O b3 loss ofH,O, and C,,H,,O, (b. p. 298"), the acetate derived from the bodyC,,H,,O. With hydrochloric acid a t 125", essence of sandal woodyields a hydrochloride boiling at about 275", but the reaction is morecomplex than with acetic acid.The cornpound, CI5Hz6O, has thereforethe properties of an alcohol ; the compound C1,H,,O has the propertiesof an aldehyde, and is probably the aldehyde of Cl5HZ6O.C. H. B.Synthesis of Salicin and of Anhydrosalicylic Glucoside.By A. MICHAEL (Ber., 16, 1928--1925).-Bg the action of sodiumamalgam on helicin obtained from salicin, Lisenko succeeded in reform-ing the latter body. The author has repeated this with artificial helicinprepared by the action of acetochlorhydrose on potassium salicylate,and has obtained salicin identical in properties with natural salicin.In an attempt to make the glucoside of salicylic acid, the action ofacetochlorhydrose (2 mols.) on disodium salicylate (1 mol.) inalcoholic solution was tried. The sodium chloride, which separatedout after several days, was filtered off, and by the spontaneous evaporaORGANIC CHEMISTRY.77tion of the filtrate, a body of the formula C2,H3,015 was obtained,crystallising in needles. A portion of the same substance also sepa-rated with the sodium chloride. This new compound melted a t 184-185"; it is almost insoluble in water and cold alcohol, moderatelysoluble in hot alcohol. It is insoluble in cold ammonia, but dissolvesgradually in cold soda. Boiling it with alkalis or acids decomposes itinto salicylic acid and dextrose. When heated with acetiLanhydrideand sodium acetate, it forms an acetyl-derivative, C26H2201,Ac,, meltingat 110-111". A. K. M.Santonous and Isosantonous Acids. By C. CANNIZZARO andG. CARNELUTTI (Gazzetta, 12, 393-41 6).- I. SANTONOUS ACID,C1,H2,0,.-This acid, containing 2 atoms of hydrogen more thansantonic acid, is prepared by heating santonin in a reflux apparatuswith hydriodic acid (b. p. 127") and amorphous pbosphorus. Onfiltering the resulting liquid through asbestos, and digesting the solidmass on the filter with cold aqueous sodium carbonate, the santonousacid dissolves, and on acidifying with hydrochloric acid and leavingthe liquid to cool. separates iii needle-shaped crystals, which may bepurified by repeating this treatment several times, and finally crpetal-lising from ether. The acid thus purified crystallises in white needles,melts at 178-179", and resolidifies on cooling. Under a barometricpressure of 5 mm, it distils unaltered at 200-260" ; under ordinarypressure, i t is partly decomposed by distillation.It is very soluble inabsolute alcohol and in ether, slightly in cold water, and crystallisesfrom a boiling aqueous solution on cooling. Its solutions are opticallydextrogyrate, a character by which it is most readily distinguishedfrom isosantonous acid, which is optically inactive. It dissolves at theordinary temperature in aqueous solutions of the alkaline carbonates,and of the earthy-alkaline hydroxides. Its alkali salts are verysoluble in water and in alcohol, slightly also in a mixture of alcoholand ether.-The sodium salt, C15H19Na03, crystallises in very smallneedles ; the silver salt, obtained by precipitation, blackens veryquickly even in the dark.-The barium salt, Ba(C15H190J)2, is solublein water, and on evaporation in a vacuum separates in efflorescentcrystals ; on the other hand a cold saturated aqueous solution whenheated deposits a salt which is not efflorescent, although it containswater of crystallisation; it is also much more soluble than the saltdeposited a t higher temperatures.E t h y l santonite, C17H2403 = C15H1903.C2H,, prepared in the usualway, and purified by repeated crystallisation from ether, forms whitecrystals, soluble in alcohol and ether, melting a t 116-117".Its solu-tions are dextrogyrate.-Methy I santonite, prepared in like manner, iswhite, very soluble i n ether, and melts a t 81--84°.-BthyZic sodium-santowite, C15H1,Na03.Et, obtained by boiling under pressure a solu-tion of ethyl santonite in absolute ether with sodium, separates as awhite powder, and is instantly resolved by cold water into ethyl santo-nite and sodium hy droxide.-Bthylic bei~zoyZ-sa,ntonite, C2,H,,O3 =C,,H,,EO,Et, formed byv heating ethyl santonite with benzoyl chlo-ride in a reflux apparatus, is a white crystalline body, very soluble inether, melting at 78". By boiling with alcoholic potash it is resolve78 ABSTRACTS OF CHEJIICAL PAPERS.into benzoic and santonous acids.-EthyZic ethyLanton,ite, C,,H,,O, =CI5H1,EtO3.Et, obtained by heating ethylic sodium-santonite withethyl iodide under pressure, crystnllises in long needles, melts a t 31 -32", dissolves in alcohol, and very easily in ether.--Etlz?~Z-sa~ito~ousacid, C17H,,03 = CI5H,,( C2H5)03, obtained by boiling ethylic ethyl-santonite with alcoholic potash, crystallises in long slender needles,melts between 115.5" and 116", and exhibits strong acid properties.It is reconverted into the ethylic ether by passing hydrogen chloridethrough its alcoholic solution.The preceding facts show that san-tonous acid contains, in addition to acid hydroxyl-groups, an alcoholicor phenolic hydroxyl.ISOSANTONOUS ACID, C15H,o03.-When a mixture of santonous acid(1 pt.) and barium hydroxide (3 pts.) is heated t o n temperature abovethe melting point of lead, a fused yellowish mass is obtained ; and onexhausting this mass with hot water, and passing carbonic anhydrideinto the filtered solution, barium carbonate is precipitated together witha, phenol ; and on again filtering and treating-the filtrate with hydro-chloric acid, isosantonous acid is precipitated in larger or smallerquantity, according to the time for which the heating with baryta hasbeen prolonged.The acid is purified by dissolving it in alcohol, pre-cipitating with hot water, pressing the precipitate between cloth, andwashing with water, till the liquid passes through clear. This treat-ment is repeated several times, and the prodact finally crystallisedfrom ether. Isosantonons acid crystallises in laminae, different in'appearance from those of santonous acid, me3ts a t 153-155", andresolidifies on cooling. It distih unaltered a t 150-160" under a pres-sure of 4 mm. ; under ordinary pressure, it partly distils, partly decorn-poses like santonons acid.It is soluble in alcohol and in ether, verysparingly in cold-water, and separates from a boiling aqueous soluticnas it cools in shining plates.Theethy Zic ether, C17H203, prepared by passing hydrogen chloride throughthe alcoholic solution of the acid, forms white crystals melting a t 125".In this ether, as in ethyl santonite, an atom of hydrogen may bereplaced by benzoyl, sodium, or potassium, or by ethyl, whereby a seriesof derivatives is obtained isomeric wit'h the corresponding santonites,but differing therefrom in melting point and other characters, especiallyby the absence of rotatory power.The following table exhibits a comparative view of the meltingpoints of the two isomeric acids and their ethereal derivatives :-Santonous acid, C,5H200s Isosantonous acid,178".154".Ethylic santonite, CI5Hl9O3. E t E thylic isosantonite,117". 125'.The solutions are optically inactive.Isosantonous acid is a strong acid, and is easily etherified.Ethylic benzoylsantonite, C16HlA&03.Et Ethylic benzoylisosantonite,78". 91".Ethylic eth y lsnntonite, C15H18Et O,.E t31". 54O.Ethylsantonous acid, CI5Hl8EtO3.H Ethylisosantonous acid,116". 143".E th ylic e thylisosantoniteORGXSIC CHEXISTRY. 79These two isomeric acids further yield the same products of decom-position, vie., dimethyl-naphthol and dimethyl-naphthalene.DIMETHYL-NAPHTHOL, ClzH120 = CloH7Me,.0H.-This is the phenolobtained, as already observed, together with isosantonous acid, byheating santonous acid with barium hydroxide.It is also formed,together with dimethyl-naphthalene, by distilling santonous acid withzinc-powder, and may be separated by agitating the distilhte withpotash-ley, and extracting with ether the portion not dissolved by thealkali. The impure phenol, prepared in either way, may be purifiedby dksolving it in alcohol, precipitating with hot water, washing theprecipitate on a cloth filter, and repeating this treatment till the pro-duct presents a homogeneous appearance. Dimethyl-naphthol thuspurified crystallises in shining needles, melts without alteration a t135-136", sublimes under ordinary pressure a t loo", and may beboiled and distiJled under reduced pressure. It is very soluble inether, soluble also in alcohol, very sparingly soluble in cold water, andseparates ou cooling from its solution in boiling water in very smallneedles.It dissolves in aqueous baryta, soda, and potash, and is pre-cipitated by excess of the latter in a crystalline form.Afethylic dinaethylnayhtho late, prepared by heating the phenol underpressure with methyl alcohol and methyl iodide, crystallises in hardwhite prisms, melts at 68", is volatile, and dissolves in ethyl alcohol,methyl alcohol, and more abundantly in ether.-The ethylic ether is aviscid liquid, the solution of which in chloroform gives with brominea crystalline prodtuct which melts at 90".Acety I-dimethy Zn~plLthol, Cl,Hl4O2 = C1?H11.GO, ppepared by boilingthe phenol with fused sodium acetate and excess of acetic anhydride,crystallises after purification in white scales melting ,at 77-78".Dimethyl -naphthol, oxidised in acetic acid solution with chromic acid,yields yellowish rhombic plates, and a very small quantity of white,apparently rhomboNa1 prisms, both of which melt between 104" and105".The yellow crystals gave by analysis numbers agreeing nearlywith the formula C1,Hl20,.-This substance when treated with potashblackens without dissolving. Heated with hydriodic acid and redphosphorus, it is reconverted into dimethylnaphthol.DIMETBYL-NAPHTHALENE, Cl,H,, = C10H6Me2 may be prepared byheating dimethyl-naphthol with 10 parts of zinc-powder, and passingthe resulting vapour through a column of the same powder heated tolow redness, whereupon a yellow liquid distils over, from which potashdissolves out unaltered dimethyl-naphthol.The whole is then dis-tilled with steam, and the watery distillate, holding an oil in suspen-sion, is mixed with potash and shaken with ether, which dissolves outthe dimethyl-naphthalene, tlogether with a small quantity of naphtha-lene. The ether having been evaporated off, the remaining oil isboiled several times with sodium in a reflux apparatus till the globulesof the metal remain bright, and is then distilled in a Sprengel vacuumat the heat of a salt-bath. By careful fractionation in this manner, itis possible to separate small quantities of naphthalene, but the removalof the last traces is very difficult.Dimethyl-naphthalene purified in this manner as completely a81) ABSTRACTS O F CHE3IICAL PAPERS.possible, boils at 262-264" under a pressure of 751 mm., has a densityof 1.0283 a t 0", and 1.10199 a t 1 2 O , and a vapour-density = 77.8"(H. = l), the calculated density being 78.I t unites with picric acid,forming a very characteristic compound, which may be obtained bymixing the two bodies in hot concentrated alcoholic solution, andcrystallises on cooling in long orange-yellow needles melting a t 139".Dimethyl-naphthalene also forms a characteristic tribromo-derivative,C12HHSBr3, which crystallises in white needles melting at 228".The dimethyl-naphthalene obtained as above from diniethyl-naphthol,may also be prepared by the action of inethyl iodide on GLaser'sdibromonaphthalene melting at 81" (Annalen, 135, 49) ; and finally,together with the above-mentioned dimethyl-naphthol, and a smallquantity of xylene, by distilling santonous acid over zinc-powder in anatmosphere of hydrogen.S a n t o nin, C15H1803 (from wormseed), distilled with zinc-powder ina stream of hydrogen, yields the same dimethyl-naphthalene, togetherwith propylene and a dimethyl-naphthol, apparently identical with thatwhich is obtained by the decomposition of santonons acid.Theauthors have not been able to confirm the statement of Saint-Martin( C o q ~ t . rend., 75, 1120), according to which santonin distilled withzinc-powder yields a compound, which he calls santonal, partly liquid,partly crystalline, and having the composition C3,,H1802.Psoromic Acid, a New Acid extracted from Psoromacrassum.By G. SPKA (Gazzetta, 12, 431--43S).-This lichengrows in a few localities in Sicily, and the small quantity with whichthe author's experiments were made was gathered near Dahlia, provinceof Caltanisetta. By exhaustion with ether in a percolator, i t yieldeda yellow substmanee (A') crystallising in needles from the ether on cool-ing, and a brown residue (B), which remained in considerable quantityon distilling off the solvent.The crystallised body is soluble in warm alcohol, et'her, chloroform,and acetic acid, and recrystallises from these solvents more or less oncooling, but benzene, unless employed in large excess, dissolves onlya part of it, leaving a nearly white crystalline residue.The consti-tuent soluble in benzene was purified by repeated crystallisation fromthat liquid ; the insoluble portion by crystallisation from alcohol andrepeated washing with cold alcohol.The yellow substance crystallised from benzene is usn ic acid,C,eH1808, melting at 195-197", and yielding a sodium salt,H. W.which crystallises from warm water in stellate groups of needles.The white substance only slightly soluble in benzene crystallises fromalcohol in silky needles, dissolves in the solvents above mentioned,and t o a slight amount in water, to which it imparts a faint acidreaction. It dissolves also in alkalis and dkaline carbonates, and insulphuric, nitric, and hydrochloric acids, melts with decomposition a t263-264", and begins to sublime, but resolidifies a t a high teKpera-ture, about 215".Dried at loo0 it gave by analysis 60*23--60.2!4 percent. carbon, and 3.71-3.97 hydrogen, leading t o the formula CzoH,,09ORGANIC CHEMISTRY. 81which requires 60.30 carbon and 3.51 hydrogen. Its silver salt, obtainedby precipitation, forms white flocks, which alter on exposure to light.The analysis of this salt leads to the formula CZOH15Ag010, Ahowingthat the corresponding acid (psoromic acid) has the compositionC2,H,,0,,, and that the compound C2,H,,09 extracted from the lichenas above described, is not the acid but the anhydride. The acid itsel€has not been obtained in the free state.Psoromic anhydride boiled with aniline is converted into a crystallineyellow substance, which when further heated does not melt, but decom-poses, yielding a carbonaceous residue, and a liquid having a charac-teristic acetic odour, probably psoromic anilide. The anhydride heat'edwith water in sealed tubes a t 240°, jields a yellow-brown liquid and abrown residue, which, as well as the residue left on evaporating thesolution, exhibits the characters of an acid, and gives with ferricchloride a dark green coloration, not produced by psoromic acid.The brown residue B, left 011 evaporating the ether nsed for theextraction, yields to benzene a small quantity of a resinous substance,together with psoromic acid.The lichen, after exhaustion with ether, yields to boiling alcohol asubstance having the characters of a wax.This the author reservesfor further examination.H. YY.Laws of Variation of the Specific Rotatory Power of Alka-loids under the Influence of Acids: By A. C. OUDEMANS, J u n .(Bec. Il'rav. Chim., 1, 18--4O).-The author records and tabulates alarge number of observations relating to the influence of acids, orgacicand inorganic, on the mon-acid bases quinamine and conquinnniine,and on the biacid bases quinine, yuinidine, cinchonine, and cinchoni-dine, both in aqueous and in alcoholic solution,-and deduces fromthese observations the following general conclusions :-1. The specific rotatory power of the mon-acid bases, as mani-fested in the aqueous solut'ions of their normal salts, is the same forall the salts, and is independent of the chemical character of the acidwith which the base is united.Small differences occasionally ob-served are due to partial and unequal decomposition of these saltsunder the influence of water, and to the varying influence of thedegree of conceiitration on the different salts.2. As long as the normal salt is not decomposed by water, thisspecific rotatory power coincides with the maximum value, the smalldifferences sometimes observed arising from partial decomposition.3. Biacid bases form two series of salts, in each of which series thebase exhibits a distinct specific rotatory power, the value of which isusually much smaller in the basic: than in the normal salts.4. The real specific rotatory power of the biacid bases in the formof mormal saZts and in aqueous solution is probably the same for allthe salts, and independent of the chemical nature of the acid withwhich the base is combined ; but in consequence of partial decomposi-tion and of the unequal influence of concentration on the various salts,the specific rotatory power cannot show itself with its true value.6.The real specific rotatory power of the biacid bases in the formof9 VOL. XLIV82 ABSTRACTS OF CHEMICAL PAPERS.basic salts is probably the same for all the s a h , the differences betweenthe observed values being due to partial decomposition, and for themost part to the unequal influence of concent,ration on the differentsalts. El. W.Action of Nascent Hydrogen on Pgrroline. By G. L. CIAMICIANand M. DENX'STEDT (Ber., 15, 1831-1832).-An acetic acid solutionof pyrroline is heated with zinc-dust for some days, the excess of pyrroldistilled off with steam, the zinc removed by sulphnretted hydrogen,and the acetic replaced by hydrochloric acid.The solution is thentreated with potash and steam-distilled, the distillate treated withhydrochloric acid and evaporated t o dryness on a water-bath, redis-solved, and steam-distilled with potash. The firsti portions of the dis-tillate richest in the base are mixed with solid potash, whereby thebase is separated as an oil, and, after drying over fresh potash isagain distilled. It boils a t 90--91", and is a colourless liquid havingtt strongly alkaline reaction and ammoniacal odour ; it is very solublein water, from which it is not easily separated.The plat'inochloridealone was analysed, as the free base could not be obtained in a suffi-ciently dry state. The former is a yellow precipitate almost insolublein cold water. Analysis of this compound leads to the formula C,H,Nfor the free base. J. I(. C.Synthesis of Pyridine Derivatives from Ethyl Acetoacetateand Aldehydammonia. By A. HANTZSGH (Annulen, 215,l-82).-Bietlayl hydroco7lidine~icarto~~late, CaMes( COOEt),H,N, is prepared bywarming a mixture of 52 grams of ethyl acetoacetate and 13.5 gramsof aldehydammonia for five minutes, and then adding an equal bulkof dilute hydrochloric acid to the mixture. After extracting thecrude product with dilute hydrochloric acid and with w:Lter, it isrecrystallised from boiling alcohol.Diethyl hydrocollidinecarboxylatecrystalhes in monoclinic or triclinic plates or needles (m. p. 131")freely soluble in chloroform and hot alcohol. It begidins to boil at 3 1 5 O ,but rapidly decomposes a t this temperature. This ethereal salt' resiststhe action of aqueous solutions of potash, but is completely decom-posed by alcoholic potash. By the action of warm fuming hydro-chloric acid, it is split up, yielding acetone, ethyl chloride, ammoniumchloride, and aldehyde, CI,Hz,04N + 3H20 + 3HC1 = 2C02 +2CZH5Cl + 2C3HeO + CZH4O + NH,Cl.Ethyl dibromhydrocolli~inedicarboxylate dibronzidle,C,H,BI.~(COOE~)~H,N,B~,,formed by the action of bromine diluted with carbon Fisulphide on thepreviously-mentioned ethylic salt, crystallises in thick prisms (m.p. 88")of a yellow d o u r . The substance dissolves freely in hot alcohol.By the action of strong nitric acid, it, is converted into ethyZ dibromo-co7Zidinedicnl.boxylate d i b r o i d e , C,H,Br,( COOEt),NBr,, which crystal-lises in white needles (m. p. 102") soluble in ether and in alcohol.When chlorine is passed into a solution of ethyl hydrocollidinecar-boxylate in chloroform, the hepta-derivative, C8H4C15( COOEt),Cl,NORGANIC CHENISTRY. 83is produced. This substance crystallises in needles (m. p. 150')sparingly soluble in hot alcohol.E t h y l coll.idiiLedicarBoxylate, C,NMe,(COOEt),, is best prepared bythe action of nitrous acid on a mixture of equal weights of alcoholand ethyl hydrocollidinedicarboxylate. When the reaction is complete,the excess of alcohol is removed by evaporation, and a dilute solutionof sodium carbonate is added to the residue, which causes the ethylcollidinedicarboxylate to separate out in the form of a heavy oil boilingat 310".It combinesreadily with acids. The hydrochloride, C14Hg04N,HC1, is deliquescent.The platinochloride, ( C14H,g0,N)zH,,PtC16, forms pink-coloured tri-clinic plates melting a t 184", insoluble in alcohol and ether, but solublein water. The nitrate crystallises in vitreous needles which melt at 92'and decompose at 122'. The hlydriodide crystallises in plates, solublein water and in hot alcohol. Itf melts at 170" with decomposition.By the action of an alcoholic solution of iodine, this salt is convertedinto the triodide, C14H190LNHI,13. The methiodide, C14H1904N,McI,crystallises in white needles soluble in alcohol and water.Althoughit is precipitated from its aqueous solution by soda, i b has a stronglyacid reaction. The crystals melt a t 138" and decompose at 160".Ethyl collidinedicarboxylate is not attacked by strong hydrochloricacid or by ammonia a t 150°, but it is easily saponified by alcoholicpotash. From the potassium salt, 1 ead collidinedicarboxylate and thefree acid can be prepared. Colli~inedi.carboxylic acid, C3Me3( COOH),,forms needle-shaped crjstals, sparingly soluble in alcohol, ether, andcold water. The salts which this acid forms with the alkalis andalkaline earths are very soluble in water and do not crystallise well ;C,HgN(C00)2Ba .+ 3H20 is more solubie in water than the calciumsalt C6H,N(C00)zCa + H20, which crystallises in needles.Thesilver salt, C6H9N(COOAg)2, is an amorphous body insoluble in water.The pale-green precipitate, obtained by the addition of potassiumcollidinedicarboxylate to a solution of copper sulphate, has the com-position 2C6H,N(CO),0 + 3CuO + 11H20. On boiling the mixturea pale-blue salt is produced which has the composition C8HgN(CO),0-t 3CuO.The hydrochloride of collidinedicarboxylic acid, CloHllOaNHC1 +2H,O, a:d the platinochloride, ( C,,Hl104N),,H2PtCI,, are crystalline.On heating potassium collidinedicarboxylate with lime, 6-coZlidine,or /3-trimethylpyridine, C6NMe3H2, is obtained. The following tableshows the most marked points of difference between a- and 6-colli-dine :-This ethylic salt has the sp.gr. 1.087 a t 15'84 ABSTRACTS OF CHEJlICAL PAPERS.a Gollidine.3. p. 178', sp. gr. 0.953.~~Solubility ..............Exposure to a i r . . ........The addition of CrO, giresMn, Co, and Fe salts ....C,HiiN,HAuCI,. .........AgN03 ................p-Collidine.B. p. 1'71', sp. gr. 0.917 at 15".Very slightly solublein water.No change.Does not melt underwater.Red oil.No precipitate.No precipitate.-- I- ---More soluble in cold than hotTurns brown.Melts under water; the dryRed crystalline precipitate ofSlow precipitation of hydr-White crystalline precipitatewater.salt melts at. 112'.(C*HllN) 2H2Cr207.oxides.soluble in hot water.An ethereal solution of ethyl hydrocollidinedicarboxylate absorbshydrochloric acid gas, forming ethyl collidinedicarboxylate and otherproducts.Dilute hydrochloric acid decomposes ethyl dihydrocolli-dinedicarhoxylate at loo", yielding ethyl chloride, carbonic anhydride,and ethyl dihydl.~ol1idinemonocarboxyln.te, CeHllNH.COOEt, as acolourless oil. On treating the alcoholic solution of this ethylic saltwith nitrous acid, it yelds ethyl colIidinemonocarboxylate,C,NHMe,,COOEt.The platinochloride, (CllH,,0,N)2,H2PtC16, cryshllises in prismsmelting at 194", soluble in water. By the action of dilute hydrochloricacid on ethyl dihydrocollidinedicarboxylate at 125", a mixture of di-hydrocollidine, tetrnhydrodicollidine, a ketone, C8HI20, and anotherbody of the composition C8HI4O2, is obtained.On distilling the crudeproduct in a current of steam, the two bases are found in the residue.Dihyd roc011 idine, ChHI3N, is a strongly alkaline liquid, boiling a t175-180", and having a penetrating odour. It dissolves in coldwater, but is reprecipitated on heating the solution. The pZati9zo-chloride, (C,H,,N)z,H,PtC1,, and the hydriodide, CsH,,N,HI, are crys-tzlline. Dihydrocollidine readily precipitates the hydroxides of mag-nesium, iron, manganese, and nickel from solutions of their salts,and forms a crystalline compound with methyl iodide. It is notoxidised by nitrous acid. Tetrah7JIJroajcoIZidine7 C,,H,,N,, boils at 255-260". The hydriodide, ClcH&N2,HI, is very soluble in water andalcohol. The ylatiriochZoride, C16H2,Nz,H2PtCIc, crystallises withdifficulty.The ketone, C,H,,O, is a mobile liquid having a pleasant odour andboiling at 208".It combines directly with bromine to form the tetra-bromide CsH12Brr0, an oily liquid. By the action of bromine on t h i scompound a crystalline substance is obtained of the compositionChH,Br,O or C8H6Br40, melting at 138".0% id atiorz-products of Collid ined icarboxy lic Acid .-Potassium colli-dineciicarboxylate is converted into the lutidinedicarboxylate by boil-ing i t with the theoretical amount of potassium permanganate solutionfor two hours. From the potassium salt, the lead salt and the freORGANIC CHEMISTRT. 85acid are prepared. Lutidinetricnrboxyzic acid, C,H,O,N + 2H20,resembles collidinedicarboxylic acid.It crystallises in rhombohedrons,which lose their water of crystallisation a t 120" and melt a t 212" withdecomposition. The neutral potassium salt of this acid is deliquescent ;the ammonia salt is very soluble in water : (C,,H,06N),Ba3 + 8H20forms hygroscopic needles ; (C10H606N)2Ca3 + 8H,O is gelatinous ;(Cl,,H60,N)2Mg3 + 10H20 is also amorphous and freely soluble.CloH6O6NAg3 and the lead and mercurous salts are insoluble orsparingly soluble. Lut idine, C5MezH3N, obtained by heating a mix-ture of potassium lutidinetricarboxylate and lime, boils a t 154'.By the prolonged act ion of potassium pernianganate on potassiumcollidinedicarboxjlat e, the potassium salts of picolinetetracarboxylicacid and py ridinepeiit~acarboxylic acid are produced.To obtain pico-linetetracarboxylic acid, strong nitric acid is added to a solution of thecrude potassium salt, which precipitates an acid salt of the compositionC5NMe(COOH),(COOK)2 + 4H,O. The concentrated solution of thissalt is decomposed by strong sulphuric acid, and the free acid extractedwith ether. Pyridinepentacarboxylic acid is obtained by a similarprocess. PicoZi?ietetracarbole?lZic acid, C5NMe(COOH)4 + 2Hz0, crys-tallises in prisms which lose their water of crystallisation at 120", andmelt with decomposition a t 199". The acid dissolves freely in water.I t s salts do not crystallise well. The dipotassium salt forms largerhombic plates ; the mono-potassium salt, C5NMe(COOH)3.COOK +2H20, crystallises in needles.C5NMe( C,04Ca), + 4H,O is sparinglysoluble.Pyri~~ne~entacarboz2/Zic acid, C,N(COOH), + 2H,O, dissolves freelyin water, formiiig a strongly acid solution. The crystals lose theirMrater of crystallisation a t 120", and decompose without melting a t220". It is a powerful acid, resembling oxalic acid in its property offorming acid and double salts. The following pyridinepentacarboxyl-ntes were prepared:--C,,H4010NK + 3 or 2H,O, shining needles.C10H3010NK2 + 4 or 3$H20, cubes. C,N(COOK),, crystalline powder,freely soluble in water. (C;,oOloN)2Ba5 + l l H z O is deposited as acrystalline powder when barium chloride is added to the free acid.(C,0010N)2Ca5 + 12H20, sparingly soluble non-crystalline powder.Clo0,,NH3Ca + iHtr,O, sparingly soluble crystalline powder.C16010NCa,.NH4 + 5H,O is deposited as an amorphous precipitatewhen pyridinepentacarboxylic acid is added to an ammoniacal solut,ionof calcium chloride.The ammonium in this salt can be replaced bypotassium or sodium. Acid potassium osalate also forms a double saltwith potassium pyridinepentacarboxylate, viz., C,,O,,NH,K + C204HK + 5&0. Pyridine, C5H5N, obtained by the action of lime on potas-Picoline, C6NMeH,, boils at 135".sium pyridinepentacarboxylate, boils at 120". w. c. w.Dipyridyl Derivatives. By Z. H. SKRAUP and G. VORTMAN~(il.Zbii,atsh. Chem., 3, 570--602).--In this paper, the authors show thatthe reaction which takes place in the synthesis of quinoline, hithertoapplied only to mono-substitu ted derivatives of benzene and phenol(Abstr., 1881, 919; also this vol., p.89), may be extended to thediamidobenzenes, and in particular they describe the results ob-tained by heating a mixture of m-diamido- and in-diaitro-benzen56 ABSTRACTS O F CHEMICAL PAPERS.with sulphuric acid and glycerol. The diamidobenzene-which wasemployed in the form of stannochloride-was prepared by the actionof tin and hydrochloric acid on nt-nitraniline; and the solutionobtained by treating this stannochloride with glycerol and sulphuricacid-after being freed from separated resin and rendered alkaline--was shaken up with alcoholic ether. The ethereal liquid was thenexhausted with hydrochloric acid ; the solution of the new base thusobtained was evaporated ; and the hydrochloride which crystallisedout from it after addition of alcohol was converted by potassiumdichromate into a sparingly soluble chromate (foreign matters beingat the same time destroyed by oxidation); this chromate, heatedwith ammonia, yielded the base in the form of a hydrate, which whenleft over sulphuric acid, or mvJre quickly when heated a t lOO", gave offits water, leaving the anhydrous base, which was purified by distil-lation.The base thus obtained is regarded by the authors, for reasons to beexplained further on, as formed by the attachment of .two pyridine-rings to a benzene-ring, in the manner represented by the right-handfigure below, and may be called phenanthroline, from the analogyof its struc$ure to that of phenanthrene.Phenanthrene.Phenanthroline.Pure phenanthroline forms a white crystalline mass made up of four-sided plates. It has L faint odour when cold, becoming stronger onheating, and resembling that of naphthaquinoline.It melts a t 78-78*S0, remains liquid for some time after cooling, but then solidifiesinstantaneously on being tonched with a solid body. It is somewhathygroscopic, the clear crystals when exposed to the air becomingcovered with a white opaque coating, and ultimately falling to powder.When the fused substance is covered with a very thin film of waterand rubbed with a glass rod, it is completely converted into thehydrate, which is thus obtained as a perfectly dry mass. Phenanthro-line is nearly insoluble in cold, more easily soluble in boiling water,dissolves in all proportions in alcohol, but is nearly insoluble in ether,benzene, and light petlrolenm ; dilute acids dissolve it readily.Theaqueoiis solution is nearly neutral when cold, but has a distinct alka-line reaction a t the boiling heat. The pure base may be distilled with-out decomposition, and boils a t a temperature much above 360". Itvolatilises to a slight extent with the vapour of water. The hydratedcompound, C12H8N2,2H20, crystallises in long soft needles, which donot effloresce on exposure to .the air, but give off their water oversulphuric acid, and melt in a capillary tube a t 65.5".Phenanthroline in most of its salts appears as a mon-acid base, andit is only with a great excess of acid and very strong solutions thatnormal salts can be obtained in which it is bi-acid.The basic hydi.0-chloride, C,2H8N2,HC1 + H20, separates from alcoholic solution, evenpresence of excess of acid, in long white prisms, easily soluble iORGANIC CHEMISTRY. 87water, sparingly in a'rcohol. The normal salt, C12H8N2,2HC1 + 2H20,separates in small prisms on cooling from a warm solution of the basein a small quantity of strong hydrochloric acid. It is veryunstable,and is decomposed by water. The pZatinochZoride, C,H8Nz,HzP tCl4 +H,O, forms small reddish-yellow prisms, sparingly soluble in alcohol.The chromate, (CI2H8N2),Cr20,, forms golden-yellow needles, slightlysoluble in cold water. The picrate, Cl,H6NZ,C6H2(NO2)3.OH, crystallisesin light-yellow prisms, very silghtly soluble in alcohol, melting at238-240".The sdpkate is sparingly soluble in alcohol ; the tartruteboth in alcohol and in water.A nzethiodide. ClZH8N2,McI + H20, obtained by heating phenan-throline a t 100" with methyl alcohol and excess of methyl iodide,crystaJlises in broad prisms, dissolves easily in water, sparingly inalcohol, and gives off its water of crystallisation with great facility.I t s aqueous solution turns red on addition of potash-lye, and depositsa non-solidifying oil.BROMIDES.-on adding bromine to a hot concentrated alcoholicsolution of phenanthroline, an octobromkcle, C12HeN, Br8, separates inred crystals melting a t 1 76-178". The dibromide, CIzH8N2,Br2, sepa-rates on adding bromine-water to an aqueous solution of phenan-throline hydrochloride, as a light yellow crystalline precipitate meltingat 149"; heated for a short time with a small quantity of alcohol,it is converted into dark-red crystals which have the composition(C1zH6Nz)zBr3, or C12H8N2,Br2 + CIZH8N2,HBr, melting at 178", andgiving off bromine when heated with water.By prolonged boiling withalcohol, the dibromide is converted firs& into orange-red slender needles,then into thick yellow prisms, and finally into nearly colourless needles,consisting of phenanthroline hydrobromide, Cl2H6N,H Br + +H20,melting a t 278-280". When, on the other hand, phenanthroline isheated at 120-130" with excess of bromine and water, it yields a,brownish-yellow bromine-compound, which dissolves in glacial aceticacid, and separates therehorn in non-crystalline Crusts, and appears tobe a mixture of CI2H,Br2N2 and ClZH5Br3N2.HYDRIDES.- By redaction with tin and hydrochloric acid, phenan-throline is converted into an amorphous compound purifiable by dis-tillation, and probably consisting of a mixture of tetra- and octo-hydrideof phenanthroline, C12H,N2,H4 and Cl2H8N2,H8.Dipyridyl-carboxylic Acids.-Phenan throline is readily oxidisedby potassium permanganate in very dilute solution ( 5 : lUOU), yjeldingas chief product-together with a small quantity of quinolinic orpyridine-dicarboxylic acid-an acid, C12HRNP04, or C,,H,N,( COOH)?,called p h e n a n t h r o l i n i c or dipyridyl-di carboxylic acid, whichmay be isolated by nearly neutralising the concentrated filtrate withnitric acid, adding the calculated quantihy of silver nitrate, and pre-cipitating the resulting silver salt of phenanthrolinic acid by furthercautious addition of nitric acid.This silver salt decomposed byhydrogen sulp hide, yields the phenanthrolinic acid in large triclinictablets, having the axes a : b : c = 0-5909 : 1 : 0.9773, and exhibitingthe faces wP&, OP, mP:, m:P, P', 'P, ,P, P,. They contain crystal-water, have a slightly acid taste, dissolve sparingly in cold, morefreely in boiling water, easily in alcohol, very sparingly in ether an88 ABSTRACTS OF CHEMICAL PAPERS.in benzene. They give off their water a t loo", melt with evolution ofcarbonic anhydride a t 217", give a blood-red to yellow-red colorationwith ferroas sulphate, a yellowish gradually crystallising precipitatewith ferric chloride and sodium carbonate, no precipitate with bro-mine- water.Phenanthrolinic acid forms salts both with bases and with acids.The norinnl potassizm saZt is extremely deliquescent, and remains onevaporating its aqueous solution, as a vitreous mass, which becomescr.yst alline when left, in contact with alcohol.The acid potnssiurn s d t ,Cl,H7N20~K,1~Hz0, may be crystnllised in like manner. The calciumsaZt, ClzH6N2O4Ca,3H2O, forms transparent shimmering laminae ; theBicrium salt, C,2H6N,04Ba,l&H,07 very sparingly soluble granules ; thecopper salt, Cl2H6NzO4Cu,3H2O, nearly insoluble greenish-blue granules ;the normal silver salt forms microscopic lamintt? ; the acid silvey salt,C,,H7N204,Ag,4H20, is a precipitate composed of stellate groups ofneedles.The hydrocldoride, C,,H,N204,2HCI, prepared with stronghydrochloric acid, forms transparent prisms. The pJatimchZor;de,( Cl~H8Nz0,,HCi),,PtC14 4- 6H20, separates gradually in large thickyf~llow prisms, and the mother-liquor when left to evaporate yields thesalt CJ€I,N,Oi,HzPtCl, in orange-red tablets.Dipyridyl-monocarboxylic acid,ClIHsN202 = CJI,N2(COOH),is obtained by heating phenanthrolinic acid to its melting point, andcrystallises in delicate white needles containing 2H20, which they giveoff at 100". The dehydrated acid cakes together a t 17Y", melts a t182*5-184", solidifying to a vitreous mass on cooling, and is butslightly decomposed by distillation. It dissolves with difficulty in coldwater and alcohol, easily with the aid of heat; gives no colorationwith ferrous sulphate, yellow-brown with ferric chloride ; a light-bluecrystalline precipitate with cupric acetate, and with silver nitrate awhite precipitate soluble in excess of the acid and of the precipitant;with bromine-water a cinnabar-red precipitate.The culciwn sult,(C,,H,N202),Ca,2H20, forms long shining easily soluble needles, whichgive off their water a t 2.20" ; the silver salt, C,,H,N,02Ag,$H20, is adense precipitate, which becomes crystalline on standing.A d i p y r i d y I, CIoH8N2, is obtained by distilling calcium dipyridyl-monocarboxylate with quicklime, and passes over as a colourless oil,boiling a t 149.5". Its picmte, CloH8N,,C6H,(N02)3.0H, forms smalldull-yellow needles, slightly soluble in cold water, melting a t 149.5" ;ar,d its plntinochloride, CioHBNO, H2PtCl, + +HzO, is a light-yellowprecipitate, very slightly soluble in water and in hydrochloric acid.This dipyridyl, which differs distinctly from, Anderson's dipyridine,and from the isodipyridine of Cahours and Etard, is related to pyri-dine in the same manner that diphenyl is related to benzene.Theformation of dipyridyl-dicarboxylic acid has led the authors to assignto phenanthroline the constitutional formula above given (p. 86),analogous to that of phenanthrene. H. W.Quinoline from Cinchonine. By 0. DE COKIXCK (BUZZ. XocORGANIC CHEJIISTRY. 89Chim. [2], 37, 208-209 ; see this vol., 414).-The hydrochloric acidsolution of the fraction of crude quinoline boilin? between 226-231"is repeatedly treated with ether, which removes a small quantit'y of aneutral compound having a strong odour, and boiling a t about 220".The purified base is then distilled.It is a t first colourless, but darkenssomewhat rapidly, even when protected fwm air and light ; sp. gr. at 0"= 1,1055 ; at 11.5, 1.0965 ; b. p. 236-237" at] 775 mm. The quinolineobtained by adding potash to crystallised quinoline tartrate, also boilsa t 236-237" under the same pressure. Quinoline obtained by synthesisboils at 228" (Skraup and Koenigs), or 232" (Baeyer and others).Quinoline hydrochloride forms white; deliquescent crystals, which emitan odour of quinoline, and melt a t 93-94" to a colourless liquid.Thehydrochloride is very soluble in warm, slightly less soluble in coldwater, Eoluble in all proportions in absolute alcohol and chloroform,only slightly soluble in cold, but very soluble in hot ether or ben-zene. C. H. B.The Quinoline of Coal-tar and of the Cinchona Alkaloyds,and its Oxidation by Potassium Permanganate. By S. HOOGE-WERFF and W. A. v. DORP (Bee. 'Ikav. Chim., 1, 1-17 and 107-131).-After a historical sketch of the discussion as to the identity orisomerism of the bases C9H7N, obtained from the cinchona alkaloYds(quinoline), and from caal-tar (leucoline), the authors describe themethods which they adopted for purifying the bases obtained fromthese two sources, and give as the mean results of their analysesof both bases C = 835.58 per cent., H = 5.8.The boiling pointsfound were for quinoline 238%" to 239*25O, and for leucoline'239.25" to 240.25" (thermometer wholly in vapour). Moreover,both yield the same hydrate, 2CgH7N,3Hz0, platinochloride,(C9H,N),,HZPtCI, + 2H@,dichromate, (CgH7N) ,H2Cr2O7, and argentonitrate. By oxidation withpotassium permanganste in alkaline solution, both bases yield, asprincipal products, carbonic anhydride and q ci noleic ac id, C7H5N03,according to the equation C9H7K + O9 = C7H,N04 + 2C0, + H20,together with very smsll quantities of oxalic acid and ammonia. Theidentity of the bases from the two sources may therefore be regardedas established, and the name " leucoline" may be dropped.The quinoleic acid may be separated from the products by neutra-lising with nitric acid, removing the crystals of potassium nitratewhich separate on concentration, then precipitating with calciumnitrate, treating the concentrated filtrate with lead nitrate, decom-posing the resulting precipitate with hydrogen sulphide, and con-centrating the solution filtered therefrom.Quinoleic acid is thendeposited in small honey-yellow monocliiiic crystals, having the axesa : b : c = 0.5418 : 1 : 0.6075 and /il = 64" 54'. Observed faces, KIP,PA, mP&, and a pyramidal face not determined. Cleavage, parallelto the clinopinacold.Quinoleic acid is but slightly soluble in cold, rather more so in hotwater, very slightly soluble in alcohol, insoluble in benzene, and isremoved from its aqueous solution by ether.It is but very slightl90 ABSTRACTS OF CHEMTCAL PAPERS.attacked by pot,assium permangnnate in alkaline solution, easily inacid solution. When heated to loo", it gives off CO, and leavesn i c o t i c acid, C6'H,N02. Heated in capillary tubes, it begins to turnbrown a t 175", and melts a t 228-230", but if rapidly lieat'ed it meltsat about 180", giving off gas and resolidifying, after which it meltsa t 228".A cold moderately dilute aqueous solution of this acid exhibits thefollowing reactions. With-Heatjed with lime, it yields an oil smelling of pyridine.CaCl, : gelatinous pp., graduallyBaC1, : gelatinous pp.ZnSOa : pp. of microscopic needlesafter a few hours.MnSO,: like the last, but smallercrystals.Co(NO,), : like the last ; pp.rose-coloured.NiSOa and HgCl,: no pp.Peso4 : orange colour ; yellow-brown crystalline pp. after sometime.becoming crystalline.Fe2CI, : yellow - brown, amor-phous.CuSOl: light - blue, apparentlyamorphous, nearly insoluble inwater and acetic acid, even atboiling heat.Hg(N03),: white pp. ; micro-scopic needles.Pt(C2H30,), ; like t'he last.AgN03 : shining needles of acidsalt (infra).Quinoleic acid is a pyridine-dicarboxylic acid,C5H3N (CO OH) (C ;OH).1 2It is therefore bibasic. The acid potassizcm saZt, C7HaN01R,2H,0,forms limpid triclinic crystals, which give off their water at 100". The?iorvnal barium sali, C7B,NO4Ba, obtained by adding a soluble bariumsalt to a cold solution of the acid neutralised with ammonia, crgstal-lises sometimes with 16, sometimes with 2$ mols.H20, part of whichgoes off a t loo", the last semi-molecule only at 260". The normalsiher salt, C7H3N04Ag2, is obtained by adding silver nitrate to a coldneutralised solution of the acid, as a gelatinous precipitate whichbecomes granular or crystalline on standing.is obt,ained by adding a hot aqueous solution of the acid to an acidsolution of silver nitrate diluted with boiling water, and separates oncooling in concentric groups of shining needles. Sometimes, how-ever, a hyper-acid salt, C7H4N04A g,C7H5NO4, is deposited under theseconditions, in concentric groups of small needles.Quinoleic acid, when heated a t 120-140° and upwards, gives off waterand carbonic anhydride, and is converted into nicotic acid, CsH5N02= C7H,N04 - C02.The same result is obtained by heating quinoleicacid with acetic acid. The nicotic acid thus produced agrees incharacter with that which is obtained by other methods. Its calciumsalt, (CBH,N02),Ca, forms monoclinic cryst,als; a : b : c = 1.5372 : 1 :0.6293. = 62.50. Observed faces, COP, PA. H. W.The acid salt,CTH,NO,Ag + &O,Nitro- and Amido-bromoquinoline. By W. LA COSTE (Bey., 15,191 8--1922).-Bromoquinoline (prepared from parabromaniline) iORGANIC CHEMISTRY. 9.1added gradually to a mixture of two parts sulphuric acid and onepart fuming nitric acid, the whole being cooled if necessary. Onpouring the product into water and neutralising with sodium carbo-nate, nitrobromoquinoline is precipitated, and can be purified bycrystallisation from alcohol.I t forms long Fellowish-white needles,which melt a t 133". It dissolves readily in ether and in boilingalcohol, and is slightly soluble in boiling water, from which it crys-tallises in long thin colourless needles. With platinum chloride, nitro-bromoquiioline gives a bright-yellow crystalline precipitate,[ C,H6NBr(NO2) ,HCl],,Pt C1,.Bromoquinoline, obtained by the bromination of qninoline, also yieldsa nitro-compound which melts at 133". It crystallises from hotalcohol in short yellowish needles, grouped together in nodules. I tgives a yellow granular precipitate with platinum chloride.For the reduction of nitro- to amido-bromoyuinoline, it is best toheat it in alcoholic solution with an acid (HC1) solution of stannouschloride. The double salt which crystallises out on cooling is dissolvedin water, and treated with dilute soda-solution, when amidobromo-quinoline separates in flocks, and may be crystallised from boilingwater.It forms long almost colourless needles, containing 1 mol.H,O, which it loses over sulphuric acid. It melts (anhydrous) a t164O.1 Amidobromoquinoline is a weak base, which forms salts withacids. The nitrate, C9H,NBr(NH2),HN0,, forms gold-coloured groupsof needles ; it explodes on heating. The hydrochloride crystallises invery soluble red prisms, which contain water of crystallisation ; it formsa platinochloride. Acetn?nidohromoquiizoZi?ze, CgH,NBr.NH.COllIe,crystallises in colourless plates melting at 104-10.5".By 0.FISCHER (Ber., 15, 1979-1981) .-Quinoline yields two isomeric monosulphonic acids, of which theortho-acid, as previously described (Abstr., 1882, SSS), yields thehydroxyquinoline of melting point 75-76'. The meta-acid crystal-lises in long thin colourless needles, and is more readily soluble inwater than the ortho-acid; it is best separated by the difference ofsolubility of the calcium salts, the meta-salt being the more soluble.The best yield of the meta-acid is obtained by conducting the reactionat. 140-150', the yield being then 10-15 per cent.Netahydroxyquinoline forms colourless silky needles, melting a t about230', i t is readily soluble in alcohol and benzene, sparingly in water,ether, and light petroleum.With ferric chloride, it yields no colora-tion in the cold, but on heating a faint red tilit appears. The platino-chloride forms brownish-yellow prisms.Metametho~~pitinoline, prepared in a similar manner to the ortho-compound (Zoc. cit.), is a limpid oil, boiling with partial decompositiona t 275' under 720 mm. pressure. The platinochloride crystallises inlong brownish-yellow prisms ; the picrate crystallises in tufts of thinneedles, both salts are sparingly soluble in water. The oxalate formssilk7 needles, readily soluble in water.On distilling sodium quinolinorthosulphonate with potassiumcyanide, the distillate was found to contain a mixture of ortho- andA. R. M.Hydroxyquinoline92 ABSTRACTS OF CHEMICAL PAPERS.heta-cyanoqninolines, the latter being in excess, intra-molecularchange having occurred. A.J. G.Synthetic Researches in the Quinoline Series. By Z. H.SKRAUP (Jfonatsh. Chem., 3, 531-569) .-HYDROXYQUINOLINES,These bases (ortho, meta, and para, according to the relative positionsof the N-atoms and the OH-group) are formed by heating a mixtureof an amidophenol (or better its hydrochloride) and the correspondingnitrophenol, with sulphuric acid and glycerol, according to the equationC,H,(NH2).OH + C,H,Os = C,H,NOH + 3Hz0 + H2. The amido-phenols used for the purpose must be pure, as even small quantities offoreign substances greatly diminish the yield of hydroxyqninoline.Ortho-hydroxyquinoline is but very slightly soluble in water,easily soluble in absolute alcohol, less soluble in aqueous alcohol.From water and from dilute alcohol, it separates in anhydrous brittleprisms, from absolute alcohol in more compact crystals.Ether dis-solves it with difficulty, warm benzene in all proportions. The solu-tions in nearly absolute alcohol and in benzene are colourless; theformer becomes deep yellow on addition of a small quantity of water,colourless agaiu when mixed with a large quantity of alcohol. Thesolutions in acids and alkalis are yellow.o-H:y droxy y uinoline quickly becomes reddish on exposure to sun-shine; it has a peculiar phenolic odour and burning taste; sublimesvery easily bot'h from its solutions and in the solid state, softens at i2",melts a t 73-74", and usually solidifies a t 53-55'.Under a pressureof 752 mm. it boils at 258.2" (cow.). The impure substance decom-poses on distillation, the pure substance scarcely a t all. The dilutealcoholic solution is coloured blackish-green by ferric chloride, thecolour becoming darker on addition of sodium carbonate, whichultimately throws down a dingy brownish-green flocculent precipitate.The coloration is prevented by the presence of free hydrochloric acidbut not by acetic acid. Ferrous sulphnte forms a dark brown-red pre-cipitate soluble in acetic acid with silver nitrate. The solution ofthis hydroxy quinoline in potash gives a yellow flocculent precipitatebecoming crystalline on standing ; with mercuric chloride an orange-yellow crystalline precipitate ; with lead nitrate a light yellow floccu-lent precipitate, and with barium chloride a white pulverulent pre-cipitate.The acid su@hate, CgH7N0,H,S04, crystallises in light yellowprisms containing 2 mol. H20, 1 mol. of which is given off over sul-phuric acid. The hydrochlode, CgH7N0,HC1 + H,O, forms yellowprisms easily soluble in water and in alcohol; the jdatinockloride,(CgH7N0,HCl)2PtC14 + 2H20, forms long golden-yellow sparinglysoluble needles ; the picrate, C9H7N0, C6H2(N02)3.0H, crystallises inyellow prisms very slightly soluble in cold alcohol, caking together a t170" and melting a t 203-204". A characteristic copper-compound,(CgHENO)lCu, is precipitated as a siskin-yellow powder on addingcupric acetate to an alcoholic solution of the hydroxyquinoline.The acetyl-corn pound, CIIHgNO = C9H,BEN0, prepared by boilORGANIC CHEMISTRY.93ing the hydroxyquinoline with acetic anhydride and sodium acetate, isa nearly colourless oil which remains fluid a t - Z O O , boils at about280°, is gradually decomposed by exposure t o the air, more quicklyby bases, with separation of o-hydrosyquinoline ; it dissolves readily inhydrochloric acid, and the solution mixed with platinic chloride formsthe salt (Cg€€6&N0,HCl)2PtC14 + 2H20, which separates in tufts ofsmall yellow needles.Nitro-com P O unds.-Strong nitric acid converts o-hydroxyquino-line into a mixture of the mono- and dinit1.o-derivatives, C9H6(NOz)0and C9H,(N0,),0, the latter greatly predominating. The mixturedissolves in hot dilute potash-ley, forming a deep yellow solution,which on cooling deposits a potassium derivative in slender yellowneedles.The alcoholic solution is coloured deep garnet-red by ferricchloride.Bromine-co mpound, C9H5BrzN0.-This compound separates ondropping bromine (1 mol.) into an alcoholic solution of o-hydroxy-quinoline, as a mass of needles, and may be obtained by recrystallisa-tion from alcohol or benzene in white britt'le prisms. It appears to beconverted into a bromine addition-product by excess of bromine,o-Methoxyquinoline or o-Quinanisoil, CIOHQNO = CgH6NOMe,is prepared, not from the hydroxyquinoline, but directly by treating itmixture of o-miidanisoil and o-nitranisoll with glycerol and sulphuricacid. It is a nearly colourless oil, which boils at, 265-268", turnsbrown on exposure to the air and forms a platinochloride-CIoHgNO,HzPtCI6 + 2Hz0,which crystallises in short reddish-yellow prisms.Hydro-o-hy droxyquinoline, CQHIINO, previously obtained byBedall u.Fischer (Ber., 11, 1368), is prepared by the action of tin andhydrochloric acid on the hydroxyquinoline. The aqueous solution ofits hpdrochloride gives a blood-red colour with ferric chloride, and isdistinguished from that of the para-derivative by not emitting theodour of yuinone when boiled.Para-hydroxyquino1ine.-This base, prepared like the o-compound,is best purified by reci-ystallisation of its hydrochloride. The free basecrystallises from alcohol in small brittle prisms, melts a t 1 9 3 O , boilsabove 360", dissolves Fery sparingly in water and ether, still less inbenzene and in chloroform, more freely in alcohol, easily in acids andalkalis.Ferric chloride colours the alcoholic solution faintly yellow ;ferrous sulphate produces no coloration. The alkaline solution giveswith silver nitrate a yellowish gelatinous precipitate ; with mercuricchloride a light yellow, with lead nitrate a nearly white precipitate,with barium nitrate none ; with cupric acetate, after neutralisationwith ammonia, a green precipitate.The hydrochloride, C9H,N0,HCl -!- HzO, is colourless when pure, verysoluble in water, sparingly in absolute alcohol, insoluble in ether, veryslightly soluble in strong hydrochloric acid, and in a saturated solutionof sodium chloride ; it gives off its crystal-water easily at 100".ThepZati~ochloride, ( CQH,N0,HC1)2,PtC14 + 2H20, is a reddish-yellow crys-talline precipitate. A copper-puinoZinelacetate, (CzHE-I,N02)zCu,2C2H40z,separates gradually from an alcoholic solution of p-hydroxyquinolin94 ABSTRACTS OF CHEMICAL PAPERS.mixed with a dilute solution of cupric acetate, in groups of acutewedge-shaped crystals nearly black by reflected, amethyst-blue bytransmitted light.Nitro-p-hydroxyquinoline is obtained as a nitrate-CsH6(NO2)NO,HNO3 + EL),on adding y-hydroxyquinoline to 4-5 parts strong nitric acid, warm-ing the liquid till the whole is dissolved, and diluting the red-brownsolution with water. The salt then separates in orange-red acuteprisms which become whitish at 100".It dissolves easily on heatingwith a small quantity of water, less easily in a largez. quantity, easilyin alcohol. By dissolving it in sodium carbonate and acidulating withacetic acid, the free nitrohydroxyquinoline, CgH6(N02)N0, is obtainedin small yellow needles, insoluble in water, sparingly in cold, easily inhot alcohol, easily also in acids and alkalis. It melts at 139-140", andsublimes when cautiously heated. Its alcoholic solution is colouredreddish by ferric chloride, gives st yellow-brown precipitate withcupric acetate, and orange-yellow with silver nitrate. Its potassiumsalt forms yellowish-brown brittle needles ; the barium salt, orange-yellow needles slightly soluble in cold water.Brcmo-p-hydroxy yuino l i n e , C9H6BrN0, is obtained on slowlyadding bromine to an alcoholic solution of p-hydroxyquinoline, as ahydrobromide, CgH6BrN0,HBr, which separates in reddish-yellow heavygranules.This salt dissolves sparingly in absolute, easily in hotaqueous alcohol, and with partial decomposition in a large quantity ofhot water. Its dilute alcoholic solution, when treated with sodiumcarbonate, deposits the free bromhydroxyquinoline, C9H6BrN0, innearly colourless needles, easily soluble in hot dilute alcohol, meltinga t 184-185". With silver nitrate, on addition of ammonia, it givesa yellowish flocculent precipitate ; with cupric acetate, after neutrali-sation, an olive-green precipitate.The a c e t y 1-c o m p o u n d, C9H6ZN0, prepared like the correspond-ing ortho-compound, is a light yellow scentless oil, boiling a t 298",easily soluble in alcohol and ether, soluble also in hot water.Whencooled to -20", i t remained liquid for nearly half an hour, but beganto crystallise soon after its removal from the freezing mixture. Thewhite crystals thus obtained melted between 36" and 38" to a colour-less liquid which solidified only in contact with the solid substance.The yZntinochZoride, (C,1H,NO,,HCl),,PtG11, is a yellow crystalline pre-cipitate. The benzoyl-compound, C9H6EN0, prepared by boilingthe hydroxyquinoline with benaoic chloride, crgstallises from glacialacetic acid in white slender needles, nearly insoluble in water, alcohol,et,her, and hydrochloric acid, slightly soluble in alkalis, and melting a tp-Quinani so'il, CgHsN.OMe, prepared like the ortho-compound,is a non-solidify ing-oil.This hydrochloride crystallises in long whiteprisms, deliquescing in water, moderately soluble in alcohol, sparinglyin ether alcohol. The pZatiizocliZor.icle, (CgH6N.0Me,~C11),,EJtCld + H,O,crystallises in acute orange-red prisms, easily soluble in hot water.Hydro-p-hydroxyquinoline, C,H,,NO, has been obtained as ahydrochloride, though not quite pure, by the action of tin and hydro-230--231"ORGAXIC CHEJIISTRY. 95ahloric acid on p - hydroxyquinoline. The hydrochloride is easilysoluble in water and separates by evaporation over sulphuric acid, infeathery groups of large white prisms,. afterwards in small whiteneedles. The free base is coloured reddish-violet by ferric chloride,becoming brownish on boiling, and emitting a strong odour ofquinone.Meta-hydroxyquino1ine.-This base is most readily purified byfractional precipitation of the acid oxalate.It crystallises fromabsolute alcohol in prisms, from dilute alcohol and from ether inneedles, from chloroform, and by spontaneous evaporation of itsaqueous solution, mostly in grariular aggregates. It melts, withpartial blackening, a t 235--238", sublimes undecomposed when quicklyheated, and boils with rapid decomposition a t a higher temperaturethan the para-compound. It is inodorous and nearly tasteless,slightly soluble in water, much less soluble in alcohol than p-hydroxy-quinoline, more soluble in chloroform, moderately in cjther solvents.Its soli~tions in alkalis and acids have a deep yellow colour, so long a8any of the undissolved substance is present, but they become colourlesswhen Dhe whole is dissolved.It dissolves readily in caustic potashand barytn, sparingly in ammonia. All the solutions, especiallythe dilute alcoholic, have a distinct green fluorescence. Ferric chlorideadded to the dilutic alcoholic solution, produces a, fine brown-redcolour, becoming lighter on addition of sodium carbonate ; ferroussulphate produces no reaction. The meta-compound withstands theaction of potassium dichromate m o ~ e completely than its isomerides,which are thereby oxidised.The liydrochZorid~, C9H,N0,HC1 + 1+H20, crystallises in prisms,colourless when quite pure, but mostly light yellow, freely soluble inwater, very sparingly in alcohol ; the platinochloride-(CgH,KO,HC1)2,PtC14 + 2H20,in orange-yellow needles ; the picrate, in light yellow needles meltingwith decomposition a t 244-245".( C9H6NO)2Cu,2C2H402,is obtained in violet crystals when an alcoholic solution of hydroxy-quinoline mixed with an equivalent quantity of cupric acetate and asmall quantity of acetic acid, is left to evaporate.N i t r o-m-h y d r o xy q u i n o line, C,H,(NO,)NO, is obtained on addingm-hydroxyquinoline to fuming nitric acid, precipitating with water,and recrystallising the yellow granules thereby thrown down from hotwater, in ello ow shining laminae which melt with evolution of gas a t255", and unite with acids, forming salts which are decomposed bywater.Bromine-compound.-On adding bromine-water to the hydro-chloride of m-hydroxyquinoline, a bromide of bromhydrox pquinolineis obtained, which when boiled with alcohol, is converted into a,hydrobromide, CgH6BrN0,BrH.A benzoyl-derivative is obtained in the same manner as thecorresponding para-compound in the form of an oil which slowlyThe copper-cornpound96 ABSTRACTS OF CHEMICAL PAPERS.solidifies, melting at 88-89", and yields a platinochloride having thecomposition (C,H,~N0,HC1),,PtC14.Hydro-m- hy droxyquino1ine.-The hydrochloride of this base isobtained in colourless well-defined prisms by heating a solution of332- h ydroxyquinoline in hydrochloric acid with excess of metallic tin,precipitating the excess of tin with hydrogen sulphide, and evaporating.When heated with ferric chloride, it first turns light yellow, thenbrown-red, and gives off an odour slightly resembling that of quinone.Quinoline-derivatives.By A. RHOUSSOPOULOS (Ber., 15, 2006-2009).-By the union of quinoline with ethyl monochloracetate, a com-pound, C,sH14N0,C1 = C,H,N(C; H2.COOF: t) C1, is obtained, crystallisingin stellatle groups of white needles. It is extraordinarily soluble inwater, readily soluble in alcohol, insoluble in ether. The platino-chloride, C,,H,,NO,CI,,PtCI,, crystallises in small thin needles. Thecompound, C,sH14N0,CI, treated with freshly precipitated silver oxide,yields quinoline-betainne, according to the equation-H. W.C,H,N(C,H,O,Et)Cl + AgOH + H,O = AgCl +EtOH + CgH7NCzHzOz,HzO.Quinoline-betajine forms short, thick crystals, readily soluble in waterand alcohol.It begins to decompose at 168", and fuses at 171".Hydrochloric acid converts i t into the hydrochloride, which uniteswith plat'inum chloride, yielding stellate groups of orange-colouredneedles of the formula (ClIH9N02,HC1),,PtC&.Bromoquinolinesulphonic Acids. By W. LA COSTE (Bey., 15,1910-1918) .-Bromoquinoline, prepared as previously described bythe author (Abstr., 1882, 978), was gradually added to five times itsweight, of warmed fuming sulphuric acid, and the product when coldwas mixed with a considerable quantity of water and well stirred ; theheavy crystalline precipitate consisted of two isomeric bromoquinoline-sillphonic acids, which can be easily separated by means of theirpotassium salts.The acid from the less soluble potassium salt iscalled by the author a-, and that from t h e more readily soluble salt,G-bromocyuiiiolinesulphonic acid.The a-acid crystallises from boiling water in short thin anhydrousneedles, sparingly soluble in cold water and in alcohol. The potas-siunc salt, CgH5KBr.S03K, forms shortt prisms, which decrepitat'e onheating. The b a ~ i u n ~ salt, (CgH,NBr.S03),Ba, is a sparingly solublecrystalline precipitate. The magnesiunz salt, (CgH,NBr.8O3),Mg +10H20, forms colourless plates, which lose their water at 120". Thezinc salt, (CgH,NBr.SO,),Zn + 4H20, slender needles, which losetheir water at 120" F. The manganese salt, (CgH6NBr.SOs),Mn +4H20, forms short greenish-yellow needles ; and the d v e r salt,C9H5NBr.S0,Ag, anhydrous needles.6-Bromoquinolinesulphonic acid crystallises in short] needles with1 mol.H20, which it loses at 150-160". It is sparingly soluble in coldwater, although considerably more soluble than the a-acid. The potas-sizlrn salt, C,H,Br.SO,K + l+H,O, crystallises in plates of moderate size,which are easily soluble in water. The barium salt, (CSH6NBr.SO3),BaA. J. GORGANIC CHEMlSTRY. 97+ 2R20, forms crystalline groups of needles; the magnesium salt,(C,H,NBr.SO,>,Mg + 9H,O, small needles, and the zizzc salt,( C9H5NBr.SO3),Zn + 9H,O, large transparent six-sided plates, easilysoluble in hot water. The inctngaiiese salt, (CgH5NBr.S03),Mn + 6H,O,crystallises in colourless plates, easily soluble in hot water, and thesilver salt, CgH5NBr.S0,Ag, forms colourless needles.The a- and /I-acidsboth form crystallisable salts with aniline.By TANRET (,J. Pharm. Chim. [5], 5, 591--595).-Thesalts of caffeine which it is generally supposed to form, are here shownfor the most part not to exist. Owing to its weak basic properties andneutral reaction, it does not neutralise the smallest trace of acid, andeven relatively concentrated solutions of it do not give a precipitatewith potassium-mercuric iodide.Acetic, valeric,lactic, and citric acids merely dissolve it, and on cooling the solution,pure caffeine separates out. Caffeine crystallised from valeric acidretains the odour of the acid, which, however, may be removed bywashing, so that the substance sold for cafleine valerate is only thebase, whilst caffeine citrate is a mixture of caffeine and the acid.Todissolve one equivalent of caffeine, three equivalents of citric acid arerequired, which is the inverse of the proportion which would berequired for the formation of the citrate.With mineral acids, however, caffeine does form salts, the sul-phate being cryst8allised with difficulty, whilst the hydrochloride andhydrobromide crystallise well. They are, however, decomposed bywater into caffeine, which is precipitated, and the free acid ; the hydro-chloride decomposes even on exposure to the air. Such compounds,as well as its solutions in organic acids, are useless for hypodermicinjections.It appeared, however, that the compound which exists in coffee,chlorogenate of potassium and caffeine might be used for this purpose ;bat the difficulty of preparing it in large quantities, its instability,and sparing solubility in water, prohibit its use. It was found, how-ever, that caffeine forms with benzoate, cinnamate, and salicylate ofsodium, compounds similar to the natural compound, and very solublein water.They are prepared by treating caffeine with its equivalentof the sodium salt, dissolved in a small quantity of water. One equi-valent of sodium cinnamate dissolves one equivalent of caffeine,yielding a compound containing 58.9 per cent. caffeine. The doublebenzoate contains 48.5 per cent., and the salicylate 61 per cent.These compounds are not stable, however, being readily decomposedby chloroform.100 parts of water dissolve 2 parts of the benzoateand cinnamate, and 3 parts of the salicylate.Similar compounds have been obtained with sodium acetate, lactate,citrate, sulphate. and chloride.By means of these compounds, caffeine may be used for hypodermici 11 j ec t ions.Hydrocinchonidine. By 0. HESSE (Anna?%, 114, 1-17).-Hydrocinchonidine, ClgHz4Kz0, is contained in considerdble quantitiesVOL. XLIV. hA. K. M.Caffeine.Caffeine does not form salts with the organic acids.L. T. 0’s98 ABSTRACTS OF CHEMICAL PAPERS.in the aqueous mother-liquor from the preparation of homocinchonidinesulphate. The alkalo'ids are precipitated from this solution by ammo-nia and recrystallised from alcohol.The crystalline mass is dissolvedin hydrochloric acid, and by fractional precipitation with sodium tar-trate the homocinchonidine is separated from the hydrocinchonidinetartrate ; the latter is contained in the last precipitate. The tartrateis converted into the neutral chloride : this is purified by recrystallisa-tion from water, and then decomposed by ammonia, when it yields purehydrocinchonidine. The pure alkaloid melts at 230" (uncorr.), anddoes not decolorise potassium permanganate immediately. The sul-phuric acid solution is not fluorescent. Hydrocinchonidine is depositedfrom an alcoholic solution in six-sided plates or prisms, which are inso-luble in boiling chloroform, and but sparingly soluble in ether or inwater.It is scarcely attacked by strong hydrochloric acid at 160".The following salts were prepared :-C19H,4N,0,HC1 + 2H,O, shortsix-sided prisms, soluble in water and in alcohol. ( C,,H,,N,O),,H,PtCI,, + 3H20, yellow amorphous precipitate. C19Hz,N20,H,PtC16, orange-coloured six-sided plates. The thiocyannte and the neutral oxalnteform anhydrous needles. The salicy Zate does not crystallise. Thequinate crystallises in anhydrous needles, soluble in water. The tar-trate, (C,H24N20)2,C4H606 + 2H20, is sparingly soluble in cold water.The crystals of the thiostdplznte containing 1 mol. H,O dissolve in117 parts of water at 10". C19Hz4N20,HzS0, + 4H20, is deposited inlustrous prisms! sparingly soluble in cold water. ( C,,H?4NzO)2,HzSOa + 7H,O, dissolves freely in alcohol and hot water.At 10" one partof the sulphate requires 57 parts of water for solution. The phenolsubhate, ( C19H,4N,0),S0,,CsH60 4- 5H&, forms whiteprisms, sparinglysoluble in cold water. The acetic derivative, CI9H,,AcN2O, is a hygro-scopic amorphous powder, soluble in alcohol, ether, acetone, andchloroform.Amorphous hydrocinchonidine is formed when the acid sulphnte ofthis base is heated a t 160" with hydrochloric acid, and is precipitatedin the form of a resin on the addition of soda to the aqueous solutionof the crude product. It is easilysoluble in ether, alcohol, chloroform, and acids. Hydrocinchonidinedeviates the ray of polarised light to the left much more powerfully inan acid than in a neutral solution. w. c. w.The pure base melts below 100".Xeronic and Pyrocinchonic Acids.By W. ROSER (Bey., 15,2012-2014).-In a previous communication (Abstr., 1882, 1114) theauthor has shown that pyrocinchonic acid is probably dimethylfumaricacid, and stated his belief that xeronic acid is the homologous diethyl-fumaric acid. In accordance with this view, he now finds that calciumxeronate yields propionic acid when oxidissd.By beating pyrocinchonic acid with hydriodic acid, an acid, CGH,,O,,is obtained, which from its reactions is probably identical with theunsymmetrical dimethylsuccinic acid of Pinner (Ber., 15, 582). Asacetic acid is obtained by the oxidation of pyrocinchonic acid (2 mols.),pointing t o a symmetrical constitution, intermolecular change musthave occurred in one or other of these reactions.A.J. GORGANIC CHEMISTRY. 99Strychnine. By A. GOLDSCHMIDT (Ber., l5,1977).-A preliminarynotice that the author has obtained indole by fusing strychnine withcaustic potash. A. J. G.Distillation of Strychnine with Zinc. By S. SCICHILONE and0. MAGNAWMI (Gazzetta, 12, 444-448) .-By heating strychnine withzinc-powder in small glass retorts to a temperature near the meltingpoint of the glass, a distillate is obtained, separable by treatment withether and fractional distillation, into two portions, boiling respectivelyat 165-180" and 230-300". In a second distillation the first ofthese fractions yielded n light yellow fragrant oil boiling at 173", andthe second yielded two yellow liquids, one boiling at 240-250", theother at about 292", and crystallising in a mixture of snow and salt.The liquid boiling at 173" gave by analysis numbers agreeing withthe formula C7H9N, which was confirmed by its vapour-density, deter-mined by Meyer's method (exp.3.89 ; calc. 3-70) ; and from the odourof this base and the pyridic nature of strychnine, the authors inferthat it is a lutidine, distinguishing it as ylutidine (a-lutidine boilsat 145", P-lutidine at 163-168"). This base is insoluble, or nearly so,in water, soluble in alcohol and ether, aud smells somewhat likeliquorice. The other two liquids, which were obtained in very smallquantity only, are also nitrogenous compounds, and the second, whichboils at about 292", solidifies in a mixture of snow and salt, whereasthe first remains liquid.The behaviour of the three bases with the usual tests for alkaloids,is shown in the following table:-Sodium phospho-molybdate.Potassio - mercuricIodised potassiumMercuric chloride.iodide.iodide.Auric chloride . . . .FrGhde's reagent..Picric acid . . . . . .Platinic chloride . ,y-Lutidine @. p.1'73').Dark-yellow preci-pitate soluble inNH, with faintblue colour.Yellow amorphousprecipitate.Crimson precipitateinsoluble in dilutehy$irochloric acid.White curdy preci-pitate soluble inNH,Cl.Dirty white preci-pitate.Faint red colour. -Liquid,b. p. 240-250'.White precipitatesoluble in ammo-nia withoutcoloration.Dirty yellow preci-pitate.White precipitatesoluble in N,H4Cl.Brown precipitate.Yellow amorphousReddish piecipitate.precipitate.Liquid,b. p. about 292".Light Fellow preci-pitate soluble inammonia, withoutcoloration.Red-brown precipi-tate.White precipitatesoluble in NH,Cl.Brown precipitate.Yellow amorphousRed-brown precipi-precipitate.tate.H. W.h 100 ABSTRACTS OF CHEMICAL PAPERS.Action of Dehydrating Agents on Lupinine. By G. BAUMERT(Annulen, 214, 361-376) .-Anhydrolupinine, C,,H3JY,O, and diun-hydrolupinine, C21H36N2, are formed by the action of phosphoric anhy -dride or of fuming hydrochloric acid at 200" on lupinine, C,,H,,N,O,.Anhydrolupinine is an oily liquid insoluble in water. It turns brownon exposure t o the air, and begins to decompose at 150". The platino-chloride, C21H99N20,H2PtC16, forms quadratic plates, soluble in waterand in alcohol. Dianhydrolupinine is an oily liquid (b. p. 220°), whichrapidly absorbs oxygen from the air. It yields a platinochloride,C2&6N2,H2PtC16 crystallking in dark red needles.Oxylupinine, C21H40N205, prepared by the action of phosphoric anhy-dride on lupinine hydrochloride at 175", is an unstable oily liquid.The platinochloride C,,H4,N205,H2PtC16, forms orange-coloured plates,insoluble in water and alcohol. This salt is decomposed by pro-longed boiling with water. If the mixture of phosphoric anhydrideand lupinine hydrochloride is heated at 185-190" for five hours,hydrochloric acid is evolved, and anhydrolupinine is produced.Colouring Matter (Ruberine) and Alkaloid (Agarythrine) inAgaricus Ruber. By T. L. PHIPSON (Chem. News, 46, 199).-Ruberine is insoluble in water and in alcohol; it is rose-red by re-flected, bright blue by transmitted light, and gives two wide and darkabsorption-bands in the green. As it is soluble in water, a heavyfall of rain washes it out from the head of the fungus. Frequentlythe upper surface of A. Tuber is eaten through by slugs, which, how-ever, do not penetrate deep. A yellowish-white alkaloyd (agarythrine)is extracted by ether from the fungus itself, after removal of the skin.It has a bitter taste at first, which changes to a burning sensation,resembling that produced by aconitine; the chloride is soluble inwater, but the sulphate, although insoluble in water, is soluble inalcohol. Nitric acid solutions become red. Bleaching powder pro-duces also s red coloration with agarythrine, but the colour is soonbleached. When the solution is shaken up with ether, it is oxidised bythe air to a red colouring matter; this is probably the cause of thered colour OE the surface of the fungus, the alkalo'id being oxidised bythe air in presence of light.Bases formed by Putrefaction. By A. GAUTIER and A. ~ T A R D(BUZZ. Xoc. Chirn. [2], 37,305-307).-The authors have extracted fromputrid animal mattler two liquid alkaloids, which have a strongly alka-line reaction, attack tissues in the same manner as potash, saturatestrong acids, and appear to absorb carbonic anhydride from t,he atmo-sphere with formation of crystalline carbonates. One of these alka-loYds boils at about 210°, and is a colourless, syrupy, bitter, and verycaustic liquid; its sp. gr. at 0" is 1.0296. Its hydrochloride formsslender needles, somewhat stable when pure, but rapidly reddenedby excess of acid. It is very soluble, and has a cery bitter taste. Theplatinochloride is also stable, and crystallises well. It is precipitatedimmediately from moderately concentrated solutions, dissolves onheating, but separates out again on cooling in slightly curved needles.The aiirochloride is very unstable, and rapidly deposits metallic gold.w. c. w.E. W. PORGANIC CHEMISTRY. 101The various salts of this base rapidly reduce ferric chloride to theferrous state.The second alkalojid boils at a higher temperature, but decomposeson boiling into ammonia and products which have a carbolic odour, andare only slightly soluble in ether.These alkalo'ids appear to be accompanied in the putrid matter byother more complex and more unstable basic compounds. When thecrude ethereal solution of the alkaloids is evaporated to dryness, andthe residue treated with potash, zt strong odour of carbylamine is givenoff. The carbylamines are doubtless produced by the action of thepotash on the complex basic compounds.Formation of Alkaloids from Normal Human Fluids. ByA. GAUTIER (Bied. Centr., 1882, 710).-If saliva be evaporated and theresidue dried for some hours, it will act as a poison on birds ; this sub-stance, like the ptomaines, turns potassium ferricyanide and ferrichlo-ride blue. An easily oxidisable alkaloid, which combines and formscrystalline compounds with gold and platinum chloride, has been pre-pared from urine.Urorosei'n. By M. NENCKI and N. SrEBER (J. pr. Chem. [2], 26,333-336).-The urine of a diabetic patient was found to becomebright pink on the addition of pure hydrochloric acid. The colouringmatter is extremely unstable. It dissolves in amylic alcohol, and thesolution shows a characteristic absorption-band between the lines Dand E, the maximum of intensity corresponding to 557 millionthmillimetres wave-length. 0. H.Behaviour of Unorganised Ferments at High Temperatures.By F. HUPPE (Bied. Centr., 1882, 718).-Pepsin, when dry and heatedt o 100", is not injured, but at 170" its power is diminished, althoughnot entirely destroyed.Pancreatinstill dissolves albumin, even after being heated to 160" ; the tempera-ture at which all are killed is about 160-170".C. H. B.E. W. P.Malt diastase is not affected by a temperature of 100".E. W. P.The Temperature most Favourable to the Action of Inver-tin. By A. MAYER, W. HAGEMANN, and W. HEUBACH (Bied. Centr.,1882, 706).--In a previous communication, it has been shown that pre-cipitation by alcohol destroys the fermenting power of invertin, andfurther experiments have not resulted in the discovery of any methodfor the separation of this ferment in the pure state. The temperatureat which action is most intense is about 30", but if an acid be present,then the temperature may be raised to boiling ; with various prepara-tions the temperature may be different, ranging from 31-2 48".Influence of Invertin on the Fermentation of Cane-sugar.By E. BAUER (Bied. Oentr., 1882, 707).-It is generally stated that thefermentation of cane-sugar induced by invertin proceeds with equalrapidity, whether it is previously inverted before the ferment is intro-duced or not ; such a supposition is incorrect, as nnkss the sugar beE. W. P102 ABSTRACTS OF CHEMICAL PAPERS.previously inverted, the fermentation will proceed but slowly, althoughthe complete change does finally take place, and the time occupied islonger. E. W. P

ISSN:0368-1769    

DOI:10.1039/CA8834400037

出版商:RSC    

年代:1883

数据来源: RSC

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102 ABSTRACTS OF CHEMICAL PAPERS.P h y si ol o g i c a1 Chemistry.Nutritive Value of Skim Milk. By J. Ko~ic, (Bied. Centr.,1882,693-696).--Comparing skim milk (N.R. 1 : 2) with whole milk(N.R 1 : 3*5), the author shows that skim milk is by far the cheapestand most nutritious food for adults ; also it is shown that the pricepaid €or the albuminoids in skim milk is lower than that paid for themin any of the ordinary foods which appear in the markets, exceptingstockfish; as for example 1000 nutritive units in skim milk cost41.7 pfennings, whilst in pork they cost 71.4 ; in butter, 81.7 ; and ineggs, ‘201.2. Stohmann has calculated that 1 litre skim milk corre-sponds in nutritive value to 160 grams boneless meat, the latter costing19.2 pfennings, whilst the former costs only 8.10.Skim Milk as Food.By RITTHAUSEN (Bied. Centr., 1882, 641).-Skim milk is a valuable food for man and beast, as 2.8 litres of itcontain as much nitrogenous matter as a pound of meat, and it ismuch cheaper. E. W. P.Feeding Horses with Flesh Meal. By FINDEISEN (Bied. Celztr.,1882, 651).-Old horses fed with Huch’s flesh meal increased inweight, and this food was found t o be very satisfactory in cases ofillness. E. W. P.E. W. P.Researches on the Digestibility of Purified Lupine Seedsby the Horse, and Observations on the Working Power of theHorse when Fed with Lupines and Oats. By 0. KELLXER ( B i dCentr., 1882, 588-592) .-The digestive coefficients of lupine seedswhen eaten by horses, in combination with hay, are as follows :-Dry matter.Org. matter. Albumindids. Fibre. Fat. Extractives.70.63 72-29 94.16 50.82 27.32 50.79Lupine seeds therefore approach in feeding power to peas, beans,and maize, being more easily, and oats less easily digestled. To deter-mine the comparative value of oats and lupines as food during labour,a horse was fed with 6 kilos. purified lupine seeds, corresponding to2.77 dry untreated seeds, and 8.5 kilos. hay. After the performance ofcertain labour in a wheel, the amount of labour being so regulated thatthe live weight remained the same, the lupines were replaced by 4 kilos.oats daily, and again labour was performed under the same conditions.The labour performed during the “ oat ” period was i n excess of thaPHYSIOLOGICAL CHEMISTRY.103done during the “ lupine ” period by 380,300 kilogram-meters, thenutrient ratio in the oat period being 1 : 738; during the other,1 : 304. From the calculations given it would appear that 1 kilo.oats produces the same working power in a horse as 1 kilo. of air-dried and purified lupines, but as the ratio in the lupines is so narrow,it is not advisable to replace more than 2.5 kilos. oats by lupines,otherwise a, great decrease in fat is likely to take place.The Gastric Juice. By J. CHAPOTEAITT (Cowzpt. rend., 94, 1722).-On evaporating an aqueous solution of gastric juice, prepared fromthe stomach of a sheep, a pepsin is obtained capable of dissolving3000 times its weight of fibrin. Alcohol precipitates from the solu-tion a white neutral pulverulent substance, while the liquid acquiresan acid reaction: the liquid freed from alcohol is without solventpower, but the white substance when acidified possesses a considerable.power of dissolving fibrin, and indeed appears to retain the special pro-perties of pepsin.It precipitates metallic salts and solutions of limeand baryta, and froths with a solution of albumin. The acid liquid is,however, certainly one of the active elements of pepsin, for the solventpowers of the white substance are much inferior to those of theoriginal liquid. R. R.E. W. P.Decomposition of Hydrogen Peroxide by certain OrganisedBodies. By A. BBCHAMP (Compt. rend., 94, 1601--1604).-Thepaper discusses previously published observations by the author(Compt.rend., 59, 713) in relation to investigations by Dumas,Thhard, Bert, Regnard, and others. He will shortly show that thegranulations which decompose oxygenated water can be isolated fromblood without formation of fibrin, and that the more the serum ofblood is deprived of microzymas and globules, the less energetic is itsaction in decomposing oxygenated water.Microzymas the Cause of the Decomposition of HydrogenPeroxide by Animal Tissues. By A. BBCHAMP (Compt. rend., 94,1653-1656) .--The paper discusses some observatioiis of Thenard’son the decomposition of hydrogen peroxide by various animal tissues,and the results of the author’s experiments are given in a tabularform. The removal of the microzymas of the blood itself from theseveral tissues presented some difficulties, but the author conceivesthat he has proved by these experiments t h a t the microzymas of thedifferent tissues are not only functionally different, bnt that they act onhydrogen peroxide with different degrees of energy.R. R.R.R.Action of Hydrogen Peroxide on the Red Colouring Matterof the Blood, and on Haematosin. By A. BBCHAMP (Compt. rend.,94, 1720--1722).-The serum of ox blood freed from microzynias bypassing it through a filter covered with barium sulphate is withoutaction on hydrogen peroxide ; but the red solution obtained from theblood globules, even after passing through a similar filter, disengagesoxygen. He,moglobin is distinguished from fibrin and from tissuesthat act like it, in that it is capable, after coagulation by alcohol o104 ABSTRACTS OF CHEMICAL PAPERS.by heat, of being dried a t 120" without losing its power of decom-posing hydrogen peroxide and becoming colourless. This phenomenoncorresponds with a profound chemical reaction, and the oxygen disen-gaged is due to an action analogous to those observed by ThBnard,in which the action of hydrogen peroxide on sugar and starch gaverise to both oxygen and carbonic anhydride a t the same time.Bloodcontains two causes for this decomposition, the microzymas andlxemoglobin, and if hydrogen peroxide is ever formed in the bloodit is immediately employed in effecting transformations similar tothose described. R. R.Rattlesnake Poison. By H. H. CROFT (Chem. News, 46, 165).-A favourite antidote for rattlesnake poison, in Mexico, is a strong solu-tion of iodine in potassium iodide.The author has tested some of thepoison itself with this solution, and finds that a light brown amor-phous precipitate is formed, the insolubility of which explains thebeneficial action of the antidote. When iodine cannot be readilyobta,ined, a solution of potassium iodide, to which a few drops of ferricchloride has been added, can perhaps be used as an antidote to snakepoison ; it is a very convenient test for alkaloids. D. A. L.Physiological Action of p-Collidine. By MARCUS and 0. DECONIKCK (BUZZ. Xoc. Chim. [2], 37, 457).-&collidine exerts a strongpoisonous action, and in this respect has no analogy with the cinchoninefrom which it is derived. Subcutaneous injection of 0.05-0.15 gramproduce general and progressive weakness, with paralysis of the psycho-motor centres. Reflex motions are not affected, with the exception ofthat of the cornea, which is destroyed. The blood pressure diminishes,the cardiac muscle becomes weaker and weaker, the temperaturedecreases, and the heart stops from diastole.Weak doses produce a temporary effect characterised by the samesymptoms. The alkalo'id is eliminated by the organs of secretion,which it excites, and the organisms reassume their normal functions,The reflex action of the cornea, however, does not return.C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8834400102

出版商:RSC    

年代:1883

数据来源: RSC

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104 ABSTRACTS OF CHEMICAL PAPERS.Chemistry of Vegeta:ble Physiology and Agriculture.Influence of Alcohol on the Development of Yeast. By 1\11.HAYDUCK (Bied. Centr., 1882, 635-637) .-From this continuation offormer experiments (Abstr., 1882, 761) we learn that the presence ofalcohol retards the development of yeast, and that fermentationproceeds more slowly in proportion as the amount of alcohol originallypresent is greater. E. W. PVEGETABLE PHYSIOLOGY AND AGRICULTURE. 105Nature and Formation of Dextran. By E. BAUER (Bied.Cerbtr., 1882, 630) .-The microscopic appearance of the organismswhich induce the formation of dextran is described, and it is statedthat mucus fermentation can occur only in neutral or slightly alkalinesolutions ; it does not occur, therefore, in the fermentation of must,as much acid is present; but it does occur in the fermentation ofmolasses, owing to the presence of alkali in small quantity.Elimination of Oxygen from Plant Cells.By T. W. ENGEL-MANN (Bied. Centr., 1882, 673).-By means of his bacteria method(Abstr., 1882, 335) and with a microspectroscope, the author findsthat the action of the light between the B and C lines is the mostintense, and not, as according to other authors, in the yellow.E. W. P.E. w. P.Elimination of Carbonic Anhydride by Plants in Absenceof Oxygen. By W. P. WILSON (Bied. Centr., 1882, 67$).-Diminu-tion of the amount of oxygen admitted to plants is accompanied by areduction in the quantity of carbonic anhydride expired. For example,in air, Lupi?zzcs Zuteus expired 5.7 CO, in the first half-hour, whereasin hydrogen only 1.5 GO,.Plants, whether in air or in hydrogen, arenot influenced by the presence or absence of light.Action of Various Gases, especially Nitrous Oxide, on PlantCells. By W. DETMER ( B i e d . Qentr., 1882, 675--677).-Seeds ofPisum sativuni and Triticum vulgare cannot germinate in pure nitrousoxide, but they do not lose the power of germinating afterwards inair, if they be not kept too long in the former gas ; still t o a certainextent harm is inflicted on the embryo, reducing its energy and theintensity of evolution, and this reduction in its activity is the greaterthe longer it has been in contact with the gas, and the higher thetemperature. Seeds can germinate in a mixture of air and nitrousoxide, but the giaowth ceases as soon as the free oxygen is absorbed, anddecomposition of nitrous oxide never occurs.Heliotropic motion doesnot take place, neither do etiolated plants become green in nitrous oxide.These observations were also made when the atmosphere consisted ofpure hydrogen or carbonic anhydride. Chloroform vapour kills ger-minating. plants, or at least stops their growth, breathing however,still continues. Dead cells do not breathe, so that respiration isdependent on the presence of living protoplasm ; but it sometimesoccurs that carbonic anhydride is eliminated from dead plants: thismust be due to the action of lower but live organisms acting on thedead cellulose matter. E. W.P.E. W. P.Influence of the Electric Light on the Development ofPlants. By P. P. D ~ H ~ R A I N (Annales Agrorzomiques, 7, 551-575).-The author’s experiments were made at the Palais d’hdustrie duringthe Electric Exhibition of August, 1881. A greenhouse was con-structed and divided into two compartments, one of which was glazedwith blackened perfectly opaque glass, whilst the other was exposedto the ordinary diffused daylight, of the Exhibition building. Thedarkened chamber was illuminated continuously, night and day, by 106 ABSTRACTS OF CHEMICAL PAPERS.2000-candle arc-light from a Gramme machine, driven by an Otto gas-engine. The transparent chamber was illuminated a t night only bythe electric light. Five series of comparative observations were made,viz.:-1. Plants exposed night and day to the electric light alone,2. Plants exposed during the day to the diffuse daylight of the3. Plants living during the day in the open air, and receiving the4. Plants passing the day in the diffuse daylight of the Palais, and5. Plants living normally in a garden.The plants submitted to experiment were barley, fhx, beans, and anumber of garden and greenhouse plants.Action of the Unprotected Light.-At the end of seven days the nakedelectric light was seen to have an injurious effect both on those plantswhich were constantly subjected to it, and in a less degree on thosewhich were exposed to it during the night only. The leaves blackened,withered, and dropped off; the injury was confined to the epidermallayers, and was due to the direct impact of the luminous radiations(and not to the formation of nitrogen oxides) ; for where one leaf waspartly shaded by another, a sharp line was photographically im-pressed.Experiments on EZodea canadensis, submerged in flasks of water,showed that whilst the diffuse daylight of the building was unable tocause decomposition of carbonic anhydride and evolution of oxygen,the direct rays of the electric light were able to do so, about as muchoxygen being obtained during an exposure of fonr or five days andnights to the electric light as could be obtained in an hour or so inbright sunlight. At the end of 15 days the arc lights were enclosedin globes of transparent glass, Siemens’ just published experimentshavjng shown that the injurious action of the direct radiations wasthereby modified.Action of the Protected Light.-A number of fresh and uninjuredplants were placed in the greenhouse, and in addition sowings ofbarley, oats, peas, maize, beans, which had just appeared above theground.All the seedlings exposed exclusively to the electric lightperished sooner or later, and the leaves of some of them were blackenedas with the naked light. The mature plants, on the other hand, con-tinued to vegetate, but in no case, save a plant of barley, were flowersand seeds produced, the vegetation being purely foliaceous. Thebarley grains were normal, and germinated on being sown. Theelectric light employed was clearly insufficient by itself to determinethe assimilatioii of any considerable quantity of material ; direct expe-riments also proved that it is not more powerful in exciting trans-piration of water, a leaf exposed to i t giving off in an hour only aboutone-fiftieth of the quantity of water evaporated under similar circum-stances in sunlight.As the evaporation of water by the leaves is oneof the chief agencies in causing the migration of material necessaryfor the maturation of seed, the failure of the plants to produce flowersand seeds receives its explanation. It, is known that yellow and redPalais, and during the night to the electric light.electric illumination at night.the night in darknessVEGETABLE PHYSIOLOGY AND AGRICULTURE. 107rays are most powerful in causing transpiration, whilst the electriclight is particularly rich in blue and violet rays.The author considersthe electric light employed AS too feeble to allow of any conclusion as tothe necessity of a nocturnal rest to plants. I t was, however, evidentthat the electric illumination during the night was advantageous tothose plants which passed the day in the rather feeble diffused day-light of the palace. In a third series of experiments, the intensity ofthe electric light was practically augmented by placing the plantsnearer the lamp, The experiment was again fatal to young seedlingsreceiving the electric light exclusively, but many of the hardier andmore mature plants survived, although the leaves of some wereblackened by their too great proximity to the light; and again thenocturnal electric illumination was decidedly favourable t o the plantswhich passed the day in the light of the palace.The author sums uphis conclusions thus :-1. The electric arc-light emits radiations which are injurious tovegetation.2. Most of these radiations are arrested by colonrless glass.3. The electric light emits radiations powerful enough to maintainmature plants in vegetation for two months and a half.4. The beneficial radiations are not sufficiently powerful to causethe growth of germinating seeds, or to allow of the maturation of fruitin older plants. J. M. H. M.Embryos of Ungerminated Rye. By I(. NACHBAUR. (Monntslb.Clzern., 3, 673--676).-Analyses of the sample of Russian ryeemployed, and of the embryos carefully separated from it, gave thefollowing results :-Rye.Embryos.Water .................. 11-92 9-58Prote’in substances ........ 14.1 2 42.12Fat ...................... 1.16 12.04Ash .................... 1.63 4.44Gum, starch, dextrin, and } 71.17 - woody fibres ...................... 45.11 Soluble matter -~Sp. gr. .................. 1.245 1.13The especial object of the investigation was to ascertain if thediastatic ferment observed in the grain was contained in the embryo,which for this purpose was extracted by glycerol according to Gorup-Besanez’s method, but with negative resu1t.s.By W. R. CRIPER (Chem. News, 46,187).-After exposure t o the sun, the woods chiefly used for fuel havethe following composition :-A.J. G.Analyses of Indian Wood108 ABSTRACTS OF CHEMICAL PAPERS.Carbon ..........Hydrogen ........0 + N ..........Ash ............Sand. ...........Water ..........Heat - units calc.from analysis,not includingsand ........Mango.42.725.7036.232-882.979.50100~003634SB1.43.585.4538.091.240.4411.20Dhsika.40.615-1135.366.251.0011.67100.003458100~003259During the rainy season, the wood contains about 20 per cent. ofwater ; the heat-units for SAZ would be 3054; therefore for equalweights coal has 2.32 times the heating power of ordinary wood.Inorganic Constituents of some Epiphytic Ferns. By W. A.DIXON (J. Roy. Xoc. N e w South Wales, 15, 175--183).--The fernsexamined were Platicycerium grande, P.alcicorne, and Asplenium nidzcs,from the Clarence River, and a specimen of the second from New-castle, N.S.W. The following table exhibits the results obtained byanalysis of the ash of these ferns, the live fronds and the humus mass,consisting mainly of dead fronds mixed with rootlets, being analysedin each case. Contrary to what might have been expected from theirmode of growth, the amount of ash in the growing fronds is quite ashigh as in the leaves of most plants; and those of A s p l e n i u m nidusare rather rich in inorganic matter. Of Pladycerium alcicorne, twospecimens were examined, one growing on a rock, the other on a tree.The humus mass of the rock specimen contains a considerablequantity of sand, consisting almost wholly of white quartz.Thewithered fronds and humus of the tree-plant contain copper oxide,proceeding from t,he smoke of copper-works situated about three-quarters of a mile from the locality in which the fern grew. I n thetable, the sand and copper oxide have been deducted.The high percentage of sand in the ashes of the humus masses, aswell as the copper oxide in the specimens from Newcastle, show thatthe ferns must obtain much of their inorganic matter in the form ofdust, as with the exception of P. alcicol-ne, which grew upon a rock,they could not obtain it directly. They are all plants requiring con-sidemble quantities of alkalis, and when these are deficient, the grow-ing parts take up as milch as possible from the withered fronds andhumus.The humus being partly composed of rootlets, must neces-sarily retain some of the inorganic constituents. Thus P. alcicorne,growing upon a rock, is very deficient in potash and soda, and, as willbe seen from the table, has extracted almost the whole of these con-stituents from the humus and dead fronds, and has made up for itsdeficiency of alkalis by assimilating a large quantity of magnesia,lime, and alumina. The same species from Newcastle contains morethan double the quantiky of alkalis, which it has removed chiefly fromE. W. PQuantities of Diferent Consthefits in 10,000 partsPlatycerium alcicornefrom rock.--Potash. .....................Soda ......................Potassium chloride ...........Sodium chloride .............Lime ......................Magnesia ...................Alumina....................Ferric oxide ................Manganese oxide ............Phosphoric ,, ............Sulphuric ,, ............Platycerium Platycerium grande.Livefronds.292 -0497 *66-15-26189 -5548 -1070 '3421 -293 '8779 *1312 -67Humusmass. --22 -727 *29-7 *2985 -937 -2941.515.86-4 -0720 -40Livef Fonds.--92 '5080 -73 -54 -4361.9265.7147 '395 -687 -8514 '1211 -63Humusmass.----12 *a451 -7211 -3847 *1342 -1316 -6232 *94Lirefronds--191 .a'/102 -r - 1 48.1523 -22 -34.503 '2221 68118 '7110 ABSTRACTS OF CHEMICAL PAPERS.the withered fronds, but has still left considerable quantities in themand in the humus, whilst, although lime and magnesia are present inthe humus in greater abundance than in the other plant, the livingplant has not taken up so much.P. grarde seems to have had anabundant supply of all its constituents, whilst A . nidus has beendeficient only in sodium salts, which it has removed completely fromthe humus. H. W.Percentage of Ash in the Sugar-cane. By W. RNOP (Dingl.17oZyt. J., 245, 435).-The following is an analysis of a sample ofsugar-cane from Pernambuco, the cane having been overgrown withfungi. 100 parts of the driedsubstance gave-It contained 80 per cent. of water.Si02. Y20,. SO,. C1. E20. Na20. CaO. MgO.0.81 0.07 0.08 0.29 0.86 traces 0.06 0.16 partsalso traces of ferric and manganic oxides.It is a remarkable coincidence that the a6h, although small inquantity, contains so large an amount of magnesia and chlorine.Whether this peculiarity in the composition of the ash favours thespreading of fungoid disease cannot be ascertained without ma,king anumber of ash determinations of sound canes.D. B.Parasitic Diseases of Plants, and their Prevention. By L.DANGER and others (Bied. Centr., 1882, 615-613).--Cabbages andcauliflowers suffer from a sudden fall in tLhe temperature ; the damageis due to rending of the epidermis cells, whereby the flow of sapis impeded.Sugar-beet is frequently destroyed by the larvae of AtomariaZineayis or of the centipede, which eat the rootlets, but so long asthe inner bundle of rootlets remains unattacked, the beets willflourish. To provide other food for these larvze, J.Kuhn recom-mends that the weeds should be allowed to grow up to the fifthleaf, and that the beet seed should be pickled with a mixture of5 parts of magnesium sulphate dissolved in 100 of water, to whichmay be added 1 part of phenol. Hess describes the slightly knownlarva of Xilpha reticdata, which destroys the cotyledon leaves ; thislarva prefers, however, to feed on Atriplex lzortensis and the Cheno-podiaceq which should therefore be carefully weeded out.Prillieux describes a fungoid growth belonging to the Discomycetes,which attacks beans, hemp, clover, carrots, and chicory. The un-usable portion of these plants should be burnt, and not placed incompost heaps.G. Ereiss states that all plants of berberry, buck-thorn, blackberry, and several belonging to Boraginaceze should beremoved from the neighbourhood of fields bearing grain, as theseplants harbour the germs of Accidium, which produces rust in thegrain. E. W. P.By 3’. v. THGMEN and others( B i e d . Centr., 1882, 688-690) .-Thumen recommends a mixturecontaining one-twelfth road dust, one-twelfth ferrous sulphate, andVine Diseases, and RemediesVEGETABLE PHYSIOLOGY AND AGRICULTURE. 111five-sixths gypsum as a remedy against Peronospora viticola, thewinter spores of which Prillieux has found on leaves to the numberof 200 per square mm. of surface. Clissey burns all portions of thevines affected with Xphaceloma ampelinurn.T humen describes theappearance of a new disease, called in France " Aubernage," which isproduced by Xphaerella pampini. J. Kubler describes the effects ofdisease produced in Switzerland by Cicada or Typhlociba &is.E. W. P.Diseases of Sugar-beet. By J . K ~ H N and H. JOULIE (Bied. Centr.,1882, 607-612) .--Various methods were tried for the destruction ofnematodes, which destroy sugar- beet. The most satisfactory plan ist o sow some fine-rooted variety of garden-cabbage, or the same mixedwith cress. The nematodes feed on this, and the larvae then remainingmay be burnt when this supplementary crop is removed, which shouldbe in about 30 days after brairding.Experiments show that this method relieves a soil of beet-sickness.Jonlie has noticed that sugar-beet does not thrive on reclaimed forestlands without the addition of manures containing potash, such asfarmyard dung, &c. ; the roots being feeble and wanting in sugar, andthe leaves weakly. The ash of these weak roots on analysis shows thatpotash is decidedly in too small a quantity, and consequently the plantis enfeebled.E. W. P.Composition of Fodders. By A. PETERMANN (Bied. Cenfr., 1882,642).-Tables of analyses of a dozen kinds of fodder.Specific Gravity of Cereal Grains. By DRECHSLER (Bied.Centr., 1882, 715).-The sp. gr. of cereal grains has no connectionwith their agricultural value, which is determined by their absoluteweight, the heavier corns producing the highest yield. To estimatethe actual weight, it is iwcessary to weigh a t least 400 grains.It hasbeen found, from an extended series of experiments, that 100 grains ofwinter rye, wheat, and oats weigh 4 grams, and 100 grains Gf barley6 grams. E. W. P.Composition of Malt from 1877 Barley. (Bied. Centr., 1882.632--634.)-Tables showing the composition of the original andmalted barley from various districts, as also of the ash of the barleyand malt. Malt contains more lime than barley.By A. RENOUARD (Awnales Agronomipues, 7, 511-524).-Since 1872 the consumption of cotton cake in France has beenextending, and it is now largely used for feeding cattle. In 1880 theamount of cotton cake imported was 446,467 kilos., and of cottonseed 21,588,363 kilos. In the same year the quantity of cotton cakeexported (almost entirely to England) was 2,704,807 kilos.The chiefsupply, both of cake and seed, is derived from Egypt, Turkey, andItaly, very little coming into France from the United States.England, on the other hand, imports cotton cake chiefly from theUnited States, and cotton seed chiefly from Egypt. The cotton-seedoil, expressed a t Marseilles and Rouen, is used by painters and varnishmakers, and in soap making. The extraction of this oil on a corn-E. W. P.Cotton Cake112 ABSTRACTS OF CHEMICAL PAPERS.mercial scale dates from 1860, before which time vast heaps accumu-lated and perished on the cotton plantations ; a t the present day theseed is often more profitable to the planter for its oil and oil-cake thanfor its cotton, of which it contains only about 25 per cent.by weight.In the United States, the cotton-seed harvest takes place in Octoberand November, and the seed, after having been carefully gathered bywomen, is spread out to dry until hard to the teeth : the cotton woolis then separated from the remainder of the seed by suitable machines.The earlier seeds are of inferior quality to those gathered later in theseason ; they are more watery, the kernel is greener and softer, thecotton less easily removed, and they are apt to be crushed by thedecorticators : the oil obtained from them contains more water, resin,and mucilage, clarifies with difficulty and easily becomes rancid. Inorder to extract the oil, the seeds are screened, crushed between flutedrollers, ground into a paste which is heated in an oven to coagulatethe albumin ; then submitted to a pressure (in England) of 8500 lbs.per square inch in a hydraulic press.The greater part of the oil isextracted a t the first pressure, which lasts five minutes; the cakesare then crushed, with addition of 5 per cent. water, dried by steam-heat, and re-pressed ; the pressing is sometimes repeated a third time,after which the cake does not retain more than 9-10 per cent. of oil.The cakes are finally trimmed and allowed to dry for about 20 days,when they become hard enough for transport. French cotton cakesare generally square, 35 x 35 x 0.5 centimetre, and weigh 2.4 kilos.There are three qualities :-1. cot tom^, so called because they contain de'bris of cotton.TheSyrian cakes contain more cotton than the Catanian.2. BrowrL. Levantine or Alexandrian cakes are made from Egyp-tian seed, and are free from cotton.3. Purijied cake, made at Marseilles, and consisting of the browncake deprived of a portion of the husks by a summary method.In England, the only qualities are rough or common cotton cake(answering to the tourteaux bruts), and decorticated cotton cake, whichis unknown in France.Cottony Cake has a deep-brown colour and granular fracture,showing fibres of cotton.Catanian.Water ................ 8.4Oil .................... 5.20 rganic matter ........ 79 -8 1Ash .................. 6-59Syrian.7.46-9280.335.28100*00Nitrogen .............. 3.23Phosphoric acid ........ 2.02100.002.861.12Cottony cake is chiefly used in the south of France as manure.Ifgiven to stock, the cotton-fibres are apt to collect into balls whichobstruct the intesthes. Cottony cake is sometimes adulterated withearthy matterVEGETABLE PHYSIOLOGY AND AGRICULTURE. 113Brown Cake.-The fresh cake has a greenish colour which becomesbrown with age. The fracture shows a large number of hard, blackfragments of the testaceous covering of the seed. It is used solelyfor feeding stock, in admixture with pulped potatoes or mangel, an6with hay or chaff after maceration for 12 hours. I t is never given topigs. In England and America, it has to a considerable extent takenthe place of linseed cake. Cotton cake should never be boiled, for itthen developes an essential oil which animals dislike.Composition.Water ..............10.98Oil.. ................ 6.09Organic matter ...... 77.03Ash ................ 6.00100~00Nitrogen ............ 4.03Phosphoric acid ...... 2.07Pzcri$ed Cake is yellow, sprinkled with numerous dark spots.Cattle like it better than the preceding, and it is excellent for fatten-ing, and, above all, for producing milk, being preferred even to rapecake for this purpose.Composition.Water .............. 11.26Oil.. ................ 4.80Ash ................ 5.28Organic matter ...... 78'76100-00Nitrogen ............ 4.43Phosphoric acid ...... 1-96Decorticated Cotton Cake has a pale-yellow colour, and is madeonly in England and America. The seeds are crushed by decorticatorsand the husks then winnowed from the kernels, which are ground tomeal and then made into cakes in the ordinary manner.The husksare used to make paper. The cakes are hot pressed only when the oilis to be used for industrial pur oses ; virgin oil for use a t table isIn the Ur,ited States, a salad oil is obtained by cold pressing equalparts of sesame meal and cotton-seed meal. The semi-solid fat, whichis a bye-product in this operation, is used for making artificial butter.always obtained by pressing in t R e cold.Ordinarydecorticatedcotton cake.Water.. .......... 9.52Oil .............. 11.58Ash .............. 6.63100*00Pu'itrogen. ......... 7.64Organic matter.. .. 73.27VOL. XLIV.Cold-pressed(Voelcker),9.0819.3464.27.38Hot-pressed(Voelcker).9.2826-0566.628-05100*006.93100~006.58114 ABSTRACTS OF CHEMICAL PAPERS.The varieties of cotton cake in the market vary so much in com-position, that buyers should always require a specification andguarantee of quality.Cultivation of Lupines.By J. KONIG ( R i e d . Centr., 1882, 642).-Continuous cropping with lupines cannot be carried on for morethan 5-10 years.Potato Culture. By A. LEYDHECKER and others ( B i e d . CYentr.,1882, 598--605).-Leydhecker finds that the best yield of potatoes isobtained by removal of the side eyes rather than of the end eyes, whetherthe sets be planted shallow or deep ; also that deep setting lowers theyield of tubers and haulms. E. Wollny having planted potatoes, ofwhich the sets were half-potatoes cut either along the long diameteror short diameter, found that the pointed half produced the highest,the other half the lowest yield ; that the tubers from the pointed setswere larger than those produced from medium-sized whole sets ; andthat large whole sets gave a larger yield than halved potatoes. Therest of this article consists of tables merely showing the yields andpercentage of starch of varieties of potatoes grown by several experi-men t em.E. W. P.J. M. H. M.E. W. P.Sugar-beet Culture. By W. RIMPAU and others ( B i e d . Centr.,1882, 594-598).-Rimpau notices that the earlier the beet is sown,the greater will be the number of young shoots, and that their growth isaided by the cold frosty nights of March ; also that a greater number ofshoots will be thrown up if the seed be planted deep.From France itis reported that it is best to plant deep, as the percentage of sugar isthen higher, and that the shallow-sown roots generally grow up forked.Desprez reports that the beets with compact flesh and wrinkled skincontain a higher percentage of sugar than other kinds.Cultivation of the Sugar-beet. By A. LADUREAU (AnnaZesAgronomiques, 7, 575--587).-1n this paper are detailed the results ofexperiments carried out in 1880. The manuring experiments are theonly ones of chemical interest.The soil of the experimental plots has received no manure for manyyears, and is remarkable a s being quite destitute of phosphoric acid.Sample taken to a depth of 40 cm.contained per cent. :-Pp06, none ;N as NH,, 0.012 ; organic N, 0.065 ; nitisic N, 0.022 (total N, 0.099) ;K,O, 0.035 ; CaO, 0.370 ; MgO, 0.151 ; A1203 and Fe203, 3.259 ; N&O,0.084; C1, 0.091 ; SO3, traces.Nitrogenous Il.laiture.s.-These were employed izl equivalent quanti-ties, at the rate of 200 kilos. nitrogen per hectare, the size of eachexperimental plot being one “ are.” The leather used in experimentNo. 9 had been torrefied by superheated steam. The (‘ azotine ” usedin No. 9 is prepared by the action of steam on torrefied wool-waste(Aianules Agronnmiques, 7, 28), and contains organic nitrogen in asoluble form; it can be bought a t 2 francs per kilo. of contained N.The trimethylamine of No. 10 is produced by the destructive distilla-tion of certain beet-distillery residues, and is sold as a brown, badlyE.W. PVEGETABLE PHYSIOLOGY AND AGRICULTURE. 115smelling liquid, containing about 10 per cent. nitrogen, at a priceequivalent to 1-50 francs per kilo. of N; the principal results ayeembodied in the annexed table.Manure.1. Unmanured. ...............2. Ammonium sulphate ........3. Sodium nitrate .............4. PotascJium nitrate. ..........5 . Arachida cake. .............6. Wool refuse.. ..............7. Torrefied woo1 .............8. Torrefied leather.. ..........9. Azotine ...................10. Trimethylamine ............Nper cent.O fManure.-20 -815 -813 *337 -2’74 *543 -306 *079 ‘209 -56Kilos.ManurePerhectare.-9601265150027504406660333021702090Kilos.BeetPerhectare.32,4004’7,40054,80051,20052,MO49,60050,10048,10060,10043,600Kilos.SugarPerhectare.32924569531.043925622492549546334577544Q7The seed was sown on April 7th, and the roots lifted November 13t,h.These experiments show clearly the superiority of nitrate of soda tosulphate of ammonia, and even to nitrate of potash (for this soil), andthe value of the organic nitrogen in such manures as arachida cake,wool refuse, and azotine.Phosphatic Manures.-The quantity of each was so adjusted as t orepresent 100 kilos.phosphoric anhydride per hectare. To the super-phosphate in No. 5 was added the same quantity of ammonium snl-phate as was used in No.2 of the preceding experiments.Manure.1. Unmanured ................2. Ardennes phosphates. ........3. Burgundy phosphate.. .......4. Superphosphate .............5. Superphosphate and ammoniumsulphate.p20,per cent.O fManure.IKilos.ManurePerhectare.I-- -34 ‘829 *513.5-280340’750Kilos.BeetPerhectare,---32,40033,80033,40044,700 } 55,400Kilos.Sugarperhectare.32923596361045595246Nitrification in Soils. Bv R. WARINGTONJ. M. H. M.(Bied. Cen.tr., 1882,660-663 ; from Jozcr. Xoc. A k , 1882, 532-544) .-The followingtable represents the average quantity of nitrogen as nitrates in thedrainage-water which flowed from depths of 20 and 60 inches of un-manured and uncultivated soil at Rothamsted during the years 1877-1882 :-i 116 ABSTRACTS OF CHEMICAL PAPERS.20 ins.Rainfall in inches.60 ins.January .....March ......April........Nay .........June ........July. ........September ...October .....November ...December,. ..February ....August.. ....---1 -572 -851.362 -512.682 $23.044 202 -832 *953 -382 -512 *740.531.030 -630 -560 '751 -861 -231 -682 -552 .01Total.. , ,I 32 -50 I 16 *832 -390 -611 *330 *680 $20.681 -641 -141 '502 -402 -0116 '34Nitrogen as nitratesin 1,000,000.20 ins.9 -88.66 .O9 . 511 -69 . 316 -415 -917.215 *511 *88.911.860 ins.11.19 -8I) ' 29 -111 *510 514 *214 .O13 '313 -011 -80.9Kilos.per acre.~20 ins.1 -252.390 -321 -000 -740 *541.253 -012 *152.663 .051 -82 --11.05 ~ 20.1760 ins.1 -512 3 80 *571 '130 *860 *660 -982 -341 *541 9 92 -892 -2419 *09--The greatest amount is eliminated during the summer and autumnperiod, the summer being the season when nitrification proceeds mostrapidly. The analyses of drainage of fallows, at a, depth of 27 inches,show a loss of nitrate nitrogen amounting to about 26 kilos. per acre ;but although the nitrates are formed in the upper portion of the soil,rain has carried them down, and they appear in larger quantities inthe second 9 inches of soil below the surface. The conclusions drawnfrom these and other analyses are, that so long as the winter is notwet, no great loss of nitrates occurs,jbut that nearly all are removed ifthe winter be otherwise, consequently the crops will suffer.To avoidthis loss, it is recommended that some rapid growing crop, as mustard,be sown during the summer ; this will retain the nitrates, and convertthem into an insoluble form which can then be utilised by the cropsown during the winter months. E. W. P.Nitrification ill the Soil. By MA4R16-DAVY (Bied. Centr., 1832,663).-Water containing 20.6 mgrm. N as ammonia, and 0.8 as nitrates,was brought in contact with a mixture of sand and flint; 31 litres ofthis water appeared after its passage through the soil (in 31 days) as25.2 litres clear water, which cont'ained only 1.7 mgrm.N as ammonia,but 21.5 mgrm. per litre N as nitrates. In another experiment rye-grass was allowed to grow in the soil, and was watered with the saiiiewater, which, after its passage through, contained only 0.8 mgrm. Nas ammonia, aod 20.5 mgrln. N as nitrates per litre; nearly all thephosphoric acid present in the water was absorbed. E. W. P.Comparative Manuring Experiments. By A. SALFELD (Bied.Centr., 1882, 583-587) .-At three different stations on sandy soilsVEGETABLE PHYSIOLOGY AND AGRICULTURE. 117the effects of various combinations of lime, kainite and bone-meal withChili saltpetre, &c., were tried on oats, grass, and rye. Kainite andlime alone were nowhere found to be a financial success, but mixturesof kainite and bone-meal with a little saltpetre, and of kainite withMejillones phosphate gave satisfactory returns.Influence of the State of Division of Manures on their Action.By P.WAGNER (Bied. Ceiztr., 1882, 665).-With the exception ofsodium nitrate, all ninnures should be in a fine state of division,whereby they can be more readily absorbed by the soil. Even super-phosphates, when finely ground, produce better crops than the samein a coarse state of division, as experiments on peas show (Comp.E. w. P.Manuring Potatoes with Potassium Nitrate. By EDLER(Bied. Cetztr., 1882, 577-580) .-In previous communications fromthe agricultural station at Gottingen, it was shown that the use ofpotassium nitrate raised the yield above that produced by sodiumnitrate, that both manures produce larger tubers, a,nd that with potashmanures the disease was less than with the sodium compound.More-over it was shown that the percentage of starch was lowered by sodiumnitrate, but not by the potassium salts. The experiments have beencontinued during the two succeeding seasons (1880 and 188l.), butowing to the bad season of 1880 the results obtained were iacon-clusive ; the season of 1881, however, was more favourable, and theresults obtained corroborate those obtained in 1879. Potash saltpetredistinctly increased the total yield, as also the yield of large tubers,and it did not lower the percentage of starch in the large tubers,whereas sodium nitrate did ; the percentage of starch in the mediumand small-sized tubers grown on the unmanured plots, was, however.,higher than that cont)ained in the corresponding sized tubers, butwhich had been manured.The application of potassium nitrate wasalso a financial success. E. W. P.By G. LECOUTEUX (BieJ. Centr.,1882, 640).-According to Gassend, pig dung consists of water 80.57per cent., N 0.711, P205 0.187, K20 1.859. The pigs were fed withbarley and potatoes, and the production of the manure cost 7-11 M per1000 kilos. The value of the manure, calculated from the marketprices of its components, was 24.66 M per 1000 kilos. (7.11 kilos. N~ 1 4 . 2 2 M, 1.87 P205 = 1.52 M, 18.59 K20 = 8.92 M), consequentlythere was a gain of 17.5 M per 1000 kilos.Analysis of Mud from the Mouth of the Eider.(Bied.Centr., 1882, 639.)E. W. P.Abstr., 1882, 90, 550).Composition of Pig Dung.E. W. P.Hydrochloric acid extract of the air-dried mud.P205. CaO. I CaO combinedwith GO,.--- ---4 -89 4 -42 0 ’15 0 *15 0 -184.09 1 3-63 I 0.07 1 0.08 1 0.07 18 ABSTRACTS OF CHEMICAL PAPERS.HZO. N. C1. Loss on ignition.I.. .... 2.91 0.26 0-56 3-8811.. .... 0.79 0.10 0.09 3.25I. Within harbour of Toning. 11. Outside harbour.E. w. P.Mineral Phosphates on Arable Soil. By L. GTJILLAUME( A n d e s Agronornipues, 7,587-59 1) .-Experiments were undertakenby the author to test D6h6rain’s statement that soils containing lessthan 0.04 per cent. of phosphoric anhydride are benefited by theaddition of mineral phosphate. D6hBrain considers that most arablesoils which have been cultivated for a long time with the aid of farmyardmanure, are by that means sufficiently supplied with assimilable phos-phoric acid, and that addition of mineral phosphate is useless. Thesoil on which the author’s experiments were conducted is a loam ofjurassic origin, and has been for a long time iinder cultivation and inreceipt of a large dressing of farmyard manure. It contains 0.05 percent. phosphoric anhydride, 3.61 per cent. calcium carbonate, and aconsiderable amount of ferric oxide. The experimental plots werefifteen in number, each of 1 acre, and a mineral phosphate fromAuxois was used, containing 24 per cent. P205.The results, per hectare, are annexed:-----1. Wheat (Bordeaux)-Stmw ................Grain ................2. Oats (Yellow P1anders)-straw ................Grain ................3. Maize.. ................(cut green August 22nd)4. Potatoes ..............5. Beet ..................Unmanured.4,900 kilos.70s 394,900 9 92,544 9 915,200 ,,160 hectolitres26,400 kilos.15,000rilos. farmyardmanure.--5,6001,5965,9003,25617,36026527,60015,OOO kilos. farm-yard manureand 1,OOO kilos.phosphate.5,7001,7605,9503,39717,8002 a027,900Thus, in no case was the increase sufficient to cover the cost of theThe author intends to repeat the experi- mineral phosphate applied.ments with superphosphates. J. M. H. M

ISSN:0368-1769    

DOI:10.1039/CA8834400104

出版商:RSC    

年代:1883

数据来源: RSC

摘要:

7 18 ABSTRACTS OF CHEMICAL PAPERS.A n a1 y t i c a 1 Chemistry.A New Condensation Hygrometer. By A. CROVA (Compt. rend.,94, 1514--1516).-The hygrometers now in use are subject to severalcauses of errors more or less considerable. To obviate these, the authorhas contrived an instrument consisting of a, tube of highly polishednickel, closed at each end by discs of glass, one clear, the other groundANALYTICAL CHEMISTRY. 119Through this tube the air is slowly drawn, and the moment of depo-sition of moisture can be very sharply observed by viewing the inte-rior of the tube through a lens. The cooling is effected by passing acurrent of air through bisulphide of carbon contained in a vesselsurrounding the tube. R. R.Direct Estimation of Chlorine in Presence of Bromine andIodine.By G. VORTMANN (Monatsh. Chem., 3,510-530) .-Two yearsago the author published a short notice on the detection of chlorine inpresence of bromine and iodine, depending on the reactions of chlo-rides, broniides, and iodides with the peroxides of lead and manganese,in presence of acetic acid of various degrees of dilution (Abstr., 1880,509) ; and more recently he has given a sketch of the application ofthese reactions to quantitative analysis (ibid., 1882, p. 1230). I n thepresent paper, the reactions concerned in these processes are morefully discussed, and the methods of estimation are described indetail, and illustrated by numerous examples.Estimation of Chlorine in Presence of Bromine.-When the quantityof bromine present is but small, it is sufficient to heat the mixture ofchloride and bromide with lead dioxide and acetic acid of 2-3 percent.two or three times on the water-bath. With larger quantitiesof bromine, complete separation is somewhat difficult ; the method ofefiecting it will be further considered in connection with the separationof chlorine from bromine and iodine together.Estimation of Chlorine in Presence qf Iodiiie.-This is effected in thesame manner as in the last case, lead dioxide being used when thequantity of iodide present is but small, manganese dioxide being pre-ferable when it is large. I n this case also, the evaporation with diluteacetic acid must be repeated several times. The expulsion of theiodine may be accelerated by first boiling the liquid for a few minutesin a small flask ; this, however, can be done only when lead dioxide isemployed, as the use of manganese dioxide quickly gives rise toviolent percussive ebullition.In the latter case, the liquid must beheated in a beaker on the water-bahh, while a stream of air is passedthrough it. The estimations come out sharp, even when large quan-tities of iodine are present. I n using lead dioxide when small quan-tities of chlorine are to be estimated in presence of much iodine,the results are apt to come out too high.Estirnictiom of Bronaine in Presence oj' Iodine.-This estimation is veryeasily performed by eva,porating down the mixture of bromide andiodide with manganese dioxide and dilute acetic acid several times onthe water-bath, the evaporation being accelerated, if desired, by pass-ing a stream of air through the liquid.Estinaation of Chlorine in Presence of Bromine and Iodine together.-This may be effected either by boiling with lend dioxide and diluteacetic acid, whereby the iodides and bromides are decomposed simul-taneously ; or by first expelling the iodine by evaporating down withmanganese dioxide and acetic acid, and then the bromine by repeatingthis operation after addition of lead dioxide.I n operating by thefirst method, the mutual action of iodine and bromine gives rise tothe formation of iodic acid, to prevent which, as far as possible, it i120 ABSTRACTS OF CHEMICAL PAPERS.advisable to add the lead oxide to t,he boiling solution by small portionsa t a time.The liquid having been boiled for about half an honr, andthe water as it evaporates renewed from time to time, the dissolved leadis precipitated by hydrogen sulphide, without previous filtration ; andthe liquid, after being once more treated with hydrogen sulphide, iswarmed for some time on the water-bath and filtered. The filtrate isthen evaporated to complete dryness on the water-bath, the residuedrenched with dilute acetic acid, and the liquid evaporated down afteraddition of a small quantity of lead dioxide. The evaporation to dry-ness is then once more repeated, the residue finally dissolved in water,and the chlorine precipitated from the filtrate by nitrate of silver. Inworking by the second of the methods above mentioned, the mixtureof the halogen-compounds is several times evaporated down on thewater-bath with lead dioxide and acetic acid, and the chlorine in theresidue is estimated in the usual way.This method is preferable tothe former, in so far as it affects the expulsion of all the iodine andbromine without formation of oxy-acids, and may also afford themeans of estimating these two halogens a t the same time. Moreover,it gives more exact results than the first method; but, on the otherhand it has the disadvantage that in decomposing the iodides bymanganese dioxide, manganese passes into solution and is precipitatedin the subsequent treatment with lead dioxide, in the form of manga-nese dioxide, or rather of a compound of this oxide with dioxide oflead, Mn02,4Pb0,: this precipitate is difficult to wash, and it isonly after prolonged treatment with boiling water that filtrates areobtained which no longer become opalescent on addition of silvernitrate.The numerous analyses given in the paper show that the methodtherein described is applicable in all cases to the separation of chlorinefrom bromine and from iodine.Moreover it gives satisfactory resultsin the estimation of relatively large quantities of chlorine in presenceof small quantities of bromine. When on the other hand muchbromine is present, the results, even with careful working, come outtoo high by several units per cent.Fiitally the author observes that it is not necessary to briug thechlorine into combination with an alkali-metal by decomposing thelead chloride obtained in the process with potassium sulphnte, inas-much as the entire process is performed with hot dilute solutions, andthe solubility of the lead chloride is very considerably increased bythe presence of the dilute acetic acid and solution of lead acetate, sothat an incomplete solution of the lead salt is not to be apprehended.The manganese dioxide and lead dioxide added i n excess are very easyto wash, and the filtrates after a short time give not the slight,estturbidity with silver nitrate.The bromine or iodine given off in tthese processes of separatingchlorides from bromides and iodides may be collected and estimated.With regard to the estimation of iodine i n presence of chlorine orbromine, the author has already obtained satisfactory results.Forbromine, the numbers hitherto obtained are less satisfactory ; but hehopes soon to arrive at more exact results, which may form thesubject of a further communication. H. WANALYTICAL CHEMISTRY. 121Estimation of Carbonic Anhydride in the Air at Cape Horn.By A. M ~ N T Z and E. AURIN (Cow@. .rend., 94, 1651). -The scientificmission to Cape Horn has been provided with an apparatus for esti-mating the carbonic anhydride in the air. There are two sheet-ironaspirators, representing 300 litres of air ; and drawn-out tubes con-taining potassium hydroxide are fixed in metallic cases, to guardthem from accident, and are so arranged that they need not be re-moved from the cases when the air is being drawn through them.R.R.-Estimation of Phosphoric Acid. By 0. v. n. PFORDTEN (Ber.,15, 1929-1 930) .-This method depends upon the conversion of phos-phoric acid into ammonium phosphomolybdate, and subsequent esti-mation of the molybdenum (see p. 122).Estimation of Sulphur in Iron and Steel. By G. E. CRAIG (Clhem.News, 46, 199).-The method now recommended is more rapid andquite as accurate as that in which potassium chlorate and hydrochloricacid are employed ; 100 grains of the metal are placed in a 10 oz. flask,with 9 oz. water, 1+ oz. hydrochloric acid is added by means of astoppered funnel ; the gas evolved is passed by means of tubes, &c.,through an empty flask or test-tube (to condense vapours) into a nitro-gen bldb containing oz.hydrogen peroxide, and + oz. ammonia;when the action becomes sluggish heat is to be applied. After blow-ing air through, the contents of the nitrogen bulbs and the precedingcondensing flask are washed out into a beaker, and barium chlorideis added after acidifying the solution with hydrochloric acid and boil-ing. A blank experiment should be made with each new sample ofhydrogen peroxide. The presence of copper has no influence on theresults. E. W. P.A. K. 31.Estimation of Oxygen and Carbon in Iron. By A. LEDEBUR(Ding7.polyt. J;, 245,293).-The author found oxygen in many kindsof malleable iron, wrought iron Containing ferrosoferric oxide as amixture principally, whilst ingot iron contains ferrous oxide, either inthe dissolved state or as an alloy.The oxygen, especially in the latteycase, has a marked influence on the properties of the iron: hence itsdetermination in ingot iron is almost as important as that of thesulphiir and phosphorus. For analysis, clean dry iron filings free fromfatty constituents should be employed. For the removal of the lasttraces of moisture and organic matter, the filings are heated in acurrent of pura dry nitrogen gas, obtained by heating a mixture of1 pt. sodium nitrite, 1 pt. ammonium nitrare, 1 pt. potassium dichro-mate, and 10 pts. water, passing the gas through a solution of ferroussulphate, and over red hot copper turnings, and finally drying it bymeans of phosphoric anhydride. The hrdrogen gas is made fromzinc and eulphuric acid.It is passed through soda-lye and analkaline solution of lead, then through a heated tube filled with plati-nised asbestos, and eventually dried over concentrated sulphnric acidand phosphoric anhydride ; ?5 grams of iron borings are placed in aporcelain boat, and pnshed into a glass tube of which one end isconnected by means of a T-piece with the nitrogen and hydroge122 ABSTRACTS OF CHEMICAL PAPERS.tubes, whilst the other end is drawn out and communicates with hheabsorption- tube containing phosphoric anhydride. In con1 m encingthe analysis, the tube with the copper turnings is heated, and a slowstream of nitrogen passed through the apparatus. After two hours thetube wit,h the iron borings is heated, nitrogen gas being passed over con-tinuously, in order to expel all volatile constituents.The absorption-tube is then attached to the apparatus, the current of nitrogen stopped,and hydrogen passed through. After 30-45 minutes’ heating, theapparatus is cooled slowly, hydrogen still being passed over. Theabsorption-tube is then removed, and after expelling the hydrogenin the tube by means of air dried over phosphoric anhydride, it isweighed. The porcelain boat and contents are also weighed, and theweight of the oxygen of the water absorbed should agree with theloss in the weight of the porcelain boat. Analyses of a variety ofsamples of iron are given, the high percentage of oxygen in wroughtiron being explained by the admixture of slag. The determination ofoxygen is therefore said to afford a means of determining approxi-mately the quantity of slag present.For determining the carbon, t,heauthor recommends M’Greath acd Ullgren’s method. D. B.Electrolytic Estimation of Zinc. By A. MILLOT (BUZZ. SOC. Chin%.[el, 37, 339-341) .-2*5 grams of the mineral are dissolved in 50 C.C. ofhydrochloric acid, and a small quantity of potassium chlorate is addedto the boiling solution in order to precipitate the iron. If the mineralcontains much silica, it is previously evaporated to dryness with hydro-chloric acid. The liquid is cooled, diluted, and mixed with 100 C.C. ofammonia and 50 C.C. of a saturated solution of ammonium carbonatein order to precipitate the lead and calcium. The liquid is diluted to500 c.c., filtered, and 100 c.c., corresponding to 0.5 gram of the mineraland containing from 0.2 to 0.3 gram of zinc, are mixed with 1 gram ofpure potassium cyanide and placed in a beaker in which is suspendeda cylinder of platiaum gauze which acts as the positive pole, and aplatinum cone like that.in Riche’s apparatus which acts as a negativepole. Two Bunsen cells or a Clamond thermo-electric pile of 1.50 ele-ments may be used to effect precipitation, which is complete in aboutten hours. The firmly adhering deposit is washed with water, thenwith alcohol, and dried. If the mineral contains copper the latter isdeposited with the zinc. The deposit on the cone must in this case bedissolved in nitric acid and the copper precipitated from the acid solu-tion. If cadmium is present, it must be removed by treatment withhydrogen sulphide.The potassium cyanide should be used in theproportion given above ; if more is added, the metal is deposited veryslowly, whilst if less is added the deposit of zinc is not adherent. Anyaction on the electrodes may be prevented by mixing the solution withammonium aceta’te or nitrate. The latter, however, retards the pre-cipitation of the zinc.Reduction of Molybdenum Compounds. By 0. I-. D. PFORDTEN(Ber., 15, 1925--1929).-The author has examined Pisaiii’s methodfor estimating molybdenum. He finds that the end-product of thereduction of molybdic acid with zinc and hydrochloric acid is notC. H. BANALYTICAL CHEMISTRY. 133Mo,O, but Mo50,(= 2M0203 + MOO). This, however, becomesoxidised, by exposure to air, to BIo,O,.A method for the volumetricestimation of molybdic acid is founded on this reduction, and subse-quent oxidation with standard potassium permangauate.A. K. M.Otto's Method for the Estimation of Fuse1 Oil in Brandy.By C. KRAUCH (Bied. Centr., 1882,718).-Krauch does not find Otto'smethod of any use. The oxidation-products, which according to Ottocontain valeric acid, the author finds to be acetic acid.E. W. P.Estimation of Glycerol in Fatty Matters. By J. DATID(Compt. rend., 94, 1477--1479j.-lOO grams of the fat are melted;65 grams of barium hydrate, BaO,SH,O, are added with briskstirring ; when most of the water has been expelled, the heating isdiscontinued ; 80 C.C. of alcohol of 95" are poured on the mass, andthe whole is well stirred ; 1 litre of water is then added, and the wholeboiled for an hour.The barium soap remains insoluble, whilst theglycerol is dissolved by the water, which is freed from the excess ofbarium, reduced in volume by boiling, and finally evaporated in avacuum a t a low temperature ; or, preferably, the quantity of glycerolis inferred from the density of the solution. The barium soap afterbeing boiled with water is decomposed by hydrochloric acid and thefatty acid separated and weighed. Its melting point will indicateapproximately the proportions of stearic and oleic acids it contains.R. R.Estimation of Dextrose, Maltose, and Dextrin in Starch-sugar. By H. W. WILEY (Chent. News, 46,175-177).-The methodemployed was as follows:-(1) 10 grams undried sugar dissolved in1000 C.C.water ; (2) 10 grams dissolved in 100 C.C. and polarised in200 mm. tube ; (3) 10 C.C. of the solution (2) is treated with excess ofmercurous cyanide (120 grams HgCyz and 120 grams NaHO per litre)boiled, and excess of strong hydrochloric acid added and made up to50 C.C. ; this solution is polarised in 500 mm. tube and the angular rota-tion multiplied by 2. Solution (1) reduced by Fehling gives the totalpercentage of reducing matt'er, viz., dextrose with reducing value of100, maltose 62. The first polarisation gives the apparent specificrotation due t o all optically active bodies present, viz., dextrose = 52,maltose = 139 ; dextrin = 195. The second reduction (3) leaves onlydextrin unaffected, and the amount of this is determined by the secondpolarisation.If solid starch-sugar is employed, it must be boiled forsome time to destroy birotation; after reduction by cyanide, it isunnecessary to use charcoal, as the addition of the acid destroys thered colour generally present.Calculation of the results: from (1) we obtain the reducing percent. of dextrose d, + that of maltose w, which latter, compared withthe former, is only 0.62.(1.) R = d + 0.62 m.(2.) P = 5 2 d + 139m + 193Z.(3.) P' = 193d'. (Second polarisation)124 ABSTRACTS OF CHEMICAL PAPERS.To find d and m.Multiply (1) by 52 and substract from (4).(4.) P - P' = 5 2 d + 139 m.(5.) P - P' - 52 R = 106.76 m.P-€"-552R106.76 '(6.) Whence rn =(7.) d = R - 0.62 nz.. I P' (8.) d' = - 193'This process agrees well with that proposed by Allen. Severalanalyses are given. E. W. P.Diffusion of Sugar in Beet. By G. MARECK (Dingl. polyt. J.,245, 345--350).-1n determining the differences in the sp. gr. ofwhole roots and of roots cut into sections, the author found that theweight of the former was generally below that of the separate partsof the root, the differences being greater the smaller the sp. gr. of thewhole root. The valuation of beet according to the density of thejuice is said to give more accurate results than the determination ofthe sp. gr. of the roots. A table is given showing the results ofexperiments on the distribution of sugar in the beet. D. B.Estimation of Rice-starch. By F.SALOJION (J. pr. Chem. [el,26, 324-333).-The results of a series of experiments are givenwhich show tjhat while potato-&arch, when heated with hydrochloricacid, yields the full theoretical amount of glucose (111.11 per cent.),rice-starch cannot be made to yield more than about 107 per cent.The sp. gr. of the invert,ed solution is, however, identical with thatobtained from potato-starch, proving that about 4 per cent. of sub-stances are formed which have no reducing action on Fehling'ssolution. 0. H.Volumetrical Estimation of Phenol. By T. CHANDELON (BUZZ.SOC. Chiq~z. [ S ] , 38, 69-71).-The introduction of phenol as an anti-septic has necessitated a rapid and easy method for its estimation.Koppershoor has proposed to act on phenol with a standard solution ofbromine in potassium bromide so as t o convert the phenol into tribromo-phenol.The excess of bromine used may be determined by sodiumthiosulphate ; or a mixture of potassium bromide and bromate acidifiedby hydrochloric acid may be substituted for bromine-wat,er. Giacosaused a solution of bromine-water which has been standardised by aphenol solution of known strength, but as the precipitate of tri-bromophenol invariably retains a, certain quantity of bromine, theresults are far from being exact.The author proposes potassium hgpobromite which, like bromine,converts the phenol into tribromophenol. The method of operation is asfollows :-The hypobromite solution is prepared by dissolving 14-15grams pure potassium hydroxide in 1 litre of water and adding gra-dually to it 10 grams bromine.The solution is then diluted until iANALYTICAL CHEMISTRY. 125is of such a strength that 50 C.C. corresponds to 10 C.C. of a normal solu-tion of phenol of 10.5 per cent. or 0.05 gram of pure phenol. In orderto ascertain the strength of any phenol solution, 50 c.c, of the hypo-bromite is placed in a flask and the phenol solution is added until adrop of the solution gives no blue coloration with potassium iodide andstarch solntion. The method is sufficiently exact for clinical purposes,the error being about 1.2 per cent. If it is required to estimatephenol in urine, the latter is distilled with dilute sulphuric acid : in thecase of lint or cotton, the vapours of water, slightly acidulated withhydrochloric acid, are passed over them and subsequently condensed,and the phenol in the distillate estimated after rieutralisntion withpotassium hydroxide.V. H. V.Ammoniacal Alkaline Silver Solution as a Test for Form-aldehyde. By B. TOLLENS (Ber., 15, 1828-1830). - Salkowskihaving noticed the formation of fulminating silvei. in a solution ofsilver wliich had been treated witb caustic soda and ammonia, theauthor states that this has not occurred with his solution when pre-pared in the way described. If, however, it is allowed to evaporate ina shallow dish, small quantities of a detonating compound are formed,but not when it is kept in a stoppered bottle. The best way is tokeep the component parts separate, and mix them when required.With regard to the quantitative determiriation of aldehydes by theabove solution, for each molecule of formaldehyde 2 atoms of silveringeneral are thrown down ; but irregnlarities have occurred whichhave not yet been avoided. The best proportions for the solutionas yet have been found to be equal weights of a solution of 1 partsilver nitrate in 10 parts water, and 1 part caustic soda in 10 parts ofwater mixed together, and the ammonia added drop by drop untilcomplete solution of the silver oxide is effected.Examination of Fat.By H. Y. DE SCHEPPER and A. GEIRET,(Dingl. polyt. J., 245, 295-302).-1n order to ascertain the value ofa fat, it is necessary to determine the non-fatty constituents, i.e., theamoiint of water, sand, fibrous matter, &c., the total quantity of fattyacids and glycerol, and the amount of " candle material," Le., the solidfatty acids present in the latter.The water is determined by placing50-60 grams of the substance in a tared beaker and drying it a t110" for one hour, stirring the mixture occasionally with a tared glassrod. The temperature is then increased t o 125", and after two hours'heating the beaker with contents is weighed, the loss in weight givingthe amount of water. The sand and other substances are determinedby filtering 50-60 grams of the fat through a tared filter at 60--70",washing with hot benzene, drying and weighing. I f , owing to thepresence of glycerol, the dried product is deliquescent, it is washedwith alcohol before weighing.The process for determining the fattyacids and glycerol is based on the following conclusions. From theequation indicating the decomposition of fats in general :J. K. C.it follows that (calling a the molecular weight of the fatty acid126 ABSTRACTS OF CHEMICAL PAPERS.an equivalent of fat, ex.pressed by (3a + 92 - 3 x 18)g, gives3u grams fatty acids and 92 grams glycerol (9). Tf a represents themean molecular weight of the different fatty acids contained in fat,we obtain the following formulae for the quautity of fatty acids andglycerol calculated as per cent. on the fat :-To ascertain the factor a in a fat, 50 grams of the latter are saponifiedwith 40 C.C. potash-ley of sp. gr. 1.4 and 40 C.C. alcohol ; boiled in alitre of water for about an hour, decomposed with snlphuric acid, andthe fatty acids, after washing and drying, titrated with standardpotash-ley, 10 C.C.neutmlising exactly 1 gram margaric acid, or100 C.C. = 1000 : 270 = 37.037 C.C. standard acid. By calling a thetenths of C.C. necessary to neutralise I gram of fatty acid, we obtainthe following ratio between a and at :-a = 270 - ___ loo. Todetermineathe amount of neutral fat N, 1 gram of dried and filtered fat istitrated with the above solution. By taking r~, to indicate the tenthsof c.c., and assuming that the various triglycerides are all decomposedin the same manner, the amount of free fatty acids is equal t o thefollowing :-E'=- 1o09L, also N = 100 - ___ ''On per cent. of the fat.a aBy making use of these formulse we obtain the following generalequations :-3C)0a + 100 !! and 100 [l - (9%: a)]f = 100 3n + 38 a100 [l - (n : a ) ] 9200 -____300 .3a + 38' 9 =It was found that the molecnlar weight of fatty acids from tallowsranged between 280 and 274-hard tallows being nearest t o the highernumber. For palm oils, the molecular weight is 270 : without, there-fore, causing too serious an error, this number may be taken to repre-sent the molecular weight of tallows and palm oils, or mixtures ofboth, which simplifies the above method. The percentage of neutralfat in this case is N = 100 - n, whilst the above formule may bemodified as follows :-f = 95.52 ~F!!?.ZP + n, per cent., and g = 10.85 ?!!kZ? per cent. 100 100By taking into consideration the fact that all fats contain from 1 to1.5 per cent. albumin or cellulose, and that the percentage of fattyacids in tripalmitines is less than 95.5, and the glycerol more than10.85, the above formulae require a further alteration, viz. :-100 - n + 32, and g = 10.5 -100 '100 - n100f - 945 ___TECHSIC AL CHEMISTRY. 127or, f = 94.5 and y = 10.5 if n = 0, ondf = 100, and g = 0 if ?z =100, i.e., an increase in the percentage of neutral fat N from 0 to 100raises the percentage of fatty acids 5.5, whilst the glycerol is reducedby 10.5 per cent. ; so that the following formulae are obtained whichmay be used for determining the percentages of fatty acids andglycerol :-f = 100 - 0.055 N, and g = 0,105 N.The value of the fatty acids is ascertained by deterzining the crys-tallising points. It is, however, necessary to test, the acids for neutralfat by dissolving 1 gram in hot alcohol and adding strong ammoniato the solution. I n the presence of mere traces of neutral fat, thesolution is rendered turbid ou the addition of ammonia. D. B.Occurrence of Organic Bases in Commercial Amy1 Alcohol.By L. HAITINGER (Honatsh. Clzern., 3, 688-692) .-With reference tothe use of amyl alcohol in testing for alkaloi'ds, the author calls atten-tion to the fact that pyridine and other bases are frequently present,even in the commercially " pure " alcohols. A. J. G

ISSN:0368-1769    

DOI:10.1039/CA8834400118

出版商:RSC    

年代:1883

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TECHSIC AL CHEMISTRY. 127T e c hn i c a1 C h em i s try,Influence of Coal-dust in Colliery Explosions, By W. GAL-LOWAT (Proc. Roy. Xoc., 33, 437-445, and 490-495).-A continua-tion of the author's experiments.. The apparatus finally adopted toinvestigate the influence of coal-dust consists of (1) an explosionchamber 6 feet by 2 feet, lined with strips of wood, with three open-ings for admitting the fire-damp, letting out t'he air displaced, andfor igniting the mixture respectively. It is provided with a smallcentrifugal fan for mixing the air and the fire-damp. (2.) A gallery126 x 2 x 2 feet, consisting of seven pieces, each 18 feet long,placed end to end and hooped by iron bands, one side of which, ofdimeiisions 18 feet by 2 feet 3 inches, can be opened like a door.Before an experiment, these doors are opened and coal-dust strewed onthe floor t o a thickness of one-eighth t o a quarter of an inch, andsome laid on shelves in the several sections.The method of procedureis as follows :-The explosion chamber is drawn back, and severalsheets of paper inserted between it and the gallery t o act as adiaphragm; the chamber and gallery are then bolted together, thefiredamp introduced from a measuring cylinder, and mixed with theair by the aid of the fan, and the mixture exploded. When no coal-dust was introduced, or the floor or shelves damped, the fire-dampexplosion travels along the gallery for about 12 feet; if the coal-dust was dry, and all the sections closed so as to make the gallerycontinuous, the flame extended to 50 or 60 feet (experiments showedthat the greater or less moisture in the atmosphere exerted an nppre128 ABSTRACTS OF CHEMICAL PAPERS.ciable effect on the coal-dust), and finally if the doors and the fourthand fifth sections mere opened, the flame reached to 60 or 70 feet.I nall cases, a thick cloud of coal-dust and air was driven by the explo-sion-wave through the gallery, and on emerging into the open airassumed large proportions, and exhibited all the phenomena ofincipient explosive combustion. Crusts of coked coal-dust werefound on the shelves the farthest removed from the explosionchamber, which corroborated the hypothesis proposed in connectionwith explosions a t collieries, that these crusts are deposited during a,retrograde movement of the air, travelling back towards the origin ofthe explosion. From observations made by the author a t the Peny-graig Colliery after an explosion, similar crusts of coked coal-dustwere found deposited in a direction opposite to that of the explosion.The results of the experiments given in the papers confirm theview put forward by the author as to the manner in which theflame of an explosion is originated and propagated, but they furthershow that the presence of fire-damp is unnecessary, provided that thescale of the experiments be large, and the coal-dust be sufficiently firieand dry.V. H. V.Water of Rangoon. By R. ROMANIS (Chern. News, 46, 187).-Inthe water st,ored in reservoirs a t Rangoon, thn vegetation increaseslargely during the hot season, but the quantity of free ammonia ishighest during March.Albumino’id ammonia sometimes reaches ashigh as 0.82 in July, the minimum quantity during two yearsBy A. H. ALLEN (Chem. News, 46,145--146).-1n a recent trial (J. J. Milnes against the HuddersfieldCorporation), the question arose as to the influence which the presenceof sulphuric acid had on the intensity of the action of water on lead ;and from the scientific evidence given it was inferred that a trace offree sulphuric acid was rather beneficial than otherwise, as it wouldtend to protect the pipes from the action of the water by depositinginsoluble lead sulpbate. The author has proved this suggestion falla-cious, for he has found by experiment that water containing free sul-phuric acid dissolves more lead than water which is either altogethertree from acid or which has been neutralised.The experiments weremade by adding definite quantities of decinormal sulphuric acid to250 C.C. of water, and then immersing in the liquid equal sized piecesof sheet lead, scraped clean immediately before use. The resultsvary. Some water after standing in lead pipes all night contained0.61 grain of lead per gallon. Water taken from the main, havingmarked acid reaction to Poirier’s orange, left in contact with clean lead,dissolved 0.42 t o 0.56 grain per gallon, but when previously renderedfaintly alkaline with lime-water, only 0.14 of lead mas dissolved. Theauthor is of opinion that the free acid in drinking-water is more likelyto be hydrochloric than sulphuric acid.Antiseptic Action of Salicylic Acid. By E.ROBINET andH. PELLET (Bied. Centr., 1882, 63?).-Salicylic acid added to must inbeing 0.24. E. w. P.Action of Water on Lead.D. A. LTECHNICAL CHEJIISTRY. 129quantities of 0.3 gram per litre preserves it perfectly from fermenta-tion, and when yeast has been added to the must, 0.5 gram per litre issufficient to destroy its action.Certain Properties of Hydrogen Cyanide. By C. BRAME( Compt. rend., 94, 1656).-Aqueous solution of hydrocyanic acidcopiously precipitates albumin from its aqueous solutions. Bodiesof animals poisoned by hydrocyanic acid have been preserved for ayear. When the bodies of animals injected with hydrocpnic acidhave been preserved in closed receptacles for several months, they loseall odour of the acid, and acquire that of ammonium formate, whichsalt may be found in the serous liquids.In embalming by means ofhydrocyanic acid, it is necessary to introduce into the body, after theBoiler Explosions. (Dingl. polyt. J., 245, 517.)-It is menbionedthat a silent boiling of liquids is due to the formation of gases. Ifinstead of feeding a boiler with fresh water, boiled or condensedwater be used, which contains less absorbed air, explosive boiling mayoccur after heating the boiler for some time, and as in this case a,large amount of steam is formed in a short time, the plates of theboiler are endangered, owing to the sudden increase in the pressureof steam.D. B.E. W. P.acid, a small quantity of zinc chloride. Ru R.Recovery af Sulphur by Mond's Process. By SUHAEPPL (Dingl.p o l j t . J., 246, 341--345, and 387--392).-The following i s a sum-mary of the author's results and conclusions :-The longer the timethe liquors and oxidised residue are allowed to remain in contact, themore sulphide is dissolved. It is best to oxidise in as concentrated asolution as possible, and to lixiviate for two or three hours. Theweaker the liquor, the more sulphides does it contain ; the stronger it isthe larger is the quantity of thiosulphates : hence the longer t;he liquoris oxidised the greater is the importance of working with weaker solu-tions. In the commencement, a solution was used of 16" T. ; subse-quently this was reduced to 12", so that it was possible to oxidisewith twice the quantity of air without over-oxidising the liquor,whereby a considerable increase in the yield of sulphur was obtained.A further modification was the use of hot water, which not only dis-solves a larger proportion of sulphides in a shorter time, but preventsthe cooling of the residue.Formerly this residue required four to sixhours' heating to render it effective, whilst a t the present time it canbe used a t once for a further oxidation. By mixing the liquor andacid in closed vessels before bringing them into the decomposer, theloss of sulphuretted hydrogen due to defective decomposition is re-duced, whilst, owing to the possibility of working with smaller vessels,the operation is considerably facilitated.It is necessary, however, tolieat the liquor to 80- go", otherwise the sulphur is deposited in a formdifficult to filter. D. B.The Currents of the Gases in Sulphuric Acid Chambers.By K. ABRAHAM (Dingl. po7yt. J., 245, 416--421).-The success ofVOL. XLlV. Ir130 ABSTRACTS OF CHEMICAL PAPERS.the manufacture of sulphuric acid depends largely on the uniformityof the admixture of the reacting gases, not only at the point ofentrance but throughout the chamber. Schwarzenberg’s theory isthat these currents move in horizontal strata from the roof to the floorof the chamber. His views are based on observations of the tem-perature and sp. gr. of the gaseous mixture at successive points. Theauthor from his own investigations concludes that Schwarzenberg’stheory is untenable.He states that the gases on entering come intocontact with a gaseous mixture which differs only slightly from themin sp. gr., and therefore undergo a uniform distribution over the firstportion of the chamber considered in vertical section, the productionof sulphuric acid showing a corresponding uniformity. The coolingaction of the sides and roof of the chamber effects a decrease inthe temperahre : hence the gases travel upwards from the centre anddownwards along the side walls of the chamber. The author for-mulates these phenomena in the following manner :-The gases movein vertical strata perpendicular to the exit, each gaseous moleculedescribing a spiral line whose axis is parallel to the length of thechamber.The practical conclusions arrived at are these :-The inletof the gases should be at the middle height of the chamber, and todetermine the point of origin of the screw motion as closely to thefore side of the chamber as possible and prevent the ingress of thegases in too rapid a manner, the tube is enlarged with a conicalopening. Thesteam should not be introduced in jets along the chamber, but shouldbe admitted through several openings in the roof, each tube to supplytwo perpendicular jets, the orifices of the tubes being sufficiently largeto prevent the entrance of the steam in powerful jets.Utilisation of the Nitrogen-compounds from the Manufac-ture of Sulphuric Acid. By G. WACHTEL (DingZ. polyt. J., 245,517).-Although the loss of potassium nitrate in the manufacture of sul-phuric acid has been greatly diminished, about 50 per cent.of the totalnitrogen in the potassium nitrate still escapes with the exit gases fromthe Gay-Lussac tower. For recovering these nitrogen compounds,the exit gases are drawn by means of a Korting’s injector throughcast iron or clay retorts filled with iron filings heated to redness. Theoxygen compounds of the nitrogen are thereby converted into ammo-nia, which may be absorbed by means of sulphuric or hydrochloricacid. This process is specially adapted for sulphuric acid works notusing the Gay-Lnssac tower.Preparation from Bauxite of Aluminium Sulphate freefrom Iron. By C. FAHLBERG (BUZZ. SOC. Chim. [2], 38,154-156).-Attempts to prepare aluminium sulphate free from iron from banxitehave hitherto been unsuccessful, for the methods proposed have beenfound to be too costly or too complex.The author, in conjunctionwith Semper, has practically solved the problem by the use of lead per-oxide, which is prepared by first triturating a mixture of 2 parts leadmonoxide and 1 part sodium chloride, until the mass assumes thewhite tint of lead oxychloride ; the product is then boiled with bleach-The outlet tube is arranged in a similar manner.D. B.D. BTECHNICAL CHEMISTRY. 131ing powder until lead peroxide is formed, which is washed and pre-served in the damp tjtate. This paste is added to a neutral or slightlyalkaline solution of bauxite in snlphuric acid ; for every part of ironcontained in the solution 20 parts of the dioxide are required. It isnecessary to work with concentrated solutions and to avoid a rise oftemperature ; the iron must also be as a ferric salt.In order to recoverthe peroxide employed, the solid matter is separated by a filter-press,suspended in water, and then dilute sulphuric or nitric acid added,which leaves the peroxide undissolved, so that it can be employed anumber of times without losing any of its properties.V. H. V.Japanese Soils : a Natural Cement. By 0. KORSCHICLT (Chem.News, 46, 187) .-The soil below Tokio yields to hot hydrochloric acidas much as 80 per cent., and this contains about 30 per cent. Si02 and30 per cent. Al,O, + Fe203, and 1.5 to 3.0 per cent.K20 was found inthe lower layers ; it contains little or no quartz, but 50 to 60 per cent.of zeolites. The tufa soils have a low sp. gr., varying from 2.097-2.291. Pull analyses of many samples taken from different depths aregiven. When mixed with lime paste, they form a satisfactory cement,the temperature rising 7" during the mixing ; the proportions used are1 vol. lime to 6 vols. earth. The analyses show a decrease of nitrogenfrom the surface downwards : in the top layer it amounts to 0.521 percent. E. W. P.On Cement and its Appliaation. (Dingl. poZyt. J., 245, 381-387, 456-464, and 499-506) .-Delbruck mentions that in tender-ing for large cement contracts it no longer suffices to give the priceonly, but that the strength of extension forms an important item.The value of cement is determined, therefore, according to the priceand the guaranteed weight which 1 part cement mixed with 3 partssand bears after 28 days' setting.In comparing cements differing inthe rate of setting (slow, medium, and rapid), it is necessary to con-sider the time. According to G. Dyckerhoff, the packing of cement inbags is 10 per cent. cheaper than in casks. It is also mentioned thatwhen rollers are used in the grinding of cement, the motive powerconsumed is less than in the case of the ordinary cement mills. Thisis confirmed by Heyn, Delbriick, Nagel, and Kaemp, who add, that notonly is a more finely divided product obtained, but the wear and tearof the machinery is considerably reduced.For sifting the groundcement, Nagel and Kaemp recommend the use of shaking sieves, madeof perforated sheets of steel, the holes being 1 mm. in diameter.These are said to be stronger than wire sieves, but, like the latter, donot produce a cement fine enough to pass through a sieve with5000 meshes per sq. cm., without leaving a residue of about 30 percent. on the sieve. The air sieve constructed by Michaelis is said toovercome this difficulty. The cement is put into a centrifugal machineand whirled, the fine dust produced being collected in a chamber incommunication with the machine. The process, however, is notpracticable, owing to the excessive consumption of motive power andthe enormous wear and tear of the machine. According to Heintzel132 ABSTRACTS OF CHEMICAL PAPERS.cement made u p with 339 per cent.water hardens in 94 hours ; with30 per cent. in 7$ hours ; with 26+ per cent. in 4 hours ; with 233 percent. in 37 minutes ; and with 20 per cent. in 4 minutes. I n com-paring the time which cement requires for setting, it is usual to mix itwith water to the consistency of a thick paste. It is difficult, how-ever, to fix the quantity of water necessary to effect, this result, assome kinds of cement absorb more water than others. It is best,therefore, to use an excess of water in all cases. Herzog has foundthat in preparing a large block of cement, the temperature increasesconsiderably, especially after the mass has been beaten down. Inbuying cement, it is often stipulated that during the hardening thetemperature should not rise more than 3" to 5", although the quantityof cement to be used to determine this point is not mentioned, eo thatby using larger quantities greater differences are obtained, the resultbeing the rejection of good samples of cement.I n order to economiseheat, Tomei, in burning cement, uses a battery of shaft furnaces con-nected with one another, and worked continuously. Dyckerhoff hasmade a series of useful experiments as to the profitable application ofPortland cement to the preparation of mortar and concrete. He showsthat concrete, when beaten down in the air, requires twice as muchflint as sand, and that it is not economical to throw concrete directinto water. For concreting under water, not more than equal parts ofsand and flint should be used, otherwise the firmness of the concretewill not be the same as that of the mortar used in its preparation.The firmness of mortar and concrete, when beaten down or broughtinto water depends a n the quantity of sand used and the quality ofthe cement, Mortars were examined as to their impermeability towatei- and resistance to atmospheric influences.The followingmixtures were found to give good results :-1 part cement with 1 partfine sand, or 2 parts ordinary sand and 0.5 part lime, or 3 parts sandand 1 part lime, or 6 parts sand and 2 parts lime. D. B.Iron Industry. (Biwgl. polyt. J., 245, 392--394.)-h 1877 thePrussian Chamber of Commerce made a series of %tests with a viewof comparing Rhenish-Westphalian foundry pig with English andScotch brands. It was shown that the prevailing prejudices againstGerman cast iron were no longer tenable, so that since that time theimports of foreign foundry pig into Germany have decreased 'by about12 per cent., whilst the home production has been doubled.Analysis of flue-dust from a, Whitwell apparatus :-K20. Na20.CaO. MgO. Fe20,. ZnO. M U ~ .17-05 9.53 25.95 2.31 0.91 1.30 0.37COz, H,O, CN, and residue. s. SiO,. &03. L-----J1-71 24-05 10.09 6.73The silica is partly free, partly combined ; the sulphur is present aspotassium and calcium sulphides, also as alkaline thiosulphate. Thepotash and soda are in combination with silicic acid, thiosulphuricacid, thiocyanstes, cyanides, and ferrocyanidesTECHNICAL CHEMISTRY* 133The following table gives the chemical analysis of the various ironsexamined in the comparison mentioned above :-Kame of pig iron.Coltness No.1 .. . . ,. . . ..Langloan No. 1 , . . . . . . , . .Clarence No. 3 , . . . . . . . . .Clarence No. 3 , . . . . . . . . .No. 1. Foundry A . . .NO. 3. Foundry c . . .2 No. 1. Foundry D . . .2 No. 1. Foundry D . . .F4 (No. 3. Foundry D . . .NO. 3 from Lorraine.. . . ,.No. 2 from Luxemburg . . .-$.4 4 .4 m -3 -502 -932 -523 *082 -451 '872 -451 9 52 -111 *611.302.013 *502 -701 '86 --dk 2@80,9840 -7521 '4901 '8000 '9770 -9350 9880 '8120.8500.7900 -9300.8500.9661 -8302 -210 -$4 .dau30 *0220.0410 *0550 -0250 -0110 -0080 -0350 *0340 *0210 .c440 *0050 *0180 *010D -041)D -058 --0'2 4 2a$--3 '303.403 '393 '333 '282 -933 '403 *123 *162 *973 -223 '383-27-i-84g 2 -pu--0 *200 -460.130 *120 -260 -500 *190 *150 *490.610 -230 '420 '153 *08,0*1L2 -88 1 0 '55IF:!a4U E?0 -0990 *0710 -0380 -0450 -0600 -0550.0390 -0390 -0400 *0550 *055traces0 *0390'0600 *820 --93 bD 81 -581 *620 -680 -820 *180 -161 q4.81 -920 -970 *860 -720 *990 "790 -630 *099 --dH90 -2490 -5191 -4089.8292 -4093 -4591 '1091 -8092 '0092.7893 '3291 *5092 '1091 -2091 -50 -The following is an analysis of the slags from samples Nos.1 to 3compared with slag obtained from fibrous puddled iron :-No. 1. No. 2. Puddledf--- r--A-, No. 3. iron.SiO, . . 27.50 28.30 31.37 53.30 31.20 32.20A1,0, . . 9-75 11.61 13.09 13.09 10.81 8-17CaO.. . . 58.90 54-94 58-04 52.04 53.17 48.92MgO .. 1.37 0.98 1.16 1-16 1.08 4.79The ratio of the oxygen of the silicic acid to that of the bases inslag No. 1, is as 2 : 3 ; in No. 2, 3 : 4 ; in No. 3, 4 : 5, and in puddlediron, 8 : 9. D. B.Utilisation for Agricultural Purposes of the Basic Slagobtained in the Dephosphorising Process. (Diiagl. polylt. J., 245,513.)-At a large steel works 'in Westphalia some investigations weremade as to the possibility of using the slag from the dephosphorisingprocess for agricultural purposes in the place of phosphaf,e.Thecinder gave on analysis :-Al,Oij andBand, alkalis,SiO,. COz. 8. Pz05. Fe. Mn. CaO. magnesia, &c.6.20 1-72 0.56 19.33 9.74 9.50 47.60 2.68It was found that 10.94 per cent. phosphoric acid, corresponding to56.6 per cent. of the total phosphoric acid, was soluble in ammoniu134 ABSTRACTS OF CHEMICAL PAPERS.citrate, and therefore mesent in a form which will allow it t o beassimilated readily by &ants (compare Abstr., 1882, p. 1229).D. B.Desilvering of Lead. By HAMPE (Dingl. polyt. J., 245, 515).-The author mentions that while the refining of copper by means ofelectricity is being worked with success on a large scale, Keith’s pro-cess of desilverising lead by electrolysis has not made much progress.This is mainly due to the fact that the refined lead does not answerthe requirements of commercially pure lead, and that lead precipitatedelectrolytically from acid solutions does not give a compact substance,but forms lamellar masees, diffused over the whole of the solution.To obtain crystals of lead sufficientlylarge to fall to the bottom of thesolution, it is necessary to increase the distance between the elec-trodes ; however by doing this the resistance, and with it the consump-tion of electricity required to surmount it, are proportionatelyincreased.D. B.Reactions of the Mexican Amalgamation Process. By A. K.HUNTINGTON (Chem. News, 46, 177).-Mercury worked up with silversulphide and sodium chloride extracted seven-eighths of the silverchloride, which was three times as much as that extracted whensodium chloride was absent: ferric oxide causes loss when sodiumchloride is present, as calomel and ferric chloride are formed ; verylittle iron causes much loss.When cupric sulphate is present in themixture, loss of mercury is greater, and the yield of silver less. Theaction of cuprous and cupric chlorides on silver sulphides occurs intwo stages :-Ag2S + CuClz = 2AgC1 + CUS cus + ‘CUC12 = CU2ClZ + s,which results in the formation of silver chloride and free sulphur.The amount of free sulphur and cuprous chloride formed depends onthe strength and qaantity of a solvent for cuprous chloride present,such as sodium chloride or CnC12, the temperature and the pressure.The action of the air in facilitating the action is due to the conversionof cuprous chloride into insoluble oxychloride :3C~zC12 + 3H20 + 30 = ~ C U O , C U C ~ ~ , ~ H ~ O + 2CuCIZ.Cuprous chloride and free sulphur are formed when cupric chlorideand silver sulphide are heated in a closed vessel to a high temperature,an6 if heated long enough, the sulphur is oxidised to sulphuric acid ;if, however, all air be excluded, no sulphur is formed, but cupricRulphate and cuprous chloride instead.Cuprous chloride and silversulphide yield silver chloride and cuprous sulphide. This is contraryto the statements of Malaguti and Durocher, who obtained metallicsilver, but it was because they employed ammonium as a solvent, andnot sodium chloride.Extraction of the Precious Metals from all Kinds of Ores byElectrolysis.By BLAS and MIEST (Chem. News, 46, 121-122).-The authors have discovered that if, in electrolysis, compressed sulphur-E. W. PTECHNICAL CHEMISTRY. 135ores are used as anode in a bath of an electrolyte containing the samemetal as the metal of the ore, on the passage of the current the ore isdecomposed, the sulphur, &c., being precipitated at the anode, whilstthe metal collects at the cathode. Thus with pure galena in a leadnitrate bath, the separation is complete and easy. If the ore containssilica as well, then the silica is deposited along with the sulphur, andremains uncombined ; antimony and arsenic, if present, behave in asimilar manner, being precipitated as insoluble oxides ; they are veryeasily separated by subsequent electrolysis.When large quantities ofarsenic are present, a part of it combines with the sulphur, and formsrealgar or orpiment. When ores containing several metals areoperated on, the precious metals, being most easily precipitated, arethrown down first in the metallic: state at the cathode under the actionof a moderate current. The final separation of these metals requiresvery little battery power, for the mass of metal when dissolved underthe action of the current regenerates sufficient heat for the ulteriorseparation of each metal separately. The products a t the anode areextracted and purified by treatment with carbon bisulphide, and after-wards by separate electrolysis.The decanted carbon bisulphidesolution of sulphur is distilled, the latter being left pure. If the oreis a polysulphide, and is mixed with much iron, sulphur and ironoxide are obtained in the first operation. These are best separated byelectrolysing in a dilute sulphuric acid-bath ; pure sulphur is obtainedat the anode and basic iron sulphate at the cathode. By this process, 18 horse-power is required to produce 1 kilo. of copper from a sul-phurous ore in one hour. As an example of the working with a com-plex ore, they describe the treatment of an argentiferous lead orecontaining iron, copper, and zinc. The curreut being sufficientlystrong, the iron and zinc will dissolve as readily as the other metals,but will not be precipitated so easily, therefore the solution willgradually become saturated with iron and zinc; the current is thenregulated so that only the lead, silver, gold, and copper are precipitatedon the cathode, while the zinc remains dissolved as nitrate.As thebath becomes saturated, the iron yields to the zinc, and is precipitatedto the bottom as ferric oxide, and as soon as the solution is nearlysaturated with zinc nitrate, it is syphoned off; the metals are thenremoved from the cathode, the sulphur and silica from the anode, and theiron oxide from the bottom, of course all separately. The sulphur, &c.,and the metals are treated as above described. The zinc nitratesolution is treated with a small quantity of zinc oxide, which throwsdown the iron ; the lead, copper, and silver retained (if any) are pre-cipitated by passing a current through the solution, using a zinc anode.The pure zinc nitrate may be treated by a stronger electric currentif metallic zinc is required, or chemically if zinc oxide is wanted.Freezing of Wine.By J. MORITZ (Bkd. Centr., 1882, 716).-Wine shows a tendency t o remain liquid below its true solidifyingpoint ; the percentage of alcohol present determines the freezingpoint ; the higher the percentage the lower will be that point, rangingfrom 3.3-5-9" for an alcoholic strength of 7.8-12-5 of alcohol byvolume. E. W. P.D. A. L136 ABSTRACTS OF CHEMICAL PAPERS.Preservation of Beer. By A. H. BAUER (Ried.Centr., 1882, 719).Unless salicylic acid is present in large quantities, it will not preservebeer, but Pasteurising and a small addition of acid preserves beer for3-6 months.Borax is useless as a preservative.(Bied. Ceiitr., 1882, 717.)-To estimate the amountof wort removed in the grains, 50 grams of the grains are shaken upwith 200 C.C. water for 10 minutes, the sp. gr. of the liquid after filter-ing is then taken, and the percentage of extract deduced. To estimatethe starch left in the grains, a sample is weighed and dried andpowdered, and then submitted to the action of dimtase a t 60” ; an ex-tract is then made, and the difference between the sp. gr. of the firstand second extract corresponds to the staroh in the grains.Loss of Sugar by long Steaming of the Mash.” By V. GRIESS-MAYER (Bied. Cenlr., 1862, 717).-l’his loss has been attributed tothe formation of furfural, but the author believes it to be due to thephosphoric acid in the nucle’in, which converts the starch into laevu-linic acid.Maltose is converted by acids under pressure into dextrose,and then furfuaal and formic acid may be produced. In sugar-beet,however, the action of the acid is to produce dextrose and I~evulose,and from the latter lavulinic acid is formed. E. W. P.E. W. P.Beer-grains.E. W. P.Does Potato-sugar contain any Deleterious Matter ? Byv. MERING (Bied. Cer~tr., 1882, 699).-It has been st’ated by Schmitzand Nessler that in the unfermeniable portion of potato-sugar thereis some substance which produces ill effects on animals. By experi-ments the author proves that this unfermentable substance is not dele-terious, but that it is a compound allied to the carbohydrates, and isof some nutritive value. E. W. P.Purification of Sugar-beet Juice. By SCHOTT and others (Ried.Centr., 1882, 697).-According to Schott’s patent, the amount ofpotassium present in the juice must first be estimated, and then jfthere is not a sufficiency of lime present, gypsum is to be added, so asto have 0.593 part CaO for every 1 part K20, then a dilute solutionof ferrous sulphate is poured in, and the whole heated nearly toboiling, finally allowing it to settle, filtering through ‘‘ charred peat,”and evaporating.Siegert in his patent states that after boiling the juice with lime afresh supply of lime is to be added, and after passing it through a,filter-press, the lime is to be removed by carbonic anhydride. Bythis process, treatment wit’h charcoal may be avoided. Licht haspatented a “ barium chloride” method, whereby the organic acids areprecipitated as salts of barium. A similar patent is that of Kottmann,in which strontium chloride is employed. E. W. P

ISSN:0368-1769    

DOI:10.1039/CA8834400127

出版商:RSC    

年代:1883

数据来源: RSC

摘要:

137 G e n e r a l a n d P h y s i c a l Chemistry. Observations on the Solar Spectrum. By LANGLET (Compf. rend., 95, 482 - 487). - Tho observations were made on Mount Whitney, which is almost as high a s Mont Blanc, and overlooks the dryest and most deserted district of South California. 0 bservations of the total solar radiation were made with the spectro-bolometer, and also with Pouillet’s heliometer, and Violle’s actinometer. The calcu- lations are not yet completed, but the author obtains a value of about 3 cal. ; in other words, if the terrestrial atmosphere were removed, the sun’s rays would raise the temperature of 1 gram of water through 3” C. for every square centimeter of earth’s surface exposed under normal conditions. This number is higher than that obtained by Pouillet (1.7 cal.), or by Sdret, or Crova, and Violle (2-2-2.5 cal.).The author has already shown that Pouillet’s formula is only appli- cable to homogeneous rays, and gives results too low. On Mount Whitney, and also a t the Alleghany Observatory, the author has examined both with a prism and with a diffraction grating the distribution of energy in the spectrum from X 3,500 to h. 28,000. The length of the ultra-red portion of the spectrum is much greater than was supposed. If the terrestrial atmosphere were entirely removed, this portion of the spectrum would doubtless extend much further, whilst the ultra-violet portion would not be affected to any- thing like the same extent, there being but little terrestrial absorption in this region. The actual results obtained with the prism and with the grating are given in the form of two curves. One-fourth of the total energy is situated in the visible and ultra-violet portion of the spectrum, the remaining three-fourths being in the ultra-red region. I n the latter region, there are several broad absorption-bands or cold spaces, probably made up of a number of lines which are not separated by the bolometer. In the visible spectrum, the maximum energy is in the orange, Contrary to the usual opinion, theauthor finds that in a dry climate the general terrestrial absorption diminishes up to the extreme infra- red.I n both the terrestrial and solar atmospheres absorption in- creases as the wave-lengths diminish. Combining, by means of Maxwell’s discs, the coiours which would be visible a t the surface of the photosphere if all intervening absorbing layers were removed, it is found that the true colour of the photosphere is similar to that of the spectrum near F, i.e., blue.C. El. B. Absorption Spectrum of the Earth’s Atmosphere. By EGOROFF (Compt. rend., 95, 447--449).--The electric light a t Moiit ValBrien, 10 kilos. distant, was observed at the Paris Observatory by means of a spectroscope with two Thollon’s prisms attached to the VOL. YLLV. 1138 ABSTRACTS O F CHEMICAL PAPERS. Foucault telescope. The brilliant spectrum thus obtained was crossed by a large number of absorption lines. Four could easily be distin- guished between I) and D2, and on either side of D, but especially on the less refrangible side, they are very numerous and distinct.The group a is almost complete, and the region of C contains a large number of lines. B is partially resolved into eleven pairs separated by equal distances, and A can be easily distinguished by using a cobalt glass. All the groups are characteristic and easily distin- guished. With a Drummond light, a t a distance of 1600 meters, B, a, and A could be clearly distinguished, between B and a there were two faint nebulous lines, and traces of absorption lines could be seen between L) and C. With a Drummond light, a t a distance of 240 meters, the only lines visible were : A very distinct, and a very feeble, but apparent,ly intensified by a heavy shower of rain. When the light was 80 meters from the end of the telescope, A could still be seen, although with difficulty ; all the other lines had disappeared.Reflection of Actinic Rays : Influence of the Reflecting Surface. By DE CHARDOXNET (Compt. rend., 95, 449-451).-The author has photographed the spectrum of sunlight reflected from the surfaces of a large number of substances, including white and black enamel, uranium glass, crude hematite, polished hematite, diamond, compressed carbon both rough and polished, vermilion, gold, lead, nickel, Arcet’s alloy, copper, polished steel and rough steel, Prussian blue, green leaves, speculum metal, mercury, and mercury covered with a plate of quartz. His results show that there is no selective absorption, precisely the same spectrum being obtained in all cases. Silver a t first appears to be an exception, because it becomes trans- parent to the second half of the ultra-violet ; but with suficiently long exposure this part of the spectrum also becomes distinctly visible.I n this case it is better to push the exposure to the first degree of inversion pointed out by Janssen. A positive impression is thus obtained in the neighbourhood of H, and a negative in the neighbour- hood of P. Similar results were obtained with a number of liquids, including water, solution of magenta, quinine acetosulphate, ammonio-copper sulphate, potassium dichromate, milk, and ink. The author contiyms the statement of Cornu that platinum mirrors, speculum metal, and mercury covered with quartz, do not absorb any of the more refrangi- ble rays radiated from the sun. With regard to the visible rays, the author arrives a t the following conclusions. Every surface reflects in varying proportion all the rays of the spectrum ; pure colours can conseqnently never be obtained by reflection.The reflecting power of a liquid is independent of the substances which i t holds in solution or in suspension. This law apparently holds good for solid media,for a mirror of black enamel gave the same spectrum as a mirror of white enamel. It is not necessary to conclude that the incident rays do not penetrate into the reflecting surface to a depth comparable with the wave-lzngtlis. These lengt,hs would be too small to produce appreciable absorption. A layer of C. H. B.GENERAL AND PHYSICAL CHEUISTRY. 139 quinine acetosulphate showing Newton’s rings (yellow of the first and blue of the second order) has no absorptive effect on the solar spectrum.The same substance gives the same reflection whether rough or polished: the polished surfnce increases the total quantity of reflected rays, but the relative intensity of different regions of the spectrum, i.e., the actznic colour of the substance, depends on the nature of the substance employed. Widening of the Lines in the Hydrogen Spectrum. By D. v. MONCKHOVEN (Compt. rend., 95, 378--38l).-The author employed a, vacuum tube in the shape of a capital H, the horizontal part being a capillary tube 0.5 mm. in diameter, whilst tlhe vertical limbs were wider and were provided a t each end with an electrode, of which there were consequently two pairs. Under varying degrees of pressure, and with induction coils of different power, he found that the widening of bhe hydrogen lines begins a t different pressures, but always at the point where the silent discharge passes into a spark discharge.Under con- stant pressure, variations in temperature obtained by using different coils, produced no effect on the width of the hydrogzn lines. When the current from a powerful coil is passed through a hydrogen tube under low pressure for one minute, the temperature rises considerably but t8he lines remain narrow. If, however, the coil is connected with a Leyden jar, the gas is scarcely warmed, but the lines C and F are broad. If the current from an induction coil connected with a Leyden jar is passed through the tube previously described, the tube being filled with hydrogen a t a pressure of 1-2 mm., the hydrogen lines are broad. If now a current from a powerful coil is passed through the tube, by means of the other pair of electrodes, the lines do not thicken, but a bright fine line is seen down the centre of each broad line; in other words two spectra are superposed.Since the use of vacuum tubes and disruptive discharges gave no satisfactory proof as to whether the widening of the hydrogen lines is due to pressure or to temperature, the author passed an electric arc, obtained from a con- tinuous current, through pure hydrogen contained in a tube connected with a Sprengel pump. At atmospheric pressure the hydrogen lines, C and F, are seen on the continuous spectrum of the incandescent carbon particles, F is considerably widened, C less so.The lines are uniformly brilliant, and have an appearance identical with that of the hydrogen lines in the sun and some stars; whereas in the vacuum tubes the widened lines decrease in brilliancy from the centre to the edges. At 0.25 m., the width of the lines C and F decrease, and a t 0.09 m. they are almost narrow, H.1 is invisible, but the arc arid the lines increase Considerably in brilliancy. At 0.02 m., C and F are quite narrow and very brilliant, and Hp/ becomes visible. At 0.008 m., H y becomes still more brilliant. By varying the distance between the electrodes, or by altering the power of the current, the temperature was made to vary considerably, but the breadth of t)he lines always remaoined the same. The author therefore concludes that the widening of the lines in the spectrum of hydrogen i s d u e solely topre+sure and is nbso lutely independent oj’ teniperatzcre.C. H. B. C. H. B. 1 2140 ABSTRACTS O F CHEMICAL PAPERS. Spectrum of Water. By G. D. LIVEIXG and J. DEWAR (Proc. Roy. Xoc., 33, 274--276).-This paper is illustrative of a photograph of the spectrum of an oxyhydrogen flame ; in no cases were lines of a wave-length less than X 2200 observed. Influence of Temperature on the Spectra of Non-metals. By D. v. MONCKHOVEN (Comnpt. r e d , 95, 520-522) .-Plucker has shown that most of the non-metals give two perfectly distinct spectra, one of which he regards as being due to a high, the other to a low temperature. If the H-shaped tube with four electrodes, previously described (preceding page), is filled with oxygen or some other non-metal, and the gas is subjected t,o the simultaneous action of two currents, one from an induction-coil alone, the other from a coil con- nected with a Leyden jar, the high temperature spectrum and the low temperature spectrum are seen superposed.According to Plucker’s hypothesis, the gas must therefore be at two different temperatures at the same instant, a supposition which is inadmissible. The superposi- tion of the two spectra is not due to the fact that the contact breakers of the two coils do n o t vibrate in unison, thus producing alteriiations of the two spectra which appear to be superposed, owing to the per- Ristence of the images, for in some tubes, especially if the tube be filled with oxygen, the light is radiated for several tenths of a second after the current is interrupted.The author attributes the changes in the spectra of the non-metals to a particular siate of vibration of their molecules, depending directly on the nature of the electricity employed. A hydrogen vacuum tube subjected to the action of ordinary sparks presents an appearance very different from that produced by induction sparks. The stratification in a vacuum tube changes entirely accord- i n g as it is produced by ordinary sparks, by induction sparks, or by a battery of high tension. Further, each variation in the appearance of an incandescent gas (ie., change of stratification, alterat,ion of the colour of the light emitted, &c.) always corresponds with a partial, often an entire, change in the character of the spectrum, the effect being certainly independent of the temperature. Note by Abstractor.-The author’s supposition that the change in the spectra of the non-metals is due to a particular form of molecular vibration, depending on the nature of the electricity employed, is sup- ported by Schuster’s observation of the peculiar spectrum of oxygen in the neighbourhood of the negative pole.V. H. V. C. H. B. C. H. 13. Circular Polarisation of Quartz. By J. L. SORET and E. SAKASIN (Compt. rend., 95, 635-638) .-In continuing their rasearches, the authors have adopted the folloairig improved method of determining the original plane of polarisation. Between the polariser and the analyser is placed a first quartz plate, say I~evogyrate, of thickness E, a black band is brought into coincidence with a line in the spectrum, and the position of the analyser noted.The first quartz being left in position, a second quartz is added of inverse rotation, and of a, thickness equal to 2E. The general appearance of the spectrum is not modified in the least, but there is a, rotation t o the right equal to 2Eg5 degrees, where q denotes the angle of rotation forGENERAL AND PHYSICAL CHEMISTRY. 141 a thickness of 1 mm. A black band is brought into coincidence with the same spectral line, and from the angle through tv hich it is necessary to tarn the analyser, plus a certain multiple of 180", the value of @ is deduced. The results obtained by this method agree with those previously published. A table is given of the values of the angle of rotation for different rays at 20°, deduced from observations on two pieces of quartz, one 30 mm., the other GO mm.thick. The observed values agree closely with those calculated by Boltzmann's formula reduced to its two first terms, 7.1082930 + 0.1477086 @ = 1 ( ~ 6 ~ % 1 ( ~ 1 ; 2 ~ 4 ' k being the length in millimeters of the wave in air, and this for- mula may be used to calculate the angle of rotation of a ray of any wave-length between A and 0. For rays more refrangible than 0, the formula no longer holds good, even though three or four terms of the series are taken. By substituting I, the wave-length in quartz, for A, the wave-length in air, a formula is obtained, which when reduced to two terms, approximately represents the observed rotation throughout the entire spectrum. The agreement between the observed and calculated values is not, however, complete, and the differences are greater than errors of observation would be.No better results are obtained by using three terms. By addition of a third term, H6, the divergence usually becomes greater. The influence of temperature on the rotation is not constant for all rays, as is generally supposed, but increases with the refrangibility. For line 24 of cadmium, the formula for correction between 0' and 20' is @ = Go (1 + OW0179t). This coefficient is greater than the number 0*000149 obtained by several observers as the mean coefficient between 0" and 100" for sodium light, and is, of course, still greater than the coefficient for the same light between 0" and 20".C. H. B. The Metallic Galvanic Circuit of Ayrton and Perry. By B. J. GOOSSENS (Ann. Phys. Chem. [a], 16, 551--554).-According to Perry and Ayrton (Proc. Roy. ec., 27, 219) a galvanic circuit is obtained by dipping strips of platinum and magnesium into mercury, but they were unable to obtain a similar effect with other metals. The author shows that the current obtained as above by Ayrton and Perry is a true thermo-current, caused by the evolution of heat in the formation of the magnesium amalgam (cotnpare Obach, Pogg. -4nn., SupyL., 7, 300). T. C. By J. ELSTER and H. GERTEL (Ann. P ~ I J S . Chem. i2] , 16, 193--222).--The longitudinal polarisation of flame is only.appare~xt, and is caused by the unequal immersion of the mire3 serviiig as electrodes.I n its cross section, however, the flame appears t o be strongly polarised, the electrode in the zone of sir immediately surrounding the flame being always positive towards the one in the flame. The electromotive power is independent of the size of the flame. The change in the polnritly of the flame may be produced by a suitable shifting of the electrodes. The electromotive force of the Electricity of Flame.142 ABSTRACTS OF CHEMICAL PAPERS. flame is dependent ofi the nature of the metals used as electrodes, and on the nature of the burning gas. It is especially great with elec- trodes of aluminium or zinc, and very weak if the electrode situated in the surrounding zone of air is covered with a salt, such as potassium chloride. An undoubted electrical action is obtained by the use of water electrodes and exclusion of metals, the electrode in the air being positive towards that in the flame.Flames may be comhined like galvanic elements, and a number of them may be united so as to form a flame battery. The following theory is advanced in explanation of the above facts. Free electricity is not produced within the flame during combustion ; but the gases from the flame, and the zone of air surrounding the flame, have the property in contact with met& or liquids, of exciting t,he latter like an electrolyte ; and in addition to this there is a thermoelectric excitement determined by the glow- ing condition of the electrodes. This being so, the amount and nature of the electric excitement is independent of the size of the flame, but dependent on the nature and superficial condition of the electrodes, on the nature of the burning gases, and on the glowing condition of the electrodes.These conclusions have been confirmed by numerous experiments. The authors conclude therefore that Hankel’s (Pogg. Ann., 81, 212) theory as to the electricity of flames is incorrect. T. c. Electrolysis of Hydrochloric Acid. By n. TomiAsI (Con@. rend., 95, 689-691) .-With platinum electrodes and concentrated acid, the positive electrode is attacked by the chlorine, and conse- quently behaves as a soluble electrode ; with dilute acid, on the other hand, chlorine compounds are liberated a t the positive pole, but the platinum is not attacked. Conce&ated Acid-The decomposition of 2 mols.of hydrochloric acid in solution absorbs 78.6 cals., but since the positive electrode is attacked, the heat of formation of platinum chloride must be sub- tracted from this number. The electromotive force necessary to effect decomposition is consequently much less than 78.6 cals. A single Daniel1 element is indeed sufficient to produce very slow de- composition, but a Daiiiell element (49 cals.) and a zinc-cadmium element (16.6 cals.) decompose the acid rapidly, with liberation of hydrogen at the negative pole, but no liberation of gas a t the positive pole, After 20 hours, the evolution of gas continues a t the negative pole only. With two Daniel1 elements (98 cals.) decomposition is very rapid. At first there is no evolution cf gas a t the positive electrode, but after about a n hour bubbles of gas begin to form.After 20 hours, decomposition continues with evolution of hydrogen at the negative and oxides of chlorine a t the positive pole. Similar results are obtained with acid of different degrees of concentration, but the limit is reached with acid of 10 per’ cent., when the amount of platinum dissolved is very small. Dilute Acid.-On closing the circuit, gas is evolved a t the negative pole, whilst the liquid round the positive pole becomes coloured faintly yellow, and bleaches litmus- paper. Even after continuous passage of the current for 100 hours, no trace of platinum is dissolved.GENERAL AND PHYSICAL CHEMISTRY. 143 Similar results were obtained with acid of different strengths down to 1 per cent. The chlorine appears a t the positive pole in the form of oxides of chlorine, wit>h probably hypoc Ldorous acid, and perhaps traces of free chlorine.Whether the oxides of chlorine are produced by the decomposition of the hydrate HCI,GH,O, or by the action of the oxygen of the water on the hydrochloric acid, cannot be ascertained. Distribution of Heat in the Ultra-red Region of the Solar Spectrum. By P. DESAIXS (Con2pt. Tend., 95, 433--436).-The author has continued his measurements of the distribution of heat in that portion of the solar spectrum less refrangible than the red (Abstr., 1879, 854), using respectively flint glass and crown glass prisms with a refracting angle of 60". In the following hble d and d' indicate in minutes the angular distance of the cold band from the line D, i and i' the relative intensities of the bands.I t must not be assumed, however, that the inten4ty of the band at 15' from D with a crown glass prism is equal to that of the band at 42' from D with it flint glass prism. Crown Glass (Jd!j l l t h , 12th, 13th, 1881). i. 20.0 19.0 22 26.6 23.5 17.0 19.0 d. 60.5 80.5 92 117.4 127.4 147.0 i. 15.0 5.5 10 - 2.5 - C. H. B. d. 15.0 18 0 24 31.0 34.5 444.5 5Q.5 Flint Glass (July 17512, 19th, 1881). d'. 42 45.0 55 58.0 68.0 73 77.2 82 88 92.5 96 i f . 20 18.0 1 6 23.0 26.5 24 25.0 24 16 20.0 16 d'. 100 103.0 108 122.0 130.0 148 157.0 170 175 185.0 i'. 25 21.5 26 16.5 20.0 6 15.5 7 2 - With prisms of flint and crown glass, the spectrum extends t o a much greater distance beyond the extreme red than with a prism of rock salt. With rock salt, the limit is only 80' from the extreme red, whilst with flint glass it extends as far as 1" 40'.C. H. R. Law of Thermal Constants of Substitution. By D. TOMMASI (Cornpt. Tend., 95, 453--456).-It has been stated that the author's law (Abstr., 1882, 12-57) does not hold good in the case of soluble salts formed by weak acids. He therefore cites a number of examples to show that wherever the calculated number differs from that actually obtained, the difference is due to the dissociation which takes place on solution, the coefl-icient of dissociation of the particular substance not being the same as that of the corresponding potassium salt. The close agreement between the calculated and actual numbers in the case of sodium, ammonium, lithium, strontium, and calcium sulphides sllows that the coefficient of dissociation of these compounds is the same as that of potassium sulphide.The difference between the numbers found and calculated is considerable in the case of ammonium carbonate and ammonium phenate, where also the dissociation is con-144 ABSTRACTS OF CHEMICAL PAPERS. siderably greater than that of the potassium compounds. For the Eame reason there is a considerable difference between the two numbers in the case of mercuric cyanide. C. H. B. Law of Cooling. By C. R ~ T I ~ R E (Compt. rend., 95, 452-453.- The radiating body was a platinum wire heated by means of an electric current. The temperature was calculated from variations in its conductivity, and the quantity of heat lost was calculat,ed by Joule's law.Under the low pressures a t which the experiments were made, the cooling effect due to the gas present becomes of consider- able importance. The quantity of heat carried off by the air under a pressure of 0.12 mm. of mercury is given approximately in the follow- ing table :- Heat radiated in a vacuum. A 200 .................... 10 times. A 400 .................... 3 ,, A 600 .................... 1 ,, A 800 .................... 3 9 ) A 1000 4 ,) - 1 .................... With a, platinum thread 0.1 TTIM. diameter placed horizontally in a glass cylinder 0.17 mm. in diameter, and surrounded by air under a pressure of less than 0.0001 mni. of mercury, the cylinder being cooled by a current of cold water, t,he following numbers were obtained :- Temperature of the cylinder 17.3". Excess.50" 100 150 200 250 300 400 500 600 700 800 900 1000 Heat lost. 38.5 94.8 175.6 284.0 448.0 708.0 16lO*O 3300.0 6035.0 10160*0 15980.0 241 10.0 34800.0 mae (at - 1). 38.4 94.7 177-4 298.7 476.7 738.0 1684.0 3721.0 8107.0 17552.0 37891.0 81688.0 176006.0 aT2 (T - 0). 35.4 93.0 177.6 293% 445.7 638.0 11 64.0 1907.0 2904.0 4193.0 58C8.0 7788.0 10168-0 The values in the third and fourth columns are calculated from the formulm of Dulong and Petit, and of Rosetti respectively, the constants being obtained from an experiment in which the excess of the temperature of the wire was 136.3" above that of the surrounding space. These results afiord further proof of the fact that the numbers given by Dulong and Petit's formula increase far too rapidly.C. H. B. Comparison of Mercurial Thermometers with the Hydrogen Thermometer. By J. M. CRAFTS (Compt. rend., 95, 836-839).-QENERAL AND PHYSICAL CHEMISTRY. 145 The table of corrections for mercurial thermometers, which is to be found in ordinary text-books, was compiled 30 years ago by Regnault, but that experimenter himself pointed out that owing to the great variation in the composition of glass, errors might arise from the application of his tables to all mercurial thermometers. Regnault's instruments have been destroyed, and the manufactory in which they were made has ceased to exist ; moreover the composition of the glass now used in France differs very considerably from that of the glass used by Regnault. The author has therefore undertaken a revision of the table.The boiling of water a t different pressures gives the means of determining accurately temperatures between 80" and 150". Between 140" and 350" the author uses naphthalene and benzophenone a t varying pressures. He has described elsewhere the methods used for determining with the aid of a hydrogen thermometer the exact pressures corresponding to any given boiling points of these liquids. By tabulating these results, he obtains hhe pressure under which it is necessary to boil either liquid to maintain for any required time a constant temperature. By these means, he has compared 15 ther- mometers with hydrogen thermometers. Two sets of seven of these thermometers were of flint glass, by two different French makers, and the other of soda glass, by a German maker.A table* showing the amount of error of the mercurial thermometers for temperatures from 110-330" accompanies the paper. The same table gives the com- parison of these errors with those given by Regnault. The results have been confirmed by experiments with twelve other thermometers of peculiar construction. E. H. R. Limit of the Liquid State. By J. B. HANNAY (Proc. Roy. Xoc., 33, 294-321) .-A continuation of the author's researches (Abstr., 1882, 268). After some remarks on the uncertainty of our knowledge of the exact condition of a fluid immediately above and below its critical point, the author proceeds to divide fluids into three classes- (1) l i p i d s , which exhibit surface tension, as capilla,rity or a permanent limiting surface; ( 2 ) gases, which cannot be reduced to liquids by pressure alone ; and ( 3 ) ucrpours, which can be so reduced.A further distinction of gases and vapours lies in the fact that the curve repre- senting pressure and volume of a gas is a continuous straight line, whereas a part of the curve representing pressure and volunie of a vapour is asymptotic. The author proposes to show that the gaseous state is entirely dependent on the mean velocity, and not on the free path of the molecule. Numerous experiments were made to ascertain the critical temperature and pressure of alcohol under its own vapour, and under that of certain gases, as hydrogen and nitrogen. which do not attack and are not dissolved by the alcohol. A modified form of Andrews's apparatus was used.The manometers were filled with hydro- gen, as the only gas which follows Boyle's law at high pressures, and the alcohol was carefully purified by an elaborate method. T'he mean of over 100 experiments gave a critical point for alcohol * The author has informed the editor that there is a misprint in the table in the original ; the letters B and C should be transposeJ.--C. 4. G.146 ABSTRACTS O F CHENICAL PAPERS. nnder its own vapour of 235.47" under a pressure of 67.07 atmo- spheres. In order to study the critical temperature of alcohol nnder greater pressures, hydrogen was introduced over the alcohol, in order t o allow of the limiting surface of the liquid to be seen; but it was found that the crit,ical temperature was practically unaltered, even under a pressure of 178.8 atmospheres.Similar results were obtained when nitrogen was substituted for hydrogen. The method of measur- ing the capillary height of a liquid under various temperatures and pressures was also tried, and it was shown that the capillary height of a liquid is lowered by a gas under pressure impinging on its surface ; this phenomenon would follow naturally from a constant distnrbance of the surface of the liquid, owing to the high velocity of the hydro- gen molecules striking it. Capi1larit.y is not then a true measure of the cohesion of a fluid, for were the pressure sufficiently high, the surface of the liyuid might be made to disappear while its interior was in a truly liquid condition. Similar experiments were made with carbon bisulphide and tetra- chloride and with methyl alcohol, the same general results being ob- tained. The critical point of carbon bisulphide under its own vapour was found to be 277.68" at 78.14 atmospheres ; under hydrogen, 274.93" a t 171.54 atmospheres ; under nitrogen, 273.12" a t 141.45 atmospheres ; this last result is probably affected by the solubility of the nitrogen in the carbon bisulphide.The capillary action of this liquid is also weakened by a gas impinging upon its surface. Determinations of the critical point of methyl alcohol under its own vapour gave the following results:--232*76" at a pressure of 72.55 atmospheres ; under hydrogen 230.14" at 128.60 atmospheres ; and uuder nitrogen, 277.92" at 191.40 atmospheres, or 225.82" at 262 atmospheres. With carbon tetrachloride, the results were 28251" a t 57.57 atmospheres under the pressure of its own vapour, and 277.5t;O at 142.82 atmospheres under nitrogen.It was found impossible to use hydrogen, for it attacked the tetrachloride, with formation of chlo- roform, and other compounds. I n conclusion, the author views the four states of matter thus :-lst, the gaseous, which exists from the highest temperature down to an isothermal passing through the critical point, and depending on temperature or molecular velocity ; 2nd, the vaporous, bounded on the upper aide by the gaseous, and on the lower by absolute zero, and dependent, upon the length of the mean free path of the molecule; 3rd, the liquid, bounded on the upper side by the gaseous, and on the lower by the solid state; 4th, the solid. The gaseous state is thus the only one which is not affected by pressure alone, or in which the molecular velocity is so high that the collisions cause a rebound of sufficient energy to prevent grouping.Another distinction between the gaseous and vaporous states lies in the fact t'hat t>he former is capable of acting as a solvent of solids (Abstr., 1382, 271). V. H. V. By W. SPRING (Bey., 15, 1940--1945).-Between 0" and 100" the expansions of ammonium and rubidium sulphates are sensibly equal, potassium chromate only expands at a slightly greater rate, but in the case of potassium sulphate Expansion of Isomorphous Salts.GENERAL AND PHYSICAL CHEMISTRY. 147 the expansion is about 10 per cent. greater. The discrepancy is explained by the fact that a given volume of potassium sulphnte con- tains a larger number of molecules than the other salts, for on dividing the sp.gr. by the molecular weight of each salt there is obtained : K,S04 : *015316; Am2S04 : *013664 ; Rb,S04:*013657 ; K2Cr04 : .01412. Taking the ratio of the molecules of K2S0, to Am2SO4, there is obtained 0.015316 + 0.013664 = 1.21, whilst the ratio of the expan- sions of the same two salts is about the same figure, 0.012645 + 0.011191 = 1.29. E’rorn these results, i t is probable that the expan- sions of the alums are not absolutely the same, although the differences fall within the limits of error (cf. Spring, Abstr., 1882, 1020 ; Petter- son, Abstr., 1882, 1259). Modification of the Usual Statement of the Law of Iso- morphism.By D. KLEIN (Conzpt. rend., 95, 781--784).-Mitscher- lich stated the law of isomorphism as follows:-1. Two bodies are called iPomorphous when, having the same crystalline form, they can crystallise together in the same crystal. 2. Isomorphous bodies have an analogous chemical composition. The author girea in the order of their discovery certain exceptions to the second part of this law. He goes ou to state that in previous communications he has described a t uiigstoboric acid, 9WOJ,B203,2H20 + 22Aq, isornorphoics with lSlarignac’s octohedral silicotungstic acid, 12W0,,Si02,4H20 + 29Aq ; also a monosodium tungstoborate, 9\VO:{, B,O,,Na,O + 23 Aq, iso- n ~ o r p k o ~ s with the acids just mentioned ; and further a diammonium tungstoborate, 9W0,,B,0,,2NK40 + 19Aq, isomorphous with an ammonium metatungstate described by Marignac, and a dibariiim tungstoborate, 9W03,BL03,2Ba0 + 18Aq, isomorphous with the cor- responding metatungstate, The author states that the tungstoboric acid employed by him contained only a trace of silica, and that his analyses have in this respect been confirmed by Mnrignac.In con- sequence of these facts, a modification of Mitscherlich’s law has become necessary, and the author therefore gives the following, already pro- posed by Marignac, as a substitute tor the second part of the law in question :-Isomory?~ozcs bodies haue eitlier a siinilay clfemical cornposition, or possess only a slightly diferent perceutage comnposition, avid a1 1 coutain either a common group of eleinerhts or groups of elements qf iclenticul cliertiicw fuILctiows, which form by far the gyeater part of’ their weight.Observations on Crystallisation. By G. BR~~GELXANN ( B e r . , 15, 1833--1839).-After giving a short account of the deveiopment of the theories of isomorphism, dimorphism, &c., with special reference to their bearing on chemical composition, the author proceeds to show a t some length that crystallisation of two sulnstauces in the same form or tlie same crystal does not always depend on any relation in their chemical composition, a fact which has already beell pointed out in several instances, notably by G. Rose, in the case of sodium nitrate and calcspar. The examples brought forward by tbeauthor are copper sulphate and potassium dichromate, copper sulphate and cobalt chlo- ride, borax and potassium chlorate ; in most cases the cold saturated solutions were mixed in varying proportions, but in some crystals of the A.J . (3. R. H. R.148 ABSTRACTS O F CHEMICAL PAPERS. one substance were introduced into saturated solutions of the other. In all cases coloured solutions were used, and perfect co-crystallisation was observed, the colours being different, in various parts of the same crystal. Compounds therefore of the most dissimilar atomic constitu- tion can crystallise together, their power of so doine; being a function of the physical conditions in which they are found, and not of their chemical composition. The occurrence therefore of a body in a definite crystalline form is no criterion of its individuality, and the conception of isomorphism possesses only a nominal significance, as it cannot be used as a separate means of classificat,ion, but only in confirmation of facts otherwise obtained.J. I(. C. Experiments in Crystallisstion Exemplifying Berthollet’s Law of Affinity. By G. BXUGELMANN (Bey., 15, 1840--1841).-The following experiments are of interest as touching Berthollet’s law, that a liquid in which two salts have been dissolved contains the acids and bases of each reciprocally combined. Equal volumes of cold saturated solutions of cobalt chloride and nickel sulphate were mixed and allowed to evaporate spontaneously ; the crystals obtained consisted of both metals in the forrn of sulphates, and the chlorides of the two metals were left in solution. Similar results mere obtained with copper sul- phste and cobalt chloride, as well as with copper sulphate and potas- sium dichromate ; in the former case, the first crop of crystals contained both metals as sulphates, together with small quantities of chlorides ; in the latter, crystals of the mixed sulphates of copper and potassium were first deposited, then various mixtures of tlie chromates and sulphates, and finally a mixture of chromates of tlie two metals.In every case the crystallisation seems to have proceeded in a liquid con- taining four different salts. Nature of the Vibratory Movements which accompany the Propagation of Flame in Mixtures of Combustible Gases. Abstr., 1881, 971).-The authors employed a tube 3 meters long and 0 03 meter in diameter. The combustible gas was a mixture of nitric oxide and vapour of carbon bisulphjde.An image of the tube was thrown on to a, cylinder covered with sensitive paper and rotating with a known velocity. The photographs show that the flame travels at first with a uniform velocity, but afterwards performs a series of very rapid osciilations, the regularity, duration, and amplitude of which vary a t different parts of the tube. Uniform motion cothinixes with a velocity of 1.10 meter per second to a distance of 0.75 meter from the mouth of the tube. Beyond this point the flame, and con- sequently the mass of gas, is thrown into vibration, the vibrations being both simple and compound. The points a t which the vibration is simple are generally spaces of one or two-fifteenths the length of the tube. The duration of successive vibrations varies between 0.025 and 0.0034 of a second. The durations are in the simple ratios of 1, 2, 3, 4, 5, 6, but no relations could be traced between these times and the position of the flame in the tube.As a matter of fact, the vibrating mass of gas is composed of two distinct columns, one of burnt gas, the other of cold gas, the lengths and densities of which J. K. C. By AlALLARD and LE CHaTELIER (Co???pt. rend., 95, 599-560 ; see alsoINORGANIC CHEMISTRY. 149 vary a t every instant. The amplitude appears to be greatest for vibrations of long period, and is particularly great in the last third of the tube, a t the poiiit where one of the vibrating segments is situated when the tube gives the first harmonic from its fundamental note.The amplitude a t this point is as high as 1-10 meter. Since the oscillations of the flame are simply those of layers of burning gas, these experiments gave the first precise idea of the amplitude of the vibrations of a mass of gas emitting a sound. These vibratory move- ments necessarily correspond with high pressures. From calculations bssed on the variation in volunie, measured by the oscillation of the flame, it is found that the mean pressure is a t Ieast five atmospheres, and for mixtures in which the initial velocity is greater than 1 meter, the pressures will be considerably higher. The mean velocity of pro- pagation appears to increase with the amplitude and rapidity of the vibrations. I n one experiment, the limits were 1.10 meter and 5.40 meters, in anotber, 0.97 meter and 8.60 meters.I n another experiment, the explosive wave was formed a t a distance of two-thirds the length of the tube from the mouth, Le., a t the point where the amplitude of vibration was greatest, and the last third of the tube was completely shattered. The brilliancy of the flame varies a t successive phases of the same vibration, being greater when the flame moves forward than when it moves backward ; these differences increase wit'h the amplitude of vibration, and are undoubtedly connected with variations in pressure. With a tube 0.01 meter in diameter, the flame is extinguished a t a distance of about 1.5 meter from the mouth. The vibratory move.. ment is produced at a distance of 0.18 meter from the mouth of the tube, instead of at 0.75 meter. and tthe amplitude of vibration increases more rapidly.The mean velocity of propagation is at first very small, but attains a rate of 4.50 meters per second a t a distance of 0.5 meter, and becomes almost nothing just. before the extinction of the flame. The narrowing of the tube favours the development of the vibratory motion with all its consequences, C. H. B.137G e n e r a l a n d P h y s i c a l Chemistry.Observations on the Solar Spectrum. By LANGLET (Compf.rend., 95, 482 - 487). - Tho observations were made on MountWhitney, which is almost as high a s Mont Blanc, and overlooks thedryest and most deserted district of South California. 0 bservationsof the total solar radiation were made with the spectro-bolometer, andalso with Pouillet’s heliometer, and Violle’s actinometer.The calcu-lations are not yet completed, but the author obtains a value of about3 cal. ; in other words, if the terrestrial atmosphere were removed,the sun’s rays would raise the temperature of 1 gram of water through3” C. for every square centimeter of earth’s surface exposed undernormal conditions. This number is higher than that obtained byPouillet (1.7 cal.), or by Sdret, or Crova, and Violle (2-2-2.5 cal.).The author has already shown that Pouillet’s formula is only appli-cable to homogeneous rays, and gives results too low.On Mount Whitney, and also a t the Alleghany Observatory, theauthor has examined both with a prism and with a diffraction gratingthe distribution of energy in the spectrum from X 3,500 to h.28,000.The length of the ultra-red portion of the spectrum is much greaterthan was supposed. If the terrestrial atmosphere were entirelyremoved, this portion of the spectrum would doubtless extend muchfurther, whilst the ultra-violet portion would not be affected to any-thing like the same extent, there being but little terrestrial absorptionin this region. The actual results obtained with the prism and withthe grating are given in the form of two curves. One-fourth of thetotal energy is situated in the visible and ultra-violet portion of thespectrum, the remaining three-fourths being in the ultra-red region.I n the latter region, there are several broad absorption-bands or coldspaces, probably made up of a number of lines which are not separatedby the bolometer.In the visible spectrum, the maximum energy is inthe orange,Contrary to the usual opinion, theauthor finds that in a dry climatethe general terrestrial absorption diminishes up to the extreme infra-red. I n both the terrestrial and solar atmospheres absorption in-creases as the wave-lengths diminish. Combining, by means ofMaxwell’s discs, the coiours which would be visible a t the surface ofthe photosphere if all intervening absorbing layers were removed, it isfound that the true colour of the photosphere is similar to that of thespectrum near F, i.e., blue. C. El. B.Absorption Spectrum of the Earth’s Atmosphere. ByEGOROFF (Compt. rend., 95, 447--449).--The electric light a t MoiitValBrien, 10 kilos.distant, was observed at the Paris Observatory bymeans of a spectroscope with two Thollon’s prisms attached to theVOL. YLLV. 138 ABSTRACTS O F CHEMICAL PAPERS.Foucault telescope. The brilliant spectrum thus obtained was crossedby a large number of absorption lines. Four could easily be distin-guished between I) and D2, and on either side of D, but especially onthe less refrangible side, they are very numerous and distinct. Thegroup a is almost complete, and the region of C contains a largenumber of lines. B is partially resolved into eleven pairs separatedby equal distances, and A can be easily distinguished by using acobalt glass. All the groups are characteristic and easily distin-guished.With a Drummond light, a t a distance of 1600 meters, B, a, and Acould be clearly distinguished, between B and a there were two faintnebulous lines, and traces of absorption lines could be seen between L)and C.With a Drummond light, a t a distance of 240 meters, the onlylines visible were : A very distinct, and a very feeble, but apparent,lyintensified by a heavy shower of rain. When the light was 80 metersfrom the end of the telescope, A could still be seen, although withdifficulty ; all the other lines had disappeared.Reflection of Actinic Rays : Influence of the ReflectingSurface. By DE CHARDOXNET (Compt. rend., 95, 449-451).-Theauthor has photographed the spectrum of sunlight reflected from thesurfaces of a large number of substances, including white and blackenamel, uranium glass, crude hematite, polished hematite, diamond,compressed carbon both rough and polished, vermilion, gold, lead,nickel, Arcet’s alloy, copper, polished steel and rough steel, Prussianblue, green leaves, speculum metal, mercury, and mercury coveredwith a plate of quartz. His results show that there is no selectiveabsorption, precisely the same spectrum being obtained in all cases.Silver a t first appears to be an exception, because it becomes trans-parent to the second half of the ultra-violet ; but with suficientlylong exposure this part of the spectrum also becomes distinctly visible.I n this case it is better to push the exposure to the first degree ofinversion pointed out by Janssen.A positive impression is thusobtained in the neighbourhood of H, and a negative in the neighbour-hood of P.Similar results were obtained with a number of liquids, includingwater, solution of magenta, quinine acetosulphate, ammonio-coppersulphate, potassium dichromate, milk, and ink.The author contiymsthe statement of Cornu that platinum mirrors, speculum metal, andmercury covered with quartz, do not absorb any of the more refrangi-ble rays radiated from the sun.With regard to the visible rays, the author arrives a t the followingconclusions. Every surface reflects in varying proportion all the raysof the spectrum ; pure colours can conseqnently never be obtained byreflection. The reflecting power of a liquid is independent of thesubstances which i t holds in solution or in suspension.This lawapparently holds good for solid media,for a mirror of black enamel gavethe same spectrum as a mirror of white enamel. It is not necessary toconclude that the incident rays do not penetrate into the reflectingsurface to a depth comparable with the wave-lzngtlis. These lengt,hswould be too small to produce appreciable absorption. A layer ofC. H. BGENERAL AND PHYSICAL CHEUISTRY. 139quinine acetosulphate showing Newton’s rings (yellow of the first andblue of the second order) has no absorptive effect on the solarspectrum. The same substance gives the same reflection whetherrough or polished: the polished surfnce increases the total quantityof reflected rays, but the relative intensity of different regions of thespectrum, i.e., the actznic colour of the substance, depends on thenature of the substance employed.Widening of the Lines in the Hydrogen Spectrum.By D.v. MONCKHOVEN (Compt. rend., 95, 378--38l).-The author employeda, vacuum tube in the shape of a capital H, the horizontal part beinga capillary tube 0.5 mm. in diameter, whilst tlhe vertical limbs werewider and were provided a t each end with an electrode, of which therewere consequently two pairs. Under varying degrees of pressure, andwith induction coils of different power, he found that the widening ofbhe hydrogen lines begins a t different pressures, but always at the pointwhere the silent discharge passes into a spark discharge. Under con-stant pressure, variations in temperature obtained by using differentcoils, produced no effect on the width of the hydrogzn lines.Whenthe current from a powerful coil is passed through a hydrogen tubeunder low pressure for one minute, the temperature rises considerablybut t8he lines remain narrow. If, however, the coil is connected witha Leyden jar, the gas is scarcely warmed, but the lines C and F arebroad. If the current from an induction coil connected with a Leydenjar is passed through the tube previously described, the tube beingfilled with hydrogen a t a pressure of 1-2 mm., the hydrogen linesare broad. If now a current from a powerful coil is passed throughthe tube, by means of the other pair of electrodes, the lines do notthicken, but a bright fine line is seen down the centre of each broadline; in other words two spectra are superposed.Since the use ofvacuum tubes and disruptive discharges gave no satisfactory proof asto whether the widening of the hydrogen lines is due to pressure or totemperature, the author passed an electric arc, obtained from a con-tinuous current, through pure hydrogen contained in a tube connectedwith a Sprengel pump. At atmospheric pressure the hydrogen lines,C and F, are seen on the continuous spectrum of the incandescentcarbon particles, F is considerably widened, C less so. The lines areuniformly brilliant, and have an appearance identical with that of thehydrogen lines in the sun and some stars; whereas in the vacuumtubes the widened lines decrease in brilliancy from the centre to theedges.At 0.25 m., the width of the lines C and F decrease, and a t0.09 m. they are almost narrow, H.1 is invisible, but the arc arid thelines increase Considerably in brilliancy. At 0.02 m., C and F arequite narrow and very brilliant, and Hp/ becomes visible. At 0.008 m.,H y becomes still more brilliant. By varying the distance between theelectrodes, or by altering the power of the current, the temperaturewas made to vary considerably, but the breadth of t)he lines alwaysremaoined the same. The author therefore concludes that the wideningof the lines in the spectrum of hydrogen i s d u e solely topre+sure and isnbso lutely independent oj’ teniperatzcre.C. H. B.C. H. B.1 140 ABSTRACTS O F CHEMICAL PAPERS.Spectrum of Water. By G. D. LIVEIXG and J.DEWAR (Proc.Roy. Xoc., 33, 274--276).-This paper is illustrative of a photographof the spectrum of an oxyhydrogen flame ; in no cases were lines of awave-length less than X 2200 observed.Influence of Temperature on the Spectra of Non-metals.By D. v. MONCKHOVEN (Comnpt. r e d , 95, 520-522) .-Plucker hasshown that most of the non-metals give two perfectly distinct spectra,one of which he regards as being due to a high, the other to a lowtemperature. If the H-shaped tube with four electrodes, previouslydescribed (preceding page), is filled with oxygen or some othernon-metal, and the gas is subjected t,o the simultaneous action of twocurrents, one from an induction-coil alone, the other from a coil con-nected with a Leyden jar, the high temperature spectrum and the lowtemperature spectrum are seen superposed.According to Plucker’shypothesis, the gas must therefore be at two different temperatures atthe same instant, a supposition which is inadmissible. The superposi-tion of the two spectra is not due to the fact that the contact breakersof the two coils do n o t vibrate in unison, thus producing alteriiationsof the two spectra which appear to be superposed, owing to the per-Ristence of the images, for in some tubes, especially if the tube befilled with oxygen, the light is radiated for several tenths of a secondafter the current is interrupted. The author attributes the changes inthe spectra of the non-metals to a particular siate of vibration of theirmolecules, depending directly on the nature of the electricity employed.A hydrogen vacuum tube subjected to the action of ordinary sparkspresents an appearance very different from that produced by inductionsparks.The stratification in a vacuum tube changes entirely accord-i n g as it is produced by ordinary sparks, by induction sparks, or by abattery of high tension. Further, each variation in the appearance ofan incandescent gas (ie., change of stratification, alterat,ion of thecolour of the light emitted, &c.) always corresponds with a partial,often an entire, change in the character of the spectrum, the effectbeing certainly independent of the temperature.Note by Abstractor.-The author’s supposition that the change inthe spectra of the non-metals is due to a particular form of molecularvibration, depending on the nature of the electricity employed, is sup-ported by Schuster’s observation of the peculiar spectrum of oxygenin the neighbourhood of the negative pole.V.H. V.C. H. B.C. H. 13.Circular Polarisation of Quartz. By J. L. SORET andE. SAKASIN (Compt. rend., 95, 635-638) .-In continuing theirrasearches, the authors have adopted the folloairig improved methodof determining the original plane of polarisation. Between thepolariser and the analyser is placed a first quartz plate, say I~evogyrate,of thickness E, a black band is brought into coincidence with a line inthe spectrum, and the position of the analyser noted. The first quartzbeing left in position, a second quartz is added of inverse rotation,and of a, thickness equal to 2E.The general appearance of thespectrum is not modified in the least, but there is a, rotation t o theright equal to 2Eg5 degrees, where q denotes the angle of rotation foGENERAL AND PHYSICAL CHEMISTRY. 141a thickness of 1 mm. A black band is brought into coincidence withthe same spectral line, and from the angle through tv hich it is necessaryto tarn the analyser, plus a certain multiple of 180", the value of @ isdeduced. The results obtained by this method agree with thosepreviously published. A table is given of the values of the angle ofrotation for different rays at 20°, deduced from observations on twopieces of quartz, one 30 mm., the other GO mm. thick. The observedvalues agree closely with those calculated by Boltzmann's formulareduced to its two first terms,7.1082930 + 0.1477086@ = 1 ( ~ 6 ~ % 1 ( ~ 1 ; 2 ~ 4 'k being the length in millimeters of the wave in air, and this for-mula may be used to calculate the angle of rotation of a ray of anywave-length between A and 0.For rays more refrangible than 0,the formula no longer holds good, even though three or four terms ofthe series are taken. By substituting I, the wave-length in quartz,for A, the wave-length in air, a formula is obtained, which whenreduced to two terms, approximately represents the observed rotationthroughout the entire spectrum. The agreement between the observedand calculated values is not, however, complete, and the differencesare greater than errors of observation would be.No better results areobtained by using three terms. By addition of a third term, H6,the divergence usually becomes greater.The influence of temperature on the rotation is not constant for allrays, as is generally supposed, but increases with the refrangibility.For line 24 of cadmium, the formula for correction between 0' and20' is @ = Go (1 + OW0179t). This coefficient is greater than thenumber 0*000149 obtained by several observers as the mean coefficientbetween 0" and 100" for sodium light, and is, of course, still greaterthan the coefficient for the same light between 0" and 20".C. H. B.The Metallic Galvanic Circuit of Ayrton and Perry. ByB. J. GOOSSENS (Ann. Phys. Chem. [a], 16, 551--554).-According toPerry and Ayrton (Proc.Roy. ec., 27, 219) a galvanic circuit isobtained by dipping strips of platinum and magnesium into mercury,but they were unable to obtain a similar effect with other metals.The author shows that the current obtained as above by Ayrton andPerry is a true thermo-current, caused by the evolution of heat in theformation of the magnesium amalgam (cotnpare Obach, Pogg. -4nn.,SupyL., 7, 300). T. C.By J. ELSTER and H. GERTEL (Ann. P ~ I J S .Chem. i2] , 16, 193--222).--The longitudinal polarisation of flame isonly.appare~xt, and is caused by the unequal immersion of the mire3serviiig as electrodes. I n its cross section, however, the flame appearst o be strongly polarised, the electrode in the zone of sir immediatelysurrounding the flame being always positive towards the one in theflame.The electromotive power is independent of the size of theflame. The change in the polnritly of the flame may be produced bya suitable shifting of the electrodes. The electromotive force of theElectricity of Flame142 ABSTRACTS OF CHEMICAL PAPERS.flame is dependent ofi the nature of the metals used as electrodes, andon the nature of the burning gas. It is especially great with elec-trodes of aluminium or zinc, and very weak if the electrode situatedin the surrounding zone of air is covered with a salt, such as potassiumchloride. An undoubted electrical action is obtained by the use ofwater electrodes and exclusion of metals, the electrode in the air beingpositive towards that in the flame.Flames may be comhined likegalvanic elements, and a number of them may be united so as toform a flame battery. The following theory is advanced in explanationof the above facts. Free electricity is not produced within the flameduring combustion ; but the gases from the flame, and the zone of airsurrounding the flame, have the property in contact with met& orliquids, of exciting t,he latter like an electrolyte ; and in addition tothis there is a thermoelectric excitement determined by the glow-ing condition of the electrodes. This being so, the amount andnature of the electric excitement is independent of the size of theflame, but dependent on the nature and superficial condition of theelectrodes, on the nature of the burning gases, and on the glowingcondition of the electrodes.These conclusions have been confirmedby numerous experiments.The authors conclude therefore that Hankel’s (Pogg. Ann., 81, 212)theory as to the electricity of flames is incorrect. T. c.Electrolysis of Hydrochloric Acid. By n. TomiAsI (Con@.rend., 95, 689-691) .-With platinum electrodes and concentratedacid, the positive electrode is attacked by the chlorine, and conse-quently behaves as a soluble electrode ; with dilute acid, on the otherhand, chlorine compounds are liberated a t the positive pole, but theplatinum is not attacked.Conce&ated Acid-The decomposition of 2 mols. of hydrochloricacid in solution absorbs 78.6 cals., but since the positive electrodeis attacked, the heat of formation of platinum chloride must be sub-tracted from this number.The electromotive force necessary toeffect decomposition is consequently much less than 78.6 cals. Asingle Daniel1 element is indeed sufficient to produce very slow de-composition, but a Daiiiell element (49 cals.) and a zinc-cadmiumelement (16.6 cals.) decompose the acid rapidly, with liberation ofhydrogen at the negative pole, but no liberation of gas a t the positivepole, After 20 hours, the evolution of gas continues a t the negativepole only. With two Daniel1 elements (98 cals.) decompositionis very rapid. At first there is no evolution cf gas a t the positiveelectrode, but after about a n hour bubbles of gas begin to form.After 20 hours, decomposition continues with evolution of hydrogenat the negative and oxides of chlorine a t the positive pole.Similarresults are obtained with acid of different degrees of concentration,but the limit is reached with acid of 10 per’ cent., when the amount ofplatinum dissolved is very small.Dilute Acid.-On closing the circuit, gas is evolved a t the negativepole, whilst the liquid round the positive pole becomes coloured faintlyyellow, and bleaches litmus- paper. Even after continuous passage ofthe current for 100 hours, no trace of platinum is dissolvedGENERAL AND PHYSICAL CHEMISTRY. 143Similar results were obtained with acid of different strengths down to1 per cent. The chlorine appears a t the positive pole in the form ofoxides of chlorine, wit>h probably hypoc Ldorous acid, and perhapstraces of free chlorine. Whether the oxides of chlorine are producedby the decomposition of the hydrate HCI,GH,O, or by the action of theoxygen of the water on the hydrochloric acid, cannot be ascertained.Distribution of Heat in the Ultra-red Region of the SolarSpectrum.By P. DESAIXS (Con2pt. Tend., 95, 433--436).-Theauthor has continued his measurements of the distribution of heatin that portion of the solar spectrum less refrangible than the red(Abstr., 1879, 854), using respectively flint glass and crown glassprisms with a refracting angle of 60". In the following hble d and d'indicate in minutes the angular distance of the cold band from the line D,i and i' the relative intensities of the bands. I t must not be assumed,however, that the inten4ty of the band at 15' from D with a crownglass prism is equal to that of the band at 42' from D with it flintglass prism.Crown Glass (Jd!j l l t h , 12th, 13th, 1881).i. 20.0 19.0 22 26.6 23.5 17.0 19.0d.60.5 80.5 92 117.4 127.4 147.0i. 15.0 5.5 10 - 2.5 -C. H. B.d. 15.0 18 0 24 31.0 34.5 444.5 5Q.5Flint Glass (July 17512, 19th, 1881).d'. 42 45.0 55 58.0 68.0 73 77.2 82 88 92.5 96i f . 20 18.0 1 6 23.0 26.5 24 25.0 24 16 20.0 16d'. 100 103.0 108 122.0 130.0 148 157.0 170 175 185.0i'. 25 21.5 26 16.5 20.0 6 15.5 7 2 -With prisms of flint and crown glass, the spectrum extends t o amuch greater distance beyond the extreme red than with a prism ofrock salt. With rock salt, the limit is only 80' from the extreme red,whilst with flint glass it extends as far as 1" 40'.C. H. R.Law of Thermal Constants of Substitution. By D. TOMMASI(Cornpt. Tend., 95, 453--456).-It has been stated that the author'slaw (Abstr., 1882, 12-57) does not hold good in the case of solublesalts formed by weak acids. He therefore cites a number of examplesto show that wherever the calculated number differs from that actuallyobtained, the difference is due to the dissociation which takes place onsolution, the coefl-icient of dissociation of the particular substance notbeing the same as that of the corresponding potassium salt. Theclose agreement between the calculated and actual numbers in thecase of sodium, ammonium, lithium, strontium, and calcium sulphidessllows that the coefficient of dissociation of these compounds is thesame as that of potassium sulphide.The difference between thenumbers found and calculated is considerable in the case of ammoniumcarbonate and ammonium phenate, where also the dissociation is con144 ABSTRACTS OF CHEMICAL PAPERS.siderably greater than that of the potassium compounds. For theEame reason there is a considerable difference between the twonumbers in the case of mercuric cyanide. C. H. B.Law of Cooling. By C. R ~ T I ~ R E (Compt. rend., 95, 452-453.-The radiating body was a platinum wire heated by means of anelectric current. The temperature was calculated from variations inits conductivity, and the quantity of heat lost was calculat,ed byJoule's law. Under the low pressures a t which the experiments weremade, the cooling effect due to the gas present becomes of consider-able importance.The quantity of heat carried off by the air under apressure of 0.12 mm. of mercury is given approximately in the follow-ing table :-Heat radiated ina vacuum.A 200 .................... 10 times.A 400 .................... 3 ,,A 600 .................... 1 ,,A 800 .................... 3 9 )A 1000 4 ,)-1 ....................With a, platinum thread 0.1 TTIM. diameter placed horizontally in aglass cylinder 0.17 mm. in diameter, and surrounded by air under apressure of less than 0.0001 mni. of mercury, the cylinder being cooledby a current of cold water, t,he following numbers were obtained :-Temperature of the cylinder 17.3".Excess.50"1001502002503004005006007008009001000Heat lost.38.594.8175.6284.0448.0708.016lO*O3300.06035.010160*015980.0241 10.034800.0mae (at - 1).38.494.7177-4298.7476.7738.01684.03721.08107.017552.037891.081688.0176006.0aT2 (T - 0).35.493.0177.6293%445.7638.011 64.01907.02904.04193.058C8.07788.010168-0The values in the third and fourth columns are calculated fromthe formulm of Dulong and Petit, and of Rosetti respectively, theconstants being obtained from an experiment in which the excess ofthe temperature of the wire was 136.3" above that of the surroundingspace. These results afiord further proof of the fact that the numbersgiven by Dulong and Petit's formula increase far too rapidly.C.H. B.Comparison of Mercurial Thermometers with the HydrogenThermometer. By J. M. CRAFTS (Compt. rend., 95, 836-839).QENERAL AND PHYSICAL CHEMISTRY. 145The table of corrections for mercurial thermometers, which is to befound in ordinary text-books, was compiled 30 years ago by Regnault,but that experimenter himself pointed out that owing to the greatvariation in the composition of glass, errors might arise from theapplication of his tables to all mercurial thermometers. Regnault'sinstruments have been destroyed, and the manufactory in which theywere made has ceased to exist ; moreover the composition of the glassnow used in France differs very considerably from that of the glassused by Regnault. The author has therefore undertaken a revision ofthe table.The boiling of water a t different pressures gives the meansof determining accurately temperatures between 80" and 150".Between 140" and 350" the author uses naphthalene and benzophenonea t varying pressures. He has described elsewhere the methods usedfor determining with the aid of a hydrogen thermometer the exactpressures corresponding to any given boiling points of these liquids.By tabulating these results, he obtains hhe pressure under which it isnecessary to boil either liquid to maintain for any required time aconstant temperature. By these means, he has compared 15 ther-mometers with hydrogen thermometers. Two sets of seven of thesethermometers were of flint glass, by two different French makers, andthe other of soda glass, by a German maker.A table* showing theamount of error of the mercurial thermometers for temperatures from110-330" accompanies the paper. The same table gives the com-parison of these errors with those given by Regnault. The resultshave been confirmed by experiments with twelve other thermometersof peculiar construction. E. H. R.Limit of the Liquid State. By J. B. HANNAY (Proc. Roy. Xoc.,33, 294-321) .-A continuation of the author's researches (Abstr.,1882, 268). After some remarks on the uncertainty of our knowledgeof the exact condition of a fluid immediately above and below itscritical point, the author proceeds to divide fluids into three classes-(1) l i p i d s , which exhibit surface tension, as capilla,rity or a permanentlimiting surface; ( 2 ) gases, which cannot be reduced to liquids bypressure alone ; and ( 3 ) ucrpours, which can be so reduced. A furtherdistinction of gases and vapours lies in the fact that the curve repre-senting pressure and volume of a gas is a continuous straight line,whereas a part of the curve representing pressure and volunie of avapour is asymptotic.The author proposes to show that the gaseousstate is entirely dependent on the mean velocity, and not on the freepath of the molecule. Numerous experiments were made to ascertainthe critical temperature and pressure of alcohol under its own vapour,and under that of certain gases, as hydrogen and nitrogen. which donot attack and are not dissolved by the alcohol.A modified form ofAndrews's apparatus was used. The manometers were filled with hydro-gen, as the only gas which follows Boyle's law at high pressures, andthe alcohol was carefully purified by an elaborate method.T'he mean of over 100 experiments gave a critical point for alcohol* The author has informed the editor that there is a misprint in the table in theoriginal ; the letters B and C should be transposeJ.--C. 4. G146 ABSTRACTS O F CHENICAL PAPERS.nnder its own vapour of 235.47" under a pressure of 67.07 atmo-spheres. In order to study the critical temperature of alcohol nndergreater pressures, hydrogen was introduced over the alcohol, in ordert o allow of the limiting surface of the liquid to be seen; but it wasfound that the crit,ical temperature was practically unaltered, evenunder a pressure of 178.8 atmospheres.Similar results were obtainedwhen nitrogen was substituted for hydrogen. The method of measur-ing the capillary height of a liquid under various temperatures andpressures was also tried, and it was shown that the capillary height ofa liquid is lowered by a gas under pressure impinging on its surface ;this phenomenon would follow naturally from a constant distnrbanceof the surface of the liquid, owing to the high velocity of the hydro-gen molecules striking it. Capi1larit.y is not then a true measure ofthe cohesion of a fluid, for were the pressure sufficiently high, thesurface of the liyuid might be made to disappear while its interiorwas in a truly liquid condition.Similar experiments were made with carbon bisulphide and tetra-chloride and with methyl alcohol, the same general results being ob-tained.The critical point of carbon bisulphide under its own vapour wasfound to be 277.68" at 78.14 atmospheres ; under hydrogen, 274.93" a t171.54 atmospheres ; under nitrogen, 273.12" a t 141.45 atmospheres ;this last result is probably affected by the solubility of the nitrogen inthe carbon bisulphide. The capillary action of this liquid is alsoweakened by a gas impinging upon its surface.Determinations of the critical point of methyl alcohol under itsown vapour gave the following results:--232*76" at a pressure of72.55 atmospheres ; under hydrogen 230.14" at 128.60 atmospheres ;and uuder nitrogen, 277.92" at 191.40 atmospheres, or 225.82" at262 atmospheres.With carbon tetrachloride, the results were 28251" a t57.57 atmospheres under the pressure of its own vapour, and 277.5t;Oat 142.82 atmospheres under nitrogen. It was found impossible touse hydrogen, for it attacked the tetrachloride, with formation of chlo-roform, and other compounds. I n conclusion, the author views thefour states of matter thus :-lst, the gaseous, which exists from thehighest temperature down to an isothermal passing through the criticalpoint, and depending on temperature or molecular velocity ; 2nd, thevaporous, bounded on the upper aide by the gaseous, and on the lowerby absolute zero, and dependent, upon the length of the mean free pathof the molecule; 3rd, the liquid, bounded on the upper side by thegaseous, and on the lower by the solid state; 4th, the solid.Thegaseous state is thus the only one which is not affected by pressurealone, or in which the molecular velocity is so high that the collisionscause a rebound of sufficient energy to prevent grouping. Anotherdistinction between the gaseous and vaporous states lies in the fact t'hatt>he former is capable of acting as a solvent of solids (Abstr., 1382,271). V. H. V.By W. SPRING (Bey., 15,1940--1945).-Between 0" and 100" the expansions of ammonium andrubidium sulphates are sensibly equal, potassium chromate onlyexpands at a slightly greater rate, but in the case of potassium sulphateExpansion of Isomorphous SaltsGENERAL AND PHYSICAL CHEMISTRY.147the expansion is about 10 per cent. greater. The discrepancy isexplained by the fact that a given volume of potassium sulphnte con-tains a larger number of molecules than the other salts, for on dividingthe sp. gr. by the molecular weight of each salt there is obtained :K,S04 : *015316; Am2S04 : *013664 ; Rb,S04:*013657 ; K2Cr04 : .01412.Taking the ratio of the molecules of K2S0, to Am2SO4, there isobtained 0.015316 + 0.013664 = 1.21, whilst the ratio of the expan-sions of the same two salts is about the same figure, 0.012645 +0.011191 = 1.29. E’rorn these results, i t is probable that the expan-sions of the alums are not absolutely the same, although the differencesfall within the limits of error (cf.Spring, Abstr., 1882, 1020 ; Petter-son, Abstr., 1882, 1259).Modification of the Usual Statement of the Law of Iso-morphism. By D. KLEIN (Conzpt. rend., 95, 781--784).-Mitscher-lich stated the law of isomorphism as follows:-1. Two bodies arecalled iPomorphous when, having the same crystalline form, they cancrystallise together in the same crystal. 2. Isomorphous bodies havean analogous chemical composition. The author girea in the order oftheir discovery certain exceptions to the second part of this law. Hegoes ou to state that in previous communications he has describeda t uiigstoboric acid, 9WOJ,B203,2H20 + 22Aq, isornorphoics withlSlarignac’s octohedral silicotungstic acid, 12W0,,Si02,4H20 + 29Aq ;also a monosodium tungstoborate, 9\VO:{, B,O,,Na,O + 23 Aq, iso-n ~ o r p k o ~ s with the acids just mentioned ; and further a diammoniumtungstoborate, 9W0,,B,0,,2NK40 + 19Aq, isomorphous with anammonium metatungstate described by Marignac, and a dibariiimtungstoborate, 9W03,BL03,2Ba0 + 18Aq, isomorphous with the cor-responding metatungstate, The author states that the tungstoboricacid employed by him contained only a trace of silica, and that hisanalyses have in this respect been confirmed by Mnrignac.In con-sequence of these facts, a modification of Mitscherlich’s law has becomenecessary, and the author therefore gives the following, already pro-posed by Marignac, as a substitute tor the second part of the law inquestion :-Isomory?~ozcs bodies haue eitlier a siinilay clfemical cornposition,or possess only a slightly diferent perceutage comnposition, avid a1 1 coutaineither a common group of eleinerhts or groups of elements qf iclenticulcliertiicw fuILctiows, which form by far the gyeater part of’ their weight.Observations on Crystallisation.By G. BR~~GELXANN ( B e r . , 15,1833--1839).-After giving a short account of the deveiopment of thetheories of isomorphism, dimorphism, &c., with special reference totheir bearing on chemical composition, the author proceeds to show a tsome length that crystallisation of two sulnstauces in the same form ortlie same crystal does not always depend on any relation in theirchemical composition, a fact which has already beell pointed out inseveral instances, notably by G.Rose, in the case of sodium nitrateand calcspar. The examples brought forward by tbeauthor are coppersulphate and potassium dichromate, copper sulphate and cobalt chlo-ride, borax and potassium chlorate ; in most cases the cold saturatedsolutions were mixed in varying proportions, but in some crystals of theA. J . (3.R. H. R148 ABSTRACTS O F CHEMICAL PAPERS.one substance were introduced into saturated solutions of the other.In all cases coloured solutions were used, and perfect co-crystallisationwas observed, the colours being different, in various parts of the samecrystal. Compounds therefore of the most dissimilar atomic constitu-tion can crystallise together, their power of so doine; being a functionof the physical conditions in which they are found, and not of theirchemical composition.The occurrence therefore of a body in a definitecrystalline form is no criterion of its individuality, and the conceptionof isomorphism possesses only a nominal significance, as it cannot beused as a separate means of classificat,ion, but only in confirmation offacts otherwise obtained. J. I(. C.Experiments in Crystallisstion Exemplifying Berthollet’sLaw of Affinity. By G. BXUGELMANN (Bey., 15, 1840--1841).-Thefollowing experiments are of interest as touching Berthollet’s law, thata liquid in which two salts have been dissolved contains the acids andbases of each reciprocally combined. Equal volumes of cold saturatedsolutions of cobalt chloride and nickel sulphate were mixed and allowedto evaporate spontaneously ; the crystals obtained consisted of bothmetals in the forrn of sulphates, and the chlorides of the two metalswere left in solution.Similar results mere obtained with copper sul-phste and cobalt chloride, as well as with copper sulphate and potas-sium dichromate ; in the former case, the first crop of crystals containedboth metals as sulphates, together with small quantities of chlorides ;in the latter, crystals of the mixed sulphates of copper and potassiumwere first deposited, then various mixtures of tlie chromates andsulphates, and finally a mixture of chromates of tlie two metals. Inevery case the crystallisation seems to have proceeded in a liquid con-taining four different salts.Nature of the Vibratory Movements which accompany thePropagation of Flame in Mixtures of Combustible Gases.Abstr., 1881, 971).-The authors employed a tube 3 meters long and0 03 meter in diameter.The combustible gas was a mixture of nitricoxide and vapour of carbon bisulphjde. An image of the tube wasthrown on to a, cylinder covered with sensitive paper and rotatingwith a known velocity. The photographs show that the flame travelsat first with a uniform velocity, but afterwards performs a series ofvery rapid osciilations, the regularity, duration, and amplitude ofwhich vary a t different parts of the tube. Uniform motion cothinixeswith a velocity of 1.10 meter per second to a distance of 0.75 meterfrom the mouth of the tube. Beyond this point the flame, and con-sequently the mass of gas, is thrown into vibration, the vibrationsbeing both simple and compound. The points a t which the vibrationis simple are generally spaces of one or two-fifteenths the length ofthe tube. The duration of successive vibrations varies between 0.025and 0.0034 of a second. The durations are in the simple ratios of1, 2, 3, 4, 5, 6, but no relations could be traced between these timesand the position of the flame in the tube. As a matter of fact, thevibrating mass of gas is composed of two distinct columns, one ofburnt gas, the other of cold gas, the lengths and densities of whichJ. K. C.By AlALLARD and LE CHaTELIER (Co???pt. rend., 95, 599-560 ; see alsINORGANIC CHEMISTRY. 149vary a t every instant. The amplitude appears to be greatest forvibrations of long period, and is particularly great in the last third ofthe tube, a t the poiiit where one of the vibrating segments is situatedwhen the tube gives the first harmonic from its fundamental note.The amplitude a t this point is as high as 1-10 meter. Since theoscillations of the flame are simply those of layers of burning gas,these experiments gave the first precise idea of the amplitude of thevibrations of a mass of gas emitting a sound. These vibratory move-ments necessarily correspond with high pressures. From calculationsbssed on the variation in volunie, measured by the oscillation of theflame, it is found that the mean pressure is a t Ieast five atmospheres,and for mixtures in which the initial velocity is greater than 1 meter,the pressures will be considerably higher. The mean velocity of pro-pagation appears to increase with the amplitude and rapidity of thevibrations. I n one experiment, the limits were 1.10 meter and5.40 meters, in anotber, 0.97 meter and 8.60 meters. I n anotherexperiment, the explosive wave was formed a t a distance of two-thirdsthe length of the tube from the mouth, Le., a t the point where theamplitude of vibration was greatest, and the last third of the tube wascompletely shattered. The brilliancy of the flame varies a t successivephases of the same vibration, being greater when the flame movesforward than when it moves backward ; these differences increase wit'hthe amplitude of vibration, and are undoubtedly connected withvariations in pressure.With a tube 0.01 meter in diameter, the flame is extinguished a t adistance of about 1.5 meter from the mouth. The vibratory move..ment is produced at a distance of 0.18 meter from the mouth of thetube, instead of at 0.75 meter. and tthe amplitude of vibration increasesmore rapidly. The mean velocity of propagation is at first very small,but attains a rate of 4.50 meters per second a t a distance of 0.5 meter,and becomes almost nothing just. before the extinction of the flame.The narrowing of the tube favours the development of the vibratorymotion with all its consequences, C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8834400137

出版商:RSC    

年代:1883

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. I n o r g a n i c Chemistry. 149 Action of the Galvanic Current on Chlorides and Chlorates. By A. LIDOFF and W. TICHOMIROFF (Jour. Russ. Chern. Xoc., 1882, 341- 349).-In a former paper (Abstr., 1882, 925) the authors have found that by the action of the electric (galvanic) current on a solution of chlorides, hypochlorites are first formed, which, by an elevation of tem- perature, are converted into chlorates. But later on they found that even a t the ordinary temperature, as soon as the solution becomes more concentrated, hjpochlorites are converted into a mixture of chlo- rates and chlorides by the sole action of the current. They propose to apply this process to the manufacture of chlorates, more especially of the sodium salt, which is difficult to prepare in the ordinary way.On150 ABSTRAC’J S OF CHElllICAL PAPERS. acting with a current of a powerful Gramnie machine for 25 hours, on a solution of 400 granis of potassium chloride in 900 grams of water, 210 grams of crystals, containing 70 per cent. of chlorate, were obtained. The crystals contain, together with potassium chlorate, a considerable quantity of the chloride, and 5-12 per cent. of carbon from the electrodes. As soon as about 30 per cent. of the original salt is transformed into the clllorate, the positive electrode is most strongly corroded, and no further separation of the crystals from the liquid takes place. If, instead of a high tension-current (2 electrodes) a divided current (8 electrodes) is employed, far less chlo~ide is converted into chlorate in tlie same space of time.The corrosive action of the liquid on the positive electrode is due to its oxidation by the oxygen of the potassium chlorate, which is reduced to chloride (about 30 per cent. in 10 hours). For this reason, potassium chloride csnnot be com- pletely converted into chlorate, but a limit is reached after some time, when the energy of formation of potassium chlorate from the chloride becomes equal to the energy of its decomposition. Electrodes of another material than carbon cannot be used for the conversion of chlorides into chlorates, for all metals, even platinum, are corroded by the chlorine which is set free at the same time. If, however, a solu- tion of potassium chlorate be electrolysed by means of platinum electrodes, 110 chlorine, but ozone, is evolved on the positive pole.At tlie same time crystals of potassium perrhlorate separate from the liquid, and oiily traces of potassium chloride are formed at the same time. I n this respect the act’ion of electricity on potassium chlorate is analogous to the action of heat on the same salt; in both cases oxygen is evolved, and potassium chlorate and chloride are formed, although the proportion in the quantities of these two salts is widely different. The corrosion of carbon in the above case is due t o the action of ozone, and the products of this action in presence of water Oxidation of Carbonic Oxide by Palladium Hydride and Oxygen. By M. TRAUBE (Ber., 15, 2325--2326).--The changes which occur when carbonic oxide is converted into the anhydride by the action of palladium hydride snd oxygen are as follows:-In the first place palladium hydride and moist oxygen form hydrogen per- oxide, and this compound in presence of metallic palladium oxidises are mellitic and hydromellitic acids. B.R. carbonic oxide t o carbonic anhydride. w. c. w. Compressibility of Nitrogen. By E. H. AMAGAT (Co?npt. rend., 95, 638--641).-A summary of t,he experiments made by Cailletet and by the author with a view to determine the compressibility of nitrogen. Curves are given representing the results obtained by both observers. The author considers Cailletet’s method inferior i n accuracy to his own. The curve representing Cailletet’s results is rery irregular, whilst t h a t representing the author’s results is perfectly regular.Black Phosphorus. By P. THENARD (Compt. rend., 95, 409--4110). -A quantity of phosphorus was being cast in the usual way, and a, C. H. B.IWORGAXIC CHEMISTRY. 151 dozen sticks had been obtained of the usual colour, when the thirteenth suddenly blackened atl the moment of congelation. Subsequently a second stick, about 20 cm. long, blackened for about 4 cm. of its length, the remainder being unchanged. A portion of the black phos- phorus was brought in contact with ordinary phosphoriis, in a state of superfusion a t 10" under ice. I n the first experiment, the white phos- phorus became black on solidifying, but the s3me effect was not again obtained once in more than twenty experiments under precisely similar conditions. The specimen of black phosphorus became white when fused, and remained white if cooled suddenly, but if super-cooled it again became black when brought in contact with either black or white phosphorus.Black phosphorus dissolves almost entirely in carbon bisulphide, leaving a slight yellow residue apparently consist- ing of amorphous phosphorus. Neutral Phosphates of the Alkalis. By E. FILHOL and SENDERENS (Bied. Centr., 1882, 641).-Careful neutralisation of phos- phoric acid with sodium hydroxide results in the formation of a mixture which reacts on red or blue litmus ; crysbals obtained from the solution contain 1 mol. of the mono- and 1 mol. of the di-sodium phosphate. Neutral potassium or ammonium phosphates have not been obtained, whilst potassium sodium and sodium ammonium phos- phates crystallise readily.Calcium Chloride. By A. WEBER (Bey., 15, 2316--2317).- Calcium chloride dried a t 180-200" is practically anhydrous. It contains from 0.12 to 0.24 per cent. of water and 0.047 per cent. ClaO. C. H. B. E. W. P. w. c. w. Properties of Pure Aluminium. By J. W, MALLET (Chern. News, 46, 178).-Sp. gr. a t 4" = 2.585 ; atomic vol., 10.45 ; sp. heat = 0.2253 between 0-100" ; atomic heat, 6.09" ; less fusible than the commercial metal, and less easily acted on by alkalis and acids. It is nearly pure tin-white, with no bluish tinge, and has a lustre like that of tin. It is more malleable and less easily hardened by hammering than ordinary aluminium. E. W. P. Decomposition of Phosphate by Potassium Sulphate at High Temperatures. By €3. GRANDEAU (Comnpt.rend., 95, gal-- 922).-Debray (BUZZ. SOC. Chim., 3, 251) has shown that on heahing to a high temperature aluminium phosphate with excess of an alka- line sulphate, an alkaline phosphate and crystallised aluminium are obtained. This reaction has been used by Derdme (Compt. r e d , 89, 92.5, and this Journal, 38, 286) for the separation of phosphoric acid from iron and aluminium. To determine the conditions of the re- action, a mixtiire of aluminium phosphate and potassium sulphnte was heated for several hours in a platinum crucible. At a high temperature, not only is alumina formed, but also a crystalline double phosphate of aluminium and potassium. At a still higher tempe- rat me, the quantity of alumina increases, but even on very vigorous heating it is impossible to completely decompose the double phos-152 ABSTRACTS OF CHEMICAL PAPERS.phate. Similar results were obtained by subst,ituting phosphates of glucinum, cerium, and didymium for aluniinium phosphate. But when phosphates of calcium, magnesium, &c., were used, the doable phosphate alone was formed under the conditions of the experiment ; whilst with nickel and cobalt; phosphates results similar to those with aluminium phosphates were obtained. With chromium and uranium phosphates, the final products are potassium chromate and uranate. The investigation is being continued. Determination of the Equivalent of Thorium. By L. I?. NILSON (Compt. j-end., 95, 729--730).-As a mean of ten determiua- tions, the author finds 58.10 to be the equivalent of thorium, that of oxygen being 8, and of sulphur 16.H e makes the atomic weight, therefore, to be 232.36. These results were obtained by calcining two different specimens of the sulphate, a aud b. Specimen b was obtained from the mother-liquors of a. The first six determinations were made on specimen a, which contained nine molecules of water. I n these six experiments the author used the hydrated salt, because the dehy- drated substance was found to be extremely hygroscopic. In the other four experiments this was impossible, because specimen b (tlie crystals of which differed from those of specimen a ) contained only eight molecules of water, and absorbed water during the process of weighing. I n the latter four experiments, therefore, the anhydrous sulphate was used.The two specimens gave practically identical results. L. T. 0's. Sulphate a. Water. SO3. Thoa. Equiv. At. Wt. Mean of six experiments 27.573 27.336 45.091 58.11 232.43 Sulphate b. Mean of four experiments - 37.703 62.297 58.09 232.30 The author concludes by drawing attention to the wide diwrepancies in the values of the atomic weight as determined by other chemists. E. H. R. Metallic Thorium. By L. F. NILSON (Conyf. rend., 95, 727- 729).-The author obtains metallic thorium by heating with sodium i n an iron crucible a mixture of the anhydrous double chloride of thorium and potassium with sodium chloride. After treatment of the residue with water, metallic thorium remains as a heavy greyish brilliant powder. Examined under the microscope, the powder is seen to con\ist of minute crystals, more or less brilliant and united in groups. The metal is brittle and almost infusible.The powder assumes a metallic lustre under pressure, is unalterable in air up to 120", takes fire in air or ox)-gen below a red heat, and burns with dazzling brilliancy, leaving a perfectly white oxide. It takes fire when heated with chlorine, iodine, bromine, and sulphur. It is not attacked either by hot or by cold water. Dilute sulphuric acid causes a feeble evolution of hydrogen in the cold, becoming more rapid on the application of heat, but the metal is attacked slowly; hot con- centrated sulphuric acid also acts but slowly, disengaging sulphurousINORGANIC CHEMISTRY. 153 anhydride. Nitric acid, whether hot or cold, strong or dilute, exerts no sensible action.Dilute hydrochloric acid dissolves the metal slowly even when heated, but concentrated acid attacks it very easily. Aqua regia acts like hydrochloric acid. The metal obtained by hhe author behaves, therefore, exactly like that obtained by Berzelius. The mean sp. gr. is nearly 11; this is much higher t,han that found by Chydenius (7.657 to 7.795) : hence the specimen obtained by the latter chemist must have contained much impurity, probably derived from the glass tube in which it was preptred. The densities of two different specimens of the oxide were 10.2207 and 20.2198 respectively. These numbers are again much higher than those obtained by Berzelius, Damour, and Chydenius (9.402, 9.366, 9.288). Admitting that the metal is quadrivalent, the atomic volume is 21.1.This number coincides with the atomic volume of zirconium (21*7), cerium (21*1), lanthanum (22.6), and didymium (21.5) ; and this fact serves to confirm the author’s opinion that the rare earth- metals form a series of quadrivalent elements. Magnesia Alba. By R. KRAUT (Arch. Pharm. [ 3 ] , 20, 180-187). -In this criticism of Beckurts’ paper on the composition of magnesia aZbu (this vol., p. 13), the author shows that analytical errors have crept in, as no direct estimation of the water lost by heating was made, &c.; the formula proposed by Beckurts therefore is incorrect, and the original formula 5Mg04C02,Hz0, as proposed by Kraut, is the right one; also by boiling for some time, the composition may be altered to 4Mg0,3COZ,6HzO, but never to 7Mg0,5C02. Separation of Gallium.By L. DE BOISBAUDRAN (Cowzpt. Tend., 95, 410-413 ; 503-506. See also Abstr., 1882, 897, 1323).--From Indium .-Precipit#ation of the gallium by potassium ferrocyanide, in presence of hydrochloric acid, is to be recommended only when it is required to separate a little indium, together with other metals, such as aluminium and chromium. The following is the only trustworthy method :-The moderately concentrated solution is boiled for some minutes with a slight excess of potassium hydroxide ; the precipitated indium hydroxide retains small quantities o€ gallium, which may be removed by a repetition of the process. The alkaline solutioas contain only very slight traces of indium ; to remove these, hydrochloric acid is added in slight excess, and the gallium and indium are precipitated together by boiling with an excess of ammonia, or better, by means of cupric hydroxide.The gallium and indium chlorides are then converted into sulphates; the slightly acid solution mixed with a quantity of ammonium sulphate rather more than sufficient to convert the gallium into alum is evaporated to small bulk, and, after cooling, mixed with four or five times its volume of alcohol of 70 per cent. Gallium alum is thus thrown down as a crystalline powder, which is washed once or twice with alcohol, dissolved in warm water containing a minute quan- tity of sulphuric acid, and reprecipitated. By several repetitions of tlhis process, the gallium is obtained in the form of alum, free from indium. The alcoliolic washings, which contain small quantities of gallium and indium, are evaporated to small bulk, the metals pre- Alkalis ha.ve no action.E. H. R. E. W. P. VOL. XLIV. m154 ABSTRACTS OF CHEXICAL PAPERS. cipitated by boiling with ammonia or by means of cupric hydroxide, the precipitate dissolved in hydrochloric acid, and the solution boiled with a slight excess of potassium hydroxide; a small quantity of indium hydroxide is thus obtained free from gallium. The galliuin remaining in solution may be separated as alum. Usually the indium dissolved by tlie potash is removed by four crystallisations of the ammonium-gallium alum ; but if the gallium hydroxide contains more than 4 per cent. of indium hydroxide, seven or eight crystallisations are necessary. Froin CadnLiurrz.- In presence of much free hydrochloric acid, cadmium is not completely precipitated by hydrogen sulphide, whilst if the solut'ion is but feebly acid, the cadmium sulphide contains gallium. The somewhat acid solution is treated with hydrogen sulphide, the precipihate redissolved in hydrochloric acid, the solution diluted, and again treated with hydrogen sulphide. By two or three repetitions of the process, the greater part of the dadmium is obtained as sulphide free from gallium. The filtrates which contain the gallium, mixed with a little cadmium, are evaporated to expel excess of acid, dilutled with water, and saturated with hydrogen sulphide. The cadmium sulphide thus thrown down is reprecipitated two o r three times. Excess of boiling potassium hydroxide precipitates cadmium oxide, and dissolves gallium hydroxide ; the cadmium oxide is redissolved and again precipitated, in order to separate the last traces of gallium.If the amount of cadmium is large, this process must be repeated four or five times. The alkaline solution which contains gallium and a small quantity of cadmium is slightly acidified wjth hydrochloric acid, and the gallium precipitated by means of cupric hydroxide, the filtrate is mixed with ammonium acetate, and treated with hydrogen sulphide, which throws down copper and cadmium : this precipitate is dissolved in aqua regia, evaporated with hydrochloric acid, and hydrogen sulphide is passed into the strongly acid solution ; copper sulphide is thus precipitated, whilst cadmium remains in solution.The following methods are more rapid:-(1.) The solution, which must contain a sufficient quantity of ammonium chloride, is boiled with excess of ammonia: cadmium then remains in solution, and gallium hydroxide is precipitated ; this precipitate is redissolved and again precipitated, in order to remove the last traces of cadmium. (2.) Gal- lium is precipitated by means of potassium ferrocyanide in a solution which contains at least one-third of its volume of strong hydrochloric acid ; the cadmium ferrocyanide remains in solution. (3.) Cupric hydroxide precipitates gallium on gently warming ; the precipitate retains small quantities of cadmium, which may be removed by a repetition of the process. (4.) When it is necessary to remove iron as well as cadmium, the warm solution is reduced by metallic copper and then mixed with a slight excess of cuprous oxide: the pre- cipitated gallium hydroxide contains traces of cadmium, which may be removed by reprecipitation.The reactions with cupric hydroxide, and with metallic copper and cuprous oxide, are the most satisfactory. Fronz Ur.cr.nium.-(l.) The boiling slightly acid solution of the chloride is treated with cupric hydroxide ; the precipitate is then dis-INORGANIC CHEMISTRY. 155 solved in hydrochloric acid, diluted, and again precipitated with cupric hydroxide, the treatment being repeated four or five times. (2.) If it is required to separate iron a t the same time, the solution is reduced with metallic copper, and then boiled with excess of cuprous oxide; tbe precipitate is redissolved and the treatment repeated about four times.Neither of these methods is affected by the presence of con- siderable quantities of alkaline salts. (3.) The slightly acid solution of the chloride is mixed wit11 an excess of acid ammonium acetate, zinc chloride free from gallium added, and the liquid is treated with hydrogen sulphide : the zinc sulphide formed carries down the gallium, whilst the uranium remains in solution. The precipitate is difficult to wash and must be redissolved in hydrochloric acid, and again preci- pitated in presence of an acetate. The zinc and gallium are separated by the method previously described. (4.) The uranium is preci- pitated in the form of alkaline uranate by adding a slight excess of potassium hydroxide, the precipitate dissolved in hydrochloric acid, and again precipitated. To remove traces of uranium from the fil- trate, the latter is slightly acidified with hydrochloric acid, and boiled with cupric hydroxide.When the potassium hydroxide contains car- bonate, the quantity of uranium in the filtrate is increased. From Lead.-(1.) The slightly acid solution of the chloride is boiled with cupric hydroxide, the last trace of lead being removed by a second precipitation. The reagents must be free from sulphuric acid. This method is very accurate, and may be used to separate gallium sulphat,e from the minute quantities of lead which remain in solution after precipitation of lead as sulphate. (2.) The solution of chloride o r sulphate is boiled with metallic copper and then with cuprous oxide, traces of lead being removed by a second precipitation. If a solution of the chlorides is used, the presence of sulphuric acid in the reagents must be avoided.(3.) The moderately acid solution is treated with hydrogen sulphide, the filtrate evaporated almost to dryness to expel free acid, diluted with water, and again treated with hydrogen sul- phide. If sulphuric acid is present, i t should be partially neutralised with ammonia. To extract the gallium retained by the lead sulphide, the latter is treated with strong hydrochloric acid, alcohol is added, the liquid is filtered, and the filtrate, after evaporation to expel water and alcohol, is diluted, and saturated with hydrogen sulphide. (4.) The gallium is then precipitated as ferrocyanide by means of potassium ferrocyanide in a solution containing one-third or one-fourth its volume of stroug hydrochloric acid.A second precipitation is sometimes necessary in order to remove the last traces of lead. (5.) The solu- tion is mixed with sulphuric acid, and two volumes of alcohol of 90" added; the precipitated lead sulphate, after being washed with alcohol acidified with sulphuric acid, is suspended in dilute hydrochloric acid and treated with hydrogen sulphide; and the filtrate, after being boiled to expel excess of the gas, is treated with cupric hydroxide to precipitate the last traces of gallium. The gallium in the alcoholic solutions is precipitated by cupric hydroxide, after boiling off the alcohol. (6.) The solution is mixed with twice its volume of 90 per cent.alcohol ; a slight excess of hydrochloric acid is added, and the precipitated lead chloride is washed with acidulated alcohol, whereby it nz 2156 ABSTRACTS OF CEEMICAL PAPERS. is obtained free from gallium. The filtrate is evaporated to small bulk, the nitric acid removed, and the liquid treated either with hydro- gen sulphide, with cupric hydroxide, or with metallic copper and cuprons oxide. C. H. B. Separation of Gallium. By L. DE BOISBAUDRAN (COW& re12d., 95, 703-706) .--Xepayation from Tin.-Sulphide of tin pre- cipitated from a hydrochloric acid solution containing tin and gallium, retains none of the latter metal. On adding hydrochloric acid in excess to a solution of the sulphides of tin and gallium in an alkaline sulphide, sulphide of tin free from gallium is thrown down.Salts of manganese added to a solution of the mixed sulphides in an a1 kaline sulphide give a precipitate of manganese snlphide, which contains gallium: this makes it possible to extract the latter metal from large quantities of sulphide of tin. The author draws atten- tion to one or two points, of which notice must be taken in analysing mixtures containing gallium. A solution containing even a con- siderable amount of gallium is not precipitated by potassium ferro- cyanide if a large amount of stannic chloride is present; so that tin must be separated before attempting to estimate gallium by ferro- cyanide. Tin and gallium, when alloyed, cannot be completely separated by nitric acid, because the metastannic acid formed retains sensible quantities of gallium, even after prolonged washing with nitric acid.It is difficult to obtain a complete separation of gallium and tin by precipitating the latter metal with zinc, because in a solu- tion strongly acid the tin is not entirely thrown down, and in a nearly neutral solution a certain quantity of gallium becomes insoluble. Finally, tin dioxide, precipitated by boiling with sulphuric acid, retains much gallium. Xeparation from Antimony.-Gallium may be separated from anti- mony by sulphuretted hydrogen, or by addition of an acid to a solution of the sulphide in an alkaline solution, just as described in the case of tin, except that in the case of the solution in the alkaline sulphide, it is advisable to repeat the process. Potassium ferrocyanide precipitates gallium from a solution containing antimony, but the precipitate contains traces of the latter metal, which must be removed by dis- solving it in potash and reprecipitating by addition of a large excess of hydrochloric acid and a few drops of ferrocyanide.Salts of man- ganese can be used to separate traces of gallium from antimony, just as in the case of tin. Precipitation of the antimony by zinc does not answer well. E. H. R. Compouhds of Tin Disulphide and Diselenide. Compt. rend., 9 5, 641- 644) .---Potassiunz thiostannafe, By A. DITTE SnS,,K2S,3H,0, forms transparent colourless or very sIightly yellow prisms, very solu- ble in water, but decomposed by a large quantity of that liquid, with precipit,ation of hydrated stannic sulphide.It is obtained by dissolv- i n g stannous sulphide in a solution of potassium polysulphide, or more easily by boiling a concentrat,ed solution of potassium mono-INORQANIC CBERIISTRY. 157 sulphide with the theoretical amount of sulphur and a slight excess of tin, and evaporating the clear yellow solution by boiling or in a vacuum. Potassium seZen,iothiostarLi~,ate, SnSe2,K2S,3H20, is obtained by substituting selenium for sulphur in the preceding operation. It forms yellow octohedrons, very soluble in water, with formation of a rose or red solution, according to the degree of concentration. Bokh the solution and the crystals alter when exposed to air, black crystal- line selenium being liberated. SnSez,K2Se,3Hz0, is obtained by saturating a solution of potassium selenide with tin diselenide and evaporating in a vacuum.It forms crystals which alter rapidly when exposed to air. Sodium thiostnnnate and sodium seleniostannate are obtained in the same way as the corresponding potassium compounds, and have similar properties. Ammomiurn thio- stannate, 3Sn Sp, (NHd)zS,6H,0, is obtained by heating sheet tin with a solution of ammonium polysalphides, and evaporating the clear yellow liquid in a vacuum over potassium hydroxide and sulphuric acid. It forms yellow plates, which are decomposed by water with sepnration of hydrated stannic sulphide. The crystals a1 ter quickly even in a vacuum, losing water and acquiring a superficial violet tint. When gently heated, t$hey lose water, ammonium sulphydrate, and sulphur, a residue of tin salphide being left.Ammunium seleniotlzio- stnnnate, 3SnSe2,(NH4),S,3H,0, is obtained by treating an excess of hydrated tin diselenide with a concentrated solution of ammonium sulphydrate in the cold, filtering, and evaporating the red filtrate in a vacuum over potassium hydroxide and sulphuric acid. It forms yellowish-red plates, less stable than the preceding compound. The crystals are decomposed by water, with separation of red flakes of tin diselenide. Tellurium dissolves in boiling concentrated solutions of the alkaline sulphides, but yields no compounds with tin analogous to those already described. Tellurium is deposited in crystals when the solu- tion cools. Barium tkiostannate, SnSz,BaS,8H20, obtained by dissolving tin in a boiling solution of barium polysulphides and evaporating the solu- tion in a vacuum, forms transparent citron-yellow crystals, soluble in cold water without decomposition.From this solution dilute acids immediately precipitate yellow fitannic sulphide. Strontium thio- stannate, SnS2,SrS, 12Hz0, produced in a similar manner, forms bulky, transparent, colourless prisms, soluble in cold water without decom- position. Ca Zeium tlAmkmanate, SnS2,2CaS, 14H20, also obtained in a similar manner, forms transparent citron- yellow crystals, soluble in cold water without decomposition. Potassium se Ze?aiostunnate, C. H. B. Preparation of Lead Dioxide. By A. FEHRMANN (Bey., 15, 1882). -A concentrated solution (60-70" C.) of lead chloride is treated with solution of chloride of lime until a filtered sample does not show further separation of the dioxide ; the latter is then filtered off and washed out of contact with air.Lead dioxide so prepared is quite pure and nearly black, and keeps best in the moist state. When158 ABSTRACTS O F CHEMICAL PAPERS. prepared from sugar of lead it is not so cheap, and liable to undergo decomposition from the impurities of the lead acetate. Barium Compounds of Bismuth Peroxide. By I. MESCHTCHER- SKY (Journ. Russ. Chem. SOC., 1886, 280--281).-0n fusing a mixture of bismuth trioxide, baryta, and potassium chlorate, a black mass is obtained, which, when washed with water, begins to decompose, with evolution of oxygen. The black or reddish-brown residue remaining after the extraction of soluble salts by water consists of compounds of bismuth peroxide with barium, and decomposes hydrochloric acid with evolution of chlorine.Analogous compounds with calcium or magne- sium could not be obtained. If the above compound has been well washed with water, it does not lose oxygen under pure water, but decomposition takes place suddenly in contact with barium peroxide or solution of potassiiim chlorate. Fusion with potassium nitrate gives rise to compounds containing more oxygen, e.g., one of the following composition : 14Ba0, 5Bi205, S O 2 , 3H20. A Hydrate of Molybdic Acid. By F. PARMENTIER (Compt. rend., 95, 839--841).-The author has examined the yellowish crystalline substance which always separates after a time from solutions of alka- line molybdates in nitric acid. He finds that it contains no nitrogen, b u t is a hydrate of molybdic acid, having the composition Mo03,2H20.This substance is not formed in hydrochloric acid solutions of alkaline molybdates, It is very sparingly soluble in water, a litre dissolving only 0.5 gram a t 15". The crystals are efflorescent, and lose half their water in a vacuum over sulphuric acid. Heated to 200°, they lose all their water, and leave a white residue which sublimes completely on further heating. E. H. R. J. K. C. B. B.INORGANIC CHEMISTRY.I n o r g a n i c Chemistry.149Action of the Galvanic Current on Chlorides and Chlorates.By A. LIDOFF and W. TICHOMIROFF (Jour. Russ. Chern. Xoc., 1882, 341-349).-In a former paper (Abstr., 1882, 925) the authors have foundthat by the action of the electric (galvanic) current on a solution ofchlorides, hypochlorites are first formed, which, by an elevation of tem-perature, are converted into chlorates.But later on they found thateven a t the ordinary temperature, as soon as the solution becomesmore concentrated, hjpochlorites are converted into a mixture of chlo-rates and chlorides by the sole action of the current. They propose toapply this process to the manufacture of chlorates, more especially ofthe sodium salt, which is difficult to prepare in the ordinary way. O150 ABSTRAC’J S OF CHElllICAL PAPERS.acting with a current of a powerful Gramnie machine for 25 hours, ona solution of 400 granis of potassium chloride in 900 grams of water,210 grams of crystals, containing 70 per cent.of chlorate, wereobtained. The crystals contain, together with potassium chlorate, aconsiderable quantity of the chloride, and 5-12 per cent. of carbonfrom the electrodes. As soon as about 30 per cent. of the originalsalt is transformed into the clllorate, the positive electrode is moststrongly corroded, and no further separation of the crystals from theliquid takes place.If, instead of a high tension-current (2 electrodes) a dividedcurrent (8 electrodes) is employed, far less chlo~ide is converted intochlorate in tlie same space of time. The corrosive action of the liquidon the positive electrode is due to its oxidation by the oxygen of thepotassium chlorate, which is reduced to chloride (about 30 per cent.in 10 hours). For this reason, potassium chloride csnnot be com-pletely converted into chlorate, but a limit is reached after some time,when the energy of formation of potassium chlorate from the chloridebecomes equal to the energy of its decomposition.Electrodes ofanother material than carbon cannot be used for the conversion ofchlorides into chlorates, for all metals, even platinum, are corroded bythe chlorine which is set free at the same time. If, however, a solu-tion of potassium chlorate be electrolysed by means of platinumelectrodes, 110 chlorine, but ozone, is evolved on the positive pole. Attlie same time crystals of potassium perrhlorate separate from theliquid, and oiily traces of potassium chloride are formed at the sametime. I n this respect the act’ion of electricity on potassium chlorateis analogous to the action of heat on the same salt; in both casesoxygen is evolved, and potassium chlorate and chloride are formed,although the proportion in the quantities of these two salts is widelydifferent.The corrosion of carbon in the above case is due t o theaction of ozone, and the products of this action in presence of waterOxidation of Carbonic Oxide by Palladium Hydride andOxygen. By M. TRAUBE (Ber., 15, 2325--2326).--The changeswhich occur when carbonic oxide is converted into the anhydride bythe action of palladium hydride snd oxygen are as follows:-In thefirst place palladium hydride and moist oxygen form hydrogen per-oxide, and this compound in presence of metallic palladium oxidisesare mellitic and hydromellitic acids.B. R.carbonic oxide t o carbonic anhydride. w. c. w.Compressibility of Nitrogen. By E. H. AMAGAT (Co?npt. rend., 95,638--641).-A summary of t,he experiments made by Cailletet and bythe author with a view to determine the compressibility of nitrogen.Curves are given representing the results obtained by both observers.The author considers Cailletet’s method inferior i n accuracy to his own.The curve representing Cailletet’s results is rery irregular, whilst t h a trepresenting the author’s results is perfectly regular.Black Phosphorus. By P. THENARD (Compt. rend., 95, 409--4110).-A quantity of phosphorus was being cast in the usual way, and a,C. H. BIWORGAXIC CHEMISTRY. 151dozen sticks had been obtained of the usual colour, when the thirteenthsuddenly blackened atl the moment of congelation.Subsequently asecond stick, about 20 cm. long, blackened for about 4 cm. of itslength, the remainder being unchanged. A portion of the black phos-phorus was brought in contact with ordinary phosphoriis, in a state ofsuperfusion a t 10" under ice. I n the first experiment, the white phos-phorus became black on solidifying, but the s3me effect was not againobtained once in more than twenty experiments under precisely similarconditions. The specimen of black phosphorus became white whenfused, and remained white if cooled suddenly, but if super-cooled itagain became black when brought in contact with either black orwhite phosphorus. Black phosphorus dissolves almost entirely incarbon bisulphide, leaving a slight yellow residue apparently consist-ing of amorphous phosphorus.Neutral Phosphates of the Alkalis.By E. FILHOL andSENDERENS (Bied. Centr., 1882, 641).-Careful neutralisation of phos-phoric acid with sodium hydroxide results in the formation of amixture which reacts on red or blue litmus ; crysbals obtained fromthe solution contain 1 mol. of the mono- and 1 mol. of the di-sodiumphosphate. Neutral potassium or ammonium phosphates have notbeen obtained, whilst potassium sodium and sodium ammonium phos-phates crystallise readily.Calcium Chloride. By A. WEBER (Bey., 15, 2316--2317).-Calcium chloride dried a t 180-200" is practically anhydrous. Itcontains from 0.12 to 0.24 per cent. of water and 0.047 per cent.ClaO.C. H. B.E. W. P.w. c. w.Properties of Pure Aluminium. By J. W, MALLET (Chern.News, 46, 178).-Sp. gr. a t 4" = 2.585 ; atomic vol., 10.45 ; sp. heat= 0.2253 between 0-100" ; atomic heat, 6.09" ; less fusible than thecommercial metal, and less easily acted on by alkalis and acids. It isnearly pure tin-white, with no bluish tinge, and has a lustre like thatof tin. It is more malleable and less easily hardened by hammeringthan ordinary aluminium. E. W. P.Decomposition of Phosphate by Potassium Sulphate atHigh Temperatures. By €3. GRANDEAU (Comnpt. rend., 95, gal--922).-Debray (BUZZ. SOC. Chim., 3, 251) has shown that on heahingto a high temperature aluminium phosphate with excess of an alka-line sulphate, an alkaline phosphate and crystallised aluminium areobtained.This reaction has been used by Derdme (Compt. r e d , 89,92.5, and this Journal, 38, 286) for the separation of phosphoric acidfrom iron and aluminium. To determine the conditions of the re-action, a mixtiire of aluminium phosphate and potassium sulphntewas heated for several hours in a platinum crucible. At a hightemperature, not only is alumina formed, but also a crystalline doublephosphate of aluminium and potassium. At a still higher tempe-rat me, the quantity of alumina increases, but even on very vigorousheating it is impossible to completely decompose the double phos152 ABSTRACTS OF CHEMICAL PAPERS.phate. Similar results were obtained by subst,ituting phosphates ofglucinum, cerium, and didymium for aluniinium phosphate.Butwhen phosphates of calcium, magnesium, &c., were used, the doablephosphate alone was formed under the conditions of the experiment ;whilst with nickel and cobalt; phosphates results similar to those withaluminium phosphates were obtained. With chromium and uraniumphosphates, the final products are potassium chromate and uranate.The investigation is being continued.Determination of the Equivalent of Thorium. By L. I?.NILSON (Compt. j-end., 95, 729--730).-As a mean of ten determiua-tions, the author finds 58.10 to be the equivalent of thorium, that ofoxygen being 8, and of sulphur 16. H e makes the atomic weight,therefore, to be 232.36. These results were obtained by calcining twodifferent specimens of the sulphate, a aud b.Specimen b was obtainedfrom the mother-liquors of a. The first six determinations were madeon specimen a, which contained nine molecules of water. I n thesesix experiments the author used the hydrated salt, because the dehy-drated substance was found to be extremely hygroscopic. In theother four experiments this was impossible, because specimen b (tliecrystals of which differed from those of specimen a ) contained onlyeight molecules of water, and absorbed water during the process ofweighing. I n the latter four experiments, therefore, the anhydroussulphate was used. The two specimens gave practically identicalresults.L. T. 0's.Sulphate a.Water. SO3. Thoa. Equiv. At. Wt.Mean of six experiments 27.573 27.336 45.091 58.11 232.43Sulphate b.Mean of four experiments - 37.703 62.297 58.09 232.30The author concludes by drawing attention to the wide diwrepanciesin the values of the atomic weight as determined by other chemists.E.H. R.Metallic Thorium. By L. F. NILSON (Conyf. rend., 95, 727-729).-The author obtains metallic thorium by heating with sodiumi n an iron crucible a mixture of the anhydrous double chloride ofthorium and potassium with sodium chloride. After treatment of theresidue with water, metallic thorium remains as a heavy greyishbrilliant powder. Examined under the microscope, the powder isseen to con\ist of minute crystals, more or less brilliant and united ingroups. The metal is brittle and almost infusible. The powderassumes a metallic lustre under pressure, is unalterable in air up to120", takes fire in air or ox)-gen below a red heat, and burns withdazzling brilliancy, leaving a perfectly white oxide.It takes firewhen heated with chlorine, iodine, bromine, and sulphur. It is notattacked either by hot or by cold water. Dilute sulphuric acid causesa feeble evolution of hydrogen in the cold, becoming more rapid onthe application of heat, but the metal is attacked slowly; hot con-centrated sulphuric acid also acts but slowly, disengaging sulphurouINORGANIC CHEMISTRY. 153anhydride. Nitric acid, whether hot or cold, strong or dilute, exertsno sensible action. Dilute hydrochloric acid dissolves the metal slowlyeven when heated, but concentrated acid attacks it very easily.Aquaregia acts like hydrochloric acid. The metalobtained by hhe author behaves, therefore, exactly like that obtainedby Berzelius. The mean sp. gr. is nearly 11; this is much highert,han that found by Chydenius (7.657 to 7.795) : hence the specimenobtained by the latter chemist must have contained much impurity,probably derived from the glass tube in which it was preptred. Thedensities of two different specimens of the oxide were 10.2207 and20.2198 respectively. These numbers are again much higher thanthose obtained by Berzelius, Damour, and Chydenius (9.402, 9.366,9.288). Admitting that the metal is quadrivalent, the atomic volumeis 21.1. This number coincides with the atomic volume of zirconium(21*7), cerium (21*1), lanthanum (22.6), and didymium (21.5) ; andthis fact serves to confirm the author’s opinion that the rare earth-metals form a series of quadrivalent elements.Magnesia Alba.By R. KRAUT (Arch. Pharm. [ 3 ] , 20, 180-187).-In this criticism of Beckurts’ paper on the composition of magnesiaaZbu (this vol., p. 13), the author shows that analytical errors have creptin, as no direct estimation of the water lost by heating was made,&c.; the formula proposed by Beckurts therefore is incorrect, andthe original formula 5Mg04C02,Hz0, as proposed by Kraut, is theright one; also by boiling for some time, the composition may bealtered to 4Mg0,3COZ,6HzO, but never to 7Mg0,5C02.Separation of Gallium. By L. DE BOISBAUDRAN (Cowzpt. Tend.,95, 410-413 ; 503-506.See also Abstr., 1882, 897, 1323).--FromIndium .-Precipit#ation of the gallium by potassium ferrocyanide, inpresence of hydrochloric acid, is to be recommended only when it isrequired to separate a little indium, together with other metals, suchas aluminium and chromium. The following is the only trustworthymethod :-The moderately concentrated solution is boiled for someminutes with a slight excess of potassium hydroxide ; the precipitatedindium hydroxide retains small quantities o€ gallium, which may beremoved by a repetition of the process. The alkaline solutioas containonly very slight traces of indium ; to remove these, hydrochloric acidis added in slight excess, and the gallium and indium are precipitatedtogether by boiling with an excess of ammonia, or better, by means ofcupric hydroxide.The gallium and indium chlorides are then convertedinto sulphates; the slightly acid solution mixed with a quantity ofammonium sulphate rather more than sufficient to convert the galliuminto alum is evaporated to small bulk, and, after cooling, mixed withfour or five times its volume of alcohol of 70 per cent. Gallium alumis thus thrown down as a crystalline powder, which is washed once ortwice with alcohol, dissolved in warm water containing a minute quan-tity of sulphuric acid, and reprecipitated. By several repetitions oftlhis process, the gallium is obtained in the form of alum, free fromindium. The alcoliolic washings, which contain small quantities ofgallium and indium, are evaporated to small bulk, the metals pre-Alkalis ha.ve no action.E.H. R.E. W. P.VOL. XLIV. 154 ABSTRACTS OF CHEXICAL PAPERS.cipitated by boiling with ammonia or by means of cupric hydroxide,the precipitate dissolved in hydrochloric acid, and the solution boiledwith a slight excess of potassium hydroxide; a small quantity ofindium hydroxide is thus obtained free from gallium. The galliuinremaining in solution may be separated as alum. Usually the indiumdissolved by tlie potash is removed by four crystallisations of theammonium-gallium alum ; but if the gallium hydroxide contains morethan 4 per cent. of indium hydroxide, seven or eight crystallisationsare necessary.Froin CadnLiurrz. - In presence of much free hydrochloric acid,cadmium is not completely precipitated by hydrogen sulphide, whilst ifthe solut'ion is but feebly acid, the cadmium sulphide contains gallium.The somewhat acid solution is treated with hydrogen sulphide, theprecipihate redissolved in hydrochloric acid, the solution diluted, andagain treated with hydrogen sulphide.By two or three repetitionsof the process, the greater part of the dadmium is obtained as sulphidefree from gallium. The filtrates which contain the gallium, mixedwith a little cadmium, are evaporated to expel excess of acid, dilutledwith water, and saturated with hydrogen sulphide. The cadmiumsulphide thus thrown down is reprecipitated two o r three times.Excess of boiling potassium hydroxide precipitates cadmium oxide,and dissolves gallium hydroxide ; the cadmium oxide is redissolvedand again precipitated, in order to separate the last traces of gallium.If the amount of cadmium is large, this process must be repeatedfour or five times.The alkaline solution which contains gallium anda small quantity of cadmium is slightly acidified wjth hydrochloricacid, and the gallium precipitated by means of cupric hydroxide, thefiltrate is mixed with ammonium acetate, and treated with hydrogensulphide, which throws down copper and cadmium : this precipitateis dissolved in aqua regia, evaporated with hydrochloric acid, andhydrogen sulphide is passed into the strongly acid solution ; coppersulphide is thus precipitated, whilst cadmium remains in solution.The following methods are more rapid:-(1.) The solution, whichmust contain a sufficient quantity of ammonium chloride, is boiled withexcess of ammonia: cadmium then remains in solution, and galliumhydroxide is precipitated ; this precipitate is redissolved and againprecipitated, in order to remove the last traces of cadmium.(2.) Gal-lium is precipitated by means of potassium ferrocyanide in a solutionwhich contains at least one-third of its volume of strong hydrochloricacid ; the cadmium ferrocyanide remains in solution. (3.) Cuprichydroxide precipitates gallium on gently warming ; the precipitateretains small quantities of cadmium, which may be removed by arepetition of the process. (4.) When it is necessary to remove ironas well as cadmium, the warm solution is reduced by metallic copperand then mixed with a slight excess of cuprous oxide: the pre-cipitated gallium hydroxide contains traces of cadmium, which maybe removed by reprecipitation.The reactions with cupric hydroxide, and with metallic copper andcuprous oxide, are the most satisfactory.Fronz Ur.cr.nium.-(l.) The boiling slightly acid solution of thechloride is treated with cupric hydroxide ; the precipitate is then disINORGANIC CHEMISTRY.155solved in hydrochloric acid, diluted, and again precipitated with cuprichydroxide, the treatment being repeated four or five times. (2.) Ifit is required to separate iron a t the same time, the solution is reducedwith metallic copper, and then boiled with excess of cuprous oxide;tbe precipitate is redissolved and the treatment repeated about fourtimes.Neither of these methods is affected by the presence of con-siderable quantities of alkaline salts. (3.) The slightly acid solutionof the chloride is mixed wit11 an excess of acid ammonium acetate,zinc chloride free from gallium added, and the liquid is treated withhydrogen sulphide : the zinc sulphide formed carries down the gallium,whilst the uranium remains in solution. The precipitate is difficult towash and must be redissolved in hydrochloric acid, and again preci-pitated in presence of an acetate. The zinc and gallium are separatedby the method previously described. (4.) The uranium is preci-pitated in the form of alkaline uranate by adding a slight excess ofpotassium hydroxide, the precipitate dissolved in hydrochloric acid,and again precipitated.To remove traces of uranium from the fil-trate, the latter is slightly acidified with hydrochloric acid, and boiledwith cupric hydroxide. When the potassium hydroxide contains car-bonate, the quantity of uranium in the filtrate is increased.From Lead.-(1.) The slightly acid solution of the chloride is boiledwith cupric hydroxide, the last trace of lead being removed by a secondprecipitation. The reagents must be free from sulphuric acid. Thismethod is very accurate, and may be used to separate gallium sulphat,efrom the minute quantities of lead which remain in solution afterprecipitation of lead as sulphate. (2.) The solution of chloride o rsulphate is boiled with metallic copper and then with cuprous oxide,traces of lead being removed by a second precipitation.If a solutionof the chlorides is used, the presence of sulphuric acid in the reagentsmust be avoided. (3.) The moderately acid solution is treated withhydrogen sulphide, the filtrate evaporated almost to dryness to expelfree acid, diluted with water, and again treated with hydrogen sul-phide. If sulphuric acid is present, i t should be partially neutralisedwith ammonia. To extract the gallium retained by the lead sulphide,the latter is treated with strong hydrochloric acid, alcohol is added, theliquid is filtered, and the filtrate, after evaporation to expel water andalcohol, is diluted, and saturated with hydrogen sulphide. (4.) Thegallium is then precipitated as ferrocyanide by means of potassiumferrocyanide in a solution containing one-third or one-fourth its volumeof stroug hydrochloric acid.A second precipitation is sometimesnecessary in order to remove the last traces of lead. (5.) The solu-tion is mixed with sulphuric acid, and two volumes of alcohol of 90"added; the precipitated lead sulphate, after being washed with alcoholacidified with sulphuric acid, is suspended in dilute hydrochloric acidand treated with hydrogen sulphide; and the filtrate, after beingboiled to expel excess of the gas, is treated with cupric hydroxide toprecipitate the last traces of gallium. The gallium in the alcoholicsolutions is precipitated by cupric hydroxide, after boiling off thealcohol. (6.) The solution is mixed with twice its volume of 90 percent. alcohol ; a slight excess of hydrochloric acid is added, and theprecipitated lead chloride is washed with acidulated alcohol, whereby itnz 156 ABSTRACTS OF CEEMICAL PAPERS.is obtained free from gallium.The filtrate is evaporated to smallbulk, the nitric acid removed, and the liquid treated either with hydro-gen sulphide, with cupric hydroxide, or with metallic copper andcuprons oxide. C. H. B.Separation of Gallium. By L. DE BOISBAUDRAN (COW&re12d., 95, 703-706) .--Xepayation from Tin.-Sulphide of tin pre-cipitated from a hydrochloric acid solution containing tin andgallium, retains none of the latter metal. On adding hydrochloricacid in excess to a solution of the sulphides of tin and gallium in analkaline sulphide, sulphide of tin free from gallium is thrown down.Salts of manganese added to a solution of the mixed sulphides in ana1 kaline sulphide give a precipitate of manganese snlphide, whichcontains gallium: this makes it possible to extract the latter metalfrom large quantities of sulphide of tin.The author draws atten-tion to one or two points, of which notice must be taken in analysingmixtures containing gallium. A solution containing even a con-siderable amount of gallium is not precipitated by potassium ferro-cyanide if a large amount of stannic chloride is present; so that tinmust be separated before attempting to estimate gallium by ferro-cyanide. Tin and gallium, when alloyed, cannot be completelyseparated by nitric acid, because the metastannic acid formed retainssensible quantities of gallium, even after prolonged washing withnitric acid.It is difficult to obtain a complete separation of galliumand tin by precipitating the latter metal with zinc, because in a solu-tion strongly acid the tin is not entirely thrown down, and in a nearlyneutral solution a certain quantity of gallium becomes insoluble.Finally, tin dioxide, precipitated by boiling with sulphuric acid,retains much gallium.Xeparation from Antimony.-Gallium may be separated from anti-mony by sulphuretted hydrogen, or by addition of an acid to a solutionof the sulphide in an alkaline solution, just as described in the case oftin, except that in the case of the solution in the alkaline sulphide, itis advisable to repeat the process.Potassium ferrocyanide precipitatesgallium from a solution containing antimony, but the precipitatecontains traces of the latter metal, which must be removed by dis-solving it in potash and reprecipitating by addition of a large excess ofhydrochloric acid and a few drops of ferrocyanide. Salts of man-ganese can be used to separate traces of gallium from antimony, justas in the case of tin. Precipitation of the antimony by zinc does notanswer well. E. H. R.Compouhds of Tin Disulphide and Diselenide.Compt. rend., 9 5, 641- 644) .---Potassiunz thiostannafe,By A. DITTESnS,,K2S,3H,0,forms transparent colourless or very sIightly yellow prisms, very solu-ble in water, but decomposed by a large quantity of that liquid, withprecipit,ation of hydrated stannic sulphide. It is obtained by dissolv-i n g stannous sulphide in a solution of potassium polysulphide, ormore easily by boiling a concentrat,ed solution of potassium monoINORQANIC CBERIISTRY.157sulphide with the theoretical amount of sulphur and a slight excess oftin, and evaporating the clear yellow solution by boiling or in avacuum. Potassium seZen,iothiostarLi~,ate, SnSe2,K2S,3H20, is obtainedby substituting selenium for sulphur in the preceding operation. Itforms yellow octohedrons, very soluble in water, with formation of arose or red solution, according to the degree of concentration. Bokhthe solution and the crystals alter when exposed to air, black crystal-line selenium being liberated.SnSez,K2Se,3Hz0,is obtained by saturating a solution of potassium selenide with tindiselenide and evaporating in a vacuum.It forms crystals whichalter rapidly when exposed to air. Sodium thiostnnnate and sodiumseleniostannate are obtained in the same way as the correspondingpotassium compounds, and have similar properties. Ammomiurn thio-stannate, 3Sn Sp, (NHd)zS,6H,0, is obtained by heating sheet tin witha solution of ammonium polysalphides, and evaporating the clearyellow liquid in a vacuum over potassium hydroxide and sulphuricacid. It forms yellow plates, which are decomposed by water withsepnration of hydrated stannic sulphide. The crystals a1 ter quicklyeven in a vacuum, losing water and acquiring a superficial violet tint.When gently heated, t$hey lose water, ammonium sulphydrate, andsulphur, a residue of tin salphide being left.Ammunium seleniotlzio-stnnnate, 3SnSe2,(NH4),S,3H,0, is obtained by treating an excess ofhydrated tin diselenide with a concentrated solution of ammoniumsulphydrate in the cold, filtering, and evaporating the red filtrate in avacuum over potassium hydroxide and sulphuric acid. It formsyellowish-red plates, less stable than the preceding compound. Thecrystals are decomposed by water, with separation of red flakes of tindiselenide.Tellurium dissolves in boiling concentrated solutions of the alkalinesulphides, but yields no compounds with tin analogous to thosealready described. Tellurium is deposited in crystals when the solu-tion cools.Barium tkiostannate, SnSz,BaS,8H20, obtained by dissolving tinin a boiling solution of barium polysulphides and evaporating the solu-tion in a vacuum, forms transparent citron-yellow crystals, soluble incold water without decomposition. From this solution dilute acidsimmediately precipitate yellow fitannic sulphide.Strontium thio-stannate, SnS2,SrS, 12Hz0, produced in a similar manner, forms bulky,transparent, colourless prisms, soluble in cold water without decom-position. Ca Zeium tlAmkmanate, SnS2,2CaS, 14H20, also obtained ina similar manner, forms transparent citron- yellow crystals, soluble incold water without decomposition.Potassium se Ze?aiostunnate,C. H. B.Preparation of Lead Dioxide. By A. FEHRMANN (Bey., 15, 1882).-A concentrated solution (60-70" C.) of lead chloride is treated withsolution of chloride of lime until a filtered sample does not showfurther separation of the dioxide ; the latter is then filtered off andwashed out of contact with air. Lead dioxide so prepared is quitepure and nearly black, and keeps best in the moist state. Whe158 ABSTRACTS O F CHEMICAL PAPERS.prepared from sugar of lead it is not so cheap, and liable to undergodecomposition from the impurities of the lead acetate.Barium Compounds of Bismuth Peroxide. By I. MESCHTCHER-SKY (Journ. Russ. Chem. SOC., 1886, 280--281).-0n fusing a mixtureof bismuth trioxide, baryta, and potassium chlorate, a black mass isobtained, which, when washed with water, begins to decompose, withevolution of oxygen. The black or reddish-brown residue remainingafter the extraction of soluble salts by water consists of compounds ofbismuth peroxide with barium, and decomposes hydrochloric acid withevolution of chlorine. Analogous compounds with calcium or magne-sium could not be obtained. If the above compound has been wellwashed with water, it does not lose oxygen under pure water, butdecomposition takes place suddenly in contact with barium peroxide orsolution of potassiiim chlorate. Fusion with potassium nitrate givesrise to compounds containing more oxygen, e.g., one of the followingcomposition : 14Ba0, 5Bi205, S O 2 , 3H20.A Hydrate of Molybdic Acid. By F. PARMENTIER (Compt. rend.,95, 839--841).-The author has examined the yellowish crystallinesubstance which always separates after a time from solutions of alka-line molybdates in nitric acid. He finds that it contains no nitrogen,b u t is a hydrate of molybdic acid, having the composition Mo03,2H20.This substance is not formed in hydrochloric acid solutions of alkalinemolybdates, It is very sparingly soluble in water, a litre dissolvingonly 0.5 gram a t 15". The crystals are efflorescent, and lose half theirwater in a vacuum over sulphuric acid. Heated to 200°, they lose alltheir water, and leave a white residue which sublimes completely onfurther heating. E. H. R.J. K. C.B. B

ISSN:0368-1769    

DOI:10.1039/CA8834400149

出版商:RSC    

年代:1883

数据来源: RSC