摘要:

General and Physical Chemistry .BAILEY Gt.H.Absorption’-spectra of the Rare Earths.LEA M.C.Action of Light and Reducing Agents on Silver Salts For-mation of Photo-salts.SCHRAMM J. and I.ZAERZEWSKI.Spectrum Researches on the Energyof the Action of Bromine on Aromatic CompoundsMOSEP J.Increase of Photo-electric Currents.BRAUN F.Electric Properties of Rock Salt.JAHN H.Validity of Joule’s Law for Electrolytes..PFEIFFEE E. .RICHARZ F.Conductivity of Pure Water and its Temperature Co-efficients.Formation of Hydrogen Peroxide a t the Anode during theElectrolysis of Dilute Sulphuric Acid.MIESLER J.Electromotive Dilution Constants.SCHIFF R.Specific Heat of Liquid Carbon-compounds.GUNTZ.Heat of Formation of Zinc Ethyl.PUSCHL C.Highest Boiling Point of Pluids.PUSCHL C.Relation of Hydrogen to Marriotte’s Law.ISAMBEPT F.Compressibility of Solutions of k e s.DURHAM W.Solution.PICEEEING S.U.Solution.PICKERING S.U.Nature of Solution.BENDER C.Salt Solutions.Compressibility of dilute Stblt.Solu-tious and of Solid Sodium Chloride.KALLIE J.Water of Crystallisation of dissolved Cobalt Salts.IHMORI T.Condensation of Water Vapour by Solid Substances.DREYFVS.Rate of Oxidation of Carbon-compounds by Potassium Per-manganate.Relation between the Composition and the Absorption-HERTZ H.Influence of Ultra-violet Light on the Electric Discharge .PUSCHL C.RAMSAY W. and S.YOUNG .Relations of Gases to the Laws of Marriotte and Gay-LussacEraporation and Dissociation Coiitinuous.Change from the Gaseous to the Liquid State a t all TemperaturesRONTGEN W.C.and J.SCHNEIDER .GIBSON J.Laboratory Fittings.spectra of Organic Dyes.BOISBAUDRAN L.DE .Fluorescences with Well-defined Spectra.tivity of Selenium.FRIEDEICHS F.New Galvanic Batkry.STEEINZ F.Galvanic Polarisstion.Vapour.HELMHOLTZ H.v.Electrolysis of Water.VOGEL H.W.GERNEZ D..BELLATI M. and S.LUSSANA.Influence of Light on the Heat Conduc-KALISCHER S.Bffeat of Light on the Conductivity of Selenium.Rotatory Power of Solutions of Ammonium Molybdate .PALMIEBI L.Production of Electricity by the Con3ensation of Aqueousa dPAGE99GUBKIN J.Electrolytic Separation of the Metal on the Free Surface ofthe Solution of its Salt.YITZPATRICK T. C..GRINALDI G. P.Influence of a blagnetic Field on the ‘l‘h8rmoelectricProperties of Bismuth.RIQRI A.Rotation of Isofliermic Lines of Bismuth placed in a MagneticField.RIGHI A.Theimic Condiartivity of Bismuth in a Magnetic Field.CARDANI P.and F. TOMASINI.BARRETT W. F.New Form of Calorimeter.JOLY J.Specific Gravity Determination.MULLER-ERZBACH W.Dissociation of Copper Sulphate.SCHULZE R.Rate of Dissociation of Hydrated Salts.VELEY V. H.Interaction of Metals and Sulphuric Acid.MENSCHUTKIN N.Velocity of Formakion of Ethereal Salts.PRINGSHEIN E.Chemical Action of Light on a Mixture of Chlorine andHydrogen.WINKELBCANN A.Anomalous Dispersion produced by Glowing Vapours .KRUSS G. anti L. F. NILSON. Components of Rare Earth yielding Ab-sorption-spectra.BAILEY G. H.Components of Rare Earths yielding Absorption-spectra .E X N E ~ ~ V.Theory of Researclies on Contact-electricity.MOSER J.Resolution of Xlectromotive Forces of Galvanic Elements ink0their Differences of Potential.KOOSEN a.H.Propeyty of the Alkalis of increasing the E.M.F. of Zinc .TBAUBE M.Electrolytic Form2ttrion of Hydrogen Peroxide a t theA n o d e.HANPE W.Electrolytic Conduction of Halogen Compounds.LE CHATELIER H.Molecular Heats of Gases.TAMMAN G.Influence of Small Amounts of Impurity on the Vapour-tension of Liquids.MULLCR-ERZBACH W.Dissociation of Crystallised Lead Acetate andSodium Thiosulphate.BRAUN F.Relation between the Compressibilities of a Solution and of itsConstituent Parts.AMAQAT E. H.Dilatation and Compressibility of Liquids.ISAMBERT F.Compressibility of ttn Aqueous Solution of Etliylamiue .MEPER L.Oxygen-carriers.BERTHELOT. Explosive Uecomposition of Picric Acid and of her Nitro-conipounds.JAGER G.Relative Size of Molecules calculated from the Electric Con-dactivity of Salt Solutions.LOSSEN W.Representation of Atoms in Space.BOISBAIIDRAX L.DE.Degree of Oxidation of Chromium and Manganesein Fluorescent Compounds.GRIMBRRT L.Rotatory Dispersion.MIESLER J.Distribution of Electromotive Force in the Cells of BatteriesOSTWALD W.Electrochemical Studies.MENSCHI~G J. and V. MEYER. Pyyometer.YICKERING 5. U.Constancy in the Heat prdduced by the Reaction ofcertain Salts on each other.STOHMAX” F. ,P. RODATZ,and W. HERZBERG. Heat Equivalents ofBenzoyl Compounds.DOBRINER P.Boiling Points and Specific Volumes of the Normal FattyEthers.DOBRINER P.Specific Volumes of Normal Alcoholic Iodides.YINNETTB J.Boiling Points and Specific Volumes of Phenols and theirEthers.LOSSES TI-.Boiline Points and SDecific Volumes.Action of the Solvent in Electrolytic ConductionSpecific Heat of Superfused Water .FABRE C.Specific Heat of Tellurium.PAGE329CONTEX'I'S .SCHALL C.Estimation of Vapour-densities.MALFATTI H.and P.SCHOOP.Determination of Vapour-densities atLow Prewire.ARRHENIUS S.Viscosity of Dilute Aqueous Solutions.FROWEIN P.C.F.Dipsociation of Hydrated Salts.O~TWALD w.Nature of Chemical Affinity.URECH F.Influence of the Rate of Pressure on Chemical Change.SARRAU and VIEILLE.Chemical Equilibrium of Homogeneous GaseousSystems.ARRHENIUS S.Influence of Neutral Salts on the Rate of Hydrolysis ofEthyl Acei ate.KONOWALOFF I.Decomposition of Liquid Terti.Lry inigl Acetate.SPRING W. iInd J.H.VAN'T HOFF.Cheiuiual Dt.composition producedby Pressure.LEHMANN C.Crystallisation of Mixtures.RUDORFF F.Constitution of Solutions.GNIEWOSZ S. and A.WALFISZ.MEYER V.Lecture Experiments with Nitrogen Chloyide.GLADSTONE J.€I.Dispersion Equivalents.SELMONS F.Action of Sulphurous Acid on Periodic Acid.Absorption of Bases hp Petroleum .GR~NWALD A.KKUSS G. and L.NILSON .Mathematical Analgsis of the Spectra of Magnesium andCarbon.Components of the Rare Earths yieldingAbsorption-spectra.ULJANIN W.v.Contact Electricity.FROMXE C.Maximum Galvanic Polarieation.TEOMPSON S.P..MIESLEB J..MEYER G.Thermal Alteration in a Daniel1 Cell and in an Accumulator .COHN E.and L.ARONS.Determination of the Specific Inductive Capacityof Conducting Liquids.C O ~ N E. and L.ARONS.Conductivity and Specific Inductive Capacity .Electromotive Forces of Metals in Cpanldc SolutionsResolution of the Electromotive Forces of Galvanic Cells'I'OMASZEWSKI F.Specific Inductive Capacity of Liquids.SCHUSTER A.Electric Discharge through Gases.KARR F.Conductivity of Electricity through Gases.JAGER G.Electrical Conductivity of Solutions of Neutral Salts.JABER G.Comparative Properties of the Elect8ricstl Conductivities of SaltSolutions.HARTWIG K.Electrical Conductivity of Solutions.THOMSON J.J. and H.F.NEWALL.Electric Dischargethe Heat' Conductivity of Bismuth..ETTINGSHAUSEN A.v.RICHARDS T.W.FAY I.W.~NUSTROM K.Influence of Magnetic E'orces on the Nature ofHeat produced by the Reaction of Silver Nitrate withSolutions of Metallic Chlorides.Relation between the Heats of Formation of Chlorides andSulphates in Aqueous Solution.Alteration in the Volume acd Density of Liquids by theTAMMANN G.Dynamical Method of Determining Vapour Pressure .SABATIER P.Rate of Transformation of Metaphosphoric Acid.Absorption of Gases.BREMER G.J.W.Differential Tonometer.BRAUN F.Compressibility of Rock-salt.VAN'T HOFF J.H.WISLICENUS J.The Position of Atoms in Space.BAZAROFF A.The Atomic Weights of the Elements.Point of Transition and Point of Fusion.MEFER V.Raoult's Method of Determining Molecular Weights.AUWERS I.Application of Raoult's Method for Determining MolecularWeights.BECKMA" E.Ieonitroso-compounds.VAN DER PLAATS J.D.Desiccation of Gases. a 9VPAGE400vi CONTENTS .YOUNQ S.Delicate Thermometer for Lecture Purpose-.LEPSIUB B.Lecture Experiment for Demonstrating tne Valency ofMetals.KETTELER E.Refraction of Liquids between Wide Limits of Tempera-ture.WYSS a.H.v.Determination of the Rotatory Dispersion of an ActiveSubstance.LOVE E.F.J.Comparing Spectra.STENQER F.Modifications of the Absorption Spectrim of a Substance .BOISBAUDRAN L.DE .Fluorescent Mixtures.STREINZ F.Galvanic Polarisation.ARRHENIUS S.Conductivity of Illumined Air.BOUTY E.Molecular Conductivity of Fuming Nitric Acid.GRAY T.Electrolysis of Copper.TOYLINSON H.Recalescence of Iron.HEMPEL IT.Evaporation of Liquids.REISSMANN A.Bumping during Distillation.AUBEL E.v.Electrical Resistance of Bismuth and its Alloys.ETTINGSHAUSEN A.v.and W.NERNST.Thermal and Electrical Behariourin the Magnetic Field of some Bismuth Tin Alloys.PUSCHL C.Relation of Bases to Mariotte’s Law a t High Temperatures .TAYLOR A.B..RONTGEN W.C. and J.SCHNEIDER.Compressibility of Water. Easy Method of finding the Sp.Gr.of Liquids .ETARD A.Decrease in the Solubility of Sulphates.LE CHATELIER H.Laws of Chemicnl Equilibrium.MEYER V. and E.RIICCKE.The Carbon-atom and ValencyARMSTRONG H.E.Valency.HEYES J.F.Tetravalency of Oxygen.Hypothesis.Weighte by Raoult’s Method.OETTINQEN A.v.and A.v.GERNET.Explosion of Water Gas.AUWERS K. and V.MEYER.Investigation of the Second Van’t HoffHOLLEYANN A.F.Simple Procedure for the Determination of MolecularBRRTHELOT.Ancient Process for making Gems and Glasses PhosphorescentLIVEING G.D. and J.DEWAR.DESLANDRES H.Wave-lengths of two Red Lines in the Spectrum ofPotassium.DESLANDRES H.Ultra-violet Band-spectrum of Carbon-compounds .LOCEYEB J.N.Spectra of Meteorites.ROBERTS.Galvanic Elements.PRATT J.H.Experiments wilh Lippmann’s Capillary Electrometer .WRIQHT C.R.A. and C.THOYPFON.Aeration Currents.DUTER E.Electrical Conductivityof Sulphur.BOTJTP E.Electrical Conductivity of Concentrated Nitric Acid.WEBEB R.Influence of the Composition of Glass on the DepressionPhenomena of Thermometers.CHREE C.Conduction of Heat in Liquids.DE FORCRAND.Bibasic Glyceroxides.BACHMAN I.A.Freezing Mixture.RAYLEIQH LORD .Densities of Hydrogen and Oxygen.DE PORCRAND and VILLARD.Hydrate of Hydrogen Sulphide.DE FORCEAND and VILLARD.Hydrates of Gases.MAUMENB E.J.and C.LIMB .BTARD A.Solubility of Sulpbatee.DUUEM P.Laws of Chemiral Equilibrium.AUWERS 9 and V.MEYER .Spectrum of the Oxyhydrogen FlameMethod for obtaining Definite Hydrates .Raoult’s Method €or the Determination ofMolecular Weights.PAQB637BECKMANN E.lkolecular Weight of Oximes. 64CONTENTS.viiCLAUDON E. and E.C.MOBIN.Apparatus for Fractional Distillation .NORTON T.H. and A.H.OTTEN.Apparatus for Fractional Distillation .WARREN H.N.Pressure Tubes.RABE H.Turbine for Laboratory Purposes.HODGEINSON W.R.and F.K.LOWNDES.Lecture Apparatus for makingSulphuric Anhydride.ZBHNDER L.Influence of Pressure on the Index of Refraction of Watsrfor Sodium Light.JANSSEN J.Spectra of Oxygen.DEMAR~AY E.Spectrum of Gold.EBERT H.Application of the Method of High Interferences to Quantita-tive Spectrum AnalgsL.SOBOKIN B.Relation between the Constitution and Specific RotatoryPower of Organic Compounds.ELOBUKOFF N.v.New Apparatus for Electrochemical Research.SHELDON S.Alternate Currents and Electrolytes.RICHAIZZ F.Electrolytic Formation of Persulphuric Acid and HydrogenPeroxide at the Anode.RICEIARZ F.Constitution of Peroxides.HENRICHSEN S.Magnetism of Organic Compounds.SCHIFF R.Specific Heat of Liquid Carbon Compounds.CAILLETET L.Air Thermometers.CRAP~S.Air Thermometers.CHAPPKJIS J.Latent Heat of Vaporistxtion of Volatile Substances.MATHIAS E.Measurement of the Latent Heat of Vaporisation of Lique-fied Gases.PETIT P.Heat of Formation of Aniline.VIGNON L.Thermochemistry of Diazo-derivatives.SCHEURER.~ESTNER.Heat of Combustion of Coals from the North ofFrance.NADESCHDIN A.Expansion of Liquids and Change of Substances fromthe Liquid to the Gaseous State.BLUYCKE A.Determination of the Specific Weight and Vapour-pressureof Mixtures of Sulph-uous and Carbonic Anhydrides.GBAETZ L.Internal Friction of Liquids.VAN’T HOFF J.H.Osmotic Pressure in the Analogy between Solutionsand Gases.PLANCK M.Chemicrtl Equilibrium in Dilute Solutions.LE CHATELIER H.Laws of Chemical Equilibrium.QABTENMEISTEB R.Liebreich’s Inactivespace.TRAKJBE J.and 0.NEUBEBG.Formation of Layers in Mixtures c€Alcohol,Water,and Salte or Bases.HWFNER G.Absorption of Gases by Grey Vulcanised Caoutchouc.PULPBICH C.Refraction of Light by Ice,and by Water cooled below ZeroWALTER B.Influence of Concentration on Fluorescence.BOISBAUDBAN L.DE .Fluorescence of Cupriferous Calcium Oxide.UBUNWALD A.Spectral Analysis of Magnesium and Carbon.GOUY and H.RIQOLLET.Electrochemical Actinometer.ULJANIN W.v.Electromotive Force produced by the Action of Lighton Selenium.OSTWALD W.Study of Contact Electricity.GEE W.W.H. and H.HOLDEN.Electrolysis.HAMPE W.Electrolytic Conductivity of Halogen Compounds.WALDEN P.Determination of the Size of Molecules of Salts from theElectrical Conductivity of their Aqueous Solutions.PAGLIANI S.Crystallisation of Salts during the Electrolysis of their Solu-tions.NAHRWOLD R.Conduction of Electricity through Bases.LE CHATELIER H.Molecular Heats of h e o u s Substances.D’ABSONVALL A.Calorimetry at Constant Temperatures.PAGE782tfiii CONTENTS .TOMLIXSON H.Magnetic Properties of Nickel.NEWALL H.F.Recalescence of Steel.KOPP H.Molecular Heat of Solid Compounds.LOUGUININE W.Heats of Combustion of Fumaric,Maleic,and the Pyro-citric Acids.LOUGUIMINE W.Heat of Combustion of the Solid Isomeride of Ben-HALLER A.and A.GUNTZ.Heat of Neutralisation of Ethyl Cyano-malonate,Acetoacetate. and Benzoylcyanacetate.GERLACII G.T.Specific Gravity of Aqueous Solutions.NEUBECK F.Molecular Volumes of dromlttic Compounds.PLANCK M.Molecular Constitution of Dilute Solutions.AREHENIUS S.Dissocistion of Substances Dissolved in Water.DE FORCRAND and VILLARD.Hydrates of Hydrogen Sulphide t ~ n d 31ethj1Chloride.DE FONCRAND and VILLARD.Hydrate of Methyl Chloride.TAMMAN 3.Osrnose through Precipitated Diaphragms.VAN BEMWELEN J.M.Absorptive Power of Colloid Substances.BOGUSKI J.J.Rate of the Reaction between Marble and HydrochloricAcid.SPRING W.Rate of the Reaction between Iceland Spar and Hydro-chloric Acid.MENSCHUTKIN N.Rate of Formation of Ethereal Salts.zene.ROOZEBOOM H.W.B.Hydrates of Gases.RWDORF F.Constitution of Solutions.DELAUNEY.Equivalents of the Elements.PEARSON K.A certain Atomic Hypothesis.OETTEL B.F.Lecture Experiment.KUNDT A.Refractive Indices of the Metals.Ethane and Ethylene.LENARD P.and M.WOLF.Lnminescence of Pyrogallol.Fluorescence of Ferruginous Calcium Oxide.Degree of Oxidation of Chromium and ManganeseFluorescent Xixtures.Constant Battery with a Negative Electrode ofCarbon.BLONDLOT R. and E.BICHAT.Determination of the Potential DifferencesMANEUVRIER G. and J.CHAPPUIS.Electrolysis with AlternatingCurrents.BERSON G. and A.DESTRBM.Electrolysis of Solutions of PotassiumWALDEN P.Determination of the Size of the Molecules of Salts fromLANGLEY J.W.Apparent Manifestation of Chemical Attraction asMechanical Attraction.DEECKER J.Expansion. Compressibility. and Specific Heat of Solutionof the Chlorides of Potassium and CalciumWEEGMAKN R.Molecular Refraction of some Brozine-derivatives ofBOISBAUDEAN L.DE .BOISBAUDRAN 11.DE .STAATS 3.Photochromatic Properties of Silver Chloride.HEIM C.Use of Magnesium in Prirnary Batteries.FABINGI and FARKAS .between Mercury and Electroljtes.AYETON W.E.and J.PERRY.Alternate Current Electrolysis.Hydroxide.the Conductivity of their Aqueous Solutions.OSTWALD W.Chromic Acid..THOMSEN J.Heat of Formation of Mercury Compounds.NERNST W.Heat of Formation of Mercwy Compounds.VIGNOX L.Heat of Formation of Salts of Phenylenediamine.VIGNON L.Heat of Neutralisation of Aromatic Amines.STOHMANN F.Heats of Combustion of Organic Compounds.PETIT P.' Thermochemistry of Nitrogen-depivatives of Benzene.KAYSER H.Disintegration of Glowing Platinum.1014PAQE1005COllil’ENTY.isBARUS 0.Viscosity of Bases a t High Temperatures.BRAUN F.Change of Volume in Gases on Admixture.PICTET R.Determination of the Specific Weight and Vnpour-pregsure ofMixtures of Sulphurous and Carbonic Anhydrides.MULLER-ERZBACH W.Determination of Vapour-pressure from the Rateof Evaporation.DWEM P.Some Properties of Solutions.KONOWALOFF D.Theory of Liquids.BOQUSKI J.J.Attempt to Eliminate the Change in Volume of theVessel when Measuring the Compressibility of Liquids.RONTQEN W.C.and J.SCHNEIDER.Compressibility of Sylvin,Rock-salt,and Aqueous Solutions of Potassium Chloride.OSTWALD W.Theory of Solution.VILLARD.Hydrates of Gases.WIEDEMANN E.Hypotliesis of the Dissociation of Salts in very DiluteSolutions.MULLER-ERZBACH W.Dissociation of some Alums and of SodiumAcetate.DUHEY P.Osmotic Pressure.LIETZMANN E.Permeability of Vegetable Membranes for Air.MULLER-ERZBACH W.Equilibrium in the Retention of Water by Dilute.OSTWALD W.Studies in Chemical Dynamics.RAICH $3.Decomposition of Ammonium Salts by Bromine-water.NEBHEANO.Velocity of Etherification detertnined by Means of ElectricalConductivity.SPOHR J.Influence of Neutral Salts in Chemicill Reactions.CAILLETET L.and E.COLARDEAU.Freezing Mixtures containing SolidCarbonic Anhydride.HERRMAPI” F.Configiiration of the Molecule of Benzene.NASNYTH T. 3.Air of Coal Mines.KRUSS G.Relations between the Composition and Absorption-spectrumof Organic Compounds.BREMER G.J.W.Cause of the Change of Specific Rotattory Power underthe Influence of various SolventsLODSINSEY.Reactions in Secondary Coils.OSTWALD W.Theory of the Dissociation of Electrolytcs.HENTSCHEL W.Raoult’s Law of Freezing.GRIMALDI Gt.P.Theory of Liquids.PLANCK M.Hypothesis of the Dissociation of Salts in very DiluteSolutions.ARRHENIUS S.Theor7 of Isohydric Solutions.SCHEPFER J.D.R.Experiments on the Diffusion of Aqueous Solutions .RAOULT F.M.Vapour-tensions of Ethereal Solutions.PLANCK M.Vapour-tension of Dilrite Solutions of Volatile Substances .MICHAEL A.A Criticism on “The Arrangement in Space of the AtomsROOZEBOOM H.W.B.The Different Forms of Heterogeneous ChemicalROOZEBOOM H.W.B.Triple and Multiple Points regarded as TransitionPoints.KABLUKOFF I..MARKOWNIKOFP W.Method for Avoiding “Bumping ” in Distillation .LIEBERYANN C.New Apparatus.BOISBAUDRAN L.DR .Chromium and Manganese in Fluorescent MixturesP~IBRAM R.- Influence of Inactive Substances on the Specific RotatoryPower of Tartaric Acid.WIEN W.Transparency of Metals.GORE 3.Voltaic Balance.Sulphuric Acid and Hydrated Salts.in the Molecules of Organic Compounds”Equilibrium.DE TRIES H.Osmotic Experiments with Living Membranes..The Laws Governing the Reactiom of Direct AdditionX CONTENTS.NAHRWOLD R..BOUTY E. and L. POINCAB~. Conductivity of Fused Mixtures of Sodiumand Potassium Nitrates.KOHLRAUSCH F.Theory of the Electrolysis of Solutions.DRECHSEL E.Electrolysis with Alternating Currents.BICHAT and GUNTZ.WARREN H.N.Electrical Dialysis.NACCARI A.Spec& Heats of some Metals.BOQUSKI J. J.Measurement of the Expansion of Liquids.BERQET A.Thermal Conductivity of Mercury above 100".JOANNIS A.Alloys of Sodium and Potassium.DE FOBCRAND. Sodium Glycol Oxide.MASSOL 3.Potassium and Sodium Malonates.PETIT P.Heat of Formation of Toluidines,Benzylamine,and Metbyl-aniline.MASSOL 3.Heat of Neutralisation of Malonic Acid.BILTZ H.Influence of the Shape of the Bulb in Vapour-density Deter-minations.BILTZ H.Estimating the Molecular Weight of Volatile Chlorides.VILLARD. Hydmtes of Methaneand Ethylene.RAOULT F. M.Freezing Points of Dilute Aqueous Solutions.ARRHENITJS S.Freezing Points of Dilute Aqueous Solutions.KALISHER S.Apparent Manifestation of Chemical as Mechanical Attrac-tion.LIEBRICH 0.The Dead Space in Chemical Reactions.SPBINQ W..SPRING W..NEQREANO.Determination of the Velocity of Etherification by Means ofElectrical Conductivity.BEKETOFF N.Energy of Compounds and the Orid- of Potassium andSodium.BINDER 0.Aspirator with Constant Flow.KLOBUEOFP N. v.Safety Retort for Preparing Gases.CRAIQ 3.Lecture Apparatus for Showing Combustion of Air in Coal-gasHODQKINSON W. R. and F. K. LOWNDES. Combustion of Oxygen inElectrification of a Gas by a Glowing Platinum WireProduction of Ozone by the Electric Discharge ,Compression of the Moist Powder of Solid Substances.Chemical Action between Substances in the Solid StateAmmonia and of Hydrogen in Nitric Acid.Inorganic Chemist y.RASCHIG F.Compound of Iodine with Ammonia.26WARREN H.Method for decomposing Arnenical Bulphides.26LBVY L.Zinc Titanates.27WARREN H.Electrolytic Method of preparing Metallic Alloys. 27STROEECEER J. R.Ceriferous Hainstadt Clays.28FAUBIE G. A.Reduction of Aluminium Oxide.28KRUSS G. and F. W. SCHMIDT. Halogen-compounds of Bold.28HOPFIUNN L. and 8. KRUSS. Gtold Sulphides. 28CAVAZZI A.Action of Carbon Bisulphide on Metals. 106G ~ ~ ~ T T I Q C.Hydrates of Lithium Hydroxide. ,.106BELLATI M. and R. ROYANESE. Transformation of Ammonium Nitrate.106AYAT L.Ammonium Phosphites. 107SCULLY J.Effect of Bismuth on the Ductility of Silver. 108LEA M. 0.Combination of Silver Chloride with Metallic Chlorides.109DE SCHULTEN A.Silver Potassium Carbonate.110BAILEY Q.H.Lead Aluminium Sulphate. 110PICCINI A.New Oxide of Thallium.110PICKERING S. U.Constitution of Basic Salts. 111STBOYAN A.Gystallised Mercurous Bromide and Iodide.111Process for obtaining the Rare Earths from thCONTENTS.xiRAMMELSBERQ C. ,Atomic Weight of Yttrium Metals in their NaturalCompounds.JUTTKE J.Water of C stallisation of Alums.BAUBIQNY H.Action o7Hydrogen Sulphide on Cobalt Salts.DITTE A.Action of Vanadic Anhydride on Potassium Fluoride.MEYER L.Prepemtion of Hydrogen Iodide.POTILITZIN A.Products and Rate of Decomposition of the Salts ofPOTILITZIN A.Mutual Substitution of the Halogens in their Compoundswith Oxygen.WINKLEB C..BOULZOUREANO.Selenite8.CAVAZZI A.Preparation of Hydrogen Arsenide.TIVOLI D..PPORDTEN 0.v.D.Lowest Compounds of Silver.REIS M.A.v..HILGENSTOCP G.Tetrabasic Calcium Phosphate and the Rasicity of theSilicate in Basic Slag.BEYEE A.Behaviour of the Soluble Phosphoric Acid in SuperphosphatesHalogen Gxy-acids by Heat.Preparation of Hydrogen Sulphide free from Arsenic .Action of Hydrogen Arsenide on Arsenious Anhydride .Action ol Aqueous Carbonic Anhydride on Basic SlagPAQBafter keeping in Bulk.-.BUCHNEB 0.Cadmium Sulphide Commercial Cadmium PigmentsMULLEZ M.Action of Water on Lead.SPRING W.and 0.DE BOECP.Colloi'dal Copper 8ulphide.MEYER V.Stability of Mercuric Chloride Solutions.GORQEIJ A.Action of Aluminium and Kaolin on Calcium Chloride .SPBINQ W.and G.DE BOECK.Soluble Manganese Oxide.JOLLES A.Potassium Manganite.FEANKE B.Manganese Compounds.KLOBB T.Permanganates.BORCHERS W.Electrolytic Extraction of Ant. imony.KNORBE G.v. and P.OLSCHEWSKY.Antimoniates.MENDEL~EPF D.Specific Gravity of Sulphuric Acid Solutions.MEYSZTOWICZ W.Pgrosulphites.XEICHABDT E.Action of Water on Lead.FEIT W.Tungsten Compounds.BILTZ H. and V.MEYEB.Stannous Chloride.KRUSS GI.Atomic Weight of Gold.SCOTT A., ComDosition of Water bv Volume.. 223.224.225.227.228.228.228.229.229.230.230.231.343.344.344.3M.345.345.345.411DEWAI~ J.Whdon-Pechiney Proiess for Manufacturing Chlorine fromGATTERMANN L. ,Nitrogen Chloride.KNOI~YE G.v. and E.OPPELT.SCHNEIDEB R.Action of Arsenious Sulphide on Iodine.WARREN H.N.Silicon.FBIEDHEIM C.Silver Suboxide and the Action of Potassium Perman-SIRVERS W.Crystallised Salts of Mercuq.HAUTEFETJILLE P.and J.MARQOTTET.Ferric and Aluminium Phos-phates.BACKSTROM H. and Gc.PAIJKULL. Volume and Carbon Contents of theQ-as evolved during Solution of Iron in Acids.DRAPER C.N..SCHNEIDER L.Influence of Phosphorus on Iron.GtauNEwar. D W. and V.MHYEB.Vapour-density of Ferric Chloride atBAUBIQNY H.Use of Hidrogen Siphide to purify Nickel and Cobalt .CLASSEN A.Titanium Trioxide.Magnesium Chloride.Pyrophosphatesganate on Silver.ILES M.w.Leait siags.Action of Sea-water on Cast Ironvarious Temperatures.L6w L.Alloy of Titanium,Silicon,and Aluminium.xii C9NTEKTS.ANSCHUTZ R. and P. N. EVANS. Antimony Pentachloride.DITTMAR W.and J. MCARTIIUR. Atomic Weight of Platinum.ALEXANDER H.Hydroxylamine Platinum Rases.DEBRAY H. and A. JOLY. Ruthenium Oxides.PATTINSON J.Rate at which Bleaching Powder loses its available Clilorinewhen kept at Different Temperatures.CURTIUS T. mid F. HENPEL. Preparation of Tetrathionates from Wack~n-roder's Solution.,. ,.MOISSAN H.Hydrofluorides of Potassium Fluoride.HEMPEL W.Preparation of Cakes of Ammonium Chloride and' Am:moniurn Carbonate.OTTO H.Soluble Phosphates in Superphosphates.HEMPEL W.Anhydrous Magnesium Chloride.,.DITTMAR W.Instability of the Double Sulphates of the MagnesiumSeries.REICHARDT E.Action of Potable Waters on Lead Pipes.CARNELLEY T. and W. FREW. Corrosion of Leaden Water-pipes.DESTREN A.Displacement of Copper by Zinc.WARREN EL N .Action of Sulphur-vapour on Copper.HEMPEL W.Absorption of Carbonic Oxide by Cuprous Chloride.BOTTINGER C.Basic Aluminium Snlphate.,.JOLLER A.Preparation of Potassium Manganate.HEMPEL W.Combination of Carbon with Iron under Pressure.MARSHALL H .Cobaltic Alums.VIVIER A.New Hydrate of Molybdic Acid.,.WAGNER k. F.Titanium Chloride and Titanic Acid.DITTE A.Action of Vanadic Anhydride on Alkaline Fluorides.ENGEL. Actioii of Hydrogen Chloride on Cupric Chloride.THOXSEN J.Preparation of Auroso-auric Chloride.DEBRAY H. and A. JOLY. Ruthenium Peroxide.COOKE J. P. and T. W. RICHARDS. Relative Values of the Atomic Weightsof Hydrogen and Oxygen.,.MORLEY E. W.Atomic Weight of Oxygen.BACHMAN I. A.Oxidation of Solutions of Sulphurous Anhydrideand Sulphites.R~HRIGF A.Sulphites.DONATH E.and F. MULLNER.VILLIERS A.New Sulphur Oxy-acid.MICHEL L.Formation of CrystaUised Selenates in the Dry Way.BACHMAN I. A .Arsenic Nitride.JURISCH I.W.Decomposition of Ammonium Chloride by PhosphoricAcid.LE CHATELIER H.Oxidation of Silver.NORTON T. H. and E. TWITCHELL. Alloys of Calcium and Zinc.A N D R ~ G.Action of Metallic Oxides on Solutions of Zinc and ManganeseChlorides.MORSE H. N. and W. M. BURTON. Supposed Dissociation of Zinc Oxide :Atmosphere within a Platinum Vessel heated by a Bunsen Flams.PROST E.Colloidal Cadmium Srilphide.G~ORQEU A.Action of Heat on Oxides and Salts of Manganese.FLEURY 3.Action of Iodine on Iron.NEUMANN Gt.Double Salts of Sesquichlorides wihh other MetallicChlorides.ANDR~ 3.Ammoniacal Derivatives of Nickel Salts.MATTHEY E.Metallurgy of Rismut.h.PIRNQRUBER H.Separation of Platinum from Rare Metals.,NEUMANN G.Methods for obtaining Constant Streams of HydrogenChloride. Ammonia. and Nitrogen.Simple Formation of Thiosulphates ."KLUSS K.' Hyposulphates. *.GEUTHXR A.Nitrous Anhydrihe and Nitrosyl Chloride. 785PAGEQUANTIN H.Action of Carbon Tetrachloride on Inorganic Chlorides.785HTTGOUNENQ L. and J.MOREL.'786COMEY A.M. and C.L.JACKSOX .Hydroxide. 706VORTMANN G.Action of Sodium Thiosulphate on Cupric Salts. 787NILSON L.F. and 0.PETTERSSON .ride and the Valency of Metals of the Aluminium-group.788SAINT-EDME E.Passivity of Iron and Nickel. 788KRAUT K.Nickel Ammonium Oxalate.788XEHRMANN F.Phosphotungstatea and Arsenotungstates. '788KOENIG T. and 0.v.D.PFORDTEN.788PICCINI A.Titanium Trioxide.789CLASSEN A.Titanium Trioxide. 789FXIT W. and K.KUBIERSCEKY.Thio-derivatives of Antimonic Acid.789LUDEKINQ c.Anomalous Density of Liquid Bismuth. 790HABERLAND W. and Q-.HANEKOP.Sodium Platosammonium Sulphite.'790LEIDI~ E.Rhodium Sesquichloride. '790COOKE J.P. and T.W.RICHARDS.Relative Value of the Atomic Weightsof Hydrogen and Oxygen.910VAN DEVENTER C.M. and H.L.VAN'T HOFF. 911WINSSINGER c. Colloidal State of Sulphides. 911VILLIERS A.Sodium Dithiopersu!phate.912SETLICK B.Preparation of Nitrogen Tetroxide.913RASCHIG I?.Acid and of Hydroxylsmine.913JANE~EK G.Electrolysis of the Acids of Phosphorue.914AMAT L.Pgrophosphorous Acid. 914PREIS K.Arsenic Compounds.914HAGER H.Crystalline Silicic Acid. 915AMAT L.Alkaline Phospliites.915V~LLIERS A.Sodium Trithioiiate. 915PILOST E.ture of Zinc. 915G-RISSOM R.G. and B.THORP. 916RICHARDS T.W.Eelation of the Atomic Weights of Silver and Copper 916RICHARDS T.W.Atomic Weight of Copper. 91'7HOUSSEAU G. and J.BERNHEIM.Formation of Crystalline FerricHydroxides in the Dr.v Way.91'7CARSON A.J. and T.H.NORTON.Uranates. 918ENGEL.Influence of Hydrochloric Acid on the Solubilitj of Stannous Chlo-ride. 918LINDET L.Action of Chlorine on Gold.919LEIDIB E.ahodium Sesquiiulphide.919DEBRAY H. and A.JOLY.Rutheniates and Per-rutheniates.920SEUBERT K.Atomic Weight of Osniiuiii.921PAT ERN^ E.and R.NASINI .Bromine,and Iodine in Solutions. 1027BLITZ H.Molecular Weight of Sulphur.1027MEYER V.Molecular Weight of Sulphur. 1088HIRN G.A.1028LANQ J.Heating Gas. 1029PFORDTEN 0.v.D.Lowest Oxide of Silver. 1029ALLEN A.H.Solubility of Calcium Compounds.1030LE CHATELIER H.Constitution of Hydraulic Cements. 1030OUVRARD L.Action of Alkaline Phosphates on the Alkaline Earths.1033ROUSSEAU G. and J.BERNHEIM .High Teniperatures. 1034OLWRARD L.Double Phosphates in the Magnesium-group.1035Sodium Potassium Carbonate.Compoundof Zinc Oxide with SodiumVapour-density of Aluminium Chlo-Titanium.Potassium HypoioditePreparation of the Alkali Salts of HydroxjlaminedisulphonicExtraction of Lead from Residues obtained in the Manufac-New Halogen Compounds of Lead .Molecular Weight of Sulphur,Phosphorus,Property of Carbon similar to that of Spongy PlatinumAbsorption of Carbonic Oxide by Cuprous Chloride .Reactions occurring in the Preparation of Water-gas andDecomposition of Barium Ferrate a xiv CONTESTS .PAGEDE SCHULTEN A.Action of Calcium Carbonate on Cadmium Chlori :e.1036SABATIEB P.Hydrochloride of Cupric Chloride.1036SABATIER P.Hydrochloride of Cupric Chloride.1037KIESEWETTEB P.and G.KRUSS .FRIEDEL C. and J.M.CRAFTS .PFORDTEN 0.v.D.Mercurous Oxide.1037OUVBARD L.Phosphates of the Cerite Metals.1037Absorption-spectra of the Rare Earths .Vapour-density and Molecular Weight ofAluminium Chloride.SABATIER P.Hydrochloride of Cobalt Chloride.VAN BEMMELEN J.M.VAN BEMMELEN J.M.Germanium Oxide.ENGEL.Hydrochlorides of Bismuth and Antimony Chlorides.GORZ A.Reduction of Gold Chloride by Wood Charcoal.SEUBERT K.Atomic Weight of Platinum.VAN BEMMELEN J.M.Collo'ids and the Water they contain.Explosion of a Tube containing CrystalsChromous Sulphate.REBS H.Sulphur Compounds.ELUSS K.Dithionates.VAN BEMMELEN J.M.ColloPdal Silica.VAN BEMMELEN J.M.Colloydal Alumina.VAN BEMMELEN J.M.Collo'idd Stanoic Acid.VAN BEMMELEN J.M.ColloYdal Berric Oxide.VAN BEMMELEN J.M.ColloYdal Chromic Oxide.KNAP I?.Ultramarine Blue.HALLOCK W.New Method of Forming Alloys.ROOZEBOOM 8.W.B.Astracanite and Eydrated Double Salts .POLECK T.'and C.GOERCKI .COOKE 5.MORSE H.N. and W.M.BURTON .Chlorosulphides of Mercury.Reducing Action of Hydrogen in Presence of Platinum .Removal of Iodate from Iodide ofPotassium.LORENZ R.Valency of Boron.GEORGIEVIE P.Boric Acid.VEENEUIL A.Phoaphorescent Hexagonal Blende.ENGEL.Hydrochlorides of Cupric and Cobalt Chlorides.BALBIANO L.Basic Cnpric Chromate.Fox W.Action of Petroleum on Lead.DUBOIN A.Yttrium Compounds.FAUEE A.Preparation of Metallic Chlorides from Oxides.PESCI L.Action of Potassinm Nitilite on Ferric Chloride.BOWLER T.I.Chinese Treatment of Cobalt Ores.HUNT T.S.Dissociation of Fused Metallic Sulphides.LBVY L.Zinc Titanates.PICCINI A.Fluorine-derivatives of Pertitanic Acid.HBRAED F.Amorphous Antimony.WARREN H.N.Bismuth and Lithium in Iron and SlagsKRUSS 3.and F.W.SCHMIDT.Halogen Compounds of Gold.LEIDIB E.Rhodium Salts.MORSE H.N.and W.M.BURTON.Atomic Weight of Zinc.PRIEDEL C. and J.M.CRAFTS .FRIEDEL C. and J.M.CRAFTS.Vapour-density of Galliuin Chloride .Vapour-density of Chlorine and FerricChloride.Crystallised Hydrated Potassium Ferrite ROUSSEAU G. and J.BERNHEIM .M$meralogical Chemistry .FLETCHER L.Cliftonite. a Cubic Form of Chaphitic Carbon.30SOBGE K.Natural Gas of Pennsylvania.30LOSANITSCH 8.M.Servian Coal. 31KLEIN C. and P.JANNASCH.Ullmannite from Lolling and from Sambus 3CONTENTS.xvLOUIS H.Bismuthite from the Transvaal.HAUEB F.v.Barytes in the Carpathians.LACROIX A.Identity of Dreelite and Barytes.Bnsz K.Titanite.BRAUN~ R.Palreopicrite of Amelose and the Products of its Alte-ration.KLEXENT C.Rocks from the Congo.SPICA M.and G.HAKAGIAN.XARPINSKY A.Metamorphic Graphite Garnet in the Ural Mountains .DOLLFUS G. and S.MEUNIEE.Mineral Wax.SOLLAS W.J.Artifhial Deposition of Calcite-cystale on the Spicules ofPENPIELD 5.L. and E.S.SPERBY.BOURGEOIS L.Celestine and Anglesite by Senarmont’s Process.KOKSCHAROFF N.v.Mursinskite.SAUER A.Minerals in Granulite.Water Supply of OdessaaSponge.HowiteJOLY J.Harmotome in Wicklow.JOSY J.Beryl and Iolite of Glencullen.CLARICE F.W.Studies i n the Mica-group.GUMBEL C.W.v.Glauconite.CHESTER A.H. and F.I.CAIRNS.HARTLEY W.N.Black Marble of Eilkenny.VERRI and TROTTARELLI.Calcareous Rocks and Pozzuolana from Tevere .WILLIAMS G.H.Serpentine from Syracuse,New York.GOWNARD F..RIGGS R.B.An Iron of Doubtful Origin.HAGUE A.DeDosition of Scorodite from Arsenical Waters in the Yellow-Crocidolite from Cumberland .Peperite of the Puy de 1 a.PiquetteRIGGS R.B.New Meteoric Iron.BAILEY S.C.H.Aerolite from Reneselaer Co.,New York.NORDENSKI~LD A.E.Arksutite from Ivigtut,Greenland .FLINK U .Mineralogical Notes.RAMMELSBERG C.Manganese and Uranium Oxides.BRUNLECHNER A.Minerals from Carinthia,.KLOOS J.H.Martinite from the West Indies.CESARO G.Diadochite from Vise.DRASCHE E.Mineral from Krems. Austria.ARZRUNI A.Manganotantalite from the Urals.NORDENSPIOLD A.E.Kainosite from Hittero,Norway.DAEAPSKY L.Zeolites from Ckli.IGELSTROM L.J.Manganese-bearing Iodocrase from Sweden .RAMMELSBERG C.Eudialite.DAMOUR A.Beryl from Madagascar.GERHARD A.So-called Soda-granites.LACROIX A.Albite in Norwegian Pegmatites.BEOKJGH B.H.Griqualandite.SANDBERGER F.Mineral Veins.KL~MENT C.Meteorite of Saint-Denis-Westrem.DAMBERGIS A.K.Mineral Springs of Menthana.KL~MENT C.SCEEURER-KESTNER and MEUNIER.DOLFUS.Water from Artesian WellsAn ‘English CoalDE SCHULTEN A.Artificial Pyrochroite.EUNZ GI.I?.Mineralogical Notes.WELLS H.L.1. BismuthosDhserite from Connecticut.WHITFIELD J.E.Natural Borates and Borosilicates.GONNARD F.MALLARD E.Crystalline Compounds prepared by Ebelmen.PENFIELD S.L. and F.L.SPERRY.Peeudomorphs in the Lead Mines of the Puy de DomeTriclinic FeleparsRIGGS R.B.So-called Indicolite from Harlem.WILLIAXS G.H.Pyroxene from New York.xri CONTESTS .ROBINSON F.C.Blue Clay from Farmington,Maine.FISHER D.1.Meteorite from St.Croix Co.,Maine.WHITFIELD J.E.The Rockwood Meteorite.XUNZ G.F.The Powder Mill Creek Meteorite.KVNZ G.F.Some American Meteorites.BOURGOIN and CHASTAING.Phosphatic Mineral Water at Viry.MACIVOR R.W.E.A New Zealacd Sulphur Island.COLLINS W.H.Graphite from the Bagoutal Mountains,Siberia.HOLLAND P.Gold Quartz from the Transvaal.SCHUSTER M.Braunite from Jakobsbei-g.MACIVOR R.W.E.Chrome Iron Ore in Australia.GOBNARD F.Genesis of the Plumbiferous Phosphates and Ardeno-.HATLE E. and H.TAZTFS.Mineralogical Observations in Styria.FOULLON H.v.New Discoveries of Minerals.K~EMENT 2.Ilmenite from the Ardennes.RAMMELSBERG C.Composition of Idocrase.BEDSOR P.P.Colliery Waters.phosphates of Rome and de Rosiers,PontgibaudDOELTER C.Synthesis of Pprrhotine.HARRINGTON 13.J.Canadian Minerals.Doss B.Pelspar and Olivine from Syria.SCHUSTER M.Albite of the Icdsbek.LACROIX A.Anorthitefrom Saint-ClBment.SCHUSTER M. and R.PRZIBRAM.Beryl from the Ifinuer.SCHARIZER R.Micas of the Pegmatite-granite of Sc;iittenhofen.HONIG 0.A.Schorlomite,a Variety of Melanite.GRODDECK A.v.Tin-oise Deposits of Mount Bischoff.MIERISCH B.Volcanic Elocks of Monte Somma.WARREN H.N.Selenium in Meteoric Iron.LEPSIUS B.Water from the Tonnissteiner Medicinal Spring.MACIVOR It.W.E.Gold,Alunite,and Sulphur from New SouthWales Native Antimony from Quee.lsland.KONIG G.A.Stromeyerite from Zacatecas. Mexico.near Pontgibaud.WEBSKY M.Caracolite and Percylite.FEEMY E. and A.VERNEUIL.Artificial Rubies.Minera!ising Action of AlkaliceIGELSTROM L.J.Jacobsitefrom the Sjo Mine.IGELSTROM L.J.Jacobsite from Nordmarken.LACROIX A.COREX E.Pseudoniorph after Marcasite.MACIVOR It.W.E.Occurrence of Epsomite on White Island,NewZealand.GENTH F.A .Mineralogical Notes.IQELSTR~V L.J.j.COHEN X.Pleochroism of Biotite.E~NIG G.A.Manganese-zinc-serpentine from Franklin,New Jersey .JANNETAZ E.Chrysocollafrom California.MULLER W.Chiastolite.OSANN A.Sandinites from SLo Miguel.GRODDECK A.v.Copper Ores containing Tourmaline Geological Occur-rence of Boron Minerals.LINCK G.The Basalts of Alsace.HOLLAND P.Quartz Conglomerate from Witwatersrand,Transvaal .CATHREIN A.Chloritoi'd-schist from Grossarl.OSANN A.Labrador-porphyries of the Vosges.PEILE H.Analpis of Shotley Bridge Spa Water.SANDBEROER F.v.GONNAXD F.New Mineral in the S t.Bernard Lode a t Hausach .Association of Fluorsp ir with Babel Quartz at Ville-VielleHAUTEFEUILLE P.and A.PERREY .Sulphides Formation of Cymopliane.Two Varieties of Goethite from Sabne et Loire.Pyrrho.arsenite,a new Mineral from the Sjo MinePAOI:661CONTEXTS.xviiPAGESELLA A.Sellaite.657MIERS H.A. and Gt.T.PRIOR.Proustite containing Antimony. 657LAIST A. and T.H.NORTON.Copper Antimonide.658WALKER P.H.Varvacite.658ROSSIER EL .Occurrence of Oxide of Cobalt. 658BECKENKAMP J.Strontianite and Celestine from the Kaiserstuhl. 659CLARKE F.W.659RIGGS R.B.Compoaition of Tourmaline.659WALKER P.H.Genthite. 660BACHMAN I.A.Nickeliferous Talc.661PRICE R.C.Tscheffkinite.661ROTH J.Zobtenite.661FLETCHER L.Meteoric Iron from Nejed,Central Africa. 662FLETCHER L.1. Meteoric Iron from Greenbrier Co.,West Virginia. 663ROBIXSON F.C.So-called Northport Meteorite.662VERNEUIL A.Phosphorescent Blende.791STONE G.C.Analyses of Franklinite.791GORGEU A.Artificial Formation of Pyrolusite.792GEXTH F.A.Lansfordite,a New Mineral. '793MAREOWNIKOFF W.j. Occurrence of Thenardite in Russia.793MARKOWNIKOFF W.Dihydrothenardite,a New Mineral. 794DUFET H.Pharmacolite. 794FOUQUB F.A Crystallised Slag. 794JANNASCH P.Spodumene from Brazil.795CHESTER A.H.Alteration-products of Rhodonite.795URODDECK A.v.Clay Slate and Sericite Slate.795GLASER 24. and W.EALMAN.Analysis of Roncegno Water.796EATZER F.Minerals from New Localities in Bohemia.922HOCKAUF J.Halotrichite from the Tyrol. 923FRENZEL A.Mineralogical Notes. 923FRENZEL A.New Analysis of Hohmannite. 924HERSCH C.Analyses of Zeolites. 924SPRING W.Proportion of Carbon and Hydrogen in CarbonaceousSchists.925WELD H.W.Analysis of Lockport Sandstone. 925WULFING E.A.Nepheline-syenite from the Transvaal. 925~ C H A D O J. .and S.Paolo. 926FRESENIUS R.Hot Springs of Wiesbaden. 928HILLEBRAND W.F. and H.S.WASHINGTON.Rare Copper Mineralti fromUtah.1043HAUTEFETJILLE P. and A.PERREY.Production of Phenacite and Emerald 1044CLARKE F.W.Pl'ickel Ores from Oregon. 1045EEMP J.F.Diorite Dyke in Orange Co.,New York. 1045DOELTER.Artificial Production of Micas and Scapolite. 1045MERRIL G.P.New Meteorite from California.1046VOLLHARDT 3.Cobalt Ores.1257CATHREIN A.Calciostrontianite Emmonite from Brixlegg.1258UIGLIOLI I.Phosphorite of Capo di Leuca.1259WEISBACH A.Arnimite. 1259VOGT 1.LI.L.1259WEINSCHENK E.Alteration of Quartz and Talc.1259VOGT 1.H.L.Artificial Magnesia-mica.1260SANNASCH P.Biotite from Christiana.1260VRBA K.Cronstedtite from Kuttenberg in Bohemia. 1260SCHNEIDER.New Manganese Ore from Dillenberg.1260MANGINI F.Chalybeate Water of Raffanelo. 1261MUNTZ A.Water of the Nile.1261DICKIE A.Water of the Clyde Sea Area. 669Chemical Structure of Natural Silicates.Petrography of the South-western Frontier between MinasTetragonal Minerals in Crystallised Slags.VOL.LIV.xviii CONTENTS.Organic ChernzstryPAGEWISLICENUS J.Arrangement in Space of the Atoms in the Molecules ofCarbon-compounds.WALLACH. 0.Nitrosates. Nitrosites. and their Derivatives.FISCHER E. and J.TAFEL.Synthetical Experiments in the Sugar-group .RISCHBIETH P.Isonitrosogalactose.WEHMER C.The Carbohydrate Character of Formose.BONDONNEAU and FORET.Saccharification in Vegetable Tissues.MALBOT.Amines of the Paraffin and Benzene Series.SMOLKA A.Allgl-diguanidine and its Derivatives.BECKMANN F.Isonitroso-compounds.WURSTER C.Oxidation by Means of Hydrogen Peroxide.RISCHBIETH P.Isonitrosovaleric Acid and y-Valeruximidolactone.ETTISINE A. and P.BUISINE.NORTON L.M. and H.A.RICHARDSON.OTTO R. and A.ROSSINQ.Butanedicarboxylic Acids.DE CLEBMONT P. and P.CHAUTARD.Distillation of Citric Acid withGlycerol.EILIANI H.Double Lactone of Metasaccharic Acid.ANDREASCH R.Thiohydantoh.GR~NEWALD W.Orthothioxen and Orthothiophendicarboxylic Acid .DITTE A.Action of Carbonic Anhydride on Aromatic Amines.EOHLER L.Benzy1idene.compounds.FISCHEE 0.Reduction Products of Benzylidene-compounds.EMMERICH 0.Hydroxybenzylidene-compounda.New Source of Capric AcidLinoleic AcidSTEINHART 0.J.Anisylamines.SMOLKA A. Picramates.MORAWSKI T. and J.KLAUDY.Chlorine- and Bromine-derivatives of Citra-conanil.BENDER G.Action of Pheiiylhydrazine on Chloracetoacetates.PELLIZARI G.Isomeric Phthalophenylhydrazines.GRAWITZ S.Dyes from Aniline Chromates.EARBIEB P. and L.VIGNON.Substituted Safranines.LEWY M.Action of Acid Amides on Bromacetophenone.BECKMANN E.Isonitroso-compounds Isobenzaldoxime.JACOBSEN E.and P.JULIUS.Condensation of Cinnamio Acid with GallicAcid.SCEMITT R. and C.KRETSCHMAR.Paradiphenoldicarboxylic Acid.EMMERT A.Two Dihydroxynaphthalenes.SCHMITT R. and E.BTJRKARD.Naphtholcarboxylic Acids.CIAMICIAN G. and P.SILBER.Constitution of some Pyrroline-deri-rativesPAAL C. and C.STRASSER.Synthesis of Pyridine and Piperidine-derivativesSCEULTZ M.2 6 Methylethylpyridine and 2 4 Methylethylpyridiue .RALLY 0.Phenylated Piperidine and Pyridine Bases.SCRMITT R. and F.ENGELMANN.Orthohydroxyquinolinecarboxylic Acid .SCEMITT R. and J.ALTSCHUL.Parahydroxyquinolinecarboxylic Acid .WERNECKE 34.Reactions of Caffe'ine and Caffei'dine.COMSTOCK W.J. and W.KOENIGS.Apocinchine and Apochinine.WITT 0.N.Azophenine.FISCHER C.and A.FRANKEL.Orthamidotriphenylmethane.RIS C.Derivatives of Di-B-naphthylamine.BEUNNER. P. and 0.N.WITT.Naphthaphenazine.WALLACH 0.Terpenes.STOEHR C.3-Methylpyridine and 3-Methylpiperidine.BAURATH H.a-SQrylpyridine.REHER L.Ethylqninoline.PECHBIANN H.v.Constitution of Gtlutazine.HESSE C.Hydroquinine.CONTENTS.xixSTOEHR C.Strychninesulphonic Acids.SALEOWSKI E.Peculiar Modification of Urobilin.KRUKEKBERG C.I?.W.Chemical Formation of AlbuminMICEAILOFF V.Coagulation of Albumin.Albumin and Myosin.VILLON M.Animal Tannin.CHITTENDEN R.H. and P.R.BOLTON.CHITTENDEN R.H. and H.H.WHITEHOUSE.Metallic Compounds.ofCHITTENDEN R.H. and H.M.PAIRTER.RONDAKOFF J.Action of Chlorine on Amylene.PRZYBYTEK S.Action of Hypochlorous Acid on the HydrocarbonCsHI6.OBERMEYER J.Methyl Mercaptan and its Derivatives.MORIN E.0.Brandy from a Wine from the Charente Infhrieure.MORIN E.C.Normal Amy1 Alcohol from the Fermentation of Glycerolby Bacillus butylicus.KUVSINOFF J.Action of Zinc Methyl on Taleraldehyde.SOKOLOFF E..Egg-albumiii and AlbumosesCase’in and CaseosesVARET R.Ammonio-zinc Cyanides.Action of Zinc Isoamyl and Zinc Isobutjl on AldehydeEONDAEOFF J.Methyl Isopropenyl Cai-binol.STOCES H.B.Iodide of Starch.SOSTEGNI L.Constituents of Rice Starch.HONIQ M.and S.SCHUBERT.Lichenin.REBUFFAT 0.Reactions of Chloral.MARCKWALD W.Trithioacetaldehyde.COMBES A.Metallic Derivatives of Acetylacetone.VOLHARD J.Preparation of a-Bromo-acids.WISLICENUS W.Ethereal Salts of Aldehydo-acids.HANTZSCH A.Conversion of Benzene-derivatives into Fatty CompoundsEORNER G.and A.MEXOZZI.Derivatives of Isosuccinic Acid.LEVY S.and P.ENGLANDER.Oxidation of Copaiba 3alsa.m.CLAUS A. and T.STEINKAULER.Dibromosebacic Acid and some of itsDerivatives.MICHAEL A.Constitution of Levulinic and Malei’c Acids.POLEO 3.Butenyltricarboxplic and Ethylsuccinic Acids.BARNSTEIN F.Isobutenyltricarboxylic Acid and Unsymmetrical Di-methylsucc~inic Acid.MARCEWALD W.Furfuran-derivatives.JACKSON C.L. and J.F.WING.Action of Nitric Acid on SymmetricalTrichloro benzene.JACOBSEN 0.Action of Sulphuric Acid on Bromodurene.DITTE I.Aniline Salts.WITT 0.N.Homologues of Aniline.COLSON A.Eutylenic Bases Characteristics of Ethylenic Diamines .POSP~CHOPF V.Azopseudocumene.BARZILOFFSKY J.Aniline Dyes from Aromatic Diamines.WURSTER C.Formation of byes by means of Eydrogen Peroxide.BARBIER P.and L.VIGNON.MIXTER W.S. and F.0.WALTHER.MIXTER W.G. and C.P.WILLCOX.Nitro-derivatives of Dibrom-oxanilide.PELLIZZARI 3.Compounds of Alloxan with Aromatic Amines.GABRIEL S.Benzylidenephthalide and Isobenzalphthalide.GABRIEL S. and H.HENDESS.Benzyl-derivatives.EHRLICH E.Resazoiin and Resorufin.MICHAELIS A. and U.GENZKEPI’.Tritolylstibines.PECHMANN H.v.Isonitroso-compounds.MEYER V.Negative Nature of Organic Radicles.MEYER H.Derivatives of Dimethyl-a-resorcylic Acid.Formation of SafraninesNitro-derivatiqes of OxanilideREESE L.Action of Phthalic Anhydride on Amido-acids.PAGg’73’74xx CONTENTS .WISLICENUS J.Action of Phthalyl Dichloride on Ethyl Sodiomalonate .JAcKsoN C.L.and J.F.WING.Benzenetrisulphonic AcidREMSEN I. and C.W.HAYES.Sulphonefluoresceln.GRAEBE C. and P.JUILLARD.Diphthalic Acid.FEHRMANN W.Auramines.GRAEBE C.Auramine.ZINCKE T.8-Naphthaquinone..BAMBERGER E.Eydro-deri-atives of Aromatic Bases.ZINCKE T. and A.T.LAWSON.Orthamidoazo- and Hydrazimido-com-pounds.LAWGE M.Sulphonation of Acet. onaphthalide.WEINBERG A.a-Naphthalenedisulphonic Acid.JULIUS P.Dinaphthyl-derivatives.JAHODA R.Diamidopyrene.RENARD A.Diterebenthyl.THOMS H.Bitter Principle of Calaxus-root.POMERANZ C.Cubebin.CLAUS A. and V.TORNIER.Brominated Quinolines.JAHODA R.Pyrenoline.FRIEDEL C.Cinchonanline.FREIRE D.AlkaloYd from Solanurn grandtyora.JAHNS E.Trigonelline.GIACOSA and MONARI.AikaloYds from the Bark of Xanthoxylon senega-Zelzse.,.HAMMARSTEN 0.Mucin of the Submaxillary Gland.PAIJKULL L.Mucin of Bile.UUSTATSON 3.Preparation of Trimethylene.GUSTAVSON G.Conversion of Trimethylene Bromide into PrapyleneBromide.BBHAL A.Ethylpropylacet.ylene.B ~ H A L A.Hydrolysis of Diallyl.CIAMICIAN 3.Pyrrolylene Tetrabromide.MEYER E.v.Hydrocjanic Acid and Cyanogen Iodide.BRAUN E.Sulphuranes.WINSSINGER C.Propane-derivatives.UEGTHER A.Bitter Principle of Cnlamus.root.LIPPMANN E.CHASTAINQ P. and E.BABILLOT .Ethyl Hydroxyquinoline Carbonate.Action of Sulphuric Acid on Morphineand Bibasic Acids.CLERMONT A.Formation of Peptone.MILLOT A.Oxidation of the Azulmic Matter obtained by the Electro-lysis of Ammonia with Carbon Electrodes.REPORMATSKY A.Synthesis of Diethyl Methyl Carbinol.FINE I.Bromination of Ally1 Alcohol.PBIBYTEK S.Diisobutenyl Oxide.FAUCONNIER A. and J.SANSON.Action of Hydrogen Chloride on GlycerolLOEW 0.Sugar-like Nature of Formose.LORIN.Inosite.EKSTRAND A.G. and C.J.JOHAN60N.Inulin.GRIMAWX E.Fermentation of GlycPraldehyde.PECHMANN H.v.Decomposition of Nitrosoketones.MENSCHIKOFF P.Action of Zinc Ethide and Zinc Iodoethide on Di-PECHMANN H.v.niacetvl and its Homologues.P~IBYTEK S.Erythrene Dioxide.HONIG M. and S.SCHUBERT .Carbohydratespropyl Ketone.PAGEHENTSCHEL’ ~.‘ Chlorinated Methyl Formates. 248. 249DUVILLIER E.Act. ion of Triethylamine on a.Bromobut.p i c Acid. 249SEDLITZKY L.Isobutyric Acids.250Solubility of Salts of Isovaleric,Methylethylacetic. anCONTENTS .GROGER M.AUTENRIETH W.Mixed Anhydrides.Oxidation of Palmitic Acid.Oxidation-products of the a-Hydroxy-Lactones and Lactonic Acids.Action of Ammonia on Ethyl Acetoacetateand its Derivatives.Action of Ammonia on Alkylated Acetoacetates,and of Alcoholson the Carboxyl-group in Acetoacetates.ARISTOFF V. and N.DEMJANOFF .FITTIG R.CONRAD M. and W.EPSTEIN .PETERS T. .acids of the Fatty Series.BISCHOFF C.A.Isomeric Dialkylsuccinic Acids.HJELT E.Symmetrical Diethylsuccinic Acids.RUHEYANN S.Action of Ammonia on Alkyl Salts of Fatty Acids.KAULFUSS A..OTTO R. and R.C.CASANOVA.Disulphones.HORBACZEWSKI J.Synthetical Researches on,and Constitution oE UricAcid.HILL H.B.Furfuracrylic Acid.HANTZSCH A.and J.H.WEBER.LEROY A.J.Bromobenzenes.ISTRATI.Action of Sulphuric Acid on Chlorobenzenes.ISTEATI.Nitrochlorethylbenzenes.GABRIEL S. and B.WEISE.Orthocyanotoluene.GO~TSCHALK M.Action of Nitric Acid on PentamethTlbenzene.NOLTINQ E. aiid T.STRICKER.Iodophenols.SCHALL C.Solid Orthiodophenol.LIPPYANN E.0.v.Catechol in Raw Beet-sugar.NIETZKI R. and F.KEHBMANN.Hydroxyqmnones.KOSTANECKI S.v.Dinitrocresorcinol.TOENNIES P.Action of Nitzous Acid on Anetho'il.AHRENS F.Sandmeyer's Reaction Substitution of Cyanogen for theAmido-group.MEY ER V.Orthocyanophenol.GELZER C.Derivatives of Paramidoisobutylbenzene.KNOFLER 0. and P.BOESSRECK.Condensation of Chloral Hydrate withTertiary Aromatic Amines.QRIESS P.and G.HARROW.REMSEN I. and W.R.OINDORFF.BANDROWSKI E.v.Diphenylparazophenylene.NOLTINQ E.Substitution in Azo-compounds.NOLTINQ E. and F.BINDER.Diazoarnidocompounds.NOLTING E. and A.ABT.Constitution of Azimido.compounds.SKINNER S. and S.RUHEMANN.Action of Phenylhydrtbzine on Membersof the Carbamide Series.BOSTANECKI S.v..HOLLENANN A.F.Products of the Action of Nitric Acid on Aceto-phenone.CLAUS A. and C.FOECKING .Methyl Duryl Ketone.TIXMAXN F.Nitrile of Salicylic Acid.REISSERT A.Condensation Products from /I-Anilido-acids.ANSCHUTZ It.Formation of Anilic Acids from Bibasic Acids.MOLCANOPFSEI N.Hydrszocumic Acid.OGLIALORO A.Synthesis of Phenosycoumarin.HARTZSCH A.and A.ZECEENDOELF.Derivatives of Ethyl Quinonepam-dicarbox ybte.BRACEETT R.N. and C.W.HAYES.Preparation of OrthosulphobenzoicAcid.Apparatus for Distilling Zinc Methyl and Zinc EthylThiazole CompoundsHOLLEMANN A.F.Phenylacetylene and Diphenyldiscetylene.KNOP A.Action of Yhospliorus Pentasulphide on Aniline.Action of Aromatic Diamines on SugarDecomposition of Diazo-compoundsDyes which can be fixed with MordantsHEDRICK W.A.Paramidorthosulphobenzoic Acid.~ Cuus A. and J.KRAUSS.Metwresolsulphonic Acids. 260XXiPAQE%62x xii CONTENTS .HANTKE E.Orthocresolsulphonic Acids.OTTO R. and A.MILCH.BRACKETT R.N.Ethereal Salts of Benzoic Sulphinide.POLIS A.Aromatic Lead-compounds.WAGNER P.Azo- and Amido-derivatives of Methylketole.STECHE A.Derirativesof B-Naphthindole.WEINBERG A.Hydroxydiphenyl Bases.BANDROWSKI E.v.Dinitrobenzidine.TROGER J.Bases obtained with Nascent Formaldehyde.BISCHLER A.Condensation Products from Paratoluidine and Paranitro-DOBNER 0.and 3.PETSCHOW.Compounds of Ketones with Dimethyl-ULLMANN C.Derivatives of Triphenylmethane.BAITHLR 0.Tetramethyldiamidothiobenzophenone.LELLMANN E. and 0.SCHMIDT.Ring Formation with Elimination ofSCHULTZ G.Isomeric Naphthylaminesulphonic Acids.WEINBERG A.Intramolecular Migration in P-NaphthylaminesulphonicAcids.ERDMANN H.Conversion of Naphthylaminesulphonic Acid into Dichloro-ZINCKE T. and C.GERLAND.Action of Bromine on Diamido.$.naphthol .KOSTAXECKI S.v.Synthesis of Antbracoumarins from Cinnaruic andSynthesis of Aromatic Sulphinic AnhydridesOTTO R.and W.Sulphoneketones.FISCHER E.Methylketole.benzaldehyde.aniline and Diethylaniline.Hydrogen Bromide or Nitrous Acid.naphthalene.Metahydroxybenzoic Acids.HOOKER S.C.Purpurogallin.DAM~KY A.Sulphocamphglic Acid.TESTERBERG A.Pimaric Acids.GRASSI C.Action of Phenylhydrazine on Santonin.HARTLEY W.N.Ltlkmo'id and Litmin.SCHALL C.and C.DRALLE .CLAUS A. and A.STIEBEL.Metanitroquinoline.FREYDL J.Constitutionof Quinoline-derivatives.GEORGIEVICS 3.v.Sulphonation of Quinoline.LELLMANN E. and 3.LANQE.Quinoline.LA COSTE W. and F.VALEUB. 3-Quiirolinedisulphonic Acid.MOLLER M.Tetmhydroquinaldlne.MOLLEB M.Quinaldine Alkyl Iodides.DOBN-ER 0.a-Alkylcinchonic Acids and a-Alkylquinolines.logues.HINZ E.Parabenzoylquinoline and Pttradiquinaldine.BAMBERQER E.Quinoline.Bnsz J. and A.KEKULB.Acetic Tripiperidide.GOLDSCHMIEDT G.Oxidation Products of Piperidine.ROWEL A.Adenine.GAUTIER A.Ptomai'nes and Leucomaynes.MACMUNN C.A.Hsematoporphyrin.and Ethyl.BAMBERQER E. and W.LODTEB.Hydrogenation of Aromatic Hydro-carbons.Action of Sulphuric Acid on Tere-benthene.BOUCHARDAT 3. and J.LAFONT .New Brazilin.derivative.FISCHER E. and A.STECHBDOBNER 0. and ?M.GIESEKE .Conversion of Indoles into Hydroquinolinesa-Phenylcinchonic Acid and its Homo-.LATSCHINOPF P.Empirical Formula of Cholic Acid.GREEN J.R.Action of Sodium Chloride in Dissolving Fibrin.G~OTTING Gt.Constitution of Nitroethane.KLASON P.Preparation of Sulphides and Hydrosulphides of MethylPAQBWN'l'EN'l'S.xxiiiKLASON P.Alkyl Polysulphidee.LOEW 0.Condensation of Formaldehyde.KLINQER H.and A.MAASSEN.Sidphines and the Valency of Sulphur .FI~OXM E.Disulphones.FISCHER E. and J.TAFEL.Synthetical Experiments in the Sugar-group .KRASNICKI E.v.Solubility of Calcium and Barium Formates,Acetates,and Propionates.REICHER L.T.Temperature of Conversion of Copper Calcium Acetate .MEYER V.Prcparation of P-Iodopropionic Acid.OTTO R.Analogy between Ketonic Acids and the Alkyl-sulphones of theFatty Acids.DEMUTH R. and V.MEYER.Isodibromosuccinic Acid.WISLICENUS W.Ethyl Oxalacetate.WISLICENUS W. and E.ARNOLD.Ethyl Methyloxalacetate.RAOULT F.M..WALLACH 0. and F.HEUSLER.Organic Fluorine-compounds.BRUNNER H. and P.CHEIT.Dichro'ins.MOHLAU R.and C.W.KROHN.Action of Sulphur on Methylaniline andBILLETER 0. and A.STROHL.Action of Thiocarbonyl Chloride onSecondary Amines.MEYER V.Constitution of Mixed Azo-compounds.LAUBMANN H.Compounds of Phenylhydrazine with Ketone Alcohols .POLONOWSKY &I.Action of Phenylhydrazine on Dioximes.BRAUN E. and V.MEYER.Aldines and Amidoacetophenone.ANSCHUTZ R.Phenylhydrazile Acids from the Anhydrides of BibasicAcids.FAHLBERG C. and R.LIST.Orthosulphaminecarboxylic Acids.KORNER A.Derivatives of Phenyldibromoisobutyric Acid.DOBRZYCKI L.v.Paraisobutylhydroxybenzoic Acid.RAIKOW P.a-Methylcinnamic Acid.REESE L.Action of Phthalic Anhydride on Amido.acids.JANOVSKY J.V.Azotoluenesulphonic Acid.PICTET A. and L.DUPARC.Ethylindole.SCHMIDT G.and E.I.MEYER.TSCHACHER 0.Condensation of Metanitrobenzaldehjde with Benzeneand Toluene.WISLICENUS J. and H.REINHARDT.Action of Dichlorether on Phenol .WISLICENUS J. and M.SIEGFRIED.Action of Dichlorether on the Di-LANQE M.Action of Sulphur on the Salts of Aromatic Hydroxy-com-pounds.MAUZELIUS R.Action of Sulphuric Acid on a-Naphthylamine Hydro-chloride.Cryoscopic Studies on Racemic Acid and RncematesPICTET A.Formation of Secondary Aromatic Amines.Dimethylaniline.MEYER R.Benzeneazomalonic Acid.WOLFF L.Dimethylindole.HINSBERG 0.Action of Glyoxal on Aromatic Amines. Isatoic Acidhy droxy benzenes.BAMBERQER E. and W.LODTER.a-Naphthaldehyde.MAUZELIUS R.Naphthalenesulphonic Acid [l 4'1.BAMBERQER E. and W.LODTER.Reductionof the Thiamides of Aromat. icAcids.WISLICENUS J.and G.ZWANZIQER.Action of Dichlorether on Naphthol .BRUHL J.W.Terpenes and their Derivatives.HARTMANK W.Specific Rotation of Dextrocamphoric Acid and its Salts .MARPMANN.Alantic Acid and Alantole.ZURCHER H.Oxidation of l-Quinolinesulphonic Acid.PLUGGE P.C.Opium Alkalo'ids.HESSE 0.Quinine Alkalo'ids.JUNGFLEISCH E. and E.LEQEE.Optical Isomerides of Cinchonine.PAGExxiv CONTENTS .EINHOBN A.Coca'ine.LISSENKO K.Decomposition of Petroleum by Heat.LOSCHEE K.Action of Bromine on Iodoform.EISSEL J.Action of Zinc Ethyl on Nitroethane.GUARESCRI I. and L.GABZINO.Isobutylene Bromide BromotrimethylCarbinol.GOTTIG C..NICOL W.W.J..WERMER C. and B.TOLLENS.Action of Boiling Acids on Methylenitan .Compounds of Sodium Hydroxide and Methyl Alcohol .Specific Gravities of Aqueous Glycerol Solutions .WINTER H.Levulose.WALLACH 0.Irisin.LADENBURG A.and J.ABEL.Ethylenimine Spermine .hydes and Ketonic Acids.WOHL A.Amidoacetals.EKSTKAND 8.G. and C.J.JORANSON.GABRIEL 3.Ethylamine-derix atives.MESSINOER J. and C.ENGELS.Action of Hydrogen Phosphide on Alde-SCHOLL R.Conversion of Ketoxilnes into Pseudonitroles.LETT 9. and K.JEDLICKA.Tetraclilorinated Diacetyl.BERGREEN H.Thiocarbonyl Chloride.RUDORFP F.Calcium Copper Acetate.ROMBURQH P.v.PP-Methylethylpropionic Acid.GEITEL A.C.Borneo Tallow.FRAXCHIMONT A.P.N.Action of Nitric Acid on Amides and Alkjl:amides.ANSCH~~TZ R.Isomerism of Fumaric and Maleic Acids.BULITSCH P.Oxidation of Diallyloxalic Acid.BULITSCH P.Action of Sulphnric Acid on Diallyloxalic Acid.HILL H.B.and A.W.PALMER.Mucohydroxybrornic and Mucohydroxy-chloric Acids.Ronx L. and E.LOUISE.Vapour-density of Aluminium Etliide.MEHNE P.Condensation of Furfuraldehpde with Chloraldelij de.FRENTZEL ;W.Polymerisation Products of the Toljl Cyanates.Carbohydrates.BBUNN 0.Murexoin.HOLLEMAN A.F.P-Nitrocymene.M 0 s so U.Chlorophenols.FISCHER 0. and E.HEPP.Dibromonitrosophenol.SEITBERT K.Benzyl Chloracetates.RIZZA B. and A.BOUTLEBOW.Asarone.FISCHEE 0. and E.HEPP .MEHNE P.Nitrosotoluidines.LIMPACH L.Laws of Substitution of the Aromatic Amines.LIMPACH L. Methylation of Sjmmetrical Metaxylidino.SCHNEIDER A.Amides of' Tribasic Fatty Acids.WACKEB L.Arcmatic 'Nitroso-bases.KLOBBIE E.A.Nitramine from Mesidine.IKUTA M.Paranitrosodiphenylamine.RIS C.Action of Catechol on Alkylenediamines.EOCK E.Aromatic Nitroso-bases.BERNTHSEN A.Relations between Hydrazides and Azo-compounds.SCHUMOFB G.Nitrocymene and Azocymene.ZINCKE T. and H.JAENKE.Orthamidoazo-compounds of Xylene andPseudocumene.NIETZKI R. and A.L.GUITERMANN.Quinonedioximes.MUHLHXUSEE 0.Manufacture of Rosaniline.FISCHER 0. and E.HEPP.Azophenine Quinonanilide.PAWLEWSKI B.Action of Chloracetone on Diplienylthiocarbamide.WILL W.Trimethoxjbenzenes and the Constitution of Asarone.Paranitrosoaniline.Anilides of Unsaturated PolgbasicAcids.MICHAEL A. and G.M.PALMER .PAGECONTENTS.SSVKGHN B. and E.HENSCHEL.Substituted Biurets.LEDERMANN B.Tetrabenzylphosphonium Compounds.STBASSMANN H.Derivatives of Ortho-xylene.WILLGERODT C.Conversion of Ketones and Aldehydes into Acids and.SAT,OMONSON H.W.Perkin’s Reaction.EINHORN A. and J.P.QRABFIELD.BONGARTZ J.Compounds of Aldehydes,Ketones,and Ketonic Acids withThioglycollic Acid.THOMAS J.C.A.S.Preparation and Nitration of Dibenzylmalonic AcidSALOMONSON H.W.Nitrophenylparaconic Acid.OTTO R.Formation of Monosulphones.OTTO R.Methylenechlorophenylsulphone.MOHLAU R.Identity of Diphenyldiisoindole and 3’ Phenylindole.GOLENKIN M.Hjdrogenation of Triphenylmethane.GERBER A.Derivatives of Orthotolidine.NEYER V.Thio-derivatives of Desoxybenzoin and its Analogues.POLONOWSKA N.Oxinies of Benzil.GUNTHER E.Intramolecular Change in Benzildioximes.HASSELBACH E.Hydrodiphthallactonic Acid and Hy drodiphthallyi :WITT 0.JY.Derivatives of a-Naphthol.JACOBSON P.Action of Carbon Bisulphide on Benzeneazo-p-Naphthol .MELDOLA R.Substitution of the Acetyl-group for the Amido-group byAid of the Diazo-reaction.HEIM E.Nitro-derivatives of Phenyl-8-naphthylamine.ERDMANN H.Ketonapthol Aceto-a-Naphthol.ZINCKE T.8-Naphthaquinone.BROYME C.Action of Bromine on the Naphthaquinoneoximes.BROMME C.Action of Monamines on the Naphthaquinoneoximes.ERDMANN H.B-Naphthylamine-E-Sulphonic Acid and B-Naphthjlamine-sulphonic Acid F.WITT 0.N.Eurhodines and Saffranines.WITT 0.N.Naphthalene-derivatives.LIRBERXANN C.Leuco-compounds from the Anthraquinone Dyes.Acid Amides by Means of Ammonium SulphideGRAEBE C.Phenylsalicylic Acid Diphenyleneketone Oxide.Paramethoxyphenylacrylic AcidCIAMICIAK G.and Gc.MAGCNANINI.Indolecarboxjlic Acids.B R ~ H L J.W.Terpenes and their Derivatives.LAFONT J.Action of Formic Acid on French Terebenthene.Yield of Essential Oils by Drugs and Plants.GUARESCHI A.Camphorimide.SCHUTT F.PhycophEYn.MICHAUD 2.Cyclarnin.VAUGHAN V.C.Tyrotoxicon.LINTNER C.J. ,Diastase.PETERSEN F.C.Pyrrolidine.BACHBR F.P-Picoline.DUREOPF E. and 1M.SCHLAUGK.LADENBURG A.y-Picoline and y-Pipecoline.LELLMANN E. and H.REUSCH.Pseudoquinolineananitrile.Roos J.Thio-derivatives of Quinoline.GEORGIEVIC~ G.v.Action of Sulphuric Acid on QuinolineConstitution of Aldehydecollidine.EINHORN A ,and R.LAUCH.Action of Hypochlorous Acid on Quinolineand its Derivatires.RUOHEIMEIL L.and C.S.SCHRAMM.Action of Phosphorus Pents-chloride on Aniline Ethylmalonate and Orthitoluidine Ethylmalo-nate.CONRAD M. and L.LIMPACH.Synthesis of the Homologues of 4’ Hydr-oxyquinaldine.COMBES A.Syntheses in the Quinoline Series by Means of Acetyl-acetone.PAGExxvi CONTENTS .CONRAD M. and L.LIMPACH.Synthesis of 2' 4' Phenylhgdrox~quinolineSALKOWSKI E.Has Creatinine Basic Properties?.JOHNSON G.5. Creatinines.DOTT D.B. and R.STOCKMAN.DOTT I .B.Morphine Hydrate.CAVENTOU and C.GIRARD.Action of Oxalic Acid on Cinchonine in Presenceof Sulphuric Acid.STOCKMAN R.Hygrine.MYLITJS [F.Cholic Acid.SALKOWSKI E.Colour Reactions of Prote'ids.NEUMEISTER R.Albumoses and Peptones.LIEBERMANN L.Nucle'in from Yeast Artificial Preparation of Nucle'infrom Albumin and Metaphosphoric Acid.KRUGER F.Resistance of Hsemoglobin towards Different DecomposingAgents.Formula of MorphineJUNGFLEISCH A.and E.LBGER.Derivatives of Cinchonine.HENOCQTJE A.Activity of Reduction of Oxyhsemoglobin.FRAKEE B. Fire-damp.DE ST.MARTIN L. .WERNER H.Purification of Chloroform.MEYER V.Geuther's Views on the Constitution of the Nitro-derivativesof the Fatty Hydrocarbons.FREUND M.Ethyl Ferrocyanide.FRETJND M.Ethyl Platinocyanide.HENNIGER and SANSON.Formation of a Glycol in the Alcoholic Fermenta-LOEW 0.Formose and Methylenitan.BORQUELOT E.Alcoholic Fermentation of Galactose.SCHIFF H.Compounds of Sugar with Aldehydes and Acetones.MORIN E.C.Bases formed by Alcoholic Fermentation.TANRET.Bases formed by Alcoholic Fermentation.HANTZSCH A.and V.TRAUMA".Amidothiazoles from ThiocarbamideandHalogenated Ketonesand Aldehydes.HANTZSCH A. and L.ARAPIUES.Methylthiazole.HANTZSCH A.Synthesis of Thiazoles and Oxttzoles.GUSTATSON G..CIJRTIUS T. and F.GOEBEL.Ethereal Amidoacetates.OTTO R. and W.OTTO.Analogy between Alkylsulplionated Fatty Acidsand Ketonic Acids.KBEILING P. Occurrence of Lignoceric and Arachidic Acids in Earth-nut Oil.SCHON L.Occurrence of Oleic Acid in Earth-nut Oil.GEITEL A.C..GEUTHER A.Constitution of Acetoacetic,Succinosuccinic,and Quinone-Decomposition of Chloroform by Alcoholic Potashtionof Sugar.GATTERMANN L.Chloroformamide and its Use in Synthesis.Action of Aluminium Chloride on Acetic Chloride .Action of Sulphuric Acid on Oleic Acid and Triolei'ndicarboxylic Acids.HALLER A.and A.HELD.Methyl Acetocyanacetate.LEIPEN R.Compounds of Ethylidenelactic Acid.MAQUENNE.Galactosecarboxylic Acid.KILIANI H.Action of Hydrocyanic Acid on Galactose.HAGEN M.Trimethyluracil.RATHEE B.Cyanuric Derivathes of Taurine.CLAUS A.2,5,Dibromocymene.BEHREND R. and 0.ROOSEN.Synthetical Experiments in the Uric AcidSeries.LOUISE E. and L.Roux.Vapour-density of Aluminium Methyl.TOHL A..GARZINO L.Bromodichlorophenol and Dibromodichlorobenzene.POUCHET A. 3.Compounds of Phenoxides with Cuprous and MercurousDerivatives of 1 2 3 4 Tetramethylbenzene Prehnitene PAGEChlorides.*.58CONTENTS ssviiPAGEFAFCONNIER A.Action of Aniline on Epichlorhydrin.KOHLEB L.Metahydroxyparanitrosodiphenylamine.BOESSNECK P.Condensation of Chloral Hydrate with SecondaryAmines.GUCCI P.Reaction between Metaphenjlenediamine and Carbon Bi-QRIESS P.Diazo-compounds.LOCHER M.Action of Potassium Ferrocpnide on Diazobenzene Nitrate.PISCHER E.Compounds of Phenylhydrazine with Sugars.ISTRATI C.Prance'ins.RATHKE B.Phenylisocyanuric Acid a Fourth Triphenylmelamine .LEWY M.Bases from Bromacet'ophenone and Acetamide.ANSHUTZ R..ANSCHUTZ R.and F. REUTER. Itaconanilic Acid.CLAUS A. and H. KURZ. Chloronitrobenzoic Acids.KROHN C.Hydroxy-/3-isodurylic Acid.FITTIG R.Oxidation of Unsaturated Acids.OSTERMAYER E.Iodophenolsulphonic Acids.CLEVE P. T.Action of Chlorine on a- and P-Kaphthol.AUWERS K.and V. MEYER. Investigation of the Second Van't HoffHypothesis Benzildioximes.BAMBERGER E. and R. MULLER. P-Tetrahydronaphthylamine.EVERS F.Bases from Dinaphthylthiocarbamide.CLAUS A. and S. VAN DER CLOET. Dichlor-a-naphthaquinonesdphonicAcid.BAMBERQER E. and W. LODTER. Characteristics of partly HydrogenisedAromatic Substances.EELBE W.Retene from Resin Oil.KINQZETT C. T.Atmospheric Oxidation of Turpentine,Camphor Oil,sulphide.FISCHER E.Hydrazones.FOGH J.Dimethylanilinequinonimide.Action of Phosphorus Pentachloride on Anilic Acids .KEHRMANN F. ,Iodophenolsulphonic Acids.ZIEQLER J. H.New Synthesis of Tetraphenylethylene.and Oil of Sunflower.VOIRY R. and G. BOUCHARDAT. Oil of Spike.CIAMICIAX G. and P. SILBER. Apiole.LOEW 0.Unorganised Ferments.DURKOPF E.andM. SCHLAUGK. New Parvoline.BAURATH H.a-Stilbazole a-Cinnamylp-ridine .ZIEGLER J.Molecular Migrations in the Q.uinoline Series.KONIQ W.Orthohydroxyquinaldinecarboxylic Acid.AHRENS F. B.Sparteiine.GOLDSCHMIEDT G. Optical Rotatory Power of Papaverine.CLAUS A. and A. MEIXNER. Narceiine.JUNGFLEISCH E. and E. LBGER. Cinchonigine.ZEISEL G.Colchicine.BOTTINGER C.Compounds of Gelatin and Tannin.MACMUNN C. A.Urohaematoporphyrin and Allied Pigments.BBHAL fa.Allvlene.PRASER T. R.Strophanthin.WINCKLEB C.Fire-damp.DELACR~ M..SPRING W. and A. LECRENIER. Constitution of' Guthrie s Chloret,hylBisulphide.PATEIN G.Cyanogen-compounds of Sulphines.SPRING W. and A. LECRENIER. Action of Chlorine on the Sulphides ofTORNOE H.Trimethylene Formation of Ally1 Alcohol from SymmetricalWAQNEE 3..&ichloralcohol Action of Zinc Ethyl on Aldehydes .Alcohol Radicles Preparation of New Chlorine-derivatives.Dichlorhy drin.Oxidation of Olefines and Alcohols of the Ally1 Seriesxxviii CONTENTS .COMBES A.Derivrltives of Acetylacetone Synthesis of PolyatomicAlcohols.HEEZFELD A.Levulose.RAYMANN B.and J.KRUIS.Isodulcitol.DE VEIES H.Molecular Weight of Raffinoae.MAUMENB I3.J.Inactose of Neutral Sugar.STOCKS H.B.Iodide of Starch.GABRIEL S.Vinylamine.CHODOUNSKY K.Action of Zinc-dust on Chloral.COTTON S.Action of Chloral Hydrate and Iodoform on MercuricSalts.LOCHERT H.Compounds of Glycol with some Aldehydes.LOCHERT H.Action of Bromine on the Compounds of Ulycol withCLAISEN L.and R.STYLOS.Acetoacetaldehyde.OTTO R.Action of Carbonyl Chloride on Sodium Formate.DELACRE M.Chloro-derivatives of Ethyl Acetate.BUISINE A.Volatile Acids of Suint.KASSNER 3.Millet Oil and some of its Products of Decomposition.HORN F.M.Oils from the Seeds of Curcas purgalzas.MICHAEL A.Constitution of Ethyl Sodacetoacetate and Ethyl Sodaceto-malonat e.HANTZSCH A. and F.HERRMANIT.Acetoacetic Acid and Ethyl Succino-succinate.MEISTER J.Condensation of Urethane with Ethyl Acetoacetate.KAY P.Antimony Potassium Oxalate.XEEUND M. and B.B.GOLDSMITH.CLAISEN L. and N.STYLOS.Action OF Ethyl Oxalate on Acetone.MAQUENNE.Derivatives of Saccharic and Mucic Acids.PIIJTTI A.Synthesis of Aspartic Acid.MAECKWALD W.Furfuran-derivatives.MAILCXWALD W.Furfuralmalonic Acid.KONOVALOFP M.Hexahydropseudocumene and its Relation to Nono-n aph t hene.SCRUMANN A.Action of Titanium Chloride on Phenol.DIG LA HARPE C.and F.REVERDIN.PETERSEN A.S.F.Ethereal Oil of Asarum Zuropczum.BOYEN E.v.Bromeugenol-derivatives.CONSTAM E.J. and K.GOLDSCRMIDT.Amidoisopropylbenzenes.PELLIZZARI 3.Compounds of Alloxan with Aromatic Amines.JACOBY R.Action of Chlorine on Carbonylorthamidophenol.COLSON A.Secondary Diamines containing an Ethylene Group.LOSSEN W. and P.MIEEAU.Action of Nitrous Acid on some OrganicBases.GOLDSCHMIDT H. and J.HOLM.Mixed Diazo-compounds.JANOPSKY J.V. and K.REIMANN.Substitution-products of Azo-parazo-toluene.FEEUND M. and B.B.GOLDSMITH.Action of Carbon71 Chloride onPIKNER A.,Action of Carbamide on Hydrazines.PICTET A. and P.CEBPIEUX.Alkylformanilides.NIETZKI R. and A.SCnMIDT.Benzenetriphenazine.BEOMME E. and L.CLAISEN.Action of Ethyl Oxalate on Acetophenone .MEYER A.Phenylacetic Acid and Benzyl Cyanide.RACINE S.Derivatives of Orthophthalaldehydic Acid.CABELL+ A.Derivatives of Phenylparacoumaric Acid and MethylatropicAldehydes.Derivatives of Ethylmalonic AcidNitrosonitroresorcinolHydritzides.BARBIER P. and L.VIGBON.Phenosafranine.CLAISEN 11. and L.FISCHER.Benzoylaldehyde.CLAISEN L. and 0.LOWMANN.Benzoylacetone.PA O.EAcid.694COXTENTS.xxixREISSERT A.Condensation-products from Anilido-acids.NORTON T.H. and T.W.SCHMIDT.Metallic Salts of BenzenesulphonicAcid.NORTON T.H.and J.H.WESTENHOPF.Amine Salts of BenzenesulphonicAcid.NORTON T.H. add A.'H. OTTEN.Amine Salts of ParatoluenesulphonicAcid.CLEVE P.T.Sulphimido-compounds.FISCHER E. and T.SCHMITT.2'-Phenylindole.STOLLE E.Metaditolyl.BRAUN E. and V.MEYER.Aldines.PAPCKE V.Substitution in Benzo'in and in Analogues of Desoxybenzo'inand Benzyl Cyanide.MEYER V.Negative Nature of Organic Radicles; Qnestion of theExistence of True Nitroso-compounds.MEYER V. and L.OELTERS.Negative Nature of Organic Radicles;Examination of Desoxybenzo'in.RATTNER 2.Negatire Nature of Organic Radicles.SCHNEIDEWIND W.Substitution in Organic Compounds containingNegative Radicles.KNOEVENAGEL E.Negative Nature of Organic Radicles.JUILLARD I?.Diphthalylic Acid.HOBBS P.L.Derivatives of Orthotolidine.ZINCKE T.Action of Chlorine on Phenols.BAMBERGER E.and R.MULLER.Tetrahydro-@-naphthylamine.MEERSON S.Derivatives of Diamido-a-naphthol.WOLFFENSTEIN R.Action of Phosphordus Pentachloride on a-Hydroxy-naphthoic Acid.GOLDM ANN F.An thranol.LIEBERMANN C.Me thyloxyan thranol.LIE BERMANN C. and Gt.JELLINEK.LIEBERMANN C.Leuco-compounds from Anthraquinone Dyes.SACHSE H.Additive Derivatives of Dianthryl.LAFONT J.Action of Acetic Acid on Citrene.BOVCHARDAT G. and R.VOIRY.Terpinol.TANRET C.Oxidation of Hydrazocamphenes.RENARD A.Diterebenthyl.BAMBERGER E.Camphor-bases.HESSE 0.Lactucerin.GINSBERG J.Apiole.BACHMANN E.Emodin in Nephrorna Lusitamica.WOLLHEIM J.Chlorophyll.KNORR L.Identity of Phenylmethylpyrazoloneazobenzene with Phenyl-hydrazineketophenylmethylpyrazolone.KNORR L.and H.LAUBMANN.Pvrazoles and Pvrazolines.KNOEVENAQEL E.Bidesyls.Ethylated HydroxyaathraquinonesLAUBMANN H.1 5-Diphenylpykzoline. ".BISCHOFF C.A.Decomposition of Anilides at a High Temperature .MOHLER J.Pyridine-bases from Coal-tar.BLAU F.Distillation of Salts of Pyridinecarboxylic Acid.RUHEMANN S.Amide of Dihydroxyisonicotinic Acid.CLAUS A.Quinolinesulphonic Acid.JUNQFLEISCH E. and E.LBGER.Cinchoniline.CONINCK 0.DE .Ptoma'ines.GUARESCHI I. Ptoma'ines.AMTHOR C.Cadaveric Alkalo'id behaving like Strychnine.JAQUET A.Haemogiobin of Dog's Blood.KOWALEWSKI N.Action of Alloxantin on Blood.HENRY L.Volatility of Poly-oxygen Carbon Compounds.HENRY L.Volatility of Oxpgenised Carbon Compounds.PAQE'703'704'706'717'728'731xxs CONTENTS.SOKOLOFF N.Action of Feeble Baies on Nitroethane.ALBITZKY A.8ome.Broperties and Transformations of Dimethplallene .FAVORSKY A.C.Isomeric Change of Acetylenic Hydrccarbons by Hcat-ing them with Alcoholic Potash.CIAMICIAN G. and G. MAGNANINI. Pyrrolylene Tetrabromides.VARET R.Action of Zinc Cyanide on Metallic Chlorides.MEYER E. v..TROEGER J.Action of Sodium on Isobutyl Cyanide and IsoamylCyanide.MEYER E. v.Format,ion of Cyanethine from Ethyl Cyanide.KONDAKOFF J.Tertiary Ethyl Amy1 Ether.TISHTCHENKO W.Action of Halogen Hydrides on Oxymebhylene.TISHTCHENKO W.Action of Halogens on Oxymethylene.TISHTCHEKKO W.Action of Zinc Organic Compounds on Oxymetliylene :Synthesis of Primary Alcoliols.PASBENDER H.Ethylene Disulphides and Ethylene Disulphones.SOLONINA W.Action of Feeble Mineral Acids on Ally1 Alcohol.FISCHER E.and J. TAFEL. Isodulcitol.MAQUENNE. Perseite.HERZFELD A.Products of the Action of Red Mercuric Oxide and BarytaWater on Glucoses.SOROKIN B..TOLLENS B. and W. E. STONE. Fermentation of Galactose.TOLLENS B. and F. MAYER. Determination of the Molecular Weight ofRaffinose and Formaldehyde.WOLFF L.Acetalamine and Diacetalamine.BEHREND R.Diazo-dsriratives of Methyluracil.CHAUTARD P.Cyanaldehyde.WILLOERODT C. and A. GENIESER. Acetonechloroform.PECHMANN H. v.a-Diketones.OTTO R. and W. OTTO. Action of Ethyl Chlorocarbonate on Salts of Fattyand Aromatic Acids.HELL C.Brominating Organic Acids.GEUTHER A.Action of Ammonia on Ethylidene Oxyacetate.GORBOFF A.and A. KESSLER. Action of Iodoform,Methylene Iodide,and Iodine on Sodium Isobutoxide.SAYTZEFF M. C. and A. Isole'ic Acid.HAZTJRA K.Acids from Drying Oils.HAZURA K. and A. GRUSSNER. Acids from Drying Oils.MEWES W.Halogen Substitution Products of Ethyl Acetoacetate andtheir Behaviour with Sodium Ethoxide.HALLER A.Homologues of Ethyl Acetocyanacetate.MA~NANINI G.Action of Acetic Anhydride on Levulinic Acid.PINGEL C.Methyl Propiopropionate.REFORMATSKY S.New Synthesis of Dihydric Monotasic Acids fromKetones.SOROKIN B.Actionof Aniline on Isosaccharin.GORODETZKY J. and C. HELL. Preparation of Dibromosuccinic Acid .MARTINOFF B. and 5. SHUKOFFSEY. Action of Ethyl Iodide and Zinc andof Ally1 Iodide and Zinc on Ethereal Malonates.,.SOHST 0. and B. TOLLENS. Crystallised Saccharic Acid.MAUZELITJS R.Alkyl Salts of Sulphoacetic Acid and EthylidenedisulphonicAcid.BETTTHER A.Action of Iodobenzene on Silver'Nitrate.JACKSON C. L. and 0. D. MOORE. Additive Product of Tribromodinitro-benzene and Tetrabromodinitrobenzene.HERZIG J. and S. ZEISEL. Desmotropy in Phenols Bisecondary Pent-e thylphloroglucinol.Action of Sodium on Homologues of Ethyl Cyanide .FASBENDER H.Diethylene Tetrasulphide.Anilides of Glucoses and some of their TransformationsKILIANI H.Metasaccliaric Acid.PAGE'798'799CONTENTS.xxsiBARR A.Preparation of Nitramines from'NitrophenolsHALLER A. Cyanacetates of the Benzene Series.ABERIUS P.W.Lactones derived from Glycines.PALMER A.W.and C.L.JACKSON .POSPECHOFF W.Orthazotoluene.GRIESS l'.Diazo-compounds.BEYER C. and L.CLAISEN.Mixed Azo-compounds.preparation of Amidoazobenzene.WILLGERODT C. and M.FERKO.Phenylhydrazines.Biguanides Derivatives of Phenylbiguanide.ABENTUS P.W. and 0.WIDMANN.Bromaceto-orthotoluide and some ofits Derivatives.Pentamidobenzenes.GATTERMANN L. and G.WICHMANN.Two Bye-products in the TechnicalSMOLKA A. and A.FRIEDREICH.New Method for the Preparation ofNIETZKI R. and R.OTTO.Ssfranines and Dyes related therewith.KNECHT E.Dyeing of Wool and Silk with 'Basic Coal-tar Dyes.DORKEN C. Derivatives of Diphenylphosphorous Chloride and Diphenyl-SCHENK A. and A.MICHAETJS.Derivatives of Dimethylaniline contain-WELLER J.Xylylphosphorus Compounds and Toluphosphonic Acids .DENNSTEDT M.and J.ZIMMERMANN.Action of Methylamine and Ethyl-TUST P.Tetrachlorobenzoic Acid from Tetrachlorophthalic Acid..phosphine.ing Phosphoms and Mercury Dimethylanilineamine on Salicnldehyde.NIEJIENTOWSKI S.Metahomo-anthranilic Acid.BARGIONI G. and H.SCHIFF.Anhydrides of Cresotic AcidDENINGER A.Dicresoldicarboxylic Acid.KAPF S. and C.PAAL.Ethyl Phenacylbenzoylacetate.SCHIFF H.Isomerides of Tannic Acid.Ethyl Stlccinosuccinate.Substituted Hydrocarbons.KEHRMANN F.Iodophenolsulphonic Acids.KEHRMANN F.Di-iodophenolsulphonic Acid...LEVY S. and A.ANDREOCCI .OTTO R. and W.OTTO .Action of Phosphorus Pentuchloride onAction of Alkaline Sulphinates on TrihalogenHENRTQUES R.Splitting of the Naphthalene and Benzene Rings byOxidation.NIETZEI R.and R.OTTO.Action of Quinonedichlorimide on Naphthyl-amine.Molecular Refraction as a means of Determining the Con-QUINCKE F.Nitro-derivatives of Acenaphthene.LAFONT J.Action of Acids and Anhydrides on Terpilenols.RIZZA B.Camphor from the Ethereal Oil of Ledzcmpalustre.RENARD A.Hydrocarbons in Resin Oils.BENEDIKT R. and E.EHRLICH.Shellac.CIAMICIAN G. and P.SILBER.Apiole.MARCK B.v.D.Picrotoxin.BETTINK W.Ophioxylin.Hydrochloric Acid on Pyrrolines.LANG W.Action of Pyridine on Metallic Salts.WALLACH 0.stitution of Members of the Terpene-group.ARNAUD.Crystalline Arrow Poison of the Comalis,extracted from theWood of the Ouabai'o.DENNSTEDT M. and J.ZIMMERMANN.Bases formed by the Action ofDENNSTEDT M. and Je ZIMMERMANN.Reduction of Pyrrolinephtha-lide.Condensation of Ethyl Tetramethylphenyl-amidocrotonate.CONRAD M.and L.LIMPACH .MATHEUS J.Azo-dyes of the Hydroxvquinolines.HEYMANN B. and W.KOENIGS.Lepidine-derivatives. 852PAGExxxii CONTENTS .CONRAD M. and L.LIMPACH.Synthesis of Dihydroxyquinaldine-deisiva-tives.ABEKIUS P.W.Aromatic Halogen Acetamido -compounds and theirDerivatives.WILL W.Atropine and Hyoscyamille.WARNECKE H.Wrightine Conessine and Oxywrightine.SCHMIDT E. and H.HENSCHKE.Alkaloiids of Scopoliajaponica.SCHMIDT E.SOLOVIEFF A.Application of Dialyais to the Study of the GcluhiousState of Albuminoid Substances.WEYL l’. Silk.SATIN M.Alkaline and Acid Albumin-derivatives.BERTIN-SANS H.Spectrum of Acid Metheemoglobin.ENGLER C.Formation of Petroleum.VENABLE F.P.Bromination of.Heptane.Q-RISSOM R.3.Action of Chlorous Anhydride on Heptylene.B ~ H A L A.Conversion of Enanthylidene and Caprylidene into IsomericB%HAL A.Alcoholic Nitrate of Silver as a Reagent for Acetylenic Hydro-carbons.B ~ H A L A.Preparation of Isopropylacetylene from Methyl IsopropylKetone.BOISSIEU P.DE .Methyliodoform.MANNING I.H.Decompoaition of Potassium Cyanide.WILM T.Potassium Platinocyanide.NORTON T.H.Metallic Nitroprussides.GENTRESSE P.Combination of Aluminium Chloride with Acetonitrileand Chloracetonitriles.’.U~TTIO 0.Compound of Metcyl Aicohol with Potash.WILL W. and C.PETERS.DENIG~S GI. and E.BONNANS.Rotatory and Reducing Power ofLactose.B’ISCHER E.and J.HIRSCHBEROER.Mannose.ANDERLINI F.Compounds of Glycogen with Sulphuric Acid.BEMBRITZRI F.Succinylamidoxime and its Derivatives.LOCHERT H.Acetals of Normal Propyl Glycol.BBUNINO 3.v.Methylhydrazine.NORTON T.H. and J.H.WESTENHOPF.Action of Silicon Tetrafluoride onAcetone.NORTON T.H. and J.H.WESTENEOFF.LORIN.GORODETZKY J. and C.HELL.Action of Silver on Ethyl Dibromo-succiii ate.HALLER A. and L.BARTHE.Ethyl Cyttnosuccinate and Ethyl Cyanotri-carball ylate.HALLEE A.Inhence of Negative Radicles on the Functions of certainGroups.ENOPS C.Molecular Refraction of Fumaric and Malei’c Acids,&c.GERNEZ D.Action of Normal Alkaline Tungstates on Solutions ofTartaric Acid.SPRINQ W. and C.WINSSINGEE.Action of Chlorine on Sulphonic andZELIRSKY N.2 4-Thioxen and Tetramethylthiophen.WILLGEEODT C.Iodation of the Phenols by Nitrogen Iodide.KEHRMANN F.Action of Alkali Nitrites on Halogen-derivatives ofQuinones.KUNZ H.Morphine Hydriodide.Alkalo‘ids of Scopolia Hlardnackiana.Hydrocarbons.Derivatives of IsodulcitolBromination of Acetone .Action of some Organic Acids on Ethyl CyanideOxythio-derivatives of Heptyl.CLAUS A.Constitution of Benzene.CHIOZZA L.Formation of Eugeiiol from Coniferin.SAGLIER A.Combinations of Aniline with Copper Salts.a56CONTEXTS.xxxii iPAGECOMEY A.M. and C.L.JACKSON.Action of Fluoride of Silicon onOrganic Bases.ECEENBOTH H. and J.RUCKEL.Action of Phenylamine and DiphenjlamineBORSSNECK P.Compounds of Acetone with the Sulphites of AromaticAmines.~ANDROWSEI E.v.Derivatives of Paraphenolphenylamine.NIETZKI R.and A.W.SCHMIDT.FORRSTER F.Tautoinerism of Thiocarbamides.HIRSCH L.Bnanidines and Guanidine Cyanides.FINGER H.Benzazmide.WILLGEROD T C.H y drazines.NIETZEI R. and R.OTTO.BAMBERGER E. and lt.MULLER.Phthalimide.GAZZARRINI A.Action of Su!phur on Benzaldehyde.MEUNIER J.Combination of Mannitol with Benzaldehyde.GENVRESSE P.Action of Chloracetonitrlle on Benzene in Presence ofAluminium Chloride.BARTHE L.Methyl Benzojlcyanacetate and Cysnacetophenone.Hydrochlorides on some Fatty Aniines.Nitrogenous &uinone.derivatives .Indamines and IndophenolsBURC‘EER E.Synthesis of Toluoylpropionic Acid.GORODETZEY J. and C.HELL.Dianllidosuccinic acid.AUGER V.Chlorides of Bibasic Acids.REISSERT A.Constitution of Pyranilpyroic Acid,Pyranilpyroi’nlactoneand Anilsuccinic Acid.HANTZSCH A.and F.HERRMANN.Desmotropy.BONIGER M.Desmotropic Derivatives of Ethyl Succinosuccinate.JOUILLARD P.Isomeride of Orr hophenylphthalidecarbox~lic Acid.BALLY 0.Ethyl Phloroglucinoltricarboxylate.MICHAEL A.Action of Ethyl Sodomalonate on Resorcinol.JANOVSKY J.V.Toluidinesulphonic Acids.CIAMICIAN G. and C.ZATTI.lndolecarboxylic Acids.MAGNANINI G. # Acetyl-compounds of Methylketole and Scatole.MAGNANrNI G.Couversion of Methylketole into Quinaldine.CIAMICIAN G. and G.MAGNANINI.Methylindolecarboxylic Acid.FISCHER E. and T.SCHMIDT.3’-Phenyliudole.ADAM P.Diphenyl-derivatives.B$HAL A.Hydration of Tolane.UE BOISSEU P.New Method for the Preparation of TetraphenylethyleneBAMBERaER E. and A.ALTHAUSSE.a-Tetrahydronaphthylamine.KEBLER J.T. and J.H.NORTON.WALDER J.ColouSing Matter from Anthraquinonedisulphonic Acid andSodium Nitrite.Acenaphthene and ChlorineBOUCHARDAT and VOIRY.Terpinol.VOIRY R.Essence of Eucalyptas globulus.VOIRY R.Essence of Cajeput.JANDOUS A.Oil of Pepperniint.CAZENEUVE P.Nitrocamphorates.TANRET C.Sugars from Hesperidiii and Isohesperidin.HECKEL E. and F.SCHLAGDENHAUFFEN .MANNING I.H. and G.W.EDWARDS.Salts of Camphoric Acid.Vernonin.BALLY 0.Action of Chlorine on Pyridine,Piperidine,and their Deriva-tives.JEAURENARD A.Condensation of Phenylacetaldehyde with Ammoniaand Ethyl Acetoacetate.MATHEUS J.A New Quinolinequinone.MILLER W.v.Action of Sulphur on Quinaldine.WEIDEL H.and M.BAMBERGER.Quinoline-denvatives.COMBES A.Nnphthaquinoliiies. WEIDEL H. and G.v.GEO 1iGIEVICS.Phenylquinoline-derivatives.CAVAZZI A.Action of Silicon Tetrafluoride on Quinine Solutions.VOL.LIV.Cxxxiv CONTENTS .JUNGFLEISCH E. and E.L&ER.Cinchonchibine.LELLMANN E. and W.GELLER.Piperidine.LELLMANN E.Piperylene Nitrogen Chloride.SCHMIDT E.Conversion of Hyoscyamine into Atropine.BOMBELON E.Ergotinine and Cornutine.NENCEI M. and N.SIEBEE.HBematoporphyrin.SCHUTZENBERGER P.Synthetical Studies on AlbuminoYds and Protelds .MULDER E.Constitution of Paracyanogen and Cyamelide.REINHABDT C.Titanium Nitrocyanide.WARREN H.N.Fulminates.ERAFFT F.Isolation of the Higher Normal ParadEns from LigniteYe troleum.DUNSTAN W.R.and T.S.DYMOND.FISCHEB E. and J.TAFEL.Isodulcitol.MEUNIER J.Compounds of Mannitol.SEYFEBT F.Composition of Iodide of Starch.HOFMANN A.W.Anhydro-bases of Fatty Diamines.HORTON H.I3.L.Hexamethylenetlmine-derivatives.PLOCHL J.Reaction of 3'ormddeh;yde.ZEDEL W.Action of Hydroxylamine on Acetylacet.one.PECHMANN H.v. and R.OTTE.Homologues of Diacetyl.FBANCHIMONT A.P.N.Influence of Negative Groups on the PropertiesFITTIG R. and A.EELENBACH.Action of Sodium on Ethyl Chlor-acetate.EONOWALOFF D.F.Action of Acids on Tertiary Amy1 Acetate.FURTH E.Preparation of Normal Valerie Acid and Dipropylacetic Acidfrom Ethyl Malonate.MICHAEL A.Constitution of Ethyl Sodacetoacetate.MELIEOFF P.and N.ZELINSKY.Ethyl Glpcidate.ELEBER C.Action of Ethyl Sodiomalonate on Chloromethyl Ether .BISCHOFP C.A. and E.BJELT.WISLICENUS J.Fumaric and Maleic Acids.PUN G.Unsaturated Acids.PAT ERN^ E. and R.NASINI.Molecular Weight of Citraconic,Itaconic,Mesaconic,Fumaric,and Maleic Acids.GAUS R. ,W.E.STONE. and B.TOLLENS.Formation of Saccharic Acidas an Indication of Dextrose,and of Furfuraldehyde 88 an IndicationSCHROTTER ET..BISCHOFF C.A.Ethyl Acetylenetetracarboxylate.GUTHZEIT M. and 0.DBESSEL.Ethyl Dicarboxyglutarate.BISCHOFF C.A.Synthesis of Polybasic Fatty Acids.FBANCHIMONT A.P.N. and E.A.KLOBBIE.Methylamides and Ethyl-amides of Trichloraeetic and Trimethylacetic Acids.FBANCHIMONT A.P.N. and E.A.KLOBBIE.Methylamides and Ethyl-amides of Heptylic Acid.ENGEL.Formation of Amidobutyric Acid by the Action of Ammonia onCrotonic Acid.EMICH F.Amides of Carboruc Acid.MULDER E.Urethane and some of its Derivatives.KUTSCHIG C.v.Reaction Product of Phosphorus Pentasulphide andCarbamide.MARQUARDT A.and A.MICHAELIS.Ethil Teliuride.MARQUARDT A .Alkyl-derivatives of Bismuth.PALM R.Chemical Nature of the Peptones.BLYTHE G.W.Arsenic Cyanide.Preparation of Ethyl Nitrite .RAYMAN B.Ehamnose Isodulcitol.of Compounds.Symmetrical Diethylsuccinic Acids .of Arabinose in Carbohydrates.Action of Dilute Mineral Acids on Saccharic Acid .FRANCHIMONT A.P.N.Ureides.ENOEL.Aspartic Acids.PAGRlowCONTENTS.xxxvPAGEPOLONOWSKY M.Acetoacetate. 1067PAWLEWSKI B.Thiophen.1068LACHOWICZ B.Constants of Benzene.1068HORSTMANN A.Physical Constants of Benzene.1069BAEYER A.v.Constitution of Benzene.1069SODERBAUM H.a-. and 0.WIDMAN.Preparation and Oxidation Productsof Nitrocymene.1076REINITZER F.Cholesterin.1076ZAUNSCHIRM H.Alkyl-derivatives of Benzylamine Reduction ofAmarine.1077UEBEL C.Ammonia-derivatives of Cumaldehyde.10’78VAN ROMBURGH P.,1079HOLZMANN E.1080BANDROWSKI E.v.MINTJNNI G.1081NIETZKI R. and J.DIESTERWEQ.Disazo-compounds. 1082WESSEL R.Carbodi-imides of the Aromatic Series and Phenylhydrazine 1083PINNEB A.Action of Carbamide on Hydrazines.1084THEURER C.A.Xanthopllol.1084WIDMAN 0.Acetopropylbenzene,Acetocumene. and their Derivatives.1085KRAFFT F.Benzene-derivatives of High Molecular Weight.1087PECHMANN H.v.and H.MULLER.Aromatic Diketones. 108’7MANASSE 0.Action of Amy1 Nitrite on Nitrosoketones. 1088NIEMENTOTVSKI S. and B.ROZAUSKI.Nitrotoluic Acids. 1088STIERLIN R.Derivatives of Ethyl Benzoylacetate.1089FITTIQ R. and H.SCHLOESSER .with Succinic Acid.1089WILL W.BOTTINGER C.Gallic Acid and Tannin.1090WARDEN C.J.H.Cocatannic Acid.1090LETT S. and A.AKDREOCCI .BAEYER A.v.1091JACKSON C.L. and W.S.ROBINSON .Tribromodinitrobenzene. 1091ANEICHUTZ R. .Anilsuccinic Acid.1092LIPPMANN E. and I?.FLRISSNER.Phenoldicarboxylic Acids.1092HARTSHORN q.T. and C.L.JACKSON.Anilinetrisulphonic Acid. 1093STAEDEL W.Phenacyl Compounds. 1093BRAUN E. and V.MEYER.Aldine Formation. 1093BISCHOFF C.A.OrthodinitrostiIbene.1094BISCHOFF C.A.Azo-dyes from Orthodiarnidost#ilbene.10941CARNELLEY T. and J.DUNN .GRAEBE C. and P.JUILLARD.Benzilorthocarboxylic Acid.1095MORAWSKI T. and M.GLASEB .arnine.1096HEIM E.Action of Ammonium Sulphide on some Dinitro-compounds.1096ZINCKE T. and H.THELEN.Phenylhydrazine-derivatives of Hydroxy-naphthaquinone.1097WALLACH 0.Terpenes. 1098WEISS F.Cheken Leaves.1100CIAMICIAN G. and P.SILBER.Apiole.1100POMERANZ C.Cubebin. 1100DE REP PAILHADE J.1101Condensation of Glyoxal with Ethyl Malonate andNitramines derived from Alkyl Aromatic Diamines .Thio-derivatives of some Secondary and Tertiary AmiriesAction of Aniline on Quinonephenyliniide arid Di-Action of Paratoluidine and of Aniline on Phloroglucinolphenylparazophenylene. 1081Condensation of Ethyl BenzoylacetateConstitution of the Compound obtained by acting on Tri-methylpyrogallol with Nitric Acid.BAEYER A.v.Hydrophthalic Acids.1090hydroterephtbalic Acid.1091Dichloroterephthalic Acid and Diehlorodi-The Reduction Products of Terephthalic Acid.Action of Ethyl Sodiomalonate onReissert’s Ppnilpyroinlactorie,Pyranilpyroic Acid,andAction of Heated Copper on a Mixture ofthe Tapours of Phenol m d Carbon Bisulphide.1095Action of Citraconic Acid on Naphthyl-Organic Compound which Hydrogenises Sulphura xxxvi CONTENTS .DE REY PAILHADE J.Philothion.LEWY M.Oxyazoles and their Derivatives.PINNER A .Hydanto'ins.Piperidines.into Oxypiperidine.JAECKLE A.Higher Homologues of the Synthetical Pyridines andSCHOTTEN C.Conversion of Piperidine into 8-Aniidovaleric Acid audLELrxaNN E.and w.GELLER.Tertiary Phenylpipcridine.LELLMANN E. and W.GELLER.Derivatives of Tertiary PhenglpiperidineLELLXANN E. and W.GELLER.Formation of Colouring Matters fromALTSCHUL J.Orthonitroparahydroxyquinoline and Orthamidoparahydr-Paramidophenylpiperidine.oxyquinoline.CONRAD M. and L.LIMPACH.y-aydroxyquinaldine.KSORR L.Syntheses with Ethyl Acetoacetate.KLOTZ C.a-Amidolepidine.HEYXANN B. and W.KOENIGS.Lepidine-compounds.LE BLANC M.Isoquinoline and its Derivatives.KOSSEL A.New Vegetable Base.~IESSE 0.Morphine.ROSER W.Narcotine.GOLDSCHMIEDT G.Papaverine.GOLDSCHMIEDT G.Constitution of Papaverine.PAUL B.H.Cocaine and its Salts.CONINCK 0.DE .Ptoma'ines.TiraJDIcHuM L.L.w.MALY R.Oxidation of Albumin with Permangaiiate.Alkalo'ids in Human Urine.KOKOWALOFF I. Formation and Decomposition of Ethereal Salts :Compounds of Amylene Trimethylet hylene with Acids,as Bases ofChemical Equilibrium.The Hydrocarbons C,H,,and C9Hl8,obtained from MethylDipropyl Carbonyl and Ethyl Dipropyl Carbinol.Isomeric Change of Disubstituted Acetylenes and of Di-methylallene under the Influence of Metallic Sodium Sjntheses ofMethyl Chlorothioformate Polymeric Thiocarbonyl ChlorideAction of Methyl Iodide and Zinc on Ethyl Propyl KetoneAction of Ethyl Iodide and Zinc on Ethyl Propyl Ketone .SOKOLOFF X.FAVORSKY A.Acetglenecarboxylic Acids.KABLUKOFF I.Butdlyl Methyl Pinacone.KABLUKOFF I.Derivatives of Hexyl Glycerol.Sodium Hydrogen Carbonate.TCRPIN G.S.beptdecylamine.RATHKE B.SOKOLOFF E.SOKOLOFF E.JEHN C.Action of Polyatomic Alcohols on Solutions of Boric Acid andSTRacriE H .Propylenediamine and Trimethylenediamine.POLONOWSKY M.FRANCHIMONT A.P.N.Sulphacetic Acid and its Derivatives.BRUGGEMANN R.Action of Sodium on Ethyl Butyrate and Isobu-MICHAEL A. and H.PENDLETON.Alloiscmerism in the Crotonic AcidSeries.~IELIKOFF P.Action of Hypochlorous Acid on Angelic Acid.WISLICENUS W.Synthesis of Ketonic Acids.ARNOLD E.Ethylic Methjloxalacetate and Ethploxalacetate.SCHUKOFFSKY S..GORBOFF A.Oxytetric and Hydroxytetric Acids.FRANCHIMONT A.P.N.and E.A.RLOBBIE.Derivatives of Carbamide .LADENBURG A .Constitution of Benzene.SACHSE H. Configtiration of the Benzene Molecule.KIETZKI R.and F.SCHMIDT.Dihydroxyquinone and l'etrahydroxy-benzene.Condensation of Glyoxal with Ethyl Acetoacetate .tyrate.Action of Eth;rl Iodide and Zinc on Ethyl MalonatePAGECONTENTS.xxxviiBBUNNEIL H. and P.CHUIT.DichroYns obtained by the Action of AquaBANKIEWICZ Z.Reduction-products of Metadinitroparncetotoluide.VAN ROMBURGH P.Trinitrometaphenylenedimethyldinitramiue.RICHTER V.v.Chromogenic Carbins Constitution of Rosaniline Salts .WITT 0.N.Eurhodines.FREUND M. and B.B.GOLDSMITH.Derivatives of Carbizin and Thio-carbizin.BENDER 3.Action of Phenylhydrazine on the Alkyl Salts of HalogenRICHTER V.v.New Chromogenic Groups.HANTZSCH A.Decomposition Products of Chloranilic and BronianilicAcids.ZINCKE T. and C.CERLAND.Conversion of Hydrindonaphtliene- andIndonaphthene-derivatives into Substituted AcetophenonecarboxylicAcids.WISLICENUS W.Action of Ethyl Isobutyrate and of other Ethereal Saltson Ethyl Oxalate.TTISLICENUS W.Action of Ethyl Acetate OE Ethyl Phthalate.WISLICENUS W.Action of Ethyl Oxalate on Lactones.HOOGEWERFF S.and W.A.VAN DORP.Action of Potassium Hypo-bromite on Amides.VAN ROMBURGH P.Nitramine derived from Tetramethyldiamidobenzo-phenoiie.BISCHOEF E.Action of Nitrous Acid on Tetramethylcliamidobenzophe-none.NEY E.DesoxybenzoPn and Desaurins.ZINCKE T. and C.GERLAND.Action of Hrpochlorous and Hppo-bromous Acids on Chlor- and Brom-hydroxynaphthaquinone and theirConversion into Hydrindonaphthene- and Indonaph thene-derivatives .HIRSCH R.a-Naphthylamine-6-monosulphonic Acid.MEERSON S.An lsollueride of Oximidonaphthol.WEGERHOFF P.Intramolecular Change of l'henanthraquinoneinonoximeSACHSE H.Derivatives of Dianthranyl.GOLDJIANN I?.Derivatives of Anthranol.BALLGARTEN F.Derivatives of Anthranol.LIEBERMANN C.Spectra of the Alkoxy-anthraquinores.LiEBERMANN c.A New Dihydroxyitnthraquinone Hystarazin.SUHOELLER A.Hystazarin.JELLINEK 3.Purification of Flaropurpurin.WALLACH 0.Terpenes and Ethereal Oils.WALLACH 0.and E.GILDMEISTER.'I'erpenes and Ethereal Oils.SHIMOYAMA Y.Chemistry of Buchu Leaves.GINSBEHG J. ,Apiole.DAVIDOFF D.Methysticin.PFITZINGEB W.a-y-Dimethylparatoluquinoline.EINHOHK A. and P.LEIINKERING.A P-Lactone of t h o Quinolinc Series .~ISTRZPCKI A.Opianio Acid.LIEBERMANN C.I satropylcoca'ine.SCHMIDT E.and F.WILHELM.The Berberine Alkaloids.JOLIN S.The Acids of Pig's Bile.MOISSAN H.Ethyl Fluoride.MALBOT H.Propylene Iodide.LUDEKING C.Cbemistry of Combustion.LINDET L.Influence of Temperature on the Productim of HigherAlcohols by Fermentation.HAMLET W.M.Fuse1 Oil in Beer.Regia and Bromine Aqua Regia.KASSNER G.Decomposition Products of Panicole.Ketonic Acids and Halogen Ketones.LUCAS L.Anthrwene Hydride.GILSON E.Lecithin.PAGExxxviii CONTENTS .PAGEDE FORCRAND.Polybasic Glyceroxides.1264MEUNIER J.Mannitol Dibenzoate. 1265HONIB M. and L.JESSER.Carbohydrates. 1266GRIESS P. and G.HARROW.Hexamethylenetriamine. 1268LADENBURG A. and J.ABEL.Ethylenimine. 1268HANTZSCH A. and G.POPP.Thiazole.1269FITTIG R.and A.ERLENBACH.1269BENEDIKT R.Hydrolysis of Fat. 1269BATTER A. and K.HAZURA.Drying Oils.1269HAZURA K.1270KRAFFT F.Ricinoleic Acid.1270MOSCHELES R. and H.CORNELIUS.Tetric Acid and its Homologues.1272Constitution of Mesitonic Acid.1272WISLICENUS W.Ethyl Oxallevulinate.1273ARTH G.Pimelic Acid from Menthol.1273ANSCHUTZ R.Diacetylracemate by Raoult’s Method.1273BOTTINGER C.Water of Crystallisation of certain Pyrotritartrates. 1274BUCHNER E.Salts of Unsaturated Acids.1274HERZIG J.1275JACKSON C.L. and J.F.WING.Tribromotrinitrobenzene.1276DRECHSEL E.Electrolysis of Phenol by Alternating Currents. 1276ZINCKE T. and F.KUSTER .amidophenol. 1277METZELER K.Iodine-derivatives of Quinone. 1278KORNER M.E.G. and V.WENDER. 1278FAUCONNIER A.Action of Aniline on Epichlorhydrin.1280LOSCHER K. and R.KUSSEROFP.Action of Aniline on Bromofumarimide 1281LACHOWICL B. and F.BANDROWSKI.Compounds of Organic Bases withMetallic Salts.1281GTJDEMAN E.Anhydro-bases from Unsymmetrical Metaxylidine. 1282VIGNON L.Dimethylaniline and Diphenylamine Sulphates.1282COMEY A.31. and F.W.SMITH. 1283GOLDSCHMIDT H.and E.MOLINARI.Diazoamido.compounds.1283RICHARDSON W.H.New Phenylhydrazine Salts.1286FISCHER 0. and L.WACKER.1.286CVLMANN J. .Bromacetophenone.1287PECHMANN H.v.Osazones.1287GLOCK G.Paratolenylimido Ethyl Ether. 1289GLOCK 3.Phenyleneparadiacetoimido Ethyl Ether.1290FISCHER 0. and E.HEPP.Azophenine and Induline. 1291BORELLI S.Benzotribromanilide. 1292GABXIEL S. and J.WEINEE.Derivatives of Propylamine.1292GOEDECKEMEYER 0.Compounds. 1294BB~MME R.Amido-derivatives of Metaxylene.1295UDR~~NSKY L.v. and E.BAUMANN. 1296HALLEB A.Cyanacetates.1298CHODOUNSKI K.Acid.1298FISCHER E. and J.TAPEL.Oxidation of Glycerol.1264FAUCONNIER A.Action of Ammonia on Epichlorhydrin. 1265JUNGFLEISCH E. and L.GRIMBERT.Levulose. 1266FISCHER E.Compounds of Phenylhydrazine with Sugar.1263GABRIEL S.Vinylamine and Bromethylamine. 1267Action of Sodium on Ethyl Chloracetate .Oxidation of Unsaturated Fatty Acids with Permanganate .HAZURA K. and A.GRUSSNER.Acids from Drying Oils. 1270FRETTND M. and E.GUDEMAN.Tetraiuethylene-derivatives.1271ANSCHUTZ R. and C.GILLET .Determination of the Molecular Weight of DimethylAction of Ethereal Salts of Diazoacetic Acid on EtherealAction of Sulphuric Acid on Bromo-derivatives of Benzene .Action of Chlorine on Catechol and Orth-Some New Benzene-derivativesSilicotetrafluorides of Certain BasesAction of Nitroso-bases on PhenylhydrazineAction of Secondary Aromatic Amines and Hydrazines onAction of Potassium Phthalimide on OxyhalogenBenzoic Chloride as a ReagentSTIERLIN R.Derivatives of Ethyl Benzolylacetate.1298Decomposition of Quinic Acid by dilute HydrochloriCONTENTS.xxxixPAGEHOTTER E.Phenaceturic Acid and its Derivatives.1298GUARESCHI I.Bromophthalic Acid.1300ROSER W.Action of Strong Sulphuric Acid on Diphenylsuccinic Acid.1301EQER E.Paranitrometamidobenzenesuhhonic Acid.EICHELBAUM G.a-Benzylhomo-orthophthalic Acid.1300PELLIZ'ZSRI G.and V.MATTEUCCI.Amidosulphonic Acids.ROSER W.Indene-derivatives.ROSER TV.Methylindenecarboxylic Acid.ROSER W. and E.HASELOPF .Roux L.EHRLICH E. and R.BENEDIKT .Dibromindone-derivatives.Application of the Aluminium Chloride Method to the Naph-thalene Series.Oxidation of /3-Nwphthol to Orthocarb-oxycinnamic Acid.JACOBSON P.Orthamidated Aromatic Mercaptans.KEQEL 0.Isomeric Naphthgl Phenyl Ketones.MORIN H.Essence of Rosewood.BENEDIKT R. and F.ULZER.Shellac.CLAASSEN E.Catalpin.HERZIQ J.Quercetin.HERZIG J.Quercgtin-derivatires.PHIPSON T.L.Rhinanthin.ARNATJD.Strophnntin.SPICA P.Diosmin.OLIVERI V.Constitution of Quassin.BALDI D.Jecorin in the Animal Body.N ETTLEFOLD F.Dye from Sea-weed.metbylenetetramine.ammonia and Paraldehyde.LACHOWICZ B.Piperidine Dyes.MERCK E.Furfurethenepjridine.ROSER W.Narcotine.BRIEQER L.Tetanine and Mytilotoxine.HAXDY E.and N.GALLOIS.Anagyrine.ZALOCOSTAS P.Constitution of Spongin.MARCANO V.Peptonic Fermentation of Meat.RICHARDSON W.H.Frobable Orthoquinone derived from AnthraquinoneDURKOPP E.GEIESS P. and G.HARROW .DURKOPF E. and M.SCHLAUGK .Pyridine and Piperidine Bases formed from Acetone.Action of Ethyl Acetoacetate on Hexa-Parvoline obtained from Propaldehyde-GAUTIER A. and L.MOURGUES .WILT. W. and G.BREDIQ .Alkaloids from Cod-liver Oil.. Conversion of Hyoscyamine into AtropinePh,y sio logical Chemistry .CHITTENDEN R.H. and G.W.CUMMINS .CHITTENDEN R.H. and M.T.HUTCHINSON .Influence of some Opganic Sub-stances on Gas Metabolism.Action of Uranium Salts onDigestive Ferments.GREENWOOD M.Digestion in Rhizopods.CHITTENDEN R.H.Dehydration of Glucose in the St.omacli and Intes-tines.CHITTENDEN R.H. and J.A.BLAKE.Influence of Antimonious Oxide onMetabolism.WEISKE H.Asparagine as a Nourishing Constituent of Food.CHITTENDEN R.H. and J.A.BLAKE.Distribution of Antimony in theENGEL and KIENER.Formation and Elimination of a Ferruginous PigmentMASON W.P.Ash in Bones of Different Ages.Organs and Tissues.in Poisoning with Toluylenediamine.XI CONTENTS.STUTZER A. and A. ISBEBT. Relation of Carbohydrates in Food to Diges-tive Ferments.SEEGEN J.Changes in Carbohydrates in the Alimentary Canal.SEEQEN J. - From what Material does the Liver form Sugar ?.HAEEBROEK K.Fate of Lecithin in the Body.KELLNER 0.Relative Nutritive Value of Fat and Carbohydrates.SCHRODT M.Feeding with Earth-nut and Palm-cake.MONARI A..MONARI A.Pormation of Xanthocreatinine in the Organism.MESTER B.Scatoxylsulphuric Acid and Scatole-pigment.LANDWEUR H.A.Animal Gum.LIEBERMANN L.Animal Dextrin.GEIFFITHS A. B.Nephridia and Liver of Patella vulgata.SANARELLI G.Absence of Uric Acid and Alkaline Reaction in t’he Urineof Carnivore.MULLER F.Presence of Hydrogen Sulphide in Urine.HOPPE-SEYLER G.Ethereal Hydrogen Sulphates in Morbid Urines .GLEY E. and C. RICHET. Hourly Excretion of Urea and Total Nitrogeiiin Urine.LETTBE W.New Pathological Colouring-matter in Urine.UDR~NSZKY L. T.Urinary Pigments.JAKSCH R.v.Ferments in Human Feces and in the Contents of Cysts .BOND C. J.Hemoglobin Crystals in Septic Diseases.GLEP E. and P. RONDEAU. Physiological and Therapeutical Action ofHyoscine Hydrochloride.HECKEL E.Sodium Benzenesulphinate as an Antiseptic for Wounds .BOUCHARD C.Naphthol as an Antiseptic Medicine.LINOSSIER G.Localisation of Barium in the Organism after ChronicPoisoning with a Barium Salt.LBPINE R.Action of Acetoiiaphthalide and Dihydroxynaphtlislene onBlood.WEYL T.Saffron Substitules.DE SAINT MARTIN L.Influence of Sleep on the Activity of RespiratoryCorn bustion.KRUGER F.Coagulation of Fibrin and Intravascular Clotting.GREEN J. R.Influence of Calcium Sulphate on the Coagulation of theBlood.BIRCH B. and H. SPONB. ‘Secretion of the Gall Bladder.ATWATER W.0.Analyses of American Fishes.STADELMANN E.Ferments in Noriiial Urine.PELLACANI P. and 8. BERTONI. Physiological Action of Ethyl Lactate .CERVELLO V.Physiological Action of Trimethylethoxyammoniuni andTrimethylvinylammonium Hydroxides.ADUCCO V. and U. Mosso. Physiological Action of Saccharin.COPPOLA F.Physiological Action of Santonin and its Derivatives.PISENTI G.Physiological Action of Thallin.MAYS T. J.Action of Brncine and Strychnine -.COePOLA I?.Physiological Action of Caffelne.SIGHICELLI C.Physiological Action of Cocaine.BBUCEE E.Behaviour of Congo-red with Human Urine and with AcidS a l t s.- .D’ARSONVAL A.Rapid Absorption of Carbonic Anhydride from ExpiredAir.HANRIOT M. and C. RICHET.Absorption o€ Carbonic Anhydride,andGraphic Record of the Carbonic Anhydride Expired.STADELMANN E.Formation of Ammonia in the Pancreatic Digestion ofXibrin. -SALKOWSEI E. and A. KOTOFF. In%uence of Phenylacetic Acid onProte’id Metabolism.KAST A.The Output of Chlorides in its Relation to Metabolism.Change of Chemical Composition of Muscle by FatiguePAGECONTEXTS. XliCONINCE 0. DE.Fate of Pyridine in the Organism.RUTGERS J.Nutritire Value of Vegetable Prote'ids compared withAnimal Prote'ids.KRIERIEM W. v.Cellulose in the Nutrition of Herbivorous Animals .NEUMEISTER R.Physiological Action of Albumoses and Peptones.GRBHANT N.Physiological Action of the Products of Incomplete Com-bustion of Illuniinating Gas.DUBOIS R. and P. Ronx.MORNER K.A. H.Pigments of Melanotic Sarcomata.LIEBERMANN C.Therapeutic Substitutes for Chiyai-obin.CAMERER W.Urea and Total Nitrogen in Human Urine.GOLDMANN E. and E. BAUMANN. Cybtiri in Normal Urine.SALKOWSKI E.Spontaneous Decomposition of Bilirubin.WEYL T,.Poisonous Properties of Dinitrocresol.HANRIOT M. and C. RICHET. Influence of Diet on the Elimination andAbsorption of Carbon ,.HANRIOT M. and C. RICHET. Infliience of Diet on Respiratory Changes .WURTZ R.Volatile Bases in the Blood and Breath.JAWORSKI W.Action of Acids on the Functional Activity of the HumanStomach.ROSPNHEIM T.Amount of Acid in the Stomach on an Amylaceous Diet.GUNZBURG A.Free Hydrochloric Acid in the Stomach Contents.WEISKE H.Does Cellulose econornise the Decomposition of Yroteid inthe Nutrition of Herbivora ?.WOOLDRIDGE L.C.Changes Effected by Digestion on Fibrinogen andFibrin.MARTIN S. H. C. and D. WILLIAMS.DASTBE A.Influence of Bile on the Digestion of Fats.GAGLIO G.Stability of Carbonic Oxide and Oxalic Acid in the AnimalOrganism.WOOLDRIDGE L. C.Coagulation of the Blood.MACMUNN C. A.Chromatology of Sponges.VIETH Y.Compositjon of Cow's Milk.LATSCHENEERGER J.Formation of the Colouring Natter of Bile.STICKER G.Influence of the Secretion of Gastric Juice on the Quantityof Chlorine in Urine.VANNI L. and E. PONS. Phosphates in Urine.ADUCCO. Urine Reaction.CRUCI. Physiological Action of Alkalis and Alkaline Earths.MAXIMOTITCH J.Antiseptic Properties of a-Naphthol.GRBHANT N.Poisoning by Carbonic Oxide.WURTZ R.Toxic Action of Bascs Procluccd by Alcoholic Fermentation .ATWATER W.0.Chemistry of Fish.TAMMANN G.Occurrence of Fluorine in the Organisni.BOAS J.Digestion of Albumin.PLANTA A. v.Food of Larval Bees.WOLFF E. and others. Foddering of Horses,and the Circulation ofMineral Xatter in the Horse.JAFFE M. and P. HILBERT. Acetanilide and Acetotoluide in Relation toAnimal Metabolism.,HASEBOEK K.Chylous Pericardisl Fluid. ,.LABORDE and MAGNAN. Toxic Action of Alcohols and Artificial Bouquets .LABORDE and A. RICHE. Physiological Action of Nickel Salts.CAHN A and V. MERING. IJigestion of Flesh in Normal Stomachs.SIEVERT. Influence exerted by Sodium Chloride on the Digestion ofAlbumin in Fodder.MORNER C. T.Microchemical Observations on Hyaline Cartilage.MOSCATELLI R.Lactic Acid of the Thymus and Thyroid.WISSOKOWITSCH.Productioii of Lsctic Acid during Artificial Circulation ofBlood through the Liver.Action of Ethylene Chloride on the CoriieaInfluence of Bile on DigestionPAGExlii CONTENTS .HOFYEISTEB V.Nitrogenous Constituents of the Contents of the Intes-.NILSON L.F.Variations in the Fat of Milk.FABER H.Changes in the Composition of Nilk.ELAVEOFF N.Obtaining Non-organised Ferments in Pure AqueousInfusions.WUR~TER C.Active Oxygen in Living Tissue.DDR~NSZKY L.v.Furfuraldehyde Reactions.NEUMANN E.Pathological Pigments.Mosso.Physiblogical Action of Coca’ine.SALKOWSEI E..KR~LTKOWSKI C. and M.NENCKI.Behaviour of Urthohydroxyquinoline-carboxylic Acid and its Derivatives in the Organism.EZ~OCQWE A.and G.BAUDOIN.Reduction of Oxyhsemoglobin in TyphoidFever.ROSENHEIY T.Acids in Healthy and Disordered Stomach during aPFEIFFER T. and F.LEHMANN.ALBEILTONI.Formation and Change of Alcohol and Aldehyde in theOrganism.BERLINERBLAU M.Occurrence of Lactic Acid in Blood,atid its Forma-HALLIBURTON W.D.Coagulation of the Blood.BKJISINE A. and P.BUISINE.NENCKI M. and N.SIEBEL.Animal Melanin.STROHMER F.BuN’alo’s Milk and Butter.ZALESEI S.Excretion of Iron from the Animal Organism.BODLANDER G.Secretion of Perspiration by the Skin after taking AlcoholMARCHAND F.Toxic Action of Chlorates.CAHN J.Action of Chlorates.HAYCRAFT J.B. and F.W.CALLIER.KIRK R.Alcaptonuria.WEYL T.Action of Artificial Dyes on the Animal Organism.HUFNER G.,Tension of Oxygen in the Blood. and in Solutions oE Oxy-haemoglobin.MITTELBACH F.Uric Acid in the Urine of Herbivora.LAKGLEY J.N..STOCKMAN R.Physiological Action of Borneo1.BPUXTON T.L. and J.T.CASH.Action of Caffeine and Theine onVoluntary Muscle.LOPETT R.W.Strychnine Poieoning.FJORD N.J.Feeding of Calves and Pigs.HENRY.LECLERC A.Cutaneoue Excretion of Albumin by the Horse.YVON and BERLIOZ.Mean Composition of Normal Urine.LDPINE R. and E.PORTERET.Secretion of Urine when pressure is exertedon the Urinary Canals.COLASANTI G. and R.MOGCATELLI.Paralaotic Acid in the Urine ofSoldiers after a Forced March.EDLEFSEN.Behaviour of Urine after the Ingestion of Naphthalene.HAIG A.Excretion of Uric Acid.NEBELTHAU E.Lactic Acid in the Urine of Cold-blooded Animals afterExtirpation of the Liver.BRUYLANTS J.Thiocyanic Acid in the Animal Organism.LATHAX P.W.Blood Changes in Disease.HUNTER W.Pernicioue Anremia.SKVOLTZOFF.Physiological Action of Iron.BRADFORD J.R.Physiological Action of Ulexine.OTT I.and C.COLLMAR.Albumose,Peptone,and Neurine as T’yrexialAgents.tine which arise from the BodyBehaviour of Benzoic Anhydride in the Organism .Carbohydrate Diet.Fat Equivalent of Starchtion in the Organiem.Malic Acid in SuintCoagulation of the BloodInfluence of Atropine on Salivary SecretionInfluence of Fodder on the Productiom of Lean and F a t in PigsPA QECONTESTS.x liiiPAGETEISSIER J. and GF.ROQUE.Toxic Effect of Albuminous Urine.1326GLEY E.Toxic Action of Ouaba’in and Strophentin. 1326SEWALL H.Preventive Inoculation of Rattlesnake Venom.1326Chemistry of Vegetable Physidogy and Agriculture .MUNRO J.M.H.Formation of Nitrites during the Nitrification of Am-rnoniacal Solutions.HENSCHKE H.Constituents of Scopolia Root.Oil of LaZZemantia Iberica.PITSCH G..RAULIN J.Agricultural Experiments.AMTHOR C.Studies on Pure Yeast.REQNARD P.Influence of the Age of Yeast on the Alcoholic Fermenta-tion.KELLNER 0. and T.YOSHII.Development of Free Nitrogen in Putrefac-tion and Nitrification.EHRENBERG A .Formation of Nitrogen during Putrefaction.PRIKGSHEIM N.Dependence of Assimilation of Green Cells on theirRespiration of Nitrogen.WESTERMAIER M.Physiological Signification of Tannin in VegetableTissues.HAYDUCK.The Hop and its Constituents.REALE N.Compounds Extracted from Artugyris fatida.LECHARTIER G.The Freezing of Ciders.MENGABINI F.Effects of an Electric Current on Wine.LIEBENBERQ v.Manuring Barley.LIEBENBERQ v.Manuring Oats.BAESSLER.Comparative Experiments with Oats Manured with Basic Slagon Moorlands.LIEBENBERQ v.Manuring of Winter Wheat and Winter Rye.BEBTHECOT and ANDB~.Condition of Potassium in Soil,Plants,andMoulds..SPICA M.Chemical Nature of Aristolochia Serperttaria.RICHTER L.Are Nitrates Indispensable to the Growth of Field Crops?KREUBLER U.Assimilation and Reepiiation in Plants.MORITZ J.and P.SEUCEEE.Manuring of VinesBAESSLEIZ.Best Time for Ploughing Yellow Lupines Under.HERAEUS W.Reducing and Oxidising Properties of Bacteria.HORNBERGER R.Spring Sap of the Birch and Hornbeam.KOSSOVI~ P.Citric Acid in OX~~COCCZLS palustris.LIPPMANN E.0.v.Organic Constituents of Beet-root Juice..MAYER A.Analyses of Rubbish Heaps employed to Improve Soils .LOEW 0.and T.BOKORNY.WOLLNY E.Effects of Atmospheric Deposits on Plants and Soil.ATTEBBERQ A.Testing Soil by the Growth of Oats.HILGARD E.W.Effect of Lime as a Soil Constituent on the Develop-ment of Plants.JUST L.Injury to Vegetation by Sulphurous Acid.ERAUS 3.Manuring Hops.FLEISCHEB M.Comparison of Manure made with Straw and with TurfLitter.WOLPF E. and C.EREUZHAGE.Behaviour of Various Plants towardsNitrogenous Manures.ENGELMANN T.W.Colour of Leaves in Relation to the Assimilation ofCarbon.LIEBSCHER G.Supply of Food Constituents a t different periods of PlantGrowth.Chemico-physiological Study of Algre .PROSEOWITZ E.v.Manuring Sugar Beets with Basic Slag.LADUEEAU A.and MOUSSEAUX.Wheat Experiments in 188’7.xliv COXTEXTS .DEHBRAIN P.P.Experimental Cultivation of Sugar-beet in 1887.SAMBUC.Iron in Wine.BRBAL E.Nitrates ir,Soils and Waters.BERTHELOT and ANDRB.Sulphur and Phosphorus in Plants,Soils. andMoulds.PLATH H.Nitrification of Ammonia and its Salts.CSERH~TI A.Ensilage Processes.BARTH M.Ensilage in the Open Air.MACIVOE R.W.E.Exhaustion of Virgin Soils in Australasia.KONJO J.Maintenance and Increase of the Amount of CombinedMULLER K.Manuring Experiments with Bats.WAGNER P.Increase in Yield of Crops by Nitrogenous Manures.JEPI'SCH E.Manurial Action of the Free Lime in Basic Slag.LINDNER P.New Lactic Ferment Occurring in Malt Wort.GRIFFITHS A.B.and Mi's.GRIFFITHS.Influence of Certain Rays of theSolar Spectrum on Root Absorption.HUPPE F.Plants Free from Chlorophyll acting like Chlorophyll-contain-ing Plants.GR~~HANT AND QUINQUAUD.RespiraLtion of Yeast Cells at Different Tem-peratures.SCHULZE E. and T.SELIWANOFF.Presence of Saccharose in UnripePotatoes.SCHULZE E.Detection of Saccharose in Vegetable Substances.SELIWANOFF T.Composition of Etiolated Potato Sprouts.BRENSTEIN G. Action of Ether on Plant Life.YOUNQ W.C.Aluminium as a Natural Constituent of Wheat Flour .BERTHELOT.General Conditions favourable to the Absorption of FreeNitrogen by Vegetable Soils.MACADAM W.I.Natural and Artificial Manures.JACQUEMIN 3.Saccharomyces ellipsoideus,and its Use in the Prepara-tion of Wine from Barley.KOCH L.Direct Assimilation of Vegetable Remains by Chlorophyll-con-tcining Plants.WEHMER C.Behaviour of Formose in Contact with Vegetable Cellsdeprived of Starch.BERTHELOT and ANDRB.Absorption of Salts by Plants.PRINGSHEIM N.Production of Oxjgen by Green Calls.REINEE J.Oxidation in the Plant.JOHANNSEN W.Continuation of Respiration in Dead Vegetable Cells .KREUSLER U.Assimilation and Expiration of Plants.HELLRIEGEL and WILLFARTH.Absorption of Nitrogen by Plants.BUROERSTEIN A.Influence of Camphor on the Germination of PlantSeeds.WEBER.Distribution of Ash in Trees.BERTIIELOT and 8.ANDEB.LANGE.Acidity of Cell Sap.BAUER R.W.Saccharin Matter in Peach Gum.Sulphurous Anhydride.MCCALEB G.F.Titanic Oxide in Soils.Compounds.DACCOMO 3.AspidzumJilix.Mas.L.Nitrogen on the Farm.Phosphorus and Phosphoric Acid in PlantsPREVOST E.W..MACH E.Percentage of Sulphuric Acid in Plants destroyed byLAWES J.B. and J.H.GILBERT.BERTHELOT.Conversion of Nitrates in Soils into Nitrogenous OrganicGAUTIER A. and R.DROUIN.Absorption of Nitrogen by Soils andPlants.SCHLOESSIXQ T.Relation between Atmospheric Nitrogen and VegetableSoils.Injury to Plants by Kiln SmokeSources of Nitrogen in VegetationPA@E'139COSTESTS.JOHASKSEN W.Mealy and Steely Barley.LADD E. F..DEHBRAIN P. P.Farmyard Manure.PETERMANN A.Waste Products as Manures.MAGERSTEIN V.T.Addition of Wood-ashes to Superphosphates.GATELLIEB E.Manuring Experiments with Various Phosphates.BAGINSKY A.Bacteria of Normal Milk Fasces.SNYDERS A. J. C.Influence of Filters on Water.ELLENBERGER and V. HOFMEISTER. Proteolytic and other Ferments inOats and their Action on the Digestive Organs.FANKHAUSER J.Diastase.HANSEN A. Function of the Colouring Matter of Chlorophyll.LEPLAY H.Formation of Organic Acids,Nitrogenous Compounds,andPotassium Nitrate in Beetroot.CHRAPOWITZKI. Synthesis of Albumin in Chlorophyll-containing Plants .SCHULZE E.Some Nitrogenous Constituents of the Seedlings of SojaHispada. ,.JOHANNSEN W.Distribution of Amygdalin and Emulsin in Almonds .SMITH J.Substance containing Sulphur formed in Cruciferous Plants .KEANDAUER.Influence of Manures on the Composition of Barley.LEVALLOIS A.Effect of Chemical Manures on the Composition of Soja .SCHLOESING T.Relation between Atmospheric Nitrogen and VegetableSoils.BERTHELOT. AbsorptionofNitrogen by Soils.BERTHELOT. Absorption of Nitrogen by Vegetable Soils. ,.GAUTIER A. and R. DROUIN. Absorption of Nitrogen by Soils andPlants.KLIEN G.Value of Nitrogen in Sodium Nitrate and in AmmoniumS ulphate.HEIDEN E.Experiments with Farmyard Manure.DIETZELL B. C.Prevention of the Loss of Nitrogen in FarmyardManure.MAXIMOVITCH J.Antiseptic Properties of Naphthols.FRANCK B.Origin and Fate of Nitric Acid in Plants.RODEWALD H.Estimation of the Heat and of the Carbonic Anhydridegiven out by Parts of Plants.SCHLOESING T.Slow Combustion of Organic Substances.CHEVREUL E.Atmospheric Nitrogen and its Relations to Vegetation .WILFARTH. Assimilation of Nitrogen by Plants.BOKORWY T.Liberation of Silver by Living Cells.ERBERA L.Accumulation and Consumption of Glycogen in Fungi .LATTRENT E.Formation of Glycogen in Beer Yeast.SCHIMPER A.F. W.Formation of Calcium Oxalate in Leaves.CAMPANI G. and S. GRIMALDI.LOEW 0. and T. BOEORNY. Presence of Albumin in Cell Fluid.SCHWARTZ F.Morphological and Chemical Composition of Protoplasm .THOMS H.Constituents of Calamus,Roots.TSCHIRCH.VAN BEMMELEN J. M.Absorption Compounde and the AbsorptivePower of the Soil.AUDOYNAUD A.Rapid Fermentation of Grape-juice.HARZ C. 0.Effect of Nitrogenous Manures on Tobacco.PETEBMANN A.Organic Nitrogenous Manures.EUNZ J.Bacteriological and Chemical Investigation of some Brtcilli .RAKE B.Cultivation of Bacillus lep9-a.JODIN V.Unicellular Algae.JENTYS S..PALLADIN W.The Rble of Oxygen in Plant Life.HUEPPE.Decomposition of Carbonic Anhydride by Plants Deprived ofChloroDhvll.Sugars and Starch in Fodders and their DetermiiiationVanillin in the Seeds of Lupinus albusInfluence of Sterilisation of Soil on the Growth of PlantsInfluence of Compressed Oxygen on the Growth of PlantsxlvPAGRxlvi CONTENTS.LAVRENT E.Formation of Starch from Organic Solutions by Plants .PALLADIN W.Formation of Organic Acids in Growing Plants.WAKKER J. H. Formation of Crystals of Calcium Osalate in PlantCells.,.HINDORF R.Influence of Magnesium and Calcium Chlorides on Germi-nation.SHIMOYAMA-YUKICHIRO. Glutinous Rice.GAUTIER A.and R. DROUIN. Absorption of Nitrogen by Soils andPlants. ,.NANTIER A.Experimental Plots a t La Somme.PAQNOUL A.Richness and DenAity of Wheat.PETERMANN A.Application of Potassium Chloride to Sugar-beet onHearg Soil.AMTHOR C.Succharomyces Apiculatus.LADD E. F..ASBOTH A. v.Doe0 Grain contain Sugar ?.KUNZ H.The Constituents of Acorus Calamzcs.BAUMERT 3.Constituents of Lupin Seeds.WOLLNY E.Influence of a Crop or Covering on the Physical Charactersof a Soil.,.SAMEK J.Manuring of Clover.FLEISCHRR M.Manuring with Nitre.EMMERLIXG A.Basic Slag as a Manure for Oats.STORCH V.Fossil Milk.SALKOWSEI E.A Ferment from Putrefactive Bacteria which dissolvesFibrin.CHIBRET.Antiseptic Properties of Mercuric Cyanide,Oxycyanide,andChloride.TABSINARI V.Tobacco and Bacteria.LANDOLT H.Nitrification of Ammonium Salts.HEIDEN E.Growth of Maize and Peas in Nutritive Solntions.ABBOT H. C. S. and H. TEIMBLE. Solid Hydrocarbons in Plants.BAUER R. W.Galactose from Plum-gum.BCHULZE E.Changes which the Nitrogenous Matters in Silage undergo .BRBAL E.Absorption of Nitrogen by Leguminosse.SCHLOESINQ T.Relation between Atmospheric Nitrogen end VegetableChanges occurring in Timothy Urass PhZezcm prateme Soils.BEBTHELOT. Absorption of Nitrogen by Vegetable Soils and by PlantsBEHBEND. Composition of Barleys grown in Wurtemberg in 1887 .Egyptian Cigarettes.SESTINI F.Composition of Stable Manure.MACH E.Lime and Ash in Tyrolese and other Wines.Analytical Chemistry.ZULKOTSKY R.Grinding Mill for Minerals.WESTMORELAND J.W.Determination of Sulphur in Pyrites.LUNQE C3.j. Determination of Sulphur in Pyrites.DAPERT F. W.Kjeldahl's Method of Estimating Nitrogen.MILNE J. M.j. Notes on Nesslerising.BAUMANN A,.Estimation of Ammonia in Soils.RUFFLE J.' Moisture and Free Acid in guperphosphatee and similarFertilisera.ROSSLER 0.Detection of' 8mdl Amounts of Carbonic Anhydride andother Gases.DREHSCHMIDT H.Absorption of Carbonic Oxide by Cuproue Chloride .WOVSSEN. Estimation of Potassium by Reductmion of the Platinochloridewith Sodium Formtdre.PAGELTNDO D.Estimation of Potash in Commercial Manures.WILLIAMS R.Estimation of Sodium Hydroxide in Soda Ash.Estimation of the Relative Amounts of Sodium Hydroxide andCarbonate in Soda Ash.WILLIAMS R.Analysis of Alum Cakes.TATLOCK R.R.Determination of Iron in Alum and Aluminium SulphateSMITH J.H.Detection and Estimation of Organic Substances.TEAUBE J.The 8tabgmometer Determination of Fuse1 Oil in SpirituousLiquors.MUTER J.and L.DE KONINGH.Assay of Commercial Carbolic Com-pounds.HART P. .TONY.GARCIN.Acidimetry with Red Wines.Dairy Products.MILNE J.M.Extractmion of Fats by Soxhlet’e Apparatus.SPICA P.Examination of Oils and Wines.PROCTER 8.R.Gravimetric Estimation of Tannin.MEURER V.Support for Funnels while. Drying.SOXU~N E.Hygienic Air Analysis..’MORLEY E.W.Moisture Remaining in a Gas after Drying with Phos-nllovic Anhydride.VOLHARD J.Estimation of Sulphurous Acid by Standard Iodine.YOUNQER W.Determining the Total Acidity in Flue Gases from VitriolChambers.ATWATER W.0. and C.D.WOODS.Soda-lime Method for DeterminingNitrogen.ISBERT A.and A.STUTZER.Determination of Phosphoric Acid.MORGAN J.J.Estimation of Silicon in Iron and Steel.TURNER T.Estimation of Silicon in Iron and Steel.KRAUT K..SCULLY J.Assay of Silver containing Bismuth.CHESTER A.H. and F.I.CAIRNS.Determination of Ferrous Oxide inInsoluble Silicates.LBVY L.Estimation of Titanic Oxide.STONE F.B.Test for Bismuth.BINDER 0.Detection of Nitrates in Well-waters.BINDER 0.Water Analysis.KASSNER G.Elementary Analysis of Highly Volatile Organic Liquids .TRAUBE J.The StaIagmometer.ELIEBAHN G.Recognition of Pyrogallol.AUDDE V..JONES E.W.T.Examination of Starch and Wort.WINDISCH W.Estimation of Lactic Acid.WARREN T.T.P.B..WOLLNY R.The Reichert-Meissl Process for the Estimation of ButterFat.SALKOWSKI E.Examination of Cod-liver Oil and Vegetable Oil.PFLUQER E.Titration of Ures with Mercuric Nitrate.MINATI T.,H.BOOTH,and J.B.COHEN.Fractional. Reduction of Ortho-and Para.nitroto1uene. and Analysis of Ortho- and Para-toluidine.HAEUSSERMANN C.Estimation of Paratoluidine in Orthotoluidine.HERETH F.S.Volnmetric Estimation of Alkalo’ids by Mayer’s Reagent .BRASSE I. L.Tanret’s Reaction for Albumin,Peptone,and Alkalo‘ids inLENZ L.Determination of Nitrogen by Kjeldahl’s Method.ERATSCHMER.Apparatus for Nitric Acid Determination.CLARK J.Estimation of Arsenic in Pyrites.Indirect Determination of Alkalis in Presence of LithiumMILNE J.M.Determinal ion of Ammonia.BRASSE L.Estimation of Mercury in Urine.DATIDSON R.Estimation of Iron in Chars.MUCK F.Determination of Antimony.Estimation of Grape-sugar in Vi*ine by Roberts’ MethodNew Method of Examining ButterCONTENTS.xlviiUrine.204PACIBXI riii CONTEN'I'P .HBNOCQUE A.Hmnatoscopic Study of Blood.WILBER F.A.Gas Receiver for Absorption AnalTsis.FEESENIVS W.Use of Asbestos to aid the Subsidence of SuspendedXatter.CLASON P.Determination of Sulphur,Chlorine,Bromine.and Iodine inOrganic Substances.WALDEN P.Comparative Value of some proposed Tests for Nitric Acid .BETTENDORF A.Presence of Sodium Phosphate in Glacial PhosphoricAcid.EENNEPOHL G.Estimation of Phosphoric Acid in Bmic Slag.FRESENIUS H.Estimation of Arsenic in Pyrites.SINIBALDI J.Estimation of Oxygen,Carbonic Anhydride,and CarbonicOxide.OSTERSETZER 0.Apparatus for Direct Estimation of Carbonic d n -by dr ide.OETTEL F.Analysis of German-silver.ZIMMERNANN A.Separation of Aluminium and Beryllium.BLTJM L.Determination of Aluminium in Presence of Iron and Phos-phoric Acid.JUNGFER P.Determination of Traces of Bismuth and Antimony in Com-mercial Coppey.VIUNON L.KOBRICH A.Estimalion of Ash in Organic Substances.LIEBXRMANN C.Thioplieii Reaction with Nitrous Sulphuric Acid.DATIDSEN.Examination of Cane-sugar for Sulphuroils Andydride.BURKHARD G.Detection and Estimation of Starch in Liquids containingDextrin.GAYON U.Detection and Estimation of Aldehydes in CommercialAlcohols.LOKENZ N.T.Analysis of Materials containing Tartaric Acid.F~NKXNER.Points of Difference between Linseed-oil and Linseed-oilVarnish.CAZE~ETTVE P.and HUGOUNENQ.Apparatus for Estimating Urea.Volatile Alkaloi'ds.Estimation of Eissolved Carbonic Anhydride in Water .CONINCK 0.DE .LANDOLT M.Polaristrobometric Analysis.RUFFLE J.Correct Analysis of Superphosphates.Separation of Zinc from Nickel and Manganese,and Estima-tion of Nickel.BAYLBY T.Reaction of Iron with Nitric Acid.BISEOP W.Action of Oils on Polarised Light.ALLIEIN F.Filtration Apparatus.LTJNGB G.lmproved Form of Nitrometer.MCCULLOCH N.Estimation of Iodine.REIN S.Indirect Dehermination of Fluorine.WARREN H.N.Estimation of Selenium.VIVIER E.Estimation of Nitrites.MELLON W.W.Free Acid in Superphosphates.MCCAY L.W.Determination of Arsenic as Pentadphide.CLASSEN A.Quantitative Analysis by Electrdjsis.NEUNANN G.Estimation of Thallium.TAMM A.Analysis of Iron and Iron Ores.BYA H.Estimation of Iron with Potassium Dichromate.BLOUNT B.Determination of Carbon in Steel.LAKGBEIN G.Analysis of Nickel.FORM~NEK J.Quantitative Separation of Chromium and Uranium.DONATH E.and F.MULLNEB.Separation,,o f Tin Oxide from TnngsticAcid.CLASSEN A.Quantitative Separation of Titanium from Iron.CAENELLEY T. and J.S.HALDLNE .BAYLEY T.. ILES M W.Analysisof Lead SlagsThe Air of Sewera.PAGECONTENTS.BOECHEBS W..PHIPSON T.L.Determination of Phosphoric Acid in contaminatedWaters.-. ,.LOTT F. E.Heisch's Method for Detecting Sewage Contamination inWater.ENOP W.Determination of Ammonia in Arable Soils.STACHOVSKY 0. K.Estimation of Carbon in Arable Soils.WILT H.Estimation of Grape-sugar in Urine.WEHMER C. and B. TOLLENS. Formation of Levulinic Acid,a Reaction forthe Detection of Carbohydrates.GAKTTER F.Determination of Tartaric Acid.BORNTRAQER A.Determination of Tartaric Acid in Wine Lees and inTartar.STORCH L.Qaalitatire and Quantitative Test for Resin Oils in Mineraland Lubricating Oils.BARLOW J. J.Modified Soxhlet's Appamtus.MORSE H. N. and W. N. BURTON.GANTTEE F.Determination of the Dry Residue and Fat in Milk andButter.WARREN T. T.P. B.New Method of Examining Butter.WARREN T. T. P. B.Action of Sulphur Chloride on Oib.PPEIFFER T-.Estimation of Uma by Titration.SCHFLZE K. E.Titration of Pyridine Bases.CONINCK 0. DR.Volatile Alkalo'ids.SMITH E. D.Improved Method of Estimating Cafle'ine in Coffee.PAUL B. H. and A. J. COWNLEP. Estimation of CaffeSne in Tea.CRIPPS R. A.Estimation of trhe Alkalo'ids of Conium.GANTTEB 33.Determination of Tannin. ,SALKOWSKI E.Hoppe-Seyler's Soda Test for Carbonic Oxide Haemo-RIDSDASE 6. H.Simpliged Chromometer.BRUCKE E.Bebaviourof Congo-red with Acidsand Salts.MCCULLOICH N.Volumetric Estimation of Iodide in Presence of Bromineand Chlorine.-.SCHWARZ 42.Detection of Iodine in Urine.WURSTEE C.Estimation of Active Oxygen.ALLEN A.H.Determination of Sulphur in Oils.BROWN A. CRUM.Ferric Fmricyanide as B Reagent fop. Detecting TracesMELDOLA R. and E. R. MOLITZ. Kjeldahl's Method of estimating Ni-t r o g e n.RIDSDACE C. 33.Determination of Vanadium.DIBCKS V. and F,WERENSKIOLD. Estimation of Reduoed Phosphate .WILL H.Voluinetric Detesminatbn of Boric Acid.RUSSMANN A.Separation of Barium,Strontium and Calcium.GUCCI P.separation of Copper and Arsenic.ALT K.Detection of Mereury in Urine.SCHACET C.Estimation of Iron.ALLEN A. H.Aluminium in Wheat.MOORE T.Separation .of Iron,Nicbl,Cobdt,Manganme,Zinc andAluminium. *.WARREN Hi N.Separation of Tin from Antimony.VULPIUS G. - Testing Chloroform.CHABCEL G. andP. PARYENTIER. Estimakioa of Chloroform.SPEHCE J. N.Estimation of Staxch.JOHNSON 3.S.Detection of Aceilc Acid in Presence of Morphine.WAXBEN T. T. P. B.3,Action of Sulphur on Oils.MILLTAU E.Detection of Cotiton-seed Oil.BUHRING L.Estimation of Fat in Fodder.VIETH P. - Relation betmeen Sp. Gr.,Fat,and Solids in Milk.l3eterrnima'tbn of Csrbonic Acid in Mineral Watera .Determination of Butter in Milkglobin -.of ReducingGases,.VOL. LIY. dxlisPAQEL CONTENTS .COCHRAN C.B.Action of Alcoholon Butter Fat.LINDET L.Bases in Alcoholic Liquids.EREMEL A.Estimation of Morphine in Opium.I'ESCHEMACHER E.F. and J.D.SMITH.Estimation of Mor. hinp inOpium.WILLIAMS R.Estimation of Morphine in Opium.SCHAFER L.Testing Neutral Quinine Salts.SCHAFER L.Estimation of Cinchonidine in Quinine Sulphate.BATJMERT 3.Colchicine-like Decomposition Product.SCHETJRER.KESTNER.Thompson's Calorimeter.WILLARD J.T.Improved Form of Gas Apparatus.LINDO D.Preservation of Solutions of Hydrogen Sulphide.CONTAMINE.Determination of Hydrogen Peroxide.BOKORNY T.Supposed Occurrence of Hydrogen Peroxide in Animal andSTOLBA F.Determination of Chlorine.GAWALOWSEI A.Volumetric Determination of Sulphuric Acid.WHITE J.T.Volumetric Determination of Sulphuric and PhosphoricAcids.HOTJZEAU.Determinationof Total Nitrogen.ATWATER W.0. and E.M.BALL.Sources of Loss in Nitrogen Deter-minations.HAYNES I.S.Absorption af Ammonia by Acid Solukions in NitrogenDeterminations.BOEGMANN E.Examination of Wine for Nitric Acid.BENTE I?.Determination of Phosphoric Acid.SCHINDLER C.Volumetric Determination of Phosphoric Acid.FRESENIVS R.and E.HINTZ.Detection of Arsenic in Fabrics,Paper,&c .LESSER E.Separation and Determination of Arsenic,Antimony. and TinMORSE H.N. and W.M.BURTON.Separation and Estimation of BoricAcid.ROSSLER H.Estimation of Silver in Alloys of Silver and Copper.VORTMANN G.Estimation and Separation of Metals by Means of SodiumSTOLBA F.Reduction with Lead.SABAN~EFF and KISLAEOWSEI.Colorimetric Determination of XinimalBLUM L.Determination of Iron in Iron Ores by the Tartaric AcidMethod.ARNOLD J.0. and H.J.HARDY.Estimation of Chromium in Iron orSWINDLER 3.Volumetric Determination of Molybdenum and Lead .BINDER 0.Determination of the Amount of Soda and Lime requisite forVegetable Juices.Pyrophosphate.Quantities of Iron.Steel in Presence of PhcwphorusPurifying Water.REESE L.Ash Determination.CARLES P.Plastering of Wine..ZALOZIEEI R.Determination of Paraffin.HINTZ E.Determination of Acetone in Wood Spirit,&c.BORNSTEIN E.Detection of Fahlberg's '' Saccharin " in Articles of FoodP~TER.Action of Oils on Polarised Light.FOEESTER 0.Apparatus for the Extraction of Pat in the Cold.FLUCKICIER F.Test for Acetanilide.KLIEBAHN G.Separation of Resins.RAWSON C.Valuation of Indigoes.ARNOLD J.0.Allen's Method for the Detection of Hop-substitutes inBeer.ALLEN A.H.Precipitation of Hop-bitter by Lead Acetate.ALLEN A.H.Precipitation of Hop-bitter by Lead Acetate.JOHNSTONE W.Precipitation of Hop-bitter by Lead Acetate.MARTIN S.H.C.Detection of Proteids in Urine.PAGE'752CONTENTS.IRTINE R.Action of Bleaching Agents on Writing Tnk.FELS T.Testing Mercury Oxide for Chlorides.GIGLI.Detection of Copper in Wine.SCHNEIDER L.New Method for the Estimation of Manganese .LATIEU. Determination of Free Oxygen in Water.COCHENHAUSEN E. v.Determination of the Hardness of Water .GODEFROY L.Detection of Impurities in Commercial Alcohols .GBBHANT and QUINQUAD. Estimation of Glucose by Fermentation .GEDULT R.Estimation of Reducing Sugar.IHL A.Testing Beet-sugar for Purity.BRULL& R.Adulteration of Olive Oil.BIEL J.Estimation of Nicotine in Tobacco-ash Extract.KREMEL c.A.1. Estimat,ion of Caffehe in Guarana.RAWSON C.Detection and Estimation of Magenta in Orchil and CudbearPOLLACCI E.Methods for Detecting Vinoline.PALM R.Detection of Picrotoxin in Beer,&c.JACQUEMIN G.Estimation of Urethane in Urine.PORL.Estimation of Globulin.UDRANSZKY L. v.The Furfuraldehyde Colour Reaction.MICHAILOFF W.,.Detection and Estimation of Indican and its Homo-logues in Urine.SOBIRCKY J. and V. HOLBLINGF. Improved Wash-bottle.BRIGNONE. Different Methods of Estimating Chlorides in Urine.ATWATER W. 0.Nitrogen Determinations by Soda-lime.CAZEYEUVE P. and L. HUQOUNENQ. Estimation of Total Nitrogen inOrganic Compounds.WURSTEB C.Determination of Ammonia in Urine.VOGEL J. H.Estimation of Phosphoric Acid in Basic Slag.WEISSMANN 3.Estimation of Manganese in Pig-iron and Steel.SCHWARTZ Y.Estimation of Lead in Tin Allojs.LOVITON.Estimation of Antimony in Tin.GRIESS P.Detection of Organic Matter in Water.KRONBERQ H.Incineration of OrganicSubstances. ,ROCQUES X.Detection of Impurities in Alcohols.WOHL A.Behaviour of Catechol with Fehling’s Solution.CAZENEUVE P. and L. HUQOUNENQ. Supposed Rcaction of PhloroglucinolJODLBAUER M.Determination of Sugar by Alcoholic Fermentation .PETEEMANN A.Estinzation of Sugar in Beet.WOHL A.,POLLATSCHEK A..SCHMITT C.Detection of “ Saccharin ”.KOST G.Modification of the Met hyl-violet Reaction for the Detection ofFree Hydrochloric Acid in Gastric Juice.SALZER T.Behaviour of solile Acids towards Chromic Acid and Perman-ganate.VOGEL I€. W.Spectroscopic Notes.DROWN T. M..Funnel for Filtering Carbon.WHITE J. T.Estimation of Bromine.MEINEEE C..ISBERT A.and VENATOB. Determination of Alkaline Hydroxides inPresence of Carbonates.WHITE J. T.Volumetric Estimation of Potassium and Sodium.WAKEMANN A. J.Solubility of Magnesium Ammonium Phosphate inAlcohol.WARREN H. N.Solbent Action of Rochelle Salt on Metallic HjdroxidesMEINEKE C.Determination of Manganese as Sulphide.REINHARDT 2.Determination of Small Quantities of Manganese in IronRich in Silicon.MEINEKE C.Determination of Iron by Nitrosonaphthol.WOLFF C. H.Detection of Blood in Urine.Reduction of a Solution of Methyl-violet by Invert SugarEstimation of Small Quantities of Sugar in UrineDetermnation of Phosphorus in Iron by Molybdate .d 2fiPAQElii COSTENTS .K ~ Y E B.Determination of Alcohol.FILSINGEB F.Deterirlination of Glycerol.P~BRAM R.Influence of Inactive Substances on the PolaristrobometricEstimation of Grape-sugar.MONHEIM.Determination of Starch in Grain.SEYPERT F.Determination of Starch by Baryta.KING C.M.Fat Extraction Apparatus.ROSE B.Determination of Fat in Milk.SCHREIB H.Determination of Fat in Milk.BOCKAIBY P.Adulteration of Butter.JEAN F.Detection of Cotton-seed Oil in Olive Oil.ZIPPEBER I?.Detection of Sesame Oil in Cocoa Butter.VITALI D.Detection of Acetanilide.WEPPEN and LUDEBS.Detection of Pyridine Bases.TPSCHEMACHEB E.F.and J.I .SMITE.Estimation of Morphme in OpiumARNITAGE J.L.Delicate Test for Morphine.VOGEL H.W.Difference between the Colouring Matters of Bilberry andWine.KOCH X.The Vienna Gravimetric Method for Estimating Tannin inConcentrated Solutions.COLLIN C.and L.BEKOIST.Estimation of Tannin.LINOSSIER G.Spectroscopic Examination of Blood.FERRY DE LA BELLORE.Detection of Blood Stains.POSNER C.Detection of Albumin,Propeptone,and Peptone.BOHLIG E.Testing Potassium Carbonate.BRUNN 0 .VITALI.Detection of Poisoning by Caustic Alkalis.HERRMANN A.Haycraft's Me1 hod of Estimating Uric Acid in Urine .CZAPEK F.Estimation of Uric Acid in Urine.HUPPEBT and H.ZBHO~~.Densimetric Estimation of Proteids.Z B H O ~ H.Densimetric Estimation of Albumin in Urine.FAULKNER F. and W.VIRTUE.Biological Test for Malt.GREINER and FRIEDRICHS.Instruments for Measuring Liquids.KNAPP t.Testing for Santonin.Action of Icdine on Hydrogen Arsenide and AntimonideNEIJMANN G.Apparatus for Quantitative Analysis.MUNROE C.E.Metallic Felt Filters.Iron for Steel Making.BLUM LL .Determination of Sulphur in Coke.ARNOLD J.0. and H.*T.HARDY.Estimation of Sulphur in Steel and inMORGAN J. J. and others.ATWATER W.0.Sources of Error in Determinations of Nitrogen bySoda-lime.BERTHELOT and G.ANDRB.ScHLoEsraa T.Estimation of Carbon and Nitrogen in Vegetable Soils .Estimation of Sulphur in Iron and SteelEstimation of Nitrogen in Vegetable SoilsBAUMANN A.Azotometric Method of Soil Analysis.WILFARTH H.Determination OC Nitric Acid.Nitrites,Nitrates,and Chlorates.that of Animal Origin in Artificial ManuresLINDO D.Phenol,&c.,as Tests with Conwntrated Sulphuric Acid forLINDO D.Griess' Yulphanilic Acid Test for Nitrous' Acii Mo&d .LORENZ N.v.Discrimination of Phosphoric Acid of Mineral Origin fromBRETE A.Volumetric Estimation of Phosphoric Acid.Determination of Carbon in IronSCHUTT F.Polaristrobometric Analpie of a,Mixture of Sodium andPotassium Chlorides..DE KONINCK L.L.CARNOT A.Estimation of Lithium as Fluoride.CARNOT A.Estimationaf Lithium in Mineral Waters.RIBAN {J.Estimation and Sepriration of Zinc.WESTMORELAND J.W.Copper Assays..LAmER A.Hjdroxylarnine Hydrochlonide in Quantitative Analysis .PAOBCONTENTS.liiiZIEGELER.Detection of Mercury by Electi*olysis.SMITH E.F.The Electrolytic Method as applied to IronSeparation of Arsenic. Antimony.and Tin from Gold and Platinum.BURPEIND W.H.Bromine for Gold Extraction.BLAREZ.Determination of Oxrgen Dissolved in Water.BENEDIKT R. and M.CANTOR.Estimation of Glycerol.PLANCHON V.Estimation of Glycerol by Oxidation.RATHQEN F.Determination OP Sugar in Liqueurs. Confectionery. andChocolate.WINDISCH W.Detection of Aldehyde.LEGAL.Acetone in Urine.NEUMANN G.Valuation of Crude Sodium Acetate.HAAS B.Estimation of Hydrogen Potassium Tartarate and Free TartaricAcid in Wines..DE KONINCK L.L. Ltnd A.LECREMIER .DENIG~S G.Test for Uric Acid.SCHMID C.Determination of Fat in Milk. Cream. &c.MORSE H.N. and W.3%.BURTON.Analysis of Butter. Oleomargarine. &c .WARREN J.T.P.B..MILLAU E.Detection of Sesame Oil in Olive Oil.KLOPSCH R.Determination of the Oil in Linseed Cake.FORSTEE 0.Estimation of Mustard Oil in Seeds of Crucifer=.LINDO D.Tests for Antifebrin. Antipyrine. and Fahlberg’s “ Saccharin ’’KREXEL A.Estimation of Emetine.OSBORNE T.B..Action of Sulphur Chloride on OilsMILLAIJ E.Detection of Cotton-seed Oil in Olive Oil.Filtering Crude Fibre and Silver ChloridePAQE

ISSN:0368-1769    

DOI:10.1039/CA88854FP001

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

26 ABSTRACTS OF CHEMICAL PAPERS. I n o r g a n i c C h e m i s t r g . Compound of Iodine with Ammonia. By F. RASCHIG (Annulen, 241, 253-255).-Iodiiie absorbs dry ammonia gas, forming a dark- blue liquid ; Bineau (Ann. Chim. Phys. [3], 15, SO) assigns to this substance the formula 3NH3,2I, but according to Millon (Annulen, 62, 54) iodine absorbs less than half the volume represented by this formula. The anthor finds that the volume of ammonia absorbed by the iodine Taries with the temperature. At 20°, the amount of ammonia absorbed corresponds with Bineau's formula, but a t 80" it carresponds with NHJ, a t 0" with I(NH3)2, and at -10' with 12(NH3)5. The liquid is decomposed by water, yielding ammonium iodide and nitrogen iodide, but it dissolves completely in alcohol Method for Decomposing Arsenical Sulphides.By . H. WARREN (ahem. News, 56, 193--194).-The cobalt speiss or arsenical alloy is digested in hydrochloric acid containing copper nitrate, and after a day or so, the insoluble portions are calcined at a low red heat with plentiful access of air ; the calcined mass is then easily dissolved by hydrochloric acid and mixed with the other solution. The copper is separated by means of metallic iron, which also removes some bismuth and arsenic ; and the iron and remaining arsenic are precipitated by adding milk of lime. The culcium salts are removed by treatment with sulphuric acid, and the solution containing nickel and cobalt is precipitated by means of sodium carbonate. The precipitate is then suspended in water and chlorine passed to saturation, when the nickel goes into solution, whilst the cobalt remains undissolved.The solu- without undergoing any change. w. c. w.INORGANIC CHEMISTRY. 27 tion is boiled, and on adding caustic soda the nickel is obtained as hydroxide, which is ignited and reduced in the usual way. D. A. L. Zinc Titanates. By L. LEVY (Compt. rend., 105, 378-380).- When a mixture of 6 grams of titanic oxide, 2.5 grams of zinc oxide, and 5 to 10 grams of anhydrous zinc chloride is heated in a glass tube, the reaction is incomplete, and a violet product is obtained which contains an excess of titanic oxide. With excess of zinc chloride, the product is yellowish. If the mixture is heated in a Perrot's furnace in a crucible brasqued with charcoal and rutile, the zinc chloride volati- lises, but if the heating takes place in a long porcelain tube closed at one end, a violet or green, crystalline mass is formed, which contains titanium, zinc, silicon, and potassium.I f a mixture of 7 grams of titanium oxide, 5 grams of zinc oxide, and a small quantity of zinc fluoride, or 7 grams of titanium oxide and 30 grams of zinc fluoride is heated under a thin layer of potassium fluoride in a graphite crucible in a Perrot's furnace for an hour and a half, washed with water, and then treated with concentrated sul- phuric acid to remove zinc oxide and titanium fluoride, beautiful violet needles are obtained. With potassium chloride in place of the fluoride, the product is a greenish mass. With a mixture of potassium and sodium chlorides the violet needles are obtained mixed with yellowish needles of potassium titanate.The violet crystals are zinc trititanate, Zn0,3TiU2, a small quantity of the zinc being displaced by iron. They are insoluble in water, alcohol, and ether, are not affected by hot dilute sulphuric, nitric, and hydrochloric acids, nor by boiling concentrated solutions of alkaline hydroxides, butl are attacked with difficulty by boiling concentrated sulphuric acid, and are decom- posed by fusion with potash. They are infusible before the blowpipe, but change to a greenish mass without loss of weight ; sp. gr. at l 5 O = 4.92. The crystals are not attacked by hydrogen at a red heat, but partially volatilise in a mixture of chlorine and hydrogen chloride. When treated with acidified hydrogen peroxide, the latter acquires a characteristic yellow colour, but decomposition is never complete. Electrolytic Method of preparing Metallic Alloys, &c.By H. WARREN (Chem. h'ews, 56, 153--154).-The following method is recommended for the preparation of alloys such as phoaphor-bronzes, silicides, &c. The metal and substance containing alloying material are placed in a deep, conical crucible, through the bottom of which passes a rod of graphite, extending about one inch within the crucible and protected on the outside by au iron tube. The metal is melted and the graphite put in connection with the negative pole, whilst the molten substance on the surface is connected with the positive pole of a battery of two large ferric chloride cells. In this manner silicon copper and silicon-eisen are easily prepared from pobassium silico- fluoride and the respective metal ; the salt being taken in sufficient quantity to form a molten layer 2 inches deep.By some slight variation in the details, phosphor-bronzes can be produced ; moreover, native cryolite can be decomposed in contact with metallic zinc, and on C. H. B.28 ABSTRACTS OF CHEMICAL PAPERS. subsequently volatilising the zinc, pure aluminium is obtained. Mag- nesium, barium, strontium, and calcium have not yielded satisfactqry alloys as yet. Process for obtaining the Rare Earths from the Ceriferous Hainstadt Clays. By J. R. STROHECKER (Chem. News, 56,175-1'76). --The author attributes the failure of other chemists to obtain cerium from these clays (compare Abstr., 1886, 678) to the fact that in the presence of more than 0.5 per cent.of iron, the cerium precipitated by oxalic acid and potassium sulphate is much contaminated with iron, the oxide prepared therefrom being so colonred by iron oxide as to be mistaken for that substance. He describes the processes by which he affirms that he has separated the various rare earths from these clays. A. J. G. Reduction of Aluminium Oxide. By G. A. FAURIE (Compt. rend., 105, 494).-Two parts of pure finely-powdered aluminium oxide is made into a paste with one part of petroleum or some other hydrocarbon, and then mixed with one part of sulphuric acid. When the masc is homogeiieous with a pale yellow tint, and begins to give off sulphurous anhydride, it is wrapped in paper and thrown into it crucible heated to above 800" in order to decompose the hydrocarbon, The compact product thus obtained is powdered and mixed with its own weight of a finely-divided metal, the mixture being then heated to a whit>e heat in a plumbago crucible.The regulus after being allowed to cool is found to contain grains of an aluminium alloy in the midst of a metallic powder. This method of reduction is applicable to silica, calcium oxide, magnesium oxide, &c. Halogen Compounds of Gold. By G. K R ~ S and F. W, SCl-TMtuT (Bey., 20: 2634--2643).--Experiments made with a view to prepare aurous chloride and bromide by the action of chlorine and bromine respectively on gold, .gave negative results. The gold is con- verted into auric compounds in both cases ; if, is difficult to complete the reaction.I t is suggested that the numbers obt'ained by Thornsen, pointing to the formula Au,C14, were obtained from a product from which the adbeling chlorine had not been removed. When gold is warmed in bromine vapour, a black compound is formed which decom- poses into its constituents when heated at loo", even when kept in bromine vapour. The product contains a large amount of unattacked gold together with auric bromide. The compound AuzBr4 is not formed. The authors conclude that Thomsen's auro-auric chloride and bro- mide (this Journal, 1877, ii, 485) do not exist. By L. HOFFMANN and G. K R ~ ~ S S (Ber., 20, 2704--8710).-Oberkampf believed that he obtained an auro-auric sulphide, Au&, by heating a solution of auric chloride with hydrogen sulphide, but the product, according to Levol and Pellenberg, had a composition varying between that of Au,Sp and Au2S3, whilst Schrotter and Priwoznik state that an auro-auric sulphide of constant composi- I>.A. L. C. H. B. N. H. M. Gold Sulphides.INORGANIC DHE MISTRY. 29 tion cannot be obtained. These results are probably to be attributed to an incomplete removal, by mere washing on a filter, of sulphur pre- cipitated simultaneously, since the authors find that to remove free sulphur from the precipitate it is necessary to wash the sulphicle by decantation with absolute alcohol, anhydrous ether, and carbon bi- sulphide successively (compare Abstr., 1887, 1019 j. When a neutral solution of auric chloride is treated with hydrogen sulphide in the cold until all colour has disappeared from the solu- tion, and the precipitate, after repeated washing with water, is washed by decantation as above, auro-auric sulphide, AuZS2, of constant com- position is obtained, and the reaction is represented quantitatively by Levol's equation, 8AuC13 + 9H2S + 4H,O = 4Au2S2 + 24HCl + H2S04.Auro-auric sulphide is a black powder in thc dry state, and when moist is also black by reflected light, but in the finely-divided state it transmits light of a reddish-brown colour. On, porcelain, it gives a black streak. When heated in a tube, sulphur begins to vola- tilise at 140°, as sulphurous anhydride, and is completely expelled at 250-270" without the intermediate formation of aurous sulphide. With the exception of aqua regia, auro-auric sulphide is insoluble in all acids.Bromine water, gradually converts it, especially on warming, into auric bromide and snlphuric acid. Alkaline monosulphides dis- solve it slowly in the cold, but readily on heating, yielding brown solutions which beoome greenish-yellow when the heating is con- tinued ; alkaline polysulphides dissolve it in the cold, and the solu- tions on heating become brown and eventually yellow; yellow sulphide of ammoniurq, however, dissolves the compound less readily than the sulphides of the alkalis. Concentrated aqueous potash does not attack it in the cold, but on heating converts it into gold, potas- sium gold sulphide, and potassium gold oxide. Potassium cyanide dissolves it readily. When heated in a currenk of oxygen, the sulphide ignites, and is converted into gold and sulphurous anhydride, whilst hydrogen sulphide is formed when the heating occurs in a current of hydrogen.By fusing gold with potassium pentasulphide, Berzelius states that he obtained a sulphide which he believed to have the composition AuZS3, although no analyses were made. The authors have endeavoured to prepare a gold sulphide of this composition in four ways :-(1) By Berzelius' method ; (2) by Obei-kampf's and by Yorke's method (this Journal, 1848, 236), which consists in precipitating a saturated solu- tion of auro-auric sulphide in sodium bisulphide with an acid ; (3) by precipitating a saturated solution of auPo-auric sulphide in sodium monosulphide with hydpochloric acid ; and (4) saturating a solution of sodium gold oxide with hydrogen sulphide and heating the normal sodium thioaurate with an acid ; the precipitates in every case were washed by decantation with alcohol, ether, and carbon bisulphide.The precipitated sulphide obtained by the first two methods, however, contained more sulphur than required for the formula Au2S3, and had not a const'ant composition; whilst that prepared by the last two methods had a composition intermediate between that of Au,S, and Au2Ss. The authors therefore conclude that auric sulphide, Au2SJ, does not exist, and show that the properties of the so-called com-30 ABSTRACTS OF CHEMICAL PAPERS. pound are those of a mixture of suro-auric sulphide and sulphur, the latter being left as an insoluble, white powder on digestion with potassium cyanide.w. P. w.26 ABSTRACTS OF CHEMICAL PAPERS.I n o r g a n i c C h e m i s t r g .Compound of Iodine with Ammonia. By F. RASCHIG (Annulen,241, 253-255).-Iodiiie absorbs dry ammonia gas, forming a dark-blue liquid ; Bineau (Ann. Chim. Phys. [3], 15, SO) assigns to thissubstance the formula 3NH3,2I, but according to Millon (Annulen,62, 54) iodine absorbs less than half the volume represented by thisformula. The anthor finds that the volume of ammonia absorbed bythe iodine Taries with the temperature. At 20°, the amount ofammonia absorbed corresponds with Bineau's formula, but a t 80"it carresponds with NHJ, a t 0" with I(NH3)2, and at -10' with12(NH3)5. The liquid is decomposed by water, yielding ammoniumiodide and nitrogen iodide, but it dissolves completely in alcoholMethod for Decomposing Arsenical Sulphides. By .H.WARREN (ahem. News, 56, 193--194).-The cobalt speiss or arsenicalalloy is digested in hydrochloric acid containing copper nitrate, andafter a day or so, the insoluble portions are calcined at a low red heatwith plentiful access of air ; the calcined mass is then easily dissolvedby hydrochloric acid and mixed with the other solution. The copper isseparated by means of metallic iron, which also removes some bismuthand arsenic ; and the iron and remaining arsenic are precipitated byadding milk of lime. The culcium salts are removed by treatmentwith sulphuric acid, and the solution containing nickel and cobaltis precipitated by means of sodium carbonate.The precipitate is thensuspended in water and chlorine passed to saturation, when the nickelgoes into solution, whilst the cobalt remains undissolved. The solu-without undergoing any change. w. c. wINORGANIC CHEMISTRY. 27tion is boiled, and on adding caustic soda the nickel is obtained ashydroxide, which is ignited and reduced in the usual way.D. A. L.Zinc Titanates. By L. LEVY (Compt. rend., 105, 378-380).-When a mixture of 6 grams of titanic oxide, 2.5 grams of zinc oxide,and 5 to 10 grams of anhydrous zinc chloride is heated in a glass tube,the reaction is incomplete, and a violet product is obtained whichcontains an excess of titanic oxide. With excess of zinc chloride, theproduct is yellowish. If the mixture is heated in a Perrot's furnacein a crucible brasqued with charcoal and rutile, the zinc chloride volati-lises, but if the heating takes place in a long porcelain tube closed atone end, a violet or green, crystalline mass is formed, which containstitanium, zinc, silicon, and potassium.I f a mixture of 7 grams of titanium oxide, 5 grams of zinc oxide,and a small quantity of zinc fluoride, or 7 grams of titanium oxideand 30 grams of zinc fluoride is heated under a thin layer of potassiumfluoride in a graphite crucible in a Perrot's furnace for an hour anda half, washed with water, and then treated with concentrated sul-phuric acid to remove zinc oxide and titanium fluoride, beautifulviolet needles are obtained. With potassium chloride in place of thefluoride, the product is a greenish mass. With a mixture of potassiumand sodium chlorides the violet needles are obtained mixed withyellowish needles of potassium titanate.The violet crystals are zinctrititanate, Zn0,3TiU2, a small quantity of the zinc being displacedby iron. They are insoluble in water, alcohol, and ether, are notaffected by hot dilute sulphuric, nitric, and hydrochloric acids, nor byboiling concentrated solutions of alkaline hydroxides, butl are attackedwith difficulty by boiling concentrated sulphuric acid, and are decom-posed by fusion with potash. They are infusible before the blowpipe,but change to a greenish mass without loss of weight ; sp. gr. at l 5 O =4.92. The crystals are not attacked by hydrogen at a red heat, butpartially volatilise in a mixture of chlorine and hydrogen chloride.When treated with acidified hydrogen peroxide, the latter acquires acharacteristic yellow colour, but decomposition is never complete.Electrolytic Method of preparing Metallic Alloys, &c.ByH. WARREN (Chem. h'ews, 56, 153--154).-The following method isrecommended for the preparation of alloys such as phoaphor-bronzes,silicides, &c. The metal and substance containing alloying materialare placed in a deep, conical crucible, through the bottom of whichpasses a rod of graphite, extending about one inch within the crucibleand protected on the outside by au iron tube. The metal is meltedand the graphite put in connection with the negative pole, whilst themolten substance on the surface is connected with the positive pole ofa battery of two large ferric chloride cells.In this manner siliconcopper and silicon-eisen are easily prepared from pobassium silico-fluoride and the respective metal ; the salt being taken in sufficientquantity to form a molten layer 2 inches deep. By some slightvariation in the details, phosphor-bronzes can be produced ; moreover,native cryolite can be decomposed in contact with metallic zinc, and onC. H. B28 ABSTRACTS OF CHEMICAL PAPERS.subsequently volatilising the zinc, pure aluminium is obtained. Mag-nesium, barium, strontium, and calcium have not yielded satisfactqryalloys as yet.Process for obtaining the Rare Earths from the CeriferousHainstadt Clays. By J. R. STROHECKER (Chem.News, 56,175-1'76).--The author attributes the failure of other chemists to obtain ceriumfrom these clays (compare Abstr., 1886, 678) to the fact that in thepresence of more than 0.5 per cent. of iron, the cerium precipitatedby oxalic acid and potassium sulphate is much contaminated withiron, the oxide prepared therefrom being so colonred by iron oxideas to be mistaken for that substance. He describes the processes bywhich he affirms that he has separated the various rare earths fromthese clays. A. J. G.Reduction of Aluminium Oxide. By G. A. FAURIE (Compt.rend., 105, 494).-Two parts of pure finely-powdered aluminiumoxide is made into a paste with one part of petroleum or some otherhydrocarbon, and then mixed with one part of sulphuric acid.Whenthe masc is homogeiieous with a pale yellow tint, and begins to giveoff sulphurous anhydride, it is wrapped in paper and thrown into itcrucible heated to above 800" in order to decompose the hydrocarbon,The compact product thus obtained is powdered and mixed with itsown weight of a finely-divided metal, the mixture being then heatedto a whit>e heat in a plumbago crucible. The regulus after beingallowed to cool is found to contain grains of an aluminium alloy inthe midst of a metallic powder.This method of reduction is applicable to silica, calcium oxide,magnesium oxide, &c.Halogen Compounds of Gold. By G. K R ~ S and F. W,SCl-TMtuT (Bey., 20: 2634--2643).--Experiments made with a view toprepare aurous chloride and bromide by the action of chlorine andbromine respectively on gold, .gave negative results.The gold is con-verted into auric compounds in both cases ; if, is difficult to completethe reaction. I t is suggested that the numbers obt'ained by Thornsen,pointing to the formula Au,C14, were obtained from a product fromwhich the adbeling chlorine had not been removed. When gold iswarmed in bromine vapour, a black compound is formed which decom-poses into its constituents when heated at loo", even when kept inbromine vapour. The product contains a large amount of unattackedgold together with auric bromide. The compound AuzBr4 is notformed.The authors conclude that Thomsen's auro-auric chloride and bro-mide (this Journal, 1877, ii, 485) do not exist.By L.HOFFMANN and G. K R ~ ~ S S (Ber., 20,2704--8710).-Oberkampf believed that he obtained an auro-auricsulphide, Au&, by heating a solution of auric chloride with hydrogensulphide, but the product, according to Levol and Pellenberg, had acomposition varying between that of Au,Sp and Au2S3, whilst Schrotterand Priwoznik state that an auro-auric sulphide of constant composi-I>. A. L.C. H. B.N. H. M.Gold SulphidesINORGANIC DHE MISTRY. 29tion cannot be obtained. These results are probably to be attributedto an incomplete removal, by mere washing on a filter, of sulphur pre-cipitated simultaneously, since the authors find that to remove freesulphur from the precipitate it is necessary to wash the sulphicle bydecantation with absolute alcohol, anhydrous ether, and carbon bi-sulphide successively (compare Abstr., 1887, 1019 j.When a neutral solution of auric chloride is treated with hydrogensulphide in the cold until all colour has disappeared from the solu-tion, and the precipitate, after repeated washing with water, is washedby decantation as above, auro-auric sulphide, AuZS2, of constant com-position is obtained, and the reaction is represented quantitatively byLevol's equation, 8AuC13 + 9H2S + 4H,O = 4Au2S2 + 24HCl +H2S04.Auro-auric sulphide is a black powder in thc dry state, andwhen moist is also black by reflected light, but in the finely-dividedstate it transmits light of a reddish-brown colour. On, porcelain, itgives a black streak. When heated in a tube, sulphur begins to vola-tilise at 140°, as sulphurous anhydride, and is completely expelled at250-270" without the intermediate formation of aurous sulphide.With the exception of aqua regia, auro-auric sulphide is insoluble in allacids.Bromine water, gradually converts it, especially on warming,into auric bromide and snlphuric acid. Alkaline monosulphides dis-solve it slowly in the cold, but readily on heating, yielding brownsolutions which beoome greenish-yellow when the heating is con-tinued ; alkaline polysulphides dissolve it in the cold, and the solu-tions on heating become brown and eventually yellow; yellowsulphide of ammoniurq, however, dissolves the compound less readilythan the sulphides of the alkalis. Concentrated aqueous potash doesnot attack it in the cold, but on heating converts it into gold, potas-sium gold sulphide, and potassium gold oxide.Potassium cyanidedissolves it readily. When heated in a currenk of oxygen, the sulphideignites, and is converted into gold and sulphurous anhydride, whilsthydrogen sulphide is formed when the heating occurs in a current ofhydrogen.By fusing gold with potassium pentasulphide, Berzelius states that heobtained a sulphide which he believed to have the composition AuZS3,although no analyses were made. The authors have endeavoured toprepare a gold sulphide of this composition in four ways :-(1) ByBerzelius' method ; (2) by Obei-kampf's and by Yorke's method (thisJournal, 1848, 236), which consists in precipitating a saturated solu-tion of auro-auric sulphide in sodium bisulphide with an acid ; (3) byprecipitating a saturated solution of auPo-auric sulphide in sodiummonosulphide with hydpochloric acid ; and (4) saturating a solutionof sodium gold oxide with hydrogen sulphide and heating the normalsodium thioaurate with an acid ; the precipitates in every case werewashed by decantation with alcohol, ether, and carbon bisulphide.The precipitated sulphide obtained by the first two methods, however,contained more sulphur than required for the formula Au2S3, and hadnot a const'ant composition; whilst that prepared by the last twomethods had a composition intermediate between that of Au,S, andAu2Ss. The authors therefore conclude that auric sulphide, Au2SJ,does not exist, and show that the properties of the so-called com30 ABSTRACTS OF CHEMICAL PAPERS.pound are those of a mixture of suro-auric sulphide and sulphur, thelatter being left as an insoluble, white powder on digestion withpotassium cyanide. w. P. w

ISSN:0368-1769    

DOI:10.1039/CA8885400026

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

30 ABSTRACTS OF CHEMICAL PAPERS. M in e r a 1 o g i c a 1 C h e m i s t r y. Cliftonite, a Cubic Form of Graphitic Carbon. By L. FLETCHER (Min. Mag., 7, 121-130).-A meteoritic iron found on 5th January, 1884, in the district of Youndegin, Western Australia, contains a remarkable form of carbon resembling graphite but crystal- lising in the cubic form. Four fragments of the meteorite were found, weighing 252, 24, 17, and 6 lbs. respectively. I n addition there was about 1 7 lbs. of what appeared to be an outer shell, doubt- less due to the weathering of the original mass. The meteorite is extremely hard, and contains numerous inclixsions of schreibersibe. I t has a sp. gr. of 7.85. No distinct figures were obtained on etching. Analysis gave- Fe. Ni. Co. Cu. Mg. P. S. Insol. cubes.Total. 92-67 6.46 0.55 trace 0.42 0.24 nil 0.04 100.38 The insoluble residue consists of about a hundred small cubes of an opaque greyish-black mineral with metallic lustre. The hardness is 2.5, the sp. gr. 2.12, and the streak black and shining. It is not attacked by acids, and but slowly by fused nitre. It burns away very slowly in air, leaving a minute residue. Chemical tests show that the residue resembles graphite, but it is harder and occurs in definite cubic crystals. The author is of opinion that it is an allotropic modi- fication of carbon distinct from diamond and graphite, and names it cZiftonite after Professor R. B. Clifton, of Oxford. Natural Gas of Pennsylvania. By K. SORGE (Ja6rb.f. Min., 1887, ii, Ref., 318-320 ; from Xtahl und Eisen, 7, 93--108).-Since 1821, natural gas has been used in Pennsylvania in a limited and irregular way for illuminating and heating purposes.Since 1883, however, it has attained an extraordinarily repid development for industrial pur- poses. The chemical composition of the gas varies in the different wells, and even in the same well after a short lapse of time. In all cases, marsh-gas is the principal constituent. The mean volumetric com- position of the gas is as follows :- B. H. B. At the present time, 15 towns are supplied with natural gas. CHI. H. 0. N. C2H6. C,H,. COz. CO. Total. 67 22 0.8 3 5 1 0.6 0.6 100.0 The composition is said to vary within the following limits :- 60-80 5-20 1-12 1-8 0-2 0-3-2 trace CHI. H. N. C,HB. C,H,. COP CO.MIXERALOGICAL CHEMISTRY.31 Experiments made by Ford show that gas from the same well may vary considerably. In the gas-pipes of the Edgar Thomson steel- works at Pittsburgh, on different days, the gas contained per cent. :- Nitrogen. Carbonic anhydride. 0 xy gen . 0 to 23 0 to 2 0.4 to 4 The natural gas of Pennsylvania is strikingly similar in composi- Servian Coal. By S. M. LOSANITSCH (Bey., 20, 2716-2718).- Large coal seams occur in Sorvia in strata varying in age from that of the carboniferous to that of the tertiary formations, and in the paper, analyses are given of graphite, of 33 specimens of coal, and of 4 specimens of shale yielding paraffin, obtained from different locali- ties. Corrections are applied for the amount of hygroscopic water and of ash in the estimation of the percentage of volatile matter and coke obtained from each sample of coal.The table (p. 32) gives the percentage composition of the samples of coal from each formation yielding the greatest and least number of calories respectively. On dry distillation, the paraffin shale from Subotinci gave the fol- lowing results :-Tar, 34.00 ; water, 8.00 ; ash, 29.25 ; carbon (in the ash), 17.28 ; gas, 11.47. A poorer specimen gave 10 per cent. of tar, and the shale from Mijonica, from Ora3ac, and from Bovan, gave 7 to 18 per cent., 31.5 per cent., and 30 per cent. of tar respectively. w. P. w. Ullmannite from Lolling and from Sarrabus. By C. KLEIN and P. JANNASCH (Jahrb. f. Min., 1887, ii, Mem., 169--173).--The ullmannite, NiSbS, discovered at Sarrabw in Sardinia in 1883, crys- tallises in the regular system in hemihedral crystals with parallel faces.A comparison of this mineral with the hemihedral crystals with inclined faces, having the same empirical constitution, had previoiisly not been instituted. The authors having secured some of the extremely rare material from Lolling, have now been enabled to make the comparison. The percentage compositions of the ullmannites analysed were as follows :- tion to the illuminating gas obtained from Westphalian gas-coal. B. H. B. 8. Sb. As. Ni. Co. Fe. Insoluble. Total. Sp. gr. I. 14.69 55.71 1.38 28.13 0.25 0.09 0.27 100.52 6.625 11. 14.64 55-73 0.75 28.17 trace 0.17 0.11 99.57 6.733 I. ITllmannite from Lolling ; 11. from Sarrabus. It is thus evident that the two specimens have the same chemical composition and specific gravity. Crystallographical investigations, however, prove that the Liilling crystals are hemihedral with inclined faces, whilst the Sarrabus crystals are hemihedral with parallel faces.The authors are unable to prove that these differences are only apparentl, and that the crystals are tetartohedral. B. H. B. Bismuthite from the Transvaal. By H. LOUIS ( N i m . Mag., 7 , 139-140) .-Bismuthite occurs plentifully, though finely disseminated,Dusci5ption and source. Volatile matter. Graphite ----- Coke* Coal (3) from carboniferous for- mations ---_ - ---- 10.94 1’7’23 37.12 37’02 40’70 ---- ---_ ---_ ---- ---- 39.61 49-36 29’61 -- Cod (6) from Jura formations - 83.35 61.77 49.45 39.59 47.61 27-65 16.80 2.48 -- Coal (12) from chalk formatiom Coal (12) from tmtiary forma- tions.Paraffin shale Locali by. ---- ~ Stol 92 -59 Miistapid- Miiljenovuc 82.61 Kladurovo 74 -34 _L___--- ----- I -I -- Milanovac don ji 64 -54 Mrtvica 63 * 42 Jelovac 51 *75 ---__- ----I_ Miliva 59 *44 Kostolw 43 -45 -___I-__- Subotinoi 4’7 *23 ----- Mi jonica 1’7 *09 H. 3.81 3 -10 6.80 2 -32 -- 3 (& N). - 6 ‘48 4 -80 4 -06 11.04 l a -55 21 ’39 -- -- --- -- I-I2O. I Ash. I-- -- - l - I-- -- Calories. -- - -- ’7’725 7007 8089 --.-- 5845 5771 4257 5158 -- -- 3497 5541 -- -MINERALOGICAL CHEMISTRY. 33 in the auriferous quartz veins in the Lydenburg district of the Trans- vaal. It is amorphous, pulverulent, opaque, and of a yellow colour. Its hardness is about 3, and its sp. gr. 6-86, Analysis gave tihe fol- lowing reaults :- Quartz.Bi20,. CO,. H20. FepO,. Totd. 0.9 79.6 7.2 2.7 9.6 100.0 This corresponds with the formula BizHzCOB. A similar para- genesis of bismuthite wibh auriferous quart5 has been recorded from South Carolina. B. H. B. Barytes in the Carpathians. By F. v. HAUER (Jahrb. f. Milz., 1887, ii, Ref., 284; from Verh. d. geol. Reichsanst., 18, 387).-About three-quarters of a mile to the north-west of Losoncz, an extensive deposit of barytes has been found in association with the melaphyre which bursts through the new red sandstone at. that locality. The mineral exhibits a coarsely crystalline texture, and has a sp. gr. of 9-47. Fully developed crystals are not found. B. H. B. Identity of Dreelite and Barytes. By A. LACROIX (Jahrb. f. Miw., 1887, ii, Ref., 266; from Bull.SOC. Franc. Min., 8, 435-437). -The mineral termed dreelite by Dufrhoy is shown by the angles of the cleavage planes and by the optical characters to be identical with barytes. On account of deficiency of material, an analysis was im- possible. Probably, however, the percentage of calcium sulphate given by Dufr6noy was due to impurities. B. H. B. Titanite. By IC. Bnsz (Jahrb. f. Min., 5, Beilage, 330-380).- This elaborate monograph is divided into two parts, one giving the results of a chemical and optical examination of a large number of specimens of titanite, the other giving the results of the crystallo- graphical examination. The research was undertaken primarily to determine whether there is any relation between the chemical com- position of titanite and its optical constants.The specimens ex- amined were from t'he following 10 localities :-Schwarzenstein in the Zillerthal, Eisbruckalp, Val Maggia, St. Gothard, Wildkreuzjoch in Tyrol, Laacher See, Arendal in Norway, Renfrew and Grenville in Canada, and Monroe in Michigan. As a rule, the author finds that in titanites containing iron, the angle of the optic axes is larger than that of titanites containing no iron. Exceptions to this rule are, the titanite from Monroe, which wit,h a very high percentage of iron has a comparatively small axial angle, and the titanite from the Zillerthal, which with 1.07 per cent. of ferric oxide has the smallest axial angle of all the titanites examined. It is, however, evident that the mag- nitude of the axial angle of titanites rich in iron is not in proportion to the percentage of iron. In his crjshallographic investigation, the author observed 75 planes occurring on titanite crystals.Of this number, 22 have not hitherto been observed. B. H. B. TOL. LIV. d84 ABSTRACTS OF CHEMICAL PAPERS. Palaeopicrite of Amelose and the Products of its Altera- tion. By R. BRAUNS (Jahrb. f. Mi~t., 5, Beilage, 275-3?9).-Sincc 1831, when Breithaupt first showed that the well-known crystals found at Snarum, Norway, were pseudomorphs of serpentine after olivine, the alteration of olivine and the new minerals formed thereby have frequently been the objects of careful investigation. In no place, however, is the immediate connection of olivine with the products of its alteration so apparent as at Amelose, near Biendenkopf, in Hesse, where within an area of a hundred square yards is found not only the olivine rock in place, but also all the recent minerals formed from it.The latter inclnde serpentine, chrysotile, metaxite, picrolite, a new magnesium iron silicate, calcite, and quartzite interesting on account of the occurrence of the extremely rare planes $El$-, +R%. The matrix of these minerals differs from that of most serpentines in that, it is of Devonian age, aud not interstratified in crystalline schists. The new mineral is named by the author webskyite, after the late Professor Websky of Berlin. It is amorphous, and has a pitch-black colour with a brownish-green streak. In thin fragments, the colonr is bright green. The hardness is 3, and the sp.gr. only 1.771. Its constituents are qualitatively the same as those of serpentine. It8 qaantitative composition, however, is different, since it contains 31 per cent. of water, 21 per cent. of which is lost a t 100". Analysis shows that the mineral has the formula, H6R4Si,Ol3 + 6H20, in which R represents Mg and Fe. The new mineral is probably of more fre- quent occurrence than might be imagined ; the author having dis- covered it on specimens of diopside and of serpentine in the Berlin and Marburg museums. A Variety of Granulite, the Matrix of two New Minerals. Ry H. SAUER (Jahrb. .f. &!in., 1887, ii, Ref., 295 ; from Zed. deutsck. 9eo.L Ges., 38, 704-706).-11~ a new quarry by the railwa7 station of Waldheim in Saxony, the following two new minerals were found in the granulite :--Prismathe, crpstallising in rhombic prisms with- out terminal planes, gronped radially.It resembles andalusite or sillimanite. It easily alters to a finely fibrous substance, termed cryptotile (Analysis 11) :- It is, in fact, an olivine-diabase (pakeopicrife). B. H. B. Its composition is given under I. SiO,. A1203. FeO. MgO. Na2O. KZO. H20. Total. J. 30.89 43-06 6-26 15.08 2.04 0.79 1.36 99.50 11. 48.43 41.63 - 2.13 - I 7.70 99-89 B. H. B. Rocks from the Congo. By C . KLEMENT (Ja7trb.f. M h . , 1887, ii, Ref., 300-301 ; from T.schermak Min. Mitth., 8, 1--27).-The author gives analyses of two specimens of laterite from the Congo. 'J'hey are composed of a conglomerate of quartz grains cemented by a brown to yellowish-red material. The red rock (I) is more porous than the brown (11), and seems to be a product of the decomposition of the latter.These laterites are said to be a detritus of the crystal- line schists in the interior of the continent. For the analyses, the Wterial was freed from the coarsest quartz grains.ORG ANIU CHEMISTRY. 35 Lia. -- 0 -287 0 *00206 0 -04703 0 *00425 0 -00125 0 -09188 0 -03081 very dight traces SiOn. P20,. SO,. C1. Fe,O,. FeO. A120,. CaO. MgO. I. 52-91 0.51 0.29 0.08 36-26 0.29 4-13 0.19 0.07 11. 63.08 1-22 0.27 0.13 27-65 0.52 2-30 0.57 0.41 Na20. &O. H,O. Tot& I. 0.08 0.04 6-16 101.01 11. 0.19 0.06 4.71 101.11 B. H. B. The Water Supply of Oderza. By M. SPICA and G. HALAGIAN (Gmzzetta, 17, 317--323).-The water supply of the municipality of Oderzo is taken from three mountain springs, Monticano, Lia, and Navisego, which pass through a clap soil.The analyses tabulated below show that these waters are of t,be highest order of purity. The colour viewed through a tube was a pale-yellow. With an alcoholic eolution of tannin (Hager's test), they remained perfectly dear for several days. With phenolphthalein, they showed no reaction, but with litmus they appeared slightly alkaline. Navisego. 0 * 289 0 -00197 0 -04446 0 *0028 0 '003 0 *09632 0 -03099 ---- Results of Analyses expressed i!n grams per litre. 0 -168 0.0841 235 *5 12'-4 ------ Total residue .................... Chlorine ........................ Sulphuric anhydride. ............. Silica .......................... Ferric oxide and alumina.. ........ Lime. ..........................Magnesia ....................... Nitric acid ...................... Organic matter .................. Oxygen required fox organic mstker. Total carbonic: acid.. ............. Free carbonic acid.. .............. Total hardness French ......... Permanent ,, } scde { ......... 0.175 0 -0853 2'7" -0 13"'O Monticano. --- 0 -31 0 -00797 0 * 02782 0 -001 0*0015 0 -08888 0 -06036 0.02136 0-00108 0 * 2064 0 -1004 24" *o. 12O *o V. H. V.30 ABSTRACTS OF CHEMICAL PAPERS.M in e r a 1 o g i c a 1 C h e m i s t r y.Cliftonite, a Cubic Form of Graphitic Carbon. By L.FLETCHER (Min. Mag., 7, 121-130).-A meteoritic iron found on5th January, 1884, in the district of Youndegin, Western Australia,contains a remarkable form of carbon resembling graphite but crystal-lising in the cubic form.Four fragments of the meteorite werefound, weighing 252, 24, 17, and 6 lbs. respectively. I n additionthere was about 1 7 lbs. of what appeared to be an outer shell, doubt-less due to the weathering of the original mass. The meteorite isextremely hard, and contains numerous inclixsions of schreibersibe.I t has a sp. gr. of 7.85. No distinct figures were obtained on etching.Analysis gave-Fe. Ni. Co. Cu. Mg. P. S. Insol. cubes. Total.92-67 6.46 0.55 trace 0.42 0.24 nil 0.04 100.38The insoluble residue consists of about a hundred small cubes of anopaque greyish-black mineral with metallic lustre. The hardness is2.5, the sp. gr. 2.12, and the streak black and shining. It is notattacked by acids, and but slowly by fused nitre.It burns away veryslowly in air, leaving a minute residue. Chemical tests show that theresidue resembles graphite, but it is harder and occurs in definitecubic crystals. The author is of opinion that it is an allotropic modi-fication of carbon distinct from diamond and graphite, and names itcZiftonite after Professor R. B. Clifton, of Oxford.Natural Gas of Pennsylvania. By K. SORGE (Ja6rb.f. Min., 1887,ii, Ref., 318-320 ; from Xtahl und Eisen, 7, 93--108).-Since 1821,natural gas has been used in Pennsylvania in a limited and irregularway for illuminating and heating purposes. Since 1883, however, ithas attained an extraordinarily repid development for industrial pur-poses.The chemical composition of the gas varies in the different wells,and even in the same well after a short lapse of time.In all cases,marsh-gas is the principal constituent. The mean volumetric com-position of the gas is as follows :-B. H. B.At the present time, 15 towns are supplied with natural gas.CHI. H. 0. N. C2H6. C,H,. COz. CO. Total.67 22 0.8 3 5 1 0.6 0.6 100.0The composition is said to vary within the following limits :-60-80 5-20 1-12 1-8 0-2 0-3-2 traceCHI. H. N. C,HB. C,H,. COP COMIXERALOGICAL CHEMISTRY. 31Experiments made by Ford show that gas from the same well mayvary considerably. In the gas-pipes of the Edgar Thomson steel-works at Pittsburgh, on different days, the gas contained per cent. :-Nitrogen. Carbonic anhydride. 0 xy gen .0 to 23 0 to 2 0.4 to 4The natural gas of Pennsylvania is strikingly similar in composi-Servian Coal.By S. M. LOSANITSCH (Bey., 20, 2716-2718).-Large coal seams occur in Sorvia in strata varying in age from thatof the carboniferous to that of the tertiary formations, and in thepaper, analyses are given of graphite, of 33 specimens of coal, andof 4 specimens of shale yielding paraffin, obtained from different locali-ties. Corrections are applied for the amount of hygroscopic waterand of ash in the estimation of the percentage of volatile matter andcoke obtained from each sample of coal. The table (p. 32) gives thepercentage composition of the samples of coal from each formationyielding the greatest and least number of calories respectively.On dry distillation, the paraffin shale from Subotinci gave the fol-lowing results :-Tar, 34.00 ; water, 8.00 ; ash, 29.25 ; carbon (in theash), 17.28 ; gas, 11.47.A poorer specimen gave 10 per cent. of tar,and the shale from Mijonica, from Ora3ac, and from Bovan, gave7 to 18 per cent., 31.5 per cent., and 30 per cent. of tar respectively. w. P. w.Ullmannite from Lolling and from Sarrabus. By C. KLEINand P. JANNASCH (Jahrb. f. Min., 1887, ii, Mem., 169--173).--Theullmannite, NiSbS, discovered at Sarrabw in Sardinia in 1883, crys-tallises in the regular system in hemihedral crystals with parallelfaces. A comparison of this mineral with the hemihedral crystalswith inclined faces, having the same empirical constitution, hadprevioiisly not been instituted. The authors having secured some ofthe extremely rare material from Lolling, have now been enabled tomake the comparison.The percentage compositions of the ullmannites analysed were asfollows :-tion to the illuminating gas obtained from Westphalian gas-coal.B.H. B.8. Sb. As. Ni. Co. Fe. Insoluble. Total. Sp. gr.I. 14.69 55.71 1.38 28.13 0.25 0.09 0.27 100.52 6.62511. 14.64 55-73 0.75 28.17 trace 0.17 0.11 99.57 6.733I. ITllmannite from Lolling ; 11. from Sarrabus.It is thus evident that the two specimens have the same chemicalcomposition and specific gravity. Crystallographical investigations,however, prove that the Liilling crystals are hemihedral with inclinedfaces, whilst the Sarrabus crystals are hemihedral with parallelfaces. The authors are unable to prove that these differences areonly apparentl, and that the crystals are tetartohedral.B.H. B.Bismuthite from the Transvaal. By H. LOUIS ( N i m . Mag., 7 ,139-140) .-Bismuthite occurs plentifully, though finely disseminatedDusci5ption and source.Graphite -----Coal (3) from carboniferous for-mationsCod (6) from Jura formationsCoal (12) from chalk formatiomCoal (12) from tmtiary forma-tions.Paraffin shaleLocali by.---- ~Stol 92 -59Miistapid-Miiljenovuc 82.61Kladurovo 74 -34_L___--------I-I --Milanovac don ji 64 -54Mrtvica 63 * 42Jelovac 51 *75---__-----I_Miliva 59 *44Kostolw 43 -45-___I-__-Subotinoi 4’7 *23 -----Mi jonica 1’7 *09H.3.813 -106.802 -32--3 (& N).-6 ‘484 -804 -0611.04l a -5521 ’39---------I-I2OMINERALOGICAL CHEMISTRY.33in the auriferous quartz veins in the Lydenburg district of the Trans-vaal. It is amorphous, pulverulent, opaque, and of a yellow colour.Its hardness is about 3, and its sp. gr. 6-86, Analysis gave tihe fol-lowing reaults :-Quartz. Bi20,. CO,. H20. FepO,. Totd.0.9 79.6 7.2 2.7 9.6 100.0This corresponds with the formula BizHzCOB. A similar para-genesis of bismuthite wibh auriferous quart5 has been recorded fromSouth Carolina. B. H. B.Barytes in the Carpathians. By F. v. HAUER (Jahrb. f. Milz.,1887, ii, Ref., 284; from Verh. d. geol. Reichsanst., 18, 387).-Aboutthree-quarters of a mile to the north-west of Losoncz, an extensivedeposit of barytes has been found in association with the melaphyrewhich bursts through the new red sandstone at.that locality. Themineral exhibits a coarsely crystalline texture, and has a sp. gr. of9-47. Fully developed crystals are not found. B. H. B.Identity of Dreelite and Barytes. By A. LACROIX (Jahrb. f.Miw., 1887, ii, Ref., 266; from Bull. SOC. Franc. Min., 8, 435-437).-The mineral termed dreelite by Dufrhoy is shown by the angles ofthe cleavage planes and by the optical characters to be identical withbarytes. On account of deficiency of material, an analysis was im-possible. Probably, however, the percentage of calcium sulphategiven by Dufr6noy was due to impurities. B. H. B.Titanite. By IC. Bnsz (Jahrb. f. Min., 5, Beilage, 330-380).-This elaborate monograph is divided into two parts, one giving theresults of a chemical and optical examination of a large number ofspecimens of titanite, the other giving the results of the crystallo-graphical examination.The research was undertaken primarily todetermine whether there is any relation between the chemical com-position of titanite and its optical constants. The specimens ex-amined were from t'he following 10 localities :-Schwarzenstein inthe Zillerthal, Eisbruckalp, Val Maggia, St. Gothard, Wildkreuzjochin Tyrol, Laacher See, Arendal in Norway, Renfrew and Grenville inCanada, and Monroe in Michigan. As a rule, the author finds thatin titanites containing iron, the angle of the optic axes is larger thanthat of titanites containing no iron.Exceptions to this rule are, thetitanite from Monroe, which wit,h a very high percentage of iron hasa comparatively small axial angle, and the titanite from the Zillerthal,which with 1.07 per cent. of ferric oxide has the smallest axial angleof all the titanites examined. It is, however, evident that the mag-nitude of the axial angle of titanites rich in iron is not in proportionto the percentage of iron.In his crjshallographic investigation, the author observed 75 planesoccurring on titanite crystals. Of this number, 22 have not hithertobeen observed. B. H. B.TOL. LIV. 84 ABSTRACTS OF CHEMICAL PAPERS.Palaeopicrite of Amelose and the Products of its Altera-tion. By R. BRAUNS (Jahrb. f. Mi~t., 5, Beilage, 275-3?9).-Sincc1831, when Breithaupt first showed that the well-known crystals foundat Snarum, Norway, were pseudomorphs of serpentine after olivine,the alteration of olivine and the new minerals formed thereby havefrequently been the objects of careful investigation.In no place,however, is the immediate connection of olivine with the products ofits alteration so apparent as at Amelose, near Biendenkopf, in Hesse,where within an area of a hundred square yards is found not onlythe olivine rock in place, but also all the recent minerals formed fromit. The latter inclnde serpentine, chrysotile, metaxite, picrolite, anew magnesium iron silicate, calcite, and quartzite interesting onaccount of the occurrence of the extremely rare planes $El$-, +R%.The matrix of these minerals differs from that of most serpentines inthat, it is of Devonian age, aud not interstratified in crystallineschists.The new mineral is named by the author webskyite, after the lateProfessor Websky of Berlin.It is amorphous, and has a pitch-blackcolour with a brownish-green streak. In thin fragments, the colonris bright green. The hardness is 3, and the sp. gr. only 1.771. Itsconstituents are qualitatively the same as those of serpentine. It8qaantitative composition, however, is different, since it contains 31 percent. of water, 21 per cent. of which is lost a t 100". Analysis showsthat the mineral has the formula, H6R4Si,Ol3 + 6H20, in which Rrepresents Mg and Fe. The new mineral is probably of more fre-quent occurrence than might be imagined ; the author having dis-covered it on specimens of diopside and of serpentine in the Berlinand Marburg museums.A Variety of Granulite, the Matrix of two New Minerals.Ry H.SAUER (Jahrb. .f. &!in., 1887, ii, Ref., 295 ; from Zed. deutsck.9eo.L Ges., 38, 704-706).-11~ a new quarry by the railwa7 stationof Waldheim in Saxony, the following two new minerals were foundin the granulite :--Prismathe, crpstallising in rhombic prisms with-out terminal planes, gronped radially. It resembles andalusite orsillimanite. It easily alters to afinely fibrous substance, termed cryptotile (Analysis 11) :-It is, in fact, an olivine-diabase (pakeopicrife).B. H. B.Its composition is given under I.SiO,. A1203. FeO. MgO. Na2O. KZO. H20. Total.J.30.89 43-06 6-26 15.08 2.04 0.79 1.36 99.5011. 48.43 41.63 - 2.13 - I 7.70 99-89B. H. B.Rocks from the Congo. By C . KLEMENT (Ja7trb.f. M h . , 1887,ii, Ref., 300-301 ; from T.schermak Min. Mitth., 8, 1--27).-Theauthor gives analyses of two specimens of laterite from the Congo.'J'hey are composed of a conglomerate of quartz grains cemented bya brown to yellowish-red material. The red rock (I) is more porousthan the brown (11), and seems to be a product of the decompositionof the latter. These laterites are said to be a detritus of the crystal-line schists in the interior of the continent. For the analyses, theWterial was freed from the coarsest quartz grainsORG ANIU CHEMISTRY. 35Lia.--0 -2870 *002060 -047030 *004250 -001250 -091880 -03081very dight tracesSiOn. P20,. SO,. C1. Fe,O,. FeO. A120,. CaO. MgO.I. 52-91 0.51 0.29 0.08 36-26 0.29 4-13 0.19 0.0711. 63.08 1-22 0.27 0.13 27-65 0.52 2-30 0.57 0.41Na20. &O. H,O. Tot&I. 0.08 0.04 6-16 101.0111. 0.19 0.06 4.71 101.11B. H. B.The Water Supply of Oderza. By M. SPICA and G. HALAGIAN(Gmzzetta, 17, 317--323).-The water supply of the municipality ofOderzo is taken from three mountain springs, Monticano, Lia, andNavisego, which pass through a clap soil. The analyses tabulatedbelow show that these waters are of t,be highest order of purity. Thecolour viewed through a tube was a pale-yellow. With an alcoholiceolution of tannin (Hager's test), they remained perfectly dear forseveral days. With phenolphthalein, they showed no reaction, butwith litmus they appeared slightly alkaline.Navisego.0 * 2890 -001970 -044460 *00280 '0030 *096320 -03099----Results of Analyses expressed i!n grams per litre.0 -1680.0841235 *512'-4------Total residue ....................Chlorine ........................Sulphuric anhydride. .............Silica ..........................Ferric oxide and alumina.. ........Lime. ..........................Magnesia .......................Nitric acid ......................Organic matter ..................Oxygen required fox organic mstker.Total carbonic: acid.. .............Free carbonic acid.. ..............Total hardness French .........Permanent ,, } scde { .........0.1750 -08532'7" -013"'OMonticano.---0 -310 -007970 * 027820 -0010*00150 -088880 -060360.021360-001080 * 20640 -100424" *o.12O *oV. H. V

ISSN:0368-1769    

DOI:10.1039/CA8885400030

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

ORG ANIU CHEMISTRY. 35 Organic Chemistry. Arrangement in Space of the Atoms in the Molecules of Carbon-compounds. By J . WISLICENJS (Chem. Centr., 188’7, 1005 -1009).--Van’t Hoff and Le Be1 were the first to explain the optical diflerence of certain carbon-compounds by a difference in the relative arrangement of the atoms in space within the mo.lecde ; since their work, however, no serious attempt has been made t o apply their theory t o explain the isomerism of certain compounds, whose com- position, according to present views, is identical. a 236 ABSTRACTS OF CHEMICAL PAPERS. Such peculiar cases as those established by the researches of Fittig on the isomerism of male’ic and fumaric acids, however, and the dis- covery of a third and fourth monobromocinnamic acid, have been classified under the generic term of alloisomerism.Chemists hitherto seem to have contented themselves with a name. Adopting the hypothesis of van’t HoiYand Le Be1 that t.he atoms occupy the solid angles of a tetrahedron, being arranged around a central carbon-atom it is evident that two carbon-atoms, associated together in the parafflno‘id form of combination, would revolve around one common axis, passing through the point of union of the atoms and the direction of attractiou of two associated atoms, such as those of hydrogeu. When two carbon-atoms are combined together, as in the olefines, they can only revolve round an axis which is the straight line connecting the two common carbon-atoms. Supposing all four of the affinities of the saturating atoms are unequal, then six isomerides are possible, in the case of two pairs three isomerides, and three also if two affinities are equal and two unequal.For male‘ic acid, van’t Hoff has proposed the formula CH*COOH II CH-COOH , so that for fumaric acid the formula will be COO*HCH II CH-COOH In order to explain the conversion of malei’c into fumaric acid through the intervention of halogen-derivatives of succinic acid, it is sup- posed that the atoms combined with neighbouring carbon-atoms mutually react on one another according to their chemical affinity. Hence, it follows that two carbon-atoms combined together by one affinity, and being in a poRition by revolution around their axis to give way to this attraction, will so arrange themselves that the associated radicles interchange positions in the syshem.Such a relative arrange- ment will be stable in the cold, but at a higher temperature, as the interoscillation of tbe elements will be more frequent, there is a loosening of the affinities, and a different configuration ensues. When an unsaturated compound passes into one that is saturated, it is in- different to which of the two carbon-atoms each particular radicle attaches itself ; the compounds formed are identical. But if an atom is combined with two different radicles, then by addition an asymmetri- cal carbon-atom results according as the added atoms attach them- selves to one or other position of affinity. This explains the forma- tion of optically inactive compounds under these conditions, since both modifications are produced in equal quantities.As regards the nomenclature of these dieerent geometrically isomeric configurations, it is proposed to call the arrangement aCb aCb 11 the centrally or axially symmetrical, and the arrangement 11 bCa aCb the plane symmetrical. The following examples are given in illustration of the aboveOROANIC GHEMISTRT. 37 views :-Tolane dichloride exists in two modifications ; according to the author's hypothesis, the modification of higher me1 ting point, obtained by the direct chlorination of tolane, is the plane symmetrical Ph*C*Cl Ph*C-Cl 11 , whilst the other is the axially symmetrical 11 As fumaric acid is principally formed by heating malic acid, in which, doubtless, the carboxyl-group has more inclination towards the hydrogen-atom than to the hydroxyl- or other carboxyl-group, its Ph.C*Cl C1.C.Ph C 0OH.C H-OH constitution may be represented by a configuration I HHOC o OH' from which by the abstraction of a molecule of water the formula COOHGH II results.The conversion of ethyl maleate into ethyl fnmarate by iodine is explained by the intermediate formation of diiodosuccinnic acid, an interchange of position of the iodine- and hydrogen-atoms ; the removal of a, molecule of hydrogen iodide gives ethyl iodofumarate, which in its turn is reduced by the hydrogen iodide to ethyl fumarate. The reverse process of conversion of fumaric into male'ic acid through the intervention of dibromosuccinic acid can be explained in like manner. The isomerism of crotonic and isocrotonic acid is also of a similar order, the constitution of the one being expressible by a formula 11 , of the other as 11 .Cinnamic acid should also exist in two geometrically isomeric forms, of which, as yet, only one has been obtained. HC-COOH H*C*Me Me43.H HOCOOH H*C*COOH /it-Coumaric acid has the plane symmetrical arrangement HC CeH,. 0 H as it is easily converted into its lactone, conmarin ; i n its isomeride, the atoms are arranged in the axially symmetrical configuration ; this, by fuming hydrobromic acid, is converted into coumarin, by temporary addition of a, molecule of the acid, and by an inclination towards formation of the lactone. By this theory, the removal of the elements of a halogen acid and simultaneously of carbonic anhydride from the sodium salt' of a p-halogen substituted acid is expiained, as also the foi-mation of anhydrides and lactones when two carbDxyl- or a hydroxyl- and carboxyl-group are in the y-position.The author is engaged on experimental evidence in favour of this theory. V. H. V. Nitrosates, Nitrosites, and their Derivatives. By 0. WALLACH (dnnalen, 241, 288--315).-The crystalline compound which Guthrie38 ABSTRACTS OF CHEMICAL PAPXRS. (Annulen, 116, 248 ; 119, 84) obtained by the direct union of amylene with nitrogen peroxide, is most conveniently prepared by passing the nitrous fumes evolved by the action of strong nitric acid on arsenious oxide into a well-cooled mixture of amylene (1 vol.) and glacial acetic acid (2 vols.). The operation is interrupted when the colour of the liquid changes from blue to green.The crystals are washed with acetic acid, afterwards with water. As commercial amylene is a mixture, the product is not homogeneous. On recrystallisation from chloroform or benzene, two substances having the composition C5H,,N20a are deposited, namely, cubes melting at 96-97', and needles melting a t 89". This compound is not a dinitrite but 8 nitroso-nitrate or nitrosate. On boiling with alcohol and aniline, it yields aniline nitrate and nmyZenenitrolaniZine, NHPh*C5Hg : NOH. The base melts a t 140-141". It dissolves freely in ether, chloroform, warm alcohol, and in dilute acids, and crystallises well. The hydrochloride, CIIHl,N20,HC1, is deposited from a hot aqueous solution in anhydrous crystals. It is best prepared by passing hydrogen chloride into an ethereal solution of the base, when the hydrochloride is precipi- tated in the form of a crystalline powder.The w'troso-compound, NO*NPh*C,H,:NOH, is deposited as a crystalline powder when a solution of sodium nitrite is poured into ail acid solution of tLe base. It melts at 327-128", and is soluble in alcohol and in alkalis. The nitroso-compound is reprecipitated on adding an acid to t,he alkaline solution. The hydrochloride is decomposed by boiling with water, or better with hydrochloric acid, yielding hydroxylamine and a ketond base, NHPh*C,H,: 0. The new base melts a t 61", and is soluble in alcohol, ether, and in hot, 6ater. AmyleiLenitro123ctratolzl.idine, CI2HlsN20, and its hydrochloride and nitrate form well-developed crystals. The base melts a t 111-112", and the nitroso-derivative a t 147-148".The hydrochloride is decom- posed on boiling it with hydrochloric acid, yielding hydroxylamine and the base C,,H,,N20 melting a t 98". The nitroso-derivative melts with decomposition a t 149-150". The hydrochloride is more soluble in water than the corresponding para-salt. Amylenenitrolorthoanisidine melts a t 138-139". The hydrochloride is deposited from its aqueous solution in prisms. Amylene nitrosate and piperidine act on each other very energetically, forming a crystal- line base, C,,H,,N,O. It melts at 95-96", and is insoluble in water and in alkalis. The hydro- chloride is art oily liquid, but the platinochloride (c,,H,oN,0)2,HB,PtC:16, forms beautiful prisms. Arnylenerzitroldiethyla~t~ine crystallises i4 plates and melts a t 71-72".ArnylenenitroEalLylamine is soluble in water. The hydrochloride, C8H16N20,HCl, is crystalline. This base is isomeric with nitrosoconiine. Amylene nitrosate acts on sodium ethoxide, forming a crystalline compound which melts a t loo", and also on ethyl acetoacetate, yielding a crjstalline compound of the composition Amylenenitrolorthotoluidine melts a t 115". The Yalts dissolve freely in water. C,H,,NO*CH(C OMe) *COOEt. Guthrie (bc. cit.) observed that amyl nitrosate acts on potassiumORQANIC CHENISTRY. 39 cjanide, but the author finds that a crystalline compound and potas- sium nitrate, not a liquid and a m i t r i t e , are formed in the reaction. A blue crystalline compound is formed by passing nitrous fumes into brornamylene dissolved in acetic acid, and pouring the crude product into water.This compound acts on piperidine at the ordinary temperature, yielding a colonrlesg, crystalline substance which exhibits neither acid nor basic properties. It is soluble in alcohol, is rich in bromine, and has an odour resembling that of camphor. Synthetical Experiments in the Sugar-group. w. c. w. By E. FISCHEB and J. TAFEL (Ber., 20, 8566-2575).-1t was previously shown (Abstr., 1887, 651) that acraldehyde bromide is converted by baryta into what is probably a glucose. With phenylhydraaine, the product of the reaction yields a- and P-phenlylacrosazones, melting a t 205' and 148" respectively. When isoglucosamine oxalate (Fischer, Abstr., 1886, 934) is dis- solved in ice-water (10 parts) and treated with sodium nitrite, an evolution of nitrogen takes place ; after three hours, the temperature is aliowed to rise to 20".The product is exactly neutralised with aqueous soda, evaporated in a vacuum, and the residue extracted n-ith absolute alcohol. On evaporating the solution, levulose is obtained as a yellowish syrup ; the spec. rotatory power a t 80"=25". It produces strong fermentation with yeast in 10 minutes, gives a precipitate of pheny lglucosazone wit'h phenylhydrazine, and yields Kiliani's levu- lose hydrocyanide when treated with hydrocyanic acid. The consti- t ution of isoglucosamine is probably NH2.C &,*GO. [ CH( OH) I3.CH2.OH. Ledderhose's isomeric glucosamine has possibly the constitution C: 11 0. C H ( N H,) [ C H ( 0 H ) ] BG H i 0 H . a-Phenylncrosazone is obtained in the following manner : A solu- tion of 75 grams of pure, crystallised barium hydroxide in 1-25 litre OF water is cooled with ice-water; 50 grams of freshly-distilled acraldehyde bromide is then added by drops, the baryta solution being kept violently shaken.Eight preparations are united, made slightly acid with sulphuric acid, and treated with a strong solution of sodium sulphate until the barium is completely precipitated. After 12 hours, it is filtered, neutralieed with aqueous soda, and evapo- rated in it vacuum to 18 litre. When cold, a solution of phenyl- hy drazine hydrochloride (50 grams) and sodium acetate (50 grams) in 100 C.C. of water is added, and the whole left for 12 hours; it is then filtered and warmed on it water-bath wikh 150 grams more of phenylhydrazine hydrochloride and 150 grams of sodium acetatre.In the course of foul. hours, a half crystalline and half resinous preci- pitate separates; this is washed with water and extracted with ether, when the greater part of the resin and the /I-phenylacrosazone dissolves, leaving the a-phenylacrosazone. After filtration, the a-com- pound is repeatedly extracted with boiling alcohol, and treated with hot water, after which it is almost pure. The yield from $00 gi*ams of bromide is 18 grams. It melts a t 205" (uncorr.), and is very sparingly soluble. On addiug water to the hot alcoholic solution, it sepwntss in long, slender needles. a-Acrosaniine, Cs&N05, is prepared similarly to isoglucosamino40 ABSTHACTS OF CHEMICAL PAPERS.(Zoc. cit.) by reducing the acrosazone with zinc-dust and acetic acid, and is purified by means of the oxnlate. It shows all the reactions of the glucosamines. When the oxnlate is dissolved in ice-water and treated with sodium nitrite, a-acrose, C6H120,, is formed; this is obtained as a light-brown syrup, having a sweet taste. It reduces Fehling's solution. p-Pheiiy Lncrosazolte, C,aH22N404, is obtained by evaporating its ethereal extract' (obtained in the purification of the a-compound), dis- solving in alcohol, and precipitatiag with water. The dried product is exhausted with cold benzene several times. The yellow crystalline ~esidue is boiled with acetone (2 parts), filtered, and precipitated with ether and light petroleum. It crystallises in slender, yellow nsedles melting at 148", dissolves in alcohol and acetone much more readily than the a-compound, but is almost insoluble in ether when pure.The yield is small. The resemblance of a-phenylacrosazone to phenylglucosazone makes i t probable t.hat a-acrose has the constitution expressed by the formula OH.CH,*[CH(OH)]4*CIEE0 ; the constitution of p-acrose would then be OH*CH,*CEI(OH)*CH(OH)*C(OH) (CH2*OH)GH0 or OH.CH,.CH(OH).CH( OX).CO-CH(OH)*CH2*OH. The lower melting point and more ready solubiIity of the p-osazone point to its being a derivative of a sugar with an abnormal carbon-chain. Isodulcitolphett yllydrazine, CsHl,04 N2H Ph, mystallises from alcohol in colourless plates melting at 159'. It is insoluble in ether, readily soluble in water and in alcohol.The aqueous solution is dextro- rotatory. Lactosephen?/Zhyarazine, C16HPBOION2, is prepared by adding phenyl- hydrazine (1 part) to a solution of milk-sugar (2 parts), in hot water (2 parts). After two days, twice the volume of absolute alcohol is added, and the whole treated with much ether. The syrupy preci- pitate after being repeatedly dissolved in alcohol and precipitated with ether, is obtained as a solid mass. I t is filtered, quickly washed with ether, and dried in a vacuum over sulphuric acid. It dissolves readily in water and in alcohol, and is insoluble in ether. It is laevorotatory. N. H. M. Isonitrosogalactose. By P. RISCHBIETH (Bw., 20, 2673-2674). -When galactose (1 gram) and hydroxylamine hydrochloride (0.4 gram) are dissolved in a sniall quantity of water, treated with sodium carbonate (0.65 gram), and allowed to remain for 24 hours, isolzitrosogaZwttose, C6H1,0, : NOH, is obtained as a colourless, crys- talline substance which melts at 175-176", and is readily soluble in hot water, soluble in hot dilute alcohol, and practically insoluble in ether and absolute alcohol.Under similar conditions, no separation could be obtained from dextrose, levulose, or arabinose. w. P. w. By C. WEHMER (Ber., 20, 2614--2618).-Plants which readily produce starch from dextror;le, cane-sugar, mannitol, and glycerd, do not produce starch in any determinable amount from formose. The Carbohydrate Character of Formoee.ORGANIC CHERIISTRY. 41 When 28 grams of formose syrup is boiled with 100 C.C. of wuter and 5 grams of hydrochloric acid (sp.gr. 1.2) for 11 hours, a sepa- ration of humic suhstance (3.5 grams) takes place. The filtrate shows the iodoform reaction distinctly and reduces Fehling's solution. No levulinic acid is formed. 13 per cent. phosphoric acid produced the same decornposition, also without formation of levulinic acid. The author concludes t h a t formose is not a carbohydrate. Saccharification in Vegetable Tissues. By BONDONNEAU and FORET (Compt. rend., 105, 61 7--618).-The amylaceous plant is heated at 90-100" with acid of 1 t o 2 per cent., and the starch is gradually and completely converted into dextrin, glucose, saccharose, &c., and the soluble products thus formed diffuse through the cell- walls into the surrounding liquid. When the proportion of sugar in the liquid ceases to increase, the process is finished. This method is readily applied on a large scale.The exhausted pulp is free from starch, but constitutes a valuable nitrogenous food-stuff for cattle. The pulp from maize has the composition,-Water, i9.15 ; ash, 1.22 ; nitrogenous matter, 8-38 (containing nitrogen, 1.31) ; oil, 5.48 ; cellu- lose and loss, 5-77 = 100. It will be observed that water has been substituted for the starch. N. H. M. C. H. B. Amines of the Paraan and Benzene Series. By MALBOT (Compt. rend., 105, 574-576) .-In the reactions described, unless otherwise stated, the substances were mixed in equal molecular pro- portions. Ethylamine and aqueous ammonia at 100" yield triethylamine, but st 130" tetrethylammoniurn chloride is obtained in considerable quantity.Propyl iodide under the same conditions yields tripropyl- ltmine at loo", snd tetrapropylammonium iodide at 150". Although pure tripropylamine combines but slowly with propyl iodide in the cold, combination becomes complete at 150". Tripropylamine has no action on propyl chloride in the cold, and the reaction takes place slowly at 150", but becomes very rapid at 190", the products being tripropylamine and dipropylamine hydrochlorides and propylene. Rutyl iodide and aqueous ammonia at 160" yield only tributylamine, and the action of tributylamine on butyl iodide is strictly analogous t o that which takes place with the corresponding propyl-derivatives, Tributylamine acts slowly on -butyl chloride at 80°, but at 170" piire dibutylamine hydrochloride and butylcne are obtained.Dibutyl- amine and butyl iodide in the cold yield dihutylamine hydriodide and free tributylamine; at a higher temperature, the reaction is analogous to that obthined with the chloride. Isoamsl iodide and aqueous ammonia at 150" yield tetramyl- ammonium iodide. T'riamylamine acts slowly on amyl iodide in the cold, but at 150" triamylamine hydriodide and amylene are formed. At ZOO", the reaction is very rapid, and the products are diamylamine hydriodide and amylene. With amyl chloride, a salt of trinmylamine is formed at 17O", and undergoes no further alteration even at '210". Dinmy lamine and amyl iodide yield diarnylamine hpdriodide, free trismglamine, and te tramylarnmonium iodide.42 ABSTRACTS OF CHEMICAL PAPERS. Capryl chloride with aqueous ammonia in equal molecular propor- tions at 170" yields monocaprylamine together with a small quantity of the dinmine and caprylene.With twice the proportion of ammonia, the diamine is the chief product,, and no caprylene is formed. Capryl iodide with an equivalent quautity of ammonia a t 160" yields only monocaprylamine, either free or tocether with caprylene, the latter occupying a t 120" a volume equal to half the volume of capryl iodide used. Benzyl and metatolyl chlorides yield the tertiary amines almost exclusively, whilst cinnarnyl chloride yields the secondary amine, The bases are obtained in the form of salts by the action of the correspond- ing alcoholic chlorides. The formation of a bivalent hydrocarbon is especially marked with styrolylamines, cinnamene being obtained in large quantity.It is identical w i t h the synthetical cinnamene of Berthelot, and part of it is obtained in the form of metacinnamene. Whether the products of these reactions are in the free stmate or in the form of salts is determined by the conditions of equilibrium between the rival attractions of the ammonia and the amines for the ethereal salt which is present, and the acid contained in this salt. The increasing complexity of the amines is the result of a series of successive tlransformations, a bivalent hydrocarbon being produced simultaneously. This last fact is i u favour of the ethylene theory of the constitution of amines. C. H. B. Allyl-diguan idine and its Derivatives. By A. SMOLEA (Monatsh.; 8,3i9--390) .-Allyldiguanidine copper silkhate, ( C,H,,N,),Cu,H,S04, is obtained by dissolving dicyandiamide in aqueous copper sulphato and adding allylamine; the mixture is then heated for some hours at 100".This salt is more soluble in alkaline solutions than in pure water ; it separates from boiling solutions in carmine-red, anhy- drous crystals, from cold solutions in pale rose-coloured, microscopic needles with 1 mol. H,O. The other salts were made from the fore- going by double decomposition. The chloride, (C5H,0N,),C~i,2HC,1 + 2H,O, yields groups of rose-red crystals easily soluble in water to an amet hyst-coloured solution. The nitrate, ( C5H1,N5) Jh,2HN 03, forms dark-red crystals easily soluble in water. Other salts were prepared. Copper-allyldiguanidine, ( C6H10N6)2C~, was obtained by precipitating a boiling solution of the sulphate with soda.It crystallises in dark rose-red needles, sparingly soluble in cold, more soluble in boiling water. A solution of this base precipitates metallic hydroxides from solutions of metallic chlorides, the chloride described above remaining i n solution. Allyldiguanidine sulphute, ( C3H,lN5)2,H2SO* + QH20, was obtained by the action of hydrogen sulphide on the copper salt suspended in water. It crystallises in prisms, and is soluble in water, insoluble in alcohol. The acid sukhate, C5Hl,N5,H2SO~ + $H,O, crystallises in scales. The chloride, C5H,lN5,HCI, yields transparent prisms easily soluble in water and alcohol. It yields no precipitate with PtCl,, nor with potassium tartrate. The acid chloride, C5HllN6,2HCl, forms small, transparent prisms easily soluble in water and alcohol.AIZyl- diguanidine, CZH6N5*CBH5, was prepared by treating a solution of the When heated above 130°, the base decomposes.ORGANIC CHEMISTRY. 43 raulphate with the calculated quantity of barium hydroxide and also by the action of hydrogen sulphide on copper all yldiguanidine sus- pended in water. It forms a dightly crystalline, very hygroscopic mass, is strongly alkaline in character, displacing ammonia from its salts and absorbing carbonic anhydride from the air. When heated with potash and chloroform, it yields allylcarbamine (C,H,*NC). In chemical characteristics, the above copper compound somewhat resembles the alkalilie earthy metals, the allyldiguanidine, the alkali metals and especially sodium.Isonitroso-compounds. By E. BECKMANN (Ber., 20,2580-2585 ; compare Abstr., 1887, 826) .-The intramolecular change which takes place when diphenylketoxime is treated with phosphorus pentacliloride or with sulphuric acid, is also produced by hydrochloric acid, acet,ic chloride, acetic anhydride, and acetic acid. When a cooled soluti.on of diphenylketoxime in 10 parts of glacial acetic acid containing acetic anhydride is saturated with hydrogen chloride, and then heated at TOO", the oxime is completely converted into benzanilide; this is precipitated by sodium carbonate, and re- crystallised from alcohol. ~~ethy~phenylk~toxime when similarly treated yields acetanilide, which separates as hydrochloride on coo 1- iiig the solution; the reacfion takes place in the cold, but requires some days.Methylpropylketoxime is converted by hydrochloric acid into the compound NHPr*CMeO,HCl, and not into the compound NHMe-CPrO. When diphenylketoxime is heated with acetic anhydride in presence of hydroxylamine hydrochloride a t 150", acetanilide and benzoic acid are formed. Methylphenjlketoxime when heated with 10 parts of acetic anhydride for six hours a t loo", yields the compound CMePh : N*OAc (Rattner, Rer., 20, 506). This crystallises from light petroleum in forked needles mel6ing a t 55". Glacial acetic acid at 180" acts on diphenylketoxinie with forma- tion of benzanilide, acetanilide, and benzoic acid. Methylphenyl- ketoxime is converted by hot glacial acetic acid into oily products ; acetanilide is not formed.I?. H. M. L. T. T. Oxidation by Means of Hydrogen Peroxide. By C. WURSTER ( B e y . , 20, 2631--263S).-The author showed previously (Centr. fiir Yhysiol., 1887, 33) that organic acids are quickly oxidised by hydro- gen peroxide to carbonic anhydride ; the higher fatty acids and oils, cane- and grape-sugar, are rather stable towards hydrogen peroxide, whilst boiled starch is converted first into crythrodextrin and then into sugar. Hydrogen peroxide (6 mols.) reacts with hydroxylamine sulphate a t 40" with formation of sulphnric acid, nitric acid (2 mols.), and water (12 mols.) . Hydroxylamine hydrochloride is similarly converted into hydrochloric and nitric acids and water. When an aqueous solution of phenol is treated with a hydroxyl- amine salt aud hydrogen peroxide, nitrosophenol is formed.Phenylhydrazine is converted by hydrogen peroxide into benzene and diazobeuzeneiinide. The production of benzene makes it pro- The yield is quantitative.44 ABSTRACTS OF CHEhlICAL PAPERS. bable that free diazobenzene is first formed in the oxidation of the h y drazi ne. By P. RISCHBIETH (Ber., 20, 2669-2673).-Isonitrosovaleric mid (Abstr., 1883, 1129) can readily be obtained by dissolving hydroxylamine hydrochloride (50 grams) and levulinic acid (83 grams) in a small quantity of water and adding a concentrated aqueous solution of sodium carbonate (38 grams) ; a separation of the acid immediately occurs, and this is pi-rrified by recrystallisation froni water. The yield amounts to 90 per cent. of that theoretically possible.When treated with hydrogen chloride, the acid melts and absorbs the gas, and on warming the product, a sudden reaction occurs with the evolu- tion of nitrogen, and production of a black residue. On oxidation with dilute nitric acid, a large volume of gas is evolved, and acetic and succiriic acids are formed; the residue is, moreover, found to be free from nitrogen. If the acid (6 grams) is heated with sulphuric acid( 10 grams) in a vacuum at 150", succinic acid sublimes, and nitrogen is evolved ; when, however, a much larger proportion of sulphuric acid (36 grams) is employed, and the heating is continued jor 6 to 12 hours at 100" at the ordinary pressure, the elements of a molecule of water are withdrawn from the molecule of isonitrosovaleric acid, and the " inner anhydride," npvaleroximidolactone, together with succinic acid, resu1t.s.N. H. M. Isonitrosovaleric Acid and v-Valeroximidolactone. r- Valeroximidolactone, CM&EH<g2>C0, cryskllises from ether and water in long, white prisms; it melts at 69-70" when slowly heated, and at a somewhat higher temperature when the heat'ing ia rapid, and boils at 232" without decomposition. When heated with aqueous alkalis, it yields the corresponding salts of isonitrosovaleric acid, but dilute sulphuric acid, hydrogen chloride, fuming hydrochloric acid, and ammonia are without action on it at 100". O n distillation with nitric acid (sp. gr. = 1*4), a distillate is obtained which contains in addition to unaltered lactone at least two distinct crystalline com- pounds ; these have not yet been further examined.New Source of Capric Acid. By A. BUISINE and P. BUTSINE: ( C o n y t . rend., 105, 61&617).--Capric acid does not exist as such in suint, but au aqueous solution of suiiit undergoes fermentation under the influence of microbes, and the quantity of fatty acids and especi- ally of capric acid is greatly increased, the proportion of the latter rising to 5 per cent. The capric acid ir;; separated by distillation, saponification, and subsequent fractionation, and is finally crystallised from boiling water. It forms a crystalline, buttery mass, with an odour of rancid butter, melts at 31", is soluble in alcohol and ether, and is slightly soluble in boiling water, from which it crptallisea in white needles. The barium salt is soinble in alcohol.C. H. B. W. P. W. Linoleic Acid. By L. M. NORTOX and H. A. RICHARDSON (Ber., 20, 2735--2736).-When endeavouring to dry linoleic acid at 100" in aORQANIC CHEM ISTRT. 45 current of hydrogen, the authors found that a. continued loss of weight occurred even after 28 hours, although no change in composition took place. Linoleic acid can be distilled without any appearance of de- composition at 290" under 89 mm. pressure, and a colourless product is obtained amounting to about three-fourths of the mid taken. This consists of an acid, CmH%O2, which cannot again be distilled in a vacuum without decomposition; its sp. gr. is 0.9108 a t 15", and its vapour-density = 153. Under similar conditions, ricinoleic acid yields an acid agreeing in Butanedicarboxylic Acid.By R. OTTO and A. R~SSING (Ber., 20, 2736-2747).-By the reduction of dimethylmale'ic acids, two batane- dicarboxylic acids are obtained, the one, melting at 193-194', which has been shown to be symmetrical dimethylsuccinic acid, the other, ethylmethylmalonic acid, melting at 118-120". I n this paper, the anhydrides of these acids are more particularly studied. The former on dry distillation yields an anhydride melting at 87", previously described by Bischoff and Rach ; but thiR substance on rehydration and crystallisation from the aqueous solution yields not only the original or symmetrical dimethylsuccinic acid, but also the above- mentioned isomeric ethylmethylmalonic acid. On the other hand, the symmetrical dimet hylsuccinic acid, when treated with excess of acetic chloride, yields an anhydride isomeric with the above, which crystallises in rhombic tables melting at 38"; this on rehydration yields the original acid only.Again the butanedicarboxylic or ethylmethylmalonic acid, melting at 121", remains unaltered on dry distillation, but when treated with acetic chloride i t yields a n anhydride of the same melting point, 86-87", and crystalline form as the former of the anhydrides mentioned above, but which, however, differs from it in yielding on rehydration the original acid only. Distillation of Citric Acid with Glycerol. By P. DE CLERMONT and P. CHAUTARD (Compt. rend., 105, 520-523).-500 grams of crystallised citric acid mixed with 750 grams of ordinary glycerol of 28" are distilled in a glass retort of 3 litres capacity, and the product redistilled.The first fraction consists of about 250 grams of water contbining a small quantity of acraldehyde, &c. ; some crystals also separate in the colder part of the apparatus. The mass then swells up, and the teriiperature musk be reduced, but it is afterwards gradually raised until the distillation is complete. The distillate during this second stage consists of 650 to 700 grams of liquid. The total products of the decomposition are 950 grams of liquid, 30 grams of a bulky, carbonaceous residue, carbonic oxide and carbonic anhydride, and vapours of acetone and acraldehyde. I n addition to water containing small quantities of acraldehyde, the only products in the distillate are unaltered glycerol and pyruvine or the pyruvic ether of glycide, MeCO*COO-CH,.CH<-O->, which is also obtained by the distillation of glycerol with tartaric acid or glyceric acid.Probably composition with that just described. w. P. w. V. H. V. CH,46 ABSTRACTS OF CHEMICAL PAPERS. the pyruvine is a product of the reaction between glycerol and glyceric acid, the latter being formed as an intermediate product. The pyrnvine thus obtained crystallises in large, prismatic needles, or tables, which melt a t 82" and boil a t 241" under a pressure of 764 mm. C. H. B. Double Lactone of Metasaccharic Acid. By H. KILIANI (Bw., 20,2710-2716) .-The oxidation product of the lactorie of arabinose- carboxylic acid (Abstr., 1887, 465) dissolves readily in aqueous ammonia, and from the solution the diumide of metasaccharic acid, C,H,,O,N,, separates as a white powder, consisting of microscopic, tabular, monoclinic crystals, which become yellow a t 170" and melt a t 189-190" with complete decomposition.The compound has a neutral reaction, and when heated at 100" with potassium hydroxide Fields the potassium salt of metasaccharic acid as a colourless syrup ; this becomes crystalline on stirring, and in aqueous solution does not reduce Pehling's solution. On treatment with a cold solution of phenylhydrazine hydrochloride (1 part) and sodium acetate (1.5 pwt), in water (10 parts), the oxida- tion product yields the monophenylh ydrazide of the lactone of meta- snccharic acid, Cl2HI40,N2 ; this crystallises in colourless, microscopic males with 8 mol. H,O, dissolves readily in hot water and alcohol, and when rapidly heated becomes yellow at 185", and melts a t 130-192" with decomposition. If the mixture w i t h phenylhydrazine (which, to obtain the preceding compound is allowed to remain for 20 minutes for the crysta,llisxtion to take place) is a t once poured into boiling water, the diphenylhydj-azide of metasaccharic acid, CleH2206N,, separate8 after 10 to 15 minutes in yellowish-white, microscopic scales, which become yellow a t 210°, melt at 21 2-213" with decomposition, and are very sparingly soluble in boiling water aiid alcohol.The solution in concentrated sulphuric acid is coloured red or bluish-violet by ferric chloride. When the oxidation product (12 grams) is dissolved in water (300 grams), treated with 3 per cent.sodium amalgam (200 grams), and dilute sulphuric acid added gradually so that the solution never becomes alkaline, allowed to remain fire days with a farther 200 grams of sodium amalgam, then treated with sulphuric acid and alcohol to free the product from sodium sulpliate, and the mother-liquor evaporated, a syrup is obtained which still reduces alkaline copper solution, and from which mannite (2 grams) crystallises on standing over sulphuric acid. The strongly acid mother-liquor seems to consist of the lactone of a bibasic acid (? metasaccharic acid), a strongly acid syrup having similar properties being also obtained by continued heating of the oxidation product with water, or by repeated evapora- tion of its aqueous solution. The oxidation product of the lactone of nrabinose-carboxylic acid dissolves in 18, not, 8, parts of cold water (compare loc.cit.), and readily reduces alkaline copper solution. The aqueous solutions of its potassium and sodium salts, even in the absence of free alkali, become colonred intensely red on heating, or when allowed to evaporate spontaneously (Ber., 20, 343). The author, however, concludes, fromORGASIC CHEhlISTRP, 47 the preceding experiments, that the oxidation product is not the lactone of a ketonaldehydic acid, but is a double lactone of meta- CH(OH)*CH*O.CO - saccharic acid, I ), or which, on account of its peculiar constitution is very labile, and on treatment with alkalis even at the ordinary temperature undergoes molecular change, or perhaps reduction to an aldehyde -compound jielding mannite by the action of nascent hydrogen. Thiohydantoin.By R. ANDREASCH (Monatsh., 8, 407-424).- Loven has recently shown (Abstr., 1885, 241) that a methylene-group situated between a carbonyl-group and a sulphur-atom possesses similar properties to the methylene-group in ethyl malonate and acetoacetate. With the object of ascertaining whether this is the case in hydanto'in, the author has prepared the disilver-derivative, and from that the dimethyl-compound, Disilz~e~-tJ~iohydan.to'i?z, Ag2C3N,H2S0, was obtained by adding a warm aqueous solution of thiohydantoTn to ammoniacal silver nitrate. It forms a white, granular substance, sparingly soluble in nitric acid, insoluble in ammonia. I t blackens when exposed to light. When treated with methyl iodide, the silver compound yields P-dimethyithio- hydantozn, XH C<,,.,,>.This substance is easily soluble in water, sparingly in cold alcohol, crrstallises in hexagonal scales, melts at 114", and decomposes at a slightly higher temperature. When oxidised in hydrochloric solution by barium chlorate, carbonic anhy- dride and mei-captan are evolved, and the residue is found to contain carbamide, and a mixture of barium salts which cannot be separated, but one of which seems to be barium methylsulphonate. When heated wit,h barium hydroxide, the hydantoi'n yields cyanamide and some sulphur compounds which could not be isolated. Witlh the aim of determining the constitution of tlhe above com- pound, the author atternpted to prepare the two isomeric dimethyl- hydanto'ins in other ways.a-Dimethylthiohydan.tozn, W. P. W. S*CMe2 may be prepared by heating together dimethylthiocarbamide and chlor- acetic acid in aqueous solutioi~. It is easily soluble in water, alcohol, ether, and carbon bisulphide, crystallises in long, thin, colourless prisms, melts at 71", and boils a t a rather higher temperature. It volatilises slowly a t ordiuary temperatures. It bas an odour some- what resembling that of nicotine. When heated with aqueous alkalis, it yields thioglycollic acid. The isonitl.oso-derivative, C,H,N,SO,, yields yellowish scales melting at 220". Imidocarbnminethioisobzl,tyri,: anhydride, C5N2H8S0, was prepared by heating together thiocarb- amide and x-bromisobutyric acid. It crystallises in plates, is easily48 ABSTRACTS OF CHEMEIIICAL PAPERS.soluble in alcohol and boiling water, sparingly in cold water, and melts at 242". When oxidised with nitric acid, this substance yields carbamide and sdphoisohufyric mid, SO,EI*C,H,~COOH, which forms a barium salt, BaC,H,SO, + 4H,O, crystallising in needles, easily Roluble in water, insoluble in alcohol. The sodium salt, Na,C,H,SO, + &H20, forms glistening needles eiisily soluble in water, insoluble in alcohol. The same sulpho-acid is obtained by the action of chloro- sulphonic acid on isobutyric acid. The action of ammonium sulphite on a-bromisobutyric acid produces, however, an isomeric sulpho-acid, yielding an easily soIuble barium salt, BaC4H,S05 + 2H20, cryeta1- lising in needles. It is thus clear that this imido-anhydride is not, identical with the /3dimethglthiohydantoYn, as the author had anticipated.As it was possible that in the formation of the imido-anhydride a transformation from the iso- to the normal butvric series had occurred, the author S*CHEt prepared imidocarbaminethiobu~~,yric anhydride, NH : C<NH.co >, by the action of a-bromobutyric acid on thiocarbamide. This crystal- liRes in short, thick needles, easily soluhle in boiling water, and melts at 200". It is not identical with the compound obtained from iso- butyric acid. The constitution of the latter is therefore still doubtful, but its formation may perhaps be due to the action of thiocarbamide on the methacrylic acid formed by the elimination of hydrogen bromide from the bromisobutyric acid, CH,: CMe*COOH + CS(NH2)2 = CHMe<Co.2GH>C 1 NH + H20.The consitution of the ,&compound would then be correctly expressed by the formula given above. Thiohydantok when treated with benzaldehpde yields amidinethio- cinnanzic ( b e n z ~ l i d e n e t h i o h y d n ~ ~ o ~ c ) acid, NH C(NH,)(COOH) CHPh ; this forms white, microscopic needles, insoluble in water, soluble in alcohol. Several salts of thioliydantoin are described. The subphate, (C3H,N,S0)2,H2S04, forms plates soluble in water ; the nitrate, flat needles or prisms ; the ozalate, C,H4N2S0,C2H,04 + H20, prisms ; the pzcrate yellow, microscopic needles. Thiohydantoin is best prepared as follows : 50 grams of thiocarb- amide is dissolved in + litre water, and 62 grams of chloracetic acid dissolved in 50 C.C.of water added. The whole is heated a t 80-90" until reaction has ceased, and when cold it is gradually neutralised with soda, care being taken never to let the solution become alkaline. Orthothioxen and Orthothiophendicarboxylic Acid. By W. GR~NEWALD (Ber., 20, 8585-2587).-0rthothioxen (Paal, Abstr., 1887, 1101) is prepared by distilling an intimate mixture of 10 grams of p-methyllerulinic acid and 17 grams of phosphorus trisulphide in a, capacious retort. 250 gi*ams of methyllevulinic acid yielded 150 grams of pure product. It is a colourless, strongly refractive oil, h%ving an odour of petroleum ; it boils a t 136-137" (corr.). Sp. gr. at 21" = 0.9938. When treated with 1 per cent. solution of potassiizm per- manganate, a monocarboxylic acid only is formed ; this melts a t 134.5".CH S Similar a,cids seem to be produced with other aldehydes. L. T. T.ORGANIC CHEMISTRY. 49 Ort7~othiophendicarboxylic acid, C4SH,(COOH)2, is obtained by the action of 1 per cent. permanganate solution on the monocarboxylic acid ; the product is steam-distilled to remove unchanged mono- carboxylic acid. It crystallises in long needles which do not melt a t 860", but decompose at a higher temperature. When heated with rcsorcinol at 200", a product is obtained which dissolves in strong aqueous alkali with dark-red coloration ; the colour changes to yellow on diluting with water; the solution then shows a yellowish-green fluorescence. The silver salt forms white flakes irisoluble in water ; the barium saZt separates in colourless crystals, readily soluble in hot water.The dimethyl salt crptallises from alcohol in colourless plates melting at 595". N. H. M. Action of Carbonic Anhydride on Aromatic Amines. By A. DITTE (Compt. rend., 105, 612--614).-When an aniline salt is mixed with an aqueous solution of a normal or hydrogen carbonate, carbonic anhydride is given off, and aniline separates in the free state, no aniline carbonate being formed. Carbonic anhydride is not soluble in aniline, and does not combine with i t under ordinary pressure even at -8', the temperature at which aniline solidifies. I€, however, dry carbonic anhydride and aniline are compressed in a Cailletet's apparatus, the auiline dissolves the carbonic anhydride, jncreasiug to about twice its original volume, and a limpid layer of the liquefied gas swims on the surface of the solution and volatilises at 15" under a pressure of 40 atmos.If the compressed liquid is cooled to 8-10", it crystallises in transparent, white needles, and when the aniline and carbonic anhydride are in equal molecular pro- portions, solidification is complete. When the carbonic anhydride is in excess, it forms a, layer above the crystals. When aniline is in excess, it does not at once dissolve the carbonic anhydride, and the fwo liquids form distinct layers, but on gentle agitation the carbonic anhydride is dissolved, and crystallisation takes place a t 8". It is evident that carbonic anhydride and aniline combine in equal molecu- lar proportions to form a compound which crystallises a t 8", and is liquid or remains in superfusion at loo, and decomposes when the pressure is released.The tension of dissociation a t different tempe- ratures is as follows :- Temperature . . . . . . . . . . 0" 2" 5" 7" Pressure in atmos. . . . . 6 9 17 28 Orthotoluidiiie behaves in a precisely similar manner, and the com- pound crystallises in brilliant, white needles. The behaviour of meta- xylidene is similar in that the two liquids mix, but no crjstals form even a t -12". Pyridine and its homoIogues show no tendency to combine with carbonic anhydride ; the two liquids do not mix. C. H. B. Benzylidene Compounds. By L. ROHLER (,4nrzaZen, 241, 358- 362) .-An alcoholic solution of berizylidenepara toluidine is converted into benzylparatoluidine by the action of sodium amalgain. The VOL.LIV. B50 ABSTRACTS OF CHEMICAL PAPEM. base distils at 33.2-313", and solidifies in the course of several weeks. it is freely soluble in alcohol and ether. The hydrochloride is soluble in alcohol and in hot benzene, and the sulphate is soluble in water. The nitroso-compound melts a t 53". Benxyl-~-na~~hthylamime cr;gstallises in prisms, and melts a t 68". The nitroso-derivative forms yellow needles, soluble in alcohol, ether, benzene, and light petroleum. Benzy Zarnidodimethy Zaniline, prepared from the condensation-product of benzaldehyde and smidodimethylaniline, melts st 48", and distils without decomposition. The nitrosnnzins is deposited from alcohol in yellow needles. It melts a t 111-112°. It melts a t 127-128" with decomposition. w. c. w. Reduction Products of Bensylidene Compounds.By 0. FISCHER (AnnaZen, 241, 328-331).-The author has previously pointed out (Abstr., 1886, 546) that 3 per cent. sodium amalgam reduces a solution of hydrobenzamide in absolute alcohol to dibenzyl- amine and monobenzylamine ; ammonia and toluene are always liberated during the reaction. Under similar treatment, benzylidene- aniline is converted into benzylsniline. The salt which is deposited when nit,rosobenzyIa,niline is treated with a,lcoholic hydrogen chloride is a mixture of benzylaniline hydro- chloride and benzylidene aniline. w. c. w. Hydroxybenzyliden 8 Compounds. By 0. EM MERICH (AnmaZen, 241, 343-358) .-Orthohydroxy benzy Zandine, HO*C,H,*CH,-NHPh, is obtained by the action of sodium amalgam on a solution of hydroxy- benzylideneaniline in absolute alcohol.It melts at 106", and is soluble in alcohol and ether. The sulphate and hydrochloride are freely soluble in water. The platinochloride forms reddish-yellow needles, melting a t 184" with decomposition. A tetranitro-derivative, C,H9NO(X02),, is formed when the base is treated with a mixture of sulphuric and nitric acids. It melts a t 66" with decomposition, and is soluble in alcohol, acetic acid, and light petroleum. Orthohydroxz~ber~zyl~aratoZuid~ne, HO.C,H,.CH,.NH.CsH,Me, ob- tained by the reduction of the hydroxybenzylideneparatoluidine, crystallises in white plates and needles, and melts at 116". It is soluble in alcohol and ether. The sulphate and hydrochloride dissolve freely in water. The platinochloride crystallises in needles. The tetranitro-derivative formR yellow needles, soluble in alcohol, benzene, and acetic acid.By the action of methyl iodide, the base is converted into ortl~omethoellben~uy~aratoluidine, It melts a t 168". OMe.CsH4*CH,-NH*C6H4Me, a crystalline compound melting at 110", and soluble in alcohol, ether, hnd benzene. Orthodih ydroxydibenzylarnine is prepared by the action of sodium amalgam on an alcoholic solution of hydrosalicylamide. It crystal- ]ifies in needles, melts a t 170°, and dissolves freely in ether, alcohol, benzene, and light petroleum. The sulphate, nitrate, and hydro-ORGANIC CHEMISTRY. 51 chloride are soluble in water. needles, and is soluble in water. yields on reduction orthoh2/dro;eybe.1~zyl-p-n~ph~h~lam~t~e, The platinochloride crystallises in The condensation compound of salicylaldehgde and p-naphthylemine n crystalline substance melting at 147".It is soluble in alcohol, ether, benzene, and light petroleum. The alcoholic solution exhi bits a reddish-violet fluorescence. The sulphate is liquid, and the platino- chloride crystallises with difficulty. Orthohydrozy benayl-p-n,a~hlhylnitrosamin,e melts at 165" with decom- position. On exposure to the air, the compound decomposes spon- taneously at the ordinary temperature. It is soluble in alcohol and ether. Orthomethoxybenzyl-~-naphthylain,ine crystallises in needles, melts at 92", and dissolves freely in alcohol and ether. Parahydroaybenxy laniline, prepared from parahydroxybenzylidene- aniline, is soluble in alcohol and ether. It melts a t 208", and forms a crystalline platinochloride.Pal.ahydroxybenzyZtol1~idine melts at 186". Parahydroxybenzyl-P- nnphthylamine melts: at 117". The sulphate is soluble in alcohol, but almost insoluble in water. The nitrosamine melts at 142", and dis- solves in alcohol and ether. It is unstable. w. c. w. Anisylamines. By 0. J. STEINHART (AnubaZen, 241, 332-343).- A solution of anishydramide in absolute alcohol is converted into a mixture of mono- and di-anisylamine by the action of sodium amalgam a t the ordinary temperature. Dianis?ylanaine, NH(CH2.C6H,*OMe)2, forms white, needle-shapsd crystals soluble in alcohol and ether, It melts a t 34", and decomposes on distillation. The hydrochloride is soluble i n alcohol, and crystallises in fiat prisms. It melts at 243".The platinochloride is crystalline but unstable. The nitroso-derivative, (OMe-C,H,-CH,),N*NO, crystallises in needles, and melts at 80". Anisyk amine is a colourless liquid boiling at 220-223". It, is miscible with alcohol, ether, and water, and it absorbs carbonic anhydride from the air. It can be separated from dianisylamine by its volatility in a current of st,eam. The hydrochloride forms white plates which are freely soluble in water, and melt at 230". The platinochloride crystal- lises in pale-yellow, glistening needles. An i s y 1 nnil ine, MeO*C6H4*C H,*NH P h , prepared from a nish ydrani lid e, crystallises in prisms, and dissolves freely in the usual solvents. It melts at 64*5", and forms a crystalline hydrochloride, sulphate, and platinochloride. The nitroso-derivative melts a t 104". It crystallises in prisms, and is soluble in alcohol.Anish ydroparatoluide, OM&C6H4-CH NC6RbMe, forms whiLe needles, and melts a t 92". Anisyl~aratoluidilze, OMe.C6H4*CH2*NH2*CsH4Me, forms white prisms, melting a t 68". It is soluble in all the usual solvents with the exception of water. The hydrochloride and platino- chloride are crystalline, but the salts have a tendency to decom- pose when their solutions are evaporated. The rdrosamine melts at 108". Anisaldehyde and orthotoluidine condense, forming anishydrortho- It melts at 210". e 252 ABSTRACTS OF CHEMICAL PAPERS. toluide, which yields orthotoluylanisylamine on reduction. The base melts a t 55". Anis y Zid enenap hi! h y lam ine ( /3) , OMe C6H4* C H N C 1oH7, crys t alli ses in plates, and melts at 98".Anisyl-P-naphthyZa??/,ine is soluble in alcohol, benzene, and in light petroleum. It melts at 101". The salts are sparingly soluble in water, and are rather unstable. The nitros- amine melts at 133", and crystallises in plates. AnisylidenedimethyZ- paraphenylenediamhze forms greenish-yellow needles. It melts at 148", and yields on rednction anisyldimethylpcrr~pheny lenediamine, OMc*CsH4.CH,*NH.CsH4.~Me~. This base crystallises in plates, and melts a t 104". The alcoholic solution decomposes on exposure to the The nitrosamine is an oily liquid. air, and the nitroso-compound is unstable. w. c. w. Salts of Picramic Acid. By A. SMOLKA (Monatsh., 8, 391-398). -The salts of this acid having heen but little studied, the nut,hor has prepared and examined a number of them. Tn some cases they were obtained by the direct action of picramie acid on the metallic carbon- ate, in others by double decomposition.The following table shows the results obtained :-- Formula of salt. Description. Dark red crystals Dark reddish- brown wales Yellow, microsco- pic needles Greenish - yellow needles Scarlet, microaco- pic crystals Dull yellow, mi- croscopic needle Small, reddiuh- brown needles Dark &eel-green needles Greenish- yellow, amorphous powder amorphous powder Dark olive-green, Ratio of solubility in water. I. Boiling. 1 :4Q% at 15 -5' 1 : 19.9 ,, 17 '0 1 : 5890 ,, 23 '0 1 : 1215 ,, 23 *O 1:21010 ,, 17.5 1?3172 ,, 18.0 1 :2632 ,, 20.5 1 : 97 *5 ,, 19 -0 insoluble insoluble 11. Cold -- freely freely 1 : 1842 I : 318 1: 12481 1 : 1151 1 : 1494 freely I : 3292 I : 3538 Tempera- ture of decompo- sition.-- abont 150' 140 140-150° 140° 120 140-145O 140-150 Moo 140 1 a-1 45' If the salt is heated slowly, the decomposition takes place quietly, but if rapidly, explosions occur, especially with the sodium and lead salts. The aqueous solutions vary in colonr from pale orange to dark blood-red. L. T. T.ORGANIC CHEMISTRY. 53 Chlorine and Bromine-derivatives of Citraconanil. By T. MORAWSICI and J. KLAUDY (Monatsh., 8, 399-406) .-Citraconpara- chloranil, C5H402 : N-C6H,C1, is formed (together with chloranilines) when a stream of chlorine is passed into water in which finely-divided citraconanil is suspended. It crystallises in white, glistening needles, soluble in alcohol and melting a t 114,5".With care i t may be sub- limed in long, glass-like needles. When heated with ammonia, it yields parachloraniline and citraconic acid, showing the correctness of the above formula. When bromine acts on citraconil, bronzocitraconprLrabrornani1, C,H,BrO, : N*CsHpBr, is formed. This crystallises in white, shining needles, soluble in alcohol and melting at 178". It can be sublimed, b u t decomposes if heated rapidly. When heated with ammonia, parabromaniline is formed, together with hydrogen bromide, much resinous matter, and an acid of the formiila C7H,BrOa. This acid yields a silver salt, AgzC7€3,B.rO4, crystallising in prisms, and a lead salt, PbC7H7Br04, forming microscopic crystals. It appears, therefore, that the original bromo-derivative contained one bromine-atom in the citraconic nucleus, and that when heated with ammonia this nucleus is converted into a higher brominated homologue of the citraconic series, together with other bye-products. When only enough bromine is employed for the formation of eitraconparabromanil, white, crystalline needles melting at about 11 8" were obtained, but this compound has not yet been obtained in a pure state.L. T. T. Action of Phenylhydrazine on E thy1 Chloracetoacetate. By G. RENDER (Ber., 20, 2747--2752).--Ethyl chloracetoacetate reacts with phenylhydrazine in ethereal solution to form a compound, C12H14N202 ; it is probable that a hydrazine-derivative, NHPh*N CMeCHCl-COOEt, is at first formed, which is subsequently converted into a compound, NPli : N*CHMe*CHCl*COOEt, and finally by abstraction of the elements of hydrogen chloride into NPh : N-CMe : CH-COOEt, or ethy lic P-phenylazocrotonate. This substance crys tallises in long, red needles, meltling at 50*5", very soluble in alcohol ; on saponification, it yields a potassium salt, NPh N*CMe: CH-COOK, which forms reddish-yellow scales, very soluble in water, insoluble in alcohol.The salt on acidification yields the corresponding anhydride as a brownish-yellow powder, whose purification presents considerable difficulty. Ethylic /3-phenylazocrotonate when reduced yields phenyl. rnethylpyrazolone and its first oxidation product or its bis-derivn- tive, together with a substance not further examined. The bis-deri- vative yields with bromine a compound, C2,€€,,NaO,Br, which crystal- lises in colourless needles, melting a t 217" with decomposition.a-Naphthylamine with ethylic chloracetoacetate yields a compound, C,,J316N02C1 ; this crystallises in colourless prisms, meltiiig at 75" ; its formation is due to a change analogous to the first of the reactions given above in the case of phenylhydrazine. V. H. V.54 ABSTRACTS OF CHEMICAL PAPERS. Isomeric Phthalophenylhydrasfnes. By G. PELLIZARI (Gaxnetta, 17, 278--285).-The author has previously described two isomeric phthalyl-derivatives of phenylhydraxine obtained by the action of this base on phthalimide and phthalic anhydride respectively (Abstr., 1886, 125). To the former, melting at 179", the constitution NHPh*N <Co>C6HH", to the latter, melting a t 210°, the constitution GO NPh-CO <NH-CO>CGHa was assigned.If these formule are correct, a methyl-derivative of the former, or anilophthalimide, on separation of the phthalyl grouping, should yield a symmetrical methylphenyl- hydrazine, NPhMe*NH2, that of the latter, or phthalophenylhydrazine, the symmetrical derivative, NHPh-NHMe. Phthalophenylhydrazine, heated with methyl iodide and alcohol, yields a methyl-derivative, crystallising in long, yellowish-white prisms, which melt at 125" without decomposition ; this is decomposed by concentrated hydro- chloric acid, yielding methylphen ylhydraeine, NHPh-NHMe. The constitution of the isomeride has previously been proved by Eotte, but in answer to his criticisms (Abstr., 1887, 770) it is shown that phthalic anhydride and phenylhydrazine, reacting in molecular pro- portions, give either anilophthalimide or phthalophenylhydraxine, according to the temperature ; at ordinary t'emperatures, phenyl- hydrazine-phthalic acid is at first formed, which on subsequent heat.- ing yields ariilophthalimide ; if, however, the reaction proceeds at 163", the melting point of the acid, a t which temperature it is unstable, phthalophenylhydrazine is formed in the greater proportion.Dyes from Aniline Chromates. By S . GRAWITZ (Compt. rend., Azophenine. By 0. N. WITT (Bey., 20, 2659-2660).-A yply to Fischer and Hepp (Abstr., 1887, 1105), in which the author poiiits out that the constitutional formula proposed by them is inadmissible, since azoplienine does not form an acetyl-derivative when heated with acetic anhydride, and yields a considerable quantity of aniline on treatment with tin and hydrochloric acid.On these grounds, the author adheres to his published views on the constitution of azo- By P. BARBIER and L. VIGNON (Compt. rend., 105, 670-672) .-Paranitrosodimethylaniline has no action on aniline at the ordinary temperature in presence of water, glacial acetic acid, or an excess of aniline, but a t 80" there is an extremely violent reaction. If equal molecular proportions of aniline and paranitrosodimethyl- aniline are dissolved in eight times their weight of ethyl alcohol of 92", and heated on a water-bath, a reaction takes place a t 80", with con- siderable development of heat, and is complete in about three hours. When the liquid is cooled, a solid separates, which is washed with dilute hydrochloric acid, and then crystallised from boiling toluene. I'etranaethyZlliumido-azobe.nzene is thus obtained in brilliant, brown, V.H. V. 105, 576--577).-A question of priority and patent right. phenine (Abstr., 1887, 821). w. P. w. Substituted Safranines.OHBAKIC CHEMISTRY. 35 crystalline plates, which melt imperfectly a t 218-220" without vola- tilisation, and when reduced with zinc and salphuric acid, yield dimethylparaphenylenediamine in almost theoretical quantity. It. is almost insoluble in water, and only slightly soluble in dilute acids, but dissolves in concentrated acids forming deep red solutions. The alcoholic liquid separated from the tetramethpldiamido-azo- hneene has a deep, violet-red colour, and when evaporated leaves a viscid residue, which dissolves almost completely in water.When this solution is mixed with sodium carbonate, a precipitate is formed, and if the filtrate is mixed with sodium chloride, dimethylphenosafra- nine Beparates, and is purified by repeating the treatment with sodium carbonate and chloride. The equation representing the reaction is- ZNHzPh + ~C~EIANO*NM~~,HC~ = ClsHZON, + CWHIgNdCl + 3H20 + 2HC1. C. H. B. Action of Acid Amides on Bromacetophenones. By M. LEWY (Ber., 20, 2576-2580) .-When bromacetophenone is heated with acetamide (2 parts) a t l't0-130", for one hour, a base, C,,H,NO, is ob- tained. This forms long, colourless needles, readily soluble in alcohol and ether; it melts a t 45", and boils a t 241-242'; it has slightly basic properties.The hydrochloride, CloH9N0,HCl, crystallises in small needles ; when treated with an excess of hydrogen chloride, it yields a heavy, fuming oil, possibly an acid salt. The platino- k&m&, (CloN,NO),,H,PtC16 + 2Hz0, separates in dense, yellow flakes, consisting of' orange-coloured needles, which melt a t 130-140 with decomposition. The subhate forms white, lustrous plates, which decompose in contact with water. The picrate crystallises in lemon- coloured needles, melting at 133-134'. The formamide base, CgH,NO, prepared by heating bromaceto- phenone with formamide, is a thick, colourless oil, which becomes yellow when exposed to air ; it solidifies when cooled with a freezing mixture, melts at 6", and boils at 220-222'. The hydrochZoride melts at 80".The pZutinochZoride (with 2 mols. HzO) crystallises in slender, yellow needles. The hermawtide base, CIBHIINO, is prepared by heating bromacetophenone and benzamide a t 140-150" ; the product is extracted several times with boiling water, and the residue fractionally distilled. It crystallises from alcohol in large, colourless plates, readily soluble in the usual solvents, melts a t 102-103", and boils a t 338-340". The hydrochloride crystallises in slender, matted needles ; it is slowly decomposed by boiling water. N. H. hL Isonitroso-compounds : Isobenzaldoxime. By E. BECKMANN (Ber., 20, 2766-2768) .-When benzaldoxime is mixed with sulphuric acid in presence of ice, a solid, white substance separates out under certain conditions ; sometimes an oil is obtained.The former, pro- bably a poly rneride of benzaldoxime, crystallises in glistening needles, melting at 128-1.30"; it is distinguishable from benzamide by its crystalline form. The oil is benzaldehyde, produced by the re-forma-56 ABSTRACTS OF CHEMICAL PAPERS. tion of the oxime and its subsequent decomposition by the acid present. V. H. V. Condensation of Cinnamic Acid with Gallic Acid. By E. JACOBSEN and P. JULIUS (Bey., 20, 2,588-25,89).--St?lrogaZZo7, CI6Hl0O5, is prepared by heating cinnamic acid (10 parts), gallic acid (12 parts), and sulphuric acid (150 parts) at 45-55', for two to three hours. The product is poured into water, filtered, and the precipitate washed with slightly acidified boiling water. It crystallises in bright- yellow, microscopic needles, which do not melt a t 350"; it is very sparingly soluble, except in boiling alcohol, aniline, and glacial acetic acid, and sublimes when carefully heated in large, yellow, lustrous needles. Alkalis dissolve it with green colour, which changes to blue, and then red, when the solution is heated.The solution in sulphuric acid is yellowish-red. When oxidised with dilute nitric acid, it yields a large amount of phthalic acid. The triacetyl-cleri~nfive, C22H1606, crystallises in pale-yellow needles. With mordants, styrogallol yields shades similar to those obtained with nitroalizarin. N. H. M. Paradiphenoldicarboxylic: Acid. By R,. SCHMITT and C. KRETZSCHMAR (Bey., 2 0, 2 703-2 704) .-Pu~*adiphenoZdicarboayl~c acid, COOH-C6H,( OH).C6H,( OH)*COOH, is obtained when sodium para- diphenol is heated in an autoclave with liquid carbonic anhydride at 200" for nine hours, and the resulting product is treated with an acid.It crystallises in small, microscopic needles, melts at 131" with the evolution of carbonic anhydride, is not volatile with steam, has a slightly bitter taste, and is readily soluble in ethyl and methyl alcohol and in ether, sparingly soluble in water (100 C.C. of water at 15" dis- solving 0*0052 gram of the acid), and insoluble in benzene and chloro- form. Suspended in water, it is coloured bluish-violet with ferric chloride, the colour changing to a dull brown on heating, whilst the sodium salt when similarly treated yields a deep blue solution, from which indigo-blue flocks separate. w.P. nT. Orthamidotriphenylmethane. By 0. FISCHER and A. FRANKE L (Annalen, 241, 362-368) .--The preparation of diphenylquinolyl- methane has been previously described by the authors (Abstr., 1886, 561). The sulphate and picrate are precipitated on the addition of sulphuric or picric acid to alcoholic solutions of the base. The nitro- derivative melts a t 213" with decomposition, and the amido-compound on oxidation forms a riolet-coloured solution. Triphenylmethaneorthocarboxy lic acid is prepared by slowly adding a solution of the hydrochloride of the diazo-compound of amidotri- phenvlmethane to a solution of potassium cyanide and copper sulphate a t 9d". The crude product is sa,ponified with alcoholic potash, and the acid precipitated from the aqueous solution of the potassium salt by hydrocliloric acid.Alcohol, ether, acetic acid, and benzene dis- solve the acid freely. It melts a t 162" and volatilises without decom- position ; i t is identical with the acid Baeyer (Abstr., 1880, 650) obtained f r o n phthalophenone. Orthoh ydrozytri~he?zylmet}~ane is formed by passing air through aORGANIC CHENISTRY. 57 solution of dia zoamidotrip henylmet hane sulp hate, and boiling the product in a current of carbonic anhydride. It is soluble in alcohol and ether, and melts a t 118". The acetic derivative of amidotriphenylmethane melts a t 168-169", and is freely soluble in alcohol, benzene, and acetic acid. The thio- carbamide melts a t 12fjo, and dissolves readily in ether, carbon bisul- phide, and hot alcohol. w. c. w. Two Dihydroxynaphthalenes. By A.EMMERT (Anna.len, 241, 368-373) .-$-Naphthol yields t w o sdplionic acids on treatment with sulphuric acid, and each acid is converted into a dihydroxynaphtha- lene by fusion with potmh. ~-~-DihydroxynapJ~tl~alene melts a t 615-216", and dissolves freely in alcohol and et,her. Ferric chloride produces a yellowish-white precipitate. A t 120" alcoholic potash and ethyl iodide coiivert the dihydroxynaphthalene into an ethyl ether, Cl0H6( OEt,). It forms silky plates and melts at 162". The diacetate, C,oHt-I,(OAc)2, melts a t 175". P-a- Dihydroxynaphthalene is soluble in alcohol, ether, benzene, and water. It melfs a t 1 7 8 O , and gives a blue precipitate with ferric chloride. The dietliyl ether crystallises in prisms, melting at, 67", and the diacetate forms rhombic plates and melts at 108".W. C. W. Derivatives of Di-p-naphthylamine. By C. RIS (Ber., 20, 261 8-2628). -Crude di-/3-nap hthylamine is purified by distillation and crystallisation from benzene ; it melts at about 471". Met7&yldi-P-naphlh?/Inmine, NMe( C1,H7)2, is prepared by heating di- naphthylamine and methyl iodide (equal molecular weights) for five hours at 150", and ci-ystallises from alcohol in nearly colourless needles melting a t 139-140". It dissolves rather readily in warm alcohol, glacial acetic acid, benzene, and ether, and is almost insoluble in light petroleum. The alcoholic solution shows a bluish-violet fluorescence. It is insoluble in dilute mineral acids; the hydrochZoride forms slender, lustrous crystals, which decompose quickly in presence of water.The solution in strong sulphuric acid is yellow, and acquires an intense brown colour on addition of a trace of a nitrite or nitrate. Ethyldi-/3-naphthyZamine, NEt(C&€,),, crystallises in almost colour- less prisms melting a t 231"; it resembles the methyl compound in solubility ; the hydi-och Zoride is a white, crystalline powder. H e t h y l di-~-)taphth!iZcarba;lriate, N( CloH,),.COOMe, is obtained by heating di-/3-naphthylamine and methyl chloroformate (equal weights) at 150-160" for two and a half hours. It crystallises from alcohol in slender, white needles, melting at 113-114", dissolves readily in alcohol, ether, and benzene. It crystallises from benzene with $ mol. CcH6. Tetrabromodi-p-naph tJyEamine, C20H,,Br,N, is prepared by the action of bromine (4 mols.) on a well-cooled solution of di-p-naphthylamine in glacial acetic acid.It crystallises in long, white, matted needles, which melt a t 245-2246". It dissolves rather readily in hot benzene and cumene, very sparingly in ether, light petroleum, and alcohol. It distils almost without decomposition.58 ABSTRACTS OF CHEMICAL PAPERS. It is not attacked by boiling concentrated aqueous potash ; bromine does not act on it. Octobromodi-P-?taphthyZanzine, CzoH,Br,N, is formed when /3-dinaph- thylamine, as dust, is added to an excess of bromine in presence of alnminium bromide. The product is stirred well, and the yellow pre- cipit'ate, after being treated with alkali and with boiling hydrochloric acid to remove adhering bromine and aluminium, is crystallised from cumene.It forms slender, white needles, which melt at about 300", and dissolve readily in boiling nitrobenzene, less in boiling cumene ; in other solvents it is sparingly or not at all soluble. is prepared by adding the calculated amount of sodium nitrite dissolved in a little water to it mixture of alcohol and sulphuric acid containing di-P-naphthylamine in the form of dust. It crystallises from benzene in groups of white needles, melting at 139-lPO", sparingly soluble in alcohol, readily in benzene. Dinit.l.odi-P-naphthy~amin.e, Cz0H,3N(N0z)2, is formed when strong nitric: acid is slowly added to a cooled solution of the amine in glacial acetic acid; it separates after some time as a yellow powder. It crystallises in yellowish-red needles, melting at 224-225", readily soluble in boiling cumene, less soluble in benzene, and almost in- soluble in alcohol and ether.T~tran.itrorZi-p-na~hthz/Z~zmine, CzOHllN(N02)P, is obtained by gradu- ally adding nitric acid (3 pn.rts) mixed with glacial acetic acid to a solution of dinaphthylamine (1 part), in glacial acetic acid. It crystallises from nitrobenzene in grains, which melt at 285-286", and detonate when more strongly heated. It is sparingly or not at all soluble in the ordinal-y solvents, readily soluble in boiling nitro- benzene. Hexanitrodi-P-naphthylamine, CzoH9N( NOz),, prepared by heating the finely-powdered amine with fuming nitric acid, could not be ob- tained in crystals. It dissolves readily in alcohol, less in glacial acetic acid, and is almost insoluble in ether, benzene, cumene, and nitrobenzene.Alkaline carbouahes dissolve it readily. When mixed with excess of copper oxide, it decomposes with explosive violence, and was therefore not analysed. The potassium and ba&m salts were aualysed ; they are both amorphous. Benzoylortko?iitrodi-P-n~phthylscmine, C2THlsNO*N02, is prepared by adding a mixture of fuming nitric and sulphuric acids to a solution of benzoyldi-p-naphthylamine in cold glacial acetic acid, and subse- quently heating the whole at 50-60". It crystallises from benzene in well-formed, yellow, transparent crystals (with 1 mol. C6H6), melt- ing at 95". Crystallised from alcohol it melts at 168". It dissolves readily in warm benzene, less in alcohol. Benzenylriap?~thyle7Leanzidine, N< CPh >NGlaH,, is obtained by re- GoH, ducing benzoylnitrodinaphthylamine dissolved in glacial acetic acid with excess of tin and hydrochloric acid.It crystallises from benzene in transparent, slender needles (with 1 mol. c,H6) melting at 113- 114" ; when crystallised from other solvents it melts at 163". It sub- limes when carefully heated in small, colourless plates, and distils Nitrosodi-P-naphthyZn?nine, M0.N ( C1,ORGANIC CHEMISTRY. 59 with slight decomposition. I t is readily soluble. The hydrochloride forms slender, matted needles which decompose in contact with water. Naphthaphenaaine. By P. BRUNNER and 0. N. WITT (Ber., 20, 2660-2663). - Naphthaphenasinesulplzowic acid is obtained when naphthaphenazine is heated with 10 times its weight of 35 per cent.fuming sulphuric acid at 100" for 12 hours. It crystallises in orange- red needles, melts above 290°, and is soluble in water and alcohol. In concentrated sulphuric acid it dissolvss with a deep orange-brown colour, which becomes orange-yellow on dilution. The sodium salt,, C16H,N2*SOsNa + 2H,O, was prepared. On fusion with potassium hydroxide, a ewrhodol is obtained which differs from that previously described (Abstr., 1887, 153), since it dissolves in hydrochloric acid with a red colour, and in concentrated sulphuric acid with A dark- green colour changing to red on dilution. A similar compound has been prepared by diasotising the eurhodine formed by the reduction of nitronap h t haphenazin e. Cy artowph thaph enazine, C16H9N2* CN, is obtained when sodium naphthaphenazinesulphonate is distilled with potassium cyanide or dry potassium ferricyanide.Crystallised from cumene, it melts at 236-5237', and dissolves in concentrated snlphuric acid with a cherrj- red colour, which changes through orange to yellow on dilution. If heated with hydrochloric acid under pressure, it is decomposed into naphthaphenazine and formic acid, but when heated with alcoholic potash at 220-250" it is partially converted into naphthaphenaxine- carboxylic acid. This is sparingly soluble in the ordinary solvents, melts above 360", and dissolves in concentrated sulphuric acid with a deep-red colour, changing to yellow on dilution. The potassium salt crystallises in white needles and is sparingly soluble in water.N. H. M. w. P. w. Naphtholcarboxylic Acids. By R. SCHMITT and E. BURKARD (Ber., 20, 2699-2704) .-a-NnpIit?~olcarbo~l~c acid (m. p. 187") can be prepared by heating sodium a-naphthol with liquid carbonic anhy- dride in an autoclave at 130°, and is a comparatively stable compound (compare Abstr., 1887, 732), since it is only partially decomposed by prolonged boiling with water, in which it is very sparingly soluble. The aqueous solution is coloured greenish-blue by ferric chloride. The sodiurn salt, with 3 mols. HzO, crystallises in large, thin, nacreous scales; the ammoniurri salt forms long needles; the calcium and barium salts crystalhe in long needles. The methyl salt, OH*CloH6*COOMe, melts at 78", the ethyl salt at 49', and the phenyl salt at 96". The acetgl-derivative, OAc.Cl~~6*COOH, melts at 158" ; the bromo-deriva- tive, OH*CloH&r*COOH, melts at 238" ; the nitro-derivative, melts at 202", and yields P-nitro-a-naphthol when 'heated with lime ; the amido-derivative melts above 200", and its acetyl-compound at 183".paraxobenzenesulphonic acid-a-naphtholcarboxylic acid, OH.C1&L,( NO,) .C 0 OH, Metadiazonaphtholcarboxylic acid, OH*CloH5<, CO@ N>, and S03H*C6H4*N2* C~oH~(OE€) *C 0 OH,60 ABSTRACTS OF CHEMICAL PAPERS. were also obtained, and the latter on reduction with zinc and hydrochloric acid yields an amido-a-naphtholcarboxylic acid which crystallises in colourless, prismatic needles, is very sparingly soluble in water, and melts above 200", but differs from the amido-derivative just described since its acet y I-compound melts at 195O.When sodium P-naphthol is similarly heated with liquid carbonic anhydride in an autoclave at 130", /I-naphtholcarboxylic acid is ob- tained, and is sepnrahed by treating the product with ammonium carbonate and precipitating with hydrochloric acid. This acid readily decomposes on heating, and shows all the properties of Kauffmann's acid (Abstr., 7 882, lOtj8). Ferric chloride colours its aqueous solu- tion a pure blue. The ammoniim salt crystallises in yellow needles, whilst the barium, calcium, and silver salts. resemble the corresponding salts of the a-acid. The methyl salt melts at 76", and the ethyl salt a t 5 5 O . When sodium P-napht,hol is heated a t 280-290" in a current of carbonic anhydride, absorption of the gas rapidly takes place, and a product is obtained consisting of &naphthol, undecomposed sodium &naphthol, and ~-?LaphthoZcarboxylic acid.This acid is extremely stable, and crystallises from water in lustrous, rhombic, Tellow scales, which melt a t 216" without decomposition, and are readily soluble in alcohol and ether, soluble in tolnene, benzene, and chloroform, and sparinrrlv soluble in hot water. Ferric chloride colours the aqueous solution blue. w. P. w. Terpenes. Part VI. By 0. WALLACH (Annulen,, 241,315-328). -The compound which the author (Abstr., 1887, 967) recently de- scribed as terpene nitrite is terpinene nitrosite. It forms monoclinic crystals ; a : b : c = 1.0103 : 1 : 0.66978 ; /3 = 80" 31'. Terpinene nitroZeth,yZarnine, NHEt2*CIoHl, : NOR, is obtained by boiling for a short time an alcoholic solution of the nitrosite with a strong aqueous solution of ethylamine.The crude product is poured into water, the precipitate dissolved in hydrochloric acid, and the base reprecipitated by ammonia, The base melts a t 130-131", and dis- solves in boiling alcohol, ether, chloroform, and in warm dilute solutions of alkalis. The hydrochloride, C12H,N,0,HC1, is crystalline, and dissolves freely in water and alcohol. The nitroso-compound melts a t 133-133". It is decomposed by boiling with an excess of hydrochloric acid, yielding hydroxylamine. Terpinene nitroldiethylamine, NEt2*CloHl, : NOH, melts at 11 7-1 18". Terpinene gzitrohethylarnirze, NHMe.CloH15 : NOH, crystallises in prisms and melts at 141". The dimethylamine, NiNe,*CloHl, NOH, melts a t 160-161". It dissolves in chloroform.The amylamine-compound is less soluble in alcohol and ether than the preceding substances. It melts a t 118-119". The piperidiwe, CloHlsNO,NCsHlo, melts a t 153-154'. It is insoluble in alkalis, but its salts are freely soluble in water. The hydrochloride is obtained as an oil on passing dry hydrogen chloride into an ethereal solution of the base. Terpinene rritrolamine is formed by adding ammonia to a hotORGANIC CKEiWSTRT. G1 alcoholic solution of terpinene nitrosite. After recrystallisation from hot water it melts at 116-118". By adding a mixture of nitric acid and amyl nitrite to carvene or citronene saturated with dry hydrogen chloride, Maissen (Gazzettu, 13, 99) obtained a crystalline compound melting with decomposition a t 1 1 ~ 1 1 5 " .The author has obtained the same or similar deriva- tives from cinnamene and dipentene. They melt at 109" and 110- 111" respectively, and act oh organic am"ines, yielding crystalline bases. vv. c. w. Constitution of some Pyrroline-derivatives. Ry G. CIAMICIAN and P. SILBER (Ber., 20, 2594-2607 ; compare Abstr., 1887, 597). -Uibromodiacetyl~~rrol~ne, C4NHAc,Pr2, is prepared by the action of bromine vaponr on a warm solution of 2 grams of pyrrylenedimethyl- diketone in 700 C.C. of water. It crystallises from alcohol in white needles melting a t 1'71-1 72", insolrible in waber, soluble in alcohol, ether, and in alkaline carbonates. Nitric acid oxidises it readily a t the ordinary temperature t o dibromomale'irnide ; the constitution of the base is therefore [Br, : Ac, = 3 : 4 : 2 : 51.C4NHBr2Ac*NOZ [Br2 : Ac : NO, = 3 : 4 : 2 : 51, is formed when dibromodiacetylpyri-oline (8 grams) is dissolved in fuming nitric acid (80 grams), and crystallises from alcohol in long, white needles melting at 206". It is soluble in alcohol, ether, ethyl acetate, hot glacial acetic acid, and benzene, very sparingly soluble i n water, insoluble in light petroleum. Alkalilie carbonates dissolve it readiiy with intense yellow colour. Dinitrodibromopyrroline, C4NHBr,(N02)2 [= 3 : 4 : 2 : 51, is ob- tained by the action of a well-cooled mixture of sulphuric and fuming nitric acids on the mononitro-compound. It crystallises from water in large, yellow plates (with 1 mol. €LO), which melt at about 169" with decomposition ; it is readily soluble in ether, alcohol, hot.water, and hot benzene, and dissolves in alkaline carbonates with evolution of carbonic anhydride, If the mixed acids are allowed to act on the mononitro-compound at the ordinary temperature, dibromo- maleamide, melting at 227", is formed. The latter is also formed when dinitrodibromopyrroline is heated at 165" ; nitric oxide is evolved. When dinitrodibromopyrroline is heated with sulphuric acid (20 parts) it is converted quantitatively into dibroniomaleic acid. It is probable that the imide of dibromomale'ic acid, and. therefore, maleic ~-itr~dibromacetyI'PYrO'o liire, Lcid also, are symmetrically rather than unsymmetrically constituted : CBr*CO CBr *CO <Csr.Co>NH, rather tha,n <C.c&NH>.(Compare Anschutz, Abstr., 1887, 916). Dibromopyrrolinedicarboxylic acid behaves towards fuming nitric acid in a manner similar to dibromodiacetylpyrroline ; dinitro- dibromopyrroline is formed identical with that obtained from dibromodiacetylpyrroline. The reaction shows that the two carboxyl-groups in pyrrolinedicarboxylic acid have the positions 2 : 5. Methyl dibromopyrrolinedicarbox2/late, CJYHBr,(COOMe)?, is ob- [NO, : NO, : B r : Br = 2 : 5 : 3 : 41G2 ABSTRACTS OF CHEMICAL PAPERS. tained by dissolving methyl pyrrolinedicarboxylate (3 grams) in water (1 litre), and saturating the lukewarm solution with bromine vapour. The yield is 4.5 grams of pure product. It crystallises from alcohol in long, white needles, melting a t 222", soluble in ether, almost insoluble in water.When 2 grams of the salt is a,dded to 40 grams of fuming nitric acid a t -Is", and the whole poured into 400 C.C. of ice-wa,ter, and treated with potash (30 grams), the compound C4H,BrNOa is obtained. It is a crystalline compound, melting a t 168-171" with deconiposition, soluble i n ether, alcohol, and hot benzene, rather sparingly soluble i n water, and insoluble in light petroleum. It dissolves in alkaline carbonates with evolution of car- bonic anhydride. The constitutional formula CBrO*C(NOH)*COOMe is suggested for it. Methyl dibromacetylcnrbopyrrolate, C*NHBr,Ac*COOMe, is pre- pared in a manner similar to the methyl salt of the bromodicarboxylic acid, which it completely resembles in its behaviour towards fuming nitric acid.Dibromacety lmeth y lpyrroline, C7H7Br,N0, is prepared by treating a solution of 2 grams of acetylmethylpyrroline, melting a t 85-86' (Abstr., 1886, 719), with an excess of bromine. It crystallises from dilute alcohol in long, white needles, of a silky lustre, melts at 161- 162", dissolves in ether, carbon bisulphide, and chloroform, and is sparingly soluble in boiling water. When the finely-powdered compound is warmed with fuming nitric acid, dibromomalejimid e (m. p. 227") is formed. The constitution of acetylmethylpyrroline is therefore [Ac : Me = 2 : 51. In order to obtain further evidence as to the constitution of pyrnvyl methyl ketone and Schwanert's carbopyrrolic acid, tribromacetyl- pyrroline and methyl tribromocarbopyrrolate were converted into dibromomaleimide by the action of nitric acid.C4NHBr2Ac..N0, [Br : Br : Ac : NO, = 2 : 3 : 5 : 41, is prepared by the action of bromine on nitracetyl- pyrroline, melting at 197" (Abstr., 1885,810 and 992). It crystal- lises from alcohol in needles melting a t 1 7 5 O , soluble in ether, warm dcohol, and glacial acetic acid, sparingly soluble in warm water, insoluble in light petroleum. The non-identity of this compound with the dibromo-derivative described above, and the probabili t y that in the nitracetyl-compound (m. p. 197") the acetyl-group has the a-position, make it probable that the nitracetyl-compound has the constitution [NO2 : Ac = 3 or 4 : 2 or 51. A table of all pyrroline-derivatives (halogen-derivatives and ethers excepted) of known constitution is given.Synthesis of Pyridine and Piperidine-derivatives. By C. PAAL and C. STRASSER (Ber., 20, 2756--2766).-Diphenacylacetic acid (Abstr,, 1887, 261) when treated with alcoholic ammonia yields the ammonium salt of ad-dip heny ldi~y~ropyridine-cy-carboa y l i c acid, C,NH,Ph,*COONH*. This salt is soluble in water and concentrated hydrochloric acid ; on acidification with sulphuric acid, the corre- sponding acid separates, but is quickly decomposed. On dry distilla- tion, ammonia is given off, and aa'-di~heny~yridir~ecnrboxyl,ic acid, liibrornon;tracefy.?pyrroline, N. H. M.ORGANIC CHEMISTRY. 63 C5NH,Ph,.COOH, is produced, which after purification crystallises in delicate, white needles or prisms, melting at 275', soluble i n alcohol, sparingly soluble in chloroform.The acid is not altered by nitrous acid, acetic chloride, or oxidising agents. Its ammonium salt does not exist in the free state ; the silver salt is a heavy, white precipitate ; the chromate a dark-red, amorphous precipitate ; the aurochloride is crystalline. Dip heny Zppiperidine- y-carboz y Zic acid, C5NH8P h,CO 0 H, obtained together with the above mid, and separated from i t by its greater solubility, forms crystalline crusts; it melts at 339', and sublimes without decomposition, its alkaline salts are very soluble, the barium and silver salts are white precipitates. Its nitroso-derirative crystal- lises in pale-yellow, glistening needles melting at l59", and is soluble in ether and alcohol. aa-Diphenylpyridine, C5NH3Ph, obtained by the distillation of the calcium salt of the carboxylic acid with lime, crystallises in long, glistening needles melting at 81-82" ; its platinochloride forms yellow needles, and the auroclzloride a crystalline precipitate ; the rnethiodide crystallises in needles melting at 203". aa-Diphen.ti~iperinine, C5NH9Ph,, obtained by the hydrogenation of the above base, is a thick, pale-yellow oil ; its ?ydrochZoride crystallises i n white needles; the platimchloride and the aurochloride and the nitroso - deriunt ive cry stallise with difficulty .V. H. V. 3-Methylpyridine and 3-Methylpiperidine. By C. STOEHR (Ber., 20, 2727--2733).--The picoline obtained by distilling strych- nine with lime (Abstr., 1887, 604) proves on further examination to be p-picoline, since nicotinic acid is found to be the sole pr-d uct on oxidation with 2 per cent.permanganate solution. Some quantity of the base was prepared to enable an examination of its properties to be made, and the results are compared with those of previous observers. P-Picoline thus obtained boils at 14.5-150" after two fractionations ; by conversion of this product into the mercurochloride and regenera- tion of the base, i t gives a product which mostly passes over between 148' a n d 149" (compare Hesekiel, Abstr., 1885, 812). The platino- chloride, (C6H,N)2,H,PtC16 + H,O, has the properties of' the salt described by Baeyer (AnnaZen, 155, 285), melts when dry at 195(: loses 1 mol. H,O when allowed to remain i n a desiccator, and when heated at 120" loses in addition I mol. HCI, the compound thus obtained, (G',H7N),,HCl,PtC14, melting at 211-212".The aiirochloride melts at 182-1 83". The mercuroch loride, C6H7N, H C1,2HgCl, (com- pare Hesekiel, Abstr., 1886, 256), crystallises from hot water in slender, ramifying needles, from dilute hydrochloric acid in indented scales, or long, compact needles, and from concentrated hydrochloyic acid, in which it is very soluble, in small, well-formed prismatic crystals melting at 139-140". The picrate crystallises in six-sided scales melting at 142-143". 3-Methylpiperidine, obtained by reduction of the P-picoline in alco- holic solution with sodium, is readily soluble in water, and yields a hydrochloride, crptallising in dazzling, white needles. w. P. w.64 ABSTRACTS OF CHEMICAL PAPERS. 2 : 6 Methylethylpyridine and 2 : 4 Methylethylpyridine.By M. SCHULTZ ( R e r . , 20, 2729-2727) .--Picoline ethiodide, when heated at 280-300" for 1 to 1 i hours, yields a mixture of bases. To separate these, the product is treated with water, acidified, dis- tilled to remove a small quantity of an arornhtic oil, then rendered alkaline and again distilled. The mixture of bases so obtained, which boils between 100" and 200", is fractionated, and the fractions boiling at 1 56-16(j0, 166-172", and 172-182" repeatedly refractionated ; in this way fractions boiling at 138-163" and 169-174'are obtained, and these consist chiefly of 2 : 6 methylethylpyridine and 2 : 4 methyl- e thy1 pyridine respectively. 2 : 6 ~feth?/lethyZpyridi.lze, C8HIIN, is a colourless, hygroscopic, oily liquid, having a sweet, aromatic! odour recalling that of picoline, and when moist, an alkaline reaction.It is sparingly soluble in water, readily volatile with steam, and yields salts which readily deliquesce in air: The platinochboride, (C8H1,N),,H,PtCl,, crptallises in tabular, triclinic crystals, melts at 173-174" (after drying a t 110"), and is readily soluble in hot water, insoluble in alcohol and ether ; the auro- clzloride, CsHllN,HAuC14, crystnllises in yellow needles, melts at 1 lo", and is sparingly soluble in water, readily soluble in ether alcohol. On reduction with sodium in hot alcoholic solution, copellidine, C,H,,N [Me : Et = 2 : 61, is obtained; this is a colourless, oily liquid, which boils a t 147-151", fumes slightly in the air, has the characteristic odour of piperidine bases, and a strongly alkaline reac- tion. The nitroso-derivative is a brown oil 5 the hydrochloride, C,H,N,HCl, crystallises in white needles, and though readily soluble in water and alcohol is only slightly hygroscopic.When oxidised with 2 per cent. permanganate solution, 2 : 6 methplethylpyridine is con- verted into a dicarboxylic acid melting a t 226", and identical with Ladenburg and Roth's dipicolinic acid (Abdtr., 1885, 557). 2 : 4 Nethybethylpyridine, [Me : Et = 2 : 41, is a hygroscopic, colourless, oily liquid, which in its properties closely resembles the 2 : &derivative. The pZntinochZoride, (C8Hl1N),,H2PtCI,, forms red- dish-yellow, tabular crystnla, which after drying a t 110" melt a t 190" ; the aurochloride, C8HI1N7HAuC14, crystallises in yellow needles, begins to fuse a t 83", melts a t 90", and is soluble in hot water, readily soluble in alcohol and ether.When the base is reduced with sodium in hot alcoholic solution, i t is converted into copeblidine, [Me : E t = 2 : 41 C,Hl,N; this is a colourless, oily liquid, which boils a t 155-160", has a strongly alkaline reaction, and an odour similar to that of the 2 : 6 base. The hydrochloride, C8HITN,HCI, crystallises in white needles, is readily soluble in water and alcohol, and is slightly hygroscopic. 011 oxidation with 2 per cent. perman- ganate aolution in the cold or on heating, 2 : 4 methylethylpyridine yields a dicarboxylic acid whose melting point rose from 204" to 211" after three crystallisations. This author regards this acid as being identical with Ladenburg and Roth's lutidinic acid (Abstr., 1885, 815), and ascribes its lower melting point to the presence of a small qnarltity of pioolinic acid.w. I?. w.ORGANIC CHEMISTRY. 65 Phenylated Piperidine and Pyridine Bases. By 0. BALLY (Ber., 20, .2590-2594).--r-Phenylpi~eridil~e. C,NH,,Ph, is prepared from r-phenylpyridine and purified by distillation. It melts at 57*5-58", and boils a t 255-2S7" under 727 mm. pressure; it is a strong base, almost insoluble in water. The salts are readily soluble. The hydrochloride crystallises in needles ; the platitrochloride forms orange-coloured plates, melting a t 204-207". It gives no precipitate with picric acid ; the original base gives a precipitate even i n vcry dilute s o h tion. C,NH,Me2Ph [Me : P h : Me = 2 : 4 : 61, is ob- tained by distilling potassium plienyllutidinegarboxylate (prepared from benzaldehyde, ethyl acetoacetate, and ammonia) with lime, a t the lowest possible temperature.It is purified by means of the hjdro- chloride, and crystallises from ether in prisms melting a t 54.5-55". I t boils a t 287" under 731 mm. pressure. The salts are generally sparingly soluble ; the hydrochloride (with 3 mols. H20) crj stallises in slender, matted needles which do not melt at 300" ; tlie platino- chloride, (C,,H,,N),,H2PtCl, + 4H20, forms orange-coloured needles ; the rzitmte and chromate melt at 177" and 228" respectively, both crystallise in needles. yPhenyZlupefidine, C,NH,PhMe,, is prepared by the action of sodium (2.5 parts) on phenyllutidine (1 part) dissolved in absolute alcohol ; it is separated from unchanged phenyllutidine by distilla- tion.It is a colourless oil of a peculiar odour, boiling a t 274" under 73L mm. pressure. The hydrocltloride and iritrate cryhtallise in prisms ; the dinitrate melts at 210" ; the platinochloride crystallises in gold-coloured plates melting a t 237". Besides pheriyliupetidine, a compound, probably hepty Zbenzene, CHPh( CH,*CH,Me),, is produced in the reduction of phenyllutidine. When .I-phenyllu~idylilcna nzethiodide (prepared by digesting the base with methyl iodide in a reflux apparatus) is treated with stroiig aqueous potash, a base is obtained which jields a hydrochloride id;Jntical with that formed by the action of silver chloride on methylpheuyl- In tidylium iodide.Methyl-yphenyllutidylium iodide is a crystalline substance s p r ingly soluble in hot water. Phenyllutidine, N. H. M. &innamylpyridine. By H. BAURATH (Ber., 20,2719-2720).- When a-piuoline and benzaldehyde in equimolecular proportions are heated with zinc chloride at 220-225" for six hours, a-cinnamylpyri- &be, C5NH,*CH : CHPh, is obtained, and after removal of unalteled benzaldehyde by steam distillation can be separated by rendering the product alkaline and distilling with superheated steam. Tlie base, already prepared but not described bF Jacobsen and Reimer (Alnstr., 1884, 335), is crystalline, melts at 90.5-91", boils at 313-314O (uncorr., under 733 mm. pressure), and is readily soluble i n carbon bisulphide and ether, soluble in alcohol, benzene, and light petro- leum, and practically insoluble in water.The salts generttlly crystal- lise in needles : the platinochloride, (C13H3,~N)z,HzPtCI, + d H 2 0 , decomposes when heated to expel the water of crptallisation. On treatment with bromine in carbon bisulphide solution, the base yields VOL. LlV. f66 ABSTRACTS OF CHEMICAL PAPERS. an additive compound, C,,H,,NBr,, which crystallises from alcohol in compact needles melting at 166-167" ; this derivative yields a. new base when heated with alcoholic potash. Derivatives of a-cinna,myl- pyridine have also been obtained by the action of hydriodic acid and by redilction of sodium and alcohol, and will be described in a later communication. w. P. w. Ethylquinoline. By L. REHER (Ber., 2 0 , 2734-2735).-Doehner having found the boiling point of n-ethylquinoline to be 24,5-246" (Abstr., 1887, 504), the author has redetermined the boiling points of a- and y-ethylquinoline (ihid., 279) by converting the bases into the platinochlorides, recrystallising these repeatedly from concentrated hydrochloric acid, and regenerating the bases from the pure salts by means of hydrogen sulphide.a-Ethylquinoline boils a t 256-6-258.6" (corr.) and y-ethylquinoline boils a t 271-274" (corr.), and the pure platinochlorides melt a t 189" and 203" respectively. From the pure bases, c3Lromates were prepared crystallising in red needles, and crys- talline zincochlorides were also obtained, that of the y-base forming white, concentrically-grouped needles melting a t 195". DiethyZquirLoZinP, obtained by the decomposition of the mercuro- chloride (Zoc.c i t . ) , is a colourless liquid having it quinoline-like odour, and boiling a t 282.8-284%0 (corr.). The plutinochloyide, (CqH,NEt,),,H,PtC1,, crystallises in orange-red needles, and melts a t 217" after previous blackening. On oxidation with chromic acid, the base yields a fimall quantity of an acid which crystallises in asbestos- By R. SCHMTTT and F. ENGELMANN (Ber., 20,2690-2695).--Further examination of ortho- hydroxyqainolinecarhoxylic acid (Abstr., 1887, 738) shows that it begins to fuse at 137", that carbonic anhydride and orthohydroxy- qninoline are formed a t 144-145", and that the decomposition is complete a t 150". The ammonium salt, OH*CgNH5*CO@NH, + H2Q, crystall ises in glistening, pnle-yellow needles, and is soluble in water ; the bal-iwn salt, (OH*C,NH,*COO),Ba + 2H20, crystallises in long, silky needles, and is sparingly soluble in water ; the caZciunz salt cry+ tnllises in stellate groups of prisms ; a basic barium salt, C10NH50aBa, and a basic calcium salt were also prepared; the former is very sparingly soluble in water.The phew$ salt, OH*CgNH5*COOPh, obtained by heating equimolecular proportions of the acid and phenol at 170", forms colourless, short prisms and melts a t 225-226". The hydrochloride of the acid, OH-C9NH,-COOH,HC1, crystallises in large prisms, and the mitrute in yellow needles ; both salts are decomposed by water. On treatment with strong nitric acid, a dinitrohydroxy- quinoline is obtained which is probably identical with that described by Bedall and Fischer (Abstr., 1881, 613 ; Ber., 14, 1368) ; it crystal- lises in golden-yellow scales, melts a t 276" with blackening and the evolution of gas, is sparingly soluble in most solvents, and readily decomposes alkaline carbonates, forming the corresponding salts.2\il.trohydroxyquinoZinecurboxZllic ncid, N02*C,NHa(OH).COOH, is prepared by heating the nitrate of orthohydroxyquinolinecarboxylic coloured needles melting a t 190". w. P. w. Orthohydroxyquinolinecarboxylic Acid.ORGANIC CHEMISTRY. 67 acid with rtcetic acid at 100" ; the resulting brown mass is extracted with acetic acid until it becomes yellow, and is then purified by soliition in hydrochloric acid and subsequent precipitation with water. It crystallises from water in yellow needles showing a vitreous lustre, decomposes at 200" with the evolution of carbonic anhydride, and dis- solves readily in concentrated hydrochloric acid, in alkalis and in alka- line carbonates, but is sparingly soluble in acetic acid.When heated above 200°, nitrohydroxyquinoline, NO,*C,NH,*OH, is formed ; this crystallises in yellow needles, melts at 173", is readily soluble in acetic acid and hot, hydrochloric acid,less so inalcohol and ether. On treatment with bromine (2 mols.) a t loo", a dibromohydroxyquinoline identical with that prepared by Bedall and Fischer (Zoc. cit.) is obtained together with bromohydroxyquiiiolinecnrboxy1l:c acid, OH*C9NHdBr*COOH ; this crystallises in matted, citron-yellow needles, melts at 233-235" with the evolution of carbonic anhydride, a,nd yields a hydrochloride which crystallises in well-formed tables, and decomposes when boiled with water.BromohydroxlJqwinoline, CgNHBByOH, formed quanti- tatively when the bromo-acid is heated a t 200°, crystralIises in white needles, melts at 119-120", and is readily soluble in the ordinary solvents except water. w. P. w. Parahydroxyquinolinecarboxylic Acid. By R. SCHMITT and J. ALTSCHUL (Ber., 20, 2695-2698).- When potassium parahyd coxv - quinoline is heated with liquid carbonic anhydride in an autoclave at 170" for six to seven hours, a quantitative yield of potassium para- hydroxyquinolinecarboxylate is obtained ; the sodium-compound cannot be substituted for the potassium-derivati.ce in this reaction. Parahydroxy~uin,r,linecarbozylic acid, OH*C9NT3,.COOH, crystallises from water in yellowish-white flocks consisting of microscopic prisms, melts at 203-204" with the evolution of carbonic anhydride and formation of parahydroxyquinoline, and is sparingly soluble in alcohol, ether, benzene, and hot water.Ferric chloride colours the aqueous solution red. The hydrochloride, OH*CgNH,~COOH,HCl, crystal- h e s in long, colourless needles, G r from concentrated hydrochloric acid in short, thick prisms, is decomposed by water, and yields a well-crystallised platinochloride ; the mitrote, formed by digesting the acid with nitric acid (sp. gr. = 1*35), crystallises in large, white needles, and is decomposed by water. The ammonium salt, with 4 mol. HzO, crystallises in long, colourless needles, and is soluble in water, the solution evolving ammonia when boiled ; the barium salt, with 2 mols.HzO, crystallises in colourless tufts of needles, and does not form a basic salt when treated with barium hydroxide. If the nitrate of parahydroxyquinolinecarboxylic acid is heated with nitric acid, yellowish-red prisms separate on cooling, which when treated with water decompose into nitric acid and nitrohydroxyquino- line ; this crystallises in yellow needles, melts a t 136", and is probably identical with Skraup's nitrohydroxyquinoline (Abstr., 1882, 92). w. P. w. Constitution of Glutazine. Ry R. V. PECHMANN (Rer., 20, 2655 -2658 ; compare Abstr., 1887, 155).--Nitroglutazina, C5H N 0 *NO*, f i 268 ABSTRACTS OF CHEMICAL PAPERS. is obtained together with dinitroglutazine when nitrous oxide is passed into a cold aqueous solution of glutazine.It crystallises from water in orange-yellow plates which decompose a t 170 -180" withon t melting. Dinitroglutazine, C5H4N,02(N0,),, crystallises from water in yellow plates. Both compounds give colourless solutions with acetic acid and zinc-dust which become red when exposed to air. When heated with alkali, they are converted, with evolution oE am- monia, into sparingly soluble salts whicb crystallise in sulphur-colonred, matted needles and explode when heated. These results make it improbable that glutazine contains an amido-group. The nitronitrosamine, N02.C5H4Wz02.N0, is obtained when glutnzine (1 part) dissolved in the smallest amount of dilute aqueous soda is treated with sodium nitrite (1 part); water is added (so that the whole amounts to 30 parts), and the whole is poured into a mixture of glacial acetic acid (5 parts) and water (30 parts). I n a short; time it solidifies to an orange-coloured magma.The sodium saZt, C5H3NaN405, so obtained ci-ystallises in yellow needles with water of crystallisation. Acids precipitate greenish-yellow needles from the solution. When the sodium salt dissolved i n glacial aeetic acid is warmed with excess of sodium nitrite, the sodium salt of the dinitronitrosamine, C5H2NaN5O7, separates as a, cinnabar-coloured, crystalline powder. This dissolves sparingly in water, readily in alkalis. When warmed with dilute acids nitrous acid is given off. Dibes7xoylgZutazine, C5H4N202Bz2, is obtained by heating glutazirie with benzoic chloride on a water-bath f o r two to three hours, and cryst,allises from glacial acetic acid in lustrous, brownish plates melting at 215-5216'.It is insoluble in water and in alkalis, sparingly soluble in alcohol. The above results show that there are only two hydrogen-atoms in glutazine displaceable by acid radicles, and that these are present as iniidoliydrogen as shown by the formula NH< c0'cH2>C NH. CO-CH, N. H. M. Reactions of Caffe'ine and Caffe'idine. By &I. WERNECKE (Chem. Cenfr., 1887, 1082--1084j .-Hydriodic acid, like hydrochloric acid, decomposes caffeine into carbonic oxide and anhydride, formic acid, sarcosirie, ammonia, and methy lamine ; if phosphorus is added, glycocine is formed instead of sarcosine, whilst hydrogen phosphide and pliosphoninm iodide are evoliied.Although methyl iodide readily combines with cafleine to form, the methiodide, the formation of the cor- respoiiding ethyl-compound presents considerable difhulty. Phenyl- hydrazine will not combine with caffeine; from this it would seem that in this casa, as an an;~loqiie of carbamide, the carbonyl-group is directly combined with the nitrogen-atom. Ca-ft h e ch lo?-iodide, CsHI,N4O2,CI1, is produced when sodium nitrite and potassium iodide are added to a, hydrochloric acid solution of this base ; it forms golden needles melting a t 182--183", and is decom- posed into it.: const,itnents by ammonia or by boiling with water. The method proposed by Mdy and Andreasch for the preparation of caffei- dine presents no advantage over that of Strecker.Caffeine sulphateORQANIC CHEMISTRY. 69 differs from the hydroiodide in that the farmer, when heated, turns purple-red, whilst the latter yields a green mass ; the anrochloride of caffeine cannot be isolated. The base is best separated from the sulphate by means of basic lead carbonate. Methy leafezdine hydr- iodide is not a well-defined substance, but the free base is crystalline and melts at 86-88' ; dimethy Zccrflei'dine forms leaflets melting at 123". The author ascribes the following constitution to cdeidine, "<NMe*C(NH) NM+CHy.~~~e. V. H. V. Hydroquinine. By 0. HESSE (Annalen, 241, 255-287) .-Hydro- quinine, C2OH26N~02, exists ready. formed in cinchona bark, and is present in varying quantities in commercial quinine.It is COII- veniently prepared from the mother-liquor obtained in the manu- facture of the acid sulphate of quinine. The mother-liquor is neutralised and the neutral salt dissolved in sulphuric acid, quinine xionosulphate crystallises, and the mother-liquor containing the hydro- quinine is again neutralised. By repeating these operations a salt is obtained containing 30 per cent. of hydroquinine sulphate. The quinine is removed by oxidising the solution in sulphuric acid with potassium permanganate, the mixture is filtered and the hydroquinine liberated by the addition of an alkali and extracted with ether. The base is deposited from its solution in chloroform in needles and from hot acetone in long plates. Many of the properties of the compound have been previously described by the author (Abstr., 1882, 1113). It is laevogyrate [a]= = -1142.2" for a 2.4 per cent.solution in 95 per per cent. alcohol at 20", and [a]= = -227.1" for an aqueous solution of the same strength under similar conditions. (40 C.C. normal hydro- chloric acid were contained i n each 100 C.C. of water used for the solu- tion.) When ammonia is added to a solution of equal molecular propor- tions of cupre'ine and hydroquinine in water containing sulphuric acid, and the acid mixture extracted with ether, a crystalline compound of cupre'ine and hydroquinine is obtained, C,oH2,N20,,C,~H2~N,02 + 2H20. Hydroquinine forms similar compounds with conchinine and hydro- conchinine. It also unites with two and with three molecules of cinchonidine, forming crystalline compounds which do not contain any water of crystallisation. Analogous compounds are formed with hydrocinchonidine and with homocinchonidine. Anethoillztldroq~inine, (CJI&zO2)2, C&,,O + 2H20, is deposited in quadratic prisms from a solution of 5 parts of hydroquinine and 1 part of anethoil in warm dcohol.Hydroquinine forms three series of salts, which are as a rule more soluble than the corresponding salts of quinine. The normal sulpl~at~e, ( Cz~H~6N20z)2,H2S04 + 6Hz0, has been previously described (Zoc. cit.). It forms a crystalline compound with phenol, ( CzoH26~zOZ),S03, C6H60 + 2H20, which is spayingly soluble in cold water. The acid sulphate, C20H26N202,S0& + 3Hz0, is freely soluble in water and alcohol. At 140°, the anhydrous salt is converted into hydroquinine sulphate.The disulphate is amorphous. Dichroic crystals resembling hydro-70 ABSTRACTS OF CHEPolICAL PAPERS. quinine herepathite are obtained by adding potassiiim iodide (2 mols.) to an alcoholic solution of the acid sulphate (4 mols.), and acting on the product with an alcoholic solution of iodine. Hydroquinine hyposulphite, ( CzOH26NzOz)a,H2Sz0, -f- 2H20, forms white prisms sparingly soluble in water. The hydrochloride, CmH26Nz02HC1 + 2Hz0, crystallises in prisms, andis freely soluble in alcohol and water. The plntinochlorides, ( C20H26Nz02)z,H2PtC16 + 3H20 and C20Hz6Nz02,~zPtCI, -t- 2Hz0, are amorphous and are sparingly soluble in water; the mercurochloride, ( CzoHz6Nz~zH~1)zH~CI,, crystallises in needles. The hydrobromides, CzoHzaN20z,HBr + 2Hz0 and C20Hz6N20R,2HBr + 3H20, also form needles.The neutral hydriodide is a colourless oily liqnid which solidifies to an amorphous mass. Potassium iodide produces in acid solutions of hydroquinine salts a yellow, crystalline precipi- tate of the acid hydriodide, CzoHz6NzO2,2HI + 4H20. On the addition of iodine to the alcoholic solution of this salt, dichroic, ueedle-shaped crystals of the composition C2,,H2,N20,2(IH,IZ) are deposited. The acetate, CmH26N202,C2H402 + 5Hz0, crystallises in needles and is freely soluble in alcohol and water. The benzoate and sdicylate dissolve freely in alcohol. The benzoate is anhydrous. The piperonate, CzoHz6NzOz,C8~604, is soluble in water and in chloro- form. Thc oxalate is deposited from hot alcohol in prisms containing 6 mols.H20. The tartrate also crystallises in prisms containing 2 mols. H,O. It is soluble in alcohol, water, and in a mixture of alcohol and chloroform. The citrate and arssnate crystallise with 10 rnols. HzO, the phosphate with 7 mols. H,O. The chromate, ( Cz0H26NzOz)zHzCr04 + 6Hz0, forms golden needles. The dichromate is an oily liquid. Hydroquinicine dissolves freely in ether, alcohol, chloroform, and in dilute acids. The solution in dilute sulphuric acid is yellow; the colour changes to green on the addition of chlorine water and ammonia, b u t the mixture is not fluorescent. An ethereal solution of oxalic acid produces in an ethereal solution of hydroquinicine an amorphous precipitate soluble in chloroform. The normal sulphate cryst,allises in needles and dissolves freely in alcohol and in water.Hydroquinine platinockloride, C20Hz6N202, HzPtCI, + HzO, forms orange-coloured crystals. Hydroquinine unites with methyl iodide, forming the compound CzoH26Nz0z,MeI + CzH60. It crystallises in prisms of a yellow colour and dissolves in hot alcohol. It melts at 218". On treatment with silver chloride, it is converted into the chloride CzoHz6Nz0z,MeCl + 2Hz0. The acid platinochlol"ide, C,Hz6N,0z,Me*HPt Cl6 + 2H20, forms orange-coloured crystals, and the normal salt, (C~OEIZ~N,O,M~),,P~CI,, pale-yellow needles. Hydro- quinine methylhydroxide is amorphous. It is soluble in alcohol and water. The solutions are caustic and absorb carbonic anhy- dride. AcetyEhy droquinhe, Cz0R25N202Ac, is amorphous. It melts at 40" and dissolves freely in alcohol, ether, benzene, and in acids.The solution is laevogyrate, and the solution in sulphuric acid is fluorescent. The platinockloride contains 2 mols. H20, and the normal sulphate,ORGANIC CHEMISTRY. 71 which is soluble in hot water and alcohol, crystallises with 9 mols. Hydroquinine is converted into hydrocupreyne dihydrochloride by the action of hydrochloric acid, sp. gr. 1.125, a t 150". Hydrocuprezize, C,9H,,N,0, + 2H20, exists as a crystalline powder freely soluble in ether, alcohol, and chloroform. It melts at 168-170°, and exhibits a strong basic reaction and forms crystalline salts. Solutions of the normal salts have a greenish-yellow colour, the acid salts are colour- less. The sulphate, ( ClgH,,N,O,),,H2SO4, is sparingly soluble in water and in alcohol.The tartrate is sparingly soluble in water, but the dihydrochloride, CleH2iNz02,2HCl + HzO, is freely soluble i n water. The acid platinochloride, C19HzrNz0z,H~PtC16, is crystalline and in- soluble in water. ~ydroquininesulpponic acid, C,oH,N,O,*SO,H + H,O, is prepared by dissolving hydroquinine in sulphuric acid a t the ordinary tempera- ture. The solution is poured into water and mixed with excess of ammonia. The acid crystallises in cubes and is soluble in boiling water, alcohol, and hot solutions of alkalis. It dissolves freely in acids, with which it forms crystalline compounds. The anhydrous acid inelts a t 239". The presence of hydroquinine in cinchona bark vitiates the results obtained in the estimation of quinine by the ordinary polariscopic met hod. w.(3. w. H,O. Apocinchine and Apochinine. By W. J. COMSTOCK and W. KOENIGS (Ber., 20, 2674-8689).-Analyses of salts and bromo- derivatives of apocinchine show that the formula, previously assigned to the base (Abstr., 1882, 224) must be altered to C19H19NO; the formula ascribed to ethylapocinchinic acid (Abstr., 1885, 1248) ig, huwever, retained. The authors now attribute the formation of the combustible, gaseous halogen compound (? methyl chloride) in the preparation of apocinchine to some secondary change in the reaction. Apocinc hine hydro bromid e, C19Hlg N 0, HBr, crystal lises from alcoholic hydrogen bromide in small, yellow needles, and melts at about 256'; the hydriodide, C1gH1gNO,HI, is a yellow, cryst'alline salt ; the PZutinG- chloride, (C,gHlgNO),,H2PtC16, forms orange-yellow crystals and melts at about 235".The acetyl-derivat,ive, ClyHI8NOAc, forms practically colourless crystals, and melts a t 118-119" ; the double phosphates of apocinchine and ammonium, barium, acd potassium, were also pro- pared, and crystallise well. Bronaapoci?i,chine, CI9H,,NOBr, is prepared by gradually adding bromine to apocinchine hydrobromide dissolved in equal parts of chloroform and acetic acid until the yellow perbromide begins t3 separate; sodiiim hydrogen sulphite is then added and the base obtained from the chloroform and aqueous layers by evaporation and precipitation. It is crystalline, melts at 186-188", and is readily soluble in aqueons soda, benzene, chloroform, and ethyl acetate, less so in alcohol, carbon bisulphide, ether, and light petroleum.Brom- apocinchine is not altered by prolonged boiling with alcoholic soda, and yields bromoform and cinchonic acid on oxidation with 4 per cent. chromic acid solution.72 ABSTRACTS OF CHEMICAL PAPERS. Dibroniethylapocinchine, ClgH,,NBr2*OEt, is prepared by adding ethyl- apocinchine (10 grams) to well-cooled bromine (15 c.c.), digesting the product after 12 hours with sodium hydrogen sulphite. and extracting with alcoholic ammonia; the deposit from the alcoholic solution is then boiled with dilute sutphnric acid, the resulting solution treated with ether and aqueous soda, and the base obtained from the ethereal layer by evaporation. It melts at 116-118". The alkaline solution, after separation from the ether, is found to contain dibromapocin- chine. Ethylapocinchinic acid forms a crystalline hydrochloride and hydro- bromide. The silver salt, C,,H,,NO?Ag, is a white, crystalline salt unaffected by light ; the platinochlorzde, (C,,H,gN0,),,H,PtC16, is pre- cipitated in volumiiious, slender, straw-yellow needles, which are con- verted into small, compact, orange-yellow crystals, when the salt is heated on a water-bath for a short time. Homupocinchina, C,H,,NO, the compound formed together with carbonic anhydride and ethyl chloride when ethylapocinchinic acid is heated a t 130" with hydrochloric acid (Zoc.cit.), crystallises from dilate alcohol in colourless crystals which contain water of crystallisa- tion and melt a t 184-185'. It is sparingly soluble in water, ether, benzene, and chloroform, readily soluble in hot alcohol, and differs from apocinchine, to which it shows much similarity, in its ready solubility in dilu te aqueous soda.The kydrob romide, CI,H,,NO,HBr + H20, crystallises in glistening, transparent, yellow needles or prisms, melts at 221-222", and is sparingly soluble in water and in excess of dilute hydrobromic acid. The ethyl-derivative yields a crystalline, yellow sulphate. On fusion with potassium hydroxide, homapocinchine is converted into a compound which probably corre- sponds to oxyapocinchine. When oxidised in very dilute solution with permangmate, ethylapocinchine yields a mixture of solid acids which dissolve in dilute sulphuric acid and alkalis. Ethylapocinchinic acid is one constituent of the mixture.To effect a separation, the product is boiled with hydrobromic acid (sp. gr. 1-49>, and the solution treated with aqueous soda which precipitates homapocinchine ; careful ncidifi- cation of the filtrate then precipitates a mixture of a t least two acids, of which the one of lower melting point is the more soluble in alcohol. The more soluble acid, C,,H,,NO, or ClgHJVO,, dissolves in dilute mineral acids, melts at 230" with the evolution of gas, and at 240" yields carbonic anhydride and a compound, CliH,,NO,. This crystallises from dilute alcohol in colourless, silky needles, melts a t 0,23", is not volatile without decomposition, and is soluble in dilute araids and alkalis. The hydrobromide, sulphate, and nit rate are crystalline, and sparingly soluble.AcetyZoxya23ocinchilzcl, CI9Hl,NO2Ac, melts at 201--203", and is soluble in alcohol, benzene, and light petroleum. From considerations based on analyses of its salts, the authors have adopted the formula Cl9H,,NO, for chinine, instead of that previously proposed (Abstr., 1885, 910). Chinine h!/ldrobrowide, C19H19N02,HBr, crys tallises in long, sulphur-yellow needles, and is decomposed by water. The remainder of the paper is devoted to a discussion of the con-ORQ AKIC CHEMISTRE'. 73 stitution of these alkalo'ids, in which the authors adhere t o the views already put forward wit>h regard to apocinchine (Abstr., 1885, 1248 ; 1887, 600), and suggest that cinchine niay possibly be a dialkyl- amidophenylquinoline, and t,hat the second benzene nucleus is present in a partially hydrogenated form.w. P. w. Strychninesulphonic Acids. Bp C. STOEHR (Ber., 20, 2i33- 2734).-A note calling attention to the fact that the results obtained by Guareschi (Abstr., 1887, 853) are essentially the same as those previously arrived at by the author (Abstr., 1886, 269). w. P. w. PecuIiar Modification of UrobiIin. By E. SALKOWSKY (Chpm. Centr., 18, 1089) -On examination of a sample of urine peculiarly rich in urobilin, itl was observed that on keeping this colouring matter disappeared without any marked change of the colour of the urine. This conversion of the urobilin seems not to be conditioned by the ammoniacal fermentation of the urine or by the presence of micro-organisms, Urobilin is a substance readily decomposed, and passes into a modification which, although still coloured, shows no absorption-bands, nor fluorescence with zinc clrloride in ammoniacal solution, and is not taken up by chloroform.It is probable that in most normal urines, urobilin, as well as its decomposition-products, is present. V. H. V. Chemical Formation of Albumin. By C. P. W. KKUKEKBEKG (Chem. Centr., 1887, lOSS).-W hen keratin, previously purified by the action of pepsin and trypsin, is heated with water in a sealed tube, it dissolves to form an alkaline liquid, possessing a strong odour of hydrogen sulphide, This liquid contains a non-dialysable substance, keratinose, precipitated by ammonium sulphate, which agrees with hemialburnose as regards these reactions, although it does not give the hydrochloric acid test,.Kemtinose is converted by pepsin and hydrochloric acid a t a blood-heat into keratinpeptone, which is not precipitated by ammonium sulphate. Under the same conditions spongin yields spongiorzose, ft soluble, indiff usible substance ; this is also converted into spoupiopeptone. By the dccomposition of spongin, carbamitle seems to be formed. The author considers that the albu- minoids and skeletins are related to albumin as methyl to methyl ether. V. H. V. Coagulation of Albumin. By V. MIcHAn,oFF (Chem. Centr., 1887, 1088).-According to the author the coagulation of albumin is due to one of two phenomena, namely, t'he true coagulation induced by the action of ferments or heat, a process analogous to etherification OK the formation of polyhydro-silicates or glycols, and a pseudo-coagula- tion caused by a loss of " gelatinose-water," which corresponds w i t h the loss of water of crystallisation of salts.The coagulating power of salts on solutions of albumin is dependent on the nature of the aoid and base therein contained; the maximum effect is produced by ammonium, the mean by sodium, and the minimum by potassium salts. Again, in the case of ammonium salts, the sulphate is more74 ABSTRACTS OF CHEXICAL PAPERS. ---- 0 ,. .. .. ,. H.. .. .. .. N.. .. .. .. S .. .. .. .. 0 .. .. .. . . efficient than the nitrate, and of potassium salts the snlphate than the chloride. V. H. V. Egg Albumin and Albumoses. By R. H.’CHITTENDEN and P. R. BOLTON (Studies from Lab. Physiol. Chem., Yale Uuiv., 2, 126-155). --These experiments were designed to contrast the products of diges- tion of egg albumin with those obtained by Kuhne and Chittenden from fibrin.Four samples of albumin were prepared ; i n some cases it was separated from globulin by saturation wi tjh magnesium sul- phate, in others by dilution and the subsequent addition of acetic acid. An elementary analysis of these four samples gave the following average percentages :-C, 52.18 ; H, 6.93 ; N, 15.81 ; S, 1.87 ; 0, 23.21. Further, coagulated products did not differ in composition from non-coagulated albumin. These results do not agree with any of the formula ascribed to albumin by previous observers. Peptic digestion of fhe albumin resulted in the formation of albu- minoses of which the percentage composition and reactions were determined.In composition they were found t o differ from each other somewhat more than the albumoses from fibrin ; collectively, however, there is less difference in composition between the albu- Moses and the egg albumin from which they were formed than in the case of the albumoses from fibrin. The following table gives the final results :- Proto- Deutero- Proto- Deutero- Egg. albumose. albumose. Fibrin’ albumose. albumose. albumin. -- ------- - 50’7’: 50.65 52.68 51-07 51.62 52.33 6-78 6.83 6 *83 6 -98 6.97 6 *98 17.14 17.17 16-91 16’00 15-82 15.85 1.08 0 -97 1 .lo 1 -95 1 *96 1 -82 24?23 24.38 22.48 24.00 23.63 23-02 Fibrili products. Egg albumin products. I I n their yeactions the different albumoses (proto-, deutero-, hetero-, and dys-albumose) obtained from egg albumin do not differ essentially from those obtained from fibrin.W. I). H. Metallic Compounds of Albumin and Myosin. By R. H. CHITTENDEN and H. H. WHITEHOUSE (Studies from Lab. Physiol. Chem., Yale Univ., 95--125).--Many researches on the subject of the metallic compounds of albumin have been carried out since Lieber- kuhn attempted to establish the molecular weight of albumin by the analysis OE copper albuminate. The more recent work of Harnack (Abstr., 1882, 747) showed that two compounds of albumin (from white of egg) with copper occur, one containing 1.35 per cent., and the otlier 2-64 per cent. of copper. I n the present research, albumin was freed from globulin by the use of dilute acetic acid, and both theORGANIC CHEMISTRY. 75 acetate and snlphate of copper were used in the preparation of the albuminate.The precipitate was well washed with water, powdered, and dried. The percentage of copper was first determined as cupric oxide by ignition and weighing : the oxide was then dissoived in dilute nitric acid, treated with hydrogen sulphide, and the amount of cuprous sulphide obtained weighed. By the former method, in 15 prepam- tions the average result was 1.17 per cent. of copper; and by the latter method 0.94 per cent. ; the preparations, therefore, contain 0.23 per cerit. of ash. I n order to obtain less ash, Harnack dissolved tthe albuminate in sodium carbonate and reprecipitated it by the careful addition of acid; this process was repeated several times. This treatment certainly increases t,he percentage of copper, but is a source of error, as the sodium carbonate withdraws a portion of the a1 bumin.Long-continued washing with water also causes partial dissociation of the compound. The results obtained correspond with the formula (C72H11,N18S022)~ + Cu - H,. A normal lead salt causes a small precipitate when added to albu- min, whilst with basic lead acetate the albumin is completely precipi- tated. This confirms the previous statement of Berzelius (Lehrbuch der Chemie, 9, 29). The preparations were well washed from both lead and albumin, dried, and the lead was determined, first by simple ignition, and then obta,ined as sulphate, which was ignited. The results indicate that more than one compound of lead is formed, that made by the addition of a large excess of the basic acetate, containing about five times as much lead as the ordinary basic lead compounds.An iron compound Tvbich was found to be more stable than the copper albuminate, and corresponded fairly well with the formula ( C72H:llzN18s02,)4 + Fe -H3, and a zinc compound, (C7,H,,,N18S02,)a + Zn - H2 ; acid compounds with uranium, (~,2Hl12N18s022)3 + U - H2 ; with mercury, (C7,Hl,,N,8S0,)4 + Hg - H,; and with silver, (C7,Hll,N,8SO,2), + Ag. - Ha, were also prepared and analysed. Much stress is not laid on such forrnu1Be;as it seems possible to form a large variety of compounds by simply modifying the conditions of precipitations. This, with the undoubted tendency of the compounds to dissociation, may account for the lack of agreement in the results of different workers.Similar compounds prepared from myosin obtained by extracting ox flesh with 15 per cent. ammonium chloride were prepared, and the percentage results show that these two forms of prote'id matter do not form corresponding compounds with the metallic salts used. This is illustrated by the following table :-76 ABSTRACTS OF CHEMICAL PAPERS. --. ......... .......... .......... .......... .......... ......... .......... .......... .......... Copper compound Iron 9 , Zinc 9 7 Ura,nyl ,, Mercury ,, Lead ?, Silver ,, Nickel ,, Cobalt ,, Egg albumin. 0 *94 per cent. Cu 0.95 ,, Fe 0.91 ,, Zn 4.60 ,, U 2.89 ,, 2.56 ,? 4.09 ,, Ag Ff - Myosia. 1-17 per cent. Cu 2.29 ,, Pe 0.72 ,, Zn 2.43 ,, Hg 4-70 ,, Ni 6-03 ,, Co 7-49 ), u - - W. D. H. Casein and Caseoses.By R. H. CHITTENDEN and H. M. PAINTER (Studies from Lab. Physiol. C'hern., Yale Univ., 2, 156-199),- Danilewsky ( Z e i t . physiol. Chem., 7, 433) has asserted that casejin is a mixture of two protejids, caseoprotalbin, partially soluble, and caseoalbumin, insoluble in hot 50 per cent. alcohol. Hammarsten (ibid., 7, 227) has shown that the peculiar behaviour of Danilewsky's case'in is due to its containing calcium phosphate, the presence of which impurit'y depends on the use of hydrochloric acid in the pre- cipitatioii of the case'in, as this acid does not favour the removal of the salt as well as acetic acid. He also considers that casein is a single prote'id. I n the present research, seTen distinct preparations of casejin were made. Elementary analyses show a close agreement throughout, and the results mcreover accord closely with those of Hainmars ten, I n the digestion of casein with hydrochloric acid, peptones are ultimately formed, and the name caseose is given to the intermediate products.These were separated by the methods of Kiihne and Chit- tenden into proto-, hetero-, and deutero-caseose, which correspond with the albunioses with similar names. The quantity of heterocaseose obtained was usually very small. The reactions characteristic of albumoses apply generally to the caseoses. Unlike proto-albumose however, protocnseose is precipihated from aqueous solutions by acetic acid. The average of the analyses of 10 preparations of proto- caseose gives the following percentage results :- I-_I-- --I---!--- Protocaseose ........1 52.89 1 7.10 I 15-94 1 0.95 1 23.12 Case'in.. ........... 53.30 7.07 15.91 0.82 22.03 Deuterocaseose contains ZL smaller percentage of carbon than proto- caseose, and heterocaseose contains fully as much carbon as case'in itself. An insoluble, semi-gelatinous substance which separates in the first stage digestion has not yet been inveshigated. Weyl's com- mercial " case'in-peptone " contains large quantities of caseoses. W. D. H."P PHYSIOLOGICAL CHEMISTRY. 1 4 Animal Tannin. By M. VILLON (Cham. News, 56, 175).-corn weevils CCaZandra graneria) were killed, ground in a mortar, and digested for one hour in boiling 90 per cent. alcohol. The residue from the evaporat,ion of the extract is taken up with ethyl acetate at SO", .and precipitated by means of ammoiiiacal zinc a,cetate.The preci- pitate is decomposed with oxalic acid, and the solution evaporated in R vacuum. In this way 3 per cent. of a substance having all the general properties of tannin is obtained from the weevils. This animal tannin, fracticomitanrzin, forms small reddis h-ye!Iow scales. D. A, L.ORG ANIU CHEMISTRY. 35Organic Chemistry.Arrangement in Space of the Atoms in the Molecules ofCarbon-compounds. By J . WISLICENJS (Chem. Centr., 188’7, 1005-1009).--Van’t Hoff and Le Be1 were the first to explain the opticaldiflerence of certain carbon-compounds by a difference in the relativearrangement of the atoms in space within the mo.lecde ; since theirwork, however, no serious attempt has been made t o apply theirtheory t o explain the isomerism of certain compounds, whose com-position, according to present views, is identical.a 36 ABSTRACTS OF CHEMICAL PAPERS.Such peculiar cases as those established by the researches of Fittigon the isomerism of male’ic and fumaric acids, however, and the dis-covery of a third and fourth monobromocinnamic acid, have beenclassified under the generic term of alloisomerism. Chemists hithertoseem to have contented themselves with a name.Adopting the hypothesis of van’t HoiYand Le Be1 that t.he atomsoccupy the solid angles of a tetrahedron, being arranged around acentral carbon-atom it is evident that two carbon-atoms, associatedtogether in the parafflno‘id form of combination, would revolve aroundone common axis, passing through the point of union of the atomsand the direction of attractiou of two associated atoms, such as thoseof hydrogeu.When two carbon-atoms are combined together, as inthe olefines, they can only revolve round an axis which is the straightline connecting the two common carbon-atoms.Supposing all four of the affinities of the saturating atoms areunequal, then six isomerides are possible, in the case of two pairsthree isomerides, and three also if two affinities are equal and twounequal. For male‘ic acid, van’t Hoff has proposed the formulaCH*COOHIICH-COOH, so that for fumaric acid the formula will beCOO*HCHIICH-COOHIn order to explain the conversion of malei’c into fumaric acid throughthe intervention of halogen-derivatives of succinic acid, it is sup-posed that the atoms combined with neighbouring carbon-atomsmutually react on one another according to their chemical affinity.Hence, it follows that two carbon-atoms combined together by oneaffinity, and being in a poRition by revolution around their axis to giveway to this attraction, will so arrange themselves that the associatedradicles interchange positions in the syshem.Such a relative arrange-ment will be stable in the cold, but at a higher temperature, as theinteroscillation of tbe elements will be more frequent, there is aloosening of the affinities, and a different configuration ensues. Whenan unsaturated compound passes into one that is saturated, it is in-different to which of the two carbon-atoms each particular radicleattaches itself ; the compounds formed are identical.But if an atom iscombined with two different radicles, then by addition an asymmetri-cal carbon-atom results according as the added atoms attach them-selves to one or other position of affinity. This explains the forma-tion of optically inactive compounds under these conditions, sinceboth modifications are produced in equal quantities.As regards the nomenclature of these dieerent geometricallyisomeric configurations, it is proposed to call the arrangementaCb aCb11 the centrally or axially symmetrical, and the arrangement 11bCa aCbthe plane symmetrical.The following examples are given in illustration of the abovOROANIC GHEMISTRT. 37views :-Tolane dichloride exists in two modifications ; according tothe author's hypothesis, the modification of higher me1 ting point,obtained by the direct chlorination of tolane, is the plane symmetricalPh*C*Cl Ph*C-Cl11 , whilst the other is the axially symmetrical 11 Asfumaric acid is principally formed by heating malic acid, in which,doubtless, the carboxyl-group has more inclination towards thehydrogen-atom than to the hydroxyl- or other carboxyl-group, itsPh.C*Cl C1.C.PhC 0OH.C H-OHconstitution may be represented by a configuration I HHOC o OH'from which by the abstraction of a molecule of water the formulaCOOHGHII results.The conversion of ethyl maleate into ethylfnmarate by iodine is explained by the intermediate formation ofdiiodosuccinnic acid, an interchange of position of the iodine- andhydrogen-atoms ; the removal of a, molecule of hydrogen iodide givesethyl iodofumarate, which in its turn is reduced by the hydrogen iodideto ethyl fumarate.The reverse process of conversion of fumaric into male'ic acidthrough the intervention of dibromosuccinic acid can be explained inlike manner.The isomerism of crotonic and isocrotonic acid is alsoof a similar order, the constitution of the one being expressible by aformula 11 , of the other as 11 . Cinnamic acidshould also exist in two geometrically isomeric forms, of which, asyet, only one has been obtained.HC-COOHH*C*Me Me43.HHOCOOH H*C*COOH/it-Coumaric acid has the plane symmetrical arrangementHC CeH,. 0 Has it is easily converted into its lactone, conmarin ; i n its isomeride, theatoms are arranged in the axially symmetrical configuration ; this, byfuming hydrobromic acid, is converted into coumarin, by temporaryaddition of a, molecule of the acid, and by an inclination towardsformation of the lactone.By this theory, the removal of the elements of a halogen acid andsimultaneously of carbonic anhydride from the sodium salt' of ap-halogen substituted acid is expiained, as also the foi-mation ofanhydrides and lactones when two carbDxyl- or a hydroxyl- andcarboxyl-group are in the y-position.The author is engaged on experimental evidence in favour of thistheory.V. H. V.Nitrosates, Nitrosites, and their Derivatives. By 0. WALLACH(dnnalen, 241, 288--315).-The crystalline compound which Guthri38 ABSTRACTS OF CHEMICAL PAPXRS.(Annulen, 116, 248 ; 119, 84) obtained by the direct union of amylenewith nitrogen peroxide, is most conveniently prepared by passing thenitrous fumes evolved by the action of strong nitric acid on arseniousoxide into a well-cooled mixture of amylene (1 vol.) and glacial aceticacid (2 vols.).The operation is interrupted when the colour of theliquid changes from blue to green. The crystals are washed withacetic acid, afterwards with water. As commercial amylene is amixture, the product is not homogeneous. On recrystallisation fromchloroform or benzene, two substances having the compositionC5H,,N20a are deposited, namely, cubes melting at 96-97', and needlesmelting a t 89". This compound is not a dinitrite but 8 nitroso-nitrateor nitrosate.On boiling with alcohol and aniline, it yields anilinenitrate and nmyZenenitrolaniZine, NHPh*C5Hg : NOH. The basemelts a t 140-141". It dissolves freely in ether, chloroform, warmalcohol, and in dilute acids, and crystallises well. The hydrochloride,CIIHl,N20,HC1, is deposited from a hot aqueous solution in anhydrouscrystals. It is best prepared by passing hydrogen chloride into anethereal solution of the base, when the hydrochloride is precipi-tated in the form of a crystalline powder. The w'troso-compound,NO*NPh*C,H,:NOH, is deposited as a crystalline powder when asolution of sodium nitrite is poured into ail acid solution of tLe base.It melts at 327-128", and is soluble in alcohol and in alkalis.Thenitroso-compound is reprecipitated on adding an acid to t,he alkalinesolution. The hydrochloride is decomposed by boiling with water,or better with hydrochloric acid, yielding hydroxylamine and a ketondbase, NHPh*C,H,: 0. The new base melts a t 61", and is soluble inalcohol, ether, and in hot, 6ater.AmyleiLenitro123ctratolzl.idine, CI2HlsN20, and its hydrochloride andnitrate form well-developed crystals. The base melts a t 111-112",and the nitroso-derivative a t 147-148". The hydrochloride is decom-posed on boiling it with hydrochloric acid, yielding hydroxylamineand the base C,,H,,N20 melting a t 98".The nitroso-derivativemelts with decomposition a t 149-150". The hydrochloride is moresoluble in water than the corresponding para-salt.Amylenenitrolorthoanisidine melts a t 138-139".The hydrochlorideis deposited from its aqueous solution in prisms. Amylene nitrosateand piperidine act on each other very energetically, forming a crystal-line base, C,,H,,N,O. It melts at 95-96", and is insoluble in waterand in alkalis. The hydro-chloride is art oily liquid, but the platinochloride (c,,H,oN,0)2,HB,PtC:16,forms beautiful prisms. Arnylenerzitroldiethyla~t~ine crystallises i4plates and melts a t 71-72". ArnylenenitroEalLylamine is soluble inwater. The hydrochloride, C8H16N20,HCl, is crystalline. This base isisomeric with nitrosoconiine.Amylene nitrosate acts on sodium ethoxide, forming a crystallinecompound which melts a t loo", and also on ethyl acetoacetate, yieldinga crjstalline compound of the compositionAmylenenitrolorthotoluidine melts a t 115".The Yalts dissolve freely in water.C,H,,NO*CH(C OMe) *COOEt.Guthrie (bc.cit.) observed that amyl nitrosate acts on potassiuORQANIC CHENISTRY. 39cjanide, but the author finds that a crystalline compound and potas-sium nitrate, not a liquid and a m i t r i t e , are formed in the reaction.A blue crystalline compound is formed by passing nitrous fumesinto brornamylene dissolved in acetic acid, and pouring the crudeproduct into water. This compound acts on piperidine at the ordinarytemperature, yielding a colonrlesg, crystalline substance which exhibitsneither acid nor basic properties. It is soluble in alcohol, is rich inbromine, and has an odour resembling that of camphor.Synthetical Experiments in the Sugar-group.w.c. w.By E. FISCHEBand J. TAFEL (Ber., 20, 8566-2575).-1t was previously shown(Abstr., 1887, 651) that acraldehyde bromide is converted by barytainto what is probably a glucose. With phenylhydraaine, the productof the reaction yields a- and P-phenlylacrosazones, melting a t 205'and 148" respectively.When isoglucosamine oxalate (Fischer, Abstr., 1886, 934) is dis-solved in ice-water (10 parts) and treated with sodium nitrite, anevolution of nitrogen takes place ; after three hours, the temperatureis aliowed to rise to 20". The product is exactly neutralised withaqueous soda, evaporated in a vacuum, and the residue extracted n-ithabsolute alcohol. On evaporating the solution, levulose is obtained asa yellowish syrup ; the spec.rotatory power a t 80"=25". It producesstrong fermentation with yeast in 10 minutes, gives a precipitateof pheny lglucosazone wit'h phenylhydrazine, and yields Kiliani's levu-lose hydrocyanide when treated with hydrocyanic acid. The consti-t ution of isoglucosamine is probably NH2.C &,*GO. [ CH( OH) I3.CH2.OH.Ledderhose's isomeric glucosamine has possibly the constitutionC: 11 0. C H ( N H,) [ C H ( 0 H ) ] BG H i 0 H .a-Phenylncrosazone is obtained in the following manner : A solu-tion of 75 grams of pure, crystallised barium hydroxide in 1-25 litreOF water is cooled with ice-water; 50 grams of freshly-distilledacraldehyde bromide is then added by drops, the baryta solutionbeing kept violently shaken.Eight preparations are united, madeslightly acid with sulphuric acid, and treated with a strong solutionof sodium sulphate until the barium is completely precipitated. After12 hours, it is filtered, neutralieed with aqueous soda, and evapo-rated in it vacuum to 18 litre. When cold, a solution of phenyl-hy drazine hydrochloride (50 grams) and sodium acetate (50 grams)in 100 C.C. of water is added, and the whole left for 12 hours; itis then filtered and warmed on it water-bath wikh 150 grams more ofphenylhydrazine hydrochloride and 150 grams of sodium acetatre. Inthe course of foul. hours, a half crystalline and half resinous preci-pitate separates; this is washed with water and extracted withether, when the greater part of the resin and the /I-phenylacrosazonedissolves, leaving the a-phenylacrosazone.After filtration, the a-com-pound is repeatedly extracted with boiling alcohol, and treated withhot water, after which it is almost pure. The yield from $00 gi*ams ofbromide is 18 grams. It melts a t 205" (uncorr.), and is very sparinglysoluble. On addiug water to the hot alcoholic solution, it sepwntssin long, slender needles.a-Acrosaniine, Cs&N05, is prepared similarly to isoglucosamin40 ABSTHACTS OF CHEMICAL PAPERS.(Zoc. cit.) by reducing the acrosazone with zinc-dust and acetic acid,and is purified by means of the oxnlate. It shows all the reactions ofthe glucosamines. When the oxnlate is dissolved in ice-water andtreated with sodium nitrite, a-acrose, C6H120,, is formed; this isobtained as a light-brown syrup, having a sweet taste.It reducesFehling's solution.p-Pheiiy Lncrosazolte, C,aH22N404, is obtained by evaporating itsethereal extract' (obtained in the purification of the a-compound), dis-solving in alcohol, and precipitatiag with water. The dried productis exhausted with cold benzene several times. The yellow crystalline~esidue is boiled with acetone (2 parts), filtered, and precipitatedwith ether and light petroleum. It crystallises in slender, yellownsedles melting at 148", dissolves in alcohol and acetone much morereadily than the a-compound, but is almost insoluble in ether whenpure. The yield is small.The resemblance of a-phenylacrosazone to phenylglucosazone makesi t probable t.hat a-acrose has the constitution expressed by the formulaOH.CH,*[CH(OH)]4*CIEE0 ; the constitution of p-acrose would thenbe OH*CH,*CEI(OH)*CH(OH)*C(OH) (CH2*OH)GH0 orOH.CH,.CH(OH).CH( OX).CO-CH(OH)*CH2*OH.The lower melting point and more ready solubiIity of the p-osazonepoint to its being a derivative of a sugar with an abnormal carbon-chain.Isodulcitolphett yllydrazine, CsHl,04 N2H Ph, mystallises from alcoholin colourless plates melting at 159'.It is insoluble in ether, readilysoluble in water and in alcohol. The aqueous solution is dextro-rotatory.Lactosephen?/Zhyarazine, C16HPBOION2, is prepared by adding phenyl-hydrazine (1 part) to a solution of milk-sugar (2 parts), in hot water(2 parts). After two days, twice the volume of absolute alcohol isadded, and the whole treated with much ether.The syrupy preci-pitate after being repeatedly dissolved in alcohol and precipitated withether, is obtained as a solid mass. I t is filtered, quickly washedwith ether, and dried in a vacuum over sulphuric acid. It dissolvesreadily in water and in alcohol, and is insoluble in ether. It islaevorotatory. N. H. M.Isonitrosogalactose. By P. RISCHBIETH (Bw., 20, 2673-2674).-When galactose (1 gram) and hydroxylamine hydrochloride(0.4 gram) are dissolved in a sniall quantity of water, treated withsodium carbonate (0.65 gram), and allowed to remain for 24 hours,isolzitrosogaZwttose, C6H1,0, : NOH, is obtained as a colourless, crys-talline substance which melts at 175-176", and is readily soluble inhot water, soluble in hot dilute alcohol, and practically insoluble inether and absolute alcohol.Under similar conditions, no separationcould be obtained from dextrose, levulose, or arabinose. w. P. w.By C. WEHMER(Ber., 20, 2614--2618).-Plants which readily produce starch fromdextror;le, cane-sugar, mannitol, and glycerd, do not produce starchin any determinable amount from formose.The Carbohydrate Character of FormoeeORGANIC CHERIISTRY. 41When 28 grams of formose syrup is boiled with 100 C.C. of wuterand 5 grams of hydrochloric acid (sp. gr. 1.2) for 11 hours, a sepa-ration of humic suhstance (3.5 grams) takes place. The filtrate showsthe iodoform reaction distinctly and reduces Fehling's solution. Nolevulinic acid is formed.13 per cent. phosphoric acid produced thesame decornposition, also without formation of levulinic acid.The author concludes t h a t formose is not a carbohydrate.Saccharification in Vegetable Tissues. By BONDONNEAU andFORET (Compt. rend., 105, 61 7--618).-The amylaceous plant isheated at 90-100" with acid of 1 t o 2 per cent., and the starch isgradually and completely converted into dextrin, glucose, saccharose,&c., and the soluble products thus formed diffuse through the cell-walls into the surrounding liquid. When the proportion of sugar inthe liquid ceases to increase, the process is finished. This method isreadily applied on a large scale. The exhausted pulp is free fromstarch, but constitutes a valuable nitrogenous food-stuff for cattle.The pulp from maize has the composition,-Water, i9.15 ; ash, 1.22 ;nitrogenous matter, 8-38 (containing nitrogen, 1.31) ; oil, 5.48 ; cellu-lose and loss, 5-77 = 100.It will be observed that water has beensubstituted for the starch.N. H. M.C. H. B.Amines of the Paraan and Benzene Series. By MALBOT(Compt. rend., 105, 574-576) .-In the reactions described, unlessotherwise stated, the substances were mixed in equal molecular pro-portions.Ethylamine and aqueous ammonia at 100" yield triethylamine, butst 130" tetrethylammoniurn chloride is obtained in considerablequantity. Propyl iodide under the same conditions yields tripropyl-ltmine at loo", snd tetrapropylammonium iodide at 150". Althoughpure tripropylamine combines but slowly with propyl iodide in thecold, combination becomes complete at 150".Tripropylamine has noaction on propyl chloride in the cold, and the reaction takes placeslowly at 150", but becomes very rapid at 190", the products beingtripropylamine and dipropylamine hydrochlorides and propylene.Rutyl iodide and aqueous ammonia at 160" yield only tributylamine,and the action of tributylamine on butyl iodide is strictly analogoust o that which takes place with the corresponding propyl-derivatives,Tributylamine acts slowly on -butyl chloride at 80°, but at 170" piiredibutylamine hydrochloride and butylcne are obtained. Dibutyl-amine and butyl iodide in the cold yield dihutylamine hydriodideand free tributylamine; at a higher temperature, the reaction isanalogous to that obthined with the chloride.Isoamsl iodide and aqueous ammonia at 150" yield tetramyl-ammonium iodide.T'riamylamine acts slowly on amyl iodide in thecold, but at 150" triamylamine hydriodide and amylene are formed.At ZOO", the reaction is very rapid, and the products are diamylaminehydriodide and amylene. With amyl chloride, a salt of trinmylamineis formed at 17O", and undergoes no further alteration even at '210".Dinmy lamine and amyl iodide yield diarnylamine hpdriodide, freetrismglamine, and te tramylarnmonium iodide42 ABSTRACTS OF CHEMICAL PAPERS.Capryl chloride with aqueous ammonia in equal molecular propor-tions at 170" yields monocaprylamine together with a small quantityof the dinmine and caprylene. With twice the proportion of ammonia,the diamine is the chief product,, and no caprylene is formed.Capryliodide with an equivalent quautity of ammonia a t 160" yields onlymonocaprylamine, either free or tocether with caprylene, the latteroccupying a t 120" a volume equal to half the volume of capryl iodideused.Benzyl and metatolyl chlorides yield the tertiary amines almostexclusively, whilst cinnarnyl chloride yields the secondary amine, Thebases are obtained in the form of salts by the action of the correspond-ing alcoholic chlorides. The formation of a bivalent hydrocarbon isespecially marked with styrolylamines, cinnamene being obtained inlarge quantity. It is identical w i t h the synthetical cinnamene ofBerthelot, and part of it is obtained in the form of metacinnamene.Whether the products of these reactions are in the free stmate or inthe form of salts is determined by the conditions of equilibriumbetween the rival attractions of the ammonia and the amines for theethereal salt which is present, and the acid contained in this salt.The increasing complexity of the amines is the result of a series ofsuccessive tlransformations, a bivalent hydrocarbon being producedsimultaneously.This last fact is i u favour of the ethylene theory ofthe constitution of amines. C. H. B.Allyl-diguan idine and its Derivatives. By A. SMOLEA (Monatsh.;8,3i9--390) .-Allyldiguanidine copper silkhate, ( C,H,,N,),Cu,H,S04,is obtained by dissolving dicyandiamide in aqueous copper sulphatoand adding allylamine; the mixture is then heated for some hoursat 100".This salt is more soluble in alkaline solutions than in purewater ; it separates from boiling solutions in carmine-red, anhy-drous crystals, from cold solutions in pale rose-coloured, microscopicneedles with 1 mol. H,O. The other salts were made from the fore-going by double decomposition. The chloride, (C5H,0N,),C~i,2HC,1 +2H,O, yields groups of rose-red crystals easily soluble in water to anamet hyst-coloured solution. The nitrate, ( C5H1,N5) Jh,2HN 03, formsdark-red crystals easily soluble in water. Other salts were prepared.Copper-allyldiguanidine, ( C6H10N6)2C~, was obtained by precipitatinga boiling solution of the sulphate with soda. It crystallises in darkrose-red needles, sparingly soluble in cold, more soluble in boilingwater. A solution of this base precipitates metallic hydroxides fromsolutions of metallic chlorides, the chloride described above remainingi n solution.Allyldiguanidine sulphute, ( C3H,lN5)2,H2SO* + QH20, was obtainedby the action of hydrogen sulphide on the copper salt suspended inwater.It crystallises in prisms, and is soluble in water, insoluble inalcohol. The acid sukhate, C5Hl,N5,H2SO~ + $H,O, crystallises inscales. The chloride, C5H,lN5,HCI, yields transparent prisms easilysoluble in water and alcohol. It yields no precipitate with PtCl,,nor with potassium tartrate. The acid chloride, C5HllN6,2HCl, formssmall, transparent prisms easily soluble in water and alcohol. AIZyl-diguanidine, CZH6N5*CBH5, was prepared by treating a solution of theWhen heated above 130°, the base decomposesORGANIC CHEMISTRY.43raulphate with the calculated quantity of barium hydroxide and alsoby the action of hydrogen sulphide on copper all yldiguanidine sus-pended in water. It forms a dightly crystalline, very hygroscopicmass, is strongly alkaline in character, displacing ammonia from itssalts and absorbing carbonic anhydride from the air. When heatedwith potash and chloroform, it yields allylcarbamine (C,H,*NC).In chemical characteristics, the above copper compound somewhatresembles the alkalilie earthy metals, the allyldiguanidine, the alkalimetals and especially sodium.Isonitroso-compounds. By E. BECKMANN (Ber., 20,2580-2585 ;compare Abstr., 1887, 826) .-The intramolecular change which takesplace when diphenylketoxime is treated with phosphorus pentaclilorideor with sulphuric acid, is also produced by hydrochloric acid, acet,icchloride, acetic anhydride, and acetic acid.When a cooled soluti.on of diphenylketoxime in 10 parts of glacialacetic acid containing acetic anhydride is saturated with hydrogenchloride, and then heated at TOO", the oxime is completely convertedinto benzanilide; this is precipitated by sodium carbonate, and re-crystallised from alcohol.~~ethy~phenylk~toxime when similarlytreated yields acetanilide, which separates as hydrochloride on coo 1-iiig the solution; the reacfion takes place in the cold, but requiressome days.Methylpropylketoxime is converted by hydrochloric acid into thecompound NHPr*CMeO,HCl, and not into the compound NHMe-CPrO.When diphenylketoxime is heated with acetic anhydride in presenceof hydroxylamine hydrochloride a t 150", acetanilide and benzoic acidare formed.Methylphenjlketoxime when heated with 10 parts ofacetic anhydride for six hours a t loo", yields the compoundCMePh : N*OAc (Rattner, Rer., 20, 506). This crystallises fromlight petroleum in forked needles mel6ing a t 55".Glacial acetic acid at 180" acts on diphenylketoxinie with forma-tion of benzanilide, acetanilide, and benzoic acid. Methylphenyl-ketoxime is converted by hot glacial acetic acid into oily products ;acetanilide is not formed. I?. H. M.L. T. T.Oxidation by Means of Hydrogen Peroxide. By C.WURSTER( B e y . , 20, 2631--263S).-The author showed previously (Centr. fiirYhysiol., 1887, 33) that organic acids are quickly oxidised by hydro-gen peroxide to carbonic anhydride ; the higher fatty acids and oils,cane- and grape-sugar, are rather stable towards hydrogen peroxide,whilst boiled starch is converted first into crythrodextrin and theninto sugar.Hydrogen peroxide (6 mols.) reacts with hydroxylamine sulphate a t40" with formation of sulphnric acid, nitric acid (2 mols.), and water(12 mols.) . Hydroxylamine hydrochloride is similarly converted intohydrochloric and nitric acids and water.When an aqueous solution of phenol is treated with a hydroxyl-amine salt aud hydrogen peroxide, nitrosophenol is formed.Phenylhydrazine is converted by hydrogen peroxide into benzeneand diazobeuzeneiinide.The production of benzene makes it pro-The yield is quantitative44 ABSTRACTS OF CHEhlICAL PAPERS.bable that free diazobenzene is first formed in the oxidation of theh y drazi ne.By P.RISCHBIETH (Ber., 20, 2669-2673).-Isonitrosovaleric mid (Abstr.,1883, 1129) can readily be obtained by dissolving hydroxylaminehydrochloride (50 grams) and levulinic acid (83 grams) in a smallquantity of water and adding a concentrated aqueous solution ofsodium carbonate (38 grams) ; a separation of the acid immediatelyoccurs, and this is pi-rrified by recrystallisation froni water. Theyield amounts to 90 per cent. of that theoretically possible. Whentreated with hydrogen chloride, the acid melts and absorbs the gas,and on warming the product, a sudden reaction occurs with the evolu-tion of nitrogen, and production of a black residue.On oxidationwith dilute nitric acid, a large volume of gas is evolved, and aceticand succiriic acids are formed; the residue is, moreover, found to befree from nitrogen. If the acid (6 grams) is heated with sulphuricacid( 10 grams) in a vacuum at 150", succinic acid sublimes, and nitrogenis evolved ; when, however, a much larger proportion of sulphuric acid(36 grams) is employed, and the heating is continued jor 6 to 12hours at 100" at the ordinary pressure, the elements of a molecule ofwater are withdrawn from the molecule of isonitrosovaleric acid, andthe " inner anhydride," npvaleroximidolactone, together with succinicacid, resu1t.s.N.H. M.Isonitrosovaleric Acid and v-Valeroximidolactone.r- Valeroximidolactone, CM&EH<g2>C0, cryskllises from etherand water in long, white prisms; it melts at 69-70" when slowlyheated, and at a somewhat higher temperature when the heat'ing ia rapid,and boils at 232" without decomposition. When heated with aqueousalkalis, it yields the corresponding salts of isonitrosovaleric acid, butdilute sulphuric acid, hydrogen chloride, fuming hydrochloric acid,and ammonia are without action on it at 100". O n distillation withnitric acid (sp. gr. = 1*4), a distillate is obtained which contains inaddition to unaltered lactone at least two distinct crystalline com-pounds ; these have not yet been further examined.New Source of Capric Acid.By A. BUISINE and P. BUTSINE:( C o n y t . rend., 105, 61&617).--Capric acid does not exist as such insuint, but au aqueous solution of suiiit undergoes fermentation underthe influence of microbes, and the quantity of fatty acids and especi-ally of capric acid is greatly increased, the proportion of the latterrising to 5 per cent.The capric acid ir;; separated by distillation, saponification, andsubsequent fractionation, and is finally crystallised from boiling water.It forms a crystalline, buttery mass, with an odour of rancid butter,melts at 31", is soluble in alcohol and ether, and is slightly soluble inboiling water, from which it crptallisea in white needles. Thebarium salt is soinble in alcohol.C. H. B.W. P. W.Linoleic Acid. By L. M. NORTOX and H. A. RICHARDSON (Ber., 20,2735--2736).-When endeavouring to dry linoleic acid at 100" in ORQANIC CHEM ISTRT. 45current of hydrogen, the authors found that a. continued loss of weightoccurred even after 28 hours, although no change in composition tookplace. Linoleic acid can be distilled without any appearance of de-composition at 290" under 89 mm. pressure, and a colourless productis obtained amounting to about three-fourths of the mid taken. Thisconsists of an acid, CmH%O2, which cannot again be distilled in avacuum without decomposition; its sp. gr. is 0.9108 a t 15", and itsvapour-density = 153.Under similar conditions, ricinoleic acid yields an acid agreeing inButanedicarboxylic Acid.By R. OTTO and A. R~SSING (Ber., 20,2736-2747).-By the reduction of dimethylmale'ic acids, two batane-dicarboxylic acids are obtained, the one, melting at 193-194', whichhas been shown to be symmetrical dimethylsuccinic acid, the other,ethylmethylmalonic acid, melting at 118-120". I n this paper, theanhydrides of these acids are more particularly studied. The formeron dry distillation yields an anhydride melting at 87", previouslydescribed by Bischoff and Rach ; but thiR substance on rehydrationand crystallisation from the aqueous solution yields not only theoriginal or symmetrical dimethylsuccinic acid, but also the above-mentioned isomeric ethylmethylmalonic acid. On the other hand,the symmetrical dimet hylsuccinic acid, when treated with excess ofacetic chloride, yields an anhydride isomeric with the above, whichcrystallises in rhombic tables melting at 38"; this on rehydrationyields the original acid only.Again the butanedicarboxylic or ethylmethylmalonic acid, meltingat 121", remains unaltered on dry distillation, but when treated withacetic chloride i t yields a n anhydride of the same melting point,86-87", and crystalline form as the former of the anhydrides mentionedabove, but which, however, differs from it in yielding on rehydrationthe original acid only.Distillation of Citric Acid with Glycerol.By P. DE CLERMONTand P. CHAUTARD (Compt. rend., 105, 520-523).-500 grams ofcrystallised citric acid mixed with 750 grams of ordinary glycerol of28" are distilled in a glass retort of 3 litres capacity, and the productredistilled. The first fraction consists of about 250 grams of watercontbining a small quantity of acraldehyde, &c.; some crystalsalso separate in the colder part of the apparatus. The mass thenswells up, and the teriiperature musk be reduced, but it is afterwardsgradually raised until the distillation is complete. The distillateduring this second stage consists of 650 to 700 grams of liquid. Thetotal products of the decomposition are 950 grams of liquid, 30 gramsof a bulky, carbonaceous residue, carbonic oxide and carbonicanhydride, and vapours of acetone and acraldehyde. I n addition towater containing small quantities of acraldehyde, the only products inthe distillate are unaltered glycerol and pyruvine or the pyruvic ether ofglycide, MeCO*COO-CH,.CH<-O->, which is also obtained by thedistillation of glycerol with tartaric acid or glyceric acid.Probablycomposition with that just described. w. P. w.V. H. V.CH46 ABSTRACTS OF CHEMICAL PAPERS.the pyruvine is a product of the reaction between glycerol and glycericacid, the latter being formed as an intermediate product.The pyrnvine thus obtained crystallises in large, prismatic needles,or tables, which melt a t 82" and boil a t 241" under a pressure of764 mm. C. H. B.Double Lactone of Metasaccharic Acid. By H. KILIANI (Bw.,20,2710-2716) .-The oxidation product of the lactorie of arabinose-carboxylic acid (Abstr., 1887, 465) dissolves readily in aqueousammonia, and from the solution the diumide of metasaccharic acid,C,H,,O,N,, separates as a white powder, consisting of microscopic,tabular, monoclinic crystals, which become yellow a t 170" and melt a t189-190" with complete decomposition.The compound has aneutral reaction, and when heated at 100" with potassium hydroxideFields the potassium salt of metasaccharic acid as a colourless syrup ;this becomes crystalline on stirring, and in aqueous solution doesnot reduce Pehling's solution.On treatment with a cold solution of phenylhydrazine hydrochloride(1 part) and sodium acetate (1.5 pwt), in water (10 parts), the oxida-tion product yields the monophenylh ydrazide of the lactone of meta-snccharic acid, Cl2HI40,N2 ; this crystallises in colourless, microscopicmales with 8 mol.H,O, dissolves readily in hot water and alcohol, andwhen rapidly heated becomes yellow at 185", and melts a t 130-192"with decomposition. If the mixture w i t h phenylhydrazine (which,to obtain the preceding compound is allowed to remain for 20 minutesfor the crysta,llisxtion to take place) is a t once poured into boilingwater, the diphenylhydj-azide of metasaccharic acid, CleH2206N,, separate8after 10 to 15 minutes in yellowish-white, microscopic scales, whichbecome yellow a t 210°, melt at 21 2-213" with decomposition, and arevery sparingly soluble in boiling water aiid alcohol. The solution inconcentrated sulphuric acid is coloured red or bluish-violet by ferricchloride.When the oxidation product (12 grams) is dissolved in water(300 grams), treated with 3 per cent.sodium amalgam (200 grams),and dilute sulphuric acid added gradually so that the solution neverbecomes alkaline, allowed to remain fire days with a farther 200 gramsof sodium amalgam, then treated with sulphuric acid and alcohol tofree the product from sodium sulpliate, and the mother-liquorevaporated, a syrup is obtained which still reduces alkaline coppersolution, and from which mannite (2 grams) crystallises on standingover sulphuric acid. The strongly acid mother-liquor seems to consistof the lactone of a bibasic acid (? metasaccharic acid), a strongly acidsyrup having similar properties being also obtained by continuedheating of the oxidation product with water, or by repeated evapora-tion of its aqueous solution.The oxidation product of the lactone of nrabinose-carboxylic aciddissolves in 18, not, 8, parts of cold water (compare loc.cit.), andreadily reduces alkaline copper solution. The aqueous solutions of itspotassium and sodium salts, even in the absence of free alkali, becomecolonred intensely red on heating, or when allowed to evaporatespontaneously (Ber., 20, 343). The author, however, concludes, froORGASIC CHEhlISTRP, 47the preceding experiments, that the oxidation product is not thelactone of a ketonaldehydic acid, but is a double lactone of meta-CH(OH)*CH*O.CO -saccharic acid, I ), orwhich, on account of its peculiar constitution is very labile, and ontreatment with alkalis even at the ordinary temperature undergoesmolecular change, or perhaps reduction to an aldehyde -compoundjielding mannite by the action of nascent hydrogen.Thiohydantoin.By R. ANDREASCH (Monatsh., 8, 407-424).-Loven has recently shown (Abstr., 1885, 241) that a methylene-groupsituated between a carbonyl-group and a sulphur-atom possessessimilar properties to the methylene-group in ethyl malonate andacetoacetate. With the object of ascertaining whether this is thecase in hydanto'in, the author has prepared the disilver-derivative, andfrom that the dimethyl-compound,Disilz~e~-tJ~iohydan.to'i?z, Ag2C3N,H2S0, was obtained by adding a warmaqueous solution of thiohydantoTn to ammoniacal silver nitrate. Itforms a white, granular substance, sparingly soluble in nitric acid,insoluble in ammonia.I t blackens when exposed to light. Whentreated with methyl iodide, the silver compound yields P-dimethyithio-hydantozn, XH C<,,.,,>. This substance is easily soluble inwater, sparingly in cold alcohol, crrstallises in hexagonal scales, meltsat 114", and decomposes at a slightly higher temperature. Whenoxidised in hydrochloric solution by barium chlorate, carbonic anhy-dride and mei-captan are evolved, and the residue is found tocontain carbamide, and a mixture of barium salts which cannot beseparated, but one of which seems to be barium methylsulphonate.When heated wit,h barium hydroxide, the hydantoi'n yields cyanamideand some sulphur compounds which could not be isolated.Witlh the aim of determining the constitution of tlhe above com-pound, the author atternpted to prepare the two isomeric dimethyl-hydanto'ins in other ways.a-Dimethylthiohydan.tozn,W. P. W.S*CMe2may be prepared by heating together dimethylthiocarbamide and chlor-acetic acid in aqueous solutioi~. It is easily soluble in water, alcohol,ether, and carbon bisulphide, crystallises in long, thin, colourlessprisms, melts at 71", and boils a t a rather higher temperature. Itvolatilises slowly a t ordiuary temperatures. It bas an odour some-what resembling that of nicotine. When heated with aqueous alkalis,it yields thioglycollic acid. The isonitl.oso-derivative, C,H,N,SO,,yields yellowish scales melting at 220". Imidocarbnminethioisobzl,tyri,:anhydride, C5N2H8S0, was prepared by heating together thiocarb-amide and x-bromisobutyric acid.It crystallises in plates, is easil48 ABSTRACTS OF CHEMEIIICAL PAPERS.soluble in alcohol and boiling water, sparingly in cold water, andmelts at 242". When oxidised with nitric acid, this substance yieldscarbamide and sdphoisohufyric mid, SO,EI*C,H,~COOH, which formsa barium salt, BaC,H,SO, + 4H,O, crystallising in needles, easilyRoluble in water, insoluble in alcohol. The sodium salt, Na,C,H,SO, +&H20, forms glistening needles eiisily soluble in water, insoluble inalcohol. The same sulpho-acid is obtained by the action of chloro-sulphonic acid on isobutyric acid. The action of ammonium sulphiteon a-bromisobutyric acid produces, however, an isomeric sulpho-acid,yielding an easily soIuble barium salt, BaC4H,S05 + 2H20, cryeta1-lising in needles.It is thus clear that this imido-anhydride is not, identical with the/3dimethglthiohydantoYn, as the author had anticipated. As it waspossible that in the formation of the imido-anhydride a transformationfrom the iso- to the normal butvric series had occurred, the authorS*CHEt prepared imidocarbaminethiobu~~,yric anhydride, NH : C<NH.co >,by the action of a-bromobutyric acid on thiocarbamide.This crystal-liRes in short, thick needles, easily soluhle in boiling water, and meltsat 200". It is not identical with the compound obtained from iso-butyric acid. The constitution of the latter is therefore still doubtful,but its formation may perhaps be due to the action of thiocarbamideon the methacrylic acid formed by the elimination of hydrogen bromidefrom the bromisobutyric acid,CH,: CMe*COOH + CS(NH2)2 = CHMe<Co.2GH>C 1 NH + H20.The consitution of the ,&compound would then be correctly expressedby the formula given above.Thiohydantok when treated with benzaldehpde yields amidinethio-cinnanzic ( b e n z ~ l i d e n e t h i o h y d n ~ ~ o ~ c ) acid, NH C(NH,)(COOH) CHPh ;this forms white, microscopic needles, insoluble in water, soluble inalcohol.Several salts of thioliydantoin are described.The subphate,(C3H,N,S0)2,H2S04, forms plates soluble in water ; the nitrate, flatneedles or prisms ; the ozalate, C,H4N2S0,C2H,04 + H20, prisms ;the pzcrate yellow, microscopic needles.Thiohydantoin is best prepared as follows : 50 grams of thiocarb-amide is dissolved in + litre water, and 62 grams of chloracetic aciddissolved in 50 C.C.of water added. The whole is heated a t 80-90"until reaction has ceased, and when cold it is gradually neutralisedwith soda, care being taken never to let the solution become alkaline.Orthothioxen and Orthothiophendicarboxylic Acid. By W.GR~NEWALD (Ber., 20, 8585-2587).-0rthothioxen (Paal, Abstr.,1887, 1101) is prepared by distilling an intimate mixture of 10 gramsof p-methyllerulinic acid and 17 grams of phosphorus trisulphide ina, capacious retort. 250 gi*ams of methyllevulinic acid yielded 150grams of pure product. It is a colourless, strongly refractive oil,h%ving an odour of petroleum ; it boils a t 136-137" (corr.).Sp. gr. at21" = 0.9938. When treated with 1 per cent. solution of potassiizm per-manganate, a monocarboxylic acid only is formed ; this melts a t 134.5".CH SSimilar a,cids seem to be produced with other aldehydes.L. T. TORGANIC CHEMISTRY. 49Ort7~othiophendicarboxylic acid, C4SH,(COOH)2, is obtained by theaction of 1 per cent. permanganate solution on the monocarboxylicacid ; the product is steam-distilled to remove unchanged mono-carboxylic acid. It crystallises in long needles which do not melt a t860", but decompose at a higher temperature. When heated withrcsorcinol at 200", a product is obtained which dissolves in strongaqueous alkali with dark-red coloration ; the colour changes to yellowon diluting with water; the solution then shows a yellowish-greenfluorescence.The silver salt forms white flakes irisoluble in water ;the barium saZt separates in colourless crystals, readily soluble in hotwater. The dimethyl salt crptallises from alcohol in colourless platesmelting at 595". N. H. M.Action of Carbonic Anhydride on Aromatic Amines. ByA. DITTE (Compt. rend., 105, 612--614).-When an aniline salt ismixed with an aqueous solution of a normal or hydrogen carbonate,carbonic anhydride is given off, and aniline separates in the free state,no aniline carbonate being formed. Carbonic anhydride is not solublein aniline, and does not combine with i t under ordinary pressure evenat -8', the temperature at which aniline solidifies.I€, however, dry carbonic anhydride and aniline are compressed ina Cailletet's apparatus, the auiline dissolves the carbonic anhydride,jncreasiug to about twice its original volume, and a limpid layer ofthe liquefied gas swims on the surface of the solution and volatilisesat 15" under a pressure of 40 atmos.If the compressed liquid iscooled to 8-10", it crystallises in transparent, white needles, andwhen the aniline and carbonic anhydride are in equal molecular pro-portions, solidification is complete. When the carbonic anhydride isin excess, it forms a, layer above the crystals. When aniline is inexcess, it does not at once dissolve the carbonic anhydride, and thefwo liquids form distinct layers, but on gentle agitation the carbonicanhydride is dissolved, and crystallisation takes place a t 8".It isevident that carbonic anhydride and aniline combine in equal molecu-lar proportions to form a compound which crystallises a t 8", andis liquid or remains in superfusion at loo, and decomposes when thepressure is released. The tension of dissociation a t different tempe-ratures is as follows :-Temperature . . . . . . . . . . 0" 2" 5" 7"Pressure in atmos. . . . . 6 9 17 28Orthotoluidiiie behaves in a precisely similar manner, and the com-pound crystallises in brilliant, white needles. The behaviour of meta-xylidene is similar in that the two liquids mix, but no crjstals formeven a t -12".Pyridine and its homoIogues show no tendency to combine withcarbonic anhydride ; the two liquids do not mix. C. H. B.Benzylidene Compounds. By L.ROHLER (,4nrzaZen, 241, 358-362) .-An alcoholic solution of berizylidenepara toluidine is convertedinto benzylparatoluidine by the action of sodium amalgain. TheVOL. LIV. 50 ABSTRACTS OF CHEMICAL PAPEM.base distils at 33.2-313", and solidifies in the course of several weeks.it is freely soluble in alcohol and ether. The hydrochloride is solublein alcohol and in hot benzene, and the sulphate is soluble in water.The nitroso-compound melts a t 53".Benxyl-~-na~~hthylamime cr;gstallises in prisms, and melts a t 68". Thenitroso-derivative forms yellow needles, soluble in alcohol, ether,benzene, and light petroleum.Benzy Zarnidodimethy Zaniline, prepared from the condensation-productof benzaldehyde and smidodimethylaniline, melts st 48", and distilswithout decomposition.The nitrosnnzins is deposited from alcohol inyellow needles.It melts a t 111-112°.It melts a t 127-128" with decomposition. w. c. w.Reduction Products of Bensylidene Compounds. By 0.FISCHER (AnnaZen, 241, 328-331).-The author has previouslypointed out (Abstr., 1886, 546) that 3 per cent. sodium amalgamreduces a solution of hydrobenzamide in absolute alcohol to dibenzyl-amine and monobenzylamine ; ammonia and toluene are alwaysliberated during the reaction. Under similar treatment, benzylidene-aniline is converted into benzylsniline.The salt which is deposited when nit,rosobenzyIa,niline is treatedwith a,lcoholic hydrogen chloride is a mixture of benzylaniline hydro-chloride and benzylidene aniline.w. c. w.Hydroxybenzyliden 8 Compounds. By 0. EM MERICH (AnmaZen,241, 343-358) .-Orthohydroxy benzy Zandine, HO*C,H,*CH,-NHPh,is obtained by the action of sodium amalgam on a solution of hydroxy-benzylideneaniline in absolute alcohol. It melts at 106", and issoluble in alcohol and ether. The sulphate and hydrochloride arefreely soluble in water. The platinochloride forms reddish-yellowneedles, melting a t 184" with decomposition. A tetranitro-derivative,C,H9NO(X02),, is formed when the base is treated with a mixture ofsulphuric and nitric acids. It melts a t 66" with decomposition, and issoluble in alcohol, acetic acid, and light petroleum.Orthohydroxz~ber~zyl~aratoZuid~ne, HO.C,H,.CH,.NH.CsH,Me, ob-tained by the reduction of the hydroxybenzylideneparatoluidine,crystallises in white plates and needles, and melts at 116".It issoluble in alcohol and ether. The sulphate and hydrochloride dissolvefreely in water. The platinochloride crystallises in needles. Thetetranitro-derivative formR yellow needles, soluble in alcohol, benzene,and acetic acid. By the action of methyl iodide,the base is converted into ortl~omethoellben~uy~aratoluidine,It melts a t 168".OMe.CsH4*CH,-NH*C6H4Me,a crystalline compound melting at 110", and soluble in alcohol, ether,hnd benzene.Orthodih ydroxydibenzylarnine is prepared by the action of sodiumamalgam on an alcoholic solution of hydrosalicylamide. It crystal-]ifies in needles, melts a t 170°, and dissolves freely in ether, alcohol,benzene, and light petroleum.The sulphate, nitrate, and hydroORGANIC CHEMISTRY. 51chloride are soluble in water.needles, and is soluble in water.yields on reduction orthoh2/dro;eybe.1~zyl-p-n~ph~h~lam~t~e,The platinochloride crystallises inThe condensation compound of salicylaldehgde and p-naphthyleminen crystalline substance melting at 147". It is soluble in alcohol, ether,benzene, and light petroleum. The alcoholic solution exhi bits areddish-violet fluorescence. The sulphate is liquid, and the platino-chloride crystallises with difficulty.Orthohydrozy benayl-p-n,a~hlhylnitrosamin,e melts at 165" with decom-position. On exposure to the air, the compound decomposes spon-taneously at the ordinary temperature. It is soluble in alcohol andether.Orthomethoxybenzyl-~-naphthylain,ine crystallises in needles,melts at 92", and dissolves freely in alcohol and ether.Parahydroaybenxy laniline, prepared from parahydroxybenzylidene-aniline, is soluble in alcohol and ether. It melts a t 208", and forms acrystalline platinochloride.Pal.ahydroxybenzyZtol1~idine melts at 186". Parahydroxybenzyl-P-nnphthylamine melts: at 117". The sulphate is soluble in alcohol, butalmost insoluble in water. The nitrosamine melts at 142", and dis-solves in alcohol and ether. It is unstable. w. c. w.Anisylamines. By 0. J. STEINHART (AnubaZen, 241, 332-343).-A solution of anishydramide in absolute alcohol is converted into amixture of mono- and di-anisylamine by the action of sodium amalgama t the ordinary temperature.Dianis?ylanaine, NH(CH2.C6H,*OMe)2,forms white, needle-shapsd crystals soluble in alcohol and ether, Itmelts a t 34", and decomposes on distillation. The hydrochloride issoluble i n alcohol, and crystallises in fiat prisms. It melts at 243".The platinochloride is crystalline but unstable. The nitroso-derivative,(OMe-C,H,-CH,),N*NO, crystallises in needles, and melts at 80". Anisykamine is a colourless liquid boiling at 220-223". It, is miscible withalcohol, ether, and water, and it absorbs carbonic anhydride from theair. It can be separated from dianisylamine by its volatility in acurrent of st,eam. The hydrochloride forms white plates which arefreely soluble in water, and melt at 230". The platinochloride crystal-lises in pale-yellow, glistening needles.An i s y 1 nnil ine, MeO*C6H4*C H,*NH P h , prepared from a nish ydrani lid e,crystallises in prisms, and dissolves freely in the usual solvents.Itmelts at 64*5", and forms a crystalline hydrochloride, sulphate, andplatinochloride. The nitroso-derivative melts a t 104". It crystallisesin prisms, and is soluble in alcohol.Anish ydroparatoluide, OM&C6H4-CH NC6RbMe, forms whiLe needles,and melts a t 92". Anisyl~aratoluidilze, OMe.C6H4*CH2*NH2*CsH4Me,forms white prisms, melting a t 68". It is soluble in all the usualsolvents with the exception of water. The hydrochloride and platino-chloride are crystalline, but the salts have a tendency to decom-pose when their solutions are evaporated. The rdrosamine melts at108".Anisaldehyde and orthotoluidine condense, forming anishydrortho-It melts at 210".e 52 ABSTRACTS OF CHEMICAL PAPERS.toluide, which yields orthotoluylanisylamine on reduction.The basemelts a t 55".Anis y Zid enenap hi! h y lam ine ( /3) , OMe C6H4* C H N C 1oH7, crys t alli ses inplates, and melts at 98". Anisyl-P-naphthyZa??/,ine is soluble inalcohol, benzene, and in light petroleum. It melts at 101". The saltsare sparingly soluble in water, and are rather unstable. The nitros-amine melts at 133", and crystallises in plates. AnisylidenedimethyZ-paraphenylenediamhze forms greenish-yellow needles. It melts at148", and yields on rednction anisyldimethylpcrr~pheny lenediamine,OMc*CsH4.CH,*NH.CsH4.~Me~. This base crystallises in plates, andmelts a t 104".The alcoholic solution decomposes on exposure to theThe nitrosamine is an oily liquid.air, and the nitroso-compound is unstable. w. c. w.Salts of Picramic Acid. By A. SMOLKA (Monatsh., 8, 391-398).-The salts of this acid having heen but little studied, the nut,hor hasprepared and examined a number of them. Tn some cases they wereobtained by the direct action of picramie acid on the metallic carbon-ate, in others by double decomposition. The following table showsthe results obtained :--Formula of salt. Description.Dark red crystalsDark reddish-brown walesYellow, microsco-pic needlesGreenish - yellowneedlesScarlet, microaco-pic crystalsDull yellow, mi-croscopic needleSmall, reddiuh-brown needlesDark &eel-greenneedlesGreenish- yellow,amorphouspowderamorphouspowderDark olive-green,Ratio of solubility inwater.I.Boiling.1 :4Q% at 15 -5'1 : 19.9 ,, 17 '01 : 5890 ,, 23 '01 : 1215 ,, 23 *O1:21010 ,, 17.51?3172 ,, 18.01 :2632 ,, 20.51 : 97 *5 ,, 19 -0insolubleinsoluble11. Cold--freelyfreely1 : 1842I : 3181: 124811 : 11511 : 1494freelyI : 3292I : 3538Tempera-ture ofdecompo-sition.--abont150'140140-150°140°120140-145O140-150Moo1401 a-1 45'If the salt is heated slowly, the decomposition takes place quietly,but if rapidly, explosions occur, especially with the sodium and leadsalts. The aqueous solutions vary in colonr from pale orange to darkblood-red. L.T. TORGANIC CHEMISTRY. 53Chlorine and Bromine-derivatives of Citraconanil. By T.MORAWSICI and J. KLAUDY (Monatsh., 8, 399-406) .-Citraconpara-chloranil, C5H402 : N-C6H,C1, is formed (together with chloranilines)when a stream of chlorine is passed into water in which finely-dividedcitraconanil is suspended. It crystallises in white, glistening needles,soluble in alcohol and melting a t 114,5". With care i t may be sub-limed in long, glass-like needles. When heated with ammonia, ityields parachloraniline and citraconic acid, showing the correctness ofthe above formula.When bromine acts on citraconil, bronzocitraconprLrabrornani1,C,H,BrO, : N*CsHpBr, is formed. This crystallises in white, shiningneedles, soluble in alcohol and melting at 178".It can be sublimed,b u t decomposes if heated rapidly. When heated with ammonia,parabromaniline is formed, together with hydrogen bromide, muchresinous matter, and an acid of the formiila C7H,BrOa. This acidyields a silver salt, AgzC7€3,B.rO4, crystallising in prisms, and a leadsalt, PbC7H7Br04, forming microscopic crystals. It appears, therefore,that the original bromo-derivative contained one bromine-atom in thecitraconic nucleus, and that when heated with ammonia this nucleusis converted into a higher brominated homologue of the citraconicseries, together with other bye-products.When only enough bromine is employed for the formation ofeitraconparabromanil, white, crystalline needles melting at about 11 8"were obtained, but this compound has not yet been obtained in a purestate.L. T. T.Action of Phenylhydrazine on E thy1 Chloracetoacetate. ByG. RENDER (Ber., 20, 2747--2752).--Ethyl chloracetoacetate reactswith phenylhydrazine in ethereal solution to form a compound,C12H14N202 ; it is probable that a hydrazine-derivative,NHPh*N CMeCHCl-COOEt,is at first formed, which is subsequently converted into a compound,NPli : N*CHMe*CHCl*COOEt, and finally by abstraction of theelements of hydrogen chloride into NPh : N-CMe : CH-COOEt, orethy lic P-phenylazocrotonate. This substance crys tallises in long, redneedles, meltling at 50*5", very soluble in alcohol ; on saponification, ityields a potassium salt, NPh N*CMe: CH-COOK, which formsreddish-yellow scales, very soluble in water, insoluble in alcohol.The salt on acidification yields the corresponding anhydride as abrownish-yellow powder, whose purification presents considerabledifficulty.Ethylic /3-phenylazocrotonate when reduced yields phenyl.rnethylpyrazolone and its first oxidation product or its bis-derivn-tive, together with a substance not further examined. The bis-deri-vative yields with bromine a compound, C2,€€,,NaO,Br, which crystal-lises in colourless needles, melting a t 217" with decomposition.a-Naphthylamine with ethylic chloracetoacetate yields a compound,C,,J316N02C1 ; this crystallises in colourless prisms, meltiiig at 75" ; itsformation is due to a change analogous to the first of the reactionsgiven above in the case of phenylhydrazine. V. H.V54 ABSTRACTS OF CHEMICAL PAPERS.Isomeric Phthalophenylhydrasfnes. By G. PELLIZARI (Gaxnetta,17, 278--285).-The author has previously described two isomericphthalyl-derivatives of phenylhydraxine obtained by the action ofthis base on phthalimide and phthalic anhydride respectively (Abstr.,1886, 125). To the former, melting at 179", the constitutionNHPh*N <Co>C6HH", to the latter, melting a t 210°, the constitution GONPh-CO <NH-CO>CGHa was assigned. If these formule are correct, amethyl-derivative of the former, or anilophthalimide, on separationof the phthalyl grouping, should yield a symmetrical methylphenyl-hydrazine, NPhMe*NH2, that of the latter, or phthalophenylhydrazine,the symmetrical derivative, NHPh-NHMe. Phthalophenylhydrazine,heated with methyl iodide and alcohol, yields a methyl-derivative,crystallising in long, yellowish-white prisms, which melt at 125"without decomposition ; this is decomposed by concentrated hydro-chloric acid, yielding methylphen ylhydraeine, NHPh-NHMe.Theconstitution of the isomeride has previously been proved by Eotte,but in answer to his criticisms (Abstr., 1887, 770) it is shown thatphthalic anhydride and phenylhydrazine, reacting in molecular pro-portions, give either anilophthalimide or phthalophenylhydraxine,according to the temperature ; at ordinary t'emperatures, phenyl-hydrazine-phthalic acid is at first formed, which on subsequent heat.-ing yields ariilophthalimide ; if, however, the reaction proceeds at 163",the melting point of the acid, a t which temperature it is unstable,phthalophenylhydrazine is formed in the greater proportion.Dyes from Aniline Chromates.By S . GRAWITZ (Compt. rend.,Azophenine. By 0. N. WITT (Bey., 20, 2659-2660).-A yplyto Fischer and Hepp (Abstr., 1887, 1105), in which the author poiiitsout that the constitutional formula proposed by them is inadmissible,since azoplienine does not form an acetyl-derivative when heated withacetic anhydride, and yields a considerable quantity of aniline ontreatment with tin and hydrochloric acid. On these grounds, theauthor adheres to his published views on the constitution of azo-By P. BARBIER and L. VIGNON (Compt.rend., 105, 670-672) .-Paranitrosodimethylaniline has no action onaniline at the ordinary temperature in presence of water, glacialacetic acid, or an excess of aniline, but a t 80" there is an extremelyviolent reaction.If equal molecular proportions of aniline and paranitrosodimethyl-aniline are dissolved in eight times their weight of ethyl alcohol of 92",and heated on a water-bath, a reaction takes place a t 80", with con-siderable development of heat, and is complete in about three hours.When the liquid is cooled, a solid separates, which is washed withdilute hydrochloric acid, and then crystallised from boiling toluene.I'etranaethyZlliumido-azobe.nzene is thus obtained in brilliant, brown,V.H. V.105, 576--577).-A question of priority and patent right.phenine (Abstr., 1887, 821). w. P. w.Substituted SafraninesOHBAKIC CHEMISTRY.35crystalline plates, which melt imperfectly a t 218-220" without vola-tilisation, and when reduced with zinc and salphuric acid, yielddimethylparaphenylenediamine in almost theoretical quantity. It. isalmost insoluble in water, and only slightly soluble in dilute acids, butdissolves in concentrated acids forming deep red solutions.The alcoholic liquid separated from the tetramethpldiamido-azo-hneene has a deep, violet-red colour, and when evaporated leaves aviscid residue, which dissolves almost completely in water. Whenthis solution is mixed with sodium carbonate, a precipitate is formed,and if the filtrate is mixed with sodium chloride, dimethylphenosafra-nine Beparates, and is purified by repeating the treatment with sodiumcarbonate and chloride.The equation representing the reaction is-ZNHzPh + ~C~EIANO*NM~~,HC~ = ClsHZON, + CWHIgNdCl +3H20 + 2HC1.C. H. B.Action of Acid Amides on Bromacetophenones. By M. LEWY(Ber., 20, 2576-2580) .-When bromacetophenone is heated withacetamide (2 parts) a t l't0-130", for one hour, a base, C,,H,NO, is ob-tained. This forms long, colourless needles, readily soluble in alcoholand ether; it melts a t 45", and boils a t 241-242'; it has slightlybasic properties. The hydrochloride, CloH9N0,HCl, crystallises insmall needles ; when treated with an excess of hydrogen chloride, ityields a heavy, fuming oil, possibly an acid salt. The platino-k&m&, (CloN,NO),,H,PtC16 + 2Hz0, separates in dense, yellowflakes, consisting of' orange-coloured needles, which melt a t 130-140with decomposition.The subhate forms white, lustrous plates, whichdecompose in contact with water. The picrate crystallises in lemon-coloured needles, melting at 133-134'.The formamide base, CgH,NO, prepared by heating bromaceto-phenone with formamide, is a thick, colourless oil, which becomesyellow when exposed to air ; it solidifies when cooled with a freezingmixture, melts at 6", and boils at 220-222'. The hydrochZoride meltsat 80". The pZutinochZoride (with 2 mols. HzO) crystallises in slender,yellow needles. The hermawtide base, CIBHIINO, is prepared by heatingbromacetophenone and benzamide a t 140-150" ; the product isextracted several times with boiling water, and the residue fractionallydistilled. It crystallises from alcohol in large, colourless plates,readily soluble in the usual solvents, melts a t 102-103", and boils a t338-340". The hydrochloride crystallises in slender, matted needles ;it is slowly decomposed by boiling water.N. H. hLIsonitroso-compounds : Isobenzaldoxime. By E. BECKMANN(Ber., 20, 2766-2768) .-When benzaldoxime is mixed with sulphuricacid in presence of ice, a solid, white substance separates out undercertain conditions ; sometimes an oil is obtained. The former, pro-bably a poly rneride of benzaldoxime, crystallises in glistening needles,melting at 128-1.30"; it is distinguishable from benzamide by itscrystalline form. The oil is benzaldehyde, produced by the re-forma56 ABSTRACTS OF CHEMICAL PAPERS.tion of the oxime and its subsequent decomposition by the acidpresent.V. H. V.Condensation of Cinnamic Acid with Gallic Acid. By E.JACOBSEN and P. JULIUS (Bey., 20, 2,588-25,89).--St?lrogaZZo7,CI6Hl0O5, is prepared by heating cinnamic acid (10 parts), gallic acid(12 parts), and sulphuric acid (150 parts) at 45-55', for two to threehours. The product is poured into water, filtered, and the precipitatewashed with slightly acidified boiling water. It crystallises in bright-yellow, microscopic needles, which do not melt a t 350"; it is verysparingly soluble, except in boiling alcohol, aniline, and glacial aceticacid, and sublimes when carefully heated in large, yellow, lustrousneedles. Alkalis dissolve it with green colour, which changes to blue,and then red, when the solution is heated.The solution in sulphuricacid is yellowish-red. When oxidised with dilute nitric acid, it yieldsa large amount of phthalic acid. The triacetyl-cleri~nfive, C22H1606,crystallises in pale-yellow needles. With mordants, styrogallol yieldsshades similar to those obtained with nitroalizarin. N. H. M.Paradiphenoldicarboxylic: Acid. By R,. SCHMITT and C.KRETZSCHMAR (Bey., 2 0, 2 703-2 704) .-Pu~*adiphenoZdicarboayl~c acid,COOH-C6H,( OH).C6H,( OH)*COOH, is obtained when sodium para-diphenol is heated in an autoclave with liquid carbonic anhydride at200" for nine hours, and the resulting product is treated with an acid.It crystallises in small, microscopic needles, melts at 131" with theevolution of carbonic anhydride, is not volatile with steam, has aslightly bitter taste, and is readily soluble in ethyl and methyl alcoholand in ether, sparingly soluble in water (100 C.C.of water at 15" dis-solving 0*0052 gram of the acid), and insoluble in benzene and chloro-form. Suspended in water, it is coloured bluish-violet with ferricchloride, the colour changing to a dull brown on heating, whilst thesodium salt when similarly treated yields a deep blue solution, fromwhich indigo-blue flocks separate. w. P. nT.Orthamidotriphenylmethane. By 0. FISCHER and A. FRANKE L(Annalen, 241, 362-368) .--The preparation of diphenylquinolyl-methane has been previously described by the authors (Abstr., 1886,561). The sulphate and picrate are precipitated on the addition ofsulphuric or picric acid to alcoholic solutions of the base.The nitro-derivative melts a t 213" with decomposition, and the amido-compoundon oxidation forms a riolet-coloured solution.Triphenylmethaneorthocarboxy lic acid is prepared by slowly addinga solution of the hydrochloride of the diazo-compound of amidotri-phenvlmethane to a solution of potassium cyanide and copper sulphatea t 9d". The crude product is sa,ponified with alcoholic potash, andthe acid precipitated from the aqueous solution of the potassium saltby hydrocliloric acid. Alcohol, ether, acetic acid, and benzene dis-solve the acid freely. It melts a t 162" and volatilises without decom-position ; i t is identical with the acid Baeyer (Abstr., 1880, 650)obtained f r o n phthalophenone.Orthoh ydrozytri~he?zylmet}~ane is formed by passing air through ORGANIC CHENISTRY. 57solution of dia zoamidotrip henylmet hane sulp hate, and boiling theproduct in a current of carbonic anhydride.It is soluble in alcoholand ether, and melts a t 118".The acetic derivative of amidotriphenylmethane melts a t 168-169",and is freely soluble in alcohol, benzene, and acetic acid. The thio-carbamide melts a t 12fjo, and dissolves readily in ether, carbon bisul-phide, and hot alcohol. w. c. w.Two Dihydroxynaphthalenes. By A. EMMERT (Anna.len, 241,368-373) .-$-Naphthol yields t w o sdplionic acids on treatment withsulphuric acid, and each acid is converted into a dihydroxynaphtha-lene by fusion with potmh.~-~-DihydroxynapJ~tl~alene melts a t 615-216", and dissolves freelyin alcohol and et,her.Ferric chloride produces a yellowish-whiteprecipitate. A t 120" alcoholic potash and ethyl iodide coiivert thedihydroxynaphthalene into an ethyl ether, Cl0H6( OEt,). It formssilky plates and melts at 162". The diacetate, C,oHt-I,(OAc)2, melts a t175".P-a- Dihydroxynaphthalene is soluble in alcohol, ether, benzene, andwater. It melfs a t 1 7 8 O , and gives a blue precipitate with ferricchloride. The dietliyl ether crystallises in prisms, melting at, 67", andthe diacetate forms rhombic plates and melts at 108". W. C. W.Derivatives of Di-p-naphthylamine. By C. RIS (Ber., 20,261 8-2628). -Crude di-/3-nap hthylamine is purified by distillationand crystallisation from benzene ; it melts at about 471".Met7&yldi-P-naphlh?/Inmine, NMe( C1,H7)2, is prepared by heating di-naphthylamine and methyl iodide (equal molecular weights) for fivehours at 150", and ci-ystallises from alcohol in nearly colourless needlesmelting a t 139-140".It dissolves rather readily in warm alcohol,glacial acetic acid, benzene, and ether, and is almost insoluble in lightpetroleum. The alcoholic solution shows a bluish-violet fluorescence.It is insoluble in dilute mineral acids; the hydrochZoride forms slender,lustrous crystals, which decompose quickly in presence of water. Thesolution in strong sulphuric acid is yellow, and acquires an intensebrown colour on addition of a trace of a nitrite or nitrate.Ethyldi-/3-naphthyZamine, NEt(C&€,),, crystallises in almost colour-less prisms melting a t 231"; it resembles the methyl compound insolubility ; the hydi-och Zoride is a white, crystalline powder.H e t h y l di-~-)taphth!iZcarba;lriate, N( CloH,),.COOMe, is obtained byheating di-/3-naphthylamine and methyl chloroformate (equal weights)at 150-160" for two and a half hours.It crystallises from alcoholin slender, white needles, melting at 113-114", dissolves readily inalcohol, ether, and benzene. It crystallises from benzene with $ mol.CcH6.Tetrabromodi-p-naph tJyEamine, C20H,,Br,N, is prepared by the actionof bromine (4 mols.) on a well-cooled solution of di-p-naphthylaminein glacial acetic acid. It crystallises in long, white, matted needles,which melt a t 245-2246".It dissolves rather readily in hot benzeneand cumene, very sparingly in ether, light petroleum, and alcohol.It distils almost without decomposition58 ABSTRACTS OF CHEMICAL PAPERS.It is not attacked by boiling concentrated aqueous potash ; brominedoes not act on it.Octobromodi-P-?taphthyZanzine, CzoH,Br,N, is formed when /3-dinaph-thylamine, as dust, is added to an excess of bromine in presence ofalnminium bromide. The product is stirred well, and the yellow pre-cipit'ate, after being treated with alkali and with boiling hydrochloricacid to remove adhering bromine and aluminium, is crystallised fromcumene. It forms slender, white needles, which melt at about 300",and dissolve readily in boiling nitrobenzene, less in boiling cumene ;in other solvents it is sparingly or not at all soluble.is prepared by adding thecalculated amount of sodium nitrite dissolved in a little water to itmixture of alcohol and sulphuric acid containing di-P-naphthylaminein the form of dust.It crystallises from benzene in groups of whiteneedles, melting at 139-lPO", sparingly soluble in alcohol, readily inbenzene.Dinit.l.odi-P-naphthy~amin.e, Cz0H,3N(N0z)2, is formed when strongnitric: acid is slowly added to a cooled solution of the amine in glacialacetic acid; it separates after some time as a yellow powder. Itcrystallises in yellowish-red needles, melting at 224-225", readilysoluble in boiling cumene, less soluble in benzene, and almost in-soluble in alcohol and ether.T~tran.itrorZi-p-na~hthz/Z~zmine, CzOHllN(N02)P, is obtained by gradu-ally adding nitric acid (3 pn.rts) mixed with glacial acetic acid to asolution of dinaphthylamine (1 part), in glacial acetic acid.Itcrystallises from nitrobenzene in grains, which melt at 285-286",and detonate when more strongly heated. It is sparingly or not atall soluble in the ordinal-y solvents, readily soluble in boiling nitro-benzene.Hexanitrodi-P-naphthylamine, CzoH9N( NOz),, prepared by heatingthe finely-powdered amine with fuming nitric acid, could not be ob-tained in crystals. It dissolves readily in alcohol, less in glacialacetic acid, and is almost insoluble in ether, benzene, cumene, andnitrobenzene. Alkaline carbouahes dissolve it readily. When mixedwith excess of copper oxide, it decomposes with explosive violence,and was therefore not analysed.The potassium and ba&m salts wereaualysed ; they are both amorphous.Benzoylortko?iitrodi-P-n~phthylscmine, C2THlsNO*N02, is prepared byadding a mixture of fuming nitric and sulphuric acids to a solution ofbenzoyldi-p-naphthylamine in cold glacial acetic acid, and subse-quently heating the whole at 50-60". It crystallises from benzenein well-formed, yellow, transparent crystals (with 1 mol. C6H6), melt-ing at 95". Crystallised from alcohol it melts at 168". It dissolvesreadily in warm benzene, less in alcohol.Benzenylriap?~thyle7Leanzidine, N< CPh >NGlaH,, is obtained by re- GoH,ducing benzoylnitrodinaphthylamine dissolved in glacial acetic acidwith excess of tin and hydrochloric acid.It crystallises from benzenein transparent, slender needles (with 1 mol. c,H6) melting at 113-114" ; when crystallised from other solvents it melts at 163". It sub-limes when carefully heated in small, colourless plates, and distilsNitrosodi-P-naphthyZn?nine, M0.N ( C1ORGANIC CHEMISTRY. 59with slight decomposition. I t is readily soluble. The hydrochlorideforms slender, matted needles which decompose in contact with water.Naphthaphenaaine. By P. BRUNNER and 0. N. WITT (Ber., 20,2660-2663). - Naphthaphenasinesulplzowic acid is obtained whennaphthaphenazine is heated with 10 times its weight of 35 per cent.fuming sulphuric acid at 100" for 12 hours. It crystallises in orange-red needles, melts above 290°, and is soluble in water and alcohol.Inconcentrated sulphuric acid it dissolvss with a deep orange-browncolour, which becomes orange-yellow on dilution. The sodium salt,,C16H,N2*SOsNa + 2H,O, was prepared. On fusion with potassiumhydroxide, a ewrhodol is obtained which differs from that previouslydescribed (Abstr., 1887, 153), since it dissolves in hydrochloric acidwith a red colour, and in concentrated sulphuric acid with A dark-green colour changing to red on dilution. A similar compound hasbeen prepared by diasotising the eurhodine formed by the reductionof nitronap h t haphenazin e.Cy artowph thaph enazine, C16H9N2* CN, is obtained when sodiumnaphthaphenazinesulphonate is distilled with potassium cyanide ordry potassium ferricyanide. Crystallised from cumene, it melts at236-5237', and dissolves in concentrated snlphuric acid with a cherrj-red colour, which changes through orange to yellow on dilution.Ifheated with hydrochloric acid under pressure, it is decomposed intonaphthaphenazine and formic acid, but when heated with alcoholicpotash at 220-250" it is partially converted into naphthaphenaxine-carboxylic acid. This is sparingly soluble in the ordinary solvents,melts above 360", and dissolves in concentrated sulphuric acid with adeep-red colour, changing to yellow on dilution. The potassium saltcrystallises in white needles and is sparingly soluble in water.N. H. M.w. P. w.Naphtholcarboxylic Acids. By R. SCHMITT and E. BURKARD(Ber., 20, 2699-2704) .-a-NnpIit?~olcarbo~l~c acid (m.p. 187") canbe prepared by heating sodium a-naphthol with liquid carbonic anhy-dride in an autoclave at 130°, and is a comparatively stable compound(compare Abstr., 1887, 732), since it is only partially decomposed byprolonged boiling with water, in which it is very sparingly soluble.The aqueous solution is coloured greenish-blue by ferric chloride.The sodiurn salt, with 3 mols. HzO, crystallises in large, thin, nacreousscales; the ammoniurri salt forms long needles; the calcium and bariumsalts crystalhe in long needles. The methyl salt, OH*CloH6*COOMe,melts at 78", the ethyl salt at 49', and the phenyl salt at 96". Theacetgl-derivative, OAc.Cl~~6*COOH, melts at 158" ; the bromo-deriva-tive, OH*CloH&r*COOH, melts at 238" ; the nitro-derivative,melts at 202", and yields P-nitro-a-naphthol when 'heated with lime ;the amido-derivative melts above 200", and its acetyl-compound at183".paraxobenzenesulphonic acid-a-naphtholcarboxylic acid,OH.C1&L,( NO,) .C 0 OH,Metadiazonaphtholcarboxylic acid, OH*CloH5<, CO@ N>, andS03H*C6H4*N2* C~oH~(OE€) *C 0 OH60 ABSTRACTS OF CHEMICAL PAPERS.were also obtained, and the latter on reduction with zinc andhydrochloric acid yields an amido-a-naphtholcarboxylic acid whichcrystallises in colourless, prismatic needles, is very sparinglysoluble in water, and melts above 200", but differs from theamido-derivative just described since its acet y I-compound meltsat 195O.When sodium P-naphthol is similarly heated with liquid carbonicanhydride in an autoclave at 130", /I-naphtholcarboxylic acid is ob-tained, and is sepnrahed by treating the product with ammoniumcarbonate and precipitating with hydrochloric acid.This acid readilydecomposes on heating, and shows all the properties of Kauffmann'sacid (Abstr., 7 882, lOtj8). Ferric chloride colours its aqueous solu-tion a pure blue. The ammoniim salt crystallises in yellow needles,whilst the barium, calcium, and silver salts. resemble the correspondingsalts of the a-acid. The methyl salt melts at 76", and the ethyl salta t 5 5 O .When sodium P-napht,hol is heated a t 280-290" in a current ofcarbonic anhydride, absorption of the gas rapidly takes place, and aproduct is obtained consisting of &naphthol, undecomposed sodium&naphthol, and ~-?LaphthoZcarboxylic acid. This acid is extremelystable, and crystallises from water in lustrous, rhombic, Tellow scales,which melt a t 216" without decomposition, and are readily soluble inalcohol and ether, soluble in tolnene, benzene, and chloroform, andsparinrrlv soluble in hot water.Ferric chloride colours the aqueoussolution blue. w. P. w.Terpenes. Part VI. By 0. WALLACH (Annulen,, 241,315-328).-The compound which the author (Abstr., 1887, 967) recently de-scribed as terpene nitrite is terpinene nitrosite. It forms monocliniccrystals ; a : b : c = 1.0103 : 1 : 0.66978 ; /3 = 80" 31'.Terpinene nitroZeth,yZarnine, NHEt2*CIoHl, : NOR, is obtained byboiling for a short time an alcoholic solution of the nitrosite with astrong aqueous solution of ethylamine.The crude product is pouredinto water, the precipitate dissolved in hydrochloric acid, and the basereprecipitated by ammonia, The base melts a t 130-131", and dis-solves in boiling alcohol, ether, chloroform, and in warm dilutesolutions of alkalis. The hydrochloride, C12H,N,0,HC1, is crystalline,and dissolves freely in water and alcohol. The nitroso-compoundmelts a t 133-133". It is decomposed by boiling with an excess ofhydrochloric acid, yielding hydroxylamine.Terpinene nitroldiethylamine, NEt2*CloHl, : NOH, melts at 11 7-1 18".Terpinene gzitrohethylarnirze, NHMe.CloH15 : NOH, crystallises inprisms and melts at 141". The dimethylamine, NiNe,*CloHl, NOH,melts a t 160-161". It dissolves in chloroform.The amylamine-compound is less soluble in alcohol and ether thanthe preceding substances.It melts a t 118-119". The piperidiwe,CloHlsNO,NCsHlo, melts a t 153-154'. It is insoluble in alkalis, butits salts are freely soluble in water. The hydrochloride is obtained asan oil on passing dry hydrogen chloride into an ethereal solution ofthe base.Terpinene rritrolamine is formed by adding ammonia to a hoORGANIC CKEiWSTRT. G1alcoholic solution of terpinene nitrosite. After recrystallisation fromhot water it melts at 116-118".By adding a mixture of nitric acid and amyl nitrite to carvene orcitronene saturated with dry hydrogen chloride, Maissen (Gazzettu,13, 99) obtained a crystalline compound melting with decompositiona t 1 1 ~ 1 1 5 " .The author has obtained the same or similar deriva-tives from cinnamene and dipentene. They melt at 109" and 110-111" respectively, and act oh organic am"ines, yielding crystallinebases. vv. c. w.Constitution of some Pyrroline-derivatives. Ry G. CIAMICIANand P. SILBER (Ber., 20, 2594-2607 ; compare Abstr., 1887, 597).-Uibromodiacetyl~~rrol~ne, C4NHAc,Pr2, is prepared by the action ofbromine vaponr on a warm solution of 2 grams of pyrrylenedimethyl-diketone in 700 C.C. of water. It crystallises from alcohol in whiteneedles melting a t 1'71-1 72", insolrible in waber, soluble in alcohol,ether, and in alkaline carbonates. Nitric acid oxidises it readily a tthe ordinary temperature t o dibromomale'irnide ; the constitution ofthe base is therefore [Br, : Ac, = 3 : 4 : 2 : 51.C4NHBr2Ac*NOZ [Br2 : Ac : NO, =3 : 4 : 2 : 51, is formed when dibromodiacetylpyri-oline (8 grams) isdissolved in fuming nitric acid (80 grams), and crystallises fromalcohol in long, white needles melting at 206".It is soluble inalcohol, ether, ethyl acetate, hot glacial acetic acid, and benzene, verysparingly soluble i n water, insoluble in light petroleum. Alkaliliecarbonates dissolve it readiiy with intense yellow colour.Dinitrodibromopyrroline, C4NHBr,(N02)2 [= 3 : 4 : 2 : 51, is ob-tained by the action of a well-cooled mixture of sulphuric and fumingnitric acids on the mononitro-compound. It crystallises from waterin large, yellow plates (with 1 mol. €LO), which melt at about169" with decomposition ; it is readily soluble in ether, alcohol, hot.water, and hot benzene, and dissolves in alkaline carbonates withevolution of carbonic anhydride, If the mixed acids are allowed toact on the mononitro-compound at the ordinary temperature, dibromo-maleamide, melting at 227", is formed.The latter is also formedwhen dinitrodibromopyrroline is heated at 165" ; nitric oxide isevolved.When dinitrodibromopyrroline is heated with sulphuric acid(20 parts) it is converted quantitatively into dibroniomaleic acid. It isprobable that the imide of dibromomale'ic acid, and. therefore, maleic~-itr~dibromacetyI'PYrO'o liire,Lcid also, are symmetrically rather than unsymmetrically constituted :CBr*CO CBr *CO <Csr.Co>NH, rather tha,n <C.c&NH>.(Compare Anschutz,Abstr., 1887, 916).Dibromopyrrolinedicarboxylic acid behaves towards fuming nitricacid in a manner similar to dibromodiacetylpyrroline ; dinitro-dibromopyrroline is formedidentical with that obtained from dibromodiacetylpyrroline. Thereaction shows that the two carboxyl-groups in pyrrolinedicarboxylicacid have the positions 2 : 5.Methyl dibromopyrrolinedicarbox2/late, CJYHBr,(COOMe)?, is ob-[NO, : NO, : B r : Br = 2 : 5 : 3 : 4G2 ABSTRACTS OF CHEMICAL PAPERS.tained by dissolving methyl pyrrolinedicarboxylate (3 grams) in water(1 litre), and saturating the lukewarm solution with bromine vapour.The yield is 4.5 grams of pure product. It crystallises from alcoholin long, white needles, melting a t 222", soluble in ether, almostinsoluble in water.When 2 grams of the salt is a,dded to 40 gramsof fuming nitric acid a t -Is", and the whole poured into 400 C.C. ofice-wa,ter, and treated with potash (30 grams), the compoundC4H,BrNOa is obtained. It is a crystalline compound, melting a t168-171" with deconiposition, soluble i n ether, alcohol, and hotbenzene, rather sparingly soluble i n water, and insoluble in lightpetroleum. It dissolves in alkaline carbonates with evolution of car-bonic anhydride. The constitutional formula CBrO*C(NOH)*COOMeis suggested for it.Methyl dibromacetylcnrbopyrrolate, C*NHBr,Ac*COOMe, is pre-pared in a manner similar to the methyl salt of the bromodicarboxylicacid, which it completely resembles in its behaviour towards fumingnitric acid.Dibromacety lmeth y lpyrroline, C7H7Br,N0, is prepared by treatinga solution of 2 grams of acetylmethylpyrroline, melting a t 85-86'(Abstr., 1886, 719), with an excess of bromine.It crystallises fromdilute alcohol in long, white needles, of a silky lustre, melts at 161-162", dissolves in ether, carbon bisulphide, and chloroform, and issparingly soluble in boiling water. When the finely-powderedcompound is warmed with fuming nitric acid, dibromomalejimid e(m. p. 227") is formed. The constitution of acetylmethylpyrroline istherefore [Ac : Me = 2 : 51.In order to obtain further evidence as to the constitution of pyrnvylmethyl ketone and Schwanert's carbopyrrolic acid, tribromacetyl-pyrroline and methyl tribromocarbopyrrolate were converted intodibromomaleimide by the action of nitric acid.C4NHBr2Ac..N0, [Br : Br : Ac : NO,= 2 : 3 : 5 : 41, is prepared by the action of bromine on nitracetyl-pyrroline, melting at 197" (Abstr., 1885,810 and 992).It crystal-lises from alcohol in needles melting a t 1 7 5 O , soluble in ether, warmdcohol, and glacial acetic acid, sparingly soluble in warm water,insoluble in light petroleum. The non-identity of this compoundwith the dibromo-derivative described above, and the probabili t ythat in the nitracetyl-compound (m. p. 197") the acetyl-group has thea-position, make it probable that the nitracetyl-compound has theconstitution [NO2 : Ac = 3 or 4 : 2 or 51.A table of all pyrroline-derivatives (halogen-derivatives and ethersexcepted) of known constitution is given.Synthesis of Pyridine and Piperidine-derivatives.By C. PAALand C. STRASSER (Ber., 20, 2756--2766).-Diphenacylacetic acid(Abstr,, 1887, 261) when treated with alcoholic ammonia yields theammonium salt of ad-dip heny ldi~y~ropyridine-cy-carboa y l i c acid,C,NH,Ph,*COONH*. This salt is soluble in water and concentratedhydrochloric acid ; on acidification with sulphuric acid, the corre-sponding acid separates, but is quickly decomposed. On dry distilla-tion, ammonia is given off, and aa'-di~heny~yridir~ecnrboxyl,ic acid,liibrornon;tracefy.?pyrroline,N. H. MORGANIC CHEMISTRY. 63C5NH,Ph,.COOH, is produced, which after purification crystallises indelicate, white needles or prisms, melting at 275', soluble i n alcohol,sparingly soluble in chloroform.The acid is not altered by nitrousacid, acetic chloride, or oxidising agents. Its ammonium salt doesnot exist in the free state ; the silver salt is a heavy, white precipitate ;the chromate a dark-red, amorphous precipitate ; the aurochloride iscrystalline.Dip heny Zppiperidine- y-carboz y Zic acid, C5NH8P h,CO 0 H, obtainedtogether with the above mid, and separated from i t by its greatersolubility, forms crystalline crusts; it melts at 339', and sublimeswithout decomposition, its alkaline salts are very soluble, the bariumand silver salts are white precipitates. Its nitroso-derirative crystal-lises in pale-yellow, glistening needles melting at l59", and is solublein ether and alcohol.aa-Diphenylpyridine, C5NH3Ph, obtained by the distillation of thecalcium salt of the carboxylic acid with lime, crystallises in long,glistening needles melting at 81-82" ; its platinochloride forms yellowneedles, and the auroclzloride a crystalline precipitate ; the rnethiodidecrystallises in needles melting at 203".aa-Diphen.ti~iperinine, C5NH9Ph,, obtained by the hydrogenation ofthe above base, is a thick, pale-yellow oil ; its ?ydrochZoride crystallisesi n white needles; the platimchloride and the aurochloride and thenitroso - deriunt ive cry stallise with difficulty .V. H. V.3-Methylpyridine and 3-Methylpiperidine. By C. STOEHR(Ber., 20, 2727--2733).--The picoline obtained by distilling strych-nine with lime (Abstr., 1887, 604) proves on further examination tobe p-picoline, since nicotinic acid is found to be the sole pr-d uct onoxidation with 2 per cent.permanganate solution. Some quantity ofthe base was prepared to enable an examination of its properties to bemade, and the results are compared with those of previous observers.P-Picoline thus obtained boils at 14.5-150" after two fractionations ;by conversion of this product into the mercurochloride and regenera-tion of the base, i t gives a product which mostly passes over between148' a n d 149" (compare Hesekiel, Abstr., 1885, 812). The platino-chloride, (C6H,N)2,H,PtC16 + H,O, has the properties of' the saltdescribed by Baeyer (AnnaZen, 155, 285), melts when dry at 195(:loses 1 mol. H,O when allowed to remain i n a desiccator, and whenheated at 120" loses in addition I mol.HCI, the compound thusobtained, (G',H7N),,HCl,PtC14, melting at 211-212". The aiirochloridemelts at 182-1 83". The mercuroch loride, C6H7N, H C1,2HgCl, (com-pare Hesekiel, Abstr., 1886, 256), crystallises from hot water inslender, ramifying needles, from dilute hydrochloric acid in indentedscales, or long, compact needles, and from concentrated hydrochloyicacid, in which it is very soluble, in small, well-formed prismaticcrystals melting at 139-140". The picrate crystallises in six-sidedscales melting at 142-143".3-Methylpiperidine, obtained by reduction of the P-picoline in alco-holic solution with sodium, is readily soluble in water, and yields ahydrochloride, crptallising in dazzling, white needles.w. P. w64 ABSTRACTS OF CHEMICAL PAPERS.2 : 6 Methylethylpyridine and 2 : 4 Methylethylpyridine.By M. SCHULTZ ( R e r . , 20, 2729-2727) .--Picoline ethiodide, whenheated at 280-300" for 1 to 1 i hours, yields a mixture of bases.To separate these, the product is treated with water, acidified, dis-tilled to remove a small quantity of an arornhtic oil, then renderedalkaline and again distilled. The mixture of bases so obtained, whichboils between 100" and 200", is fractionated, and the fractions boilingat 1 56-16(j0, 166-172", and 172-182" repeatedly refractionated ;in this way fractions boiling at 138-163" and 169-174'are obtained,and these consist chiefly of 2 : 6 methylethylpyridine and 2 : 4 methyl-e thy1 pyridine respectively.2 : 6 ~feth?/lethyZpyridi.lze, C8HIIN, is a colourless, hygroscopic, oilyliquid, having a sweet, aromatic! odour recalling that of picoline, andwhen moist, an alkaline reaction.It is sparingly soluble in water,readily volatile with steam, and yields salts which readily deliquescein air: The platinochboride, (C8H1,N),,H,PtCl,, crptallises in tabular,triclinic crystals, melts at 173-174" (after drying a t 110"), and isreadily soluble in hot water, insoluble in alcohol and ether ; the auro-clzloride, CsHllN,HAuC14, crystnllises in yellow needles, melts at 1 lo",and is sparingly soluble in water, readily soluble in ether alcohol.On reduction with sodium in hot alcoholic solution, copellidine,C,H,,N [Me : Et = 2 : 61, is obtained; this is a colourless, oilyliquid, which boils a t 147-151", fumes slightly in the air, has thecharacteristic odour of piperidine bases, and a strongly alkaline reac-tion.The nitroso-derivative is a brown oil 5 the hydrochloride,C,H,N,HCl, crystallises in white needles, and though readily solublein water and alcohol is only slightly hygroscopic. When oxidised with2 per cent. permanganate solution, 2 : 6 methplethylpyridine is con-verted into a dicarboxylic acid melting a t 226", and identical withLadenburg and Roth's dipicolinic acid (Abdtr., 1885, 557).2 : 4 Nethybethylpyridine, [Me : Et = 2 : 41, is a hygroscopic,colourless, oily liquid, which in its properties closely resembles the2 : &derivative. The pZntinochZoride, (C8Hl1N),,H2PtCI,, forms red-dish-yellow, tabular crystnla, which after drying a t 110" melt a t 190" ;the aurochloride, C8HI1N7HAuC14, crystallises in yellow needles,begins to fuse a t 83", melts a t 90", and is soluble in hot water,readily soluble in alcohol and ether.When the base is reduced withsodium in hot alcoholic solution, i t is converted into copeblidine,[Me : E t = 2 : 41 C,Hl,N; this is a colourless, oily liquid, whichboils a t 155-160", has a strongly alkaline reaction, and an odoursimilar to that of the 2 : 6 base. The hydrochloride, C8HITN,HCI,crystallises in white needles, is readily soluble in water and alcohol,and is slightly hygroscopic. 011 oxidation with 2 per cent. perman-ganate aolution in the cold or on heating, 2 : 4 methylethylpyridineyields a dicarboxylic acid whose melting point rose from 204" to 211"after three crystallisations.This author regards this acid as beingidentical with Ladenburg and Roth's lutidinic acid (Abstr., 1885,815), and ascribes its lower melting point to the presence of a smallqnarltity of pioolinic acid. w. I?. wORGANIC CHEMISTRY. 65Phenylated Piperidine and Pyridine Bases. By 0. BALLY(Ber., 20, .2590-2594).--r-Phenylpi~eridil~e. C,NH,,Ph, is preparedfrom r-phenylpyridine and purified by distillation. It melts at57*5-58", and boils a t 255-2S7" under 727 mm. pressure; it is astrong base, almost insoluble in water. The salts are readily soluble.The hydrochloride crystallises in needles ; the platitrochloride formsorange-coloured plates, melting a t 204-207".It gives no precipitatewith picric acid ; the original base gives a precipitate even i n vcrydilute s o h tion.C,NH,Me2Ph [Me : P h : Me = 2 : 4 : 61, is ob-tained by distilling potassium plienyllutidinegarboxylate (preparedfrom benzaldehyde, ethyl acetoacetate, and ammonia) with lime, a t thelowest possible temperature. It is purified by means of the hjdro-chloride, and crystallises from ether in prisms melting a t 54.5-55".I t boils a t 287" under 731 mm. pressure. The salts are generallysparingly soluble ; the hydrochloride (with 3 mols. H20) crj stallises inslender, matted needles which do not melt at 300" ; tlie platino-chloride, (C,,H,,N),,H2PtCl, + 4H20, forms orange-coloured needles ;the rzitmte and chromate melt at 177" and 228" respectively, bothcrystallise in needles.yPhenyZlupefidine, C,NH,PhMe,, is prepared by the action ofsodium (2.5 parts) on phenyllutidine (1 part) dissolved in absolutealcohol ; it is separated from unchanged phenyllutidine by distilla-tion.It is a colourless oil of a peculiar odour, boiling a t 274"under 73L mm. pressure. The hydrocltloride and iritrate cryhtallise inprisms ; the dinitrate melts at 210" ; the platinochloride crystallises ingold-coloured plates melting a t 237". Besides pheriyliupetidine, acompound, probably hepty Zbenzene, CHPh( CH,*CH,Me),, is producedin the reduction of phenyllutidine.When .I-phenyllu~idylilcna nzethiodide (prepared by digesting the basewith methyl iodide in a reflux apparatus) is treated with stroiig aqueouspotash, a base is obtained which jields a hydrochloride id;Jnticalwith that formed by the action of silver chloride on methylpheuyl-In tidylium iodide.Methyl-yphenyllutidylium iodide is a crystalline substance s p r inglysoluble in hot water.Phenyllutidine,N. H.M.&innamylpyridine. By H. BAURATH (Ber., 20,2719-2720).-When a-piuoline and benzaldehyde in equimolecular proportions areheated with zinc chloride at 220-225" for six hours, a-cinnamylpyri-&be, C5NH,*CH : CHPh, is obtained, and after removal of unalteledbenzaldehyde by steam distillation can be separated by rendering theproduct alkaline and distilling with superheated steam. Tlie base,already prepared but not described bF Jacobsen and Reimer (Alnstr.,1884, 335), is crystalline, melts at 90.5-91", boils at 313-314O(uncorr., under 733 mm.pressure), and is readily soluble i n carbonbisulphide and ether, soluble in alcohol, benzene, and light petro-leum, and practically insoluble in water. The salts generttlly crystal-lise in needles : the platinochloride, (C13H3,~N)z,HzPtCI, + d H 2 0 ,decomposes when heated to expel the water of crptallisation. Ontreatment with bromine in carbon bisulphide solution, the base yieldsVOL. LlV. 66 ABSTRACTS OF CHEMICAL PAPERS.an additive compound, C,,H,,NBr,, which crystallises from alcohol incompact needles melting at 166-167" ; this derivative yields a. newbase when heated with alcoholic potash. Derivatives of a-cinna,myl-pyridine have also been obtained by the action of hydriodic acid andby redilction of sodium and alcohol, and will be described in a latercommunication.w. P. w.Ethylquinoline. By L. REHER (Ber., 2 0 , 2734-2735).-Doehnerhaving found the boiling point of n-ethylquinoline to be 24,5-246"(Abstr., 1887, 504), the author has redetermined the boiling points ofa- and y-ethylquinoline (ihid., 279) by converting the bases into theplatinochlorides, recrystallising these repeatedly from concentratedhydrochloric acid, and regenerating the bases from the pure salts bymeans of hydrogen sulphide. a-Ethylquinoline boils a t 256-6-258.6"(corr.) and y-ethylquinoline boils a t 271-274" (corr.), and the pureplatinochlorides melt a t 189" and 203" respectively. From the purebases, c3Lromates were prepared crystallising in red needles, and crys-talline zincochlorides were also obtained, that of the y-base formingwhite, concentrically-grouped needles melting a t 195".DiethyZquirLoZinP, obtained by the decomposition of the mercuro-chloride (Zoc.c i t . ) , is a colourless liquid having it quinoline-likeodour, and boiling a t 282.8-284%0 (corr.). The plutinochloyide,(CqH,NEt,),,H,PtC1,, crystallises in orange-red needles, and melts a t217" after previous blackening. On oxidation with chromic acid, thebase yields a fimall quantity of an acid which crystallises in asbestos-By R. SCHMTTT andF. ENGELMANN (Ber., 20,2690-2695).--Further examination of ortho-hydroxyqainolinecarhoxylic acid (Abstr., 1887, 738) shows that itbegins to fuse at 137", that carbonic anhydride and orthohydroxy-qninoline are formed a t 144-145", and that the decomposition iscomplete a t 150".The ammonium salt, OH*CgNH5*CO@NH, + H2Q,crystall ises in glistening, pnle-yellow needles, and is soluble in water ;the bal-iwn salt, (OH*C,NH,*COO),Ba + 2H20, crystallises in long,silky needles, and is sparingly soluble in water ; the caZciunz salt cry+tnllises in stellate groups of prisms ; a basic barium salt, C10NH50aBa,and a basic calcium salt were also prepared; the former is verysparingly soluble in water. The phew$ salt, OH*CgNH5*COOPh,obtained by heating equimolecular proportions of the acid and phenolat 170", forms colourless, short prisms and melts a t 225-226". Thehydrochloride of the acid, OH-C9NH,-COOH,HC1, crystallises in largeprisms, and the mitrute in yellow needles ; both salts are decomposedby water.On treatment with strong nitric acid, a dinitrohydroxy-quinoline is obtained which is probably identical with that describedby Bedall and Fischer (Abstr., 1881, 613 ; Ber., 14, 1368) ; it crystal-lises in golden-yellow scales, melts a t 276" with blackening and theevolution of gas, is sparingly soluble in most solvents, and readilydecomposes alkaline carbonates, forming the corresponding salts.2\il.trohydroxyquinoZinecurboxZllic ncid, N02*C,NHa(OH).COOH, isprepared by heating the nitrate of orthohydroxyquinolinecarboxyliccoloured needles melting a t 190". w. P. w.Orthohydroxyquinolinecarboxylic AcidORGANIC CHEMISTRY. 67acid with rtcetic acid at 100" ; the resulting brown mass is extractedwith acetic acid until it becomes yellow, and is then purified bysoliition in hydrochloric acid and subsequent precipitation with water.It crystallises from water in yellow needles showing a vitreous lustre,decomposes at 200" with the evolution of carbonic anhydride, and dis-solves readily in concentrated hydrochloric acid, in alkalis and in alka-line carbonates, but is sparingly soluble in acetic acid.When heatedabove 200°, nitrohydroxyquinoline, NO,*C,NH,*OH, is formed ; thiscrystallises in yellow needles, melts at 173", is readily soluble in aceticacid and hot, hydrochloric acid,less so inalcohol and ether. On treatmentwith bromine (2 mols.) a t loo", a dibromohydroxyquinoline identicalwith that prepared by Bedall and Fischer (Zoc.cit.) is obtained togetherwith bromohydroxyquiiiolinecnrboxy1l:c acid, OH*C9NHdBr*COOH ; thiscrystallises in matted, citron-yellow needles, melts at 233-235"with the evolution of carbonic anhydride, a,nd yields a hydrochloridewhich crystallises in well-formed tables, and decomposes when boiledwith water. BromohydroxlJqwinoline, CgNHBByOH, formed quanti-tatively when the bromo-acid is heated a t 200°, crystralIises in whiteneedles, melts at 119-120", and is readily soluble in the ordinarysolvents except water. w. P. w.Parahydroxyquinolinecarboxylic Acid. By R. SCHMITT and J.ALTSCHUL (Ber., 20, 2695-2698).- When potassium parahyd coxv -quinoline is heated with liquid carbonic anhydride in an autoclave at170" for six to seven hours, a quantitative yield of potassium para-hydroxyquinolinecarboxylate is obtained ; the sodium-compoundcannot be substituted for the potassium-derivati.ce in this reaction.Parahydroxy~uin,r,linecarbozylic acid, OH*C9NT3,.COOH, crystallisesfrom water in yellowish-white flocks consisting of microscopic prisms,melts at 203-204" with the evolution of carbonic anhydride andformation of parahydroxyquinoline, and is sparingly soluble in alcohol,ether, benzene, and hot water.Ferric chloride colours the aqueoussolution red. The hydrochloride, OH*CgNH,~COOH,HCl, crystal-h e s in long, colourless needles, G r from concentrated hydrochloricacid in short, thick prisms, is decomposed by water, and yields awell-crystallised platinochloride ; the mitrote, formed by digesting theacid with nitric acid (sp.gr. = 1*35), crystallises in large, whiteneedles, and is decomposed by water. The ammonium salt, with 4 mol. HzO, crystallises in long, colourless needles, and is soluble inwater, the solution evolving ammonia when boiled ; the barium salt,with 2 mols. HzO, crystallises in colourless tufts of needles, and doesnot form a basic salt when treated with barium hydroxide.If the nitrate of parahydroxyquinolinecarboxylic acid is heated withnitric acid, yellowish-red prisms separate on cooling, which whentreated with water decompose into nitric acid and nitrohydroxyquino-line ; this crystallises in yellow needles, melts a t 136", and is probablyidentical with Skraup's nitrohydroxyquinoline (Abstr., 1882, 92).w. P. w.Constitution of Glutazine. Ry R. V. PECHMANN (Rer., 20, 2655-2658 ; compare Abstr., 1887, 155).--Nitroglutazina, C5H N 0 *NO*, f i 68 ABSTRACTS OF CHEMICAL PAPERS.is obtained together with dinitroglutazine when nitrous oxide ispassed into a cold aqueous solution of glutazine. It crystallises fromwater in orange-yellow plates which decompose a t 170 -180" withon tmelting. Dinitroglutazine, C5H4N,02(N0,),, crystallises from waterin yellow plates. Both compounds give colourless solutions withacetic acid and zinc-dust which become red when exposed to air.When heated with alkali, they are converted, with evolution oE am-monia, into sparingly soluble salts whicb crystallise in sulphur-colonred,matted needles and explode when heated.These results make itimprobable that glutazine contains an amido-group.The nitronitrosamine, N02.C5H4Wz02.N0, is obtained when glutnzine(1 part) dissolved in the smallest amount of dilute aqueous soda istreated with sodium nitrite (1 part); water is added (so that thewhole amounts to 30 parts), and the whole is poured into a mixture ofglacial acetic acid (5 parts) and water (30 parts). I n a short; time itsolidifies to an orange-coloured magma. The sodium saZt, C5H3NaN405,so obtained ci-ystallises in yellow needles with water of crystallisation.Acids precipitate greenish-yellow needles from the solution. Whenthe sodium salt dissolved i n glacial aeetic acid is warmed withexcess of sodium nitrite, the sodium salt of the dinitronitrosamine,C5H2NaN5O7, separates as a, cinnabar-coloured, crystalline powder.This dissolves sparingly in water, readily in alkalis.When warmedwith dilute acids nitrous acid is given off.Dibes7xoylgZutazine, C5H4N202Bz2, is obtained by heating glutaziriewith benzoic chloride on a water-bath f o r two to three hours, andcryst,allises from glacial acetic acid in lustrous, brownish plates meltingat 215-5216'. It is insoluble in water and in alkalis, sparingly solublein alcohol.The above results show that there are only two hydrogen-atoms inglutazine displaceable by acid radicles, and that these are present asiniidoliydrogen as shown by the formula NH< c0'cH2>C NH.CO-CH,N. H. M.Reactions of Caffe'ine and Caffe'idine.By &I. WERNECKE(Chem. Cenfr., 1887, 1082--1084j .-Hydriodic acid, like hydrochloricacid, decomposes caffeine into carbonic oxide and anhydride, formicacid, sarcosirie, ammonia, and methy lamine ; if phosphorus is added,glycocine is formed instead of sarcosine, whilst hydrogen phosphideand pliosphoninm iodide are evoliied. Although methyl iodide readilycombines with cafleine to form, the methiodide, the formation of the cor-respoiiding ethyl-compound presents considerable difhulty. Phenyl-hydrazine will not combine with caffeine; from this it would seemthat in this casa, as an an;~loqiie of carbamide, the carbonyl-group isdirectly combined with the nitrogen-atom.Ca-ft h e ch lo?-iodide, CsHI,N4O2,CI1, is produced when sodium nitriteand potassium iodide are added to a, hydrochloric acid solution of thisbase ; it forms golden needles melting a t 182--183", and is decom-posed into it.: const,itnents by ammonia or by boiling with water.Themethod proposed by Mdy and Andreasch for the preparation of caffei-dine presents no advantage over that of Strecker. Caffeine sulphatORQANIC CHEMISTRY. 69differs from the hydroiodide in that the farmer, when heated, turnspurple-red, whilst the latter yields a green mass ; the anrochlorideof caffeine cannot be isolated. The base is best separated from thesulphate by means of basic lead carbonate. Methy leafezdine hydr-iodide is not a well-defined substance, but the free base is crystallineand melts at 86-88' ; dimethy Zccrflei'dine forms leaflets melting at123".The author ascribes the following constitution to cdeidine,"<NMe*C(NH) NM+CHy.~~~e.V. H. V.Hydroquinine. By 0. HESSE (Annalen, 241, 255-287) .-Hydro-quinine, C2OH26N~02, exists ready. formed in cinchona bark, and ispresent in varying quantities in commercial quinine. It is COII-veniently prepared from the mother-liquor obtained in the manu-facture of the acid sulphate of quinine. The mother-liquor isneutralised and the neutral salt dissolved in sulphuric acid, quininexionosulphate crystallises, and the mother-liquor containing the hydro-quinine is again neutralised. By repeating these operations a salt isobtained containing 30 per cent. of hydroquinine sulphate. The quinineis removed by oxidising the solution in sulphuric acid with potassiumpermanganate, the mixture is filtered and the hydroquinine liberatedby the addition of an alkali and extracted with ether.The base isdeposited from its solution in chloroform in needles and from hotacetone in long plates. Many of the properties of the compound havebeen previously described by the author (Abstr., 1882, 1113). It islaevogyrate [a]= = -1142.2" for a 2.4 per cent. solution in 95 perper cent. alcohol at 20", and [a]= = -227.1" for an aqueous solutionof the same strength under similar conditions. (40 C.C. normal hydro-chloric acid were contained i n each 100 C.C. of water used for the solu-tion.) When ammonia is added to a solution of equal molecular propor-tions of cupre'ine and hydroquinine in water containing sulphuric acid,and the acid mixture extracted with ether, a crystalline compound ofcupre'ine and hydroquinine is obtained, C,oH2,N20,,C,~H2~N,02 + 2H20.Hydroquinine forms similar compounds with conchinine and hydro-conchinine. It also unites with two and with three molecules ofcinchonidine, forming crystalline compounds which do not contain anywater of crystallisation. Analogous compounds are formed withhydrocinchonidine and with homocinchonidine.Anethoillztldroq~inine, (CJI&zO2)2, C&,,O + 2H20, is depositedin quadratic prisms from a solution of 5 parts of hydroquinine and1 part of anethoil in warm dcohol.Hydroquinine forms three series of salts, which are as a rule moresoluble than the corresponding salts of quinine.The normal sulpl~at~e,( Cz~H~6N20z)2,H2S04 + 6Hz0, has been previously described (Zoc. cit.).It forms a crystalline compound with phenol, ( CzoH26~zOZ),S03, C6H60 + 2H20, which is spayingly soluble in cold water. The acid sulphate,C20H26N202,S0& + 3Hz0, is freely soluble in water and alcohol.At 140°, the anhydrous salt is converted into hydroquinine sulphate.The disulphate is amorphous. Dichroic crystals resembling hydro70 ABSTRACTS OF CHEPolICAL PAPERS.quinine herepathite are obtained by adding potassiiim iodide (2 mols.)to an alcoholic solution of the acid sulphate (4 mols.), and acting onthe product with an alcoholic solution of iodine.Hydroquinine hyposulphite, ( CzOH26NzOz)a,H2Sz0, -f- 2H20, formswhite prisms sparingly soluble in water.The hydrochloride,CmH26Nz02HC1 + 2Hz0,crystallises in prisms, andis freely soluble in alcohol and water. Theplntinochlorides, ( C20H26Nz02)z,H2PtC16 + 3H20 and C20Hz6Nz02,~zPtCI,-t- 2Hz0, are amorphous and are sparingly soluble in water; themercurochloride, ( CzoHz6Nz~zH~1)zH~CI,, crystallises in needles. Thehydrobromides, CzoHzaN20z,HBr + 2Hz0 and C20Hz6N20R,2HBr + 3H20,also form needles. The neutral hydriodide is a colourless oily liqnidwhich solidifies to an amorphous mass. Potassium iodide producesin acid solutions of hydroquinine salts a yellow, crystalline precipi-tate of the acid hydriodide, CzoHz6NzO2,2HI + 4H20. On theaddition of iodine to the alcoholic solution of this salt, dichroic,ueedle-shaped crystals of the composition C2,,H2,N20,2(IH,IZ) aredeposited.The acetate, CmH26N202,C2H402 + 5Hz0, crystallises inneedles and is freely soluble in alcohol and water. The benzoateand sdicylate dissolve freely in alcohol. The benzoate is anhydrous.The piperonate, CzoHz6NzOz,C8~604, is soluble in water and in chloro-form. Thc oxalate is deposited from hot alcohol in prisms containing6 mols. H20. The tartrate also crystallises in prisms containing2 mols. H,O. It is soluble in alcohol, water, and in a mixtureof alcohol and chloroform. The citrate and arssnate crystallise with10 rnols. HzO, the phosphate with 7 mols. H,O. The chromate,( Cz0H26NzOz)zHzCr04 + 6Hz0, forms golden needles. The dichromateis an oily liquid.Hydroquinicine dissolves freely in ether, alcohol, chloroform, and indilute acids. The solution in dilute sulphuric acid is yellow; thecolour changes to green on the addition of chlorine water and ammonia,b u t the mixture is not fluorescent. An ethereal solution of oxalicacid produces in an ethereal solution of hydroquinicine an amorphousprecipitate soluble in chloroform.The normal sulphate cryst,allisesin needles and dissolves freely in alcohol and in water.Hydroquinine platinockloride, C20Hz6N202, HzPtCI, + HzO, formsorange-coloured crystals. Hydroquinine unites with methyl iodide,forming the compound CzoH26Nz0z,MeI + CzH60. It crystallises inprisms of a yellow colour and dissolves in hot alcohol. It meltsat 218". On treatment with silver chloride, it is converted intothe chloride CzoHz6Nz0z,MeCl + 2Hz0.The acid platinochlol"ide,C,Hz6N,0z,Me*HPt Cl6 + 2H20, forms orange-coloured crystals, andthe normal salt, (C~OEIZ~N,O,M~),,P~CI,, pale-yellow needles. Hydro-quinine methylhydroxide is amorphous. It is soluble in alcoholand water. The solutions are caustic and absorb carbonic anhy-dride.AcetyEhy droquinhe, Cz0R25N202Ac, is amorphous. It melts at 40"and dissolves freely in alcohol, ether, benzene, and in acids. Thesolution is laevogyrate, and the solution in sulphuric acid is fluorescent.The platinockloride contains 2 mols. H20, and the normal sulphateORGANIC CHEMISTRY. 71which is soluble in hot water and alcohol, crystallises with 9 mols.Hydroquinine is converted into hydrocupreyne dihydrochloride bythe action of hydrochloric acid, sp.gr. 1.125, a t 150". Hydrocuprezize,C,9H,,N,0, + 2H20, exists as a crystalline powder freely soluble inether, alcohol, and chloroform. It melts at 168-170°, and exhibitsa strong basic reaction and forms crystalline salts. Solutions of thenormal salts have a greenish-yellow colour, the acid salts are colour-less. The sulphate, ( ClgH,,N,O,),,H2SO4, is sparingly soluble in waterand in alcohol. The tartrate is sparingly soluble in water, but thedihydrochloride, CleH2iNz02,2HCl + HzO, is freely soluble i n water.The acid platinochloride, C19HzrNz0z,H~PtC16, is crystalline and in-soluble in water.~ydroquininesulpponic acid, C,oH,N,O,*SO,H + H,O, is prepared bydissolving hydroquinine in sulphuric acid a t the ordinary tempera-ture.The solution is poured into water and mixed with excess ofammonia. The acid crystallises in cubes and is soluble in boilingwater, alcohol, and hot solutions of alkalis. It dissolves freely inacids, with which it forms crystalline compounds. The anhydrousacid inelts a t 239".The presence of hydroquinine in cinchona bark vitiates the resultsobtained in the estimation of quinine by the ordinary polariscopicmet hod. w. (3. w.H,O.Apocinchine and Apochinine. By W. J. COMSTOCK and W.KOENIGS (Ber., 20, 2674-8689).-Analyses of salts and bromo-derivatives of apocinchine show that the formula, previously assignedto the base (Abstr., 1882, 224) must be altered to C19H19NO; theformula ascribed to ethylapocinchinic acid (Abstr., 1885, 1248) ig,huwever, retained.The authors now attribute the formation of thecombustible, gaseous halogen compound (? methyl chloride) in thepreparation of apocinchine to some secondary change in the reaction.Apocinc hine hydro bromid e, C19Hlg N 0, HBr, crystal lises from alcoholichydrogen bromide in small, yellow needles, and melts at about 256';the hydriodide, C1gH1gNO,HI, is a yellow, cryst'alline salt ; the PZutinG-chloride, (C,gHlgNO),,H2PtC16, forms orange-yellow crystals and meltsat about 235". The acetyl-derivat,ive, ClyHI8NOAc, forms practicallycolourless crystals, and melts a t 118-119" ; the double phosphates ofapocinchine and ammonium, barium, acd potassium, were also pro-pared, and crystallise well.Bronaapoci?i,chine, CI9H,,NOBr, is prepared by gradually addingbromine to apocinchine hydrobromide dissolved in equal parts ofchloroform and acetic acid until the yellow perbromide begins t3separate; sodiiim hydrogen sulphite is then added and the baseobtained from the chloroform and aqueous layers by evaporation andprecipitation. It is crystalline, melts at 186-188", and is readilysoluble in aqueons soda, benzene, chloroform, and ethyl acetate, lessso in alcohol, carbon bisulphide, ether, and light petroleum.Brom-apocinchine is not altered by prolonged boiling with alcoholic soda,and yields bromoform and cinchonic acid on oxidation with 4 per cent.chromic acid solution72 ABSTRACTS OF CHEMICAL PAPERS.Dibroniethylapocinchine, ClgH,,NBr2*OEt, is prepared by adding ethyl-apocinchine (10 grams) to well-cooled bromine (15 c.c.), digesting theproduct after 12 hours with sodium hydrogen sulphite.and extractingwith alcoholic ammonia; the deposit from the alcoholic solution isthen boiled with dilute sutphnric acid, the resulting solution treatedwith ether and aqueous soda, and the base obtained from the ethereallayer by evaporation. It melts at 116-118". The alkaline solution,after separation from the ether, is found to contain dibromapocin-chine.Ethylapocinchinic acid forms a crystalline hydrochloride and hydro-bromide. The silver salt, C,,H,,NO?Ag, is a white, crystalline saltunaffected by light ; the platinochlorzde, (C,,H,gN0,),,H,PtC16, is pre-cipitated in volumiiious, slender, straw-yellow needles, which are con-verted into small, compact, orange-yellow crystals, when the salt isheated on a water-bath for a short time.Homupocinchina, C,H,,NO, the compound formed together withcarbonic anhydride and ethyl chloride when ethylapocinchinic acid isheated a t 130" with hydrochloric acid (Zoc.cit.), crystallises fromdilate alcohol in colourless crystals which contain water of crystallisa-tion and melt a t 184-185'. It is sparingly soluble in water, ether,benzene, and chloroform, readily soluble in hot alcohol, and differsfrom apocinchine, to which it shows much similarity, in its readysolubility in dilu te aqueous soda. The kydrob romide, CI,H,,NO,HBr + H20, crystallises in glistening, transparent, yellow needles orprisms, melts at 221-222", and is sparingly soluble in water and inexcess of dilute hydrobromic acid.The ethyl-derivative yields acrystalline, yellow sulphate. On fusion with potassium hydroxide,homapocinchine is converted into a compound which probably corre-sponds to oxyapocinchine. When oxidised in very dilute solution withpermangmate, ethylapocinchine yields a mixture of solid acids whichdissolve in dilute sulphuric acid and alkalis. Ethylapocinchinic acidis one constituent of the mixture. To effect a separation, the productis boiled with hydrobromic acid (sp. gr. 1-49>, and the solution treatedwith aqueous soda which precipitates homapocinchine ; careful ncidifi-cation of the filtrate then precipitates a mixture of a t least two acids,of which the one of lower melting point is the more soluble in alcohol.The more soluble acid, C,,H,,NO, or ClgHJVO,, dissolves in dilutemineral acids, melts at 230" with the evolution of gas, and at 240" yieldscarbonic anhydride and a compound, CliH,,NO,.This crystallisesfrom dilute alcohol in colourless, silky needles, melts a t 0,23", is notvolatile without decomposition, and is soluble in dilute araids andalkalis. The hydrobromide, sulphate, and nit rate are crystalline, andsparingly soluble.AcetyZoxya23ocinchilzcl, CI9Hl,NO2Ac, melts at 201--203", and issoluble in alcohol, benzene, and light petroleum.From considerations based on analyses of its salts, the authors haveadopted the formula Cl9H,,NO, for chinine, instead of that previouslyproposed (Abstr., 1885, 910). Chinine h!/ldrobrowide, C19H19N02,HBr,crys tallises in long, sulphur-yellow needles, and is decomposed bywater.The remainder of the paper is devoted to a discussion of the conORQ AKIC CHEMISTRE'.73stitution of these alkalo'ids, in which the authors adhere t o the viewsalready put forward wit>h regard to apocinchine (Abstr., 1885, 1248 ;1887, 600), and suggest that cinchine niay possibly be a dialkyl-amidophenylquinoline, and t,hat the second benzene nucleus is presentin a partially hydrogenated form. w. P. w.Strychninesulphonic Acids. Bp C. STOEHR (Ber., 20, 2i33-2734).-A note calling attention to the fact that the results obtainedby Guareschi (Abstr., 1887, 853) are essentially the same as thosepreviously arrived at by the author (Abstr., 1886, 269).w. P. w.PecuIiar Modification of UrobiIin. By E. SALKOWSKY (Chpm.Centr., 18, 1089) -On examination of a sample of urine peculiarlyrich in urobilin, itl was observed that on keeping this colouringmatter disappeared without any marked change of the colour of theurine. This conversion of the urobilin seems not to be conditionedby the ammoniacal fermentation of the urine or by the presence ofmicro-organisms, Urobilin is a substance readily decomposed, andpasses into a modification which, although still coloured, shows noabsorption-bands, nor fluorescence with zinc clrloride in ammoniacalsolution, and is not taken up by chloroform. It is probable that inmost normal urines, urobilin, as well as its decomposition-products, ispresent.V. H. V.Chemical Formation of Albumin. By C. P. W. KKUKEKBEKG(Chem. Centr., 1887, lOSS).-W hen keratin, previously purified by theaction of pepsin and trypsin, is heated with water in a sealed tube, itdissolves to form an alkaline liquid, possessing a strong odour ofhydrogen sulphide, This liquid contains a non-dialysable substance,keratinose, precipitated by ammonium sulphate, which agrees withhemialburnose as regards these reactions, although it does not givethe hydrochloric acid test,. Kemtinose is converted by pepsin andhydrochloric acid a t a blood-heat into keratinpeptone, which is notprecipitated by ammonium sulphate. Under the same conditionsspongin yields spongiorzose, ft soluble, indiff usible substance ; this isalso converted into spoupiopeptone. By the dccomposition of spongin,carbamitle seems to be formed. The author considers that the albu-minoids and skeletins are related to albumin as methyl to methylether. V. H. V.Coagulation of Albumin. By V. MIcHAn,oFF (Chem. Centr.,1887, 1088).-According to the author the coagulation of albumin isdue to one of two phenomena, namely, t'he true coagulation induced bythe action of ferments or heat, a process analogous to etherification OKthe formation of polyhydro-silicates or glycols, and a pseudo-coagula-tion caused by a loss of " gelatinose-water," which corresponds w i t hthe loss of water of crystallisation of salts. The coagulating power ofsalts on solutions of albumin is dependent on the nature of the aoidand base therein contained; the maximum effect is produced byammonium, the mean by sodium, and the minimum by potassiumsalts. Again, in the case of ammonium salts, the sulphate is mor74 ABSTRACTS OF CHEXICAL PAPERS.----0 ,. .. .. ,.H.. .. .. ..N.. .. .. ..S .. .. .. ..0 .. .. .. . .efficient than the nitrate, and of potassium salts the snlphate than thechloride. V. H. V.Egg Albumin and Albumoses. By R. H.’CHITTENDEN and P. R.BOLTON (Studies from Lab. Physiol. Chem., Yale Uuiv., 2, 126-155).--These experiments were designed to contrast the products of diges-tion of egg albumin with those obtained by Kuhne and Chittendenfrom fibrin. Four samples of albumin were prepared ; i n some casesit was separated from globulin by saturation wi tjh magnesium sul-phate, in others by dilution and the subsequent addition of aceticacid. An elementary analysis of these four samples gave the followingaverage percentages :-C, 52.18 ; H, 6.93 ; N, 15.81 ; S, 1.87 ; 0,23.21. Further, coagulated products did not differ in compositionfrom non-coagulated albumin. These results do not agree with anyof the formula ascribed to albumin by previous observers.Peptic digestion of fhe albumin resulted in the formation of albu-minoses of which the percentage composition and reactions weredetermined. In composition they were found t o differ from eachother somewhat more than the albumoses from fibrin ; collectively,however, there is less difference in composition between the albu-Moses and the egg albumin from which they were formed than inthe case of the albumoses from fibrin. The following table givesthe final results :-Proto- Deutero- Proto- Deutero- Egg.albumose. albumose. Fibrin’ albumose. albumose. albumin.-- ------- -50’7’: 50.65 52.68 51-07 51.62 52.336-78 6.83 6 *83 6 -98 6.97 6 *9817.14 17.17 16-91 16’00 15-82 15.851.08 0 -97 1 .lo 1 -95 1 *96 1 -8224?23 24.38 22.48 24.00 23.63 23-02Fibrili products. Egg albumin products. II n their yeactions the different albumoses (proto-, deutero-, hetero-,and dys-albumose) obtained from egg albumin do not differ essentiallyfrom those obtained from fibrin. W. I). H.Metallic Compounds of Albumin and Myosin. By R. H.CHITTENDEN and H. H. WHITEHOUSE (Studies from Lab. Physiol.Chem., Yale Univ., 95--125).--Many researches on the subject of themetallic compounds of albumin have been carried out since Lieber-kuhn attempted to establish the molecular weight of albumin by theanalysis OE copper albuminate. The more recent work of Harnack(Abstr., 1882, 747) showed that two compounds of albumin (fromwhite of egg) with copper occur, one containing 1.35 per cent., andthe otlier 2-64 per cent. of copper. I n the present research, albuminwas freed from globulin by the use of dilute acetic acid, and both thORGANIC CHEMISTRY. 75acetate and snlphate of copper were used in the preparation of thealbuminate. The precipitate was well washed with water, powdered,and dried. The percentage of copper was first determined as cupricoxide by ignition and weighing : the oxide was then dissoived in dilutenitric acid, treated with hydrogen sulphide, and the amount of cuproussulphide obtained weighed. By the former method, in 15 prepam-tions the average result was 1.17 per cent. of copper; and by thelatter method 0.94 per cent. ; the preparations, therefore, contain 0.23per cerit. of ash. I n order to obtain less ash, Harnack dissolved tthealbuminate in sodium carbonate and reprecipitated it by the carefuladdition of acid; this process was repeated several times. Thistreatment certainly increases t,he percentage of copper, but is asource of error, as the sodium carbonate withdraws a portion of thea1 bumin. Long-continued washing with water also causes partialdissociation of the compound. The results obtained correspond withthe formula (C72H11,N18S022)~ + Cu - H,.A normal lead salt causes a small precipitate when added to albu-min, whilst with basic lead acetate the albumin is completely precipi-tated. This confirms the previous statement of Berzelius (Lehrbuchder Chemie, 9, 29). The preparations were well washed from bothlead and albumin, dried, and the lead was determined, first by simpleignition, and then obta,ined as sulphate, which was ignited. Theresults indicate that more than one compound of lead is formed, thatmade by the addition of a large excess of the basic acetate, containingabout five times as much lead as the ordinary basic lead compounds.An iron compound Tvbich was found to be more stable than thecopper albuminate, and corresponded fairly well with the formula( C72H:llzN18s02,)4 + Fe -H3, and a zinc compound, (C7,H,,,N18S02,)a +Zn - H2 ; acid compounds with uranium, (~,2Hl12N18s022)3 + U - H2 ;with mercury, (C7,Hl,,N,8S0,)4 + Hg - H,; and with silver,(C7,Hll,N,8SO,2), + Ag. - Ha, were also prepared and analysed.Much stress is not laid on such forrnu1Be;as it seems possible to forma large variety of compounds by simply modifying the conditions ofprecipitations. This, with the undoubted tendency of the compoundsto dissociation, may account for the lack of agreement in the resultsof different workers. Similar compounds prepared from myosinobtained by extracting ox flesh with 15 per cent. ammonium chloridewere prepared, and the percentage results show that these two formsof prote'id matter do not form corresponding compounds with themetallic salts used. This is illustrated by the following table :76 ABSTRACTS OF CHEMICAL PAPERS.--.......... .......... ........................................................... ..........Copper compoundIron 9 ,Zinc 9 7Ura,nyl ,,Mercury ,,Lead ?,Silver ,,Nickel ,,Cobalt ,,Egg albumin.0 *94 per cent. Cu0.95 ,, Fe0.91 ,, Zn4.60 ,, U2.89 ,,2.56 ,?4.09 ,, AgFf-Myosia.1-17 per cent. Cu2.29 ,, Pe0.72 ,, Zn2.43 ,, Hg4-70 ,, Ni6-03 ,, Co7-49 ), u--W. D. H.Casein and Caseoses. By R. H. CHITTENDEN and H. M. PAINTER(Studies from Lab. Physiol. C'hern., Yale Univ., 2, 156-199),-Danilewsky ( Z e i t . physiol. Chem., 7, 433) has asserted that casejin isa mixture of two protejids, caseoprotalbin, partially soluble, andcaseoalbumin, insoluble in hot 50 per cent. alcohol. Hammarsten(ibid., 7, 227) has shown that the peculiar behaviour of Danilewsky'scase'in is due to its containing calcium phosphate, the presence ofwhich impurit'y depends on the use of hydrochloric acid in the pre-cipitatioii of the case'in, as this acid does not favour the removal ofthe salt as well as acetic acid. He also considers that casein is asingle prote'id. I n the present research, seTen distinct preparationsof casejin were made. Elementary analyses show a close agreementthroughout, and the results mcreover accord closely with those ofHainmars ten,I n the digestion of casein with hydrochloric acid, peptones areultimately formed, and the name caseose is given to the intermediateproducts. These were separated by the methods of Kiihne and Chit-tenden into proto-, hetero-, and deutero-caseose, which correspond withthe albunioses with similar names. The quantity of heterocaseoseobtained was usually very small. The reactions characteristic ofalbumoses apply generally to the caseoses. Unlike proto-albumosehowever, protocnseose is precipihated from aqueous solutions by aceticacid. The average of the analyses of 10 preparations of proto-caseose gives the following percentage results :-I-_I-- --I---!---Protocaseose ........ 1 52.89 1 7.10 I 15-94 1 0.95 1 23.12Case'in.. ........... 53.30 7.07 15.91 0.82 22.03Deuterocaseose contains ZL smaller percentage of carbon than proto-caseose, and heterocaseose contains fully as much carbon as case'initself.An insoluble, semi-gelatinous substance which separates in thefirst stage digestion has not yet been inveshigated. Weyl's com-mercial " case'in-peptone " contains large quantities of caseoses.W. D. H"P PHYSIOLOGICAL CHEMISTRY. 1 4Animal Tannin. By M. VILLON (Cham. News, 56, 175).-cornweevils CCaZandra graneria) were killed, ground in a mortar, anddigested for one hour in boiling 90 per cent. alcohol. The residuefrom the evaporat,ion of the extract is taken up with ethyl acetate atSO", .and precipitated by means of ammoiiiacal zinc a,cetate. The preci-pitate is decomposed with oxalic acid, and the solution evaporated inR vacuum. In this way 3 per cent. of a substance having all thegeneral properties of tannin is obtained from the weevils. This animaltannin, fracticomitanrzin, forms small reddis h-ye!Iow scales.D. A, L

ISSN:0368-1769    

DOI:10.1039/CA8885400035

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

J O U R N A L H. BAKER. CHICHESTER A. BELL, M.B. D. BENDIX. A. G. BLOXAM. C. H. BOTHAMLEY. B. BRAUNER. B. H. BROUGH. H. CROMPTON. c. E'. CROSS. W. D. HALLIBURTON, M.D., B.Sc. F. S. KIPPING, Ph.D., D.Sc. J. P. LAWS. J. W. LEATHER, Ph.D. D. A. LOUIS. T. MAXWELL, M.D., B.Sc. N. H. J. MILLER, Ph.D. OF G. T. MOODY, D.Sc. G. H. MORRIS, Ph.D. J. M. H. MUNRO, D.Sc. E. W. PREVOST, Ph.D. H. H. ROBINSON, B.A. R. ROUTLEDGE, B Rc M. J. SALTER. C. SPURGE, B.A. JAMES TAYLOR, B.Sc. L. T. THORNE, Ph.D. H. I(. TOMPKINS, B.Sc. G. W. DE TUNZELMANN, B.Sc. V. H. VELEP, M.A. W. C. WILLIAMS, B.Sc. W. P. VSTYNNE, B.Sc. THE CHEMICAL SOCIETY Qmmittee af @nbXkrrtirrrr : H. E. ~ M S T B O N G , Ph.D., F.R.S. W. CROOKES, F.R.S. WYNDHAM R. DUNSTAN. 1 W. J. RUSSELL, Ph.D., F.R.S. F. R. JAPP, M.A., Ph.D., F.R.S.A. I(. MILLER, Ph.D. S. U. PICKERING, M.A. ! W. RAMSAY, Ph.D., F.R.S. ~ J. MILLAR THOMSON, F.R.S.E. 1 T. E. THORPE, Ph.D., F.R.S. HUGH) MULLEX, Ph.D., F.R.S. 1 @,bitat. : C. E. GROVES, F.R.S. %nb-@,bitor : A. J. GREENAWAY. VOl. LIV. Part 11. 18 88. ABSTRACTS. L O N D O N : GURNEY & JACKSON, 1, PATERNOSTER ROW' 1885.ZONDON : HARRISON AND 60N8, PRINTERS IN ORDINARY TO HER MAJESTY, ST. MARTIN’S XANE.J O U R N A LH. BAKER.CHICHESTER A. BELL, M.B.D. BENDIX.A. G. BLOXAM.C. H. BOTHAMLEY.B. BRAUNER.B. H. BROUGH.H. CROMPTON.c. E'. CROSS.W. D. HALLIBURTON, M.D., B.Sc.F. S. KIPPING, Ph.D., D.Sc.J. P. LAWS.J. W. LEATHER, Ph.D.D. A. LOUIS.T. MAXWELL, M.D., B.Sc.N. H. J. MILLER, Ph.D.OFG. T. MOODY, D.Sc.G. H. MORRIS, Ph.D.J. M. H. MUNRO, D.Sc.E. W. PREVOST, Ph.D.H. H. ROBINSON, B.A.R. ROUTLEDGE, B RcM. J. SALTER.C. SPURGE, B.A.JAMES TAYLOR, B.Sc.L. T. THORNE, Ph.D.H. I(. TOMPKINS, B.Sc.G. W. DE TUNZELMANN, B.Sc.V. H. VELEP, M.A.W. C. WILLIAMS, B.Sc.W. P. VSTYNNE, B.Sc.THE CHEMICAL SOCIETYQmmittee af @nbXkrrtirrrr :H. E. ~ M S T B O N G , Ph.D., F.R.S.W. CROOKES, F.R.S.WYNDHAM R. DUNSTAN. 1 W. J. RUSSELL, Ph.D., F.R.S.F. R. JAPP, M.A., Ph.D., F.R.S.A. I(. MILLER, Ph.D.S. U. PICKERING, M.A. ! W. RAMSAY, Ph.D., F.R.S.~ J. MILLAR THOMSON, F.R.S.E. 1 T. E. THORPE, Ph.D., F.R.S.HUGH) MULLEX, Ph.D., F.R.S. 1@,bitat. :C. E. GROVES, F.R.S.%nb-@,bitor :A. J. GREENAWAY.VOl. LIV. Part 11.18 88. ABSTRACTS.L O N D O N :GURNEY & JACKSON, 1, PATERNOSTER ROW'1885ZONDON :HARRISON AND 60N8, PRINTERS IN ORDINARY TO HER MAJESTY,ST. MARTIN’S XANE

ISSN:0368-1769    

DOI:10.1039/CA88854FP057

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. P h y s i o l o g i c a1 C h e m i s t r y . Influence of some Organic and Inorganic Substances on Gas Metabolism. By R. H. CHITTENDEN and G. W. CUMMIKS (Studies from Lab. Yhysiol. Chent., Yale Univ., 2, 200-236).-Tbe question investigated was the consumption of oxygen and the elimi- nation of carbonic anhydride. The animal, a rabbit, was confined in a large bell-jar, through which air was drawn by means of three aspirators, which were arranged to work evenly, and emptied them- selves in half an hour. Two-fifths of the mixed air was drawn suc- cessively through three absorption-tubes, each of which contained 100 C.C. of standard bnryta. The carbonic anhydride was estimated by titration with standard oxalic acid. The results obhined are not absolute, but express quite well the comparative action of the various substances experimented with.It was found necessary to have the animal in a state of hunger during an experiment. Accordingly it was deprived of food for three days previous to the experiment, as well as during the three days for which the experiment lasted. During the last two of the three days, the substance experimented with was given in small and oft-repeated doses. Every day numerous deter- minations of carbonic anhydride were made, and comparison could then be made between the normal excretion of that substance and tbat during the administrakion of the drug. Observations were also made on the body temperature. The following are briefly the results obtained with the following substances :-Uranyl nitrate acts slowly, but when taken in sufficient quantity tends to raise materially the body temperature, and increase very noticeably the excretion of car- bonic anhydride.Copper sulphate shows a marked influence in depressing body temperature, and a still greater infliiense in dimi- nishing the production of carbonic anhydride. Arsenious oxide given in non-toxic doses also diminishes the excretion of carbonic anhydride, presumably through its action on the metabolic activity of the tissue cells. Tartar emetic acts similarly. Morphine sulphate has but little action ; a slight fall in the excretion of carbonic anhy- dride immediately after a dose must be attributed to the semi- somnolent condition of the animal. Quinine sulphate, which is so important as an antipyretic, is found in a healthy hungry rabbit78 ABSTRACTS OF CHEMICAL PAPERS.t o have only B very slight depi-essing influence on body tem- perature, and a minimum effect on the production of carbonic anhy- dride. Cinchonidine sulphate produced a slight rise of temperature and a gradual diminut.ion in the amount of carbonic anhydride excreted ; it also caused tetanic convulsions and finally death. Anti- pyrine had little effect, the only change being a fall in temperature just before death. W. D. H. Action of Uranium Salts on Digestive Ferments. By R. H. CHITTENDEN and M. T. HUTCHINSON (Xtudies 'from Lub. Physiol. Chew, Yule UTZ~U., 2, 55--67').-Very small quantities of uranium salts pro- niote the activity of saliva ; larger amounts hinder and finally stop its amylolytic action.100 C.C. of digestive mixture coiitained 2 C.C. of neutralised saliva, and 1 gram of pure potato-starch. The mixture was warmed at 40" for 31) minutes and then boiled to prevent further action; the amount of sugar present was estimated as dextrose by Behling's solution. This was compared with other digestive mixtures to which a certain percentage of a uranium salt was added. The following table illustrates the results obtained with uranyl nitrate :- Amount of salt added. Total amount of reducing substances, Starch converted. ReIative amylo- lytic action. 0 -000 per cent. 0'001 ,, 0'003 ,, 0.005 ,, 0~001 ,, 0.003 ,, 0.008 ,, 0 *4135 gram. 0.4.083 ,, 0.3873 ,, 0.3698 ,, 0.3612 ,, 0'3131 ,, trace 37 21 per cent. 36.74 ,, 34.85 ,, 33.28 ,, 32-50 ,, 28-17 ,, - 100.0 98 -7 93 -6 89 -4 87 *3 7 5 .5 - Uranyl acetate was more inhibitory in its action, due possibly to its greater acidity ; 0.0003 per cent. increases, 0.003 per cent. stops amylolytic action. Experiments wit,h similar results were obtained with ammonio-uranous snlphate, sodio-manic sulphate, potassio-uranic oxychloride, and ammonio-uranic citrate. The action of the salts varies with different specimens of saliva, according to the amount of protei'd present which is precipitated by them. Loss of amylolytic power is due in part to partial direct destruction of the ferment as well as to change in reaction of the fluid. There must, however, be some- thing in addition to the mere presence of these salts dependent on chemical constitut'ion that controls the action of the ferment. The same salts were also investigated in regard to their action on the proteolytic action of pepsin-hydrochloric acid.Similar series of experiments were made, and the results compared by estimating the amount of fibrin left undigested after an hour's action. The potas- sium uranic oxychloride was the only salt that produced initial stimu- lating action on the ferment; the others all retarded its activity. The difference in action of the various salts seems to depend on thePHYSIOLOGICAL CHEMISTRP. 79 acid liberated from them ; the acids which are not capable of working with pepsin will most readily retard gastric digestion; thus t'he acetate retards digestion more than the nitrate ; acetic acid mixed with pepsin is practically inactive, whilst nitric acid is about four- fifths as active as hydrochloric acid.A similar series of experiments showed that uranium salts also retarded the action of the pancreatic ferment. W. D. H. Digestion in Rhizopods. By -M. GREEXWOOD (Journ. of Physid., 8, 263--287).-The authoress has continued her observations on the digestive processes in Awmba and Actinoqsphmriwn ( Abstr., 1886, 1053) with the following results : (1.) The ingestion of solid matter is promiscuous in amceloa, that, is nutritious and innutritious matters are taken in with equal readiness. Actinosphaerium, on the other hand, rarely inqests innutritions particles. (2.) The act of ingestion i n amceba is accompanied by the emission of pseudopodia ; in actino- sphaerium these may or may not be thrown out.(3.) The nutritious matter taken in by ameba is not surrounded by fluid when it lies in the endosac. (4.) Nut,ritious particles are in both animals digested by fluid poured out around them. This fluid has no action on the cuticle of organisms, or on cellulose or siliceous cell-walls. Fat and starch are apparently not digested by it. Jt is a colourless fluid, which acts on coagulated, and still more so on non-coagulated proteid matter. It has no action on litmus or carmine particles, acci- dentally enclosed with nuritious particles, and is therefore neutral in reaction, (5.) The secretion is more active in actinosphtmium than in amceba. (6.) Chlorophyll is changed to a dark-brown colour by aniceha ; this is not so marked in actinosphzerium.(7.) Ejection is performed a t the hind end of amoeba, either by means of a vacuole, or often in the case of algae without one, An excretory vacuole is always present in actinosphaerium. (8) The time between ingestion and ejection is difficult to determine, and varies with the size and di- gestibility of the ingesta; it averages 3 to 4 days in amceba. In actinosphaerium the digestive act is shorter and occupies from 18 to 8 hours. W. D. H. Dehydration of Glucose in the Stomach and Intestines. By R. H.-CHITTENDEN (Studies from Lab. Physiol Chern., Yale Univ., 2, 46--53).-Pavy (Chem. News, 49, 128, 140, 155, 162, 172, 183) brought forward evidence to show that there exists, particularly in the stomach and intestines of rabbits, a ferment which has a de- hydrating action on glucose, transforming it into a substance with less cupric oxide reducing power, akin to maltose.This substance is formed a t a temperature of 48" by bringing a solution of glucose into contact with the stomach and intestines of a rabbit; by boiling it with dilute sulphuric acid, i t is again converted into glucose. In the present research these experiments were repeated, but gave an entirely negative result, rabbits and cats being the animals used, in different stages of digestion. Ogata (Jal~rsber. fur Thierchent., 15, 275) has also been unable to confirm Pavy's results. W. D. H.80 ABSTRACTS OF CHEMICAL PAPERS. Nitrogen. 1 Yhosphorus. Sulphur. Influence of Antimonious Oxide on Metabolism. By R. H. CHITTENDEN and J. A. BLAKE (Studies from Lab. Physiol.Chem., Yale Univ., 2, 87--9~4).-Antirnonious oxide was used instead of tartar emetic, because of its probable slower toxic action, and also because it has been so extensively used as a means to induce or to aid in the production of fatty degeneration, for instance, in tlhe production of fatty livers in geese (H. C. Wood, Therapeutics, 161). The nitrogen, phosphorus, sulphur, and chlorine were estimated daily in the urine of a dog, to whom a fixed diet was administered, first for a period without and afterwards for a period with the addi- tionof small quantities of antimonious oxide. The results of the two series may be stated as follows :- Daily Averlxge qf Constituents of Urine in grams. Chlorine. L. Without antimony.. . . 11 -743 0 9251 0 * 6708 0 *5592 2.With antimony . . . . . .I 12.028 I 0-72Y2 1 0.6539 I 0 ‘50’70 T’he conclusion is drawn that small repeated doses of antimonioiis oxide are without influence on the excretion of nitrogen, sulphur, and phosphorus, and that consequently t h i s compound, a t least when taken in non-toxic doses, has no action on protei’d metabolism. Asparagine as a Nourishing Constituent of Food. By H. WEISKE (Landw. Versuchs-Stat., 34, 303--310).-A review of the work done by various chemists. It is shown that the mass of evidence produced is in favour of asparagine being a nutrient for herbivora, and that, under appropriate conditions it prevents waste, and causes the formation of albumin. As to its influence on ornnivora and carnivora, this does appear t o be the case, but on the contrary it produces strong diuretic action, and destruction of a1 bumin ; however, more experi- ments are necessary for t,he complete elucidation of the problem. W.D. H. E. W. P. Ash in Bones of Different Ages. By W. P. MASOX (Chem. h-ews, 56, 157-1159).-The author has examined for ash and as to brittleness scveral samples of bones, both from males and females, from bodies recently dead and from living people (amputations). I n all cases the history of the bone R ~ S known, and the ash determined in portions selected from the dense portion of the middle of the khaft of the femur. All diseased bones, or bones from persons suffering from ailments affecting the bones, were excluded. His results show that from machood to old age, there is no variation i n the amount of ash in bones.That the brit tleuess of old bones is due to the material rather than the structure; that it is not therefore due to the increape of spongy tissue and diminution of the denser portions of the bone as age advances (PrBmg’s supposition) ; nor does it arise from the increase in t h e perzentage of inorganic salts. D. A. L.PEYSIOLOQlCATi CHENISTRY. 81 Distribution of Antimony in the Organs and Tissues. By R. H. CHITTENDEN and J . A. BLAKE (Studies from Lab. Pkysiol. Chem., Yale Uwiv., 2, 68-86) .-These experiments were undertaken in order that data of medico-legal importance might be obtained ; the relative distribution of the poison In the tissues giving indications of the length of time that intervenes bettween the administration of the poison and death. The only trust'worthy method of estimating small quantities of antimony was found to be the electrolytic method (Classen, Abstr.1885, 191, 932) ; preliminary experiments were performed which showed that this method acts well when antimony is mixed with organic matter, and also in urine. A feeble current was used and allowed to act for many hours ; the antimony was collected at the negative pole which was a platinum capsule. When the eeparation of the metal was complete, it was found necessary to remove all organic matter by washing with water before breaking the current, otherwise the antimony quickly redissolved. Tables are given of the results in which various compounds of antimony were giren by hypodermic injection, by the mouth, aud by the rectum in dogs and rabbits. The brain axd liver were the organs in which the metal tends most to accumulate, although if sufflcient time elapses between the giving of the poison and death, it tends to spread more uniformly through the body; the more soluble com- pounds of antimony like tartar emetic produce their effects more rapidly than the insoluble forms like antimonious oxide.W. D. H. Formation and Elimination of a Ferruginous Pigment in Poisoning with Toluylenediamine. By ENGEL and KIENER (Compt. rend., 105, 465--467).-1n acute cases which end in death i n a few hours, there is no icteria and no haemoglobinuria, but the victim falls into a state of coma and dies. There is intense conges- tion of all the organs and especially of the lungs, but the spleen and marrow contain no excess of pigment. When death ensues after a few days, there is always icteria and often hEmoglobinuria, and the urine is loaded with fat and yellow and brown pigment granules which are variable in composition but sometimes contain iron.The ferruginous pigment formed by the destruction of the haemoglobin accumulates in thc spleen and marrow. It seems to be formed from the hzemoglobin in the proto- plasm from the cellules and not from the red corpuscles. The deposits in the liver are less constant and more local. I n chronic cases ending in death after several weeks, the icteria is moderated and is often retarded for a long time, There is DO hsemoglobinuria and no granular pigment in the urine. The animal eventually succumbs to anzmia, which is followed by coma, and after death the spleen, marrow, and liver contain a greater quantity of the ferruginous pigment than in acute cases, and there is a notable quantity in the kidneys and in the lymphatic ganglions of the abdomen.C. H. €3. VOL. LIT. 9PHYSIOLOGICAL CHEMISTRY.P h y s i o l o g i c a1 C h e m i s t r y .Influence of some Organic and Inorganic Substances onGas Metabolism. By R. H. CHITTENDEN and G. W. CUMMIKS(Studies from Lab. Yhysiol. Chent., Yale Univ., 2, 200-236).-Tbequestion investigated was the consumption of oxygen and the elimi-nation of carbonic anhydride. The animal, a rabbit, was confined ina large bell-jar, through which air was drawn by means of threeaspirators, which were arranged to work evenly, and emptied them-selves in half an hour.Two-fifths of the mixed air was drawn suc-cessively through three absorption-tubes, each of which contained100 C.C. of standard bnryta. The carbonic anhydride was estimatedby titration with standard oxalic acid. The results obhined are notabsolute, but express quite well the comparative action of the varioussubstances experimented with. It was found necessary to have theanimal in a state of hunger during an experiment. Accordingly itwas deprived of food for three days previous to the experiment, aswell as during the three days for which the experiment lasted. Duringthe last two of the three days, the substance experimented with wasgiven in small and oft-repeated doses. Every day numerous deter-minations of carbonic anhydride were made, and comparison couldthen be made between the normal excretion of that substance andtbat during the administrakion of the drug.Observations were alsomade on the body temperature. The following are briefly the resultsobtained with the following substances :-Uranyl nitrate acts slowly,but when taken in sufficient quantity tends to raise materially thebody temperature, and increase very noticeably the excretion of car-bonic anhydride. Copper sulphate shows a marked influence indepressing body temperature, and a still greater infliiense in dimi-nishing the production of carbonic anhydride. Arsenious oxidegiven in non-toxic doses also diminishes the excretion of carbonicanhydride, presumably through its action on the metabolic activityof the tissue cells.Tartar emetic acts similarly. Morphine sulphatehas but little action ; a slight fall in the excretion of carbonic anhy-dride immediately after a dose must be attributed to the semi-somnolent condition of the animal. Quinine sulphate, which is soimportant as an antipyretic, is found in a healthy hungry rabbi78 ABSTRACTS OF CHEMICAL PAPERS.t o have only B very slight depi-essing influence on body tem-perature, and a minimum effect on the production of carbonic anhy-dride. Cinchonidine sulphate produced a slight rise of temperatureand a gradual diminut.ion in the amount of carbonic anhydrideexcreted ; it also caused tetanic convulsions and finally death. Anti-pyrine had little effect, the only change being a fall in temperaturejust before death.W. D. H.Action of Uranium Salts on Digestive Ferments. By R. H.CHITTENDEN and M. T. HUTCHINSON (Xtudies 'from Lub. Physiol. Chew,Yule UTZ~U., 2, 55--67').-Very small quantities of uranium salts pro-niote the activity of saliva ; larger amounts hinder and finally stopits amylolytic action. 100 C.C. of digestive mixture coiitained 2 C.C.of neutralised saliva, and 1 gram of pure potato-starch. Themixture was warmed at 40" for 31) minutes and then boiled to preventfurther action; the amount of sugar present was estimated asdextrose by Behling's solution. This was compared with otherdigestive mixtures to which a certain percentage of a uranium saltwas added. The following table illustrates the results obtained withuranyl nitrate :-Amount of saltadded.Total amount ofreducing substances, Starch converted.ReIative amylo-lytic action.0 -000 per cent.0'001 ,,0'003 ,,0.005 ,,0~001 ,,0.003 ,,0.008 ,,0 *4135 gram.0.4.083 ,,0.3873 ,,0.3698 ,,0.3612 ,,0'3131 ,,trace37 21 per cent.36.74 ,,34.85 ,,33.28 ,,32-50 ,,28-17 ,, -100.098 -793 -689 -487 *37 5 . 5 -Uranyl acetate was more inhibitory in its action, due possibly toits greater acidity ; 0.0003 per cent. increases, 0.003 per cent. stopsamylolytic action. Experiments wit,h similar results were obtainedwith ammonio-uranous snlphate, sodio-manic sulphate, potassio-uranicoxychloride, and ammonio-uranic citrate. The action of the saltsvaries with different specimens of saliva, according to the amount ofprotei'd present which is precipitated by them.Loss of amylolyticpower is due in part to partial direct destruction of the ferment as wellas to change in reaction of the fluid. There must, however, be some-thing in addition to the mere presence of these salts dependent onchemical constitut'ion that controls the action of the ferment.The same salts were also investigated in regard to their action onthe proteolytic action of pepsin-hydrochloric acid. Similar series ofexperiments were made, and the results compared by estimating theamount of fibrin left undigested after an hour's action. The potas-sium uranic oxychloride was the only salt that produced initial stimu-lating action on the ferment; the others all retarded its activity.The difference in action of the various salts seems to depend on thPHYSIOLOGICAL CHEMISTRP.79acid liberated from them ; the acids which are not capable of workingwith pepsin will most readily retard gastric digestion; thus t'heacetate retards digestion more than the nitrate ; acetic acid mixedwith pepsin is practically inactive, whilst nitric acid is about four-fifths as active as hydrochloric acid.A similar series of experiments showed that uranium salts alsoretarded the action of the pancreatic ferment. W. D. H.Digestion in Rhizopods. By -M. GREEXWOOD (Journ. of Physid.,8, 263--287).-The authoress has continued her observations on thedigestive processes in Awmba and Actinoqsphmriwn ( Abstr., 1886,1053) with the following results : (1.) The ingestion of solid matter ispromiscuous in amceloa, that, is nutritious and innutritious mattersare taken in with equal readiness. Actinosphaerium, on the otherhand, rarely inqests innutritions particles. (2.) The act of ingestioni n amceba is accompanied by the emission of pseudopodia ; in actino-sphaerium these may or may not be thrown out.(3.) The nutritiousmatter taken in by ameba is not surrounded by fluid when it lies inthe endosac. (4.) Nut,ritious particles are in both animals digestedby fluid poured out around them. This fluid has no action on thecuticle of organisms, or on cellulose or siliceous cell-walls. Fatand starch are apparently not digested by it. Jt is a colourless fluid,which acts on coagulated, and still more so on non-coagulatedproteid matter.It has no action on litmus or carmine particles, acci-dentally enclosed with nuritious particles, and is therefore neutral inreaction, (5.) The secretion is more active in actinosphtmium thanin amceba. (6.) Chlorophyll is changed to a dark-brown colour byaniceha ; this is not so marked in actinosphzerium. (7.) Ejection isperformed a t the hind end of amoeba, either by means of a vacuole,or often in the case of algae without one, An excretory vacuole isalways present in actinosphaerium. (8) The time between ingestionand ejection is difficult to determine, and varies with the size and di-gestibility of the ingesta; it averages 3 to 4 days in amceba. Inactinosphaerium the digestive act is shorter and occupies from 18 to8 hours.W. D. H.Dehydration of Glucose in the Stomach and Intestines.By R. H.-CHITTENDEN (Studies from Lab. Physiol Chern., Yale Univ., 2,46--53).-Pavy (Chem. News, 49, 128, 140, 155, 162, 172, 183)brought forward evidence to show that there exists, particularly inthe stomach and intestines of rabbits, a ferment which has a de-hydrating action on glucose, transforming it into a substance withless cupric oxide reducing power, akin to maltose. This substance isformed a t a temperature of 48" by bringing a solution of glucose intocontact with the stomach and intestines of a rabbit; by boiling itwith dilute sulphuric acid, i t is again converted into glucose. In thepresent research these experiments were repeated, but gave an entirelynegative result, rabbits and cats being the animals used, in differentstages of digestion.Ogata (Jal~rsber. fur Thierchent., 15, 275) has alsobeen unable to confirm Pavy's results. W. D. H80 ABSTRACTS OF CHEMICAL PAPERS.Nitrogen. 1 Yhosphorus. Sulphur.Influence of Antimonious Oxide on Metabolism. By R. H.CHITTENDEN and J. A. BLAKE (Studies from Lab. Physiol. Chem., YaleUniv., 2, 87--9~4).-Antirnonious oxide was used instead of tartaremetic, because of its probable slower toxic action, and also because ithas been so extensively used as a means to induce or to aid in theproduction of fatty degeneration, for instance, in tlhe production offatty livers in geese (H. C. Wood, Therapeutics, 161).The nitrogen, phosphorus, sulphur, and chlorine were estimateddaily in the urine of a dog, to whom a fixed diet was administered,first for a period without and afterwards for a period with the addi-tionof small quantities of antimonious oxide.The results of the twoseries may be stated as follows :-Daily Averlxge qf Constituents of Urine in grams.Chlorine.L. Without antimony.. . . 11 -743 0 9251 0 * 6708 0 *55922. With antimony . . . . . .I 12.028 I 0-72Y2 1 0.6539 I 0 ‘50’70T’he conclusion is drawn that small repeated doses of antimonioiisoxide are without influence on the excretion of nitrogen, sulphur, andphosphorus, and that consequently t h i s compound, a t least whentaken in non-toxic doses, has no action on protei’d metabolism.Asparagine as a Nourishing Constituent of Food.By H.WEISKE (Landw. Versuchs-Stat., 34, 303--310).-A review of the workdone by various chemists. It is shown that the mass of evidenceproduced is in favour of asparagine being a nutrient for herbivora, andthat, under appropriate conditions it prevents waste, and causes theformation of albumin. As to its influence on ornnivora and carnivora,this does appear t o be the case, but on the contrary it produces strongdiuretic action, and destruction of a1 bumin ; however, more experi-ments are necessary for t,he complete elucidation of the problem.W. D. H.E. W. P.Ash in Bones of Different Ages. By W. P. MASOX (Chem.h-ews, 56, 157-1159).-The author has examined for ash and as tobrittleness scveral samples of bones, both from males and females, frombodies recently dead and from living people (amputations).I n allcases the history of the bone R ~ S known, and the ash determined inportions selected from the dense portion of the middle of the khaft ofthe femur. All diseased bones, or bones from persons suffering fromailments affecting the bones, were excluded. His results show thatfrom machood to old age, there is no variation i n the amount of ash inbones. That the brit tleuess of old bones is due to the material ratherthan the structure; that it is not therefore due to the increape ofspongy tissue and diminution of the denser portions of the bone as ageadvances (PrBmg’s supposition) ; nor does it arise from the increase int h e perzentage of inorganic salts.D. A. LPEYSIOLOQlCATi CHENISTRY. 81Distribution of Antimony in the Organs and Tissues. ByR. H. CHITTENDEN and J . A. BLAKE (Studies from Lab. Pkysiol. Chem.,Yale Uwiv., 2, 68-86) .-These experiments were undertaken inorder that data of medico-legal importance might be obtained ; therelative distribution of the poison In the tissues giving indications ofthe length of time that intervenes bettween the administration of thepoison and death. The only trust'worthy method of estimating smallquantities of antimony was found to be the electrolytic method(Classen, Abstr. 1885, 191, 932) ; preliminary experiments wereperformed which showed that this method acts well when antimony ismixed with organic matter, and also in urine. A feeble current wasused and allowed to act for many hours ; the antimony was collectedat the negative pole which was a platinum capsule.When theeeparation of the metal was complete, it was found necessary toremove all organic matter by washing with water before breaking thecurrent, otherwise the antimony quickly redissolved.Tables are given of the results in which various compounds ofantimony were giren by hypodermic injection, by the mouth, aud bythe rectum in dogs and rabbits. The brain axd liver were the organsin which the metal tends most to accumulate, although if sufflcienttime elapses between the giving of the poison and death, it tends tospread more uniformly through the body; the more soluble com-pounds of antimony like tartar emetic produce their effects morerapidly than the insoluble forms like antimonious oxide.W. D. H.Formation and Elimination of a Ferruginous Pigment inPoisoning with Toluylenediamine. By ENGEL and KIENER(Compt. rend., 105, 465--467).-1n acute cases which end in death i na few hours, there is no icteria and no haemoglobinuria, but thevictim falls into a state of coma and dies. There is intense conges-tion of all the organs and especially of the lungs, but the spleen andmarrow contain no excess of pigment.When death ensues after a few days, there is always icteria andoften hEmoglobinuria, and the urine is loaded with fat and yellowand brown pigment granules which are variable in composition butsometimes contain iron. The ferruginous pigment formed by thedestruction of the haemoglobin accumulates in thc spleen andmarrow. It seems to be formed from the hzemoglobin in the proto-plasm from the cellules and not from the red corpuscles. Thedeposits in the liver are less constant and more local.I n chronic cases ending in death after several weeks, the icteria ismoderated and is often retarded for a long time, There is DOhsemoglobinuria and no granular pigment in the urine. The animaleventually succumbs to anzmia, which is followed by coma, and afterdeath the spleen, marrow, and liver contain a greater quantity of theferruginous pigment than in acute cases, and there is a notablequantity in the kidneys and in the lymphatic ganglions of theabdomen. C. H. €3.VOL. LIT.

ISSN:0368-1769    

DOI:10.1039/CA8885400077

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

82 ABSTRACTS OF OHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Formation of Nitrites during Nitrification of Ammoniacal Solutians. By J. M. H. MUNRO (Chem. News, 56, 62--64).-Gayon and Dnpetit have suggested that the nitrite formed during nitri- fication is produced by reduction of previously formed nitrate ; they suppose the nitrifying organism either to acquire reducing powers by living a t the bottom of a solution, or else that it is not pure but mixed with denitrifjing bacteria, and that the nitrate reduced by one or other of these, supplies oxygen for the oxidation of organio matter present in the solut'ian. The present experiments disprove this and show (1) that a solution of potassium nitrate, seeded with soil from a recently nihified solution, develaps no nitrite even though kept for a year in a stoppered bottle; (2) that a solution of ammonium chloride, seeded with the same soil, and with no other added organic matter, formed nitrite in increasiiig quantities fn,m the third day to the 139th, when almost all the ammoniacal nitiogen was present in that form, afterwards pasaing into nitrate ; (3) that a solution containing both potrassium nitrate and ammonium chloride (3KN03 + NHICl) seeded with the same soil, ran through exactly the same course aa the preoeding.If an organism were present capable of reducing nitrate to nitrite with simultaneous oxidation of ammonia to nitrite, four times the quantity of nitrite produced in the preceding case could theoretically be formed : instead of this, the amounts were almost exactly equal, and both a little under that corresponding to the whole of the amrnoniacal nitrogen.The author concludes that the nitrite i s formed by oxidation of the ammonia, J. M. H. M. Chemical Nature of Aristoloohia Serpentaria, By M. SPICA (Gazzetta, 17, 3 13-316) .-The Aristolochia serpentaria (Virginia snake-root) grows in the southern part of North America, especially in the mountainous districts of Carolina and Virginia ; various preparations of its roots are used medicinally aa febrifuges. Its chemical nature has previously been examined by Buchholz, Chepallier, and others, who have obtained besides other products a volatile ail, On distilling the ethereal extract of the root in a current of steam, a yellowish-green oil is obtained, heavier than water, and having an odour resembling that of camphor and valerian.This oil, after treatment with potash, is caoled by a freezing mixture, which causes the separation o f a crystalline stearoptene ; t h i s melts at 198", boils at 212", and is shown by chemical analysis and its physical properties to be borneol. No very definife product could be obtained from the oil from which the borseol had thus been separated. V. H. V. Constituents of Scopolia Root. By H. HEYSCHKE (Chew!. Ceutr., 1887, 108'7--10~8).-Scopolia japonica, or Japanese belladonna,VEGETABLE PHYSIOLOGY AND AGRICULTURE. 83 is a species of Solanaceae indigenous to Japan and China. Two alkaloids are manufactured commercially from its roots, namely, scopole'ine and roto'ine, and Eijkman has obtained two substances, a glucoside, scopolin, and scopoletin, its decomposition product.It is here shown that the rootl of the plant contains no peculiar alkaloyd, but the three my driatic alkalojids, atmpine, hyoscyamine, and hyoscine in variable proportions. Commercial rotoyne is not a distinct base, bnt a mixture of the sodium salts of fatty acids of high molecular weight. The fluorescent substance, scopolet.in, obtained by Eij kmann, is identical with the so-called chrysatropic acid of Kunz, whilst it is further probable that it is identical with methylssculetin. V. H. V. Oil of Lallemantia Iberica. By I;. RICHTER (Lnndw. Versuchs- Stat., 34, 383--390).-l'he oil expressed from the seeds of LaZZe- mantin iberica (Fisch et May) has the property of being the most rapidly " drying " of all known oils.The ethereal extract of the seeds may be completely decolorised by animal charcoal, and on evaporation of the ether, a pale-yellow oil is obtainable which after some time becomes slightly opaque ; the opacity may be removed by filtration, when a clear fat of faint but acrid odour, whose taste resembles that of linseed oil, is left on the filter. The oil is insoluble in cold, but readily soluble in hot alcohol, insoluble in cold acetic acid (1.0643). The sp. gr. of the oil is 0.9386 at 20', and its solidifying point -35" ; the free fatty acids melt at 22.2", and resolidify a t 11.0". When exposed to the air for five days, a crust is formed at the edge of the liquid, but complete resinification, or "drying," occurs in 24 hours, after it has been heated a t 150" for three hours.Casselman states that complete drying of linseed oil only occurs after 36 to 48 hours' heating at 150"; poppy oil requires four to five days, and hemp oil still longer. It behaves towards nascent nitrous acid in the same manner as linseed oil, a dark-red doughy mass being produced. Mixed with concentrated sulphuric acid, the temperature rises to 102" and even to 120". According to v. Hiibl's method, the oil purified from fat, unites with 162.1 grams of iodine per 100 grams oil, whilst the fat com- bines with 166.7 grams of iodine. No other oil approaches closely to thi8 figure except linseed. As the absorption of iodine by the oil corresponds with its facility for drying, it was necessary to estimate the amount of oxygen absorbable; this was done by Livache's process, when it was found that the oil absorbed 15.81 per cent. of oxygen in one day, whilst the fatty acid absorbed 16.58 per cent.in 28 days; linseed absorbs 14.3 per cent. in two days, and its fatty acid 11 per cent. in eight days. Hehner's and West-Knight's methods for determining the percentage of insoluble fatty acids in the oil were both used, the former method showed the presence of 93.3 per cent., and the latter 54 per cent., and the volatile oil (Reichert's method) amounted to 1.55. The figures representing saponitiability (KO ttstorfer) were 184.9 (milligramP KHO), and 9-75 per cent. of glycerol was found, corresponding with y B84 ABSTRACTS OF CHEMICAL PAPERS. 99.74 per cent. of glycerides.The lead salt was used to cause separation of the liquid and solid fatty acids, when it was found that clf the latter there was 6.55 per cent. and of the former 9345 per cent,. present. The quantitative reactions me given in the .original. When grown as a field mop, Lallemahtia yielded 2031 kilos. seed and 6314 kilos. straw per 'hectare. E. W. P. Are Nitrates indispensdble for the Growth of Field Crops ? By 0. PITRCH (Lmdw. Ters.uchs-;Stmt., 34, 21 7--258).--The carefuIly conducted experiments for the elucidation of the above question appear to be most satisfactory, and the decision arrived at is that a t anyrnte barley, oats, beans, and wheat can and do grow in a soil absolutely destitute of nitrates, free from all nitrifying bacteria, but in which nitrogenous manures are present? as ammonium sulphate.The experiments were made during two seasons, and all the precau- tions taken, the progress of the various plants grown, and the apparatns employed aTe fully detailed. I n outline, a rich soil was fimt heated in an oil-bath to destroy a l l bacteria, then thoroughly washed fby upward displacement, to free it from all nitrates, again heated and then placed, the first year, in 1arge"beab-er glasses, and in the second season in iron vessels 62 cm. x 25 em. ; the seeds were sown, and a thick covering of cotton wool placedton the surface of the soil in ;t suitable holder of wire net, so as to preveat access of all aerial spores ; distilled water was used for watering by a special method described in full, whereby tbe water was admitted from below.Two sets of such yessels and fieeds were emplojed. To the soils used in the first year, bicalcium potassium phosphates and ammonium sulphate wei=e added, both to t,he original and to the parallel sets, the difference between the two being that the soil of the8parallel sets was neither heated nor covered over with cotton wool. I n the second year, however, the soil under- went the same process in both sets, but in place of arnmon'ium sulphate being added to the controlling sets, sodium nitrate was added, and no cottcn wool used. The results in both years were, however, similar, namely, that the growth of the plants under such peculiar conditions as total absence of nitrates was not largely affected-certainly there was a difference, but not a t all remarkable ; .the plants were able to grow healthily, but perhaps not robnstly without ally nitrates.It was notioed that those plants which could obtain no nitrates, but had to be content with nitrogen in other forms, came to a standstill for LL short time early in their growth, and after a short period of rest, again grew normally. The author tried to account for this in the first year, by the fact that as the manure had not been mixed thoroughly with the soil throughout its whole depth, the lower roots were unable to obtain nitrogen, c3onseq.czent.ly n o growth was made until new roots were formed higher up, but a h r the experiments of the second season had been made, he was obliged to abandon this theory, for although he had mixed the manure thoroughly with the soil, yet this arrest of growth again occurred, whilst no such effect was produced in the soil containing nitrates.E. W. P.ANALYTICAL CEERZISTRP. 85 Agricultural Experiments. By J. RAUL~N (Compt. rend., 105, 411-424).-1n order to avoid, i n agricultural experiments, errors due to differences between the naturd fertility of contiguous patches of soil, the experimental plot should be divided i n k three rectangular sections, A, B, and C, which are h a t e d separately. As a rule, the results with A and C differ, and in a few cases the differences are quite irregular. Usually, however, the fertility of the plot varies gradually, so that the mean of A and C is practically identical with H , Experiments made in this way show that superphosphates and precipitated calcium phosphate prodnce a distinct increase in the wheat crop, whilst with fossil phosphates.and with slags the results are doubtful, the apparent inwease not being greater than the variations between the three sections of the plot. C. H. B.82 ABSTRACTS OF OHEMICAL PAPERS.Chemistry of Vegetable Physiology and Agriculture.Formation of Nitrites during Nitrification of AmmoniacalSolutians. By J. M. H. MUNRO (Chem. News, 56, 62--64).-Gayonand Dnpetit have suggested that the nitrite formed during nitri-fication is produced by reduction of previously formed nitrate ;they suppose the nitrifying organism either to acquire reducingpowers by living a t the bottom of a solution, or else that it is notpure but mixed with denitrifjing bacteria, and that the nitratereduced by one or other of these, supplies oxygen for the oxidation oforganio matter present in the solut'ian.The present experimentsdisprove this and show (1) that a solution of potassium nitrate,seeded with soil from a recently nihified solution, develaps nonitrite even though kept for a year in a stoppered bottle; (2) thata solution of ammonium chloride, seeded with the same soil, and withno other added organic matter, formed nitrite in increasiiig quantitiesfn,m the third day to the 139th, when almost all the ammoniacalnitiogen was present in that form, afterwards pasaing into nitrate ;(3) that a solution containing both potrassium nitrate and ammoniumchloride (3KN03 + NHICl) seeded with the same soil, ran throughexactly the same course aa the preoeding.If an organism werepresent capable of reducing nitrate to nitrite with simultaneousoxidation of ammonia to nitrite, four times the quantity of nitriteproduced in the preceding case could theoretically be formed : insteadof this, the amounts were almost exactly equal, and both a little underthat corresponding to the whole of the amrnoniacal nitrogen. Theauthor concludes that the nitrite i s formed by oxidation of theammonia, J. M. H. M.Chemical Nature of Aristoloohia Serpentaria, By M. SPICA(Gazzetta, 17, 3 13-316) .-The Aristolochia serpentaria (Virginiasnake-root) grows in the southern part of North America, especiallyin the mountainous districts of Carolina and Virginia ; variouspreparations of its roots are used medicinally aa febrifuges.Itschemical nature has previously been examined by Buchholz,Chepallier, and others, who have obtained besides other products avolatile ail, On distilling the ethereal extract of the root in acurrent of steam, a yellowish-green oil is obtained, heavier than water,and having an odour resembling that of camphor and valerian.This oil, after treatment with potash, is caoled by a freezing mixture,which causes the separation o f a crystalline stearoptene ; t h i s meltsat 198", boils at 212", and is shown by chemical analysis and itsphysical properties to be borneol. No very definife product could beobtained from the oil from which the borseol had thus beenseparated. V. H. V.Constituents of Scopolia Root.By H. HEYSCHKE (Chew!.Ceutr., 1887, 108'7--10~8).-Scopolia japonica, or Japanese belladonnaVEGETABLE PHYSIOLOGY AND AGRICULTURE. 83is a species of Solanaceae indigenous to Japan and China. Twoalkaloids are manufactured commercially from its roots, namely,scopole'ine and roto'ine, and Eijkman has obtained two substances,a glucoside, scopolin, and scopoletin, its decomposition product.It is here shown that the rootl of the plant contains no peculiaralkaloyd, but the three my driatic alkalojids, atmpine, hyoscyamine,and hyoscine in variable proportions.Commercial rotoyne is not a distinct base, bnt a mixture of thesodium salts of fatty acids of high molecular weight. The fluorescentsubstance, scopolet.in, obtained by Eij kmann, is identical with theso-called chrysatropic acid of Kunz, whilst it is further probablethat it is identical with methylssculetin. V.H. V.Oil of Lallemantia Iberica. By I;. RICHTER (Lnndw. Versuchs-Stat., 34, 383--390).-l'he oil expressed from the seeds of LaZZe-mantin iberica (Fisch et May) has the property of being the mostrapidly " drying " of all known oils. The ethereal extract of theseeds may be completely decolorised by animal charcoal, and onevaporation of the ether, a pale-yellow oil is obtainable which aftersome time becomes slightly opaque ; the opacity may be removed byfiltration, when a clear fat of faint but acrid odour, whose tasteresembles that of linseed oil, is left on the filter. The oil is insolublein cold, but readily soluble in hot alcohol, insoluble in cold acetic acid(1.0643).The sp. gr. of the oil is 0.9386 at 20', and its solidifyingpoint -35" ; the free fatty acids melt at 22.2", and resolidify a t 11.0".When exposed to the air for five days, a crust is formed at the edgeof the liquid, but complete resinification, or "drying," occurs in24 hours, after it has been heated a t 150" for three hours. Casselmanstates that complete drying of linseed oil only occurs after 36 to 48hours' heating at 150"; poppy oil requires four to five days, and hempoil still longer.It behaves towards nascent nitrous acid in the same manner aslinseed oil, a dark-red doughy mass being produced. Mixed withconcentrated sulphuric acid, the temperature rises to 102" and evento 120".According to v.Hiibl's method, the oil purified from fat, uniteswith 162.1 grams of iodine per 100 grams oil, whilst the fat com-bines with 166.7 grams of iodine. No other oil approaches closelyto thi8 figure except linseed. As the absorption of iodine bythe oil corresponds with its facility for drying, it was necessaryto estimate the amount of oxygen absorbable; this was done byLivache's process, when it was found that the oil absorbed 15.81per cent. of oxygen in one day, whilst the fatty acid absorbed16.58 per cent. in 28 days; linseed absorbs 14.3 per cent. intwo days, and its fatty acid 11 per cent. in eight days. Hehner'sand West-Knight's methods for determining the percentage ofinsoluble fatty acids in the oil were both used, the former methodshowed the presence of 93.3 per cent., and the latter 54 per cent., andthe volatile oil (Reichert's method) amounted to 1.55.The figuresrepresenting saponitiability (KO ttstorfer) were 184.9 (milligramPKHO), and 9-75 per cent. of glycerol was found, corresponding withy 84 ABSTRACTS OF CHEMICAL PAPERS.99.74 per cent. of glycerides. The lead salt was used to causeseparation of the liquid and solid fatty acids, when it was found thatclf the latter there was 6.55 per cent. and of the former 9345 percent,. present.The quantitative reactions me given in the .original.When grown as a field mop, Lallemahtia yielded 2031 kilos. seedand 6314 kilos. straw per 'hectare. E. W. P.Are Nitrates indispensdble for the Growth of Field Crops ?By 0.PITRCH (Lmdw. Ters.uchs-;Stmt., 34, 21 7--258).--The carefuIlyconducted experiments for the elucidation of the above questionappear to be most satisfactory, and the decision arrived at is that a tanyrnte barley, oats, beans, and wheat can and do grow in a soilabsolutely destitute of nitrates, free from all nitrifying bacteria, butin which nitrogenous manures are present? as ammonium sulphate.The experiments were made during two seasons, and all the precau-tions taken, the progress of the various plants grown, and the apparatnsemployed aTe fully detailed. I n outline, a rich soil was fimt heated inan oil-bath to destroy a l l bacteria, then thoroughly washed fby upwarddisplacement, to free it from all nitrates, again heated and then placed,the first year, in 1arge"beab-er glasses, and in the second season in ironvessels 62 cm.x 25 em. ; the seeds were sown, and a thick coveringof cotton wool placedton the surface of the soil in ;t suitable holder ofwire net, so as to preveat access of all aerial spores ; distilled waterwas used for watering by a special method described in full, wherebytbe water was admitted from below. Two sets of such yessels andfieeds were emplojed. To the soils used in the first year, bicalciumpotassium phosphates and ammonium sulphate wei=e added, both tot,he original and to the parallel sets, the difference between the twobeing that the soil of the8parallel sets was neither heated nor coveredover with cotton wool. I n the second year, however, the soil under-went the same process in both sets, but in place of arnmon'ium sulphatebeing added to the controlling sets, sodium nitrate was added, and nocottcn wool used.The results in both years were, however, similar,namely, that the growth of the plants under such peculiar conditionsas total absence of nitrates was not largely affected-certainly therewas a difference, but not a t all remarkable ; .the plants were able togrow healthily, but perhaps not robnstly without ally nitrates. It wasnotioed that those plants which could obtain no nitrates, but had tobe content with nitrogen in other forms, came to a standstill for LLshort time early in their growth, and after a short period of rest,again grew normally. The author tried to account for this in thefirst year, by the fact that as the manure had not been mixed thoroughlywith the soil throughout its whole depth, the lower roots were unableto obtain nitrogen, c3onseq.czent.ly n o growth was made until new rootswere formed higher up, but a h r the experiments of the second seasonhad been made, he was obliged to abandon this theory, for althoughhe had mixed the manure thoroughly with the soil, yet this arrest ofgrowth again occurred, whilst no such effect was produced in thesoil containing nitrates. E. W. PANALYTICAL CEERZISTRP. 85Agricultural Experiments. By J. RAUL~N (Compt. rend., 105,411-424).-1n order to avoid, i n agricultural experiments, errors dueto differences between the naturd fertility of contiguous patches ofsoil, the experimental plot should be divided i n k three rectangularsections, A, B, and C, which are h a t e d separately. As a rule, theresults with A and C differ, and in a few cases the differences arequite irregular. Usually, however, the fertility of the plot variesgradually, so that the mean of A and C is practically identical with H ,Experiments made in this way show that superphosphates andprecipitated calcium phosphate prodnce a distinct increase in thewheat crop, whilst with fossil phosphates. and with slags the resultsare doubtful, the apparent inwease not being greater than thevariations between the three sections of the plot. C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8885400082

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

ANALYTICAL CEERZISTRP. 85 A n a 1 y ti c a 1 C h e m i s t r y. Grinding Mill for Minerals. By K. ZULKOWSKY (Bey., 20, 2664--2669).-A description of a mill in which minerals may be readily reduced to fine powder. The grinding surfaces are of agate, and the pestle is so arranged that it can be rotated by a water-motor against the lower surface with a pressure capable of being varied at will. The material, already reduced to the coarseness of sand, is intro- duced into the mill through a sector cut in the pestle. w. P. w. Determination of Sulphur in Pyrites. By J. W. WESTMORELAND (J. SOC. Chem. Ind., 6,84-87).-1t is shown that the results obtained by Lunge’s “ old process ” (precipitation of the sulphur from ferric solutions), agree closely with those given by bhe new process (pre- cipitation after separation of the ferric oxide by ammonia), which is therefore a needless elaboration.The new method is also liable to ’losses caused by an extra filtration and washing, aiid by sulphur retained in the ferric oxide, whilst sulphur is liable to be introducrd by the ammonia and hydrochloric acid employed. The results obtained by Lunge’s processes express the total percentage of sulphur in Spanish pyrites; i t is, however, necessary to, use only a moderate excess of barium chloride for precipitation, great care being taken in the use of hydrochloric acid when washing this precipitate. D. B. Es.timation of Sulphur in Pyrites. By G. LUNGE (J. SOC. Chem. Ind., 6, Sti).---The author criticises Welch’s process (Abstr., 1887, 180) for assaying iron pjrites for sulphur available for sulphuric acid manufacture, and shows that the experiments having been made with Kjeldahl’s Method of Estimating Nitrogen. By F.W. D A F E t w ( L n d w . Versucks. Stat., 34, 311-353).-1n this article, are detailed impure lead sulphide are not conclusive. I>. 13.86 ABSTRACTS OF CHEMICAL PAPERS. in full the resnlts of experiments made for the purpose of testing the value of Kjeldahl’s process for estimating organic nihrogen, and of an examination of the various‘ modifications of this process, as recom- mended by Kreusler and others. Estirnutiom hy the Original Process.-Certain nitrogenous compounds only seem to yield their nitrogen in the arnmoniacal forms, the result being that the process is inaccurate with regard to others; of the latter class, anilines and hydrazines are special examples, but some compounds, contrary to expectation, yield their nitrogen as ammonia more readily than others ; as for instance, it was expected that hydr- azines would yield ammonia more completely and quickly than nitro- compounds, but the contrary is the cme.The Action of the Sulphuric Acid.-To aid the solution of this question, Kreusler’s modification, where phosphoric anhydride is added to the sulphuric acid, was employed; sugar was also added. The explanation which is given is, that, the sulphuric acid removes from the substance the elements of water and of ammonia, and the sulphurous anhydride formed in the reaction reduces the nitrogenous cornpound ; the addition of organic matter (sugar) to the nitrogenous compound slackens the formation of ammonia when the compound is not volatilised by the acid; consequently to obtain quantitative results, the sulphuric acid must not volatilise the compound, nor completely decompose it, for the analysis of some substances by this method free nitrogen accompanies the ammonia. The Action of Permanganate.--The presence of the permangannte when used in company with the mixture of acids, causes a destruction of the organic matter present, the nitrogen being so separated that nearly the whole of i t is transformed into ammonia; as a rule this modification of Kjeldahl’s process may be employed for all quantitative analyses, but i t is necessary that the mixture shall be thoroughly and sufficiently heated.The Addition of Metallic Salts.-This modification of Wilfarth’s renders the original procegs more rapid, although the time required for the analysis is shortened very considerably by the addition of mercury, it is a t the cost of accuracy ; it should only be introdnced in those cases where very stable compounds are under examination, or also when the compounds readily give up their nitrogen as ammonia.From careful examination, it appears that, the discrepancies which exist between the results obtained by Kjeldahl’s original method, Wilfarth’s and Ulsch’s (addition of platinum chloride), are due to loss of nitrogen at9 nitrogen, and not; to an insufficiency of heating, when the compound is only slightly stable. The author considers t h a t Wilfarth’s explana- tion of the reaction which occurs when metallic salts are present, is satisfactory, but he also adds that when those compounds which do not resist the action of sulphuric acid well, or which are readily oxidised, are dealt with, the addition of the metallic salt causing violent oxidation, ammonia may be in part replaced by nitrogen; increasing the quantity of platinum, addition of oxygen and mixing with organic substances may also result in loss, even wben the compound is not easily decomposed.Mercury 8hould be alwnjs employed when very stable compounds are to be analysed; aminesANALYTICAL CHEMISTRY. 87 and alkaloids resist oxidation, but TJlsch’s process must not be used because of its uncertainty, except in special cases, for example, with potassium nitrate. General AppZicatinn,.--Nitrogenous compounds may be divided into two clasves as regards the applicability to them of Kjeldahl’s process of analysis.In the first are placed those which can be analysed without any previous treatment, for example, all amides and ammonium bases, pyrroline and quinoline compounds, alkaloyds, bitter substances, albuminoyds and their allies, and perhaps the indole group ; whilst to the second class belong all nitro-. nitroso-, azo-, diazo-, hydrazo-, and azoamido-compounds, nitrates and nitrites, the hydrazines, and possibly the cyano-compounds. Two methods may be employed for the previous treatment of this second class : addition of an organic substance, or reduction with zincadust, and even the tlwo combined, but the choice of which is to be used must rest with the analyst.This uncertainty will for the present preclude Rjeldahl’s process, or its improvements, from supplanting Dumas’s older and exact method. For the estimation of nitro-compounds, it is recommended to dissolve the substance in 10 C.C. of alcohol (or if it is very stable, directly in sulphuric acid) decompose by zinc-dust, add 10 C.C. of acid, and warm until all alcohol is got. rid of; when this is accomplished, add 10 C.C. of the acid mixture together with mercury, and then proceed as with an ordinary compound. When distilling with sodium hy- droxide, special care must be taken to avoid shaking the flask ; it is therefore advisable to apply heat by mean8 of a sand-bath; in the same manner nitroso- and azo-compounds may be readily analysed.Hydraao-compounds must first be converted into azo-compounds, before exposing them to the action of the sulphuric acid. The author, for example, heats the sulphate of phenylhydrazine first with excess of cane-sugar in presence of sodium acetate for some hours on a water- bath ; after drying the resulting mass, the acid may be added, Most cyano-compounds, as far as the author is aware, can be analysed by this process, but some may exist which will not bear the method. E. W. P. Notes on Nesslerising. By J. M. MILNE (J. XOC, Chern. Ind., 6, 33).-The author recommends Hehner’s method in which the new- lerising is conducted in graduated cylinders having a somewhat broad foot, a glass tap being fused into their sides near the bottom, so that the solution, either standard or water distillate, may be run out until the two tints correspond.This method, a description of which was given in Chem. News, 33, 185, is very simple and readily carried out. As nesslerising cannot be done in gaslight, the author proposes to imitate the process with two shades of indigo solution. D. B. Estimation of Ammonia in Soils by the Knop-Wolf Method. By A. BAUMANN (Lanndw. Versuchs-Stat., 34, 259--276).-A reply to Knop (ibid., 33, 438). Moisture and Free Acid in Superphosphates and similar Fertilisem. By J. RUFFLE (J. SOC. Chen~ Ik.i., 6, 327-333).--It is88 ABSTRACTS OF CHEXICAL PAPERS, shown tbat the soluble phosphoric acid existing in superphosphates is not entirely present as monocalcium phosphate, and that exposure to 100" drives 08 more than the true moisture, that is, the adhering uncombined water. It is recommended to determine the moisture in the following manner:-Weigh out 2 to 5 grams of the superpbos- phate in its natural state on a double watch-glass, place under an air-pump over dry calcium chloride, exhaust, then leave f o r 18 to 24 hours and weigh.The author shows that the acidity of ordinary superphosphates and ammoniated superphosphates is due to phos- phoric acid, and not to sulphnric acid. In ammoniated superphou- phates, monocalcium phosphate is substantially absent, the free acid being phosphoric acid. I). B. Detection of Small Amounts of Carbonic Anhydride and other Gases. By 0. ROSSLER (Bey., 20, 2629-2631).-A small test-tube is drawn out at the lower end to a capillary; this is bent upwards, and cut off a t a distance o€ 1 cm.from the bend. A capil- lary funnel is then made of such a size that the upper end fits the test-tube, the lower end being a t n distance of 1.5 to 2 cm. from the bottom. The substance to be tested for carbonic anhydride is put into the outer tube, the capillary funnel containing baryta-water fitted, and the lower end of the apparatus then dipped into hydro- chloric acid. With 0.0005 gram of sodium carbonate a very distinct turbidity, with 040005 gram a distinct turbidity is produced in the drop of baryta-water a t the end of the capillary. It is possible to detect 0.02 milligram of carbonic anhydride. Sulphuric and nitric acids, hydrogen sulphide, ammonia, &c., can also be detected by means of the apparatus, using iodide of starch, ferrous chloride, lea,d acetate, and copper sulphate respectively.A sketch of the apparatus is given. N. H. M. Absorption of Carbonic Oxide by Cuprous Chloride. By H. DREHSCHMIDT (Rer., 20,2752-2755).-Hempel has recently shown that in certain cases when cuprous chloride is used as an absorbent of carbonic oxide in gas analysis, there is an increase instead of a decrease of volume. This result is explained on the supposition that the ethylene contained in the absorption-liquid is driven out by the absorbed carbonic oxide. It is here shown that this explanation is not sufficiently valid, as similar results were obtained with mixtures of carbonic oxide, with hydrogen, or nitrogen only. Experiments are described in which a given volume of hydrogen was added to the volume OE gas obtained after some of the carbonic oxide had been absorbed ; on completing the absorption, a fresh quantity of carbonic oxide was added, and the experiment repeated.I n all cases, whether an ammoniacal or hydro- chloric acid solution of cuprous chloride was used, an increase of volume of the hydrogen was observed, the increment being greater in the case of the acid solution. If is advisable, therefore, when carbonic oxide is present in small qnantities, to use a fresh ammoniacal solution, or to burn with air by means of palladium asbestos. If the amount of carbonic oxide is large, a portion of the gas is unabsorbed, and must mbsequently be determined by the above methods. V. H. V.ANALYTICAL CHEMISTRY. a9 Estimation of Potassium by Reduction of the Platinochlo- ride with Sodium Formate.By WOUSSEN (Ann. Agronwm., 13, 431--432).-The author has made Corenwinder's process workable by securing tbe agglutination of the reduced platinum. The modified process is conducted ils follows :-SO much of the substance should be taken as will yield 0.750 t o 1 gram of reduced platinum from the potassium platinochloride. This is precipitated with 18 C.C. of a solution of platinum tetrachloride, containing 200 grams per litre, and a slight excess of nit,ric acid ; 8 to 10 C.C. of hydrochloric acid is added, and the solution evaporated to dryness on the water-bath, then taken up with a mixture of nine-tenths alcohol of 96", and one-tenth ether, filtered, and washed with the same mixture.The mixture of potassium platinochloride and salts remaining on the filter is treated with a jet of boiling water, and the hot solution of the platinochloride thus formed added in portions to a boiling solution of 2 to 2.5 grams of sodium formate in 10 C.C. of water. The boiling is continued for 15 to 20 minutes, and then 8 C.C. of hydrochloric acid is added, and the boiling continued with constant agitation. After this addition the reduced platinum soon agglutinates, and leaves the solution clear; the metal is cotlected, washed with boiling water, dried, and Estimation of Potash in Commercial Manures. By D. LINDO (Chem. News, 56, 163--165).-Gladding has proposed the fol- lowing method for this purpose :-Boil 10 grams of the manure for 10 minutes with YO0 C.C.of water, when cool precipitate b~ means of a slight excess of ammonia, make up to 500 c.c., and filter. Evapo- rate 5~ C.C. of the filtrate nearly to dryness, add 1 C.C. of dilute sul- phuric acid (1 : l), continue the evaporation to dryness, and ignite. Dissolve the residue in hot water and a few drops of hydrochloric acid, add 5 C.C. of a 2 per cent. solution of sodium chloride and an excess of platinum chloride solution and wash the precipitate succesdvely with alcohol, solution of ammonium chloride (saturated with potassium platinochloride), and filially again with alcohol, dry, &c. The author has made numerous experiments with this method, and finds it simple, more expeditious, and seemingly suscept*ible of greater accuracy than the methods usually employed.D. A. L. Estimation of Sodium Hydroxide in Soda-ash. By R. WIL- LIAMS ( J . rs'oc. Chenz. h i d . , 6, 346).-The following method is found to give accurate results :-A weighed quantity of soda-ash is agitated with strong alcohol in a stoppered flask and left over night; the un- dissolved carbonat,e is filtered off and washed with strong alcohol until a drop gives no alka!ine reaction ; the filtrate and washings are then titrated with normal acid. D. B. weighed. J. M. El. 31. Estimation of the Relative Amounts of Sodium Hydroxide and Carbonate in Commercial Soda-ash. By P. HART ( J . SOC. Chem. Ind., 6, 347).-The sample under examination is titrated wit,h standard acid, using phenolphthalejin as indicator. As soon as the colour disappears, the whole of the hydroxide and one half of the soda90 ABSTRACTS OF CHEMICAL PAPERS.existing as carbonate has been neutralised, the number of C.C. being noted. To the same solution (in which the soda now exists as sodium hydrogen carbonate) a little methyl-orange is added, ahd the addition of acid from the same burette continued to neutral reaction. By doubling the difference between the two titrations and deducting the number from the number of C.C. consumed, the quantity of hydroxide in the original sample is obtained. D. B. Analysis of Alum Cakes. By R. WrLLims (Chem. Nezos, 56, 194-195) .-The author has adopted the following methods :-For alumina : neutralise the solution with sodium carbonate, add a large excess of sodium hyposulphite, boil for some time, wash, dry, ignite, and weigh the precipitate.For free sulphdric acid : digest all night with strong alcohol, and titrate the alcoholic extract directly with decinormal soda, using phenolphthale’in as ihdicator, Evaporating off the alcohol gives rise to loss, low results ate likewise obtained if the digestion is not continued for a sufficient time. In another method, a, weighed quantity of quinine, morphine, or strychnine is treated with a known quantity of alum solution, and the alkalo’id reweighed after the treatment, the loss representing the alkalojid dissolved by the free acid. Comparative results were obtained as follows :- Alcohol. Strychnine. Quinine. Morphine. Free H2SOa per cent.. . 0.41 0‘54 0.50 0.51 The alkalo’id results are all higher than the alcohol, probably on account of some alkaloid being dissolved by the alum solution and reckoned as sulphate.Determination of Minute Quantities of Iron, wi€h Special Reference to Alum and Aluminium Sulphate. By R. R. TAT- LOCK (J. Soa. Chew. Ind., 6, 276--279).-As a standard, a solution of iron-alum is used, of which 1 C.C. equals 0.001 gram iron, Place 1 gram of the finely powdered sample in an ordinary atoppered sample-tube of about 30 C.C. capacity, and having three marks at 7.5, 10, and 20 C.C. respectively. Add 1 C.C. of standard sulphuric acid, and make up to the lowest mark with water. When +he alum under examination is dissolved, add 0.2 gram of ammoninm thicjcya- nate and make up to 10 c,c. with water. Place 1 cx. of the standard iron solution in a 100-c,c. flask, and make up to the latter volume with water.Now place 1 C.C. of this diluted solution in a stoppered sample-tube, add 1 C.C. of standard acid, make up to the lowest mark with water, add 0.2 gram of the thiocyanate, and make up to the 10 C.C. with water. Then fill up both tubes to the 20 c.c, mark with ether, and agitate them thoroughly, As soon as the contents settle, compare the tints, and if unequal make one or more further trials with greater or less quantities of standard iron solution until the two tints correspond. D. B. By J. H. SMITH (J. SOC. Chem. Ind., 6, 98-111 and 260--271).-When potaa- sium permanganate is used as an oxidising agent in organic research, D. A. L. Detection and Estimation of Organic Substances.ANALPTICAL CHEMISTRY. 91 impure products are obtained, and in varying proportions depending on the amount of reagent employed, temperature, and other conditions.It has therefore only been generally employed as a qualitative reagent. From a study of the behavionr of solutions of various organic sub- stances in presence of a large excess of potassium permanganate under varying standard conditions, it occurred to the author tlhat by employ- ing an excess of the reagent, definite and sjmple compounds would be obtained whose composition in each case might be determined quali- tatively by ordinary analysis, and quantitatively by an estimation of the oxygen absorbed in the reaction. The determinations which the author had in view were the: following :-Oxygen yielded by excess of manganese dioxide in acid, alkaline and neutral solutions respectively ; oxygen yielded by excess of permanganate in such soliitions.The latter would include the former, the difference would represent oxygen yielded by permanganate in reduction to manganese dioxide only, and would necessarily correspond with more stable compounds than those represented by the reduction of manganese dioxide. The author further anticipated successive oxidations, more especially of a neutral one succeeded by an alkaline and acid one respectively, and an alkaline oxidation followed by one in acid solution. It was found, however, that on oxidising an organic or other oxidisable solution by tt large excess of permanganate in acid solution, the results generally came out much too high, even for perfect oxida- tion, which indicated a loss of oxygen due to the presence of manga- nese dioxide.In order to prevent or diminish f h e loss, a ferric salt was added to the permanganate solution, the iron acting as an accelerator in the preseiice of much permanganate and little manganese dioxide, and a retarder when the conditioiis were reversed. The ferric salt is really an accelerator, but it has the power of neutralising the action of the manganese dioxide after a certain excess has been formed. The accelerating action of iron in presence of much per- mangmate may be checked by the addition of sodium phosphate to the solution. The author has based a quantitative method of estimating organic: products on the results obtained from this investigation, The method, which is described in detail in the original, is applicable to the estima- tion of commercial organic substances, the determination of t8he organic matter in potable waters and in the waste liquors from works employing organic products, whilst for the estimation of alcoholic solutions when largely diluted, it is more rapid than the sp.gr. method. I n the second part of the paper, the author treats cf the oxidation of organic substances by means of manganese dioxide in acid soll;tion, as well as of oxidations by permanganate in neutral and alkaline solutions, and of analytical methods derived therefrom. The Stalagmometer : a New Method for the Determination of Fuse1 Oil in Spirituous Liquors. By J. TRAUBE (Rer., 20, 2644--2655).-The author previously described (Abstr., 1886, 743) a method for determining fuse1 oil in brandy by observing the height of the solution in a capillary tube. In the present paper an apparatus, D.B.92 ABSTRACTS OF CHEMICAL PAPERS. called n “stalagmometer,” is described by means of which the percentage of fusel oil is determined by counting the drops contained in a kiiown volume of liquid. As in the older method, the brandy is first diluted so as to be about 20 per cent. It is then put into the stalagmometer, and the number of drops from a given volume observed and com- pared with the number obtained from the same volume of pure 20 per cent. alcohol. An excess of 1% drop to 100 C.C. of liquid shows the presence of 0.1 per cent., an excess of 3.5 drops, of 0.2 per cent. of fusel oil. 0.05 per cent. of fusel oil can be determined readily and with certainty.To increase the delicacy of the method, the proportion of alcohol t o fusel oil must be diminished. This is done in the following manner:--300 C.C. of the liquid to be examined (diluted to 20 to 25 per cent.) is shaken in a funnel with 110 ta 120 grams of pure ammonium sulphate, and left until two layers are formed; the lower layer, which contains vePy little fusel oil, is drawn off and shaken with two to three drops of’ ethyl alcohol. or some crystals of ammonium sulphate. In this way the rest of the fusel oil is obtained as a separate laeyer. These upper layers are now mixed, dissolved in water, and distilled to about two-thirds. The distil- late is made u p to 110 c.c., the alcohol determined by means of A Westphal’s balance, and the number of drops contained in the volumc V by means OF the stalagmometer.The latter number is compared with that obtained from pure spirit containing a known amount of fusel oil. A sketch of the apparatus is gicen, as well 3s results obtained by means of it. These show that the method is as accurate as that previously described (Zoc. cit.), the new method having the advantage of being more easily worked. N. H. M. By J, MUTER and L. DE KOXINGH (Anulyst, 12, 191--195).-CarboZ~c Powders.- Where the phenols exist in the uncombined state, they are extracted by methylated spirit from 75 grams of the powder. Where the powder contains a lime base, a preliminary thorough trituration with a small excesR of dilute sulphuric acid is necessary. The alcoholic extract is mixed with 200 C.C.of a 5 per cent. solution of sodium hydroxide, and the mixture is then evaporated to half its bulk. At this point any tar oils and naphthalene will separate and are to be filtered off. The filtrate is further concentrated to 50 C.C. and trans- ferred to a graduated tube. This, which is known as Muter’s car- bolimeter, is wide in the lower portion. At 65 C.C. it is narrowed to a neck, which is graduated up to 110 C.C. in 0.35 C.C. divisions. It is stoppered, and is furnished with a long, thin, stirring rod, the volume of which must be allowed for. The solution is made up to 6.5 c.c., 25 C.C. of strong hydrochloric acid are slowly added with stirring, and then enough dry common salt t o render the phenols insoluble. The tube is plunged into water of 15.5’ and the volume of the phenols read off.Liquid Oarbolic Acid.-If this contains excess of watep, it will not give a clear solution with three volumes of benzene. The amount of Assay of Commercial Carbolic Compounds.ANALYTICAL CHEXISTRY. 93 water is ascertained by shaking 20 C.C. of the sample with 80 C.C. of a saturated solution of sodium chloride, and observing the diminntion in volume. Tar oils are estimated by shaking 20 C.C. with 80 C.C. of mda solution (5 per cent.), and a small quantity of benzene (10 C.C. for dark specimens, less for pale ones). The increase in the volume of the benzene gives the amount of t a r oils. The remainder i, taken as phenol and cresols. M. J. s. Acidimetry with Red Wines. By TONY-GARCIN (Comyt. read., 105, 577).-When red wine, prepared in the ordinary way and not more than a year old is mixed with sodiam hydroxide solution, the colour changes to carmine, which becomes deeper and duller and passes into violet-black, which afterwards becomes black, without any tinge af violet, and then changes to green, with formation of a dark, flocculent precipitate.The point a t which the colour is brownish- black, without any tinge of violet or green, is the point of exact neutralisation. C . H. €3. Dairy Products. (Bull. U, 8. Agrz‘c. Depart., No. 13, 1-128).- Butter and its Substitutes.-A series of micro-photographs is given, showing the appearance presented by butter, &c., when examined by polarised light. The black cross described by Hehner and Angel1 is seen in all the specimens of butter prepared by boiling and slow cooling, and is almost uniformly absent from the crystals obtained from the other fats, nevertheless it is shown by some specimens of birtterine and oleomargarine from Armour and Co., Chicago, as well as in a slide prepared from beef suet “oleo oil,” by dissolving in hot alcohol, and cooling slowly, thus confirming the opinion that it is not to be trusted as a characteristic of genuine butter.The following method for determining the melting point of fats is described :-Thin discs are obtained by dropping the melted fat on to a piece of ice. One of these is placed in a test-tube, t h e lower part of which contains boiled water, and the upper part strong alcohol. The disc floats between the two liquids. The tube is then warmed in a water-bath, whilst the temperature of the contents is taken by a thermometer with small bulb, situated just above and close to the disc, and kept in motion like a revolving pendulum.The ternpera- ture a t which the disc contracts to a sphere is taken a s the melting point. It is necessary to examine the discs when freshly made, as they show a higher melting point if kept for 24 hours. When the water-alcohol tube is warmed before dropping in the disc, the con- traction takes place some 6” lower than when the former method is followed. Daven- port saponifies 5 grams of the butter with only 10 C.C. of alcoholic potash (cont,aining 2 grams of KHO), operating in a flask from wThich the alcohol vapour is aspirated by a water-pump. Saponification and evaporation to dryness are complete in 15 minutes, and from the statement that genuine butters treated thus require on an average 28.8 C.C.of - alkali, there would appear to be no loss of ethyl buty- Various modifications of Reichert’s process are described. N l d94 ABSTRACTS OF CHEMICAL PAPERS. rat'e (compare Allen, Abstr., 1857, 1145). Crampton substitutes phosphoric for sulphuric acid in the distillation, but finds that with care the two give identical results. Scheffer's test for foreign fats is based on the solvent action of a mixture of amyl alcohol (40 vols.) and ether of sp, gr. .On715 (60 vols.). 1 gram of butter dissolves in 3 C.C. of this mixture at 28" ; 1 gram of lard requires 16 C.C. ; 1 gram of stearin 350 C.C. The following order of value is assigned to the various modes of examining butters for adulteration :-( 1.) Determination of volatile acids.(2.) Determination of specific gravity. (3.) Determination of saponification equivalent (Koettstorfer). (4.) Determination of the insoluble acids (Hehner, Muter, Blyth, &c.X ( 5 . ) Det,errnination of the melting point. A complete bibliography of butter analysis (up to 1882) is given by Caldwell (Seeond Ann. Rep. N . Y. S. E d . of B e a l t h , ,544-547), and i n Sell's Kunstbutter (Arbeit a. d . R a i s e d . Geswndheitsumte), MiEk.-For the determination of water, Babcock employs asbestos to absorb the milk before drying; this is much to be preferred to any powder, By placing the asbestos in a, tube between plugs of cotton- wool, and drawing air through the tube wbile it is heated a t loo", the desiccation is complete in two hours. The tube can then be transferred to the f a t extractor, Of methods for the determination of the fat, the preference is given t o that of Adams (Abstr., 1886, 583), but instead of soaking up the milk with one end of the roll of paper, the plan has been adopted of holding the unrolled strip in a horizontal position, and running the 5 C.C.of milk from a pipette along the middle. The strip is then hung up in a hot chamber, and in two or three minutes is dry and ready for rolling up. In Soxhlet's araometric method (Abstr., 1881, 656) great difficulty was encountered in ensuring the separation of the ethereal fat soln- tion, and any long delay in the separation was found to affect the final results. By placing the bottles containing the mixture in a centrifugal machine revolving about 300 times per minute, the time required for separation was reduced to a few minutes, only six samples out of 150 requiring more than quarter of an hour.The fat solution thus separated had, however, a lower specific gravity than that obtained by simple subsidence, so that the percentage of fat as given in Soxhlet's table had to he increased by 0*1:3, to bring it into agreement with the results of the older method. Cronander also separates the fat by shaking the milk with potash and ether, hut evaporates the ether after i t has risen to the surface of the milk, and measures the fat by forcing it in a melted state into a graduated tube. Pleischman and Morgen calculate the fat by the formula- 100s - 100 S-' f = 0.833 - 2.22 where f = percentage of fat, t = percentage of total solids, S = specific gravity of the milk a t 15".Morse and Piggot add 10 C.O. of milk to 20 grams of dehydrated copper sulphate. The fat The milk becomes dry in a few moments.ANALYTICAL CHEMISTRY. 95 i a then extracted by light petroleum, and its amount determined (after evaporation) by saponification. It is a graduated glass cylinder, containing in its lower part a amalley cylinder of white glass with black lines on it. 4 C.C. of milk are put jn the cylinder, and water is added until the black lines become visible. The reading of the total rolume gives at once the per- centage of fat. For the determination of the free acid in konmiss, it bright filtrate was obtained by adding to the koumiss an equal volume of alcohol Of lactoscoyes, Feser’s is said to be the most convenient.before filtering. B!. J. s. Extraction of Fats by Soxhlet’s Apparatus. By J. M. MILNE (J, SOC. C‘hem, Ind., 6, 34).-1n using the apparatus for milks, the author procwds as follows :-About 10 C.C. of the milk is weighed into a tared porcelain basin, and the milk evaporated with frequent stirring in arder to render it granular, until on being cooled the residue is semi-solid. The residue is then transferred to a paper cup and placed into the Soxhlet tube, and the fat extracted with ether in the usual way, The author having worked with Adams’ paper coils for drying np milk for fat extractions, confirms the fact pointed out by the committee of the Society of Public Analysts, that from 0.3 to 0.5 per cent.more fat is extracted by the coil method. Examination of Wines and Oils. Ry P. SPICA (Gszzetta, 17, 304--312).-The author at the outset; makes the oft-repeated com- plaint that the conditions, such as the variation of concentration, or even the nature of the acids used, required for the successful applica- tion of test-reactions, are not defined wit.h sufficient exactness in original papers. Various processes have been proposed to recognise the colouring matters, whether natmal or artificial, of wines ; but preference is given by the author to the methods proposed by Caze- neuve (AbRtr., 1886, 397), Arata (Gazzetta, 17, 44), Blarez and Deniges (Abstr., 1886, 1084), and Girard and Gautier.In the last- named process the substitution of tablets of Mugnesisc aZba for those of plaster of Paris is suggested ; hhese are immersed in egg albumin for a shart time and dried. A drop of the wine to be examined is let fall on such a prepared tablet, and the colour of the stain produced is observed. The natural colouring matters of wine give a yellowish- brown, those containing rosaniline or ‘‘ vinoline ” a reddish-jellow, those with indigo an azure-green, with orchil a violet red, and those with amaranth a greyish-violet stain. Another method suggested con- sists in shaking up the wine with barytn-water and amyl alcohol, when the latter extracts the colouring matter from the wine. It appears that certain preparations containing coal-tar colouring mat- ters, called “ vinoline,” are sold by druggists in Padua. An examina- tion of such a, preparation, called “maroon vinoline,” was found to consist of about 40 per cent.of mineral matter, in which arsenic was present in considerable quantities. As regards the method of examination of oils proposed by Maumen6, which is founded on the rise of temperature when the D. B.96 ABSTRACTS OF CHEMICAL PAPERS. sample is mixed with concentrated sulphuric acid, it appears that a confusion has arisen between grams and cnbic centimetres. Con- cordant results are obtained with mixtures of 50 grams or 55 C.C. of oil with 10 C.C. of acid. Bechi has proposed a method for the recopnit'ion of cotton-seed oil in 01iv.e oil. which consists in adding to the oil an alcoholic-ethereal solution of silver nitrate in presence of an amyl alcohol solution of petroleum ; it is here shown that this method gives fallacious results. A method of the greatest practical value is that proposed by Hubl, which has given satisfactory results in the hands of Moore, Allen, Oglialoro, and other observers. Gravimetric Estimation of Tannins.By H. R. PROCTER (J'. Xoc. Chem. Ind., 6,94--96).-The process described by the author is a combination of the methods published by Muntz and Simand, and depends on the fact that in filtration through a column of dry hide powder the upper layers absorb most of the tannin, a very com- plete and rapid separation being obtained from the large surface exposed. The author utilises the lamp chimneys employed in the common round-wicked German petroleum lamps, which are con- tracted just above the base of the flame and are cylindrical for the re- mainder of their length.A perforated disc of cork is made slightly cup-shaped on its two faces. A piece of linen is then stretched over it, and i t is pressed down the chimney until i t rests on the contracted neck. Five grams of hide powder is weighed into the tube, and when shaken down will occupy a space of about 50 C.C. The tube is now cut off, allowing only length for the insertion of a cork, which may press slightly on the powder, as it contracts in volume when wet. This cork is perforated and hollowed like the first, and after being covered with linen is pressed into the tube. A short piece of quill tubing passes through the cork, and is fitted by a second cork into a flask.The filtering tube is inverted, broad end downwards, into a beaker of 100 C.C. capacity, which is filled with the liquid to be filtered until it rises into the hide- powder. The tube is left in this position for one or two hours, after which it is reversed, and the enlarged end filled with the solution, when the filtration will be found to proceed evenly and steadily. The filtrates thus obtained are per- fectly free from tannin, and tested by,the Lowenthal method show a lower result for " aon-tannin " than those by any other method of ab- sorption. The method is, however, inapplicable in the presence of gallic acid, t,he latter being freely absorbed by hide powder. The author hopes to overcome the difficulty either by some method of V.H. V. removing the gallic acid or of preventing its absorption by the hide. D. B.Jaum . Chem .Sue. Feb. 1888. BALL No 3 . Harrison & Suns. Lith. S. Murtins Lane. W.C.ANALYTICAL CEERZISTRP. 85A n a 1 y ti c a 1 C h e m i s t r y.Grinding Mill for Minerals. By K. ZULKOWSKY (Bey., 20,2664--2669).-A description of a mill in which minerals may bereadily reduced to fine powder. The grinding surfaces are of agate,and the pestle is so arranged that it can be rotated by a water-motoragainst the lower surface with a pressure capable of being varied atwill. The material, already reduced to the coarseness of sand, is intro-duced into the mill through a sector cut in the pestle. w. P. w.Determination of Sulphur in Pyrites. By J. W. WESTMORELAND(J. SOC.Chem. Ind., 6,84-87).-1t is shown that the results obtainedby Lunge’s “ old process ” (precipitation of the sulphur from ferricsolutions), agree closely with those given by bhe new process (pre-cipitation after separation of the ferric oxide by ammonia), which istherefore a needless elaboration. The new method is also liable to’losses caused by an extra filtration and washing, aiid by sulphurretained in the ferric oxide, whilst sulphur is liable to be introducrdby the ammonia and hydrochloric acid employed. The results obtainedby Lunge’s processes express the total percentage of sulphur inSpanish pyrites; i t is, however, necessary to, use only a moderateexcess of barium chloride for precipitation, great care being taken inthe use of hydrochloric acid when washing this precipitate.D.B.Es.timation of Sulphur in Pyrites. By G. LUNGE (J. SOC. Chem.Ind., 6, Sti).---The author criticises Welch’s process (Abstr., 1887,180) for assaying iron pjrites for sulphur available for sulphuric acidmanufacture, and shows that the experiments having been made withKjeldahl’s Method of Estimating Nitrogen. By F. W. D A F E t w( L n d w . Versucks. Stat., 34, 311-353).-1n this article, are detailedimpure lead sulphide are not conclusive. I>. 1386 ABSTRACTS OF CHEMICAL PAPERS.in full the resnlts of experiments made for the purpose of testing thevalue of Kjeldahl’s process for estimating organic nihrogen, and of anexamination of the various‘ modifications of this process, as recom-mended by Kreusler and others.Estirnutiom hy the Original Process.-Certain nitrogenous compoundsonly seem to yield their nitrogen in the arnmoniacal forms, the resultbeing that the process is inaccurate with regard to others; of thelatter class, anilines and hydrazines are special examples, but somecompounds, contrary to expectation, yield their nitrogen as ammoniamore readily than others ; as for instance, it was expected that hydr-azines would yield ammonia more completely and quickly than nitro-compounds, but the contrary is the cme.The Action of the Sulphuric Acid.-To aid the solution of thisquestion, Kreusler’s modification, where phosphoric anhydride is addedto the sulphuric acid, was employed; sugar was also added.Theexplanation which is given is, that, the sulphuric acid removes fromthe substance the elements of water and of ammonia, and thesulphurous anhydride formed in the reaction reduces the nitrogenouscornpound ; the addition of organic matter (sugar) to the nitrogenouscompound slackens the formation of ammonia when the compoundis not volatilised by the acid; consequently to obtain quantitativeresults, the sulphuric acid must not volatilise the compound, norcompletely decompose it, for the analysis of some substances by thismethod free nitrogen accompanies the ammonia.The Action of Permanganate.--The presence of the permanganntewhen used in company with the mixture of acids, causes a destructionof the organic matter present, the nitrogen being so separated thatnearly the whole of i t is transformed into ammonia; as a rule thismodification of Kjeldahl’s process may be employed for all quantitativeanalyses, but i t is necessary that the mixture shall be thoroughly andsufficiently heated.The Addition of Metallic Salts.-This modification of Wilfarth’srenders the original procegs more rapid, although the time requiredfor the analysis is shortened very considerably by the addition ofmercury, it is a t the cost of accuracy ; it should only be introdncedin those cases where very stable compounds are under examination, oralso when the compounds readily give up their nitrogen as ammonia.From careful examination, it appears that, the discrepancies which existbetween the results obtained by Kjeldahl’s original method, Wilfarth’sand Ulsch’s (addition of platinum chloride), are due to loss of nitrogenat9 nitrogen, and not; to an insufficiency of heating, when the compoundis only slightly stable.The author considers t h a t Wilfarth’s explana-tion of the reaction which occurs when metallic salts are present, issatisfactory, but he also adds that when those compounds which donot resist the action of sulphuric acid well, or which are readilyoxidised, are dealt with, the addition of the metallic salt causingviolent oxidation, ammonia may be in part replaced by nitrogen;increasing the quantity of platinum, addition of oxygen and mixingwith organic substances may also result in loss, even wben thecompound is not easily decomposed. Mercury 8hould be alwnjsemployed when very stable compounds are to be analysed; amineANALYTICAL CHEMISTRY.87and alkaloids resist oxidation, but TJlsch’s process must not be usedbecause of its uncertainty, except in special cases, for example, withpotassium nitrate.General AppZicatinn,.--Nitrogenous compounds may be divided intotwo clasves as regards the applicability to them of Kjeldahl’s processof analysis. In the first are placed those which can be analysedwithout any previous treatment, for example, all amides and ammoniumbases, pyrroline and quinoline compounds, alkaloyds, bitter substances,albuminoyds and their allies, and perhaps the indole group ; whilst tothe second class belong all nitro-. nitroso-, azo-, diazo-, hydrazo-, andazoamido-compounds, nitrates and nitrites, the hydrazines, andpossibly the cyano-compounds.Two methods may be employed forthe previous treatment of this second class : addition of an organicsubstance, or reduction with zincadust, and even the tlwo combined,but the choice of which is to be used must rest with the analyst.This uncertainty will for the present preclude Rjeldahl’s process, orits improvements, from supplanting Dumas’s older and exact method.For the estimation of nitro-compounds, it is recommended to dissolvethe substance in 10 C.C. of alcohol (or if it is very stable, directly insulphuric acid) decompose by zinc-dust, add 10 C.C. of acid, and warmuntil all alcohol is got. rid of; when this is accomplished, add10 C.C. of the acid mixture together with mercury, and then proceedas with an ordinary compound.When distilling with sodium hy-droxide, special care must be taken to avoid shaking the flask ; it istherefore advisable to apply heat by mean8 of a sand-bath; in thesame manner nitroso- and azo-compounds may be readily analysed.Hydraao-compounds must first be converted into azo-compounds, beforeexposing them to the action of the sulphuric acid. The author, forexample, heats the sulphate of phenylhydrazine first with excess ofcane-sugar in presence of sodium acetate for some hours on a water-bath ; after drying the resulting mass, the acid may be added, Mostcyano-compounds, as far as the author is aware, can be analysed bythis process, but some may exist which will not bear the method.E.W. P.Notes on Nesslerising. By J. M. MILNE (J. XOC, Chern. Ind., 6,33).-The author recommends Hehner’s method in which the new-lerising is conducted in graduated cylinders having a somewhatbroad foot, a glass tap being fused into their sides near the bottom, sothat the solution, either standard or water distillate, may be run outuntil the two tints correspond. This method, a description of whichwas given in Chem. News, 33, 185, is very simple and readily carriedout. As nesslerising cannot be done in gaslight, the author proposesto imitate the process with two shades of indigo solution. D. B.Estimation of Ammonia in Soils by the Knop-Wolf Method.By A. BAUMANN (Lanndw. Versuchs-Stat., 34, 259--276).-A reply toKnop (ibid., 33, 438).Moisture and Free Acid in Superphosphates and similarFertilisem.By J. RUFFLE (J. SOC. Chen~ Ik.i., 6, 327-333).--It i88 ABSTRACTS OF CHEXICAL PAPERS,shown tbat the soluble phosphoric acid existing in superphosphatesis not entirely present as monocalcium phosphate, and that exposureto 100" drives 08 more than the true moisture, that is, the adheringuncombined water. It is recommended to determine the moisture inthe following manner:-Weigh out 2 to 5 grams of the superpbos-phate in its natural state on a double watch-glass, place under anair-pump over dry calcium chloride, exhaust, then leave f o r 18 to 24hours and weigh. The author shows that the acidity of ordinarysuperphosphates and ammoniated superphosphates is due to phos-phoric acid, and not to sulphnric acid.In ammoniated superphou-phates, monocalcium phosphate is substantially absent, the free acidbeing phosphoric acid. I). B.Detection of Small Amounts of Carbonic Anhydride andother Gases. By 0. ROSSLER (Bey., 20, 2629-2631).-A smalltest-tube is drawn out at the lower end to a capillary; this is bentupwards, and cut off a t a distance o€ 1 cm. from the bend. A capil-lary funnel is then made of such a size that the upper end fits thetest-tube, the lower end being a t n distance of 1.5 to 2 cm. from thebottom. The substance to be tested for carbonic anhydride is putinto the outer tube, the capillary funnel containing baryta-waterfitted, and the lower end of the apparatus then dipped into hydro-chloric acid. With 0.0005 gram of sodium carbonate a very distinctturbidity, with 040005 gram a distinct turbidity is produced in thedrop of baryta-water a t the end of the capillary.It is possible todetect 0.02 milligram of carbonic anhydride. Sulphuric and nitricacids, hydrogen sulphide, ammonia, &c., can also be detected by meansof the apparatus, using iodide of starch, ferrous chloride, lea,d acetate,and copper sulphate respectively. A sketch of the apparatus isgiven. N. H. M.Absorption of Carbonic Oxide by Cuprous Chloride. ByH. DREHSCHMIDT (Rer., 20,2752-2755).-Hempel has recently shownthat in certain cases when cuprous chloride is used as an absorbent ofcarbonic oxide in gas analysis, there is an increase instead of a decreaseof volume. This result is explained on the supposition that the ethylenecontained in the absorption-liquid is driven out by the absorbed carbonicoxide.It is here shown that this explanation is not sufficiently valid,as similar results were obtained with mixtures of carbonic oxide, withhydrogen, or nitrogen only. Experiments are described in which agiven volume of hydrogen was added to the volume OE gas obtainedafter some of the carbonic oxide had been absorbed ; on completingthe absorption, a fresh quantity of carbonic oxide was added, and theexperiment repeated. I n all cases, whether an ammoniacal or hydro-chloric acid solution of cuprous chloride was used, an increase of volumeof the hydrogen was observed, the increment being greater in the caseof the acid solution.If is advisable, therefore, when carbonic oxide ispresent in small qnantities, to use a fresh ammoniacal solution, or toburn with air by means of palladium asbestos. If the amount ofcarbonic oxide is large, a portion of the gas is unabsorbed, and mustmbsequently be determined by the above methods. V. H. VANALYTICAL CHEMISTRY. a9Estimation of Potassium by Reduction of the Platinochlo-ride with Sodium Formate. By WOUSSEN (Ann. Agronwm., 13,431--432).-The author has made Corenwinder's process workable bysecuring tbe agglutination of the reduced platinum. The modifiedprocess is conducted ils follows :-SO much of the substance shouldbe taken as will yield 0.750 t o 1 gram of reduced platinum from thepotassium platinochloride. This is precipitated with 18 C.C.of asolution of platinum tetrachloride, containing 200 grams per litre,and a slight excess of nit,ric acid ; 8 to 10 C.C. of hydrochloric acid isadded, and the solution evaporated to dryness on the water-bath, thentaken up with a mixture of nine-tenths alcohol of 96", and one-tenthether, filtered, and washed with the same mixture. The mixture ofpotassium platinochloride and salts remaining on the filter is treatedwith a jet of boiling water, and the hot solution of the platinochloridethus formed added in portions to a boiling solution of 2 to 2.5 gramsof sodium formate in 10 C.C. of water. The boiling is continued for15 to 20 minutes, and then 8 C.C. of hydrochloric acid is added, andthe boiling continued with constant agitation.After this additionthe reduced platinum soon agglutinates, and leaves the solutionclear; the metal is cotlected, washed with boiling water, dried, andEstimation of Potash in Commercial Manures. By D.LINDO (Chem. News, 56, 163--165).-Gladding has proposed the fol-lowing method for this purpose :-Boil 10 grams of the manure for10 minutes with YO0 C.C. of water, when cool precipitate b~ meansof a slight excess of ammonia, make up to 500 c.c., and filter. Evapo-rate 5~ C.C. of the filtrate nearly to dryness, add 1 C.C. of dilute sul-phuric acid (1 : l), continue the evaporation to dryness, and ignite.Dissolve the residue in hot water and a few drops of hydrochloric acid,add 5 C.C. of a 2 per cent. solution of sodium chloride and an excess ofplatinum chloride solution and wash the precipitate succesdvely withalcohol, solution of ammonium chloride (saturated with potassiumplatinochloride), and filially again with alcohol, dry, &c. The authorhas made numerous experiments with this method, and finds it simple,more expeditious, and seemingly suscept*ible of greater accuracy thanthe methods usually employed.D. A. L.Estimation of Sodium Hydroxide in Soda-ash. By R. WIL-LIAMS ( J . rs'oc. Chenz. h i d . , 6, 346).-The following method is foundto give accurate results :-A weighed quantity of soda-ash is agitatedwith strong alcohol in a stoppered flask and left over night; the un-dissolved carbonat,e is filtered off and washed with strong alcohol untila drop gives no alka!ine reaction ; the filtrate and washings are thentitrated with normal acid.D. B.weighed. J. M. El. 31.Estimation of the Relative Amounts of Sodium Hydroxideand Carbonate in Commercial Soda-ash. By P. HART ( J . SOC.Chem. Ind., 6, 347).-The sample under examination is titrated wit,hstandard acid, using phenolphthalejin as indicator. As soon as thecolour disappears, the whole of the hydroxide and one half of the sod90 ABSTRACTS OF CHEMICAL PAPERS.existing as carbonate has been neutralised, the number of C.C. beingnoted. To the same solution (in which the soda now exists as sodiumhydrogen carbonate) a little methyl-orange is added, ahd the additionof acid from the same burette continued to neutral reaction. Bydoubling the difference between the two titrations and deducting thenumber from the number of C.C.consumed, the quantity of hydroxidein the original sample is obtained. D. B.Analysis of Alum Cakes. By R. WrLLims (Chem. Nezos, 56,194-195) .-The author has adopted the following methods :-Foralumina : neutralise the solution with sodium carbonate, add a largeexcess of sodium hyposulphite, boil for some time, wash, dry, ignite,and weigh the precipitate. For free sulphdric acid : digest all nightwith strong alcohol, and titrate the alcoholic extract directly withdecinormal soda, using phenolphthale’in as ihdicator, Evaporating offthe alcohol gives rise to loss, low results ate likewise obtained if thedigestion is not continued for a sufficient time. In another method, a,weighed quantity of quinine, morphine, or strychnine is treated witha known quantity of alum solution, and the alkalo’id reweighed afterthe treatment, the loss representing the alkalojid dissolved by the freeacid.Comparative results were obtained as follows :-Alcohol. Strychnine. Quinine. Morphine.Free H2SOa per cent.. . 0.41 0‘54 0.50 0.51The alkalo’id results are all higher than the alcohol, probably onaccount of some alkaloid being dissolved by the alum solution andreckoned as sulphate.Determination of Minute Quantities of Iron, wi€h SpecialReference to Alum and Aluminium Sulphate. By R. R. TAT-LOCK (J. Soa. Chew. Ind., 6, 276--279).-As a standard, a solution ofiron-alum is used, of which 1 C.C. equals 0.001 gram iron, Place1 gram of the finely powdered sample in an ordinary atopperedsample-tube of about 30 C.C. capacity, and having three marks at7.5, 10, and 20 C.C.respectively. Add 1 C.C. of standard sulphuricacid, and make up to the lowest mark with water. When +he alumunder examination is dissolved, add 0.2 gram of ammoninm thicjcya-nate and make up to 10 c,c. with water. Place 1 cx. of the standardiron solution in a 100-c,c. flask, and make up to the latter volumewith water. Now place 1 C.C. of this diluted solution in a stopperedsample-tube, add 1 C.C. of standard acid, make up to the lowest markwith water, add 0.2 gram of the thiocyanate, and make up to the10 C.C. with water. Then fill up both tubes to the 20 c.c, mark withether, and agitate them thoroughly, As soon as the contents settle,compare the tints, and if unequal make one or more further trialswith greater or less quantities of standard iron solution until the twotints correspond.D. B.By J. H.SMITH (J. SOC. Chem. Ind., 6, 98-111 and 260--271).-When potaa-sium permanganate is used as an oxidising agent in organic research,D. A. L.Detection and Estimation of Organic SubstancesANALPTICAL CHEMISTRY. 91impure products are obtained, and in varying proportions dependingon the amount of reagent employed, temperature, and other conditions.It has therefore only been generally employed as a qualitative reagent.From a study of the behavionr of solutions of various organic sub-stances in presence of a large excess of potassium permanganate undervarying standard conditions, it occurred to the author tlhat by employ-ing an excess of the reagent, definite and sjmple compounds would beobtained whose composition in each case might be determined quali-tatively by ordinary analysis, and quantitatively by an estimation ofthe oxygen absorbed in the reaction.The determinations which theauthor had in view were the: following :-Oxygen yielded by excess ofmanganese dioxide in acid, alkaline and neutral solutions respectively ;oxygen yielded by excess of permanganate in such soliitions. Thelatter would include the former, the difference would representoxygen yielded by permanganate in reduction to manganese dioxideonly, and would necessarily correspond with more stable compoundsthan those represented by the reduction of manganese dioxide.Theauthor further anticipated successive oxidations, more especially of aneutral one succeeded by an alkaline and acid one respectively, and analkaline oxidation followed by one in acid solution.It was found, however, that on oxidising an organic or otheroxidisable solution by tt large excess of permanganate in acid solution,the results generally came out much too high, even for perfect oxida-tion, which indicated a loss of oxygen due to the presence of manga-nese dioxide. In order to prevent or diminish f h e loss, a ferric saltwas added to the permanganate solution, the iron acting as anaccelerator in the preseiice of much permanganate and little manganesedioxide, and a retarder when the conditioiis were reversed.The ferricsalt is really an accelerator, but it has the power of neutralising theaction of the manganese dioxide after a certain excess has beenformed. The accelerating action of iron in presence of much per-mangmate may be checked by the addition of sodium phosphate tothe solution.The author has based a quantitative method of estimating organic:products on the results obtained from this investigation, The method,which is described in detail in the original, is applicable to the estima-tion of commercial organic substances, the determination of t8heorganic matter in potable waters and in the waste liquors from worksemploying organic products, whilst for the estimation of alcoholicsolutions when largely diluted, it is more rapid than the sp.gr.method.I n the second part of the paper, the author treats cf the oxidationof organic substances by means of manganese dioxide in acid soll;tion,as well as of oxidations by permanganate in neutral and alkalinesolutions, and of analytical methods derived therefrom.The Stalagmometer : a New Method for the Determinationof Fuse1 Oil in Spirituous Liquors. By J. TRAUBE (Rer., 20,2644--2655).-The author previously described (Abstr., 1886, 743) amethod for determining fuse1 oil in brandy by observing the heightof the solution in a capillary tube. In the present paper an apparatus,D. B92 ABSTRACTS OF CHEMICAL PAPERS.called n “stalagmometer,” is described by means of which the percentageof fusel oil is determined by counting the drops contained in a kiiownvolume of liquid.As in the older method, the brandy is first dilutedso as to be about 20 per cent. It is then put into the stalagmometer,and the number of drops from a given volume observed and com-pared with the number obtained from the same volume of pure 20 percent. alcohol. An excess of 1% drop to 100 C.C. of liquid shows thepresence of 0.1 per cent., an excess of 3.5 drops, of 0.2 per cent. offusel oil. 0.05 per cent. of fusel oil can be determined readily andwith certainty.To increase the delicacy of the method, the proportion of alcoholt o fusel oil must be diminished. This is done in the followingmanner:--300 C.C. of the liquid to be examined (diluted to 20to 25 per cent.) is shaken in a funnel with 110 ta 120 grams ofpure ammonium sulphate, and left until two layers are formed;the lower layer, which contains vePy little fusel oil, is drawn offand shaken with two to three drops of’ ethyl alcohol. or some crystalsof ammonium sulphate.In this way the rest of the fusel oil isobtained as a separate laeyer. These upper layers are now mixed,dissolved in water, and distilled to about two-thirds. The distil-late is made u p to 110 c.c., the alcohol determined by meansof A Westphal’s balance, and the number of drops contained in thevolumc V by means OF the stalagmometer. The latter number iscompared with that obtained from pure spirit containing a knownamount of fusel oil.A sketch of the apparatus is gicen, as well 3s results obtainedby means of it.These show that the method is as accurate as thatpreviously described (Zoc. cit.), the new method having the advantageof being more easily worked. N. H. M.By J, MUTERand L. DE KOXINGH (Anulyst, 12, 191--195).-CarboZ~c Powders.-Where the phenols exist in the uncombined state, they are extractedby methylated spirit from 75 grams of the powder. Where thepowder contains a lime base, a preliminary thorough trituration witha small excesR of dilute sulphuric acid is necessary. The alcoholicextract is mixed with 200 C.C. of a 5 per cent. solution of sodiumhydroxide, and the mixture is then evaporated to half its bulk. Atthis point any tar oils and naphthalene will separate and are to befiltered off. The filtrate is further concentrated to 50 C.C.and trans-ferred to a graduated tube. This, which is known as Muter’s car-bolimeter, is wide in the lower portion. At 65 C.C. it is narrowed toa neck, which is graduated up to 110 C.C. in 0.35 C.C. divisions. It isstoppered, and is furnished with a long, thin, stirring rod, the volumeof which must be allowed for. The solution is made up to 6.5 c.c.,25 C.C. of strong hydrochloric acid are slowly added with stirring,and then enough dry common salt t o render the phenols insoluble.The tube is plunged into water of 15.5’ and the volume of the phenolsread off.Liquid Oarbolic Acid.-If this contains excess of watep, it will notgive a clear solution with three volumes of benzene. The amount ofAssay of Commercial Carbolic CompoundsANALYTICAL CHEXISTRY.93water is ascertained by shaking 20 C.C. of the sample with 80 C.C. of asaturated solution of sodium chloride, and observing the diminntionin volume. Tar oils are estimated by shaking 20 C.C. with 80 C.C. ofmda solution (5 per cent.), and a small quantity of benzene (10 C.C.for dark specimens, less for pale ones). The increase in the volumeof the benzene gives the amount of t a r oils. The remainder i, takenas phenol and cresols. M. J. s.Acidimetry with Red Wines. By TONY-GARCIN (Comyt. read.,105, 577).-When red wine, prepared in the ordinary way and notmore than a year old is mixed with sodiam hydroxide solution, thecolour changes to carmine, which becomes deeper and duller andpasses into violet-black, which afterwards becomes black, withoutany tinge af violet, and then changes to green, with formation of adark, flocculent precipitate.The point a t which the colour is brownish-black, without any tinge of violet or green, is the point of exactneutralisation. C . H. €3.Dairy Products. (Bull. U, 8. Agrz‘c. Depart., No. 13, 1-128).-Butter and its Substitutes.-A series of micro-photographs is given,showing the appearance presented by butter, &c., when examined bypolarised light. The black cross described by Hehner and Angel1 isseen in all the specimens of butter prepared by boiling and slowcooling, and is almost uniformly absent from the crystals obtainedfrom the other fats, nevertheless it is shown by some specimens ofbirtterine and oleomargarine from Armour and Co., Chicago, as well asin a slide prepared from beef suet “oleo oil,” by dissolving in hotalcohol, and cooling slowly, thus confirming the opinion that it is notto be trusted as a characteristic of genuine butter.The following method for determining the melting point of fats isdescribed :-Thin discs are obtained by dropping the melted fat on toa piece of ice.One of these is placed in a test-tube, t h e lower partof which contains boiled water, and the upper part strong alcohol.The disc floats between the two liquids. The tube is then warmed ina water-bath, whilst the temperature of the contents is taken by athermometer with small bulb, situated just above and close to thedisc, and kept in motion like a revolving pendulum. The ternpera-ture a t which the disc contracts to a sphere is taken a s the meltingpoint. It is necessary to examine the discs when freshly made, asthey show a higher melting point if kept for 24 hours.When thewater-alcohol tube is warmed before dropping in the disc, the con-traction takes place some 6” lower than when the former method isfollowed.Daven-port saponifies 5 grams of the butter with only 10 C.C. of alcoholicpotash (cont,aining 2 grams of KHO), operating in a flask from wThichthe alcohol vapour is aspirated by a water-pump. Saponification andevaporation to dryness are complete in 15 minutes, and from thestatement that genuine butters treated thus require on an average28.8 C.C. of - alkali, there would appear to be no loss of ethyl buty-Various modifications of Reichert’s process are described.Nl 94 ABSTRACTS OF CHEMICAL PAPERS.rat'e (compare Allen, Abstr., 1857, 1145).Crampton substitutesphosphoric for sulphuric acid in the distillation, but finds that withcare the two give identical results.Scheffer's test for foreign fats is based on the solvent action of amixture of amyl alcohol (40 vols.) and ether of sp, gr. .On715 (60 vols.).1 gram of butter dissolves in 3 C.C. of this mixture at 28" ; 1 gram oflard requires 16 C.C. ; 1 gram of stearin 350 C.C.The following order of value is assigned to the various modes ofexamining butters for adulteration :-( 1.) Determination of volatileacids. (2.) Determination of specific gravity. (3.) Determination ofsaponification equivalent (Koettstorfer). (4.) Determination of theinsoluble acids (Hehner, Muter, Blyth, &c.X ( 5 .) Det,errnination ofthe melting point.A complete bibliography of butter analysis (up to 1882) is given byCaldwell (Seeond Ann. Rep. N . Y. S. E d . of B e a l t h , ,544-547), andi n Sell's Kunstbutter (Arbeit a. d . R a i s e d . Geswndheitsumte),MiEk.-For the determination of water, Babcock employs asbestos toabsorb the milk before drying; this is much to be preferred to anypowder, By placing the asbestos in a, tube between plugs of cotton-wool, and drawing air through the tube wbile it is heated a t loo", thedesiccation is complete in two hours. The tube can then be transferredto the f a t extractor,Of methods for the determination of the fat, the preference is givent o that of Adams (Abstr., 1886, 583), but instead of soaking up themilk with one end of the roll of paper, the plan has been adopted ofholding the unrolled strip in a horizontal position, and running the5 C.C.of milk from a pipette along the middle. The strip is thenhung up in a hot chamber, and in two or three minutes is dry andready for rolling up.In Soxhlet's araometric method (Abstr., 1881, 656) great difficultywas encountered in ensuring the separation of the ethereal fat soln-tion, and any long delay in the separation was found to affect thefinal results. By placing the bottles containing the mixture in acentrifugal machine revolving about 300 times per minute, the timerequired for separation was reduced to a few minutes, only six samplesout of 150 requiring more than quarter of an hour.The fat solutionthus separated had, however, a lower specific gravity than thatobtained by simple subsidence, so that the percentage of fat as given inSoxhlet's table had to he increased by 0*1:3, to bring it into agreementwith the results of the older method. Cronander also separates thefat by shaking the milk with potash and ether, hut evaporates theether after i t has risen to the surface of the milk, and measures thefat by forcing it in a melted state into a graduated tube.Pleischman and Morgen calculate the fat by the formula-100s - 100S-'f = 0.833 - 2.22where f = percentage of fat, t = percentage of total solids, S =specific gravity of the milk a t 15".Morse and Piggot add 10 C.O.of milk to 20 grams of dehydratedcopper sulphate. The fat The milk becomes dry in a few momentsANALYTICAL CHEMISTRY. 95i a then extracted by light petroleum, and its amount determined(after evaporation) by saponification.It is agraduated glass cylinder, containing in its lower part a amalleycylinder of white glass with black lines on it. 4 C.C. of milk are putjn the cylinder, and water is added until the black lines becomevisible. The reading of the total rolume gives at once the per-centage of fat.For the determination of the free acid in konmiss, it bright filtratewas obtained by adding to the koumiss an equal volume of alcoholOf lactoscoyes, Feser’s is said to be the most convenient.before filtering.B!. J. s.Extraction of Fats by Soxhlet’s Apparatus. By J. M. MILNE(J, SOC. C‘hem, Ind., 6, 34).-1n using the apparatus for milks, theauthor procwds as follows :-About 10 C.C. of the milk is weighedinto a tared porcelain basin, and the milk evaporated with frequentstirring in arder to render it granular, until on being cooled theresidue is semi-solid. The residue is then transferred to a paper cupand placed into the Soxhlet tube, and the fat extracted with ether inthe usual way, The author having worked with Adams’ paper coilsfor drying np milk for fat extractions, confirms the fact pointed outby the committee of the Society of Public Analysts, that from 0.3 to0.5 per cent. more fat is extracted by the coil method.Examination of Wines and Oils.Ry P. SPICA (Gszzetta, 17,304--312).-The author at the outset; makes the oft-repeated com-plaint that the conditions, such as the variation of concentration, oreven the nature of the acids used, required for the successful applica-tion of test-reactions, are not defined wit.h sufficient exactness inoriginal papers. Various processes have been proposed to recognisethe colouring matters, whether natmal or artificial, of wines ; butpreference is given by the author to the methods proposed by Caze-neuve (AbRtr., 1886, 397), Arata (Gazzetta, 17, 44), Blarez andDeniges (Abstr., 1886, 1084), and Girard and Gautier. In the last-named process the substitution of tablets of Mugnesisc aZba for thoseof plaster of Paris is suggested ; hhese are immersed in egg albuminfor a shart time and dried. A drop of the wine to be examined is letfall on such a prepared tablet, and the colour of the stain produced isobserved.The natural colouring matters of wine give a yellowish-brown, those containing rosaniline or ‘‘ vinoline ” a reddish-jellow,those with indigo an azure-green, with orchil a violet red, and thosewith amaranth a greyish-violet stain. Another method suggested con-sists in shaking up the wine with barytn-water and amyl alcohol,when the latter extracts the colouring matter from the wine. Itappears that certain preparations containing coal-tar colouring mat-ters, called “ vinoline,” are sold by druggists in Padua. An examina-tion of such a, preparation, called “maroon vinoline,” was found toconsist of about 40 per cent. of mineral matter, in which arsenicwas present in considerable quantities.As regards the method of examination of oils proposed byMaumen6, which is founded on the rise of temperature when theD. B96 ABSTRACTS OF CHEMICAL PAPERS.sample is mixed with concentrated sulphuric acid, it appears that aconfusion has arisen between grams and cnbic centimetres. Con-cordant results are obtained with mixtures of 50 grams or 55 C.C. ofoil with 10 C.C. of acid.Bechi has proposed a method for the recopnit'ion of cotton-seedoil in 01iv.e oil. which consists in adding to the oil an alcoholic-etherealsolution of silver nitrate in presence of an amyl alcohol solution ofpetroleum ; it is here shown that this method gives fallacious results.A method of the greatest practical value is that proposed by Hubl,which has given satisfactory results in the hands of Moore, Allen,Oglialoro, and other observers.Gravimetric Estimation of Tannins. By H. R. PROCTER(J'. Xoc. Chem. Ind., 6,94--96).-The process described by the authoris a combination of the methods published by Muntz and Simand,and depends on the fact that in filtration through a column of dryhide powder the upper layers absorb most of the tannin, a very com-plete and rapid separation being obtained from the large surfaceexposed. The author utilises the lamp chimneys employed in thecommon round-wicked German petroleum lamps, which are con-tracted just above the base of the flame and are cylindrical for the re-mainder of their length. A perforated disc of cork is made slightlycup-shaped on its two faces. A piece of linen is then stretched overit, and i t is pressed down the chimney until i t rests on the contractedneck. Five grams of hide powder is weighed into the tube, andwhen shaken down will occupy a space of about 50 C.C. The tube isnow cut off, allowing only length for the insertion of a cork, whichmay press slightly on the powder, as it contracts in volume when wet.This cork is perforated and hollowed like the first, and after beingcovered with linen is pressed into the tube. A short piece of quilltubing passes through the cork, and is fitted by a second cork into aflask. The filtering tube is inverted, broad end downwards, into abeaker of 100 C.C. capacity, which is filled with the liquid to befiltered until it rises into the hide- powder. The tube is left in thisposition for one or two hours, after which it is reversed, and theenlarged end filled with the solution, when the filtration will be foundto proceed evenly and steadily. The filtrates thus obtained are per-fectly free from tannin, and tested by,the Lowenthal method show alower result for " aon-tannin " than those by any other method of ab-sorption. The method is, however, inapplicable in the presence ofgallic acid, t,he latter being freely absorbed by hide powder. Theauthor hopes to overcome the difficulty either by some method ofV. H. V.removing the gallic acid or of preventing its absorption by the hide.D. BJaum . Chem .Sue. Feb. 1888. BALLNo 3 .Harrison & Suns. Lith. S. Murtins Lane. W.C

ISSN:0368-1769    

DOI:10.1039/CA8885400085

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

97 General and Physical Chemistry. Relation between the Composition and Absorption-spectra, of Organic Dyes. By H. W. VOGEL (Ber. Akad. Ber., 1887, 715- 718) .-Experiments made with azo-dyes gave the following results :- The substitution of methyl for hydrogen in diazobenzene gives rise t o change of position of the absorption-bands towards the red end of the spectrum. The increase of wave-length is 10 millionths mm. when the substitution takes place in the ortho-position, and 14 mil- lionths mm. in the case of the para-position. (2.) The substitution of p-naphtholsulphonic acid S or P-naph tholdisulphonic acid R for p-naphtholsulphonic acid B, causes a shifting of the ba8nds which, in the case of 6-naphtholsulphonic acid S amounts to 4 to 5 millionths mm., and in the case of p-naphtholdisulphonic acid R to 6 millionths mm.(3.) In the substitution of methyl, the space between the two bands becomes clearer, and the bands become more equal in intensity and in width. Tha substitution of p-naphtholsnlphonic acid S or 3-naph- tholdisulphonic acid R, in the place of the acid B, acts similarly on the character of the bands. The above results were obtained with sulphuric acid solutions ; the results, as well as those obtained with alcoholic solutions, are shown in tables. N. H. M. Fluorescences with Well-defined Spectra. By L. DE BOIS- BAUDRAN (Compt. rend., 105, 784- 788).-When gallium oxide is employed as a solid solvent of other oxides, it gives fluorescences which are usually much less brilliant than those obtained with alu- mina, but the results are of the same order.Calcination of t h e oxide at a very high temperature converts the bands in the spectrum into lines, the spectral groups being displaced towards the red. The bril- liancy of the spectrum increak- with the time of action of the electric discharge, a result contrary to that obtained with alumina. Measurements are gken of the spectra of the fluorescences of gallium oxide with oxides of samarium, Za and ZP. The fluorescence of Zp with gallium oxide is very feeble, the difference between Z~C and Zfl being even more strongly marked than when the oxides are mixed with alumina. A moderately calcined mixture of alumina with praseodymium oxide yields only a very faint trace of a rosy fluorescence, but if the mixture is very strongly heated, it then yields a beautiful fluorescence, the colour of which depends on the time during which the electric discharge has been passing.At first it is violet, but afterwards becomes rose-coloured. The spectrum is complicated, the principal bands, all of which are nebulous, being situated at 6457, 6237, 6162, 6035, and 5212. Rotatory Power of Solntions of Ammonium Molybdate and Tartaric Acid. By D. GERNEZ (Compt. rend., 105, 803-806).- VOL. LlV. h C. H. B.9 8 ABSTRACTS OF CHEMICAL PAPERS. The experiments previously made with solutions of tartaric acid and sodium molybdate (Abstr., 1887, 540) were repeated with ammonium molybdate. The rotatory power increases regularly as the quantity of ammonium molybdate increases, and is proportional to the quan- tity of this salt present up to a quarter of an eqnivalent.Between one-fourth and one-third of an equivalent, the increase of rotation for the same weight of malybdate changes suddenly, and beoomes little more than half its original value. The maximum rotation observed is 57 times that of tartaric acid, and corresponds with a proportion of ammonium mdybdate equal to one-t-hird of an equi- valent, it remains sensibly constant between 42.66/128 and 56/128 of an equivalent of molybdate. With large quantities, the rotatory power diminishes rapidly, and becomes practically constant when one equivalent of molybdate is present. As in. the case of sodium molybdate, the tartaric acid a t first com- bines with the whole of the ammonium molybdate, forming a com- pound of the composition 8C4Hti06 + 3(NH4),O, 7MoOs,4Hz0, which is gradually converted into a secand compound, containing 6 mnls.of tartario acid and 1 mol. of the molybdate, and this is finally trans- formed ink0 a third more stable compound, 2C4H6O6 + 3(NH4)2,0,7M00,4H20. In the caw of sodium molybdate, the maximum rotation is obtained with one equivalent of the salt, whilst i a the case of the ammonium rnolybdate, the maximum rotation is given by one-third of an equi- valent. The ammonium salt, however, contains three equivalents of the alkali in the molecule for eaoh equivalent present in the molecule of the sodium salt, and hence in each case the maximum rotation is given by compounds whioh contain the alkali and the tartaric acid in equal equivalents. C. H. B. Influenee of Light on the Heat Conductivity of Selenium.By N. BELLATI and S. LUSSANA( Gazzetta, 17,391-405).-The analogies of heat and electric conductivity induced bhe authors to study the influence of light an the heat conductivity of selenium, the electric resistarice of which, as is well known, is diminished on exposure. The plan of experiment consisted in sprinkling the double iodide of copper and mercury on the disc of selenium, on which a circular figure bad been blackened with Indian ink. Tbe selenium was heated by the passage of an electric current, which produced a t fir& a dark spof, owing ts the change in calour of the double iodide. Thib: sub- sequently extended into a fairly regular circular figure, the measure- ment of the diameter of whioh afforded a means of determining the heat conductivity of the selenium.This method was found ta be more practicable than the usual method of melting wax. I n all cases, the diameter of the circle was greater when the selenium was exposed to reflected sunlight from which the greniter part of the heat r a p had been removed by passage through solutious af alum and of nnimoniacal copper sulphate. The relation of heat conductivity without and with exposure to light was found to be in the ratio of 1 : 1.1 as the result of several concordant experiments. The sameGEKERAL AND PHYSJCAL CHEMISTRY. 99 ratio was observed between the electric conductivities without and with exposure to light under conditions similar to bhose describ-d above. The authors, however, would not insist on this concordance of results in the two phenomena. V.H. V. Effect of Light on the Conductivity of' Selenium. By S. KALTSCHER (Ann. Phys. Clbem. [2], 32, 108).--Uf the selenium cells constructed by the author, three in which copper and copper-brass electrodes are used, are found to differ from the rest in their behaviour on exposure to light, the resistance rapidly increasing after undergoing R momentary decrease, and the cell only returning to its normal condition on remaining for some time in tJhO dark. The conclusion drawn from this is, that the cells in question contain a hitherto uil- known modification of selenium, the conductivity of which decreases instead of increasing under the action of light. As the author's other cells which do not exhibit the peculiarity &scribed, differ from t,he a,bove in having zinc, copper-zinc, and copper-platinum electrodes.i t still remains 00 be ascertained whether the nature of the electrodes has any influence on this behavionr o€ selenium, The phenomenon in question has also been observed and described by Hesehus (Exn. Rep. d. Phys., 20, 490). H. C. New Galvanic Battery.. By F. FRIEDRICHS (Ann. Phys. Chetn. [2], 32,191) .-A tube running below the cells of this battery connects each with a cammon reservoir, by the raising or lowering of which the fluid used can be transmitted to or removed from t h e cells. A tap attanbed at the end of the tube opposhe the reservoir allows the fluid t o be removed when exhausted. An advantage claimed over other batteries is, that spontaneous evaporation of the liquid and consequent crystallisation of salts when the battery is not in use, is avoided.Galvanic Palarisation. By F. STRE~NTZ ( A m . Phys. Chew. [Z], 32, 116) ,-The author has examined the galvanic polarisation pro- duced on aluminium and silver plates. The results for aluminium have been already given (Abstr., 1887, 415). With silver, the oxygen plate is found Bo attain maximum polarisation when the E.M.F. of the cell used is equal to that of three Daniells ; the polarisation of the hydrogen plates is at a maximum when an E.M.F. of two Daniells is used, it decreases when a greater E.M.E. is employed, but rises again and becwmes equal to the first maximum for an E.M.F. of nine Daniells. The explanation given is that the deposition of metallic silver on the cathode, which is greater the greater the in- tensity of the ourrent, by increasing the surface decreases the relative strength of the current and amount of the polarisation, so that although a small E.M.F. produces maximum polarisation with clean plates, a very considerable one is required to attain the same maximum with plates thickly coated with silver.Production of Electricity by the Cmdensation of Aqueous Vapour. By L. PALMIER[ (Nuooo Cime?zto [3], 22, 3&39).-l'he occasion of this paper is the confirmation by Pirmin Larroque (La H. C. H. C. h 2100 ABSTRACTS OF CHEMICAL PAPERS. LzcmiZre $Zed., 1887) of the author's experiments on the production of electricity by the condensation of aqneous vaponr. On the other hand, the experiments of Kalischer (Abstr., 1884,138) led to negative results, but Tait considers that these were conducted on far too small a scale.Accordingly the author has repeated on a large scale his experiments on the condensation of aqueom vapour on a beaker of platizium containing ice, and connected with a condensing electric cup; in all cases, the production of electricity was observed. The iiithor remarks that his observations, extending over 37 years, leave no doubt in his mind as to the production of electricity under these conditions. The potential of atmospheric electricity is conditioned by the statme of the weather ; the author's observations also have more particularly shown that the potential is affected by the eruptions at Vesuvius. V. H. V. Electrolysis of Water. By H.v. HELMHOLTZ (Ber. Akad. Ber., 1887, 749--757).-Previous experiments made by the author showed that the smalIer the amount of dissolved hydrogen and oxygen near the electrodes, the smaller the electromotive force necessary to electrol yse water. The experiments described in the present paper were made with a v?ew to determine the limits for the smallest elec- tromotive force capable of producing fresh gas under a given pressure of the oxyhydrogen mixt,ure on the liquid. I n previous experiments, an error in the measurement of the electromotive € o m of the decom- position of water was caused by hydrogen or other combustible gas being occluded in the platinum anode (ir in both electrodes, so that the oxygen camied over in the current comes in contact with the gases of the modes, and thus bubbles of hydrogen will be liberated a t the cathodes with a much less expenditure of electromotive force.To avoid this, the current is kept in the same direction for weeks or months. An apparatus is described with sketch, by means of which the gases produced by the electrolysis are removed as soon as formed, and a vacuum is thus kept above the liquid ; the flask containing the solution is so inclined that a small bubble of gas is retained ; the gas under t'hese conditions occupies a space 1000 times greater than it would under normail pressme, and lfhe diameter of the bubble is measured in order to ascertain whether it remains the same size or whether it increases. To produae a current, three c a r h - i r o n ferric chloride solution elements were used ; the electromotive force was diminished daily in order to determine the limit.The limit for the evolution of gas was found to be 1-64 to 1-43 volt, wikh a pressure of oxyhydrogen gas = 10 mm. of water. The influence of pressure on elecfromotive force is expressed as follows :- A = A , + 1 0 - 7 . ~ . e { ~ ~ ~ i ~ g ~ ) 2ffh + ffo + yu = atmospheric pressure, p h andp, are the pressures of hydrogenGENERAL AND PHYSICAL CHEMISTRY. 101 and of oxygen above the liquid ; a h and a0 are the atomic weights of the two elements; 8 is the absolute temperature. where Vh is the volume of 1 gram of hydrogen ; R, the corresponding constant for oxygen, and 7 the amount of water decomposed in a second by one AmpAre. When pure oxyhydrogen gas is above the liquid, as in the experi- ments described, p = Ph + p,, the part of the electromotive force changing with the pressure becomes- 7 = 0.00009319 according to Kohlrausch.A, - A, = +. lO-’.v. 0 . Rh. log = 0.038868. log mat. ?‘). P2 N. H. 31. Electrolytic Separation of the Metal on the Free Surface of the Solution of its Salt. By J. GUBKIN (Ann. Phlp Chen~. [2j, 32, 114).-Wben an electric current passes from a solution of a salt into the atmosphere of gas or vapour immediately above it, an electrolytic separation of the metal takes place at the surface of the liquid. Apparatus is described by means o€ xhich this is made evident, the space above the liquid ‘being either vacuous or exposed to the air in the ordinary way. Silver and platinum are found to separate out in films which float on the surface ; zinc oxidises as it separates out, the white flakes of zinc oxide gradually falling to the bottom.H. C. Action of the Solvent on ElectroLytic Conduction. By T. C. FITZPATRICK (Phil. Mug. [ 5 ] , 24, 377-391).-The author continuer his researches om the conducti~it~y of salt solutions, the Bolvents being varied. The salts examined were calcium,. litbium, and magnesium chlorides asl;d nitrates, and ferric and mercuric chlorides, the solvents being water and ethyl and methyl alcohsls. Tables of conductivities are given. With mercuric chloride, which is the only salt mole soluble in alcohol than in water, the conductivihies are little more than those of the solvents alone. For aqueous solutions, the chlorides conduct better than the nitratcs ; magnesium chloride is anomdous, its conductivity being half that of calcium chloride.Ferric chloride i n dilute solution shows signs of dissociation. With alcoholic solu- tions, the conductivity is not proportional to the amount in solution. The conductivity of lithium salts in ethyl alcohol is 10 to 20 times as great as that of the other salts. I n all cases, the aqueous solutions conduct better than the alcoholic ones, the character of the solvent appearing to have an influence on the conductivity. This the author considers to be due to the formation of molecular groups in the solutions. He finds that the conductirity of salt solutions at low temperatures points to the existence in solution of cryobydrates a t temperatures above their solidifying points, and also that the con- ductivity of mixed solvents and of salts in mixed solvents differs from the calculated values, showing that an interaction has taken place with formation of new molecular gronps.The action then of the102 ABSTRACTS OY CHEMICAL PAPERS. solvent is twofold: (1) decomposition of the salt, the amount depend- ing on the temperatui-e, nature of solvent, and state of dilution ; (2) the formation of fresh molecular groups in the solution. Influence of a Magnetic Field on the Thermoelectric Pro- perties of Bismuth. BS G. P . GRIMALDI (Nuouo Cimento [3], 21, 57).-It is well known that n magnetic field influences in a remark- able degree the electric resistanw of bismuth; in this paper, the author shows that its thermoelectric force when paired with copper is varied in a similar degree.This pile was placed in the .field of an electromagnet, and coupled up with a galvanometer, in which read- ings were taken without and with a current passing round the electromagnet. After due allowance for induction, it is shown that the thermoelectric force of the bismuth-copper pair is materially decreased in the magnetic field. The experimental enquiry is, how- ever, only i n the preliminary stage. H. I(. T. V. H. V. Rotation of Isothermic Lines of Bismuth placed in a Magnetic Field. By A. RIGHI (Gazxetta, 17, 359).-In the course of experiments on the heat conductivity of bismuth when placed in a magnetic field, it was observed that the isothermic lines were rotated in a direction opposite to that of the magnetising current when a rectangular strip of the metal was placed with its planes normal to the line of force.The phenomenon is analogous to that observed by Hall, namely, the rotation a f the equipotential lines when a magnet acts on a current flowing along a thin strip of metal, and may explain the thermomagnetic currents recently discovered by Ettingshausen. v. H. v. Thermic Conductivity of Bismuth in a Magnetic Field. By A. RIGHI (Gazzetta, 17, 358--359).-The author, as well as other physicists, has observed the marked variation of the electric con- ductivity of bismuth when placed in a magnetic field (Abstr., 1887, ltO9), and the production of Hall's phenomenon under these con- di t ions. Considering the correlation of electric and thermic conduc- tivity, the effect of ningnetic field was also studied ; the results of the experiments showed Ithat with a field of 45?0 C.G.S.units the thermic conductivity of bismuth is to that of the metal under ordinary conditions as 2 : O-(U86. This result must at present be only con- sidered as approximate; further experiments are being niade with more refined apparatus. V. H. V. Specific Heat of Superfused Water. By P. CAEDAN~ and F. TOMAYINI (Nuovo Cimeuto 133, 21, 185).--The specific: heat of m t e r a t varims temperatmuyes has been the subject of numerous investiga- tions, although the results obtained are far from cnncoi*dant. Thus at temperatures 0-lo", Hirn, as also Pfaundler and Platter, has ob- served a marked increase of specific heat, whilst Rowland on the other hand observed a decrease.In this paper, a description is given of experiments made to determine the specific heat of water in t h e superfused condition. The method adopted in the investigation is practically an application of the weight thermometer; a knownGENERAL AND PHYSTOAL CHEMJSTKY. 103 volume of water is enclosed by mercury within 8 bulb, connected with which is a capillary tube bent twice at right angles. The whole apparatus is completely filled with water and mercury, and the bulb cooled by suitable freezing mixtures, then the mercury driven out by the expanding water is collected and weighed. The apparatus is then agitated, and the mercury driven out by the solidification of tthe water is also collected and weighed. Then from these data, together with a determination of the temperature at the moment of solidifica- tion, and the quantity of heat absorbed by the glass and the mercury contained, the specific heat of the water at the temperature of solidi- fication is ascertained. The various experimental errors are discussed in full, and the data of all the observations given in a series of tables.The following are the main conclusions : the specific heat of super- fused water is less than unity ; it increases with decrease of tempera- ture from a minimum at a temperature of -6.52" to 0". The final results are given below. Temperature. Specific heat. -652" to 0" 0953 --8*09 ,, 0 0.96 I -9.47 ,, 0 0.962 -10.67 ,, 0 0.985 V. H. V. New Form of Calorimeter. By W. I?. BARRETT (PTOC. R. Dublin Soc., 5, 13--16).-l'he instrument devised by the author is a modification of Bunsen's calorimeter.The cup for holding the sub- stance under experiment forms part of a mercurial thermometer. The cup has a capacity of 4 c.c., and is surrounded by a jacket of polished metal. The stem of the thermometer, of which the cup is a portion, is supported horizontally, and graduated from -5" to 80". Supported immediately above the cup is a small burette, the level of the liquid in which can be accurately read. The neck of the burette may be closed by a short thermometer graduated from 30" to 100". In making B determination of the specific heat of a liquid with this in- strument, the weight of the liquid must be found by taking its specific gravity for the temperature at which it was used ; the volume of the liquid used having been read from the bnrette.This inconvenience may be obviated by converting the thermometer into a balance, the fitem being supported by knife-edges somewhere near its centre of gravity. From the end of the stem, a pan is suspended, and beyond this a pointer, fixed to the stem, moves over a graduated arc. With a calorimeter balanced in this way, the weight of the liquid at a given air-temperature may be found directly. Determining the Specific Gravity of Small Quantities of Dense or Porous Substances. By J. JOLT ( P ~ o c . R. Dublin XOC., 5, 41-47).-The method generally employed for determining the specific gravity of small quantities of minerals of low density is by halancing in a liquid of known specific gravity. This method, however, is inapplicable when the substance has a specific gravity over 4, and also when the substance is of a porous nature.Under these conditions, the B. H. B.104 ABSTRACTS OF CHEMICAL PAPERS. substance may be mixed with another substance of much lower specific gravity in such proportion that the specific gravity of the mixed substances may be as close Go that of either of them as may be de- sired. FOP this purpose, t.he author uses the paraffin sold in the form of candles. The transparency of the paraffin enables the appearamce of the embedded mineral to be minutely examined. Results are given showing the accuracy of the method. B. H. B. Dissociation of Copper Sulphate. By W. M~~LLER-ERZBACH (Ann. Phys. Chem. [el, 32, 313). -The author has studied the dis- sociatiozl of copper sulphate at higher temperatures than those which he previously employed, and finds that his results agree with those obtained by Lesceur (Abstr., 1887, 208). The paper also contains a discussion of the dependence of chemical affinity on temperature (Abstr., 1887, 628).With sodium phosphate containing 5 mols. H,O, and sulphuric acid of 1.294 sp. gr., water passes from the acid to the salt at 32", but the changeis reversed, and water passes from the salt to the acid at 47". The equilibrium between the affinity of copper sulphate and of dilute sulphuric acid for water occurs, as might be expected, at higher temperatures the more dilute the acid. Rate of Dissociation as a Measure of the Vapour-tension of Hydrated Salts. By R. SCHULZE (Ann.Phys. Chew. [2], 32, 329). -A reply to Miiller-Erzbach. The author seeks to justify his former conclusions with regard to Muller-Erzbach's method of determining the vapour-tension of hydrated salts (Abstr., 1887, 766). Miiller- Erzbach having objected to the use of zinc sulphate as being a salt which admittedly exhibits irregularities in its bchayiour, copper sulphate is here shown to act in an irregular manner also when in- vestigated by the above method. In two out of three tubes contain- ing copper sulphate, evaporation set in at 20", but the third did not exhibit any change even at the end of 10 weeks. Interaction of Metals and Sulphuric Acid. By V. H. VELEY (Chew. News, 56, 221--222).-In this communication, the aut'hor points out that the results obtained by Spring and Aubin in their investigation on the action of acids on zinc containing lead (Abstr., 1887, 1074) do not adequately represent the Gate of chemical change as comparable, for example, with the rate of evolution of a gas from a homogeneous liquid.Thus the initial retardation or " induction " observed may be due to the adherence of bubbles of gas to the surface of the metal, and, eecondly, when the change has set in, the metal is surrounded by a concentrated solution of the metallic salt, which is ouly in part removed b r the gas bubbles. The hydrogen evolved is a resultant of a series of changes, each one of which is variable at any moment, such as the rate of diffusion of the salt of the metal in the acid liquid, the amount of surface exposed (which Spring and Aubin in some experiments kept approximately constant), and the local rise of temperature.The amount of gases other than hydrogen, such as sulphurous anhydride and hydrogen sulphide, is doubtless also dependent on the more or less perfect removal of the products of the H. C. H. C.QENERAL AND PHYSICAL CHEMISTRY. 105 change from the sphere of the dissolving metal as well as on the concentration of the acid solution. On the other hand, it does not seem that variations in the relative masses of zinc could make any difference either in the rate of solution or in the products of the change, provided that the surfaces exposed were equal. The dissolu- tion of a solid in a liquid must be regarded as R superficial action only. The author is at present studying the rate of solntion of metals in acid liquids under such conditions that not only fresh surfaces of a regular geometrical figure are continuously being exposed, but also the products of the change, whether gas or metallic salt, are at once and continuously removed from the vicinity of the dissolving rne tal.V. H. V. Velocity of the Formation of Ethereal Salts. By N. MEN- SCHUTKIN (Compt. rend., 105, 1016-1019) .--The particular reaction investigated was the action of acetic anhydride on alcohols, Ac,O + RHO = AcOR + AcOH, at 100". With most alcohols, the reaction is complete. The formation of the ethereal salt is accompaiiied by a, change of volume, which is least with methyl alcohol and increasingly greater with ethyl, propyl, and isobutyl alcohols. In order to eliminate this variable, the mixture of acetic anhydride and alcohol was diluted with 15 volumes of benzene.The constants of velocity are calculated from the equation - - = C(A - x) (B - x), in which A and B are the qnantities of the substances originally present, and x the quantity of the new substance formed in time t. A and B being equal, and ~t' and t being 0, --?-- = CAt, which gives the constant C. The results given in the following tables are the mean of several concordant ex- periments, the constants of' velocity being referred to that observed with methyl alcohol, which is taken as 100 :- dX dt A - - 0 Primary alcoliols. Methyl alcohol ............ Et,hyl ,, ............ Propyl 7, ............ Butyl 9 , ............ Isobutyl ,, ............ Octyl ), ,, ....0 cto decy 1 9 9 7 9 Melissy 1 ,7 9 , Hepttyl ,, (normal) .... Tetradecyl alcohol (normal). Hexadecyl ,, , J Ally1 9 , 7, a-Methyl ally1 alcohol ...... Benzyl alcohol ............ Constants of velocity. f--- 7 0-1053 100.0 0.0505 47.9 0.0480 4.506 0.0465 44.1 0.0401 38.1 0.0393 37.5 0.0377 315.8 0.0291 27-6 0.0269 25.5 0.0245 23.2 0.0174 16.5 0.0287 2 7.2 0-0267 25.3 0.0280 26.6106 ABSTRACTS OF CHEMICAL PAPERS. Constants of velocity. Secondary alcohols. r - 7 Isopropyl alcohol .......... 0.0148 14-1 Methyl ethyl carbinol ...... 0.0123 11.6 Methyl hexyl ,, ....... 0.0091 6 8.7 Methyl ally1 ,, ...... 0.00643 6.1 Trimethyl carbinol ......... 0.00091 0.8 Tertiary alcohol. The ethereal salts of the tertiary alcohols, phenols, and propargyl alcohol are decomposed by acetic acid, and hence in these cases the reactions are not comparable with those of primary alcohols.The greatest velocity is observed with methyl alcohol. The velocity is affected by the isomerism of the radicles in the alcohols, but is highest with primary alcohols, and much lower with secondary alcohols, whilst in the case of tertiaryaIcohols it is very small indeed. l n homologous alcohols of analogous constitution, the constant of velocity diminishes as the molecular weight increases, the difference being greatest in the normal primary alcohols. Non-saturated alcohols have a lower constant of velocity than the corresponding saturated alcohols, C. H. B.97General and Physical Chemistry.Relation between the Composition and Absorption-spectra,of Organic Dyes.By H. W. VOGEL (Ber. Akad. Ber., 1887, 715-718) .-Experiments made with azo-dyes gave the following results :-The substitution of methyl for hydrogen in diazobenzene gives riset o change of position of the absorption-bands towards the red end ofthe spectrum. The increase of wave-length is 10 millionths mm.when the substitution takes place in the ortho-position, and 14 mil-lionths mm. in the case of the para-position. (2.) The substitutionof p-naphtholsulphonic acid S or P-naph tholdisulphonic acid R forp-naphtholsulphonic acid B, causes a shifting of the ba8nds which, in thecase of 6-naphtholsulphonic acid S amounts to 4 to 5 millionths mm.,and in the case of p-naphtholdisulphonic acid R to 6 millionths mm.(3.) In the substitution of methyl, the space between the two bandsbecomes clearer, and the bands become more equal in intensity andin width.Tha substitution of p-naphtholsnlphonic acid S or 3-naph-tholdisulphonic acid R, in the place of the acid B, acts similarly onthe character of the bands.The above results were obtained with sulphuric acid solutions ;the results, as well as those obtained with alcoholic solutions, areshown in tables. N. H. M.Fluorescences with Well-defined Spectra. By L. DE BOIS-BAUDRAN (Compt. rend., 105, 784- 788).-When gallium oxide isemployed as a solid solvent of other oxides, it gives fluorescenceswhich are usually much less brilliant than those obtained with alu-mina, but the results are of the same order. Calcination of t h e oxideat a very high temperature converts the bands in the spectrum intolines, the spectral groups being displaced towards the red.The bril-liancy of the spectrum increak- with the time of action of the electricdischarge, a result contrary to that obtained with alumina.Measurements are gken of the spectra of the fluorescences ofgallium oxide with oxides of samarium, Za and ZP. The fluorescenceof Zp with gallium oxide is very feeble, the difference between Z~C andZfl being even more strongly marked than when the oxides are mixedwith alumina.A moderately calcined mixture of alumina with praseodymiumoxide yields only a very faint trace of a rosy fluorescence, but if themixture is very strongly heated, it then yields a beautiful fluorescence,the colour of which depends on the time during which the electricdischarge has been passing. At first it is violet, but afterwardsbecomes rose-coloured.The spectrum is complicated, the principalbands, all of which are nebulous, being situated at 6457, 6237,6162, 6035, and 5212.Rotatory Power of Solntions of Ammonium Molybdate andTartaric Acid. By D. GERNEZ (Compt. rend., 105, 803-806).-VOL. LlV. hC. H. B9 8 ABSTRACTS OF CHEMICAL PAPERS.The experiments previously made with solutions of tartaric acid andsodium molybdate (Abstr., 1887, 540) were repeated with ammoniummolybdate. The rotatory power increases regularly as the quantityof ammonium molybdate increases, and is proportional to the quan-tity of this salt present up to a quarter of an eqnivalent.Betweenone-fourth and one-third of an equivalent, the increase of rotationfor the same weight of malybdate changes suddenly, and beoomeslittle more than half its original value. The maximum rotationobserved is 57 times that of tartaric acid, and corresponds with aproportion of ammonium mdybdate equal to one-t-hird of an equi-valent, it remains sensibly constant between 42.66/128 and 56/128of an equivalent of molybdate. With large quantities, the rotatorypower diminishes rapidly, and becomes practically constant when oneequivalent of molybdate is present.As in. the case of sodium molybdate, the tartaric acid a t first com-bines with the whole of the ammonium molybdate, forming a com-pound of the composition 8C4Hti06 + 3(NH4),O, 7MoOs,4Hz0, whichis gradually converted into a secand compound, containing 6 mnls.of tartario acid and 1 mol.of the molybdate, and this is finally trans-formed ink0 a third more stable compound,2C4H6O6 + 3(NH4)2,0,7M00,4H20.In the caw of sodium molybdate, the maximum rotation is obtainedwith one equivalent of the salt, whilst i a the case of the ammoniumrnolybdate, the maximum rotation is given by one-third of an equi-valent. The ammonium salt, however, contains three equivalents ofthe alkali in the molecule for eaoh equivalent present in the moleculeof the sodium salt, and hence in each case the maximum rotation isgiven by compounds whioh contain the alkali and the tartaric acid inequal equivalents. C. H. B.Influenee of Light on the Heat Conductivity of Selenium.By N.BELLATI and S. LUSSANA( Gazzetta, 17,391-405).-The analogiesof heat and electric conductivity induced bhe authors to study theinfluence of light an the heat conductivity of selenium, the electricresistarice of which, as is well known, is diminished on exposure.The plan of experiment consisted in sprinkling the double iodide ofcopper and mercury on the disc of selenium, on which a circularfigure bad been blackened with Indian ink. Tbe selenium was heatedby the passage of an electric current, which produced a t fir& a darkspof, owing ts the change in calour of the double iodide. Thib: sub-sequently extended into a fairly regular circular figure, the measure-ment of the diameter of whioh afforded a means of determining theheat conductivity of the selenium.This method was found ta bemore practicable than the usual method of melting wax. I n all cases,the diameter of the circle was greater when the selenium was exposedto reflected sunlight from which the greniter part of the heat r a phad been removed by passage through solutious af alum and ofnnimoniacal copper sulphate. The relation of heat conductivitywithout and with exposure to light was found to be in the ratio of1 : 1.1 as the result of several concordant experiments. The samGEKERAL AND PHYSJCAL CHEMISTRY. 99ratio was observed between the electric conductivities without andwith exposure to light under conditions similar to bhose describ-dabove. The authors, however, would not insist on this concordance ofresults in the two phenomena. V.H. V.Effect of Light on the Conductivity of' Selenium. By S.KALTSCHER (Ann. Phys. Clbem. [2], 32, 108).--Uf the selenium cellsconstructed by the author, three in which copper and copper-brasselectrodes are used, are found to differ from the rest in their behaviouron exposure to light, the resistance rapidly increasing after undergoingR momentary decrease, and the cell only returning to its normalcondition on remaining for some time in tJhO dark. The conclusiondrawn from this is, that the cells in question contain a hitherto uil-known modification of selenium, the conductivity of which decreasesinstead of increasing under the action of light. As the author's othercells which do not exhibit the peculiarity &scribed, differ from t,hea,bove in having zinc, copper-zinc, and copper-platinum electrodes.i tstill remains 00 be ascertained whether the nature of the electrodeshas any influence on this behavionr o€ selenium, The phenomenonin question has also been observed and described by Hesehus (Exn.Rep. d. Phys., 20, 490). H. C.New Galvanic Battery.. By F. FRIEDRICHS (Ann. Phys. Chetn.[2], 32,191) .-A tube running below the cells of this battery connectseach with a cammon reservoir, by the raising or lowering of which thefluid used can be transmitted to or removed from t h e cells. A tapattanbed at the end of the tube opposhe the reservoir allows the fluidt o be removed when exhausted. An advantage claimed over otherbatteries is, that spontaneous evaporation of the liquid and consequentcrystallisation of salts when the battery is not in use, is avoided.Galvanic Palarisation.By F. STRE~NTZ ( A m . Phys. Chew. [Z],32, 116) ,-The author has examined the galvanic polarisation pro-duced on aluminium and silver plates. The results for aluminiumhave been already given (Abstr., 1887, 415). With silver, the oxygenplate is found Bo attain maximum polarisation when the E.M.F. ofthe cell used is equal to that of three Daniells ; the polarisation ofthe hydrogen plates is at a maximum when an E.M.F. of two Daniellsis used, it decreases when a greater E.M.E. is employed, but risesagain and becwmes equal to the first maximum for an E.M.F. ofnine Daniells. The explanation given is that the deposition ofmetallic silver on the cathode, which is greater the greater the in-tensity of the ourrent, by increasing the surface decreases the relativestrength of the current and amount of the polarisation, so thatalthough a small E.M.F.produces maximum polarisation with cleanplates, a very considerable one is required to attain the same maximumwith plates thickly coated with silver.Production of Electricity by the Cmdensation of AqueousVapour. By L. PALMIER[ (Nuooo Cime?zto [3], 22, 3&39).-l'heoccasion of this paper is the confirmation by Pirmin Larroque (LaH. C.H. C.h 100 ABSTRACTS OF CHEMICAL PAPERS.LzcmiZre $Zed., 1887) of the author's experiments on the productionof electricity by the condensation of aqneous vaponr.On the otherhand, the experiments of Kalischer (Abstr., 1884,138) led to negativeresults, but Tait considers that these were conducted on far too smalla scale. Accordingly the author has repeated on a large scale hisexperiments on the condensation of aqueom vapour on a beaker ofplatizium containing ice, and connected with a condensing electriccup; in all cases, the production of electricity was observed. Theiiithor remarks that his observations, extending over 37 years, leaveno doubt in his mind as to the production of electricity under theseconditions. The potential of atmospheric electricity is conditionedby the statme of the weather ; the author's observations also have moreparticularly shown that the potential is affected by the eruptions atVesuvius.V. H. V.Electrolysis of Water. By H. v. HELMHOLTZ (Ber. Akad. Ber.,1887, 749--757).-Previous experiments made by the author showedthat the smalIer the amount of dissolved hydrogen and oxygen nearthe electrodes, the smaller the electromotive force necessary toelectrol yse water. The experiments described in the present paperwere made with a v?ew to determine the limits for the smallest elec-tromotive force capable of producing fresh gas under a given pressureof the oxyhydrogen mixt,ure on the liquid. I n previous experiments,an error in the measurement of the electromotive € o m of the decom-position of water was caused by hydrogen or other combustible gasbeing occluded in the platinum anode (ir in both electrodes, so thatthe oxygen camied over in the current comes in contact with thegases of the modes, and thus bubbles of hydrogen will be liberated a tthe cathodes with a much less expenditure of electromotive force.To avoid this, the current is kept in the same direction for weeks ormonths.An apparatus is described with sketch, by means of whichthe gases produced by the electrolysis are removed as soon as formed,and a vacuum is thus kept above the liquid ; the flask containing thesolution is so inclined that a small bubble of gas is retained ; the gasunder t'hese conditions occupies a space 1000 times greater than itwould under normail pressme, and lfhe diameter of the bubble ismeasured in order to ascertain whether it remains the same size orwhether it increases.To produae a current, three c a r h - i r o n ferric chloride solutionelements were used ; the electromotive force was diminished daily inorder to determine the limit.The limit for the evolution of gas wasfound to be 1-64 to 1-43 volt, wikh a pressure of oxyhydrogen gas= 10 mm. of water.The influence of pressure on elecfromotive force is expressed asfollows :-A = A , + 1 0 - 7 . ~ . e { ~ ~ ~ i ~ g ~ ) 2ffh + ffo +yu = atmospheric pressure, p h andp, are the pressures of hydrogeGENERAL AND PHYSICAL CHEMISTRY. 101and of oxygen above the liquid ; a h and a0 are the atomic weights ofthe two elements; 8 is the absolute temperature.where Vh is the volume of 1 gram of hydrogen ; R, the correspondingconstant for oxygen, and 7 the amount of water decomposed in asecond by one AmpAre.When pure oxyhydrogen gas is above the liquid, as in the experi-ments described, p = Ph + p,, the part of the electromotive forcechanging with the pressure becomes-7 = 0.00009319 according to Kohlrausch.A, - A, = +.lO-’.v. 0 . Rh. log = 0.038868. log mat. ?‘). P2N. H. 31.Electrolytic Separation of the Metal on the Free Surface ofthe Solution of its Salt. By J. GUBKIN (Ann. Phlp Chen~. [2j,32, 114).-Wben an electric current passes from a solution of a saltinto the atmosphere of gas or vapour immediately above it, anelectrolytic separation of the metal takes place at the surface of theliquid. Apparatus is described by means o€ xhich this is madeevident, the space above the liquid ‘being either vacuous or exposed tothe air in the ordinary way.Silver and platinum are found toseparate out in films which float on the surface ; zinc oxidises as itseparates out, the white flakes of zinc oxide gradually falling to thebottom. H. C.Action of the Solvent on ElectroLytic Conduction. By T. C.FITZPATRICK (Phil. Mug. [ 5 ] , 24, 377-391).-The author continuerhis researches om the conducti~it~y of salt solutions, the Bolvents beingvaried. The salts examined were calcium,. litbium, and magnesiumchlorides asl;d nitrates, and ferric and mercuric chlorides, the solventsbeing water and ethyl and methyl alcohsls. Tables of conductivitiesare given. With mercuric chloride, which is the only salt molesoluble in alcohol than in water, the conductivihies are little morethan those of the solvents alone.For aqueous solutions, the chloridesconduct better than the nitratcs ; magnesium chloride is anomdous,its conductivity being half that of calcium chloride. Ferric chloridei n dilute solution shows signs of dissociation. With alcoholic solu-tions, the conductivity is not proportional to the amount in solution.The conductivity of lithium salts in ethyl alcohol is 10 to 20 timesas great as that of the other salts. I n all cases, the aqueous solutionsconduct better than the alcoholic ones, the character of the solventappearing to have an influence on the conductivity. This the authorconsiders to be due to the formation of molecular groups in thesolutions. He finds that the conductirity of salt solutions at lowtemperatures points to the existence in solution of cryobydrates a ttemperatures above their solidifying points, and also that the con-ductivity of mixed solvents and of salts in mixed solvents differs fromthe calculated values, showing that an interaction has taken placewith formation of new molecular gronps.The action then of th102 ABSTRACTS OY CHEMICAL PAPERS.solvent is twofold: (1) decomposition of the salt, the amount depend-ing on the temperatui-e, nature of solvent, and state of dilution ; (2)the formation of fresh molecular groups in the solution.Influence of a Magnetic Field on the Thermoelectric Pro-perties of Bismuth. BS G. P . GRIMALDI (Nuouo Cimento [3], 21,57).-It is well known that n magnetic field influences in a remark-able degree the electric resistanw of bismuth; in this paper, theauthor shows that its thermoelectric force when paired with copper isvaried in a similar degree.This pile was placed in the .field of anelectromagnet, and coupled up with a galvanometer, in which read-ings were taken without and with a current passing round theelectromagnet. After due allowance for induction, it is shown thatthe thermoelectric force of the bismuth-copper pair is materiallydecreased in the magnetic field. The experimental enquiry is, how-ever, only i n the preliminary stage.H. I(. T.V. H. V.Rotation of Isothermic Lines of Bismuth placed in aMagnetic Field. By A. RIGHI (Gazxetta, 17, 359).-In the courseof experiments on the heat conductivity of bismuth when placed in amagnetic field, it was observed that the isothermic lines were rotatedin a direction opposite to that of the magnetising current when arectangular strip of the metal was placed with its planes normal tothe line of force.The phenomenon is analogous to that observed byHall, namely, the rotation a f the equipotential lines when a magnetacts on a current flowing along a thin strip of metal, and may explainthe thermomagnetic currents recently discovered by Ettingshausen. v. H. v.Thermic Conductivity of Bismuth in a Magnetic Field. ByA. RIGHI (Gazzetta, 17, 358--359).-The author, as well as otherphysicists, has observed the marked variation of the electric con-ductivity of bismuth when placed in a magnetic field (Abstr., 1887,ltO9), and the production of Hall's phenomenon under these con-di t ions.Considering the correlation of electric and thermic conduc-tivity, the effect of ningnetic field was also studied ; the results of theexperiments showed Ithat with a field of 45?0 C.G.S. units the thermicconductivity of bismuth is to that of the metal under ordinaryconditions as 2 : O-(U86. This result must at present be only con-sidered as approximate; further experiments are being niade withmore refined apparatus. V. H. V.Specific Heat of Superfused Water. By P. CAEDAN~ and F.TOMAYINI (Nuovo Cimeuto 133, 21, 185).--The specific: heat of m t e ra t varims temperatmuyes has been the subject of numerous investiga-tions, although the results obtained are far from cnncoi*dant.Thusat temperatures 0-lo", Hirn, as also Pfaundler and Platter, has ob-served a marked increase of specific heat, whilst Rowland on theother hand observed a decrease. In this paper, a description isgiven of experiments made to determine the specific heat of water int h e superfused condition. The method adopted in the investigationis practically an application of the weight thermometer; a knowGENERAL AND PHYSTOAL CHEMJSTKY. 103volume of water is enclosed by mercury within 8 bulb, connectedwith which is a capillary tube bent twice at right angles. The wholeapparatus is completely filled with water and mercury, and the bulbcooled by suitable freezing mixtures, then the mercury driven out bythe expanding water is collected and weighed.The apparatus is thenagitated, and the mercury driven out by the solidification of tthewater is also collected and weighed. Then from these data, togetherwith a determination of the temperature at the moment of solidifica-tion, and the quantity of heat absorbed by the glass and the mercurycontained, the specific heat of the water at the temperature of solidi-fication is ascertained. The various experimental errors are discussedin full, and the data of all the observations given in a series of tables.The following are the main conclusions : the specific heat of super-fused water is less than unity ; it increases with decrease of tempera-ture from a minimum at a temperature of -6.52" to 0". The finalresults are given below.Temperature. Specific heat.-652" to 0" 0953--8*09 ,, 0 0.96 I-9.47 ,, 0 0.962-10.67 ,, 0 0.985V.H. V.New Form of Calorimeter. By W. I?. BARRETT (PTOC. R.Dublin Soc., 5, 13--16).-l'he instrument devised by the author is amodification of Bunsen's calorimeter. The cup for holding the sub-stance under experiment forms part of a mercurial thermometer. Thecup has a capacity of 4 c.c., and is surrounded by a jacket of polishedmetal. The stem of the thermometer, of which the cup is a portion,is supported horizontally, and graduated from -5" to 80". Supportedimmediately above the cup is a small burette, the level of the liquidin which can be accurately read. The neck of the burette may beclosed by a short thermometer graduated from 30" to 100".Inmaking B determination of the specific heat of a liquid with this in-strument, the weight of the liquid must be found by taking its specificgravity for the temperature at which it was used ; the volume of theliquid used having been read from the bnrette. This inconveniencemay be obviated by converting the thermometer into a balance, thefitem being supported by knife-edges somewhere near its centre ofgravity. From the end of the stem, a pan is suspended, and beyondthis a pointer, fixed to the stem, moves over a graduated arc. Witha calorimeter balanced in this way, the weight of the liquid at a givenair-temperature may be found directly.Determining the Specific Gravity of Small Quantities ofDense or Porous Substances. By J.JOLT ( P ~ o c . R. Dublin XOC.,5, 41-47).-The method generally employed for determining thespecific gravity of small quantities of minerals of low density is byhalancing in a liquid of known specific gravity. This method, however, isinapplicable when the substance has a specific gravity over 4, and alsowhen the substance is of a porous nature. Under these conditions, theB. H. B104 ABSTRACTS OF CHEMICAL PAPERS.substance may be mixed with another substance of much lower specificgravity in such proportion that the specific gravity of the mixedsubstances may be as close Go that of either of them as may be de-sired. FOP this purpose, t.he author uses the paraffin sold in the formof candles. The transparency of the paraffin enables the appearamceof the embedded mineral to be minutely examined.Results aregiven showing the accuracy of the method. B. H. B.Dissociation of Copper Sulphate. By W. M~~LLER-ERZBACH(Ann. Phys. Chem. [el, 32, 313). -The author has studied the dis-sociatiozl of copper sulphate at higher temperatures than those whichhe previously employed, and finds that his results agree with thoseobtained by Lesceur (Abstr., 1887, 208). The paper also contains adiscussion of the dependence of chemical affinity on temperature(Abstr., 1887, 628). With sodium phosphate containing 5 mols. H,O,and sulphuric acid of 1.294 sp. gr., water passes from the acid to thesalt at 32", but the changeis reversed, and water passes from the saltto the acid at 47". The equilibrium between the affinity of coppersulphate and of dilute sulphuric acid for water occurs, as might beexpected, at higher temperatures the more dilute the acid.Rate of Dissociation as a Measure of the Vapour-tension ofHydrated Salts.By R. SCHULZE (Ann. Phys. Chew. [2], 32, 329).-A reply to Miiller-Erzbach. The author seeks to justify his formerconclusions with regard to Muller-Erzbach's method of determiningthe vapour-tension of hydrated salts (Abstr., 1887, 766). Miiller-Erzbach having objected to the use of zinc sulphate as being a saltwhich admittedly exhibits irregularities in its bchayiour, coppersulphate is here shown to act in an irregular manner also when in-vestigated by the above method. In two out of three tubes contain-ing copper sulphate, evaporation set in at 20", but the third did notexhibit any change even at the end of 10 weeks.Interaction of Metals and Sulphuric Acid.By V. H. VELEY(Chew. News, 56, 221--222).-In this communication, the aut'horpoints out that the results obtained by Spring and Aubin in theirinvestigation on the action of acids on zinc containing lead (Abstr.,1887, 1074) do not adequately represent the Gate of chemicalchange as comparable, for example, with the rate of evolution of agas from a homogeneous liquid. Thus the initial retardation or" induction " observed may be due to the adherence of bubbles of gasto the surface of the metal, and, eecondly, when the change has set in,the metal is surrounded by a concentrated solution of the metallicsalt, which is ouly in part removed b r the gas bubbles.The hydrogenevolved is a resultant of a series of changes, each one of which isvariable at any moment, such as the rate of diffusion of the salt of themetal in the acid liquid, the amount of surface exposed (which Springand Aubin in some experiments kept approximately constant), and thelocal rise of temperature. The amount of gases other than hydrogen,such as sulphurous anhydride and hydrogen sulphide, is doubtless alsodependent on the more or less perfect removal of the products of theH. C.H. CQENERAL AND PHYSICAL CHEMISTRY. 105change from the sphere of the dissolving metal as well as on theconcentration of the acid solution. On the other hand, it does notseem that variations in the relative masses of zinc could make anydifference either in the rate of solution or in the products of thechange, provided that the surfaces exposed were equal.The dissolu-tion of a solid in a liquid must be regarded as R superficial actiononly. The author is at present studying the rate of solntion of metalsin acid liquids under such conditions that not only fresh surfaces of aregular geometrical figure are continuously being exposed, but alsothe products of the change, whether gas or metallic salt, are at onceand continuously removed from the vicinity of the dissolving rne tal.V. H. V.Velocity of the Formation of Ethereal Salts. By N. MEN-SCHUTKIN (Compt. rend., 105, 1016-1019) .--The particular reactioninvestigated was the action of acetic anhydride on alcohols, Ac,O +RHO = AcOR + AcOH, at 100". With most alcohols, the reactionis complete. The formation of the ethereal salt is accompaiiied by a,change of volume, which is least with methyl alcohol and increasinglygreater with ethyl, propyl, and isobutyl alcohols. In order to eliminatethis variable, the mixture of acetic anhydride and alcohol was dilutedwith 15 volumes of benzene. The constants of velocity are calculatedfrom the equation - - = C(A - x) (B - x), in which A and B are theqnantities of the substances originally present, and x the quantity ofthe new substance formed in time t. A and B being equal, and ~t' and tbeing 0, --?-- = CAt, which gives the constant C. The resultsgiven in the following tables are the mean of several concordant ex-periments, the constants of' velocity being referred to that observedwith methyl alcohol, which is taken as 100 :-dXdtA - - 0Primary alcoliols.Methyl alcohol ............Et,hyl ,, ............Propyl 7, ............Butyl 9 , ............Isobutyl ,, ............Octyl ), ,, ....0 cto decy 1 9 9 7 9Melissy 1 ,7 9 ,Hepttyl ,, (normal) ....Tetradecyl alcohol (normal).Hexadecyl ,, , JAlly1 9 , 7,a-Methyl ally1 alcohol ......Benzyl alcohol ............Constants of velocity.f--- 70-1053 100.00.0505 47.90.0480 4.5060.0465 44.10.0401 38.10.0393 37.50.0377 315.80.0291 27-60.0269 25.50.0245 23.20.0174 16.50.0287 2 7.20-0267 25.30.0280 26.106 ABSTRACTS OF CHEMICAL PAPERS.Constants of velocity.Secondary alcohols. r - 7Isopropyl alcohol .......... 0.0148 14-1Methyl ethyl carbinol ...... 0.0123 11.6Methyl hexyl ,, ....... 0.0091 6 8.7Methyl ally1 ,, ...... 0.00643 6.1Trimethyl carbinol ......... 0.00091 0.8Tertiary alcohol.The ethereal salts of the tertiary alcohols, phenols, and propargylalcohol are decomposed by acetic acid, and hence in these cases thereactions are not comparable with those of primary alcohols.The greatest velocity is observed with methyl alcohol. The velocityis affected by the isomerism of the radicles in the alcohols, but ishighest with primary alcohols, and much lower with secondaryalcohols, whilst in the case of tertiaryaIcohols it is very small indeed.l n homologous alcohols of analogous constitution, the constant ofvelocity diminishes as the molecular weight increases, the differencebeing greatest in the normal primary alcohols. Non-saturated alcoholshave a lower constant of velocity than the corresponding saturatedalcohols, C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8885400097

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

106 ABSTRACTS OF CHEMICAL PAPERS. I n o r g a n i c C h em i s t r y. Action of Carbon Bisulphide on Metals. By A. CAVAZZT (Ohern. Centr., 1887, 8&8, from Xem. R. Ace. Sc. Imt. Bologna [4], 7, 27-33).-Carbon bisulphide vapour when passed over the heavy metals in a fine state of division and heated to a high temperature yields metallic sulphides with separation of carbon in a graphitoidal form. Other compounds of carbon with sulphur seem not t o be formed in any case. Formation of Hydrates of Lithium Hydyoxide from Alcoholic Solutions : Quantitative Determination of Lithium, By C. Q i j ~ r 1 ' 1 ~ (Bey., 20, 29 12 -29 15) .-Lithium hydroxide generally sepa- rates from hot saturated soltitions in 96.8 percent. alcohol with 4 mol. H,O; when in contact with water, it ahows the movements pre- viously observed with crystals of potassium and sodium hydroxide (Alostr., 1887, 636).When lithium hydroxide is crystallised from 62.8 per cent. alcohol, a hydrate with 1 mol. H20 is obtained; the crystals do not move when placed in contact with watef. In determining lithium as sulphate, the sulphate must be ignited for a long time until of constant weight. Transformation of Ammonium Nitrate. By M. BELLATI and R. ROMANESE (Nuovo Cimento [3], 21, 5--24).-Frankenheirn, and, more recently, Lehmann 'have shown that ammonium nitrate crystal- lises in various forms, according to the temperature at which the V. H. V. N. H. M.INORGANIC CHEMISTRY. 107 crystallisation is effected. Thus at 36" it cryst'allises in the trimetric system, a t 87" in the rhombohedral, and at 120" in the monometric system.I n the present paper, it is shown that a t these various points the salt undergoes other physical modifications. Tbus, on warming, the temperature of the salt increases in direct proportion to the time up to a temperature of 35.67" ; so also the rate of cooling is regular up to 30.3", reaching a minimum at 30.07" ; it then increases to 31*05", at which point it remains constant for some time. Similar phenomena are also observable a t a temperature of 855" to 86.5" with ascending terriperature, and 82.2" to 82.6" with descending temperature, as also at 124.8" and 124.05'. The variations of volume corresponding with these crystalline changes is also determined in an accurately calibrated dilatometer containing oil of turpentine, a liquid whose expansion is regular, and which, when properly dried, does not dissolve the salt, Results show that the curve of coefficient of expansion has two points of inflection: one a t a temperature between 33 29" and 41.29", and another at about $5" ; the formula expressing the rate of expansion from 0" to the former of these points is vl = uo (1 i- 0.000339t + 0*000000346t2), whilst between 40" and 85" this becomes v1 = vo (1.04957 +- 0.00038756t + 0-0000M976ta + 0*0000000432t*).There is also an alteration in the value of the mean specific heat at the temperature of these crystalline transformations ; applying the method of mixtures and using oil of turpentine as t,he liquid, it is shown that the mean specific heat from 0-31" is 0,407, from 31" to 82.5" is 0.355, and from 82.5" to 124" is 0.426.Hence the following values are deduced for the heats of transformation at these points :- At 31.0" = 5-02 ,, 124.0 = 11.86 The values obtained for the specific heats of ammonium nitrate are compared with those of Kopp and Tillinger, and the methods of cor- rection applied by the latter are criticised. Ammonium Phosphites. By L. AMAT (Compt. ?*eizd., 105, 809- 811).-A solution of phosphorous acid mixed with ammonia until aentral to methyl-omnge, and then concentrated until the weight of the liquid is one-fourth or one-fifth more than the calculated weight of the salt, yields large, deliqnescent crystals which can be dried over sulphuric acid or at 100". Similar crystals are obtained if the liquid is concentrated i n a vacunm a t the ordinary temperature.The crystals have the composition NHa*H2P03, and seem t o be monoclinic prisms ; they melt at 123" and are very soluble in water. A t 145" they lose half their ammonia without evolution of hydrogen phos- phide, and yield a gummy mass which seems to contain crystals. At a higher temperature, ammonia and hydrogen phosphide are given off and phosphoric acid is formed. Hydrated diammonium phosphite, (NH,),HPO, + 2H,O, when kept in a dry vacuum a t the ordinary temperature or heated at loo", loses water aud ammonia, and yields the monammonium salt j u s t ,, 82.5 = 5-33 V, H. V.108 ABSTRACTS OF CHEMICAL PAPER,S. described. Both at the ordinary temperature and at loo", the water is given off before the ammonia.Monammonium phosphite has no appreciable action on ammonia gas at the ordinary temperature, but at 80" to 100" absorption is rapid, and the anhydrous diammonium salt is obtained as a white powder. The corresponding compounds of sodium and potassium have not yet been obtained. Effects produced by Small Quantities of Bismuth on the Ductility of Silver. By J. SCULLY (Clhem. News, 56, 224-926 ; 232-244 ; 247--248).-1t is observed that the Indian method of met assay is incidentally a delicate test for bismuth in presence of a large excess of silver. The bullion is dissolved in nitric acid, the solution diluted, excess of hydrochloric acid added, and tb e whole vigorously agitated to facilitate the aggregation of the silver chloride, which settles down and generally leaves a clear supernatant liquid; if, however, the liquid is turbid and the silver chloride on exposure to light, while still under the liquid, remains white, the turbidity is due to mercury, if on the other hand, the silver chloride becomes discoloured, the turbidity is due to bismuth ; tin and antimony having been proved t o be absent when dissolving in nitric acid.In such cases, to prevent the vitiation of the silver assay, the following modified method has proved successful :-The assay ponnd of bullion is dissolved in 5.5 C.C. of nitric acid, sp. gr. 1.200, the solution is mixed ;with 5 ozs. of wat'er and 10 C.C. of nitric acid, sp: gr. 1.320, then 2.5 C.C. of hydrochloric acid are added, and kbe method proceeds as usual. F o r the estimn- tion of the bismuth, having obtained a rough idea of the amount of bismuth present from the amount of turbidity in the trial assay, suflicient bullion to yield a weighable amount of bismuth is dissolved in a small quantity of nitric acid, the solution diluted and heated with excess of ammonium carbonate, which dissolves the silver and copper carbonates, but leaves the bismuth carbonate insoluble ; the latter is then washed, dried, ignited, and weighed. Jf lead or cadmium are present they would remain with the bismuth carbonate ; the latter, however, is not likely to be present, and the former may be separated by dissolving the bismuth carbonate in nitric acid, and evaporating down with sulphuric acid ; the lead sulphate is treated in the usual manner and weighed, whilst the bismuth is reconverted into carbonate and estimated as described above.Fine silver, or silver cont'aining 10 per 1000 of copper, alloyed with 1 to 5 per 1000 of bismuth and cooled rapidly, had its ductility, as tested by rolling, sensibly but slightly impaired, the straps having jagged edges ; with 6 per 1000 of bismuth, the decrease in ductility was more evident, whilst fine silver with 9 to 11 per 1000 of bismuth was so brittle as to brenk with a mere tap. When, however, the cooling was gradual, 4 per 1000 of bismuth was sufficient to make the silver or silver-copper alloy mentioned above highly brittle, the fracture being crystalline in the case of fine silver and granular in the silver- copper alloy. With Indian standard d v e r containing 83.4 per 1000 of copper, 2 per 1000 of bismuth produced red shortness and jagged straps : as the quantity of bismuth increased the evidence of diminished C.H. B.INORGANIC CHEMISTRY. LO9 ductility is more decisive, and with 10 per 1000 of bismuth the alloy was very brittle and had a granular fracture ; the mode of cooling bad no appreciable effect on the ductility of these alloys. Other experi- ments with Indian coinage bars show that the ductility of bullion is not materially affected by the presence of 0.5 per 1000 of bismuth. As the refining fine silver containing bismuth is both tedious and attended with loss of silver, the author suggests dilntion with silver free from bismuth as a, practical means of overcoming the brittleness. The anthor remarks on the concordance of his results with those of Gowland and Koga (Trans., 1887, 410-416), as regards the question of brittleness.The discrepancy in reference to refining bismuth silver he suggests is possibly due to the Japanese silver containing more base metals than the Indian silver ; it consequently supplied more slagging material and greater facilities for refining. D. A. 11. Combination of Silver Chloride with Metallic Chlorides. By M. C. LEA (Anter. J. Sci., 34, 38&387).-1f hydrochloric acid is mixed first with ferric chloride and then with silver nitrate, the silver chloride which forms is not white but buff-coloured. The ferric chloride cannot be removed by washing, and is only partially removed by treatment with hydrochloric acid. The presence of the minute quantity of ferric chloride makes the silver chloride remarkably less sensitive to light. Cobalt chloride and hydrochloric acid give a silver chloride which is pink and contains cobalt ; but the reduction in the sensitiveness to light is very much less than when iron is present.Nickel and manganese behave similarly, but cupric chloride seems to have no tendency to combine with silver chloride. The tendency of gold chloride to combine with the silver chloride is, however, well marked, and the precipitate has a reddish shade, but the influence on the sensitiveness is not easily determined, since the gold is rapidly reduced to the metallic state, and the silver chloride darkens to black instead of to chocolate or violet. as would be the case if it were pure. In analytical determinations, it is important to digest the silver chloride for a considerable time with hydrochloric acid, and even then i t is doubtful if the foreign chloride is entirely removed, especially if it is ferric chloride.These observations show that silver chloride has a great tendency t o combine with small quantities of other chlorides, and supports the author’s view as t o the nature of the ‘‘ photo-salts ” (this vol., p. 1). They also explain the fact that a small quantity of mercuric chloride very greatly reduces the sensitiveness of silver chloride to light. In order to ascertain the presence of mercury in the silver chloride, the anthor employs a solution of stannous chloride in hydro- chloric acid which has no action on silver chloride if light is carefully excluded, but gives a brown or brownish-black colour t o the precipi- tate if mercury is present. The author was unable to remove mercuric chloride from silver chloride even by very prolonged washing.Poitevin’s observation that his coloured photographic images resisted the action of light better after they were treated with dextrin and110 ABSTRACTS OF CHEXICAL PAPERS. lead chloride is explaincd by the tendency of the lead salt to prevent alteration of silver chloride. C. H. B. Silver Potassium Carbonate. By A. DE SCHULTEN (Compt. rend., 105, 811--813).-When silver carbonate is formed by the action of an alkaline cabonate on silver nitrate, the precipitate is sometimes white, sometimes yellnw, but always becomes yellow when washed. If silver nitrate is added to an excess of a concentrated Solution of potassium Carbonate containing some hydrogen carbonate, a white precipitate is formed which changes to microscopio crystals of the oomposition AgKCOs.This compound is decomposed by water, with removal of the potassium carbonate and formation of yellow silver carbonate. 150 grams of potassium carbonate is dissolved in 150 C.O. of water, cooled and agitated with 15 grams of potassium hydrogen carbonate. When the liquid is sahurated with the latter salt a t the ordinary tem- perature, it is filtered and mixed with a solution of 1 gram of silver nitrate in 25 C.C. of water. In order to obtain large crystals, the liquid contaiuing the precipitate is heated with continual agitation. The precipitate dissolves, and when the l i p i d is cooled it deposits long, transparent crystals with a brilliant lustre ; sp.gr. 3.769. They do not blacken when exposed to light except in the presence of orpnic matter, and when treated with water, the silver carbonate which remains retains the form of the osiginal crystals. When heated, the compound loses carbonic anhydride, and a t a higher tem- perature the silver oxide which i s formed gives off oxygen. The crystals are microscopic, rectangular lamell= with a terminal angle closely approaching 90". The refraction is almost identical with that of apatite ; the extinction of parallel polarised light takes place longitudinally ; twinning plane parallel with the plane of the optical axes ; sign of elongation positive ; maximum birefractir-e power approximately 0.0216.C, H. B, Lead Aluminium Sulphate, By G, H. BAILEY (J. XOC. Chem. Ind., 6, 415).-The author has examined some crystals whioh have been noticed in a mordanting liquor (aluminium nitroaoetate) pre- pared by dissolving up alum, lead acetate, and lead &rate in water and allowing to settle. The crystals form octahedra crystallising in cruciform aggregates like alum. They are, however, not transparent and are quite unaltered by exposure to air. The substance is a lead alum, Pb,A1,(S0J6 + 20H20, formed under speoial conditions of concentration and temperature. D. B. New Oxide of Thallium. By A, PICCINI (Gazzetta, 17,450-452).- Carstanjen has observed that when a rapid current of chlorine is passed through a concentrated solution of potash in which thallium sesquioxide is suspended, the solution acquires a violet colour which is considered to be due to a potassium thallste. The same liquid is also formed when thallium hydroxide is submitted to electrolysis, using a plate of thallium as an electrode, as also on adding potassium hypo- chlorite to a quarter of its weight of caustic potash to which thallium sulphate is subsequently added.On digeetinp the whole and addipg barium nitrate, a violet precipitate is finally obtained. The results ofINORGANIC CHEMISTRY. 111 analyses made to determine the relation between thallium and baiium in this precipitate led to discordant results, but sufficient evidence was afforded to point to a formula, TIOz, for the oxide of Bhallium. The isolation of this oxide brings out a further point of analog7 of the thallium compounds to those af lead.Experiments made to pre- pare the corresponding sulphur compound have not as yet been successful, although substances have been obtained which contain a proportion of sulphur greater khan that required for the trisulphide. V. H. V. Constitution of Basic Salts. By S. U. PICKERING (Chem. News, 56,210-212).-1n the author's opinion, those basic compounds, which although seemingly of indefinite composition can scarcely be regarded as mere mixtures, are preoisely analogous to the complex hydrates, which he contends conskitnte a solution of a salt in water. Hydrated basic salts of copper may be obtained of a composition come. fiponding with that of an anhydrous salt of the formula ~ ~ C U O , S O .~ , but the most basic definite sulphate known is 4Cu0,S03, therefore if these higher basic salts are to be regarded as mixtures, they must be mixtures of a basic salt with copper hydroxide and not mixtures of two different basic salts. To investigate this point, a aeries of basic copper salts were pye- pared by diluting a solution of ammonio-copper sulpha-te with increasing quantities of water; the precipitates were dried in a vacuum, and analysed. The results, although not decisive, bend to show that free copper hydroxide is not present in these compounds, for on comparing any two preparations of different basicity, the excess of copper oxide present in the more basic one is not accompanied by a constant pro- portion of water. D. A, L. Crystallisad Mercurous Iodide and Bromide.By A. STROMAN (Bey., 20, 2818-2823) .-If a saturated solution of mercuroue nikrato, as free as possible from oxide and slightly acidified with nitric acid, is heated to boiling with iodine, the latter becomes covered with a, yellow powder, which partially dissolves, and Che solution, after decantation into a warm dish, deposits, in the dark, lustrous, yellow, transparent, tetragonal scales of' mercurous iodide ; these must be dried in the dark a t the ordinary temperature. When the merourous nitrate solution is treated wihh an alcoholic solution of iodine in the cold, small, yellow spangles of mercurous iodide are obtained, but the product formed by the old methods of prepapation, that is, by rubbing together molecular proportions of mercury and iodine, and by adding patassium iodide in solution to a solution of a mercurous salt, have a green colour, and are impure, although the pure yellow compaund can be obtained by reversing the last process and adding an exoesa of a dilute solution of mercurous nitrate to potassium iadide in solution. Tbe crystallised compound shows t8he same colour- ohange as observed by Yvon (this Journal, 1873,1105), but the change does not begin at 60", as stated by him, since the salt is still a pure yellow at loo", and only passes from this colour through dark yellow and orange to garnet-red at higher temperatures.Sublimation commences at 110-120", not at 190" as stated by Yvon, and the112 ABSTRACTS OF CHEMICAL PAPERS. salt fuses at 290" with decomposition. Towards acids and solvents, the crystalliskd compound behaves like that precipitated by potassium iodide ; ammonia and caustic alkalis render it green, and on heating convert it into the corresponding alkaline iodide and metallic mercury.The crystallised iodide is less sensitive to light than the precipitated yelIow compound, which rapidly becomes black even in diffused daylight. When mercurous nitrate solution is treated with bromine under similar conditions, small, white, nacreous, tetragonal scales of mer- curous bromide are obtained, and the same compound separates in yellow, crystalline spangles when an alcoholic or aqueous solution of bromine is employed. It sublimes at 340-350" in small scales, is less sensitive to light than the iodide, dissolves in hot sulphuric acid with the evolution of sulphurous anhydride, becomes black and graduaIly decomposes when heated with dilute and concentrated hydro- chloric acid, dissolves slowly in hot nitric acid (sp.gr. = 1*42), and decomposes with the formation of the corresponding bromides when treated with ammonia and caustic alkalis. TQ. P. W. Atomic Weight of Yttrium Metals in their Natural Com- pounds: Gadolinite. By C. RAMMELSBERG (Ber. Akad. Ber., 1887, 549-556) .-According t o Nordenskiold (Abstr., 1887, log), the oxides of the yttrium metals occur in their natural compounds in proportions so nearly constant that he suggests the term gadolinium oxide for this mixture of yttrium, erbium, and ytterbium oxides. The author shows from the results of 29 analyses of minerals from different sources and by various chemists, that this mixed oxide, so far from being constant, would give atomic weights Yarying from 97.5- 132.5" for the mixture of metals. Analyses of gadolinite from Hittero and Ptterby gave the following results :- Hittero.Ytterby. Silica ............... 24.36 25-53 Yttrium earths. ....... 45.5 1 38.13 Cerium oxide. ........ 7.01 13.55 Ferric oxide .......... 2.85 4.07 Ferrous oxide ........ 11.50 7.47 Lime ................ 0.36 0.5 7 Beryllium oxide ...... 8.58 10.03 Loss on ignition ...... 0.50 1.34 100-67 100.51 N. H. M, Water of Crystallisation of Alums. By J. JUTTEE (Qh.em. Cerztr., 18, 777).--Potash alum, in a, vacuum over sulphuric acid, loses 19 mols. H20, chromium alum 12-13, and iron alum, 20-21 mols. H,O. Potash alum, heated at 100" in a current of dry air, loses 15 mols.H20 readily, but the remainder only after prolonged heating, end breaking up of the dry crust, which retains the water. At a temperature of 20-30" potash alum gives off no water, at 42" 11 mols., at 65-91" 19 mols., and att 100" the remaining 5 mols. of water areIN0 RGANIG OHELCIlSTRY. 113 given off. Potassium, chromium, and ammonium iron Flum heatcld at 100" are completely dehydrated, without becoming insoluble in water, and without undergoing any decomposition. Action of Hydrogen Sulphide on Cobalt Salts. . By EL BAUBIGNY (Compt. rend., 105, 751-754, and 806--809).-The action of hydrogen sulphide on solutions of cobalt salts varies, as in the case of nickel salts (Abstr., 1882, 1031), with the concentration of the solu- tion, the nature of the acid in the salt, the ratio between the weight of acid and metal present, the ratio of free acid to the water present, the degree of saturation with hydrogen sulphide, or in other words the tension of the gas, and also with certain other Conditions, includ- ing the temperature and the duration of the experiment.Solutions of the normal sulphates of cobalt and nickel were satu- rated with hydrogen sulphide, and hermetically sealed in glass flasks, the liquid occupying about five-sixths of the volume of the flask. After standing for some days, *precipitation is always more complete in the case of nickel than with cobalt. This, however, is only ft special result. Under comparable conditions the formation of cobalt sulphide from a solution of a cobalt salt is always more rapid than the formation of nickel sulphide from the corresponding nickel salt.This is observed, for example, if the solutions saturated with hydrogen sulphide only partially fill the vessels. It follows that the tension of the gas exercises a considerable influence on the result. Precipitation of the cobalt sulphide is prevented by the presence of free acetic acid, the proportion required to produce this result being greater the greater the concentration of the solution. More acetic acid is necessary to prevent the precipitation of cobalt than to prevent that of nickel. With sulphuric acid and similar acids, however, the differences between the two metals tend to disappear. In both cases, there is no precipitation even after several days at the ordinary tem- perature if the proportion of free sulphuric acid is equal to half that in Combination with the metal, provided that the quantity of salt present exceeds 0.15 gram per liti-e.If the solutions are more dilute, some precipitation takes place, the quantity of sulphide formed being greaterin the case of cobalt than in the case of nickel. The presence of the precipitated sulphide accelerates the reaction in both cases. Rise of temperature accelerates precipitation from solutions of cobalt sulphate, but precipitation is not as complete as with nickel sulphate under the same conditions. The precipitation of nickel iii fact takes place more readily than the precipitation of cobalt as the acidity of the solution increases. The more concentrated the original solution of the neutral salt, and consequently the greater the quantity of acid liberated during the reaction, the greater is the precipitation of the nickel as compared with that of cobalt.I t follows that, a smaller quantity of free acid is required to prevent the precipitation of cobalt than to prevent that of nickel. With weak acids, the dif- ference is still distinct. In a solution containing only a small propor- tion of free acetic acid, the precipitation is greater i n the case of colalt, but if the proportion of free acid is increased the precipitation of nickel becomes the greater of the two. V. H. V. C. H. B. VOL. LIV. i114 ABSTRACTS OF CXERIICAL PAPERS. Action of Vanadic Anhydride on Potassium Fltioride. By A. DITTE (Compt.rmad., 105,1067-1070).-When excess of vanadic anhydride is fused with potassium fluoride in a platinum crucible, care being taken to prevent access of air, a brick-red, crystalline mass is formed on cooling, and when tlhis iR treated with water, a residue of vanadic anhydride is left, and a red solution is obtained. The solu- tion first deposits a small quantity of potassium bivnnadate, formed in consequence of accesB of air, and then orange-red plates of the com- pound W205,2KE + 5H20, which melts easilyto a black liquid. The mother-liquor on fiirther concentration deposits red, transparent prisms of the composition 4V2O5,2KF + 8H20. Contact with air is more completely avoided by heating the crucible at the bottom of a, long glass tube. Under these conditions the aqueous solution first deposits the compound 3Vz05,'2KF + 5H20, then ruby-red prisms of the composition 3V205,2KF + 6Hz0, and less soluble, lemon-yellow crystals of the composition 3 V205,4KF.All these compounds are soluble in concentrated sulphuric acid, with evolution of hydrogen fluoride and formation of a red solution which becomes pale-green when diluted with much water. When an excess of potassium fluoride is employed, the residue is pale-yellow, and on treatment with cold water first yields a saturated solution of potassium fluoride, in which the vanadium compounds are practically insoluble. A further quantity of water forms a yellow solution, which deposits small plates of the composition 2V205,2KF + 8H20, and the mother-liquor when concentrated in a vacuum yields the compound W205,2KF + 4H,O.The portion of the residue least soluble in water has the cornposition V205,4KF + 3H20. With a large excess of potassium fluoride, the solution yields suc- cessively large, thin, brilliant, orange-yellow lamella of the compound 3V205,2KF + 5H20, white c~ystals with a greenish-yellow tinge of the compound V205,8KF + 3H20, and finally yellow crystals OP the compound V205,4KF + 2H20. If air has free access and vanadic anhydride is in excess, the residue is an orange-red mass with a vitreous fracture, and whon treated with hot water some vanadic anhydride remains undissolved. The solution first deposits potassinm bivanadate, and afterwards lemon- yellow crystals of the composition V205,4KF. Similar results are obtained with excess of potassium fluoride.Water first dissolves the excess of fluoride, and the solution obtained by further treatment deposits yellowish-white crystals of the compound V205,8KF + The action of potassium fluoride on vanadic anhydride yields the compounds 2V205,KF; 3Vz0,,2KF; V205,KF ; 3V205,4K3' ; V205,4KE ; V205,8KB, which may be regarded as analogous to potassium chloro- chromate. Their solutions give no coloration and no precipitate with ammonia. If these compounds are regarded as derived from an oxg- fluoride, the latter must be V20aF2. Possibly the compounds do not actually exist in the fused mass, but the aqueous solution contaics several different compounds, giving rise to conditions of equilibrium ih which the crystallisable salts described are formed.A solution of potassium duoride dissolves vanadic anhydride, and the liquid deposits 2H2O.MINERALOGICAL CHEMISTRY. 115 greenish-white crystals of the compound V,O,,bKF, which is but slightly soluble in excess of the alkaline fluoride. As the colourless solution cools it becomes yellow, and deposits lemon-yellow crystals of the compound V,05,4KF. C. H. B.106 ABSTRACTS OF CHEMICAL PAPERS.I n o r g a n i c C h em i s t r y.Action of Carbon Bisulphide on Metals. By A. CAVAZZT(Ohern. Centr., 1887, 8&8, from Xem. R. Ace. Sc. Imt. Bologna [4], 7,27-33).-Carbon bisulphide vapour when passed over the heavymetals in a fine state of division and heated to a high temperatureyields metallic sulphides with separation of carbon in a graphitoidalform. Other compounds of carbon with sulphur seem not t o beformed in any case.Formation of Hydrates of Lithium Hydyoxide from AlcoholicSolutions : Quantitative Determination of Lithium, By C.Q i j ~ r 1 ' 1 ~ (Bey., 20, 29 12 -29 15) .-Lithium hydroxide generally sepa-rates from hot saturated soltitions in 96.8 percent.alcohol with 4 mol.H,O; when in contact with water, it ahows the movements pre-viously observed with crystals of potassium and sodium hydroxide(Alostr., 1887, 636).When lithium hydroxide is crystallised from 62.8 per cent. alcohol,a hydrate with 1 mol. H20 is obtained; the crystals do not movewhen placed in contact with watef.In determining lithium as sulphate, the sulphate must be ignitedfor a long time until of constant weight.Transformation of Ammonium Nitrate.By M. BELLATI andR. ROMANESE (Nuovo Cimento [3], 21, 5--24).-Frankenheirn, and,more recently, Lehmann 'have shown that ammonium nitrate crystal-lises in various forms, according to the temperature at which theV. H. V.N. H. MINORGANIC CHEMISTRY. 107crystallisation is effected. Thus at 36" it cryst'allises in the trimetricsystem, a t 87" in the rhombohedral, and at 120" in the monometricsystem. I n the present paper, it is shown that a t these various pointsthe salt undergoes other physical modifications. Tbus, on warming,the temperature of the salt increases in direct proportion to the timeup to a temperature of 35.67" ; so also the rate of cooling is regularup to 30.3", reaching a minimum at 30.07" ; it then increases to 31*05",at which point it remains constant for some time.Similar phenomenaare also observable a t a temperature of 855" to 86.5" with ascendingterriperature, and 82.2" to 82.6" with descending temperature, asalso at 124.8" and 124.05'.The variations of volume corresponding with these crystallinechanges is also determined in an accurately calibrated dilatometercontaining oil of turpentine, a liquid whose expansion is regular,and which, when properly dried, does not dissolve the salt, Resultsshow that the curve of coefficient of expansion has two points ofinflection: one a t a temperature between 33 29" and 41.29", andanother at about $5" ; the formula expressing the rate of expansionfrom 0" to the former of these points is vl = uo (1 i- 0.000339t +0*000000346t2), whilst between 40" and 85" this becomes v1 = vo(1.04957 +- 0.00038756t + 0-0000M976ta + 0*0000000432t*).Thereis also an alteration in the value of the mean specific heat at thetemperature of these crystalline transformations ; applying the methodof mixtures and using oil of turpentine as t,he liquid, it is shown thatthe mean specific heat from 0-31" is 0,407, from 31" to 82.5" is 0.355,and from 82.5" to 124" is 0.426. Hence the following values arededuced for the heats of transformation at these points :-At 31.0" = 5-02,, 124.0 = 11.86The values obtained for the specific heats of ammonium nitrate arecompared with those of Kopp and Tillinger, and the methods of cor-rection applied by the latter are criticised.Ammonium Phosphites.By L. AMAT (Compt. ?*eizd., 105, 809-811).-A solution of phosphorous acid mixed with ammonia untilaentral to methyl-omnge, and then concentrated until the weight ofthe liquid is one-fourth or one-fifth more than the calculated weightof the salt, yields large, deliqnescent crystals which can be dried oversulphuric acid or at 100". Similar crystals are obtained if the liquidis concentrated i n a vacunm a t the ordinary temperature. Thecrystals have the composition NHa*H2P03, and seem t o be monoclinicprisms ; they melt at 123" and are very soluble in water. A t 145"they lose half their ammonia without evolution of hydrogen phos-phide, and yield a gummy mass which seems to contain crystals. Ata higher temperature, ammonia and hydrogen phosphide are given offand phosphoric acid is formed.Hydrated diammonium phosphite, (NH,),HPO, + 2H,O, whenkept in a dry vacuum a t the ordinary temperature or heated at loo",loses water aud ammonia, and yields the monammonium salt j u s t,, 82.5 = 5-33V, H.V108 ABSTRACTS OF CHEMICAL PAPER,S.described. Both at the ordinary temperature and at loo", the wateris given off before the ammonia.Monammonium phosphite has no appreciable action on ammoniagas at the ordinary temperature, but at 80" to 100" absorption israpid, and the anhydrous diammonium salt is obtained as a whitepowder. The corresponding compounds of sodium and potassiumhave not yet been obtained.Effects produced by Small Quantities of Bismuth on theDuctility of Silver.By J. SCULLY (Clhem. News, 56, 224-926 ;232-244 ; 247--248).-1t is observed that the Indian method of metassay is incidentally a delicate test for bismuth in presence of a largeexcess of silver. The bullion is dissolved in nitric acid, the solutiondiluted, excess of hydrochloric acid added, and tb e whole vigorouslyagitated to facilitate the aggregation of the silver chloride, whichsettles down and generally leaves a clear supernatant liquid; if,however, the liquid is turbid and the silver chloride on exposure tolight, while still under the liquid, remains white, the turbidity is due tomercury, if on the other hand, the silver chloride becomes discoloured,the turbidity is due to bismuth ; tin and antimony having been provedt o be absent when dissolving in nitric acid.In such cases, to preventthe vitiation of the silver assay, the following modified method hasproved successful :-The assay ponnd of bullion is dissolved in 5.5 C.C.of nitric acid, sp. gr. 1.200, the solution is mixed ;with 5 ozs. of wat'erand 10 C.C. of nitric acid, sp: gr. 1.320, then 2.5 C.C. of hydrochloricacid are added, and kbe method proceeds as usual. F o r the estimn-tion of the bismuth, having obtained a rough idea of the amount ofbismuth present from the amount of turbidity in the trial assay,suflicient bullion to yield a weighable amount of bismuth is dissolvedin a small quantity of nitric acid, the solution diluted and heated withexcess of ammonium carbonate, which dissolves the silver and coppercarbonates, but leaves the bismuth carbonate insoluble ; the latter isthen washed, dried, ignited, and weighed.Jf lead or cadmium arepresent they would remain with the bismuth carbonate ; the latter,however, is not likely to be present, and the former may be separatedby dissolving the bismuth carbonate in nitric acid, and evaporatingdown with sulphuric acid ; the lead sulphate is treated in the usualmanner and weighed, whilst the bismuth is reconverted into carbonateand estimated as described above.Fine silver, or silver cont'aining 10 per 1000 of copper, alloyedwith 1 to 5 per 1000 of bismuth and cooled rapidly, had its ductility,as tested by rolling, sensibly but slightly impaired, the straps havingjagged edges ; with 6 per 1000 of bismuth, the decrease in ductilitywas more evident, whilst fine silver with 9 to 11 per 1000 of bismuthwas so brittle as to brenk with a mere tap.When, however, the coolingwas gradual, 4 per 1000 of bismuth was sufficient to make the silveror silver-copper alloy mentioned above highly brittle, the fracturebeing crystalline in the case of fine silver and granular in the silver-copper alloy. With Indian standard d v e r containing 83.4 per 1000of copper, 2 per 1000 of bismuth produced red shortness and jaggedstraps : as the quantity of bismuth increased the evidence of diminishedC. H. BINORGANIC CHEMISTRY. LO9ductility is more decisive, and with 10 per 1000 of bismuth the alloywas very brittle and had a granular fracture ; the mode of cooling badno appreciable effect on the ductility of these alloys.Other experi-ments with Indian coinage bars show that the ductility of bullion isnot materially affected by the presence of 0.5 per 1000 of bismuth.As the refining fine silver containing bismuth is both tedious andattended with loss of silver, the author suggests dilntion with silverfree from bismuth as a, practical means of overcoming the brittleness.The anthor remarks on the concordance of his results with those ofGowland and Koga (Trans., 1887, 410-416), as regards the questionof brittleness. The discrepancy in reference to refining bismuthsilver he suggests is possibly due to the Japanese silver containingmore base metals than the Indian silver ; it consequently suppliedmore slagging material and greater facilities for refining.D. A.11.Combination of Silver Chloride with Metallic Chlorides.By M. C. LEA (Anter. J. Sci., 34, 38&387).-1f hydrochloric acid ismixed first with ferric chloride and then with silver nitrate, the silverchloride which forms is not white but buff-coloured. The ferricchloride cannot be removed by washing, and is only partially removedby treatment with hydrochloric acid. The presence of the minutequantity of ferric chloride makes the silver chloride remarkably lesssensitive to light.Cobalt chloride and hydrochloric acid give a silver chloride which ispink and contains cobalt ; but the reduction in the sensitiveness tolight is very much less than when iron is present. Nickel andmanganese behave similarly, but cupric chloride seems to haveno tendency to combine with silver chloride.The tendency of goldchloride to combine with the silver chloride is, however, well marked,and the precipitate has a reddish shade, but the influence on thesensitiveness is not easily determined, since the gold is rapidly reducedto the metallic state, and the silver chloride darkens to black insteadof to chocolate or violet. as would be the case if it were pure.In analytical determinations, it is important to digest the silverchloride for a considerable time with hydrochloric acid, and even theni t is doubtful if the foreign chloride is entirely removed, especially ifit is ferric chloride.These observations show that silver chloride has a great tendencyt o combine with small quantities of other chlorides, and supports theauthor’s view as t o the nature of the ‘‘ photo-salts ” (this vol., p.1).They also explain the fact that a small quantity of mercuricchloride very greatly reduces the sensitiveness of silver chloride tolight. In order to ascertain the presence of mercury in the silverchloride, the anthor employs a solution of stannous chloride in hydro-chloric acid which has no action on silver chloride if light is carefullyexcluded, but gives a brown or brownish-black colour t o the precipi-tate if mercury is present. The author was unable to remove mercuricchloride from silver chloride even by very prolonged washing.Poitevin’s observation that his coloured photographic images resistedthe action of light better after they were treated with dextrin an110 ABSTRACTS OF CHEXICAL PAPERS.lead chloride is explaincd by the tendency of the lead salt to preventalteration of silver chloride.C. H. B.Silver Potassium Carbonate. By A. DE SCHULTEN (Compt. rend.,105, 811--813).-When silver carbonate is formed by the action of analkaline cabonate on silver nitrate, the precipitate is sometimes white,sometimes yellnw, but always becomes yellow when washed. If silvernitrate is added to an excess of a concentrated Solution of potassiumCarbonate containing some hydrogen carbonate, a white precipitate isformed which changes to microscopio crystals of the oompositionAgKCOs. This compound is decomposed by water, with removal ofthe potassium carbonate and formation of yellow silver carbonate.150 grams of potassium carbonate is dissolved in 150 C.O.of water,cooled and agitated with 15 grams of potassium hydrogen carbonate.When the liquid is sahurated with the latter salt a t the ordinary tem-perature, it is filtered and mixed with a solution of 1 gram of silvernitrate in 25 C.C. of water. In order to obtain large crystals, theliquid contaiuing the precipitate is heated with continual agitation.The precipitate dissolves, and when the l i p i d is cooled it depositslong, transparent crystals with a brilliant lustre ; sp. gr. 3.769. Theydo not blacken when exposed to light except in the presence oforpnic matter, and when treated with water, the silver carbonatewhich remains retains the form of the osiginal crystals.Whenheated, the compound loses carbonic anhydride, and a t a higher tem-perature the silver oxide which i s formed gives off oxygen.The crystals are microscopic, rectangular lamell= with a terminalangle closely approaching 90". The refraction is almost identical withthat of apatite ; the extinction of parallel polarised light takes placelongitudinally ; twinning plane parallel with the plane of the opticalaxes ; sign of elongation positive ; maximum birefractir-e powerapproximately 0.0216. C, H. B,Lead Aluminium Sulphate, By G, H. BAILEY (J. XOC. Chem.Ind., 6, 415).-The author has examined some crystals whioh havebeen noticed in a mordanting liquor (aluminium nitroaoetate) pre-pared by dissolving up alum, lead acetate, and lead &rate in waterand allowing to settle.The crystals form octahedra crystallising incruciform aggregates like alum. They are, however, not transparentand are quite unaltered by exposure to air. The substance is a leadalum, Pb,A1,(S0J6 + 20H20, formed under speoial conditions ofconcentration and temperature. D. B.New Oxide of Thallium. By A, PICCINI (Gazzetta, 17,450-452).-Carstanjen has observed that when a rapid current of chlorine ispassed through a concentrated solution of potash in which thalliumsesquioxide is suspended, the solution acquires a violet colour which isconsidered to be due to a potassium thallste. The same liquid is alsoformed when thallium hydroxide is submitted to electrolysis, using aplate of thallium as an electrode, as also on adding potassium hypo-chlorite to a quarter of its weight of caustic potash to which thalliumsulphate is subsequently added. On digeetinp the whole and addipgbarium nitrate, a violet precipitate is finally obtained.The results oINORGANIC CHEMISTRY. 111analyses made to determine the relation between thallium and baiiumin this precipitate led to discordant results, but sufficient evidencewas afforded to point to a formula, TIOz, for the oxide of Bhallium.The isolation of this oxide brings out a further point of analog7 ofthe thallium compounds to those af lead. Experiments made to pre-pare the corresponding sulphur compound have not as yet beensuccessful, although substances have been obtained which contain aproportion of sulphur greater khan that required for the trisulphide.V.H. V.Constitution of Basic Salts. By S. U. PICKERING (Chem.News, 56,210-212).-1n the author's opinion, those basic compounds,which although seemingly of indefinite composition can scarcelybe regarded as mere mixtures, are preoisely analogous to the complexhydrates, which he contends conskitnte a solution of a salt in water.Hydrated basic salts of copper may be obtained of a composition come.fiponding with that of an anhydrous salt of the formula ~ ~ C U O , S O . ~ ,but the most basic definite sulphate known is 4Cu0,S03, thereforeif these higher basic salts are to be regarded as mixtures, they mustbe mixtures of a basic salt with copper hydroxide and not mixtures oftwo different basic salts.To investigate this point, a aeries of basic copper salts were pye-pared by diluting a solution of ammonio-copper sulpha-te with increasingquantities of water; the precipitates were dried in a vacuum, andanalysed.The results, although not decisive, bend to show that freecopper hydroxide is not present in these compounds, for on comparingany two preparations of different basicity, the excess of copper oxidepresent in the more basic one is not accompanied by a constant pro-portion of water. D. A, L.Crystallisad Mercurous Iodide and Bromide. By A. STROMAN(Bey., 20, 2818-2823) .-If a saturated solution of mercuroue nikrato,as free as possible from oxide and slightly acidified with nitric acid, isheated to boiling with iodine, the latter becomes covered with a,yellow powder, which partially dissolves, and Che solution, afterdecantation into a warm dish, deposits, in the dark, lustrous, yellow,transparent, tetragonal scales of' mercurous iodide ; these must bedried in the dark a t the ordinary temperature.When the merourousnitrate solution is treated wihh an alcoholic solution of iodine in thecold, small, yellow spangles of mercurous iodide are obtained, butthe product formed by the old methods of prepapation, that is, byrubbing together molecular proportions of mercury and iodine, andby adding patassium iodide in solution to a solution of a mercuroussalt, have a green colour, and are impure, although the pure yellowcompaund can be obtained by reversing the last process and addingan exoesa of a dilute solution of mercurous nitrate to potassiumiadide in solution. Tbe crystallised compound shows t8he same colour-ohange as observed by Yvon (this Journal, 1873,1105), but the changedoes not begin at 60", as stated by him, since the salt is still a pureyellow at loo", and only passes from this colour through dark yellowand orange to garnet-red at higher temperatures. Sublimationcommences at 110-120", not at 190" as stated by Yvon, and th112 ABSTRACTS OF CHEMICAL PAPERS.salt fuses at 290" with decomposition.Towards acids and solvents,the crystalliskd compound behaves like that precipitated by potassiumiodide ; ammonia and caustic alkalis render it green, and on heatingconvert it into the corresponding alkaline iodide and metallicmercury. The crystallised iodide is less sensitive to light than theprecipitated yelIow compound, which rapidly becomes black even indiffused daylight.When mercurous nitrate solution is treated with bromine undersimilar conditions, small, white, nacreous, tetragonal scales of mer-curous bromide are obtained, and the same compound separates inyellow, crystalline spangles when an alcoholic or aqueous solution ofbromine is employed.It sublimes at 340-350" in small scales, isless sensitive to light than the iodide, dissolves in hot sulphuric acidwith the evolution of sulphurous anhydride, becomes black andgraduaIly decomposes when heated with dilute and concentrated hydro-chloric acid, dissolves slowly in hot nitric acid (sp.gr. = 1*42), anddecomposes with the formation of the corresponding bromides whentreated with ammonia and caustic alkalis. TQ. P. W.Atomic Weight of Yttrium Metals in their Natural Com-pounds: Gadolinite. By C. RAMMELSBERG (Ber. Akad. Ber., 1887,549-556) .-According t o Nordenskiold (Abstr., 1887, log), the oxidesof the yttrium metals occur in their natural compounds in proportionsso nearly constant that he suggests the term gadolinium oxide for thismixture of yttrium, erbium, and ytterbium oxides.The author shows from the results of 29 analyses of minerals fromdifferent sources and by various chemists, that this mixed oxide, so farfrom being constant, would give atomic weights Yarying from 97.5-132.5" for the mixture of metals.Analyses of gadolinite from Hittero and Ptterby gave the followingresults :-Hittero.Ytterby.Silica ............... 24.36 25-53Yttrium earths. ....... 45.5 1 38.13Cerium oxide. ........ 7.01 13.55Ferric oxide .......... 2.85 4.07Ferrous oxide ........ 11.50 7.47Lime ................ 0.36 0.5 7Beryllium oxide ...... 8.58 10.03Loss on ignition ...... 0.50 1.34100-67 100.51N. H. M,Water of Crystallisation of Alums. By J. JUTTEE (Qh.em.Cerztr., 18, 777).--Potash alum, in a, vacuum over sulphuric acid, loses19 mols. H20, chromium alum 12-13, and iron alum, 20-21 mols.H,O. Potash alum, heated at 100" in a current of dry air, loses15 mols. H20 readily, but the remainder only after prolonged heating,end breaking up of the dry crust, which retains the water.At atemperature of 20-30" potash alum gives off no water, at 42" 11 mols.,at 65-91" 19 mols., and att 100" the remaining 5 mols. of water arIN0 RGANIG OHELCIlSTRY. 113given off. Potassium, chromium, and ammonium iron Flum heatcld at100" are completely dehydrated, without becoming insoluble in water,and without undergoing any decomposition.Action of Hydrogen Sulphide on Cobalt Salts. . By ELBAUBIGNY (Compt. rend., 105, 751-754, and 806--809).-The actionof hydrogen sulphide on solutions of cobalt salts varies, as in the caseof nickel salts (Abstr., 1882, 1031), with the concentration of the solu-tion, the nature of the acid in the salt, the ratio between the weight ofacid and metal present, the ratio of free acid to the water present,the degree of saturation with hydrogen sulphide, or in other wordsthe tension of the gas, and also with certain other Conditions, includ-ing the temperature and the duration of the experiment.Solutions of the normal sulphates of cobalt and nickel were satu-rated with hydrogen sulphide, and hermetically sealed in glass flasks,the liquid occupying about five-sixths of the volume of the flask.After standing for some days, *precipitation is always more completein the case of nickel than with cobalt. This, however, is only ftspecial result.Under comparable conditions the formation of cobaltsulphide from a solution of a cobalt salt is always more rapid than theformation of nickel sulphide from the corresponding nickel salt.This is observed, for example, if the solutions saturated with hydrogensulphide only partially fill the vessels.It follows that the tension ofthe gas exercises a considerable influence on the result.Precipitation of the cobalt sulphide is prevented by the presence offree acetic acid, the proportion required to produce this result beinggreater the greater the concentration of the solution. More aceticacid is necessary to prevent the precipitation of cobalt than to preventthat of nickel. With sulphuric acid and similar acids, however, thedifferences between the two metals tend to disappear. In both cases,there is no precipitation even after several days at the ordinary tem-perature if the proportion of free sulphuric acid is equal to half thatin Combination with the metal, provided that the quantity of saltpresent exceeds 0.15 gram per liti-e.If the solutions are more dilute,some precipitation takes place, the quantity of sulphide formed beinggreaterin the case of cobalt than in the case of nickel. The presenceof the precipitated sulphide accelerates the reaction in both cases.Rise of temperature accelerates precipitation from solutions ofcobalt sulphate, but precipitation is not as complete as with nickelsulphate under the same conditions. The precipitation of nickel iiifact takes place more readily than the precipitation of cobalt as theacidity of the solution increases. The more concentrated the originalsolution of the neutral salt, and consequently the greater the quantityof acid liberated during the reaction, the greater is the precipitationof the nickel as compared with that of cobalt.I t follows that, asmaller quantity of free acid is required to prevent the precipitationof cobalt than to prevent that of nickel. With weak acids, the dif-ference is still distinct. In a solution containing only a small propor-tion of free acetic acid, the precipitation is greater i n the case of colalt,but if the proportion of free acid is increased the precipitation ofnickel becomes the greater of the two.V. H. V.C. H. B.VOL. LIV. 114 ABSTRACTS OF CXERIICAL PAPERS.Action of Vanadic Anhydride on Potassium Fltioride. ByA. DITTE (Compt. rmad., 105,1067-1070).-When excess of vanadicanhydride is fused with potassium fluoride in a platinum crucible,care being taken to prevent access of air, a brick-red, crystalline massis formed on cooling, and when tlhis iR treated with water, a residue ofvanadic anhydride is left, and a red solution is obtained.The solu-tion first deposits a small quantity of potassium bivnnadate, formed inconsequence of accesB of air, and then orange-red plates of the com-pound W205,2KE + 5H20, which melts easilyto a black liquid. Themother-liquor on fiirther concentration deposits red, transparentprisms of the composition 4V2O5,2KF + 8H20.Contact with air is more completely avoided by heating the crucibleat the bottom of a, long glass tube. Under these conditions theaqueous solution first deposits the compound 3Vz05,'2KF + 5H20,then ruby-red prisms of the composition 3V205,2KF + 6Hz0, and lesssoluble, lemon-yellow crystals of the composition 3 V205,4KF.All these compounds are soluble in concentrated sulphuric acid, withevolution of hydrogen fluoride and formation of a red solution whichbecomes pale-green when diluted with much water.When an excess of potassium fluoride is employed, the residue ispale-yellow, and on treatment with cold water first yields a saturatedsolution of potassium fluoride, in which the vanadium compounds arepractically insoluble. A further quantity of water forms a yellowsolution, which deposits small plates of the composition 2V205,2KF +8H20, and the mother-liquor when concentrated in a vacuum yieldsthe compound W205,2KF + 4H,O. The portion of the residue leastsoluble in water has the cornposition V205,4KF + 3H20.With a large excess of potassium fluoride, the solution yields suc-cessively large, thin, brilliant, orange-yellow lamella of the compound3V205,2KF + 5H20, white c~ystals with a greenish-yellow tinge ofthe compound V205,8KF + 3H20, and finally yellow crystals OP thecompound V205,4KF + 2H20.If air has free access and vanadic anhydride is in excess, theresidue is an orange-red mass with a vitreous fracture, and whontreated with hot water some vanadic anhydride remains undissolved.The solution first deposits potassinm bivanadate, and afterwards lemon-yellow crystals of the composition V205,4KF. Similar results areobtained with excess of potassium fluoride. Water first dissolves theexcess of fluoride, and the solution obtained by further treatmentdeposits yellowish-white crystals of the compound V205,8KF +The action of potassium fluoride on vanadic anhydride yields thecompounds 2V205,KF; 3Vz0,,2KF; V205,KF ; 3V205,4K3' ; V205,4KE ;V205,8KB, which may be regarded as analogous to potassium chloro-chromate. Their solutions give no coloration and no precipitate withammonia. If these compounds are regarded as derived from an oxg-fluoride, the latter must be V20aF2. Possibly the compounds do notactually exist in the fused mass, but the aqueous solution contaicsseveral different compounds, giving rise to conditions of equilibriumih which the crystallisable salts described are formed. A solution ofpotassium duoride dissolves vanadic anhydride, and the liquid deposits2H2OMINERALOGICAL CHEMISTRY. 115greenish-white crystals of the compound V,O,,bKF, which is butslightly soluble in excess of the alkaline fluoride. As the colourlesssolution cools it becomes yellow, and deposits lemon-yellow crystalsof the compound V,05,4KF. C. H. B

ISSN:0368-1769    

DOI:10.1039/CA8885400106

出版商:RSC    

年代:1888

数据来源: RSC